Inhibiting premature vulcanization of rubber

Abstract

Claims

United States Patent 3,513,139 INHIBITING PREMATURE VULCANIZATION 0F RUBBER Aubert Y. Coran, Creve Coeur, Mo., and Chester D. Trivette, Jr., and Joseph E. Kerwood, St. Albans, W. Va., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Jan. 6, 1966, Ser. No. 518,987 Int. Cl. C086 1/00, 11/54; C08f 27/06 U.S. Cl.'260-79.5 51 Claims ABSTRACT OF THE DISCLOSURE Premature vulcanization of a vulcanizable rubber is inhibited by incorporating therein besides vulcanizing agent and accelerator an amount effective to inhibit premature vulcanization of a compound of the formula wherein x is cycloalkyl, lower alkyl, alkaryl, aryl, aralkyl, or hydrogen and x is cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl, or x and x together with the nitrogen atom are H H NCH2CH2NS-R, N\ N-SR morpholine, or lower alkyl substituted morpholine; and wherein R is aryl, aralkyl, cycloalkyl, alkyl of 1 to carbon atoms, or alkaryl. This invention relates to an improved vulcanizing process for rubber and to the rubber stocks obtained by using this improved process. The invention relates to improved accelerator-inhibitor combinations for rubber. More particularly,'the invention relates to a method for preventing the aging and premature vulcanization of rubber stocks and to the rubber compositions obtained by using this method. In the manufacture of vulcanized rubber products, crude rubber is combined with various other ingredients such as fillers, accelerators, and antidegradants to alter and improve processing of rubber and to improve the properties of the final product. The crude rubber is put through several steps in the factory before it is ready for the final step of vulcanization. Generally, the rubber is mixed with carbon black and other ingredients except the vulcanizing agent and accelerator. Then the vulcanizing and accelerating agents are added to this masterbatch in a Banbury mixer or on a mill. Scorching, viz., premature vulcanization, can occur at this stage of the processing, during extrusion or other shaping operations, during the storage period before vulcanizing, and during the actual vulcanization. After the vulcanizing and accelerating agents are added, the mixture of crude rubber is ready for calendering or extruding and vulcanization. If premature vulcanization occurs during the storage of the crude mixture or during processing prior to vulcanization, the processing operations cannot be carried out because the scorched rubber is rough and lumpy, consequently useless. Premature vulcanization is a major problem in the rubber industry and must be prevented in order to allow the rubber mix to be preformed and shaped before it is cured or vulcanized. ,There are several reasons offered for premature vulcanization. The discovery of the thiazolesulfenamide accelerators constituted a major breakthrough in the vulcanization art because thiazole sulfenamides delayed onset of the vulcanizing process, but they have not been entirely satisfactory. Mercaptobenzothiazole is a valuable Patented May 19, 1970 organic vulcanization accelerator but by present standards would be considered scorchy. It has been largely replaced by the delayed-action accelerators, but further improvement has eluded the art. The development of high pH furnace blacks which lack the inherent inhibiting effect of the acidic channel blacks and the popularity of certain phenylenediamine antidegradants which promote scorching have placed increasingly stringent demands on the accelerator system. Vulcanization retarders have long been available to rubber compounders. They include N-nitrosodiphenylamine, rosin and salicyclic acid. See Editors, Rubber World Compounding Ingredients for Rubber, 91-94 (3rd edition, 1961). Acids are generally ineffective with thiazolesulfenamide accelerators or adversely affect this vulcanizing process. Nitrosoamines are only of limited effectiveness with thiazole sulfenamides derived from primary amines. An object of this invention is to provide a method to effectively prevent the premature vulcanization of rubber. A further object of this invention is to provide a method to increase the available processing time prior to the actual vulcanization of rubber. A further object of this invention is to provide an increased cure rate for rubber. A further object of this invention is to provide a method to prevent the premature vulcanization of gum rubber in storage containing a vulcanization and accelerating agent. A further object of this invention is to improve the storage stability of an uncured rubber mixture containing an accelerator. A further object of this invention is to pro vide a method to prevent the premature vulcanization of rubber during the actual vulcanization step. A further object of this invention is to prevent the premature vulcanization of rubber at any time. A further object of this invention is to provide a safer method for processing and vulcanizing rubber. A further object of this invention is to provide new and improved vulcanized rubber products. Other objects of the invention will become apparent as the description proceeds. These objects are accomplished by using the accelerator-inhibitor combinations of this invention. We have discovered a class of sulfenamides which are outstanding inhibitors of premature vulcanization. The characteristic nucleus is wherein at and x are identical or dissimilar cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl radicals, or one may be hydrogen. When x and x are taken together with the nitrogen atom, they are morpholine, or mono-, di-, tri-, or tetra(lower alkyl) morpholine. R is a straight or branched chain alkyl of 1 to 20 carbon atoms but preferably 3 to 8 carbon atoms, alkaryl, aryl, aralkyl, or cycloalkyl. The term cycloalkyl includes cycloalkyl radicals of 5 to 8 carbon atoms. The term lower alkyl includes alkyls of 1 to 8 carbon atoms of straight or branched chains. Aryl sulfenamides derived from secondary amines have been described as vulcanization-accelerating agents. See US. Pat. Re. 19,286, Zaucker assigned to I. G. Farbenindustrie (1934). It has also been reported that certain aryl sulfenamides characterized by the presence of an elec tronegative group in the aryl nucleus which ordinarily alone have no substantial accelerating power will, nevertheless, retard the action of nitrogen-containing vulcanization accelerators and will increase their strength. See US. Pat. Nos. 2,382,813 (1944) and 2,460,393 (1945) to Paul assigned to United States Rubber Co. More recently, Lober reported that pentachlorophenyl sulfenamides were vulcanization accelerators of the delayedaction type. See U.S. Pat. 3,047,546, Lober assigned to Fanbenfabriken Bayer (1962). The aryl sulfenamides employed in the practice of the present invention contain no electronegative group, yet remarkably increase processing safety of vulvanizable stocks. The stocks are fully accelerated in the absence of the inhibitor and may contain an amine to protect the rubber from degradation. The amine usually reduces processing safety, but the new vulcanizing systems are effective to prevent premature vulcanization in the presence thereof. The data infra illustrate that a combination of an accelerator and an inhibitor of this invention is an improved rubber additive which allows significantly longer and safer processing time for rubber than that provided hitherto for the rubber industry. Further, the accelerator-inhibitor combinations of this invention may improve the modulus of a vulcanizate considerably. The storage stability of a rubber mixture containing an accelerator-inhibitor-combination of this invention is improved compared to a rubber mixture containing an accelerator alone. Inhibitors of this invention also enhance the antidegradant properties of a vulcanizate. Examples of the premature-vulcanization inhibitors of this invention are N- (phenylthio morpholine, N-(phenylthio) -2,6-dimethyl morpholine, N- (phenylthio) dicyclohexylamine, N- (phenylthio) aniline, N-(phenylthio) diisopropylamine, N- (phenylthio) diethylamine, N-(phenylthio)tert-butylamine, and N,N'-di(phenylthio ethylenediamine. The invention includes inhibitors, for example, N-(phenylthio) -N-phenyl loweralkyl amine, N-(phenylthio)cyclohexylamine, N-(phenylthio)loweralkyl amine, N-phenylthioN-tert-butyl ethylamine, N-phenylthio-N-cyclohexyl methylamine, N-phenylthio-N-phenyl ethylamine, N-phenylthio-N-phenyl cyclohexylamine, N-tolylthio-N-cyclohexyl methylamine, N-(n-butylthio)morpholine, N-(benzylthio)morpholine, 1,4bis(n-butylthio)piperazine, N-(dodecylthio)morpholine, 1,4-bis(benzylthio)piperazine, N-(tert-butylthio)morpholine, N- (n-butylthio) -N-ethyl-n-butylamine, N- (n-butylthio) -N-methylaniline, N-(n-octylthio)morpholine, 1,4-bis (decylthio piperazine, N-(n-tetradecylthio)morpholine, 1,4-bis (n-hexadecyl)piperazine, N-(n-octadecylthio)morpholine, N-(sec-tridecylthio)morpholine, N- (sec octylthio) morpholine, N-(sec-octylthio)morpholine, and 1,4-bis (tert-pentadecylthio) piperazine. The results obtained depend peculiarly on selection of the sulfenamide inhibitor. Preferably is morpholino or 2,6-dimethyl morpholino. When x is H, it is preferred that x be alkyl of 3 to 6 carbon atoms or phenyl. When neither x nor x is H and each is independent, it is preferred that both x and x are alkyl of 3 to 6 carbon atoms or that x is phenyl and x is lower alkyl. Also, when x is phenyl, cyclohexyl is comparable to alkyl of 3 to 6 carbon atoms. R of thegeneral formula is preferably phenyl, tolyl, benzyl, or primary or secondary alkyl of 3 to 12 carbon atoms. Rubber stocks containing delayed-action accelerators can be used in the process of this invention. Cheaper, more scorchy accelerators can also be used with an excellent degree of improvement. The improved vulcanizing method of this invention can be used'advantageously to process stocks containing furnace blacks as well as stocks containing other types of blacks and fillers used in rubber compounding. The invention is also applicable to gum stocks. Our invention is applicable to rubber mixes containing sulfur-vulcanizing agents, organic accelerators, and antidegradants. For the purposes of this invention, sulfur-vulcanizing agent means elemental sulfur or sulfurcontaining vulcanizing agent, for example, an amine disulfide, or a polymeric polysulfide. The invention is applicable to vulcanization accelerators of various classes. For example, rubber mixes containing the aromatic thiazole accelerators which include N-cyclohexyl benzothiazole 2 sulfenamide, 2-mercapto-benz0thiazole, N- tert-butyl-benzothiazole-Z-sulfenamide, 2 benzothiazolyl diethyldithiocarbamate, and 2 (morpholinothio)benzothiazole can be used. Thiazole accelerators other than aromatic can be used. Stocks containing accelerators, for exampe tetlramethylthiuram disulfide, tetramethylthiuram monosulfide, aldehyde amine condensation products, and guanidine derivatives, are substantially improved using the method of our invention. Stocks containing mixtures of accelerators are substantially improved by using the method of our invention. Rubber mixes containing antidegradants, for example N-1,3-dimethylbutyl N phenyl-p-phenylenediamine, N,N'-bis 1,4 dimethylpentyl) p phenylenediamine, N,N' bis (2-octyl)-p-phenylenediamine, and other phenylenediamines, ketone, ether, and hydroxy antidegradants and mixtures thereof, are substantially improved using the process of our invention. The inhibitors of our invention can be used in natural and synthetic rubbers. Synthetic rubbers that can be improved by the process of this invention include cis-4- polybutadiene, Butyl rubber, ethylene-propylene terpolymers, polymers of 1,3-butadiene, for example 1,3- butadiene itself and of isoprene and copolymers of 1,3- butadiene with other monomers, for example styrene, acrylonitrile, isobutylene, and methyl methacrylate. The invention relates to diene rubbers, and the terms rubber and diene rubber are synonymous for the purposes of this invention. The following tables illustrate the invention in greater detail and the best mode for carrying it out, but are not to be construed as to narrow the scope of our invention. For the rubber stocks tested and described, infra, as illustrative of the invention, Mooney scorch times at 121 C. and C. are determined by means of a Mooney plastometer. The time in minutes (r required for the Mooney reading to rise five points above the'minimum viscosity is recorded. Longer times are indicative of the activity of the inhibitor. Longer times on the Mooney scorch test are desirable because this indicates greater processing safety. Percentage increases in scorch delay are calculated by dividing the Mooney scorch time of the stock containing the premature-vulcanization inhibitor by the Mooney scorch time of the control stock, multiplying by 100, and subtracting 100. These increases show the percentage improvement 'in scorch delay overthe control stock which contains no inhibitor. Additionally, cure ratings are calculated from the time required to cure the stocks at 144 C., and insome cases 153 C'. Curing characteristics are determined by means of the Monsanto Oscillating Disc Rheometer described by Decker, Wise, and Guerry in Rubber World, December 1962, p. 68. From the rheometer data, R.M.T. is the maximum modulus torque in rheometer units, or t is the time in minutes for a rise of three or two rheometer units, respectively, above the minimum reading and 7 is the time required to N-(phenylthio)morpholine. Using an accelerator combination of Thiofide and DPG with N- phenylthio)morobtain a modulus 90% of the maximum. The specific rate TABLE II constant kis measured in reciprocal minutes. See Coran, 5 Stocks 37 Rubber Chemistry and Technology 689 (1964). Higher 1 2 3 4 values of k indicate higher rates of cross linking. With Xt d d t b t d, b the aid of 2 1 can be Calculated and Provides another E a I l 1 1S:elb a(l 1 211 211 211 211 measure of processing safety. Lower values of k indicate Sanmflex 2 2 2 2 N-(phenylth1o)morphol1ne 0. 25 0. 5O 1. 0 less scorch. Santocure NS 1.4 1.4 1.4 1.4 The trademarks of some compounds used in the prac- Mooney scorch at 135 0.: t1ce of th1s invention are Santocure, Santocure MOR, t 17.3 20.7 22.7 23.7 Santoflex 77, Santocure NS, DPG, and Thiofide. Santoggg gg fggg f Scorch delay 16 27 33 cure is the accelerator N-cyclohexyl benzothiazole-Z- RMT 52.4 51,5 50.7 40,4 sulfenamide. Santocure MOR is the accelerator 2-(mor- &8 ig g pholinothio)benzothiazole. Santocex 77 is the antidegradant N,N bis( 1,4 dimethylphenyl) p phenylenedi- 3- 83 Q23 ggi amine. Santocure NS is the accelerator N-tert-butylbenzo- 1 1113135 533.3515 cure 3g 35 35 35 ore 2.1 ness 6 60 58 55 thlazple 2 sulfenerfnde- P 1S 5 accelerator reported to 300% modulus 1,060 1,090 L050 17050 be diphenylguandine. Thiofide 1s an accelerator reported Ultimate tensile strength, p.s 3,300 3,400 3,400 3,400 to be benzothiazyl disulfide Ultimate elongation, percent 620 650 0 660 Table I illustrates the use of N-(phenylthio)morpholine as a premature-vulcanization inhibitor in natural rub- Pholm? and no antldegradant 116% mfirease scorch her containing santofiex 77, Santocure NS, and sulfun delay is noted. These data are illustrated in Table III. The natural rubber A-6 masterbatch is comprised of the 25 following: TABLE III Parts per Stocks hundred rubber 1 2 3 4 Natural rupber smoked Sheets 100 Oil-extended styrene-butadiene rubber H1gh abrasion furnace carbon black 50 35331103011 211 211 211 Zinc oxide 5 ur 1. 2.0 2.0 2.0 Santocure MOR. 1. 2 Stearic acid 3 g girafide 1.0 1.0 0.7 0.7 Hydrocarbon softener r 10 N-(phenylthio)morpholine 1.0 1.0 35, Moogey scorch at135 0.: 26 8 48 0 1O 23 6 .9 TABLE I Percent increase in scorch delay 60 116 Stocks 1 2 3 4 N-(phenylthio)rnorpholine increases the cure rate in A45 masterbach 168 168 168 168 40 natural rubber and synthetic rubber stocks. Further m Santoflex77 2 2 2 2 oil-extended styrenebutad1ene rubber, N-(phenylthio) 5? v 8: g g morpholine gives a marked improvement in the cross-link- M rur 2. 5 2. 5 2. 5 2. 5 mg rate. These properties are highly desirable in the manuooney a facture of rubber 26.6 33.4 35.7 40.9 Percent increase in scorch delay 25 34 54 N-(phenylth1o)morphol1ne is an active antidegradant 5&3 58.0 5&2 5&2 when used alone or with a phenylenediamine antidet2- 3.2 9.6 10.3 11.5 gradant as demonstrated b Table IV. The intermittent ten 107 180 182 133 d h 32h h m m ozone ata s ow a our lncrease over t e contro m 111.. .Ogg .ggg gig; A 2? the 70% retentlon of a rubber stock contalnlng the comg optimum cum (111m) 25 25 25 g bination Santocure MOR and N-(phenylthio)morpholin e & geA1&arldness 8g 2 g? 2 28 2 23 of this mvent1on. The known antldegradant, N-1,3,-d1- m ..1 Ultiinai e ii31i 1s t1-en th, .s.1 3,600 3,700 3,300 3,300 l y '-P y -P-P y Shows 8 f Ultimate elongation, percent 45 480 490 470 hour increase over the control and the accelerator-mhibitor combination with N-1,3-dimethylbutyl-N-phenylp-phenylenediamine shows a 64-hour increase. The meth- Th6 increased cure rate 15 1llustrated 111 Table I the 0d used for measuring the Ozone damage {0 ulcanized figures t -l' rubber is described by Decker and Wise, The Stress Re- 1 Table II illustrates the use of N-(phenylth1o)morphoaxatlon Mihod for Measurmgozon? Cracking Rubper World, April 1962, p. 66. The lntermittent test compnses hne as a premature-vulcamzanon 1nh1b1tor in an o1l-extwo-hour cycles during which rubber specimens are extended styrene-butadiene rubber containing Santoflex 77, . posed dynamlcally 15% of the tlme, and during the re- Santocure NS, and sulfur. The oil-extendlng styiene-butamainin time of the 0 C16 are ex osed Statican at 257 diene B-S masterbatch is comprised of the following: strain g y p y a I Parts per 7 hundred rubber 65 TABLE IV Oil-extending styrene-butadiene rubber containing Stocks 37.5% highly aromatic oil 137.5 1 2 3 4 lntermedlate super abrasion furnace carbon masterbach 168 168 168 168 black 68.5 Sulfur 2.5 2.5 2.5 2.5 Zinc xide 3.0 ge g gg {g phenylp 0.5 0.5 0.5 Stearic acid 2.0 pgie nyle gdiamine u 2.0 2. p eny 1o morp 0 me... 1. Mooney scorch at 121 C. t 44. 9 70.8 44. 0 64. 0 In an oil-extended B-5 masterbatch containing Santo lntermigtent Ozone. Hours to 70% cure MOR and no phenylenediamme antidegradant, a retent on.- 90 60% increase in scorch delayis noted using the inhibitor ynamm 0 66 Comparable results are obtained using the other compounds of this invention in degradation tests. rubber. N- (phenylthio)morpholine is included in Table VI. The rubber mixture of the test is an A-6 masterbatch. TABLE VI Santocure MO R. N-(phenylthio)dieyclohexylamine N-(phenylthio) diisopropylamine N-(phenylthio) N-(phenylthio) -tertbutylam N-(phenylthio)-morpholine N ,N -di(phenylthio)-ethylenediamine Mooney scorch at 121 0.: Percent increase in scorch delay Bheometer at 144 0.: TABLE V Stocks 168 168 168 168 2. 5 2. 5 2. 5 2. 5 0. 5 0. 5 Santocure 0. 5 0. 5 N-(phenylthio)morpholin 1. 1. 0 Mooney scorch at 121 0.: t nitial) 39. 3 73. 3 31. 4 70. 4 t (Aged 2 days-70 C.) 26. 2 70.4 8. 3 48. 8 Percent retention of scorch y 67. 0 96. 0 26. 0 69. 0 Rheolneter at 144 0. k (min- Initial 148 206 148 175 Aged 2 days at 70 0 123 .206 112 182 Change in effectiveness after 2 days, percent 1 17 0 l 24 I 4 B-5 masterbatch 211 211 211 211 211 211 Sulfur 2. 0 Santocure 1. 0 Santocure NS 1. 0 Santocure 1.0 N-(phenylthio)morphol1ne 1. 0 Mooney Scorch at 135 0.: t (Initial) 35.7 48.2 25.5 45.8 23.5 41.1 t (Aged 4 days at 70 C.) 22. 5 43. 4 13. 7 40. 3 11.7 35.0 Percent retention of scorch delay 63.0 90. 0 53. 0 88. 0 50. 0 85.0 Rheometer at 153 0. k (min- Ini a1 115 214 112 .236 105 .205 Aged 4 days-70 G 104 214 090 214 080 206 Loss in efiectiveness after 4 days, percent 10 0 10 24 0 1 Loss. 2 Improvements. Comparable results are obtained using the other compounds of this invention as stabilizers of rubber mixtures containing accelerated sulfur-curing systems. Table VI illustrates the use of some inhibitors of this invention with the accelerator Santocure MOR in natural One part N-(pheny1thio)aniline shows a 72% increase in scorch delay according to the Mooney scorch data from a natural rubber A-6 masterbatch also containing 3 parts Santofiex 77, 0.5 part Santocure MOR, and 2.5' parts sulfur. One part N-phenylthio-N-phenyl ethylamine shows a 108% increase in scorch delay, and one part N-phenylthio-N-phenyl cyclohexylamine shows a 77% increase in an A-6 masterbatch containing 2.5 parts sulfur and 0.50 part Santocure MOR. Table VII illustrates the use of 1,4bis(phenylthio) piperazine as a premature'vulcanization inhibitor in a natural rubber masterbatch containing the following: Parts per hundred rubber Natural rubber smoked sheets Intermediate super-abrasion furnace carbon black 60 ZlIlC oxide 5.0 Stearic acid 2.5 Hydrocarbon softener 20 TABLE VII Stocks Masterbatch 187. 5 187. 5 187. a 187. 5 Sulfur 2.5 2.5 2.5 2.5 Santocure 0. 5 0. 5 0. 5 0.5 N-1,3-d1methylbutyl-N-phenyl-p phenyllenediamine 3. 0 3. 0 l,4-bls(phenylthio) piporazine 0. 5 0. 5 Mooney scorch at 121 0.: 50.1 72.0 37.0 53. 7 Percent increase in scorch delay 44 43 Rheometer at 144 0.: RMT e1 50 Tables VIII and IX further illustrate the outstanding premature-vulcanization inhibitor properties of the compounds of this invention. N -(n-butylthio) morpholine- N- (benzylthio)morphollne 1,4-bis(n-butylthio) piperazine 1. 0 Mooney Scorch at 0.: t 12. 9 24. 1 26. 6 23. 8 Percent increase in scorch delay 87 106 85 Rheometer at 144 0.: RMT 67. 0 64. 0 19. 0 17. 7 32. 0 32. 8 173 145 0 l5. 1 TABLE IX Stocks A-6 masterbatch 168 168 168 5 Sulfur 2. 5 2. 5 2. 5 N-1,3dimethylbutyl-N-phenyl-pphenylenediamine 2. 2. 0 2. 0 Santoeure MO R 0. 0. 0. 5 N-(n-dodecylthio)morpholine l. 0 1,4-bis (b enzylthio) piperazine. 1. 0 Mooney scorch at 1 0.: t5 69. 5 10 Percent increase in scorch delay- 57 Rhaorneter at 144 0.: RM'I 64. 1 18.7 .134 Results comparable to those shown in the tables supra are obtained when the remaining compounds of this invention are tested as premature-vulcanization inhibitors. Table X illustrates the improvement of the inhibitors of this invention over the compounds of the Lober U.S. Pat. 'No. 3,047,546, supra. N-(phenylthio)morpholine shows a 45% increase in scorch delay by rheometer t over the control while Lobers N-(pentachlorophenylthio)morpholine shows a mere 4% increase under the same conditions. Thus, N-(phenylthio)morpholine shows more than a tenfold percentage improvement as premature-vulcanization inhibitor over the Lober compounds. The results in Table X are obtained in an A-6 natural rubber masterbatch containing 2.0 parts N-1,3-dimethylbutyl-N-phenylp-phenylenediamine, 0.5 part Santocure MOR, and 2.5 parts sulfur. TABLE X Stocks Masterbatch .L 168 168 168 N-(pentachlorophenylt hi0) morpholina- O. 5 N-(phenylthio) morpholine 0. 5 Mooney scorch at 121 0., t 42. 7 44. 6 57.1 Rheometer at 144 C RMT 55. 6 64. 3 65. 4 a (min.) 10.0 10. 4 14. 5 40 Percent increase in scorch delay. 4 tno (min 27.0 26. 8 29. 5 k: 136 138 173 tu -tn 17. 0 16. 4 15.0 Table X-I illustrates the improvement using the in- 45 hibitors of this invention over N-(p-nitrophenylthio)-tertbutylamine of the Paul US. Pat. 2,460,393, supra. N- (phenylthio)-morpholine is included in the table for comparison purposes. N-(phenylthio)-tert-buty1amine shows a seventeenfold improvement in scorch delay over the compound N-(p-nitrophenylthio) -tert-butylamine. The increase in scorch delay over the control using N-(p-nitrophenylthio)-tert-butylamine is a mere 3% while the increase with N-(phenylthio)-tert-butylamine of this invention is 51%. An electronegative group is actually detrimental in an attempt to increase processing time. The test results in Table XI are obtained in an A-6 natural rubber masterbatch containing 2.0 parts N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine, 0.5 part Santocure MOR, and 2.5 parts sulfur. TABLE XI N- (phenylthlo)-tert-butylamine N-(p-nitrophenylthio)-tert-butylamine N (phenylthio)morpholine Mootr ey scorch at 121 0.: 40. 5 61. 2 41. 7 60. 3 Percent increase in scorch delay 50. 5 3.0 49. 0 300% Modulus, p.s.i 1, 760 1, 970 2, 350 2,160 Ultimate Tensile Strength, p s 3, 400 3, 500 3, 600 3, 600 Ultimate Elongation, percent 500 450 440 470 Rheometer at 144 0.: RM 60.8 70. 0 75. 2 68.0 t 10. 2 16. 0 10.8 16. 3 k .124 1.65 .165 .192 '0 28. 4 31.0 27.0 28. 6 Mixtures of N-(phenylthio)morpholine and mercaptobenzothiazole exert a synergistic eifect on cure rate. With mixtures of 0.25 to 0.50 part of N-(phenylthio)morpholine and 0.75 to 50 parts of mercaptobenzothiazole, the rate of cure with 1.0 part of the mixture was greater than with 1.0 part of either ingredient alone. Accelerator-inhibitor combinations provide valuable composition for controlling the acceleration of vulcanization. Usually the inhibitor will comprise 5% to of the composition by weight, and an organic vulcanizationaccelerating agent will comprise 95% to 5% by weight of the composition. Although thiazosulfenamide accelerators are relatively unstable accelerators as compared to most other thiazole accelerators, they can be admixed with the premature-vulcanization inhibitors of this invention without impairing storage stability. In general, the premature-vulcanization inhibitor will comprise .025% to 5% of the rubber whether added neat or as a component of a mixture. It is intended to cover all changes and modifications of the examples of the invention herein chosen for purposes of disclosure which do not constitute departures from the spirit and scope of the invention. What is claimed is: 1. The method of inhibiting premature vulcanization of a vulcanizable rubber containing a sulfur-vulcanizing agent and an organic vulcanization-accelerating agent selected from the group consisting of thiazole accelerators, thiuram sulfide accelerators, aldehyde-amine accelerators, and guanidine accelerators which comprises: incorporating therein in an amount effective to inhibit premature vulcanization a compound of the formula XI RSN/ wherein x is cycloalkyl, lower alkyl, alkaryl, aryl, aralkyl, or hydrogen and x is cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl or x and x together with the nitrogen atom are H H N-CHzCHzN-SR, N NSR morpholine, or lower alkyl substituted morpholine; and wherein R i aryl, aralkyl, cycloalkyl, alkyl of 1 to 20 carbon atoms, or alkaryl. 2. Rubber vulcanizable compositions obtained by the method of claim 1 wherein the rubber is styrene-butadiene copolymer rubber. 3. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 1. 4. The method of inhibiting premature vulcanization of a vulcanizable rubber containing elemental sulfur, a thiazole sulfenamide vulcanization-accelerating agent selected from the group consisting of N-cyclohexyl-benzothiazole-2-sulfenamide, N-tert-butyl benzothiazol-Z-sulfenamide, N,N diisopro yl-benzothiazole-Z-sulfenamide, N,N diethyl benzothiazole-2-sulfenamide, N,N-dicyclohexyl benzothiazole-Z-sulfenamide, 2-(2,6-dimethylmorpholinothio)benzothiazole, and 2-(morpholinothio)benzothiazole which comprises: incorporating therein in an amount effective to inhibit premature vulcanization a compound of the formula XI RSN wherein x is cycloalkyl, lower alkyl, alkaryl, aryl, aralkyl, or hydrogen and x is cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl; or x and x together with the nitrogen atom are morpholine, or lower alkyl substituted morpholine; and wherein R is aryl, aralkyl, cycloalkyl, alkyl of l to 20 carbon atoms, or alkaryl. 5. Rubber vulcanizable compositions obtained by the method of claim 4 wherein the rubber is styrene-butadiene copolymer rubber. 6. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 4. 7. The method of claim 4 wherein the premature-vulcanization inhibitor is N-(phenylthio)morpholine. 8. Rubber vulcanizable compositions obtained by the method of claim 7 wherein the rubber is styrene-butadiene copolymer rubber. 9. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 7. 10. The method of claim 4 wherein the premature-vulcanization inhibitor is N-(phenylthio)-2,6-dimethylmorpholine. 11. Rubber vulcanizable compositions obtained by the method of claim 10 wherein the rubber is styrene-butadiene copolymer rubber. 12. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 10. 13. The method of claim 4 wherein the premature-vulcanization inhibitor is N-(phenylthio)diisopropylamine. 14. Rubber vulcanizable compositions obtained by the method of claim 13 wherein the rubber is styrene-butadiene copolymer rubber. 15. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 13. 16. The method of claim 4 wherein the premature-vulcanization inhibitor is N-(phenylthio)-tert-butylamine. 17. Rubber vulcanizable compositions obtained by the method of claim 16 wherein the rubber is styrene-butadiene copolymer rubber. 18. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 16. 19. The method of claim 4 wherein the premature-vulcanization inhibitor is N,N'-di(phenylthio)ethylenediamine. 20. Rubber vulcanizable compositions obtained by the method of claim 19 wherein the rubber is styrene-butadiene copolymer rubber. 21. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 19. 22. The method of claim 4 wherein the premature-vulcanization inhibitor is 1,4-bis(phenylthio)piperazine. 23. Rubber vulcanizable compositions obtained by the method of claim 22 wherein the rubber is styrene-butadiene copolymer rubber. 24. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 22. 25. The method of claim 4 wherein the vulcanizationaccelerating agent is 2-(morpholinothio)benzothiazole. 26. The method of claim 4 wherein the vulcanizationaccelerating agent is N-tert-butyl benzothiazole-Z-sulfenamide. 27. The method of inhibiting premature-vulcanization of a vulcanizable rubber containing elemental sulfur, a thiazole sulfenamide vulcanization-accelerating agent selected from the group consisting of N-cyclohexylbenzothiazole-Z-sulfenamide, N-tert-butyl benzothiazole-Z-sulfenamide, N,N diisopropyl-benzothiazole-Z-sulfenamide, N,N diethylbenzothiazole 2 sulfenamide, N,N-dicyclohexylbenzothiazole 2-sulfenamide, 2-(2,6-dimethyl morpholinothio)benzothiazole, and 2-morpholinothio)benzothiazole, and an amine antidegradant which comprises: incorporating therein in an amount eifective to inhibit premature vulcanization a compound of the formula XI R-sN wherein x is cycloalkyl, lower alkyl, alkaryl, aryl, aralkyl, or hydrogen and x is cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl; or x and 2: together with the nitrogen atom are 11 H -NCH2OH2N-SR, N NSR morpholine, or lower alkyl substituted morpholine; and wherein R is aryl, aralkyl, cycloalkyl, alkyl of 1 to 20 carbon atoms, or alkaryl. 28. Rubber vulcanizable compositions obtained by the method of claim 27 wherein the rubber is styrene-butadiene copolymer rubber. 29. An unvulcanized rubber composition, vulcanizable by heating, obtained by the process of claim 27. 30. The method of claim 27 wherein the antidegradant is N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine. 31. An accelerator-inhibitor combination comprised of an organic vulcanization-accelerating agent selected from the class consisting of thiazole accelerators, dithiocarbamate accelerators, thiuram sulfide accelerators, aldehyde-amine accelerators, diaryl guanidine accelerators, and mixtures thereof and a premature-vulcanization inhibitor in an amount effective to inhibit premature vulcanization in rubber of the formula wherein x is cycloalkyl, lower alkyl, alkaryl, aryl, aralkyl, or hydrogen and x is cycloalkyl, lower alkyl, alkaryl, aryl, or aralkyl; or x and x together with the nitrogen atom are morpholine, or lower alkyl substituted morpholine; and wherein R is aryl, aralkyl, cycloalkyl, alkyl of 1 to 20 carbon atoms, or alkaryl. 32. An accelerator-inhibitor combination according to claim 31 wherein the organic vulcanization-accelerating agent is a thiazole sulfenamide. 33. An accelerator-inhibitor combinatin according to claim 31 wherein the organic vulcanization-accelerating agent is mercaptobenzothiazole. 34. An accelerator-inhibitor combination according to claim 31 wherein the organic vulcanization-accelerating agent is benzothiazyl disulfide. 35. An accelerator-inhibitor combination according to claim 31 wherein the premature-vulcanization inhibitor is N-(phenylthio)morpholine. 36. An accelerator-inhibitor combination according to claim 32 wherein the premature-vulcanization inhibitor is 'N-(phenylthio)morpholine. 37. The method of claim 1 wherein the vulcanizationaccelerating agent is mercaptobenzothiazole. 38. The method of claim 1 wherein the vulcanizationaccelerating agent is benzothiazyl disulfide. 39. The method of claim 1 wherein the vulcanizationaccelerating agent is alkylthio morpholine where the alkyl is primary or secondary alkyl of 4 to 12 carbon atoms. 40. The method of claim 1 wherein the vulcanizationaccelerating agent is a thiazole accelerator and the inhibitor is benzylthio morpholine. 41. The method of claim 1 wherein R is benzyl, cycloalkyl of 5 to 8 carbon atoms, or primary or secondary alkyl of 3 to 12 carbon atoms. 42. The method of claim 1 wherein R is cycloalkyl of 5 to 8 carbon atoms. 43. The method of claim 4 wherein R is benzyl, cycloalkyl of 5 to 8 carbon atoms or primary or secondary alkyl of 3 to 12 carbon atoms. 44. The method of claim 4 wherein R is cycloalkyl of 5 to 8 carbon atoms. 45. The method of claim 27 wherein R is benzyl, cycloalkyl of 5 to 8 carbon atoms or primary or secondary alkyl of 3 to 12 carbon atoms. 46. The method of claim 27 wherein R is cycloalkyl of 5 to 8 carbon atoms. 47. The accelerator-inhibitor combination of claim 31 wherein R is benzyl, cycloalkyl of 5 to 8 carbon atoms or primary or secondary alkyl of 3 to 12 carbon atoms. 48. The accelerator-inhibitor combination of claim 31 wherein R is cycloalkyl of 5 to 8 carbon atoms. 49. The method of claim 1 wherein the rubber contains furnace carbon black. 50. The method of claim 4 wherein the rubber contains furnace carbon black. 51. The method of claim 27 wherein the rubber contains furnace carbon black. References Cited UNITED STATES PATENTS Paul 260-795 Coleman 260-795 Lober et a1. 260-79.5 Ayad. Walker 26079.5

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Cited By (14)

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    US-3681356-AAugust 01, 1972Monsanto Co1,4-bis-(cycloalkylthio)piperazines
    US-3839303-AOctober 01, 1974Monsanto CoInhibiting premature vulcanization with aminothiopyrimidines
    US-3895060-AJuly 15, 1975Goodrich Co B FCycloalkylthio (nitro substituted) aniline compounds
    US-3898202-AAugust 05, 1975Goodyear Tire & RubberEpihalohydrin cure regulators
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    US-3947429-AMarch 30, 1976Sumitomo Chemical Company, LimitedMethod for inhibiting premature vulcanization of diene rubbers
    US-3963683-AJune 15, 1976Universal Oil Products CompanyRubber formulations containing vulcanization inhibiting thioformamidine compounds
    US-3965077-AJune 22, 1976The B. F. Goodrich CompanyCycloalkylthio(electron-withdrawing group substituted)aniline compounds
    US-3984383-AOctober 05, 1976Bridgestone Tire Company LimitedSulfenamides in vulcanizable rubber composition
    US-8388784-B2March 05, 2013The Goodyear Tire & Rubber CompanyMethod for retreading a tire
    WO-03022915-A1March 20, 2003Uniroyal Chemical Company, Inc.Masterbatch comprising rubber compounds, fillers, plasticizers and curatives