Process for preparing "living" polymers

Claim 1

In a process comprising polymerizing the monomer selected from the group consisting of CH 2 ═C(Y)X, ##STR41## and mixtures thereof wherein: X is --CN, --CH═CHC(O)X' or --C(O)X'; Y is --H, --CH 3 , --CN or --CO 2 R, provided, however, when X is CH═CHC(O)X', Y is --H or --CH 3 ; X' is --OSi(R 1 ) 3 , --R, --OR or --NR'R"; each R 1 , independently, is hydrocarbyl of up to 20 carbon atoms; R is hydrocarbyl of up to 20 carbon atoms, optionally containing one or more ether oxygen atoms within aliphatic segments thereof, and optionally containing one or more functional substituents that are unreactive under polymerizing conditions; and each of R' and R" is independently selected from C 1-4 alkyl by contacting the one or more monomers under polymerizing conditions with: (i) the initiator of the formula (R 1 ) 3 MZ wherein: R 1 is as defined above; Z is an activating substituent selected from the group consisting of ##STR42## and mixtures thereof X' is as defined above for the monomer; each of R 2 and R 3 is independently selected from H and hydrocarbyl of up to 20 carbon atoms, optionally containing one or more ether oxygen atoms within aliphatic segments thereof, and optionally containing one or more functional substituents that are unreactive under polymerizing conditions; and Z' is O or NR'; m is 2, 3 or 4; n is 3, 4 or 5; and M is Si, Sn, or Ge, provided, however when Z is ##STR43## M is Sn or Ge; and (ii) a co-catalyst which is a source of bifluoride ions HF 2 .sup.⊖, to produce "living" polymer having repeat units of the one or more monomers, said process further characterized in that: (a) R 1 is H, provided that at least one R 1 group is not H; and/or (b) R is a polymeric radical containing at least 20 carbon atoms and optionally containing one or more ether oxygen atoms within aliphatic segments thereof and optionally containing one or more functional substituents that are unreactive under polymerizing conditions; and/or (c) at least one of any R group in the monomer contains one or more reactive substitutents of the formula --Z'(O)C--C(Y 1 )═CH 2 wherein Y 1 is H or CH 3 and Z' is as defined above; and/or (d) the initiator is of the formula (R 1 ) 2 M(Z 1 ) 2 or O[M(R 1 ) 2 Z 1 ] 2 wherein R 1 and M are as defined above and Z 1 is ##STR44## wherein X', R 2 and R 3 are as defined above; and/or (e) at least one of any R, R 2 and R 3 in the initiator contains one or more initiating substitutents of the formula --Z 2 --M(R 1 ) 3 wherein M and R 1 are as defined above; and Z 2 is a diradical selected from the group consisting of ##STR45## and mixtures thereof, wherein R 2 , R 3 , X', Z', m and n are as defined above, provided, however, when Z 2 is ##STR46## M is Sn or Ge; and/or (f) Z is selected from the group consisting of --SR, --OP(NR'R") 2 , --OP(OR 1 ) 2 , --OP[OSi(R 1 ) 3 ] 2 and mixtures thereof, wherein R, R 1 , R' and R" are as defined above; and/or (g) R 2 and R 3 taken together are ##STR47## provided, however, Z is ##STR48## and/or Z 2 is ##STR49## and/or (h) X' and either R 2 or R 3 taken together are ##STR50## provided, however, Z is ##STR51## and/or Z 2 is ##STR52##