FR2877347A1 - POLYOLEFINS RICH IN SYNDIOTACTIC STRUCTURE AND PROCESS FOR THEIR PRODUCTION - Google Patents

Abstract

A polymer comprising a polyolefin rich in amorphous syndiotactic structure comprising greater than about 50% by weight of C3 to C40 alpha-olefins and about 50% to less than about 80% of r dyads based on of the total number of r and m dyads present in the polymer, with a heat of fusion equal to or less than 10 J / g and an ash content equal to or less than 1% by weight. A polyolefin rich in functionalized amorphous syndiotactic structure and Polymer production processes are also described. Application: Use of the polymer to produce various articles and products and various compositions having improved properties.

Description

This application claims the benefit of the provisional application N

  60 / 622,964 filed October 28, 2004. This application is also a continuation of the United States Patent Application

  N 10/825 348 filed April 15, 2004.

  The present invention relates to a polymer, a polymer composition, an adhesive composition and / or an adhesion additive, and a process for their preparation, comprising a polyolefin rich in amorphous syndiotactic structure and / or a polyolefin rich in functionalized amorphous syndiotactic structure. In particular, the polymer comprises a polypropylene rich in amorphous syndiotactic structure, and / or a polypropylene rich in maleated amorphous syndiotactic structure, which may be present in combination with one or more additives.

  Olefin-based polymers (polyolefins) are commonly used in various applications because of their chemical inertness, low density and low cost properties. Common applications include those related to adhesives, sealants, films, fibers, articles, laminates and their combinations.

  Polyolefins can be formed into a variety of films, which can be laminated to, coated onto, or coextruded with various substrates. The film and the substrate may be combined with other materials to form a structure having a plurality of layers, each layer having a specific purpose. The packaging laminates, for example, may comprise a plurality of layers, such as a rigid central configuration layer made of paper or cardboard, a liquid-tight outer layer, a gaseous oxygen barrier such as a intermediate layer made of aluminum foil and / or other layers depending on the application requirements.

  To achieve effective adhesion, it should be preferred to achieve good bond strength or intimate integrity between layers for most applications. However, relatively non-polar olefin-based polymers do not normally adhere well to substrates that are more polar than they are.

  Thus, there is a need for an adhesive which intimately bonds to both polar and non-polar substrates, preferably an adhesive which has superior bond strength durability under various temperature conditions and in the presence of aggressive products.

  In addition, to act as an adhesion layer or other adhesive, it may be necessary for an adhesive composition to exhibit adhesion between various polar substrates and non-polar substrates over a relatively low temperature range of about - However, the polyolefins are usually devoid of adhesion characteristics over this relatively low temperature range. In addition, it may be necessary for an adhesive composition to be soluble in various solvents to facilitate application of the adhesive to the substrate. However, most polyolefins which exhibit adhesion characteristics have a degree of crystallinity which prevents their solubilization in conventional hydrocarbon solvents. Accordingly, adhesion promoters can be used with various adhesive compositions to improve adhesion bonding and other properties of an adhesive.

  For example, U.S. Patent No. 6,656,385 to Wang et al. (Wang) relates to a hot melt adhesive comprising about 15 to about 70% syndiotactic polypropylene and an amorphous poly (alpha-olefin) with a tackifier, optionally a plasticizer and / or a stabilizer. Wang defines syndiotactic polypropylene as a polypropylene comprising more than 70% r dyads. For this reason, Wang does not disclose syndiotactic polypropylene which is essentially soluble in hydrocarbon solvents.

  U.S. Patent No. 4,822,688 to Nogues relates to an adhesive composition comprising a graft modified polypropylene with an acid anhydride which is further reacted with a compound having at least two groups such as a polyol or a polyamine. Although Nogues describes functionalized polyolefins, the reference does not disclose polyolefin adhesion promoters rich in functionalized amorphous syntactic structure that improve adhesion, solubility, and processability.

  Many references relate to compositions comprising syndiotactic polypropylene as an adhesion promoter. Examples include Japanese Patent Application No. 01-152,448, Japanese Patent No. JP 2,824,082 and United States Patent Numbers 5,476,914, 6,184,326 and 6,245,870 which relate to vanadium catalysts. for producing compositions comprising syndiotactic polypropylene which comprises more than 80% r dyads. However, the crystallinity of polypropylene rich in syndiotactic structure according to these references prevents this material from being soluble in hydrocarbon solvents, which limits the use of this material. In addition, these references relate to syndiotactic specific propagation under catalytic site control conditions, resulting in rmmr segments present in the product polymer.

  This is in contrast to the chain end control of the present invention, in which rrmr segments are produced and virtually no rmmr segments are produced.

  U.S. Patent Nos. 5,326,824, 5,373,059, 5,374,685, and Japanese Patent No. 3,025,553 relate to compositions comprising functionalized syndiotactic polypropylene. However, the functionalized syndiotactic polypropylene described in these references has a crystallinity greater than about% (for example [rrrr]> 50 more preferably [rrrr]> 70%) and, thus, the polymers produced in this manner are not soluble in them. organic solvents.

  Japanese reference JP 2,837,246 relates to a syndiotactic polypropylene having an intrinsic viscosity of about 0.01 to 10 dl / g, an Mw / Mn ratio of 1.5 to about 20, a melting temperature Tm from about 130 to 170 C, and a tl / 2 value of 2 minutes. The polymers produced according to JP 2,837,246 are thus crystalline, have a melting temperature and are not soluble in organic solvents.

  In addition, the syndiotactic polypropylene produced using vanadium catalysts results in materials having an ash content, when determined as described herein, greater than about 1% by weight, due to the presence of residual materials from the catalyst.

  Accordingly, there remains a need for polymers, and polymer compositions, comprising a syndiotactic rich polyolefin and / or a functionalized syndiotactic rich polyolefin, which is substantially soluble in a variety of hydrocarbon solvents at room temperature, preferably having a content in ash less than 1% by weight. For this reason, there remains a need for polyolefins rich in syndiotactic structure at low crystallinity, for example [rrrr] <50%, with functionalized syndiotactic rich polyolefins that do not have a defined melting temperature and / or heat of fusion less than about 10 J / g.

  In one aspect of the present invention, a polymer comprises a polyolefin rich in amorphous syndiotactic structure comprising greater than about 50% by weight of C3 to 040 alpha-olefins and comprising from about 50% to less than about 80% dyads. r, based on the total number of r and m dyads present in the polymer, having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85; and an ash content equal to or less than 1% by weight.

  In another aspect of the present invention, a polymer blend comprises a polyolefin rich in amorphous syndiotactic structure comprising greater than about 50% by weight of C3 to C90 alpha-olefins, about 50% to less than about 80% dyads. r, on the basis of the total number of r and m dyads present in the polymer, a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM standard E 794-85 and an equal ash content or less than 1% by weight; and at least one additive comprising a C2 to C90 polymer, a C2 to 090 copolymer, an elastomer, a random copolymer, an impact resistant copolymer, a flow polymer, a tackifier, a crosslinking agent, an antioxidant , a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, a composition with increased tenacity by rubber, a recycled polymer, a blocking agent an antiblocking agent, a pigment, a colorant, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a color masterbatch, a flow enhancer, a crystallization aid, or a of their associations.

  In a further aspect of the present invention, a polymer comprises a polyolefin rich in amorphous syndiotactic structure that has been functionalized with a functional group; wherein, prior to functionalization, the amorphous syndiotactic rich polyolefin comprises more than about 50% by weight of C3 to C40 alpha-olefins, from about 50% to less than about 80% of r dyads, based on total number of r and m dyads present in the polymer, having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85; and an ash content equal to or less than 1% by weight.

  In a further aspect of the present invention, a polymer blend comprises a polyolefin rich in amorphous syndiotactic structure that has been functionalized with a functional group; wherein, prior to functionalization, the amorphous syndiotactic-rich polyolefin comprises more than about 50% by weight C3-C40 alpha-olefins, about 50% to less than about 80% r dyads, based on total number of dyads r and m present in the polymer, having a heat of fusion equal to or less than 10 J / g according to the procedure described in standard ASTM E 794-85 and an ash content equal to or less than 1% in weight; and comprising at least one additive comprising a C2 to C40 polymer, a C2 to C40 copolymer, an elastomer, a random copolymer, an impact resistant copolymer, a fluxionic polymer, a tackifier, a crosslinking agent, a antioxidant, a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, a composition with increased rubber toughness, a recycled polymer, an agent blocking agent, an antiblocking agent, a pigment, a dye, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a color masterbatch, a flow-improving agent, a crystallization aid, or one of their associations.

  Another aspect of the present invention is the contact product of a polyolefin rich in amorphous syndiotactic structure, a functional group and a functionalization catalyst, wherein the polyolefin rich in amorphous syndiotactic structure comprises more than about 50% by weight C3 to C40 alpha-olefins, about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polymer, having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85, and an ash content equal to or less than 1% by weight.

  In another aspect of the present invention, a polymer comprises a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride, wherein the functionalized propylene comprises from about 50% to less than about 80% dyads, based on the total number of r and m dyads present in the polymer having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85 and an ash content equal to or less than 1% .

  In a further aspect of the present invention, a polymer blend comprises a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride and at least one additive, wherein the functionalized polypropylene comprises from about 50% to less than about 80% of dyads r, based on the total number of r and m dyads present in the polymer, has a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM standard E 794-85 and an ash content equal to or less than 1% by weight, the additive being selected from the group consisting of a C2 to C40 polymer, an elastomer, a random copolymer, an impact resistant copolymer, a fluxionic polymer, a tackifier, a crosslinking agent, an antioxidant, a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, a b agent, an anti-blocking agent, a pigment, a colorant, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a masterbatch dye, a flow-improving agent, a crystallization adjuvant , or one of their associations.

  In another aspect of the present invention, an adhesive composition comprises a polyolefin rich in amorphous syndiotactic structure, a polyolefin rich in amorphous syndiotactic structure that has been functionalized with a functional group, or a combination thereof, wherein the polyolefin is rich in amorphous syndiotactic structure comprises more than about 50% by weight of C3 to C40 alpha-olefin, from about 50% to less than about 80% of r dyads, based on the total number of r and m dyads present in the polymer, with a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM standard E 794-85, and an ash content equal to or less than 1% by weight, and in which the functional group, when present, comprises a compound having a weight average molecular weight of 1000 or less, and a carbon-carbon double bond, a carbon-carbon triple bond and / or a heteroatom; the adhesive composition having a peel strength with the isotactic polypropylene of greater than about 3.5 psi and a peel strength with a polyester film greater than about 0.5 psi; pullout being measured according to ASTM D-1876 modified for the use of a 1.27 cm wide sample and a separation rate of 5.08 cm per minute.

  In a further aspect of the present invention, a polymer comprises a polyolefin rich in amorphous syndiotactic structure that has been functionalized with a functional group; wherein the polyolefin rich in functionalized amorphous syndiotactic structure comprises greater than about 50% by weight of C3 to C90 alpha-olefins, about 50% to less than about 80% of r dyads, based on the total number of dyads r and m present in the polymer, having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85.

  In another aspect of the present invention, a process for the preparation of a polymeric material comprises the steps of: melt blending a polyolefin rich in amorphous syndiotactic structure and at least one additive under high shear conditions to produce a concentrate. containing 10 to 90% by weight of the polyolefin, and then mixing the concentrate with at least one additional material to form an end product, wherein the amorphous syndiotactic rich polyolefin comprises more than about 50% by weight alpha C3 to C40 olefins from about 50% to less than about 80% of r dyads, based on the total number of r and m dyads present in the polyolefin, having a heat of fusion equal to or less than 10 J / g depending on the procedure described in ASTM E 794-85 and an ash content equal to or less than 1% by weight.

  In another aspect of the present invention, a method for producing a functionalized amorphous syndiotactic rich structure polyolefin comprises the steps of: A. introducing an olefinic monomer, a metallocene catalyst and an activator into a reactor in an aliphatic solvent ; B. catalytically polymerizing said olefinic monomer in said reactor to produce a polyolefin rich in amorphous syndiotactic structure; C. driving the monomer to remove unreacted olefinic monomer; D. performing a solvent-based functionalization, comprising combining said amorphous syndiotactic-rich polyolefin with a functional group and with a radical initiator in said aliphatic solvent, at a temperature and for a period of time sufficient to produce said polyolefin rich in functionalized amorphous syndiotactic structure; and optionally E. removing said aliphatic solvent, wherein the amorphous syndiotactic-rich polyolefin comprises greater than about 50% by weight of C3-C40 alpha-olefins, about 50% to less than about 80% dyads r, on the basis of the total number of r and m dyads present in the polyolefin, and has a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM standard E 794-85 and a content of ash equal to or less than 1% by weight.

  In another aspect of the present invention, a method for producing a polyolefin rich in functionalized amorphous syndiotactic structure comprises the steps of: A. introducing a melt comprising a polyolefin rich in amorphous syndiotactic structure, a functional group and a radical initiator in a mixing device; B. contacting said melt in said mixing device at a temperature and for a period of time sufficient to produce said functionalized amorphous syndiotactic rich polyolefin, said amorphous syndiotactic rich polyolefin comprising greater than about 50% C3 to C40 alpha-olefin weight, about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polyolefin, and having a heat of fusion equal to or less than at 10 J / g according to the procedure described in ASTM E 794-85 and an ash content equal to or less than 1 by weight.

  Blends of the aforesaid polymers with various articles comprising the aforesaid polymers are also disclosed.

  Definitions For purposes of the present invention and the appended claims, and for ease of reference herein, where a polymer and / or oligomer is mentioned as an inclusion, including, including, etc., a olefin, the olefin present in the polymer and / or the oligomer is the polymerized form of the olefin. For reasons of ease of reference, an amorphous polyolefinic polymer is designated by the abbreviation aPP, a polyolefin polymer rich in isotactic structure is designated by the abbreviation irPP, a polyolefinic polymer rich in syndiotactic structure is designated by the abbreviation srPP, a polyolefinic polymer rich in amorphous syndiotactic structure is designated by the abbreviation a-srPP, a semicrystalline polyolefin polymer is designated by the abbreviation scPP and Xg-FG indicates that the constituent X is grafted (-g-) with a group functional FG.

  For purposes of this specification, the term oligomer refers to compositions comprising 2 to 40 monomer units and the term polymer refers to compositions having 41 or more than 41 monomeric units. The term "monomer unit" denotes a unit of an oligomer or polymer which initially corresponded to the monomer (s) used in the oligomerization or polymerization reaction. For example, the monomer unit of polyethylene is ethylene. For reasons of simplicity, when polymers are mentioned, the reference can also be applied to oligomers unless otherwise specified. Accordingly, the terms polymer and oligomer may be interchangeably mentioned herein unless otherwise specified. In addition, unless otherwise indicated, the term polymer may refer to both homopolymers (i.e., a polymer comprising substantially a monomer) and / or a copolymer (i.e., a polymer comprising more than one polymer). a monomer).

  Functionalized polymeric expression means that the polymer and / or oligomer is contacted with a functional group, optionally a catalyst, heat, initiator or free radical source to bring all or part of the functional group subject to incorporation, grafting, binding or physical fixation and / or chemical fixation to the polymer.

  In addition, the term functionalized constituent is also meant to denote a polymer polymerized directly from monomers (or using an initiator having a functional group) when the polymer has a functional group at one end of a chain.

  The functionalized oligomeric expression is intended to indicate that the oligomer is brought into contact with a functional group, and optionally a catalyst, of heat, an initiator or a source of free radicals, to bring all or part of the functional group to be incorporated, grafted, bound, physically attached and / or chemically attached to the oligomer. In addition, the functionalized oligomer expression is also intended to designate an oligomer oligomer directly from monomers (or using an initiator having a functional group) when the oligomer has a functional group at one end of the chain.

  The term "functional group" refers to any compound having a weight average molecular weight of 1000 or less and a carbon-carbon double bond, a carbon-carbon triple bond and / or a heteroatom. Preferably, the functional group comprises a heteroatom, the heteroatom being a B, N, O, Si, P, F, Cl, Br, I, S, or a combination thereof.

  Preferably, the functional group is a compound containing a heteroatom and an unsaturation, such as maleic anhydride. Preferred functional groups include organic acids, organic amides, organic amines, organic esters, organic anhydrides, organic alcohols, organic acid halides (such as acid chlorides, acid bromides, etc.), organic peroxides, and their salts.

  Polyolefin Tacticality Olefinic polymers and oligomers (polyolefins or polyolefin polymers), in general, and particularly poly-alpha-olefinic polymers comprising propylene or other C3 or higher C3 alpha-olefinic monomers, include hydrocarbyl groups which are attached to the skeleton chain of the polymer. The pendant hydrocarbyl groups may be arranged in different stereochemical configurations determined with respect to the backbone chain of the polymer. These arrangements include atactic configuration, isotactic configuration, and / or syndiotactic configuration.

  The degree and type of tacticity of a polyolefinic polymer can determine the physical properties of a composition comprising such a polymer. Other factors determining such a composition may include the type and the relative concentration of the monomers, comonomers, oligomers, the weight average molecular weight (Mw) of the polymer (s) present (s), the distribution of molecular weights (MWD) of the polymer (s) present, the crystallinity of the polymer (s), etc. The tacticity may be related to the degree of crystallinity that can present an olefinic polymer, in particular a poly-alpha-olefinic polymer. As used herein, the tacticity of a polymer represents the stereochemical regularity of the hydrocarbyl groups, which are attached to the backbone of the polymer molecule (i.e., the tacticity of the polymer).

  Four types of tacticity have been described in the case of poly-alpha-olefins: atactic, normal isotactic, isotactic stereoblock and syndiotactic. Although all these tacticity configurations have been demonstrated primarily in the case of polypropylene, in theory each is also possible for polymers consisting of one or more C3 or more C3 alpha-olefins, cyclic olefins and / or internal olefins.

  Atactic polyolefins are those in which the hydrocarbyl groups attached to the backbone of the polymer molecule do not acquire a regular order with reference to the backbone. This statistical or atactic structure is represented by a polymeric backbone of carbon atoms of alternating methylene and methine groups, with branches randomly oriented as substituents on the carbon atoms of the methine groups. The methine carbon atoms randomly have R and S configurations, creating adjacent pairs having the same configuration (a meso or m dyad) or having a dissimilar configuration (a racemic or r dyad). The atactic form of a polymer contains approximately equal fractions of meso and racemic dyads. Importantly, the atactic poly-alpha-olefins, particularly atactic polypropylene, can be characterized by solubility in aliphatic solvents and aromatic solvents at room temperature. Since the atactic polymers have no regular order or no regular pattern of repeat units in the polymer chain, these atactic polymers may be referred to as amorphous materials. As the amorphous material, atactic polymers tend to lack a molecular lattice structure and may have poorly defined melting points. As a result, the atactic polyalpha-olefins are amorphous, usually having no measurable melting point, and thus have little or no crystallinity.

  Isotactic polyolefins are characterized by the presence of pendant hydrocarbyl groups arranged in space on the same side of the polymer backbone chain. Using isotactic polypropylene as an example, the isotactic structure is usually described by the presence of the pendant methyl groups attached to the ternary carbon atoms of successive monomeric units on the same side of a hypothetical plane passing through the carbon skeleton chain. polymer; for example, the methyl groups are all above or below the plane as shown below: The degree of isotactic regularity can be measured by NMR techniques. The Bovey NMR nomenclature for an isotactic pentad is each m representing a meso dyad or successive methyl groups on the same side in the plane.

  In an isotactic poly-alpha-olefin, all monomeric units have the same stereochemical configuration, with the exception of statistical errors appearing along the polymer. These statistical errors almost always appear as isolated configuration inversions that can be corrected in the nearest alpha-olefinic monomer insertion to restore the initial R or S configuration of the propagating polymer chain. Unique inverted configuration insertions yield rr triads, which differentiates this isotactic structure in its NMR spectrum from the isotactic stereoblock form shown below: This isotactic stereoblock form of a polyolefin may result from exchange mechanisms. chirality of site and / or end-chain control during the formation of a poly-alphaolefinic polymer with isotactic stereoblock. The deviation or inversion of the regularity of the chain structure decreases the degree of isotacticity, therefore, the crystallinity that the polymer may exhibit.

  The syndiotactic poly-alpha-olefins are those in which the hydrocarbyl groups attached to the molecular backbone of the polymer alternate sequentially in the order of one face or plane to the opposite or opposite plane to the backbone of the polymer. polymer, as shown below: In the NMR nomenclature, this pentad is described by ... rrrr ... where each r represents a racemic dyad, i.e., successive methyl groups on sides alternates of the plan (see JA Ewen, Catalytic Polymerization of Olefin, (Ewen's method), and Ed T. Keii, K. Soga, Kodanska Elsevier Pub., Tokyo, 1986, page 271). The percentage of dyads in the chain determines the degree of syndiotacticity of the polymer and is related to the crystallinity of the polymer.

  The molecular chain backbone of a syndiotactic polymer can be considered to be a copolymer of olefins having alternating stereochemical configurations. The highly syndiotactic polymers may be highly crystalline and thus may have defined melting points similar to their isotactic polymorphic forms and, thus, may be characterized in part by their melting point temperature.

  Crystallinity of Polyolefins The amount or purity of tacticity in a polymer is related to the crystallinity of that polymer. Isotactic polyolefins and syndiotactic polyolefins may have varying degrees of crystallinity. For purposes of the present invention, a crystalline polyolefin has a crystallinity greater than 35%, preferably greater than about 50%. As used herein, isotactic poly-alpha-olefins and syndiotactic polyalpha-olefins comprising a large amount of crystallinity comprise an amount of at least 35% by weight of material which is not soluble in the xylene at temperature. room. Poly-alpha-olefins having a high amount of crystallinity can also be characterized, at least in part, by a defined melting temperature or temperature range. Polyalpha-olefins having a large amount of crystallinity can also be characterized, at least in part, by a percentage of crystallinity equal to or greater than 65%, preferably 75% or more.

  Unlike crystalline polyolefins, amorphous polyolefins have a crystallinity of less than about 35%. A substantially amorphous polyolefin, and particularly a substantially amorphous poly-alpha-olefin (eg, substantially amorphous polypropylene), can be characterized as a substantially-soluble polymer in xylene and toluene at room temperature. A preferred substantially amorphous poly-alpha-olefinic polymer, copolymer and / or oligomer or a mixture thereof (collectively referred to as amorphous polyolefin) is a polymer in which a proportion of at least about 95% by weight, preferably at least about 96% by weight, preferably at least about 97% by weight, preferably at least 98% by weight, preferably at least about 99% by weight, preferably from about less than about 99.5% by weight of the amorphous polyolefin is soluble in xylene or toluene at room temperature, based on the total weight of the amorphous polyolefin present. The amorphous polyolefins can also be characterized by the presence of a melting point or a range of zero or barely discernible melting points.

  The heat of fusion (Hf) can also be used to determine the crystallinity of a polymer, following the procedure described in ASTM E 794-85. For example, samples of a weight of approximately 7 to 10 mg may be sealed in sample containers. Then Differential Scanning Calorimetry (DSC) results are recorded by first cooling the sample to about -50 ° C and then gradually heating it to about 200 ° C at a rate of about 10 ° C per minute. The sample can then be held at about 200 ° C for about 5 minutes before performing a second cooling-heating cycle. The first and second cyclic thermal events are recorded. The areas under the melting peaks can then be measured and used to determine the heat of fusion and the degree of crystallinity. The percentage of crystallinity is preferably calculated using the formula [area under the curve (J / gram) / B (joules / gram)] × 100 where B is the heat of fusion of the homopolymer of the essential monomer component present in the 'sample. These values of B can be obtained from the literature, for example in the Polymer Handbook, fourth edition, published by John Wiley and Sons, New York 1999. For convenience, if a polymer has peaks of fusion or multiple crystallization, the sum of the areas under the different peaks was used to calculate the crystallinity.

  Polyolefins Rich in Amorphous Syndiotactic Structure A syndiotactic rich polyolefin polymer (srPP) may comprise at least about 50% dyads r as determined by the method of Ewen. In a preferred embodiment, a srPP may comprise at least about 55% dyads, preferably at least about 60% dyads, preferably at least about 65% dyads, preferably at least about 70%. dyads, preferably at least about 75% dyads, more preferably less than about 80% dyads, based on the total number of dyads r and m present in the polymer.

  A polyolefinic polymer rich in amorphous syndiotactic structure (asrPP) may comprise a polyolefin polymer rich in syndiotactic structure, substantially all of which is soluble in hexane, cyclohexane, toluene or xylene at room temperature.

  A polyolefin polymer rich in amorphous syndiotactic structure (asrPP) may comprise from about 50% dyads to less than about 80% r dyads, based on the total number of dyads present in the polymer.

  In a preferred embodiment, an amorphous srPP may comprise from about 55% dyads to about 75% dyads, preferably from about 60% dyads to about 75% dyads, preferably about 60% dyads. at about 70% dyads, preferably about 65% dyads to about 70% dyads, based on the total number of dyads present in the polymer.

  A polyolefin polymer rich in amorphous syndiotactic structure (asrPP) may comprise from about 6.25% to about 31.6% pentad r, based on the total number of pentades r present in the polymer. In a preferred embodiment, an amorphous srPP may comprise from about 9.15% pentads to about 31.6% pentads, preferably from about 13.0% pentads to about 31.6% pentads, preferably about 13.0% pentadec at about 24.0% pentadec, preferably about 17.9% pentadec at about 24.0% pentadec, based on the total number of pentad r present in the polymer.

  In a preferred embodiment, the polyolefinic polymer rich in amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure (α-srPPr). The srPPr preferably has a weight average molecular weight (Mw) equal to or less than 5,000,000, a number average molecular weight (Mn) of less than or equal to 3,000,000, a z-average molecular weight (Mz) ) equal to or less than 1 000 000 and an index g 'equal to or less than 1.5 measured by the weight average molecular weight (Mw) of the polymer using isotactic polypropylene as a base, all of which may be determined by size exclusion chromatography, for example 3D SEC, also referred to as GPC-3D as described herein.

  In a preferred embodiment, the APRPPr of the present invention may have a Mw value of about 5,000 to about 5,000,000 g / mol, more preferably a Mw value of about 10,000 to about 1,000,000. more preferably Mw from about 20,000 to about 500,000, more preferably Mw from about 50,000 to about 300,000, Mw being determined as described herein.

  In a preferred embodiment, the asrPPr of the present invention may have a Mn of from about 5,000 to about 3,000,000 g / mol, more preferably a Mn of from about 10,000 to about 1,000,000 plus preferably Mn from about 30,000 to about 500,000, more preferably Mn from about 50,000 to about 200,000, Mn being determined as described herein.

  In a preferred embodiment, the α-srPPr of the present invention may have a Mz value of about 10,000 to about 10,000,000 g / mol, more preferably a Mz value of about 50,000 to about 1,000. 000, more preferably Mz from about 80,000 to about 500,000, more preferably Mz from about 100,000 to about 300,000, Mw being determined as described herein.

  In a preferred embodiment, the a-srPPr of the present invention may have an index value of from about 1 to about 1.5, more preferably a value of from about 1.25 to about 1. When measuring to the Mw value of the polymer using the intrinsic viscosity of the isotactic polypropylene as the base, where g 'is defined and determined as described herein.

  In a preferred embodiment, the a-srPPr of the present invention may have a crystallization temperature (Tc) measured by differential scanning calorimetry (DSC) of about 200 C or less, more preferably 150 C or less; more preferably, no crystallization temperature is discernible.

  In a preferred embodiment, the a-srPPr of the present invention may have a density of from about 0.85 to about 0.95 g / ml, more preferably from about 0.87 to 0.92 g / ml. more preferably from about 0.88 to about 0.91 g / ml at room temperature, as measured by ASTM test method D-1505.

  In a preferred embodiment, the α-srPPr of the present invention can have a melt flow rate (MFR), which is inversely proportional to the weight average molecular weight Mw, equal to or greater than 0.2 g / 10 min, preferably in the range of 2 to 500 g / 10 min, and more preferably in the range of 20 to 200 g / 10 min, as measured by the ASTM D-test method. 1238 (190 C, 2.16 kg).

  The polyolefin rich in amorphous syndiotactic structure may comprise alpha-olefins in the base polymer such that the amorphous syndiotactic rich polyolefin may comprise greater than about 50% by weight of C3-C20 alpha-olefins, advantageously more than about 50% by weight of C3 to C10 alpha olefins, and more preferably more than about 50% by weight of C3 to C10 alpha olefins.

  Preferably, the polyolefin rich in amorphous syndiotactic structure may comprise more than about 60% by weight of polypropylene, preferably more than about 70% by weight of propylene, preferably more than about 80% by weight of propylene, preferably more than about 90% by weight of propylene, preferably more than about 95% by weight of propylene, more preferably more than about 99% by weight of propylene, based on the total weight of the polymer.

  The polyolefin rich in amorphous syndiotactic structure of the present invention may further comprise more than about 0.5% by weight of ethylene, preferably more than about 1% by weight of ethylene, preferably more than about 2% by weight. % by weight of ethylene, preferably more than about 3% by weight of ethylene, preferably more than about 4% by weight of ethylene, preferably more than about 5% by weight of ethylene, on the basis of the total weight of the polymer.

  For example, α-srPPr may comprise at least about 50% by weight of propylene (C3) as the base polymer, with ethylene (C2) and C4 to C40 alpha-olefins, advantageously C4 alpha-olefins. at C20, more preferably C4 to C12 alpha-olefins, C2 and C4 to C10 alphaolefins being even more preferred.

  Examples of preferred alpha-olefins include butene-1, pentene-1, hexene-1, hepten-1, octene-1, nonene-1, decene-1, undecene -1, dodecene-1, tridecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1 and branched olefins including 3-methylbutene-1, 4- methylpentene-1 and 4,4-dimethylpentene-1.

  The amount of alpha-olefins in addition to the base polymer, when present in the α-srPP, may be greater than about 0.001% by weight, based on the total weight of the polymer. Preferably, the amount of alpha-olefins is greater than or equal to about 0.1% by weight, more preferably greater than or equal to about 1% by weight. The other alpha-olefins may also be present in the base polymer in a proportion of about 50% by weight or less. Preferably, the amount of the other alpha-olefins is less than or equal to about 20% by weight, more preferably less than or equal to about 10% by weight.

  In a preferred embodiment, substantially all of the asrPP (preferably α-srPPr) of the present invention is substantially amorphous, which means that substantially all of the α-srPP is soluble in hexane, cyclohexane, xylene, and the like. or toluene at room temperature. As used herein, the expression substantially all of the srPP means that a proportion of at least about 95% by weight, preferably at least about 96% by weight, preferably at least about 97% by weight, preferably at least about 98% by weight, preferably at least about 99% by weight, preferably at least about 99.5% by weight of the α-srPP is soluble in hexane, cyclohexane, xylene or toluene at room temperature (i.e., C), based on the total weight of α-srPP present.

  In a preferred embodiment, the α-srPP, more preferably α-srPPr, of the present invention may have a heat of fusion (Hf) determined according to the procedure described in ASTM E 794 which is less than or equal to about 10 J / g, preferably less than or equal to approximately 9 J / g, preferably less than or equal to approximately 8 J / g, preferably less than or equal to approximately 7 J / g, preferably less than or equal to approximately 6 J / g / g, preferably less than or equal to approximately 5 J / g, preferably less than or equal to approximately 4 J / g, preferably less than or equal to approximately 3 J / g, preferably less than or equal to approximately 2 J / g preferably less than or equal to about 1 joule / g, more preferably a heat of fusion which is not detectable according to the procedure described in ASTM E 794-85.

  In a preferred embodiment, the α-srPP, more preferably α-srPPr, of the present invention may have an ash content, determined according to the procedure described in ASTM D 5630, which is less than or equal to about 1% by weight, based on the total amount of polymer present, more preferably less than or equal to about 0.9% by weight, more preferably less than or equal to about 0.8% by weight, more preferably less than or equal to about 0.7% by weight, more preferably less than or equal to about 0.6% by weight, more preferably less than or equal to about 0.5% by weight, more preferably less than or equal to about 0.4% by weight, more preferably less than or equal to about 0.3% by weight, more preferably less than or equal to about 0.2% by weight, more preferably less than or equal to about 0.1% by weight, more preferably less than or about 0.05% by weight, more preferably less than or equal to about 0.01% by weight, more preferably less than or equal to about 0.005% by weight, with an ash content, as determined in accordance with the standard ASTM D-5630, an ash content less than or equal to 0.001% by weight being even more preferred.

  Preparation of polyolefinic polymers rich in amorphous syndiotactic structure A catalyst capable of producing polyolefins rich in amorphous syndiotactic structure and in particular a polypropylene rich in amorphous syndiotactic structure comprises those described in documents US 5,476,914, 6,184,326, 6,245,870, 5,373,059, 5,374,685 and 5,326,824. The preparation of srPP polymers, in particular srPPr polymers, has been described in U.S. Patent Nos. 3,305,538 and 3,258,455 to Natta et al. al., U.S. Patent No. 4,892,851 to Ewen et al., U.S. Patent No. 5,270,410 to Job, US Pat. No. 5,340,917 to Eckman et al., U.S. Patent No. 5,476,914 to Ewen et al., The total specification of these documents being incorporated thereby as reference.

  In addition to the choice of the catalyst, the concentration of the reactants and the reaction pressure used for the preparation of the amorphous syndiotactic rich polyolefins of the present invention, the regulation of the reaction temperature can also be critical. The temperature of the reaction is preferably controlled within about 10 ° C of a set point, more preferably within the range of about 9 ° C, more preferably within the range of about 8 ° C, more preferably within the range of about 10 ° C. limit of about 7 C, more preferably within the limit of about 6 C, more preferably in the limit of about 5 C, more preferably in the limit of about 4 C, more preferably in the limit of about 3 C more preferably in the range of about 2 C.

  Polymers prepared using the method described in U.S. Patent No. 5,476,914 with a metallocene catalyst system are preferred. Compared with other processes, the a-srPPr prepared with a metallocene catalyst has a narrower molecular weight distribution and / or a more uniform comonomer distribution, compared with polymers produced using other catalysts. such as the disclosed vanadium catalysts which tend to produce polymers having higher ash contents than the polymers of the present invention. Thus, a metallocene produced a-srPP may have better physical and mechanical properties and superior processability compared to other α-srPPs. The most preferred type of α-srPP polymer is a copolymer, produced with a metallocene catalyst, of propylene with ethylene or butene-1 having an ethylene or butene-1 comonomer content in the range from about 2 to 20 by weight.

  In general, a-srPP can be produced in a liquid-filled single stage reactor such as a continuous reactor using a suitable catalyst such as di- (p-triethylsilylphenyl) -methylene (cyclopentadienyl) dichloride ( 3,8-di-tert-butylfluorenyl) zirconium, di- (p-triethylsilylphenyl) -methylene- (cyclopentadienyl) - (3,8-ditertiobutylfluorenyl) -hafnium dichloride, di- (p-triethylsilylphenyl) -methylene- ( cyclopentadienyl) - (3,8-ditertiobutylfluorenyl) -zirconium-dimethyl, di- (p-triethylsilylphenyl) methylene- (cyclopentadienyl) - (3,8-di-tert-butylfluorenyl) -hafniumdimethyl, di- (p-triethylsilylphenyl) dichloride ) -methylene (cyclopentadienyl) (3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydrodibenzyl [b, h] fluorenyl) - zirconium, di ((triethylsilylphenyl) methylene- (cyclopentadienyl) (3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8,9,9-octahydro) dichloride; dibenzyl [b, h] fluorenyl) hafnium, di- (p-triethylsilylphenyl) 1) -methylene- (cyclopentadienyl) - (3, 3, 6, 6, 9, 9, 12, 12-octamethyl-4,4,5,5,8,8,9,9-octahydro-dibenzyl [b, h] -fluorenyl) -zirconium-dimethyl and di- (p-triethylsilylphenyl) -methylene- (cyclopentadienyl) (3,3,6,6,9,9,12,12-octamethyl-4,4,5,5,8,8 , 9,9-dibenzyl-octahydro [b, h] fluorenyl) hafnium dimethyl.

  The catalyst can be activated (or preactivated) with a suitable activator (cocatalyst) comprising alumoxanes, modified alumoxanes, and ionizing anion precursors that extract a reactive, α-linked metal ligand, thereby rendering the cationic metal complex and which provides a non-coordinating or weakly coordinating charge balancing anion, such as methylalumoxane (MAO) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Additional preferred activators are those described in paragraphs [00121] to [00151] of WO 2004/026921. Particularly preferred activators include those listed on pages 77-78 in [00135] of the Catalysts and Catalyst Systems described above are suitable for use in a solution, bulk, gas phase or solution polymerization process. in suspension or one of their combinations, preferably a solution or bulk polymerization process.

  In one embodiment, the present invention relates to solution, bulk, slurry or gas phase polymerization reactions involving the polymerization of one or more of the monomers having 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms. carbon and more preferably 3 to 8 carbon atoms. Preferred monomers include one or more of propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, 3-methylpentene-1, and cyclic olefins, or one of their associations. Other monomers may include vinyl monomers, diolefins such as dienes, polyenes, norbornenes, norbornadiene, vinyl norbornene, and ethylidene norbornene monomers. Preferably, a homopolymer or copolymer of propylene is produced. In another embodiment, a propylene homopolymer and a copolymer of propylene and one or more of the monomers listed above are both produced.

  One or more reactors in series or in parallel can be used in the present invention. The catalyst component and the activator can be delivered in the form of a solution or a suspension, separately in the reactor, activated in line just before the reactor or preactivated and pumping in the form of an activated solution or suspension. in the reactor. A preferred operation is an online enabled operation using two solutions. For more information on methods for introducing multiple catalysts into reactors, reference is made to US 6,399,722 and WO 0130862 A1. While these references may focus on gas phase reactors, The described techniques are equally applicable to other types of reactors, including continuous stirred tank reactors, slurry loop reactors, and the like. The polymerizations are carried out by operation in a single reactor, in which the monomer, comonomers, catalyst / activator, acceptor and any modifiers are continuously introduced into a single reactor, or into an operation in a single reactor. series of reactors, wherein the aforementioned constituents are introduced into each of two or more reactors connected in series. The catalytic components can be introduced into the first reactor in the series. The catalytic component can also be introduced into the two reactors, one component being introduced into the first reactor and the other component being introduced into the other reactors.

  In one embodiment, an amount equal to or less than 500 millionths, or less than or equal to 400 millionths, or less than or equal to 300 millionths of hydrogen may be added to the mixture subjected to the polymerization. In other embodiments, an amount of at least 50 millionths of hydrogen, or equal to or greater than 100 millionths or equal to or greater than 150 millionths of hydrogen may be added to the mixture subjected to the polymerization. Polyolefins Rich in Functionalized Amorphous Syndiotactic Structure The present invention may comprise the contact product of the polyolefin rich in amorphous syndiotactic structure described above, a functional group and a functionalization catalyst, which may result in a polyolefin rich in functionalized amorphous syndiotactic structure. . Preferably, the amorphous syndiotactic rich polyolefin is a polypropylene rich in amorphous syndiotactic structure, the functional group is maleic anhydride and a functionalization catalyst is an organic peroxide, which can result in a contact product comprising a rich polypropylene in amorphous syndiotactic structure functionalized with maleic anhydride.

  Accordingly, the present invention may comprise the polyolefin rich in amorphous syndiotactic structure described above which has been further functionalized with one or more additional compounds to impart one or more functionalities to the polyolefin. This polyolefin rich in functionalized amorphous syndiotactic structure is preferably a polypropylene rich in amorphous syndiotactic structure, functionalized with maleic anhydride. Accordingly, the polyolefin rich in amorphous syndiotactic structure can be functionalized with an unsaturated compound (for example, compounds comprising a carbon-carbon double bond, a carbon-carbon triple bond) and / or a compound containing a heteroatom (for example B, N, O, Si, P, halogens (eg F, Cl, Br, I) and / or S). The functional group may comprise an aromatic compound, a vinyl compound, an organic acid, an organic amide, an organic amine, an organic ester, an organic diester, an organic imide, an organic anhydride, an organic alcohol, an acid halide organic, an organic peroxide and / or their salts or derivatives.

  For ease of reference, unless otherwise indicated, one or more unsaturated compounds and one or more compounds comprising a heteroatom are collectively referred to herein as one or more functional groups, (abbreviation FG). The functionalized (or grafted) term means that one or more functional groups are incorporated, grafted, bound, physically and / or chemically attached to the amorphous syndiotactic-rich polyolefin (α-srPP) of the present invention to produce a polyolefin rich in amorphous syndiotactic structure functionalized with a functional group (abbreviated α-srPP-g-FG, where -g-FG is the functional group grafted). Functionalization of the polyolefin preferably occurs at or on the backbone of the polymer, but may also occur at the ends of the polymer, and at portions of the polymer that are attached to the backbone of the polymer. Functionalization can also occur at other functional groups and between various polymer chains.

  In a preferred embodiment, the polyolefin rich in functionalized syndiotactic structure is substantially amorphous in that substantially all of the α-srPP-g-FG of the present invention is soluble in hexane, cyclohexane, xylene or toluene. at room temperature. For this reason, a proportion of at least 95% by weight, preferably at least about 96% by weight, preferably at least about 97% by weight, preferably at least about 98% by weight preferably at least about 99% by weight, preferably at least about 99.5% by weight of the α-srPP-g-FG is soluble in hexane, cyclohexane, xylene or toluene. ambient temperature, based on the total weight of α-srPP-g-FG present.

  As an illustrative embodiment, functional groups (i.e. compounds comprising a functional group) can be grafted onto an amorphous syndiotactic-rich polypropylene (asrPPr) using the radical copolymerization as described in US Pat. detail herein, which may include the use of a radical initiator. Such a process is referred to herein as graft copolymerization. The end result is a propylene polymer rich in functionalized amorphous syndiotactic structure or a mixture of functionalized polymers. Accordingly, the present invention includes the result of contacting a polyolefin, preferably a polyolefin rich in amorphous syndiotactic structure, with a functional group in the presence of a radical initiator.

  Preferred examples of functional groups include unsaturated carboxylic acids and their salts, with acid derivatives including, but not limited to, maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, and the like. , 2,3-dimethylmaleic anhydride, bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic anhydride and 4-methyl-4-cyclohexene-1,2dicarboxylic anhydride, the acid acrylic, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo acid anhydride (2.2.2) oct -5-ene-2,3-dicarboxylic acid, 1,2,3,4,5,6-octa-hydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3dicetospiro (4.4) none-7-ene, bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride, maléopimaric acid, tetrahydrophthalic anhydride, norborn-5- 2,3-dicarboxylic acid, nadic anhydride, anhy methylnadic anhydride, himic anhydride, methylhimic anhydride and / or x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid anhydride (XMNA).

  Examples of carboxylic acid esters include unsaturated carboxylic acid esters including methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylate. butyl.

  Hydrolyzable unsaturated silanes may comprise an unsaturated group capable of radical polymerization and an alkoxysilyl group or a silyl group in its molecule, such that the compound has a hydrolyzable silyl group bonded to a vinyl group and / or a bound hydrolysable silyl group to the vinyl group with an alkylene group and / or a compound having a hydrolyzable silyl group attached to an ester or an amide of acrylic acid, methacrylic acid, etc. Examples of such compounds include vinyltrichlorosilane, vinyltris- (betamethoxyethoxy) -silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, monovinylsilane and monoallylsilane.

  Examples of unsaturated halohydrocarbons include vinyl chloride and vinylidene chloride.

  Preferred examples of radical initiators used in graft copolymerization include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl peroxyisopropyl carbonate, di-tert-butyl perphthalate, 2,5 dimethyl-2,5-di (tert-butylperoxy) -hexene (Lupersol 101, ElfAtochem), 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexene-3, di-tert-butyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, dilauryl peroxide and dicumyl peroxide.

  In a preferred embodiment, a-srPPr can be grafted with maleic anhydride (MA) to produce the functionalized amorphous syndiotactic rich polypropylene grafted with maleic anhydride (α-srPPr-g-MA), wherein the maleic anhydride can be covalently bonded to any of the polymer chains of which the α-srPPr is constituted. The anhydride functionality grafted onto the polymer may remain in the anhydride form, may be oxidized to acidic and / or aldehyde functional groups and / or may be additionally subjected to further reaction by methods known in the art for this purpose. inducing the formation of other functional group derivatives, such as amides, amines, esters, acid salts, etc. In a preferred embodiment, the functional group is present in the functionalized polymer (e.g., αPP-g-GF) in an amount of about 0.005 to 99% by weight, based on the total weight of the functionalized polyolefin. present. In a preferred embodiment, the functional group is present in an amount of about 0.01 to 99% by weight, preferably 0.05 to 90% by weight, preferably 0.1 to 75% by weight. more preferably from 0.5 to 60% by weight, more preferably from 0.5 to 50% by weight, more preferably from 0.5 to 40% by weight, more preferably from 0.5 to 30% by weight, more preferably preferably from 0.5 to 20% by weight, more preferably from 0.5 to 15% by weight, more preferably from 0.5 to 10% by weight, more preferably from 0.5 to 5% by weight, more preferably from 0.5 to 3% by weight, more preferably 0.5 to 2% by weight, more preferably 0.5 to 1% by weight, based on the total weight of the functionalized polyolefin or its mixture which is present .

  In a still more preferred embodiment, the functionalized amorphous polyolefin is a polypropylene rich in amorphous syndiotactic structure grafted with maleic anhydride (α-srPPr-g-MA). In a still more particularly preferred embodiment, the maleic anhydride functional group is present in the polymer or polymer blend comprising amorphous syndiotactic-rich polypropylene at a concentration of about 0.005 to 10% by weight of MA, more preferably from 0.01 to 10% by weight of MA, more preferably from 0.5 to 10% by weight of MA, more preferably from 0.5 to 5% by weight of MA, more preferably from 1 to 5% by weight of MA, more preferably 1 to 2% by weight of MA, more preferably 1 to 1.5% by weight of MA, as determined in the description herein and based on the weight of polypropylene rich in functionalized amorphous syndiotactic structure or its mixture that is present.

  The polyolefin rich in functionalized amorphous syndiotactic structure of the present invention (α-srPP-FG), preferably an amorphous syndiotactic rich-functional polypropylene functionalized with maleic anhydride (α-srPPr-g-MA), may comprise at least 50% dyads r and less than about 80% r dyads, as determined by the method of Ewen. In a preferred embodiment, α-srPPr-g-MA may comprise at least about 55% dyads, preferably at least about 60% dyads, preferably at least about 65% dyads, preferably at least about 70% dyads, preferably at least about 75% dyads, more preferably at least about 80% dyads, based on the total number of dyads r and m present in the polymer.

  A polyolefinic polymer rich in functionalized amorphous syndiotactic structure (α-srPP-g-FG), preferably an amorphous syndiotactic rich-functional polypropylene functionalized with maleic anhydride (α-srPPr-g-MA), may comprise about 6, 25% to about 31.6% pentad r, based on the total number of pentades r present in the polymer. In a preferred embodiment, α-srPP-α-FG may comprise about 9.15% pentadec at about 31.6% pentadec, preferably about 13.0% pentadec at about 31.6. % pentads r, preferably about 13.0% pentad r to about 24.0% pentad r, preferably about 17.9% pentad r to about 24.0% pentad r, based on the number total pentades r present in the polymer.

  In a preferred embodiment, the polyolefinic polymer rich in functionalized amorphous syndiotactic structure is a polypropylene rich in functionalized amorphous syndiotactic structure (α-srPPr-g-FG), preferably a polypropylene rich in amorphous syndiotactic structure functionalized with anhydride maleic (a-srPPr-g-MA). Α-srPPr-gFG, preferably amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (α-srPPr-g-MA), preferably has a weight average molecular weight (Mw) equal to or less than 5,000,000, preferably from about 5,000 to about 5,000,000, a number average molecular weight (Mn) of about 3,000,000 or less, preferably from about 5,000 to about 3,000,000, and a z-average of molecular weight (Mz) of approximately equal to or less than 10,000,000, preferably from about 5,000 to about 10,000,000; all of which can be determined by size exclusion chromatography, for example 3D SEC, also referred to as GPC-3D as described herein.

  In a preferred embodiment, the α-PrP-g-FG of the present invention, preferably the amorphous syndiotactic rich-functional polypropylene functionalized with maleic anhydride (α-srPPr-γ-MA), may be of value. Mw from about 5,000 to about 1,000,000 g / mol, more preferably Mw from about 10,000 to about 500,000, more preferably Mw from about 20,000 to about 300,000, more preferably from about 10,000 to about 100,000; Mw value from about 50,000 to about 200,000, Mw being determined as described herein.

  In a preferred embodiment, the asrPPr-g-FG of the present invention, preferably the amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (asrPPr-g-MA), may have a Mn value of about 2000 to about 500,000 g / mol, more preferably Mn of about 5,000 to about 300,000, more preferably Mn of about 10,000 to about 200,000, more preferably Mn of about From about 20,000 to about 150,000, Mn being determined as described herein.

  In a preferred embodiment, the asrPPr-g-FG of the present invention, preferably amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (asrPPr-g-MA), may have a Mz value of about 10,000 to about 10,000,000 g / mol, more preferably a Mz value of about 20,000 to about 1,000,000, more preferably a Mz value of about 40,000 to about 500,000, more preferably a value of Mz from about 100,000 to about 400,000 with Mz determined as described herein.

  In a preferred embodiment, the asrPPr-g-FG of the present invention, preferably amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (asrPPr-g-MA), may have a crystallization temperature (Tc ) measured by Differential Scanning Calorimetry (DSC) approximately equal to or less than 120 C, more preferably equal to or less than 100 C, more preferably, no crystallization temperature is discernible.

  In a preferred embodiment, the asrPPr-g-FG of the present invention, preferably amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (asrPPr-g-MA), may have a flow rate of melt (MFR), which is inversely proportional to the weight average molecular weight Mw, equal to or greater than 0.2 g / 10 min, advantageously in the range of 2 to 500 g / 10 min and more preferably in the range of the range of 20 to 200 g / 10 min, as measured by ASTM test method D-1238 (190 C, 2.16 kg).

  The polyolefin rich in the amorphous syndiotactic structure of α-srPPr-g-FG, preferably the amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (α-srPPr-g-MA), may comprise alpha-olefins in the base polymer. For example, asrPPr-g-FG may comprise propylene (C3) as the base polymer, with ethylene (C2) and C4 to C40 alpha-olefins, advantageously C4 to C20 alpha-olefins, more preferably C4 to C4 alpha olefins, C2 and C4 to C4 alpha olefins being even more preferred.

  Examples of preferred alpha-olefins include butene-1, pentene-1, hexene-1, hepten-1, octene-1, nonene-1, decene-1, undecene -1, dodecene-1, tridecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1 and branched olefins including 3-methylbutene-1, 4- methylpentene-1 and 4,4-dimethylpentene-1.

  The amount of alpha-olefins in addition to the base polymer, when present in α-srPPr-g-FG, preferably amorphous syndiotactic-rich polypropylene functionalized with maleic anhydride (a-srPPr- g-MA), may be greater than about 0.001% by weight, based on the total weight of the polymer.

  Preferably, the amount of alpha-olefin is greater than or equal to about 0.1% by weight, more preferably greater than or equal to about 1% by weight. The other alpha-olefins may also be present in the base polymer in a proportion of about 50% by weight or less. Preferably, the amount of the other alpha-olefins is less than or equal to about% by weight, more preferably less than or equal to about 10% by weight.

  In a preferred embodiment, asrPP-g-FG, more preferably α-srPPr-g-FG, more preferably amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (asrPPr-g-MA), the present invention may have a heat of fusion (Hf) determined according to the procedure described in ASTM E 794-85, which is less than or equal to about 10 J / g, preferably less than or equal to about 9 J / g , preferably less than or equal to approximately 8 J / g, preferably less than or equal to approximately 7 J / g, preferably less than or equal to approximately 6 J / g, preferably less than or equal to approximately 5 J / g, of preferably less than or equal to approximately 4 J / g, preferably less than or equal to approximately 3 J / g, preferably less than or equal to approximately 2 J / g, preferably less than or equal to approximately 1 Joule / g, better still a heat of fusion which is not detectable according to the The procedure described in ASTM E 794-85.

  In a preferred embodiment, asrPP, more preferably α-srPPr, prior to functionalization to an α-srPP-g-FG of the present invention, preferably an amorphous syndiotactic rich-functional polypropylene functionalized with maleic anhydride ( asrPPr-g-MA), may have an ash content, determined according to the procedure described in ASTM D 5630, which is less than or equal to about 1% by weight, based on the total amount of polymer present, more preferably less than or equal to about 0.9% by weight, more preferably less than or equal to about 0.8% by weight, more preferably less than or equal to about 0.7% by weight, more preferably less than or equal to about 0% by weight; 6% by weight, more preferably less than or equal to about 0.5% by weight, more preferably less than or equal to about 0.4% by weight, more preferably less than or equal to about 0.3% by weight. oids, more preferably less than or equal to about 0.2% by weight, more preferably less than or equal to about 0.1% by weight, more preferably less than or equal to about 0.05% by weight, more preferably less than or equal to about 0.01% by weight, more preferably less than or equal to about 0.005% by weight, an ash content as determined by ASTM D 5630 of less than or equal to about 0.001% by weight being even more preferred.

  In a preferred embodiment, the polyolefin rich in functionalized amorphous syndiotactic structure, preferably the amorphous syndiotactic rich polypropylene functionalized with maleic anhydride (α-srPPr-g-MA), is heat-stable, which means that the Gardner color of α-srPP-g-FG (as determined by ASTM D-1544-68) after thermal aging (eg, hold) at a temperature of 180 ° C for 48 hours, does not vary more than 7 Gardner units compared to the Gardner color of the original composition. Preferably, the Gardner color of the functionalized polymer or composition comprising the functionalized polymer, after heating at a temperature above its melting point for 48 hours, does not vary by more than 6, more preferably by more than 5, even more preferably more than 4, still more preferably more than 3, still more preferably more than 2, even more preferably more than 1, Gardner color units, compared to the initial functionalized polymer before heating (for example before hot aging) .

  In the case of a polypropylene rich in functionalized (e.g. grafted) amorphous syndiotactic structure with maleic anhydride (α-srPPrg-MA), it has been discovered that free acid groups present in the composition may result in reduced thermostability. Accordingly, in a preferred embodiment, the amount of free acid groups present in α-srPPr-g-MA, or a mixture comprising α-srPPr-g-MA, is less than about 1000 millionths, more preferably less than about 500 millionths, more preferably less than about one millionths, based on the total weight of α-srPPr-g-MA present.

  It has also been discovered that various phosphites can contribute to instability. Accordingly, in a further preferred embodiment, the α-srPP-γ-FG, more preferably the asrPPr-g-Ma, is substantially free of phosphites, which means that the phosphites are present in an amount equal to or less than 100 millionths, based on the weight of α-srPP-g-FG, more preferably α-srPPr-g-MA. Functionalization of a polyolefin rich in amorphous syndiotactic structure Functionalization of a polyolefin rich in amorphous syndiotactic structure (α-srPP) with a functional group (FG) to produce a polyolefin rich in functionalized amorphous syndiotactic structure (α-srPP-g- FG), preferably a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride (α-srPPr-g-MA) of the present invention, can be made by contacting the polymer to be functionalized with the functional group, preferably in the presence of the radical initiator. In a preferred embodiment, the combination is heated to a temperature equal to, close to, or greater than the decomposition temperature of one or more of the free radical initiators used.

  In some embodiments, no particular restriction should be imposed on the amount of functional group to be used; therefore, conventional conditions such as those which can be used for the functionalization of isotactic polypropylene can be used to produce the polyolefin rich in functionalized amorphous syndiotactic structure, preferably polypropylene rich in amorphous syndiotactic structure functionalized with anhydride maleic (a-srPPr-g-MA) of the present invention. Since, in some cases, the effectiveness of the copolymerization is relatively high, the amount of functional group may be small (ie, less than or equal to about 1% by weight of functional group, based on the total weight of the functional group). functionalized polymer).

  The radical initiator is preferably used in a ratio of 0.00001 to 10% by weight, based on the weight of the functional group. Where possible, the heating temperature depends on whether the contact (e.g. the reaction) of the polymer, the functional group and the free radical initiator when it is used, is effected or not in the presence of a solvent. The contact temperature is preferably greater than about 0 ° C and less than about 500 ° C, more preferably in the range of about 50 ° C to 350 ° C. When the heating temperature is below 50 ° C, the reaction may be slow and so the effectiveness may be low. When it is greater than 350 C, the decomposition of the polymer or other constituents may occur. Accordingly, the α-srPP, preferably the asrPPr of the present invention, can be functionalized with a functional group using a solvent-based functionalization method and / or using a solvent-free melt functionalization method. .

  In the solvent-based process, the reaction may be conducted using α-srPP, preferably α-srPPr, in solution or as a suspension at a concentration of 0.1 to 50% by weight in the presence of a halogenated hydrocarbon compound having 2 to 20 carbon atoms, an aromatic compound, a halogenated aromatic compound and / or an alkyl-substituted aromatic hydrocarbon which is stable to radicals.

  Importantly, it has been discovered in the present invention that amorphous polyolefins, more preferably amorphous syndiotactic rich polyolefins, more preferably amorphous syndiotactic rich polypropylene of the present invention, can be functionalized in aliphatic solvents comprising cyclic hydrocarbons and / or hydrocarbons having 6 to 20 carbon atoms. Preferred aliphatic solvents include cyclohexane, hexane and mixtures comprising cyclohexane and / or hexane.

  Accordingly, this unexpected discovery thus makes it possible to avoid the use of aromatic and / or halogenated solvents and, thus, the present invention can be used to reduce environmental problems and limitations that may be associated with the use of aromatic solvents and / or halogenated solvents, especially during mass production. This discovery also allows the direct use of a polymer solution from a polymerization reactor for functionalization, which avoids one or more additional finishing and / or redissolving steps, as more fully described in FIG. present memory. In addition, this discovery also offers the advantages associated with the use of solvent having lower boiling points than those associated with aromatic solvents. The use in a functionalization of solvents having lower boiling points than benzene, toluene, xylene, etc., for example, facilitates removal of the solvent from the functionalized polymer at a lower temperature and / or higher pressure relative to a particular aromatic solvent. Removal at a lower temperature can thus result in less degradation of the polymer, more efficient solvent removal and increased productivity / lower solvent removal cost resulting from operation at a lower temperature and or higher pressure with respect to the operating conditions required for the removal of an aromatic solvent.

  In the functionalization process using a melt-based functionalization process, the reaction can be carried out in the presence of a small amount or no solvent, preferably in the absence of solvent, in a device such as an extruder, a mixer, or similar device, which can produce sufficient physical contact between components which may be highly viscous components to effect contact and thus functionalization of the polyolefin rich in amorphous syndiotactic structure. In the melt functionalization method, the functionalization reaction can be conducted at a relatively high temperature, as compared to the same reaction of a solution or solvent based functionalization process.

  Other methods for the functionalization of α-srPP, preferably α-srPPr of the present invention, may include, but are not limited to, selective oxidation, ozonolysis, epoxidation, etc., both in solution. or in suspension (i.e. with a solvent and / or diluent) or in a melt or a mixer (i.e. without solvent).

  In the present invention, functionalization (e.g., graft polymerization) can also be carried out in an aqueous medium. In this case, it is possible to use one or more dispersants. Examples of suitable dispersants include: saponified polyvinyl acetate, modified celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and OH group-containing compounds such as polyacrylic acid and polymethacrylic acid. In addition, compounds which are used in customary aqueous suspension polymerization may also be commonly used.

  Functionalization in an aqueous medium can be carried out by suspending the polymer, the functional group, the water-insoluble radical initiator and / or the dispersant in water, and then heating the mixture. In this case, the ratio of water to the sum of the functional group is preferably in the range of from 1: 0.1 to 1: 200, more preferably from 1: 1 to 1: 100. The heating temperature is such that the half-life of the radical initiator is advantageously from 0.1 to 100 hours, more preferably from 0.2 to 10 hours and this temperature is advantageously in the range of 30 to 200 ° C. more preferably 40 to 150 ° C. In the heating step, it is preferred that the mixture is stirred sufficiently to be slurried. In this way, the grafted polyolefin can be obtained in granular form.

  The weight ratio of the functional group to the polyolefin or to the mixture comprising the polyolefin to be functionalized may preferably be in the range of 1: 1 to 1:10,000, and the weight ratio of the radical initiator to the functional group may be in the range of 0.00001 to 0.1.

  As mentioned above, the presence of free acid groups and phosphites in a functionalized SrPP may have an effect on the thermal stability of α-srPP-g-FG, particularly with respect to α-srPPr-g-MA. The concentration of free acid groups and other groups which may have a negative effect on thermostability in α-srPPr-g-MA can be reduced and / or regulated by: 1. regulation of the reaction, in which the materials are contacted at a temperature and for a period of time sufficient to ensure substantially complete reaction and thus substantially complete consumption of the added functional group (eg, maleic anhydride) during the functionalization process; 2. a post-wash, in which the functionalized polymer is brought into contact (for example washed) at least once with a solvent, with water, with a dilute acid, with a dilute base or one of their combinations, after the functionalization reaction; 3. formation of a masterbatch, wherein a masterbatch of the functionalized polymer is produced and / or treated to be substantially free of free acid and / or other groups, and wherein the mixture is The master has a maleic anhydride functional group concentration greater than that required in the final composition, and wherein the masterbatch is mixed in the final mixture (also referred to as a dilution operation) in an amount sufficient to produce the desired amount. asrPP-FG, preferably a-srPPr-MA, in the final mixture; or 4. a moisture adjustment, wherein the moisture content (eg, water) of the functionalized polymer is maintained at a level which maintains the anhydrous functionality of the anhydride (eg MA).

  Functionalization in solution using an aliphatic solvent is a preferred method of functionalization to improve the thermostability of α-srPP-FG, preferably α-srPPr-g-MA.

  For the solution reaction, α-srPP may be dissolved in a suitable solvent (e.g. an aromatic solvent such as benzene, toluene or xylene, or an aliphatic solvent such as hexane or cyclohexane). After heating the solution containing the α-srPP to the desired temperature (for example in the range of about 60 to 150 ° C), a radical initiator and a functional group (for example a reactive amide and / or anhydride maleic) can be added to trigger the grafting process. After stirring for about 30 minutes to about 5 or more hours, the solution is precipitated in a second solvent such as acetone to separate the functionalized polymer from the unreacted modifier. The filtered product can then be dried under vacuum (for example at 120 ° C.) to obtain the final product consisting of the functionalized amorphous polyolefin.

  Accordingly, in one embodiment, the method of functionalization may comprise the steps of: 1) introducing an olefinic monomer (e.g., propylene), a catalyst, an activator and the like into a reactor in hexane or a mixture of aliphatic solvents; 2) catalytic polymerization in solution; 3) to entrain the monomer; 4) removing the solvent and drying the product to produce a polymer; 5) redissolving the polymer in a non-aliphatic solvent (for example benzene, toluene or a non-hydrocarbon solvent) for solution functionalization; 6) performing functionalization based on the use of a solvent; and 7) removing the solvent used in the functionalization based on the use of a solvent.

  In a preferred embodiment, the method of functionalization may comprise the steps of: 1) introducing an olefinic monomer (eg, propylene), a catalyst, an activator and the like into a reactor, hexane or an aliphatic solvent mixture; 2) catalytic polymerization in solution; 3) to entrain the monomer; 15,4) to perform functionalization based on the use of a solvent; and 5) separating the functionalized polyolefin (for example by solvent addition precipitation, temperature control and / or solvent removal used in solvent based functionalization). Such a preferred process can be carried out with a continuous stirred tank reactor or a sequential reactor tank.

  Accordingly, a process for producing the functionalized amorphous syndiotactic rich-structure polyolefin of the present invention may comprise the steps of: 1) introducing an olefinic monomer, a metallocene catalyst and an activator into a reactor, in a solvent aliphatic; 2) performing a solution catalytic polymerization of the olefinic monomer in the reactor to produce a polyolefin rich in amorphous syndiotactic structure; 3) removing the monomer by stripping to remove the unreacted olefinic monomer; 4) performing solvent-based polymerization comprising contacting the amorphous syndiotactic-rich polyolefin with a functional group in the presence of a radical initiator in the aliphatic solvent used in the step of solution polymerization at a temperature and for a period of time sufficient to produce the polyolefin rich in functionalized amorphous syndiotactic structure; and optionally, 5) precipitating the functionalized amorphous syndiotactic rich polyolefin by adding a solvent such as acetone and / or removing the aliphatic solvent.

  It is desirable to functionalize propylene-based homopolymers and copolymers in solution for better regulation of the chemical functionalization process. It is further desirable in some applications that the functionalized polymer can be delivered to the target application - for example a TPO buffer primer - in solution.

  The melt functionalization involves a process similar to the solution process, except that no solvent is required, the reaction is carried out in a mixing device (for example an extruder or a Brabender mixer) and the temperature can be higher than that used in the solvent-based process. Accordingly, a method for producing the functionalized amorphous syndiotactic rich structure polyolefin of the present invention may comprise the steps of: A. introducing a melt comprising a polyolefin rich in amorphous syndiotactic structure, a functional group and a radical initiator in a mixing device; and B. contacting said melt in said mixing device at a temperature and for a period of time sufficient to produce the functionalized amorphous syndiotactic rich polyolefin.

  In a preferred embodiment, the method may comprise the steps of: A. introducing a melt comprising an amorphous syndiotactic rich polypropylene, maleic anhydride, and an organic peroxide radical initiator in a mixed; and B. contacting the melt in the mixing device at a temperature and for a period of time sufficient to produce the α-srPP-g-MA of the present invention.

  In a preferred embodiment, in which a nanoclay can be added to the polymer, a process for producing a functionalized amorphous syndiotactic rich polyolefin may comprise the steps of: A. introducing a melt comprising a polyolefin rich in amorphous syndiotactic structure, a functional group, an optional nanoclay and a radical initiator in a mixing device; B. contacting said melt and the optional nanoclay in said mixing device at a temperature and for a period of time sufficient to produce said functionalized amorphous syndiotactic rich polyolefin, said amorphous syndiotactic rich polyolefin comprising more than about 50% by weight of C3 to C40 alpha-olefins; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polyolefin; and having a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM E 794-85.

  Preferably, the process comprises the case where the polyolefin rich in amorphous syndiotactic structure furthermore has an ash content equal to or less than 1% by weight and / or the case where the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride and / or further comprises the addition of a nanoclay after said contacting step B. Applications comprising the polymers of the invention The polyolefin rich in amorphous syndiotactic structure, preferably polypropylene rich in amorphous syndiotactic structure, and polyolefin rich in functionalized amorphous syndiotactic structure, preferably polypropylene rich in functionalized amorphous syndiotactic structure, more advantageously polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride, can be used in a this number of applications. Examples include injection molded parts, films, laminates, substrates, other manufactured articles and use as a compatibilizer in the formation of various articles from a combination of recycled, pure materials or both of these types of materials.

  Injection molded parts include various manufactured articles produced by injection molding, as known to those skilled in the art. The films include meltblown films, extruded films, cast films, and the like. The laminates comprise one or more layers, with or without additional additives and / or other materials placed between the laminate layers. The substrates may be nonpolar or polar and may be influenced by the incorporation of functional groups into the functionalized amorphous syndiotactic rich polyolefins of the present invention.

  The polymer of the present invention may also comprise a masterbatch. In one embodiment, the masterbatch may comprise the polyolefin rich in amorphous syndiotactic structure described above, preferably amorphous syndiotactic rich polypropylene, and / or the functionalized amorphous syndiotactic rich structure polyolefin described above, preferably polypropylene rich in functionalized amorphous syndiotactic structure, more advantageously polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride. The masterbatch may also include various other additives and / or other constituents in accordance with the end use, so that the material in the masterbatch can be diluted in a particular end use.

  The amorphous character of the polyolefin rich in syndiotactic structure, preferably polypropylene rich in amorphous syndiotactic structure, and the polyolefin rich in functionalized amorphous syndiotactic structure, preferably polypropylene rich in functionalized amorphous syndiotactic structure, more advantageously structure-rich polypropylene An amorphous syndiotactic agent functionalized with maleic anhydride makes it possible to use the present invention in liquid form, preferably in the dissolved state in a suitable solvent. For this reason, the polymer of the present invention can be atomized and / or spray applied to a substrate by techniques known to those skilled in the art.

  Polymer Formulations Polyolefin rich in amorphous syndiotactic structure, preferably polypropylene rich in amorphous syndiotactic structure, and polyolefin rich in functionalized amorphous syndiotactic structure, preferably polypropylene rich in functionalized amorphous syndiotactic structure, more advantageously polypropylene rich in syndiotactic structure amorphous functionalized with maleic anhydride, can be used in the form of a mixture in combination with an additive, preferably at least one or more additives. The polymer of the present invention can thus be used as an additive, as an adhesive or as a base polymer in an adhesive mixture. As used herein, an additive may be any material or combination of materials that facilitates, enhances, modifies or delays the physical properties of the polymer blend, or facilitates the use of syndiotactic-rich polyolefin amorphous, preferably polypropylene rich in amorphous syndiotactic structure, and / or polyolefin rich in functionalized amorphous syndiotactic structure, preferably polypropylene rich in functionalized amorphous syndiotactic structure, more advantageously polypropylene rich in amorphous syndiotactic structure functionalized with anhydrous maleic anhydride of the present invention.

  Additives suitable for use in the present invention may include one or more C 2 to C 40 polymers, elastomers, random copolymers, impact copolymers, functional polymers, tackifiers, crosslinking agents, antioxidants, and the like. , neutralizing agents, nucleating agents, fillers, adhesion promoters, oils, plasticizers, waxes, low molecular weight polymers, ester polymers and / or other additives.

  C2 to C40 Polymers In one embodiment, an additive may comprise various C2 to C40 polyolefin polymers (polymers) alone or in admixture with other polymers and / or additives. Accordingly, the additive may comprise a single discrete polymer, or a mixture of discrete polymers. Such mixtures may comprise two or more polyolefins such as polypropylene polyethylene copolymers, two or more polypropylene copolymers, in which each of the components of the polymer blend would individually qualify as an additive.

  In a preferred embodiment, the additive comprises a metallocene-produced polyethylene (mPE) and / or a metallocene-produced polypropylene (mPPr). The homopolymers or copolymers of mPE and mPPr are usually produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an alumoxane type activator and / or a non-coordinating anion in solution, in suspension or in high pressure phase. or in the gas phase. The catalyst and activator may be supported or non-supported and the cyclopentadienyl rings may be substituted or unsubstituted. Several commercial products made with these catalyst / enhancer combinations are commercially available from ExxonMobil Chemical Company in Baytown, Texas under the trade names EXCEEDTM, ACHIEVETM and EXACTTM. For more information on the processes and catalysts / activators for producing these mPE homopolymers and copolymers, see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Patent No. 5,153,175; U.S. Patent No. 5,198,401; U.S. Patent No. 5,240,894; U.S. Patent No. 5,017,714; CA 1,268,753; U.S. Patent No. 5,324,800; EPA 129,368; U.S. Patent No. 5,264,405; EPA 520,732; WO 9200333; U.S. Patent No. 5,096,867; U.S. Patent No. 5,507,475; EPA 426,637; EPA 573,403; EPA 520,732; EPA 495,375; EPA 500,944; 570,982; WO 91/09882; WO 94/03506 and U.S. Patent No. 5,055,438.

  In another embodiment, the additive comprises a homopolypropylene, a propylene copolymerized with up to 50% by weight of ethylene or a C 4 -C 20 alpha-olefin, an isotactic polypropylene, a highly isotactic polypropylene ( for example comprising more than about 50% pentades m), a syndiotactic polypropylene, a random copolymer of propylene and ethylene and / or butene and / or hexene, a polybutene, an ethylene-vinyl acetate polymer, low density polyethylene (density in the range of 0.915 to less than 0.935 g / cm3), linear low density polyethylene, ultra-low density polyethylene (density in the range of 0.86 to less than 0.90 g / cm 3), a very low density polyethylene (density in the range of 0.90 to less than 0.915 g / cm 3), a medium density polyethylene (density in the range 0.9 Less than 0.945 g / cm 3), high density polyethylene (density in the range of 0.945 to 0.98 g / cm 3), ethylene-vinyl acetate polymer, ethylene-methyl acetate polymer, copolymers of acrylic acid, poly (methyl methacrylate) or any other polymers polymerizable by a high pressure radical process, poly (vinyl chloride), polybutene-1, isotactic polybutene, resins of ABS, elastomers such as ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer elastomers such as SBS, Nylons (polyamides), polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1-esters, graft copolymers in general, homopolymer or copolymers of polyacrylonitrile, thermoplastic polyamides, polyacetal, poly (vinylidene fluoride) and other fluorinated elastomers, polyethylene glycols and polyisobutylene.

  Other preferred propylene copolymers useful in the present invention as additives are described in detail as the second polymeric component (SPC) in copending United States applications USSN N 60/133 966 filed May 13, 1999 and USSN 60 / 342,854 filed June 29, 1999, and are further described as propylene-olefin copolymer in USSN 90 / 346,460 filed July 1, 1999, these documents being incorporated in their entirety for reference herein. practice purposes of the United States of America.

  In a preferred embodiment, the additive may comprise propylene, one or more comonomers (such as ethylene, alphaolefins having 4 to 8 carbon atoms and styrenes) and optionally one or more dienes. The amount of dienes is preferably not more than about 10% by weight, more preferably not more than about 5% by weight. Preferred dienes include those used for the vulcanization of ethylene-propylene rubbers, preferably ethylidene-norbornene, vinyl-norbornene, dicyclopentadiene, and 1,4-hexadiene (available from DuPont Chemicals).

  In one embodiment, the additive may comprise two or more polypropylene copolymers, each of which preferably differs in the α-olefin content, one comprising 7 to 13 mol% of α-olefin, while that the other comprises 14 to 22 mol% of α-olefin. The preferred α-olefin is ethylene. It is believed that the use of two polymeric components leads to beneficial improvements in the tensile elongation properties of the final blends.

  Polymers which can be suitably used in the present invention as additives also include a C3-C40 homopolymer or copolymer rich in amorphous syndiotactic structure and / or a C3-C40 homopolymer or copolymer rich in at least partially crystalline syndiotactic structure. An at least partially crystalline polyolefin is defined as a polyolefinic copolymer or homopolymer having a solubility of at least 10% by weight in xylene or toluene at room temperature. Preferably, the additive comprises a polyolefin rich in syndiotactic structure, soluble at 15% by weight, preferably at 20% by weight, preferably at 25% by weight, preferably at 30% by weight, preferably at 35% by weight. by weight, preferably 40% by weight, preferably 45% by weight, preferably 50% by weight, preferably 55% by weight, preferably 60% by weight, preferably 65% by weight preferably at 70% by weight, preferably at 75% by weight, preferably at 80% by weight, preferably at 85% by weight, preferably at 90% by weight, preferably at 95% by weight in the xylene or toluene at room temperature. Even more advantageously, the polyolefin rich in syndiotactic structure of the aforementioned additive comprises a polypropylene rich in syndiotactic structure at least partially crystalline (srPPr).

  At least partially crystalline syndiotactic structure-rich polypropylene (srPPr) may be defined herein as a polymer comprising at least about 80% [r] dyads. Preferably, at least about 85% of dyads [r], a proportion of at least about 90% of dyads [r] being more preferred, a proportion of at least about 95% of [r] dyads being more advantageous, a proportion of at least about 99% of dyads [r] being even more appreciated.

  The additive may also comprise at least one polyolefin rich in at least partially crystalline syndiotactic structure comprising a polypropylene as the base polymer, with other alpha-olefins including ethylene (C2) and C4 to C40 alpha-olefins. Examples of alpha-olefins include butene-1, pentene-1, hexene-1, hepten-1, octene-1, nonene-1, decene-1, undecene 1, dodecene-1, tridecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1 and branched olefins including 3-methylbutene-1, 4-methylpentene-1 , and 4,4-dimethylpentene-1.

  The amount of the other alpha-olefins, when present in the at least partially crystalline syndiotactic rich polypropylene, may be greater than 0.001% by weight, based on the total weight of the polymer. Advantageously, the amount of the other alpha-olefins is greater than or equal to about 0.1% by weight, more preferably greater than or equal to about 1% by weight. The other alpha-olefins may also be present in the base polymer in a proportion of about 50% by weight or less. Advantageously, the amount of the other alpha-olefins is less than or equal to about 20% by weight, more preferably less than or equal to about 10% by weight in the base polymer.

  Elastomers In another embodiment, the additive may comprise an elastomer. Examples of suitable elastomers include one or more polypropylene copolymers having elastic properties. Such preferred propylene copolymers having elastic properties can be prepared according to the procedures of WO 02/36651 which is incorporated herein by reference. Similarly, the additive may comprise polymers corresponding to those described in WO 03/040202, WO 03/040095, WO 03/040 201, WO 03/040 233 and / or WO 03/040 442. in addition, the additive may comprise polymers corresponding to those described in documents EP 1 233 191 and US Pat. No. 6,525,157.

  Preferred propylene copolymers having elastomeric properties include those prepared by polymerization of propylene with a C2 or C4 to C20 alpha olefin, preferably propylene and ethylene in the presence of a chiral metallocene catalyst with an activator and optionally a acceptor. The comonomer used with the propylene may be linear or branched. Preferred linear alpha-olefins include ethylene (C2) and C4-C8 alpha-olefins. Examples of preferred α-olefins include ethylene, 1-butene, 1-hexene and 1-octene, with ethylene or 1-butene being even more preferred. Preferred branched α-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene and 3,5,5-trimethyl-1-hexene.

  Preferred additives comprising propylene copolymers having elastomeric properties may have an average propylene content, on a molar basis, of from about 68% to about 92%, more preferably from about 75% to about 91%, even more preferably from from about 78% to about 88%, preferably from about 80% to about 88%. The remainder of the copolymer may consist of one or more α-olefins specified above and optionally small amounts of one or more diene monomers. Preferably, the polypropylene copolymer comprises ethylene as a comonomer in an amount of from about 8 to about 32 mole percent ethylene, more preferably about 9 to about 25 mole percent ethylene. more preferably about 12 to about 22 mole percent ethylene and most preferably about 13 to 20 mole percent ethylene.

  The use of a chiral metallocene catalyst to produce these propylene copolymers having elastomeric properties ensures that the methyl group of the propylene residues has predominantly the same tacticity. A syndiotactic configuration and an isotactic configuration of propylene are possible, the isotactic polymers being particularly preferred. The tacticity of the propylene residues leads to crystallinity in the polymers. With respect to the additive polymers of the present invention, the low degrees of crystallinity in the polypropylene copolymer can be derived from isotactic polypropylene obtained by incorporating alpha-olefin comonomers as described above.

  Particularly preferred additives comprising propylene copolymers having elastomeric properties include semi-crystalline propylene copolymers preferably having: 1. a heat of fusion of about 0.5 J / g to about 25 J / g, more preferably about 1 J / g to about 20 J / g, and preferably about 1 J / g to about 15 J / g; and / or 2. a crystallinity of from about 0.25% to about 15%, more preferably from about 0.5% to about 13%, and preferably from about 0.5% to about 11%. (The crystallinity of the polypropylene copolymer is expressed in terms of a percentage of crystallinity.) The thermal energy for the highest order of the polypropylene is estimated to be 189 J / g for use in the present invention. This means that for use in the present invention, it is considered that a crystallinity of 100 corresponds to 189 J / g); and / or 3. a single melting point or a single broad fusion transition. (A sample of the polypropylene copolymer may have one or more secondary melting peaks adjacent to a main peak, however, for purposes of the present invention, these peaks are considered together as a single melting point or a melting transition. unique); and / or 4. a melting point in the range of about 25 ° C to about 75 ° C, preferably in the range of about 25 ° C to about 65 ° C, more preferably in the range of about 30 ° C at approximately 60 ° C. (It is considered that the highest of the melting transition peaks corresponds to the melting point); and / or 5. a weight average molecular weight of 10,000 to 5,000,000 g / cm 3, preferably 80,000 to 500,000; and / or 6. a DMP (Mw / Mn) in the range of 1.5 to 40.0, more preferably about 1.8 to 5 and preferably 1.8 to 3; and / or 7. a Mooney viscosity ML (1 + 4) at 125 ° C less than 100, more preferably less than 75, more preferably less than 60, preferably less than 30.

  Other elastomers suitable for use in the present invention include all natural rubbers and synthetic rubbers, including those defined in ASTM D 1566. In a preferred embodiment, the elastomers may be tenacious compositions with rubber. In a particularly preferred embodiment, the rubber-toughened composition is a two (or more) phase system in which the rubber is a discontinuous phase in a continuous phase comprising the polyolefin rich in functionalized amorphous syndiotactic structure. Examples of preferred elastomers include ethylenepropylene rubber, ethylene-propylene-diene monomer rubber, neoprene rubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS, SIBS, SEBS, SEPS rubbers, etc.) ( S denotes styrene, I denotes isoprene, B denotes butadiene, EB denotes ethylene-butylene, EP denotes ethylene-propylene), butyl rubber, halobutyl rubber, copolymers of isobutylene and a para-alkylstyrene, halogenated copolymers of isobutylene and a para-alkylstyrene Statistical copolymers In another embodiment, the additive may comprise a random copolymer, and random copolymers which can be suitably used in the present invention may be produced. by copolymerizing propylene in a single reactor process with other monomers such as ethylene, butene and higher alpha-olefins, the most common of which is ethylene. The ethylene content of these copolymers as additives is preferably in the range of from 3 to 4 mol% up to 14 to 17 mol%, preferably from 1 mol% to 20 mol%.

  Examples of suitable random copolymers also include crystallizable propylene copolymers having a narrow composition distribution. The intermolecular composition distribution of the polymer can be determined by thermal fractionation in a solvent such as a saturated hydrocarbon, for example hexane or heptane. With a narrow composition distribution, this means that a proportion of approximately 75% by weight, and more preferably 85% by weight, of the polymer is isolated as one or two adjacent soluble fractions, the remainder of the polymer being present in the immediately preceding or following fractions.

  Thus, in a copolymer having a narrow composition distribution, each of these fractions can have a composition (ethylene content in% by weight) with a difference of not more than 20% (relative to each other) and more preferably 10% ( relative to each other) of the average ethylene content, in% by weight, of the polypropylene copolymer.

  The length and distribution of the stereoregular propylene blocks in the preferred synthetic crystallizable polypropylene copolymers are consistent with a substantially random random copolymerization wherein the length and distribution of the block are proportional to the copolymerization reactivity ratios. Substantially random expression means that the reactivity ratio of the copolymer is generally equal to or less than 1. In stereoseblock structures, the average length of the polypropylene blocks may be greater than that of substantially random copolymers having a similar composition, opposite of polymers having a stereosed structure having a distribution of polypropylene sequences in accordance with sequenced structures rather than a substantially random statistical distribution. The reactivity ratios and the sequence distribution of the polymer can be determined by 13C-NMR, which localizes the ethylene residues in relation to the adjacent propylene residues. The crystallizable copolymer having the required randomness and a narrow composition distribution suitable for use as an additive in the present invention is preferably prepared using (1) a single site catalyst and (2) a polymerization reactor having An efficient mixing continuous flow stirred tank which allows a single polymerization environment for substantially all of the polymer chains of the preferred polypropylene copolymers.

  Shock-Resistant Copolymers In another embodiment, the additive may comprise one or more impact-resistant copolymers, also referred to as a heterophasic copolymer or block copolymer. Shock resistant copolymers suitable for use in the present invention may be defined as a mixture of isotactic PP and an elastomer such as ethylene-propylene rubber. In a preferred embodiment, the impact resistant copolymer blend is present in a two (or more) phase system in which the impact resistant copolymer is a discontinuous phase in the adhesive composition and the a-srPP -g-FG, and / or other additives as described above, represent the continuous phase.

  Fluxional Polymers In another embodiment, the additive may comprise one or more polymers produced with a catalyst referred to as a fluxion catalyst. These polymers are referred to herein as fluxionic polymers, denoting linear isotactic copolymers having a structure of one or more C2-C20 olefins, whose isotacticity due to the statistical distribution of stereoscopic errors of the polymer chain. is in the range of 25 to 60% of the pentad concentration [mmmm]. The determination of the pentad concentration can be carried out using, for example, the method of J. A. Ewen, Catalytic Polymerization of Olefins, (the Ewan process); and Ed. T. Keii, K. Soga; Kodanska Elsevier Pub. ; Tokyo, 1986, pages 271 and following.

  Flowable polymers suitable for use as additives include those disclosed in U.S. Patent No. 6,555,643, where it is essential that the stereoscopic errors be located in the polymer chain proper so that This results in a specific concentration of pentads. Preferably, the fluxional polymers have a pentad concentration [rmrm] having a maximum of 2.5% of the total pentad area, with a pentad concentration [rmrm] of substantially zero. (that is to say totally missing).

  The total concentration of pentad [rrrr] and [rrrm] in the appropriate fluxional polymers may be greater than the pentad concentration [rmrm]. In a preferred embodiment, the fluxional polymers are linear isotactic polymers having a weight average molecular weight of from 100,000 to 800,000 g / mol, preferably from 110,000 to 500,000 g / mol and more preferably from 120,000 to 300,000 g / mol. The molecular weight distribution Mw / Mn of the polymers according to this preferred embodiment may range from about 1.2 to 3.5. Suitable fluxionic polymers may have a glass transition temperature Tg of -50 ° C to + 30 ° C, preferably -20 ° C to + 10 ° C, as determined by DSC.

  Preferred fluxionic polymers include linear isotactic polymers comprising one or more C 2 -C 20 olefins. Preferably, the olefin is a C3-C20 alk-1-ene, such as propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, -nonene, 1decene, 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene or a C 5 -C 20 cycloolefin, for example cyclopentene, cyclohexene, norbornadiene and its derivatives, polypropylene being particularly appreciated. Also preferred copolymers are copolymers prepared from propylene and a C4 to C20 olefin or cycloolefin.

  The preferred fluxionic polymers are essentially soluble in toluene at a temperature of 20 to 80 ° C. In addition, these polymers exhibit a distinct elastic behavior in a tensile strength test, exhibiting a distinct elastic rubber material plateau as compared with flow behavior or polymer failure (see Figure 1 of US Patent No. 6,555,643). Suitable fluxionic polymers may also have a crystallization melting temperature as measured by differential scanning calorimetry (DSC) in the range of -50 ° C. to 150 ° C. Suitable fluxional polymers differ markedly in their behavior. thermoplastic-elastic of the state of the art, that is to say polymers described in, for example, EP 0 707 016 Al.

  Accordingly, the flowable polymers include those produced using the fluxional catalyst of the general formula: wherein M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum; X represents a halogen or a C1-C5 alkyl, aryl or benzyl group; R1, R2, R3, R4, R6 and R7 are a linear or branched C1 to C10 alkyl group, a C5 to C7 cycloalkyl group which may itself carry one or more C1 to C6 alkyl residues as substituents, a C6-C18 aryl arylalkyl or alkylaryl group, in which case R1, R2, R3, R4 and R6, R7, may again be partially or simultaneously integrated in C5-C5 cycloalkyl or aryl rings, condensed therewith .

  In the case of the metallocene corresponding to the above formula, it is essential that the N 7 carbon atom of indenyl group adjacent to the carbon atom substituted by the R 7 residue and the N 4 carbon atom of the indenyl group adjacent to the carbon atom substituted by the residue R6 is only substituted by hydrogen, which gives a catalyst which is particularly advantageous for preparing isotactic elastomers according to the present invention. Suitable structural bridging units E are --CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CR 9 R 10 -, - SiR 9 R 10 -, and - -GeR9 R10 -, wherein R9 and R10 are C1-C8alkyl, C4-C10cycloalkyl or aryl, and R9 and R10 are capable of being joined to each other to form a cyclic structure .

  Adhesive Agents The additives may also include tackifiers. Examples of suitable tackifiers may be selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum-resins, gum esters resins, wood resins, esters of wood resins, tall oil resins, esters of tall oil resins, polyterpenes, aromatic modified polyterpenes, terpene phenolic resins, aromatic modified hydrogenated polycyclopentadiene resins, a hydrogenated aliphatic resin, hydrogenated aromatic-aliphatic resins, hydrogenated terpenes, modified terpenes, hydrogenated resin acids and hydrogenated rosin esters. In some embodiments, the tackifier may be hydrogenated.

  In other embodiments, the tackifier may be non-polar, which means that the tackifier is substantially free of monomers having polar groups. Preferably, the polar groups are not present; however, if they are present, they are preferably not present in an amount of greater than 5% by weight and are preferably present in an amount of not more than 2% by weight, still more preferably not greater than 0.5% by weight. % in weight. In certain embodiments, the tackifier may have a ball and ring softening point, measured according to ASTM E-28, in the range of 80 to 150, preferably 100 to 130 . In another embodiment, the resin is liquid and has a ball and ring softening point in the range of 10 to 70 C.

  The tackifier may be from about 1 to about 80% by weight, based on the weight of the adhesive composition, more preferably from 2 to 40% by weight, still more preferably from 3 to 30% by weight. % in weight.

  Preferred additives include hydrocarbon resins used as tackifiers or modifiers, which include: 1. Resins such as terpene C5 / C6r resins terpene styrene resins, alpha-methylstyrene terpene resins, terpene resins at C9, aromatic modified C5 / C6 resins, aromatic modified cyclic resins, aromatic modified dicyclopentadiene resins, or mixtures thereof. Additional preferred resins include those described in WO 91/07472, US 5,571,867, US 5,171,793 and US 4,078,132. These resins may be obtained by cationic polymerization of compositions containing one or more of the following monomers: C5 diolefins (such as 1,3-pentadiene, isoprene, etc.); C5 olefins (such as 2-methylbutenes, cyclopentene, etc.); C 6 olefins (such as hexene) of C 9 vinylaromatic monomers (such as styrene, alpha-methylstyrene, vinyltoluene, indene, methylindene, etc.); cyclic monomers (such as dicyclopentadiene, methyldicyclopentadiene, etc.); and / or terpenes (such as limonene, hull, thujone, etc.).

  2. Resins obtained by thermal polymerization of dicyclopentadiene and / or by thermal polymerization of dimers or oligomers of cyclopentadiene and / or methylcyclopentadiene, and / or with aromatic vinyl monomers (such as styrene, alpha-methylstyrene, vinyltoluene , indene, methylindene, etc.).

  The resins obtained after polymerization and separation of the unreacted materials can be hydrogenated if desired. Examples of preferred resins for use as additives in the present invention include those described in US 4,078,132, WO 91/07472, US 4,994,516, EP 0 046 344 A, EP 0 082 726 A and US 5,171,793.

  Crosslinking Agents In another embodiment, the additive may further comprise a crosslinking agent. Preferred crosslinking agents include those having functional groups that can react with the functional group present on α-srPP-α-FG, for example the anhydride group present on amorphous syndiotactic-rich polypropylene grafted with maleic anhydride. (for example a-srPPr-g-MA). Preferred crosslinking agents include alcohols, multiols, amines, diamines, and / or triamines. Specific examples of crosslinking agents useful in the present invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylanilinopropylamine and / or menthanediamine.

  Antioxidants In another embodiment, the additive may comprise one or more phenolic antioxidants. Preferred examples of phenolic antioxidants include substituted phenols such as 2,6-di-tert-butylphenol wherein a hydrogen atom at the 2-position and / or 6-is substituted with an alkyl residue. Typical examples of phenolic antioxidant include 2,6-di-tert-butyl-presol, 2,4,6-tri-tert-butylphenol, vitamin E, 2-tert-butyl-6- (3'-tert-butyl) acrylate. 2-methyl-2'-hydroxybenzyl) -4-methylphenyl, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenyl), 2,2'-methylene-bis- (4-ethyl-6- tert-butylphenol), 2,2'-methylene-bis (6-cyclohexyl-4-methylphenol), 1,6-hexanediol-bis- ([3- (3,5-ditertiobutyl- [4-hydroxyphenyl])] propionate , and pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate. Preferred antioxidants include phenolic antioxidants such as Irganox 1010, Irganox 1076, both available from Ciba Geigy.

  Neutralizing Agents / Nucleating Agents The additive of the present invention may also comprise a neutralizing agent such as calcium stearate, magnesium hydroxide, aluminum hydroxide or hydrotalcite, and / or a nucleating agent such as a benzoic acid salt, sodium 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) -phosphate, benzyl-sorbitol, etc. Loads In another embodiment, the additive may comprise fillers. Suitable fillers include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay, etc. Additional contemplated embodiments include a nanoclay, also referred to herein as the nanocomposite, comprising an organic clay, and the polyolefin of the present invention, preferably the polyolefin comprising stabilizing functionality, the stabilizing functionality preferably being covalent.

  The organic clay may comprise one or more ammonium, primary alkylammonium, secondary alkylammonium, tertiary alkylammonium, alkylammonium quaternary or phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or a or a plurality of sulfonium derivatives of amines, phosphines or aliphatic, aromatic or arylaliphatic sulfides.

  The organic clay may be one or more of the materials selected from montmorillonite, montmorillonite sodium, montmorillonite calcium, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminum oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite and / or fluorinated mica .

  The organic clay is preferably present in the nanocomposite in a proportion of 0.1 to 50% by weight, based on the total weight of the nanocomposite. The stabilizing functionality may consist of one or more functionalities selected from phenols, ketones, hindered amines, substituted phenols, substituted ketones, substituted hindered amines, and combinations thereof.

  The nanocomposite may further comprise at least one ethylenepropylene elastomer copolymer. Said at least one ethylene-propylene elastomer copolymer may be present in the nanocomposite in a proportion of 1 to 70% by weight, based on the total weight of the nanocomposite. The nanocomposite may further comprise at least one unfunctionalized thermoplastic polyolefin.

  Preferably, the stabilizing functionality is present in said at least one stabilizing functionalization thermoplastic polymer, and the organic clay is present in the nanocomposite, each in an effective amount such that thermal aging failure of a molded sample of the nanocomposite is 10% by comparison with a reference nanocomposite produced with a thermoplastic polyolefin containing a functionality substantially devoid of covalently bonded stabilizer functionality. In one embodiment, the stabilizing functionality may be present in said at least one thermoplastic polyolefin with stabilizing functionality in a proportion of 0.01 to 15% by weight based on the total weight of said at least one thermoplastic polymer with stabilizing functionality.

  The unfunctionalized thermoplastic polyolefin is preferably miscible with the at least one first thermoplastic polyolefin with stabilizing functionality. In such an embodiment, said at least one unfunctionalized thermoplastic polyolefin may also be present in the nanocomposite in an amount of 1 to 5% by weight based on the total weight of the nanocomposite, and the organic clay may be present in the nanocomposite in a proportion of 0.5 to 40 by weight, based on the total weight of the nanocomposite. Preferably, said at least one first thermoplastic polyolefin with stabilizing functionality and said at least one unfunctionalized thermoplastic polyolefin each comprise one of polypropylene and polyethylene polymers.

  In another embodiment, a nanocomposite suitable for use in the adhesive of the present invention may comprise: a) at least one non-functionalized first polypropylene present in the nanocomposite in a proportion of 10 to 98% by weight, based on the total weight of the nanocomposite; b) at least one second polypropylene comprising a stabilizing functionality, the stabilizing functionality consisting of one or more functional groups selected from phenols, ketones, hindered amines, substituted phenols, substituted ketones, substituted steric hindered amines, and their associations;

 and the stabilizing functionality being present in the stabilizing functionality polypropylene in a proportion of 0.05 to 15% by weight, based on the total weight of the polypropylene comprising the stabilizing functionality, said at least one second polypropylene comprising a stabilizing functionality being present in the nanocomposite in a proportion of 10 to 90% by weight, based on the total weight of the nanocomposite; c) an organic clay, the organic clay comprising one or more of the entities consisting of hexylammonium ion, octylammonium ion, 2-ethylhexylammonium ion, dodecylammonium ion, octadecylammonium ion, dioctyl ammonium ion; dimethylammonium, trioctylammonium ion, distearylammonium ion, an ammonium salt, a pyridinium salt, a sulfonium salt, a phosphonium salt or combinations thereof, the organic clay further comprising a clay of one or more selected clays between montmorillonite, montmorillonite sodium, montmorillonite calcium, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite , stevensite, vermiculite, halloysite, aluminum oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite and fluorinated mica, with organic clay present in the nanocomposite proportion of 1 to 30% by weight based on the total weight of the nanocomposite; and d) optionally further one or more of ethylene-propylene elastomeric copolymer polymers and isobutylene rubber present in the nanocomposite in a proportion of 2 to 70% by weight, based on the total weight of the nanocomposite.

  Adhesion Activators In another embodiment, the additive may comprise one or more adhesion promoters comprising polar acids, polyamino acids (such as Versamid 115, 125, 140, available from Henkel), urethanes ( such as isocyanate-terminated / hydroxy-terminated polyester systems, for example, TN / Mondur Cb-75 binding agent from Miles, Inc.), coupling agents (such as silane esters (Z-602.0 from Dow Corning). )), titanate esters (such as Kr-44 available from Kenrich), reactive acrylate monomers (such as Sarbox SB-600 from Sartomer), metal salts of acids (such as Saret 633 from Sartomer). ), polyphenylene oxide, oxidized polyolefins, acid modified polyolefins and anhydride-modified polyolefins.

  Oils Preferred oils include aliphatic naphthenic oils, white oils, and the like. Particularly preferred oils include paraffinic or naphthenic oils such as Primol 352 or Primol 876 oil available from ExxonMobil Chemical France, S.A. in Paris, France.

  Plasticizers Preferred plasticizers include mineral oils, polybutenes, phthalates, and the like. Preferred plasticisers include phthalates, such as di-iso-undecyl phthalate (DIUP), diisononyl phthalate (DINP), dioctyl phthalates (DOP) and their combinations and / or derivatives and / or the like.

  Particularly preferred plasticizers include polybutenes, such as Parapol 950 and Parapol 1300 previously available from ExxonMobil Chemical Company in Houston, Texas.

  Preferred plasticizers also include polyalphaolefins (PAO), high purity hydrocarbon fluid (HPFC) compositions, and Group III base oils such as those described in WO 2004/014998 at page 16, line 14 through on page 24, line 1. Particularly preferred PAOs include decene oligomers and decene and dodecene co-oligomers. Preferred PAOs are available under the trade name Supersyn from ExxonMobil Chemical Company in Houston, Texas. In a preferred embodiment, the PAO, the HPFC or the Group III base oil is present in a proportion of 0.5 to 60% by weight, based on the weight of the polymer and the PAO, the HPFC or Group III base oil. waxes

  Preferred waxes include polar or non-polar waxes, polypropylene waxes, polyethylene waxes and modifier waxes. Particularly preferred waxes may be selected from the group consisting of: polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene, polyethylene waxes, modifying waxes, amorphous waxes, carnauba waxes, castor oil waxes, microcrystalline waxes, beeswax, carnauba wax, castor wax, wax spermaceti, vegetable wax, candelilla wax, Japan wax, ouricury wax, Douglas fir bark wax, rice bran wax, jojoba wax, wax, wax montan, peat wax, ozokerite wax, cereal wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, wax substituted amide and their combinations and derivatives. In some embodiments, the polar and non-polar waxes may be used together in the same composition.

  Low Molecular Weight Polymers Other additives include low molecular weight polymers (i.e., a polymer having a low Mn value, the low term meaning a Mn value of less than 5000, preferably less than 4000, more preferably less than 3000, still more preferably less than 2500). Preferred polymers having a low Mn value include lower alpha-olefin polymers such as propylene, butene, pentene, hexene, and the like. (For example a polyalphaolefin comprising propylene, butene, pentene and / or hexene having a number average molecular weight of less than 5000 g / mol). A particularly preferred polymer comprises a polybutene having an Mn value of less than 1000. An example of such a polymer is available under the trade name PARAPOLTM 950 from ExxonMobil Chemical Company. PARAPOL ™ 950 is a liquid polybutene type polymer having an Mn value of about 950 and a kinematic viscosity of 220 centistokes (cSt) at 100 ° C, as measured according to ASTM D 445.

  Ester Polymers In another embodiment, the additive may comprise one or more ester polymers (polyesters). In a preferred embodiment, the additive comprises a two-phase mixture, wherein the polyester is a discontinuous phase and the phase comprising α-srPP-g-FG represents the continuous phase. Other additives Other preferred additives include blocking agents, anti-blocking agents, pigments, dyes, dyestuffs, processing aids, UV stabilizers, lubricants such as polydimethylsiloxane and calcium stearate, adjuvants, surfactants, color masterbatches, flow improvers, crystallization aids, plasticizers, oils, stabilizers, antioxidants, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, moisturizers, fillers, water, etc. The polymeric additives may include homopoly-alpha-olefins, alpha-olefin copolymers, diolefin copolymers and terpolymers, elastomers, polyesters, block copolymers, ester polymers, acrylate polymers, alkyl acrylate polymers and vinyl acetate polymers. Adhesive Composition The adhesive composition (e.g., the polymer blend) of the present invention may comprise one or more amorphous syndiotactic rich polyolefins and / or one or more syndiotactically rich polyolefins functionalized in the manner defined herein. above. In a preferred embodiment, the adhesive of the present invention comprises a polyolefin rich in amorphous syndiotactic structure, a polyolefin rich in amorphous syndiotactic structure which has been functionalized with a functional group or one of their associations, the polyolefin rich in syndiotactic structure amorphous composition comprising: more than about 50% by weight of C3 to C40 alpha-olefins; from about 50% to less than about 80 r dyads, based on the total number of r and m dyads present in the polymer; has a heat of fusion equal to or less than 10 J / g according to the procedure described in standard ASTM E 794-85 and an ash content equal to or less than 1% by weight, and the functional group, when present comprises a compound having a weight average molecular weight of 1000 or less, and a carbon-carbon double bond, a carbon-carbon triple bond and / or a heteroatom; the adhesive having a peel strength to a non-polar substrate greater than about 625.1 g / cm, and a peel strength to a polar substrate of greater than about 89.3 g / cm; strain being measured according to a modified method ASTM D-1876, as described herein.

  In addition, the adhesive composition of the present invention may comprise one or more additives as defined above, which have been combined in a weight / weight ratio of the polyolefin to the additive in the range of about 1: 1000 to 1000: 1. Preferably, the weight / weight ratio may be about 1: 100, about 1:50, about 1:20, about 1:10, about 1: 5, about 1: 4, about 1: 3, about 1: 1 : 2 or about 1: 1. Alternatively, the weight / weight ratio may be about 100: 1 to about 50: 1, about 20: 1, about 10: 1, about 5: 1, about 4: 1, about 3: 1 or about 2 1.

  The adhesive composition (e.g., the polymer blend) of the present invention may comprise one or more amorphous syndiotactic rich polyolefins and / or one or more functionalized syndiotactic rich polyolefins. In addition, the adhesive composition of the present invention may comprise one or more additives as defined above, which have been combined such that the polymer blend comprises 10 to 90% by weight of additive, based on the weight of the polymer blend. The polymer mixture advantageously comprises 20 to 80% by weight of additive, more preferably 30 to 80% by weight of additive, more preferably 40 to 80% by weight of additive, still more preferably 50 to 80% by weight of additive. additive, more preferably 60 to 80% by weight of additive, still more preferably 70 to 80% by weight of additive, based on the weight of the polymer blend.

  In the process used for the production of the adhesive composition of the present invention, no particular restriction is imposed on the type of mixture. Accordingly, the raw materials may be uniformly mixed by means of a Henschel mixer or similar mixer and may then be melted, blended and pelleted by an extruder or similar apparatus. It is also possible to use a Brabender mixer for simultaneous mixing and melting and, after melting, the material can be molded directly into films, sheets, etc. Thus, the blends described herein can be formed using standard techniques known in the art, so that blending can be accomplished using one or more static mixers, inline mixers, angled mixers, orifice mixers, baffled mixers or any of their associations.

  In a preferred embodiment, the adhesive composition comprises a blend which comprises a polyolefin rich in amorphous syndiotactic structure present in a proportion of about 1 to about 99% by weight, based on the total weight of the mixture; more preferably, the polyolefin rich in amorphous syndiotactic structure is present in an amount greater than about 5% by weight, preferably greater than about 10% by weight, preferably greater than about 20% by weight, preferably greater than about 30% by weight, preferably greater than about 40% by weight, preferably greater than about 50% by weight, preferably greater than about 60% by weight, preferably greater than about 70% by weight, preferably greater than about 80% by weight, preferably greater than about 90% by weight, based on the total weight of the adhesive composition.

  In a preferred embodiment, the adhesive composition comprises a blend that comprises a functionalized amorphous syndiotactic rich polyolefin present in an amount of about 1 to about 99% by weight, based on the total weight of the mixture; more preferably, the polyolefin rich in amorphous syndiotactic structure is present in an amount greater than about 5% by weight, preferably greater than about 10% by weight, preferably greater than about 20% by weight, preferably greater than about 30% by weight, preferably greater than about 40% by weight, preferably greater than about 50% by weight, preferably greater than about 60% by weight, preferably greater than about 70% by weight, preferably greater than about 80% by weight, preferably greater than about 90% by weight, based on the total weight of the adhesive composition.

  In a preferred embodiment, the adhesive composition comprises a blend that comprises amorphous syndiotactic rich polypropylene in an amount of about 1 to about 99% by weight, based on the total weight of the blend; more preferably, the polyolefin rich in amorphous syndiotactic structure is present in a proportion of greater than about 5% by weight, preferably greater than about 10% by weight, preferably greater than about 20% by weight, upper superior superior superior superior superior superior at about 80% by weight, preferably greater than about 90% by weight, based on the total weight of the adhesive composition.

  In a preferred embodiment, the adhesive composition comprises a blend which comprises a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride, which is present in a proportion of about 1 to about 99% by weight, on the basis of the total weight of the mixture; more preferably, the polyolefin rich in amorphous syndiotactic structure is present in an amount greater than about 5% by weight, preferably greater than about 10% by weight, preferably greater than about 20% by weight, preferably greater than about 30% by weight, preferably greater than about 40% by weight, preferably greater than about 50% by weight, preferably greater than about 60% by weight, preferably greater than about 70% by weight, preferably greater than about 80% by weight, preferably greater than about 90% by weight, based on the total weight of the adhesive composition.

  In one embodiment, the adhesive composition comprises less than 3% by weight of an antioxidant, less than 3% by weight of a low viscosity flow improving agent, less than 10% by weight of an wax and / or less than 3% by weight of a crystallization aid. However, in certain embodiments, a wax may not be desired and may be present in a preferred, preferably preferably about 30% by weight, to about 40% by weight, to about 50% by weight, from about 60% by weight, to about 70% by weight, of less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight % by weight, based on the weight of the adhesive composition.

  In another embodiment, the adhesive composition of the present invention comprises a polypropylene rich in amorphous syndiotactic structure and less than 50% by weight in total of any combination of the additives described above, preferably less than 25% by weight, preferably less than 20% by weight, preferably less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight, based on the weight of the composition of 'adhesive.

  In another embodiment, the adhesive composition of the present invention comprises a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride and less than 50% by weight in total of any combination of the additives described herein. above, preferably less than 25% by weight, preferably less than 20% by weight, preferably less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight, on the basis of the weight of the adhesive composition.

  Properties of the Adhesive Composition The adhesive composition of the present invention preferably has a peel strength to a non-polar substrate (eg, isotactic polypropylene) greater than about 625.1 g / cm 2 as measured. following an amendment to ASTM D-1876.

  Preferably the peel resistance to a polar substrate (eg, Mylar) is greater than about 89.3 g / cm, a value greater than about 178.6 g / cm being more preferred.

  As demonstrated by the fiber tearing examples herein, the adhesive composition of the present invention has excellent adhesion properties to cellulose and other similar materials. The adhesive composition of the present invention preferably has a set time of less than about 10 minutes, more preferably less than about 1 minute, even more preferably less than about 30 seconds. Setting time is defined for use in the present invention by the time required for an adhesive and a substrate in the form of a compressed assembly to bond to each other with sufficient adhesion so that to achieve tearing of the fibers of the substrate during the separation and thus to achieve a sufficiently strong bond to suppress the compression. The bond is likely to be further enhanced by additional cooling, however, it no longer requires compression. These setting times were measured by placing a melt point of adhesive on a substrate consisting of a liner attached to a flat table. A shirt leg (2.5 cm x 7.6 cm) was placed on the spot 3 seconds later and compressed by means of a weight of 500 g. The weight was allowed to stand for about 0.5 to about 10 seconds. The construct thus formed was separated to control a degree of binding sufficient to cause the fibers of the substrate to tear. The setting time was noted as the minimum time required for this bond to occur. Reference samples of commercially available adhesives were used to calibrate this process.

  The adhesive composition of the present invention preferably has a percent tearing of the substrate fibers of 75% to 100% at 25 ° C. Adhesive test samples have been created by bonding the substrates together with one part ( for example, a dot) of molten adhesive and compressing the bond with a weight of 500 g until cooled to room temperature (i.e. about 25 C). The diameter of the stitch was adjusted by the volume of adhesive so that in most cases the compressed disk that formed gave a uniform circle just within the dimensions of the substrate. Once a construct was formed, it was subjected to various aggressions to determine the effectiveness of the bond. For the low temperature fiber tear test, the bond samples were placed in a freezer or refrigerator to achieve the desired test temperature. For the tearing of the substrate fibers at room temperature, the samples were subjected to aging under ambient conditions. The bonds were separated manually and a determination was made regarding the type of break observed. The degree of fiber tearing of the substrate is expressed herein as a percentage.

  Use of the adhesive composition For any of the adhesive compositions described above, the final properties and the suitability for a particular application depend on the type of tacticity (stereoregularity), the melting point, the molecular weight means, the molecular weight distribution, the type and amount of monomer and comonomer, the sequence distribution, the presence or absence of any additional functionality and the type and quantity of adhesion additives used in this composition.

  The adhesive compositions of the present invention can be used in any adhesive application including, but not limited to, disposable articles, packages, laminates, pressure-sensitive adhesives, ribbons, and the like. , labels, wood bonding, paper bonding, nonwoven articles, road marking, reflective coatings, etc.

Disposable items

  In a preferred embodiment, the adhesive composition of the present invention can be used for disposable diaper structures and periodic napkin bodies, elastic fixation in disposable articles, conversion, packaging, labeling. , bookbinding, woodworking and other assembly applications. The most popular applications include: baby diaper leg elastics, baby diaper ribbons, baby diaper leg cuffs, baby diaper body structure, diaper center stabilization for babies, the liquid transfer layer of the baby diapers, the layering of the baby diapers, the layering of the elastic sleeves of the baby diapers, the stabilization of the central parts of the sanitary napkins, the adhesive strips of the sanitary napkins, the binding for the industrial filtration, stratification of industrial filter materials, stratification of filter masks, stratification of surgical gloves, stratification of surgical drapes and packaging of perishable products.

  In one embodiment, the adhesive composition of the present invention may be applied to at least a portion of one or more disposable elements including nonwoven fabrics, nonwoven webs, non-woven non-woven fabrics, fabrics, and the like. elastic nonwoven fabrics, pleated bonded laminates, stretch bonded laminates, spunbonded spunbonded laminates, polypropylene spunbonded layers, polyethylene layers, spunbonded polyethylene and polypropylene combined, elastic strands, styrene-isoprene-styrene copolymers, styrene-butadiene-styrene, styrene-ethylene / propylene-styrene, styrene-cobutadiene-styrene, polyurethane, woven fabrics, polypropylene, polyester, sheets body fluid-impermeable backing, body fluid impermeable layers, permeable layers, body fluids, body fluid-permeable blankets, absorbents, fabrics, elastomeric materials, hyperabsorbent polymers, polyolefinic films, polyester films, polyvinyl chloride films, poly films - (vinylidene chloride), polyvinyl acetate films, elastic fastener tapes, ribbons, wood, paper, barrier films, film laminates, composites nonwovens, textile materials, woven materials, staple fabrics, absorbents, elastomeric strands, elastomeric webs, fabrics, films, cover materials, nonwoven polyethylene, perforated polyethylene, hyper-polymers, absorbents, filaments, porous tapes, fibers, loop fasteners, spin-bonded nonwoven articles, coatings, elastic side plates, fastener tapes elastic bands, rayon, nylon, cellulosic pulp, cellulosic down, and hyperabsorbent webs.

  In addition, a disposable article according to the present invention may comprise the adhesive composition of the present invention described herein, the adhesive being applied to at least a portion of one or more disposable elements including baby diapers , training pants, sanitary napkins, panty liners, incontinence garments, alèzes, surgical gloves, surgical drapes, rodent traps, Velcro-type fasteners, clothing, medical clothing and bathing suits. Similarly, a disposable article may include a first member of the disposable article adhering to a second member of the disposable article by the adhesive composition of the present invention.

  In one embodiment, the adhesive composition of the present invention may comprise one or more solvents selected from the group consisting of hexane, heptane, mineral spirits, xylene, toluene, benzene, chlorinated hydrocarbons and their combinations or derivatives.

  In one embodiment, a disposable article comprising the adhesive composition of the present invention may further comprise one or more antioxidants including tris- (di-tert-butyl-p-hydroxybenzyl) trimethylbenzene, an alkylated bisphenol, dibutyldithiocarbamate. zinc, 4,4'-methylene-bis- (2,6-ditertiobutylphenol), tetrakis [methylene- (3,5-ditertiobutyl-4-hydroxyhydrocinnamate) -methane], lauryl stearylthiodipropionate, 3,3 ' dilauryl thiodipropionate, 2,6-di-tert-butyl-p-cresol and their combinations or derivatives.

  A disposable article comprising the adhesive composition of the present invention may further comprise one or more stabilizers comprising sterically hindered phenols, phenols comprising sulfur, phosphorus-containing phenols, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, pentaerythritol tetrakis-3- (3,5-ditertiobutyl-4-hydroxyphenyl) -propionate, 3- (3,5 n-octadecyl-di-tert-butyl-4-hydroxy-phenyl) -propionate, 4,4'-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4'-thio-bis- (6) -tertiobutyl-o-cresol), 2,6-di-tert-butylphenol, 6- (4-hydroxyphenoxy) -2,4-bis (n-octylthio) -1,3,5-triazine, 2,4 , 6-tris- (4-hydroxy-3,5-di-tert-butylphenoxy) -1,3,5-triazine, di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2- ( n-octylthio) -ethyl-3,5-di-tert-butyl-4-hydroxybenzoate, sorbitol hexa- (3,3,5-di-tert-butyl-4-hydroxyphenyl) -propionate and their combinations or derivatives. ved. In a preferred embodiment, a disposable article comprising the adhesive composition of the present invention is a consumer good.

  Laminates In one embodiment, a laminated article comprising two or more layers may be present in association with the adhesive composition of the present invention. A laminated article may comprise two or more layers in combination with the adhesive composition of the present invention, the adhesive composition being present between the layers.

  In one embodiment, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention may comprise one or more materials including wood, plastic, paper, rubber, a material, and the like. thermoplastic, cardboard, metal, foil, metallized surfaces, fabric, nonwovens, spunbond fabrics, stone, plaster, glass, rock, ceramic materials, films and foams.

  In addition, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention may comprise a laminate wherein each of the layers is individually selected from wood, plastic, paper, rubber , a thermoplastic material, cardboard, a metal, a metal foil, metallized surfaces, a fabric, nonwovens, fibers spunbonded, stone, plaster, glass, rock, ceramic materials, films and foams.

  A laminated article comprising two or more layers in association with the adhesive composition of the present invention, wherein the two or more layers comprise a first layer and a second layer, the second layer may be formed of a material which is different from a material of the first layer.

  In one embodiment, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention may further comprise a release paper or release agent present on a surface layer.

  A laminated article comprising two or more layers in combination with the adhesive composition of the present invention may also comprise a layered structure produced by any of the techniques consisting of spraying, extrusion molding, fusion bonding , polymer injection and hot melt adhesion.

  In one embodiment, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention may further comprise at least one layer comprising a combination of the adhesive composition of the present invention and one or more materials such as wood, plastic, paper, rubber, thermoplastic, cardboard, metal, foil, metallized surfaces, fabric, nonwovens, spunbond fibers , stone, plaster, glass, rock, ceramic materials, films and foams.

  In a preferred embodiment, a laminated article may comprise two or more layers in combination with the adhesive composition of the present invention, the adhesive composition having an open-container use time equal to or less than seconds. the open container time being determined according to ASTM D 4497. In a preferred embodiment, the adhesive composition of the present invention, when used in a laminated article comprising two or more than two layers, may have a setting time equal to or greater than 3 seconds, as determined by those skilled in the art.

  In a preferred embodiment, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention may comprise the adhesive having a percentage of substrate fiber tear from 75% to 100 to 22%. C, when determining according to the methods described herein. In a preferred embodiment, a laminated article comprising two or more layers in combination with the adhesive composition of the present invention is a consumer good.

  The adhesive compositions described above can also be applied in the laminate state to any substrate, including polar substrates (eg, cardboard, Mylar (polyester)), non-polar substrates (e.g. iPP), or both polar substrates and nonpolar substrates (eg between them). Preferred substrates include wood, paper, cardboard, plastic, thermoplastic, rubber, metal, metal foil (such as aluminum foil and tin foil), metallized surfaces , fabric, nonwovens (in particular spunbonded polypropylene fibers or polypropylene nonwovens), spunbond fibers, cardboard, stone, plaster, glass (including oxide coatings silicon (SiOx) applied by evaporation of silicon oxide on the surface of a film), foam, rock, ceramic materials, films, polymeric foams (such as polyurethane foam), substrates coated with inks, dyes, pigments, PVDC etc., or their combinations. Additional preferred substrates include polyethylene, polypropylene, polyacrylates, acrylic polymers, poly (ethylene terephthalate) or any of the above listed polymers as suitable polymers for blends.

  Any of the aforementioned substrates and / or the adhesive composition of the present invention may be treated by corona discharge, flame-treated, irradiated with an electron beam, irradiated with gamma rays, irradiated with micro or treated with a silane before or after the combination of the substrate and the adhesive composition.

  The adhesive composition of the present invention or formulations containing it may be applied directly to a substrate and / or may be sprayed or otherwise applied to that substrate. The composition can be melted, or heated to a semisolid state before or during application. The sputtering is defined to include atomization, such as that producing a uniform dot pattern, spiral spraying such as Nordson-controlled fiber production or oscillation of a drawn filament can be performed in the heads. ITW Dynafiber / Omega or following Nordson Summit technology. The adhesive composition can also be melt blown. Melt blowing techniques are defined to include the processes described in U.S. Patent No. 5,145,689 or any method in which drafts are used to break filaments of the extrudate and are then used to expose the broken filaments on a substrate. In general, melt blowing techniques are processes that use air to spin hot melt adhesive fibers and transport them on a substrate for bonding. The dimensions of the fibers can be easily adjusted in the range of 20 to 200 microns by changing the ratio of the melt to air. A reduced, preferably zero, number of insulated fibers is generated because of the inherent stability of the meltblowing adhesive applicators. In UV light, the bond appears as a regular, smooth, stretched dot pattern. Atomization can also be defined as a process that uses air to atomize a hot melt adhesive at very small points and transport these points onto a substrate for leaching.

  Nonwovens / Fibers In a particular embodiment, the adhesives of the present invention may be used in fiber products. The fiber products consist of fibrous materials to which an adhesive composition has been applied. The fibrous material may comprise a monocomponent fiber, a multicomponent fiber or one of their combinations. Several types of fibrous materials can be used to form fiber products and are generally differentiated based on the organization of the fibers in the fiber product. For example, one type of fibrous material is an isotropic assembly wherein the individual fibers are arranged in a totally random manner with no preferred orientation in any of the three major spatial axes. Another example of fibrous materials is textile yarns having a high degree of orientation of the fibers with respect to the main axis of the material. Textile yarns are produced from chopped fibers (of finite length) by an association of the processing steps referred to collectively as yarn spinning. After preliminary alignment of the fibers, the fibers are fixed to each other by twisting the structure to form the spun yarn, which has a continuous length and is substantially uniform. Yarns are usually used in the formulation of textile fabrics by weaving or knitting.

  Fibrous materials may include cotton, kapok, coir, flax, hemp, ramie, jute, sisal, abaca, cellulose, wool, mohair, cashmere, human hair , ordinary goat hair, camel hair, llama hair, alpaca hair, vicuna wool, silk, nylon, aramid, Kevlar, nomax, polyamides, polyacrylates, polyolefin polymers such as a propylene polymer, a butene-1 polymer, polyethylene, polypropylene, and an ethylene-vinyl acetate polymer, a polyester such as poly (ethylene terephthalate), polyethylene (butylene terephthalate), poly (ethylene terephthalate) and polyethylene-oxybenzoate, asbestos, polyamides, polycarbonate, polystyrene, thermoplastic elastomers, fluoropolymers, vinyl polymers, mineral materials, Acrylic materials, poly (vinyl chloride), organic binders glass, a metal, alumina, silicon carbide, boron nitride, boron carbide and their combinations.

  Examples of fiber products include nonwovens, carpets, carpet racks, baby diapers, swimwear, children's training pants, adult incontinence garments, hygiene products clothing, scrubbing pads, interior parts of automobiles, clothing, ribbons, fascial masks and respirators, air filters, bags of vacuum cleaners, oil residue and chemical sorbents, thermal insulators, first aid dressings, medical tape, fiber fillers, outerwear, quilts, materials furniture upholstery, filter media, scouring pads, wipers and their combinations.

  In a preferred embodiment, a carpet comprises the adhesive composition of the present invention. In another preferred embodiment, a tape comprises the adhesive composition of the present invention.

  As used herein, the term nonwoven refers to a textile material that has been produced by means other than weaving. In nonwoven fabrics, the fibers are processed directly into a flat sheet-like fabric structure by passing into the intermediate one-dimensional wire state, and then chemically bonded or mechanically entangled (or both chemically bonded and mechanically entangled). ) to obtain a cohesive fabric. The nonwoven article may comprise natural fibers, synthetic fibers or mixtures thereof. Materials commonly used in the formation of nonwoven articles include rayon, polyester, polypropylene, polyethylene, nylon and other materials. The different fibers are usually chopped fibers or continuous filaments. Examples of fibers may include polypropylene fibers, rayon fibers, polyester fibers, polyethylene fibers, nylon fibers, cellulose fibers, viscose fibers, ethylene-propylene copolymer fibers, polyolefin fibers, polyamide fibers, polycarbonate fibers, polystyrene fibers, thermoplastic elastomer fibers, fluoropolymer fibers, vinyl polymer fibers, carbon fibers, glass fibers, mineral fibers wool fibers, acrylic fibers, polyvinyl chloride fibers, polyurethane fibers, organic binder fibers and combinations thereof.

  In one embodiment a fiber product comprising one or more fibrous materials in combination with the adhesive composition of the present invention may comprise a primary support material, the fibrous materials being attached to the primary support material and the adhesive being placed on at least a portion of fibrous material. A fiber product may also include one or more fibrous materials in combination with the adhesive composition of the present invention and comprises a primary support material and a second support material adhered to the adhesive.

  A fiber product may also include one or more fibrous materials in combination with 1.a. adhesive composition of the present invention, a primary support material being woven jute, woven split polypropylene film, scrim, needled materials, nonwoven polypropylene and combinations thereof.

  In one embodiment, a fiber product comprising one or more fibrous materials in combination with the adhesive composition of the present invention may comprise a fibrous material having a cross-sectional formation that is circular, elliptical, T, Y-shaped. , +, hollow, square, multilobed, ribbon and / or polygonal.

  Accordingly, a fiber product comprising one or more fibrous materials in combination with the adhesive composition of the present invention may comprise garments, blankets, insulators, carpets, composite materials, cardboard prepregs. printed circuits, wigs, or their associations.

  In addition, in an embodiment in which a fiber product comprises one or more fibrous materials in combination with the adhesive composition of the present invention, the adhesive composition may further comprise one or more additives such as surfactants, foaming agents, polymer compatibilizers, flame retardants and water.

  In a preferred embodiment, a fiber product comprising one or more fibrous materials in combination with the adhesive composition of the present invention may comprise any of the adhesive compositions described above corresponding to a tear percentage. substrate fibers of 75% to 100% at 22 C. In a preferred embodiment, a fiber product comprising one or more fibrous materials in combination with the adhesive composition of the present invention is a consumer good. Movies

  In a particular embodiment, the polymeric components described herein may be used in a monolayer film. Alternatively, the polymeric components may be applied to at least one outer portion of a monolayer film. Monolayer films are planar shapes that are thick enough to be self-supporting but thin enough to flex, fold, or crease without cracking.

  The thickness of the film depends on the application and the production but is generally less than 125 μm. The monolayer film, which may be unoriented, uniaxially oriented or biaxially oriented, is formed by applying a polymeric component to at least a portion of a film substrate. Alternatively, the polymeric component may be mixed with a film substrate to modify its properties.

  The film substrate may comprise paper, metal foil, metal, metal alloys, polyethylene, polypropylene, polyester, poly (ethylene terephthalate), poly (vinyl chloride), poly - (vinylidine chloride), poly (vinyl acetate), polyamides, their homopolymers and their combinations and copolymers.

  The monolayer film may further comprise additional polymeric components selected from polyethylene, polypropylene, polyester, poly (ethylene terephthalate), poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl acetate), polyamides, homopolymers thereof and combinations and copolymers thereof.

  In one embodiment, a film comprising the adhesive composition of the present invention preferably comprises a polypropylene layer and / or an oriented polypropylene layer, and / or a biaxially oriented polypropylene layer.

  Hot Melt Adhesives In a particular embodiment, the adhesives of the present invention may be used in a hot melt adhesive composition. Hot melt adhesives exist as a solid at room temperature and can be converted to an adhesive liquid by heating. Hot melt adhesives are usually applied in molten form to a substrate.

  In one embodiment, a hot melt adhesive composition comprising the adhesive composition of the present invention may comprise an adhesive composition corresponding to a percentage of the fibers of the substrate being stripped from 75% to 100% at 25 ° C. Preferably, a percent tearing of the substrate fibers from 95% to 100% at 25 ° C. In a preferred embodiment, the hot melt adhesive composition comprising the adhesive composition of the present invention is a consumer good.

  Pressure Sensitive Adhesives In a particular embodiment, the adhesive compositions described herein may be used in pressure sensitive adhesive compositions. As used herein, the pressure-sensitive adhesive compositions are adhesive compositions that have the ability at or near room temperature (about 25 ° C) to sufficiently wet a substrate. under gentle pressure and to form a useful link. As used herein, useful link expression differs depending on the application of the substrate and refers to a corresponding balance between adhesion strength and cohesive strength. In one embodiment, a pressure sensitive adhesive comprising the adhesive composition of the present invention may have a setting time equal to or less than 30 minutes.

  Ribbons In a particular embodiment, the adhesives of the present invention can be used in ribbons. The ribbons are generally configured to adhere two or more substrates to each other. The tapes comprise an adhesive composition applied to a support member. The support member may be selected from the group consisting of polymeric films, polyester films, polyolefin-based films, polyurethane films, polyvinyl chloride foams, polyethylene foams, a nonwoven polyurethane, a nonwoven polyester, a fabric, a backing paper, paper, a synthetic polymeric material, a plastics material, polyolefinic polymers, such as polyethylene and polypropylene, a polyester, poly (terephthalate), ethylene), polyvinyl chloride, kraft paper, polymers, laminates, latex saturated papers, film, lithographic base paper, thin base paper, styrene foam, an expanded polystyrene foam, a woven fabric, a nonwoven fabric, a fabric, crepe paper, thermoplastic elastomers and combinations thereof. A conventional support member has a variable thickness in the range of one micrometer to several centimeters. Particularly preferred support members include oriented polypropylene, biaxially oriented polypropylene and poly (vinyl chloride) polymers. Polymer films consisting of oriented polypropylene, biaxially oriented polypropylene, and polyvinyl chloride are particularly preferred support members.

  The tapes may be single-sided or double-sided, which means that the adhesive material is applied to one or two opposite sides of the support material. The tape may comprise an adhesive composition and a release material applied to opposite sides of a support member. A double-sided tape may comprise a first adhesive composition and a second adhesive composition applied to opposite faces of a support member. At least one of the first adhesive composition and the second adhesive composition comprises the adhesive composition described herein; for example, one or both of the adhesive compositions comprise the adhesive composition of the present invention.

  The tapes may be configured to adhere a variety of substrates to each other, for example a first substrate to a second substrate, or the tapes may have a configuration allowing adhesion to a single substrate. The first substrate may be of a material identical to that of the second substrate, or the substrates may be formed of different materials. One or both substrates may comprise a plastics material, polyolefinic polymers, stainless steel, paper, cardboard, containerboard, labelstock, corrugated board, chipboard, kraft paper , cardboard, fibreboard, plastic resin, metal, metal alloys, foil, film, film, plastic film, laminates, clothing, containers, surgical instruments, medical devices , glass and sheet materials.

  The tapes may be provided in the form of rolls, sheets, pads or in other forms determined by the specific use needs, to protect the adhesive composition adhering to the support member against unwanted adhesion to surfaces other than the intended substrate. For example, the adhesive composition applied to the support material may be applied to a separation material until use. The release materials are generally applied to the tape to maintain the adhesive strength of the adhesive composition and have a configuration to separate the tape. Separation materials are generally used when the tape is supplied in sheet or roll form. The separating material usually comprises a release coating, such as a silicone coating. Tapes that are supplied in roll form can be used with a tape dispenser or can be torn manually. Ribbons that are provided in the form of a buffer may comprise an adhesive composition between two separation layers, wherein at least one separation layer is coated with a release liner composition.

  The adhesive composition may be applied to at least a portion of at least one side of the support material. In general, the adhesive composition has the ability, at a temperature equal to or approximately equal to ambient temperature, to sufficiently wet a substrate under mild pressure to form a useful bond. As used herein, useful bonding refers to an equilibrium of adhesion strength (adhesive breaking to the substrate) and cohesive strength (internal adhesive breakage), which is optimized according to the application. ribbon. For example, the adhesive composition in repositionable tapes may have a relatively low adhesive strength as compared to the cohesive strength, resulting in a tape that can be removed without leaving a residue (eg adhesive) on the tape. substrate. In contrast, high-performance ribbons, for example ribbons used for transport and packaging, can have both a high adhesive force and a high cohesive strength, resulting in rupture of the substrate or the substrate. support element.

  Packaging Adhesive In one embodiment, a packaging adhesive may comprise the adhesive composition of the present invention. A package may also comprise the adhesive composition of the present invention, wherein the adhesive described herein is applied to at least a portion of one or more packaging elements including paper, paperboard, cardboard for containers, cardboard, corrugated cardboard, cardboard, kraft, cardboard, fibreboard, plastic resin, metal, metal alloys, metal foil, film, plastic film , laminates, sheet materials.

  In one embodiment, the present invention may include a package comprising the adhesive composition described herein wherein the adhesive is applied to at least a portion of one or more packaging elements including cartons, containers, crates, boxes, corrugated boxes and trays.

  A package may also include the adhesive composition of the present invention, wherein the adhesive is applied to at least a portion of one or more elements used in the packaging of cereal products, bake products in the packaging of beer, frozen food products, paper bags, goblets, cans of milk, cans of fruit juice and containers for the transport of foodstuffs.

  Woodworking In a particular embodiment, the adhesives described herein may be used in woodworking processes. A woodworking method includes forming a wood article by applying an adhesive composition to at least a portion of a structural member. The structural member may include a variety of materials that include, but are not limited to, wood or plywood, or a plastic or wood veneer. For example, the structural element may also include timber, wood, fiber board, plasterboard, legypse, cladding board, plywood, PVC, melamine, polyester, impregnated paper and a sheet of rock. A woodworking process can be used to form interior furniture, outdoor furniture, ornamental woodwork, molded parts, doors, frames, windows, timber framing, and wood furniture. furniture elements, for example. Accordingly, a preferred embodiment is a wood consumer good comprising the adhesive composition of the present invention.

  Labels In a particular embodiment, the adhesive compositions described herein may be used in labels. In general, the labels are simply intended to adhere themselves to a substrate. In this form, the labels are not intended to be structural constituents. As a result, the labels may have low internal strength and low adhesion strength.

  The labels comprise a layer of an adhesive composition applied as a coating on a support member, which may have a release surface on the opposite side to the adhesive composition. A label release coating is intended to adhere to the label until the label is applied to its intended substrate. Label holder elements are well known in the field of labels. Any suitable support member may be used in the present invention. The support members may comprise a polymer film, a polyester film, a polyolefin film, a polyurethane film, a polyvinyl chloride foam, a polyethylene foam, a nonwoven polyurethane, a polyester nonwoven, knitted fabric, paper, synthetic polymeric material, plastic, polyolefin, polyethylene, polypropylene, polyester, poly (ethylene terephthalate), polyvinyl chloride, kraft paper, polymers, laminate, latex saturated paper, metal foil, lithographic base paper and thin base paper, styrene foam, laminated foam, expanded polystyrene foam, cloth woven fabric, a nonwoven fabric, a garment, crepe paper, a thermoplastic material and blends of polyethylene and polypropylene, for example.

  Suitable substrates may include plastic, polyolefins, stainless steel, paper, cardboard, container board, label board, corrugated cardoon, particleboard, kraft paper, cardboard, fiber board, plastic resin, metal, metal alloys, metal foil, film, film, plastic film, laminates, clothing, containers, surgical instruments, medical devices, glass and sheet materials, for example.

  The labels may be in the form of rolls, sheets or other forms determined by the specific needs of use, so that they are protected against unwanted adhesion to other surfaces. As described above, the labels can be laminated to a release liner to prevent accidental adhesion to other surfaces. The label release liner is provided with a release layer such as a silicone layer to permit easy removal of the release liner from the label. The release coatings are sheets which are coated with a release material for use in labels. It is expected that the release liner will reproducibly provide an appropriate degree of separation to the adhesive of interest, have no adverse effect on the adhesive and be resistant to aging so that the degree of separation remains relatively low. predictable over time.

  A label may include a support member, an adhesive composition, and a release liner. The adhesive composition may be applied to the support member, while the release liner may be applied to the adhesive composition.

  Alternatively, the adhesive composition may be applied to the release liner, and then the support member may be applied to the adhesive composition. The release liner can then be removed from the adhesive composition prior to applying the label to a substrate.

  Binding In a particular embodiment, the adhesives of the present invention can be used as binders. For the sake of convenience, the term binder is used to describe the process for producing books comprising a binder, where an adhesive composition is applied to at least a portion of the binder. However, the embodiments described herein are not limited to adhesive compositions suitable for binding only books. As used herein, the term books is intended to include other articles containing pages related to adhesive compositions, such as paperback books, soft cover books, instruction manuals, magazines, catalogs, newspapers, directories, etc. In one embodiment, a binding article comprising the adhesive composition of the present invention may comprise a binder member comprising thick paper or base paper. In one embodiment, the adhesive of the present invention may correspond to a percentage of the fibers of the substrate being stripped from 75% to 100% at 22 ° C. Preferably, a binding article comprising the adhesive composition of the present invention. invention is a consumer good. Road Markings In a particular embodiment, the adhesive compositions described herein may be used in a road marking composition. Road marking compositions generally comprise a binder composition and one or more fillers applied to one or more substrates. The substrate (s) may include asphalt, concrete, metal, brick, gravel, ceramic materials, polymeric materials, slag blocks, soft sport surfaces, playground surfaces, runways. flight, tartan substitutes, concrete, metals, bitumen, bricks, tiles, steel plates, wood, glass, concrete blocks, porcelain, stone, panels of wood, particle board, wooden parts of vehicles, canvas and their associations.

  The road marking composition comprises one or more fillers for increasing the weather resistance, visibility, hiding power, abrasion resistance, adhesion and / or reflectivity of the road marking composition. In addition, certain fillers may be added to improve the total rheological properties of the thermoplastic road marking material, prevent the segregation of the road marking composition, ensure the friction of the binder composition with the substrate to which it is applied and / or reduce the cost of the road marking composition. Fillers that may be used for this purpose include sand, pigments, glass beads, polymer-based beads, calcium carbonate, crushed marble, aggregate, dolomite, talc, glass beads , prismatic reflectors, lens reflectors, calcite, spar, siliceous sand, graphite, fly ash, cement dust, clay, feldspar, nepheline, ultrafine silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanates, lime, reflective inorganic fillers, diluent fillers, beads, calcium sulfate, calcium metasilicate, quartz powder, calcined fly ash, mica, calcium silicate, glass fibers, dyes, granite, plaster, slaked lime, alumina, diatomaceous earth, reflective agents, modifiers, white lead, lithopone, chromium yellow, cadmium yellow, resin beads, polymer gels, polymers, ceramic materials, crushed glass, stone, corundum, aluminum hydroxide, silicon oxide, glass bubbles and zinc nodecanoate. Examples of pigments include titanium dioxide, zinc oxide, magnesium oxide, lead chromate and mixtures thereof. The type and amount of pigment are chosen according to the specific purpose for road marking, which can be readily determined by those skilled in the art. In addition, one or more fillers may be added to the road marking composition to impart color, opacity or tint to the road marking composition.

  A key feature of road marking compositions is visibility under all ambient conditions. As a result, the road marking composition may include one or more reflective charges. Incorporation of one or more reflective fillers into the road marking composition maximizes the visibility of road markings in the rain and in the dark by reflecting light from the headlights of a vehicle. One or more reflective charges may be incorporated into the road marking composition in an amount sufficient to impart increased visibility to the composition by the reflecting light. Suitable reflective fillers include, but are not limited to, glass beads, polymer beads, sand, silica compounds, ceramic materials and / or any other reflective filler typically used for such purposes in road marking compositions. Beads represent the preferred reflective filler and include, but are not limited to, polymer-based beads or glass beads. Glass beads are highly appreciated. The beads should not have a detrimental effect on the cohesive strength of the cooled binder, so that a strong bond can be generated between the binder and the beads. The main requirement is that the beads are stable to the heat applied during the preparation of the mixture and the application of the road marking composition. Preferably, the beads should remain stable when subjected to a temperature above at least 200 C for a period of time of about 20 minutes.

  Balls prepared from polymers must be able to withstand the pressure applied by the usual road traffic without breaking or crushing. In addition, the reflective load must be evenly distributed throughout the binder to achieve uniformity of properties and longevity to the reflectivity of road markings. Regular distribution of the reflective load causes the new reflective charges to be exposed to the surface when road wear and weather conditions eliminate an upper layer of road marking. The increase in the amount of reflective filler added to the road marking composition also makes it possible to maintain satisfactory reflective properties over time while increasing the reflectivity of road marking. If the amount of reflective filler present in the road marking composition is low, the reflective capacity is deteriorated when the amount of reflective charges dispersed in the composition is reduced due to tire abrasion while, if the amount of Added reflective load is too great, the road marking composition has reduced mechanical strength.

  In a preferred embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention and one or more fillers comprises a binder further comprising a copolymer having a M w value of 100,000 to 250,000.

  In one embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention may also comprise one or more waxes such as polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, modifying waxes, polyethylenes grafted with maleic anhydride with acidic groups as pendant functionalities, waxes paraffinics, microcrystalline waxes, and their combinations.

  In one embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention may also include one or more road marking additives such as plasticizers, oils, stabilizers, antioxidants, pigments. , dyestuffs, polymeric additives, antifoaming agents, preservatives, thickeners, rheology modifiers, moisturizing agents, diluents, hindered phenolic compounds, phosphates, anti-blocking additives, lubricants, light stabilizers ultraviolet radiation absorbing agents, dispersants, thickeners, bases, wetting agents, flame retardants, crosslinking agents, hardeners, opacifiers and water. Other of these additives include oils such as aliphatic oils, naphthenic oils, white oils, soybean oils, their combinations and derivatives.

  Road marking compositions comprising a binder comprising the adhesive composition of the present invention may further comprise one or more plasticizers comprising mineral oils, polybutenes, phthalates, hydrocarbon oils, soybean oils, esters of the type phthalates, elastomers, olefin oligomers, vegetable oils, cyclohexene-dimethanol dibenzoate and their combinations and / or sand, pigments, glass beads, polymer-based beads, calcium carbonate, marble crushed, aggregate, dolomite, talc, glass beads, prismatic reflectors, lens reflectors, calcite spar, siliceous sand, graphite, fly ash, cement dust, clay, feldspar, nepheline, ultrafine silica, alumina, magnesium oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanates es, lime, reflective inorganic fillers, diluent fillers, beads, calcium sulphate, calcium metasilicate, quartz powder, calcined flint clay powder, mica, calcium silicate, fibers glass, dyes, granite, plaster, slaked lime, alumina, diatomaceous earth, reflective agents, modifiers, lead white, lithopone, chrome yellow, cadmium yellow, resin beads, polymer gels, polymers, ceramics, crushed glass, stone, corundum, aluminum hydroxide, silicon oxide, glass bubbles and zinc neodecanoate.

  In a preferred embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention and one or more fillers, comprises a binder which comprises one or more modifiers comprising polymers modified with succinic anhydride. and metal oxides.

  When used in road marking compositions, the fillers are effective in increasing the mechanical strength of the road marking and maintaining the thickness of the road markings; however, the use of loads in excessively large quantities may result in the production of fragile road markings. As a result, the road marking composition comprises 20 to 90% by weight of the charge (s). In one aspect, the one or more fillers comprise an amount equal to or less than 50% by weight or an amount of 10 to 40% by weight or 15 to 30% by weight of the one or more beads. In a further aspect, the one or more fillers comprise an amount equal to or less than 20% by weight or in the range of 2 to 15% by weight or 3 to 10% by weight of the pigment (s).

  In one aspect, the road marking composition comprises 10 to 80% by weight of the binder, the binder composition comprising the polymer of the invention described herein.

  Preferably, a road marking composition comprising a binder comprising the adhesive composition of the present invention comprises a binder which comprises an amount equal to or less than 30% by weight of one or more waxes and / or an amount equal to or less than to 80% by weight of one or more tackifiers and / or an amount equal to or less than 20% by weight of one or more plasticizers and / or an amount equal to or less than 5% by weight of one or more a plurality of tackifiers or polymers modified with an acid and / or an amount equal to or less than 5% by weight of one or more stabilizers and / or an amount equal to or less than 40% by weight of one or more polymer additives and / or an amount equal to or less than 10 by weight of one or more opacifiers and / or an amount equal to or less than 1% by weight of one or more antioxidants. In a preferred embodiment, a road marking composition comprising a binder comprising the adhesive composition of the present invention has a luminance equal to or greater than 70. Sealing Agents In a particular embodiment, the adhesive compositions described herein may be used in a sealant composition. The purpose of a sealant is to maintain a seal between two surfaces of a single substrate, thereby repairing the substrate, or, alternatively, to establish or maintain a seal between two substrates. Thus, a sealant composition comprising a blend comprising the adhesive composition of the present invention is used by applying the mixture to at least a portion of a surface of a substrate to be sealed.

  Substrates may include concrete, roofing material, marble, anodized aluminum, brick, mortar, granite, limestone, porcelain, glass, painted surfaces, wood, polychloride vinyl), polyacrylate, polycarbonate, polystyrene, fabrics, gaskets, plastic, stone, masonry materials, ducts, hoses, metal, wiring, skis, polyethylene, polypropylene, polyester, acrylic resin, PVDC, paper, ethylene-vinyl acetate copolymer, automobiles, buildings, aircraft, panels, decks, bones, pavement, folding doors , door panels, wheel arches, running boards, fire partitions, floor sills, chests and floorboards. For example, sealant compositions can be used to repair lines with leaks or cracked windshields on automobiles. Sealing agents further produce resilient seals of load carriers between two or more surfaces and prevent the passage of air, water and dust therethrough.

  Sealant compositions are useful not only for filling voids and thus bonding the surfaces of a substrate in a repair operation, but may also be used to bond a first substrate to another substrate. The automotive industry, in particular, is an important user of sealants for this purpose. Automobiles are assembled from several structural components that are joined together in different ways depending on the particular components and the degree of tension that the components will have to undergo. For example, sealants are used in assemblies of door panels, side panels, tailgates and roofs. Additional assemblies of automobiles that are welded or bolted together use sealant compositions in their junctions. Other examples of automotive applications that use sealants include wheel arches, dampers, steps, firewalls, floor flanges, bottom plates, and trunks.

  Whatever the purpose of its use, a sealant composition is a material filling gaps. Accordingly, when forming a seal, the sealant compositions must have an elasticity that is sufficiently small that the sealant can flow into and fill the gaps in the substrate to which it is applied. after solidification and thus hardening of the sealant, they still sufficiently fill the gaps so as to seal the substrate. In the uncured state, the sealant composition must remain tacky and have a sufficiently low viscosity to ensure proper wetting of the substrate.

  The sealing compositions are preferably substantially tack-free after solidification or curing. After curing, the sealants must have sufficient longevity to withstand exposure to the usual atmospheric conditions and conditions of use in many applications. Primarily, a sealant should form an effective barrier against oxygen, water and air. The cured sealants must possess crack resistance, resistance to shrinkage under mechanical stresses such as expansion in the substrate at elevated temperatures, so that the sealant does not exhibit no run-off or flow over time. Especially with glass substrates, high voltages can cause glass cracking. Although the sealant must be sufficiently rigid to maintain its overall shape and overall dimensions, it must also remain flexible enough to provide substantial stretch recovery. As a result, a balance of high adhesion strength and high percentage of elongation and low tensile modulus is desirable for the mixture used as a sealant. High adhesion compositions generally provide effective seals because the greater the adhesion strength, the greater the force required to separate the substrate from the mixture. The percent elongation of the mixture corresponds to the ability of the composition to resume approximately its initial configuration after being subjected to the indicated degree of elongation. A high percentage of elongation is desirable to provide the sealants with an extremely advantageous self-healing property. This means that the sealants deform to account for the tension exerted on the sealed portion of the substrate.

  In a preferred embodiment, the sealing mixture further comprises one or more waxes comprising polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, modifying waxes, amorphous waxes, carnauba waxes, castor oil waxes, microcrystalline waxes, beeswax, carnauba wax, castor wax, spermaceti wax, vegetable wax, candelilla wax, Japan wax, ouricury wax, Douglas fir bark wax, rice bran wax, jojoba wax, wax wax, montan wax, peat wax, ozokerite wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, amide wax substituted and their associations and derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more additives including plasticizers, oils, stabilizers, antioxidants, pigments, anti-blocking additives, processing aids, neutralizing agents, water, dyestuffs, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, moisturizers, fillers, water , crosslinking agents, thixotropic agents, surfactants, adhesion promoters, reinforcing agents, chain extenders, ultraviolet light stabilizers, colorants, organic solvents, stabilizers, desiccants, wetting agents, nucleating agents, accelerators, hardeners and their combinations or derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more fillers including silica, diatomaceous earth, calcium carbonate, iron oxide, hydrogenated castor oil, ultrafine silica, precipitated calcium carbonate, hydrophobically treated ultrafine silicas, hydrophobic precipitated calcium carbonates, talc, zinc oxides, polyethylene powders, (vinyl chloride), fungicides, graphite, carbon black, asphalt, carbon-based fillers, clay, mica, fiber, titanium dioxide, cadmium sulfide, asbestos , wood flour, polyethylene powder, milled fibers, bubbles, beads, thixotropic agents, bentonite, calcium sulfate, calcium oxide, magnesium oxide and their combinations or derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more adhesion promoters comprising silanes, titans, organosilane, acrylic compounds, and the like. , acids, anhydrides, epoxy resins, hardeners, polyamides, methyl acrylates, epoxy resins, phenolic resins, polyisobutylene, aminoalkyl, mercaptoalkyl, epoxyalkyl, ureidoalkyl, carboxy, acrylate and isocyanurate functional silanes , mercaptopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, ureidopropyltrimethyloxysilane, bis-gamma-trimethoxysilylpropylurea, 1,3,5-isis-isocyanurate. garmia.-trimethoxysilylpropyl, bis-.gamma.trimethoxysilylpropyl maleate, fumarate and gamma.methacryloxypropyltrimethoxysilane, aminopropyltriethoxysilane and their combinations and derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more crosslinking agents comprising oxime crosslinking agents, alkoxysilanes, epoxyalkylalkoxysilanes, amidosilanes, aminosilanes, enoxysilanes, tetraethoxysilanes, methyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrisopropenoxysilane, methyl-tris-isopro-penoxysilane, methyl-tris-cyclohexylaminosilane, methyl-tris-sec.- butylaminosilane, polyisocyanates and their combinations or derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more organic solvents including aliphatic solvents, cycloaliphatic solvents, mineral spirits, solvents, and the like. aromatic compounds, hexane, cyclohexane, benzene, toluene, xylene and their combinations or derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more surfactants comprising polyorganosiloxanes containing vinyl groups or containing mercapto groups, macromonomers, and the like. with a vinyl terminated polydimethylsiloxane and their combinations or derivatives.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more chain extending agents including aminosilanes, amidosilanes, acetoxysilanes, aminoxysilanes, methylvinyl-bis-N, -methylacetamidosilane, methylhydrogenodiacetoxysilane, dimethylbisdiethylhydroxylaminosilane, dimethylbis-sec-butylaminosilane, polyisocyanates and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention may further comprise one or more antioxidants including thioesters, phosphates, sterically hindered phenols, tetrakis- (methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate) methane, 2,2'-ethylene-bis- (4,6-di-tert-butylphenol), 1,1- 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris- (3,5-tert-butyl-4-hydroxybenzyl) -benzene, dipropionate dilauryl, pentaerythritol tetrakis- (beta-laurylthiopropionate), alkylaryl di- and polyphosphates, thiophosphites, and combinations or derivatives thereof.

  In one embodiment, a sealant composition comprising a blend that comprises the adhesive composition of the present invention, may comprise a proportion that is equal to or less than one by weight of one or more waxes.

  Paving Compositions In a particular embodiment, the adhesive compositions described herein may be used in paving compositions.

  Usually, the paving compositions comprise an asphalt, an aggregate, an adhesive composition. The term asphalt, as used herein, refers to any of a variety of solid or semi-solid materials at ambient temperature which progressively liquefy upon heating, and in which the predominant constituents are natural bitumens which are obtained as residues in petroleum refining. Asphalt is further defined by Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 3, third edition (1978), pp. 284-327, John Wiley & Sons, New York. An additional description is contained in the publication A Brief Introduction to Asphalt and Some of its Uses Series No. 5 (MS-5), The Asphalt Institute, 7th Edition, September 1974.

  Examples of natural bitumens include natural asphalts or asphalts produced by petroleum refining, asphaltenes, pyrogenation distillates, distillation residues, as well as other pyrogenation residues such as pyrogenic asphalts, petroleum pitch coal tar pitch and mixtures thereof, for example. Such material is often characterized by a penetration value of 0 to 300 or more than 300 (ASTM D-5-51), preferably about 40 to 300, with a softening point in the range of about 32 to 120 ° C (ASTM D-36-26), preferably 38 to 65 ° C.

  Useful sources of asphalt include most sources that are currently commercially available. For example, natural asphalts and asphalts of petroleum which are generally known for roofing and paving applications can be used. Natural asphalts include, for example, asphaltite such as gilsonite, grahamite and asphaltite, lake asphalt such as Trinidad asphalt, and rock asphalt. Petroleum asphalts include straight-run asphalts obtained by distillation of a crude oil (not blown and substantially unoxidized), blown asphalt produced by blowing an oxygen-containing gas into a straight-run asphalt in the presence of or in the absence of a catalyst, a solvent extraction asphalt obtained when an asphaltic material is separated from the petroleum fraction containing it by using propane or other solvents, and a fluxed petroleum asphalt which is a mixture of a straight-run asphalt and a light petroleum solvent. Asphalts may also include petroleum tar and asphalt cement. Petroleum tars comprise a by-product gas tar when gases are produced from petroleum fractions, such refined form tar, the fluxed tar, obtained by mixing a light petroleum fraction with such a tar, and tar pitch obtained as a residue by removing the volatile fraction of such tar. Any of these types of asphalt can be used alone or in combination. For example, a straight-run asphalt is useful for paving applications, and asphalt asphalt and asphalt asphalt are useful for roofing applications.

  The paving compositions of the present invention are particularly useful for preparing asphalt pavement compositions. These compositions include asphalts containing an aggregate such as those used in paving roads, bridges, airstrips, and sidewalks, as well as for their localized repair or connection. The paving compositions of the present invention may be mixed with an aggregate while in a fluid or molten state. Typically, the paving composition is mixed with preheated, pre-dried aggregates to form a homogeneous mixture of uniformly coated aggregates. The aggregate may be heated under conditions of time and temperature that are sufficient to drive off substantially all of the free moisture before mixing. During mixing ,. the paving composition is usually at temperatures of about 100 ° C. to about 160 ° C. Before cooling the resulting composition to a temperature at which it loses its processability, it may be spread on a road bed, for example, and then compacted and cured. After curing, the paving composition comprises an aggregate bound by an asphalt binder matrix.

  The term aggregate, as used herein, is intended to refer to solid particles having a range of sizes including fine particles such as sand to relatively coarse particles such as crushed stone, gravel or sand. slag. Typically, such an aggregate used in the preparation of paving compositions consists mainly of inorganic materials, such as crushed rock, stone and in some cases sand. The size of the aggregates depends in part on the desired final application of a particular paving composition. For example, a larger aggregate is usually used to cover a new pavement or resurfacer, compared to crack repair compositions that typically include an aggregate having smaller average particle sizes. Of course, the aggregate, especially when crushed or crushed, can be extremely irregular. Examples of aggregates comprising inorganic materials including sand, gravel, crushed stone, etc., certain organic materials including recycled pneumatic tires and recycled thermoplastics, and mixtures of one or more inorganic materials and organic materials . Other inorganic materials as well as other organic materials known as aggregate feeds, although not specified herein, can also be used in the compositions of the present invention.

  The paving composition of the present invention may also be useful for preparing improved insulating coatings. An insulating coating is generally applied in the form of hot asphalt, fluxed asphalt or emulsified asphalt. The molten or fluid asphalt is generally sprayed by a truck, and the aggregate is placed on the asphalt, followed by rolling or compacting the aggregate into the asphalt to finish the application.

  The paving compositions of the present invention, after formation, can be manipulated by conventional techniques to maintain them in fluid or molten form under the conditions of, for example, road construction. For example, asphalt can be converted into a fluxed asphalt by flowing the asphalt with a suitable volatile solvent or distillate. The fluxed asphalt can then be mixed directly with an aggregate and applied as a paving composition in a fluid form, optionally at ambient temperatures. Another conventional technique for fluidizing the asphalt before mixing with the aggregate and transformation into a paving composition is to emulsify the asphalt by known techniques. An advantage of this fluidization process is that, after mixing with the aggregate, it can be applied as a paving composition at room temperature.

  A key technical consideration in the production of a paving composition is to ensure the chemical compatibility between the asphalt cement and the intended final application of the paving composition. With regard to chemical compatibility, factors such as the presence of unwanted salts in the aggregate should be taken into account in order to minimize the likelihood of degradation of asphalt paving compositions.

  In addition, it is also necessary that a good adhesion of the aggregate and asphalt cement present in a paving composition exists to ensure that an energetic wetting of the asphalt composition and an effective mixing of these materials occurs. produce, both before and after placement of asphalt paving compositions on a surface.

  In addition, the physical characteristics of the aggregate must also be taken into consideration, ie under certain conditions in which it is expected that significant traffic and / or heavy loads will be encountered, and it is possible to choose an appropriate mixture for the intended use patterns.

  For this reason, the paving composition comprises an adhesive comprising the polymer of the present invention described herein. Preferably, a paving composition comprising asphalt, an aggregate, the adhesive composition of the present invention comprises one or more natural asphalts, petroleum asphalts or any of their combinations and / or asphaltite , gilsonite, grahamite, lustrous ore pitch, lake asphalt, Trinidad asphalt or rock asphalt and / or clay, rock, sand, rock , gravel and slag and / or carbon black, intermediate tailings, mine tailings, machefer, slag, ash, crushed tires, clay and glass.

  In a preferred embodiment, a paving composition comprising asphalt, an aggregate and the adhesive composition of the present invention comprises a proportion of 95 or less by weight of the aggregate.

  In another embodiment, a paving composition comprising asphalt, an aggregate and the adhesive composition of the present invention comprises 90 to 96% by weight of the aggregate.

  In another embodiment, a paving composition comprising asphalt, aggregate and the adhesive composition of the present invention comprises 80 to 99 by weight of the asphalt.

  Glue Sticks In a particular embodiment, the adhesive compositions described herein may be used in a glue stick. Glue sticks are sold in a variety of forms, including one consisting of hot melt adhesive glue sticks. Hot melt adhesive glue sticks are usually intended for use in glue guns. The glue guns are adapted to be held manually by an operator and include a melting chamber in which an end portion of a glue stick is received and melted by heat transmitted to the melting chamber. Progressive melting of the hot melt adhesive glue stick can be achieved by pressing the hot melt adhesive glue stick into the melting chamber. The molten adhesive is dispensed through a nozzle of the gun when the hot melt adhesive glue stick is introduced into the melting chamber and is melted therein. As a result, the hot melt adhesive glue stick is heated to an application temperature sufficient to melt the glue to a substrate. The substrate may include paper, cardboard, boxboard, label board, corrugated board, chipboard, kraft, chipboard, fiber board, plastic resin, metal, metal alloys , a metal foil, a film, a plastic film, laminates, sheet material, wood, plastic, polystyrene, nylon, polycarbonate, polypropylene, styrofoam, porous substrates, poly (vinyl chloride), walls, polyester or their combinations.

  The temperature of the hot melt adhesive glue stick application is adjusted to achieve a sufficiently low melt viscosity of the adhesive to ensure effective wetting of the substrates and provide adequate application time to position the adhesive. substrates after application of the glue to these. It is desirable for the adhesive composition to become substantially non-tacky after cooling to a temperature of approximately equal to or less than room temperature. Adhesives for use in hot melt adhesive glue sticks must also have the ability to bind to various substrates.

  Another type of glue stick is a glue stick based on pressure-sensitive adhesive. Pressure sensitive adhesive glue sticks are commercially available products comprising a solid adhesive body placed in a housing. Typically, a removable cap closes the housing, the housing having an opening at its bottom. The orifice is located in a plane perpendicular to the axis of the pressure sensitive adhesive glue stick. The cap can be removed when it is desired to use the pressure-sensitive adhesive glue stick.

  Pressure sensitive adhesive glue sticks do not require heating for application to a substrate, but produce an adhesive deposit on the substrate simply by application of pressure. Similarly, the substrate can then be adhesively attached to another substrate by application of a single pressure because the glue applied by the glue stick is adhesive at room temperature.

  For pressure-sensitive adhesives, at least one component of the adhesive composition is liquid at ambient temperature. The liquid component imparts pressure sensitivity or surface tack to the pressure sensitive adhesive glue stick at room temperature. Polymeric additives, tackifiers and / or plasticizers are often added to the adhesive composition such that the glue stick is adhesive and a portion of it remains on the substrate by contact.

  The glue sticks may consist of a mixture of an adhesive polymer, a tackifier and a wax. The amounts of the components are varied to obtain a suitable blend of melting point, application temperature, application time, bond strength, longevity, heat resistance in the adhesive composition, depending on of the application. It is desirable to obtain adhesive compositions that can effectively accept a tension without adhesive failure, which is measured by the bond strength and the bond break time. The bond strength and the bond break time are preferably high for a glue stick composition. A longer bond break time increases the flexibility of the glue.

  In a preferred embodiment, a glue stick comprising an elongated member comprises the adhesive composition of the present invention, wherein the adhesive further comprises one or more additives comprising plasticizers, oils, stabilizers, antioxidants , synergists, pigments, dyestuffs, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, moisturizers, fillers, water, fragrances, flame retardants, dyes, antibiotics, antiseptics, antifungal agents, inorganic salts, gelling agents, binders, surfactants, bases, antimicrobials, defoamers and / or one or more fillers including polyethylene, titanium oxide and calcium carbonate.

  In a preferred embodiment, a glue stick comprising an elongate member that comprises the adhesive composition of the present invention comprises 5 to 30% by weight of the inorganic salt (s).

  In a preferred embodiment, a glue stick comprising an elongated member which comprises the adhesive composition of the present invention comprises an amount of 5% or less by weight of one or more dyeing agents, dyes, antioxidants, perfumes or pigments.

  In a preferred embodiment, a glue stick comprising an elongated member that comprises the adhesive composition of the present invention comprises an amount of 1% or less by weight of one or more antimicrobial agents.

  In a preferred embodiment, a glue stick comprising an elongated member that comprises the adhesive composition of the present invention contains an adhesive that has a percent tearing of the substrate fibers from 75% to 100% at 25 C.

  Pipe Packaging In a particular embodiment, the adhesives of the present invention may be used in articles for conduit packaging. Articles for packaging ducts or conduit packages may be used to insulate or repair leaks in pressure-resistant containers, industrial containers, transformers, conduits, fittings, tanks, containers and containers . In addition, the conduit packaging articles can be used on various types of surfaces including flat surfaces, circular seals and other mechanical components. The conduit packaging articles described herein may be used in any type of industry, such as architecture, building, construction, food industry, beverage, mining, the petrochemical industry, oil and gas processing and water treatment, for example.

  Conduct packaging articles are generally formed by applying an adhesive composition to at least a portion of a packaging member. The packaging member may comprise glass fibers, fibers, woven articles, nonwoven articles, fabric, fabric, polyethylene, polypropylene, acrylic rubber, EPDM, nitrile rubber, nylon , an epichlorohydric elastomer, a polysulfide, an acrylic elastomer or butyl rubber, a polyisobutylene, for example. The conduit packing article may be formed of wood, cement, concrete, nonwoven fabric, woven fabric, aluminum, stainless steel, brass, nickel, glass , vitreous ceramics, non-vitrified ceramic, tiles, polyvinyl chloride, poly (ethylene terephthalate), plaster, stucco, asphaltic coatings, roofing felts, synthetic polymer membranes and polyurethane foam insulation, for example. The packaging element can be any thickness. For example, a conventional packaging element for use in the building may have a minimum thickness of 1.27 mm.

  Accordingly, a conduit packaging article comprising the adhesive composition of the present invention, and a packaging member, may comprise the adhesive at least partially on or in the packaging member.

  In a preferred embodiment, a conduit packaging article comprising the adhesive composition of the present invention comprises one or more polymeric additives including butyl rubber and polyisobutylene. Even more advantageously, a conduit packing article comprising the adhesive composition of the present invention is a consumer good. Safety Glasses In a particular embodiment, the adhesives described herein may be used in the safety glass. There are two types of safety glass, laminated safety glass and tempered safety glass. Laminated safety glass generally reduces the transmission of high frequency sounds and blocks 97% of ultraviolet radiation. Tempered safety glass consists of a single piece of glass which is quenched by rapid heating and cooling of the glass to cause its hardening, which increases the mechanical strength of the glass.

  As used herein, the safety glass is an article having a transparent pane. An important function of safety glass is that the adhesive composition that is used is not affected by temperature variations and that, in the case of glass breakage, the adhesive composition holds in place the pieces of glass. In addition, the adhesive composition absorbs the shear stresses applied to the safety glass because of the different expansion rates of the glass components, for example when the safety glass comprises a first glass layer and a second polycarbonate layer. The safety glass generally comprises layers of material, with a layer of adhesive applied to the outside of a layer, or applied between two or more layers to adhere to each other. The transparent pane is formed by applying an adhesive composition to one or more transparent panels, the adhesive composition optionally forming a film on the one or more transparent panels. The one or more transparent panels may be formed of polyvinyl butyral, polyurethane, vinyl acetate polymer, polyethylene, polypropylene, polycarbonate, glass, silicate glass or one of their combinations.

  In one embodiment, an article comprising a transparent pane comprises one or more transparent panels; and the adhesive composition of the present invention is applied to at least one of the portions of the panel (s). More preferably, the article comprises a transparent pane comprising one or more transparent panels; and the adhesive composition of the present invention is applied to at least a portion of the panel (s), the one or more transparent panels comprising polyvinyl butyral, polyurethane, vinyl acetate polymer, polyethylene, polycarbonate, glass , silicate glass or one of their associations. In a preferred embodiment, the article is made of bulletproof glass, soundproofing glass, and / or safety glass. In addition, the adhesive composition of the present invention can form a film on the transparent panel (s). Roofing Shingles In a particular embodiment, the adhesives of the present invention can be used in shingles. Roofing shingles are generally formed of a roofing element and an adhesive to bond the roofing element to a roof.

  The cover element is generally formed of a metal sheet, for example copper, tinted stainless steel, zinc, aluminum or their alloys.

  Important criteria for shingles include crush strength when the shingles are bundled in stacks for transportation, a relatively low melting temperature to allow self sealing without the application of a heater, and bonding between joined surfaces, with high wind resistance and good low temperature stability. Other important considerations include good resistance to photooxidation; particularly the ability to maintain adhesive properties after exposure of the adhesive to sunlight for more than two hours.

  In addition, the adhesive composition must exhibit a migration property at low temperatures of 32 C to 37 C in order to provide stronger bonds and better wind resistance. As used herein, the term migration refers to the phenomenon when the adhesive composition partially flows into the contact face of the covering material.

  Accordingly, in one embodiment, a shingle includes a cover member having a first face and a second face, the adhesive composition of the present invention being applied to at least a portion of the second face. In another embodiment, the cover member comprises a metal sheet, for example copper, steel, zinc, aluminum, their combinations or their alloys, roofing asphalt, a fabric , an aggregate and their associations. In addition, either face of the cover member may comprise rubber, fiberglass, aramid, carbon, polyester, nylon, asphalt and / or sheet metal. metal, the metal sheet comprising copper, aluminum, their associations and their alloys.

  In a preferred embodiment, a cover member has a first face and a second face, the adhesive composition of the present invention being applied to at least a portion of the second face, the adhesive composition further comprising one or a plurality of bituminous materials, the at least one bituminous material preferably comprising asphalt, the adhesive composition more preferably comprising at least 80% by weight of the at least one bituminous material.

  Reflective Coating In a particular embodiment, the adhesives of the present invention may be used in reflective articles. The reflective articles are formed by applying a reflective material to a surface of a substrate to impart reflectivity to a portion of the substrate. The reflective material may comprise any material known to those skilled in the art. For example, the reflective material may include prisms and glass beads. The substrate surface may include roads, bike lanes, road signs, soft sport surfaces, playground surfaces, ships, runways, pedestrian crosswalks, buildings, tennis courts, driving tracks, tartan substitutes, oil forge towers, tunnels, concrete, metals, asphalt, bitumen, bricks, pebbles, tiles, steel plates, wood, ceramic materials, polymeric materials, glass, right footings of tunnels, traffic barriers, barriers, ducts, ponds, safety rails, concrete blocks, curbs, parking spaces, china, stone, wood panels, particle board, wooden parts for vehicles, slag blocks, glass windows, signaling posts, traffic cones, scrims, systems of liquid crystal displays, lamps, copiers, electronic panels, diffuse white calibrations, and photographic lamps.

  An adhesive composition is applied to at least a portion of the reflective material to adhere the reflective material to the substrate. The adhesive composition comprises the polymer of the present invention described herein.

  The reflective article may include a substrate surface selected from the group consisting of roads, bike lanes, road signs, soft sport surfaces, playground surfaces, ships, runways, pedestrian crosswalks , buildings, tennis courts, driving tracks, tartan substitutes, oil forge towers, tunnels, concrete, metals, asphalt, bitumen, bricks, pebbles, tiles, steel plates, wood, ceramic materials, polymeric materials, glass, right foot tunnels, traffic barriers, barriers, ducts, ponds, safety rails, concrete blocks, curbs, parking spaces, china, stone, wood panels, particle board, wooden parts for vehicles, slag blocks, glass windows, signalisat ion cones, canvases, liquid crystal displays, lamps, copiers, electronic panels, diffuse white calibrations, and photographic lamps.

  In a preferred embodiment, a reflective article comprises a reflective material applied at least partially to a surface of a substrate with the adhesive composition of the present invention, the reflective article having a luminance equal to or greater than 70.

  Other Articles In one embodiment, the polymer of the present invention may be an injection molded article, which is a film, which is an extruded film, which is a cast film, or which is an association thereof . The article preferably comprises a polypropylene rich in amorphous syndiotactic structure and / or a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride. The article may also comprise the polyolefin rich in amorphous syndiotactic structure placed on a non-polar substrate, on a polar substrate or on these two types of substrate. Accordingly, the article of the present invention can comprise the polyolefin rich in amorphous syndiotactic structure and / or polyolefin rich in functionalized amorphous syndiotactic structure placed on wood, paper, cardboard, plastic, thermoplastic, rubber, a metal, a metal foil, metallized surfaces, a fabric, nonwoven fibers, spin-bonded fibers, stone, plaster, glass, SiOx coatings applied by silicon oxide evaporation on the surface of a film, foam, rock, ceramic materials, films, polymer foams, substrates coated with inks, substrates coated with dyes, substrates coated with pigments, 9VDC, polyethylene , polypropylene, polyacrylates, acrylic polymers, poly (ethylene terephthalate), corona discharge treated substrates, treated substrates electron-irradiated substrates, gamma-irradiated substrates, microwave-treated substrates, silanized substrates, and combinations thereof.

  Masterbatch The present invention may also include a masterbatch forming process for providing the polymer of the present invention for the production of various polymeric materials including articles, films, etc., including melt mixing. under high shear conditions of the polyolefin of the present invention with at least one additional additive to produce a concentrate containing 10 to 90% by weight of the polymer of the present invention, which may be subsequently mixed with other constituents of the final product . Examples of suitable additives include the additives described herein. The polyolefin rich in amorphous syndiotactic structure, preferably polypropylene rich in amorphous syndiotactic structure, the polyolefin rich in functionalized amorphous syndiotactic structure, preferably the polyolefin rich in amorphous syndiotactic structure grafted with maleic anhydride, of the present invention may be used in the masterbatch both as a diluent, and as a concentrated material which is then diluted in the final product. In one embodiment, a process for producing the masterbatch may comprise a step in which the polyolefin rich in amorphous syndiotactic structure is functionalized simultaneously with the formation of the concentrate.

EXAMPLES

  Preparation of α-srPP Polymerization of samples α-srPPr-1-, asrPPr-3, α-srPPr-4, α-srPPr-5, and α-srPPr-6 was performed in a continuous stainless steel autoclave reactor 0.5 liter, single-stage, liquid filled, using diphenylmethylene- (fluorenyl) (cyclopentadienyl) hafnium dimethyl pre-activated with N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The reactor is equipped with a stirrer, a water cooling / steam heating element with a temperature controller, and a pressure regulator. The solvent and propylene were purified by passage through a three-column purification system before being pumped into the reactor. All catalyst solutions were maintained under an inert atmosphere having a water content of less than 1.5 ppm and were introduced into the reactor by metering pumps. The catalyst and the monomer were contacted in the reactor.

  The reactor was first cleaned by continuously pumping hexane and an acceptor through the reactor system for at least one hour at a maximum allowable temperature (about 150 ° C). After cleaning, the reactor was heated / cooled to the desired temperature using a water / steam mixture flowing through the reactor jacket and was controlled to a selected pressure with a controlled solvent stream. The monomers and the catalyst solution were then introduced into the reactor when a steady state of operation was achieved. An automatic temperature control system has been used to control and maintain the reactor at a selected temperature. The beginning of the polymerization activity was deduced from the observation of a viscous discharged product and a lowered temperature of the water-water vapor mixture. Once the activity is established and after the system has reached equilibrium, the reactor has been put into operation by continuously operating the system under established conditions for a period of time of at least 5 times the average time. of residence before taking samples. The resulting mixture, essentially containing the unreacted solvent, polymer and monomers, was collected in a collection vessel after the system had reached a constant origin operation. Methanol was used as a catalyst deactivator. The collected samples were first air dried in a fume hood to cause evaporation and most of the solvent, and then dried in a vacuum oven at a temperature of about 90 ° C for about 12 hours. hours. Samples dried in a vacuum oven were weighed to obtain the yields. All reactions were conducted at a pressure of about 350 psig and a temperature in the range of 80 to 120 C. The detailed experimental conditions and detailed properties of the polymers are listed in the following table.

  In the examples, the polymerization temperatures were varied to vary the molecular weight and tacticity of the polymer. The polymers produced have a% dyads [r] of about 58 to 75%. Each also represents a substantially amorphous polymer. Functionalization of α-srPP The amorphous syndiotactic rich polypropylene samples were then functionalized by dissolving about 120 g of the polymer in toluene to produce a polymer solution having a polymer concentration of about 20% by weight. 15% by weight of maleic anhydride (based on the particular α-sRPPr used) was then added to the solution, with 2.5% by weight of the radical initiator 2,5-dimethyl-2,5 di- (t-butylperoxy) -hexane. The reaction temperature was 139 C for a time of about 4 hours. The amide functional group was provided using 1-vinyl-2-pyrrolidinone and the acidic functional group was provided using acrylic acid.

  The results are presented below.

  Α-srPPr-1 α-srPPr-3 α-srPPr-4 α-srPPr-5 α-srPPr-6 iPP-g-MA Polymer Comparative Intro rate 1,75E-06 1,75E-06 1,75E- Catalyst 06 145E-07 8, 76E-06 (mol / min) Propylene feed rate 14 14 14 14 14 (g / min) Feed rate 90 90 90 90 hexane (ml / min) ) 90 90 Polymer temperature 110 120 107 94 90 sation C Mn (kg / mol) 23 17 34 74 128 Mw (kg / mol) 62 43 86 188 311 Mz (kg / mol) 148 80 177 385 606 G'vis 1.08 0.98 1.05 1.11 1.19 Molar fraction of triads by 13C-NMR Mm 0.152 0.133 0.114 0.0922 mr + rm 0.483 0.464 0, 435 0.399 Rr 0.365 0.403 0.451 0.509 Molar fraction of dyads per 13C - NMR M 0.394 0.365 0.331 0.292 R 0.606 0.635 0.669 0.708 Functionalized Polymer Group Anhydride 1-vinyl-Acid Anhydride Anhydride Anhydride Anhydride Functional maleic anhydride 2-pyrrole maleic maleic maleic maleic maleic (MA) lidinone (MA) (MA) (MA) (MA) (MA) acrylic (AA) Mn (kg / mol) 8 8 8 17 23 29 60 3.7 Mw (kg / mol) 20 20 20 33 44 68 135 9 , 8 Mz (kg / mol) 38 38 38 55 71 116 263 18% by weight 3,20 1,00 1,00 1,92 1,00 1,12 1,12 5,24 FG The iPP-g- MA is a maleic modified polypropylene having an acid number of 50, a viscosity of 300 mPa.s at 190 ° C, available from Chusei in Pasedena, Texas.

  CHARACTERIZATION AND TESTS For the purposes of the present invention and the appended claims, the following tests were used, unless otherwise indicated: The tensile strength (tensile strength at break and elongation at break) is measured according to the standard ASTM D 1708. Elongation at break is also referred to herein as strain or percent elongation.

  The pull-out strength (also referred to as pull-out adhesion at a breakout angle of 180, pullout strength 180, breakout strength adhesion at 180 C, T-peel strength and T-tear) is measured according to a modified version of ASTM D-1876 (modified to use a 1.27 cm wide sample and a separation rate of 5 , 08 cm per minute).

  The tensile strength modulus at 100% elongation and the Young's modulus are determined according to ASTM E-1708.

  The dynamic storage module (also called storage module) is indicated by G 'and is determined in the following manner. Usually, samples are tested using a three-point bending pattern (TA Instruments DMA 2980). A solid rectangular molded compression bar is placed on two fixed supports; a moving clamp applies periodic deformation to the midpoints of the sample at a frequency of 1 Hz and an amplitude of 20 μm. The sample is cooled initially to-130 C, then is heated to 60 C at a rate of temperature rise of 3 C / min.

  In some cases, compression molded bars can be tested using other deformation configurations, namely cantilevered double-bending and tensile elongation (Rheometrics RSAII). The periodic deformation in these configurations is applied at a frequency of 1 Hz and a strain amplitude of 0.05 the sample is cooled to -130 C and then heated to 60 C at a rate of 2 C / min.

  Creep resistance is determined using ASTM D-2293 and sagging is also referred to as creep.

  Rolling ball adhesiveness is determined using the PSTC 6 standard.

  The hot shear strength is determined by suspending a weight of 1000 grams to a 25 mm wide band of MYLAR (polyester) film coated with the polymer or adhesive formulation that adheres to a stainless steel plate with a surface contact distance of 12.5 mm x 25 mm. The sample is placed in an oven ventilated at 40 C. The time until a break in voltage occurs is recorded.

  Probe adhesivity (also known as Polyken Probe Adhesiveness) is determined according to ASTM D 2979.

  The adhesion strength is determined according to the PSTC 7 standard and is also referred to as shear adhesion or shear strength.

  The density is determined according to ASTM D792 at 25 C.

  The Gardner color is measured according to ASTM D 1544-68.

  The luminance is Y reflectance in CIE color coordinate as determined by ASTM D 1925 divided by 100.

  Needle penetration is measured according to ASTM D5.

  Binding strength is measured according to ASTM D3983.

  Adhesion to a road surface is measured according to ASTM D4541.

  The setting time is defined for use in the present invention as the time required for an adhesive and a compressed substrate in the form of an assembly to bond to one another with sufficient adhesion to achieve tearing of the fibers of the substrate when these elements are separated. These setting times were measured by placing a melt point of adhesive on a substrate consisting of a jacket attached by an adhesive tape to a flat table. A shirt leg (2.5 cm x 7.6 cm) was placed on the spot 3 seconds later and compressed with a weight of 500 grams. The weight was allowed to sit for a time of about 0.5 to about 10 seconds. The elements of the assembly thus formed were separated to control a degree of bonding sufficient to produce a tearing of the fibers of the substrate. The setting time was noted as the minimum time required for this link to occur.

  Reference samples of commercially available adhesives were used to calibrate this process.

  Molecular weights (number average molecular weight (Mn), weight average molecular weight (Mw), and mean z molecular weight (Mz)) were determined using a Waters Size Exclusion Chromatography (SEC) apparatus. 150 equipped with a detector of different refractive indices (DRI), a small angle direct light scattering detector (LALLS) and a viscometer (VIS). The details of the detector calibrations have been described elsewhere [Reference: T. Sun, P. Brant, R. R. Chance and W. W. Graessley, Macromolecules, Vol. 34, No. 19, 6812-6820, (2001)]; the SEC with three 10 mm Mixed-B columns of PLgel from Polymer Laboratories, with a nominal flow rate of 0.5 cm3 / min, and a nominal injection volume of 300 microliters was common to both detector configurations. The various transfer ducts, the various columns and the various differential refractometers (the DRI detector, used mainly to determine the concentrations of the solution undergoing elution) were placed in a furnace maintained at 135 ° C.

  The LALLS detector was the 2040 dual-angle light scattering photometer (Precision Detector Inc.). Its flow cell, located in the SEC oven, uses a 690 nm diode laser light source and collects scattered light at two angles, equal to 15 and 90. Only the output value at 15 was used in these experiments. Its signal was sent to a data acquisition panel (National Instruments) that stores readings at a rate of 16 per second. The average of the four lowest readings was calculated, and then a proportional signal was sent to the SEC-LALLS-VIS computer. The LALLS detector was placed after the SEC columns, but before the viscometer.

  The viscometer was a high temperature model 150R viscometer (Viscotek Corporation). It consists of four capillaries placed in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, placed between the two sides of the bridge, measures the pressure difference. The specific viscosity for the solution flowing through the viscometer was calculated from their output values. The viscometer was placed inside the SEC oven, positioned after the LALLS detector but before the DRI detector.

  The solvent for the SEC experiment was prepared by adding 6 grams of butylated hydroxytoluene (BHT) as an antioxidant to a 4 liter bottle of 1,2,4-trichlorobenzene (TCB) (Aldrich reagent grade) and pending solubilization BHT. The TCB-containing mixture was then filtered through a 0.7 micron glass prefilter and then through a 0.1 micron Teflon filter. There was an additional line assembly of a 0.7 micron glass prefilter / 0.22 micron Teflon filter between the high pressure pump and the SEC columns. Then the TCB was degassed with an in-line degassing system (Phenomenex, model DG-4000) before entering the SEC.

  Polymer solutions were prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, and then heating the mixture to 160 C with continuous stirring for about 2 hours. All quantities were measured gravimetrically. The densities of the TCB used to express the polymer concentration in mass / volume units were 1.463 g / ml at room temperature and 1.324 g / ml at 135 C. The injection concentration ranged from 1.0 to 2.0 mg / ml, lower concentrations being used for higher molecular weight samples.

  Before driving each sample, the DRI detector and the injector were purged. The flow rate into the apparatus was then increased to 0.5 ml / min, allowing the DRI detector to stabilize for 8 to 9 hours prior to injection of the first sample. The argon ion laser was operated 1 to 1.5 hours prior to specimen driving by operating the laser in the off mode for 20 to 30 minutes and then controlling it at full power in light control mode.

  The index g 'was measured using SEC with an in-line viscometer (SED-VIS) and the values are indicated by g' at each molecular weight on the SEC graph. The index g 'is defined by: 1! where ib is the intrinsic viscosity of the branched polymer and refers to the intrinsic viscosity of a linear polymer having the same average molecular weight viscosity (Mv) as the branched polymer. it = KMva, K and a were the values measured for linear polymers and must be obtained on a SEC-DRI-LS-VIS apparatus identical to that used for the measurement of the index g '. For the polypropylene samples indicated in the present invention, K = 0.0002288 and a = 0.705 were used. The SECDRI-LS-VIS method eliminates the need for correction for polydispersities, since intrinsic viscosity and molecular weight have been measured at individual elution volumes, which arguably contain a narrow dispersion polymer . The linear polymers selected as reference samples for comparison purposes should have the same viscosity average molecular weight, monomer content and composition distribution values. The linear character of the polymer containing C2 to C10 monomers is confirmed by 13C-NMR according to the method of Randall (Rev. Macromol Chem Chem C29 (2 & 3), pages 285-297). The linear character for the C11 and higher C11 polymers is confirmed by GC analysis using a MALLS detector. For example, for a propylene copolymer, the NMR should not indicate a branching greater than that of the comonomer (which means that if the comonomer is butene, the branches of more than two carbon atoms should not be present) . For a homopolymer of propylene, the GC must not reveal the branches of more than one carbon atom. When a linear reference sample is desired for a polymer whose comonomer is a C9 or greater C9 comonomer, it is possible to refer to T. Sun, P. Brant, RR Chance and WW Graessley, Macromolecules, Volume 34 , number 19, 6812 - 6820, (2001) for protocols for the determination of reference values for these polymers. In the case of syndiotactic polymers, the reference sample should have a comparable amount of syndiotacticity measured by 13C-NMR.

  The viscosity average of g 'was calculated using the following equation: ## EQU1 ## The maleic anhydride (MA) contents of the maleated polymers were determined as follows. About 0.5 g of the polymer was dissolved in 150 ml of toluene at the boiling point. Potentiometric titration with TBAOH (tetra-butylammonium hydroxide) using bromothymol blue as a color indicator was performed on the heated solution in which the polymers did not precipitate during the titration.

  Mooney viscosity ML 1 + 4 at 125 was determined according to ASTM D1646-90.

  The maximum melting point (Tm), the maximum crystallization temperature (Tc), the heat of fusion and the crystallinity were determined using the following procedure according to ASTM E 794-85. Differential scanning calorimetry (DSC) results were obtained using a TA Instruments model 2920. Samples weighing approximately 7 to 10 mg were sealed in aluminum sample containers. The DSC results were recorded by first cooling the sample to -50 ° C and then gradually heating it to 200 ° C at a rate of 10 ° C per minute. The sample was held at 200 ° C for 5 minutes before performing a second cooling-heating cycle. The first and second cyclic thermal events have been recorded. The areas under the curves were measured and used to determine the heat of fusion and the degree of crystallinity. The percentage of crystallinity is calculated using the formula [area under the curve (J / gram) / B (J / gram)] × 100, where B is the heat of fusion for the homopolymer of the main monomer component. B are to be obtained in the Polymer Handbook, fourth edition, published by John Wiley and Sons, New York, 1999. A value of 189 J / g (B) was used as the heat of fusion for a 100 crystalline polypropylene. With multiple melting or crystallization peaks, the highest melting peak was taken as the maximum melting point, and the highest peak of crystallization was taken as the maximum crystallization temperature.

  The glass transition temperature (Tg) was measured on ASTM E 1356 using a TA Instruments Model 2920.

  Melt Viscosity (ASTM D-3236) (also called viscosity, Brookfield viscosity). The melt viscosity profiles were usually measured at temperatures of 120 ° C to 190 ° C using a Brookfield Thermosel viscometer and pin number 27.

  Adhesion Test Functionalized α-srPPr or iPPr was thoroughly mixed and then degassed in a vacuum oven at 180 ° C. and then cooled to 25 ° C. This was done before molding and bonding to eliminate the possibility of presence. of air bubbles during the subsequent manufacture of the adhesive layer. Each of the functionalized α-srPPr samples was then molded into a thin sheet of material having a thickness of 0.4 mm at 180 ° C for 10 seconds. For the preparation of T-tear samples, this adhesive sample thin sheet was laminated between two Mylar substrate pieces (0.0762 mm thick, used as supplied) in a teflon-coated mold in positive pressure at a temperature of 180 C and a pressure of 0.57 MPa for 10 seconds. For the iPP substrate, a 0.062 mm cast film of homopolymer, produced by means of a metallocene, at a melt flow rate of approximately 9 and a melting point of 150 to 151 ° C. was used, with a lower bond temperature, equal to 150 C. All these adhesive / substrate laminates were cut into samples of 1.3 cm in width. The adhesive thickness was approximately 0.2 to 0.3 mm. T-cut measurements using triplicate samples were performed using a modified version of ASTM-1876, in which a 1.27 cm wide sample was used due to limited sample availability. ambient temperature, at a separation rate of 850 pm / sec. instead of 25.4 cm. per minute as specified by the method, on an Instron tester. The adhesion was measured by the average pullout resistance: Pullout strength = F / w where F is the pullout force and w is the width of the test sample. AIF and CF refer to apparent interfacial fracture (adhesive with bond breakage remaining only on a Mylar substrate) and cohesive failure (adhesive with bond breakage remaining on both Mylar substrates), respectively, by visual observation. Since each T-tear measurement uses triple samples, AIF / CF means that two samples have a break in AIF mode and one sample has a break in CF mode. On the other hand, CF / AIF means that two samples break in CF mode and one sample has a break in AIF mode. The results are presented below for a number of functionalized polyolefins.

  Sample Tear Off Tear Mode T-Break Mode at iPP Mylar Break (g / cm) (g / cm) iPPr-g-MA 0.893 AIF 651.9 CF a-srPPr-3g-MA 1178.7 CF 1021 6 CF-PS-4-g-MA 1452.0 CF 1391.1 CF-PS-5-gMA 296.4 AIF 1994.9 CF a-SRP-6-g-MA 408.9 AIF> 1064 , 4 Substrate Breakdown All functionalized srPPr polymers have stronger adhesion to both Mylar and iPP compared to MA-iPPr. As a result, α-srPPr-g-MA improves Mylar adhesion without sacrificing adhesion to iPP.

  In the following tables, some compositions are mixtures of asrPPr or a-srPPr functionalized with a propylene-based polymer (POA) in the presence or absence of a tackifier and / or wax . The POA homopolypropylenes (indicated by aPP-iPP in the tables) were produced according to the general procedures described in USSN N 10/868 951 filed October 15, 2003. The catalysts used consisted of di- (p-triethylsilylphenyl) - methylene (cyclopentadienyl) - (3,8-di-tert-butylfluorenyl) -hafnium-dimethyl (catalyst N 1) and rac-dimethylsilyl-bis- (2-methyl-4-phenylindenyl) zirconium-hafnium (catalyst N 2), and The activator used was N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. Detailed polymerization conditions and detailed properties of the polymers are listed in the following tables.

  aPP-iPP-1 aPP-iPP-2 aPP-iPP-3 introduction rate of 1,65E-06 1,65E-06 1,65E-06 catalyst N 1 (mol / min) introduction rate of 9, 45E-08 9,45E-08 9,45E-08 catalyst N 2 (mol / min) Propylene (g / min) 14 14 14 Hexane (ml / min) 90 90 90 Temperature of 125 120 115 polymerization (C) Mn ( kg / mol) 17.8 19.2 21.3 Mw (kg / mol) 35.5 44.4 54.9 Mz (kg / mol) 63.8 83, 7 112.8 Tc (C) 88.1 90.2 91.8 Tm (C) 127.1 138.1 140.8 Tg (C) - 5.8 - 4.7 - 4.2 Heat of fusion (J / g) 37.4 38.3 38 Viscosity at 190 ° C (mPa · $) 1890 3970 11450 aPP-iPP-4 aPP-iPP-5 aPP-iPP-6 Polymer

_

  Catalyst N 1 in the catalyst mixture (% by mole) Polymerization temperature in the overhead reactor (C) Tail reactor polymerization temperature (C) Concentration d acceptor 24 24.5 in feedstock (millionths by weight) Catalyst concentration 4.6 4.1 4.2 in feedstock (millionths by weight) Activator concentration 73.5 4.7 in feedstock (millionths by weight) Propylene concentration 30 28.6 29.2 in feedstock (% by weight) Deactivation water (g / h) 2.72 2.72 4.54 Viscosity at 190 C (mPa. $) 2400 1600 1500 Mw (kg / mol) 41.4 41.1 29.3 Mn (kg / mol) 19, 4 19.6 13.1 Mz ( kg / mol) 76.6 76 62.6 Tc (C) 79.9 77.8 68 Tm (C) 139 132 136 Heat of fusion (J / g) 31.5 28.7 22 Adhesion to Mylar of compositions without tackifier g / cm T-mode, rupture aPP-iPP-1 5.4 AIF aPP-iPP-1 + 20% by weight a-srPPr-3 17, AIF aPP-iPP-1 + 20 wt.% IPPr-g-MA-33.9 CF aPP-iPP-1 + 20 wt.% A-srPPr-17.8 AIF 1-g-amide aPP-iPP- 1 + 20% by weight of α-srPPr-85.7 AIF 1-g-MA aPP-iPP-2 5.4 = P1 AIF / CF aPP-iPP-2 + 20% by weight of α-PrP-3 7 , 1 AIF aPP-iPP-2 + 20 wt.% IPPr-g-MA 35.7 CF aPP-iPP-2 + 20 wt.% A-srPPr- 8.9 AIF 1-g-acid aPP-iPP -2 + 20% by weight of α-srPPr- 14.3 CF 1-g-amide aPP-iPP-2 + 20% by weight of α-srPPr-216.1 -40 P1 AIF 1-g-MA aPP- iPP-2 + 20 wt.% a-srPPr- 326.8 CF / AF 3-g-MA aPP-iPP-2 + 20 wt% a-srPPr- 378.6 AF 4-g-MA aPP- iPP-2 + 20 wt.% a-srPPr-1121.6-200 Pl CF / AIF 5-g-MA aPP-iPP-2 + 20 wt.% a-srPPr817.9 AIF 6-g-MA aPP PPP-3 0.178 AIF aPP-iPP-3 + 20% by weight a-srPPr-3.57 AIF aPP-iPP-3 + 20% by weight iPPr-g-MA 57, 1 CF aPP-iPP- 3 + 20% by weight of α-srPPr-16.1 AIF 1-amide aPP-iPP-3 + 20% by weight of α-srPPr-71.4 AIF 1-g-MA The symbol = signifies is defined by.

  Mylar adhesion of compositions with a tackifier (aPP-iPP / E-5380 / polymer modifier = 72/8/20 weight ratio) T-mode tear, g / cm rupture aPP-iPP-2 / E- 5380 (weight ratio 9 7.1 = P2 AIF to 1) aPP-iPP-2 / E-5380 / α-srPP-3.7, 1AIF aPP-iPP-2 / E-5380 / iPPr-g-MA 25, ## STR1 ## iPP-2 / E5380 / a-srPPr-1-g-MA 383.9 - 50 P2 CF / AIF aPP-iPP-2 / E-5380 / a-srPPr-3-g MA 457.2 CF aPP-iPP -2 / E-5380 / a-srPPr-4 8.9 AIF aPP-iPP-2 / E-5380 / a-srPPr-4g-MA 1041.2 CF aPP-iPP-2 / E-5380 / a-srPPr 23.2 AIF aPP-iPP-2 / E-5380 / asrPPr-5-g-MA 2146.7 AIF / CF aPP-iPP-2 / E-5380 / α-srPPr-6 3.57 AIF aPP- The E-5380 is ESCOREZ 5380, which is a hydrocarbon resin based on hydrogenated dicyclopentadiene having a softening point by ring and ball method of about 85 C, available from ExxonMobil Chemical Co. in Houston, Texas.

  Modified POA Mylar or iPP Binding Tear Off Tear Mode T-Break Mode at iPP Mylar Rupture (g / cm) (g / cm) aPP-iPP-2 / iPPr- 3.57 CF 517.9 CF g-MA aPP-iPP-2 / E-25.0 CF 512.6 CF 5380 / iPP-g-MA aPP-iPP-2 / E-5380 7.1 AIF> 551.9 CF aPP-iPP-2 / E - 16.1 AIF> 1841.3 5380 / a-srPPr-3 rupture of the substrate aPP-iPP-2 / E-383.9 CF / AIF> 1523.4 Rupture 5380 / a-srPPr-1- g-MA POA substrate modified with a tackifier and PP-1 formulated wax PP-2 formulated aPP-iPP-4 79.4 aPP-iPP-5 - 81.6 E-2203 (Tg = 47 C) 13.4 - E-5690 (Tg = 45 C) - 9.02 Paraflint C80 6.7 8.68 Irganox 1010 0.50 0.69 Mylar T-cut 41.1 80.4 AIF CF rupture mode The E-2203 is ESCOREZ 2203, which is an aliphatic-aromatic hydrocarbon resin having a ring and ball softening point of about 93 C. E-5690 is ESCOREZ 5690, which is a hydrocarbon resin based on aromatic monomer of hydrogenated dicyclopentadiene having a Ring and ball softening of about 89 ° C. Both of these resins are available from ExxonMobil Chemical Co., Houston, Texas. In the absence of functionalized polyolefin, both formulated PP-1 and PP-2 exhibited poor adhesion to Mylar.

  Adhesion to Mylar of aPP-iPP-6 based compositions (aPP-iPP / E5380 / polymer modifier = 72/8/20 weight ratio) Tapping T-mode, g / cm rupture aPP-iPP-6 12.5 CF aPP-iPP-6 / E-5380 (weight ratio 9 33.9 CF to 1) aPP-iPP-6 / E-5380 / a-srPPr-3-g-MA 771.5 CF aPP-iPP6 / E-5380 ## STR1 ## As shown by the results shown in the above tables, the functionalized a-srPPr offers an advantage with respect to the Mylar T pull-out strengths of these compositions. It is clear that the functional groups improve the adhesion of a propylene-based polymer to Mylar, the MA group giving the best results. In addition, the viscosity (or molecular weight) of the propylene-based polymer may affect adhesion, with the best-performing average molecular weight polymer aPP-iPP-2.

  As also shown by the examples, the compositions of the present invention showed increased adhesion to polar substrates and nonpolar substrates. They can be applied to various fields, such as adhesives, sealants, paint finishes, adhesion promoters, interfacial agents, compatibilizers, etc. As above, certain formulations of the present invention have been prepared by mixing component 1, consisting of the αPP-iPP polymer, and a functionalized polyolefin, such as α-PrP-g-MA, with other ingredients, such as a tackifier, a wax, an antioxidant, a plasticizing oil, a liquid resin type adhesive and similar ingredients, under low or high shear mixing conditions at elevated temperatures to form a mass fluid fondue. Mixing temperatures ranged from about 130 ° C to about 190 ° C.

  Aliphatic Solvent Based Functionalization of AsrPP Amorphous or low crystallinity propylene homopolymers and copolymers have been prepared and functionalized in cyclohexane, hexane or aliphatic solvent mixtures. After functionalization, the product may optionally be left in solution to be provided as a primer for, for example, adhesion of TPO bumper paints, or may be dried for melt blending or extrusion in other applications such as sealing layers, films for films and molded articles, constituents in adhesive formulations, etc. Key inventive steps include functionalization in an aliphatic solvent: a) which avoids the use of an aromatic solvent and the environmental and treatment problems accompanying the use of an aromatic solvent, and which offers the possibility of to prepare, functionalize and deliver the base polymer for its use, always in the same solvent, and b) which allows the direct use of the polymer solution from the polymerization reactor for the functionalization avoiding steps of finishing and redissolving .

  Examples of Functionalization Comparative Example F1 5.1 g of amorphous syndiotactic rich polypropylene was dissolved in 500 ml of xylene at 130 ° C. 1.2 ml of Luperox P (tertiary butyl peroxybenzoate, AtoFina Inc., Ontario, Canada ) and 4 ml of 1-vinyl-2-pyrrolidinone were added to the solution. The solution was stirred for 2.5 hours. The product precipitated in acetone and was further washed with acetone. The product was dried under vacuum overnight at 120 ° C.

Comparative Example 2

  50 g of a polypropylene rich in amorphous syndiotactic structure were melted in a Brander mixer at 190 ° C. 2.0 g of dicumyl peroxide and 4 ml of vinyl-2-pyrrolidinone were added and the mixture was stirred for 2 hours. ,5 hours. The product was precipitated in acetone and the product was further washed with acetone. The product was dried under vacuum overnight at 120 ° C.

Example F3

  A polypropylene rich in amorphous syndiotactic structure was dissolved in 700 ml of cyclohexane at 130 ° C. 3 g of dicumyl peroxide and 10 g of maleic anhydride were added to the solution. The solution was stirred for 2.5 hours. The product was precipitated in acetone and the product was further washed with acetone. The product was dried under vacuum overnight at 120 ° C.

Example F4

  A polypropylene rich in amorphous syndiotactic structure was dissolved in 700 ml of cyclohexane at 130 ° C., 3 g of dicumyl peroxide and 4 ml of 1-vinyl-2-pyrrolidinone were added to the solution. The solution was stirred for 2.5 hours. The product was precipitated in acetone and the product was further washed with acetone. The product was dried under vacuum overnight at 120 ° C.

Example F5

  A polypropylene rich in amorphous syndiotactic structure was dissolved in 700 ml of cyclohexane at 130 ° C., 3 g of dicumyl peroxide and 8 ml of 1-vinyl-2-pyrrolidinone were added to the solution. The solution was stirred for 2.5 hours. The product was precipitated in acetone and the product was further washed with acetone. The product was dried under vacuum overnight at 120 ° C.

  The results are shown below. Sample Group Solvent Mn Mw Mz Functional SrPPr N / AN / A 46 82.4 142.8 (starting material) Comparative 1-vinyl-2-Xylene 43.2 82.1 12.8 Fi pyrrolidinone Comparative 1-vinyl-2Masse melt 27.8 56.4 91.0 F2 pyrrolidinone F3 Cyclohexane anhydride 28.5 57.7 92.0 maleic F4 1- vinyl-2- Cyclohexane 28.9 59.6 94.2 pyrrolidinone Although the present invention has been described with reference to an illustrative embodiment, it is understood by those skilled in the art that various modifications may be made to the invention. and equivalents can be introduced instead of these elements without departing from the scope of the present invention. In addition, many modifications can be made to adapt a particular situation or substance to the teachings of the present invention without departing from its essential framework. Accordingly, it is believed that the present invention should not be limited to the particular embodiment described as the best mode contemplated for the practice of the invention, but that the present invention includes all the embodiments of the invention. in the context of the appended claims.

Claims (108)

  A polyolefin rich in amorphous syndiotactic structure, characterized in that it comprises more than about 50% by weight of C3 to C40 alpha-olefins and in that it has: about 50% to less than about 80% % dyads r, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight.   2. Polymer according to claim 1, characterized in that it comprises about 55% of r dyads.   3. The polymer according to claim 1, characterized in that it comprises at least about 6.25% pentads r to about 31.6% pentad r, based on the total number of pentades r and m present in the polymer. .   4. Polymer according to claim 1, characterized in that it comprises more than about 60% by weight of propylene.   Polymer according to claim 1, characterized in that it further comprises at least 0.5% by weight of ethylene, based on the total weight of the polymer.   6. Polymer according to claim 1, characterized in that the heat of fusion is not detectable.   Polymer according to claim 1, characterized in that it has an ash content equal to or less than 0.1% by weight.   Polymer according to claim 1, characterized in that it has a density of from about 0.85 to about 0.88 g / ml.   Polymer according to claim 1, characterized in that it has a melt flow rate equal to or greater than 0.2 g / 10 min. Polymer according to claim 1, characterized in that about 95% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 ° C, based on the total weight of the polymer. polymer present.   Polymer according to claim 1, characterized in that it has a weight average molecular weight of from about 5,000 to about 5,000,000 g / mol.   Polymer according to claim 1, characterized in that it has a number average molecular weight of from about 5,000 to about 3,000,000 g / mol.   Polymer according to claim 1, characterized in that it has a z-average molecular weight of from about 10,000 to about 10,000,000 g / mol.   Polymer according to claim 1, characterized in that it has an index g from about 1.2 to about 1.5, as determined by the Mw value of the polymer.   15. Polymer according to claim 1, characterized in that it has no discernible crystallization temperature (Tc).   16. Polymer blend, characterized in that it comprises: a polyolefin rich in amorphous syndiotactic structure comprising more than about 50% by weight of C3 to C40 alpha-olefins, about 50% to less than about 80% dyads r, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g and an ash content equal to or less than 1% by weight; and at least one additive comprising a C2 to C40 polymer, a C2 to C40 copolymer, an elastomer, a random copolymer, an impact resistant copolymer, a fluxional polymer, a tackifier, a crosslinking agent, an antioxidant , a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, a composition rendered tenacious with rubber, a recycled polymer, a blocking agent, an antiblocking agent, a pigment, a colorant, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a colored masterbatch, a flow enhancer, a crystallization adjuvant, a poly- alpha-olefin, a Group III base oil or an association thereof.   17. Polymer blend according to claim 16, characterized in that the additive is selected from the group consisting of homopolypropylene, propylene copolymerized with up to 50% by weight of ethylene or a C4 to C20 alpha-olefin, an isotactic polypropylene, a random copolymer of propylene and ethylene, a random copolymer of polypropylene and butene and / or hexene, a polybutene, an ethylene-vinyl acetate polymer, the polyethylene having a density of 0.915 to less of 0.935 g / cm 3, linear polyethylene, polyethylene having a density of 0.86 to less than 0.90 g / cm 3, polyethylene having a density of 0.90 to less than 0.915 g / cm 3, polyethylene having a density of 0.935 to less than 0.945 g / cm3, a polyethylene having a density of 0.945 to 0.98 g / cm3, an ethylene-methyl acrylate polymer, an acrylic acid copolymer, a polymethyl methacrylate) poly (vinyl chloride), polybutene-1, isotactic polybutene, ABS resin, ethylenepropylene rubber, vulcanized EPR, EPDM, SBS elastomer, polyamide, polycarbonate, PET resin, cross-linked polyethylene, a copolymer of ethylene and vinyl alcohol, a polystyrene, a poly-1-ester, a polyacrylonitrile homopolymer, a polyacrylonitrile copolymer, a thermoplastic polyamide, a polyacetal, a polyvinyl fluoride, a polyethylene glycol, a polyisobutylene and a combination thereof.   18. Polymer blend according to claim 16, characterized in that the additive comprises an elastomer prepared by polymerizing propylene with ethylene in the presence of a chiral metallocene-based catalyst with an activator and optionally an acceptor, an elastomer having an average propylene content on a molar basis of from about 66% to about 92%.   19. The polymer blend according to claim 16, characterized in that the additive comprises a semicrystalline propylene copolymer having: A. a heat of fusion of about 0.5 J / g to about 25 J / g, B. a crystallinity from about 0.25% to about%, C. a single broad melting point of about 25 C to about 75 C, D. a weight average molecular weight of 10,000 to 5,000,000 g / cm3 , E. a DMP (Mw / Mn) of 1.5 to 40.0, and / or F. a Mooney viscosity ML (1 + 4) at 125 C less than 100.   20. Polymer blend according to Claim 16, characterized in that the additive comprises a composition made tough with rubber, the rubber being an ethylene-propylene rubber, an ethylene-propylene-diene monomer rubber, a Neoprene rubber and / or a styrenic block copolymer rubber, and the rubber being in the form of a discontinuous phase in a continuous phase comprising the polyolefin rich in functionalized amorphous syndiotactic structure.   21. The polymer blend according to claim 16, characterized in that the additive comprises a random copolymer produced by copolymerizing propylene in a single reactor process with ethylene, so that the random copolymer comprises about 3 to about 7 mol% of ethylene.   Polymer blend according to Claim 16, characterized in that the additive comprises a random copolymer having a narrow composition distribution, such that 75% by weight of the random copolymer is isolated in the form of a copolymer. or two adjacent soluble fractions, with the remainder of the polymer in the immediately preceding or succeeding fractions as determined by thermal fractionation in a saturated hydrocarbon.   23. Polymer blend according to claim 16, characterized in that the additive comprises a fluxionic polymer comprising a linear isotactic polymer comprising C2-C20 olefins, whose isotacticity due to the statistical distribution of stereoscopic errors in the chain of the invention. polymer has a pentad concentration [mmmm] of 25 to 60%, a weight average molecular weight of 100,000 to 800,000 g / mol, a glass transition temperature of -50 to 30 ° C, a pentad concentration [rmrm ] corresponding to a maximum of 2.5% of the total pentad area, a pentad concentration [rrrr] and [rrrm] which, in the combined state, corresponds to a pentad concentration which is greater than the concentration of pentades [rmrm], and is essentially soluble in toluene at a temperature of 20 to 80 C.   The polymer blend of claim 16, wherein the additive comprises a tackifier selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, resins, and the like. of polycyclopentadiene, gum-resins, gum-resin esters, wood resins, esters of wood resins, talldl resins, tall oil resins esters, polyterpenes, aromatic-modified polyterpenes, resins terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aromatic-aliphatic resins, hydrogenated terpenes, modified terpenes, hydrogenated resin acids and hydrogenated rosin esters.   Polymer blend according to claim 16, characterized in that the additive comprises a crosslinking agent selected from the group consisting of alcohols, multiols, amines, diamines and triamines.   26. Polymer blend according to claim 16, characterized in that the additive comprises a polar wax, a non-polar wax, a polypropylene wax, a polyethylene wax, a Fischer-Tropsch wax, a Fischer-Tropsch wax. oxidation, a hydroxystearamide wax, a functionalized wax, an amorphous wax, carnauba wax, a castor oil wax, a microcrystalline wax, beeswax, carnauba wax, castor wax, spermaceti wax, vegetable wax, candelilla wax, Japan wax, ouricury wax, Douglas fir bark wax, rice bran wax, jojoba wax, wax of wax, montan wax, peanut wax, ozokerite wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, substituted amide wax and / or their associations and derivatives.   27. Polymer blend according to claim 16, characterized in that the additive comprises a crystallization aid.   28. Polymer blend according to claim 16, characterized in that it comprises 10 to 90% by weight of additive, based on the weight of the polymer blend.   29. A polymer blend according to claim 16, characterized in that the additive is an organic clay present in the mixture in an amount of 0.1 to 50% by weight based on the total mixture, and the organic clay is selected from the group consisting of montmorillonite, montmorillonite sodium, montmorillonite calcium, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarsovite, ledikite, fluorinated mica and one of their associations.   30. Polymer blend according to Claim 16, characterized in that it consists of a masterbatch, melt blended under high shear conditions with at least one additive, to produce a concentrate containing 10 to 90% by weight. of the polymer blend.   31. A polyolefin rich in amorphous syndiotactic structure which has been functionalized with a functional group, characterized in that, prior to functionalization, the polyolefin rich in amorphous syndiotactic structure comprises: more than about 50% by weight of C3 alpha-olefin to C40; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g according to the procedure described in ASTM standard E 794-85; and an ash content equal to or less than 1% by weight.   32. The polymer according to claim 31, characterized in that it comprises at least about 6.25% from about 30 to about 31.6% pentads r, based on the total number of pentads r and m present in the polymer.   33. Polymer according to claim 31, characterized in that it comprises more than about 50% by weight of propylene.   Polymer according to claim 31, characterized in that it further comprises at least 0.5% by weight of ethylene, based on the total weight of the polymer.   35. Polymer according to claim 31, characterized in that the heat of fusion is not detectable.   36. Polymer according to claim 31, characterized in that it has an ash content equal to or less than 0.1% by weight.   37. The polymer of claim 31, characterized in that it has a melt flow rate of 0.2 g / 10 min or more. 38. The polymer of claim 31 wherein at least about 95% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 C based on the weight of the polymer. total of the polymer present.   39. The polymer according to claim 31, characterized in that it has a weight average molecular weight (Mw) of about 5,000 to about 5,000,000 g / mol.   40. The polymer of claim 31, characterized in that it has a number average molecular weight (Mn) of about 5,000 to about 3,000,000 g / mol.   41. The polymer of claim 31, characterized in that it has a z-average molecular weight (Mz) of about 5,000 to about 10,000,000 g / mol.   42. Polymer according to claim 31, characterized in that it has no discernible crystallization temperature (Tc).   43. The polymer according to claim 31, wherein the functional group comprises a compound having a weight average molecular weight of 1000 or less and a carbon-carbon double bond, a carbon-carbon triple bond and / or a heteroatom.   44. The polymer of claim 31, wherein the functional group comprises B, N, O, Si, P, F, Cl, Br, I, S, or a combination thereof.   45. The polymer according to claim 31, characterized in that the functional group is an aromatic compound, a vinyl compound, an organic acid, an organic amide, an organic amine, an organic ester, an organic diester, an organic imide, an anhydride organic, an organic alcohol, an organic acid halide, an organic peroxide and / or their salts.   Polymer according to Claim 31, characterized in that the functional group is maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo [2,2,1] -5-heptene2,3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid , fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo [2.2.2] oct-5-ene2,3-dicarboxylic acid anhydride, 1,2,3,4,5,6-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro (4.4) none-7-ene, bicyclo acid anhydride - (2.2.1) hept-5-ene-2,3-dicarboxylic acid, maleimidic acid, tetrahydrophthalic anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride , methylnadic anhydride, himic anhydride, methylhimic anhydride, acid anhydride e xmethyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate butyl methacrylate, vinyltrichlorosilane, vinyltris- (beta-methoxyethoxy) -silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, monovinylsilane, monoallylsilane, vinyl chloride or vinylidene chloride.   Polymer according to claim 31, characterized in that the functional group is present in the polyolefin rich in functionalized amorphous syndiotactic structure in a proportion of 1 to 5% by weight, based on the total weight of the functionalized polyolefin.   48. The polymer according to claim 31, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is thermostable.   49. The polymer according to claim 31, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure grafted with maleic anhydride, and in that the maleic anhydride is present in the rich polypropylene. in amorphous syndiotactic structure functionalized in a concentration of about 0.005 to 10% by weight of maleic anhydride, based on the weight of functionalized amorphous syndiotactic rich structure polypropylene.   50. The polymer according to claim 49, characterized in that the functionalized amorphous syndiotactic rich structure polypropylene comprises less than about 1000 ppm free acid groups, based on the total weight of the polypropylene, and that the high-structure polypropylene Functionalized amorphous syndiotactic comprises less than about 100 ppm phosphite, based on the total weight of the polypropylene.   51. Mixture of polymers, characterized in that it comprises: a polyolefin rich in functionalized amorphous syndiotactic structure which has been functionalized with a functional group; wherein, prior to functionalization, the amorphous syndiotactic rich polyolefin comprises: more than about 50% by weight C3 to C40 alpha-olefins, about 50% to less than about 80% r dyads, based on total number of r and m dyads present in the polymer, a heat of fusion equal to or less than 10 J / g and an ash content equal to or less than 1% by weight; and at least one additive comprising a C2 to C40 polymer, a C2 to C90 copolymer, an elastomer, a random copolymer, an impact resistant copolymer, a fluxionic polymer, a tackifier, a crosslinking agent, an antioxidant , a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, a composition rendered tenacious with rubber, a recycled polymer, a blocking agent, an antiblocking agent, a pigment, a colorant, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a colored masterbatch, a flow enhancer, a crystallization adjuvant, or a their associations.   52. The polymer according to claim 51, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure grafted with maleic anhydride, and in that the maleic anhydride is present in the rich polypropylene. in amorphous syndiotactic structure functionalized at a concentration of about 0.005 to 10% by weight of maleic anhydride, based on the weight of functionalized amorphous syndiotactic rich structure polypropylene.   53. The polymer blend according to claim 51, characterized in that the additive is selected from the group consisting of a homopolypropylene, a propylene copolymerized with up to 50% by weight of ethylene or a C4 alpha-olefin. to C20r isotactic polypropylene, a random copolymer of propylene and ethylene, a random copolymer of polypropylene and butene and / or hexene, a polybutene, an ethylene-vinyl acetate polymer, a polyethylene having a density of 0.915 to less than 0.935 g / cm3, linear polyethylene, polyethylene having a density of 0.86 to less than 0.90 g / cm3, polyethylene having a density of 0.90 to less than 0.915 g / cm3, cm 3, a polyethylene having a density of 0.935 to less than 0.945 g / cm 3, a polyethylene having a density of 0.945 to 0.98 g / cm 3, an ethylene-methyl acetate polymer, an acrylic acid copolymer, a polymethacrylate methyl), a poly (vinyl chloride), a polybutene-1, an isotactic polybutene, an ABS resin, an ethylene-propylene rubber, a vulcanized EPR, an EPDM, an SBS elastomer, a polyamide, a polycarbonate, a PET resin, a crosslinked polyethylene, a copolymer of ethylene and vinyl alcohol, a polystyrene, a poly-1-ester, a polyacrylonitrile homopolymer, a polyacrylonitrile copolymer, a thermoplastic polyamide, a polyacetal, a poly ( vinylidine fluoride), a polyethylene glycol, a polyisobutylene and one of their combinations.   54. A polymer blend according to claim 51, characterized in that the additive comprises a semicrystalline propylene copolymer having: A. a heat of fusion of about 0.5 J / g to about 25 J / g, B. a crystallinity of from about 0.25% to about 15%, C. a single broad melting point of about 25 C to about 75 C, a weight average molecular weight of 10,000 to 5,000,000 g. cm3, E. a DMP (Mw / Mn) of 1.5 to 40.0, and / or F. a Mooney viscosity ML (1 + 4) at 125 C less than 100.   55. A polymer blend according to claim 51, characterized in that the additive comprises a random copolymer produced by copolymerizing propylene in a single reactor process with ethylene, so that the random copolymer comprises about 3 to about 17 mol% of ethylene, and in that the random copolymer has a narrow composition distribution, such that 75 weight percent of the random copolymer is isolated as two or more adjacent soluble fractions, with the remainder of the polymer in the immediately preceding or following fractions, as determined by thermal fractionation in a saturated hydrocarbon.   The polymer blend of claim 51, wherein the additive comprises a tackifier selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, resins, and the like. of polycyclopentadiene, gum-resins, gum-resin esters, wood resins, esters of wood resins, talldl resins, tall oil resins esters, polyterpenes, aromatic-modified polyterpenes, resins terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resins, hydrogenated aromatic-aliphatic resins, hydrogenated terpenes, modified terpenes, hydrogenated resin acids and hydrogenated rosin esters.   57. Polymer blend according to Claim 51, characterized in that it comprises 10 to 90% by weight of additive, based on the weight of the polymer mixture.   58. A contact product of a polyolefin rich in amorphous syndiotactic structure, a functional group and a functionalization catalyst, characterized in that the polyolefin rich in amorphous syndiotactic structure comprises: more than about 50% by weight of C3 to C40 alpha olefins, from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight.   59. Contacting product according to claim 58, characterized in that the functionalizing catalyst is an organic peroxide.   60. A contact product according to claim 58, characterized in that the functionalization catalyst is selected from the group consisting of benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl peroxyisopropyl carbonate, diisocyanate perphthalate and the like. tert-butyl, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexene, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexene-3, di-tert-butyl peroxide, hydroperoxide of cumene, tert-butyl hydroperoxide, dilauryl peroxide, dicumyl peroxide and one of their combinations.   61. The contact product according to claim 58, characterized in that the functional group comprises a compound having a weight average molecular weight of 1000 or less and a carbon-carbon double bond, a carbon-carbon triple bond, and or a heteroatom.   62. Contact product according to claim 58, characterized in that the functional group comprises B, N, O, Si, P, F, Cl, Br, I, S or a combination thereof.   63. Contact product according to claim 58, characterized in that the functional group is an aromatic compound, a vinyl compound, an organic acid, an organic amide, an organic amine, an organic ester, an organic diester, an organic imide, an organic anhydride, an organic alcohol, an organic acid halide, an organic peroxide and / or their salts.   64. The contact product according to claim 58, characterized in that the functional group is maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride and 2,3-dimethylmaleic anhydride. , bicyclo [2,2,1] -5-heptene-2, 3-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo [2.2.2] oct-5-ene-2,3-acid anhydride dicarboxylic acid, 1,2,3,4,5,6-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-1,3-diketospiro (4.4) non-7-ene, anhydride bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid, maleimidic acid, tetrahydrophthalic anhydride, norborn-5-ene-2,3dicarboxylic acid anhydride, anhydride nadic, methylnadic anhydride, himic anhydride, methylhimic anhydride, anhydrid e of x-methyl-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylate of ethyl, butyl methacrylate, vinyltrichlorosilane, vinyltris- (beta-methoxyethoxy) -silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, monovinylsilane, monoallylsilane, vinyl chloride or vinylidene chloride.   Contact product according to Claim 58, characterized in that the functional group is present in the contact product in a proportion of 0.005 to 99% by weight, based on the total weight of the contact product.   Contact product according to Claim 58, characterized in that the functional group is present in the contact product in a proportion of 1 to 5% by weight, based on the total weight of the contact product.   67. Contact product according to claim 58, characterized in that it is heat-stable. 68. Contact product according to claim 58, characterized in that   the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure, in that the functional group is maleic anhydride, and in that the maleic anhydride is present in the contact product at a concentration of about 0.005 to 10% by weight of maleic anhydride, based on the weight of the contact product.   69. A contact product according to claim 58, characterized in that the polyolefin rich in amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure, the functional group is maleic anhydride, and in that the contact product comprises less than about 1000 millionths of free acid groups, based on the total weight of the contact product.   70. A contact product according to claim 58, characterized in that the polyolefin rich in amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure, the functional group is maleic anhydride, and in that the contact product comprises less than about 100 ppm phosphite, based on the total weight of the contact product.   71. A polymer comprising a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride, characterized in that the functionalized polypropylene comprises from about 50% to less than about 80% of r dyads, on the basis of the total number of r dyads. and m present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight.   72. The polymer according to claim 71, characterized in that it comprises at least about 6.25% pentads r to about 31.6% pentades r, based on the total number of pentades r and m present in the polymer. .   The polymer of claim 71 further comprising at least about 0.5% by weight of ethylene, based on the total weight of the polymer.   Polymer according to Claim 71, characterized in that the heat of fusion is not detectable.   Polymer according to claim 71, characterized in that it has an ash content equal to or less than 0.1% by weight.   Polymer according to claim 71, characterized in that it has a melt flow rate equal to or greater than 0.2 g / 10 min. Polymer according to claim 71, characterized in that a proportion of at least about 99% by weight of the polymer is soluble in hexane, cyclohexane, xylene or toluene at 25 C, based on the weight of the polymer. total of the polymer present.   78. The polymer of claim 71, characterized in that it has a weight average molecular weight (Mw) of about 5,000 to about 5,000,000 g / mol.   79. The polymer of claim 71, characterized in that it has a number average molecular weight (Mn) of about 5,000 to about 3,000,000 g / mol.   80. The polymer of claim 71, characterized in that it has a z-mean molecular weight (Mz) of about 5,000 to about 10,000,000 g / mol.   81. Polymer according to claim 71, characterized in that it has no discernible crystallization temperature (Tc).   Polymer according to claim 71, characterized in that the maleic anhydride is present in the polymer in a proportion of from 0.005 to 10% by weight, based on the total weight of the polymer.   83. Polymer according to claim 71, characterized in that the polymer is heat-stable.   84. Mixture of polymers characterized in that it comprises a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride, and at least one additive, characterized in that the functionalized polypropylene comprises about 50% to less than about 80 % dyads r, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight, and in that the additive is selected from the group consisting of a C2 to C90 polymer an elastomer, a random copolymer, an impact-resistant copolymer, a fluxional polymer , a tackifier, a crosslinking agent, an antioxidant, a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, an ester polymer, an agent blocking agent, an anti-blocking agent, a pigment, a colorant, a processing aid, a UV stabilizer, a lubricant, an adjuvant, a surfactant, a colored masterbatch, a flow-improving agent, a crystallization aid , and one of their associations.   85. A polymer blend according to claim 84, characterized in that it comprises 10 to 90% by weight of additive, based on the weight of the polymer blend.   86. An adhesive composition, comprising a polyolefin rich in amorphous syndiotactic structure, a polyolefin rich in amorphous syndiotactic structure which has been functionalized with a functional group, or one of their associations, characterized in that the polyolefin rich in amorphous syndiotactic structure comprises more than about 50% by weight of C3 to C40 alpha-olefins; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight, and in that the functional group, when present, comprises a compound having a weight average molecular weight equal to or less than 1000 and a carbon-carbon double bond. carbon, a carbon-carbon triple bond and / or a heteroatom; the adhesive composition having an isotactic polypropylene peel strength of greater than about 625.1 g / cm and a peel strength of greater than about 89.3 g / cm 3 polyester film.   87. An adhesive composition according to claim 86, characterized in that it further comprises at least one additive selected from the group consisting of a C2 to C40 polymer a C2 to C40 copolymer, an elastomer, a random copolymer , an impact-resistant copolymer, a fluxionic polymer, a tackifier, a crosslinking agent, an antioxidant, a neutralizing agent, a nucleating agent, a filler, an adhesion promoter, an oil, a plasticizer, a wax, ester polymer, tenacious composition with rubber, recycled polymer, blocking agent, anti-blocking agent, pigment, colorant, processing aid, UV stabilizer, lubricant, adjuvant , a surfactant, a colored masterbatch, a flow enhancer, a crystallization adjuvant, and a combination thereof.   88. An adhesive composition according to claim 86, characterized in that a proportion of at least about 95% by weight of the adhesive is soluble in hexane, cyclohexane, xylene or toluene at 25 ° C. based on the total weight of the adhesive present.   89. Adhesive composition according to claim 86, characterized in that the polyolefin comprises more than about 60% by weight of propylene.   90. An adhesive composition according to claim 86, characterized in that the polyolefin comprises at least 0.5% by weight of ethylene, based on the total weight of the polyolefin.   91. Adhesive composition according to claim 86, characterized in that a heat of fusion of the polyolefin is not detectable.   92. Adhesive composition according to claim 86, characterized in that the polyolefin has an ash content equal to or less than 0.1% by weight.   An adhesive composition according to claim 86, characterized in that it further comprises one or more tackifiers selected from the group consisting of aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, polycyclopentadiene resins. hydrogenated, polycyclopentadiene resins, gum-resins, gum-resin esters, wood resins, wood resin esters, tallbl resin, tall oil resins, polyterpene esters, modified polyterpenes aromatic, terpene phenolic resins, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resins, hydrogenated aromatic-aliphatic resins, hydrogenated terpenes, modified terpenes, hydrogenated resin acids and hydrogenated rosin esters, their derivatives and their associations.   An adhesive composition according to claim 86, characterized in that the adhesive further comprises one or more waxes selected from the group consisting of polar waxes, non-polar waxes, Fischer-Tropsch waxes, waxes of Oxidized Fischer-Tropsch, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, modifying waxes and combinations thereof.   An adhesive composition according to claim 86, characterized in that the adhesive further comprises one or more additives selected from the group consisting of plasticizers, oils, stabilizers, antioxidants, pigments, dyestuffs, polymeric additives, defoamers, preservatives, thickeners, rheology modifiers, moisturizers, fillers and water.   96. Adhesive composition according to claim 86, characterized in that it has a setting time equal to or less than 30 seconds.   97. Consumer goods, manufactured article, packaging adhesive, packaging, disposable article, film, pressure-sensitive adhesive, laminated article, fiber product, hot-melt adhesive, carpet, tape, shingle, roof covering element, reflective article, woodworking article, consumer article, label, binding article, road marking composition, sealant composition, paving composition, glue stick, article for conduit packing, article comprising a transparent panel, or one of their combination, characterized in that it comprises the adhesive composition of claim 1.   98. A polyolefin rich in amorphous syndiotactic structure which has been functionalized with a functional group, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure comprises: more than about 50% by weight of C3 to C40 alpha-olefins about 50 less than about 80% r dyads, based on the total number of r and m dyads present in the polymer; and a heat of fusion equal to or less than 10 J / g.   99. Process for the preparation of a polymeric material, characterized in that it comprises the steps of: melt blending, a polyolefin rich in amorphous syndiotactic structure and at least one additive under conditions of high shear to produce a concentrate containing 10 to 90% by weight of the polyolefin, and then mixing the concentrate with at least one additional material to prepare a final product, wherein the amorphous syndiotactic rich polyolefin comprises: more than about 50% by weight of alpha olefins at 25 ° C to 40 ° C; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polymer; a heat of fusion equal to or less than 10 J / g; and an ash content equal to or less than 1% by weight.   The process according to claim 99, characterized in that the polyolefin rich in amorphous syndiotactic structure has been functionalized with a functional group, the functional group comprising a compound having a weight average molecular weight of 1000 or less and a double bond carbon-carbon, a carbon-carbon triple bond and / or a heteroatom.   101. Process according to claim 100, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride.   102. Process according to claim 101, characterized in that the polyolefin rich in amorphous syndiotactic structure is functionalized simultaneously with the formation of the concentrate.   103. Process for the production of a polyolefin rich in functionalized amorphous syndiotactic structure, characterized in that it comprises the following steps: A. bringing an olefinic monomer, a metallocene-based catalyst and an activator to a reactor in a reactor an aliphatic solvent; B. catalytic solution polymerizing said olefinic monomer in said reactor to produce a polyolefin rich in amorphous syndiotactic structure; C. driving the monomer to remove the unreacted olefinic monomer.   D. performing a solvent-based functionalization, comprising combining said amorphous syndiotactic-rich polyolefin with a functional group and with a radical initiator in said aliphatic solvent, at a temperature and for a period of time sufficient to produce said polyolefin rich in functionalized amorphous syndiotactic structure; and optionally E. removing said aliphatic solvent, wherein the amorphous syndiotactic rich polyolefin comprises more than about 50% by weight of C3 to C40 alpha olefins; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polyolefin; a heat of fusion equal to or less than 10 J / g, and an ash content equal to or less than 1% by weight.   104. Process according to claim 103, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride.   105. A process according to claim 103, characterized in that it further comprises the addition of an organic clay after said solvent-based functionalization step D.   106. Process for the production of a polyolefin rich in functionalized amorphous syndiotactic structure, characterized in that it comprises the steps of: A. bringing a melt comprising a polyolefin rich in amorphous syndiotactic structure, a functional group and an initiator radical to a mixing device; B. contacting said melt in said mixing device at a temperature and for a period of time sufficient to produce said functionalized amorphous syndiotactic rich polyolefin, wherein the amorphous syndiotactic rich polyolefin comprises greater than about 50% by weight of C3 to C40 alpha-olefins; from about 50% to less than about 80% r dyads, based on the total number of r and m dyads present in the polyolefin; a heat of fusion equal to or less than 10 J / g, and an ash content equal to or less than 1% by weight.   107. Process according to claim 106, characterized in that the polyolefin rich in functionalized amorphous syndiotactic structure is a polypropylene rich in amorphous syndiotactic structure functionalized with maleic anhydride.   The process according to claim 106, characterized in that it further comprises the addition of an organic clay after said contacting step B. 20