MXPA96006050A - Interlocking procedure by hidrosilac - Google Patents

Abstract

The present invention relates to an improved process for the enrosing by hodrosilylation of a composition comprising a mixture of a thermoplastic resin and an unsaturated rubber by dynamic vulcanization, the improvement being characterized in that it comprises employing an entanglement agent by hydrosilylation and of about 0.01 at about 4 ppm, based on the weight of the rubber and expressed as platinum metal, of a hydrosilylation catalyst containing platinum in combination with an EPDM rubber containing 5-vinyl-2-norbornene as a diene monomer, by means of which a completely entangled rubber is obtained in a thermoplastic resin matrix

Description

FORMATION OF INTERVENTIONS THROUGH HYDROSILILATION RESUflEN PE Lñ DESCRIPTION, A process for the preparation of thermoplastic elastomers by hydrosilylation entanglement is described, wherein a very small amount of a hydrosilylation catalyst is used which has + + + in combination with rubs containing specific dienes. In another variant of the invention, the hydrosilylation is carried out in the presence of a processing oil which is substantially free of materials which have the chemical composition of a Lewis base. An interlaced rubber component is obtained in the thermal elastomer composition.

BACKGROUND OF THE INVENTION FIELD OF INVENTION The present invention relates to thermoplastic elastomer compositions which are prepared by forming entanglements of the elastomer of the composition by hydrosilylation. A thermoplastic elastomer is generally defined as a polymer or mixture of polymers that can be processed and recycled in the same manner as a conventional thermoplastic material, although it has properties and performance in function similar to those of vulcanized rubber at operating temperatures. The mixtures or alloys of plastic and elastomeric rubber have increased their importance in the production of high performance thermoplastic elastomers, particularly for the replacement of thermoset rubbers in different applications. High performance thermoplastic elastorres in which a vulcanized rubber polymer is intimately dispersed in a thermoplastic matrix are generally known as thermoplastic vulcanizates.

DESCRIPTION OF THE RELATED TECHNIQUE Polymer blends having a combination of thermoplastic and elastic properties are generally obtained by combining a thermoplastic resin with an elastomeric composition such that the elastomer component is dispersed intimately and uniformly with a discrete particulate phase within a continuous phase of the elastomer. thermoplastic A recent work with vulcanized rubber components is found in the U.S. patent. No. 3,307,954 which describes both the static vulcanization of the rubber and the dynamic vulcanization technique wherein a vulcanizing elastomer is dispersed in a molten resinous thermoplastic polymer and the elastomer is cured while the mixture is stirred and cut. The resulting composition is a cured elastomer microgel dispersion in an uncured matrix of thermoplastic polymer. In the patent of E.U.A. No. Re. 32,028 discloses polymer blends comprising an olefin thermoplastic resin and an olefin copolymer, wherein the rubber is dynamically vulcanized to a state of partial cure. The resulting compositions can be processed again. The patents of E.U.A. Nos. 4, 130,534 and 4,130,535 further describe thermoplastic vulcanizates comprising butyl rubber and polyolefin resin, and rubber olefins and polyolefin resins, respectively. The compositions are prepared by dynamic vulcanization and the rubber component is cured until it is essentially insoluble in conventional solvents. A range of interlacing, or curing, rubber vulcanization agents in the prior art is disclosed, including peroxides, sulfides, phenolic resins, radiation and the like. The patent of E.U.A. No. 4,803,244 discusses in general the use of multi-functional organic silicone compounds in conjunction with a catalyst as an agent for the formation of entanglements in the rubber component of a thermoplastic elastomer by hydrosilylation. Hydrosilylation includes the addition of a silicone hydride through a multiple bond, often with a transition metal catalyst. This patent discloses the rhodium-catalyzed hydrosilylation of EPDfl rubber in a mixture with polypropylene to produce thermoplastic elastomers having a gel content of up to 34% (after correction for the plastic phase). This degree of vulcanization was achieved only with a high level of catalyst. A further modification of interlacing formation by hydrosilylation of the rubber in a thermoplastic elastomer composition is described in European Patent Application No. 651, 009. A cornpatibilizing agent is incorporated which contains in the same molecule a component having affinity for the rubber and a component having affinity for the thermoplastic resin in the composition and said to improve the adhesion between the rubber and the resin in order to prevent the agglomeration SUMMARY OF THE INVENTION The present invention is based on the discovery that the process for the formation of entanglements by hydrosilylation of rubber in an elastomeric oplastics can be improved by using a catalyst containing platinum in combination with an elastomer containing a diene having predominantly carbon-carbon double bonds sterically not impeded. This combination provides the rapid entanglement of the elastomer to a fully cured state, although it requires an unexpectedly low concentration of the catalyst in order to achieve healing.

In the present invention, no cornpatibilization agent is required to produce compositions with excellent mechanical properties, no bubble formation and very good susceptibility to coloration due to extremely low levels of catalyst concentration. Surprisingly, low catalyst concentrations also produce compositions with improved characteristics of aging with heat, resistance to degradation by ultraviolet light and having a non-hygroscopic character. In another embodiment of the invention, the dynamic vulcanization of a mixture of thermoplastic resin and rubberized oil in the presence of a hydrosilylation agent, a hydrosilylation catalyst containing platinum and an extender or processing oil is unexpectedly improved. for the use of oil that is substantially free of materials that have a chemical base behavior of Le? is. The Lewis base behavior can be defined in a general way as the formation of bonds by the donation of a pair of electrons. The present embodiment of the invention requires a still lower concentration of catallizer to achieve rubber cure, and the resulting thermoplastic elastomer product has excellent tensile properties and a non-undesirable color. They also have good aging characteristics with heat, ultraviolet stability and good non-hygroscopic properties.

In a further embodiment of the invention, additives that react with the residual silicone hydride functionality in the thermoplastic elastomer are incorporated into the process. This results in a composition that has additionally improved properties of long-term heat aging. Compositions produced by the improved process have utility as substituents for thermal rubber compounds in a variety of applications, particularly where molding or extrusion is involved and the combination of thermoplastic and elastomeric properties provide an advantage. Typical uses include molded articles for parts below the car trunk, engineering and construction materials, mechanical rubber products, industrial parts such as hoses, pipe and filler, electrical appliances and household products.

DESCRIPTION OF THE PREFERRED MODALITIES The thermoplastic elastomer compositions can be prepared in a general manner by mixing a thermoplastic resin and a rubber, then melting the thermoplastic component and mixing the molten material until the mixture is homogeneous. If a vulcanized rubber composition is desired in a thermoplastic matrix, crosslinking agents (also referred to as curative or vulcanizing agents) are added to the mixture and the entanglement occurs during mixing. This last procedure is described as dynamic vulcanization. A wide range of thermoplastic resins and rubbers and / or their blends have been used in the preparation of thermoplastic elastomers, including polypropylene, HDPE, LDPE, VLDPE, LLDPE, homopolymers or cyclic olefin copolymers as well as olefin block copolymers, thermoplastic polymers, .li.esti reindeer, polyphenylene sulfide, polyphenylene oxide and ethylene propylene copolymer (EP), with ethylene propylene diene rubber (EPDM), acrylonitrile.tril butadiene rubber (NBR) and natural rubber (NR) as elastomers . When the elastomer component is entangled, agents such as sulfur, peroxide, phenolic and ionic compounds are frequently used.

Hydrosilylation agents Hydrosilylation has also been described as an entanglement method. In this method, silicon hydride having at least two SiH groups in the molecule with the carbon-carbon multiple bonds of the unsaturated rubber component (eg, containing at least one carbon-double bond) is reacted. carbon) of the thermoplastic elastomer, in the presence of the thermoplastic resin and a hydrosilylation catalyst. Silicone hydride compounds useful in the process of the invention include rnethylhydrogen polysiloxanes, rnethylhydrogen direthylsiloxane copolymers, alkyl methyl polysiloxanes, bis (dirnethylsilyl) lcans and bie (dirnethylsilyl) benzene. The preferred silicon hydride compounds can be described by the formula R 'R- S Ii- Dn- D .m- Tp S Ii- R' (1) R "R" wherein each R is independently selected from the group consisting of alkyls comprising from 1 to 20 carbon atoms, cycloalkyls comprising 4 to 12 carbon atoms and aryls. In formula 81) it is preferred that each R is independently selected from a group consisting of alkyls comprising from 1 to 6 carbon atoms. It is still preferred the = methyl. R 'represents a hydrogen atom, an alkyl or alkoxy group having from 1 to 24 carbon atoms. R "represents R or a hydrogen atom. D represents the group D 'i «presents the group T represents the group n is an integer that has a value of 1 A 50, n is an integer that i read a value of 1 a ', Q, P is an integer that has a value from 0 to h. Particularly preferred polyorganosiloxanes are those in which the silicone atom of the functionality of the silicon hydride is attached by he + ero-torates / ions having solitary electron pairs. Preferred polyorganosiloxanes can also be substituted with appropriate functionality allowing solubility in the reaction methyls. A type of functional t ilaci n n is < lescpbe in the patent of E.U.A. No. 4,04 (1,930 which teaches the alkylation of polyorganosiloxanes) The weight percent of the alkylation should not exceed a level which does not allow for adequate rates of reaction due to steric hindrance The amount of silicone hydride compound useful in the process of the present invention can be in the range of 0.1 to 10.0 mol equivalents of SiH for each carbon-carbon double bond in the rubber, and is preferably in the range of 0.5 to 5.0 mol equivalents of SiH per double bond rbono-c rbono in the rubber component of the thermoplastic elastomer.

Thermoplastic Esquinas Thermoplastic resins useful in the compositions produced by the present invention include crystalline polyolefin homopolymers and copolymers. They are prepared in a desirable manner from mononomers of rnononoolefin having from 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1- ente -tene and the like, as well as copolymers derived from linear and cyclic olefins. , with propylene being the preferred one. As used in the specification and the claims, the term "polypropylene" includes propylene homopolymers as well as reactive polypropylene copolymers which may contain from 1 to 20% by weight of ethylene or of an alpha-olefin comonomer of 4 to 20 carbon atoms. carbon, and mixtures of them. The polypropylene can be crystalline, isotactic or syndiotactic. Commercially available polyolefins can be used in the practice of the present invention. Other thermoplastic resins which are substantially inert to the rubber, the silicone hydride and the hydrosilylation catalyst may also be suitable. Mixtures of thermoplastic resins can also be used. The amount of thermoplastic resin that is provided provides useful compositions is generally from 5 to 90 percent by weight, based on the weight of the rubber and the resin. Preferably, the content of thermoplastic resin will be in the range of from 20 to 80 percent by weight of total polymer.

Hules Unsaturated rubbers useful for preparing thermoplastic elastomers in accordance with the present invention include copolymer grades of copolymers comprising nonpolar copolymers resembling the rubber of two or more alpha-olefins, preferably copolymers with at least one. a polyene, usually a diene. However, unsaturated rnonoolefin rubber such as EPDM rubber is more suitable. EPDM is a polymer of ethylene, propylene and one or more of a non-conjugated diene or non-conjugated dienes and the components of rnonornero can be polimerized using Ziegler-Natta reactions or catalyzed by etalocene, among others. Satisfactory non-conjugated dienes include 5-ethyldiene-2-norbornene (ENB); 1, 4 ~ hexadiene (HD); 5-rnetylene-2-norbornene (MNB); 1, 6-octadiene; 5-Rethyl-l, 4-hexadiene; 3,7-dimethyl-l, 6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; dicyclopentadiene (DCPD); 5-vinyl-2-norbornene (VNB) and the like, or a combination thereof. In one embodiment of the invention, it has been found that the rubber having a structure in which the diene inorganic has multiple carbon-carbon bonds which are free of steric hindrance, v. Gr.,. non-sterically hindered bonds such as terminal or pending bonds provide a greatly improved cure rate in the hydrosilylation cure process of the present invention. Included in this modality are structures in which the bonds are normally unimpeded or easily isolated to form a double bond without steric hindrance, which is rapidly hydrosylated, v. Gr.,. 1, 4-hexadiene or ENB. This improvement is particularly significant where a fully cured rubber component is desired. The use of rubber in which the diene component is selected from the group consisting of 5-ethylidene-2-norbornene, 5-rnet.yl -1,4-hexadiene; 1,4-hexadiene; 5-vinyl -2-norbornene. 5-v.ini.l-2-norbornene is particularly preferred as a diene component of such rubber. Butyl rubber is also useful in the compositions of the invention. As used in the specifications and claims, the term "butyl rubber" includes copolymers of an isoolefin and a conjugated onoolefin, terpolineros of an isoolefin, a conjugated rnononoolefin and aromatic divinyl monomers, and the halogenated derivatives of such copolymers and terpolí eros. Useful butyl rubber copolymers comprise a larger portion of isoolefin and a smaller amount, usually less than 30% by weight of a conjugated multiolefin. Preferred copolymers comprise from 85-99.5% by weight of a C4-7 isoolefin such as isobutylene and from 15-0.5% by weight of a multiolefin of 4-14 carbon atoms, such as isoprene, butadiene, dirnethyl butadiene, -rneti.ll, 4-pentadiene and piperylene. Commercial butyl rubber, useful in the invention, is a copolymer of isobutylene and minor amounts of isoprene. Other rubbers of copolymers and butyl terpolymers are illustrated in the description of the US patent. No. 4,916,180. Isobutylene / divinylbenzene is particularly preferred as an elastomer suitable for hydrosilylation entanglement, as are halogenated butyl rubber derivatives such as chlorobutyl and brizobutyl. A further suitable rubber in the present invention is natural rubber. The main constituent of natural rubber is the linear polymer cis-1,4-polyisoprene. It is commercially available in the normal way in the form of smoked leaves and crepe. Synthetic polyisoprene can also be used with particularly preferred synthetic polyisoprene elastomers, those containing the vinyl functionality pendent to the polymer backbone, eg. chains - !, 2. The polybutadiene is also an elastomer suitable for curing by hydrosilylation with polybutadienes containing vinyl functionality being preferred. Mixtures of any of the above rubs can also be used instead of a single olefinic rubber. In preparing the compositions of the present invention, the amount of rubber is generally in the range of 95 to 10 percent by weight, based on the weight of the rubber and the thermoplastic resin. Preferably, the rubber content will be in the range of 80 to 20 percent by weight of total polymer.

Hydrosilization catalysts It has been previously understood that any catalyst or catalyst precursor capable of generating a catalyst in situ can be used, which will catalyze the hydrosilylation reaction with the carbon-carbon bonds of the rubber. Such catalysts have included Group VIII transition metals such as palladium, rhodium, platinum and the like, including complexes of these metals. Chloroplatinic acid has been described as a useful catalyst in the U.S. patent.

No. 4,803,244 and European Patent Application No. 651,009, which further discloses that the catalyst can be used at concentrations of 5 to 10,000 parts per million by weight and 100 to 200,000 parts per million by weight based on the weight of the rubber respectively . It has been found in the process of the present invention that significantly lower concentrations of platinum-containing catalyst can be used, while improving both the reaction speed and the efficiency of the entanglement. Catalyst concentrations in the range of 0.01 to 20 parts per million by weight, expressed as platinum metal, are effective to quickly and completely cure rubber in the process of dynamically vulcanizing blends of thermoplastic resin and rubber. These low catalyst concentrations are particularly effective in combination with a diene-containing rubber having carbon-carbon multiple bonds which are predominantly without steric hindrance. Catalyst concentrations of from about 0.1 to about 4 parts per million by weight based on the weight of the rubber, expressed as platinum metal are particularly preferred. Platinum-containing catalysts which are useful in the process of the present invention are described, for example, in the U.S.A. No. 4,578,497; the patent of E.U.A. No. 3,220,972 and the patent of E.U.A. Do not. 2,823,218 all of which are incorporated here for your reference. These catalysts include chloroplatinic acid, chloroplatinic acid hexahydrate, chloroplatinic acid complexes with sirn-div nyltetramethyldisiloxane, dichloro-b? S (tpfen? Lfosfm) plat? No (II), c? S? D? Chloro-b? S ( aceton? tpl) platinum (II), dicarbonyldichloroplast (II), platinum chloride and platinum oxide. Zero-valent platinum metal complexes such as the Karstedt catalyst are particularly preferred, as described in p > aten + e of E.U.A. No. 3,775,452; the patent of E.U.A. No. 3,814,730 and the country of E.U.A. No. 4,288,345 all of which are incorporated here for your reference. In order for the catalyst to function in the most efficient manner in the environment of dynamic vulcanization, it is important that it be thermally stable in an inherent manner, or that its activity be inhibited to prevent too rapid a reaction or decomposition. of the catalyst. Suitable inhibitors of catalyst which are suitable for stabilizing the platinum catalyst at temperatures include 1,3,5,7-tetravmllll, 3, 5,7-tetramethylethylotetrasiloxane and its higher analogues such as the cyclic penylene vimlo However, other olefins that are stable at temperatures above 165 ° C are also useful. These include maleates, futes and the cyclic pentamer. It is particularly preferred in the invention to use a catalyst that remains soluble in the reaction medium.

Rtil-VQS The thermoplastic elastomer may contain conventional additives, which may be introduced into the composition in the thermoplastic resin, the rubber or in the mixture either before, during or after hydrosilylation and curing. Examples of such additives are anti-oxidants, processing aids, reinforcing or non-reinforcing filler material, pigments, waxes, rubber processing oil, enhancing oils, antiblocking agents, antistatic agents, stabilizers for ultraviolet, plas + ifs (including esters), foaming agents, flame retardants and other processing aids known in the art of rubber compound manufacturing. Such additives may comprise from 0.1 to 300 percent by weight based on the final thermoplastic elastoin product. The fillers and amplifiers that may be used include conventional inorganic materials such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like. Additives, fillers or other compounds that can interfere with hydrosilylation should be added after the cure reaches the desired level. In another embodiment, it has been found that the properties of aging or with heat of compositions prepared according to the present invention can be greatly improved by the addition of a metal chelating agent to the mixture. It is believed that this effect is due to the fact that the hydrosilylation catalyst is in an active valence state. This shape of the platinum metal accelerates the degradation of the thermoplastic elastomer, particularly under conditions of elevated temperature over an increased time. The chelation prevents the metal from degrading. Typical chelating agents for this purpose include such materials as 1, 2-bis (3,5-di-tert-butyl-4-hydroxy-hydroxynaroyl) hydrazine and the like. Surprisingly, these agents can be incorporated into the composition prior to or after curing by hydrosilylation. It has been found that the amounts of the chelator that fall within the range of 0.025 parts per hundred parts of rubber (pch) to 10 pch are useful, and quantities in the range of 0.1 pch to 2 pch are preferred. In a further embodiment of the invention, it has been shown that reducing the functionality of the residual or non-reactive silicone in the thermoplastic elastomer products results in compositions having improved heat stability. The non-reactive silicon hydride can be reduced or eliminated by reacting it with compounds containing active hydrogen, multiple carbon-carbon bonds, carbon-oxygen double bonds or carbon-nitrogen double bonds and the like. The residual silicone hydride reacts with these compounds to eliminate the functionality of the silicone hydride and form silicone-oxygen or carbon-silicone bonds. Typical compounds useful for this purpose are silica and water. These agents are incorporated into the composition after the cure by hydrosilylation is complete. Water can be introduced as steam at any time after curing in a one or two step operation. The amounts of such compounds can be estimated by measuring the residual silicone hydride and adding a stoichiometric amount of the compound. One may also wish to add a stoichiometric excess if necessary to remove a sufficient amount of the residual silicone hydride in order to effect the desired improvement in heat aging properties. It has been found that the amounts of such compounds which are within the range of one equivalent of rnol to 10 mol equivalents are useful and that quantities within the range of 1 to 3 equivalents of rnol are preferred.

Amplifier Oil The rubber processing or amplification oils used in thermoplastic elastomers are generally paraffinic, naphthenic or aromatic derived from petroleum fractions. The type will be that which is ordinarily used in conjunction with the rubber or specific rubbers present in the composition and the amount based on the total rubber content of the thermoplastic elastomer can range from zero to several hundred percent rubber parts. It is important for the efficiency of the catalyst that the oils and other additives do not contain or contain very low concentrations of compounds that are inhibitory or that interfere with the activity of the catalyst. These compounds include phosphines, amines, sulfides, thiols or other compounds that can be classified as Lewis bases. Lewis bases or other compounds that have an electron pair available for donation will react with the platinum catalyst, effectively neutralizing its activity. It has been found that the presence of such compounds has a surprisingly detrimental impact on the cure by hydrosilation in the dynamic vulcanization process of the rubber component of the thermoplastic elastomer compositions. If the concentration of compounds having the chemical reactivity of the bases of the wis, such compounds containing sulfur or nitrogen, is maintained at or below a level that provides less than 1000 and 300 Therefore, the amount of platinum catalyst required to promote the efficient cure by hydrosilylation in dynamic vulcanization can be reduced substantially, usually to the range of 4 ppm or less, without having an impact on the state of the sulfur and nitrogen respectively. rubber cure or stress properties of the thermoplastic elastomer product. Sulfur and nitrogen concentrations below 500 and 200 pp respectively are preferred, and concentrations lower than 30 pprn sulfur and less than 100 pprn nitrogen are the most preferred. It has been found that, even at catalyst concentrations as low as 0.25 pprn, complete cure of the elastomer can be achieved if the concentration of sulfur and nitrogen is within the most preferred ranges. Most petroleum paraffin oils for the rubber industry are derived from a distillation stream of crude oil. A typical refining history would include some kind of procedure to remove wax to reduce the pour point, an extraction of solvents to physically remove aromatic compounds and a water treatment procedure to chemically modify the aromatic structures. Both extraction and treatment with water result in a net increase in the total concentration of saturated hydrocarbon structures and a net decrease in the total concentration of sulfur and nitrogen containing compound. The degree of reduction in the concentration of these compounds in the oil depends on the type and severity of the refining process employed and the nature of the crude oil. White and paraffinic oils have been treated more extensively than aromatic and naphthenic oils and would contain a smaller concentration of 27 aromatic, sulfur and / or nitrogen compounds. It is difficult to elucidate the exact chemical structure of these compounds due to their complexity. The tendency of an oil to interfere with platinum catalyzed hydrosilylation is directly related to the concentration of the compounds containing sulfur and nitrogen as well as to the compounds containing phosphorus, tin, arsenic, aluminum and s. iron.

Prosecution The rubber component of the thermoplastic elastomer is generally present as particles, v.gr.,. rnicro-tarnaño, within a continuous matrix of res to terpnoplastic, although a contiguous morphology or a phase inversion is also possible depending on the amount of rubber relative to the plastic and the degree of cure of the rubber. It is desired that the rubber is partially interlocked and preferably that it is completely interlaced. It is preferred that the rubber be entangled by the dynamic vulcanization process. As used in the specification and the claims, the term "dynamic vulcanization" means a vulcanization or cure process for a rubber mixed with a tepnoplastic resin, wherein the rubber is vulcanized under cutting conditions at a temperature at which the mixture flows. The rubber, thus, is simultaneously entangled and dispersed as fine particles within the thermoplastic resin matrix, although as noted above other morphologies may exist. The dynamic vulcanization is effected by mixing the components of the thermoplastic elastomer at elevated temperatures in conventional mixing equipment such as roll mills, Banbury mixers, Brabender mixers, continuous mixers, mixer extruders and the like. The only characteristic of the dynamically cured compositions is that, although the fact that the rubber component is partially or completely cured, the compositions can be subjected to the process and re-subjected to the process by conventional plastic processing techniques such as extrusion, injection molding and compression molding. The dehydration or flash vaporization can be recovered and subjected to the procedure again. The terms "fully vulcanized" and "fully cured" or "fully entangled" as used in the specification and the claims mean that the rubber component to be vulcanized has been cured or entangled to a state in which the elastomeric properties of the rubber Interlaced are similar to those of rubber in its conventional vulcanized state, apart from the composition of the thermoplastic elastomer. The degree of cure can be described in terms of the gel content, or, conversely, of the components that can be extracted. The gel content reported as percentage of gel (based on the weight of the rubber in relazable) is determined by a procedure that comprises determining the amount of insoluble polymer by soaking the specimen for 48 hours in organic solvent at room temperature, weighing the dried residue and make the appropriate corrections based on the knowledge of the composition. Thus, the corrected initial and final weights are obtained by subtracting from the initial weight the weight of the soluble components, different from the rubber to be vulcanized, such as amplifying oils, plasticizers and components of the composition soluble in organic solvent, as well as the component rubber product that is not indicated to heal. Any insoluble polyolefin, pigment, filler and the like are subtracted from both initial and final weights. The rubber component can be described as fully cured when less than 5% and preferably less than 3% of the rubber that is capable of being cured by hydrosilylation can be extracted from the thermoplastic product by a solvent for that rubber. Alternatively, the degree of cure can be expressed in terms of interlacing density. All these descriptions are well known in the art, for example in the patents of E.U.A. Nos. 4,593,062, 5,100,947 and 5,157,081 all of which are incorporated herein completely for your reference. The following general procedure was used in the preparation of thermoplastic elastomers by the process of the present invention, as set forth in the examples below. The thermoplastic resin and the oil-amplified rubber are placed in a heated internal mixer, with the hydrosilylation agent and the hydrosilylation catalyst. The hydrosilylation agent and the catalyst can be incorporated into the composition by any suitable technique, for example by injection as solutions in oil or as clean components, although a diluted catalyst solution is preferred. They can be added also additives such as antioxidant.es, ultraviolet light stabilizers and fillers like? N mud in oil. Master charges of the components can also be prepared to facilitate the mixing process. The mixture is heated to a sufficient temperature to melt the component Thermoplastic and the mixture is crushed, with added processing oil if desired, until a maximum of mixing torque indicates that vulcanization has occurred. The mixing is continued until the desired degree of vulcanization is achieved. It was found that the order of addition of the hydrosilylation agent and the hydrosilylation catalyst is important. The maximum efficiency of the catalyst was obtained when the hydrosilylation agent was first added to the mixture, followed by the hydrosilylation catalyst. The '? The mechanical properties of the thermoplastic elastomer products as well as the degree of cure were improved when this order of addition was followed. The invention will be understood in a better way by referring to the following examples, which serve to illustrate but not to limit the present procedure. In the examples, the following test methods were used to determine the properties of the thermoplastic elastomer products. Hardness (Shore A / D) ASTM D 2240 Ul ma tensile strength (UTS- g / crn3) ASTM D 412 Ultimate elongation (UE -%) ASTM D 412 Modulus at 100/300% elongation (MI or M3 - kg / crn31) ASTM I) 412 Tension assembly (TS -%) ASTM D 412 Oil volume increase (OS-%) ASTM D 471 Heat aging ASTM D 473 The rubber component used in the compositions prepared according to the examples is identify as follows. HULE "A" EPDM - 2.1% ENB; 52% of e Full HULE "B" EPDM - 5% Hfl; 55% ethylene HULE "C" EPDM - 3% VNB; 64% of ethylene HULE "D" EPDM - 1.6% VNB; 50% ethylene HULE "E" EPDM - 0.9% VNB; 72% Ethylene HULE "F" EPDM - 3% VNB; 55% Ethylene HULE "G" EPDM - 5.5% ENB; 60% of leno HULE "H" EP?) M - 3% I) CPD; 66% ethylene HULE "I" EPDM - 4.2% F.NB; 0.3% VNB; 58% full e HULE "3" EPDM - 4.4% ENB; 68% full et HULE "K" EPDM - 1.1% VNB; 64% of ethylene HULE "L" EPDM - 0. 7% VNB; 62 6% etiien EJEGIPLQ I The compositions are prepared by the method of the present invention as described generally above, using polypropylene resin and EPDM rubber containing ENB as the diene compound. The plastic and rubber components are melted mixed in a Brabender mixer at 180 ° C until the polypropylene is melted. Silicone hydride (alkylated inethylsulfonyl polysiloxane) is added dropwise to the molten mixture, followed by the addition of an oil solution containing platinum [reaction product dihi rogenado, hexaclonado, pia + inato (TI), with , 4, 6,8-tetraethen? 1-2, 4, 6, 8-tetramet? 1 cyclotetrasiloxaneH. The rubber is vulcanized dynamically by stirring the mixture until the maximum torque is reached. The product is removed from the mixer, returned to it and crushed at 180 ° C for an additional minute. Plates are prepared by compression molding of the dynamic vulcanization products at 200 ° C to one yiel of 60 μl and cooled under pressure; the physical properties are determined using these plates. All products were elastomeric, as defined in ASTM D1566, v. Gr.,. all had voltage values of less than 50%. The compositions and their properties are subsequently found in Table 1. For comparison purposes, Example 1 of the U.S.A. No. 4,803,244 is found later. In this comparative example, similar resin and rubber components were dynamically vulcanized by hydrosilylation, but the equivalent of 35 pp of rhodium metal was used as the catalyst.

TABLE I ^ Composition A Ex. 1 Patent Polypropylene 67 50 Rubber "A" (parts) 100 100 Si-H (per) 2.5 6.7 Rhodium (pprn) --- 35 Platinum (ppm) 15 Hardness (A / D) 93/40 88/26 UT (kg / cm55) 2500 769 EU (%) 405 240 MI 1750 305 TS (%) 22 43 Gel (%) corrected for the plastic phase 95 15 It can be seen that the use of much lower levels of platinum catalyst in the Hydrosilylation entanglement of the EPDM rubber containing ENB results in a marked increase in the level of entanglement (as reflected by the gel content) and improved tensile properties in the thermoplastic elastomer compared to the use of rhodium as the catalyst.

EXAMPLE 2 The compositions are prepared as in Example 1, using EPDM rubber containing 1,4-hexadiene as the diene terrnonornero. Platinum (as in Example 1) is used as the hydrosilylation catalyst. Plates are prepared from the products and the physical properties are determined. The results are placed in the TI Table. Again for purposes of comparison with a rhodium-catalyzed hydrosilylation, it is > Example 7 of the US patent. No. 4,803,244. In this comparative example, a mixture of polypropylene and EPDM (containing hexadiene) is dynamically vulcanized by hydrosilylation using the equivalent of 35 pprn of rhodium as the catalyst.

TABI..A II Composition £. £ rE E E,. 7 ca n PP (par-tes) 67 67 67 67 50 Rubber "B" (parts) 100 100 100 100 100 SiH (per) 0 3 3 3 6.7 Rod.io (ppm) - - __ 35 Platinum (ppm) 0 7.6 3.3 1.8 0 Hardness (D) 32 39 39 37 25 UTS (kg / cm5 *) 1080 2210 2070 1750 .1.280 EU (%) 440 330 340 160 180 MI 940 1510 1580 1620 __ TS (%) 53 24 25 26 14 Gel (%) 0 92 91 88 34 As shown in the above data, the EPDM rubber containing 1-hexadiene as the tei-monomer is more efficiently and completely interlaced using a platinum catalyst in conjunction with a hydrosilylating agent, as compared to a rhodium catalyst. The dynamic vulcanizates prepared using the platinum catalyst have a substantially higher gel content and better tensile properties, even at catalyst concentrations whose orders of magnitude lower than those require rhodium catalyst. The interlacing speed is much faster using the platinum catalyst at low concentration compared to the rhodium catalyst at higher concentrations.

EXAMPLE 3 The compositions are prepared using a double worm extruder as the mixing means to carry out the dynamic vulcanization. The EPDM rubbers containing either 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene were used as the diene component and were dynamically vulcanized by hydrosilylation with the platinum catalyst of Example 1. The plates were prepared from of thermoplastic elastomer products and the physical properties were determined. The results are set forth in Table III.

TABLE III Composition E £ a Polypropylene (parts) 41 41 41 Rubber "F" (parts) 100 .100 __ Rubber "6" (parts) --- - 100 SiH (per) 2.2 2.2 3 Platinum (pprn) 4 2 13 Hardness (A) 69 69 63 UTS (kg / cm5 *) .1080 1039 905 EU (%) 21.1 211 406 MI 636 606 408 Gel (%) 99 99 90 The compositions obtained also contain 130 per paraffin oil, 42 per of clay, 5 per of wax, 2phr of ZnO 5 The compositions F and G, which use VNB / EPDM, have very high levels of entanglement even when the amounts of both hydrosilylation agent and catalyst were very low. Composition H (ENB / EPDM) .10 has a lower, but still acceptable, level of entanglement.

E3EI1PLQ 4, For comparative purposes, rubber was dynamically vulcanized with EPDM containing dicyclopentadiene as in Example 1, in the presence of polypropylene and using cure by platinum catalyzed hydrosilylation. The melting temperature used for compositions I and J was 180 ° C, and for composition K it was 20 at 200 ° C. The results are set forth in Table IV.

F¡ TABLE IV Composition I 2 ü Rubber "H" (parts) 100 100 100 Polypropylene (parts) 67 67 67 SiH (per) 0 3 3 Platinum (pprn) 0 30.3 30.3 Hardness (D) 31 30 31 UTS (kg / crn55) 950 1220 1180 EU (%) 170 130 110 MI 920 1150 1,160 TS (%) 43 29 30 Gel (%) 18 76 77 The high levels of hydrosilylation catalyst did not provide the complete vulcanization of this rubber, which contains double bonds v. Gr.,. internal, with steric hindrance.

EXAMPLE 5 The compositions were prepared using an EPDM rubber containing a mixture of ENB and VNB as the diene component, using the conditions described in Example 1, and the products were compared with compositions made using the same EPDM rubber but where the Hydrosilylation catalyst was the Wilkinson catalyst Cchlorotris (triphenyl) phosphine rhodium (I)]. This is a rhodium catalyst representative of the catalysts described in the US patent. DO NOT. 4,803,244. The prepared compositions and the physical properties of the products are set forth in Table V.

TABLE V Composition L 11 M Polypropylene (parts) 41 41 41 Rubber "I" (parts) 100 100 100 H as SiH (grams) 0.008 0.008 0.005 Rhodium (pprn) 39 79 - Platinum (pprn) Hardness (A) 56 55 64 UTS (kg / cm2) 351 352 1050 EU (%) 485 550 415 MI 153 152 500 TS (%) 11 10 7 Gel (%) 26 40 8 The compositions also contain 130 per cent oil paraffin, 42 per clay, 5 per wax 2 per ZnO.

Platinum is a more efficient catalyst than rhodium for curing by EPDM rubber hydrosilation containing the diene portions of ENB and VNB. A content of 98% gel (fully vulcanized) resulted from the use of 8 ppm equivalent of platinum co or catalyst, while only 40% gel content was obtained from 79 ppm of rhodium equivalent or the same conditions. The superior physical properties were obtained in the platinum catalyzed hydrosilylation products. Compositions prepared with a high level of Uil inson catalyst gave orange products.

EXAMPLE 5 As noted above, it was found that the heat-anealing properties of the thermoplastic elastomers prepared by hydrosilylation interlacing were improved when the residual SL-H functionality reacted with a compound which contained active hydrogen, multiple carbon-carbon bonds, carbon-oxygen and the like. The silica amorpho is also a useful compound for the removal of Siiicón hydride that does not react from the products. In this example, the thermoplastic elastomer that was prepared by entanglement by hydrosilylation of the rubber component was mixed in a Brabender mixer at 180 ° C with amorphous silica.

A thin film sample of each thermoplastic elastomer was prepared before and after mixing with the silica. An FTIR spectrum was measured for each one and the area under the peak assigned to the Si-H adsorption was determined. (2061 crn- "1) .The samples were aged with heat at 150 ° for 7 and 14 days and the mechanical properties were measured.The results are found in Table VI.

TABLE VI Composition at £ 0. R Elastomer (Grams) 45.8 45. B 45.8 45.8 Polypropylene (parts) 41 41 41 41 Si-H (per-) 2.7 2.7 1.6 2.7 Platinum (ppm) 27 27 27 27 Silica2 (per) - 5.5 5.5 5.5 * Si-H resi ual ** 2.8 1.5 1.0 1.5 Seven lias @ _i50 ° c Change in hardness (A) 0 0 »•! + 1% of UTS withheld 110 130 115 98% of EU withheld 107 119 108 92% of MI withheld 98 105 101 100 Fourteen years fl 150 ° C Change in hardness * 9 0 +4 0% of UTS retained 17 84 55 42% of EU retained 2 73 47 35% of MI retained • - 99 96 91 Master load consisting of 100 parts of "I" rubber, 130 parts of paraffin oil, 42 parts of clay, 5 parts of wax, 2 parts of ZnO. 2His.il R 233, which is a silica supplied by PPG aMeasured as a proportion of peak areas relative to the peak area measured for Composition 0 * Added before vulcanization The results indicate that while Si ~ H that does not react is removed from the compositions, the retention of the physical properties after aging with heat is dramatically improved.

EXAMPLE 7 The compositions prepared using hydrosilylation catalyzed by transition metals are preferably stabilized using a compound which acts as a metal chelating agent. It is believed that the transition metal catalyst residue is in an active valence, and this metal form can accelerate degradation. The chelation prevents the metal from being compromised in this reaction and the long-term heat-setting properties of the compositions are improved by such stabilization. Two thermoplastic elastomer compositions are prepared using platinum catalyzed hydrosilylation, with one (Composition S) stabilized by the addition of 1 part per hundred parts of 1, 2-b? S (3, 5-d? -ter) rubber. -but? l-4-h? drox? h? droxmamo?) h? draz? na and one (Composition T) that remains unstabilized. The physical properties of the compositions are measured immediately after the preparation and again after the addition with heat at 150 ° C for three or five days. The results are put in Table VTT.

TABLE VTI Composition "S" -Initial 5 'ls Retention In? Gl &3' Jír-üS Retention Hardness (A) 67 67 100% 69 (rot o) UTS (psi) 1190 1287 108 1121 255 23% EU (%) 405 470 116 375 2 0.5 MI (kg / cm2) 504 457 91 504 0 M3 Ug / crn2) 982 946 96 982 0 The properties of the composition containing no stabilizer dropped significantly after three days at 150 ° C, while the composition containing a metal deactivator retained its properties even after five days at 150 ° C.

EXAMPLE 8 In order to study the effect of the extender oil, compositions were prepared as described above in a general manner using polypropylene resin and EPDM rubber. Master oil charges were prepared containing three different amplifying oils with progressively smaller aromatic fractions and progressively lower concentrations of sulfur and nitrogen. The concentration of the master filler was 100 parts of rubber, 100 parts of extender oil, 42 parts of clay, 2 parts of zinc oxide and 5 parts of wax. The polypropylene (41 parts) was added to this "K" rubber masterbatch and mixed in a Brabender mixer at 180 ° C until the polypropylene log melted. Silicone hydride (3 per) was added dropwise to the mixture, followed by the addition of an oil solution containing platinum catalyst at several levels. The rubber was vulcanized dynamically by stirring the mixture until the maximum torque was reached. Additional processing oil (30 parts) was added after curing. The product was removed from the mixer, then returned to the mixer and crushed at 180 ° C for one additional minute. Test specimens were prepared by compression molding the products at 200 ° C, and volume increase was determined by the ASTM D471 test method, using IRM 903 oil at 125 ° C for 24 hours. The results, expressed as percentage of volume increase (or weight gain) of the specimen are set forth in Table VIII.

TABLE VIII Oil Oil Oil Ext nd dor n Etenter B2 Ext ng C3 Catalyst e Pt 02. S: Pt N: Pt Q =. S: Pt: Pt Q =. g7P N: Pt 0. 25 pprn 339 14300 8942 - - - 119 24 55 0. 5 285 7150 4471 105 * 227 2808 92.3 12 23 1. 0 222 3575 2236 86.4 114 1404 85.3 6 12 1. 9 140 1882 1177 85.8 60 739 85.6 3.2 6 2.4 98 1490 932 93.4 48 585 - * Prolonged from two Sunpar 150M (Sun Chemical) oil tests - contained 585 pprn of S; 164 ppm of N 2acete Sunpar LU) 150M (Sun Chemical) - contained 19 pprn of S; 103 pp of N 3acete White D-200 (Lyondell) - contained 1.0 ppm of S; 1.0 ppm N The relative degree of volume increase in oil is representative of the interlacing density of vulcanized rubber, v.gr -.,. Higher interlacing density in the rubber results in lower values of volume increase. The data in Table VIIT clearly show that the prepared materials using extender oil having low amounts of sulfur and nitrogen, and where the molar ratio of sulfur or nitrogen and platinum in the catalyst is low, results in a product of thermoplastic elastomer that is much more effectively entangled by hydrosilylation. This effect is seen at extremely low catalyst concentrations.

EXAMPLE 9 The compositions were prepared using rubber master fillers with two different amplifying oils under the conditions described in Example 8. The physical properties were evaluated and set forth in Table IX.

TABLE IX Oil Extender aaa Catalyst-of Pt (pprn) 0.22 0.23 0.45 0.59 1.03 1.0 Hardness (A) 62 55 60 57 62 62 TS (%) 8 14 6 12 6 8 UTS (kg / crn2) 950 380 900 670 880 930 MI 400 220 420 280 410 370 EU (%) 390 440 320 490 290 450 OS (%) 101.7 258.5 93.2 165.7 93.6 109.9 The use of "C" extender oil, which contains very low levels of materials that have the chemical composition of a Lens base, resulted in thermoplastic elastoin products with excellent tensile properties and a high degree of interlacing of the elastomer, yet at catalyst levels as low as 0.2 parts per million. In contrast, products prepared with an "A" extender oil, which contains higher levels of sulfur-containing compounds and nitrogen, required the use of approximately five times more catalyst in the reaction to achieve similar properties.

EXAMPLE 10 The thermoplastic elastomer compositions were prepared using an oil-amplified rubber, mixed to have an increasing concentration of sulfur compounds. The thermoplastic elastomers were prepared as described in Example 8, using a master filler of rubber "I". The properties of the products are mentioned in Table X.

TABLE X S content of ace (mg) 0.02 15.12 30.24 45.35 60.46 N content of the oil (mg) 0.02 1.39 2.76 4.13 5.5 Catalyst of Pt (pprn) / (mg) 3.7 / .07 3.8 / .07 3. /.07 3.7 / .07 4.9 / .09 Molar ratio S: Pt 0.9: 1 1316: 1 2633: l 3948: 1 4094: 1 Inol ratio r N: Pt 3.7: 1 276: 1 548: 1 821: 1 851: 1 Hardness (A) 58 55 57 55 55 TS (%) 6.5 6 8.5 9 11 UTS (kg / cm2 ') 800 760 865 800 676 MI U-g / cm2) 400 360 360 300 260 EU (%) 290 330 330 560 604 Gel (%) 97.5 97.9 97.8 97.9 OS (%) 91 100 121 126 164 Prepared by mixing White oil with Atoll (available from Petro Lube Ltd.) containing 3300 pprn e S and 300 ppm N.

The effect of increasing the sulfur and nitrogen content in the extender oil (processing) in the state of cure can be seen in the sharp increase in volume increase that occurs when the molar ratio of S: Pt is 4000: 1 and the molar ratio of N: P + is 800: 1. The molar ratio of the total material having the chemical behavior of a Lewis base in relation to the platinum catalyst is desirably less than 5000: 1, and the preferred molar proportions of sulfur and nitrogen to platinum are less than 2000: 1 and 600: 1 respectively. The molar proportions that are most preferred are less than 1000: 1 S: Pt and 100: 1 N: Pt.

EXAMPLE 11 The thermoplastic elastomer compositions were prepared following the method set forth above in Example 8, and using the rubber "3" as the elastomer. In the Table XI shows a comparison of the products using two different amplifying oils.

TABLE XI Oil content (rnrnoles) 0., 02 0.30 Catalyst of Pt (ppm) / (mg) 6., 6 / 0.12 7.8 / 0.14 SiH (per) 3., 3 3.0 Molar ratio S: Pt 1:: 1 17: 1 Hardness (A) 62 60 TS (%) 7 7.5 UTS (kg / crn2) 910 924 MI (kg / crn2) 410 345 EU (%) 420 482 OS (%) 106 174 Rubber "3" shows the same effect of improved entanglement when an extender oil is used which is essentially free of materials that behave as Lewis base with respect to the platinum containing catalyst. While the preferred mode and preferred embodiment of the invention has been mentioned in accordance with the Patent Statutes, the scope of the invention is not limited thereto, but instead is defined by the appended claims.

Claims (21)

NOVELTY OF THE INVENTION CLAIMS

1. The improvement in a process for the entanglement of an oplastic resin mixture and an unsaturated rubber by dynamic vulcanization in the presence of a hydrosilylation agent, a hydrosylation catalyst containing platinum and an extender or processing oil, characterized because it comprises using a substantial oil free of materials that have the chemical behavior of a Lewis base.

2. The process according to claim 1 further characterized in that said oil is substantially free of materials containing sulfur, phosphorus, tin, itrogen or arsenic.

3. The process according to claim 1 further characterized in that the molar ratio of materials having the chemical behavior of a Lewis base in relation to platinum is less than 5000: 1.

4. The method according to claim 1 further characterized in that said hydrosilylation catalyst is present in an amount from 0.01 to 4 parts per million.

5. The process according to claim 1 further characterized in that the thermoplastic resin is a polyolefin ream and the rubber contains a diene monomer having sterically hindered carbon-carbon double bonds in a predominant manner.

6. The process according to claim 5 further characterized in that the polyolefin resin is polypropylene and the rubber is rubber of EPDM containing 5-v? N? L-2-norbornene as a diene anther. The method according to claim 1 further characterized in that after the dynamic vulcanization the rubber is in the form of discrete particles in a matrix of the thermoplastic ream, and is interlaced to the point that less than 5 percent by weight. - Weight of the interlaxable rubber can be extracted from the tepnoplastic elastomer product by means of a rubber solvent. 8. The process according to claim 1 further characterized in that said oil is a white paraffmic oil containing less than 30 parts per million sulfur and less than 100 parts per million nitrogen. 9. A terpenoplastic material produced by the process of claim 1. 10. A process for the production of a thermoplastic elastomer composition, characterized in that it comprises the steps of: a) mixing a thermoplastic ream and an unsaturated rubber containing an extender oil - which is substantially free of materials that have the chemical behavior of a Lewis base, b) add a hydrosilylation agent to the mixture from a), c) stir the mixture b) at a temperature sufficient to cause the mixture to flow, d) optionally incorporate a substantially processing-free oil free of materials having the chemical behavior of a Lewis base, and e) incorporate a catalyst into the mixture. hydrosilylation containing platinum in an amount within the range of 0.01 to 20 parts per million rubber, expressed as platinum metal, and f) tri Treat the mixture of (e) under hot conditions and cut until the rubber interlaces. 11. The improvement in a thermoplastic elastomer composition comprising a blend of thermoplastic resin, a rubber processing oil or extender and an unsuitable rubber that has been entangled by dynamic vulcanization using a hydrosilylation agent and a catalyst that it contains platinum characterized in that it comprises a composition wherein said oil is substantially free of materials having the chemical behavior of a Lewis base. 12. The improvement in a process for hydrosilylation entanglement of a composition comprising a mixture of a tenepoplastic resin and an unsaturated rubber by dynamic vulcanization, characterized in that it comprises comprising an entanglement agent by hydrosilylation and from 0.01 to 4 parts per million of a platinum-containing hydrosilylation catalyst in combination with a rubber-containing diene monomer having predominantly carbon-carbon double bonds without steric hindrance, with which results in a rubber interlaced in a thermoplastic resin matrix. 13. The process according to claim 12 further characterized in that the thermoplastic resin is a polyolefin resin and the rubber is rubber of EPDM containing 5-vinyl-2-norbornene as diene monomer. The method according to claim 12 further characterized in that after the dynamic vulcanization the rubber is in the form of discrete particles in a matrix of the thermoplastic resin, and is entangled to the point where less than 5 percent can be extracted by Interlocking rubber weight from the elastomer-or thermoplastic product by means of a rubber solvent. 15. The process according to claim 12 further characterized in that the platinum-containing hydrosilylation catalyst is selected from the group consisting of chloroplatinic acid, complexes of chloroplatinic acid with sim-divinyltetra ethyldisiloxane, and dichloro-bis (triphenyl phosphine) Platinum (II). 16. The method according to claim 12, further characterized in that it comprises incorporating a metal chelating agent into the elastomer. 1

7. The method according to claim 12 further characterized in that it comprises incorporating into the elastomer a compound that reacts with the residual silicon hydride. 1

8. A thermoplastic elastomer product made by the process according to claim 12. 1

9. A process for the production of a thermoplastic elastomer composition, characterized in that it comprises the steps of: a) mixing a thermoplastic resin and? N rubber that contains a diene non-ion component having sterically hindered carbon-carbon double bonds predominantly, b) adding a hydrosilylation agent to the mixture from (a), c) stirring the mixture from (b) to a temperature sufficient to cause the mixture to flow; d) incorporate a hydrosilylation catalyst containing platinum in the mixture in an amount ranging from about 0.01 to about 4 parts per million parts of rubber, expressed as platinum metal, and e) chew the mixture of (d) until the rubber is intertwined. 20. A thermoplastic elastomer composition of the type comprising a blend of thermoplastic resin and unsaturated rubber that has been entangled by dynamic vulcanization, characterized in that the rubber contains a diene monomer having predominantly sterically unimpeded carbon-to-carbon double bonds, and is interlaced using a hydrosilylation crosslinking agent and from about 0.01 to about 4 parts per million, expressed as platinum metal, from a hydrosilylation catalyst containing platinum. 21. A process for the entanglement of a mixture of thermoplastic resin and an unsaturated rubber by dynamic vulcanization in the presence of a hydrosilylation agent, a hydrosilylation catalyst containing platinum and an extender or processing oil, characterized in that it comprises employing, in combination, polypropylene such as polyolefin resin, an EPDM rubber containing 5-v.inyl-2-norbornene or the unsaturated rubber, from about 0.01 to about 4 parts per million of platinum or the hydrosilylation catalyst and a white paraffinic oil containing less than about 300 parts per million sulfur and less than about 100 parts per million nitrogen as the oil. 22. A thermoplastic elastomer product produced by the process of claim 21.