US 12,723,111 B2 · Palladium catalysts for forming vinyl addition polymers having improved film forming properties

Abstract

A series of palladium compounds as described herein are found to be superior vinyl addition polymerization catalysts. Specifically the compounds of formulae (I) and (II) as described herein surprisingly exhibit much higher reactivity than the compounds known in the art in the vinyl addition polymerization of a variety of cyclo-olefinic monomers, and thus polymers of very high molecular weight can be formed. Also disclosed are the formation of a variety of solid three dimensional objects, such as for example, solution extrusion of the polymer solutions formed from the vinyl addition polymerization of a variety of cyclic-olefinic monomers utilizing very low levels of palladium compounds of formulae (I) or (II) as described herein. The polymer films formed from the polymerization composition exhibit hitherto unattainable properties, for example superior transparent properties, higher thermal and mechanical properties, among other improved properties. Accordingly, the films thus formed are useful in a variety of opto-electronic applications.

Claims14

Dependent claims

A palladium compound of formula (I):

wherein
at least two of R1, R2 and R3 are the same and are selected from the group consisting of tert-(C4-C12)alkyl, 1-(C1-C5)alkyl(C3-C5) cycloalkyl, 1-(C5-C12) bicycloalkyl, 1-(C8-C12) tricycloalkyl, (C6-C10) aryl and (C6-C10) aryl(C1-C3)alkyl;
and the remaining R1, R2 or R3 is methyl, ethyl, linear or branched (C3-C12)alkyl, (C6-C10) aryl or (C6-C10) aryl(C1-C3)alkyl;
and
R4 and R5 are the same or different and each independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C20)alkyl, trifluoromethyl, pentafluoroethyl and linear or branched (C3-C20) perfluoroalkyl.

2 more elements

A palladium compound of formula (II):

wherein
L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C6H5CN), 2,4,6-trimethylbenzonitrile, phenyl acetonitrile (C6H5CH2CN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone;
Z⊖ is selected from the group consisting of BF4⊖, tetrakis(pentafluorophenyl) borate, tetrakis(3,5-bis(trifluoromethyl) phenyl) borate, tetrakis(2-fluorophenyl) borate, tetrakis(3-fluorophenyl) borate, tetrakis(4-fluorophenyl) borate, tetrakis(3,5-difluorophenyl) borate, tetrakis(2,3,4,5-tetrafluorophenyl) borate, tetrakis(3,4,5,6-tetrafluorophenyl) borate, tetrakis(3,4,5-trifluorophenyl) borate, methyltris(perfluorophenyl) borate, ethyltris(perfluorophenyl) borate, phenyltris(perfluorophenyl) borate, tetrakis(1,2,2-trifluoroethylenyl) borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl) borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl) borate, (triphenylsiloxy) tris(pentafluorophenyl) borate, (octyloxy) tris(pentafluorophenyl) borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl) ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2, 2,2-trifluoro-1-(trifluoromethyl) ethyl]-5-(trifluoromethyl) phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl) phenyl]borate, PF6⊖, SbF6⊖, n-C4F9SO3⊖, CF3SO3⊖ and p-CH3(C6H4)—SO3⊖,
at least two of R1, R2 and R3 are the same and are selected from the group consisting of 1-(C1-C5)alkyl(C3-C8) cycloalkyl, 1-(C5-C12) bicycloalkyl, 1-(C8-C12) tricycloalkyl, and (C6-C10) aryl(C1-C3)alkyl;
and the remaining R1, R2 or R3 is methyl, ethyl, linear (C3-C12)alkyl, (C6-C10) aryl or (C6-C10) aryl(C1-C3)alkyl;
and
R6 is selected from the group consisting of methyl, ethyl, linear or branched (C3-C20)alkyl, trifluoromethyl, pentafluoroethyl and linear or branched (C3-C20) perfluoroalkyl.

4 more elements

A polymerization composition comprising:

a) a palladium compound selected from the group consisting of:
a compound of formula (I):
and
a compound of formula (II):
wherein
L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C6H5CN), 2,4,6-trimethylbenzonitrile, phenyl acetonitrile (C6H5CH2CN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran and benzophenone;
Z⊖ is selected from the group consisting of BF4⊖, tetrakis(pentafluorophenyl) borate, tetrakis(3,5-bis(trifluoromethyl) phenyl) borate, tetrakis(2-fluorophenyl) borate, tetrakis(3-fluorophenyl) borate, tetrakis(4-fluorophenyl) borate, tetrakis(3,5-difluorophenyl) borate, tetrakis(2,3,4,5-tetrafluorophenyl) borate, tetrakis(3,4,5,6-tetrafluorophenyl) borate, tetrakis(3,4,5-trifluorophenyl) borate, methyltris(perfluorophenyl) borate, ethyltris(perfluorophenyl) borate, phenyltris(perfluorophenyl) borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1-propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl) borate, (octyloxy) tris(pentafluorophenyl) borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl) ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl) ethyl]-5-(trifluoromethyl) phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)-ethyl]-5-(trifluoromethyl) phenyl]borate, PF6⊖, SbF6⊖, n-C4F9SO3⊖, CF3SO3⊖ and p-CH3(C6H4)—SO3⊖;
at least two of R1, R2 and R3 are the same and is are selected from the group consisting of tert-(C4-C12)alkyl, 1-(C1-C5)alkyl(C3-C8) cycloalkyl, 1-(C5-C12) bicycloalkyl, 1-(C8-C12) tricycloalkyl, (C6-C10) aryl and (C6-C10) aryl(C1-C3)alkyl;
and the remaining R1, R2 or R3 is methyl, ethyl, linear or branched (C3-C12)alkyl, (C6-C10) aryl or (C6-C10) aryl(C1-C3)alkyl;
and
R4, R5 and R6 are the same or different and each independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C20)alkyl, trifluoromethyl, pentafluoroethyl and linear or branched (C3-C20) perfluoroalkyl;
b) a compound of formula (III):
Md⊕Z⊖ (III);
wherein
Md⊕ is a cation selected from lithium, sodium, potassium, cesium, ammonium, dialkylanilinium or linear or branched tetra(C1-C4)alkyl ammonium;
Z⊖ is a weakly coordinating anion selected from the group consisting of B(C6F5)4⊖, B[C6H3(CF3)2]4⊖, B(C6H5)4⊖, [Al(OC(CF3)2C6F5)4]⊖, BF4⊖, PF6⊖, AsF6⊖, SbF6⊖, (CF3SO2)N⊖ or CF3SO3⊖;
and
c) at least one monomer of formula (IV):
wherein:
m is an integer 0, 1 or 2;
R7, R8, R9 and Rio are the same or different and each independently of one another is selected from hydrogen, linear or branched (C1-C16)alkyl, hydroxy (C1-C16)alkyl, perfluoro (C1-C12)alkyl, (C3-C12) cycloalkyl, (C6-C12) bicycloalkyl, (C7-C14) tricycloalkyl, (C6-C10) aryl, (C6-C10) aryl(C1-C3)alkyl, perfluoro (C6-C10) aryl, perfluoro (C6-C10) aryl(C1-C3)alkyl, di(C1-C2)alkylmaleimide (C3-C6)alkyl, di(C1-C2)alkylmaleimide (C2-C6)alkoxy (C1-C2)alkyl, hydroxy, (C1-C12)alkoxy, (C3-C12) cycloalkoxy, (C6-C12) bicycloalkoxy, (C7-C14) tricycloalkoxy, (C6-C10) aryloxy (C1-C3)alkyl, (C5-C10) heteroaryloxy (C1-C3)alkyl, (C6-C10) aryloxy, (C5-C10) heteroaryloxy or (C1-C6) acyloxy, where each of the aforementioned substituents is optionally substituted with halogen or hydroxy.

18 more elements

Dependencies are inferred from the claim text.

Palladium catalysts for forming vinyl addition polymers having improved film forming properties

Life of this patent

Palladium catalysts for forming vinyl addition polymers having improved film forming properties

Life of this patent

Abstract

Claims14