Патент USA US2404771код для вставки
Patented July 30, 1946 2,404,771 ‘UNITED STATES “PATENT OFFICE 2,404,771 MONOTHIAZYL METHOD FOR DITHIOCARBONATES PREPARING SAME Edward S. Blake, Nitro, W. Va., assignor to Mon santo Chemical Company, St. Louis, Mo., a cor poration of Delaware No Drawing. Original application February 26, 1941, Serial No. 380,677. Divided and thisap- ‘ plication June 23, 1943, Serial No. 491,921 18 Claims. (01. 260-306) 1 2 The present invention relates to new vulcaniza tion accelerators, to a process of vulcanizing rub small amount of aluminum chloride. The solu tions were mixed cold as for example at 0° C. and gradually allowed to come to room tempera-_ ture. After HCl had ceased to be evolved the product was distilled from the solvent under a ber and to the vulcanized rubber products‘ob tained with the aid of said new accelerators. The accelerators of this inVention are the monothiazyl dithiocarbonates. This class of ma» mild vacuum and puri?ed by distillation. Low' boiling solvents have been used with equally good results in which case the solvent is removed ?rst, preferably by distillation, and the residue puri?ed‘ terials is represented by the structural formula 'as-c-s-ra t v where R2 may be one of a wide variety of suitable substituting groups in which carbon is linked to the sulfur as hereinafter disclosed and R1 is a 10 as described. The pure thio ethyl chlor carbon ate boiled at 129-132“ C'. This product was re acted with the sodium salt of mercaptobenzothh azole in aqueous solution and also with the po tassium salt of mercaptobenzothiaz‘ole in ethyl thiazyl radical. Typical examples of the latter comprise benzothiazyl, methyl thiazyl, methyl 15 alcohol.’ It will be appreciated that other sol vents may be used in either step and other me benzothiazyl, nitro benzothiazyl, chlor benze thiazyl, amino benzothiazyl, 4 phenyl benzo tallic salts or. even the free mercaptothiazoles thiazyl, may be used where desired. naphthothiazyl, dihydrothiazyl ‘ (thi ‘ Other mercaptans and thio ‘phenols which may the aforementioned radicals are illustrative of 20 be used‘ for preparing the new accelerators in azolyl) and 6 phenyl benzothiazyl radicals. While clude methyl mercaptan, propyl mercaptan, bu tyl mercaptan, amyl mercaptan, thio phenol, some of the thiazyl radicals which may be em» ployed, the invention is by no means limited thereto. , benzyl mercaptan, lauryl mercaptan, nitrophenyl ‘ mercaptan, thio cresol, 'xylyl mercaptan, pinene While the new compounds may be employed alone as vulcanization accelerators they are used 25 mercaptan and cyclohexyl mercaptan. Thus, R2 in the above formula may be an alkyl, aralkyl, with greater advantage in conjunction with basic aryl or alicyclic radical including terpene radi nitrogen containing accelerators as activators cals. ' thereof and are preferably so employed. As suit As speci?c embodiments of the invention illus-, able basic nitrogen containing accelerators there trating the use of the new accelerators and the‘ may be mentioned diphenyl guanidine, 'di-o-tolyl guanidine, thiocarbam'lide, hexamethylene tetra; mine, para phenylene diamine, anhydro formal desirable results attainable thereby, but without limiting the invention, rubber stocks were com pounded comprising dehyde aniline, diphenyl guanidine phthalate, tri phenyl guanidine and butylaldehyde aniline. ' Again the foregoing list is by no means complete 35 Stock being illustrative of activators which may be used with the new accelerators but it is in nowise limi tative of the invention. The new accelerators may be prepared by methods well‘ known to chemists. For example > they may be manufactured by reacting a mer-> captothiazole, usually in the form of a metallic salt such as a Zn, K or Na salt, and a thio ester of chloro carbonic acid. ‘Somewhat better yields Stearic acid __________ ____ . Bcnzothiazyl, benzyl d1 thiocarb onate ______ _ __l . Benzothiazyl, propyl d1 are obtained by carrying out the reaction in an 45 thio carbonate______ _ ___ _ Benzothiazyl, ethyl d1~ organic solvent such as alcohol although aqueous Benzothiazyl. butyl di solution may be used where desired, in which thiocarbonate ________ _ . case a water soluble salt of the thiazole should be used. A thio ester of chloro carbonic acid thiocarbonata. Thus, one at the temperature of twenty pounds steam pres half molecular proportion of ethyl mercaptan was dissolved in dry decalin and this solution added sure-per square inch. The modulus anditensile properties of the cured rubber products are set to a solution of one molecular proportion of phosgeue dissolved in dry decalin containing a __ The stocks so compounded were vulcanized in a press by heating for different periods of time may in turn be prepared by reacting phosgene with a mercaptan or thio phenol. _ 55 forth below. i e 2,404,771 , Stock 1 y m 1of s.elastic‘; m. a Modulus T ensi_1 e tigllgin elongations of— at break 9531112" minutes 7 4 present invention is not limited to the specific examples hereinbefore set forth wherein the pre Table I ' ‘ lbs?liniz 500% percent 700% 45 45 175 135 550 355 1, 930 1, 575 45 160 ' 400 1,740 930 950 940 45 90 90 90 90 130 300 240 290 235 275 980 v 775 1, 030 665 1, 740 2, 290 2, 4,35, 2, 225 2, 450 l, 035 845 885 830 915 ferred accelerators are employed. Other ratios of the compounding ingredients than those men 5 tioned in the examples as Well as other Well known ?llers, pigments and the like may be employed in ' the production of various types of rubber com pounds and are apparent to those skilled in the art to which this invention pertains. The inven 10 tion is limited solely by the claims attached here to as part of the present speci?cation. This application is a division of co-pending application Serial No. 380,677, ?led February 26, V 1941, Patent 2,336,217, As noted, the new accelerators are used with 15 nitrogen containing accelerators as- activators thereof. As exemplary of such use but again without limiting the invention, rubber stocks were compounded comprising G H carbonate nucleus and a radical selected from 20 the group consisting of alkyl, aralkyl, aryl, ali cyclic and terpene radicals is directly' linked to .7 Parts by Paris by Parts by Parts by Parts by ~ Pale crepe rubber Zinc oxide weight 100 5 weight 100 5 weight 100 5 weight 100 5 weight 100 5 3 3 3 3 5 Sulfur. _ Stearic ac , F ‘ the second sulfur atom of the same dithiocar‘L bonate nucleus. 2. The chemical product comprising a com’ 25 pound possessing the structure Stock E ' What is claimed is: .1. The chemical product comprising a mono thiazyl dithiocarbonate in which the said thiazyl radical is linked to one sulfur atom of the dithio particular advantage in conjunction with basic , , Diphenyl guanidlne . _o. s . 0. 15 10. 5 0.15 Benzothiazyl, ben'zyl di- - thiocarbonatmrr____ _»_ 0. 6 0. 5 ,0, 5 0,5 0. l5 0. 15 0.15 36» containing carbon and hydrogen only. 3. The chemical product ‘comprisinga com= " _-_..-_.;-_ Benzothiazyl, propyl di ....... .; ________ _. , _ thiocarbon'ate ______ _-_ _______ __ Benzothiazyl, plienyl di- R,-s-<li-s-R¢ where-R1 is a thiazyl radical and R2 is a radical pound possessing the structure . 0.6 _______ . _~_ ____ __ ' »______ _. ‘ thiocarbonate _______________________ _. 0.6 Benzothiazyl, ethyl di- ______________ __ > ,thlocarbonate ________________ _ _; ____ _. >._.-_____ 0.6 where R1 is an aryl thiazyl radical and R2 is a ______ ,. Benzothiazyl, butyl di- ‘ thiccarbonate; ___________ __-.-._ .-_-____________________ __ radical containing carbon and hydrogen only. 0.6 4. The chemical product comprising a com pound possessing the structure ~ The stocks so compounded were Vulcanized in the same manner as stocks A-D the vulcanizing ares-gasses? temperature being as before, the temperature of twenty pounds of steam pressure per square inch. The modulus and tensile propertiesof the cured rubber products are set forth below‘: where R1 is a benzothiazyl radical and R2 is a radical containing carbon and hydrogen only. 415 ‘ Table Ii Mozduluslgf lelaszticé T ensn e iyln sin. a , S-tbck tgrerg ‘minutes elo'ngations oi'— » at break ' ' " ‘ 500% ' 5. The chemical product comprising a com pound possessing the structure ' ‘ lbsl‘lnm? ‘ (U) . R1'—'S-—‘—G‘—'S'—_R2 ‘_ 61212;’ ‘percent 700% '50‘Where R1 is a benzothiazyl radical and R2 is an aliphatic hydrocarbon radical containing less than5_carbon atoms.- 45 450 1, 74b 3, 350 820 45 45 45 45 90 415 330 410 335 630 1, 700 l, 230 1, 860 l, 160 2, 450 3, 450 2, 870 3, 100 3, 275 3, 850 820 830 780 870 785 90 525 90 420 1, 670 3, 290 810 90 640 2, 650 2, 255 ‘ 3, 950 3, 550 V 750 90 410 1, 460 3, 435 840 , ' ‘ 6. The chemical product corn-prising a com pound possessing the structure . 800 60 - '7. The chemical product comprising "com pound possessing the structure The data set forth in Tables I and II show the desirable physical properties of vulcanizates cured in the presence of the new accelerators alone and in conjunction with basic nitrogen containing ac celerators as activators thereof. Moreover, al though the mixture of accelerators is effective and fast, it is not so fast in action as to produce SJI‘he: chemical product comprising .3, 105m; prevulcanization or scorching of the stock during the milling, calendering or other handling opera tions. , Again resort may be had to other methods of preparing the new accelerators Where convenient or desirable. Pound possessing the structure’ 70 . N / ' '- _ 1 o This invention is not concerned ' with the preparation of the compounds and is not in any Way limited thereto. Furthermore, the ‘r 9. ‘The-method of making a monothiaz'yl-di . 2,404,771 5 thiocarbonate which comprises reacting a mer captothiazole with an ester of chlor mono thio carbonic acid the ester forming group being linked to the sulfur atom. 10. The method of making a monothiazyl di thiocarbonate which comprises reacting a mer captothiazole with a product of the structure 6 where R2 is an aliphatic hydrocarbon radical con— taining less than 5 carbon atoms. 14. The method of making benzothiazyl ethyl dithiocarbonate which comprises reacting mer captobenzothiazole with ethyl mono thio chlor carbonate the ethyl radical being linked to the sulfur atom. 15. The method of making benzothiazy‘l benzyl dithiocarbonate which comprises reacting mer 10 captobenzothiazole with benzyl mono thio chlor where R2 is a hydrocarbon radical. 11'. The method of making a monothiazyl di thiocarbonate which comprises reacting a mer capto aryl thiazole with a product of the struc ture carbonate the benzyl radical being linked to the sulfur atom. 16. The method of making benzothiazyl phenyl dithiocarbonate which comprises reacting mer captobenzothiazole with phenyl mono thio chlor carbonate the phenyl radical being linked to the sulfur atom. where R2 is a hydrocarbon radical. 12. The method of making a monothiazyl di thiocarbonate which comprises reacting mer captobenzothiazole with a product of the struc ture gene with an aliphatic mercaptan under sub stantially anhydrous conditions to remove one of the chlorine atoms as HCl and condensing the product with a. mercapto thiazole in the form of its alkali metal salt. 25 where R2 is a hydrocarbon radical. 13. The method ‘of making a monothiazyl di thiocarbonate which comprises reacting mer captobenzothiazole wtih a product of the struc ture ' 17. The method of making‘a monothiazyl di thiocarbonate which comprises reacting phos - 18. The method of making a monothiazyl di thiocarbonate which comprises reacting phos gene with a thio phenol under substantially an hydrous conditions to remove one of the chlo rine atoms as HCl and condensing the product 30 with a mercapto thiazole in the form. of its al kali metal salt. EDWARD S. BLAKE.