Polycyclic-olefinic compositions for low-loss films having improved thermal properties

Patent metadata

Field	Value
Publication number	US-11845880-B2
Application number	US-202117514400-A
Country	US
Kind code	B2
Filing date	Oct 29, 2021
Priority date	Oct 30, 2020
Publication date	Dec 19, 2023
Grant date	Dec 19, 2023

Abstract

Embodiments in accordance with the present invention encompass compositions containing one or more polycycloolefinic monomers and at least one multifunctional olefinic monomer which when subjected to a suitable temperature undergoes mass polymerization to provide a three-dimensional insulating article which exhibits hitherto unattainable low dielectric constant and low-loss properties, and very high thermal properties. The compositions of this invention may additionally contain one or more organic or inorganic filler materials, which provide improved thermo-mechanical properties in addition to very low dielectric properties. The compositions are stable at room temperature and undergo mass polymerization only when subjected to suitable higher temperatures generally above 100° C. The compositions of this invention are useful in various applications, including as insulating materials in millimeter wave radar antennas, among others.

First claim

What is claimed is:

1. A film forming composition comprising:
a) one or more olefinic monomers of the formula (I):

wherein:
m is 0 or 1;
is a single bond or a double bond;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, linear or branched (C 4 -C 16 )alkyl, linear or branched (C 2 -C 16 )alkenyl, (C 3 -C 10 )cycloalkyl, (C 3 -C 10 )cycloalkenyl, (C 6 -C 12 )bicycloalkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 6 )alkyl; or
one of R 1 and R 2 taken together with one of R 3 and R 4 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 optionally containing one or more double bonds;
b) a compound selected from the group consisting of:
a compound of formula (A1):

wherein:
b is an integer from 2 to 6;
Z is a bond or R 9 R 10 SiOSiR 11 R 12 , where each of R 9 , R 10 , R 11 and R 12 are the same or different and each independently of one another selected from the group consisting of methyl, ethyl and linear or branched (C 3 -C 6 )alkyl;

R 5 , R 6 , R 7 and R 8 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 16 )alkyl;
a compound of formula (A2):

wherein

R 13 , R 14 , R 15 and R 16 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C 3 -C 16 )alkyl; and
a compound of formula (A 3 ):

wherein

L is a bond or a divalent linking or a spacer group selected from:
methylene, ethylene, linear or branched (C 3 -C 16 )alkylene, (C 3 -C 16 )cycloalkylene, (C 5 -C 8 )heterocycle, (C 6 -C 12 )arylene, (C 5 -C 12 )heteroarylene and —(CH 2 ) c O(CH 2 ) c —, where c is an integer from 1 to 6 and optionally each of CH 2 may be substituted with methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, and (C 6 -C 12 )aryl, and wherein optionally portions of hydrogen on methylene, ethylene or (C 3 -C 16 )alkylene are replaced with a group selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched perfluoro(C 3 -C 16 )alkyl;
R 17 and R 18 are the same or different and each is independently selected from methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 12 )alkyl, where optionally portions of hydrogen on methyl, ethyl or (C 3 -C 12 )alkyl are replaced with a group selected from the group consisting of fluorine, trifluoromethyl, pentafluoroethyl and linear or branched (C 3 -C 12 )perfluoroalkyl;
Ar 1 and Ar 2 are the same or different and each is independently selected from (C 6 -C 12 )arylene or (C 6 -C 12 )heteroarylene group optionally substituted with a group selected from (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 6 -C 10 )aryl, (C 6 -C 12 )aryloxy, (C 6 -C 12 )aryl(C 1 -C 4 )alkyl and (C 6 -C 12 )aryl(C 1 -C 4 )alkyloxy;
c) an organopalladium compound selected from the group consisting of:
palladium (II) bis(triphenylphosphine) dichloride;
palladium (II) bis(triphenylphosphine) dibromide;
palladium (II) bis(triphenylphosphine) diacetate;
palladium (II) bis(triphenylphosphine) bis(trifluoroacetate);
palladium (II) bis(tricyclohexylphosphine) dichloride;
palladium (II) bis(tricyclohexylphosphine) dibromide;
palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785);
palladium (II) bis(tricyclohexylphosphine) bis(trifluoroacetate);
palladium (II) bis(tri-p-tolylphosphine) dichloride;
palladium (II) bis(tri-p-tolylphosphine) dibromide;
palladium (II) bis(tri-p-tolylphosphine) diacetate;
palladium (II) bis(tri-p-tolylphosphine) bis(trifluoroacetate);
palladium (II) ethyl hexanoate;
dichloro bis(acetonato)palladium (II);
dichloro bis(benzonitrile)palladium (II);
platinum (II) chloride;
platinum (II) bromide; and
platinum bis(triphenylphosphine)dichloride; and

d) an activator selected from the group consisting of:
lithium tetrafluoroborate;
lithium triflate;
lithium tetrakis(pentafluorophenyl)borate;
lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA);
lithium tetrakis(pentafluorophenyl)borate isopropanolate;
lithium tetraphenylborate;
lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate;
lithium tetrakis(2-fluorophenyl)borate;
lithium tetrakis(3-fluorophenyl)borate;
lithium tetrakis(4-fluorophenyl)borate;
lithium tetrakis(3,5-difluorophenyl)borate;
lithium hexafluorophosphate;
lithium hexaphenylphosphate;
lithium hexakis(pentafluorophenyl)phosphate;
lithium hexafluoroarsenate;
lithium hexaphenylarsenate;
lithium hexakis(pentafluorophenyl)arsenate;
lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate;
lithium hexafluoroantimonate;
lithium hexaphenylantimonate;
lithium hexakis(pentafluorophenyl)antimonate;
lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate;
lithium tetrakis(pentafluorophenyl)aluminate;
lithium tris(nonafluorobiphenyl)fluoroaluminate;
lithium (octyloxy)tris(pentafluorophenyl)aluminate;
lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate;
lithium methyltris(pentafluorophenyl)aluminate;
dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and

wherein the film formed from the composition has a dielectric constant (Dk) less than 2.4 at a frequency of 10 GHz, a glass transition temperature greater than 150° C. and a coefficient of thermal expansion (CTE) less than 150 ppm/K.

2. The film forming composition according to claim 1 , wherein
m is 0;
is a single bond;
R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl and norbornyl.

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

4. The film forming composition according to claim 1 , wherein the compound of formula (A1) or (A3) is selected from the group consisting of:

5. The film forming composition according to claim 1 , wherein the compound of formula (A 2 ) is:

1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethanobiphenylene ((NBD)2).

6. The film forming composition according to claim 1 , wherein the composition contains at least one monomer of formula (I) and one compound of formula (A1) or (A2) or (A3).

7. The film forming composition according to claim 1 , wherein the film formed from the composition has dielectric constant (Dk) of 2.0 to 2.38 at a frequency of 10 GHz, a glass transition temperature from about 160° C. to about 350° C. and a coefficient of thermal expansion (CTE) fr

Assignees

• Promerus Llc
• Sumitomo Bakelite Co

Inventors

• Kandanarachchi Pramod
• Rhodes Larry F
• Kubota Sho

Classifications

• C08F232/08 Primary

  having condensed rings (coumarone-indene polymers C08F244/00) · CPC title

• C09D165/00 Primary

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C08F36/20

  unconjugated · CPC title

• C08F212/06

  Hydrocarbons · CPC title

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title