Polycycloolefin monomers and catalyst activated by compound capable of generating photoacid as optical materials

Patent metadata

Field	Value
Publication number	US-10675614-B2
Application number	US-201916257137-A
Country	US
Kind code	B2
Filing date	Jan 25, 2019
Priority date	Jan 26, 2018
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

Embodiments in accordance with the present invention encompass compositions encompassing a latent catalyst and a compound capable of generating a Bronsted acid along with one or more monomers which undergo ring open metathesis polymerization (ROMP) when said composition is exposed to a suitable radiation to form a substantially transparent film. The monomers employed therein have a range of refractive index from 1.4 to 1.6 and thus these compositions can be tailored to form transparent films of varied refractive indices. The composition of this invention also features low dielectric constant (low k in the range of from about 2.2 to 3). Accordingly, compositions of this invention are useful in various opto-electronic applications, including as coatings, encapsulants, fillers, leveling agents, among others.

First claim

What is claimed is:

1. A composition comprising:
an one or more monomers of formula (I):

wherein;
m is an integer 0, 1 or 2;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, hydroxy(C 1 -C 16 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (CH 2 ) a —(C 6 -C 12 )bicycloalkenyl, (C 7 -C 14 )tricycloalkyl, substituted or unsubstituted (C 6 -C 10 )aryl, substituted or unsubstituted (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 and a group of formula (A):
—Z-Aryl  (A)

wherein:
Z is a bond or a group selected from the group consisting of:
(CR 5 R 6 ) a , O(CR 5 R 6 ) a , (CR 5 R 6 ) a O, (CR 5 R 6 ) a —O—(CR 5 R 6 ) b , (CR 5 R 6 ) a —O—(SiR 5 R 6 ) b , (CR 5 R 6 ) a —(CO)O—(CR 5 R 6 ) b , (CR 5 R 6 ) a —O(CO)—(CR 5 R 6 ) b and (CR 5 R 6 ) a —(CO)—(CR 5 R 6 ) b , where a and b are integers which may be the same or different and each independently is 1 to 12, inclusive;
R 5 and R 6 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, acetoxy, (C 2 -C 6 )acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C 3 -C 6 )alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted phenoxy;

Aryl is phenyl or phenyl substituted with one or more of groups selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, acetoxy, (C 2 -C 6 )acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C 3 -C 6 )alkyl, phenyl and phenoxy; or
one of R 1 or R 2 taken together with one of R 3 or R 4 and the carbon atoms to which they are attached to form a (C 5 -C 7 )carbocyclic ring optionally containing one or more double bonds;
b) a latent organo-transition metal catalyst comprising a metal selected from the group consisting of ruthenium and osmium; and
c) a compound capable of releasing a Bronsted acid when subjected to photolytic conditions which is of the formula:

wherein
Y is halogen; and
R 30 and R 31 are the same or different and independently of each other selected from the group consisting of hydrogen, 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 and (C 6 -C 10 )-aryloxy; and wherein
said composition is in a clear liquid form at room temperature.

2. The composition according to claim 1 , wherein said composition comprises first and second monomer of formula (I) distinct from each other and one of said first and second monomers having a refractive index of at least 1.5 and viscosity below 50 centipoise, and wherein said first monomer is completely miscible with said second monomer to form a clear solution.

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

4. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 90 percent of the visible light.

5. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 95 percent of the visible light.

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

7. The composition according to claim 1 , wherein the latent catalyst is an organo-ruthenium compound selected from the group consisting of a compound of formula (HIA), a compound of formula (IIB), a compound of formula (IIIA), a compound of formula (IIIB) and a compound of formula (IIIC):

wherein:
X is selected from the group consisting of chlorine, bromine, iodine, —OR a , —O(CO)R a and —OSO 2 R a , where R a is selected from the group consisting of (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl and (C 6 -C 14 )aryl;
Y is selected from the group consisting of O, S and NCOCF 3 ;
Y′ is selected from the group consisting of OR 9 , SR 9 and —N—CHC(O)O(C 1 -C 6 )alkyl, where R 9 is selected from the group consisting of methyl, ethyl, linear or branched (C 1 -C 6 )alkyl, (C 6 -C 10 )aryl, methoxy, ethoxy, linear or branched (C 1 -C 6 )alkoxy, (C 6 -C 10 )aryloxy and —OCH(CH 3 )C(O)N(CH 3 )(OCH 3 );
L is selected from the group consisting of pyridine, PR 3 or O═PR 3 , where each R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C 5 -C 10 )alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy phenoxy and benzyloxy;
R 7 is selected from the group consisting of isopropyl, sec-butyl, tert-butyl substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
R 8 is selected from the group consisting of chlorine, methyl, ethyl, linear or branched (C 1 -C 6 )alkyl, (C 6 -C 10 )aryl, methoxy, ethoxy, linear or branched (C 1 -C 6 )alkoxy, (C 6 -C 10 )aryloxy, —NHCO(C 1 -C 6 )alkyl, —NHCO-perfluoro(C 1 -C 6 )alkyl, —SO 2 N((C 1 -C 6 )alkyl) 2 and —NO 2 ;
Ar 1 , Ar 2 Ar 3 and Ar 4 are the same or different and each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl, phenyl and OSi(SiMe 3 ) 3 , where Me is methyl.

8. The composition according to claim 7 , wherein the organo-ruthenium compound is selected from the group consisting of:

1,3-bis(2,4,6-trimethylphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(VI) chloride;

where Cy is cyclohexyl and X is selected from the group consisting of bromine, iodine, —OR a , —O(CO)R a and —OSO 2 R a , where R a is selected from the group consisting of (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl and (C 6 -C 14 )aryl;

where X is Cl or I, Cy is cyclohexyl an R 8 or Cl;

cis-[1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1H-inden-1-ylidene)(triisopropylphosphite)ruthenium(II).

9. The composition according to claim 1 further comprisi

Assignees

• Promerus Llc

Inventors

• Burtovyy Oleksandr

Classifications

• G06F2203/04104

  Multi-touch detection in digitiser, i.e. details about the simultaneous detection of a plurality of touching locations, e.g. multiple fingers or pen and finger · CPC title

• G06F3/165

  Management of the audio stream, e.g. setting of volume, audio stream path · CPC title

• C08G61/12

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08L2203/16

  used for films · CPC title