Патент USA US2407183код для вставки
2,407,133 Patented Sept. 3, 1946 UNITED STATES PATENT OFFICE RUBBER COMPOSITION Frank J. Soday, Swarthmore, Pa., assignor to The i United Gas Improvement Company, a corpora tion of Pennsylvania No Drawing. Application October 17, 1942, _ Serial No. 462,411 17 Claims. 1 (Cl. 260-36) 2 . This invention relates to‘ new compositions of ylethyl alcoholareunusually Well adapted for use matter comprising natural and/or synthetic rub as softening agents for natural and/or synthetic ' ber and one or more esters of alkyl phenylethyl alcohol. rubber. Particularly desirable results are ob tained when such esters are incorporated in syn More particularly, this invention pertains to thetic rubber compositions. rubber compositions comprising a mixture of one or‘more natural and/ or synthetic rubbers or elas tomers, and one or‘ more esters of alkyl phenyl ethyl alcohols, either alone or in combination ‘ The excellent results obtained when esters of the type described herein‘ are used as plasticizing and/0r softening agents for natural and/ or syn thetic rubber are largely due to the pronounced solubility characteristics of such esters, and their excellent compatibility with natural and/or syn with other softening and/ or plasticizing agents. An object of the invention is to provide’ natural and/or synthetic rubber compositions suitable for thetic rubbers and elastomers. This enables each use as tire or tube stocks; for molding and‘ ex~ mill to operate at maximum.throughput, with a truding purposes, for the fabrication of‘ printers’ very substantial saving in power. rolls, hose, sheets, tubes, gaskets, and other‘ ob The use of such esters in natural and/or syn jects and specialties; for the preparation of ad hesives and cements ; and for coating, impregnat ing, Waterproo?ng, and other specialized uses; thetic rubber compounding results in the produc tion of uniform compounds and ?nished articles remarkably free from bleeding, blooming, lea?ng, comprising one or more natural and/ or synthetic or lamination rubbers and/ or elastomers and one or more esters 20 In addition the low viscosity characteristics of of alkyl phenylethyl alcohols with or without the ‘ esters of the type described greatly assists in the incorporation of other additives selected from a milling and blending operations, and insures list comprising sulfur, accelerators, pigments, res rapid and complete penetration. Uniform stocks ins, antioxidants, ?ller-s, extenders, and/or other possessing ‘good calendering and extruding char plasticizing and/or softening agents, such as 25 acteristics are thus obtained. stearic acid, pine oil and pine tar. Another ob Esters of the type‘described'are quite stable and ject of the invention is the use of esters of alkyl strongly resistant to thermal decomposition, thus phenylethyl alcohol in conjunction with other in~ insuring the production of uniform compounds gredients, such as resins, resinous materials, plas and ?nished articles free from decomposition tic product, and dibutyl phthalate, tricresyl phos 30 products. Such compounds, and the ?nished ar phate, or other high boiling compounds, as sof ticles prepared therefrom, possess very good aging tening and/or plasticizing agents for natural and/or synthetic rubber. Other objects and advantages of the invention will be apparent to characteristics. those familiar withthe art upon an inspection of the'speci?cation‘ and claims. I r ‘ These esters also contain substantially no free carbon or other extraneous materials. This is of considerable importance from the standpoint of the preparation of clean, uniform rubber com pounds and finished articles and from the stand V A considerable number of the softening and/or plasticizing agents employed in rubber com point of smooth, trouble-free mill operation. pounds, and particularly synthetic rubber com By a choice of the proper compounding ingre pounds, at the present time suffer from many 40 dients and reaction conditions, rubber composi— disadvantages, among which is their lack of com tions possessing almost any desired property may patibility with natural and, more particularly, with synthetic‘rubber. This lack of compatibil be obtained readily. Thus, products ranging ity renders it extremely difficult to obtain a uni form mixture or dispersion of the softener in the hard rubbers may be obtained at will. from very soft, mildly cured types to the so-called rubber compound, resulting in the production of non-uniform- objects or products.‘ In addition, the use of'such ‘softening agents ‘frequently re sults in the Iea?ng or‘ lamination of the ‘rubber compound during the mastication or calendering 50 . Esters of the type desired maybe regarded as derivatives of alcohols having the following struc tural formula process. Finally, the incorporation of such in-' compatible softeners in rubber compounds results in the production of ?nished objects which fre— quently exhibit bleeding or blooming during use. I have discovered that the esters of alkyl phen inwhich one of the group consisting of a and b 55 is an hydroxyl. group, the other ‘being. hydrogen, 2,407,183 3 and R is an alkyl group, and n denotes that from one to ?ve alkyl groups may be present in the mole cule. Alcohols of this type are readily esteri?ed with acids to give esters which are unusually CHzCHzOH / CHOH.CHa stable, light in color, and possess exceptionally Ci desirable odors. Acids which maybe reacted with alcohols of the type described include aliphatic monobasic E! acids, such as formic, acetic, propionic, butyric, _ E3 beta para tolylethyl alcohol valeric, caproic, oenanthic, caprylic, pelargonic, alpha para tolylethyl alcohol are particularly desirable plasticizing agents for resinous and plastic materials. The preparation of alpha tolylethyl alcohol is capric, and similar acids having a higher num- 7 her of carbon atoms; unsaturated acids, such as acrylic acid, crotom'c acid, isocrotonic acid, meth acrylic acid, vinylacetic acid, and the like; halo genated fatty acids, such as chloroformic acid, monochloroacetic acid, dichloroacetic acid, alpha chloropropionic acid, and the like; hydroxy. acids, such as glycollic acid, lactic acid, alpha-hydroxy disclosed and claimed in my U. S. Patent 2,293,744, dated Aug. 25, 1942. The preparation of the acetic, propionic, butyr i0, and valeric acid esters of tolylethyl alcohols are disclosed and claimed in my copending appli cations, Serial Nos. 313,342, ?led January 11, butyric acid, and the like; amino acids, such as ' glycine, alanine, valine, leucine, and the like; 20 1940, now Patent 2,316,912, dated April 20, 1943; and in my U. S. Patent 2,293,775, dated August dibasic acids, such as oxalic acid, malonic acid, 25, 1942. methyl malonic acid, succinic acid, maleic acid, Such esters may be prepared by the reaction fumaric acid, and the like; aromatic carboxylic of the desired tolylethyl alcohol, or mixtures of acids, such as benzoic acid, anthranilic acid, sali cylic acid, phthalic acid, and the like; and aryl 25 tolylethyl alcohols, or derivatives of tolylethyl alcohols containing an atom or group capable of substituted aliphatic acids, such as phenylacetic being replaced with an ester group correspond ing to the desired acid or mixture of acids, with acid, hydrocinnamic acid, phenyl propionic acid, cinnamic acid, and the like. ~ » - the desired acid or anhydride, or salts or deriva tives thereof. Such esters may be regarded as having the fol lowing structural formula CH-CH: / \ \ a The preparation of such esters may be illus trated by the preparation of the valeric acid esters of tolylethyl alcohols. . b Valeric acid occurs in four isomeric forms, as Rn follows. ' CHa.CH2.CH2.CHz.COOH n-valeric acid in which one of the group consisting of a and b is'an —OOC—X group, in which X is hydrogen, alkyl, alkenyl, substituted alkyl, substituted al kenyl, aryl, substituted aryl, alkyl-aryl, substi tuted alkyl-aryl, aryl-alkyl, substituted aryl alkyl, the /oH,-<lJH, CHa\ CH.CHz.COOH 40 CH3 isovaleric acid CH:.GH2.CH.COOH Ha ' active valeric acid. group, or the I ~ , is CHa.O-COOH ' (‘m-on, H3 ' 7 (I. The conversion of tolylethyl derivatives to tol ylethyl esters of valeric acids may be carried out in any suitable manner, and with any suitable esteri?cation group, the other of said group consisting of a and b being hydrogen, R. is an alkyl group, and n denotes that from one to ?ve alkyl groups may be present in the molecule. ' Esters of tolylethyl alcohols, CH2.CH:OH / pivalic acid CHOH.CHa , —CH; —CH: apparatus. , Y 1 Any suitable esteri?cation reagent, such as a valeric acid, its anhydride, its salt or mixtures thereof, may be employed as desired. For example, valeric acid or acid halides there of may be employed for the conversion of tolyl ethyl alcohols or metallic derivatives thereof to valerates, and salts of valeric acid may be used 'for the conversion of tolylethyl halides to val 65 crates. , Illustrative of the salts of valeric acid which beta ortho tolylethyl alcohol‘ / CHZCHzQH CH: beta meta tolylethyl alcohol alpha ortho tolylethyl alcohol. / CHOEGH: may be employed as esteri?cation reagents may be mentioned sodium valerate, potassium val erate, calcium valerate, iron valerate, lead val 70 erate and other salts. These salts may be the normal valerates, or the isomeric valerates, or ——CH3 alpha meta vtolylethyl alcohol any desired mixture thereof. The esteri?cation reaction may be carried out in the presence of a solvent, such as for exam ple, benzene, if desired. ' 2,407,188 5 6 Any suitable reaction temperature may be: ‘em ployed, suchas: for‘ example,.the boiling pointed tion. containing the desired proportion: of. the iso meric: Also: a‘ forms mixture of:oftolylethyl ‘valeric; acids esters. ororvalerie .anhydrides", or 7 , The esteri?cation reaction. may be carried out derivatives. thereot, may be employed in?ore at atmospheric, subatmospheric, or superatmos U! going processes. pheric pressures, as desired. When mixtures: oi isomeric forms. of. tolylethyl Suitable esteri?cation catalysts, such as, for esters: of Valerie acid are. obtained, they may it example, sulfuric acid, phosphoric acid or anhy desired. be separated into fractions‘: containing the drous hydrogen chloride, may be ‘advantageously individual‘ isomers by anysuitable. method, such the solution. employed in certain of the reactions. particularly 10. in the conversion of tolylethyl alcohols to esters of valeric acids. The use of a system whereby any water formed by the esteri?cation reaction can be continu as for‘ instance. by fractionation. lowing examples'are given? be found advantageous: from the standpoint of tolylethyl chloride: time , > ‘ One suitable method for effecting the esteri? ‘ 108 gram (0.7 mole)v portion 0! alpha, para the yield of ester secured, as; well as from the. necessary to complete the. reaction. 8 Example: 1 ously removed‘ from the system will, in‘general, 15v standpoint. of. the considerablereduction ‘ illustrative of the methods for preparing various‘ tolylethyl esters. of Valerie. acids, the 1.01. onorom 20 cation processes of the present invention com prises re?uxing the derivatives wih esteri?cation reagents. tor a. period or several hours. > For example... salts of. yaleric. acids. may be re~. ?uxed, with tolylethyl halides to produce. the cor was added with stirring to a mixture of 127 grams (0.91 mole) of freshly prepared potassium n valerate in 100 grams of n-valeric acid, the addi tion being carried out in a 1-liter ?ask ?tted with responding tolylethyl esters. This: reaction. may. if. desired... be e?ected in the presence oi; the cor responding valeric acid. ;/ ~ The tolylethyl esters thus produced may be suitably separated from the. halogen salts in the reaction mixture, for example,‘ by ?ltration. a re?ux condenser. The mixture was heated to 140° C. by means of an oil-bath and maintained If a valeric acid has been employed in the esteri?-cation reaction, it may be removed such as by distillation under reduced’ pressure. Any un removed acid may then be: neutralized such as 35 with an. alkaline solution. > v The tolylethyl esters obtained'by the processes at this: temperature with good stirring‘ for a. pe riod of ?ve hours. It was allowed to cool‘. and. then. treated with 10% sodium bicarbonate solu tion to neutralize the unchanged Valerie. acid present. The neutral mixture was then extracted with ether and dried over anhydrous sodium sulphate. herein described may be isolated and puri?ed in ‘ After the ether had been. removed. by heating. For example,_ the reaction mixture may,‘ if‘ de 40 on a hot- water bath. the ester was distilled in. vacuo, giving 110' grams of alpha,‘ para-tolylethyl sired, be repeatedly extracted‘ with any suitable n-valerate. ‘l _ i solvent, ‘suchas ether or benzeneyto increase the This compound had the following structural yield and purity of." the tolylethyl esters, therein. formula and physical properties: The extracts maythen be‘combined and. dried over a drying agent such‘as, for example, anhy any desired‘ manner. ' ‘ drous sodium sulfate, after which‘ the, extraction solvent employed.’ may be removed by ,‘ distilla tion at atmospheric pressure. The residue may 1 /C5.QIHT . oo oicormacni then befractionally distilled invacuo to obtain a. puri?ed tolylethyl‘ ester of valericacid. Mixtures of alpha and beta tolylethyl; deriva tives, in any proportion, may be employed in the preparation of mixtures of. alpha and beta tolyl-. 50 ‘H: . Boiling range=126-127.° at 6 mm. Hg absolute Density (d 20/4) =0.9697 ' ethyl esters of Valerie‘ acids." Such mixtures of the alpha and beta forms of 55. Refractive index (n 20/d) =1.48805 para tolylethy1 esters or valeric. acids may be de The yield was 71.4% of theoretical. sired in orderto obtain a product‘ possessing a The compound was a. colorless, somewhat vis desired boiling range, or desired volatility char cous liquid with a very pleasant odor. acteristics, or other desired properties. Example II For example, a mixture containing the desired 60a proportion of each of the isomeric forms of tolylé A.'solution' ofpotassium n-valerate in‘ n-valeric ethyl halides may be reacted with a salt of valeric acid was" made by stirring 210 grams (1.5“ mols) acid to obtain a tolylethyl ester fraction contain of the fused salt into 250 grams of the anhydrous ing the desired proportion of the isomeric forms. acid heated to 100°‘ C. When a clear‘ syrupy of tolylethyl esters of the acid. Mixtures con 65. solution was obtained, 199 grams (1 mol) of taining the desired proportion of alpha. and beta beta, para-tolylethyl bromide: tolylethyl halides suitable, for use in my process may be obtained, for example, by adding‘ a hy drogen halide to methyl styrene under theprop er conditions. to give the desired. mixture of iso~~ meric tolylethyl- halides. . Similarly, a. mixture of the isomeric forms of other tolylethyliderivatives, such as for example the tolylethyl alcohols, in the desired proportions, may ‘bees‘teri?ed to obtain a tolylethyl ester trac CH; was added slowly through the ‘re?ux condenser 2,407,183 8 7 and the temperature was raised gradually to 170°. Distillation under reduced pressure gave 166 This temperature was maintained for a period grams of alpha, para-tolylethyl isovalerate: of 13.hours, during-which time a ?neprecipitate of potassium bromide separatedfrom the reac tion mixture. . CH.CH; CH: ‘ ' ' OOC.CH:.C - CH2 The mixture was cooled and ?ltered bysuction to remove the potassium bromide and excess potassium valerate, and the clear filtrate was distilled under reduced pressure to remove the " Ha ' major portion of the valeric acid which came over 10 _' This compoundv had the following physical at a temperature of 50-60“. at 4 mm. pressure ab properties: solute. The potassium bromide and excess po Boiling range=127~132° at ‘7 mm. Hg absolute tassium valerate were dissolved in cold water and Density (d 20/4) =Q.9642 extracted twice with ether to recover the small amount of absorbed ester. This extract was 15 Refractiveindex ('n 20/d) =1.48532 combined with thecrude ester and treated with 10% sodium bicarbonate solution to, neutralize the residual acid. The yield was ‘75.5% based on the weight of alpha, para-tolylethyl chloride used. It was then extracted with ether, dried with anhydrous sodium sulphate, and distilled. 20 Distillation under reduced pressure gave 172 grams of beta, para-tolylethyl n-valerate: This product was a colorless, somewhat viscous liquid with an agreeable ester odor. Example IV A 210 gram portion (1.5 mols) of potassium isovalerate was added with stirring to 250 grams of isovaleric acid and heated to 100° C. until all 25 the salt was dissolved. To this clear, syrupy solu tion was'added dropwise, with continued stirring, 200 grams (1 mol) of beta, para-tolylethyl bro mide: - - CH: / 30 CH .011 B I I ' ‘This compound had the following physical properties; ' . 7 ~ , Boiling-.range-—§113-116v° at 4 mm. Hg absolute Density (0! 20/4)=0.9720 , v ' 35 in 50 minutes after which the temperature was raised to 165°. The temperature was kept at This represented a yield conversion of 78.2%, based; on the amount of beta, para-tolylethyl 163-167“, producing mild re?uxing of the acid, for aperiod of 14 hours. The reaction mixture bromide used in the esteri?cation. ' The ester was obtained as a colorless, somewhat viscous liquid with an agreeable odor. ‘ Hz ' Refractive index (n 20/d)-__—1.48855 ' Example 111 A solution of potassium isovalerate in isovaleric acid was made by stirring 210 grams (1.5 mols) of freshly fused potassium isovalerate into 300 grams of the anhydrous acid at a temperature of was then cooled and ?ltered to‘ remove the po tassium ‘bromide and excess. potassium 'iso valerate, and this solid matter was‘ dissolved in water and extracted with ether to recover any . absorbed ester. The clear ?ltrate was distilled to remove‘ most'of the isovaleric acid which came over at 491-51°at 3 mm.‘Hg absolute. The crude ester,combinedwith the ether extract, ‘was treat ed with 110 %, sodium bicarbonate solution to neu When a clear syrupy solution was ob tralize the residual acid. It was then extracted tained, 155 grams (1 mol) of alpha para-tolyl with ether, dried with anhydrous sodium sulphate ethyl chloride: and distilled. 90° C. / ' ' ‘Distillation under reduced pressure gave 156 CHCLCH: grams of beta, para-tolylethyl isovalerate: , I ) CHa ‘ omcinoodomoé ' ’ ' OH: 111' 60 was added slowly through the re?ux condenser, H: and the temperature was raised gradually to 140° C. The temperature was .kept at 140-145’ 'for " This compound had the following physical five hours with vigorous stirring, during which‘ properties: ‘ time a ?ne precipitate of potassium chloride sep 65 Boiling range=99—104.5° at 1 mm. Hg absolute arated out as a by-product of the reaction. The Density (d20/4).=0.9645 _ . . ' , mixture was cooled and ?ltered by suction to re Refractive index (11.20/01) =1.48527 move the potassium chloride and excess potas sium isovalerate, and the clear ?ltrate was dis This weight of product represented a yield of tilled under reduced pressure to remove most of 70 ‘73.4%, based on the weight of beta, para-tolyl the isovaleric acid. The higher boiling liquid containing the ester was treated in the cold with 10% sodium bicarbonate solution to neutralize the residual acid. It was then extracted with ether, dried and distilled. ethyl bromide used in the esteri?cation. ‘ ‘The ester was ‘obtained as a colorless, some whatv viscous liquid with a very sweet odor. ' It .‘will be understood, of course, that tolylethyl 75 esters of Valerie acids may be prepared from ,9‘ 2,407,183 10 pure methyl‘ styrene or ‘hydrocarbon fractions such as light oil fractions containing methyl styrene by processes which may be conducted and phenyl-beta-naphthylamine (Neozone D); reinforcing pigments, such as, for example, car bon blacks, such as channel black, clay, and blanc ?xe; ?llers and/or diluents, such as, for exam on a continual, continuous, semi-continuous, or batch basis. For example, such a, process may ple, lithopone, barytes, whiting, and asbestine; other softeners and plasticizing agents such as, for example, para?in wax, factice, dibutyl phthal ate, tricresyl phosphate, pine oil, oils, fatty acids, comprise ?rst converting the methyl styrene into a tolylethyl derivative containing a substituent capable of being replaced with an ester group corresponding to the desired valeric acid, and thereafter effecting esteri?cation ‘of said deriva tive. and synthetic or natural resins or resinous ma terials. A preferred embodiment of the invention is the use of esters of the type described in conjunction with resins, such as thosederived by the poly merization of light oil vand/‘0r coal tar fractions For example, a tolylethyl halide or a mixture of tolylethyl halides may be, prepared from a light oil methyl styrene fraction obtained by the vcontaining coumarone and/orindeneor theresins derived by the polymerization of the high-boil distillation of light oil from oil gas and contain ing meta, para and. ortho methyl styrenes and these tolylethyl halides may then be .esteri?ed ing monomeric materialderived from tar by ?ash distillation and/or solvent extraction processes, and/or other organic liquids, such as the high acid. ' Likewise, a mixture of tolylethyl alcohols may 201 boiling aromatic oils derived by the flash distilla tion and/or solvent extraction of tar, as soften be prepared from such a methyl styrene frac ing agents ‘for natural and/or synthetic rubber. tion, after which the tolylethyl alcohols may be A preferred embodiment of this invention is the converted into tolylethyl esters of valeric acid by to form the desired tolylethyl esters of valeric use of an‘aromatic oil of the type described in ' The use of fatty acid ormixed ‘fatty acid'es 25 combination with one or more resinous materials esteri?cation. and an ester of the type described as a softener ters of a mixture ‘of m-, ‘p- and o-tolylethyl also for natural and/ or ‘synthetic rubber compositions. hols as a plasticizing agent or agents for natural, and more particularly synthetic, rubber is a pre ferred embodiment of this invention. Examples of the rubber or rubber-like mate rials with which esters of the type described herein may be compounded are the various grades and types of natural rubber and rubber-like ma A preferred resin for incorporating with the ester and aromatic oil is the resin obtained by the polymerization, by thermal, and/or catalytic methods, of certain high-boiling monomeric ma terial separated in monomeric form from tar formed during the production of combustible gas by processes involving the pyrolytic decomposi terials, and synthetic rubbers or elastomers, such as, for example, those ‘obtained by ‘the polymeri tion of petroleum oil with or without the aidof catalysts. Such resins may be formed in situ in zation of one or ‘moreqd-iole?n'es, >or substituents thereof,--such ias butadiene, isoprene, piperylene, Z-chlorobuta-dienmand the-like, either :alone or aromatic oils of the type described herein. terials such as ole?nes, unsaturated nitriles, acids, fractions containing indene and/or coumarone. Other desirable ingredients which may be blended with an ester'of the type described either Another desired resin ‘which may be incor porated in the ester as a softener for natural in admixture, or in‘lcombination with one or'm‘ore and/or synthetic rubber‘ isnthe resin derived by unsaturated‘and/or‘reactive compounds ‘0r ‘ma: 40 the polymerization of petroleum and/or coal tar estersgethers, ‘ketones, aldehydes, and/or substit uents thereof, such ‘as, :for example,‘ styrene, acrylic nitrile, isobutylene, acrylic ‘esters, and?the like; Important examples of [synthetic rubbers 41) alone or in combination with one or more resinous or ‘elastomers :are those ‘obtained by the cop'oly materials and/or aromatic oils, as a softener for merization of onevsor more diole?nes with (1’) dimers of petroleum or coal tar fractions con natural ‘and/or synthetic rubber include the acrylic nitrile, ‘(29 styrene lorsubstituents thereof, taining indene and/or coumarone, dibutyl phthalate, tricresyl phosphate, and pine oil. and/ or ‘(3) isobutylene or similar “ole?nes'; These materials are known in the art under different ‘Reclaimed rubber is also included among the materials which may be. plasticized with the esters trade names, such as, for example, Buna, .Buna S; Buna .N, Perbunan; Chlorop'rene, Neoprene, herein described, together with natural and/or Ameripol, Hycar, Buty’ltrubber, and _the like. synthetic rubber, and with or without other in The‘ ouantitywof esters of “the type described herein which :may be incorporated in natural or synthetic rubbers, or elastom'er-s, may be ‘varied over very wide limits, depending upon the ‘prop? gredients. The ester or esters, and other ingredientamay ‘ be mixed or compounded with the natural rubber and/or synthetic rubber onmixing or compound ing rolls or mills, ‘or they may be compounded by erties wdesired. . Thus, for example, quantities varying from a few percent, or less, to an amount any other method known in the art. The rubber equal to, or greater ‘than, the quantity ofvrub 6%) composition then may be vulcanized, if desired, her, "or rubber mixture, employed in the‘ l'com by any of the methods employed for this pur position, m'aybeused.‘ Q , , posein the art. In addition to‘esters of the type described ‘here Examples of rubber compositions containing in, other ingredients which may be incorporated esters of the type described herein are as follows: in natural rubber and/or synthetic ‘rubber com Example 5 positions “include rvulcanizin-g agents 'and/ or ac celera‘tors, such as, for example, sulfur or sulfur Component containing compounds such‘ as tetramethyl thiuram disul?de ‘mje'rcaptoa‘rylenethiazoles, such as mercaptobenzothiazole, benzothiazyl disul?de, litharge, and dithio carbamates; pigments, such 1322211?’ 70 as, for example, magnesium erode, zinc oxide, and lead oxide; antioxidants, such as, tor-exam ple phenyl-alpha-naphthylamine (Neozone ,A), 75, Natural rubber _______________________________________ ._ 109 Butyric acid esters of a mixture of 0-, m-, and p-tolyl ethyl alcohol Zinc. __.,__ , Sulfur ____ ,. Iercaptobenzothiazole ...... _. - 10 - 5 2.5 0- 3 2,407,183, 12 Example 6 Component Example 12 ragga}?! Pale crepe rubber ____________________________________ __ Zinc oxide ........ __ Parts by 3 Component weight 100 Butadiene-isobutylene rubber ________________________ . _ 45 Sulfur _______________________________ _ _ Butyric acid ester of tolylethyl alcohol _______________ ._ 2. 5 Resin obtained from monomeric material boiling above Resin obtained from monomeric materia 210° C. and isolated from petroleum tar. Butyric acid esters of a mixture of 0', In 210° C. and isolated from petroleum tar ____________ .. Carbon black __________________________ _. Sulfur . 10 Stearic acid _______ __ _ _ _ _ . _ _ . _ _ . . __ lvlercaptobenzothiazole. . _ I . ._- _ to » Phenyl-alpha-naphthylamine.__ Zinc oxide Example 7 ov-lyernm to meal Eaiample 13 A natural rubber tire tread mix may be com pounded as follows: Parts by' Weight Component Parts by Component weight Perbunan ____________________________________________ _ . Zinc oxide __________ _ _ Smoked sheet rubber ________________________________ _, Channel black ________ __ H was 20 Sul Zinc oxide: __________________________________________ _. Valerie acid esters of a mixture of 0-, m-, and p-tolyl ethyl alcohols ______________________________________ _. Resin obtained from monomeric material boiling above 210° C. and isolated from petroleum tar Sulfur ____________________ __ _ cNgoriwn Stearic aci_d__.::::::::::: .... .. Valerie acid ester of tolylethyl alco _ Stearic acid 25 Mercaptobenzothiazole ______________________________ -_ Example 8 A synthetic rubber tire tread mix may be com pounded as follows: Component Neoprene ____________________________________________ .1 Parts by weight 100 Zinc oxide ____________ 1 Mercaptobenzothiazole. The foregoing compositions may be sheeted out, shaped and vulcanized, if desired, such as by the application of a temperature of, say, 140° C. in a press for a period of,v say; 45 minutes. Other procedures may, of course, be used if de 30 sired. Rubber-ester compositions of the type de scribed, either as such or with the incorporation of other ingredients such as the resin and/or aromatic oil derived from monomeric material 35 boiling above 210° C. and isolated from petroleum tar, may be used for a variety of purposes, such as for the manufacture of tires; tubes, and other Channel black ________________ __ Valerie acid ester of tolylethyl al Phenyl-alpha-naphthylamine_ objects, and as adhesives, coating, impregnating, and waterproo?ng agents. Such compositions Sulfur _________________________ . . 40 may or may not be vulcanized prior to, ‘during, Example 9 or subsequent to the use thereof. ' ' I While various procedures and formulas have Component been particularly described these are of course subject to considerable variation. Therefore, it will be understood that the foregoing speci?c ex amples are given by way of illustration, and that Buna S ______ __ Plantation crep Zinc oxide. _ _ Channel blac _ changes, Age Rite resin Pine tar _____ _. Valerie acid ester of phenylethyl alcohol Stearie acid_ Sulf 50 omissions, additions, substitutions and/or modi?cations might be made within the scope of the claims without departing from the spirit of the invention. ’ ' I claim: 1. A new composition of matter comprising an Example 10 Component ester of alkyl phenyl ethyl alcohol in which said Parts by weight alkyl substituent appears on the ring, and rub 55 ber selected from the group consisting of natural rubber and rubber-like polymers of butadiene, isoprene, piperylene, and 2-chlorobutadiene. Butadiene-styrene rubber ____________________________ __ Butyric acid ester of tolylethyl alcohol ______________ 1. ' 2. A new composition of matter vcomprising a vulcanized mixture of an ester of alkyl phenyl 60 ethyl alcohol in which said alkyl substituent ap pears on the ring and rubber selected from the group consisting of natural rubber and rubber Resin obtained from monomeric material boiling above 210° C. and isolated from petroleum tan...‘ ........ ., Carbon black __________________________ _. Sulfur _ _ _ _ _ _ _ _ _ v _ _ _ _ _ . __ ltfercaptobenzothiazole. _ _ . . Zinc oxide ________________ __ Phenyl-alpha-naphthylamine ________________________ . _ like polymers of butadiene, isoprene, piperylene, Example 11 and 2-chlorobutadiene. 65 Component Butadiene-acrylic nitrile rubber ______________________ .. Valerie acid ester of tolylethyl alcohol ________________ ._ Resin obtained from monomeric material boiling above 210° C. and isolated from petroleum tar Carbon black Parts by ' 3. A new composition of matter comprising an ester of tolyl ethyl alcohol, and rubber selected from the group consisting of natural rubber and _ weight rubber-like polymers of butadiene, isoprene, piperylene, and 2-chlorobutadiene. 70 4. A new composition of matter comprising a“ vulcanized mixture of an ester of tolyl ethyl alco-1 hol, and rubber selected from the group consist ing of natural rubber and rubber-like polymers of butadiene,‘ isoprene, piperylene, and z-chloro-j Zine oxide __________ _ _ Phenyl-alpha-naphthylamin 75 butadiene, 13 2,407,183 14 5. A new composition of matter comprising at least one fatty acid ester of tolyl ethyl alcohol, and rubber selected from the group consisting of natural rubber and rubber-like polymers of buta diene, isoprene, piperylene, and >2-chlorobuta4 diene. 6. A new compostion of matter comprising a ‘ vulcanized mixture of at least one fatty acid ester of tolyl ethyl alcohol, and rubber selected from 12. A new composition of matter comprising a vulcanizate of a mixture containing butadiene acrylic nitrile copolymer rubber and an ester of alkyl ‘phenyl ethyl alcohol in which said alkyl the group consisting of natural rubber and rub 10 substituent appears on the ring. ber-like polymers of butadiene, isoprene, piper ylene,and 2-chlorobutadiene. i 11. A new composition of matter comprising the vulcanizate of a mixture which comprises butadiene-isobutylene copolymer rubber and an ester of alkyl phenyl ethyl alcohol in which said alkyl substituent appears on the ring. 13. A new composition of matter comprising a - 7. A new composition of matter comprising [a vulcanized mixture of a propionic acid ester of tolyl ethyl alcohol, and rubber selected from the ' group consisting of natural rubber and rubber; like polymers of butadiene, isoprene, piperylene, > and 2-chlorobutadiene. 8. A new composition of matter comprising a vulcanized mixture of a butyric acid ester of tolyl ethyl alcohol, and rubber selected from the group consisting of natural rubber and rubber-like vulcanized mixture of butadiene-styrene copoly-' mer rubber, and a fatty acid ester of tolyl ethyl alcohol. 14. A new composition of matter comprising vulcanized material selected from the group con‘ sisting of natural rubber and rubber-like poly mers of butadiene, isoprene, piperylene, and 2 chlorobutadiene, said vulcanized material being plasticized with a fatty acid ester of tolyl ethyl alcohol. 15. A new composition of matter comprising a polymers of butadiene, isoprene, piperylene, and 2-chlorobutadiene. vulcanized mixture of butadiene-styrene copoly mer rubber, and propionic acid ester of tolyl ethyl 9. A new composition of matter comprising a 25 alcohol. vulcanized mixture of a valeric acid ester of tolyl 16. A new composition of matter comprising a ethyl alcohol, and rubber selected from the group consisting of natural rubber and rubber-like polymers of butadiene, isoprene, piperylene, and 2-chlorobutadiene. 10. A new composition of matter comprising vulcanized mixture of butadiene-isobutylene co polymer rubber, and butyric acid ester of tolyl‘ ethyl alcohol. 30 copolymer rubber, and valeric acid ester of tolyl ethyl alcohol; alkyl phenyl ethyl alcohol in which said alkyl sub stituent appears on the ring. 17. A new composition of matter comprising a ‘ vulcanized mixture of butadiene-acrylic nitrile the vulcanizate of a mixture comprising buta diene-styrene copolymer rubber and an ester of 35 FRANK J. SODAY.