MXPA98000060A - Preferred structure of phenoline resin conservative for vulcanization product termoplast - Google Patents

Abstract

It was unexpectedly found that phenolic resin healers having a majority of dibenzyl ligaduraster, were very effective in curing unsaturated rubbers in a mixture of a crystalline polyolefin and rubber. Its effectiveness exceeds that of conventional phenolic resins for many thermoplastic vulcanized compositions, which allows the reformulation of formulas with lower amounts of healers and equivalent or superior physical properties in the thermoplastic vulcanization product resulting

Description

PRELIMINARY STRUCTURE OF RESIN CONSERVATIVE FENOLICfl PflRfl PRODUCT OF VULCANIZATION TERMOPLflSTICQ REFERENCE This application is a continuation in part of the US application Serial No. 08 / 775,853, filed on December 31, 1996, for "Preferred Structure of Phenolic Resin Curator for Terruloplastic Vulcanization Product".

FIELD OF THE INVENTION The invention relates to thermoplastic vulcanization products, made from a crystalline polyolefin and unsaturated rubber, such as EPBrI, butyl rubber, natural rubber, synthetic rubber made from a conjugated diene or synthetic rubber made from a diene conjugated together with another olefin donor; or their combinations, and that are phenolic resin healers. They are also useful as rubber articles formed with conventional thermoplastic forming equipment.

BACKGROUND OF THE INVENTION The phenolic resin healers for EPDM, butyl rubber, natural rubber and synthetic rubber, formed from conjugated diene monomers or combinations thereof, are known. The use of phenolic curing agents in combinations with EPDM, butyl rubber, natural rubber and synthetic rubber, from common conjugated dienes in thermoplastic elastomers, is also known. The structure of the phenolic resins used in curing elastomers varies depending on the reaction conditions used to prepare them. Res resins have two types of structures between the aromatic rings *: the dibenzyl ether bonds and / or the methylene bonds. The dibenzyl ether linkages are preferably formed under basic conditions and low reaction temperatures. The rnetylene bridge bonds are preferably formed under acidic conditions and higher reaction temperatures. However, both structures are typically formed in the synthesis of resole resin. According to textbooks, such co o Principles of Polyrnerizations by George Odian, 2nd. edition pages 128-133, the relative importance of the phenolic resin structure (resole resin) has not been well established. However, publications such as ñpplications of a Cone / Plate Rheorneter for the Characterization of Resol-Type Phenol Forrnaldehyde Resins, by Solornon So and co-authors, Journal or Polyrner Science, пpplied Polyrner Syrnposiurn 51, 227-291 (1992), pages 287-289, teach that resins of the phenol res type - Formaldehyde, which have a high level of rnetylene bridges, have shorter healing times.

The resol resins that have a high content or that exclusively contain rnetileno bonds, are the preferred ones for the vulcanization of elastors, in the thermocracked rubber industry.

BRIEF DESCRIPTION OF THE INVENTION The thermoplastic elastomer compositions, formed from a crystalline polyolefin and an unsaturated rubber, can be cured more effectively with a phenolic resin healer having approximately 50 to 99 dibenzyl ether linkages per 100 aromatic rings. Unexpectedly, these phenolic resin healers are more active than conventional phenolic healers. The dynamic vulcanization may require about 30 to 80 weight percent less of these curing agents than with conventional phenolic resin, with a high content of methylene bridges, to impart an equivalent degree of entanglement. Phenolic resin healers, with a high percentage of dibenzyl ether (ether) bridges also retain more of their activity as healers, after storage or after processing at elevated temperatures, than conventional phenolic resin healers.

BRIEF DESCRIPTION OF THE DRAWINGS Figure T illustrates the weight loss (0-4% by weight) of phenol-formaldehyde resins, of the resol type, measured after aging at 200 ° C for six minutes in a circulating air oven, as a function of the equivalent weight of rnetilol (120-240 g / equivalent). Figure II is a graph of the flSTM D471 values of oil milling (50-150% by weight) of the TPV of Table V, made from the phenolic reams of different equivalent weights of rnetilol (120-240 g / eq) after aging at 200 ° C for six minutes.

DETAILED DESCRIPTION The phenol-formaldehyde resins are characterized by formulas such as the one shown below: CH, OH HOCH, where x is the number of aromatic rings with a subsequent meti.leno bridge, and "y" is the number of aromatic rings with a subsequent dibenzyl ether (ether) bridge (CH2-O-CH2). The phenolic resin healers do not need to be linear (for example, they can be branched) and the rnetylene bridges and the ether bridges are randomly present in the structure, such that sequences such as 1, 2, 3, etc., rnetylene bridges and / or ether are present randomly. In phenolic resin healers the sum of x + y can generally vary from 1 to 15 or more, approximately. In conventional phenolic resin healers for earth-damaged elastomers, the values of x and y are such that on average there are less than 10 dibenzyl ether bridges per 100 aromatic rings. In conventional phenolic resin healers for dynamic vulcanization products, the values of x and y are such that there are approximately 20 to 46 dibenzyl ether bridges per 100 aromatic rings. In the phenolic resin of this invention, the average values of x and y vary from the number of 50 to 99 dibenzyl ether bridges per 100 aromatic rings; more conveniently, from 60 to 99 and, preferably due to the number of bridges which is slightly less than the number of aromatic rings, from 60 to 90 or 93 dibenzyl ether bridges per 100 aromatic rings. A preferred alternative scale of dibenzyl ether bridges is 50 or 55 to 80 or 86, better still, 55, 60 or 65 to about 75, 80 or 85. Ra, in the above formula, independently in each aromatic ring, is an H atom or an alkyl of 1 to 12 carbon atoms. In such a manner, the phenolic reams can be phenolic resins substituted with alkyl. It should also be understood that some inethylene bridges may be present in the preferred phenolic resin, but the number of bridges in rne + full will be less than the number of dibenzyl ether bridges per 100 aromatic rings. The level of dibenzyl ether bridges can also be expressed in terms of the equivalent weight of rnetilol. Since each di-benzyl ether bridge is viewed as two methylol groups, increasing the number of dibenzyl ether bridges (by reducing the number of methylene bridges) increases the equivalents of rnetylol in a phenolic resin. The equivalent weight of rnetylol is the average molecular weight of the number of the phenol res, divided by the average sum of the inethylol groups per molecule, thus twice the number of dibenzyl ether groups per molecule. Conventional phenolic resins for curing heat-set rubbers have equivalent weights of rnetilol of about 400 to 1700 or more. The equivalent weight of desirable rnetylol for the thermoplastic vulcanization products in the present invention is from about 100 to 200, most conveniently from 125 to 165, 175 or 185 and, preferably, from about 125 or 135 to 165 or 175. equivalent weights of aforementioned rnetylol would vary at lower rates for the terbutyl groups and more for the terdodecyl groups in the phenol. These phenolic resins conveniently have in them their terbyltyl, teroctium or terdodecyl + + substituents. Conveniently a majority of the phenolic back units (eg, 50, 60, 70? 80 mole%) have one of these substituents. It can be anticipated, based on the chemical structure shown in the detailed description, that a desirable optimization of the dibenzyl ether bridges would result in the equivalents of 2 ethyl per pungent repeating unit, when each dibenzyl ether bridge is calculated as equivalent to 2 rnetilol groups. This would produce an estimated minimum equivalent weight of rnetylol of half the molecular weight of an average repeating phenolic unit. Conveniently the netilol equivalent weight is 0.5 to 0.8 times, approximately, the average molecular weight of a repeating phenolic unit; More conveniently, from 0.55, 0.60 or 0.65 to 0.72, 0.76 or 0.80 times, approximately, the average molecular weight of a repeating phenolic unit in the particular phenolic resin heater. The scale of the equivalent weight of rnetilol can be calculated, which are equivalent to the scales for the dibenzyl ether bridges per 100 aromatic rings. For a terbutyl-substituted phenolic ream, having an average molecular weight per phenolic repeating unit of about 192), an estimated scale of equivalent inethylolol weights, desirable, would be 100, 110 or 120 to about 130, 140 or 150 For a phenol resin substituted with teroctyl (having an average molecular weight per phenolic repeating unit of about 249), a desirable estimated scale of equivalent molecular weight of rnetylol is about 125 or 135 or 145 to about 180, 190 or 200. For a phenolic resin substituted with terdodecyl (molecular weight per repeating phenolic unit, about 306), a desirable estimated scale of equivalent weights of rnetylol would be about 150, 165 or 175 to about 215, 225, 235 or 245 The resol phenol-formaldehyde resin with para-ter-octyl substituents is preferred. Preferred phenolic resin healers of this description can be made by altering the process in which phenol-formaldehyde reagents are formed. It is believed that phenolic resins with a greater number of dibenzyl ether bridges (bonds), during acid-catalyzed curing, are separated to give more fragments which are active to crosslink the unsaturated rubber. It is also believed that phenolic resins with a high number of dibenzyl ether bridges were not used in traditional vulcanized rubber products because volatiles can be released in higher amounts from their decomposition, and these volatiles would generate undesirable voids in the product. vulcanized rubber, traditional. The preparation of phenolic resins with different proportions of brinene and dibenzyl ether bridges is well known in the art. The following references give additional information for preparing phenolic resins: G.

They hate, chapter 2-12b4 Principies of Polyrnerization, 2a. edition, Wiley Interscience, New York, 1981; I. H. Updegraff and T. 3.? Uen, Condensations with Forrnaldeh e; Chapter 14, in Polymerization Processes, C. E. Schildneckt and I.? keist, Wiley-Interscience, New York, 1977; M. F. Drurnrn and 3. R. LeBlanc, The Reactions of Formaldehyde with Phenols, llelarnine, ñnaline and Urea, chapter 5 in Step-Trowth Polyrnerization, D. H. Solornon, Ed., Marcel Dekker, New York, 1972; and R. Ul. Lenz, Qrganic Chernistry of Synthetic High Polyrners, chapters 4-8, Uiley-Interscience, New York, 1967. The number of dibenzyl ether bridges can be determined according to the procedure of Journal of Polyrner Science, part A, lane 3, pages 1079-1106 (1965), entitled flcetilation and H-NMR Procedure for Phenolic Resin Structure ñnalysis. The use of conventional phenolic resin healers for interlacing EPDM in a thermoplastic elastomer is described in U.S. Patent 4,311,628, hereby incorporated by reference, with respect to its teachings. Those types of phenolic resin healers, only modified to have more dibenzyl ether linkages, could be used in this invention. Phenolic curing systems comprising phenolyl phenol resins, a halogen donor and a metal compound are especially recommended. Halogenated phenol healers containing 2 to 10 percent halogen, with bromine being the preferred halogen, do not require halogen donors. Ordinary non-allogenated phenol healers are more effective with a halogen donor. When the halogens are present in the healer or donor, it is convenient to use at least one hydrogen halide scrubber, such as the metal oxides which include the iron oxide, the titanium oxide, the magnesium oxide, the magnesium silicate and silicon dioxide and, preferably, zinc oxide. Examples of halogen donors are: stannous chloride, ferric chloride and halogen-donating polymers, such as for chlorinated, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Typically, the phenolic resin healer (also known as phenol ream heater) with high content of dibenzyl ether linkages, is used in amounts ranging from 0.5 to 20 parts by weight, approximately, per 100 parts by weight of rubber more saturated Appropriate amounts of cure activators, such as halogen donors, are conveniently 0.01 part by weight to 10 parts by weight or about one part per 100 parts of the rubber. It has been found that the phenolic resin healer, activators and halogen scavengers do not result in significant amounts of rubber grafts in the polyolef to crystalline. The major portion of the polymers in the iron-plastic elastoin is the crystalline polyolefin and unsaturated rubber. Examples of polyolef to crystalline are: polyethylene or polypropylene or its copolymers and mixtures thereof. The unsaturated rubber may be a polyolefin, such as EPDM rubber, which due to the randomness of its repeating structure or its side groups, tends not to crystallize or, in the case of EPDM, is not predominantly the ethylene or propylene portions. that tend to crystallize. Examples of the unsaturated rubber include: EPDM rubber, butyl rubber, natural rubber or synthetic rubber from at least one unsaturated dienic material, or combinations thereof. Minor amounts of other polymers may be added to modify the flow properties, such as fillers or diluents, or as additives, such as polymeric antioxidants. The quantities of the majority of the components in the mixture will be specified: 1) per 100 parts by weight of the mixture of the crystalline polyolefin and the unsaturated rubber; or 2) per 100 parts by weight of unsaturated rubber. The crystalline polyolefin may conveniently be from 15 to 75 parts by weight, approximately; better still, from 25 to 7 parts by weight, suitably, and preferably from 25 to 50 parts by weight, per 100 parts of the mixture of the crystalline polyolefin and the unsaturated rubber. The unsaturated rubber suitably is from 25 to 85 parts by weight, approximately, better yet, from 25 to 75 parts by weight, approximately and, most preferably, from 50 to 75 parts by weight, approximately, per 100 parts by weight of the mixture . If the amount of crystalline polyolefin is based on the amount of rubber 1? unsaturated, is conveniently from 17.5 to 300 parts by weight, more conveniently from 33 to 300 parts and, preferably, from 33 to 200 parts by weight per 100 parts by weight of the rubber. The terms "mixture", "terrnoplastic elastomer" and "thermoplastic vulcanization product" used herein means a mixture ranging from small interlaced rubber particles, well dispersed in the thermoplastic elastomer matrix, to continuous phases of the polyolef to crystalline and a partial to fully interlaced rubber, or combinations thereof. While the thermoplastic elastomer may include block copolymers that do not need to be vulcanized, the term thermoplastic vulcanization product is limited to when the rubber phase is at least partly vulcanized (entangled). The term "thermoplastic vulcanization product" refers to compositions that may possess the properties of a thermofixed elastomer and that are reprocessable in an internal mixer. Upon reaching temperatures above the softening point or the melting point of the crystalline polyolefin phase, continuous sheets and / or molded articles can be formed with complete bonding or melting of the thermoplastic vulcanization product under conventional conditions of shaping and shaping. the terrnoplasticos. After the dynamic vulcanization (cure) of the rubber phase of the thermoplastic elastomer or thermoplastic vulcanizing opener, suitably less than 3% by weight and better still less than 1% by weight of the unsuitable rubber can be extracted from the sample of the thermoplastic elastomer in boiling xylene. The techniques for determining the extractable rubber are given in US Pat. No. 4,311,628, which is incorporated herein by reference. The crystalline polyolefin comprises crystalline thermoplastic polymers derived from the polymerization of rnononoolefin monomers by a high pressure, low pressure or intermediate pressure process; or by Ziegler Natta catalysts or by rnetalocene catalysts. Conveniently, rhonohorn moieties converted to repeating units are at least 95% by weight rnononoolefins of the formula CH 2 = C (CH 3) -R or CH 2 = CHR, wherein R is an H or a linear or branched alkyl group , from 1 to 12 carbon atoms. Preferred crystalline polyolefins are polyethylene and polypropylene or their copolymers and mixtures thereof. The polyethylene can be high density, low density, low linear density or low density. The polypropylene can be a polypropylene furnace as well as a polypropylene reactor copolymer. The unsaturated rubber can be any rubber that has residual unsaturation, which can react and be entangled with the phenolic resin, under conventional interlacing conditions. Such rubbers may include natural rubber, EPDM rubber, butyl rubber, halogenobutyl rubber, or synthetic rubber from at least one conjugated diene, or combinations thereof. Also included are rubbers comprising at least one alpha-olefin, at least one vinylidene-aromatic compound and at least one diene. Reference is made to EPDM, butyl and halogenobutyl rubber with rubbers of low residual unsaturation, and are preferred when the vulcanization product needs good thermal stability or good oxidative stability. The rubber with low residual unsaturation conveniently has less than 10% by weight repeating units which have unsaturation. The acrylate rubber and the epichlorohydrin rubber are conveniently excluded from the unsaturated rubbers. For the purposes of this invention, the copolymers of the invention will be used to define polymers from two or more rnonomers, and polymers having repeating units from one or more different rnonomers. The rubber of low residual unsaturation, conveniently, is an olefinic rubber, such as the rubber of the EPDM type. EPDM-type rubbers are generally terpolymers derived from the polymerization of at least two rnononoolefin moieties having from 2 to 10 carbon atoms, preferably from 2 to 4 carbon atoms, and at least one polyunsaturated olefin having 5 to 20 carbon atoms. Said mononucleotides suitably have the formula CH 2 = CH-R, wherein R is an H or an alkyl of 1 to 12 carbon atoms and, preferably, are ethylene and propylene.

Conveniently ethylene and propylene are present in the polymer in weight proportions of 5:95 to 95: 5 (ethylene / propylene) and constitute from 90 to 99.6% by weight of the polymer. The saturated polyii olefin can be a straight chain, branched, cyclic, bridged ring, bicyclic, bicyclic ring, etc. compound. Preferably it is a non-conjugated diene. The repeating units, conveniently, of the unconjugated polyunsaturated olefin, constitute approximately 0.4 to 10% by weight of the rubber. The rubber of low residual unsaturation can be a butyl rubber. The butyl rubber is defined as a polymer that consists predominantly of repiso.ent.es units of .isobutylene, but that includes some repeating units of a rnonornero that provides sites for entanglement. The commoners who provide sites for entanglement can be a polyunsaturated monomer, such as a conjugated diene or divinylbenzene. Suitably from 90 to 99.5% by weight of the butyl rubber is constituted by repi ient units derived from the polymerization of isobutylene; and from 0.5 to 10% by weight of the repeating units, is a polyunsaturated monomer having from 4 to 12 carbon atoms. Preferably, the polyunsaturated monomer is isoprene or divinylbenzene. The polymer can be halogenated to further increase the reactivity in the entanglement. Preferably, the halogen is present in amounts of 0.1 to 10% by weight, approximately; better still, from 0.5 to 3.0% by weight, approximately, and preferably the halogen is chlorine or bromine. Another rubber can be used, such as natural rubber or a synthetic rubber, of at least a conjugated diene, in the product of dynamic vulcanization. These rubber are of greater unsaturation than the rubber EPDM and the butyl rubber. Natural rubber and synthetic rubber may optionally be partially hydrogenated to increase thermal and oxidative stability. Synthetic rubber may be non-polar or polar, depending on the comonórneros. Conveniently the synthetic rubber has repeating units of at least one conjugated diene monomer having from 4 to 8 carbon atoms. Coronorneros can be used and include one or more vinyl-arornáticos that have from 8 to 12 carbon and acrylonitrile or one or more alkyl-substituted acrylonitrile rnonomers having from 3 to 8 carbon atoms. Other cormnornally used suitably include repeating units of rnonorders having unsaturated carboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides of dicarboxylic acids and other commons having from 3 to 20 carbon atoms. Examples of synthetic rubbers include: synthetic polyisoprene, polybutadiene rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, etc. It is possible to use synthetic rubs functionalized with amine or functionalized with epoxy. Examples thereof include amine-functionalized EPDM and epoxy-functionalized natural rubbers. Mixtures of any of the above elastomers may be employed in place of a single elastomer. The thermoplastic elastomers of this description are generally prepared by melt mixing the crystalline polyolefin, the unsaturated rubber and other ingredients (filler, plasticizer, stabilizer, etc.) into a heated mixer above the melting temperature of the polyolefin. crystalline The optional fillers, plasticizers, additives, etc. can be added at this stage or later. After mixing in a sufficient molten state, to form a well-mixed mixture, phenolic resin vulcanizing agents (also called healers or interleavers) are generally added. It is preferred to add the vulcanizing agent in solution with a liquid, for example rubber oil processor, which is compatible with the other components. It is convenient to follow the progress of vulcanization, monitoring the torque of the mixing or the energy requirements of the mixing, during that operation. The mixing torque or mixing energy curve generally passes through a maximum, after which the mixing can be continued for a longer time to improve the manufacturing capacity of the mixture. If desired, some of the ingredients can be added after the dynamic vulcanization is completed. After the mixer is discharged, the mixture contains vulcanized rubber and the thermoplastic can be ground, shredded, extruded, pelletized, injection molded or processed by any other convenient technique. It is usually convenient to allow the fillers and a portion of any plasticiser to be distributed in the rubber or in the crystalline polyolefin phase before interlacing the rubber phase or phases. Entanglement (vulcanization) of the rubber may occur in a few minutes or less, depending on the temperature of the mixture, the shear rate and the activators present for the phenolic resin healer. Suitable cure temperatures include 120 ° C for a crystalline polyethylene or 175 ° C for a crystalline polypropylene phase, up to around 250 ° C; the most preferred temperatures are 150 or 170 ° C up to 200 or 225 ° C. Mixing equipment can include Banbury mixers < MR > , BrabenderCMR mixers) some mixer extruders. The thermoplastic elastomer may include a variety of additives. Additives include particulate fillers, such as carbon black, silica, titanium dioxide, color pigments, clay, zinc oxide, stearic acid, stabilizers, anti-degradants, flame retardants, processing aids, adhesive, thickeners, plasticizers , wax, discontinuous fibers (such as wood cellulose fibers) and extender oils. When extender oil is used it may be present in amounts of from 5 to 300 parts by weight, approximately, per 100 parts by weight of the mixture of crystalline polyolefin and unsaturated rubber. The amount of extender oil (eg, hydrocarbon oils and ester plasticizers) can also be expressed as 30 to 250 parts, better still, 70 to 200 parts by weight per 100 parts by weight of the unsaturated rubber. Suitable amounts of black of or, when present, are from 40 to 250 parts by weight, approximately, per 100 parts in unsaturated rubber; from 10 to 1,000 parts by weight, approximately, per 100 parts by weight, in total, of the total unsaturated rubber and extender oil, The thermoplastic elastomeric compositions of the invention are useful for forming a variety of articles, such as tires. , hoses, belts, gaskets, moldings and molded parts. In particular they are useful for forming articles by extrusion, injection molding and compression molding techniques. They are also useful for modifying terrnoplastic resins, in particular polyolefin resins. The compositions can be mixed with thermoplastic resins using conventional mixing equipment, to form a rubber-modified thermoplastic resin. The properties of the modified thermoplastic resin depend on the amount of blended thermoplastic elastomer composition. The stress-strain properties of the compositions are determined in accordance with the test procedures expressed in ASTM D412. These properties include the traction adjustment (TS), the extreme tensile strength (UTS), the 100% modulus (MlOO), the 300% modulus (M300) and the extreme elongation to bursting (UE). The term "thermoplastic elastomer" or "elastomeric", as used herein and in the claims, means a composition possessing the tension setting property of forcibly retracting within a given period of time (10 minutes) at less than one hour. 160% of its original length, after having been stretched at room temperature to double its original length and maintained for the same period of time (1 to 10 minutes), before releasing it. The compression set (CS) is determined in accordance with ASTM D-395, method B, by compressing the sample for 22 hours at 100 ° C. Swelling in oil (OS) (percentage weight change) is determined in accordance with ASTM D-471, immersing the sample in ASTM No. 3 oil for 70 hours at 123 ± 2 ° C. Especially preferred compositions of the invention are hulled compositions having tensile setting values of about 50% or less than compositions that meet the definition for rubber, as defined by ASTM standards, V. 28, page 756 ( D1566). The most preferred compositions are hulled compositions having a Shore D hardness of 60 or less or 100% modulus of 180 kg / cm 2 or less, or a Young's modulus of 2,500 kg / cm2.

EXAMPLES The following examples were prepared to illustrate the effectiveness of the phenolic resin healer with a greater number of dibenzyl ether ligatures per 100 aromatic rings in the cure of EPDM rubber in thermoplastic elastomers. The mixing process is as generally indicated in this specification. In Table I, controls A-D used a conventional phenolic resin healer, at a concentration of 2 phr (parts per 100 parts of resin), based on EPDM rubber. In Examples 1-6, the phenolic resin healers had 53 to 71 dibenzyl ether ligatures per 100 aromatic rings and were used at a concentration of 2 phr. Examples 1-6 had a higher tensile strength (UTS) higher, higher modulus at 300% (M300) and lower compression set (CS), as well as a lower oil swelling (OS) than the controls cured with the same amount by weight of conventional phenolic resin healers. These differences in physical properties illustrate that preferred phenolic resin healers give additional entanglements when healers are used in low amounts.

TABLE I * All formulas are based on one hundred parts by weight of rubber. In Table II, the tepnoplast elastomers were prepared with a formula almost identical to that in Table I, but the amount of phenolic resin healer was increased to 4.5 parts per hundred parts of ream (phr *). Examples 7 and 8 of the TI frame have less oil swelling than controls E, F and 6. This change in oil swelling illustrates that examples 7 and 8 cured with phenolic resins, which have a greater number of Ether bonds or ligatures are more resistant to oil leakage, presumably due to more interlacing. The rest of the physical properties of controls E and F were similar to examples 7 and 8. This illustrates that, with larger amounts of conventional phenolic resin, some properties equivalent to those obtained with phenolic resins can be obtained. that have a higher number of dibenzyl ether ligatures. The control (3 with a low rn? And low ether bridging content (ligature) gave lower interlacing density, as evidenced by its lower Shore A hardness, lower extreme tensile strength and greater compression adjustment and greater oil swelling. The physical properties of examples 5 and 6 of Table i, which used 2 phr of the phenolic resin with a greater number of ether ligatures, can be compared to the physical properties of controls E, F and G of Table II, cured with 4.5 phr of a conventional phenolic resin healer, to illustrate that 2 phr of phenolic resins with a greater number of dibenzyl ether ligatures, produces thermoplastic elastomers with properties comparable to those of the same formulations cured with 4.5 phr of resin healers conventional phenolic.

TABLE II Ctrl. E Ctrl. F Ctrl.6 Ejei .1 Ejei.8 Rubber EPDH 100 * 100 100 100 100 Polypropylene 45 45 45 45 45 Oil 135 135 135 135 135 Wax 5 5 5 5 5 Clay 42 42 42 42 42 ZnO 2 2 2 2 2 SnC12 1.26 1.26 1.26 1.26 1.26 CHARACTERIZATION OF PHENOLIC RESIN Ether bridges / 100 aromatic rings 40 46 23 70 71 Equivalent weight for? Ethylol 223.4 215.6 411.8 159.9 158.5 Resin type SP1045 SP1045 SP1045 HRD1224? SHD9938 '• JE- TABLE II (continued) Ctrl. E Ctrl. F Ctrl. G Ejei .7 Ejei. 8 PROPERTIES OF ELASTOHERO TERHOPLASTICO Shore A 63 64 58 63 64 TSZ 6 6 7.5 6 8 UTS, flPa 6.48 6.41 4.55 5.07 6.28 11100, HPa 2.69 2.69 2.28 2.62 2.83 H300, upa 6.00 6.07 - 5.17 - ÜEZ 330 310 290 300 290 CS, Z Í100 ° C, 22 hours) 19.4 21.8 30 22.0 16.2 OS, l (123-2% 70 hours) 83.2 82.0 108 68.0 64.7 * All formulas are based on one hundred parts by weight of rubber. The compositions of Table III were prepared using a continuous mixer instead of an intermittent mixer, as in Tables I and II. Table III compares the physical properties of dynamic vulcanization products, elastomeric, cured with 4.5 phr of conventional phenolic healer (control H) and cured with 4.5, 3.6 and 2.7 phr of a phenolic healer that has a greater number of dibenzyl ether ligatures (examples 9, 10 and 11). ). Example 11 shows that the vulcanization product with only 2.7 phr of the phenolic healer, which has a higher number of bonds or dibenzyl ether ligatures, had an extreme tensile strength greater than the control H cured with much greater amounts of? n Conventional phenolic resin heater. The extreme, large tensile strength of Examples 9, 10 and 11 was indicative of effective entanglement using the phenolic resin with a greater number of dibenzyl ether linkages. The physical properties of examples 9, 10 and 11 showed differences due to the use of a decreased amount of phenolic resin healer, which had a higher number of dibenzyl ether ligatures. The extreme tensile strength was raised to a maximum as the phenolic resin was decreased. The 300% modulus showed a gradual decrease with the use of smaller amounts of phenolic resin. The swelling values in oil increased as the amount of phenolic reein decreased, indicating lower interlacing density. Table III illustrates that the amount of phenolic resin may decrease when a resin with a greater number of dibenzyl ether ligatures is used.

TABLE III C * i rl .H E ern.9 Exercise.10 Exercise.11 Rubber V3666 100 * 100 100 LOO Poli rop le o 45 45 45 Aceit e 135 135 135 135 Ce to 5 5 5 5 Clay 42 42 42 42 ZnO 2 2 2 2 Res to phenolic 4.5 4.5 3.6 2.7 SnC12 1.26 1.26 1.26 1.26 CHARACTERIZATION OF THE FENOL ICA RESIN Bridges ether / 100 aromatic ani-wastes 40 70 70 70 Equivalent weight 233.4 159.9 159.9 159.9 T ream unit SP1045 SMD 9938 ...

PROPERTIES OF ELAS THERMOPLASTIC TOMER Shore A 61 60 59 58 TS% 8 8 9 9 UTS, MPa 6.07 6.76 7.17 6.21 MlOO, MPa 3.24 2.69 2.76 2.48 M300, MPa 4.97 5.66 5.45 4.83 EU% 350 370 410 410 CS,% (100 ° C, 22 hours) 24.8 22.8 24.4 25.4 OS,% (123 ± 2 ° C, 70 hours) 78.1 79.8 82.5 93.7 * All formulas are based on one hundred parts by weight of rubber. Table IV summarizes the compositions and physical properties of the harder thermoplastic elastors, which have more polypropylene and oil, along with a conventional phenolic resin or a phenolic resin that has a greater number of dibenzyl ether ligatures. In table IV the oil swelling values for the elastors are lower for an example elastomer, cured with the phenolic resin healer which has a greater number of dibenzyl ether ligatures, than for an elastomeric control, cured with conventional phenolic resin. This indicates that more entanglements were formed with the phenolic resin having a higher number of dibenzyl ether ligatures. In general, Table IV illustrates that for most physical properties, the lower concentration of the phenolic resin having a higher number of dibenzyl ether ligatures gave rn? And adequate properties, as compared to the thermoplastic elastomer cured with a resin conventional phenolic.

TABLE IV Ctrl.I Exercise.12 Exercise.13 Exercise.14 Rubber V3666 100 * 100 100 100 Polypropylene 22.3 22.3 22.3 22.3 Oil 130 130 130 130 Wax 5 5 5 5 Clay 42 42 42 42 ZnO 2 2 2 2 Phenolic resin 7.0 7.0 5.6 4.2 SnC12 1.26 1.26 1.26 1.26 CHARACTERIZATION OF PHENOLIC RESIN Ether bridges / 100 aromatic ani-wastes - 70 70 70 Resin type SP1045 ..... "SMD 9938 .... .......

PROPERTIES OF THE THERMOPLASTIC ELASTOMER Shore D 46 48 48 46 TS% 44 39 39 42 UTS, MPa 11.93 14.83 13.03 11.38 MlOO, MPA 9.38 9.17 9.24 8.97 M300, MPa 11.10 11.72 11.86 11.03 EU% 410 430 360 340 CS,% (100 ° C, 22 hours) 64.9 58.2 64.2 64.3 CS,% (123 ± 2 ° C, 70 hours) 45.8 40.0 41.5 44.6 * All formulas are based on one hundred parts by weight of rubber. The thermoplastic elastors of Table V were made using formulations such as those in Tables I and II. Controls K and L were made using the same formulation as controls E and G, using 4.5 phr of the conventional phenolic resin heater; and Examples 15 and 16 were made using the same formulation as Examples 5 and 6, using 2.0 phr of phenolic resin, with 70 'or 71 dibenzyl ether ligatures per 100 aromatic rings. The quartz-V elastiners were prepared from phenolic resin heaters that were first aged 6 minutes in air at 200 ° C. This aging was to determine if the exposure to high temperature aging (which simulates the temperature conditions to which the resin is exposed in the conventional mixing process) could move away from the efficiency of the phenolic resin healers with a number greater than dibenzyl ether ligatures, than with the conventional phenolic resin healer. A comparison of examples 15 and 16, wherein the phenolic resin with the highest number of dibenzyl ether ligatures was aged at 6 minutes at 200 ° C, with examples 5 and 6, where no aging occurred, illustrates that the resin Phenolic containing more ether bridges was as effective in entanglement, after aging, as before. Test values that increase with entanglement (Shore A, UTS, MlOO and M300) increased with aging, whereas the tests that decrease with the entanglement (EU, CS and 05) decreased with the year. A comparison of those with roles K and L, which used conventional phenolic reams, which were first aged for 6 minutes at 200 ° C with contours E and F of Table II, illustrates that conventional phenolic resins lose their effectiveness for interlacing during the year. The physical properties of the cured dynamic vulcanization product, which increase with entézamiento (Shore A, UíS, MlOO and M300) were consistently lower in the K and L controls, with respect to the conventional, thermally aged ream phenol. The physical properties that decrease with the entanglement (UE, CS and OS) were consistently greater in the K and L controls with respect to the conventional, thermally aged phenolic reams. This illustrates that phenolic resins that have a high number of dibenzyl ligations have a higher retention of their activity for crosslinking more saturated rubber than conventional phenolic reams. A comparison of the physical properties of controls K and L, cured with 4.5 phr of conventional resin, with respect to the physical properties of examples 15 and 16, cured with 4.5 phr of phenolic resin with high content of dibenzyl ether bridges, illustrates The combined effectiveness of the phenolic resin with a greater number of dibenzyl ether ligatures and the retention of the activity of this phenol-formaldehyde resin with high content of dibenzyl ether bridge, after aging, were obtained in the examples that had better entanglement than the controls (as illustrated by the physical properties of the vulcanization product). Thus, 4.5 phr of the phenolic resins with a higher number of dibenzyl ether ligatures resulted in an entanglement greater than 4.5 phr of conventional phenolic resin. Resins having a preferred scale of dibenzyl ether bridges also show improved thermal stability with respect to conventional resins, as reflected in a minor loss of weight when thermally aged. Figure I shows the weight loss measured after aging at 200 ° C for six minutes, against the equivalent weight of methylol. As can be seen, resins that have a lower equivalent weight of rilethyl, that is, with higher dibenzyl ether bridge levels, exhibit less weight loss during the thermal aging test, compared to conventional resins. The improved thermal stability of the resin leads to TPV compositions that have lower oil swelling. The lower swelling in oil reflects a greater density of interlacing of the rubber, which is strongly desirable. The ratio between the equivalent weight of rnetilol and the swelling in oil of a TPV cured with a thermally aged phenolic resin, of equivalent weight of specific methylol, is shown in Figure II and Table 5, TABLE V PHYSICAL PROPERTIES OF ELASTOMERQS TERMQPLASTICQS PREPARED FROM PHENOLIN RESIN CONSERVATORS ADJUSTED SIX MINUTES AT 200 ° C IN AIR Ctrl. J Ctrl. K Ctrl. L Axes.15 Axes.15 Rubber EPD? 100 * 100 100 100 100 Polypropylene 45 45 45 45 45 Oil 135 135 135 135 135 Wax 5 5 5 5 5 Clay 42 42 42 42 42 ZnO 2 2 2 2 2 Phenolic resin 4.5 4.5 4.5 4.5 4.5 SnC12 1.26 1.26 1.26 1.25 1.26 CHARACTERIZATION OF THE PHENOLIC RESIN Ether bridges / 100 aroaatic rings 0.01 40 46 70 71 Weight per equivalent of letilol 1,700 233.4 215.6 159.9 158.5 Resin type HRJ10518 SP1045 SP1D45 HRJ12247 SHD 9938 TABLE V (continued) Ctrl. ] Ctrl. K Ctrl. L Axes.15 Ejei.16 PROPERTIES OF ELASTOhlRO TERI10PLASTICQ CURED WITH THE PHENOLIC RESIN Shore A 58 60 59 62 61 TSZ 8 9 10 8 8 UTS, llPa 5.24 5.24 5.80 6.48 5.86 moo, upa 2.00 2.21 2.21 2.90 2.62 11300, HPa 4.21 4.48 4.83 6.41 5.86 EU: 420 380 390 300 300 CS, T (100 ° C, 22 hours) 23.2 30.4 3.4 170 20.9 OS, l (123 ° C2, (70 hours) 134 120.4 118.4 80.0 72.9 To determine the effect of the dibenzyl ether bridge level on the cure regimes and the efficiency of the entanglement of two different phenolic resin healers, they were studied incorporating them into terrnofraced EPDM compositions. The formulation was 100 parts by weight of EPDM rubber, 3 or 4.5 parts by weight of phenolic resin, 2 parts by weight of ZnO and, optionally, 1.26 parts by weight of SnCl2. Table VI below illustrates how the time for a torque increase of 1 dNm and the maximum torque due to the type and amount of phenolic resin and the presence of an activating SnC.2 are affected. The time for an elevation in the torque of 1 dNm is an indicator that the initial curing regime retards the surface burn. The maximum torque is related to the efficiency of the heater to react with the double bonds available in the production of entanglements.

TABLE VI HEALING CHARACTERISTICS OF EPDtl WITH PHENOLIC RESINS Without SnC12 With SnC12 Bridges Time Pair of Torque Pair of Ether-Torque Bridges 1 torsion for 1 ether / benzyl torsion dNrn of maximum dNrn of more than 100 years will increase the number of rheostats. of torsion twist. - sion. --- HRJ 10518 3 phr 3.66 2.65 0.61 3.33 1 SMD 9938 3 phr 2.19 3.68 0.53 4.69 71 HRJ10518 4.5 phr - __ 0.53 3.68 1 SMD 9938 4.5 phr - - 0.51 4.56 71 The results of Table VI are quite contrary to the generally accepted theories about the effect of the netnethylene versus the dibenzyl ether bridges, for the curing regimes. For the conventional thermosetted rubbers, the manufacturers of phenol-formaldehyde of the resol type recommended resins such as HRJ 10518 which has around 1 dibenzyl ether bridge per 100 aromatic rings, as it is an optimal resin. Other sources, such as the article on res cures of the res type, mentioned in the background of the application, and which is in the Journal of Applied Polyrner Science, Applied Polymer Syrnposiurn, 51, 277-291 (1992) teach that the content The bridge of the network bridge provides fast healing times. Table VI is the first data that shows a faster cure rate in a thermowashed rubber compound, when phenol-formaldehyde of the resole type is used with a high content of dibenzyl ether bridges. Although it has been indicated, according to the patent statutes, the best way and the preferred modality of the invention, s? scope is not limited to them but rather by the scope of the claims that follow.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - A thermoplastic vulcanization product, characterized in that it comprises: a) from about 15 to 75 parts by weight of a crystalline polyolefin resin; and b) from 25 to 85 parts by weight, suitably, of an unsaturated rubber; said parts by weight being based on 100 parts by weight of the total crystalline polyolefin and unsaturated rubber; wherein the vulcanization product comprises entanglements in the unsaturated rubber, derivatives of the cure with about 0.5 to 20 parts per hundred parts of resin, of a phenolic resin healer having about 50 to 99 dibenzyl ether bridges per 100 aromatic rings; and wherein the parts by weight refer to 100 parts by weight of unsaturated rubber.

2. A vulcanization product according to claim 1, further characterized in that the unsaturated rubber comprises repeating units in amounts of 90 to 99.6% by weight, originating from the polymerization at least two of the alpha-rnononoolefins of the formula CH2 = CHR, wherein R is H or an alkyl of 1 to 12 carbon atoms and 0.4 to 10% by weight of repeating units, from the polymerization of at least one polyunsaturated, unconjugated monorne, having 5 to 20 carbon atoms; and wherein said resin heater has about 55 to 80 dibenzyl ether bridges per 100 aromatic rings. 3"- A thermoplastic vulcanization product in accordance with claim 2, further characterized in that the phenolic resin heater has about 60 to 80 dibenzyl ether bridges per 100 aromatic rings. 4. A thermoplastic vulcanization product according to claim 1, further characterized in that the unsaturated rubber comprises a polymer having 90 to 99.5 weight percent repeating units of isobutylene and 0.5 to 10 weight% of units repeat lenses of a polyunsaturated monomer having from 4 to 12 carbon atoms; the polymer being optionally halogenated, and wherein the resin heater has about 55 to 80 dibenzyl ether bridges per 100 aromatic rings. 5. A thermoplastic vulcanization product according to claim 4, further characterized in that the Lea phenol resin has about 60 to 80 dibenzyl ether bridges per 100 aromatic rings. 6. A thermoplastic vulcanization product according to claim 1, further characterized in that the crystalline polyolefin is polyethylene or polypropylene. 7. A thermoplastic vulcanization product according to claim 6, further characterized in that the amount of phenolic resin is from 0.5 to 14 parts by weight, based on 100 parts by weight of rubber. unsaturated; and the phenol resin has about 60 to 90 ether bridges d bencilLCO per 100 aromatic rings 8.- A tepnoplastic vulcanization pduct according to claim 7, further characterized by the fact that the phenolic ream has a from 60 to 80 liters ter dibenc l co by 100 aromatic rings of said phenol resin healer ca. 9. A thermoplastic vulcanization product according to claim 8, further characterized in that the unsaturated rubber comprises a polymer having from 90 to 99.6 weight percent of refining units from the polymerization of at least two nanorodiums. alpha-rnonoolefins of the formula CH 2 = CHR or CH 2 = C (C 1 - R 3) R wherein R is H or an alkyl of 1 to 12 carbon atoms and from 0.4 to 10% by weight of units repeat entities from the copolunerization of at least one unconjugated polynunsaturated monomer having 5 to 20 carbon atoms; wherein the percentages by weight are based on the weight of the polymer; and wherein in the polymer having from 90 to 99.6 wt.% repotent units from the polymerization of at least two rnonoolefins, rubber is present in about 25 to 85 parts by weight, approximately. 10. A thermoplastic vulcanization product according to claim 8, further characterized in that the unsaturated rubber comprises a polymer having from about 90 to 99.5% by weight of isobutylene repeating units and from 0.5 to 10% by weight, imatically, of repeating units of a polyunsaturated monomer having from 4 to 12 carbon atoms; said polymer being optionally halogenated and the polymer having 90 to 99.5 weight percent repeating units of isobutylene, which are present in about 25 to 85 parts by weight. 11. A thermoplastic vulcanization product according to claim 1, further characterized in that the natural rubber comprises natural rubber or at least one synthetic rubber having at least 50% by weight of its repeating units from one or most common conjugated diene having 4 to 8 carbon atoms; or combinations of natural rubber and said at least one synthetic rubber. 12. A product of thermoplastic vulcanization according to claim 11, further characterized in that the phenolic resin has about 60 to 80 dibenzyl ether bridges per 100 aromatic rings. 1

3. A thermoplastic vulcanization product according to claim 8, further characterized in that the majority of the repeating units of the phenolic resin has an octyl substituent. 1

4. A process for dynamically vulcanizing a rubber of a mixture of thermoplastic elastomers.; said mixture of thermoplastic elastomers including a crystalline polyolefin, an unsaturated rubber and a phenolic resin heater; characterized in said method because it comprises the steps of: a) mixing said unsaturated rubber with the crystalline polyolefin in molten form, forming a mixture; and b) interlacing the unsaturated rubber with the phenolic resin healer during said mixing; wherein the phenolic resin healer, before curing, comprises about 50 to 99 dibenzyl ether bridges per 100 aromatic rings of the phenolic resin healer. 1

5. A method according to claim 14, further characterized in that it additionally comprises adding an activator for the phenolic resin healer. 1

6. A process according to claim 15, further characterized in that the unsaturated rubber is present in a 25 to 85 parts by weight, approximately, per 100 parts in total, by weight, of the thermoplastic polyolefin and an unsaturated rubber; wherein the unsaturated rubber comprises about 90 to 99.6% by weight of repeating units derived from the polymerization of at least two alpha-nonoolefin monomers of the formula CH2 = CHR, where R is H or an alkyl of 1 to 12 carbon atoms and from 0.4 to 1.0% by weight of repeating units from the copolymerization of at least one polyunsaturated monomer having from 5 to 20 carbon atoms. 1

7. A process according to claim 16, further characterized in that the phenolic resin has about 60 to 85 dibenzyl ether bridges per 100 aromatic rings. 1

8. A process according to claim 15, further characterized in that the unsaturated rubber comprises about 90 to 99.5 percent by weight of repeating units from isobutylene and from 0.5 to 10% by weight of repeating units from a non-zero polyunsaturated having 12 carbon atoms; and said polymer is optionally halogenated. 1

9. A process according to claim 18, further characterized in that the phenolic resin has about 60 to 85 dibenzyl ether bridges per 100 aromatic rings. 20. A process according to claim 14, further characterized in that the unsaturated rubber comprises natural rubber or at least a synthetic rubber having at least 50% by weight of its repeating units, one or more conjugated dénénicos rennen q They have from 4 to 8 carbon atoms, or combinations of natural rubber and said at the end a synthetic rubber. 21. A process according to claim 20, further characterized in that the phenolic resin heater has about 60 to 80 dibenzyl ether bridges per 100 aromatic rings of the phenolic resin heater. 22. A thermoplastic vulcanization product, characterized in that it comprises: a) about 15 to 75 parts by weight of a polyolefin to crystalline resin; and b) about 25 to 85 parts by weight of an unsaturated rubber; wherein said parts by weight are based on 100 parts by weight of the total crystalline polymer and the more saturated rubber; wherein the vulcanization product comprises entanglements in the mineralized rubber by curing the cure with 0.5 to 20 parts per hundred parts of resin, of a phenolic resin healer having an equivalent weight of methyl] of about 0.5 to 0.8 times the average molecular weight of the phenolic repeating unit of the phenolic resin healer; wherein the equivalent weight of rnetilol is calculated after equalizing each dibenzyl ether bridge as if they were two methylol groups; and the parts per hundred parts of ream refer to 100 parts by weight of rubber ns tu ado. 23. A vulcanization product according to claim 22, further characterized in that the phenolic resin has an equivalent weight of rnetilol of approximately 125 to 185. 24.- A vulcanization product according to claim 22, further characterized because the phenolic resin has an equivalent weight of methylol from 145 to 200, approximately, and has a majority of repeating units with an octyl substituent in them. 25. A vulcanization product according to claim 22, further characterized in that the equivalent weight of methylol is from 175 to 245, approximately, and a majority of the repeating units in the phenolic resin healer has a dodecyl substituent thereon. . 26. A vulcanization product according to claim 22, further characterized in that the equivalent weight of rnetilol is about 120 to 150, and a majority of the repeating units of the phenolic resin healer has a butyl substituent thereon. .