Oxyanion-catalyzed polymerization

Claim 2

Polymerization process comprising contacting under polymerizing conditions at least one polar, acrylic type alpha-olefinic monomer with (i) a tetracoordinate organosilicon, organotin or organogermanium polymerization initiator having at least one initiating site, and (ii) a catalyst which is a salt comprising a suitable cation and an oxyanion which can form a conjugate acid having a pKa (DMSO) of about 5 to about 24.

Claim 3

Process of claim 1 wherein the polar monomer is selected from the group consisting of CH 2 ═C(Y)X, ##STR13## 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 H or a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one R 1 group is not H; R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon atoms, any of said radicals optionally containing one or more ether oxygen atoms within aliphatic segments thereof, optionally containing one or more functional substituents that are unreactive under polymerizing conditions, and optionally containing one or more reactive substituents of the formula --Z'(O)C--C(Y 1 )═CH 2 wherein Y 1 is H or CH 3 and Z' is O or NR'; and each of R' and R" is independently selected from C 1-4 alkyl.

Claim 4

Process of claim 2 wherein the initiator is selected from the group consisting of (R 1 ) 3 MZ, (R 1 ) 2 M(Z 1 ) 2 and O[M(R 1 ) 2 Z 1 ] 2 wherein: R 1 is as defined for the monomer; Z is an activating substituent selected from the group consisting of ##STR14## --SR, OP(NR'R") 2 , --OP(OR 1 ) 2 , --OP[OSi(R 1 ) 3 ] 2 and mixtures thereof; Z 1 is the activating substituent ##STR15## R, R 1 , R', R", X' and Z' are as defined above for the monomer; each of R 2 and R 3 is independently selected from H and hydrocarbyl, defined as for R above; m is 2, 3 or 4; `n is 3, 4 or 5; and M is Si, Sn or Ge, provided, however, when Z is ##STR16## M is Sn or Ge, (a) at least one of any R, R 2 and R 3 in the initiator optionally containing one or more initiating substituents of the formula --Z 2 --M(R 1 ) 3 wherein M and R 1 are as defined above; Z 2 is an activating diradical selected from the group consisting of ##STR17## thereof, wherein R 2 , R 3 , X', Z', m and n are as defined above, provided, however, when Z 2 is ##STR18## M is Sn or Ge, (b) R 2 and R 3 taken together are ##STR19## if Z is ##STR20## and/or Z 2 is ##STR21## and (c) X' and either R 2 or R 3 taken together are ##STR22## if Z is ##STR23## and/or Z 2 is ##STR24##

Claim 5

Process of claim 1 wherein the conjugate acid has a pKa (DMSO) of 6<pKa<21.

Claim 6

Process of claim 1 wherein the conjugate acid has a pKa (DMSO) of 8<pKa<18.

Claim 7

Process of claim 3 wherein the conjugate acid has a pKa (DMSO) of 6<pKa<21.

Claim 8

Process of claim 3 wherein the conjugate acid has a pKa (DMSO) of 8<pKa<18.

Claim 9

Process of claim 1 wherein the conjugate acid is of the formula [Q(X 1 OH) p ] q wherein Q, of valence p, is CN, N(O), P(O), PH(O), R 4 or R 4 3 Si; each R 4 , independently, is C 1-20 hydrocarbyl or a polymeric radical containing at least 20 carbon atoms; X 1 is C(O), S(O) or a single bond; and each of p and q is an integer and is at least 1.

Claim 10

Process of claim 8 wherein X 1 is C(O).

Claim 11

Process of claim 9 wherein Q is CN or N(O) and each of p and q is 1.

Claim 12

Process of claim 9 wherein Q is R 4 and q is 1 or 2.

Claim 13

Process of claim 11 wherein R 4 is C 1-20 hydrocarbyl.

Claim 14

Process of claim 12 wherein R 4 is C 1-8 alkyl, phenyl or substituted phenyl and q is 1 or 2.

Claim 15

Process of claim 8 wherein X 1 is a single bond.

Claim 16

Process of claim 14 wherein Q is R 4 which is phenyl or substituted phenyl and q is 1 or 2.

Claim 17

Process of claim 8 wherein X 1 is S(O) and Q is R 4 .

Claim 18

Process of claim 16 wherein R 4 is C 1-20 hydrocarbyl.

Claim 19

Process of claim 17 wherein R 4 is phenyl or substituted phenyl and q is 1 or 2.

Claim 20

Process of claim 1 wherein the oxyanion is a monooxyanion.

Claim 21

Process of claim 1 wherein the oxyanion is a bioxyanion.

Claim 22

Process of claim 1 wherein the oxyanion is a mixture comprising mono- and bioxyanions.

Claim 23

Process of claim 21 wherein the mixture contains a conjugate acid having a pKa (DMSO) of about 5 to about 24.

Claim 24

Process of claim 19 wherein the oxyanion is a carboxylate.

Claim 25

Process of claim 23 wherein the oxyanion is acetate, benzoate or substituted benzoate.

Claim 26

Process of claim 24 wherein the substituted benzoate is a chlorobenzoate.

Claim 27

Process of claim 20 wherein the bioxyanion is biacetate, bibenzoate or substituted bibenzoate.

Claim 28

Process of claim 19 wherein the oxyanion is a phenolate or substituted phenolate.

Claim 29

Process of claim 20 wherein the bioxyanion is a biphenolate or bi(substituted phenolate).

Claim 30

Process of claim 1 wherein the oxyanion is a sulfinate.

Claim 31

Process of claim 29 wherein the oxyanion is an aryl- or substituted aryl sulfinate.

Claim 32

Process of claim 1 wherein the oxyanion is a nitrite or cyanate.

Claim 33

Process of claim 1 wherein the suitable cation is a quaternary ammonium, tris(dialkylamino)sulfonium or an alkali or alkaline earth metal cation.

Claim 34

Process of claim 32 wherein the cation is a tetraalkylammonium cation.

Claim 35

Process of claim 33 wherein the cation is tetrabutylammonium.

Claim 36

Process of claim 32 wherein the cation is tris(dimethylamino)sulfonium.

Claim 37

Process of claim 24 wherein the suitable cation is tetraalkylammonium.

Claim 38

Process of claim 36 wherein the cation is tetrabutylammonium.

Claim 39

Process of claim 37 wherein the oxyanion salt is tetrabutylammonium acetate.

Claim 40

Process of claim 25 wherein the oxyanion salt is tetrabutylammonium m-chlorobenzoate.

Claim 41

Process of claim 26 wherein the suitable cation is tetraalkylammonium.

Claim 42

Process of claim 40 wherein the cation is tetrabutylammonium.

Claim 43

Process of claim 27 wherein the suitable cation is tetraalkylammonium.

Claim 44

Process of claim 42 wherein the cation is tetrabutylammonium.

Claim 45

Process of claim 28 wherein the suitable cation is tetraalkylammonium.

Claim 46

Process of claim 44 wherein the cation is tetrabutylammonium.

Claim 47

Process of claim 21 wherein the mixture comprises mono- and bicarboxylates.

Claim 48

Process of claim 21 wherein the mixture comprises mono- and biphenolates or mono- and bi(substituted phenolates).

Claim 49

Process of preparing the mixture of claim 21 wherein a suitable monooxyanion salt is reacted in situ with one or more conjugate acids having a pKa (DMSO) of about 5 to about 24.

Claim 50

Process of claim 48 wherein one equivalent of salt is reacted with 0.1 to about 2 equivalents of conjugate acid.

Claim 51

Process of claim 1 wherein the polymer produced is "living" and contains the silicon, germanium or tin of the initiator at "living" ends.

Claim 52

Process of claim 3 wherein the polymer produced is "living" and contains the silicon, germanium or tin of the initiator at "living" ends.

Claim 53

Process of claim 20 wherein the bioxyanion is admixed with a conjugate acid having a pKa (DMSO) of about 5 to about 24.