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United 'States Patented Dec. 31, 1940 2,226,984 UNITED ‘STATES PATENT DFFICE 2,226,984 ACCELERATOR OF VULCANIZATION Arthur W. Sloan, Akron, Ohio, assignor to The B. F.‘Goodrich Company, New York, N. Y., a corporation of New York ‘ No Drawing. vApplication January 7, 1938, , Serial No. 183,837 2 Claims.‘ (01. 260-455) I, This invention relates to a process of vulcan place, the method is good for the preparation ization of rubber, synthetic rubber, rubber-like of the mono or di-sul?de in high yield. materials, etc., and to materials used as accelera Many of the products of the condensation re tors of the vulcanizing process. action described above are quite stable. Such for example are obtained by reacting the sodium; The object of the‘ invention is to bring about 5 the vulcanization at a rapid rate even at moder salt of mercaptobenzothiazole in aqueous solu ate temperatures, at the same time not increase tion with phenyl imino carbon dichloride, or the the tendency of the unvulcanized mass to pre sodium salt of Z-mercaptoquinoline with phenyl vulcanize, and to give vulcanizates which‘ age imino carbon dichloride, or the sodium salt of his (aryl tetrahydro beta-naphthyl) dithiocar- »' well. The materials herein described can also 10 be used in the vulcanization of rubber and the bamic acid with phenyl imino carbon dichloride. like with large proportions of sulfur to produce These products are extremely useful as accel hard rubber or ebonite. erators of vulcanization. » I have found that compounds of the formula The condensation reaction outlined above ap R-NICXa where R is an aliphatic radical or pears to‘ be quite general in that substituted 152 an aromatic radical, and X is one of the hal imino‘carbon dihalides (especially chlorides and ogens, will undergo a condensation reaction with bromides) in which the, substituent may be not mercapto compounds in general, or their salts, only phenyl, but tolyl, xenyl, naphthyl, anisyl, such as ammonium, quaternary ammonium, so benzyl, or even an aliphatic group, such as ethyl, propyl or the like will condense with mercapto 2 20 dium, zinc, etc., salts, in aqueous suspension or solution, to form products of the desired type. acids (or their simple salts) including thiol Probably the reactions are of the type shown carboxylic acids such as dithiofuroic or dithio by the equation:, benzoic acids, thiol carbonic acids such as butyl xanthogenic acid, thiol carbamic acids such as substituted dithiocarbamic acids (preferably 25 those in which both free valencies of the nitro gen are occupied by organic radicals such as where A is an organic group and M is hydrogen alkyl or aryl radicals), and mercapto hetero or a salt--forming group. The dithiocarbamic cyclic bases such as Z-mercapto quinoline, 2 acids, and their salts, the mercaptothiazoles and mercapto thiazole, mercapto thiodiazole, mer 30 their salts, and the mercapto quinolines and cap-to thiazine and ‘the like; and the resulting their salts, are examples of the materials which react with the halogen compounds to give prod condensation products greatly accelerate the vulcanization of rubber. It will be understood ucts which are accelerators. These products that suitable substituents, preferably hydrocar can be considered as being the mixed anhydrides bon substituents or those not differing greatly 35 03 Ch of substituted imino dithiocarbonic acids with in e?ect from hydro-carbon substituents, may be mercap-to acids. present in any case. Thus, in place of mercapto Some of the products are not su?iciently stable thiazole, any of the following may be employed: to be practically useful as accelerators or" vul mercapto methyl-thiazole, mercapto dimethyl canization, since during the reaction, or during thiazole, mercapto ethyl thiazole, mercapto 4° puri?cation or storage they tend to decompose, phenyl-thiazole, mercapto benzothiazole, mer losing, sometimes a carbylamine, and some capto methyl-benzol thiazole, mercapto methoxy times an iso thiocyanate. In these cases, the benzothiazole, _ mercapto naphthothiazole and products remaining are‘ disul?des or monosul the like. ?des. The decomposition reactions are probably The preparation of phenylimino' carbon di- 45‘ 45 of the types illustrated by the equations: chloride by reacting phenyl isothiocyanate with chlorine in the presence of chloroform has been described by Nef, in Liebigs Ann. 270, 284 (1892) and by Sell and Zierold, in Ber. '7, 1228 (1874); also by Not, in Liebig’s Ann. 270, 282, by the ‘0 reaction of phenyl isocyanide with chlorine; and by A. W. Hofmann, in Ber. 12, 1127 (1879), by C=N——R _-__> A-—S-A+R—N=C=S the reaction of phenyl mustard. oil with phos ,A-s phorus pentachloride. 55 Where these decomposition reactions do take I have found that'phenyl mustard oil can be 55 2 2,226,984 made to react with chlorine very easily, merely When a rubber composition (A) containing by passing the chlorine gas through the liquid rubber 100 parts, zinc oxide 10 parts, sulfur 3.5 mustard oil maintaining the temperature at parts, blanc ?xe 40 parts, stearic acid 1 part, and 48°-50° C. Besides the phenylimino carbon di his (benzothiazyl mercapto) phenylimino-dithio chloride, there are formed sulfur monochloride carbonic anhydride 0.5 part was heated under and sulfur dichloride, the ratio of these depend pressure in a mold for 120 min. at 260° F., the ing upon the amount of chlorine used. They vulcanized composition had ,a tensile strength are lower, boiling than the phenylimino carbon 3l60#/sq. in. and an ultimate elongation of 750%. dichloride, and can be removed by distillation. When in a similar mixture (B), the above ac 10 The product itself can be distilled, but in general celerato-r was replaced by 0.2 part of di bis (tetra can be used in the crude state after removal of hydro beta naphthyl) dithiocarbamic phenyl~ the sulfur chlorides. ‘ ‘ imino-dithiocarbonic anhydride, and the compo Phenylimino carbon dichloride is a,high boil sition vulcanized for 30 min. at 260° F., the vul ing heavy liquid, almost colorless when pure. It ' canized product had a tensile strength of has a corrosive action on the skin, and is a bad 3365#/sq. in. and an ultimate elongation of 770%. lachrymator, so that it must be handled care; In a similar mixture (C), the above accelera fully. It reacts slowly with water, but in ‘the tor was replaced by 0.5 part of bis (4.5 dimethyl dry state it can be safely stored in glasscon- 'thiazyl 2-mercapto) phenylimino-dithiocarbonic tainers. Similar compounds can be made from 'anhydride. When this composition was Vulcan other mustard oils. ‘ ' ized for 1 hr. at 287° F., the vulcanized product 20 As an example of its reaction with the sodium had a tensile strength of 3375#/sq. in., and an salt of mercaptobenzothiazole the following ex ultimate elongation of 790%. periment may be cited. 33.4 g. of mercaptoben None of the above‘compositions showed any zothiazole were dissolved in a solution of 8.0 g. tendency to vulcanize in30‘min. at 220° F. of sodium hydroxide in 8 cc. of water and 110 cc. When to mixture C, 0.05 part of a polybutyral 25 of denatured alcohol. To this solution, at dehyde-aniline accelerator was added, the com 20-25° C., there was added with stirring, and position vulcanized in 30min. at 260°'F. to give a during 15-20 min., 17.4 g. of phenylimino car tensile of 4020#/sq. in., and an ultimate elonga 'bon dichloride. The product separated at once tion of 815%. 53.9 as a yellow, ?nely divided solid. It was ?ltered When stock A was aged for 96 hours in an 30 o?, washed with water, and dried. The weight oxygen bomb at 70° C. and 300# pressure, the was 36.6 g. representing a‘yield of 84%. M. P. aged sample still had a tensile strength of 140°_144° C. ~ 2325#/sq. in., and an ultimate elongation of 670%. As a further example, the reaction of phenyl The examples given are merely illustrative of imino carbon dichloride with the sodium salt of bis(aryl tetrahydro beta-naphthyl) dithiocar the large number of materials which belong to bamic acid may be cited. 18.2 g. of sodium bis the class described, and of their usefulness as accelerators, and are not intended to place a (aryl tetrahydrobeta-naphthyl) dithiocarbamate limit upon the claims of this invention. were dissolved in 200 cc. of denatured alcohol. 111.0 To this solution, at 30°-35° 0., there were added The use of the term “rubber”, is meant to in with stirring, during 1 hour, 4.8 g. of phenyl imino clude caoutchouc, balata, gutta-percha, synthetic carbondichloride. The product separated at rubber, or natural or arti?cially prepared latex. It is to be understood that the accelerators once, as an orange colored, ?nely divided solid. may be used in admixture with other accelerators, It was ?ltered oif, washed with water, and dried. with antioxidants, softeners, pigments, ?llers, The weight was 11.3 g., representing a yield of .45 58%. M. P. 78°-81° C. Other dithiocarbamates etc., and that. the rubber may be vulcanized with and particularly diaryl dithiocarbamates may be these accelerators in other ways than that par substituted for the reagent employed in this ex ticularly set forth above; speci?cally, it may be ample. vulcanized in hot air, steam, hot water, etc. As a further example, the reaction of phenyl In the following‘ claims the term acid and the names of speci?c types of acid will be employed in imino carbon dichloride with the sodium salt of 2-mercapto 4.5-dimethyl thiazole may be cited.
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