Group transfer polymerization and initiators therefor

Claim 2

A Group Transfer Polymerization process comprising contacting under Group Transfer Polymerizing Conditions at least one polar acrylic or maleimide monomer with (i) a tetracoordinate organosilicon polymerization initiator having at least one initiating site and (ii) a co-catalyst which is a source of bifluoride, fluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion, the process further characterized in that the initiator is of the formula Z 1 --Si(Q') 3 , (Z 1 ) 2 --Si(Q') 2 , [Z 1 (Q')) 2 Si] 2 O, or Z 2 --Si(Q') 3 wherein: each Q', independently, is selected from R 1 , OR 1 , SR 1 and N(R 1 ) 2 , provided, however, all of the Q' groups are not R 1 ; Z 1 is ##STR24## Z 2 is --CN or 13 NC; X 2 is --OSi(R 1 ) 3 , --R 6 , --OR 6 or --NR'R"; R 6 is (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (c) a radical of (a), (b) or (c) containing one of more functional substituents that are unreactive under polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) containing on or moe initiating sites; each R 1 , independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least R 1 group is not --H; each of R 2 and R 3 is independently selected from (a) --H; (b) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (c) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (d) a radical of (b) or (c) containing one or more ether oxygen atoms with aliphatic segments thereof; (e) a radical of (b), (c) or (d) containing one or more functional substituents that are unreactive under polymerizing conditions; and (f) a radical of (b), (c), (d) or (e) containing one or more initiating sites; and each of R' and R" is independently selected from C 1-4 alkyl.

Claim 3

Process of claim 1 wherein each Q', independently, is selected from R 1 , OR 1 and N(R 1 ) 2 , provided, however, all of the Q' gropups are not R 1 .

Claim 4

"Living" polymer of the formula Rp(Z 3 PQsi[Q'] 3 ) p , Z"PQSi(Q') 3 , [Z"PQ] 2 Si(Q') 2 or [Z"PQ(Q') 2 Si] 2 O wherein: Z" is selected from the group consisting of ##STR25## Z 3 is a diradical selected from the group consisting of --Z'--C(O)--C(R 2 )(R 3 )--, --C(R 2 )(C(O)X 2 )-- and mixtures thereof; Rp is a radical, of valence p, selected from (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic ormixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; and (c) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; P is a divalent polymeric radical consisting essentially of at least three repeat units of at least one polar acrylic or maleimide monomer; Q is a divalent radical consisting essentially of one or both tautomeric forms of a polar acrylic or maleimide unit; p is an integer and is at least 1; each Q', independently, is selected from R 1 , OR 1 , SR 1 and N(R 1 ) 2 , provided, however, all of the Q' groups are not R 1 ; each R 1 , independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R 1 group is not --H; each of R 2 and R 3 is independently selected from (a) --H; (b) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (c) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (d) a radical of (b) or (c) containing one or more ether oxygen atoms within aliphatic segments thereof; (e) a radical of (b), (c) or (d) containing one or more functional substituents that are unreactive under polymerizing conditions; and (f) a radical of (b), (c), (d) or (e) containing one or more initiating sites; X 2 is --OSi(R 1 ) 3 , --R 6 , --OR 6 or --NR'R"; R 6 is: (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites; Z' is O or NR'; and each of R' and R" is independently selected from C 1-4 alkyl.

Claim 5

"Living" polymer of the formula Rp(Z 3 PQsi[Q'] 3 ) p , Z"PQSi(Q') 3 , [Z"PQ] 2 Si(Q') 2 or [Z"PQ(Q') 2 Si] 2 O wherein: Z" is selected from the group consisting of ##STR25## Z 3 is a diradical selected from the group consisting of --Z'--C(O)--C(R 2 )(R 3 )--, --C(R 2 )(C(O)X 2 )-- and mixtures thereof; Rp is a radical, of valence p, selected from (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic ormixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; and (c) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; P is a divalent polymeric radical consisting essentially of at least three repeat units of at least one polar acrylic or maleimide monomer; Q is a divalent radical consisting essentially of one or both tautomeric forms of a polar acrylic or maleimide unit; p is an integer and is at least 1; each Q', independently, is selected from R 1 , OR 1 , SR 1 and N(R 1 ) 2 , provided, however, all of the Q' groups are not R 1 ; each R 1 , independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R 1 group is not --H; each of R 2 and R 3 is independently selected from (a) --H; (b) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (c) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (d) a radical of (b) or (c) containing one or more ether oxygen atoms within aliphatic segments thereof; (e) a radical of (b), (c) or (d) containing one or more functional substituents that are unreactive under polymerizing conditions; and (f) a radical of (b), (c), (d) or (e) containing one or more initiating sites; X 2 is --OSi(R 1 ) 3 , --R 6 , --OR 6 or --NR'R"; R 6 is: (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites; Z' is O or NR'; and each of R' and R" is independently selected from C 1-4 alkyl.

Claim 6

Polymer of claim 3 wherein each Q', independently, is selected from R 1 , OR 1 and N(R 1 ) 2 , provided, however, all of the Q' groups are not R 1 .

Claim 7

Process of claim 1 wherein the product is a "living" polymer.

Claim 8

Process of claim 1 wherein the monomer is a polar acrylic monomer of the formula CH 2 ═C(Y)X 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 a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R 1 group is not --H; R is: (a) a hydrocarbyl radical whichis an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) containing one or more reactive subsitutents 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' wherein R' is as defined below; and each of R' and R" is independently selected from C 1-4 alkyl.

Claim 9

Process of claim 6 wherein Y is --CH 3 and X is --C(O)X'.

Claim 10

Process of claim 7 wherein X' is --OR.

Claim 11

Process of claim 8 wherein R is C 1-4 alkyl.

Claim 12

Process of claim 9 wherein R is --CH 3 .

Claim 13

Process of claim 2 wherein X 2 is --OR 6 and R 6 is a C 1-4 alkyl.

Claim 14

Process of claim 11 wherein R 6 is --CH 3 .

Claim 15

Process of claim 8 wherein R 1 is --CH 3 or --C 2 H 5 .

Claim 16

Process of claim 2 wherein R 2 and R 3 , independently, are H or hydrocarbyl containing up to 20 carbon atoms.

Claim 17

Process of claim 14 wherein hydrocarbyl contains one or more functional substituents that are unreactive under polymerizing conditions.

Claim 18

Process of claim 14 wherein hydrocarbyl contains one or more initiating sites.

Claim 19

Process of claim 15 wherein hydrocarbyl contains one or more initiating sites.

Claim 20

Polymer prepared by the process of claim 1.

Claim 21

Polymer of claim 3 wherein P consists essentially of repeat units of at least one polar acrylic monomer.

Claim 22

Polymer of claim 19 wherein the repeat units are of the formula --CH 2 C(Y)(X 3 )-- wherein: X 3 is --CN, --CH═CHC(O)X 2 or --C(O)X 2 ; and Y is --H, --CH 3 , --CN or --CO 2 R, provided, however, when X 3 is --CH═CHC(O)X 2 , Y is --H or CH 3 .

Claim 23

Polymer of claim 20 wherein Y is --CH 3 , X 2 is OR 6 and R 6 is a hydrocarbyl radical containing up to 20 carbon atoms.

Claim 24

Polymer of claim 21 wherein R 6 also contains one or more functional substitutents that are unreactive under polymerizing conditions.

Claim 25

Polymer of claim 21 wherein R 6 is C 1-4 alkyl.

Claim 26

Polymer of claim 23 wherein R 6 is --CH 3 .

Claim 27

Polymer of claim 3 wherein R 1 (in Q') is --CH 3 or --C 2 H 5 .

Claim 28

Polymer of claim 3 wherein p is at least 2.

Claim 29

Polymer of claim 3 wherein Rp is a C 1-8 aliphatic hydrocarbon radical.

Claim 30

Polymer of claim 3 dissolved or dispersed in an aprotic solvent to produce a solution or dispersion.

Claim 31

Film prepared from the solution or dispersion of claim 28.

Claim 32

Coated substrate prepared from the solution or dispersion of claim 28.

Claim 33

Fiber prepared from the solution or dispersion of claim 28.

Claim 34

Process of preparing a living block polymer from the "living" polymer of claim 3 by adding unsatured monomers to said living polymer.

Claim 35

Living polymer of the process of claim 32.

Claim 36

Process comprising quenching the polymer of claim 3 with an active hydrogen source.