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US 11,897,991 B2Granted
UV active derivatives of Pd(AcAc)2 catalyzed polycycloolefin compositions as optical materials
AssigneePromerus, LLC
InventorsGuodong Deng, Shun Hayakawa, Larry F Rhodes
Life of this patent
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Abstract
Embodiments in accordance with the present invention encompass compositions comprising a organopalladium compound, a photoacid generator, a photosensitizer and one or more olefinic monomers which undergo vinyl addition polymerization when said composition is exposed to a suitable actinic radiation to form a substantially transparent film. The monomers employed therein have a range of optical and mechanical properties, and thus these compositions can be tailored to form films having various opto-electronic properties. Accordingly, compositions of this invention are useful in various applications, including as coatings, encapsulants, fillers, leveling agents, among others.
Claims20
A composition comprising:
- a) one or more olefinic monomers;
- b) an organopalladium compound of formula (I):
- wherein:
- 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, methyl, ethyl, linear or branched (C3-C20)alkyl, (C1-C16)perfluoroalkyl, (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 (III):
- a compound of formula (IV):
- wherein:
- a is an integer from 0 to 5;
- AnΘ is selected from the group consisting of ClΘ, BrΘ, IΘ, BF4Θ, 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, PF6Θ, SbF6Θ, n-C4F9SO3Θ, CF3SO3Θ and p-CH3(C6H4)—SO3Θ;
- and
- 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)bicycloalky, (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.
20 more elements
A kit for forming a substantially transparent film comprising:
- a) one or more olefinic monomers;
- b) an organopalladium compound of formula (I):
- wherein:
- 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, methyl, ethyl, linear or branched (C3-C16)alkyl, (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;
- AnΘ is selected from the group consisting of ClΘ, BrΘ, IΘ, BF4Θ, 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, PF6Θ, SbF6Θ, n-C4F9SO3Θ, CF3SO3Θ and p-CH3(C6H4)—SO3Θ;
- and
- 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)bicycloalky, (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.
21 more elements
Dependencies are inferred from the claim text.