KR20010113933A - Highly Crystalline EAODM Interpolymers - Google Patents

Abstract

Highly crystalline ethylene / with or without grafted with unsaturated monomers, with or without crosslinking if grafted The -olefin / polyene interpolymer can be used as is to form the polymer composition, or blended with other natural or synthetic polymers to form the polymer blend composition. Both the polymer composition and the polymer blend composition have the desired physical properties useful for making various end products.

Description

Highly Crystalline EAODM Interpolymers

Polyolefins are used in a variety of applications, including but not limited to wire and cable insulators, automotive interior surfaces, impact modifiers of other polyolefins, foams, and films. Many of these applications are always required to improve heat resistance. One way to improve the heat resistance of polyolefins is to crosslink or cure the polyolefin using radiation sources such as electron beam (EB) radiation, gamma radiation or ultraviolet (UV) radiation, or by thermally activated chemical crosslinkers such as peroxides. It involves doing. In addition, when the polyolefin includes an unsaturated moiety, the thermally activated chemical crosslinker may be sulfur, phenolate or silicone hydride. Manufacturers of cured elastomeric parts are continuing to seek polyolefins with improved curing properties that provide one or more additional benefits, such as faster productivity, which reduces manufacturing costs.

For polyethylene (PE), increasing the crosslink density typically requires using more peroxide, or increasing the level of radiation exposure, all of which increase the cost. Those who work with PE want an effective, but more economical approach.

The interpolymers of the present invention have unsaturated sites that allow the polar material to be grafted to the backbone of the interpolymer. Those skilled in the art recognize that nonpolar polyolefins, in particular PE, provide a poor substrate for coating polar coating materials such as paints. In order for the pate to adhere effectively to the PE, the PE surface is usually treated with techniques such as flame surface treatment and corona discharge to improve compatibility. The alternative involves altering the polymer itself and grafting the polar material onto the polymer backbone.

The present invention is a random ethylene / alpha containing 84% by weight or more of ethylene ( ) -Olefin / polyene (EAODM) interpolymers and the use of such interpolymers in combination with other polyolefin, rubber and thermoplastic formulations. The present invention also provides crosslinked or cured EAODM interpolymers and such crosslinks to prepare articles including, but not limited to, wire and cable products, foams, automotive components, tubing, tapes, laminates, coatings, and films. It relates to the use of bonded interpolymers. The invention also relates to blends of the polymers of the invention with natural or synthetic polymers, in particular thermoplastic polyolefins (TPO). The invention also relates to EAODM polymers grafted with other monomers, such as unsaturated carboxylic acid monomers, and the use of such grafted interpolymers, for example, as impact modifiers, compatibilizers and adhesion promoters.

Summary of the Invention

One aspect of the invention comprises (a) 84 to 99 weight percent ethylene, (b) greater than 0 weight percent (> 0 weight percent) less than 16 weight percent (<16 weight percent) 3 to 20 carbon atoms (C _3-20 ) -Olefin, and (c) greater than 0% to 15% by weight of polyene (all% based on interpolymer weight, selected to be a total of 100% by weight) crystallinity> 16% and glass transition temperature (T _g ) is an interpolymer composition comprising a random EAODM interpolymer having at least -45 ° C. For example, T _g of -40 ℃ is greater than T _g of -45 ℃. By comparison, EAODM with 85 wt% ethylene, 10 wt% propylene and 5 wt% diene has an ethylene content of 91.5 mol%. The interpolymer obtained can be crosslinked if desired chemically using reagents such as peroxide, sulfur, phenolate and silicon hydride, or by radiation using either EB, gamma and UV radiation.

As used herein, “interpolymer” refers to a polymer that polymerized three or more monomers. This includes, but is not limited to, terpolymers and tetrapolymers. "Copolymer" is a polymerization of two monomers.

When crosslinked, the ethylene interpolymers of the present invention are made of the same monomers but exhibit improved mechanical strength, heat resistance and curing properties compared to crosslinked ethylene interpolymers having a low ethylene content.

Detailed description of the invention

Those skilled in the art recognize that unsaturated polyolefins have a higher crosslinking efficiency than those which are not unsaturated. Improved crosslinking efficiency generally translates into faster cure, increased mechanical strength and increased productivity for the final manufacturer. The EAODMs of the present invention, when blended with polyolefins, provide a means to increase the polyolefin crosslink density without using more peroxide or relying on conventional techniques such as increasing radiation exposure.

Polymer crystallinity affects physical properties such as tensile strength, green strength and flexural modulus. The decrease in polymer crystallinity typically leads to a corresponding decrease in tensile strength, wet strength and flexural modulus. Commercially available polyolefins, such as high density polyethylene (HDPE), typically have a crystallinity ranging from 45% to 95%. Typical EAODM polymers have a crystallinity of 0% to 16%. When such conventional EAODM polymers are blended with HDPE or other crystalline polyolefins, the resulting blend has reduced crystallinity compared to crystalline polyolefins. In contrast, the EAODMs of the present invention have a crystallinity of greater than 16 weight percent to less than 75 weight percent, preferably greater than 19 weight percent and 40 weight percent as measured by differential scanning calorimetry (DSC).

Unless otherwise specified herein, numerical ranges include their endpoints.

EAODM interpolymers suitable for the present invention are ethylene, at least one C _3-20 , preferably C _3-10 -Olefins and polymers polymerized with one or more polyenes. Those skilled in the art can readily select suitable monomer combinations for the desired interpolymer such that the interpolymer meets requirements such as the ethylene content and crystallinity requirements stated herein.

The EAODM interpolymers of the present invention are at least 84% by weight, preferably at least 88% by weight, more preferably at least 90% by weight, and in any case have an ethylene content of 99% by weight or less. The ethylene content may be a few percent or more depending on the amount and weight of polyene in the EAODM. Generally, ethylene, The choice of the amount of -olefins and polyenes is greater than 95: 5, preferably greater than 95: 5 Provide the proportion of olefins. EAODMs with more than 84% by weight of ethylene have DSC crystallinity as described above. This crystallinity is believed to provide most of the mechanical strength of the polymer. Increasing the crystallinity of the polymer proportionally leads to an increase in the T _g of the polymer. The interpolymer of the present invention has a T _g as measured by DSC -45 ° C. or higher, preferably -40 ° C. or higher. Those skilled in the art recognize that the endothermic melt peaks cloud T _g as the polymer crystallinity increases. As such, there is no significant upper limit for Tg.

The -olefin may be an aliphatic or aromatic compound and may contain a vinyl unsaturated moiety, or the positions 5 and 6 are substituted with cyclic compounds, such as cyclobutene, cyclopentene, or C _1-20 hydrocarbyl groups Norbornene, including norbornene. The olefin is preferably a C _3-20 aliphatic compound, more preferably a C _3-16 aliphatic compound, even more preferably a C _3-10 aliphatic compound such as propylene, isobutylene, butene-1, pentene- 1, hexene-1, 3-methyl-1-pentene, 4-methyl-1-pentene, octene-1, decene-1 and dodecene-1. Other preferred ethylenically unsaturated monomers include 4-vinylcyclohexene, vinylcyclohexane, norbornadiene and mixtures thereof. Most desirable Olefins are propylene, butene-1, hexene-1 and octene-1. The -olefin content is preferably more than 0% and less than 16% by weight, more preferably 1% by weight to 10% by weight, most preferably 2% by weight to 8% by weight, based on the total interpolymer weight.

The polyene, sometimes referred to as diolefin or diene monomer, is preferably a C _4-40 polyene. The polyene is preferably a nonconjugated diolefin, or may be a conjugated diolefin. Non-conjugated diolefins may be C _6-15 straight, branched or cyclic hydrocarbon dienes. Examples of non-conjugated dienes include branched bicyclic dienes such as 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, Mixed isomers of 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene and dihydromircene; Single ring alicyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; Multi-ring fused and bridged alicyclic dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene (DCPD), bicyclo- (2,2,1) -hepta-2,5 Dienes (norbornadiene or NBD), methyl norbornadiene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, for example 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propenyl-2 -Norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene. When the diolefin is a conjugated diene, it is 1,3-pentadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene or 1,3-cyclo It may be pentadiene.

The diene is preferably a non-conjugated diene selected from ENB and NBD, more preferably ENB. The polyene monomer content of EAODM is ethylene, It is preferably in the range of more than 0 mol% to less than 5 mol% based on the moles of olefin and polyene. Based on weight, the polyene monomer content of EAODM is equivalent to the mole percent limit and can vary depending on the weight of the polyene. Generally speaking, the polyene content is more than 0% to 15% by weight, more preferably 0.3 to 12% by weight and most preferably 0.5 to 10% by weight based on the weight of the interpolymer. When the polyene monomer is ENB, the monomer content of more than 0% to less than 11% by weight, based on the weight of the interpolymer, is generally equivalent to the range of more than 0% to less than 3% by mole.

Molecular weight distribution (MWD) is a well known variable in polymers. It is sometimes described as the ratio of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ) (ie M _w / M _n ), measured directly or more typically ASTM D-1238 (I ₁₀ for I ₁₀₎ . For 190 ° C./10 kg) I ₂ , the polymer melt index (I) can be measured using ASTM D-1238 (190 ° C./2.16 kg), and the I ₁₀ / I ₂ ratio can be calculated and measured. Polymers with narrow MWDs have the same monomer composition but exhibit higher toughness, better optical properties and higher crosslinking efficiency than polymers with relatively wider MWDs. The MWD values of the interpolymers of the invention prepared using metallocene catalysts, in particular constrained geometry catalysts (CGCs), are from 1 to 15, preferably from 1 to 10, most preferably from 1 to 4

The EAODM interpolymers of the present invention have a melting point (mpt) of at least 70 ° C. mpt is preferably at least 80 ° C, preferably at least 85 ° C. mpt is preferably below 135 ° C, preferably below 125 ° C. Mpts below 70 ° C. virtually exclude certain applications that require relatively high UST, such as wire and cable jacket materials with an upper service temperature (UST) higher than 70 ° C. Those skilled in the art recognize that the theoretical upper melting point limit is determined by HDPE homopolymers having an mpt of about 135 ° C. (depending on the polymer molecular weight).

The EAODM interpolymer of the present invention has a heat of fusion greater than 11 cal / g. The heat of fusion is preferably greater than 12 cal / g, preferably greater than 13 cal / g. The heat of fusion can be as large as 30 cal / g or even higher, depending on various factors, one of which is interpolymer crystallinity.

The EAODM interpolymers of the present invention may be prepared using one or more limited geometric catalysts (CGCs) or metallocene catalysts with activators in solution, slurry or gas phase processes. The catalyst is preferably a mono- or bis-cyclopentadienyl, indenyl or fluorenyl transition metal (preferably Group 4) catalyst, more preferably mono-cyclopentadienyl, mono-indenyl or mono Fluorenyl CGCs. Solution processes are preferred. U. S. Patent No. 5,064, 802, WO 93/19104 (US Patent Application No. 8,003, filed Jan. 21, 1993) and WO 95/00526 disclose limiting geometric metal complexes and methods for their preparation. Various substituted indenyl containing metal complexes are taught in WO 95/14024 and WO 98/49212. The related teachings of all the foregoing patents and corresponding US patent applications are incorporated herein by reference.

In general, the polymerization is carried out in a Ziegler-Natta or Kaminsky-Sinn type polymerization reaction, conditions known in the art, i.e. 0-250 ° C, preferably 30-200 ° C, and It may be carried out at a pressure of atmospheric pressure to 10,000 atmospheres (1013 megapascals (MPa)). Suspensions, solutions, slurries, gas phase, solid state powder polymerization or other process conditions may be applied if desired. Supports, in particular silica, alumina or polymers (particularly poly (tetrafluoroethylene) or polyolefins) can be used, preferably when the catalyst is used in a gas phase polymerization process. The support is preferably in a weight ratio of catalyst (based on metal) to support in the range of 1: 100,000 to 1:10, more preferably 1: 50,000 to 1:20, most preferably 1: 10,000 to 1:30. It is used in an amount sufficient to provide. In most polymerization reactions, the molar ratio of polymerizable compound used in the catalyst for from 10 ^-12: 1 to 10 ^-1: 1: 1, most preferably from 10 ^-9: 1 to 10 ^-5.

Inert liquids serve as solvents suitable for polymerization. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; Cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; Perfluorinated hydrocarbons such as perfluorinated C _4-10 alkanes; And aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and ethylbenzene. Suitable solvents are also butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, Liquid olefins that can act as monomers or comonomers, including 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene and vinyltoluene (including all isomers alone or in mixtures). Mixtures of the above are also suitable. If desired, normally gaseous olefins can be used herein after being converted to liquid by applying pressure.

The catalyst can be used with one or more additional homogeneous or heterogeneous polymerization catalysts in the same reactor or in separate reactors connected in series or in parallel to produce a polymer blend with the desired properties. Examples of such processes are disclosed in WO 94/00500, page 4, line 4 to page 33, line 17. The process uses one or more other continuous stirred tank reactors (CSTRs) or continuous stirred tank reactors (CSTRs) connected in series or in parallel to the tank reactors. WO 93/13143 (pages 19-31, page 2) discloses polymerization of monomers in a first reactor using a first CGC having a first reactivity and a second reactor using a second CGC having a second reactivity The polymerization of monomers in and the joining of the products from the two reactors are taught. Lines 25-32 of page 3 of WO 93/13143 teach the use of two CGCs with different reactivity in one reactor. WO 97/36942 (pages 4 to 30 to 6) Line 7 teaches the use of a two-loop reactor system. The relevant teachings of this application specification and its corresponding US patent application specification are incorporated herein by reference. In addition, the same catalyst can be used in two reactors operating at different process conditions.

The EAODM interpolymer of the present invention may be mixed with other natural or synthetic polymers to form a blend comprising 2 to 98 weight percent of the EAODM interpolymer (s) based on the total blend weight. Natural and synthetic polymers may be selected from natural rubber, styrene-butadiene rubber (SBR), butadiene rubber, butyl rubber, polyisoprene, polychloroprene (neoprene), homopolymers of monoolefins or copolymers or interpolymers of two or more monoolefins, preferably Makes C _2-20 It is derived from an olefin monomer. The -olefin monomer is more preferably selected from the group consisting of ethylene, propylene-1, butene-1, hexene-1 and octene-1. Olefin homopolymers or polyolefins include, for example, polyethylene, polypropylene and polybutene. Examples of different copolymers of two different monoolefins and at least three interpolymers are ethylene / propylene, ethylene / butene, ethylene / hexene and ethylene / octene copolymers, ethylene / propylene / carbon monoxide polymers, ethylene / styrene interpolymers and ethylene / Vinyl acetate copolymers. The EAODM interpolymers of the present invention may also be blended with conventional ethylene / propylene / diene monomers (EPDM) or EAODM interpolymers having an ethylene content of up to 80% by weight. Preferred polyolefins for blending with the interpolymers of the present invention are polyethylene (PE), polypropylene (PP) and blends thereof. The term "PE" includes HDPE, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and ultra low density polyethylene (ULDPE).

The interpolymers and blends thereof of the invention can be crosslinked or cured using conventional processes and compounds.

Suitable peroxides for crosslinking or curing are trade name bullcups. (VULCUP ) Hercules, Inc. Available from Hercules, Inc. , A series of vulcanizing and polymerization reagents, including '-bis (t-butylperoxy) -diisopropylbenzene, trade name Di-cup (Di-cup Lupesol, manufactured by Elf Atochem, North America, as well as a series of the above reagents including dicumyl peroxide available from Hercules, Inc. (Lupersol ) Trioxide, manufactured by Peroxide and Moury Chemical Company (Trigonox ) Organic peroxides. Lupesol Peroxide is Lupesol 101 (2,5-dimethyl-2,5-di (t-butylperoxy) hexane), lupesol 130 (2,5-dimethyl-2,5-di (t-butylperoxy) hexyn-3) and lupesol 575 (t-amyl peroxy-2-ethylhexanoate). Other suitable peroxides are 2,5-dimethyl-2,5-di- (t-butyl-peroxy) hexane, di-t-butyl-peroxide, 2,5-di (t-amylperoxy) -2 , 5-dimethylhexane, 2,5-di- (t-butylperoxy) -2,5-diphenylhexane, bis (alpha-methylbenzyl) peroxide, benzoyl peroxide, t-butyl perbenzoate and bis (t-butylperoxy) -diisopropylbenzene.

Peroxides may be added by any conventional method known to those skilled in the art. If process oils are used to prepare polymer blends and other compositions comprising the EAODM interpolymers of the invention, the peroxide may be injected during the preparation of the blend or composition in solution or dispersion in process oil or other dispersing aids. Peroxides may also be fed into the process apparatus at the point where the polymer blend or composition is in the molten state. The concentration of peroxide in solution or dispersion varies over a wide range, but concentrations of 20-40% by weight based on the weight of the solution or dispersion provide acceptable results. The solution or dispersion can also be mixed with and absorbed with anhydrous and anhydrous blended polymer pellets. If the peroxide is a liquid, it can be used as it is, without having to prepare it first as a solution or dispersion in process oil, for example. In other words, the liquid peroxide can be added to the high speed blender with anhydrous polymer pellets, and the blender content can be mixed for a short period of time, and then the content can be left until the absorption action is considered complete. The absence of a separate and identifiable liquid peroxide fraction may be considered complete. At small scale, the mixing takes place for 30-45 seconds in a Welex Papenmeier-type TGAHK20 blender (Pafenmeier Corporation) and then left to stand for 30 minutes. More preferred processes include introducing peroxides into the compounding device together with the polymer pellets as a solid when the polymer pellets enter the compounding device, such as at the inlet of the extruder. A separate preferred process includes adding peroxide to the polymer melt in a compounding device, such as a Haake, Banbury mixer, Farrel continuous mixer or Buss kneader. It is also possible to introduce anhydrous blends of preformed solid peroxides and polymer pellets into the device. Peroxides are suitably present in amounts ranging from 0.05 to 10 weight percent based on total polymer weight in the blend or composition. Low levels of peroxide may not show measurable gel content as measured by boiling xylene extraction, but demonstrate that it improves fluidity to a discernible degree over the same composition that still does not contain peroxide. In other words, the amount of peroxide must be suitable to at least partially result in crosslinking of the EAODM interpolymer of the present invention. Peroxide contents above 10% by weight produce materials that are too brittle to be practical.

For efficient peroxide crosslinking, the sample needs to be heated for a time sufficient to decompose the peroxide and thus generate free radicals for crosslinking. Depending on the peroxide, the crosslinking may be initiated at temperatures ranging from 70 ° C. to 80 ° C. (if using a low temperature peroxide) to temperatures ranging from 220 ° C. to 230 ° C. (if using a high temperature peroxide). Can be. Crosslinking times can vary from as short as a few minutes up to 30 minutes. One skilled in the art can determine the time and temperature required for peroxide crosslinking based on known half-life temperature data for various peroxides.

Sulfur and phenolates (alkylphenol formaldehyde resins) and silicone hydrides serve as functional substitutes for peroxides. Sulfur results in satisfactory results at levels of 1-8% by weight based on the total weight of polymer in the blend or composition. Phenolates such as 2,6-dihydroxymethyl alkylphenols also result in satisfactory results at levels of 1-15% by weight based on the total weight of polymer in the blend or composition. Silicone hydrides produce satisfactory results at levels of 1-10% based on the total weight of polymer in the blend or composition.

As mentioned above, crosslinking can also occur by EB irradiation. One advantage of using EB irradiation is that, if desired, crosslinked polymer systems with at least partial crosslinking of the EAODM interpolymers of the invention can be made without the use of peroxides or other crosslinking aids. Preferred doses of EB irradiation range from 0.1 Mrad to 30 Mrad, preferably from 0.1 Mrad to 10 Mrad, more preferably from 0.1 Mrad to 8 Mrad, most preferably from 0.1 Mrad to <5 Mrad. Although doses above 30 Mrad (eg 70 Mrad) may be used, doing so simply increases costs without providing offsetting physical property improvements sufficient to justify the increase in cost. The actual irradiation dose required will depend on various variables including the source of irradiation, the intensity of the irradiation, the thickness of the polymer, material or article being crosslinked, and the environment and other factors. A preferred source of radiation is a high energy beam from an electron accelerator. The high energy beam provides a suitable curing dose and a processing speed of 1200 meters per minute. Various types of high power electronic linear accelerators are commercially available. Electrocurtains are required because the radiation levels required to achieve crosslinking in the EAODMs of the present invention are relatively low. (Electrocurtain Low power units such as (Energy Science, Inc., Wilmington, Mass.) Provide sufficient radiation. As mentioned above, other sources of high energy radiation such as gamma rays can also be used.

Crosslinking can additionally occur via UV irradiation. In this embodiment, the interpolymer composition of the present invention may preferably comprise one or more photoinitiator reagents. Suitable photoinitiators include benzophenone, ortho- and para-methoxybenzophenone, dimethylbenzophenone, dimethoxybenzophenone, diphenoxybenzophenone, acetophenone, o-methoxy-acetophenone, acenaphthequinone, methyl ethyl ketone, valerian Rophenone, hexanophenone, (x-phenyl-butyrophenone, p-morpholinopropiophenone), dibenzosuberon, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, 3-o -Morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, (x-tetrarone, 9-acetylphenanthrene, 2-acetylphenanthrene, I 0-T Oxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, I-indanon, 1,3,5-triacetylbenzene, thioxanthene-9-one, xanthene-9-one, 7-H-benzophenanthracene-7-one, benzoin tetrahydropyranyl ether, 4,4'-bis (dimethylamino) -benzophenone, F-acetonaphtone, 2'-acetonaphtone, acetonaphtone And 2,3-butane On, benzalanthracene-7,12-dione, 2,2-dimethoxy-2-phenylacetophenone, x-diethoxy-acetophenone, cw-dibutoxyacetophenone, anthraquinone, isopropyl thioxanthone and the like Polymeric initiators include, but are not limited to, poly (ethylene / carbon monoxide), oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], polymethylvinyl ketone And polyvinylaryl ketones Since photoinitiators generally provide faster and more efficient crosslinking, it is desirable to use photoinitiators in combination with UV irradiation.

Commercially available photoinitiators include benzophenones, anthrones, xanthones, and other 2,2-dimethoxy-2-phenylacetophenones (Irgacure 65 1); Igakur including 1-hydroxycyclohexylphenyl ketone (Igaku 184) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-I-one (Igaku 907) (Irgacure ) Photoinitiator (Ciba-Geigy Corp.). Most preferred photoinitiators not only move less from the formulated resin but also have low vapor pressure at the extrusion temperature and have sufficient solubility in the polymer or polymer blend to achieve good crosslinking efficiency. Vapor pressure and solubility or polymer miscibility of many conventional photoinitiators can easily be improved if the photoinitiators are derivatized. Derivatized photoinitiators include, for example, high molecular weight benzophenone derivatives such as 4-phenylbenzophenone, 4-aprilyloxybenzophenone, 4-dodecyloxybenzophenone and the like. The photoinitiator may be covalently bound to the interpolymer of the invention or to the polymer diluent as described below. Thus, the most preferred photoinitiator is one that is substantially non-mobile from the polymeric material.

The radiation should be emitted from an irradiation source capable of emitting radiation in the wavelength of 170 to 400 nanometers (nm). The radiation dose is at least 0.1 J / cm 2, preferably 0.5 to 10 J / cm 2, most preferably 0.5 to about 5 J / cm 2. The dose required for a particular application may depend on the arrangement of the layers in the film, the composition of the layers, the temperature of the irradiated film and the particular wavelength used. The dose required to induce crosslinking for any particular set of conditions can be determined by one skilled in the art.

EP 0 490 854 A2 teaches a continuous process of crosslinking polyethylene with UV light.

The EAODM interpolymers of the invention can be modified or grafted with other monomers. Any unsaturated that is organic, contains one or more ethylenically unsaturated moieties (eg, one or more double bonds) and one or more carbonyl groups (--C═O) or is an unsaturated alkoxysilane and may be grafted to the EAODM interpolymer Prepared compounds can also be used. The grafted interpolymer can be blended with other natural or synthetic polymers in the same manner as the non-grafted EAODM interpolymer.

Suitable monomers for grafting or modification include unsaturated carboxylic acids as well as anhydrides, esters and salts of both acids (both metal and nonmetal) and unsaturated alkoxysilanes. The unsaturated carboxylic acid monomer preferably comprises a carbonyl group and a conjugated ethylenically unsaturated moiety. These acids include, for example, maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, alpha-methyl crotonic acid and cinnamic acid. Unsaturated alkoxysilanes include, for example, vinyltrimethoxysilane and vinyltriethoxysilane. The monomer is most preferably maleic anhydride.

The grafted EAODM interpolymer has a minimum content of unsaturated compounds or grafted monomers of at least 0.01 wt%, preferably at least 0.05 wt%, based on the weight of the grafted EAODM interpolymer. Unsaturated compound content may vary from minimum to upward depending on convenience, but is typically at most 10% by weight, preferably at most 5%, more preferably at most 2% by weight based on the weight of the grafted EAODM interpolymer. .

Unsaturated compounds may be grafted to EAODM interpolymers by known techniques such as those taught in US Pat. No. 3,236,917 and US Pat. No. 5,194,509, the relevant teachings of which are incorporated herein. For example, US Pat. No. 3,236,917 introduces a polymer into a two-roll mixer and mixes at a temperature of 60 ° C. The unsaturated organic compound is then added with a free radical initiator such as benzoyl peroxide and the components are mixed at 30 ° C. until grafting is complete. In US Pat. No. 5,194,509, the process is similar except that the reaction temperature is higher (eg, 210 to 300 ° C.), and that no free radical initiator is used or at reduced concentration.

Preferred alternatives for grafting are taught in US Pat. No. 4,950,541, which is incorporated herein by reference and is part of this specification. U.S. Patent No. 4,950,541 teaches the use of a twin screw non-volatile extruder as a mixing device in column 4, lines 16-28. When using such a device, the EAODM interpolymer and the unsaturated compound are properly mixed with each other and react in the presence of free radical initiators at temperatures above the EAODM interpolymer mpt in the extruder. Unsaturated compounds are preferably injected into the molten EAODM in the extruder zone maintained under pressure.

In another embodiment of the present invention, the graft-modified EAODM interpolymer is anhydrous blended or melt blended with other thermoplastic polymers and then molded or extruded into shaped articles. Such other thermoplastic polymers include any polymers that are miscible with the grafted EAODM interpolymers, and include grafted and grafted stars as well as olefin and non-olefin polymers and engineering thermoplastics. The amount of graft-modified EAODM interpolymer blended with one or more other polymers varies and includes the properties of the other polymer (s), the intended end use of the blend, the presence or absence of additives, and the properties of such additives, if present. Depends on many factors. In applications where the grafted ethylene interpolymer is blended with other polyolefin polymers (eg, non-grafted ethylene interpolymers or conventional polyolefin polymers (LLDPE, HDPE, PP)), the blend composition is applied to the total weight of the blended polymer. Graft-modified ethylene interpolymer (s) on the basis of 70 wt% or less, preferably 50 wt% or less, most preferably 30 wt% or less. The presence of graft-modified EAODM interpolymers in all these blends for engineered materials and wire and cable compositions provide impact and / or strength properties to the materials and compositions.

In other embodiments, the graft-modified EAODM interpolymers comprise a relatively small amount, for example, as small as 10% by weight of the final product to 100% by weight of the final product. In applications where the paintability of the final product is important, the graft-modified EAODM interpolymer content in the range of 10 to 50% by weight, based on the total weight of the final product, may not be applied to molded articles (eg, polyethylene, Articles made from polyolefins such as polypropylene). Graft-modified EAODM interpolymer content of less than 10% by weight provides little or no advantage in improving the paintability of polyolefins. Conversely, the properties of the final product, such as flexural modulus, compared to articles made without graft-modified EAODM interpolymers, although using a graft-modified EAODM content of more than 50% by weight (eg, at least 70% by weight). Is unacceptably low, while other properties such as thermal denaturation may be too high.

The EAODM interpolymers of the present invention may be compounded with one or more materials that are typically added to the polymer, whether or not graft-modified or graft-modified, or blended with other polymers. These materials include, for example, process oils, plasticizers, special additives and pigments. These materials may be compounded with the EAODM interpolymer or blend comprising it before or after the EAODM interpolymer crosslinking occurs. The choice of such materials and their addition to EAODM interpolymers and compounds containing such interpolymers is within the ability of those skilled in the art.

Process oil is often used to reduce any one or more of the viscosity, hardness, modulus and cost of certain compositions. The most common process oils have a specific ASTM name depending on whether they are classified as paraffinic, naphthalene or aromatic oils. In general, those skilled in the art of processing elastomers, particularly EAODM compositions, can recognize which type of oil is most beneficial. Useful amounts of process oils are in the range of more than 0 up to 200 parts by weight per 100 parts by weight of the EAODM interpolymer.

Advantageously, various special additives can be blended with the interpolymers of the present invention to make useful compositions. Special additives include antioxidants; Surface tension modifiers; Antiblocking agents; Glidants; Antimicrobial agents such as organometallic; Isottazolone, organosulphur and mercaptan; Antioxidants such as phenolic, secondary amines, popites and thioesters; Antistatic agents such as quaternary ammonium compounds, amines and ethoxylated, propoxylated or glycerol compounds; Fillers and reinforcing agents such as carbon black, glass, metal carbonates (eg calcium carbonate), metal sulfates (eg calcium sulfate), talc, clay or graphite fibers; Hydrolysis stabilizers; Glidants such as fatty acids, fatty alcohols, esters, fatty amines, metal stearates, paraffinic and microcrystalline waxes, silicones and orthophosphoric acid esters; Mold release agents such as fine particle or powder solids, soaps, waxes, silicones, polyglycols and complex esters such as trimethylolpropane tristearate or pentaerythritol tetrastearate; Pigments, dyes and colorants; Plasticizers, for example esters of dibasic acids (or their anhydrides) with monohydric alcohols (eg o-phthalates, adipates and benzoates); Heat stabilizers such as organotin mercaptide, octyl esters of thioglycolic acid and barium or cadmium carboxylates; Far-infrared stabilizers such as hindered amines, o-hydroxy-phenylbenzotriazoles, 2-hydroxy, 4-alkoxyenzophenones, salicylates, cyanoacrylates, nickel chelates and benzylidene Malonate and oxalanilide; And zeolites, molecular sieves and other known deodorants. Preferred hindered phenolic antioxidants are Iganox available from Ciba-Geigy Corporation (Irganox 1076 is an antioxidant. Each of these additives, if used, of greater than 0 to 45% by weight, preferably 0.001 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, based on the total composition weight Present in quantities. If one or more special additives may be present, the amount of each additive is selected such that the total additive content is 90 wt% or less based on the total composition weight.

Blends with EAODMs or other polymers of the present invention may be compounded with one or more other materials and additives to extrude profiles, parts, using any one of a number of conventional methods for processing thermoplastic or thermoset elastomers. It can be made from a variety of molded articles including, but not limited to, sheets, belts, wire and cable insulators, foaming agents, shrink tubing, and films. EAODMs, blends and obtained compounds can also be molded, spun or stretched into films, fibers, multilayer laminates or extruded sheets, coated or thin coextruded sheets, or compounded with one or more organic or inorganic materials in machines suitable for the purpose. Can be. The molded articles may be multilayer.

The following examples are illustrative, but do not limit the invention, explicitly or implicitly. Unless indicated otherwise, all parts (pbw) and percent (% by weight) are parts by weight and weight percent based on total weight. Examples of the invention are indicated in Arabic numerals, and control examples are shown in alphabetical characters.

Experiment

Examples 1-4 and Control Examples A-D

Polymer manufacturing

Examples 1-4 (Interpolymer of the Invention) and Control Example A were prepared using a 3.8 liter (l) stirred reactor providing continuous addition of reactants and continuous removal of polymer solution, non-volatile and polymer recovery. The catalyst system is (t-butylamido) -dimethyl ( ^{5-methyl-2--s-} indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene CGC, tris (phenyl) borane (FAB) co-catalyst and modified methyl alumoxane (MMAO), pentafluorophenyl It was a scavenging compound. Tables 1D-4 show the physical properties of Examples 1-4 and Control Example A.

Combine ethylene (C ₂ ), propylene (C ₃ ) and hydrogen (H ₂ ) into one stream, then combine this stream with a mixed alkane solvent (Isopar-E , Exon Chemical Inc. (Available from Exxon Chemical Inc.) and a diluent mixture comprising polyene (ENB) to form a combined feed mixture. The combined feed mixture was continuously injected into the reactor. The catalyst (Cat) and the blend of cocatalyst (Cocat) and scavenging compound (Scav) were combined into a single stream and this was continuously injected into the reactor.

Table 1A shows the flow rates of solvent, C ₂ , C ₃ and ENB in phr (pounds per hour). Table 1B shows the concentrations and flow rates of Cat, Cocat and Scav in parts per million (ppm) and pounds per hour (ppr), respectively. Table 1B also shows the Cocat / Cat and Scav / Cat ratios. Table 1C shows the hydrogen flow rates (sccm; standard cubic centimeters), amount of polymer produced (phr), reactor temperature (Temp) (° C.) and reactor pressure (MPa; megapascal).

The reactor discharge stream was introduced continuously with a separator to separate the molten polymer from the solvent and unreacted C ₂ , C ₃ , H ₂ and ENB continuously. The molten polymer was cooled in a water bath or pelletizer and the cooled polymer was cut or pelletized into strands and the resulting solid pellets were collected.

Monomer and Solvent Flow Rate (phr) Example Solvent flow rate Ethylene flow rate Propylene flow rate ENB flow rate A 36.9 4.5 2.37 0.60 One 38.9 4.7 0.86 0.41 2 38.9 4.7 0.82 0.04 3 38.9 4.5 0.44 0.34 4 31.2 4.0 0.41 0.03

Catalyst component flow rate Examples & Control Examples Cat concentration (ppm) Cat flow rate (phr) Cocat concentration (ppm) Cocat flow rate (phr) Scav concentration (ppm) Scav flow rate (phr) Cocat / Cat Ratio (B / Ti) Scav / Cat Ratio (Al / Ti) A 19.9 0.261 950 0.176 64 0.18 3 3.9 One 11.5 0.641 4611 0.513 43 0.58 3 6 2 11.8 0.494 461 0.405 43 0.46 3 6 3 24.7 0.546 965 0.448 75 0.61 3 6 4 24.7 0.441 965 0.362 75 0.49 3 6

Reactor condition Examples and Control Examples H ₂ flow rate (sccm) Polymer Production (phr) Reactor temperature (℃) Reactor pressure (MPa) A 52 4.21 121 3.102 One 106 5.00 120 2.103 2 92 4.05 121 2.344 3 260 3.82 130 2.985 4 286 3.42 130 2.841

Composition data Examples and Control Examples C ₂ (% by weight) C ₂ (mol%) ^* C ₃ (% by weight) C ₃ (mol%) ^* ENB (% by weight) C ₂ / C ₃ weight ratio One 84.9 92.7 9.9 7.3 5.2 8.58 2 85.3 90.5 13.4 9.5 1.3 6.37 3 88.7 95.5 6.2 4.5 5.1 14.3 4 94.1 96.9 4.6 3.1 1.3 20.5 A 72.1 82.8 22.4 17.2 5.5 3.2

(* Based on C ₂ and C ₃ content.)

Gel Permeation Chromatography (GPC) Data Examples and Control Examples M _w M _n MWD (M _w / M _n ) One 117,500 57,100 2.06 2 115,600 53,200 2.17 3 110,900 49,500 2.24 4 119,700 56,500 2.12 A 138,100 68,500 2.02

Density and Thermal Properties Data Examples and Control Examples Density (g / cc) Crystallization Initiation (℃) Peak Melting Point (℃) Crystallinity (%) Heat of fusion (J / g) Heat of fusion (cal / g) Tg ^* (℃) One 0.899 64.7 72.6 19.6 57.2 13.7 -20.1 2 0.898 73.0 80.5 20.5 59.9 14.3 -27.9 3 0.909 80.0 87.3 26.8 78.3 18.7 -20.0 4 0.916 96.1 105.5 39.9 116.5 27.8 -22.5 A 0.881 35.9 45.5 15.5 45.3 10.8 -35.0

Physical property data Examples & Control Examples Tensile Strength at Yield (MPa) Tensile Strength at Break (MPa) Yield at Yield (%) Elongation at Break (%) Mooney viscosity ^* One 2.91 21.7 31 575 30.7 2 3.41 12.4 20 686 29.2 3 4.1 23.0 19 579 29.5 4 8.41 16.7 17 756 30.2 A 1.5 9.3 34 718 41.3

* Measured according to ASTM D1646 (ML _{1 + 4} at 125 ° C.).

Probe test

EB irradiation was used to crosslink (a) the interpolymers of Examples 1-4 and (b) the polymers of Control Example BD. Control Example B is an elastomeric ethylene / octene with a density of 0.885 g / cc, melt index (MI) of 1 dg / min (decigram / min) or I ₂ , GPC molecular weight (M _w ) of 125,000 and MWD of 2.0 Engage available from DuPont Dow Elastomers LLC (Engage 8003). Control Example C is from LLDPE (The Dow Chemical Company) with a density of 0.92 g / cc, MI or I ₂ of 1 dg / min, GPC molecular weight (M _w ) of 110,000 and MWD of 4.0 Ethylene / octene copolymer available as Dowlex 2045). Control Example D is an ethylene-vinyl acetate (EVA) copolymer with a density of 0.941 g / cc, a MI of 2.5 dg / min, a GPC molecular weight (M _w ) of 80,000, a MWD of 5 and a vinylacetate content of 18% by weight. Elbox available from E.I.Dupont de Nemoa and Company (Elvax 460). MI measurement applies ASTM D1238 or its modified version (for EVA copolymer) at 190 ° C.

The same two sets of plaques were prepared from Examples 1-4 and Control Example B-D each. The plaques were compression molded to 0.125 inch (0.32 cm) thickness using the following cycle: heated at 190 ° C. for 3 minutes without pressure; Applying a pressure of 18,200 kg while maintaining the temperature at 190 ° C .; Water cooled to ambient temperature (about 25 ° C.) while maintaining a pressure of 18,200 kg; And releasing pressure. One set of seven plaques was used as a control (no irradiation) and the other set of seven plaques was EB irradiated at a dose of 2 Mrad. The data in Table 5 compares the irradiated and unirradiated plaques.

Hot creep was measured as described in Insulated Cable Engineers Association Publication T-28-562, Published 3/81, Revised 1/83. Hot creep testing involves hanging a weight on a dumbbell test specimen in an oven heated to 200 ° C. to generate a stress of 29 psi (200 kPa). When the crosslinking level of the sample was low, the sample elongated to 600% and then reached the bottom of the oven. As used in Table 5 below, "failure" means that the sample reached the bottom of the oven. When the level of crosslinking is high, the sample is less stretched and gives measurable percent elongation. "Hot" creep measurements indicate the degree of crosslinking as hot creep, and the degree of crosslinking is inversely proportional. In other words, the decrease in hot creep value is equivalent to the increase in the degree of crosslinking. Insoluble gel fraction (gel content) was measured as described in ASTM D 2765 using hot xylene as solvent.

Comparison of plaque properties (irradiated vs nonirradiated) Examples and Control Examples Irradiation% gel Irradiated hot creep (%) Non-irradiated% gel Non-irradiated hot creep (%) B <3 failure <3 failure C <3 - <3 failure D 54.2 failure <3 failure One 81.9 220 <3 failure 2 38.9 failure <3 failure 3 84.7 218 <3 failure 4 81.8 525 <3 failure

(-Means no measurement.)

The data in Table 5 shows that the EAODM interpolymers of Examples 1-4 had a higher crosslinking response to EB irradiation compared to the polymers of Control Examples B and C (ie more crosslinked more efficiently as indicated by% gel). Shows. Except for one (Example 2), EAODM polymers provide acceptable hot creep performance.

The theoretical explanation for the difference between Example 2 and Example 4 is based on the evidence set by the difference in crystallinity rather than crosslinking. The interpolymer of Example 2 has a crystallinity of 20.5%, while the interpolymer of Example 4 has a crystallinity of 39.9%. As noted in Radiation Technology Handbook, Richard Bradley, Marcel Dekker, Inc., 1984, p. 106, EB hardening tends to occur in the amorphous portion of the polymer. ENB is C ₂ and It is in the amorphous or amorphous region of the EAODM polymer due to its larger size compared to the -olefin monomer. As such, even with the same percentage of ENB, a higher crystallinity polymer (eg, Example 4 than Example 2) provides a greater concentration of ENB in the amorphous zone. Thus, this leads to higher crosslinking potential. As mentioned above, the increase in crosslinking results in a decrease in elongation in the hot creep test. In view of the relatively low crosslinking potential, one method of increasing hot creep test results of the interpolymer of Example 2 involves increasing the radiation dose from 2 Mard to 4 Mrad or more.

Example 5-8

Four sample compositions, each of Examples 5-8, were prepared from the interpolymers of Examples 1-4, each EAODM interpolymer was 200 grams (g) 2 wt% lupesol using a Hake mixer. Prepared by blending with 130 peroxide (2,5-dimethyl-2,5-dibutylperoxy hexin 3 available from Elf Atochem). Blends were prepared by mixing at 130 ° C. for 4 minutes at a rotation speed of 20 revolutions per minute (20 rpm). After four sample compositions were prepared, each composition was pressed into 0.32 cm plaques for cure testing using a modified process. The modified process applies the following cycles: heating at 130 ° C. for 2 minutes under pressure or force of 18,200 kg; Water cooled to ambient temperature (about 25 ° C.) over 3 minutes while maintaining a pressure of 18,200 kg; Relieve pressure. Samples of each uncured plaque were left for vibration disc rheometer (ODR) tests in accordance with American Society for Testing and Materials test ASTM D-2084. The plaques were cured according to the following cycle. Heated at 180 ° C. with a force of 18,200 kg for 20 minutes; Cool to ambient temperature for 3 minutes while maintaining an applied force of 18,200 kg; And releasing the applied force. Percent gel analysis and hot creep elongation were measured (see Table 6). See Table 7 for ODR data. Plaques prepared from interpolymers of Examples 1-4 without peroxide had less than 2% gel and the hot creep test failed.

Plaque nature Example % Crosslinking gel using peroxide Crosslinked Hot Creep with Peroxide (%) 5 98.5 21.9 6 98.4 15.6 7 97.5 36.6 8 97.5 39.8

ODR data at 180 ° C Example Torque Torque talk T2 (min) T90 (min) 5 0.097 1.081 0.984 0.58 8.54 6 0.107 1.266 1.159 1.10 11.11 7 0.108 1.370 1.262 1.10 11.31 8 0.120 1.416 1.296 1.22 13.40

(Torque values are in kg-m (kg). ODR is measured using ASTM D-2084.)

The results shown in Table 6 and Table 7 confirm that the EAODM interpolymers of the present invention can be crosslinked using peroxides. ODR data indicate that the increase in the ethylene content of EAODM polymers is higher than delta ( ) Generates a torque value. (See Table 1 for ethylene content.) It is recognized that an increase in torque value corresponds to an increase in the degree of crosslinking. This allows the use of lower levels of peroxide than required for EAODM polymers with low ethylene content to achieve the desired degree of crosslinking. High crosslinking can be achieved with less use of expensive peroxides, thus allowing end users to achieve similar crosslink densities at lower cost. In contrast, conventional EAODM polymers prepared from the same monomer but having an ethylene content of up to 80% by weight are low. A higher amount of peroxide is required to generate the torque value and correspondingly achieve the same crosslinking level.

Example 9-10 and Control Example E

The sample composition of Example 9 was prepared from a blend of 90 wt% control Example C polymer and 10 wt% Example 1 interpolymer. The sample composition of Example 10 was prepared from a blend of 70 wt% control Example C polymer and 30 wt% Example 1 interpolymer. 100% by weight of the polymer of Control Example C was used as control and was referred to as Control Example E. The blend is a tumble anhydrous blend of polymer pellets and melt compounded at Leistriz micro 18 millimeters (mm) for idling the anhydrous blended pellets with a Hake 9000 torque rheometer to produce an extruded rod. By providing. Extrusion conditions are shown in Table 8 below.

Extrusion Conditions for Compounding Examples 9-10 and Control Example E Heating zone location Temperature (℃) water jacket Zone 1 190 Zone 2 190 Zone 3 190 Zone 4 190 Zone 5 190 Zone 6 190 Die zone 190 Screw speed 60 rpm Output speed 1.36 kg / hr

The extruded rod was cooled in a water bath and the cooled rod was pelleted. Plaques were prepared using the process described in Examples 1-4 above. One plaque of each example was EB irradiated at a dose of 1 Mrad using a 10 megavolt (MeV) EB unit, and one plaque of each example was EB irradiated at a 2 Mrad dose. One plaque of each example without irradiation exposure was left for use as a control. The degree of crosslinking was used as in Example 1-4.

Comparison of plaque properties (irradiated vs nonirradiated) Examples and Control Examples Irradiation at 1 Mrad (gel%) Irradiation at 2 Mrad (gel%) Unirradiated at 0 Mrad (% gel) E <3 <3 <3 9 35.6 58.0 <3 10 59.3 67.0 <3

The results in Table 9 demonstrate that addition of 10-30% by weight of a representative EAODM interpolymer of the present invention can increase the gel response (degree of crosslinking) to EB irradiation in LLDPE (Control Example E). The gel levels of the compositions of Examples 9 and 10 at 1 Mrad and the compositions of Example 9 at 2 Mrad are within the 20-60 wt% gel content range desirable for free rise foam expansion. More preferred is a gel level of 30-40% by weight. (Reference: Polymeric Foams, D. Klempner and K. Frish, ed., Chapter 9, pp. 201-203, Hanser Publishers, 1991). Increasing the gel reaction at low EB doses such as 1 Mrad will significantly increase the capacity of existing EB units. Those skilled in the art can readily determine the optimal level of EAODM and radiation dose for LLDPE and other polymers disclosed herein.

Example 11 and Control Example F-G

Propylene copolymer (Himont with melt flow rate (ASTM D 1238) of 2, density 0.9 g / cc (ASTM D 792A-2) and flexural modulus (ASTM D 790B) of 140,000 psi (965 MPa) Profax available on the market (Profax 8623) Control Example F containing 100% by weight was used as a control. The compositions of Control Example G and Example 11 each contain 70% by weight of Control Example F copolymer and 30% by weight of the second polymer (copolymer of Control Example C for Control Example G, with respect to Example 11). Interpolymer of Example 1). Test plaques were prepared using the process of Examples 1-4. One set remained the control (no irradiation) and the remaining sets were exposed to EB irradiation doses of 2, 5 and 10 Mrads, respectively. Gel content was measured using the process described in Examples 1-4. Table 10 summarizes the gel test results.

Comparison of plaque properties (irradiated vs nonirradiated) Examples and Control Examples Irradiated at 2 Mrad (% gel) Irradiation at 5 Mrad (% gel) Irradiation at 10 Mrad (% gel) Unirradiated at 0 Mrad (% gel) F <3 <3 <3 <3 G <3 21.2 31.5 <3 11 31.4 37.4 44.9 <3

The copolymer of Control Example F in Table 10 did not show a gel response to e-beam irradiation. Polypropylene is known to undergo chain break rather than crosslinking under EB irradiation. See Radiation Technology Handbook, pp. 114-129. The composition of Control Example G showed only a slight irradiation response at doses of 5-10 Mrad. On the other hand, the sample composition of Example 11 had an irradiation reaction at a dose of 2 Mrad comparable to the irradiation reaction at 10 Mrad of the control example G composition. Other EAODMs representing the present invention will have similar results when mixed with the polypropylene of Example 11 or other polymers disclosed herein.

Example 12 and Control Example H

Table 11 summarizes the flexural modulus (ASTM D-790) and tensile / extension (ASTM D-638) properties for the interpolymers of Control Examples A and 3, and the compositions of Control Examples H and 12. will be. The sample compositions of Control Example H and Example 12 were each 30 using the process and apparatus of Example 5-8 except that the time was increased to 5 minutes, the temperature to 190 ° C., and the rotation speed to 40 rpm. Weight percent Control Example A interpolymer and Example 3 interpolymer were prepared by blending with 70 weight percent Control Example C copolymer. The interpolymers of Control Examples A and 3, and the compositions of Control Examples H and 12 were converted to test plaques using the process of Examples 1-4, and the plaques were subjected to flexural modulus and tensile / elongation testing. .

Comparison of Physical Properties of Control Example H and Example 12 (Uncured System) Property (unit) Control Example A Control Example H Example 3 Example 12 Flexural Modulus (MPa) 12.7 100.6 74.4 138.2 Tensile Strength at Break (Mpa) 9.3 19.1 23 22.8 Elongation at Break (%) 718 759 579 816 Tensile Strength at Yield (Mpa) 1.5 7.2 4.1 9.2 Yield at Yield (%) 34 62 19 7.1

The data in Table 11 show that the interpolymer of Example 3 has better mechanical strength than the Control Example A interpolymer as shown by having higher flexural modulus and tensile properties than the Control Example A interpolymer. This superiority is maintained even after blending with the copolymer of Control Example C, as can be seen by comparing the properties of Control Example H with the properties of Example 12.

Example 13-14 and Control Example I-J

The interpolymers of Control Example A and Example 3 were prepared in 2% by weight based on the polymer weight, except that the temperature was reduced to 130 ° C. and the rotational speed was reduced to 10 rpm. Peroxide (Lupesol 130, blended with 2,5-dimethyl-2,5-di- (t-butylperoxy) hexin-3) available from Elf Atochem to obtain Control Example I and Example 13, respectively. In the same way, 70% by weight of the copolymer of Control Example C was blended with 30% by weight of Example 3 interpolymer and Control Example A interpolymer, respectively, to combine the blends of Example 14 and Control Example J Prepared with 2% by weight of the same peroxide. The blend was converted to test plaques and the plaques were exposed to curing conditions using the process of Examples 5-8. Table 12 summarizes the flexural modulus and tensile / elongation test results.

Comparison of Physical Properties of Control Examples I-J and Examples 13-14 (Peroxide Curing) Property (unit) Control Example I Control Example J Example 13 Example 14 Flexural Modulus (MPa) 12.7 100.6 74.4 138.2 Tensile Strength at Break (MPa) 9.3 19.1 23 22.8 Elongation at Break (%) 718 759 579 816 Tensile Strength at Yield (MPa) 1.5 7.2 4.1 9.2 Yield at Yield (%) 34 62 19 71

The data in Table 12 shows that the interpolymers of peroxide cured Example 13 have superior mechanical properties compared to that of Control Example I. The peroxide cured blend composition (Example 14) also has superior mechanical properties compared to the blend composition of peroxide cured control Example J. This superior physical property is even more surprising when considering that the interpolymer of Control Example A used in these blends has a higher M _w (higher Mooney) than the EAODMs of the present invention. These improved mechanical properties allow these EAODMs to be used in blends of other polymers disclosed herein where preservation of mechanical properties is important. Examples of such improved blends include more stable crosslinked polyolefin foams, stronger crosslinked wire and cable jackets, and more rigid, harder crosslinked articles.

Example 15 and Control Example K

The interpolymer and polypropylene (PP) homopolymer of Example 3 (Profax available from Himont using the processes and apparatus of Examples 9 and 10) PD-191) was blended at a weight ratio of 70/30 (PP / Example 3) to prepare the composition of Example 15. The extrudate was compression molded into two sets of test plaques using the process described for the irradiation test. The PP homopolymer alone was compression molded to make two sets of control Example K test plaques. One set of test plaques was EB irradiated at a dose of 2 Mrad. IZOD bars were cut at all test plaques and the bars were tested for notched IZOD impact strength (ASTM D-256-Method A) at two different temperatures (23 ° C. and 0 ° C.). Table 13 summarizes the IZOD test results in kilojoules per minute (kJ / m).

IZOD impact strength data on polypropylene / EAODM blends (kJ / m) Examples and Control Examples Before irradiation (23 ℃) Before irradiation (0 ℃) After irradiation (23 degrees Celsius) After irradiation (0 degrees Celsius) K 0.080 0.021 0.043 0.043 15 0.821 0.080 0.48 0.085

These results clearly show that the interpolymer of the present invention improves the IZOD impact strength of polypropylene both before and after irradiation. It is expected that similar results will be obtained when this interpolymer of the invention and other EAODMs are blended with any of the other polymers disclosed herein.

Example 16-18 and Control Example L-P

Three interpolymers (control examples L, M and N) each having an ethylene content of less than 75% by weight were prepared using the methods of control examples A and 1-4. Compositions and physical properties for the interpolymers of Control Example L-N are described in Tables 14 and 15.

The compositions of Examples 16, 17 and 18 were prepared from different amounts of the interpolymers of Control Example N and blends of the interpolymers of Examples 1, 3 and 4, respectively. The composition of Control Example P was prepared from a blend of interpolymers of Control Examples M and N. The amount of each polymer was chosen such that the average ethylene weight percent of the blend was about 70 weight percent. Blends were prepared using a Hake mixer. The polymer was added to a mixer set at a temperature of about 120 ° C. The rotation speed was 30 rpm. Under this condition the polymer was melted and blended for 10 minutes, the temperature of the mixer was reduced to about 100 ° C. and the rotational speed was increased to 60 rpm.

The compositions of Examples 16-18 and Control Example P were prepared by adding carbon black and oil to a mixer and mixing for about 3 minutes. Sulfur and other curing agents were added to the mixer and mixed for about 2 minutes. After a total of 15 minutes, the rotation was stopped and the uncured blend was removed from the mixer. The composition represented by Control Example O, comprising 100% by weight of the interpolymer of Control Example L, was prepared using the same apparatus and method. Table 16 summarizes the blend compositions of Examples 16-18 and Control Examples O-P.

Composition data Control Example C ₂ (% by weight) C ₃ (% by weight) ENB (% by weight) Crystallinity (%) Heat of fusion (cal / g) Tg (℃) Melting point (℃) L 69.0 26.0 5.0 11.5 8.0 -38.1 32.0 M 74.5 23.7 1.8 16.7 11.7 -34.8 68.9 N 48.3 47.0 4.7 N.A. N.A. -47.5 N.A.

(N.A. means that the EAODM interpolymer is amorphous and not applicable.)

GPC data Control Example M _w M _n MWD (M _w / M _n ) L 105,000 50,000 2.10 M 97,200 38,700 2.51 N 114,000 50,200 2.27

Composition data ingredient Control Example O Control Example P Example 16 Example 17 Example 18 Control Example L 100 Control Example M 80 Control Example N 20 40 50 60 Example 1 60 Example 3 50 Example 4 40 Carbon Black N-550 80 80 80 80 80 Shipment 2280 Oil 50 50 50 50 50 Butyl Zymate 2 2 2 2 2 MBT One One One One One TMTD 0.5 0.5 0.5 0.5 0.5 Zinc oxide 5 5 5 5 5 Stearic acid One One One One One sulfur 1.5 1.5 1.5 1.5 1.5 Average Ethylene Content (wt%) 69 69 70 68 67

(Carbon Black N-550 is available from Engineered Carbons.

Sunwave 2280 is a paraffinic plasticizer available from Sun Refining.

Butyl zimate is zinc dibutyl dithiocarbonate available from RT Vanderbilt.

MBT is mercaptobenzo-thiazole.

TMTD is tetramethyl thiuram disulfide.)

The curing (vulcanization) properties of Examples 16-18 were measured on a rotoless cure meter (movable die rheometer -MDR) according to ASTM D-5289 at a temperature of 160 ° C. The minimum torque (M _L ) and maximum torque (M _H ) (both expressed in Newton-meters (NM)), and time (T ₉₅ ) values up to 95% of the maximum torque are shown in Table 17.

Test specimens for shrinkage test (TR) at low temperature were prepared and tested according to ASTM D-1329. Test specimens were cut from the vulcanized plaques prepared from each composition. Each shaped plaque was vulcanized at 160 ° C. for a total of T ₉₅ + 3 minutes. Table 18 shows the temperature at which the test specimens shrink 50% (TR50).

The results in Tables 17 and 18 show that the interpolymers of the present invention can be vulcanized at approximately the same rate as the control EPDM (Control Example O) and control EPDM blend (Control Example P), and also have better TR50 values. Shows that there is. Surprisingly, shrinkage temperature data indicate that the addition of crystalline EAODM polymer can improve the performance of the vulcanized blend. Lower shrinkage temperatures indicate that they are more elastic or rubber-like materials at lower temperatures. This improved low temperature performance was unexpected because the shrinkage temperature increased with increasing crystallization tendency.

Vulcanization Properties Examples and Control Examples M _H (Nm) M _L (Nm) T ₉₅ (min) O 2.26 0.17 12.7 P 1.73 0.1 17.9 16 2.35 0.19 11.6 17 2.08 0.12 14.1 18 1.76 0.12 14.6

Shrinkage data Examples and Control Examples TR 50 (℃) O 3.9 P 8.0 16 -1.8 17 -3.4 18 -12.9

Example 19-21

The interpolymer of Examples 19-21 uses the method of Examples 1-4, with a production rate 10 times (10 ×) greater than that of Examples 1-4 (ie, the reactor is 10 times larger, Flow rate 10 times greater). Table 19-22 shows the composition and physical properties of Examples 19-21.

Composition data Example C ₂ (% by weight) C ₂ (mol%) ^* C ₃ (% by weight) C ₃ (mol%) ^* ENB (% by weight) C ₂ / C ₃ weight ratio 19 91.8 95.9 4.5 3.1 3.6 20.4 20 93.6 97.7 1.7 1.2 4.7 55.1 21 85.4 91.4 10.6 7.7 4.0 8.1

(*: Based only on C ₂ and C ₃ content.)

GPC data Example M _w M _n MWD (M _w / M _n ) 19 95,300 49,400 1.93 20 93,200 46,300 2.01 21 91,700 40,700 2.25

Density and Thermal Properties Data Example Density (g / cc) Crystallization Initiation (℃) Peak Melting Point (℃) Crystallinity (%) Heat of fusion (J / g) Heat of fusion (cal / g) Tg ^* (℃) 19 0.922 - 108 37 108.9 26.1 -15 20 0.924 - 110 38 113.1 27.1 -10 21 ND - 88 23 67.6 16.2 -24

(-Means no measurement.)

Tensile Strength, Elongation and Viscosity Data Examples and Control Examples Tensile Strength at Yield (MPa) Tensile Strength at Break (MPa) Elongation at Break (%) Elongation at Break (%) Mooney viscosity * 19 7.9 21.6 7 666 16.9 20 8.9 19.5 8 706 15.2 21 - - - - -

* Measured according to ASTM D1646 (ML _{1 + 4} at 25 ° C.)

Examples 22-30 and Controlled Example Q-T

The interpolymers of Examples 1, 3, 19 and 20 were blended with various polymers and additives to obtain the compositions of Examples 22-30. The various polymers were blended with additives and in some cases with other polymers to obtain compositions of control examples Q, R, S and T. The compositions of Examples 22-30 and Control Example Q-T are shown in Tables 23-25. Petrorothene NA 940000, a low density polyethylene (LDPE), was obtained from Equistar Corporation. These LDPE polymers have a melt flow rate of 0.25, a polymer density of 0.918 and a crystal melting point of 104 ° C. SMR CV-60, a natural rubber, was obtained from Akrochem Corporation, which is characterized by a 60 Malaysia Mooney viscosity stabilized Standard Malaysian Rubber (SMR). Plioflex 1712 and Plioflex 1502, styrene-butadiene rubber (SBR), were obtained from Goodyear Tire and Rubber Company. Plioplex 1712 is characterized as a 46 Mooney viscosity SBR polymer extended with about 37.5 phr (parts per hundred) aromatic process oil. Plioflex 1502 is characterized by a 50 Mooney viscosity SBR polymer. Polybutadiene rubber was obtained from Aldrich Chemical. The additives were sulfur hardeners consisting of carbon black, oil, zinc oxide, stearic acid, and butyl or mate or methyl zate (dimethyl dithiocarbonate available from RT Vanderbilt), MBT, TMTD and sulfur.

Various polymers, interpolymers of Examples 1, 3, 19, and 20, and carbon black, oil, zinc oxide and stearic acid, if present, were added to a Farrell BR half-buri mixer. The temperature of the half beak was about 120 ° C to 150 ° C. The rotation speed was set at about 80 rpm. The mixture was blended for about 5 minutes. The mixture was removed from the beak and made into a sheet on a reliable roll mill. The roll mill was set to a temperature of about 110 ° C. The rotation speed was about 10 rpm. The sheet was cut into strips and added to a Farrell BR beak mixer. During this mixing step, a sulfur curing agent was added at about 100 ° C to about 110 ° C. The rotation speed was set at about 30 rpm. The mixture was blended for about 2 minutes. The mixture was removed and made in sheet form on a releasable roll mill. The roll mill was set at about 100 ° C to 110 ° C. The rotation speed was set at about 10 rpm. Sheets prepared from each blend were cooled and subsequently subjected to additional tests.

Composition data ingredient Control Example Q Control Example R Example 22 Example 23 Example 24 Example 25 Natural rubber SMR-CV-60 100 100 100 100 100 100 LDPE 10 Example 1 10 Example 3 10 Example 19 10 Example 20 10 Carbon Black N-550 50 50 50 50 50 50 Shipment 2280 Oil 6 6 6 6 6 6 Butyl Zymate 2 2 2 2 2 2 MBT One One One One One One TMTD 0.5 0.5 0.5 0.5 0.5 0.5 Zinc oxide 5 5 5 5 5 5 Stearic acid One One One One One One sulfur 1.75 1.75 1.75 1.75 1.75 1.75

Composition data ingredient Control Example S Example 26 Example 27 Natural rubber SMR-CV-60 75 75 75 Plioplex 1712 25 25 25 Example 19 10 Example 20 10 Carbon Black N-550 55 55 55 Shipment 2280 Oil 6 6 6 Butyl Zymate 2 2 2 Mercaptobenzo-thiazole (MBT) One One One Tetramethyl Thiuram Disulfide (TMTD) 0.5 0.5 0.5 Zinc oxide 5 5 5 Stearic acid One One One sulfur 1.75 1.75 1.75

Composition data ingredient Control Example T Example 28 Example 29 Example 30 Plioflex 1502 85 85 85 85 Polybutadiene 15 15 15 15 Example 1 10 Example 19 10 Example 20 10 Carbon Black N-550 60 60 60 60 Shipment 2280 Oil 6 6 6 6 Methyl Zymate 2 2 2 2 Mercaptobenzothiazole (MBT) One One One One Tetramethyl Thiuram Disulfide (TMTD) 0.5 0.5 0.5 0.5 Zinc oxide 5 5 5 5 Stearic acid One One One One sulfur 1.75 1.75 1.75 1.75

The vulcanization properties of the interpolymers of Examples 22-30 and Control Example QT were measured on a Rotational Curing Meter (Movable Die Rheometer-MDR) according to ASTM D-5289. These vulcanization properties were measured at a temperature of 160 ° C. Table 26 shows the minimum torque (M _L ), maximum torque (M _H ) and time to reach 90% of the maximum torque value (T ₉₀ ) for each blend.

Vulcanization Properties Examples and Control Examples M _H (Nm) M _L (Nm) T ₉₀ (min) Q 2.02 0.26 1.3 R 1.77 0.04 1.6 22 1.82 0.27 1.6 23 1.75 0.25 1.7 24 1.73 0.27 1.8 25 1.68 0.17 1.8 S 2.51 0.19 2.0 26 2.24 0.35 2.2 27 2.12 0.17 2.0 T 2.69 0.18 4.6 28 2.4 0.21 5.7 29 2.36 0.23 5.8 30 2.19 0.24 6.4

Test specimens for wear resistance testing were prepared and tested according to ISO 4649-1985 (E). Test specimens were cut from vulcanized plaques prepared from each blend. Each shaped plaque was vulcanized at 160 ° C. for a total of T ₉₀ +5 minutes. Plaque size was about 6.5 mm thick and 7.6 cm x 7.6 cm. Wear data is shown in Table 27 and reported as volume loss for the standard. Lower values are believed to indicate higher wear resistance.

Abrasion Resistance Data Examples and Control Examples Abrasion Resistance (Volume Loss) Q 125.8 R 122.3 22 115.4 23 110.5 24 103.2 25 98.2 S 125.7 26 111.6 27 112.9 T 106.2 28 96.4 29 91.6 30 88.8

Examples 22-30 add the crystalline EAODM of the invention to different rubber formulations (e.g., natural rubber, styrene-butadiene rubber and polybutadiene rubber) when compared to blends that do not include these polymers. It is demonstrated that this is improved without affecting the vulcanization performance as shown in Table 26. Applications that require wear resistance and that benefit from improved wear resistance include pneumatic tires, footwear, and conveyor belts.

Examples 31-44 and Control Example U

Examples 31-44 illustrate the utility of the interpolymers of the invention in foam applications. Data was obtained for different crosslinked formulations. Typical methods for crosslinking foam formulations comprising EAODM polymers include peroxides, sulfur, vinylalkoxysilanes, hydrosilation, phenolic, electron beams, gamma and ultraviolet radiation. Foam data is especially blended with other ethylene interpolymers including low density polyethylene (LDPE), ethylene-vinyl acetate (EVA), ethylene copolymers such as ethylene-octene and ethylene-butene, ethylene-styrene, LLDPE and HDPE polymers This demonstrates the increased foaming power and utility of crystalline EAODM polymers. These data also illustrate the increased foaming capacity of crystalline EAODM polymers when blended with polypropylene polymers including homopolymers and copolymers. Other types of blowing agents (eg, carbonates) may be used that give rise to closed or open foamed foams.

The low density polyethylene (LDPE) of Example 40 was Petrorothene NA 940000 obtained from Iquistar Corporation. Typical properties of this LDPE polymer are a melt flow rate of 0.25, a polymer density of 0.918 and a crystal melting point of 104 ° C. The ethylene-vinyl acetate copolymer of Example 39 is E. I. Elvax 460 from Dupont de Nemoa and Company. Typical properties of this EVA polymer are a density of 0.941 g / cc, a melt flow rate of 2.5 dg / min, a GPC molecular weight (M _w ) of 80,000 and a molecular weight distribution of 5.0 and a vinyl acetate content of 18% by weight.

The interpolymers of Examples 19, 20 and 21 were blended as shown in Table 28 in a Farrell BR beak mixer. For Examples 31-33, blowing agent and activator were added to a Farrell BR half-blow mixer at a melt temperature of about 130 ° C. For Examples 34 and 35, and Control Example U, polypropylene and blowing agent were added to a Farrell BR half-blow mixer at a melt temperature of about 175 ° C. After about 5 minutes of mixing, each formulation was removed from the half and made into a sheet on a releasable roll mill. From this sheet, two compression molded test plaques were prepared. Plaque size was 12.7 cm × 12.7 cm at a thickness of about 0.3175 cm. One set of test plaques was electron beam irradiated at 2 Mrad, while one set of test plaques was electron beam irradiated at 5 Mrad. After irradiation, the plaques were tested for gel content using standard test methods for determining gel content as described in ASTM D-2765 Test Method. Gel content for each plaque after irradiation is shown in Table 29.

Composition data ingredient Control Example U Example 31 Example 32 Example 33 Example 34 Example 35 Example 19 100 Example 20 100 30 Example 21 100 30 Polypropylene 100 70 70 Cellogen AZ 130 6 6 6 6 6 6 Zinc oxide 0 One One One 0 0 Stearic acid 0 0.5 0.5 0.5 0 0

(All quantities are pph (parts per hundred).

Polypropylene was Himont's Profax PD-191.

Celogen AZ130 is azodicarbonamide available from Uniroyal Chemical.)

Gel content data Examples and Control Examples Gel content% at 2 Mrad Gel content% at 5 Mrad Example 31 72 91 Example 32 81 91 Example 33 38 75 Example 34 15 26 Example 35 19 29 Control Example U 0.3 0.5

Bun foams were prepared from Examples 31-33 irradiated at both 2 Mrad and 5 Mrad. A 5.1 cm × 5.1 cm test sample was cut from the compression plaque irradiated and irradiated and placed in a mold cavity of the same size and thickness. The mold cavity was mounted into a heated hydraulic molding press set at 165 ° C. with a molding pressure of 20,000 lbs (9100 kg). The cavity mold was left in the press for about 10 minutes, and then the pressure was released rapidly. The sample was removed from the press and expanded freely. After expansion, the foam density of each sample was measured by weighing a known volume. Foam density data is shown in Table 30.

Foam Density Data Example Foam Density (g / cc) 2 Mrad Foam Density (g / cc) 5 Mrad Example 31 0.16 0.47 Example 32 0.28 0.56 Example 33 0.55 0.19

Table 30 shows that the interpolymer blends of Examples 31-33 can be foamed after irradiation crosslinking and the optimal irradiation dose depends on the ethylene content and gel content. For the polymer of the present invention, a low irradiation dose is preferred in order to obtain an optimum foam density.

Free growth foam using a hot air oven was prepared from Examples 31-35 and Control Example U irradiated at 2 Mrad. Test samples of size 2.54 cm × 2.54 cm were cut from the test plaques examined by compression molding. For Examples 31-33 the test sample was placed in a hot air oven at 180 ° C. for about 10 minutes. For Examples 34-35 and Control Example U, the test sample was placed in a hot air oven at 220 ° C. for about 10 minutes. The foamed test samples were removed from the oven and the foam density of each sample was measured by weighing a known volume. Foam density data are shown in Table 31.

Foam Density Data Examples and Control Examples Foam density at 2 Mrad dose (g / cc) Example 31 0.14 Example 32 0.21 Example 33 0.39 Example 34 0.08 Example 35 0.08 Control Example U 0.37

Table 31 shows that free growing foams using hot air ovens can be prepared from the interpolymers and interpolymer blends of the present invention. Foam density data shows that blends comprising the interpolymers of the present invention exhibit lower foam densities. Foam density data for the polypropylene blend shows improved foaming of blend samples (Examples 34 and 35) comprising the interpolymer of the present invention as compared to polypropylene blend samples (Control Example U). The polymers of the invention can be blended with other ethylene polymers such as LDPE, EVA, LLDPE, EAODM, ethylene alpha-olefin copolymers and terpolymers, ethylene-styrene and HDPE, and then irradiated to obtain foams with low foam density. This is expected.

The formulations shown in Table 32 were prepared using a combination of Farrell BR Banburi mixer and Rheocord 9000 mixer. All formulation components except the peroxide were premixed using a Farrell BR Baburi mixer at a melt temperature of about 130 ° C. After about 5 minutes of mixing, each blend was removed from the halves and made into a sheet on a releasable roll mill. This sheet was then cut into irregular cubes of about 2 cm in size. For the peroxide addition, each premixed sample (cube) was added to the Hake Leocord, melted and then Di-Cup 40 KE dicumyl peroxide was added. The melting temperature was 130 ° C. and the rotation speed was about 5 rpm. After about 5 minutes of melt blending, each sample was removed from the rake and cooled.

Composition data ingredient Example 36 Example 37 Example 38 Example 39 Example 40 Example 19 100 Example 20 100 40 Example 21 100 40 EVA 60 LDPE 60 Cellogen AZ 130 6 6 6 6 6 Zinc oxide One One One One One Stearic acid 0.5 0.5 0.5 0.5 0.5 D-Cup 40 KE 0.806 0.806 0.806 0.806 0.806

(All quantities are pph (Parts per Hundred).)

Each formulation sample was compression molded at a preform temperature of 130 ° C. using a heated hydraulic press. The mold cavity used here was about 10.2 cm x 10.2 cm with a 1.3 cm thickness. After molding at 130 ° C., the mold cavity containing the sample was then crosslinked at a temperature of 160 ° C. using a total pressure of about 20,000 lbs. The mold cavity containing the sample was left in the press for about 20 minutes. After this time, the pressure was released quickly. Samples were removed from the press and expanded freely. For each foamed sample, the gel content (%) and foam density values were measured as described above. These data are shown in Table 33.

Gel Content and Foam Density Data Example Gel content (%) Foam Density (g / cc) Example 36 82 0.15 Example 37 82 0.19 Example 38 70 0.10 Example 39 71 0.09 Example 40 70 0.10

The data in Table 33 demonstrate that foams can be prepared from examples of the invention using peroxide crosslinking. The optimum amount of peroxide can be adjusted depending on the interpolymer applied and the desired foam density.

The formulations shown in Table 34 were prepared using a combination of Farrell BR Halfburi mixer and Hake Leocord 9000 mixer. All formulation components except the sulfur curing agent were premixed using a Farrell BR Baburi mixer at a melt temperature of about 130 ° C. After about 5 minutes of mixing, each formulation was removed from the half and made into a sheet on a releasable roll mill. These sheets were then cut into irregular cubes of about 2 cm in size. For the sulfur curing agent addition, each premixed sample (cube) was added to the Hake Leocord, allowed to melt and then the sulfur curing agent was added. Blending conditions in the Hake mixer were a melt temperature of 130 ° C. and a rotation speed of about 5 rpm. After about 5 minutes of melt blending, each sample was removed from the rake and cooled.

Composition data ingredient Example 41 Example 42 Example 43 Example 44 Example 20 100 40 Example 21 100 40 EVA 60 LDPE 60 Cellogen AZ 130 6 6 6 6 Zinc oxide 5 5 5 5 Stearic acid One One One One Butyl Zymate 0.33 0.33 0.33 0.33 MBT 0.17 0.17 0.17 0.17 TMTD 0.88 0.88 0.88 0.88 sulfur 0.25 0.25 0.25 0.25

(All quantities are pph (Parts per Hundred).)

Each blend sample was compression molded into plaques at a preform temperature of 130 ° C. using a heated hydraulic press. Plaque size was about 12.7 cm x 12.7 cm about 0.3175 mm thick. Smaller test samples were cut from each plaque. These test samples were 2.54 cm x 2.54 cm in size with a thickness of 0.3175 cm. These test samples were placed in a hot air oven at a temperature of 200 ° C. for about 5 minutes. The foamed test sample was removed from the oven and tested. For each foamed sample, the gel content% and foam density values were measured as described above. The results are shown in Table 35.

Gel Content and Foam Density Data Example Gel content (%) Foam Density (g / cc) Example 41 64 0.22 Example 42 75 0.24 Example 43 65 0.3 Example 44 55 0.24

Table 35 demonstrates that foams that are acceptable for sulfur crosslinking of the polymers of the present invention can be made. The optimum amount of sulfur curing agent can be adjusted depending on the interpolymer and the desired foam density. The interpolymers of the present invention are blended with other ethylene polymers such as LDPE and EVA (other ethylene polymers may include LLDPE, ethylene alpha-olefin copolymers, ethylene-styrene and HDPE), other sulfur cured natural or synthetic rubbers Sulfur crosslinking may then be followed to obtain a foam having a low foam density.

Examples 45-47

Ethylene-butene-ethylidene norbornene terpolymer of the present invention was prepared in a similar manner to Examples 1-4. Compositions and properties for EAODM polymers are shown in Table 36.

Composition, Thermal Properties and GPC Data C ₂ (% by weight) C ₄ (% by weight) ENB (% by weight) Crystallinity (%) Heat of fusion (cal / g) Tg (℃) Melting point (℃) M _w M _n MWD Example 45 88.5 7.5 4.0 35 24.7 -20 103 94,400 47,000 2.01

The formulations of Examples 46 and 47 were prepared by blending the interpolymer of Example 45 with sulfur and phenolic curing agent / promoter in a Hake Leocord 9000 mixer. The formulation of Example 46 was prepared using the interpolymer, sulfur curative and accelerator of Example 45. The formulation of Example 47 was prepared using the interpolymer, phenolic curing agent and accelerator of Example 45. The conditions for blending in the Hake mixer are a melt temperature of 130 ° C. and a rotation speed of about 5 rpm. The polymer was added to the mixer and melted. After about 3 minutes, sulfur or phenolic curing agent and accelerator were added. After about 2 minutes of melt blending, the sample was removed from the mixer and cooled. Sulfur and phenolic formulations are shown in Table 37.

Composition data ingredient Example 46 Example 47 Example 45 100 100 Zinc oxide 5 2.1 Stearic acid One Butyl Zymate 2 MBT One TMTD 0.5 sulfur 1.5 Dimethylol Phenolic Curing Agent SP-1045 10.1 Tin Chloride Dihydrate 2.8 MgO 2.0

The blends were tested for vulcanization properties using a standard test method for rubber vulcanization using a Rotorless Meter as described in ASTM D-5289 (Movable Die Rheometer-MDR). The blend of Example 46 with a sulfur cure and accelerator was tested at a temperature of 160 ° C. The blend of Example 47 with a phenolic curing agent and accelerator was tested at a temperature of 200 ° C. The values of minimum torque (M _L ), maximum torque (M _H ) and time to reach 95% of the maximum torque (T ₉₅ ) are shown in Table 38.

Vulcanization Properties Example M _H (Nm) M _L (Nm) T ₉₅ (min) Example 46 1.55 0.12 13.64 Example 47 0.66 0.03 16.00

The data in Table 38 shows that the EAODM of Example 45 can be vulcanized with sulfur and phenolic curing agents / promoter. Other types of crosslinks can be used, including peroxides, irradiation (E-beam, gamma, UV), silanes and hydrosilylation. Possible end uses of these polymers are in polyolefin foams (shoes, automotive interiors), vulcanized rubber blends (tires, weatherstripping), crosslinked polyolefin blends (films, fibers, tubing) and thermoplastic vulcanizates (TPV's). Can be.

Example 48

The interpolymer of Example 20 was vulcanized using a hydrosilylation curing agent and a platinum catalyst. First, the interpolymer (100 pph) of Example 20 was added to a Hake Leocord 9000 mixer and melted at a melting temperature of 130 ° C. After about 3 minutes, 3 pph of hydrosilylation curing agent (Silicide Type 1107 Fluid from Dow Corning) and 20 ppm of platinum catalyst (SIP 6831.0 from Gerest, Inc.) were added, and Mix at a rotation speed of 5 rpm. After about 5 minutes of melt blending, the sample is removed from the mixer and cooled to obtain the vulcanized interpolymer of Example 48, using a rotationless meter as described in ASTM D-5289 (Moving Die Rheometer-MDR). The vulcanization properties were tested using standard test methods for rubber property vulcanization. The composition of the polymer blended with the hydrosilylation curing agent and catalyst was tested at a temperature of 190 ° C. The minimum torque (M _L ) was 0.04 Nm, the maximum torque (M _H ) was 0.1 Nm, and the time (T ₉₅ ) to reach 95% of the maximum torque was 16.50 minutes. These results show that the interpolymer of the present invention can be successfully cured using hydrosilylation vulcanization.

Example 49 and Control Example V

The following control examples and examples compare the biaxial orientation of linear low density polyethylene (LLDPE) with the biaxial orientation of the blend of LLDPE and the interpolymer of the present invention. Subsequently, the utility of both in shrink film applications is also compared.

The blend of Example 49 was prepared by blending the interpolymer of Example 19 with the LLDPE of Control Example C each at a 10/90 weight ratio. Blending was performed on a 64 mm 36/1 L / D (length / diameter) single screw extruder. The following conditions were used on a 64 mm extruder: Barrel temperature zones were Zone 1 = 82 ° C., Zone 2 = 127 ° C., Zone 3-5 = 190 ° C., Screen Changer Temperature = 204 ° C. and adapters. And die temperature = 218 ° C. The extruder speed was 31 rpm. The strands were extruded, quenched with water and then cut into pellets. These pelletized compounds were extruded into sheets using a 50 m 24 / l L / D single screw extruder. The extruder barrel temperature zones were Zone 1 = 216 ° C., Zone 2 = 238 ° C., Zone 3 = 249 ° C., Adapter and Die Temperature = 218 ° C. The extruder speed was 34 rpm at 19.5 amps. The casting roll temperature was 39 ° C., the die width was 30.5 cm, the sheet thickness was 0.64 mm, and the sheet width was 52.4 cm.

A sheet of the LLDPE of Control Example C and the blend of Example 49 was wound around a cardboard core. These sheets were then electron beam irradiated at a dose of 4.0 Mrad at a linear speed of 6.1 m / min to prepare irradiated sheets of the LLDPE of Control Example V and the blend of Example 49. The irradiated sheet was then oriented in the machine direction (MDO) at a 5: 1 draw rate using a series of heated rollers with different roll speeds. Conditions for MDO stretching are: preheating temperature of 98.3 ° C., 2.4 m / min and 109 ° C. for slow draw roll operation, 12.3 m / min and 109 ° C. for fast draw roll operation, 12.3 m / min and 36 ° C. for annealing roll, The cooling roll was 12.3 m / min and 19.4 ° C. The sheet thickness was 0.13 mm.

The MDO stretched sheet was oriented in the transverse direction using a tender frame device equipped with a parallel chain and flexible grip system for transverse orientation (TDO) and heated through a convection oven. Conditions using TDO stretching for Control Example V were preheating temperature of 113 ° C., stretch temperature of 113 ° C., and annealing temperature of 96 ° C. The conditions used for TDO stretching for the blend of Example 49 were a preheat temperature of 116 ° C., a stretch temperature of 116 ° C., and an annealing temperature of 99 ° C. The film was cooled by circulating ambient air and then wound up. The film thickness was 0.025 mm.

The film was tested for crosslinked gel according to ASTM D-2765, Method A. The film of Example 49 has an average gel content of 25.41%. The film of Control Example V has an average gel content of 0.68%. These results show a large increase in the crosslinking capacity of the blends comprising the polymers of the invention.

Tensile strength at break of the films of Example 49 and Control Example V was measured in MDO and TDO according to ASTM D-882. The results are shown in Table 39. The film of Example 49 showed higher tensile strength at break in both MDO and TDO than Control Example V.

Tensile strength data Film direction MDO Control Example V MDO Example 49 TDO Control Example V TDO Example 49 Tensile Strength at Break (Mpa) 65.3 72.4 94.3 117.0

Shrink tension was measured in MDO at 125 ° C. according to ASTM D2838, Method A. The film of Example 49 has an MDO shrinkage tension of 1.73 Mpa and control Example V has an MDO shrinkage tension of 1.13 Mpa. Thus, electron beam irradiated biaxially oriented films comprising the highly crystalline interpolymers of the present invention exhibit higher levels of crosslinking, tensile strength at break, and shrinkage tension than films without the interpolymers of the present invention. These interpolymers of the present invention can be used alone or as a blend component to exhibit higher gel response to electron beam irradiation on biaxially oriented shrink films.

Examples 50-51 and Control Example W-X

The interpolymer of Example 20 was either low density polyethylene (LDPE) LD 400.09 (available from Exxon Chemical Company) or a melt index of 0.7 dg / min and a melt index of 2.8 dg / min and a density of 0.917 g / cc. Blended with high density polyethylene (HDPE) Sclair 59A (available from Nova Chemicals) with a density of / cc. The blend with LDPE obtained a composition referred to as Example 50, and the blend with HDPE obtained a composition referred to as Example 51. 100 wt% LDPE was referred to as Control Example W. 100 wt.% HDPE was referred to as Control Example X. Blend compositions were prepared on a Werner Pfleiderer ZSK-30 idle twin screw extruder with a medium-high shear screw arrangement. The blend composition is shown in Table 40 and the blend conditions are shown in Table 41.

Composition data ingredient Control Example X Control Example W Example 50 Example 51 Example 20 30 30 HDPE 100 70 LDPE 100 70

Extruder condition Extruder condition Control Example X Control Example W Example 50 Example 51 Zone 1 temperature 145 110 145 110 Zone 2 temperature 209 180 215 185 Zone 3 temperature 225 200 230 200 Zone 4 temperature 240 220 245 235 Zone 5 temperature 230 220 235 240 Die temperature 210 200 205 210 Speed (rpm) 250 270 250 240

(The temperature is ℃)

After mixing and pelletizing according to Table 41, the pelletized blends of Table 40 are extruded into sheets using a 50 mm 24/1 L / D Killion single screw extruder equipped with a 15 cm wide sheet die It was. The conditions used to extrude these sheets are shown in Table 42.

Extruder condition Extruder condition Control Example X Control Example W Example 50 Example 51 Zone 1 temperature 205 85 205 90 Zone 2 temperature 205 188 205 165 Zone 3 temperature 205 188 205 165 Die temperature 82 175 82 160 Speed (rpm) 28 31 32 28

(The temperature is ℃)

A 1 mm thick sheet of the blend of Control Examples W-X and Examples 50-51 was prepared and cooled on a Killion 25 cm wide 3-roll stack. The sheet was then irradiated with an electron beam at a 2 Mrad dose. The irradiated sheets were tested for gel reactions measured according to ASTM D2765, Method A. The results are shown in Table 43. Sheet samples comprising the polymers of the present invention exhibited much higher gel levels than Control Examples W and X, which did not include the polymers of the present invention.

Gel content data Control Example X Control Example W Example 50 Example 51 Average gel (%) 2.64 9.37 51.2 59.93

The irradiated sheet was cut into 20 cm x 10 cm strips. These strips were drawn in the machine direction in an integrated tensile test machine equipped with an environmental chamber. Tensile test machines were equipped with multihead grips that could span 10 cm widths. Prior to stretching, the sample was preheated for 10 minutes to a preset temperature in an environmental chamber. Preset environmental chamber temperatures for each blend are shown in Table 44. Different chamber temperatures were used depending on the type of polyethylene used. The chamber temperature was set at or near the melting point of the polyethylene. After 10 minutes of preheating, the sheet samples were drawn at a 2: 1 draw ratio in the machine direction using a crosshead speed of 50 mm / min. Immediately after reaching the 2: 1 draw ratio, the crosshead was stopped, the environmental chamber was opened, and the sample, which was still under tension, was cooled with air from the pressure tube. Shrink tension was tested at 150 ° C. according to ASTM D2838, Method A for stretched sheet samples. Table 45 shows the shrinkage tension results. The shrinkage tension was 4-5 times higher for the inventive examples (Examples 50-51) than for the control example W-X which did not include the inventive polymer. Highly crystalline EAODM can be used as a blend with LDPE, HDPE or other polyethylene to obtain shrink articles such as shrink sleeves, shrink tubing, shrink linings, etc. with higher crosslinking and shrink tension at equivalent orientation and electron beam irradiation levels. Can be.

Preset environmental chamber temperature Control Example X Control Example W Example 50 Example 51 Temperature (℃) 134 110 134 110

Shrinkage tension data Examples and Control Examples Orientation Temperature (℃) Shrinkage tension (MPa) Control Example X machine 150 0.09 Control Example W machine 150 0.08 Example 50 machine 150 0.50 Example 51 machine 150 0.36

Example 52

The formulation of Example 52 was obtained by mixing the interpolymer of Example 2 (85 pph) with 1 part 4-chlorobenzophenone and 15 parts hexanediol diacrylate on a 2-roll mill. A 2 mm thick slab was then pressed from the formulation. The slab was then exposed to a 80 W / cm 5 cm long UV lamp. The lamp was placed 10 cm away from the slab and the exposure time was 4 minutes. After exposure, the crosslinked interpolymer of Example 52 had a 45% compression set (25% deflection) at 125 ° C. for 70 hours. These results clearly show that the highly crystalline EAODM based compounds of the present invention can be crosslinked using ultraviolet light.

Examples 53-56 and Control Example Y

The interpolymers of Examples 2, 19 and 20 were grafted with maleic anhydride. 240 g of each interpolymer was added to a Hake mixer at a temperature of 200 ° C. Rotational speed was set at 50 rpm. The polymer was melted for about 1 minute, followed by 7.2 g of maleic anhydride. This operation was performed with a metal ram in the closed state. After about 5 minutes, the rotation was stopped and the grafted interpolymer of Examples 53-55 was removed from the shake mixer. The amount of grafted maleic anhydride on each polymer was measured using infrared absorbance. As a result, the interpolymer of Example 53 had 0.35 wt% maleic anhydride, and the interpolymer of Example 54 had 0.40 wt% maleet or anhydride. And the interpolymer of Example 55 had 0.50% by weight maleic anhydride.

The interpolymers of Example 53 and Example 2 were blended with a polyamide polymer (Capron 8200 obtained from Allied Signal). The polyamide polymer was previously dried at 70 ° C. for 24 hours before use. The interpolymers of Example 53 and Example 2 were granulated to an average diameter of about 0.1875 inches (0.4762 cm) in a K-Tron granulator before blending in the extruder. Blends were prepared on an 18 mm Hake co-rotating twin screw extruder with a 30: 1 L / D ratio. The extruder speed was set to 50 rpm. Zone temperatures were distributed from 240 ° C. to 260 ° C. from the feeder inlet to the die. The melting temperature at the die was about 260 ° C. The extruder was equipped with a 2-hole die, a water bath, an air knife and a strand cutter. The molten polymer strands were cooled in a water bath and pelletized to an average pellet size of about 0.125 inches (0.3175 cm) to control Example Y (80 wt% Capron 8200 and 20 wt% interpolymer of Example 2) and The interpolymer blend of Example 56 (80 wt% of Capron 8200 and 20 wt% of grafted interpolymer of Example 53) was obtained.

The grafted interpolymers of Control Example Y and Example 56 were injection molded on an Arburg injection molding machine using standard ASTM molds. IZOD test bars were molded to a standard thickness of 0.125 inches (0.3175 cm). Molding conditions were 80 degreeC casting temperature and 260 degreeC melting temperature. Gold was injected into the injection molded IZOD test bars and the impact properties were tested at room temperature according to ASTM conditions. The room temperature IZOD impact properties are shown in Table 46. Maleic anhydride grafted interpolymers of the invention can impact modify polyamide polymers (nylon 6). When the interpolymer of the present invention is not grafted with maleic anhydride, miscibility is poor and reflected in poor IZOD impact performance.

Impact strength data Examples and Control Examples Room Temperature IZOD Impact Strength (J / cm) Capron 8200 0.67 Control Example Y 0.58 Example 56 5.50

Examples 58-61 and Control Example Z-AA

These examples compare the attachment of low density polyethylene LDPE, HDPE, and the EAODM polymer of the present invention to styrene-butadiene rubber (SBR) substrates. Plioflex 1502, a styrene-butadiene rubber (SBR), was obtained from Goodyear Tire and Rubber Company. The Flioflex 1502 sample is characterized by 50 Mooney viscosity styrene-butadiene rubber. Petroten NA 940000, an LDPE, was obtained from Iquistar Corporation. Typical properties for this LDPE polymer include a melt flow rate of 0.25, a polymer density of 0.918, and a crystal melting point of 104 ° C. HDPE Petroten LR 73200 was obtained from Iquistar Corporation. Typical properties of this HDPE polymer include a melt flow rate of 0.30, a polymer density of 0.955, and a crystal melting point of 125 ° C.

Extruded plaques were prepared from the respective styrene-butadiene rubbers, LDPE, HDPE and the interpolymers of Examples 1, 3, 19 and 20. The plaques were 15.2 cm x 15.2 cm in size with a thickness of about 3.17 mm. Adhesion test specimens of 2.54 cm (width) x 5.58 cm (length) were cut from the plaques. Attachment of LDPE, HDPE, and the interpolymers of Examples 1, 3, 19, and 20 to SBR evaluated three test specimens of each polymer type in contact with styrene-butadiene rubber. The polymer / styrene-butadiene rubber laminate was placed in an oven set at 150 ° C. After 1 hour, the polymer / styrene-butadiene rubber laminate was removed from the oven, cooled and checked by hand for adhesion. The adhesion test was performed by pulling 90 by hand. The adhesion level was measured as evidence of the failure of adhesion between the test polymer and the styrene-butadiene rubber gas. LDPE (Control Example Z) and HDPE (Control Example AA) laminates showed no adhesion, whereas the laminates of Examples 58, 59, 60 and 61 (from the interpolymers of Examples 1, 3, 19 and 20, respectively) Prepared) showed adhesion. In addition, better adhesion was obtained as the ethylene content of the crystalline EAODM polymer increased. The adhesion of crystalline EAODM polymers can be used in tires (eg, low permeability inner liners), automotive weather strips (eg, in low COF (friction coefficient) and wear resistant layers), vulcanized rubber composites (eg, windshield wipers Blades and engine motor mounts) and many other elastomeric applications, including other laminated or coextruded articles.

Example 62 and Control Example AB

The blend of Example 62 was obtained by blending 15 wt% of the interpolymer of Example 1 with 85 wt% Nordel IP 4770 EPDM (available from DuPont Dow Elastomer) on a Farrell 1D half beak. Typical properties for Nordel IP 4770 are 70 wt% ethylene content and Mooney viscosity ML (1 + 4) 70 at 125 ° C. 100 wt% Nordel IP 4770 was used as a control to refer to Control Example AB. The polymer of Control Example AB and the blend of Example 62 were extruded on a Davis-Standard extruder using a standard rubber screw (L / D 20: 1) with a screw of 17 RPM using a weather stripping die, respectively. The barrel temperature was 65.5 ° C. in Zone 1, 71 ° C. in Zone 2, 82 ° C. in Zone 3, and the die temperature was 37.8 ° C. Extruder speed was 81.3 mm / sec. Post die measurements were performed at 15 cm from the die. End of Line Measurement The dms extruded material was run at about 6 cm from the die after exiting through the room temperature air blowing chamber. The interpolymer blend of Example 62 has a post die height of 4.76 mm and a line tip height of 4.76 mm, while Control Example AB has a post die height of 5.56 mm and a line tip height of 3.97 mm.

Tensile Wet Strength Data Examples and Control Examples Tensile Wet Strength 50 ℃ (Mpa) Tensile Wet Strength 70 ℃ (Mpa) Example 62 0.24 0.115 Control Example AB 0.16 0.098

Adding the interpolymer of Example 1 to Control Example AB improves both tensile wet strength (Table 47) and the collapse resistance of the materials, all of which are desirable improvements for release extrusion applications such as hoses and weather stripping, This is because the releases need to maintain their die shape until the material can be cured.

Examples 63-72 and Control Example AC-AD

The blends of Table 48 are "right mixing processes" (filling polymer and resin in front of filler and oil) in a releasable (B size, 1.7 L chamber volume) tangential-rotor internal mixer operating at 70 rpm. It was prepared using. The component weight was adjusted to fill 70% of the mixer volume. Amorphous EPDM interpolymers, Nordel IP 4570 and Nordel IP 4770, were used. Typical properties of Nordel IP 4570 were ethylene content 50% by weight and Mooney viscosity ML (1 + 4) was 70 at 125 ° C. The amorphous interpolymer and the crystalline interpolymer of the present invention were first put into a mixer and then filled with filler (carbon black, calcium carbonate) and oil. The ram was lowered and the blend was mixed at 88 ° C. At 88 ° C., the ram was raised and the disheveled filler was removed from the inlet and ram. The ram was lowered, the compound released at 127 ° C. and sheeted on a 40.6 cm mill. The compound was conditioned at 23 ° C. for 24 hours before adding the curing agent. Compounds were charged to a mixer and mixed at 66 ° C. The ram was raised, cleaned and then the curing agent added. The ram was lowered, the compound was taken at 88 ° C. and the inlet and ram were cleared. The ram was lowered, the compound released at 104 ° C. and sheeted on a 40.6 cm mill.

(Nordel IP 4570 is available from DuPont Dow Elastomers. Tetron A (dipentamethylene thiuram hexasulfide) is available from DuPont Dow Elastomers.)

The process for measuring the wet strength of the blends of Table 48 was based on ASTM D412, modified as follows. The blend was pressed in the mold at 115 ° C. for 0.5 minutes. The mold was then cooled for 2 minutes before removing the pressed sheet. The pressed sheet was 1.91-21.6 mm thick. Test samples were cut from the sheet using a 12.7 mm wide, 114.3 mm long die. The sample was stressed at a rate of 127 mm / min. Stress at low strain (10-50% strain) provides a good measure of the "wet strength" defined in the extrusion process.

(Hardness measured using ASTM D2240. Elastic modulus measured using ASTM D412-92. Compression set measured using ASTM D395-89 at -25 ° C after 22 hours. TR-shrinkage temperature is ASTM D1329. Measured using -88.)

The formulations of Examples 63-72 (Table 49) show that as the levels of the interpolymers of the invention increase, the hardness, 100% modulus and wet strength increase. This increase was greater than predicted by the average ethylene level of the blend compared to the results obtained with pure 50% or 70% ethylene polymers. In conclusion, high hardness and modulus levels can be achieved at low average ethylene levels. Low ethylene levels provide an improvement in cold sealing performance as measured by temperature shrinkage and compression sets.

Examples 73-76 and Control Example AE-AF

Some applications require compositions of high hardness (ie, Shore D hardness greater than about 40). Examples 73-76 and Control Example AE-AF demonstrate that the compositions of the present invention exhibit beneficial properties for high hardness applications.

The interpolymer of Control Example AE is Nordel IP 4725P (EPDM available from Dupont Dow Elastomer). The interpolymer of Control Example AF is Nordel IP 4520 (another EPDM available from Dupont Dow Elastomer). A comparison of the composition and physical properties of the interpolymers of Examples 1, 4 and 20 and Control Examples AE and AF are shown in Table 50.

The interpolymers of Examples 1, 4 and 20 were blended with control examples AE and AF. The blend was prepared in two stages in a 1.2 liter internal mixer (Shaw-Intermixer KO). The filling efficiency was 64%.

In the first step, all components except sulfur, CaCO ₃ and hardener are introduced into the mixer at 40 rpm, then sulfur and CaCO ₃ are introduced 30 seconds before the Black Incorporation Time (BIT), after 90 seconds or 120 BIT. Master batches were prepared in a semi-conventional manner by dumping at &lt; RTI ID = 0.0 &gt; BIT is the point in time required for introducing the filler during the mixing operation. However, BIT is more than just a measure of mixing cycle time: it also represents mixing efficiency and filler dispersion rate. In a plot of mixing curves plotting time on the x-axis and power on the y-axis, power consumption peaks during the blending operation. The time when this power is generated is BIT.

In the second step sulfur and curing agent were added to the masterbatch in an internal mixer at 30 rpm and then released after 2 minutes or at 11 ° C. Table 51 shows the composition of the blends and Table 52 shows the blending ratios of the various polymers used.

Composition and Viscosity Data Physical properties Control Example AE Control Example AF Example 1 Example 20 Example 4 Ethylene Content (wt%) 70 50 84.9 93.6 94.1 ENB content (% by weight) 5 5 5.2 4.7 1.3 Crystallinity (%) 11 <2 20 37 39 Mooney Viscosity (ML _{1 + 4} , 125 ℃) 25 20 27 14 15

Composition data Master Batch (First Steps) ingredient Phr Introduction time EAODM 100 T = 0 Carbon black FEF-N550 130 T = 0 Shipment 2280 Oil 45 T = 0 CaO 5 T = 0 Zinc oxide 5 T = 0 Stearic acid 2 T = 0 Polyethylene Glycol 4000 One T = 0 Styrene Resin-Floride S6H 20 T = 0 Polyethylene Wax-AC 617A 2 T = 0 sulfur 0.2 T = BIT 30 seconds ago CaCO ₃ 40 T = BIT 30 seconds ago Curing agent (second stage) sulfur 2.8 T = 0 Zinc Ethyl Petrol Dithiocarbamate One T = 0 n-cyclohexylbenzothiazyl sulfenamide-CBS 2 T = 0 TMTD 0.5 T = 0 Tellurium diethyl dithiocarbamate-TDEC 0.2 T = 0 Vulkalent EC 0.5 T = 0 total 357.2

(Carbon Black FEF-N550 is available from Cabot Corporation.

Sunwave 2280 is a paraffinic plasticizer available from Blazer Swisslube AG.

Pliolite S6H is available from Goodyear Tire and Rubber Company.

Polyethylene wax-AC 617A is available from Allied Chemicals.

Vulcanrent EC is a sulfonamide derivative available from Bayer AG.)

Composition data Examples and Control Examples Example 73 Example 74 Example 75 Example 76 Control Example AE 70 70 70 0 Control Example AF 0 0 0 50 Example 1 30 0 0 0 Example 4 0 0 30 0 Example 20 0 30 0 50

Crystallinity and Black Incorporation Data Property Control Example AE Example 1 Example 70 Example 71 Example 72 Example 73 Blend Crystallinity (%) 11 20 14 19 19 19 BIT (seconds) 157 360 180 170 185 180

Physical property data Measured properties Standard used Control Example AE Example 73 Example 74 Example 75 Example 76 Tensile Strength (Mpa) +/- 0.4 ISO 37 11.1 11.4 12 11.2 11.6 Elastic modulus at 10% elongation (Mpa) +/- 0.2 ISO 37 3.2 4.6 5 4.9 5.3 Hardness, Shore D +/- 1 ISO 868 39 44 46 46 46 Tear strength (kN / m) +/- 1 ISO 34DieC 37 43 45 47 43 Compression set 70 hours, 23C (%) +/- 2 ISO 815 48 55 48 49 44 Compression set 22 hours, -10C (%) +/- 2 ISO 815 93 91 88 Do not measure 76 TR10 (C) +/- 1 ISO 2921 -23 -24 -22 -17 -31 TR20 (C) +/- 1 ISO 2921 -9 -11 -10 -2 -21

The results in Tables 53 and 54 show that the incorporation of the interpolymers of Examples 1, 4 or 20 into the interpolymers of Examples AE and AF contrasted the tensile strength, modulus, tear strength and hardness of the blends of Examples 73-76. EXAMPLES Shows increasing beyond interpolymers. Hardness levels above about 40 (?) Shore D allow such polymers to be used in high hardness automotive or building weather-striping applications. For this application, the mixing operation must be fast (productive) and efficient (good filler dispersion is required to meet surface aspect requirements). Surprisingly, the blend of interpolymers of the invention and the control examples AE and AF provide fast carbon black incorporation (short BIT) and efficient mixed dispersion. In contrast, pure interpolymer (Example 1) has about 2 times the BIT of the blended product.

It can be expected that the addition of high crystalline material will change the low temperature performance (TR) and compression set of Control Example AE-AF. However, as Table 54 shows, both the compression set and the TR value were substantially unchanged when the interpolymer of Control Example AE was blended with the interpolymer of the present invention. Low crystalline EAODM is used (Control Example AF), but when loaded with higher crystallinity material (Example 76) to obtain the same total crystallinity as the interpolymer blends of Examples 74 and 75, the cold compression set and The TR value is substantially improved even though the interpolymer blend of Example 76 has the highest weight percent of 50% by weight of high crystallinity material. In addition, the roll mill process has been significantly improved since the compound provides better banding on the device. The total crystallinity of the blends of Examples 74-76 remained constant at around 19%, comparable to 20% crystallinity of the interpolymers of Example 1. This type of property is found in applications such as profiles, injection molded parts, hoses and belts where this improvement is often beneficial.

Example 77 and Control Example AG-AH

The interpolymer of Example 7 was injection molded into 0.5 inch (12.7 mm) x 0.25 inch (6.35 mm) bar for impact testing according to ASTM D 4020. These bars were exposed to 5 Mrad e-beam irradiation to prepare the irradiated interpolymer of Example 77.

Control Example AG is a commercially available high density polyethylene (ALATHON 6017 available from Iquistar) with density 0.962, melt index 17.5, M _{n of} 17,700 and M _w of 58,600. Control Example AG was injection molded under conditions similar to those used for molding the interpolymer of Example 7. Control Example AH is a commercially available 0.25 inch (6.35 cm) thick ultra high molecular weight HDPE sheet (obtained from Laboratory Supply Corporation) and was cut to 0.5 inch (12.7 mm) bar for testing. The unirradiated interpolymer of Example 7 with the irradiated interpolymer of Example 77 was tested with control examples AG and AH in accordance with ASTM D 4020 (modified to use dropping weight instead of pendulum). The drop weight was 5.42 Kg and dropped at a distance of 73.66 cm. The impact energy was 39.2 newtons.

Table 55 shows that the impact strength of the interpolymers of the present invention is significantly better than the interpolymers of control examples AG and AH. Table 55 also reveals that 5 Mrad irradiation produces vulcanized interpolymers with impact performance substantially equivalent to the unirradiated interpolymers of Example 7.

Impact strength data Examples and Control Examples Impact Strength (kN / m ² ) Example 7 124.5 Example 77 122.7 Control Example AG 4.8 Control Example AH 57.6

Claims (36)

(a) 84 to 99 weight percent ethylene, (b) greater than 0 to less than 16 weight percent of 3 to 20 carbon atoms Crystallinity greater than 16% including -olefins and (c) greater than 0% to 15% by weight of polyenes (all% selected based on interpolymer weight and totaling 100%) and -45 ° C or greater Random ethylene / with glass transition temperature An interpolymer composition comprising an olefin / polyene monomer interpolymer. The interpolymer composition of claim 1, wherein the interpolymer has a melting point greater than 70 ° C. and a heat of fusion greater than 11 cal / g. The ethylene of claim 1 wherein the interpolymer is greater than 95: 5: -An interpolymer composition having a molar ratio of olefins. The interpolymer composition of claim 1, wherein the interpolymer has a molecular weight distribution (M _w / M _n ) in the range of greater than 1 to 15. The interpolymer composition of claim 4, wherein the interpolymer has a molecular weight distribution (M _w / M _n ) in the range of greater than 1 to 4. The process of claim 1, wherein the interpolymer is selected from ethylene, in the presence of at least one metallocene or An interpolymer composition prepared by polymerizing an olefin and a polyene monomer. The interpolymer composition of claim 1 further comprising at least one natural or synthetic polymer in an amount sufficient to form a blend comprising from 2 to 98% by weight interpolymer based on the weight of the blend. 8. The interpolymer composition of claim 7, wherein the natural or synthetic polymer is a monoolefin homopolymer or a polymer in which at least two different monoolefins are polymerized. The _interpolymer composition of claim 8, wherein the monoolefin is a C _2-20 alpha-olefin monomer. The interpolymer composition of claim 9, wherein the alpha-olefin monomer is selected from the group consisting of ethylene, propylene-1, butene-1, hexene-1 and octene-1. The conventional EAODM interpolymer, polyethylene, polypropylene, ethylene / propylene, ethylene / butene, ethylene / hexene and ethylene / octene copolymer, ethylene, wherein the natural or synthetic polymer has an ethylene content of 80% by weight or less. / Propylene / carbon monoxide interpolymer, ethylene / styrene interpolymer, and ethylene / vinyl acetate copolymer. The interpolymer composition of claim 11 wherein the natural or synthetic polymer is a polyethylene selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, and ultra low density polyethylene. 8. The interpolymer composition of claim 7, wherein the natural or synthetic polymer is natural rubber, butadiene rubber, styrene-butadiene rubber, polyisoprene, polyisobutylene or polychloroprene. The method of claim 1 wherein random ethylene / The -olefin / polyene monomer interpolymer further comprises a grafted monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic anhydrides, unsaturated carboxylic esters and unsaturated carboxylic acid salts (both metal and nonmetal). Composition. The composition of claim 14, wherein the grafted monomer is maleic anhydride. The composition of claim 14, wherein the grafted monomer is present in an amount in the range of 0.01 to 10 weight percent based on the weight of the grafted ethylene / alpha-olefin / polyene monomer interpolymer. The composition of claim 1, further comprising at least one additive selected from the group consisting of plasticizers, special additives, and pigments. 18. The composition of claim 17, wherein each additive is present in an amount in the range of greater than 0% to 45% by weight based on the total composition weight and the total additive content is 90% by weight or less based on the total composition weight. 18. The process of claim 17 wherein ethylene / And a process oil in an amount greater than 0 to 200 parts by weight per 100 parts by weight of the olefin / polyene monomer interpolymer. 20. A crosslinkable ethylene / comprising an interpolymer composition of claim 1 and a chemical crosslinker selected from the group consisting of peroxides, sulfur compounds, phenolates and silicone hydrides. -Olefin / polyene monomer interpolymer composition. The method of claim 20, wherein the chemical crosslinker is dicumyl peroxide, , '-Bis (t-butylperoxy) -diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, t-amyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di- (t-butyl peroxy) hexane, di-t-butylperoxy, 2,5-di (t-amyl peroxy) -2,5-dimethylhexane, 2,5-di- (t-butylperoxy) -2,5-diphenylhexane, bis (alpha-methylbenzyl) fur A crosslinkable composition, which is a peroxide selected from the group consisting of oxides, benzoyl peroxides, t-butyl perbenzoate and bis (t-butylperoxy) -diisopropylbenzene. The crosslinkable composition of claim 21, wherein the peroxide is present in an amount of from 0.05 to 10% by weight, based on the total weight of the polymer in the composition. a) providing a crosslinkable composition of claim 20, and b) converting the crosslinkable composition to an ethylene / -Exposing the olefin / polyene monomer interpolymer to a temperature condition sufficient to at least partially crosslink. a) providing the interpolymer composition of any one of claims 1 to 19, and b) ethylene / -Exposing the olefin / polyene monomer interpolymer to an amount of radiation sufficient to at least partially crosslink. The method of claim 24, wherein the ionizing radiation is supplied in an 0.1 to 30 Megarad dose by the electron beam. The method of claim 24, wherein the ionizing radiation is supplied at a dose of at least 0.1 J / cm 2 by ultraviolet irradiation. A crosslinked interpolymer composition prepared by the method of claim 23. A crosslinked interpolymer composition prepared by the method of claim 24. 20. An article made from the interpolymer composition of any one of claims 1-19. An article made from the crosslinkable interpolymer composition of claim 20. An article made from the crosslinked interpolymer composition of claim 27. An article made from the crosslinked interpolymer composition of claim 28. 20. One of the adjacent layers comprises the interpolymer composition of any one of claims 1 to 6 or 14 to 19, and the other adjacent layer comprises at least one natural or synthetic polymer. Multilayer article comprising two or more adjacent layers. The multi-layered product of claim 33 in ethylene / An article prepared by exposure to radiation in an amount sufficient to at least partially crosslink the olefin / polyene monomer interpolymer. The layer of one of the adjacent layers is selected from the group consisting of the interpolymer composition of any one of claims 1 to 6 or 14 to 19 and a peroxide, sulfur compound, phenolate and silicon hydride. Crosslinkable ethylene / including crosslinker A multi-layer article comprising at least two adjacent layers, wherein the olefin / polyene monomer interpolymer composition is included and the other adjacent layer comprises at least one natural or synthetic polymer. 36. The multilayer article of claim 35 activates a chemical crosslinker to An article prepared by exposing the olefin / polyene monomer interpolymer to a temperature condition sufficient to at least partially crosslink.