Hindered amine stabilized UV active organopalladium catalyzed polycycloolefin compositions as optical materials

Patent metadata

Field	Value
Publication number	US-11299566-B2
Application number	US-202117356637-A
Country	US
Kind code	B2
Filing date	Jun 24, 2021
Priority date	Jun 24, 2020
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

Embodiments in accordance with the present invention encompass compositions comprising a organopalladium compound, a photoacid generator, a photosensitizer, one or more olefinic monomers and a stabilizer, such as for example a hindered amine, which undergo vinyl addition polymerization when said composition is exposed to a suitable actinic radiation to form a substantially transparent film. The compositions of this invention are stable at room temperature for several days to several months and can also be stored at higher temperatures from about 40° C. to 60° C. for several days and undergo mass polymerization only when subjected to suitable actinic radiation. 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, sealants, adhesives, 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), a compound of formula (IA) and a compound of formula (IB):

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 methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 1 -C 16 )perfluoroalkyl, (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, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, (C 1 -C 16 )perfluoroalkyl, (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):

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 ⊖ , BF 4 ⊖ , 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-l]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 ⊖ , SbF 6 ⊖ , n-C 4 F 9 SO 3 ⊖ , CF 3 SO 3 ⊖ and p-CH 3 (C 6 H 4 )—SO 3 ⊖ ;

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;
d) a compound selected from the group consisting of:
a compound of formula (X):

where Z 1 , Z 2 and Z 3 are the same or different and each independently is ((CH 2 ) g O) h (CH 2 ) g ) where g and h are integers from 2 to 4;
a compound of formula (XI):

where R 49 , R 50 , R 51 and R 52 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 20 )alkyl; and
a compound of formula (XII):

a compound of formula (XIII):

where j is an integer from 6 to 16;
R 53 , R 54 , R 56 , R 57 and R 58 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 20 )alkyl;
R 55 is selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 20 )alkyl, methoxy, ethoxy and linear or branched (C 3 -C 20 )alkoxy; and
a compound of formula (XIV):

where each m maybe same or different and is an integer from 2 to 6;
R 59 is a group of formula:

R 60 , R 61 , R 62 , R 63 , R 64 and R 65 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 20 )alkyl; and
a compound of formula (XV):

where p is an integer from 1 to 5;
each R 66 maybe the same or different and each independently selected from the group consisting of halogen, methyl, ethyl and linear or branched (C 3 -C 20 )alkyl and NR 67 R 68 , where each R 67 and R 67 are the same or different and each independently selected from the group consisting of methyl, ethyl and linear or branched (C 3 -C 20 )alkyl; and
e) a photosensitizer.

2. The composition according to claim 1 , wherein said olefinic monomer is of 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, epoxy(C 1 -C 10 )alkyl, epoxy(C 1 -C 10 )alkyloxy(C 1 -C 10 )alkyl, epoxy(C 3 -C 10 )cycloalkyl, 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

Assignees

• Promerus Llc

Inventors

• Hayakawa Shun
• Deng Guodong
• Burtovyy Ruslan
• Langsdorf Leah
• Rhodes Larry F

Classifications

• C08F4/7027 Primary

  OO · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F32/00

  Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system · CPC title

• C08F2500/17

  Viscosity · CPC title

• C08F2/02

  Polymerisation in bulk · CPC title