IP Library › Granted Patent US 11,897,991

Granted Patent B2

US 11,897,991 · App. 17/137,497 · Granted Feb 13, 2024

UV active derivatives of Pd(AcAc)

Inventors: Guodong Deng (Akron, OH); Shun Hayakawa (Akron, OH); Larry F Rhodes (Akron, OH)

Assignee: PROMERUS, LLC

C08F32/08 C08J5/18 C08J2345/00

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Quick Facts

Patent No.: US 11,897,991
App. No.: 17/137,497
Granted: Feb 13, 2024
Kind: B2

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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.

Claims (208)

1. 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;

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 20 )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 (III):

a compound of formula (IV):

wherein:

a is an integer from 0 to 5;

An Θ is selected from the group consisting of Cl Θ , Br Θ , I Θ , BF 4 Θ , 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 Θ , SbF 6 Θ , n-C 4 F 9 SO 3 Θ , CF 3 SO 3 Θ and p-CH 3 (C 6 H 4 )—SO 3 Θ ; and

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 )bicycloalky, (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 Rib 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 20 )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 3 )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 12 )aryloxy, (C 6 -C 12 )aryloxy(C 1 -C 6 )alkyl, (C 6 -C 12 )aryl(C 1 -C 6 )alkoxy, perfluoro(C 6 -C 12 )aryloxy, perfluoro(C 6 -C 12 )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 ) b 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 ) b 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 unsubstituted (C 6 -C 14 )aryl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, and substituted or unsubstituted (C 6 -C 14 )aryloxy; and

b 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 said substituents are selected from the group consisting of halogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (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 3 )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 )aryloxy, (C 6 -C 12 )aryloxy(C 1 -C 6 )alkyl, (C 6 -C 12 )aryl(C 1 -C 6 )alkoxy, perfluoro(C 6 -C 12 )aryloxy and perfluoro(C 6 -C 12 )aryl(C 1 -C 3 )alkoxy;

k is an integer from 1 to 12;

R 23 , R 24 and R 25 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 12 )alkoxy, (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 and perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl; or

R 23 and R 24 taken together with the intervening carbon atoms to which they are attached to form a substituted or unsubstituted (C 5 -C 14 )cyclic, (C 5 -C 14 )bicyclic or (C 5 -C 14 )tricyclic ring; and Arylene is substituted or unsubstituted bivalent (C 6 -C 14 )aryl;

one of R 13 or R 14 taken together with one of R 15 or R 16 and the carbon atoms to which they are attached to form a substituted or unsubstituted (C 5 -C 14 )cyclic, (C 5 -C 14 )bicyclic or (C 5 -C 14 )tricyclic ring.

3. The composition according to claim 2 , wherein said composition comprises at least two distinctive monomers of formula (V) and is in a clear liquid state having a viscosity below 100 centipoise.

4. The composition according to claim 2 , wherein said composition contains said two distinctive monomers of formula (V) in a molar ratio of from 1:99 to 99:1.

5. The composition according to claim 1 , wherein said composition forms a substantially transparent film when exposed to suitable actinic radiation.

6. The composition according to claim 5 , wherein said film has a transmission of equal to or higher than 90 percent of the visible light.

7. The composition according to claim 5 , wherein said film has a transmission of equal to or higher than 95 percent of the visible light.

8. The composition according to claim 1 , wherein said bidentate monoanionic ligand is selected from the group consisting of:

9. The composition according to claim 2 further comprising one or more monomers selected from the group consisting of a monomer of formula (VI) and a monomer of formula (VII), wherein said monomer of formula (VI) is:

wherein:

o is an integer from 0 to 2, inclusive;

D is SiR 29 R 30 R 31 or a group selected from:

—(CH 2 ) c —O—SiR 29 R 30 R 31 (E);

—(CH 2 ) c —SiR 29 R 30 R 31 (F); and

—(SiR 29 R 30 ) c —O—SiR 29 R 30 R 31 (G); wherein

c is an integer from 1 to 10, inclusive, and where one or more of CH 2 is optionally substituted with (C 1 -C 10 )alkyl or (C 1 -C 10 )perfluoroalkyl;

R 26 , R 27 and R 28 are the same or different and independently of each other selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyl is selected from 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 or (C 6 -C 10 )aryloxy; and

R 29 , R 30 and R 31 are each independently of one another methyl, ethyl, linear or branched (C 3 -C 9 )alkyl, substituted or unsubstituted (C 6 -C 14 )aryl, methoxy ethoxy, linear or branched (C 3 -C 9 )alkoxy or substituted or unsubstituted (C 6 -C 14 )aryloxy;

said monomer of formula (VII) is:

wherein:

Z 1 is selected from the group consisting of substituted or unsubstituted (C 1 -C 12 )alkylene, —(CH 2 ) d (SiR 38 R 39 )(OSiR 40 R 41 ) f (CH 2 ) e —, —(CH 2 ) d O(CH 2 ) e —, where d, e and f are independently integers from 0 to 6, inclusive, R 38 , R 39 , R 40 and R 41 are the same or different and independently of each other selected from methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, and an arylene selected from the following:

R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are the same or different and independently of each other selected from hydrogen, halogen and hydrocarbyl, where hydrocarbyl is selected from 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 or (C 6 -C 10 )aryloxy.

10. The composition according to claim 2 , wherein the monomer of formula (V) is selected from the group consisting of:

2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)naphthalene;

1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)naphthalene;

2-((3-methylbicyclo[2.2.1]hept-5-en-2-yl)methyl)naphthalene;

2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-7-methylnaphthalene;

5-([1,1′-biphenyl]-3-ylmethyl)bicyclo[2.2.1]hept-2-ene;

54(2′-methyl-[1,1′-biphenyl]-3-yl)methyl)bicyclo[2.2.1]hept-2-ene;

5-([1,1′-biphenyl]-4-ylmethyl)bicyclo[2.2.1]hept-2-ene:

5-([1,1′-biphenyl]-2-ylmethyl)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1′-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtPhPh);

5-(2-(4′-ethyl-[1,1′-biphenyl]-4-yl)ethyl)bicyclo[2.2.1]hept-2-ene;

5-(3-([1,1′-biphenyl]-4-yl)propyl)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1′-biphenyl]-4-yl)ethoxy)bicyclo[2.2.1]hept-2-ene;

5-(2-(2′,4′-dimethyl-[1,1′-biphenyl]-4-yl)ethoxy)bicyclo[2.2.1]hept-2-ene;

bicyclo[2.2.1]hept-5-en-2-yl 2-([1,1′-biphenyl]-4-yl)acetate;

bicyclo[2.2.1]hept-5-en-2-ylmethyl [1,1′-biphenyl]-4-carboxylate;

5-(2-([1,1′-biphenyl]-4-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene;

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh);

[1,1′-biphenyl]-4-yl 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetate;

2-((4-(bicyclo[2.2.1]hept-5-en-2-yl)butoxy)methyl)naphthalene;

5-(4-([1,1′-biphenyl]-4-yl)butyl)bicyclo[2.2.1]hept-2-ene;

(9H-fluoren-9-yl)methyl (bicyclo[2.2.1]hept-5-en-2-ylmethyl) carbonate;

1-(4-bicyclo[2.2.1]hept-5-en-2-ylethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione;

1-(4-bicyclo[2.2.1]hept-5-en-2-ylpropyl)-3,4-dimethyl-1H-pyrrole-2,5-dione;

1-(4-bicyclo[2.2.1]hept-5-en-2-ylbutyl)-3,4-dimethyl-1H-pyrrole-2,5-dione;

5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

5-(2-phenoxyethyl)bicyclo[2.2.1]hept-2-ene;

5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

5-phenethoxybicyclo[2.2.1]hept-2-ene;

5-((benzyloxy)methyl)bicyclo[2.2.1]hept-2-ene;

5-(phenoxymethyl)bicyclo[2.2.1]hept-2-ene;

5-phenethylbicyclo[2.2.1]hept-2-ene;

5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

5-(2-chloroethyl)bicyclo[2.2.1]hept-2-ene (NBEtCl);

5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-dodecylbicyclo[2.2.1]hept-2-ene (DoDecNB); and

5-tetradecylbicyclo[2.2.1]hept-2-ene (TetraDecNB).

11. The composition according to claim 9 , wherein the monomer of formula (VI) or the monomer of formula (VII) is selected from the group consisting of:

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH 2 OSiMePh 2 );

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane;

bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC 2 H 5 ) 3 ;

bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane;

(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)benzene;

4,4′-di(bicyclo[2.2.1]hept-5-en-2-yl)-1,1′-biphenyl;

4,4″-di(bicyclo[2.2.1]hept-5-en-2-yl)-1,1′:4′,1″-terphenyl;

1,3-bis(norbornenylethyl)-1,1,3,3,-tetramethyldisiloxane; and

1,5-bis(norbornenylethyl)-1,1,3,3,5,5,-hexamethyltrisiloxane.

12. The composition according to claim 1 , wherein the organopalladium compound of formula (I) is selected from the group consisting of:

palladium (acetylacetonate) 2 (Pd(acac) 2 or Pd304);

palladium (hexafluoroacetylacetonate) 2 (Pd(hfac) 2 or Pd520);

palladium (tetramethylheptenonoate) 2 (Pd(tmhd) 2 or Pd473);

palladium (trifluoroacetylacetonate) 2 (Pd(tfacac) 2 );

palladium (pentafluoropropionyltrifluoroacetonate) 2 ;

13. The composition according to claim 1 , wherein the compound of formula (III) or the compound of formula (IV) is selected from the group consisting of:

tolylcumyliodonium-tetrakis pentafluorophenylborage;

4-(octyloxy)phenyl)(phenyl)iodonium hexafluorophosphate (OPPI-PF 6 );

4-(octyloxy)phenyl)(phenyl)iodonium hexafluoroantimonate (OPPI-SBF 6 );

bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate;

bis(4-tert-butylphenyl)iodonium p-toluenesulfonate;

bis(4-tert-butylphenyl)iodonium triflate;

where R 42 and R 43 are the same or different and each independently selected from linear or branched (C 10 -C 13 )alkyl;

diphenyliodonium chloride;

(4-thiophenyl)phenyl-diphenylsulfonium hexafluorophosphate;

bis-(triphenylsulfonium) sulfide bis-hexafluorophosphate;

tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate;

tris(4-tert-butylphenyl)sulfonium triflate;

triphenylsulfonium chloride;

(4-phenoxyphenyl)diphenylsulfonium triflate;

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis-pentafluorophenylborate; and

(2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis-pentafluorophenylborate.

14. The composition according to claim 1 , wherein the photosensitizer is a compound of formula (VIII):

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, chlorine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, propoxy and phenoxy.

15. The composition according to claim 1 , wherein the compound of formula (VIII) or the compound of formula (IX) is selected from the group consisting of:

1-chloro-4-methoxy-9H-thioxanthen-9-one;

1-chloro-4-ethoxy-9H-thioxanthen-9-one;

1-chloro-4-propoxy-9H-thioxanthen-9-one;

1-chloro-2-propoxy-9H-thioxanthen-9-one;

1-chloro-2-ethoxy-9H-thioxanthen-9-one;

1-chloro-2-methoxy-9H-thioxanthen-9-one;

1-chloro-4-methyl-9H-thioxanthen-9-one;

1-chloro-4-ethyl-9H-thioxanthen-9-one;

1-chloro-4-phenoxy-9H-thioxanthen-9-one;

2-chlorothioxanthen-9-one (CTX);

2-isopropyl-9H-thioxanthen-9-one (ITX);

9,10-dimethoxyanthracene (DMA);

9,10-diethoxyanthracene (DEA); and

9,10-di-n-butoxyanthracene (DBA).

16. The composition according to claim 1 , which is selected from the group consisting of:

5-(2-chloroethyl)bicyclo[2.2.1]hept-2-ene (NBEtCl), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (acetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-chloro-9H-thioxanthen-9-one (CTX);

5-(2-chloroethyl)bicyclo[2.2.1]hept-2-ene (NBEtCl), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-chloro-9H-thioxanthen-9-one (CTX);

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , 4-(octyloxy)phenyl)(phenyl)iodonium hexafluorophosphate (OPPI-PF 6 ) and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , 4-(octyloxy)phenyl)(phenyl)iodonium hexafluoroantimonate (OPPI-SbF 6 ) and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (hexafluoroacetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (hexafluoroacetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-chloroethyl)bicyclo[2.2.1]hept-2-ene (NBEtCl), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-chloro-9H-thioxanthen-9-one (CTX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (acetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (tetramethylheptenonoate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , (2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis-pentafluorophenylborate (TAG 382) and 9,10-diethoxyanthracene (DEA);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis-pentafluorophenylborate and 9,10-diethoxyanthracene (DEA); and

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , Iodonium, diphenyl-4,4′-di-(C 10 -C 13 )-alkyl derivatives, tetrakis(2,3,4,5,6-pentafluorophenyl)borates and 2-isopropyl-9H-thioxanthen-9-one (ITX).

17. 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;

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 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;

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

18. The kit according to claim 17 , which contains at least two distinct first and second monomers of formula (V), wherein the first monomer is completely soluble in the second monomer, and when said composition is exposed to suitable actinic radiation for a sufficient length of time it forms a substantially transparent film having at least 90 percent of visible light transmission.

19. The kit according to claim 17 , which is selected from the group consisting of:

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , 4-(octyloxy)phenyl)(phenyl)-iodonium hexafluorophosphate (OPPI-PF 6 ) and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , 4-(octyloxy)phenyl)(phenyl)-iodonium hexafluoroantimonate (OPPI-SbF 6 ) and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (acetylacetonate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), 5-(2-([1,1′-biphenyl]-2-yloxy)ethyl)bicyclo[2.2.1]hept-2-ene (NBEtOPhPh), 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), palladium (tetramethylheptenonoate) 2 , tolylcumyliodonium-tetrakis pentafluorophenylborate and 2-isopropyl-9H-thioxanthen-9-one (ITX);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (hexafluoroacetylacetonate) 2 , tris(4-((4-acetylphenyl)thio)phenyl)-sulfonium tetrakis-pentafluorophenylborate and 9,10-diethoxyanthracene (DEA).

20. A film formed from the composition of claim 1 .

Assignments (2)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 21, 2024

From: PROMERUS, LLC

To: SUMITOMO BAKELITE CO., LTD.

Reel/Frame 069364/0733 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 5, 2021

From: DENG, GUODONG; HAYAKAWA, SHUN; RHODES, LARRY F

To: PROMERUS, LLC

Reel/Frame 056143/0030 →

Continuity (2)

Provisional Application 62954911 · Dec 30, 2019

Related Publication 20210198392A1 · Jul 1, 2021

Cited By (1)

US 12,391,775