CPC C08F 132/08 (2013.01) [H10K 85/141 (2023.02); H10K 50/858 (2023.02)] | 20 Claims |
1. A composition comprising:
a) one or more olefinic monomers;
b) an organopalladium compound selected from the group consisting of a compound of formula (I) and a compound of formula (IA):
wherein:
L is a ligand selected from the group consisting of P(R)3, P(OR)3, O═P(R)3, RCN and substituted or unsubstituted pyridines, where R is selected from the group consisting of linear or branched alkyl and fluoroalkyl having the formula CqHxFy, where q is an integer from 1 to 16, x and y are integers from 0 to 2q+1, and the sum of x and y is 2q+1, (C6-C10)aryl(C1-C16)alkyl and substituted or unsubstituted (C6-C10)aryl;
R3, R4 and R6 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula CqHxFy, where q is an integer from 1 to 16, x and y are integers from 0 to 2q+1, and the sum of x and y is 2q+1, (C3-C10)cycloalkyl, (C6-C10)aryl(C1-C16)alkyl and substituted or unsubstituted (C6-C10)aryl;
each A independently is a bidentate monoanionic ligand of formula (II):
wherein:
n is an integer 0, 1 or 2;
X and Y are independently of each other selected from O, N and S;
R1, R2, R3, R4, R5, R6 and R7 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula CqHxFy, where q is an integer from 1 to 16, x and y are integers from 0 to 2q+1, and the sum of x and y is 2q+1, (C3-C10)cycloalkyl, (C6-C10)aryl(C1-C16)alkyl and substituted or unsubstituted (C6-C10)aryl; provided when either X or Y is O or S, R1 and R5, respectively, do not exist;
c) a photoacid generator selected from the group consisting of:
a compound of formula (III):
and
a compound of formula (IV):
wherein:
a is an integer from 0 to 5;
An− is selected from the group consisting of Cl−, Br−, I−, 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−;
R8, R9, R10, R11 and R12 are the same or different and each independently selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-C20)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C6-C10)aryloxy, (C6-C10)thioaryl, (C1-C6)alkanoyl(C6-C10)thioaryl, (C1-C6)alkoxy(C6-C10)aroyl(C1-C6)alkyl and (C6-C10)thioaryl-(C6-C10)diarylsulfonium salt; and
d) a photosensitizer selected from the group consisting of a compound of formula (VIII) and a compound of formula (IX):
wherein
R44, R45 and R46 are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, hydroxy, NO2, NH2, methyl, ethyl, linear or branched (C3-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12) bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C3)alkyl, (C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy(C1-C3)alkyl, (C6-C10)aryloxy, C(O)(C1-C6)alkyl, COOH, C(O)O(C1-C6)alkyl, and SO2(C6-C10)aryl; and
R47 and R48 are the same or different and independently of each other selected from the group consisting of methyl, ethyl, linear or branched (C3-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl and (C6-C10)aryl(C1-C3)alkyl.
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