Patent GB-1463963-A (GB)
Title: Azoalkane free radical initiators
IPC: C07C239/00
Filed: 1975-03-21
Abstract: 1463963 Azo-free radical initiators PENNWALT CORP 21 March 1975 [21 March 1974] 11949/75 Heading C3P [Also in Division C2] Unsaturated compounds may be polymerized in the presence of a free radical initiator of the formula where n is 1 or 2; R<SP>1</SP>, when taken separately, is a C 1 -C 12  alkyl, C 3 -C 12  cycloalkyl or C 7 -C 12  aralkyl (including arylcycloalkyl) group; or any such group containing a substituent group selected from C 1 -C 5  alkoxy, aryloxy, hydroxy, carboxy provided that X is not OH, C 1 -C 5  alkoxycarbonyl, alkenyl, alkynyl, cycloalkenyl, cycloalkynyl, cycloalkoxy, cycloalkoxycarbonyl, cycloalkylcarbonyl, aryloxycarbonyl, halogen, C 1 -C 5  alkylcarbonyloxy, arylcarbonyloxy, cyano and amino; R<SP>11</SP>, when taken separately is a group as defined for R<SP>1</SP>; or an aryl, including substituted aryl, group of 6-14 carbon atoms; R<SP>1</SP> and R<SP>11</SP>, when taken together, jointly with the carbon atom to which they are attached represent a cycloalkyl group of from 3-12 carbon atoms optionally containing a ketonic oxygen substituent on a ring carbon atom; R 1 , when taken separately, is a C 1 -C 8  alkyl, C 3 -C 12  cycloalkyl, aralkyl, including arylcycloalkyl, group of from 7-12 carbon atoms, or a 5- or 6-membered heterocyclic group in which the hetero atom is oxygen, sulphur or nitrogen; or any such group containing a substituent group as defined above for R<SP>1</SP>; R 2 , when taken separately, is a group as defined for R 1 , or an aryl, including substituted aryl, group of from 6-14 carbon atoms; R 1  and R 2 , when taken together, jointly with the carbon atom to which they are attached represent a cycloalkyl group of from 4-12 carbon atoms, optionally containing a ketonic oxygen atom on a ring carbon atom; X is selected from -Cl, -Br, -CN, -C(=O)NH 2 , X<SP>1</SP> is oxygen or sulphur; R 3  is an C 1 -C 12  alkyl, C 3 -C 12  cycloalkyl, C 7 -C 12  aralkyl, including arylcycloalkyl, group or any such group containing substituent as defined for R<SP>1</SP>, or C 6 -C 14  aryl, including substituted aryl; R 4  is hydrogen or a group as defined for R 3 ; R 5  is C 4 -C 12  tertiary alkyl or C 9 -C 12  tertiary phenalkyl; R 6  is C 1 -C 12  alkyl, C 3 -C 12  cycloalkyl or C 6 -C 14  aryl optionally containing a substituent group as defined under R<SP>1</SP> or a substituent group selected from C 1 -C 5  alkyl-  amino, di-(C 1 -C 5 )alkylamino, C 1 -C 5  alkylcarbonyl, arylcarbonyl, alkylthio and arylthio; R 7  is C 2 -C 10  alkylene or alkenylene, or C 6 -C 14  arylene, including substituted arylene; R 8  and R 9 , when taken separately, are each hydrogen, C 1 -C 8  alkyl, C 3 -C 12  cycloalkyl, C 7 -C 12  aralkyl, or such a group containing a substituent as defined under R<SP>1</SP> or a substituent selected from carbamoyl, N-C 1 -C 5  alkylcarbamoyl, N,N - di - (C 1 -C 5 )alkylcarbamoyl, N - phenylcarbamoyl and N,N-diphenylcarbamoyl; or C 6 -C 14  aryl, including substituted aryl; R<SP>1</SP> 8  and R<SP>1</SP> 9 , when taken separately are each organic groups as defined for R 8  and R 9 ; R 8  and R 9  or R<SP>1</SP> 8  and R<SP>1</SP> 9 , when taken together in pairs, are C 3 -C 11  alkylene; R 10  is primary or secondary alkyl of 1-12 carbon atoms or C 3 -C 12  cycloalkyl, or such a group containing C 1 -C 5  alkoxy, hydroxy, halo or cyano substituents; R 11  is C 2 -C 12  alkylene, C 3 -C 12  cycloalkylene, C 7 -C 12  aralkylene or C 6 -C 14  arylene; R 12  is C 1 -C 6  alkyl; R 13  is C 1 -C 9  alkylene, C 2 -C 10  alkenylene or alkynylene, C 3 -C 9  cycloalkylene, C 7 -C 9  phenalkylene or C 6 -C 10  arylene; R 14  is C 1 -C 20  alkylene, C 3 -C 12  cycloalkylene, C 7 - C 20  aralkylene, or C 4 -C 20  cycloalkylalkylene, or such a group optionally containing one or more -non-adjacent, non-terminal atoms or groups selected from -O-, -S-, -OC(O)-, -NHC(O)-, -OC(S)O-, and -OC(S)S-; or a C 6 -C 14  arylene, including substituted arylene, group; R 15  is C 6 -C 10  aryl, optionally containing C 1 -C 5  alkyl substituents; and R 16  is hydrogen, C 4 -C 8  tertiary alkyl, C 9 -C 12  tertiary aralkyl or C 6 -C 14  aryl, the latter optionally containing C 1 -C 5  alkyl or halo substituents. Examples describe the curing of an unsaturated polyester-styrene resin, the polymerization of styrene and of vinyl chloride and the foaming of an saturated polyester resin.