Патент USA US2409110код для вставки
Patented Oct. 8, 1946 2,409,109 UNlTED STATES PATENT OFFICE 2,409,109 DIARYL GUANIDINE ADDITION PRODUCTS Arnold Rogers Davis, Riverside, Conn., assignor to American Cyanamid Company, New York, 'N. Y., a corporation of Maine No Drawing. Application August 7, 1944, Serial No. 548,497 ‘ (Cl. 260—306.6) 5 Claims. 1 . . . 2 '. These new products are variously useful but, in particular, are adapted for use in vulcanization of rubber, both natural and synthetic. Both the diarylguanidines and mercaptans and dithiocar bamic acids are known. These have been previ the reaction by gentle heating as on a steam bath. Products of the reaction may be either amorphous or crystalline, many of- them appear ing as clear resins and others as clear white crys tals. Whichever the form in which the product is obtained it has a ?xed analysis, and in the case of the crystalline forms, a de?nite melting point, indicating that a true chemical compound is formed by the reaction and not simply a complex mixture. The invention will be more fully illustrated in ously used in vulcanization, for example, the’ diarylguam'dines and the zinc salt of mercapto conjunction with the following examples which are intended to be illustrative only and not by benzothiazole, as well as the dithiocarbamates way of limitation. All parts are by weight unless This invention relates to a group of new chem ical products. More particularly, the invention relates to a series of chemical compounds which constitute addition products of a diarylguanidine and a zinc salt of a mercaptan or a dithiocar bamic acid. otherwise noted. In these examples the follow have been used in conjunction with each other to ing abbreviations are used for the sake of sim obtain results which could not'be obtained using pli?cation: these agents alone. The present group of new D. P. G.-diphenyl guanidine chemical combines both types of agent into a sin D. O. T. G.-—di-o-toly1 guanidine gle compound, having the advantage that a plu rality of agents need not be used by the industry 2,0 D. X. G.--dixylyl guanidine ' M. B. 'I'.—mercaptobenzothiazole to obtain the desired results; The present appli D. T. C.—dithiocarbamic acid cation relates to the new products, per se, vul canization processes using the same being set forth in my copending application for United States Letters Patent, Serial No. 548,498, ?led of 25 even date. EXAMPLE 1 _ (D. P. G.)zZn(M. B. T.) 2 199 parts of the zinc salt of mercaptobenzo thiazole and 211 parts of diphenyl guanidine were heated together with stirring until they fused at The new compounds of the present invention are most simply described as reaction products which may be designated by the formula about 110“ C. A clear resin formed in a few min AxZn(B)2. A represents such diaryl guanidines 30 utes. The fusion product was held at l00-110° as diphenyl guanidine, ditolyl guanidines, par C. for about 15 minutes after which the melt was ticularly the diorthotolyl guanidine, the dixylyl cooled, crushed, ground and remelted at about guanidines, dinaphthyl guanidine, and the like. In the present invention :1: represents the integers 1 and 2. The group designated as B may be quite 35 widely varied since Zn(B)2 represents salts of both marcaptans and dithiocarbamic acids. In 100° C. A clear resin was formed. EXAMPLE 2 /C3H1 (D. P. G.)1Zn(SSCN\ ) this group are such compounds as the zinc salts C5H5 of mercaptobenzothiazole, the dialkyl dithiocar bamic acids such as the dimethyl, diethyl, dibutyl 40 435 parts of zinc N,N-n-propyl, phenyl dithio and 'bis-alkoxyalkyl; the alkyl, aryl dithiocar-' carbamate and 211 parts of diphenyl guanidine bamic acids such as the'N,N-propyl, phenyl and were fused together and held at 95-l00° C, for N,N-butyl, phenyl, dithiocarbamic acids and the about 15 minutes. A clear liquid form which, on like. i A cooling. gave a clear resin. ' The proportions in which the diaryl guanidine 45 EXAMPLE 3 and the zinc salt are combined may be quite widely varied. In general, however, it has been found preferable to use from'one to two mol parts of the diaryl guanidine with one mol part of the zinc salt, The products may be readily produced 50 by heating the reactants to the fusion point and, ‘ ‘ continuing the‘ heating until reaction is complete. Alternatively’, the reacti'on'may be carried‘ out by suspending ‘or dissolving diaryl guanidine in a volatile solvent such as benzene and carrying out .. (D. P. G.) lZll<SSON The process of Example 2 ‘was repeated, using 513 parts of zinc N,N-n-butyl, phenyl dithiocar bamate and 211 parts of diphenylguanidine. As in Example 2,. a clear liquid was formed which 455 give a clear ?lm on cooling. ' ' ' ‘ I ‘21469, 10s . 4 3 Optically, the product shows’crystals di?ering' EXAMPLE 4 from either di-o-tolyl guanidine or zinc merc'ap- ' (D. P. G.)Zn(M. B. T..)2' The procedure of Example 1 was repeated, using 199 parts of the zinc mercaptobenz-othiazole tobenzothiazole. EXAMPLE 11 47.8 parts of di-o-tolyl guanidine were suspend and 106 parts, diphenylguanidine. The mass ed in 500'parts of ,benzol and 39.8 parts of zinc fused at 125-130‘? C. and after being cooled, mercaptobenzothiazole added thereto. Both ma . crushed, and ground, melted at about 130° C. terials dissolved on'heating to about ‘YB-80° C., The product was a light brownish-yellow resin. the temperature being held at this point until 10. about one-half the benzol was evaporated. On EXAMPLE 5 ' standing for about one hour,’ crystals formed and the‘ mass solidi?ed-1 About 250 parts of ben'zol were added to dissolve the crystals, the solution "was ?ltered and cooled, crystals separated out, 513 parts of zinc butylphenyldithiocarbamate .. »washed with benzol and dried in air for about 48 and 211 parts of diphenylguanidine were fused v ‘ hours.‘ ‘The product was ahomogeneous crystal together for about 15 minutes at 95° C. A sub-r _' line mass melting at 152'-153° C. and having a ~ nitrogen content of 12.30% and a sulfur content stantially water-white resin was formed. ' EXAMPLE 6 of 13.81%. 20 ' C2135 . ~ ~ '.EXAMPLE 1.2 _ _~The same lamountsof material used in EXain-V / \czHs 2 The procedure of Example 5 was repeated using 107 parts of dixylylguanidine and '7 3 parts of zinc diethyldithiocarbamate. 1 ple 11 ‘were fused together at 170° C. and heated" at 153-155‘? Cgu-ntil the melt was clear. A glassy amorphous product-was obtained. 25 7 . After about one-half EXAMPLE 13 ~ Exam-ch11 was repeated using 51.3. parts of hour’s heating at 100-105° C. a clear, resinous zinc N-propyl. nhenyl dithiocarbajmate and 422 product was obtained. ' parts of diphenyl guanidine...‘ After .30 minutes 30 of heating, the'solution allowed crystals of the u). EXAMPLE '7 product to form when cooled. ; ,, ' . EXAMPLE 14 _ Example 11 was repeated using 39.8‘partsof ,lzinc Q The procedure in Example 6 was repeated using 3.5 mercaptobenzothiaz‘ole and 147.8 parts of. di-'o:-,t_ol_e yl guanidine 500 ‘parts of benzol. A cleanse half the quantity of zinc diethyldithiocarbamate. lution formed‘v after aboutvone-ha-lf hour" at '70‘: A similar appear resin vwas obtained. . C. 7, Heating was continued for one hour, ‘followed, by ?ltrationg-l» On cooling, no crystals V'for/m d. About one-half the solvent was then evaporated. , EXAMPLE 8 40 The crystals forrnegl afterevaporating part ofthe solvent were redissolved inr-benzol'an'd recrystal-lv lized. The resultant crystals ‘formed were washed twiceinbenzol and ‘dried at 100° C. for’about' 534 parts of dixylyl guanidine were added to a solution of 362 parts of zinc diethyldithiocar bamatein benzene at 30° C. The temperature Was raised to 75-78” C. and held for about 40 minutes after which the solution was filtered, the ?lter washed with hot benzene and the wash ings added to the original ?ltrate. The ?ltrate was rapidly evaporated to about ‘one quarter its original volume and then allowed to stand in air one hour. The crystalline product had a melting point of 15,5—157° C; and the following analysis: ‘ " (D. P. G.)Z11(SSCN\ ) C2H5OG3H7 2 60 119 parts of.zinc mercaptobenzctmhiazole~ and 143 parts of di-o-tolyl guanidine were fused to gether at 125.‘? 9, to give, a clear melt which 'was cooled, crushed and ground and again-heated at, 125° C- for about 15 mmlites. elite: which the fur‘ sion product was allowed to stand overnight. ‘. ' ~ 'EXAMPLE15V'.1'N,rT.. A portion of ‘zinc mcrcaptobenzothiazolev was’ the mass was c00led.;er0und and; r@m§1ted;1;h¢ temperature beinecheldat 1.57:?‘ qguntilreec?en clarity of the melt; T 211 parts of diphenyl guanidine, for a suficient . time to form a clear liquid. ‘ On cooling 2. thick EXAMPLE10 ‘ appeared tube: oinp16te,"a$ evideneedjhy lthel bamate were fused together at about 100° C. with talline growth. 7.44 Washed inyhexane. benzol and. acetone “1193 parts of washed salt was fused with‘ 143.5 parts of di-o-tolyl euanidine at 1.25%‘)? C, .,,Aft§1'.fll5i<m 297 parts of zinc bis-ethoxypropyldithiocar light colored paste was formed indicating crys 7.26 eating that auniform product was'obtained.‘ EXAMPLE 9 /c'2H5ooaH1 14.60 %'___.____v______ __ 7.1-1. _____ __ 14.40 A second bath. of crystals recovered from the mother liquor had the same melting point ‘indie 55 1 12.78 s, 50 Zn, a’ (0 ---- --V-_--_---' _____________ -__" at room temperature. No crystals appeared even after long standing. The product is a soft resin. N,',%'___V _____ __'_____' _______ __.____ 12.74 1 65 . . - V EXAMPLE. 1.6 . , wléaniéa?ée '11} bitty-l‘ rubzlii ‘ r1; P; 2.‘: 'The product of Example-‘3 "(DZ 1’: (NZN C.) 2 was, rfn'ade intof-t'he fol lowing’ composition bywinilli“ :' the comp hents butyl, phenyl" Di 0 togetherz" ’ 3 ~» ‘Butyl B‘ (containsisa, .z'rlo‘,i1.5%' gm Stearioaci? j Pelletexr black. " 75 Accelerator ' ~ “ ' f __ 2,409, 105 . 6 5 After curing for 60 minutes at 153° C. the prod present invention are prepared by fusion or by uct was found to be a Shore Hardness of 44. EXAMPLE 17 the solvent process, the compositions shown in the following table were prepared and tested. It was made up into the following composition: G. R.-S ______________________ __ 100 will be noted that substantially equivalent results Vulcanization of Buna S 5 were obtained. Compounds The same accelerator produced in Example v3 Buna S_ 100 5 Zinc oxide ____________________ __ 5 5 5 10 E. P. C. black _________________ __ 50 50 Sulfur _______________________ __. 2 2 Coal tar softener _____________________ __ Zinc oxide E. P. C. black 5 50 Sulfur ______ Above accelerator_____' ________________ __ 2 0.65 14) ________________________ __ Modulus minutes °C. 15 30 60 141 141 141 Tensile 15) _______________________ __ 490 985 1, 295 61 59 Mod. at 300%________________ 1,150 Shore hardness (30") _______ __ 1,100 Tensile ____________________ __ 3,050 2° Elongation % ______________ __ 580 2,950 600 elong. 1,945 3, 090 2, 750 0.90 Cured 55 minutes at 141° C. Per cent @ 300% strength 0.90 (D. O. T. G.)2Zn (M. B. T02 (Ex. 15 Temp" 5 (D. O. T. G.)2Zn(M. B. T.)2 (Ex. C1116 Time’ 100 Bardol (coal tar softener) _____ __ 710 605 490 Set at break, % _____________ .._ 26 26 280° F ___________________ __ .168 .174 DeMattra out growth rate mils./kc__ Effect of varying proportions of diaryl guanidine 25 33 27 Torsional hysteresis “K” at EXAMPLE 18 0n vulcanization I claim: 1. A reaction product of one to two mols of a In order to show the distinction between the use of diaryl guanidine in the ratio of l and 2 diaryl-guanidine and one mol of a zinc salt hav parts of diaryl guanidine per part of zinc salt, 30 ing the formula Zn(X)z in which X represents a member of the group consisting of the the following compositions were prepared and tested and the results shown in the table were ob tained. N ’ _SC// \S Compounds G. R.-S _____________________ __ 100 Bardol (coal tar softener) ____ __ 5 Zinc oxide __________________ __ 5 100 5 5 E. P. C. black__________________ 50 50 Sulfur _____________________ _.. 2 2 (D. P. G.)zZn(M. B. T02 ______ __ 35 40 .89 .90— 60' cure at 141° 0. 60 61 Mod. at 300% ______________ __ 1,070 755 Tensile ____________________ __ 2,610 Elongation ________________ __ 535 2,285 590 Torsional hysteresis “K” at 280° F ____________________ __ .180 alkyl ; phenyl ethoxyalkyl (From Example 4) Shore hardness _____________ __ /alkyl ; —SSCN and (From Example 1) D. P. G.Zn(M. B. T02 _______ __ /alkyl ; -—SSCN .184 --SSCN ethoxyalkyl radicals. 2. A reaction product of one to two mols of a diaryl-guanidine and one mol of a zinc mercap 45 tobenzothiazole. 3. A reaction product of one to two mols of di phenylguanidine and one mol of zinc mercapto benzothiazole. 4. A reaction product of one to two mols of di 5 0 o-tolyl guanidine and one mol of zinc mercapto benzothiazole. 5. A reaction product of one to two mols of Comparison of solvent as. fusion products dixylyl guanidine and one mol of zinc mercap In order to show that substantially the same 55 tobenzothiazole. ARNOLD ROGERS DAVIS. results are obtained whether the products of the EXAMPLE 19 / /// Certi?cate of Correction Patent No. 2,409,109. October 8, 1946. ARNOLD ROGERS DAVIS It is hereby certi?ed that error appears in the printed speci?cation of the above numbered patent requiring correction as follows: Column 4, line 59, Example 15, for “125-104° C.” read 125-140" 0.; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent O?ice. Signed and sealed this 15th day of July, A. D. 1947. ' [am] LESLIE FRAZER, First Assistant C’ommissioner of Patents.