Ni or Pd-catalyzed cationic polymerization of polycyclic olefins with silane chain transfer agents

1. A method of polymerizing poly(cyclic)olefin monomers comprising:

combining a monomer composition comprising one or more poly(cyclic)olefin monomers, a non-olefinic chain transfer agent and an activator compound in a reaction vessel to form a mixture; and

adding a polymerization catalyst containing Ni, the polymerization catalyst causing the mixture to polymerize;

wherein the non-olefinic chain transfer agent includes one or more compounds selected from the group consisting of alkylalkoxysilanes, alkylgermanes, alkylalkoxygermanes, alkylstannanes, and alkylalkoxystannanes;

wherein the polymerization catalyst containing Ni is selected from the group consisting of,

(i) polymerization catalysts containing Ni represented by Formula (XII),

[L′yNiX*z]WCA  (XII)

wherein L′ represents a ligand containing 1, 2, or 3 olefinic π bonds; X* represents a ligand containing 1 Ni—C σ bond and between 0-3 olefinic π bonds; y is 0, 1, or 2 and z is 1 or 2 and wherein y and z cannot both be 0 at the same time, and

(ii) polymerization catalysts containing Ni represented by Formula (XI),

[LnNi(R ewg ) 2 ]  (XI)

wherein n is an integer of 0, 1 or 2, L represents a monodentate ligand or a bidentate ligand, and R ewg represents an electron withdrawing ligand; and

wherein the activator is characterized as having a functional group containing an active hydrogen with a pKa of at least about 5.

2. The method of claim 1 , wherein the functional group is hydroxyl or carboxylic acid.

3. The method of claim 1 , wherein the functional group is —OH.

4. The method of claim 1 , wherein the activator is a compound containing an —OH functional group selected from water and C 1 -C 24 linear, branched, and cyclic alkyl, aryl, and alkaryl moieties containing at least one hydroxyl group.

5. The method of claim 1 ,

wherein the poly(cyclic)olefin monomers comprise a first monomer according to Formula (I):

wherein X is selected from O, S, —NH—, —CH 2 —, and —CH 2 —CH 2 —; m is 0;

R 1 is selected from a hydroxy alkyl ether according to Formula (IV):

-A-O—[—(CR 35 2 —) q —O—] p —(CR 35 2 —) q —OH  (IV)

wherein A is a linking group selected from C 1 to C 6 linear, branched, or cyclic alkylene, each occurrence of R 35 is independently selected from H, methyl, ethyl and a halide, q is from 1 to 5, and p is from 0 to 3; and

R 2 , R 3 , and R 4 are each H in the poly(cyclic)olefin monomer.

6. The method of claim 1 ,

wherein the poly(cyclic)olefin monomers comprise a first monomer according to Formula (I):

wherein X is —CH 2 —; m is 0; R 1 and R 2 are each hydrogen; and

R 3 and R 4 are each independently, C 1 X″ 2r+1 , wherein X″ is independently a halogen selected from fluorine, chlorine, bromine or iodine and r is an integer from 1 to 20.

7. The method of claim 1 , wherein said polymerization catalyst containing Ni represented by Formula (XII) is selected from the group consisting of [(ally)Ni(1,5-cyclooctadiene)]PF 6 , [(crotyl)Ni(1,5-cyclooctadiene)]PF 6 , [(allyl)Ni(1,5-cyclooctadiene)]SbF 6 and combinations thereof.

8. The method of claim 5 , wherein said polymerization catalyst containing Ni represented by Formula (XII) is selected from the group consisting of [(allyl)Ni(1,5-cyclooctadiene)]PF 6 , [(crotyl)Ni(1,5-cyclooctadiene)]PF 6 , [(allyl)Ni(1,5-cyclooctadiene)]SbF 6 and combinations thereof.

9. The method of claim 6 , wherein said polymerization catalyst containing Ni represented by Formula (XII) is selected from the group consisting of [(allyl)Ni(1,5-cyclooctadiene)]PF 6 , [(crotyl)Ni(1,5-cyclooctadiene)]PF 6 , [(allyl)Ni(1,5-cyclooctadiene)]SbF 6 and combinations thereof.

10. The method of claim 1 , wherein said polymerization catalyst containing Ni represented by Formula (XI) is selected from the group consisting of nickel(2,4,6-tris(trifluoromethyl)-phenyl) 2 , nickel(η 6 -toluene)(pentafluorophenyl) 2 , nickel(tetrahydrofuran) 2 (pentafluorophenyl) 2 and combinations thereof.

11. The method of claim 5 , wherein said polymerization catalyst containing Ni represented by Formula (XI) is selected from the group consisting of nickel(2,4,6-tris(trifluoromethyl)-phenyl) 2 nickel(θ 6 -toluene)(pentafluorophenyl) 2 , nickel(tetrahydrofuran) 2 (pentafluorophenyl) 2 and combinations thereof.

12. The method of claim 6 , wherein said polymerization catalyst containing Ni represented by Formula (XI) is selected from the group consisting of nickel(2,4,6-tris(trifluoromethyl)-phenyl) 2 nickel(η 6 -toluene)(pentafluorophenyl) 2 , nickel(tetrahydrofuran) 2 (pentafluorophenyl) 2 and combinations thereof.