Long shelf-life stable mass polymerizable polycycloolefin compositions containing pyridine ligated palladium compounds

A kit for forming a substantially transparent film dispensed therein a composition comprising:

• a) a palladium compound of formula (I):
• wherein:
• a is an integer from 1 to 4, inclusive;
• B is a heteroaromatic compound containing at least one nitrogen atom selected from the group consisting of substituted or unsubstituted pyridine, substituted or unsubstituted bipyridine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyridazine and substituted or unsubstituted oxazole, where each of the substituent is independently selected from the group consisting of methyl, ethyl, linear or branched (C3-C16)alkyl, a fluorinated alkyl of formula CqHXFy, where q is from 1 to 16, x is from 0 to 32, y is from 1 to 33 and sum of x+y=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 (IA):
• 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 and R3 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C16)alkyl, a fluorinated alkyl of formula CqHxFy, where q is from 1 to 16, x is from 0 to 32, y is from 1 to 33 and sum of x+y=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 does not exist;
• b) a photoacid generator selected from the group consisting of:
• a compound of formula (II):
• and
• a compound of formula (III):
• wherein:
• b is an integer from 1 to 5, inclusive;
• 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]pheny-1]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⊖, p-CH3(C6H4)—SO3⊖, (CF3SO2)CH and (CF3SO2)N⊖;
• 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;
• c) one or more olefinic monomers of formula (IV):
• wherein:
• m is an integer 0, 1 or 2;
• is a single bond or a double bond;
• R13, R14, R15 and R16 are the same or different and each independently selected from the group consisting of hydrogen, halogen, a hydrocarbyl or halohydrocarbyl group selected from methyl, ethyl, linear or branched (C3-C16)alkyl, a fluorinated alkyl of formula CqHxFy, where q is from 1 to 16, x is from 0 to 32, y is from 1 to 33 and sum of x+y=2q+1, epoxy, epoxy(C1-C12)alkyl, epoxy(C1-C12)alkoxy(C1-C12)alkyl, (C3-C12)cycloalkyl, epoxy(C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C6)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C6)alkyl, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, (C1-C16)alkoxy(C1-C12)alkyl, perfluoro(C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C12)bicycloalkoxy, (C7-C14)tricycloalkoxy, (C6-C10)aryloxy, (C6-C10)aryl(C1-C6)alkoxy, perfluoro(C6-C10)aryloxy,
• perfluoro(C6-C10)aryl(C1-C3)alkoxy,
• a group of formula (A):
• —Z-Aryl (A);
• a group of formula (A1):
• a group of formula (A2):
• a group of formula (A3):
• and
• a group of formula (A4):
• wherein:
• Z is selected from the group consisting of:
• O, CO, C(O)O, OC(O), OC(O)O, S, (CR17R18)d, O(CR17R18)d, (CR17R18)dO, C(O)(CR17R18)d, (CR17R18)dC(O), C(O)O(CR17R18)d, (CR17R18)dC(O)O, OC(O)(CR17R18)d, (CR17R18)dOC(O), (CR17R18)dOC(O)O, (CR17R18)dOC(O)O(CR17R18)d, OC(O)O(CR17R18)d, S(CR17R18)d, (CR17R18)dS, (SiR17R18)d, O(SiR17R18)d, and (SiR17R18)dO, where
• R17 and R18 are the same or different and each independently selected from hydrogen, methyl, ethyl, linear or branched (C3-C12)alkyl, substituted or unsubstituted (C6-C14)aryl, methoxy, ethoxy, linear or branched (C3-C6)alkyloxy, (C2-C6)acyl, (C2-C6)acyloxy, and substituted or unsubstituted (C6-C14)aryloxy;
• and
• d is an integer from 0 to 12, inclusive;
• Aryl is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl substituted or unsubstituted fluorenyl, wherein the substituents are selected from the group consisting of halogen, methyl, ethyl, linear or branched (C3-C6)alkyl, perfluoro(C1-C12)alkyl, (C3-C12)cycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C6)alkyl, perfluoro(C6-C10)aryl, perfluoro(C6-C10)aryl(C1-C6)alkyl, methoxy, ethoxy, linear or branched (C3-C16)alkoxy, perfluoro(C1-C12)alkoxy, (C3-C12)cycloalkoxy, (C6-C10)aryloxy, (C6-C10)aryl(C1-C6)alkoxy, perfluoro(C6-C10)aryloxy and perfluoro(C6-C10)aryl(C1-C3)alkoxy;
• k is an integer from 1 to 12, inclusive;
• R23, R24 and R25 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C3-C12)alkyl, a fluorinated alkyl of formula CqHxFy, where q is from 1 to 16, x is from 0 to 32, y is from 1 to 33 and sum of x+y=2q+1, methoxy, ethoxy, linear or branched (C3-C12)alkoxy, (C3-C12)alkoxy(C3-C12)alkyl, (C3-C12)cycloalkyl, (C6-C12)bicycloalkyl, (C7-C14)tricycloalkyl, (C6-C10)aryl, (C6-C10)aryl(C1-C6)alkyl, perfluoro(C6-C10)aryl and perfluoro(C6-C10)aryl(C1-C6)alkyl;
• or
• R23 and R24 taken together with the intervening carbon atoms to which they are attached to form a substituted or unsubstituted (C5-C14)cyclic, (C5-C14)bicyclic or (C5-C14)tricyclic ring;
• and Arylene is substituted or unsubstituted bivalent (C6-C14)aryl;
• or
• one of R13 and R14 taken together with one of R15 and R16 and the carbon atoms to which they are attached to form a substituted or unsubstituted (C5-C14)cyclic, (C5-C14)bicyclic or (C5-C14)tricyclic ring;
• and
• d) a photosensitizer.