NO126733B

NO126733B -

Info

Publication number: NO126733B
Application number: NO411669A
Authority: NO
Inventors: Aubert Yaucher Coran; Joseph Edward Kerwood
Original assignee: Monsanto Co
Priority date: 1965-05-27
Filing date: 1969-10-16
Publication date: 1973-03-19
Also published as: CH477481A; JPS4922940B1; AT313571B; CA926538A; BE691486A; JPS4922939B1; JPS4922938B1; FR1500844A; DE1620823C3; BE694563A; DE1620822A1; CA926537A; DE1620822B2; DE1620823A1; SE362645B; GB1155213A; PH10758A; NO121118B; SE383755B; LU51210A1

Description

Kjemiske forbindelser for anvendelse som Chemical compounds for use as

vulkaniseringsinhibitorer. vulcanization inhibitors.

Foreliggende oppfinnelse angår nye kjemiske forbindelser The present invention relates to new chemical compounds

som forhindrer for tidlig vulkanisering av gummi. which prevents premature vulcanization of rubber.

Ved fremstilling av vulkaniserte gummiprodukter, forenes rågummi med forskjellige andre bestanddeler som fyllstoffer, akseleratorer og anti-nedbygningsmidler for å endre og forbedre behandlingen av gummien og for å forbedre egenskapene av sluttproduktet. Rågummien gjennomgår flere trinn i fabrikasjonen for den er ferdig til det siste trinn, vulkaniseringen. I alminnelighet blandes gummi med carbon black og de andre bestanddeler unntatt vulkaniseringsmidlet og akseleratoren. Så tilsettes vulkaniserings- og akselereringsmidlene til resten av chargen i en "Banbury"-blander eller en molle. Anvulkanisering, dvs. for tidlig vulkanisering, kan inntre på dette trinn av fremstillingen, under lagringer for vulkanisering og under selve vulkaniseringen. Etter at vulkaniserings- og akselereringsmidlene er tilsatt, er blandingen av rågummi ferdig til kalandrering eller ekstrudering og vulkanisering. Hvis for tidlig vulkanisering inn-trer under lagringen av råblandingen eller under behandlingen under vulkanisering, kan ikke behandlingsoperasjonene utfores fordi den anvulkaniserte gummi er ujevn og klumpet og fblgelig ubrukbar. For tidlig vulkanisering er et hovedproblem i gummiindustrien og må forhindres for å tillate at gummiblandingen forformes og fortnes for den herdes eller vulkaniseres. In the manufacture of vulcanized rubber products, raw rubber is combined with various other ingredients such as fillers, accelerators and anti-degradants to modify and improve the processing of the rubber and to improve the properties of the final product. The raw rubber goes through several stages in the manufacture before it is finished until the last stage, the vulcanisation. In general, rubber is mixed with carbon black and the other ingredients except the vulcanizing agent and the accelerator. Then the vulcanizing and accelerating agents are added to the rest of the charge in a "Banbury" mixer or a molle. Unvulcanization, i.e. premature vulcanization, can occur at this stage of manufacture, during storage for vulcanization and during the vulcanization itself. After the vulcanizing and accelerating agents have been added, the mixture of raw rubber is ready for calendering or extrusion and vulcanization. If premature vulcanization occurs during the storage of the raw mixture or during the processing during vulcanization, the processing operations cannot be carried out because the unvulcanized rubber is uneven and lumpy and therefore unusable. Premature vulcanization is a major problem in the rubber industry and must be prevented to allow the rubber compound to preform and harden before it cures or vulcanizes.

Der er flere grunner til for tidlig vulkanisering. Opp-dagelsen av thiazolsulfenamid-akseleratorene utgjorde et stort fremskritt i vulkaniseringsfaget fordi thiazolsulfenamidene forsinket begynnelsen av vulkaniseringsprosessen, men når den en gang begynner, forte den innebyggede aminaktivering av thiazolen til sterk og hurtig herding. Mercaptobenzothiazol er en verdifull organisk vulkaniseringsakselerator, men virker anvulkaniserende. Den er stort sett blitt erstattet av akseleratorene med forsinket virkning, men ytterligere forbedringer har ikke funnet sted i faget. Utviklingen av furnace blacks med hoy pH som mangler den iboende inhibiterende virkning hos de sure channel blacks, og populariteten av visse fen-ylendiamin-antinedbrytningsmidler, som fremmer anvulkanisering, har medfort stadig strengere krav til akseleratorsystemet. There are several reasons for premature vulcanization. The discovery of the thiazolesulfenamide accelerators was a major advance in the vulcanization field because the thiazolesulfenamides delayed the onset of the vulcanization process, but once it began, the inherent amine activation of the thiazole accelerated strong and rapid curing. Mercaptobenzothiazole is a valuable organic vulcanization accelerator, but has an unvulcanizing effect. It has largely been replaced by the delayed-action accelerators, but further improvements have not taken place in the subject. The development of high pH furnace blacks that lack the inherent inhibitory effect of the acid channel blacks, and the popularity of certain phenylenediamine antidegradants, which promote vulcanization, have led to increasingly stringent requirements for the accelerator system.

Retarderingsmidler har lenge vært tilgjengelige for gum-mifabrikanter. Disse innbefatter N-nitrosodifenylamin, nåletrehar-piks og salicylsyre og et dispergeringsmiddel, jfr. Editors of Rubber World, Compounding Ingredients for Rubber, 91 - 9^ (3rd Ed., 1961). Syrer er i alminnelighet ineffektive med thiazolsulfenamidakselera-torer eller påvirker vulkaniseringsprosessen uheldig. Nitrosaminer har bare begrenset virksomhet med thiazolsulfenamider avledet fra primære aminer. Visse sulfenamider som ikke i og for seg er akseleratorer, har vist seg å sinke mercaptobenzothiazol og andre anvulkaniserende • akseleratorer , men virkningen på et annet sulfenamid in.'-korporert som hovedakselerator, har vært i minste laget. Likeledes har blandinger av akselererende sulfenamider vært foreslått som en måte for å forbedre behandlingssikkerheten, men ingen av disse nye trekk har forbedret en god forsinket virkende akselerator særlig. Retardants have long been available to rubber manufacturers. These include N-nitrosodiphenylamine, needle resin and salicylic acid and a dispersant, cf. Editors of Rubber World, Compounding Ingredients for Rubber, 91 - 9^ (3rd Ed., 1961). Acids are generally ineffective with thiazole sulfenamide accelerators or adversely affect the vulcanization process. Nitrosamines have only limited activity with thiazole sulfenamides derived from primary amines. Certain sulfenamides which are not in and of themselves accelerators have been shown to slow down mercaptobenzothiazole and other vulcanizing • accelerators, but the effect on another sulfenamide incorporated as the main accelerator has been minimal. Likewise, mixtures of accelerating sulfenamides have been proposed as a way to improve treatment safety, but none of these new features have significantly improved a good delayed-acting accelerator.

Et mål ved foreliggende oppfinnelse er å skaffe nye kjemiske forbindelser som er nyttige som inhibitorer av for tidlig vulkanisering, særlig med forsinket virkende thiazolsulfenamider. An aim of the present invention is to provide new chemical compounds that are useful as inhibitors of premature vulcanization, particularly with delayed-acting thiazole sulfenamides.

Foreliggende oppfinnelse angår kjemiske forbindelser for anvendelse som vulkaniseringinhibitorer, karakterisert ved at The present invention relates to chemical compounds for use as vulcanization inhibitors, characterized in that

de har formelen: they have the formula:

hvor p where p

a) R er hydrogen, R1-^- er N-(arylthio)-carbamoyl, N-(halogenaryl-thio)-carbamoyl, N-(aralkylthio)-carbamoyl, N-(alkarylthio)-carbamo-yl, N-(alkylthio)-earbamoyl eller N-(cycloalkylthio)-carbamoyl, a) R is hydrogen, R1-^- is N-(arylthio)-carbamoyl, N-(haloarylthio)-carbamoyl, N-(aralkylthio)-carbamoyl, N-(alkarylthio)-carbamoyl, N-( alkylthio)earbamoyl or N-(cycloalkylthio)carbamoyl,

2 2

R er aryl, halogenaryl, aralkyl, alkaryl, cycloalkyl eller alkyl, eller R is aryl, haloaryl, aralkyl, alkaryl, cycloalkyl or alkyl, or

b) hvor R og R"^" med carbonylgruppen og N-atomet er 3-arylthio-2-benzimidazolinon-l-yl, 3-cycloalkylthio-2-benzimidazolinonTl-yl, 2-benzimidazolinon-l-yl, 3-aralkylthio-2-benzimidazolinon-l-yl, 3-ni-troarylthio-2-benzimidazolinon-l-yl, 3-halogenarylthio-2-benzimida-zolinon-l-yl, 3-alkarylthio-2-benzimidazolinon-l-yl, 3-(alkylthio)-2-benzimidazolinon-l-yl, 3-imidazolinon-l-yl, 3-cycloalkylthio-2-imidazolinon-l-yl, 3-arylthio-2-imidazolinon-l-yl, 3-halogenarylthio-2-imidazolinon-l-yl, 3-aralkylthio-2-imidazolinon-l-yl, 3-alkaryl-thio-2-imidazolinon-l-yl, 3-(alkylthio)-2-imidazolinon-l-yl, 1-maleimidyl, 55 5-dimethyl-3-hydantoinyl, 5,5-difenyl-3-hydantoinyl, h-cyclohexan-l,2-dicarboximld-l-yl, 1 ,*f,5,6,7 ,7-hexaklor-bicyclo[2."2.l]-hept-5-en-2,3-dicarboximid-l-yl, bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid-l-yl, alkylbicyclo[2.2.l]-hept-5-en-2,3-dicarboximid-l-yl, N- (arylthio )-l ,2,)+, 5-benzente tracarboxylsyre-1,2:*+, 5-diimid-N' -yl, N-(aralkylthio)-1,2, h,5-benzentetracarboxylsyre-1,2: k,5-diimid-N * - yl, N-(halogenarylthio)-1,2, h,5-benzentetracarboxylsyre-1,2: h,5-diimid-N * -yl, N- (nitroarylthio)-1,2 , 5-benzentetracarboxylsyre-1,2: k,5-diimid-N'-yl, N-(alkylthio )-l ,2,*+, 5-benzente tracarboxylsyre-1,2: h, 5-diimid-N' -yl, N- (cycloalkylthio)-1,2,*f, 5-benzentetracarboxylsyre-1, 2 x V,5-diimid-N'- yl eller N-(alkarylthio)-1,2, h,5-benzentetracarboxylsyre-1 ,2:^,5-diimid-N1-yl, og b) where R and R"^" with the carbonyl group and the N atom are 3-arylthio-2-benzimidazolinon-1-yl, 3-cycloalkylthio-2-benzimidazolinon-1-yl, 2-benzimidazolinon-1-yl, 3-aralkylthio- 2-benzimidazolinon-l-yl, 3-nitroarylthio-2-benzimidazolinon-l-yl, 3-halogenarylthio-2-benzimidazolinon-l-yl, 3-alkarylthio-2-benzimidazolinon-l-yl, 3- (alkylthio)-2-benzimidazolinon-1-yl, 3-imidazolinon-1-yl, 3-cycloalkylthio-2-imidazolinon-1-yl, 3-arylthio-2-imidazolinon-1-yl, 3-haloarylthio-2- imidazolinon-1-yl, 3-aralkylthio-2-imidazolinon-1-yl, 3-alkaryl-thio-2-imidazolinon-1-yl, 3-(alkylthio)-2-imidazolinon-1-yl, 1-maleimidyl, 55 5-dimethyl-3-hydantoinyl, 5,5-diphenyl-3-hydantoinyl, h-cyclohexan-1,2-dicarboximld-1-yl, 1,*f,5,6,7,7-hexachloro-bicyclo[ 2.2.1]-hept-5-en-2,3-dicarboximid-1-yl, bicyclo[2.2.1]-hept-5-en-2,3-dicarboximid-1-yl, alkylbicyclo[2.2 .1]-hept-5-en-2,3-dicarboximid-1-yl, N-(arylthio )-1,2,)+, 5-benzenetracarboxylic acid-1,2:*+, 5-diimide-N ' -yl, N-(aralkylthio)-1,2,h,5-benzenetetracarboxylic acid- 1,2:k,5-diimid-N*-yl,N-(haloarylthio)-1,2,h,5-benzenetetracarboxylic acid-1,2:h,5-diimid-N*-yl,N-(nitroarylthio )-1,2 , 5-benzenetetracarboxylic acid-1,2: k,5-diimid-N'-yl, N-(alkylthio )-1 ,2,*+, 5-benzenete tracarboxylic acid-1,2: h, 5 -diimid-N'-yl, N-(cycloalkylthio)-1,2,*f,5-benzenetetracarboxylic acid-1,2 x V,5-diimid-N'-yl or N-(alkarylthio)-1,2, h,5-benzenetetracarboxylic acid-1,2:^,5-diimid-N1-yl, and

R 2 er aryl, aralkyl, alkaryl, halogenaryl, nitroaryl, cycloalkyl eller alkyl, idet R 2 is aryl, aralkyl, alkaryl, haloaryl, nitroaryl, cycloalkyl or alkyl, wherein

R og R med carbonylgruppen og N-atomet også kan være 1-fthalimidyl, 1-nafthalimidyl eller 1-(3 ,>+,5,6-tetrahalogenf thalimidyl) R and R with the carbonyl group and the N atom can also be 1-phthalimidyl, 1-naphthalimidyl or 1-(3,>+,5,6-tetrahalophthalimidyl)

når when

R 2er aralkyl, cycloalkyl eller alkyl. R 2 is aralkyl, cycloalkyl or alkyl.

Eksempler på de nye forbindelser ifolge oppfinnelsen er N-(cyclohexylthio)-fthalimid, N-(cyclooctylthio)-fthalimid, N-(ben-zyl thio )*fthalimid, N- (methylthio)-f thalimid-, N-(ethylthio)-fhtalimid, N- (propyl.thio)-f thalimid, N- (isopropylthio)-f thalimid, N- (n-butylthio)-fthalimid, "N-(t-butylthio)-fthalimid, N-(isobutylthio)-fthalimid, N-(sek.-but<y>lthio)-fthaliraid, N-(n-pentylthio)-fthalimid, N-(n-heptylthio)-fthali mid, N-(n-hexylthio)-fthalimid, N-(n-octylthio)-fthalimid, N-(n-dodecylthio)-fthalimid, 1,3-bis-(cyclohexylthio)-2-imidazolinon, 1,3-bis-(cyclooctylthio)-2-imidazolinon, 1,3-bis-(fenylthio)-2-imidazolinon, 1,3-bis-(klorfenylthio)-2-imidazolinon, 1,3-bis-(benzylthio)-2-imidazolinon, 1,3-bis-(tolylthio)-2-imidazolinon, 1,3-bis-(nitrofenylthio)-2-imidazolinon, 1,3-bis-(t-butylthio)-2- imidazolinon, 1,3-bis-(methylthio)-2-imidazolinon, 1,3-bis-(ethyl-thio)-2-imidazolinon, 1,3-bis-(propylthio)-2-imidazolinon, 1,3-bis-(isopropylthio)-2-imidazolinon, 1,3-bis-(n-dodecylthio)-2-imidazolinon, 1-(n-dodecylthio)-2-imidazolinon, N,N'-di-(fenylthio)-urea, N, N'-di(cyclohexylthio)-urea, N,N'-di-(cyclooctylthio)-urea, N,N'-di-(klorfenylthio)-urea, N,N'-di-(benzylthio)-urea, N,N'-di-(tolylthio)-urea, N,N'-di-(t-butylthio)-urea, N,N!--di- (methylthio )-urea , N,N' - di-(ethylthio)-urea, N,N'-di-(propylthio)-urea, N,N'-di-(isopropyl-thio )-urea,. N,N' -di- (n-dodecylthio )-urea, N- (cyclohexylthio)-maleimid, ■ N-(cyclooctylthio)-maleimid, N-(fenylthio)-maleimid, N-(klorfenylthio)-maleimid, N-(tolylthio)-maleimid, N-(nitrofenylthio)-maleimid, N-(benzylthio)-maleimid, N-(t-butylthio)-maleimid, N-(methylthio )-maleimid , N-(ethylthio)-maleimid, N-(propylthio)-maleimid, N-(isopropylthio)-maleimid, N-(n-dodecylthio)-maleimid, 5?5-dimethyl-3- (cyclohexylthio)-hydantoin, 5»5-dimethyl-3-(cyclooctylthio)-hyd-antoin, 555-dimethyl-3-(fenylthio)-hydantoin, 5j5-dimethyl-3-(klorfenylthio)-hydantoin, 5,5-dimethyl-3-(benzylthio)-hydantoin, 5»5-di-me thyl-3-(tolylthio)-hydantoin, 5>5-dimethyl-3-(nitrofenylthio)-hy-dantoin, 5,5-dimethyl-3-(t-butylthio)-hydantoin, 55 5-dimethyl-3-(methylthio )-hydantoin, 5 > 5-dime thyl-3- (e thyl thio)-hydantoin., _ 5>5-dime-thylthio)-3-(propylthio)-hydantoin, 5?5-dimethyl-3-(isopropylthio)-hydantoin, 5,5-dime thyl-3-(n-dodecylthio)-hydantoin, 1,^,5,6,7,7-hexaklor-N-(cyclohexylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 1,<*>f,5,6,7,7-hexaklor-N-(cyclooctylthio)-bicyclo[2.2.l]-hept-5-en-di~ carboximid, 1,^,5,6 ,7,7-hexaklor-N- (f enylthio )-bicyclo[2.2. l]-hept-5-en-2,3-dicarboximid, 1 , 5 >6,7 ,7-hexaklor-N- (klorfenylthio)-bicyclo[2. 2.1 ]-hept-5-en-2,3-dicarboximid, 1 , 5)6,7 ,7-hexaklor-N- (ben-zyl thio)-bicyclo[ 2.2.1]-hept-5-en-2,3-dicarboximid, 1,^,5)6 ,7,7-b.exa-klor-N-(tolylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 1 ,>+,5, 6,7,7-hexaklor-N-(nitrofenylthio)-bicyclo[2.2.1]-hept-5-en-2,3-dicarboximid, 1,^,5)6,7,7-hexaklor-N-(t-butylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 1,<*>+,5,6,7,7-hexaklor-N-(methylthio)-bicyclo- Examples of the new compounds according to the invention are N-(cyclohexylthio)-phthalimide, N-(cyclooctylthio)-phthalimide, N-(benzyl thio)*phthalimide, N-(methylthio)-phthalimide-, N-(ethylthio) -phthalimide, N-(propyl.thio)-phthalimide, N-(isopropylthio)-phthalimide, N-(n-butylthio)-phthalimide, "N-(t-butylthio)-phthalimide, N-(isobutylthio)- phthalimide, N-(sec-but<y>lthio)-phthaliraide, N-(n-pentylthio)-phthalimide, N-(n-heptylthio)-phthalimide, N-(n-hexylthio)-phthalimide, N- (n-octylthio)-phthalimide, N-(n-dodecylthio)-phthalimide, 1,3-bis-(cyclohexylthio)-2-imidazolinone, 1,3-bis-(cyclooctylthio)-2-imidazolinone, 1,3- bis-(phenylthio)-2-imidazolinone, 1,3-bis-(chlorophenylthio)-2-imidazolinone, 1,3-bis-(benzylthio)-2-imidazolinone, 1,3-bis-(tolylthio)-2- imidazolinone, 1,3-bis-(nitrophenylthio)-2-imidazolinone, 1,3-bis-(t-butylthio)-2- imidazolinone, 1,3-bis-(methylthio)-2-imidazolinone, 1,3- bis-(ethyl-thio)-2-imidazolinone, 1,3-bis-(propylthio)-2-imidazolinone, 1,3-bis-(isopropylthio)-2-imidazolinone, 1,3-bis-(n-dodecylthio )-2-imidazolinone, 1-(n-dodecylthio)-2-imidazolinone, N,N'-di-(phenylthio)-urea, N,N'-di(cyclohexylthio)-urea, N,N'-di- (cyclooctylthio)-urea, N,N'-di-(chlorophenylthio)-urea, N,N'-di-(benzylthio)-urea, N,N'-di-(tolylthio)-urea, N,N'- di-(t-butylthio)-urea, N,N!--di-(methylthio)-urea, N,N'-di-(ethylthio)-urea, N,N'-di-(propylthio)-urea, N,N'-di-(isopropyl-thio)-urea,. N,N' -di-(n-dodecylthio )-urea, N-(cyclohexylthio)-maleimide, ■ N-(cyclooctylthio)-maleimide, N-(phenylthio)-maleimide, N-(chlorophenylthio)-maleimide, N- (tolylthio)-maleimide, N-(nitrophenylthio)-maleimide, N-(benzylthio)-maleimide, N-(t-butylthio)-maleimide, N-(methylthio)-maleimide, N-(ethylthio)-maleimide, N- (propylthio)-maleimide, N-(isopropylthio)-maleimide, N-(n-dodecylthio)-maleimide, 5?5-dimethyl-3-(cyclohexylthio)-hydantoin, 5?5-dimethyl-3-(cyclooctylthio)- hyd-antoin, 55-dimethyl-3-(phenylthio)-hydantoin, 5j5-dimethyl-3-(chlorophenylthio)-hydantoin, 5,5-dimethyl-3-(benzylthio)-hydantoin, 5»5-dimethyl -3-(tolylthio)-hydantoin, 5>5-dimethyl-3-(nitrophenylthio)-hydantoin, 5,5-dimethyl-3-(t-butylthio)-hydantoin, 55 5-dimethyl-3-(methylthio )-hydantoin, 5 > 5-dime thyl-3-(e thyl thio)-hydantoin., _ 5>5-dime-thylthio)-3-(propylthio)-hydantoin, 5?5-dimethyl-3-(isopropylthio )-hydantoin, 5,5-dimethyl-3-(n-dodecylthio)-hydantoin, 1,^,5,6,7,7-hexachloro-N-(cyclohexylthio)-bicyclo[2.2.1]-hept- 5-a-2,3- dicarboximide, 1,<*>f,5,6,7,7-hexachloro-N-(cyclooctylthio)-bicyclo[2.2.1]-hept-5-ene-di~ carboximide, 1,^,5,6 , 7,7-hexachloro-N-(phenylthio)-bicyclo[2.2. 1]-hept-5-ene-2,3-dicarboximide, 1 , 5 >6,7 ,7-hexachloro-N-(chlorophenylthio)-bicyclo[2. 2.1 ]-hept-5-ene-2,3-dicarboximide, 1 , 5)6,7 ,7-hexachloro-N-(benzyl thio)-bicyclo[ 2.2.1]-hept-5-ene-2 ,3-dicarboximide, 1,^,5)6 ,7,7-b.exa-chloro-N-(tolylthio)-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide, 1 , >+,5,6,7,7-hexachloro-N-(nitrophenylthio)-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide, 1,^,5)6,7,7- hexachloro-N-(t-butylthio)-bicyclo[2.2.l]-hept-5-ene-2,3-dicarboximide, 1,<*>+,5,6,7,7-hexachloro-N-(methylthio )-bicyclo-

[2.2.l]-hept-5-en-2,3-dicarboximid, 1,>+, 5,6,7',7-hexaklor-N- (ethyl-thio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, N-(propylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 1,W,5,6,7,7-hexaklor-N-(isopropylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 1,W,5, 6,7,7-hexaklor-N-(n-dodecylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid , N-(cyclohexylthioJ-^-cyclohexen-l,2-dicarboximid, N-(cyc-looc tyl thio )-1+-cyclohexen-l ,2-dicarboximid, N- (f enylthio )-1+-cyclo-hexen-1,2-dicarboxiraid, N- (klor fe ny 1 thio) - h-cyc-lohexen-1,2-dicarboximid , N- (benzylthio )-1+-cyclohexen-l ,2-dicarboximid , N- (tolylthio )--^-cyclohexen-1,2-dicarboximid, N-(nitrofenylthio)-^-cyclohexen-l,2-dicarboximid , N- (t-butylthio )-!+-cyclohexen-l ,2-dicarboximid, N- (methylthio )-!+-cyclohexen-l ,2-dicarboxiraid , N- (ethylthio)-'+-cyclohexen-1.2- dicarboximid , N-(propylthio )->+-cyclohexen-l ,2-dicarboximid, N-(n-dodecylthio )->+-cyclohexen-l,2-dicarboximid og N- (isopropylthio)-'f-cyclohexen-l,2-dicarboximid. Eksempler på andre nye forbindelser ifblge oppfinnelsen er 1,3-bis-(cyclohexylthio)-2-benzimidazolinon, 1.3- bis-(cyclooctylthio)-2-benzimidazolinon, 1,3-bis-(fenylthio)-2-benzimidazolinon, 1,3-bis-(tolylthio)-2-benzimidazolinon, 1,3-bis-(m-tolylthio)-2-benzimidazolinon, 1-fenylthio-2-benzimidazolinon, 1-benzylthio-2-benzimidazolinon, 1-klorfenylthio-2-benzimidazolinon, 1- nitrofenylthio-2-benzimidazolinon, 1-cyclohexylthio-2-benzimidazol-inon, 1-cyclooctylthio-2-benzimidazolinon, l-tolylthio-2-benzimida-zolinon, 1-t-butylthio-2-benzimidazolinon, l-methylthio-2-benzimida-zolinon, l-ethylthio-2-benzimidazolinon, 1-propylthio-2-benzimida-zo li non , l-isopropylthio-2-benzimidazolinon, 1,3-bis-(klorfenylthio)-2- benzimidazolinon, 1,3-bis-(benzylthio)-2-benzimidazolinon, 1,3-bi s-(nitrofenylthio)-2-benzimidazolinon, 1,3-bis-(t-butylthio)-2-benzimidazolinon, 1,3-bis-(propylthio)-2-benzimidazolinon, 1,3-bis-(methylthio)-2-benzimidazolinon, 1,3-bis-(ethylthio)-2-benzimidazol-inon, 1,3-bis-(isopropylthio)-2-benzimidazolinon, 1,3-bis-(n-dodecylthio ) -2-benz iaridazoli.non, N-fenylthio-3,'+,5,6-te traklorf thalimid, N-tolylthio-3,^,5,6-tetraklorfthalimid, N-klorfenylthio-3 ,^,5,6-tetra-klorfthalimid, N-benzylthio-3,V,5>6-tetraklorfthalimid, N-nitrofenyl-thio-3,>+, 5,6-te traklorf thalimid, N-n-butylthio-3,<>>+,5,6-tetraklorfthal-imid, N-n-dodecylthio-3,^,5,6-te traklorf thalimid-, N-cyclohexylthio-3,^,5,6-tetraklorfthalimid, N-cyclooctylthio-3,^,5,6-tetraklorfthal-imid , N-fenylthio-3 ,*+,5,6-tetrabromf thalimid, N-fenylthio-3 tetrabromfthalimid, N-Car-tolylthio)-3,^,5,6-tetraklorfthalimid, N-(ar-tolylthio)-3,■+,5,6-tetrabromfthalimid, N-fenylthionafthalimid, N-tolylthionafthalimid, N-klorfenylthionafthalimid, N-benzylthionaf-thalimid, N-nitrofenylthionafthalimid, N-n-butylthionafthalimid, [2.2.l]-hept-5-ene-2,3-dicarboximide, 1,>+, 5,6,7',7-hexachloro-N-(ethyl-thio)-bicyclo[2.2.l]-hept -5-ene-2,3-dicarboximide, N-(propylthio)-bicyclo[2.2.l]-hept-5-ene-2,3-dicarboximide, 1,W,5,6,7,7-hexachloro- N-(isopropylthio)-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide, 1,W,5,6,7,7-hexachloro-N-(n-dodecylthio)-bicyclo[2.2 .1]-hept-5-ene-2,3-dicarboximide , N-(cyclohexylthioJ-^-cyclohexene-1,2-dicarboximide, N-(cyclooctylthio)-1+-cyclohexen-1,2- dicarboximide, N-(phenylthio)-1+-cyclo-hexene-1,2-dicarboxiraide, N-(chloro feny 1thio)-h-cyclohexene-1,2-dicarboximide, N-(benzylthio)- 1+-cyclohexene-l ,2-dicarboximide , N-(tolylthio )--^-cyclohexene-1,2-dicarboximide, N-(nitrophenylthio)-^-cyclohexene-1,2-dicarboximide , N-(t-butylthio )-!+-cyclohexene-1 ,2-dicarboximide, N-(methylthio )-!+-cyclohexene-1 ,2-dicarboxiraide , N-(ethylthio)-'+-cyclohexene-1,2-dicarboximide, N-(propylthio ) ->+-cyclohexene-1,2-dicarboximide, N-(n-dodecylthio)->+-cyclohexene-1,2-dicarboximide and N-(isopropylthio)-'f-cyclohexene-1,2-d icarboximide. Examples of other new compounds according to the invention are 1,3-bis-(cyclohexylthio)-2-benzimidazolinone, 1,3-bis-(cyclooctylthio)-2-benzimidazolinone, 1,3-bis-(phenylthio)-2-benzimidazolinone, 1, 3-bis-(tolylthio)-2-benzimidazolinone, 1,3-bis-(m-tolylthio)-2-benzimidazolinone, 1-phenylthio-2-benzimidazolinone, 1-benzylthio-2-benzimidazolinone, 1-chlorophenylthio-2- benzimidazolinone, 1-nitrophenylthio-2-benzimidazolinone, 1-cyclohexylthio-2-benzimidazolinone, 1-cyclooctylthio-2-benzimidazolinone, l-tolylthio-2-benzimidazolinone, 1-t-butylthio-2-benzimidazolinone, l- methylthio-2-benzimida-zolinone, l-ethylthio-2-benzimidazolinone, 1-propylthio-2-benzimida-zo li non , l-isopropylthio-2-benzimidazolinone, 1,3-bis-(chlorophenylthio)-2- benzimidazolinone, 1,3-bis-(benzylthio)-2-benzimidazolinone, 1,3-bis-(nitrophenylthio)-2-benzimidazolinone, 1,3-bis-(t-butylthio)-2-benzimidazolinone, 1,3-bis -(propylthio)-2-benzimidazolinone, 1,3-bis-(methylthio)-2-benzimidazolinone, 1,3-bis-(ethylthio)-2-benzimidazolinone, 1,3-bis-(is opropylthio)-2-benzimidazolinone, 1,3-bis-(n-dodecylthio )-2-benz iaridazolinone, N-phenylthio-3,'+,5,6-te trachlorphthalimide, N-tolylthio-3,^ ,5,6-tetrachlorophthalimide, N-chlorophenylthio-3 ,^,5,6-tetra-chlorophthalimide, N-benzylthio-3,V,5>6-tetrachlorophthalimide, N-nitrophenyl-thio-3,>+, 5, 6-te trachlorf thalimide, N-n-butylthio-3,<>>+,5,6-tetrachlorophthal-imide, N-n-dodecylthio-3,^,5,6-te trachlorf thalimide-, N-cyclohexylthio-3,^, 5,6-tetrachlorophthalimide, N-cyclooctylthio-3,^,5,6-tetrachlorophthalimide , N-phenylthio-3 ,*+,5,6-tetrabromophthalimide, N-phenylthio-3 tetrabromophthalimide, N-Car-tolylthio )-3,^,5,6-tetrachlorophthalimide, N-(ar-tolylthio)-3,■+,5,6-tetrabromophthalimide, N-phenylthionaphthalimide, N-tolylthionaphthalimide, N-chlorophenylthionaphthalimide, N-benzylthionaphthalimide, N -nitrophenylthionaphthalimide, N-n-butylthionaphthalimide,

N-n-dodecylthionafthalimid, N-cyclohexylthionafthalimid, N-cyclooc-tylthionafthalimid og N,N'-bis-(ar-tolylthio)-l,2, k, 5-benzentetracarboxylsyre-1 ,2: ^-,5-diimid. N-n-dodecylthionaphthalimide, N-cyclohexylthionaphthalimide, N-cyclooctylthionaphthalimide and N,N'-bis-(ar-tolylthio)-1,2,k,5-benzenetetracarboxylic acid-1,2:^-,5-diimide.

De foretrukne forbindelser ifolge oppfinnelsen er N,N'-di-(fenylthio)-urea, 1,3-bis-(fenylthio)-2-benzimidazolinon, 1,3-bis-(fenylthio)-2-imidazolinon, N-(fenylthio)-maleimid, N-(fenylthio)- k-cyclohexen-1,2-dicarboximid, 15,6,7,7-hexaklor-N-(fenylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid, 5,5-dimethyl-3-(fenylthio)-hydantoin, 1-(fenylthio)-2-benzimidazolinon, N-(cyclohexylthio)-fthalimid, N-(isopropylthio)-fthalimid, N-(n-butylthio)-fthalimid og N-(n-dodecylthio)-fthalimid. The preferred compounds according to the invention are N,N'-di-(phenylthio)-urea, 1,3-bis-(phenylthio)-2-benzimidazolinone, 1,3-bis-(phenylthio)-2-imidazolinone, N-( phenylthio)-maleimide, N-(phenylthio)-k-cyclohexene-1,2-dicarboximide, 15,6,7,7-hexachloro-N-(phenylthio)-bicyclo[2.2.l]-hept-5-ene- 2,3-dicarboximide, 5,5-dimethyl-3-(phenylthio)-hydantoin, 1-(phenylthio)-2-benzimidazolinone, N-(cyclohexylthio)-phthalimide, N-(isopropylthio)-phthalimide, N-(n -butylthio)-phthalimide and N-(n-dodecylthio)-phthalimide.

Foreliggende forbindelser er anvendbare i gummiblandinger inneholdende svovel-vulkaniseringsmidler , peroxyd-vulkaniseringsmidler, organiske akseleratorer for vulkanisering og .antinedbrytningsmidler, hvorav ingen er den anvendte inhibitor. Uttrykkt "svovel-vulkaniser-ingsmiddel" er' anvendt for å betegne elementært svovel .eller svovel-holdige vulkaniseringsmidler, f.eks. et amindisulfid eller et polymert polysulfid. Foreliggende forbindelser er anvendbare med vulkaniser-ingsakseleratorer av forskjellige klasser. Eksempelvis kan gummiblandinger inneholdende de aromatiske thiazolakseleratorer som innbefatter benzothiazyl-2-monocyclohexyl-sulfenamid, 2-mercaptobenzothiazol, N-tert-butyl-2-benzothiazol-sulfenamid, 2-benzothiazolyl-diethyldithio-carbamat og.2-(morfolinothio)-benzothiazol, anvendes. Aminsalter av mercaptobenzothiazol-akseleratorer, f.eks. t-butylaminsaltet av mercaptobenzothiazol, og lignende salter av morfolin og 2,6-dimethylmor-folin kan anvendes sammen med foreliggende forbindelser. Thiazolakseleratorer andre enn aromatiske kan også anvendes. Materialer inneholdende akseleratorer, f.eks. tetramethylthiuram-disulfid, tetramethylthiuram-mo.nosulf id, aldéhyd-amin-kondensas jonsprodukter,. thiocar-bamylsulfenamider, thioureaer, xanthater og guanidinderivater, forbedres betraktelig ved anvendelse av foreliggende forbindelser. Eksempler på thiocarbamylsulfenamid-akseleratorer finnes i US patenter nr. 2.381.393, 2.388.236 og 2. k2.921. The present compounds are useful in rubber compounds containing sulfur vulcanizers, peroxide vulcanizers, organic accelerators for vulcanization and antidegradation agents, none of which is the inhibitor used. The term "sulfur vulcanizing agent" is used to denote elemental sulfur or sulfur-containing vulcanizing agents, e.g. an amine disulfide or a polymeric polysulfide. The present compounds are usable with vulcanization accelerators of various classes. For example, rubber mixtures containing the aromatic thiazole accelerators which include benzothiazyl-2-monocyclohexyl-sulfenamide, 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazole-sulfenamide, 2-benzothiazolyl-diethyldithio-carbamate and .2-(morpholinothio)-benzothiazole, are used. Amine salts of mercaptobenzothiazole accelerators, e.g. The t-butylamine salt of mercaptobenzothiazole, and similar salts of morpholine and 2,6-dimethylmorpholine can be used together with the present compounds. Thiazole accelerators other than aromatic can also be used. Materials containing accelerators, e.g. tetramethylthiuram-disulfide, tetramethylthiuram-monosulfide, aldehyde-amine condensation ion products,. thiocarbamylsulfenamides, thioureas, xanthates and guanidine derivatives are greatly improved by the use of the present compounds. Examples of thiocarbamylsulfenamide accelerators are found in US Patent Nos. 2,381,393, 2,388,236 and 2,921.

Forbindelsene ifolge oppfinnelsen er anvendbare på materialer inneholdende amin-anti-nedbrytningsmi.dler. Gummiblandinger inneholdende anti-nedbrytningsmidler, f.eks. N-l,3-dimethylbutyl-N'-f enyl-p-fenylendiamin, N,N'-.bis- (1 ,^-dimethylpentyl)-p-f enylendiamin og "andre fenylendiaminer, keton-, ether- og hydroxy-anti-nedbrytningsmidler, og blandinger derav, forbedres betraktelig ved anvendelse av foreliggende forbindelser. Blandinger av anti-nedbrytningsmidler, f.eks. en blanding av N-l,3-dimethylbutyl-N'-fenyl-p-fenylendiamin og N,<N>'-bis-(1,^-dimeth<yl>pentyl)-p-fenylendiamin gir et meget forbedret sluttprodukt når de anvendes med de inhiberende forbindelser ifolge foreliggende' oppfinnelse. The compounds according to the invention are applicable to materials containing amine anti-degradation agents. Rubber compounds containing anti-degradation agents, e.g. N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, N,N'-.bis-(1,^-dimethylpentyl)-p-phenylenediamine and "other phenylenediamines, ketone, ether and hydroxy anti-degradants , and mixtures thereof, are greatly improved by the use of the present compounds. (1,^-dimeth<yl>pentyl)-p-phenylenediamine gives a much improved end product when used with the inhibitory compounds of the present invention.

Forbindelsene ifolge oppfinnelsen kan anvendes i naturlig og syntetiske gummier og blandinger derav. Syntetiske gummier som kan forbedres ved anvendelse av foreliggende forbindelser, innbefatter cis-M—polybutadien, butylgummi, ethylen-propylen-terpolymere, polymere av 1,3-butadien, f.eks. 1,3-butadien selv og av isoprencopolymere av 1,3-butadien med andre monomere, f.eks. styren, acrylonitril, isobu-tylen og methylmethacrylat. The compounds according to the invention can be used in natural and synthetic rubbers and mixtures thereof. Synthetic rubbers that can be improved using the present compounds include cis-M-polybutadiene, butyl rubber, ethylene-propylene terpolymers, polymers of 1,3-butadiene, e.g. 1,3-butadiene itself and of isoprene copolymers of 1,3-butadiene with other monomers, e.g. styrene, acrylonitrile, isobutylene and methyl methacrylate.

De nye forbindelser ifolge oppfinnelsen fremstilles som folger: For å fremstille N-(cyclohexylthio)-fthalimid opploses 23,2 g (0,2 mol) cyclohexylmercaptan i 150 ml n-pentan, derpå fores lh, 2 g (0,2 mol) vannfri klorgass gjennom denne opplosning ved 0 - 5°C i 25 minutter. Den dannede sulfenylkloridopplosning tilsettes dråpevis i lopet av 30 minutter til en opplosning av 29,<*>+ g (0,2 mol) fthalimid og 27,0 g (0,27 mol) triethylamin i 120 ml dimethylformamid. Reaksjonstemperaturen heves fra ca. 25°C til ca. 39°C. Den dannede blanding får lov til å avkjole. Den fortynnes så med 2 liter iskoldt vann. Et hvitt krystallinsk produkt felles. Utbyttet er kvantitativt. Smeltepunktet av N-(cyclohexylthio)-fthalimidet er 89 - 91°C. Efter omkrystallisasjon av en prove av produktet er smeltepunktet 93 - 9Lt-°C. Jodometrisk titrering av det krystalliserte N-(cyclohexylthio)-fthalimid viser 99$ renhet. Analyse av produktet viser 5,<1>+8$ nitrogen og 12, lh% svovel. Beregnede prosenter for C-^H^NO^ er 5,36$ nitrogen og 12,26$ svovel. De nye cycloalkyl- og alkylforbindelser angitt ovenfor, fremstilles på lignende måte med tilsvarende resultater. The new compounds according to the invention are prepared as follows: To prepare N-(cyclohexylthio)-phthalimide, 23.2 g (0.2 mol) of cyclohexyl mercaptan are dissolved in 150 ml of n-pentane, then lh, 2 g (0.2 mol) are added anhydrous chlorine gas through this solution at 0 - 5°C for 25 minutes. The sulfenyl chloride solution formed is added dropwise over 30 minutes to a solution of 29.<*>+ g (0.2 mol) phthalimide and 27.0 g (0.27 mol) triethylamine in 120 ml of dimethylformamide. The reaction temperature is raised from approx. 25°C to approx. 39°C. The resulting mixture is allowed to cool. It is then diluted with 2 liters of ice-cold water. A white crystalline product common. The yield is quantitative. The melting point of N-(cyclohexylthio)-phthalimide is 89 - 91°C. After recrystallization of a sample of the product, the melting point is 93 - 9Lt-°C. Iodometric titration of the crystallized N-(cyclohexylthio)-phthalimide shows 99% purity. Analysis of the product shows 5.<1>+8$ nitrogen and 12.lh% sulphur. Calculated percentages for C-^H^NO^ are 5.36$ nitrogen and 12.26$ sulfur. The new cycloalkyl and alkyl compounds indicated above are prepared in a similar manner with similar results.

For å fremstille l,3-bis-(fenylthio)-2-imidazolinon avkjoles en opplosning av 8,6 g (0,1 mol) 2-imidazolinon, 25,0 g (0,25 mol) triethylamin og 200 ml dimethylformamid (DMF) til 0°C i en 500 ml tre-halset reaksjonskolbe forsynt med mekanisk rorer og termometer. To prepare 1,3-bis-(phenylthio)-2-imidazolinone, a solution of 8.6 g (0.1 mol) 2-imidazolinone, 25.0 g (0.25 mol) triethylamine and 200 ml dimethylformamide ( DMF) to 0°C in a 500 ml three-necked reaction flask fitted with a mechanical stirrer and thermometer.

Til denne opplosning tilsettes 28,8 g (0,2 mol) benzensulfenylklorid opplost i 77 ml carbontetraklorid dråpevis, idet temperaturen reguleres ved utvendig avkjoling under tilsetningen. Reaksjonsblandingen overfores til et h-liters begerglass,' og under kraftig omrbring tilsettes 3,0 liter isvann for å felle en olje. Det oljeaktige produkt opploses i ether og skilles fra vannfasen. Etherskiktet vaskes to ganger med 300 ml vann. Efter fraskillelse tilsettes vannfritt natriumsulfat til , etherskiktet for å fjerne gjenværende vann fra produktet. Opplosningen filtreres for å fjerne natriumsulfatet, og etheren får lov til å for-dampe hvorved man får et morkt brunt, fast stoff. Dette materiale omkrystalliseres fra alkohol hvorved man får et hvitt fast stoff som smelter ved 77 - 78°C. Analyse av produktet viser 8,96$ nitrogen og 21,1*4-$ svovel. Beregnede prosenter for C<->L^<H->Ll+N20S2 er 9,30$ nitrogen og 21,20$ svovel. Det infrarode spektrum er i samsvar med den foreslåtte struktur. De nye imidazolinoner angitt ovenfor, fremstilles på lignende måte med tilsvarende resultater. To this solution, 28.8 g (0.2 mol) of benzenesulphenyl chloride dissolved in 77 ml of carbon tetrachloride are added dropwise, the temperature being regulated by external cooling during the addition. The reaction mixture is transferred to a 1-liter beaker, and with vigorous stirring, 3.0 liters of ice water are added to precipitate an oil. The oily product is dissolved in ether and separated from the water phase. The ether layer is washed twice with 300 ml of water. After separation, anhydrous sodium sulfate is added to the ether layer to remove residual water from the product. The solution is filtered to remove the sodium sulfate, and the ether is allowed to evaporate, yielding a dark brown solid. This material is recrystallized from alcohol, whereby a white solid is obtained which melts at 77 - 78°C. Analysis of the product shows 8.96$ nitrogen and 21.1*4-$ sulphur. Calculated percentages for C<->L^<H->Ll+N20S2 are 9.30$ nitrogen and 21.20$ sulfur. The infrared spectrum is consistent with the proposed structure. The new imidazolinones indicated above are prepared in a similar manner with similar results.

For å fremstille N,N'-di-(fenylthio)-urea avkjoles en opplosning av 6,0 g (0,1 mol) urea og 25,0 g (0,25 mol) triethylamin i 200 ml DMF'til -10°C i en tre-halset 500 ml kolbe forsynt med mekanisk rorer og termometer. 28,8 g (0,2 mol) benzensulfenylklorid opplost i 77 ml carbontetraklorid tilsettes langsomt til denne opplosning. Under tilsetningen får temperaturen lov til å stige til 5°C, og en suspensjon av triethylaminsaltet dannes. Denne suspensjon overfores til et <*>f-liters begerglass, og produktet felles ved tilsetning av 3,0 liter isvann under kraftig omroring. Det brune faste stoff oppsamles ved filtrering, og efter omkrystallisasjon fra ethanol fåes et gulbrunt pulver som smelter ved 10<*>+ - 105°C. Analyse av produktet gir 9,58$ nitrogen og 23,13$ svovel. Beregnede prosenter for C-^H-^2^2^2 er 9,60$ nitrogen og 22,00$ svovel. Det infrarode spektrum stemmer overens med den foreslåtte struktur. De nye ureaer angitt ovenfor, fremstilles på lignende måte med tilsvarende resultater. To prepare N,N'-di-(phenylthio)-urea, a solution of 6.0 g (0.1 mol) urea and 25.0 g (0.25 mol) triethylamine in 200 ml DMF' is cooled to -10 °C in a three-necked 500 ml flask fitted with a mechanical stirrer and thermometer. 28.8 g (0.2 mol) of benzenesulphenyl chloride dissolved in 77 ml of carbon tetrachloride are slowly added to this solution. During the addition, the temperature is allowed to rise to 5°C, and a suspension of the triethylamine salt is formed. This suspension is transferred to a <*>f-litre beaker, and the product is precipitated by adding 3.0 liters of ice water with vigorous stirring. The brown solid is collected by filtration, and after recrystallization from ethanol a yellow-brown powder is obtained which melts at 10<*>+ - 105°C. Analysis of the product gives 9.58$ of nitrogen and 23.13$ of sulphur. Calculated percentages for C-^H-^2^2^2 are 9.60$ nitrogen and 22.00$ sulfur. The infrared spectrum agrees with the proposed structure. The new ureas indicated above are prepared in a similar manner with similar results.

N-(fenylthio)-maleimid fremstilles på folgende måte: N-(phenylthio)-maleimide is prepared as follows:

lk, k g benzensulfenylklorid tilsettes langsomt ved 15 - 20°C til en blanding av 9,8 g (0,1 mol) maleimid og 20,0 g (0,2 mol) triethylamin opplost i 200 ml torr benzen i en tre-halset 500 ml reaksjonskolbe forsynt med mekanisk rorer og termometer. Reaksjonsbland ingen får lov til å omrores inntil den når værelsetemperatur. Dette tar ca. 30 minutter. Triethylaminsaltet oppsamles ved filtrering, og kaken vaskes med 100 ml benzen. Filtratet inndampes under nedsatt trykk inntil produktet begynner å felles fra opplosningen. Suspensjonen overfores til et >+-liters begerglass, og 3,0 liter heptan tilsettes under kraftig omroring. Dette feller resten av produktet som oppsamles ved filtrering og vaskes med kold heptan. • Produktet får lov til å torre over natten ved værelsetemperatur. Der fåes 12,0 g produkt som, efter omkrystallisasjon fra ethanol, har et smeltepunkt på 81 - 82°C. Det infrarode spektrum stemmer overens med den foreslåtte struktur. De nye maleimider -angitt ovenfor, fremstilles på lignende måte med tilsvarende resultater. 1,000 g of benzenesulfenyl chloride is added slowly at 15 - 20°C to a mixture of 9.8 g (0.1 mol) maleimide and 20.0 g (0.2 mol) triethylamine dissolved in 200 ml dry benzene in a three-necked 500 ml reaction flask equipped with mechanical stirrer and thermometer. No reaction mixture is allowed to stir until it reaches room temperature. This takes approx. 30 minutes. The triethylamine salt is collected by filtration, and the cake is washed with 100 ml of benzene. The filtrate is evaporated under reduced pressure until the product begins to precipitate from the solution. The suspension is transferred to a >+ liter beaker, and 3.0 liters of heptane are added with vigorous stirring. This precipitates the rest of the product, which is collected by filtration and washed with cold heptane. • The product is allowed to dry overnight at room temperature. 12.0 g of product is obtained which, after recrystallization from ethanol, has a melting point of 81 - 82°C. The infrared spectrum agrees with the proposed structure. The new maleimides -indicated above, are prepared in a similar manner with similar results.

N- (f enylthio) -*4--cyclohexen-l,2-dicarboximid fremstilles N-(phenylthio)-*4-cyclohexene-1,2-dicarboximide is prepared

på folgende måte: lk, k g (0,1 mol) benzensulfenylklorid opploses i 30,0 g carbontetraklorid og tilsettes langsomt til en blanding av l<*>f,9 g (0,1 mol) *+-cyclohexen-l,2-dicarboximid -og 12,0 g (0,12 mol) triethylamin i 250 ml benzen ved 15°C i en 500.ml tre-halset kolbe forsynt med rorer og termometer. Temperaturen holdes på 15°C ved utvendig kjoling under tilsetning av benzensulfenylkloridet. Reaksjonsblandingen får så lov til å oppvarmes til værelsetemperatur, og triethylamin sal tet fjernes ved filtrering, vaskes med en liten mengde benzen, og 200 ml heptan tilsettes filtratet for å felle produktet. 3enzenen og heptanet fjernes under nedsatt trykk. Der fåes 25,2 g av et hvitt fast stoff som smelter ved 105 - 108°C. Produktet omkrystalliseres fra carbontetraklorid og har et smeltepunkt på 121 - 122,5°C. Analyse gir 5,29$ Ncg 11,69$ svovel. Beregnede prosenter for C-^H-^NO^ er 5,^2$ nitrogen og 12,39$ svovel. De nye U—cyclohexen-1,2-dicarbox-imider angitt ovenfor, fremstilles på lignende måte med tilsvarende resultater.. in the following manner: 1,000 g (0.1 mol) of benzenesulfenyl chloride is dissolved in 30.0 g of carbon tetrachloride and added slowly to a mixture of 1,9 g (0.1 mol) *+-cyclohexene-1,2 -dicarboximide -and 12.0 g (0.12 mol) of triethylamine in 250 ml of benzene at 15°C in a 500 ml three-necked flask fitted with stirrups and a thermometer. The temperature is kept at 15°C by external cooling while adding the benzenesulfenyl chloride. The reaction mixture is then allowed to warm to room temperature, and the triethylamine salt is removed by filtration, washed with a small amount of benzene, and 200 ml of heptane is added to the filtrate to precipitate the product. The 3-ene and the heptane are removed under reduced pressure. 25.2 g of a white solid is obtained which melts at 105 - 108°C. The product is recrystallized from carbon tetrachloride and has a melting point of 121 - 122.5°C. Analysis gives 5.29$ Ncg 11.69$ Sulphur. Calculated percentages for C-^H-^NO^ are 5.^2$ nitrogen and 12.39$ sulfur. The new U-cyclohexene-1,2-dicarbox-imides indicated above are prepared in a similar manner with similar results.

De nye 5,5-dimethylhydantoiner og 5,6,7,7-hexaklorbi-cyclo-[2.2.l]-hept-5-en-2,3-dicarboximider angitt ovenfor, fremstilles på lignende måte som N-(fenylthio)-<*>f-cyclohexen-l,2-dicarboximid med' tilsvarende resultater. The new 5,5-dimethylhydantoins and 5,6,7,7-hexachlorobi-cyclo-[2.2.1]-hept-5-ene-2,3-dicarboximides indicated above are prepared in a similar manner to N-(phenylthio) -<*>f-cyclohexene-1,2-dicarboximide with' similar results.

l,3-bis-(fenylthio)-2-benzimidazolinon fremstilles på folgende måte: 28,8 g (0,2 mol) benzensulfenylklorid opplost i 31,2 g carbontetraklorid tilsettes i en porsjon til en godt omrort opplosning av 13g (0,1 mol) 2-hydroxybenzimidazol opplost i 250 ml DMF avkjolt til 0°C. Temperaturen holdes mellom 0 og 5°C ved avkjoling med et utvendig aceton/isbad. 25,0 g (0,25 mol) triethylamin tilsettes langsomt til den dannede opplosning i lopet av 15 minutter. Efter tilsetning av alt amin overfores den erholdte rbdlige suspensjon til et 1,3-bis-(phenylthio)-2-benzimidazolinone is prepared in the following way: 28.8 g (0.2 mol) of benzenesulphenyl chloride dissolved in 31.2 g of carbon tetrachloride is added in one portion to a well-stirred solution of 13 g (0. 1 mol) of 2-hydroxybenzimidazole dissolved in 250 ml of DMF cooled to 0°C. The temperature is kept between 0 and 5°C by cooling with an external acetone/ice bath. 25.0 g (0.25 mol) of triethylamine is added slowly to the resulting solution over the course of 15 minutes. After the addition of all the amine, the obtained soluble suspension is transferred to a

*f-liters begerglass under kraftig roring, og reaksjonen avkjoles ved tilsetning av 3 liter isvann. Aminsaltet opploses', og en tykk viskos olje erholdes. Efter dekantering av vannet fra oljeskiktet storkner sistnevnte til et rodt fast stoff. Dette materiale omkrystalliseres fra ethylacetat hvorved man får 15,0 g av et hvitt fast stoff med smeltepunkt 115 - 117°C. Det infrarode spektrum stemmer overens med den foreslåtte struktur. Analyse av produktet gir 7,98$ nitrogen og .18,12$ svovel. Beregnede prosenter for C^H^^OSg er 7,98$ nitrogen og 18,39$ svovel. *f liter beaker under vigorous stirring, and the reaction is cooled by adding 3 liters of ice water. The amine salt is dissolved, and a thick viscous oil is obtained. After decanting the water from the oil layer, the latter solidifies into a red solid. This material is recrystallized from ethyl acetate whereby 15.0 g of a white solid with a melting point of 115 - 117°C is obtained. The infrared spectrum agrees with the proposed structure. Analysis of the product gives 7.98$ nitrogen and .18.12$ sulphur. Calculated percentages for C^H^^OSg are 7.98$ nitrogen and 18.39$ sulfur.

Reaksjonsproduktet av 2-hydroxybenzimidazol med sulfenyl-kloridet fra blandede thiocresoler fremstilles på samme måte som 1,3-bis-(fenylthio)-2-benzimidazolinon. Det erholdte halvfaste stoff omkrystalliseres fra ethanol hvorved man får 15,0 g av et kremfarvet fast stoff som smelter fra 115,5 - 125°C. Det infrarode spektrum stemmer overens med den foreslåtte struktur. Analyse av dette produkt gir 6,9>+$ nitrogen og 16, h0% svovel. Beregnede prosenter for <C>21H18N20S2 er 7'1+lf$ nitrogen og 16,97$ svovel. 1,3-bis-( klorf enylthio)-2-benzimidazolinon, 1,3-bis-(benzylthio)-2-benzimidazolinon, 1,3-bis-(nitrofenylthio)-2-benzimidazolinon, 1,3-bis-(t-butylthio)-2-benzimidazolinon og l,3-bis-(m-tolylthio)-2-benzimidazolinon fremstilles på samme måte som 1,3-bis-(fenylthio)-2-benzimidazolinon beskrevet ovenfor. The reaction product of 2-hydroxybenzimidazole with the sulfenyl chloride from mixed thiocresols is prepared in the same way as 1,3-bis-(phenylthio)-2-benzimidazolinone. The semi-solid obtained is recrystallized from ethanol, whereby 15.0 g of a cream-colored solid is obtained which melts from 115.5 - 125°C. The infrared spectrum agrees with the proposed structure. Analysis of this product gives 6.9>+$ nitrogen and 16.h0% sulphur. Calculated percentages for <C>21H18N20S2 are 7'1+lf$ nitrogen and 16.97$ sulfur. 1,3-bis-(chlorophenylthio)-2-benzimidazolinone, 1,3-bis-(benzylthio)-2-benzimidazolinone, 1,3-bis-(nitrophenylthio)-2-benzimidazolinone, 1,3-bis-( t-butylthio)-2-benzimidazolinone and 1,3-bis-(m-tolylthio)-2-benzimidazolinone are prepared in the same way as 1,3-bis-(phenylthio)-2-benzimidazolinone described above.

N-(fenylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid fremstilles på folgende måte: Til en blanding av 16,3 g (0,1 mol) av imidet av endisk anhydrid og 11,1 g (0,11 mol) triethylamin i 300 ml benzen tilsettes dråpevis under omroring 0,105 mol benzensulfenylklorid som en carbontetrakloridopplosning i lopet av 30 minutter. Temperaturen på blandingen holdes ved 30°C under tilsetningen. Reak-sjon sbland ingen omrores i ytterligere 10 minutter efterat sulfonyl-kloridopplosningen er tilsatt. Reaksjonsblandingen filtreres for å fjerne triethylamin-hydroklorid, og filtratet tilsettes til 3,5 1 av-' kjolt heptan. 17,6 g hvitt fast stoff erholdes. En prove av N-fenylthio-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximidet smelter ved 123 - 125°C. Analyse gir 5,37$ nitrogen og 11,09$ svovel. Beregnede prosenter for C-L^H1^N02S er 5,16$ nitrogen og 11,80$ svovel. N-fenyl-thionaf thalimid , N-fenylthio-3 ,*+, 5,6-tetraklorf thalimid , N-f enylthio-3 ,*+, 5,6-tetrabromfthalimid og lignende forbindelser fremstilles på lignende måte som N-(fenylthio)-bicyclo[2.2.l]-hept-5-en-2,3-dicarboximid med tilsvarende resultater. N-(phenylthio)-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide is prepared as follows: To a mixture of 16.3 g (0.1 mol) of the imide of endic anhydride and 11 .1 g (0.11 mol) of triethylamine in 300 ml of benzene is added dropwise with stirring to 0.105 mol of benzene sulphenyl chloride as a carbon tetrachloride solution over the course of 30 minutes. The temperature of the mixture is kept at 30°C during the addition. The reaction mixture is stirred for a further 10 minutes after the sulfonyl chloride solution has been added. The reaction mixture is filtered to remove triethylamine hydrochloride, and the filtrate is added to 3.5 L of cooled heptane. 17.6 g of white solid is obtained. A sample of the N-phenylthio-bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide melts at 123 - 125°C. Analysis gives 5.37$ nitrogen and 11.09$ sulphur. Calculated percentages for C-L^H1^N02S are 5.16$ nitrogen and 11.80$ sulfur. N-phenyl-thionaphthalimide, N-phenylthio-3,*+, 5,6-tetrachlorophthalimide, N-phenylthio-3,*+, 5,6-tetrabromophthalimide and similar compounds are prepared in a similar manner to N-(phenylthio)- bicyclo[2.2.1]-hept-5-ene-2,3-dicarboximide with similar results.

N,N'-bi s-(fenylthio)-1,2,3,^-benzentetracarboxylsyre-1,2: h,5-diimid fremstilles på folgende måte: ■ Til en opplosning av 21,6 g (9,1 mol) pyromellitsyre-bis-dicarboximid og 22,2 g (0,22 mol) triethylamin i 300 ml dimethylformamid, tilsettes dråpevis under omroring 0,21 mol benzensulfenylklorid som en carbontetrakloridopplosning. Temperaturen holdes ved 20 - 30°C. 3,0 1 isvann tilsettes til den erholdte suspensjon for å felle produktet. N,N'-bis-(fenylthio)-1,2,*+, 5-benzentetracarboxylsyre-l ,2:*f, 5-diimidproduktet er et gult fast stoff. En prove av produktet smelter ved 260°c. Analyse av produktet'gir 6,05$ nitrogen og l<1>+,60$ svovel. Beregnede prosenter for <c>22Hl2N20LfS2 er ^^Qfo nitr°gen og 1*4-,82$ svovel. N,N' -bis-(ar-tolylthio)-1, 2, h, 5-benzentetracarboxylsyre-l,2:1+, 5-diimid , og lignende forbindelser fremstilles på lignende måte med tilsvarende resultater. N,N'-bi s-(phenylthio)-1,2,3,^-benzenetetracarboxylic acid-1,2:h,5-diimide is prepared as follows: ■ To a solution of 21.6 g (9.1 mol ) pyromellitic acid bis-dicarboximide and 22.2 g (0.22 mol) of triethylamine in 300 ml of dimethylformamide, 0.21 mol of benzenesulfenyl chloride as a carbon tetrachloride solution are added dropwise with stirring. The temperature is kept at 20 - 30°C. 3.0 1 of ice water is added to the resulting suspension to precipitate the product. The N,N'-bis-(phenylthio)-1,2,*+,5-benzenetetracarboxylic acid-1,2:*f,5-diimide product is a yellow solid. A sample of the product melts at 260°c. Analysis of the product'gives 6.05$ nitrogen and 1<1>+.60$ sulphur. Calculated percentages for <c>22Hl2N20LfS2 are ^^Qfo nitrogen and 1*4-.82$ sulfur. N,N'-bis-(ar-tolylthio)-1,2,h,5-benzenetetracarboxylic acid-1,2:1+,5-diimide, and similar compounds are prepared in a similar manner with similar results.

De folgende tabeller belyser anvendelsen av forbindelsene ifolge oppfinnelsen mere detaljert. For alle gummimaterialer som er provet og beskrevet nedenfor som eksempler, ble.Mooney-anvulkaniser-ingstider ved 121°C og 135°C bestemt ved hjelp av et Mooney-plasto-meter. Tiden i minutter (t^) som kreves for at Mooney-avlesningen skal stige fem points over den minimale viskositet, noteres. Lengre tider er tegn på aktiviteten av inhibitoren. Lengre tider ved Mooney-anvulkaniseringsproven er bnskelig fordi dette indikerer storre produk-sjonssikkerhet. Prosentokninger i anvulkaniseringsforsinkelsen beregnes ved å dividere Mooney-anvulkaniseringstiden av materialet inneholdende inhibitoren mot for tidlig vulkanisering med Mooney-anvulkaniseringstiden for kontrollmaterialet, multiplisere med 100 og trekke fra 100. Disse okninger viser den prosentvise forbedring i anvulkani-seringsforsinkelse i forhold til kontrollmaterialet som ikke inne-holder noen inhibitor. Dessuten beregnes herdehastigheter fra den tid som kreves for å herde materialene ved lMt°C og i noen tilfeller 153°C. Herdeegenskapene bestemmes ved hjelp av "Monsanto Oscillating Dise Rheometer" beskrevet av Decker, Wise og Guerry i Rubber World, desember 1962, side 68. Fra rheometerdata er RMT den maksimale modu-lusvridning i rheometerenheter, t^ eller er tiden i minutter for en okning på henholdsvis tre og to rheometerenheter, over den minimale avlesning, og t^Q er åen- tid som kreves for å få en modulus på 90$ The following tables illustrate the use of the compounds according to the invention in more detail. For all rubber materials tested and described below as examples, Mooney vulcanization times at 121°C and 135°C were determined using a Mooney plastometer. The time in minutes (t^) required for the Mooney reading to rise five points above the minimum viscosity is noted. Longer times are indicative of the activity of the inhibitor. Longer times in the Mooney vulcanization test are desirable because this indicates greater production reliability. Percentage increases in vulcanization delay are calculated by dividing the Mooney vulcanization time of the material containing the inhibitor against premature vulcanization by the Mooney vulcanization time of the control material, multiplying by 100 and subtracting 100. These increases show the percentage improvement in vulcanization delay compared to the control material which does not contain -holds some inhibitor. Also, cure rates are calculated from the time required to cure the materials at 1Mt°C and in some cases 153°C. Curing properties are determined using the "Monsanto Oscillating Dise Rheometer" described by Decker, Wise and Guerry in Rubber World, December 1962, page 68. From the rheometer data, RMT is the maximum modulus distortion in rheometer units, t^ or is the time in minutes for an increase on three and two rheometer units, respectively, above the minimum reading, and t^Q is the time required to obtain a modulus of 90$

av det maksimale. of the maximum.

Varemerkene på noen forbindelser som anvendes ved provene, er "Santocure MOR", "Santoflex 77", "Santocure NS", "DPG", "Thiofide" og "Vultrol". "Santocure MOR" er akseleratoren 2-(morfolinothio)-benzothiazol. "Santoflex 77" er anti-nedbrytningsmidlet N,N'-bis-(1,^-dimethylpentyl)-p-fenylendiamin. "Santocure NS" er akseleratoren 'N-tert-butyl-2-benzothiazolsulfenamid. "DPG" er en akselerator som angies å være difenylguanidin. "Thiofide" er en akselerator som angies å være benzothiazyldisulfid. "Vultrol" er en vulkanisasjons-sinker som angies å være N-nitrosodifenylamin. The trademarks of some compounds used in the sample are "Santocure MOR", "Santoflex 77", "Santocure NS", "DPG", "Thiofide" and "Vultrol". "Santocure MOR" is the accelerator 2-(morpholinothio)-benzothiazole. "Santoflex 77" is the anti-degradant N,N'-bis-(1,^-dimethylpentyl)-p-phenylenediamine. "Santocure NS" is the accelerator 'N-tert-butyl-2-benzothiazolesulfenamide. "DPG" is an accelerator stated to be diphenylguanidine. "Thiofide" is an accelerator stated to be benzothiazyl disulfide. "Vultrol" is a vulcanization sink stated to be N-nitrosodiphenylamine.

Tabell I illustrerer de utmerkede resultater som fåes ved anvendelse av N-(cyclohexylthio)-fthalimid som en inhibitor mot for tidlig vulkanisering i materialer av naturgummi, olje-modifisert styren-butadiengummi og et naturgummi/cis->+-polybutadienblandings-dekkmateriale. Naturgummi-dekkraaterialet besto av folgende: Table I illustrates the excellent results obtained using N-(cyclohexylthio)-phthalimide as an inhibitor against premature vulcanization in materials of natural rubber, oil-modified styrene-butadiene rubber, and a natural rubber/cis->+-polybutadiene blend tire material. The natural rubber cover material consisted of the following:

•Det oljemodifiserte styren-butadiengummi-dekkmaterialet besto av folgende: •The oil-modified styrene-butadiene rubber tire material consisted of the following:

Naturgummi/cis-^-polybutadien-blanding-dekkmaterialet besto av folgende:'The natural rubber/cis-^-polybutadiene mixture tire material consisted of the following:

l,3-bis-(cyclohexylthio)-2-benzimidazolinon viser en M-ll$ okning i anvulkaniseringsutsettelsen i forhold til naturgummi-materiale inneholdende "Santocure MOR" alene. Disse resultater er 1,3-bis-(cyclohexylthio)-2-benzimidazolinone shows a M-11$ increase in vulcanization delay compared to natural rubber material containing "Santocure MOR" alone. These results are

beregnet fra Mooney-anvulkaniseringstiden, t^, ved 121°C. calculated from the Mooney vulcanization time, t^, at 121°C.

Tabell II viser resultatene av anvendelsen av N-(benzylthio)-fthalimid og N-(n-dodecylthio)-fthalimid i oljemodifisert styrenbutadiengummi. Gummimaterialet er det samme som det oljemodifiserte styren-butadien-gummimateriale beskrevet i tabell I ovenfor. Table II shows the results of the use of N-(benzylthio)-phthalimide and N-(n-dodecylthio)-phthalimide in oil modified styrene butadiene rubber. The rubber material is the same as the oil-modified styrene-butadiene rubber material described in Table I above.

Tabell III viser resultatene av f?rsok med kjent N-(t-butylthio)-fthalimid, N,N'-di-(fenylthio)-urea, 1,3-bis-(fenylthio)-2-imidazolinon og N-(fenylthio)-maleimid som inhibitorer for for tidlig vulkanisering i gummi. N-(fenylthio)-maleimid ga 17<*>+$ okning i anvulkaniseringsutsettelsen i forhold til kontrollproven. Gummiblandingen i forsoket var en A-6-grunncharge. En A-6-grunncharge er sammen-satt som folger: Table III shows the results of experiments with known N-(t-butylthio)-phthalimide, N,N'-di-(phenylthio)-urea, 1,3-bis-(phenylthio)-2-imidazolinone and N-( phenylthio)-maleimide as inhibitors of premature vulcanization in rubber. N-(phenylthio)-maleimide gave a 17<*>+$ increase in vulcanization delay compared to the control sample. The rubber compound in the trial was an A-6 base charge. An A-6 basic charge is composed as follows:

Alle materialer inneholdt tre deler "Santoflex 77", 0,5 deler "Santocure MOR" og 2,5 deler svovel. All materials contained three parts "Santoflex 77", 0.5 parts "Santocure MOR" and 2.5 parts sulphur.

Lignende resultater ble erholdt når akseleratoren "Santocure NS" og anti-nedbrytningsmidlet, N-l,3-dimethylbutyl-N'-fenyl-p-fenylendiamin eller en blanding av dette anti-nedbrytningsmiddel og "santoflex 77" ble anvendt. Similar results were obtained when the accelerator "Santocure NS" and the anti-degradant, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine or a mixture of this anti-degradant and "santoflex 77" were used.

Tabell IV viser N-(fenylthio)-maleimid som en anvulkaniser-ingsinhibitor i en 3-5-grunncharge av styren-butadiengummi. Table IV shows N-(phenylthio)-maleimide as a vulcanization inhibitor in a 3-5 base charge of styrene-butadiene rubber.

Tabell V viser de nyttige egenskaper mot for tidlig vulkanisering i en A-6-gummigrunnblanding av N-(isopropylthio)-fthalimid og N-(n-butylthio)-fthalimid. Materialene inneholdt 2,0 deler Table V shows the useful properties against premature vulcanization in an A-6 rubber base mixture of N-(isopropylthio)-phthalimide and N-(n-butylthio)-phthalimide. The materials contained 2.0 parts

N-l,3-dimethylbutyl-N'-fenyl-p-fenylendiamin, 0,5 deler "Santocure MOR" og 2,5 deler svovel. N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, 0.5 parts "Santocure MOR" and 2.5 parts sulfur.

I lignende prover viser N-(sek-butylthio)-nafthalimid en 212$ okning i anvulkaniseringsutsettelse, og 1,3-bis-(n-dodecylthio)-benzimidazolinon viser en 52$ okning i anvulkaniseringsutsettelse. In similar samples, N-(sec-butylthio)-naphthalimide shows a 212% increase in vulcanization retardation, and 1,3-bis-(n-dodecylthio)-benzimidazolinone shows a 52% increase in vulcanization retardation.

I en A-6-grunncharge inneholdende 0,5 deler "Santocure MOR", 2,5 deler svovel og 3 deler "Santoflex 77", viser den kjente forbindelse N-(fenylthio)-fthalimid en 108$ okning i anvulkaniseringsutsettelse. N-(fenylthio)-fthalimid er vanskelig å dispergere i gummi, antagelig på grunn av sitt hoye smeltepunkt (163 - 165°C). In an A-6 base charge containing 0.5 parts "Santocure MOR", 2.5 parts sulfur and 3 parts "Santoflex 77", the known compound N-(phenylthio)-phthalimide shows a 108 increase in vulcanization delay. N-(phenylthio)-phthalimide is difficult to disperse in rubber, presumably because of its high melting point (163 - 165°C).

l,3-bis-(fenylthio)-2-benzimidazolinon er en utmerket inhibitor av for tidlig vulkanisering. I en A-l-grunncharge oker denne forbindelse anvulkaniseringsutsettelsen 170$ som vist i tabell VI. 1,3-bis-(phenylthio)-2-benzimidazolinone is an excellent inhibitor of premature vulcanization. In an A-1 basic charge, this increases the vulcanization delay by 170$ as shown in Table VI.

En A-l-grunncharge består av: An A-l basic charge consists of:

Mooney- anvulkanisering ved 121°C Rheometer ved li+ i+ °C Mooney vulcanization at 121°C Rheometer at li+ i+ °C

Tilsvarende resultater fåes ved anvendelse av akseleratoren "Santocure NS". Corresponding results are obtained by using the accelerator "Santocure NS".

l,3-bis-(fenylthio)-2-benzimidazolinon er en inhibitor 1,3-bis-(phenylthio)-2-benzimidazolinone is an inhibitor

av for tidlig vulkanisering i cis-^-polybutadien som vist i tabell VII. 1,3-bis-(f enylthio)-2-benzimidazolinon viser en h^% okning i anvulkaniseringsutsettelse og N-(fenylthio)-succinimid viser en 31$ okning. Grunnchargen for tabell VII besto av: of premature vulcanization in cis-^-polybutadiene as shown in Table VII. 1,3-bis-(phenylthio)-2-benzimidazolinone shows a h^% increase in vulcanization delay and N-(phenylthio)-succinimide shows a 31% increase. The basic charge for table VII consisted of:

Mooney- anvulkanisering ved 135°C Rheometer ved 153°C l,3-bis-(fenylthio)-2-benzimidazolinon er en inhibitor av for tidlig vulkanisering i ethylen-propylen-terpolymere som vist i tabell VIII. Ethylen-propylen-terpolymer er det godtatte og vanlig anvendte navn på det polymeriserte produkt fra polymerisasjonen av ethylen, propylen og en liten mengde av et ikke-konjugert dien. Ter-polymeren anvendt i tabell VIII er kjent kommersielt som "Nordel 1070", l,3-bis-(fenylthio)-2-benzimidazolinon viser en 80$ okning når det anvendes som inhibitorer av for tidlig vulkanisering i ethylen-propylen-terpolymere. Grunnchargen i tabell VIII består av: Mooney vulcanization at 135°C Rheometer at 153°C 1,3-bis-(phenylthio)-2-benzimidazolinone is an inhibitor of premature vulcanization in ethylene-propylene terpolymers as shown in Table VIII. Ethylene-propylene terpolymer is the accepted and commonly used name for the polymerized product from the polymerization of ethylene, propylene and a small amount of a non-conjugated diene. The terpolymer used in Table VIII is known commercially as "Nordel 1070", 1,3-bis-(phenylthio)-2-benzimidazolinone shows an 80% increase when used as inhibitors of premature vulcanization in ethylene-propylene terpolymers. The basic charge in table VIII consists of:

Mooney- anvulkanisering ved 135°C Mooney anvulcanization at 135°C

$ okning i anvulkaniserings- $ increase in vulcanization

utsettelse - 28 80 postponement - 28 80

Rheometer ved 160°C Rheometer at 160°C

1,3-bis-(o-nitrofenylthio)-2-benzimidazolinon viser en 57$ okning i anvulkaniseringsutsettelse i en A-6-grunncharge. Resultatene fremgår av tabell IX. Mooney- anvulkanisering ved 121°CRheometer ved l¥+ °C 1,3-bis-(o-nitrophenylthio)-2-benzimidazolinone shows a 57% increase in vulcanization delay in an A-6 base charge. The results appear in Table IX. Mooney vulcanization at 121°CRheometer at l¥+ °C

Tilsvarende resultater fåes med forbindelsen l,3-bis-(klorfenylthio)-2-benzimidazolinon. Similar results are obtained with the compound 1,3-bis-(chlorophenylthio)-2-benzimidazolinone.

En ortho-, meta- og para-blanding av 1,3-bis-(tolylthio)-2-benzimidazolinon gir en 163$ okning i anvulkaniseringsutsettelse i forhold til kontrollproven, og l,3-bis-(m-tolylthio)-2-bénzimidåzoli-non oker utsettelsen lh2%. Disse data fremgår av tabell X. An ortho-, meta- and para-mixture of 1,3-bis-(tolylthio)-2-benzimidazolinone gives a 163$ increase in vulcanization delay compared to the control sample, and 1,3-bis-(m-tolylthio)-2 -benzimidazoli-non increases the delay lh2%. These data appear in table X.

Mooney- anvulkanisering ved 121°C Rheometer ved lM* °C Mooney vulcanization at 121°C Rheometer at 1M* °C

Ortho-, me ta- og para-blandingen av 1., 3-.M s-( tolylthio)-2-benzimidazolinon blé provet i en B-5-grunncharge av styren-butadiengummi- En 113$ okning i anvulkaniseringsutsettelse i forhold til kontrollproven ble erholdt med en akseleratorblanding av "DPG" og "Thiofide" og inhibitoren-. Inhibitoren gir en 80$ okning i anvulkaniseringsutsettelse ved anvendelse med "Santocure NS" _I styren-butadiengummi. Disse resultater fremgår av tabell XI. Mooney- anvulkanisering ved 135° C The ortho-, meta- and para-mixture of 1., 3-.M s-(tolylthio)-2-benzimidazolinone was tested in a B-5 base charge of styrene-butadiene rubber- A 113$ increase in vulcanization delay compared to the control sample was obtained with an accelerator mixture of "DPG" and "Thiofide" and the inhibitor-. The inhibitor provides an 80$ increase in vulcanization delay when used with "Santocure NS"_In styrene-butadiene rubber. These results appear in table XI. Mooney anvulcanization at 135°C

Rheometer ved T53°- C- •.. Rheometer at T53°- C- •..

Tilsvarende resultater til dem i ovenstående tabeller som viser anvendbarheten, fåes med forbindelsene ifolge oppfinnelsen som ikke er illustrert. Corresponding results to those in the above tables which show the applicability, are obtained with the compounds according to the invention which are not illustrated.

Konsentrasjonsundersokelser viser at forbindelsene ifolge oppfinnelsen er virksomme inhibitorer i gummi ved konsentrasjoner på 0,25 til 5,0 deler pr. 100. Konsentrasjonsundersokelser viser at forbindelsene ifolge oppfinnelsen er virksomme inhibitorer i gummi ved konsentrasjoner på 0,25 til 5,0 deler pr. 100. Konsentrasjoner fra 0,25 til 3,0 deler pr. 100 foretrekkes. Concentration studies show that the compounds according to the invention are effective inhibitors in rubber at concentrations of 0.25 to 5.0 parts per 100. Concentration studies show that the compounds according to the invention are effective inhibitors in rubber at concentrations of 0.25 to 5.0 parts per 100. Concentrations from 0.25 to 3.0 parts per 100 is preferred.

Claims

1. Chemical compounds for use as vulcanization inhibitors, characterized in that they have the general formula where a) R is hydrogen, is N-(arylthio)-carbamoyl, N-(halo-genarylthio)-carbamoyl, N-(aralkylthio)-carbamoyl, N-(alkarylthio)- carbamoyl, N-(alkylthio)-carbamoyl or N-(cycloalkylthio)-carba- Moyle, 2 R is aryl, haloaryl, aralkyl, alkaryl, cycloalkyl or alkyl, or b) R and R' with the carbonyl group and the N atom are 3-arylthio-2-benzimidazolinon-1-yl, 3-cycloalkylthio-2-benzimidazolinon-1-yl, 2-benzimidazolinon-1- yl, 3-aralkylthio-2-benzimidazolinon-1-yl, 3-nitroar-ylthio-2-benzimidazolinon-1-yl, 3-halogenarylthio-2-benzimidazolin- on-l-yl, 3-alkarylthio-2-benzimidazolinon-1-yl, 3-(alkylthio)-2-benzimidazolinon-1-yl, 2-imidazolinon-1-yl, 3-cycloalkylthio-2-imidazolinone- 1-yl, 3-arylthio-2-imidazolinon-1-yl, 3-halogenarylthio-2-imidazolinon-1-yl, 3-aralkylthio-2-imidazolinon-1-yl, 3-alkarylthio-2- imidazolinon-1-yl, 3-(alkylthio)-2-iaridazolinon-1-yl, 1-maleimidyl, 5,5-dimethyl-3-hydantoinyl, 5,5-diphenyl-3-hydantoinyl, <1>+-cyclohexene -1,2- dicarboximid-1-yl, 1,^,5,6,7,7-hexachlorobicyclo[2.2.1]-hept-5-en-

2.3- dicarboximid-l-yl, bicyclo[2.2.l]-hept-5-ene-2,3-dicarboximid-1-yl, alkylbicyclo[2.2.l]-hept-5-ene-2,3-dicarboximid- 1-yl, N-(arylthio)-

1,2,5-benzenetetracarboxylic acid-1,2:*f,5-diimid-N'-yl,N-(aralkylthio)-1,2,^,5-benzenetetracarboxylic acid-1,2:k,5-diimid- N,-yl, N-(haloarylthio)-1,2,h,5-benzenetetracarboxylic acid-1,2:•+,5-diimid-N'-yl, N- . (ni troarylthio )-1 ,2 j^f,5-benzenetetracarboxylic acid-1 ,2: *f,5-diimide-N' - yl, N-(alkylthio)-1,32,5-benzenetetracarboxylic acid-1,2:h,5-diimid-N'-yl,N-(cycloalkylthio)-1,2,h,5-benzenetetracarboxylic acid-1,2: *f,5-diimid-N1-yl or N-(alkarylthio)-1,2,h,5-benzenetetracarboxylic acid- 1, 2:h,5-diimid-N'-yl, and R 2 is aryl, aralkyl, alkaryl, haloaryl, nitroaryl, cycloalkyl or alkyl, wherein R and R' with the carbonyl group and the N atom can also be 1-fthalimidyl, 1-naphthalimidyl or 1-(3,*f,5,6-tetrahalogenphthalimidyl) when R is aralkyl, cycloalkyl or alkyl. 2. Compound according to claim 1, characterized in that it is N,N'-di-(phenylthio)-urea with the formula: 3. Compound according to claim 1, characterized in that it is 1,3-bis-(phenylthio)-2 -benzimidazolinone with the formula: <*>f. Compound according to claim 1, characterized in that it is 1,3-bis-(phenylthio)-2-imidazolinone with the formula: 5. Compound according to claim 1, characterized in that it is N-(phenylthio)-maleimide with the formula: 6. Compound according to claim 1, characterized in that it is N-(cyclohexylthio)-phthalimide with the formula: 7. Compound according to claim 1, characterized in that it is N-(isopropylthio)-phthalimide with the formula: 8. Compound according to claim 1, characterized in that it is N-(n-butylthio)-phthalimide with the formula: Cited publications: