UV active derivatives of pd(AcAc)2L catalyzed polycycloolefin compositions as optical materials

Patent metadata

Field	Value
Publication number	US-11746166-B2
Application number	US-202017137518-A
Country	US
Kind code	B2
Filing date	Dec 30, 2020
Priority date	Dec 30, 2019
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

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.

First claim

What is claimed is:

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 C q H x F y , 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, (C 6 -C 10 )aryl(C 1 -C 16 )alkyl and substituted or unsubstituted (C 6 -C 10 )aryl;
R 3 , R 4 and R 6 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula C q H x F y , 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, (C 3 -C 10 )cycloalkyl, (C 6 -C 10 )aryl(C 1 -C 16 )alkyl and substituted or unsubstituted (C 6 -C 10 )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;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched alkyl and fluoroalkyl having the formula C q H x F y , 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, (C 3 -C 10 )cycloalkyl, (C 6 -C 10 )aryl(C 1 -C 16 )alkyl and substituted or unsubstituted (C 6 -C 10 )aryl; provided when either X or Y is O or S, R 1 and R 5 , 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 {circle around (−)} is selected from the group consisting of Cl {circle around (−)} , Br {circle around (−)} , I {circle around (−)} , BF 4 {circle around (−)} , 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, PF 6 {circle around (−)} , SbF 6 {circle around (−)} , n-C 4 F 9 SO 3 {circle around (−)} , CF 3 SO 3 {circle around (−)} and p-CH 3 (C 6 H 4 )—SO 3 {circle around (−)} ;
R 8 , R 9 , R 10 , R 11 and R 12 are the same or different and each independently selected from the group consisting of halogen, methyl, ethyl, linear or branched (C 3 -C 20 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 6 -C 10 )thioaryl, (C 1 -C 6 )alkanoyl(C 6 -C 10 )thioaryl, (C 1 -C 6 )alkoxy(C 6 -C 10 )aroyl(C 1 -C 6 )alkyl and (C 6 -C 10 )thioaryl-(C 6 -C 10 )diarylsulfonium salt; and
d) a photosensitizer selected from the group consisting of a compound of formula (VIII) and a compound of formula (IX):

wherein
R 44 , R 45 and R 46 are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, hydroxy, NO 2 , NH 2 , methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 ) bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, C(O)(C 1 -C 6 )alkyl, COOH, C(O)O(C 1 -C 6 )alkyl, and SO 2 (C 6 -C 10 )aryl; and
R 47 and R 48 are the same or different and independently of each other selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 3 )alkyl.

2. The composition according to claim 1 , wherein said olefinic monomer is of the formula (V):

wherein:
m is an integer 0, 1 or 2;
is a single bond or a double bond;
R 13 , R 14 , R 15 and R 16 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 (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 16 )alkoxy, perfluoro(C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy, (C 6 -C 10 )aryl(C 1 -C 6 )alkoxy, perfluoro(C 6 -C 10 )aryloxy, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )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, (CR 17 R 18 ) b , O(CR 17 R 18 ) b , (CR 17 R 18 ) b O, C(O)(CR 17 R 18 ) b , (CR 17 R 18 ) b C(O), C(O)O(CR 17 R 18 ) b , (CR 17 R 18 ) b C(O)O, OC(O)(CR 17 R 18 ) b , (CR 17 R 18 ) b OC(O), (CR 17 R 18 ) b OC(O)O, (CR 17 R 18 ) 6 OC(O)O(CR 17 R 18 ) b , OC(O)O(CR 17 R 18 ) b , S(CR 17 R 18 ) b , (CR 17 R 18 ) b S, (SiR 17 R 18 ) b , O(SiR 17 R 18 ) b , (SiR 17 R 18 ) 6 O, where

R 17 and R 18 are the same or different and each independently selected from hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, substituted or

Assignees

• Promerus Llc

Inventors

• Deng Guodong
• Burtovyy Oleksandr
• Hayakawa Shun

Classifications

• C08F4/7091

  OOOO · CPC title

• H10K50/858

  comprising refractive means, e.g. lenses · CPC title

• C08F132/08 Primary

  having condensed rings · CPC title

• C08L45/00 Primary

  Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers (of cyclic anhydrides or imides C08L35/00; of cyclic esters of polyfunctional acids C08L31/00) · CPC title

• C08F4/80

  selected from iron group metals or platinum group metals · CPC title