Free radically polymerizable siloxanes and siloxane polymers

1. A free radically polymerizable compound comprising the formula:

X—[—R 3 N—Z—NR 3 ]—{—(CO)(CO)—[NH—Y—Sir 1 2 —(OSir 1 2 ) n —OSir 1 2 —Y—NH—(CO)(CO)—] p —[—R 3 N—Z—NR 3 ]—} r —X

wherein each R 1 is independently an alkyl, haloalkyl, aralkyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo;

each Y is independently a divalent alkylene, aralkylene, or a combination thereof;

each Z is independently a divalent or higher-valent polydiorganosiloxane, alkylene, aralkylene, heteroalkylene, or branched alkylene group;

each R 3 is hydrogen or alkyl or R 3 taken together with Z and with the nitrogen to which they are both attached forms a heterocyclic group;

each X is independently a free radically polymerizable group;

n is independently an integer of 0 to 1500;

p is an integer of 1 or greater; and

r is an integer of 1 or greater.

2. The free radically polymerizable compound of claim 1 , wherein each R 1 is methyl.

3. The free radically polymerizable compound of claim 1 , wherein Y is an alkylene having 1 to 4 carbon atoms.

4. The free radically polymerizable compound of claim 1 , wherein Z is a —Y—Sir 1 2 —(OSir 1 2 ) m —OSir 1 2 —Y— group wherein m is an integer of 0 to 1500.

5. The free radically polymerizable compound of claim 1 , wherein Z is an alkylene, aralkylene, heteroalkylene, or branched alkylene group comprising 2-20 carbon atoms.

6. The free radically polymerizable compound of claim 1 , wherein each X group comprises a (meth)acrylate group, an acrylamide group, or an ethylenically unsaturated aromatic group.

7. The free radically polymerizable compound of claim 1 , wherein the X group comprises a group with the structure:

—A—O—(CO)—CR 4 ═CH 2 ; —A—(CO)—CR 5 2 —NH—(CO)—CH═CH 2 ; or —A—Ar—CR 4 ═CH 2 , wherein

each A is a single bond or a linking group comprising —(CO)—NH—B—, where B is an alkylene group of from 1-4 carbon atoms;

each R 4 is a hydrogen atom or an alkyl group of 1-4 carbon atoms;

each R 5 is a methyl group; and

Ar is a substituted or unsubstituted aromatic group.

8. The free radically polymerizable compound of claim 7 , wherein the X group comprises a group with the structure:

—A—O—(CO)—CR 4 ═CH 2 , wherein

A is a linking group comprising —(CO)—NH—B—, where B is an ethylene group; and

R 4 is a hydrogen atom or a methyl group.

9. The free radically polymerizable compound of claim 7 , wherein the X group comprises a group with the structure:

—A—(CO)—CR 5 2 —NH—(CO)—CH═CH 2 ,

wherein A is a single bond; and

each R 5 is a methyl group.

10. The free radically polymerizable compound of claim 7 , wherein the X group comprises a group with the structure:

—A—Ar—CR 4 ═CH 2 ,

wherein A is a linking group comprising —(CO)—NH—B—, where B is a dimethyl substituted methylene group;

R 4 is a hydrogen atom or a methyl group: and

Ar is a phenylene group.

11. A method of making a free radically polymerizable compound comprising mixing together under reaction conditions:

a compound of the formula:

H—[—R 3 N—Z—NR 3 ]—{—(CO)(CO)—[NH—Y—Sir 1 2 —(OSir 1 2 ) n —OSir 1 2 —Y—NH—(CO)(CO)—] p —[—R 3 N—Z—NR 3 ]—} r —H

wherein each R 1 is independently an alkyl, haloalkyl, aralkyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo;

each Y is independently a divalent alkylene, aralkylene, or a combination thereof;

each Z is independently a divalent or higher-valent polydiorganosiloxane, alkylene, aralkylene, heteroalkylene, or branched alkylene group;

each R 3 is hydrogen or alkyl or R 3 taken together with Z and with the nitrogen to which they are both attached forms a heterocyclic group;

n is independently an integer of 0 to 1500;

p is an integer of 1 or greater; and

r is an integer of 1 or greater; and

an amine-reactive compound, wherein the amine-reactive compound comprises an isocyanate-functional (meth)acrylate, an isocyanate-functional vinyl-substituted aromatic compound, or a vinyl azlactone.

12. The method of claim 11 , wherein Z is a —Y—Sir 1 2 —(OSir 1 2 ) m —OSir 1 2 —Y— group wherein m is an integer of 0 to 1500.

13. The method of claim 11 , wherein Z is an divalent or trivalent alkylene, aralkylene, heteroalkylene, or branched alkylene group comprising 2-20 carbon atoms.

14. The method of claim 11 , wherein the amine-reactive compound comprises vinyl dimethyl azlactone, or a group with the structure:

OCN—A—O—(CO)—CR 4 ═CH 2 ; or OCN—A—Ar—CR 4 ═CH 2 , wherein

each A is a linking group comprising an alkylene group of from 1-4 carbon atoms;

each R 4 is a hydrogen atom or an alkyl group of 1-4 carbon atoms;

Ar is a substituted or unsubstituted aromatic group.

15. The method of claim 14 , wherein the amine-reactive compound comprises a group with the structure:

OCN—A—O—(CO)—CR 4 ═CH 2 , wherein

A is is an ethylene group; and

R 4 is a hydrogen atom or a methyl group.

16. The method of claim 14 , wherein the amine-reactive compound comprises a group with the structure:

OCN—A—Ar—CR 4 ═CH 2 , wherein

A is a dimethyl substituted methylene group;

R 4 is a hydrogen atom or a methyl group: and

Ar is a phenylene group.

17. A polymer composition comprising a polymer prepared from a reaction mixture comprising:

a free radically polymerizable compound comprising the formula:

X—[—R 3 N—Z—NR 3 ]—{—(CO)(CO)—[NH—Y—Sir 1 2 —(OSir 1 2 ) n —OSir 1 2 —Y—NH—(CO)(CO)—] p —[—R 3 N—Z—NR 3 ]—} r —X

wherein each R 1 is independently an alkyl, haloalkyl, aralkyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo;

each Y is independently a divalent alkylene, aralkylene, or a combination thereof;

each Z is independently a divalent or higher-valent polydiorganosiloxane, alkylene, aralkylene, heteroalkylene, or branched alkylene group;

each R 3 is hydrogen or alkyl or R 3 taken together with Z and with the nitrogen to which they are both attached forms a heterocyclic group;

each X is independently a free radically polymerizable group;

n is independently an integer of 0 to 1500;

p is an integer of 1 or greater; and

r is an integer of 1 or greater; and

an initiator.

18. The polymer composition of claim 17 , wherein the reaction mixture further comprises at least one additional free radically polymerizable monomer.

19. The polymer composition of claim 17 , wherein the reaction mixture further comprises at least one crosslinking agent.

20. The polymer composition of claim 17 , further comprising at least one additive.