Catalyst and methods for polymerizing cycloolefins

A process for preparing a polymer containing polycyclic repeating units comprising contacting at least one polycycloolefin monomer with a high activity Group 10 transition metal catalyst complex of the formula:

• [(R′)zM(L′)x(L″)y]b[WCA]d
• to obtain a polymer product that contains 100 ppm or less of residual Group 10 transition metal prior to purification, wherein [(R′)zM(L′)x(L″)y] is a cation complex where M represents a Group 10 transition metal;
• R′ represents a ligand selected from the group consisting of R″C(O)O, R″C(O)CHC(O)R″, R″C(O)S, R″C(S)O, R″O, R″2N, and R″2P, wherein R″ represents hydrogen, linear and branched C1-C20 alkyl, C5-C10 cycloalkyl, linear and branched C2-C20 alkenyl, C6-C15 cycloalkenyl, allylic ligands or canonical forms thereof, C6-C30 aryl, C6-C30 heteroatom containing aryl, and C7-C30 aralkyl, wherein each of the foregoing radicals are optionally substituted with a substituent selected from the group consisting of linear or branched C1-C5 alkyl, linear or branched C1-C5 haloalkyl, linear or branched C2-C5 alkenyl C2-C5 haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus, and phenyl, wherein said phenyl group is optionally substituted with linear or branched C1-C5 alkyl, linear or branched C1-C5 haloalkyl, and halogen;
• L′ represents a Group 15 neutral electron donor ligand;
• L″ represents a labile neutral electron donor ligand;
• x is 1 or 2;
• and y is 0, 1, 2, or 3;
• and z is 0 or 1, wherein the sum of x, y, and z is 4;
• [WCA] represents a weakly coordinating counteranion complex;
• and b and d are numbers representing the number of times the cation complex and weakly coordinating counteranion complex are taken to balance the electronic charge on the overall catalyst complex.

A process for preparing a polymer containing polycyclic repeating units comprising contacting at least one polycycloolefin monomer with a high activity Group 10 transition metal catalyst complex of the formula:

• [(R′)zM(L′)x(L″)y]b[WCA]d
• to obtain a polymer product that contains 100 ppm or less of residual Group 10 transition metal prior to purification, wherein [(R′)zM(L′)x(L″)y] is a cation complex where M represents a Group 10 transition metal;
• x is 1 or 2;
• andy is 0, 1, 2, or 3;
• and z is 0 or 1, wherein the sum of x, y, and z is 4;
• [WCA] represents a weakly coordinating counteranion complex;
• and b and d are numbers representing the number of times the cation complex and weakly coordinating counteranion complex are taken to balance the electronic charge on the overall catalyst complex;
• R′ represents an anionic hydrocarbyl containing ligand selected from the group consisting of hydrogen, substituted and unsubstituted C5-C10 cycloalkyl, substituted and unsubstituted linear and branched C2-C20 alkenyl, substituted and unsubstituted C6-C15 cycloalkenyl, substituted and unsubstituted allylic ligands or canonical forms thereof, C6-C30 aryl, C6-C30 heteroatom containing aryl, and C7-C30 aralkyl, wherein said substituted hydrocarbyl containing ligands are monosubstituted or multisubstituted with linear or branched C1-C5 alkyl, linear or branched C1-C5 haloalkyl, linear or branched C2-C5 alkenyl and haloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus, and phenyl optionally monosubstituted or multisubstituted with linear or branched C1-C5 alkyl, linear and branched C1-C5 haloalkyl, and halogen;
• L′ represents a Group 15 neutral electron donor ligand;
• and L″ represents a labile neutral electron donor ligand.

A process for preparing a polymer containing polycyclic repeating units in the substantial absence of solvent comprising contacting at least one polycycloolefin monomer with a Group 10 transition metal containing procatalyst complex of the formula [R′M(L′)x(A′)], a weakly coordinating anion salt containing a cation complex and a weakly coordinating anion complex of the formula [C(L″)z″]b″[WCA]d″, and an optional labile neutral electron donor compound, wherein M represents a Group 10 transition metal selected from the group consisting of nickel, platinum, and palladium;

• R′ is an anionic hydrocarbyl containing ligand;
• L′ represents a Group 15 neutral electron donor ligand;
• A′ represents an anionic leaving group that can be displaced by said weakly coordinating anion complex;
• L″ represents a labile neutral electron donor ligand compound;
• C represents a cation selected from the group consisting of a proton, a Group 1 metal cation, a Group 2 metal cation, and an organic group containing cation;
• WCA represents a weakly coordinating anion complex;
• x is 1 or 2;
• z″ is an integer from 0 to 8;
• and b″ and d″ represent the number of times the cation and anion complex of said weakly coordinating anion salt are taken to balance the charge on said salt.

A process for preparing a polymer containing polycyclic repeating units in the substantial absence of solvent comprising contacting at least one polycycloolefin monomer with a Group 10 transition metal containing procatalyst complex of the formula [M(A′)2], a Group 15 neutral electron donor compound, and a weakly coordinating anion salt containing a cation complex and a weakly coordinating anion complex of the formula [C(L″)z″]b″[WCA]d″, wherein M represents a Group 10 transition metal selected from the group consisting of nickel, platinum, and palladium;

• A′ represents an anionic leaving group that can be displaced by said weakly coordinating anion complex;
• C represents a cation selected from the group consisting of a proton, a Group 1 metal cation, a Group 2 metal cation, and an organic group containing cation;
• WCA represents a weakly coordinating anion complex;
• z″ is an integer from 0 to 8;
• and b″ and d″ represent the number of times the cation and anion complex of said weakly coordinating anion salt are taken to balance the charge on said salt.

A process for preparing a polymer containing polycyclic repeating units comprising contacting at least one polycycloolefin monomer in the substantial absence of solvent with a Group 10 transition metal containing procatalyst complex of the formula:

• [R′M(L′)x(A′)]
• a weakly coordinating anion salt containing a cation complex and a weakly coordinating anion complex of the formula [C(L″)z″]b″[WCA]d″, and an optional labile neutral electron donor compound, wherein M represents a Group 10 transition metal selected from the group consisting of nickel, platinum, and palladium;
• R′ represents hydrogen or an allylic ligand;
• L′ represents a Group 15 neutral electron donor ligand;
• A′ represents an anionic leaving group that can be displaced by said weakly coordinating anion complex;
• L″ represents a labile neutral electron donor ligand compound;
• C represents a cation selected from the group consisting of a proton, a Group 1 metal cation, a Group 2 metal cation, and an organic group containing cation;
• WCA represents a weakly coordinating anion complex;
• x is 1 or 2;
• z″ is an integer from 0 to 8;
• and b″ and d″ represent the number of times the cation and anion complex of said weakly coordinating anion salt are taken to balance the charge on said salt.