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 other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
• • 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 other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof
  • 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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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Moulding By Coating Moulds (AREA)
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• 1999
  • 1999-09-10 FR FR9911353A patent/FR2798388B1/fr not_active Expired - Fee Related
• 2000
  • 2000-09-05 PL PL00353133A patent/PL353133A1/xx not_active Application Discontinuation
  • 2000-09-05 BR BR0013682-4A patent/BR0013682A/pt not_active Application Discontinuation
  • 2000-09-05 CZ CZ2002865A patent/CZ2002865A3/cs unknown
  • 2000-09-05 WO PCT/FR2000/002441 patent/WO2001019911A1/fr active Application Filing
  • 2000-09-05 AU AU72979/00A patent/AU7297900A/en not_active Abandoned
  • 2000-09-05 JP JP2001523685A patent/JP2003509560A/ja not_active Abandoned
  • 2000-09-05 RU RU2002109229/04A patent/RU2247753C2/ru not_active IP Right Cessation
  • 2000-09-05 KR KR1020027003103A patent/KR20020057959A/ko active IP Right Grant
  • 2000-09-05 US US10/070,555 patent/US6774188B1/en not_active Expired - Fee Related
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  • 2000-09-05 EP EP00960794A patent/EP1228141A1/de not_active Withdrawn
  • 2000-09-05 CA CA002383478A patent/CA2383478A1/fr not_active Abandoned

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