MXPA00005522A - Compatibilized blends of non-polar thermoplastic elastomers and polar thermoplastic polymers - Google Patents

Abstract

The invention relates to compatibilized blends comprising a non-polar thermoplastic elastomer, a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chloro containing polymers, fluoro containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymer, polyacetal, polycarbonate, polyphenylene oxide, and a suitable compatibilizer.

Description

COMPATIBILIZED MIXTURES OF NON-POLAR THERMOPLASTIC ELASTOMERS AND POLARIZED THERMOPLASTIC POLYMERS BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to compatibilized blends of non-polar polyolefin thermoplastic elastomers and polar thermoplastic polymers that have been compatibilized by a suitable compatibilizer. In addition, the present invention relates to shaped articles consisting of said compatibilized mixtures. The concept of using compatibilizers as an interfacial agent in polymer blends is almost as old as the polymers themselves. For detailed background information reference is made to: "Polymer Blends" by D.R. Paul and S. Newman, Volume 1, 2, Academic Press, Inc., 1978. As widely described in the literature, a remarkable balance of various properties can be achieved with mixtures of different polymers, provided that adequate morphological stability is achieved between the different polymeric ingredients of the mixture. The object of the present invention is to provide mixtures of specific polymers which, under normal conditions and circumstances, would be incompatible with each other, and consequently their mixtures would show deficient physical properties or in many cases could not or could only be mixed hardly, combined or another way to process yourself. In detail, an object of the present invention is to provide compatibilized blends of non-polar thermoplastic elastomers with polar thermoplastic polymers thereby achieving improved properties of the final product mixture which simulate the properties of both components in the blends. For example, polyvinylidene fluoride (PVDF) is an inert flexible thermoplastic that is known for its excellent resistance to chemicals and fluids and its resistance to abrasion. In addition, the PVDF has a high service temperature and low surface friction coefficient. Another example of thermoplastic polymer would be the thermoplastic urethanes (TPU) which are known for their attachment to different polar substrates such as ABS, PVC, etc., their paint capacity, abrasion resistance and gloss. Both PVDF and TPU are incompatible with non-polar thermoplastic elastomers, that is, they do not form a homogeneous mixture nor can they be processed satisfactorily. The general physical properties of such incompatible "mixtures" are deficient. The same situation is faced when an attempt is made to mix polar polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) or polyesters with non-polar thermoplastic elastomers. The object of the present invention has been surprisingly solved by the addition of a suitable compatibilizer to the mixture comprising the non-polar thermoplastic elastomer and the polar thermoplastic polymers. A further object of the present invention is the provision of a compatibilized mixture of non-polar thermoplastic elastomers with polar thermoplastic polymers which shows adequate adhesion to polar substrates, in particular to polar polymeric substrates.

DESCRIPTION OF THE INVENTION In detail, the present invention relates to a compatibilized mixture comprising: a non-polar thermoplastic elastomer, a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chlorine-containing polymers, fluorine-containing polymers, polyesters, acrylonitrile copolymers -butadiene-styrene, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymer, polyacetal, polycarbonate, polyphenylene oxide, and - a compatibilizer. The compatibilized blends of the present invention comprise: 50 to 98% by weight, preferably 60 to 95% by weight, most preferably 70 to 90% by weight, of the non-polar thermoplastic elastomer; -50 to 2% by weight, preferably 40 to 5% by weight, most preferably 30 to 10% by weight, of the polar thermoplastic polymer, based on the total amount of the non-polar thermoplastic elastomer and the polar thermoplastic polymer. In the present invention, the term "non-polar thermoplastic elastomer" means that the thermoplastic component is a polyolefin polymer that includes optional additives. Also, the term "polar thermoplastic polymer" means a thermoplastic polymer that contains in its molecular structure at least one atom selected from nitrogen, oxygen and halogen in addition to carbons and hydrogens. The term "non-polar thermoplastic elastomer" also extends to mixtures of different but compatible non-polar thermoplastic elastomers.The term "polar thermoplastic polymer" as used in the description and claims also extends to mixtures of different polar thermoplastic elastomers. but compatible polar thermoplastic polymers Of course, the compatibilized mixture may contain optional additives which may be added or mixed as such or as additives to their constituents.

DESCRIPTION OF THE PREFERRED MODALITIES 1. Non-polar thermoplastic elastomer The term "thermoplastic elastomer" (TPE) generally defines mixtures of polyolefin and rubbers in which the rubber phase is not cured, ie the so-called thermoplastic olefins (TPO), mixtures of polyolefins and rubbers in the which the rubber phase has been partially or completely cured by a vulcanization process to form thermoplastic vulcanizates (TPV), or unvulcanized block copolymers or mixtures thereof. According to the present invention, the non-polar thermoplastic elastomer is selected from: (A) (a) a thermoplastic polyolefin homopolymer or copolymer, and (b) an olefinic rubber that is completely interlaced, partially entangled or non-interlaced, and optionally (c) common additives; (B) (a) a styrene / conjugated diene / styrene block copolymer and / or its complete or partially hydrogenated derivative, optionally mixed with (b) a thermoplastic polyolefin homopolymer or copolymer and / or (c) common additives and (b) C) any mixture of (A) and (B). 1. 1 Non-Polar Thermoplastic Elastomer (A) 1.1.1 Thermoplastic Poleolefin Poleolefins suitable for use in compositions (A), (B) or (C) of the invention include crystalline and thermoplastic polyolefin homopolymers and copolymers. They are prepared in desirable form from monoolefin monomers having from 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1 -hexene, 1-octene, 3-methyl-1 -pentene, 4-methyl-1-pentene, 5-methyl-1-hexen, mixtures thereof and copolymers thereof with (meth) acrylates and / or vinyl acetates. However, monomers having 3 to 6 carbon atoms are preferred, with propylene being preferred. As used in the description and claims, the term "polypropylene" includes propylene homopolymers as well as reactor and / or polypropylene random copolymers which may contain from about 1 to about 30% by weight of ethylene and / or an α-olefin comonomer of 4 to 6 carbon atoms, and mixtures thereof. The polypropylene may be highly crystalline isotactic or syndiotactic polypropylene. Commercially available poleolefins can be used in the practice of this invention. Additional poleolefins which can be used in terms of the invention are high, low, linear, low, very low density polyethylenes and ethylene copolymers with (meth) acrylates and / or vinyl acetates. The poleolefins mentioned above can be made by conventional Ziegler / Natta catalyst systems or by single-site catalyst systems. The amount of poleolefin found to provide useful compositions (A) is generally from about 8 to about 90 weight percent, with the proviso that the total amount of poleolefin (a) and rubber (b) is at least less about 35 weight percent, based on the total weight of the polyolefin (a), rubber (b) and optional additives (c). Preferably, the polyolefin content will vary from about 10 to about 60 weight percent. 1. 1.2 Olefinic rubber Suitable monoolefin copolymer rubbers comprise non-polar rubberized copolymers of two or more α-monoolefins, preferably copolymerized with at least one polyene, usually a diene. Saturated monoolefin copolymer rubber, for example, styrene-propylene copolymer rubber (EPM) can be used. However, unsaturated monoolefin rubber such as EPDM rubber is more suitable. The EPPDM is a terpolymer of styrene, propylene and a non-conjugated diene. Successful non-conjugated dienes include 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene; 5-methylene-2-norbomeno (MNB); 1, 6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; dicyclopentadiene (DCPD) and vinyl norbornene (VNB). Butyl rubs are also useful in the compositions of the invention. As used in the description and claims, the term "butyl rubber" includes copolymers of an isoolefin and a conjugated monoolefin, terpolymers of an isoolefin with or without a conjugated monoolefin, divinyl aromatic monomers and the halogenated derivatives of said copolymers and terpolymers .

Useful butyl rubber copolymers comprise a higher proportion of isoolefin and a smaller amount, usually less than about 30% by weight, of a conjugated multiolefin. Preferred copolymers comprise about 85-99.5% by weight of a C4-7 isoolefin such as isobutylene, and about 15-0.5% by weight of a multiolefin of 4-14 carbon atoms, such as isoprene, butadiene, dimethyl butadiene and piperylene. The butyl rubber, chlorobutyl rubber, commercial bromobutyl rubber, useful in the invention, are the copolymers of isobutylene and minor amounts of isoprene with less than about 3% halogen for the halobutyl derivatives. Other butyl co- and terpolymer rubbers are illustrated by the disclosure of US-A-4 916 180, the disclosure of which is hereby incorporated by reference. Another suitable copolymer within the scope of the olefinic rubber of the present invention is a copolymer of a C4.7 isomonoolefin and a para-alkylstyrene, and preferably a halogenated derivative thereof. The amount of halogen in the copolymer, predominantly para-alkylstyrene, is from about 0.1 to 10% by weight. An example that is preferred is the brominated copolymer of isobutylene and para-methylstyrene. These copolymers are described in more detail in US-A-5 162 445, the disclosure of which is incorporated herein by reference. An additional olefinic rubber suitable in the invention is natural rubber. The main constituent of natural rubber is the linear polymer cis-1, 4- polyisoprene. This is commercially available normally in the form of smoked leaves and crepe. Synthetic polyisoprene can also be used. In addition, polybutadiene rubber and styrene-butadiene copolymer rubbers can also be used. Mixtures of any of the above olefinic rubs can be used, instead of a single olefinic rubber. Suitable and additional rubbers are nitrile rubbers. Examples of the rubber containing a nitrile group include a copolymer rubber comprising an ethylenically saturated nitrile compound and a conjugated diene. In addition, the copolymer can be one in which the conjugated diene units of the copolymer rubber are hydrogenated. Specific examples of the ethylenically unsaturated nitrile compound include acrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and methacrylonitrile. Among these, acrylonitrile is particularly preferred. Examples of the conjugated diene include 1,3-butadiene, 2-chlorobutadiene and 2-methyl-1,3-butadiene (isoprene). Among these, butadiene is particularly preferred. Especially preferred nitrile rubbers comprise 1, 3-butadiene copolymers and about 10 to about 50 percent acrylonitrile. Other rubbers suitable in terms of the present invention are based on polychlorinated butadienes such as polychloroprene rubber. These rubbers are commercially available with the Neoprene® and Bayprene® brands.

To prepare the compositions of the invention, the amount of rubber in the composition (A) generally ranges from about 70 to about 10 weight percent, with the proviso that the total amount of polyolefin (a) and rubber (b) it is at least about 35% by weight, based on the weight of the polyolefin (a), the rubber (b) and the optional additives (c). Preferably, the olefinic rubber content will be in the range of about 50 to about 10 weight percent. 1. 1.3 Vulcanization If cured, the procedure of dynamically curing the rubber in the polyolefin matrix is used. The method of dynamically curing the rubber in a polyolefin matrix is well known in the art. Initial works found in US-A-3,037,954 describe the technique of dynamic vulcanization in which a vulcanizable elastomer is dispersed in a resinous thermoplastic polymer and the elastomer is cured in the presence of a curator while continuously mixing and the polymer mixture is subjected to shear strength. The resulting composition [dynamically vulcanized or thermoplastic vulcanized alloy (TPV)] is a cured elastomer microgel dispersion in an uncured matrix of thermoplastic polymer. Since then technology has advanced significantly. For additional general background information, refer to EP-A-0 473 703, EP-A-0 657 504, WO-A-95/25380 and other patent applications of the applicant whose description is incorporated herein by reference. The elastomer (rubber) component of the TPV can be uncured, partially or completely vulcanized (interlaced). Those skilled in the art will appreciate the amounts, suitable types of curing systems and vulcanization conditions that are required to carry out vulcanization of the rubber. The elastomer can be vulcanized using varying amounts of curing agent, variable temperatures and variable curing time to obtain the desired optimum interleaving. Any known curing system can be used, as long as it is suitable under the vulcanization conditions for the elastomer or combination of elastomers that are being used and is compatible with the thermoplastic polyolefin component of the TPV. These healers include sulfur, sulfur donors, metal oxides, phenolic resin systems, maleimides, peroxide-based systems, high-energy radiation and the like, both with accelerators and with co-agents. Another curing system that can be used is the hydrosilylation system which consists of the use of a silicon hydride heater catalyzed with a platinum or radium derivative. Such systems are described, for example, in EP-A-0776937. Phenolic resin healers are preferred for the preparation of the TPV composition of the invention, and such curing systems are well known in the art and literature of the vulcanization of elastomers. Its use in POS compositions is described in more detail in US-A-4,311,628, the disclosure of which is hereby incorporated by reference in its entirety. Normally, 5 to 20 parts by weight of the healer or curing system are used per 100 parts by weight of the rubber to be cured. 1. 2 Thermoplastic elastomer (B) Another thermoplastic elastomer (B) is a styrene / conjugated diene / styrene block copolymer, with the conjugated diene being optionally fully or partially hydrogenated, or mixtures thereof. Generally, this block copolymer may contain from about 10 to about 50% by weight, most preferably from about 25 to about 35% by weight of styrene and from about 90 to about 50% by weight, most preferably from about 75 to about 35. % by weight of the conjugated diene, based on said block copolymer. However, most preferably it is a block copolymer containing about 30% by weight of styrene and about 70% by weight of the conjugated diene. The conjugated diene is selected from butadiene, isoprene or mixtures thereof. The specific block copolymers of the styrene / conjugated diene / styrene type are block copolymers SBS, SIS, SIBS, SEBS and SEPS. These block copolymers are known in the art and are commercially available. Optionally, the block copolymer can be further mixed with a polyolefin or a common additive or mixtures thereof. In this manner, the thermoplastic elastomer (B) optionally further comprises about 60% by weight of (b) the thermoplastic polyolefin homopolymer or copolymer or the additives or mixtures thereof, based on the total weight of the block copolymer (a) and (b). Preferably, the thermoplastic elastomer (B) comprises at least 10% by weight of the thermoplastic polyolefin. The thermoplastic polyolefins are selected from those mentioned above in context with the thermoplastic elastomer (A). 1. 3 Thermoplastic elastomer (C) Other thermoplastic elastomers that can be modified with the modifier mentioned below are mixtures of the thermoplastic elastomer (A) comprising the polyolefin, rubber and optional additives with the thermoplastic elastomer (B) comprising the block copolymer , optionally polyolefins and / or additives. The mixtures (C) that are preferred contain about 5 to about 95% by weight of (A) and about 95 to about 5% by weight of (B) respectively, based on the total amount of (A) and (B) ). These mixtures can be prepared by common mixing procedures known in the art. 2. Polar thermoplastic polymer According to the present invention, the polar thermoplastic polymer is selected from thermoplastic polyurethanes (TPU), chlorine-containing polymers, for example, polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), chlorinated polyethylene (CPE) , polymers containing fluorine, for example, polyvinylidene fluoride (PVDF), polyesters, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymers (SAN), styrene-maleic anhydride copolymer (SMA), polyacetals, polycarbonates and polyphenylene oxide. 2. 1 Thermoplastic Polyurethane (TPU) The polyurethane component has no limitation with respect to its formulation, other than the need to be thermoplastic in nature, which means that it is prepared from substantially dysfunctional ingredients, ie, organic diisocyanates and components that are substantially difunctional in groups containing active hydrogen. However, minor proportions of ingredients with functionalities higher than 2 may commonly be employed. This is particularly true when extenders such as glycerol, trimethylol propane and the like are used. Said plastic polyurethane compositions are generally known as TPU materials. Accordingly, any of the TPU materials known in the art can be employed within the scope of the present invention. For a representative teaching about the preparation of TPU materials see Polyurethanes: Chemistry and Technology, Part II, Saunders and Frisch, 1964, pp 767-769, Interscience Publishers, New York, N.Y. and Poiyurethane Handbook, Edited by G. Oertel 1985, pp 405 or 417, Hanser Publications, distributed in E.U.A. by Macmillan Publishing Co., Inc., New York, N.Y. For a particular teaching of various TPU materials and their preparation see the patent publications of E.U.A. US-A-2,929,800; 2,948,691; 3,493,634; 3,620,905; 3,642,964; 3,963,679; 4,131, 604; 4,169,196; Re 31, 671; 4,245,081; 4,371, 684; 4,379,904; 4,447,590; 4,523,005; 4.621, 1 13; 4,631, 329; and 4,883,837, the descriptions of which are incorporated herein by reference. The TPU that is preferred is a polymer prepared from a mixture comprising at least one organic diisocyanate, at least one polymer dioxide and at least one difunctional extender. The TPU can be prepared by the prepolymer, or quasi-prepolymer or firing methods according to the methods described in the references mentioned above. Any of the organic diisocyanates previously employed in the preparation of TPU may be employed, including cycloaliphatic copolymers and diisocyanates, blocked or unblocked aromatic aliphatics, and mixtures thereof. Illustrative but non-limiting isocyanates thereof are methylene (bisphenyl isocyanate) including the 4,4'-isomer, the 2,4'-isomer and mixtures thereof, m- and p-phenylene diisocyanates, diisocyanates chlorophenylene, α-, α'-xylylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures of these latter two isomers that are commercially available, tolidine diisocyanate, hexamethylene diisocyanate, diisocyanate 1, 5 naphthalene, isophorone diisocyanate and the like; cycloaliphatic diisocyanates such as methylene bis (cyclohexyl) isocyanate including the 4,4'-isomer, the 2,4'-isomer and mixtures thereof, all the geometric isomers thereof including trans / trans, cis / trans, cis / cis and mixtures thereof, cyclohexylene diisocyanates (1, 2-, 1, 3-, 1, 4-), 1-methyl-2,5-cyclohexylene diisocyanate, 1-methyl-2-diisocyanate , 4-cyclohexylene, 1-methyl-2,6-cyclohexylene diisocyanate, bis- (cyclohexyl isocyanate) of 4,4'-isopropylidene, 4,4'-dicyclohexyl diisocyanate and all geometric isomers and mixtures thereof and Similar. Also included are modified methylene bis (phenyl isocyanate) forms. By this last it is tried to say those forms of bis (phenyl isocínate) of methylene that have been treated to make them stable liquids at room temperature (approximately 20 ° C). Such products include those that have been reacted with a minor amount (up to about 0.2 equivalents per equivalent of polyisocyanates) of an alpha glycol or a mixture of aliphatic glycols such as modified methylene bis (phenyl) socianates described in US-A- 3,394,164; 3,644,457; 3,883,571; 4.031, 026; 4,115,429; 4,118,411; and 4,299,347, the disclosure of which is incorporated herein by reference. The modified methylene bis (phenyl isocyanates) also include those that have been treated such that a minor portion of the diisocyanate is converted to the corresponding carbodiimide which then interacts with additional diisocyanate to form urethane-imine, the resulting product being a stable liquid at ambient temperatures as described, for example in US-A-3,384,653.

Also, if desired, mixtures of any of the polyisocyanates mentioned above can be used. Classes of organic diisocyanates that are preferred include aromatic and cyclo-phiiphatic diisocyanates. Preferred species within these classes are methylene bis (phenyl isocyanate) including the 4,4'-isomer, the 2,4'-isomer, and mixtures thereof, and methylene bis (cyclohexyl isocyanate) including the isomers described above. The polymeric diols that can be used are those commonly employed in the art for the preparation of TPU elastomers. The polymeric diols are responsible for the formation of soft segments in the resulting polymer and advantageously have molecular weights (average number) which are on the scale of 400 to 4000 and preferably 500 to 3000. It is not usual, and, in some cases could it is advantageous to employ more than one polymeric diol. Examples of the diols are polyether diols, polyester diols, hydroxy-terminated hydroxy-terminated polycarbonates, hydroxy-terminated polybutadiene-acrylonitrile copolymers, hydroxy-terminated dialkyl siloxane copolymers and alkylene oxides such as ethylene oxide, propylene and the like, and mixtures in which any of the above polyols is used as the main component (more than 50% w / w) with amino-terminated polyethers and amino-terminated polybutadiene-acrylonitrile copolymers. Examples of polyether polyols are polyoxyethylene glycols, polyoxypropylene glycols, which have been optionally blocked with ethylene oxide residues, random and block copolymers of ethylene oxide and propylene oxide, polytetramethylene glycol, random and block copolymers of tetrahydrofuran and ethylene oxide and / or propylene oxide, and products derived from any of the above reactions with dysfunctional carboxylic acids or esters derived from said acids in which case the ester exchange occurs and the esterification radicals are replaced by polyether glycol radicals. Preferred polyether polyols are random and block copolymers of ethylene oxide and propylene with a functionality of about 2.0 and polytetramethylene glycol polymers of a functionality of about 2.0. Examples of polyester polyols are those prepared by polymerizing e-caprolactone using an initiator such as ethylene glycol, ethanolamide and the like; and those prepared by the esterification of polycarboxylic acids such as phthalic, terephthalic, succinic, glutaric, adipic, azelaic, and the like; acids with polyhydric alcohols such as ethylene glycol, butanediol, cyclohexane dimethanol and the like. Examples of the amino-terminated polyethers are the structurally derived aliphatic primary diamines and polyoxpylene glycols. Polyether diamines of this type are available from Jefferson Chemical Company under the tradename JEFFAMINE®. Examples of polycarbonates containing hydroxyl groups are those prepared by the reaction of diols such as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, 1,9-non-ammoniol, 2-methyloctane. -1,8-diol, diethylene glycol, triethylene glycol, dipropylene glycol, and the like, with diarylcarbonates such as diphenylcarbonate or with phosgene. Examples of silicon-containing polyethers are copolymers of alkylene oxides with dialkylsiloxanes such as dimethylsiloxane, and the like; see, for example, US-A-4,057, 595 or US-A-4,631, 329 mentioned above. Examples of the hydroxy-terminated polybutadiene copolymers are the compounds available under the trademark Poly BD Liquid Resins. Examples of the butadiene-acrylonitrile hydroxy- and amine-terminated copolymers are the materials available under the tradename HYCAR® hydroxyl-terminated liquid copolymers (HT) and amine-terminated liquid polymers (AT), respectively. Preferred diols are the polyether and polyester diols described above. The difunctional extender used can be any of those known in the TPU technique described above. Typically, the extenders may be straight chain or branched chain aliphatic diols having from 2 to 10 carbon atoms, inclusive, in the chain. Examples of said diols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol and the like; 1,4-cyclohexanedimethanol; bis- (hydroxyethyl) ether of hydroquinone, cyclohexylenediols (1, 4-, 1, 3-, and 1, 2-isomers), isopropylidene bis (cyclohexanols); diethylene glycol, dipropylene glycol, ethanolamine, N-methyl diethanolamine and the like; and mixtures of any of the foregoing. As previously mentioned, in some cases minor proportions (less than about 20 equivalent percent) of the difunctional extender can be replaced by trifunctional extensors without departing from the thermoplasticity of the resulting TPU; examples of said extenders are glycerol, trimethylolpropane and the like. Although any of the diol extenders described and exemplified above may be employed alone, or mixed; it is preferred to use 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol and diethylene glycol, either alone or in a mixture with each other or with one or more aliphatic diols mentioned above. Particularly preferred diols are 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. The equivalent proportions of polymeric diol to said extender can vary considerably depending on the hardness desired for the TPU product. Generally speaking, the proportions are within the respective scale of about 1: 1 to about 1: 20, preferably about 1: 2 to about 1: 10. At the same time, the general ratio of isocyanate equivalents to equivalents of active hydrogen-containing materials is within the range of 0.90: 1 to 1.10: 1, preferably 0.95: 1 to 1.05: 1. TPUs can be prepared by conventional methods known to the person skilled in the art, for example from US-A-4,883,837 and the additional references cited therein. 2. 2 Chlorine-containing polymers Chlorine-containing polymers are selected from polyvinyl chloride, polyvinylidene copolymer, chlorinated polyvinyl chloride, chlorinated polyethylene, and the like. 2. 3 Fluorine-containing Polymers Fluorine-containing polymers are selected from polydivilidene fluoride, polyvinylidene-hexafluoropropylene fluoride copolymer and the like. 2. 4 Polyester In the terms of the present invention, any commercial thermoplastic polyester such as polyethylene terephthalate, polybutylene terephthalate, saturated or unsaturated aliphatic polyesters, or the like, can be used. 3. Compatibilizer According to the present invention, the compatibilizer is selected from: i) a copolymer obtainable by the condenative reaction of: - about 10 to about 90% by weight of a functionalized polymer with - about 90 to about 10% by weight weight of a polyamide, based on the total weight of the functionalized polymer and the polyamide, or ii) a mixture of functionalized polymer and a polyamide in the amounts defined in i) or iii) a mixture of (i) and (i), with the proviso that the functionalized polymer contains not less than about 0.3% by weight, based on the total weight of the functionalized polymer, of at least one comonomer containing a functional group. The compatibilizer is added to the blend of the non-polar thermoplastic elastomer and the polar thermoplastic polymer in an amount of about 1 part by weight, preferably 3 to 40 parts by weight and most preferably 5 to 20 parts by weight, based on 100 parts. by weight of the mixture comprising the non-polar thermoplastic elastomer and the polar thermoplastic polymer. In accordance with the present invention, the functionalized polymer used in the compatibilizer is selected from functionalized polyolefins and styrene / conjugated diene / styrene block copolymers. In the functionalized styrene / conjugated diene / styrene block copolymers, the conjugated diene can be hydrogenated, non-hydrogenated or partially hydrogenated. The presence of a copolymer of functionalized polymers and polyamide in the thermoplastic elastomers significantly improves the compatibility of the non-polar thermoplastic elastomers with the polar thermoplastic polymers. The copolymers of functionalized polymers and polyamides can be prepared by the condensation reaction of functionalized polymers and polyamides. This type of reaction is known to those skilled in the art (F. Ide and A. Hasegawa, J. Appl. Polym, Sci., 18 (1974) 963, S. Hosoda, K. Kojima, Y. Kanda and M. Aoyagi, Polym, Networks Blends, i (1991) 51, SJ Park, BK Kim and HM Heong, Eur. Polym, J., 26 (1990) 131). The reactions described in that reference can be easily transferred to the other functionalized polymers described below. The polyolefins of the functionalized polyolefins include thermoplastic and crystalline polyolefin homopolymers and copolymers. They are desirably prepared from α-monoolefin monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butane, isobutene, 1-pentene, 1-hexen, 1-ketene, 3-methyl-1 pentene, 4-methyl-1-pentene, 5-methyl-1-hexen, mixtures thereof and copolymers thereof with methacrylate and / or vinyl acetates. However, monomers having from 3 to 6 carbon atoms are preferred, polypropylene being preferred. As used in the description and claims, the term polypropylene includes propylene homopolymers as well as polypropylene reactor copolymers which may contain from 1 to 20% by weight of ethylene or an α-olefin comonomer of 4 to 16 carbon atoms, and mixtures thereof. The polypropylene may be highly crystalline isotactic or syndiotactic polypropylene. Commercially available polyolefins can be used in the practice of the invention. Among the polyolefins that are preferred are low density polyethylenes, linear low density polyethylene, medium and high density polyethylene, polypropylene and random copolymers or propylene-ethylene block, as well as ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA) and their ionomeric derivatives, such as the salts containing Zn and Na, and ethylene- (meth) acrylate copolymer, such as EMA. In styrene / conjugated diene / styrene block copolymers, which are traditionally made by anionic polymerization and in which the conjugated diene can be hydrogenated, not hydrogenated or partially hydrogenated, the conjugated diene is selected from butadiene, isoprene or a mixture from both. The styrene / conjugated diene / styrene specific block copolymers are the block copolymers of SBS, SIS, SIBS, SEBS and SEPS. The functionalized polymers contain one or more functional groups that have been incorporated either by grafting or by copolymerization. Preferably, the functionalized polymers used in this invention are those obtained by grafting at least one type of functional group-containing monomer into the base structure of the polymer, which, as mentioned above, is selected from polyolefins or copolymers of block. It is preferred, however, to use a type of monomer containing functional group. The monomers containing functional groups are selected from carboxylic acids, dicarboxylic acids, their derivatives such as their anhydrides, monomers containing an oxasoline or epoxy group, or monomers containing an amino or hydroxyl group. Examples of the monomers containing one or two carboxylic groups are those having 3 to 20 carbon atoms per molecule, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid or derivatives thereof. Unsaturated dicarboxylic acid monomers having 4 to 10 carbon atoms per molecule and anhydrides (if any) thereof are the preferred graft monomers. These graft monomers include, for example, maleic acid, fumaric acid, taconic acid, citraconic acid, cyclohex-4-ene-1,2-dicarboxylic acid, bicyclo [2.2] hept-5-ene-2,3-dicarboxylic acid. , maleic anhydride, itaconic anhydride, cycloconic anhydride, alisuccinic anhydride, 4-methylcyclohex-4-ene-1, 2-dicarboxylic anhydride and bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride and the like. Examples of oxazoline group-containing monomers are oxazole, ricinoloxazoline maleinate, vinyloxazoline, 2-isopropenyl-2-oxazoline and the like. Examples of epoxy group-containing monomers are epoxide esters of unsaturated carboxylic acids containing at least 6, preferably 7, carbon atoms. Glycidyl acrylate and glycidyl methacrylate and the like are particularly preferred. Examples of the amino group-containing monomers are the reaction products of primary and / or secondary diamines with an unsaturated carboxylic acid anhydride as mentioned above. Examples of the hydroxyl group-containing monomers are the reaction products of primary or secondary amino alcohols (primary or secondary amine) with an anhydride of an unsaturated carboxylic acid such as mentioned above. In case an amino or hydroxyl group is present in the resulting functionalized polymer, a coupling agent such as a diisocyanate may be necessary to bind this type of functional polymer to the polyamide. Various known methods can be used to graft the graft monomer to the basic polymer. For example, this can be achieved by heating the polymer and graft monomer at high temperatures from about 150 ° to about 300 ° C in the presence or absence of a solvent with or without a radical initiator. Another vinyl monomer may be present during the grafting reaction. Suitable solvents that can be used in this reaction include benzene, toluene, xylene, chlorobenzene and cumene. Suitable radical initiators that can be used include t-butyl hydroperoxide, diidopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, benzoyl peroxide, isobutyl peroxide and methyl ethyl ketone peroxide and Similar. The functionalized polymer can also be made by the copolymerization of the functional group-containing monomer with the monomers mentioned above in relation to the polyolefins. In the functionalized polymer obtained in this way, the amount of the functional group containing monomer is preferably from about 0.3 to about 10%, most preferably about 0. 3 to about 5%, and more preferably at least about 1% by weight, based on the weight of the functionalized polymer. The polyamides are preferably selected from polymers of e-caprolactam, aminocaproic acid, enantholactam, 7-amino-heptanoic acid, 1-aminoundecanoic acid, etc., or polymers obtained by the polycondensation of diamines (such as butanediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, m-xylenediamine, etc.) with dicarboxylic acids (such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedibic acid, glutaric acid, etc.), copolymers thereof or mixtures thereof. Specific examples include aliphatic polyamide resins (such as polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 11, polyamide 12 and polyamide 6.12) and aromatic polyamide resins (such as poly (hexamethylenediamine terephthalamide), poly (hexamethylene phosphthalamide), polyamides containing amorphous xylene and polyamide groups, among which polyamide 6, polyamide 6.6, and polyamide 12 are preferred. It should be mentioned that the copolymer of the functionalized polymer and the polyamide can be prepared first as such (for example, in an individual worm extruder). or twin) and then melt-blended or dry-blended with the non-polar thermoplastic elastomer and the polar thermoplastic composition before processing As an alternative, the functionalized polymer and the polyamide can be melt-blended with the non-polar thermoplastic elastomer and the thermoplastic composition polar in one step.The compatibilizer can also be mixed in sec or either mixed by fusion with either the non-polar thermoplastic elastomer or with the polar thermoplastic. The melt blending of the latter option can be done either downstream during the manufacture of the non-polar thermoplastic elastomer or in a second pass in a twin or twin Banbury extruder. Preferably, the amount of functionalized polymer is from about 20 to about 70% by weight, and the amount of the polamide is from about 80 to about 30% by weight. Most preferably, however, the amount of the functionalized polymer is from about 30 to about 60% by weight and the amount of the polyamide is from about 70 to about 40% by weight, all amounts based on the total weight of the functionalized polymer and the polyamide. The amount of copolymer obtainable by the reaction of the functionalized polyolefin and the polyamide and the amount of copolymer obtainable by the reaction of styrene / conjugated diene / styrene block copolymer (hydrogenated, non-hydrogenated or partially hydrogenated) ) and the polyamide in the mixture comprising the non-polar thermoplastic elastomer and the polar thermoplastic polymer, either added to said mixture or as the copolymer (already reacted) or as a mixture (without having reacted) as described above, is of at least 3 parts by weight [(i), (ii) or (iii)] per 100 parts by weight of the total non-polar thermoplastic elastomer (A), (B) or (C), and polar thermoplastic polymer as the one defined above. 4. Additives The non-polar thermoplastic elastomer, the polar thermoplastic polymer, the compatibilizer and the final compatibilized mixture can independently contain reinforcing and non-reinforcing fillers, plasticizers, antioxidants, stabilizers, rubber processing oils, extender oils, lubricants, antiblocking agents, agents antistatic, waxes, foaming agents, pigments, flame retardants or other processing aids known in the rubber blending art. Said additives may comprise up to about 40% by weight, preferably up to 20% by weight of the total compatibilized mixture. Fillers and extenders that can be used include conventional inorganic materials such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like. Rubber processing oils are generally paraffinic, naphthenic or aromatic oils derived from petroleum fractions. The oils are selected from those normally used in conjunction with the rubber or specific rubbers present in the composition.

. Preparation of the compatibilized mixture The compatibilized blends of a non-polar thermoplastic and polar thermoplastic elastomer comprising the compatibilizing copolymer are prepared by melt blending the polymers in the presence of the compatibilizer in a conventional internal mixer, a single worm extruder, an extruder of twin co-or counter-rotating worms, an open mill or any other suitable equipment known in the art. The mixture is heated to a temperature sufficient to melt or soften the component of the composition having the highest softening or melting point. The compatibilizer may be melt blended first or spin blended with the non-polar thermoplastic elastomer or with the polar thermoplastic and then melt blended with the second component of the composition. 6. Utility of the compatibilized mixture The compatibilized blends of non-polar thermoplastic elastomer and polar thermoplastic according to the present invention can be used in different applications such as: i. to obtain a good adhesion between the compatibilized mixture of the invention and polar thermoplastic polymers, which is necessary if, for example, parts with a multilayer structure are provided. This type of parts can be produced using traditional processing methods such as co-injection molding and / or over-injection molding, co-extrusion and / or over-extrusion, co-blowing molding and / or over-blowing molding. Representative polar thermoplastic polymers are selected from those mentioned above. In all the cases mentioned above, the compatibilized mixture of the invention can also be used as a layer of adhesive bond between a non-polar thermoplastic elastomer and a polar thermoplastic polymer. ii) to improve the painting capacity of non-polar thermoplastic elastomers; iii) to produce new polymeric materials which possess the combined properties of the non-polar thermoplastic elastomer and polar thermoplastic polymers. The invention will be better understood by reference to the following examples which serve to illustrate but not to limit the present invention.

EXAMPLES The following abbreviations were used in the examples: S 8211-60: Santoprene® rubber (mixture of polypropylene and fully vulcanized EPDM and common adhesives with a Shore A hardness of 60 durometer), [Advanced Elastomer Systems, Akron, Ohio, USA] . S 691-55: Santoprene® rubber (mix of polypropylene and fully vulcanized EPDM and common adhesives with a shore A hardness of 55 durometer), [Advanced Elastomer Systems, Akron, Ohio, E.U.A.]. PP-b-PA maleated polypropylene reaction product containing 1.1% maleic anhydride grafted with polyamide 6 (Ultramid® B3 from BASF) at 40/60% by weight Solef® 11010: polyvinylidene fluoride-hexafluoropropylene copolymer [Solvay] Elastollan® C 85 A (TPU): polyether-based polyurethane thermoplastic [BASF] The following measurement methods were used in the determination of physical properties: Hardness (Shore A): ISO 868-85 Module; Elongation and tensile strength: DIN 53405 Tear strength: ASTM D-624 TYPICAL EXAMPLES 1. Preparation of the compatibilizer (PP-b-PA) 40% by weight of a maleated homo-polypropylene containing 1.1% by weight of grafted maleic anhydride was melt blended with 60% by weight of polyamide 6 (Ultramid® B3 from BASF) in a twin-screw extruder with co-rotating gear type Leistritz LSM 33/34. The following temperature setting profile was used: Zone 1 and 2 229 ° C Zone 3 and 4 230 ° C Zone 5 231 ° C Zone 6 to 10 232 ° C An underwater strand cut system was used for pelleting of the compatibilizer obtained in this way. 2. Preparation of a compatibilized mixture of a non-polar thermoplastic elastomer with a polar thermoplastic polymer S8211-60, PVDF Solef 11010 and the compatibilizer were rotationally mixed first and then fed to an individual laboratory extruder. The extrusion graph type 19/25 D with dosing worm (worm with mixing element) with the following temperature setting profile: 180 ° C (supply zone) -190-210-200 (given) Melting temperature (current measurement) = 250 ° C RPM = 70 Recoil pressure = 20 barias The final product is pelleted through a system of cutting strands under water.

TABLE 1 The product was not processable due to heavy delamination TABLE 2 A comparison of Inventive Example 3 with Comparative Example 4 shows that the final product of Example 4 has poor physical properties due to delamination caused by non-compatibility of the non-polar thermoplastic elastomer (S 691-55) with the polar thermoplastic polymer (Elastollan® ).

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A compatibilized mixture comprising: a non-polar thermoplastic elastomer, a polar thermoplastic polymer selected from polar thermoplastic polyurethane (TPU), chlorine-containing polymers, fluorine-containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, styrene-copolymers acrylonitrile, copolymers of styrene-maleic anhydride, polyacetal, polycarbonate, polyphenylene oxide and a compatibilizer.

2. The mixture according to claim 1, further characterized in that the non-polar thermoplastic elastomer is selected from: (A) (a) a thermoplastic polyolefin homopolymer or copolymer, and (b) an olefinic rubber that is completely entangled, partially interlaced or non-interlaced, and optionally (c) common additives; (B) (a) a styrene / conjugated diene / styrene block copolymer and / or its complete or partially hydrogenated derivative, optionally mixed with (b) a thermoplastic polyolefin homopolymer or copolymer and / or (c) common additives and (b) C) any mixture of (A) and (B).

3. The mixture according to the preceding claims, further characterized in that the compatibilizer is selected from: (i) a copolymer obtainable by the condensation reaction of about 10 to about 90% by weight of a polymer functionalized with about 90 to about 10% by weight of a polyamide, based on the total weight of the functionalized polymer and polyamide; or (i) a mixture of a functionalized polymer and a polyamide in the amounts defined in (i), or (iii) a mixture of (i) and (ii), with the proviso that the functionalized polymer contains not less than about 0.3% by weight, based on the total weight of the functionalized polymer, of at least one comonomer containing functional groups.

4. The mixture according to the preceding claims, further characterized in that at least 1 part by weight of the compatibilizer is added per 100 parts by weight of the mixture comprising the non-polar thermoplastic elastomer and the polar thermoplastic polymer.

5. The mixture according to claim 2, further characterized in that the polyolefin is selected from a homopolymer or copolymer of a C2-7 monomer, or a copolymer thereof with (meth) acrylates and / or vinyl aces.

6- The mixture according to claim 5, further characterized in that the copolymer is a copolymer of ethylene with (meth) acrylates and / or vinyl aces.

7. The mixture according to claim 2, further characterized in that the rubber is selected from the group consisting of EPDM rubber, EPM rubber, butyl rubber, halogenated butyl rubber, copolymers of jsomonoolefin and para-alkylstyrene or their halogenated derivatives, natural or synthetic rubber, polyisoprene polybutadiene rubber, styrene-butadiene copolymer rubbers, nitrile rubbers, polychloroprene rubbers and mixtures thereof.

8. The mixture according to claim 2, further characterized in that the styrene / conjugated diene / styrene block copolymer consists of from about 10 to about 5% by weight of styrene and from about 90 to about 50% by weight of the conjugated diene .

9. The mixture according to claim 8, further characterized in that the conjugated diene is selected from butadiene, isoprene or mixtures thereof.

10. The mixture according to claim 8 or 9, further characterized in that the conjugated diene of the block copolymer is partially or completely hydrogenated.

11. The mixture according to claim 2 or 8, further characterized in that the block copolymer is mixed with up to about 60% by weight of the thermoplastic polyolefin or a common additive or mixtures thereof, based on the total weight of the block copolymer, polyolefin and / or additive.

12. The mixture according to claim 2, further characterized in that the mixture (C) comprising (A) and (B) contains about 5 to about 45% by weight of (A), based on the total weight of ( A) + (B).

13. - The mixture according to claim 3, further characterized in that the functionalized polymer is selected from functionalized polyolefins or functionalized styrene / conjugated diene / styrene block copolymers, wherein the conjugated diene can be hydrogenated, non-hydrogenated or partially hydrogenated.

14. The mixture according to claim 13, further characterized in that the functionalized polymers can be obtained by grafting in the polyolefins or styrene / conjugated diene / styrene block copolymers graft monomers selected from carboxylic acids, dicarboxylic acids or their derivatives, oxazoline group containing monomers, epoxy group-containing monomers, monomers containing amino or hydroxy groups.

15. The mixture according to claim 14, further characterized in that the derivatives of the carboxylic acid monomers are selected from their anhydrides.

16. The mixture according to claim 3, further characterized in that the polyamide is selected from polymers of e-caprolactam, aminocaproic acid, enantolactam, 7-amino-heptanoic acid, 1-aminoundecanoic acid, polymers obtained by the polycondensation of diamines with dicarboxylic acids, copolymers thereof or mixtures thereof.

17. The mixture according to any of the preceding claims, further characterized in that the thermoplastic polyurethane is obtained by the reaction of at least one organic diisocyanate, at least one polymeric diol and at least one difunctional chain extender.

18. A method for compatibilizing mixtures comprising: a non-polar thermoplastic elastomer and a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chlorine-containing polymers, fluorine-containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, copolymers of styrene-acrylonitrile, styrene-maleic anhydride copolymer, polyacetals, polycarbonates, polyphenylene oxide, by mixing therewith a compatibilizer selected from: (i) a copolymer obtainable by the condensation reaction of from about 10 to about 90% in weight of a functionalized polymer with from about 90 to about 10% by weight of a polyamide, based on the total weight of the functionalized polymer and polyamide; or (ii) a mixture of a functionalized polymer and a polyamide in the amounts defined in (i), or (iii) a mixture of (i) and (ii), with the proviso that the functionalized polymer contains not less than about 0.3% by weight, based on. total weight of the functionalized polymer, of at least one monomer containing functional groups.

19. A shaped article comprising the compatibilized mixture according to any of claims 1 to 18.

20. The use of: (i) a copolymer obtainable by the condensation reaction of from about 10 to about 90% in weight of a functionalized polymer with from about 90 to about 10% by weight of a polyamide, based on the total weight of the functionalized polymer and polyamide; or (i) a mixture of a functionalized polymer and a polyamide in the amounts defined in (i), or (iii) a mixture of (i) and (ii), with the proviso that the functionalized polymer contains not less than about 0.3% by weight, based on the total weight of the functionalized polymer, of at least one monomer containing functional groups, to compatibilize mixtures comprising: a non-polar thermoplastic elastomer and a polar thermoplastic polymer selected from thermoplastic polyurethane (TPU), chlorine-containing polymers, fluorine-containing polymers, polyesters, acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymer, polyacetals, polycarbonates, polyphenylene oxide.