Polymerization of ethylenically unsaturated monomers employing secondary-aliphatic α-substituted azoalkanes

Claim 1

A process which comprises polymerizing ethylenically unsaturated monomer in the presence of an initiating amount of a compound of the formula ##STR23## where: R' and R" are separately selected from alkyl of 1-12 carbons, cycloalkyl of 3-12 carbons, and aralkyl of 7-12 carbons, or join to form cycloalkyl of 3-12 carbons, and R" is further selected from aryl of 6-14 carbons; R 1 and R 2 are separately selected from alkyl of 1-8 carbons, cycloalkyl of 3-12 carbons and aralkyl of 7-12 carbons or join to form cycloalkyl of 4-12 carbons, and R 2 is further selected from aryl of 6-14 carbons; X is selected from --Cl, --Br, --CN, --C(═O)NH 2 , --C(═NOH)NH 2 , --OH, --OR 3 , --OC(═O)OR 3 , --OOR 5 , --SR 6 , --N 3 , --SCN, --NCX', --NHC(═X')OR 3 , --NHC(═X')N(R 8 )R 9 , --NHC(═X')NHNHC(═X')R 4 , --NHC(═X')NHN(R 8 )C(═X')N(R 8 )R 9 , --NHC(═X')N(NH 2 )R 10 , --NHC(═X')NHNHR 16 , --NHC(═X')NHN(R' 8 )R' 9 , --NHC(═X')NHNHC(═X')X'R 3 , and ##STR24## X' is oxygen or sulfur; R 3 and R 4 are separately selected from alkyl of 1-12 carbons, cycloalkyl of 3-12 carbons, aralkyl of 7-12 carbons, and aryl of 6-14 carbons, and R 4 is further selected from hydrogen; R 5 is tertiary alkyl of 4-12 carbons or tertiary phenalkyl of 9-12 carbons; R 6 is selected from alkyl of 1-12 carbons, cycloalkyl of 3-12 carbons, and aryl of 6-14 carbons; R 8 , r 9 , r' 8 and R' 9 are separately selected from alkyl of 1-8 carbons, cycloalkyl of 3-12 carbons, aralkyl of 7-12 carbons, and aryl of 6-14 carbons or R 8 and R 9 or R' 8 and R' 9 taken together form alkylene of 3-11 carbons, and R 8 and R 9 are further selected from hydrogen; R 10 is primary or secondary alkyl of 1-12 carbons or cycloalkyl of 3-12 carbons; R 15 is aryl of 6-10 carbons; and R 16 is selected from hydrogen, tertiary alkyl of 4-8 carbons, tertiary aralkyl of 9-12 carbons, and aryl of 6-14 carbons.