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EP1228141A1 - Crosslinkable compositions of functionalised polyolefin powders - Google Patents

Crosslinkable compositions of functionalised polyolefin powders

Info

Publication number
EP1228141A1
EP1228141A1 EP00960794A EP00960794A EP1228141A1 EP 1228141 A1 EP1228141 A1 EP 1228141A1 EP 00960794 A EP00960794 A EP 00960794A EP 00960794 A EP00960794 A EP 00960794A EP 1228141 A1 EP1228141 A1 EP 1228141A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
acrylate
chosen
copolymers
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00960794A
Other languages
German (de)
French (fr)
Inventor
Patrice Robert
Jean-Michel Pierrot
Philippe Annoot
Martin Baumert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atofina SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1228141A1 publication Critical patent/EP1228141A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0884—Epoxide-containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to crosslinkable compositions of functionalized polyolefin powder which can be used in the slush molding process or in thermoforming of sheets or also by injection on an insert and more particularly compositions based on functionalized polyethylene.
  • PVC or polyolefin powders are used to obtain skins by the free flow powder molding process on a hot mold (hereinafter called slush molding process).
  • Slush molding is used for the manufacture of skins for dashboards, door panels and consoles in the automotive sector.
  • the powder is brought into contact with the hot mold for example by the technique of free flow, by melting the powder forms a skin.
  • These skins have a very soft feel and have no residual stresses which makes it possible to avoid, during aging of the skin, the risk of the appearance of cracks caused by relaxing residual stresses.
  • Patent FR 2 721 319 describes powder compositions for slush molding based on polypropylene and ethylene-propylene rubber (EPR). The skins obtained do not have good creep resistance.
  • the present invention is therefore a crosslinkable composition of functionalized polyolefin powder comprising:
  • composition having a particle size between 100 and 400 ⁇ m.
  • (A) is chosen from copolymers of ethylene and an unsaturated carboxylic acid anhydride and (B) is chosen from copolymers of ethylene and an epoxide unsaturated.
  • (A) is chosen from copolymers of ethylene and of an unsaturated carboxylic acid anhydride and (B) is chosen from polyamines adsorbed on a zeolite.
  • (A) is chosen from copolymers of ethylene and of an unsaturated epoxide and (B) is chosen from polyamines adsorbed on a zeolite.
  • the composition of the invention is transformed into skin on contact with the mold.
  • Crosslinking takes place at a higher temperature than the melting temperature of (A) when it is made while the skin is in the mold, for example in the three embodiments mentioned above.
  • Crosslinking takes place at a temperature between the ambient and the softening point of (A) when this crosslinking is subsequently triggered by a process of diffusion of moisture through the skin as for example in the second and third embodiment if it is chosen to allow the moisture to drive out the amine from the zeolite after the formation of the skin.
  • the copolymers (A) can be polyethylenes grafted with an unsaturated carboxylic acid anhydride or copolymers of ethylene and an unsaturated carboxylic acid anhydride which are obtained for example by radical polymerization.
  • the unsaturated carboxylic acid anhydride can be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4-methylenecyclohex-4-ene-1, 2-dicarboxylic anhydrides, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid, and x - methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid.
  • maleic anhydride is used. It would not be departing from the scope of the invention to replace all or part of the anhydride with an unsaturated carboxylic acid such as for example (meth) acrylic acid.
  • polyethylenes to which the unsaturated carboxylic acid anhydride is grafted polyethylene is understood to mean homo- or copolymers.
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms
  • alpha olefins mention may be made of propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-octene, 1-dececene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1-triacontene; these alpha-olefins can be used alone or as a mixture of two or more than two, esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates,
  • the polyethylene which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density can be between 0.86 and 0.98 g / cm 3 .
  • the MFI viscosity index at 190 ° C, 2.16 kg
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene catalysis that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, VA, and VI A. Metals of the lanthanide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
  • copolymers of ethylene and of the unsaturated carboxylic acid anhydride that is to say those in which the unsaturated carboxylic acid anhydride is not grafted
  • these are the copolymers of l ethylene, unsaturated carboxylic acid anhydride and optionally another monomer which can be chosen from the comonomers mentioned above for the ethylene copolymers intended to be grafted.
  • the ethylene-maleic anhydride and ethylene - alkyl (meth) acrylate - maleic anhydride copolymers are advantageously used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to 40% and preferably 5 to 40% by weight of alkyl (meth) acrylate. Their MFI is between 20 and 100 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described above. The melting temperature is between 80 and 120 ° C.
  • the copolymer (A) is commercially available, it is produced by radical polymerization at a pressure which may be between 200 and 2500 bars, it is sold in the form of granules.
  • the copolymers of ethylene and of an unsaturated epoxide they can be obtained by copolymerization of ethylene and of an unsaturated epoxide or by grafting of the unsaturated epoxide onto the polyethylene.
  • the grafting can be carried out in the solvent phase or on the molten polyethylene in the presence of a peroxide.
  • aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl (meth) acrylate, and - alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-digly
  • the copolymer is obtained from the grafting of a homo or copolymer polyethylene as described for (A) except that an epoxide is grafted instead of an anhydride.
  • a copolymerization it is also similar to (A) except that an epoxide is used, there may also be other comonomers as in the case of (A).
  • the product (B) is advantageously an ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymer.
  • it can contain up to 40% by weight of alkyl (meth) acrylate, preferably 5 to 40% and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%.
  • the epoxide is advantageously glycidyl (meth) acrylate.
  • the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
  • the amount of alkyl (meth) acrylate is advantageously from 20 to 35%.
  • the MFI is advantageously between 5 and 100 (in g / 10 min at 190 ° C. under 2.16 kg), the melting temperature is between 60 and 110 ° C.
  • This copolymer can be obtained by radical polymerization of the monomers. The powdering is carried out as for (A).
  • the composition included several polymers (A) and / or several polymers (B).
  • (A) and (B) are such that there is 0.1 to 1.5 (preferably 0.2 to 0.6) anhydride function by epoxy function.
  • a catalyst that is to say a product capable of accelerating the reaction between the anhydride functions and the epoxy functions. This catalyst acts upon the fusion of (A) and (B) which must be close.
  • the proportion of catalyst is easily determined by a person skilled in the art, these reactions between anhydride and epoxide functions being known in themselves.
  • the crosslinking is carried out by heating the mold to a temperature higher than the melting temperature of (A).
  • - tertiary amines such as dimethyllaurylamine, dimethylstearylamine, N-butylmorpholine, N, N-dimethylcyclohexylamine, benzyldimethylamine, pyridine, dimethylamino-4-pyridine, methyl-1-imidazole, tetramethylethylhydrazine, N, N-dimethylpiperazine, N, N, N ', N'-tetramethyl-l , 6-hexanediamine, a mixture of tertiary amines having from 16 to 18 carbons and known under the name of dimethylsuifamine,
  • acids such as polymers such as Lucalen (ethylene terpolymer / butyl acrylate / acrylic acid) - Magnesium salts such as mixtures of 65% stearate salt and 35% palmitate salt.
  • the functionalized polyethylene (A) has already been described in the first mode.
  • (B) is a polyamine adsorbed on a zeolite, under the effect of a rise in temperature the polyamine is desorbed and comes to crosslink (A). It suffices to choose a polyamine-zeolite pair such that the desorption takes place at least at the melting temperature of (A). Desorption is also caused by water or humidity, which is why it is recommended to add to the polyamine-loaded zeolite another zeolite capable of absorbing moisture to avoid crosslinking during storage.
  • This technique of crosslinking a polymer containing carboxylic acid anhydride groups by zeolites releasing polyamines under the effect of temperature or humidity has been described in US patent 5792816, the content of which is incorporated into the present application.
  • polyamine By way of example of polyamine, there may be mentioned: ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, the isomers of the preceding amines, 1, 2-diaminocyclohexane, 1,4-diaminocyclohexane, diethylenetriamine , triethylenetetramine, tetraethylenepentamine, N-aminoethyl-3-aminopropyltrialkoxysilane, triaminopropyltrialkoxysilane, piperazine, Paminoethylpiperazine, diaminoethylpiperazine, xylylenediamine, isophoronediamine, 3,3'-dimethylocyclin 1,4-diaminobenzanilide.
  • Part of the polyamine can be replaced by polyols or amino alcohols such as for example: ethylene glycol, propylene glycol, triethylene glycol, dipropylene glycol, butanediol, neopentyl glycol, cyclohexane-dimethanol, hydroquinone bis -hydroxyl-ether, triethanolamine, methyl-diethanolamine, tripropanolamine, N, N-di (2-hydroxyethyl) -aniline, ethanolamine, diethanolamine, propanolamine, dipropanolamine and N-hydroxyethyl-aniline.
  • the zeolites advantageously those having pore diameters between 0.3 and 1.5 nm are used and preferably a zeolite chosen from the following four (the pore diameter is indicated): 0.38 nm designated under the type 4A,
  • zeolites 0.44 nm designated as type 5A, 0.8 nm designated as type 10X, 0.84 nm designated as type 13X. All these zeolites are available in a particle size of the order of 20 to 50 ⁇ m.
  • the zeolite can be loaded with a catalyst for the reaction of the anhydride and the amine.
  • desorption temperatures are given below:
  • the crosslinking can be carried out by heating beyond the melting point of (A) or later, the skin being removed from the mold, by diffusion of ambient humidity at a temperature between ambient and softening point of (A).
  • the third embodiment of the invention is of the same kind as the second mode, but the copolymer of ethylene and of a carboxylic acid anhydride is replaced by a copolymer of ethylene and of a epoxide, such a copolymer has already been described as polymer (B) in the first mode, it only suffices that it has an MFI of at least 20.
  • the grafting reaction is carried out in a single or twin screw extruder fed with polyolefins in a feed hopper, for example in the form of granules; in a first zone of the extruder, the polyolefins are melted by heating and in a second zone, the reactants are introduced into the polyolefin melt.
  • the radical initiators can be chosen from peroxides, peracids, peresters, peracetals. They are generally used in an amount of 0.01% to 0.5% by mass relative to the polyolefins to be grafted.
  • compositions of the invention can also comprise anti-caking agents such as silica Aérosil R972, fluidifying agents such as ethylene-bistearamide, release agents such as calcium stearate or magnesium stearate and other ingredients such as tackifying resins such as Rlichite R1115 resin.
  • anti-caking agents such as silica Aérosil R972
  • fluidifying agents such as ethylene-bistearamide
  • release agents such as calcium stearate or magnesium stearate
  • other ingredients such as tackifying resins such as Rlichite R1115 resin.
  • processing stabilizers such as Irgafos 168, DDPP, P-EPQ, TNPP, TPP, PS 800, PS 802, antioxidants such as Irganox 1010, 245, 259, 565, 1035, 1076, 1098, 1135, 1141, 1330, 1425, 3052, 3114, 5057, M1024, mixtures of antioxidants and process stabilizers such as Irganox B225, anti UV agents such as the Tinuvin and Chimassorb range from CIBA.
  • processing stabilizers such as Irgafos 168, DDPP, P-EPQ, TNPP, TPP, PS 800, PS 802, antioxidants such as Irganox 1010, 245, 259, 565, 1035, 1076, 1098, 1135, 1141, 1330, 1425, 3052, 3114, 5057, M1024, mixtures of antioxidants and process stabilizers such as Irganox B225, anti UV agents such as the Tinuvin and Chi
  • fillers and coloring pigments such as carbon black and Ti ⁇ 2-
  • deodorizing agents such as activated carbon: for example 3S, CXV (CECA), undecylenic acid, ethyl undecylenate, calcium undecylenate, zinc undecylenate, cyclodextrin, zeolites such as Flavith and perfumes .
  • the skin having been formed by melting the mixture of powders (A) + (B) on the hot mold, the excess of unmelted powder is eliminated, then the crosslinking can be continued or triggered by placing it in an oven at a temperature included between 200 and 350 ° C for a time between 10 s and 10 min. The skin is then separated from the mold after cooling. It is also possible in the second and third embodiment to remove the skin from the mold and then cross-link with moisture.
  • compositions of the invention make it possible to obtain skins having a very soft feel, a hardness of less than 90 shore A without the use of liquid plasticizers and having no hot creep.
  • these skins have the following characteristics:
  • the thickness is between 0.6 and 1.1 mm
  • compositions of the products % of acrylate, etc.
  • compositions of the powders of the invention are by weight. The following products were used:
  • MM carbon black MAGNESIUM STEARATE mixtures of 65% stearate salt and 25% palmitate salt AEROSIL R972 (Degussa) ACTIVE CARBON 3S and CXV (CECA).
  • the various constituents above have been reduced to powder with a particle size of 200 ⁇ m by cryogenic grinding.
  • compositions of the invention were prepared by mixing the constituents in a powder mixer. We made skins using the slush molding technique. The mold was brought to a temperature of 250 ° C in an oven. The mold taken out of the oven was then covered with an excess of powder of the composition used. After approximately 10 s, the unmelted powder is removed by inverting the mold. The mold is then brought back to the oven at 250 ° C for 3 min. The mold is then cooled in cold water. The skin is then released from the mold.
  • Table 1 The compositions and properties are collated in Table 1 below.
  • Example 5 is black skin and Example 6 is gray skin. These examples have better performance than examples 1 and 4 in terms of abrasion, mechanical properties, toxicity (no dimethylsuifamine), better resistance to thermal aging (antioxidants) and less odor.
  • the formulas were then cryogenically ground into a powder with a particle size of 200 ⁇ m, then added to the rapid mixer with 2% magnesium stearate and 0.6% AEROSIL silica. 4. Slush molding
  • the mold was treated at 100 ° C with a release agent and baked at 120 ° C for 20 min. (Chem-Trend S.A. Mono Coat MC-708A) and was brought to a temperature of 250-300 ° C in an oven. The mold taken out of the oven was then covered with an excess of powder of the composition used. After approximately 10 s, the unmelted powder is removed by inverting the mold. The mold is then brought back to the oven at 250-300 ° C for 1-5 min. The mold is then cooled in cold water. The skin is then released from the mold.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention concerns a crosslinkable composition of functionalised polyolefin powder comprising a functionalised polyolefin (A) having an MFI of at least 20 (190 DEG C 2.16 kg), a product (B) having a function for crosslinking (A), the composition having a grain size distribution between 100 and 400 mu m. Said composition is useful for slush moulding, for thermoforming sheets or injection on an insert.

Description

COMPOSITIONS RÉTICULABLES DE POUDRES DE POLYOLÉFINES CROSSLINKABLE COMPOSITIONS OF POLYOLEFIN POWDERS
FONCTIONNALISÉESFUNCTIONALIZED
[Domaine de l'invention][Field of the invention]
La présente invention concerne des compositions réticulables de poudre de polyoléfines fonctionnalisées utilisables dans le procédé slush molding ou en thermoformage de feuilles ou encore en injection sur un insert et plus particulièrement des compositions à base de polyéthylène fonctionnalisé. On utilise des poudres de PVC ou de polyoléfines pour obtenir des peaux par le procédé de moulage par écoulement libre de poudre sur un moule chaud (appelé ci-après procédé slush molding). Le slush molding est utilisé pour la fabrication de peaux pour planches de bord, panneaux de portes et consoles dans le domaine automobile. La poudre est mise en contact du moule chaud par exemple par la technique de l'écoulement libre, par fusion la poudre forme une peau. Ces peaux ont un toucher très doux et n'ont pas de contraintes résiduelles ce qui permet d'éviter pendant le vieillissement de la peau le risque d'apparition de craquelures provoquées par des contraintes résiduelles se relaxant.The present invention relates to crosslinkable compositions of functionalized polyolefin powder which can be used in the slush molding process or in thermoforming of sheets or also by injection on an insert and more particularly compositions based on functionalized polyethylene. PVC or polyolefin powders are used to obtain skins by the free flow powder molding process on a hot mold (hereinafter called slush molding process). Slush molding is used for the manufacture of skins for dashboards, door panels and consoles in the automotive sector. The powder is brought into contact with the hot mold for example by the technique of free flow, by melting the powder forms a skin. These skins have a very soft feel and have no residual stresses which makes it possible to avoid, during aging of the skin, the risk of the appearance of cracks caused by relaxing residual stresses.
[Le problème technique][The technical problem]
Les planches de bord automobiles sont très souvent en polyuréthane et recouvertes d'une peau en PVC obtenue par le procédé slush molding. Le PVC est de moins en moins utilisable à cause du risque de pollution causé par sa combustion. Il est donc nécessaire de mettre au point des peaux en polyoléfme. L'art antérieur a déjà décrit des peaux en polypropylène mais ces peaux ne résistent pas suffisamment aux températures élevées qu'on peut trouver dans les automobiles en plein soleil et vitres fermées, cette résistance se mesure par le fluage à chaud. [L'art antérieur]Automobile dashboards are very often made of polyurethane and covered with a PVC skin obtained by the slush molding process. PVC is less and less usable because of the risk of pollution caused by its combustion. It is therefore necessary to develop polyolefin skins. The prior art has already described polypropylene skins but these skins do not sufficiently withstand the high temperatures that can be found in cars in direct sunlight and with the windows closed, this resistance is measured by hot creep. [The prior art]
Le brevet FR 2 721 319 décrit des compositions de poudres pour slush molding à base de polypropylène et de caoutchouc éthylène-propylène (EPR). Les peaux obtenues n'ont pas une bonne tenue au fluage.Patent FR 2 721 319 describes powder compositions for slush molding based on polypropylene and ethylene-propylene rubber (EPR). The skins obtained do not have good creep resistance.
[Brève description de l'invention][Brief description of the invention]
On a maintenant trouvé des compositions de poudres de polyoléfines utilisables en slush molding, en thermoformage de feuilles ou en injection sur un insert et qui sont réticulables ainsi on obtient une bonne tenue au fluage et une résistance à l'abrasion. La présente invention est donc une composition réticulable de poudre de polyoléfine fonctionnalisée comprenant :We have now found compositions of polyolefin powders usable in slush molding, in thermoforming of sheets or in injection on an insert and which are crosslinkable so a good creep resistance and an abrasion resistance are obtained. The present invention is therefore a crosslinkable composition of functionalized polyolefin powder comprising:
• une polyoléfine fonctionnalisée (A) ayant un MFI d'au moins 20 (190°C 2,16 kg) contenant une fonction anhydride et/ou époxy,A functionalized polyolefin (A) having an MFI of at least 20 (190 ° C. 2.16 kg) containing an anhydride and / or epoxy function,
• un produit (B) ayant pour fonction de réticuler (A),• a product (B) having the function of crosslinking (A),
• la composition ayant une granulométrie entre 100 et 400 μm.• the composition having a particle size between 100 and 400 μm.
Selon un premier mode de réalisation de l'invention (A) est choisi parmi les copolymères de l'éthylène et d'un anhydride d'acide carboxylique insaturé et (B) est choisi parmi les copolymères de l'éthylène et d'un époxyde insaturé.According to a first embodiment of the invention (A) is chosen from copolymers of ethylene and an unsaturated carboxylic acid anhydride and (B) is chosen from copolymers of ethylene and an epoxide unsaturated.
Selon un deuxième mode de réalisation de l'invention (A) est choisi parmi les copolymères de l'éthylène et d'un anhydride d'acide carboxylique insaturé et (B) est choisi parmi les polyamines adsorbées sur une zéolite.According to a second embodiment of the invention (A) is chosen from copolymers of ethylene and of an unsaturated carboxylic acid anhydride and (B) is chosen from polyamines adsorbed on a zeolite.
Selon un troisième mode de réalisation de l'invention (A) est choisi parmi les copolymères de l'éthylène et d'un époxyde insaturé et (B) est choisi parmi les polyamines adsorbée sur une zéolite.According to a third embodiment of the invention (A) is chosen from copolymers of ethylene and of an unsaturated epoxide and (B) is chosen from polyamines adsorbed on a zeolite.
Dans le procédé de slush molding la composition de l'invention se transforme en peau au contact du moule. La réticulation a lieu à une température plus élevée que la température de fusion de (A) lorsqu'elle est faite pendant que la peau est dans le moule comme par exemple dans les trois modes de réalisation cités ci dessus. La réticulation a lieu à une température comprise entre l'ambiante et le point de ramollissement de (A) lorsque cette réticulation est déclenchée ultérieurement par un processus de diffusion d'humidité à travers la peau comme par exemple dans le deuxième et troisième mode de réalisation si on choisit de laisser l'humidité chasser l'aminé de la zéolite après la formation de la peau.In the slush molding process, the composition of the invention is transformed into skin on contact with the mold. Crosslinking takes place at a higher temperature than the melting temperature of (A) when it is made while the skin is in the mold, for example in the three embodiments mentioned above. Crosslinking takes place at a temperature between the ambient and the softening point of (A) when this crosslinking is subsequently triggered by a process of diffusion of moisture through the skin as for example in the second and third embodiment if it is chosen to allow the moisture to drive out the amine from the zeolite after the formation of the skin.
[Description détaillée de l'invention][Detailed description of the invention]
S'agissant du premier mode de réalisation les copolymères (A) peuvent être des polyéthylènes greffés par un anhydride d'acide carboxylique insaturé ou des copolymères de l'éthylène et d'un anhydride d'acide carboxylique insaturé qu'on obtient par exemple par polymérisation radicalaire.As regards the first embodiment, the copolymers (A) can be polyethylenes grafted with an unsaturated carboxylic acid anhydride or copolymers of ethylene and an unsaturated carboxylic acid anhydride which are obtained for example by radical polymerization.
L'anhydride d'acide carboxylique insaturé peut être choisi par exemple parmi les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène-1 ,2-dicarboxylique, 4 — méthylènecyclohex-4-ène-1 ,2- dicarboxylique, bicyclo(2,2,1)hept-5-ène-2,3-dicarboxylique, et x — méthylbicyclo(2,2,1)hept-5-ène-2,2-dicarboxylique. On utilise avantageusement l'anhydride maléique. On ne sortirait pas du cadre de l'invention en remplaçant tout ou partie de l'anhydride par un acide carboxylique insaturé tel que par exemple l'acide (meth)acrylique. S'agissant des polyéthylènes sur lesquels on vient greffer l'anhydride d'acide carboxylique insaturé on entend par polyéthylène des homo- ou copolymères.The unsaturated carboxylic acid anhydride can be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4-methylenecyclohex-4-ene-1, 2-dicarboxylic anhydrides, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid, and x - methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid. Advantageously, maleic anhydride is used. It would not be departing from the scope of the invention to replace all or part of the anhydride with an unsaturated carboxylic acid such as for example (meth) acrylic acid. As regards the polyethylenes to which the unsaturated carboxylic acid anhydride is grafted, polyethylene is understood to mean homo- or copolymers.
A titre de comonomères, on peut citer : les alpha-oléfines, avantageusement celles ayant de 3 à 30 atomes de carbone ; à titre d'exemples d'alpha oléfines on peut citer le propylène, le 1 -butène, le 1-pentène, le 3-méthyl-1 -butène, le 1-hexène, le 4- méthyl-1-pentène, le 3-méthyl-1-pentène, le 1-octène, le 1 -décène, le 1- dodécène, le 1-tétradécène, le 1-hexadécène, le 1-octadécène, le 1 — eicocène, le 1-dococène, le 1-tétracocène, le 1-hexacocène, le 1 — octacocène, et le 1- triacontène; ces alpha-oléfines peuvent être utilisées seules ou en mélange de deux ou de plus de deux, les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acryiates d'alkyle, les alkyles pouvant avoir jusqu'à 24 atomes de carbone, des exemples d'acrylate ou méthacrylate d'alkyle sont notamment le méthacrylate de méthyle, l'acrylate d'éthyle, Pacrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle, les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle. les diènes tels que par exemple le 1 ,4-hexadiène. le polyéthylène peut comprendre plusieurs des comonomères précédents.As comonomers, mention may be made of: alpha-olefins, advantageously those having from 3 to 30 carbon atoms; as examples of alpha olefins, mention may be made of propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-octene, 1-dececene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1-triacontene; these alpha-olefins can be used alone or as a mixture of two or more than two, esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, vinyl esters of saturated carboxylic acids such as, for example, vinyl acetate or propionate. dienes such as, for example, 1,4-hexadiene. the polyethylene can comprise several of the preceding comonomers.
Avantageusement le polyéthylène qui peut être un mélange de plusieurs polymères, comprend au moins 50% et de préférence 75% (en moles) d'éthylène, sa densité peut être comprise entre 0,86 et 0,98 g/cm3. Le MFI (indice de viscosité à 190°C, 2,16 kg) est compris avantageusement entre 20 et 1000 g/10 min.Advantageously, the polyethylene which may be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density can be between 0.86 and 0.98 g / cm 3 . The MFI (viscosity index at 190 ° C, 2.16 kg) is advantageously between 20 and 1000 g / 10 min.
A titre d'exemple de polyéthylènes on peut citer :Examples of polyethylenes that may be mentioned:
- le polyéthylène basse densité (LDPE)- low density polyethylene (LDPE)
- le polyéthylène haute densité (HDPE)- high density polyethylene (HDPE)
- le polyéthylène linéaire basse densité (LLDPE) - le polyéthylène très basse densité (VLDPE)- linear low density polyethylene (LLDPE) - very low density polyethylene (VLDPE)
- le polyéthylène obtenu par catalyse métallocène, c'est-à-dire les polymères obtenus par copolymérisation d'éthylène et d'alphaoléfine telle que propylène, butène, héxène ou octène en présence d'un catalyseur monosite constitué généralement d'un atome de zirconium ou de titane et de deux molécules cycliques alkyles liées au métal. Plus spécifiquement, les catalyseurs métallocènes sont habituellement composés de deux cycles cyclopentadiéniques liés au métal. Ces catalyseurs sont fréquemment utilisés avec des aluminoxanes comme cocatalyseurs ou activateurs, de préférence le méthylaluminoxane (MAO). Le hafnium peut aussi être utilisé comme métal auquel le cyclopentadiène est fixé. D'autres métallocènes peuvent inclure des métaux de transition des groupes IV A, V A, et VI A. Des métaux de la série des lanthanides peuvent aussi être utilisés. - les élastomères EPR (éthylène - propylène - rubber)the polyethylene obtained by metallocene catalysis, that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, VA, and VI A. Metals of the lanthanide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
- les élastomères EPDM (éthylène - propylène - diène)- EPDM elastomers (ethylene - propylene - diene)
- les mélanges de polyéthylène avec un EPR ou un EPDM- polyethylene blends with an EPR or an EPDM
- les copolymères éthylène-(méth)acrylate d'alkyle pouvant contenir jusqu'à 60% en poids de (méth)acrylate et de préférence 2 à 40%.- ethylene- (meth) acrylate copolymers which may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%.
Le greffage est une opération connue en soi.Grafting is an operation known in itself.
S'agissant des copolymères de l'éthylène et de l'anhydride d'acide carboxylique insaturé c'est-à-dire ceux dans lesquels l'anhydride d'acide carboxylique insaturé n'est pas greffé il s'agit des copolymères de l'éthylène, de l'anhydride d'acide carboxylique insaturé et éventuellement d'un autre monomère pouvant être choisi parmi les comonomères qu'on a cité plus haut pour les copolymères de l'éthylène destinés à être greffés.As regards the copolymers of ethylene and of the unsaturated carboxylic acid anhydride, that is to say those in which the unsaturated carboxylic acid anhydride is not grafted, these are the copolymers of l ethylene, unsaturated carboxylic acid anhydride and optionally another monomer which can be chosen from the comonomers mentioned above for the ethylene copolymers intended to be grafted.
On utilise avantageusement les copolymères éthylène-anhydride maléique et éthylène - (méth)acrylate d'alkyle - anhydride maléique. Ces copolymères comprennent de 0,2 à 10 % en poids d'anhydride maléique, de 0 à 40 % et de préférence 5 à 40 % en poids de (méth)acrylate d'alkyle. Leur MFI est compris entre 20 et 100 (190°C - 2,16 kg). Les (méth)acrylates d'alkyle ont déjà été décrits plus haut. La température de fusion est comprise entre 80 et 120°C. Le copolymère (A) est disponible dans le commerce il est produit par polymérisation radicalaire à une pression pouvant être comprise entre 200 et 2500 bars, il est vendu sous forme de granulés. On peut le mettre en poudre par microgranulation par exemple en utilisant la technique de la coupe sous eau de la société GALA (Virginie, USA) ou par broyage cryogénique. S'agissant de (B), les copolymères de l'éthylène et d'un époxyde insaturé, ils peuvent être obtenus par copolymérisation de l'éthylène et d'un époxyde insaturé ou par greffage de l'époxyde insaturé sur le polyéthylène. Le greffage peut être effectué en phase solvant ou sur le polyéthylène en fusion en présence d'un peroxyde. Ces techniques de greffage sont connues en elles- mêmes. Quant à la copolymérisation de l'éthylène et d'un époxyde insaturé, on peut utiliser les procédés dits de polymérisation radicalaire fonctionnant habituellement à des pressions entre 200 et 2 500 bars. A titre d'exemple d'époxydes insaturés, on peut citer : les esters et éthers de glycidyle aliphatiques tels que l'allyl glycidyléther, le vinyle glycidyléther, le maléate et l'itaconate de glycidyle, le (méth)acrylate de glycidyle, et - les esters et éthers de glycidyle alicycliques tels que le 2- cyclohexène-1 -glycidyléther, le cyclohexène-4,5-diglycidyl carboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-glycidyl carboxylate et l'endo cis-bicyclo(2,2,1)-5-heptène-2,3-diglycidyl dicarboxylate.The ethylene-maleic anhydride and ethylene - alkyl (meth) acrylate - maleic anhydride copolymers are advantageously used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to 40% and preferably 5 to 40% by weight of alkyl (meth) acrylate. Their MFI is between 20 and 100 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described above. The melting temperature is between 80 and 120 ° C. The copolymer (A) is commercially available, it is produced by radical polymerization at a pressure which may be between 200 and 2500 bars, it is sold in the form of granules. It can be powdered by microgranulation for example using the technique of cutting under water from the company GALA (Virginia, USA) or by cryogenic grinding. As regards (B), the copolymers of ethylene and of an unsaturated epoxide, they can be obtained by copolymerization of ethylene and of an unsaturated epoxide or by grafting of the unsaturated epoxide onto the polyethylene. The grafting can be carried out in the solvent phase or on the molten polyethylene in the presence of a peroxide. These grafting techniques are known in themselves. As for the copolymerization of ethylene and an unsaturated epoxide, it is possible to use the so-called radical polymerization processes usually operating at pressures between 200 and 2,500 bar. As examples of unsaturated epoxides, there may be mentioned: aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl (meth) acrylate, and - alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
S'agissant du greffage le copolymère s'obtient à partir du greffage d'un polyéthylène homo ou copolymère comme décrit pour (A) sauf qu'on greffe un époxyde au lieu d'un anhydride. S'agissant d'une copolymérisation c'est aussi semblable à (A) sauf qu'on utilise un époxyde, il peut aussi y avoir d'autres comonomères comme dans le cas de (A).As regards grafting, the copolymer is obtained from the grafting of a homo or copolymer polyethylene as described for (A) except that an epoxide is grafted instead of an anhydride. As it is a copolymerization, it is also similar to (A) except that an epoxide is used, there may also be other comonomers as in the case of (A).
Le produit (B) est avantageusement un copolymère éthylène/(méth)acrylate d'alkyle/époxyde insaturé. Avantageusement il peut contenir jusqu'à 40% en poids de (méth)acrylate d'alkyle, de préférence 5 à 40 % et jusqu'à 10% en poids d'époxyde insaturé, de préférence 0,1 à 8%. L'époxyde est avantageusement le (méth)acrylate de glycidyle. Avantageusement le (méth)acrylate d'alkyle est choisi parmi le (méth)acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle. La quantité de (méth)acrylate d'alkyle est avantageusement de 20 à 35%. Le MFI est avantageusement compris entre 5 et 100 (en g/10 min à 190°C sous 2,16 kg), la température de fusion est comprise entre 60 et 110°C. Ce copolymère peut être obtenu par polymérisation radicalaire des monomères. La mise en poudre s'effectue comme pour (A).The product (B) is advantageously an ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymer. Advantageously, it can contain up to 40% by weight of alkyl (meth) acrylate, preferably 5 to 40% and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%. The epoxide is advantageously glycidyl (meth) acrylate. Advantageously, the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate. The amount of alkyl (meth) acrylate is advantageously from 20 to 35%. The MFI is advantageously between 5 and 100 (in g / 10 min at 190 ° C. under 2.16 kg), the melting temperature is between 60 and 110 ° C. This copolymer can be obtained by radical polymerization of the monomers. The powdering is carried out as for (A).
On ne sortirait pas du cadre de l'invention si la composition comprenait plusieurs polymères (A) et/ou plusieurs polymères (B). (Ceci s'applique à tous les modes de réalisation). S'agissant des proportions de (A) et (B) avantageusement elles sont telles qu'il y ait 0,1 à 1 ,5 (de préférence 0,2 à 0,6) fonction anhydride par fonction époxyde. Il est avantageux d'utiliser un catalyseur c'est-à-dire un produit capable d'accélérer la réaction entre les fonctions anhydride et les fonctions époxyde. Ce catalyseur agit dès la fusion de (A) et (B) qui doivent être proches. La proportion de catalyseur est déterminée facilement par l'homme de l'art, ces réactions entre des fonctions anhydrides et époxydes étant connues en elles mêmes. Avantageusement la réticulation est effectuée par chauffage du moule à une température plus élevée que la température de fusion de (A).It would not go beyond the scope of the invention if the composition included several polymers (A) and / or several polymers (B). (This applies to all embodiments). As regards the proportions of (A) and (B) advantageously, they are such that there is 0.1 to 1.5 (preferably 0.2 to 0.6) anhydride function by epoxy function. It is advantageous to use a catalyst, that is to say a product capable of accelerating the reaction between the anhydride functions and the epoxy functions. This catalyst acts upon the fusion of (A) and (B) which must be close. The proportion of catalyst is easily determined by a person skilled in the art, these reactions between anhydride and epoxide functions being known in themselves. Advantageously, the crosslinking is carried out by heating the mold to a temperature higher than the melting temperature of (A).
Parmi les composés capables d'accélérer la réaction entre la fonction epoxy présente dans (B) et la fonction anhydride présente dans (A) on peut citer notamment : - des aminés tertiaires telles que la diméthyllaurylamine, la diméthylstéarylamine, la N-butylmorpholine, la N,N-diméthylcyclohexylamine, la benzyldiméthylamine, la pyridine, la diméthylamino-4-pyridine, le méthyl-l- imidazole, la tétraméthyléthylhydrazine, la N,N-diméthylpipérazine, la N,N,N',N'- tétraméthyl-l,6-hexanediamine, un mélange d'aminés tertiaires ayant de 16 à 18 carbones et connues sous l'appellation de diméthylsuifamine,Among the compounds capable of accelerating the reaction between the epoxy function present in (B) and the anhydride function present in (A) there may be mentioned in particular: - tertiary amines such as dimethyllaurylamine, dimethylstearylamine, N-butylmorpholine, N, N-dimethylcyclohexylamine, benzyldimethylamine, pyridine, dimethylamino-4-pyridine, methyl-1-imidazole, tetramethylethylhydrazine, N, N-dimethylpiperazine, N, N, N ', N'-tetramethyl-l , 6-hexanediamine, a mixture of tertiary amines having from 16 to 18 carbons and known under the name of dimethylsuifamine,
- des phosphines tertiaires telles que la triphénylphosphine- tertiary phosphines such as triphenylphosphine
- des alkyldithiocarbamates de zinc- zinc alkyldithiocarbamates
- des acides tels que des polymères comme le Lucalen (terpolymère éthylène/acrylate de butyle/acide acrylique) - sels de Magnésium tels que des mélanges de 65 % de sel de stéarate et 35 % de sel de palmitate.- acids such as polymers such as Lucalen (ethylene terpolymer / butyl acrylate / acrylic acid) - Magnesium salts such as mixtures of 65% stearate salt and 35% palmitate salt.
S'agissant du deuxième mode de réalisation de l'invention le polyéthylène fonctionnalisé (A) a déjà été décrit dans le premier mode. (B) est une polyamine adsorbée sur une zéolite, sous l'effet d'une élévation de température la polyamine est desorbée et vient reticuler (A). Il suffit de choisir un couple polyamine-zéolite tel que la desorption ait lieu au moins à la température de fusion de (A). La desorption est aussi provoquée par l'eau ou l'humidité c'est pourquoi il est recommandé d'ajouter à la zéolite chargée de polyamine une autre zéolite capable d'adsorber l'humidité pour éviter la réticulation pendant le stockage. Cette technique de réticulation d'un polymère contenant des groupes anhydride d'acide carboxylique par des zéolites libérant des polyamines sous l'effet de la température ou de l'humidité a été décrite dans le brevet US 5792816 dont le contenu est incorporé dans la présente demande.As regards the second embodiment of the invention, the functionalized polyethylene (A) has already been described in the first mode. (B) is a polyamine adsorbed on a zeolite, under the effect of a rise in temperature the polyamine is desorbed and comes to crosslink (A). It suffices to choose a polyamine-zeolite pair such that the desorption takes place at least at the melting temperature of (A). Desorption is also caused by water or humidity, which is why it is recommended to add to the polyamine-loaded zeolite another zeolite capable of absorbing moisture to avoid crosslinking during storage. This technique of crosslinking a polymer containing carboxylic acid anhydride groups by zeolites releasing polyamines under the effect of temperature or humidity has been described in US patent 5792816, the content of which is incorporated into the present application.
A titre d'exemple de polyamine on peut citer : l'éthylènediamine, la propanediamine, la butanediamine, la pentanediamine, l'hexanediamine, les isomères des aminés précédentes, la 1 ,2-diaminocyclohexane, la 1,4- diaminocyclohexane, la diéthylènetriamine, la triéthylènetetramine, la tetraéthylènepentamine, la N-aminoethyl-3-aminopropyltrialkoxysilane, la triaminopropyltrialkoxysilane, la piperazine, Paminoethylpiperazine, la diaminoethylpiperazine, la xylylènediamine, l'isophoronediamine, la 3,3'- dimethyl-4,4'-diaminocyclohexylmethane, la 1,4-diaminobenzanilide. Une partie de la polyamine peut être remplacée par des polyols ou des aminoalcools tels que par exemple : l'éthylèneglycol, le propylèneglycol, le triéthylèneglycol, le dipropylèneglycol, le butanediol, le neopentylglycol, le cyclohexane-di- methanol, l'hydroquinone-bis-hydroxyl-ether, la triethanolamine, la methyl- diethanolamine, la tripropanolamine, la N,N-di(2-hydroxyethyl)-aniline, l'ethanolamine, la diethanolamine, la propanolamine, la dipropanolamine et la N-hydroxyethyl-aniline. Quant aux zéolites on utilise avantageusement celles ayant des diamètres de pores entre 0,3 et 1,5 nm et de préférence une zéolite choisie parmi les quatres suivantes (on indique le diamètre de pores) : 0,38 nm désignée sous le type 4A,By way of example of polyamine, there may be mentioned: ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, the isomers of the preceding amines, 1, 2-diaminocyclohexane, 1,4-diaminocyclohexane, diethylenetriamine , triethylenetetramine, tetraethylenepentamine, N-aminoethyl-3-aminopropyltrialkoxysilane, triaminopropyltrialkoxysilane, piperazine, Paminoethylpiperazine, diaminoethylpiperazine, xylylenediamine, isophoronediamine, 3,3'-dimethylocyclin 1,4-diaminobenzanilide. Part of the polyamine can be replaced by polyols or amino alcohols such as for example: ethylene glycol, propylene glycol, triethylene glycol, dipropylene glycol, butanediol, neopentyl glycol, cyclohexane-dimethanol, hydroquinone bis -hydroxyl-ether, triethanolamine, methyl-diethanolamine, tripropanolamine, N, N-di (2-hydroxyethyl) -aniline, ethanolamine, diethanolamine, propanolamine, dipropanolamine and N-hydroxyethyl-aniline. As for the zeolites, advantageously those having pore diameters between 0.3 and 1.5 nm are used and preferably a zeolite chosen from the following four (the pore diameter is indicated): 0.38 nm designated under the type 4A,
0,44 nm désignée sous le type 5A, 0,8 nm désignée sous le type 10X, 0,84 nm désignée sous le type 13X. Toutes ces zéolites sont disponibles dans une granulométrie de l'ordre de 20 à 50 μm. La zéolite peut en plus de la polyamine être chargée avec un catalyseur de la réaction de l'anhydride et de l'aminé. On donne ci-dessous différents exemples de températures de desorption : 0.44 nm designated as type 5A, 0.8 nm designated as type 10X, 0.84 nm designated as type 13X. All these zeolites are available in a particle size of the order of 20 to 50 μm. In addition to the polyamine, the zeolite can be loaded with a catalyst for the reaction of the anhydride and the amine. Various examples of desorption temperatures are given below:
Une fois la peau formée la réticulation peut être effectuée par chauffage au delà de la température de fusion de (A) ou ultérieurement, la peau étant sortie du moule, par diffusion de l'humidité ambiante à une température comprise entre l'ambiante et le point de ramollissement de (A).Once the skin has been formed, the crosslinking can be carried out by heating beyond the melting point of (A) or later, the skin being removed from the mold, by diffusion of ambient humidity at a temperature between ambient and softening point of (A).
S'agissant du troisième mode de réalisation de l'invention il est du même genre que le deuxième mode mais on remplace le copolymère de l'éthylène et d'un anhydride d'acide carboxylique par un copolymère de l'éthylène et d' un époxyde, un tel copolymère a déjà été décrit comme polymère (B) dans le premier mode il suffit seulement qu'il ait un MFI d'au moins 20.As regards the third embodiment of the invention, it is of the same kind as the second mode, but the copolymer of ethylene and of a carboxylic acid anhydride is replaced by a copolymer of ethylene and of a epoxide, such a copolymer has already been described as polymer (B) in the first mode, it only suffices that it has an MFI of at least 20.
La réaction de greffage est mise en oeuvre dans une extrudeuse mono ou double vis alimentée par des polyoléfines dans une trémie d'alimentation, par exemple sous forme de granulés ; dans une première zone de l'extrudeuse, on procède à la fusion des polyoléfines par chauffage et dans une seconde zone, on introduit les réactifs au sein de la masse fondue des polyoléfines.The grafting reaction is carried out in a single or twin screw extruder fed with polyolefins in a feed hopper, for example in the form of granules; in a first zone of the extruder, the polyolefins are melted by heating and in a second zone, the reactants are introduced into the polyolefin melt.
Les initiateurs radicalaires peuvent être choisis parmi les peroxydes, peracides, peresters, peracétals. On les utilise en général à raison de 0,01 % à 0,5 % en masse par rapport aux polyoléfines à greffer.The radical initiators can be chosen from peroxides, peracids, peresters, peracetals. They are generally used in an amount of 0.01% to 0.5% by mass relative to the polyolefins to be grafted.
Les compositions de l'invention peuvent comprendre aussi des agents anti-mottants tels que la silice Aérosil R972, des agents fluidifiants tels que l'éthylène-bistéaramide, des agents démoulants tels que du stéarate de calcium ou du stéarate de magnésium et autres ingrédients tels que des résines tackifiantes telles que la résine Régalite R1115.The compositions of the invention can also comprise anti-caking agents such as silica Aérosil R972, fluidifying agents such as ethylene-bistearamide, release agents such as calcium stearate or magnesium stearate and other ingredients such as tackifying resins such as Régalite R1115 resin.
Elles peuvent aussi comprendre des stabilisants de procédé (= processing stabilizers) tels queque Irgafos 168, DDPP, P-EPQ, TNPP, TPP, PS 800, PS 802, antioxydants tels que Irganox 1010, 245, 259, 565, 1035, 1076, 1098, 1135, 1141 , 1330, 1425, 3052, 3114, 5057, M1024, des mélanges des antioxydants et stabilisants de procédé tels que Irganox B225, des anti UV tels que la gamme de Tinuvin et Chimassorb de CIBA.They can also include processing stabilizers such as Irgafos 168, DDPP, P-EPQ, TNPP, TPP, PS 800, PS 802, antioxidants such as Irganox 1010, 245, 259, 565, 1035, 1076, 1098, 1135, 1141, 1330, 1425, 3052, 3114, 5057, M1024, mixtures of antioxidants and process stabilizers such as Irganox B225, anti UV agents such as the Tinuvin and Chimassorb range from CIBA.
Elles peuvent aussi comprendre des charges et des pigments de coloration tel que noir de carbone et le Tiθ2-They can also include fillers and coloring pigments such as carbon black and Tiθ2-
Elles peuvent aussi comprendre des agents désodorisants tels que le charbon actif : par exemple 3S, CXV (CECA), acide undécylénique, undécylénate d'éthyle, undécylénate de calcium, undécylénate de zinc, de la cyclodextrine, des zéolites tels que Flavith et des parfums. La peau ayant été formée par fusion du mélange de poudres (A)+(B) sur le moule chaud on élimine l'excès de poudre non fondue, puis on peut poursuivre ou déclencher la réticulation en la plaçant dans un four à une température comprise entre 200 et 350° C pendant un temps compris entre 10 s et 10mn. La peau est ensuite séparée du moule après refroidissement. On peut aussi dans les deuxième et troisième mode de réalisation retirer la peau du moule puis reticuler à l'humidité.They can also include deodorizing agents such as activated carbon: for example 3S, CXV (CECA), undecylenic acid, ethyl undecylenate, calcium undecylenate, zinc undecylenate, cyclodextrin, zeolites such as Flavith and perfumes . The skin having been formed by melting the mixture of powders (A) + (B) on the hot mold, the excess of unmelted powder is eliminated, then the crosslinking can be continued or triggered by placing it in an oven at a temperature included between 200 and 350 ° C for a time between 10 s and 10 min. The skin is then separated from the mold after cooling. It is also possible in the second and third embodiment to remove the skin from the mold and then cross-link with moisture.
Les compositions de l'invention permettent d'obtenir des peaux ayant un toucher très doux, une dureté inférieure à 90 shore A sans usage de plastifiants liquides et ne présentant pas de fluage à chaud. Avantageusement ces peaux ont les caractéristiques suivantes :The compositions of the invention make it possible to obtain skins having a very soft feel, a hardness of less than 90 shore A without the use of liquid plasticizers and having no hot creep. Advantageously, these skins have the following characteristics:
- l'épaisseur est comprise entre 0,6 et 1 , 1 mm- the thickness is between 0.6 and 1.1 mm
- la résistance à la rupture (RR) est d'au moins 5 MPa- the breaking strength (RR) is at least 5 MPa
- l'allongement à la rupture (AR) est d'au moins 300%- the elongation at break (AR) is at least 300%
- le vieillissement après 500 h à 100°C exprimé par la variation d'allongement est d'au plus 40 %- the aging after 500 h at 100 ° C expressed by the variation in elongation is at most 40%
- le vieillissement après 250 h à 120°C exprimé par la variation d'allongement à la rupture est d'au plus 50 % - le vieillissement après 250 h à 120°C exprimé par la variation de la contrainte à la rupture est d'au plus 10 %- the aging after 250 h at 120 ° C expressed by the variation in elongation at break is at most 50% - the aging after 250 h at 120 ° C expressed by the variation of the breaking stress is at most 10%
- l'allongement après fluage à 140°C sous une charge de 0,5 bar est au plus de 30% - Fogging DIN 75201 (3 h à 100°C) : aucun dépôt (mesure de la migration de phtalates).- the elongation after creep at 140 ° C under a load of 0.5 bar is at most 30% - Fogging DIN 75201 (3 h at 100 ° C): no deposit (measurement of phthalate migration).
- Rayure par abrasion et résistance à l'usure par abrasion après 30 min conforme avec les normes.- Scratch by abrasion and resistance to wear by abrasion after 30 min in accordance with standards.
- Brillance conforme avec les normes. - Tenue chaleur (22 h à 100°C) : conforme avec les normes.- Gloss compliant with standards. - Heat resistance (10 p.m. at 100 ° C): complies with standards.
[Exemples][Examples]
Sauf indication contraire les compositions des produits ( % d'acrylate etc..) et les compositions des poudres de l'invention sont en poids. On a utilisé les produits suivants :Unless otherwise indicated, the compositions of the products (% of acrylate, etc.) and the compositions of the powders of the invention are by weight. The following products were used:
LOTADER® 8900 copolymère éthylène/ acrylate de méthyle/méthacrylate de glycidyle (GMA) à 28 % d'acrylate et 7,8 % de GMA et MFI 6LOTADER® 8900 ethylene / methyl acrylate / glycidyl methacrylate (GMA) copolymer containing 28% acrylate and 7.8% GMA and MFI 6
LOTADER® 6600 copolymère éthylène/acrylate d'éthyle/anhydride maléique (MAH) à 27,5 % d'acrylate et 2,9 % de MAH et MFI 40LOTADER® 6600 ethylene / ethyl acrylate / maleic anhydride (MAH) copolymer with 27.5% acrylate and 2.9% MAH and MFI 40
LOTADER® 7500 copolymère éthylène/acrylate d'éthyle/anhydride maléiqueLOTADER® 7500 ethylene / ethyl acrylate / maleic anhydride copolymer
(MAH) à 20,0 % d'acrylate et 3,0 % de MAH et MFI 70(MAH) with 20.0% acrylate and 3.0% MAH and MFI 70
LOTADER® AX 8999 copolymère éthylène/ acrylate de butyle/méthacrylate de glycidyle (GMA) à 28 % d'acrylate et 1 % de GMA et MFI 70 XX 1275 catalyseur, dimethylsuifamine (DMS) sous forme de mélange maitre àLOTADER® AX 8999 ethylene / butyl acrylate / glycidyl methacrylate (GMA) copolymer with 28% acrylate and 1% GMA and MFI 70 XX 1275 catalyst, dimethylsuifamine (DMS) in the form of a masterbatch
3 % dans un copolymère éthylène/acrylate de butyle/MAH à 32 % d'acrylate et3% in an ethylene / butyl acrylate / MAH copolymer containing 32% acrylate and
3 % de MAH et MFI 73% MAH and MFI 7
LUCALEN A3110M copolymère éthylène/acrylate de butyle/acide acrylique àLUCALEN A3110M ethylene / butyl acrylate / acrylic acid copolymer
8 % d'acrylate et 4 % d'acide acrylique et MFI 6-8 (190° 2.16 kg) IRGANOX B 225 1 : 1 Irganox 1010/lrgafos 1688% acrylate and 4% acrylic acid and MFI 6-8 (190 ° 2.16 kg) IRGANOX B 225 1: 1 Irganox 1010 / lrgafos 168
RESINE tackifiante REGALITE R1125REGALITY R1125 tackifying RESIN
MM noir de carbone STEARATE DE MAGNESIUM : mélanges de 65 % de sel de stéarate et 25 % de sel de palmitate AEROSIL R972 (Degussa) CHARBON ACTIF 3S et CXV (CECA). Les différents constituants ci-dessus ont été réduits en poudre de granulométrie 200 μm par broyage cryogénique.MM carbon black MAGNESIUM STEARATE: mixtures of 65% stearate salt and 25% palmitate salt AEROSIL R972 (Degussa) ACTIVE CARBON 3S and CXV (CECA). The various constituents above have been reduced to powder with a particle size of 200 μm by cryogenic grinding.
Les différentes compositions de l'invention ont été préparées par mélange des constituants dans un mélangeur à poudre. On a réalisé des peaux par la technique de slush molding. Le moule a été porté à une température de 250°C dans un four. On a ensuite recouvert le moule sorti du four par un excès de poudre de la composition utilisée. Après environ 10 s, la poudre non fondue est éliminée par retournement du moule. On porte ensuite à nouveau le moule dans le four à 250°C pendant 3 mn. Le moule est ensuite refroidi dans l'eau froide . La peau est ensuite dégagée du moule. Les compositions et les propriétés sont rassemblées sur le tableau 1 suivant.The various compositions of the invention were prepared by mixing the constituents in a powder mixer. We made skins using the slush molding technique. The mold was brought to a temperature of 250 ° C in an oven. The mold taken out of the oven was then covered with an excess of powder of the composition used. After approximately 10 s, the unmelted powder is removed by inverting the mold. The mold is then brought back to the oven at 250 ° C for 3 min. The mold is then cooled in cold water. The skin is then released from the mold. The compositions and properties are collated in Table 1 below.
Exemples 5 et 6Examples 5 and 6
L'exemple 5 est une peau noire et l'exemple 6 est une peau grise. Ces exemples possèdent de meilleures performances que les exemples 1 et 4 en terme d'abrasion, propriétés mécaniques, toxicité (pas de dimethylsuifamine), une meilleure tenue au vieillissement thermique (antioxydants) et moins d'odeurExample 5 is black skin and Example 6 is gray skin. These examples have better performance than examples 1 and 4 in terms of abrasion, mechanical properties, toxicity (no dimethylsuifamine), better resistance to thermal aging (antioxidants) and less odor.
(charbon actif).(charcoal).
La fabrication de la poudre se décompose en différentes étapes. Cette fabrication est identique pour toutes les formules. 1. Compoundage de la formulation sur base Lotader 8900 (=A) et Lotader 7500 (=B) (exemple 5). Les formules A suivantes ont été compoundées sur extrudeuse double vis LEISTRITZ avec dégazage à une température de 160°C et les formules B ont été compoundées sur extrudeuse double vis LEISTRITZ avec dégazage à une température de 180°C. The production of the powder is broken down into different stages. This production is identical for all formulas. 1. Compounding of the formulation based on Lotader 8900 (= A) and Lotader 7500 (= B) (example 5). The following formulas A were compounded on a LEISTRITZ twin screw extruder with degassing at a temperature of 160 ° C and formulas B were compounded on a LEISTRITZ twin screw extruder with degassing at a temperature of 180 ° C.
2. Dry blend des granulés des 2 composants dans les proportions définies2. Dry blend of the granules of the 2 components in the defined proportions
Les granulés A et B ont été mélangés en dry blend suivant le rapport massique A / B = 1.575. 3. Fabrication de la poudre par broyage crvogénigue et additivationThe granules A and B were mixed in a dry blend according to the mass ratio A / B = 1.575. 3. Manufacture of the powder by crogogenic grinding and additivation
Les formules ont ensuite été broyées cryogéniquement en poudre de granulométrie 200 μm, puis additivées au mélangeur rapide par 2 % de stéarate de magnésium et 0.6 % de silice AEROSIL. 4. Slush molding Le moule a été traité à 100°C avec un agent de démoulage et cuit à 120°C pendant 20 min. (Chem-Trend S.A. Mono Coat MC-708A) et a été porté à une température de 250-300°C dans un four. On a ensuite recouvert le moule sorti du four par un excès de poudre de la composition utilisée. Après environ 10 s, la poudre non fondue est éliminée par retournement du moule. On porte ensuite à nouveau le moule dans le four à 250-300°C pendant 1-5 mn. Le moule est ensuite refroidi dans l'eau froide. La peau est ensuite dégagée du moule.The formulas were then cryogenically ground into a powder with a particle size of 200 μm, then added to the rapid mixer with 2% magnesium stearate and 0.6% AEROSIL silica. 4. Slush molding The mold was treated at 100 ° C with a release agent and baked at 120 ° C for 20 min. (Chem-Trend S.A. Mono Coat MC-708A) and was brought to a temperature of 250-300 ° C in an oven. The mold taken out of the oven was then covered with an excess of powder of the composition used. After approximately 10 s, the unmelted powder is removed by inverting the mold. The mold is then brought back to the oven at 250-300 ° C for 1-5 min. The mold is then cooled in cold water. The skin is then released from the mold.
Les compositions et propriétés de formules d'exemples 5 et 6 sont les suivantes : TABLEAU 1The compositions and properties of the formulas of Examples 5 and 6 are as follows: TABLE 1

Claims

REVENDICATIONS
1 composition réticulable de poudre de polyoléfine fonctionnalisée comprenant : une polyoléfine fonctionnalisée (A) ayant un MFI d'au moins 20 (190°C1 crosslinkable composition of functionalized polyolefin powder comprising: a functionalized polyolefin (A) having an MFI of at least 20 (190 ° C.
2,16 kg) contenant une fonction anhydride et/ou époxy ; un produit (B) ayant pour fonction de reticuler (A), la composition ayant une granulométrie entre 100 et 400 μm.2.16 kg) containing an anhydride and / or epoxy function; a product (B) having the function of crosslinking (A), the composition having a particle size between 100 and 400 μm.
2 Composition selon la revendication 1 dans laquelle (A) est choisi parmi les copolymères de l'éthylène et d'un anhydride d'acide carboxylique insaturé et (B) est choisi parmi les copolymères de l'éthylène et d'un époxyde insaturé.2 Composition according to claim 1 in which (A) is chosen from copolymers of ethylene and an unsaturated carboxylic acid anhydride and (B) is chosen from copolymers of ethylene and an unsaturated epoxide.
3 Composition selon la revendication 2 dans laquelle (A) est choisi parmi les copolymères éthylène - (méth)acrylate d'alkyle - anhydride maléique, ces copolymères comprenant de 0,2 à 10 % en poids d'anhydride maléique, de 5 à 40 % en poids de (méth)acrylate d'alkyle.3 Composition according to claim 2 in which (A) is chosen from ethylene - alkyl (meth) acrylate - maleic anhydride copolymers, these copolymers comprising from 0.2 to 10% by weight of maleic anhydride, from 5 to 40 % by weight of alkyl (meth) acrylate.
4 Composition selon la revendication 2 ou 3 dans laquelle le produit4 Composition according to claim 2 or 3 in which the product
(B) est avantageusement un copolymère éthylène/(méth)acrylate d'alkyle/époxyde insaturé qui peut contenir jusqu'à 40% en poids de (méth)acrylate d'alkyle et jusqu'à 10% en poids d'époxyde insaturé.(B) is advantageously an ethylene / (meth) acrylate / unsaturated epoxide copolymer which can contain up to 40% by weight of (meth) acrylate and up to 10% by weight of unsaturated epoxide.
5 Composition selon la revendication 1 dans laquelle (A) est choisi parmi les copolymères de l'éthylène et d'un anhydride d'acide carboxylique insaturé et (B) est choisi parmi les polyamines adsorbées sur une zéolite.5 Composition according to claim 1 in which (A) is chosen from copolymers of ethylene and of an unsaturated carboxylic acid anhydride and (B) is chosen from polyamines adsorbed on a zeolite.
6 Composition selon la revendication 1 dans laquelle (A) est choisi parmi les copolymères de l'éthylène et d'un époxyde insaturé et (B) est choisi parmi les polyamines adsorbées sur une zéolite. 7 Procédé de fabrication d'un objet moulé par slush molding comprenant la fusion d'une composition selon l'une quelconque des revendications précédentes, puis la réticulation de celle-ci. 6 Composition according to claim 1 in which (A) is chosen from copolymers of ethylene and of an unsaturated epoxide and (B) is chosen from polyamines adsorbed on a zeolite. 7 A method of manufacturing an object molded by slush molding comprising melting a composition according to any one of the preceding claims, and then crosslinking thereof.
EP00960794A 1999-09-10 2000-09-05 Crosslinkable compositions of functionalised polyolefin powders Withdrawn EP1228141A1 (en)

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US6797222B2 (en) * 1999-04-15 2004-09-28 E. I. Du Pont De Nemours And Company Slush molding process
US8129450B2 (en) 2002-12-10 2012-03-06 Cellresin Technologies, Llc Articles having a polymer grafted cyclodextrin
US7166671B2 (en) 2002-12-10 2007-01-23 Cellresin Technologies, Llc Grafted cyclodextrin
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US7829628B2 (en) * 2006-11-03 2010-11-09 Polyone Corporation Colorant concentrates for thermoplastic biofiber composites
MX2017016616A (en) * 2015-06-29 2018-05-15 Dow Global Technologies Llc Compositions and methods for making crosslinked polyolefins with peroxide initiator.
CN111491956A (en) * 2017-12-22 2020-08-04 Sabic环球技术有限责任公司 Process for preparing amorphous polyolefin ionomers
JP2024533497A (en) * 2021-09-19 2024-09-12 ダウ グローバル テクノロジーズ エルエルシー Curing of anhydride-functionalized polymers with multifunctional epoxy or oxetane compounds

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