Патент USA US2370253код для вставки
Patented Feb. 27, 1945 I 2,370,253 UNITED STATES PATENT‘ OFFICE 2,370,253 ARYLENE THIAZYL ,SULPHENAMIDES William E. Messer, Cheshire, Conn., assignor to United‘ States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Original applications June 24, 1939, _Serial No. 280,929, and May 10, 1940, Serial No. 334,343. Divided and this application Septem ber 18, 1942, Serial No. 458,860 ' , 3 Claims. ( CI. 260-30613) chloride and aniline ('N-phenyl benzothiazy1sul phenamide). This invention relates to a new class of com pounds which have been found valuable as accel~ erators for the vulcanization of rubber. This case is a division of my copending appli ‘cations Serial No. 280,929, ?led June 24, 1939, Patent 2,321,305, and Serial No. 334,343, ?led May 10, 1940, Patent 2,321,306. The new class of chemicals may be represented ' by the general formula 66 grams crude 1,1’ dithio bis benzothiazole are stirred with 300 to 600 cc.- carbon tetrachloride and‘ dry chlorine passed in until complete solu tion ensues and about 14.1 grams of chlorine has been absorbed. About 70 cos. of aniline are then 16 added with stirring and after standing a short ,where AR is an arylene group. while the resulting. solution is filtered and the The materials are derivatives of arylene-thiazyl precipitate washed with a little carbon tetra sulphur chloride, wherein the chlorine is replaced chloride, recovering some 47 grams pure aniline by the hydrochloride (aniline salt). The carbon tetra 20 chloride ?ltrates are evaporated to dryness (con radical above, when one mole of the arylene thiazyl sulphur chloride is reacted ‘with one mole of a primary arylamine, such as aniline, naph thylamine, alpha, naphthylamine, beta naphthyl amine, etc. During such reaction‘ hydrogen chlo ride is eliminated. densing and recovering carbon‘ tetrachloride used) leaving 105 grams of dark gray, oily crys tals. These may be puri?ed by washing with alcohol and drying, thereby obtaining 60 grams of 25 light gray colored crystals, melting at 119-122°'C. \ In the following illustrative example, benzo 66 grams of pure 1,1’ dithio bis benzothiazole thiazyl sulphur chloride is used as the reagent; it may be prepared in solution, for purposes of 30 (made by recrystallizing the product used in A from benzene) are treated in the same way as in reaction by passing dry chlorine into a slurry of 1,1’ dithio bis benzothiazole in benzene, carbon tetrachloride, etc. A. ‘52.7 grams pure aniline salt are recovered. guanidine, thiuram sulphides such as tetramethyl thiuram monosulphide, etc., which have the ac 40 tion of activating the accelerating ability of ized and tested. 97.5 grams‘of crude N-phenyl benzothiazyl sul phenamide of melting point 114-118“ C. are ob The materials are delayed-action accelerators similar in this respect to 1,1’ dithio bis benzo 35 tained and this will yield 75.3 grams N-phenyl benzothiazyl sulphenarnide melting point 118 thiazole itself. They may be used alone or in 120° C. on puri?cation. conjunction with basic nitrogen compounds such The following rubber mixes were made, vulcan as ammonia, amines, guanidines such as diphenyl - I Stock thiazole accelerators. They may also, if desired, be used in admixture with other thiazole accel erators such as the mercapto-ibenzothiazyl sul phides. The following example is given to illustrate the invention in which comparison is made with a stock containing 1,1’ dithio bis benzothiazole (parts are by Weight) : 1 46 Pale crepe ________________ ._ Zinc oxide... . . Lithopone_.___ Whiting ______________________________ . Suprex clay _________________ __ , Zinc soap of cocoanut oil so Sulphur ____________________ __ EXAMPLE The reaction product of benzothiazyl sulphur 50 1,1’ dithio bis benzothiazole-_.._ N-phenyl benzothiazyl sulfenamide .............. __ ,_. posh-$0 maukWHhOIlQg mu-1o H 2 Tensiles-Unayed A B Minutes cure at 30 lbs/sq. in steam ' pressure '1‘ E 953 T 2,370353 _ other well known ?llers, pigments and the like may be employed in the production 01' various types of rubber compounds as will be apparent to those skilled in the art to which this invention pertains. E 300 843 513 460 , 666 546 626 1, 160 1,860 673 563 596 2,160 636 Search test AS A B [5 where AR is an arylene hydrocarbon group. Minutes cure at 5 lbs.lsq. in steam pressure \ Having thus described my invention, what I claim and desire to protect by Letters Patent is: 1. A compound having the general formula 2. A N-monoaryl monobenzothiazyl sulphen ‘ amide‘having the general formula 130 137 155 192 132 1, 330 1, 515 1, 445 1, 337 l, 050 200 203 210 215 225 305 855 652 577 247 275 1, 437 1,280 1, 243 1, 197 II 107 852 810 3. A compound having the general formula T=Ultimate tensiles in pounds per square inch. E=% elongation at break. The term “rubber” herein is to be understood as including caoutchouo and similar vulcanizable gums, natural or synthetic, including latices thereof. Other ratios of the compounding ingredients 30 than those mentioned in the example as well as N / \ \s WILLIAM E. MESSER.