# US 12,180,385 B2 · Shelf life stable and improved mass polymerizable polycyclic-olefinic compositions

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- Number: US 12,180,385 B2
- Document ID: US12180385B2
- Status: Granted
- Kind: B2
- Application number: 17/514,579
- Filed: 2021-10-29
- Published: 2022-05-05
- Granted: 2024-12-31
- Earliest claimed: 2020-10-30
- Assignees: Promerys, LLC
- Applicants: Promerus, LLC
- Inventors: Pramod Kandanarachchi
- Web page: https://patentgrep.com/patent/US12180385B2

## CPC

- C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
- C09D 165/00: 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
- C08F 232/08: having condensed rings (coumarone-indene polymers C08F244/00)
- C08F 2500/26: Use as polymer for film forming
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/1414: Unsaturated aliphatic units
- C08G 2261/144: Side-chains containing silicon
- C08G 2261/148: Side-chains having aromatic units
- C08G 2261/3324: derived from norbornene
- C08G 2261/418: Ring opening metathesis polymerisation [ROMP]
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Embodiments in accordance with the present invention encompass compositions containing one or more polycycloolefinic monomers, optionally at least one multifunctional olefinic monomer and a suitable solvent, which exhibits long shelf life stability and undergoes mass polymerization only when subjected to a suitable temperature to provide a three-dimensional insulating articles. Embodiments of this invention exhibit hitherto unattainable properties, such as for example, low dielectric constant and low loss properties, and very high thermal properties, among others. 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. In general the compositions are stable at room temperature for an extended period of time lasting up to a few weeks 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.

## Claims

### Claim 1

A film forming composition comprising:
a) one or more olefinic monomers selected from the group consisting of:
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD);
tetracyclododecene (TD);
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);
2,2′-bi(bicyclo[2.2.1]heptan-5-ene (NBANB);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);
bicyclo[2.2.1]hepta-2,5-diene (NBD);
and
3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3);
b) an organopalladium compound selected from the group consisting of:
palladium (II) bis(tricyclohexylphosphine) dichloride;
palladium (II) bis(tricyclohexylphosphine) dibromide;
palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785); and
palladium (II) bis(tricyclohexylphosphine) bis(trifluoroacetate); and
c) an activator selected from the group consisting of:
tolylcumyliodonium-tetrakis pentafluorophenylborate;
4,4′-di-(C10-C13) alkyldiphenyl iodonium tetrakis(2,3,4,5,6-pentafluorophenyl) borate;
lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); and
dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and
d) a solvent selected from the group consisting of water, toluene, trifluorotoluene, tetrahydrofuran, ethyl acetate, cyclohexane, methylcyclohexane, and a mixture in any combination thereof; and
wherein the composition exhibits shelf life stability from about one hour up to seven weeks at about 25° C. and undergoes mass polymerization only when subjected to a suitable temperature above 100° C.

### Claim 2 (depends on 1)

The film forming composition according to claim 1, which further comprises 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 R9R10SiOSiR11R12, where each of R9, R10, R11 and R12 are the same or different and each independently of one another selected from the group consisting of methyl, ethyl and linear or branched (C3-C6) alkyl;
R5, R6, R7 and R8 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C16) alkyl; and
a compound of formula (A2):
wherein
R13, R14, R15 and R16 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C16)alkyl.

### Claim 3 (depends on 1)

The film forming composition according to claim 1, wherein the monomer is selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD);
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD);
and
3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3).

### Claim 4 (depends on 2)

The film forming composition according to claim 2, wherein the compound of formula (A1) is selected from the group consisting of:
1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl) ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB); and
1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBC4NB).

### Claim 5 (depends on 2)

The film forming composition according to claim 2, wherein the compound of formula (A2) is:
1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethanobiphenylene ((NBD)2).

### Claim 6 (depends on 1)

The film forming composition according to claim 1, which further comprises an inorganic filler.

### Claim 7 (depends on 1)

The film forming composition according to claim 1, which is selected from the group consisting of:
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA);
2,2′-bi(bicyclo[2.2.1]heptan-5-ene (NBANB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA);
5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and tolylcumyliodonium-tetrakis pentafluorophenylborate;
5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and 4,4′-di-(C10-C13)alkyldiphenyl iodonium tetrakis(2,3,4,5,6-pentafluorophenyl) borate;
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

### Claim 8

A kit for forming a film comprising a composition comprising:
a) one or more olefinic monomers of formula (I) selected from the group consisting of:
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD);
tetracyclododecene (TD);
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);
2,2′-bi(bicyclo[2.2.1]heptan-5-ene (NBANB);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);
bicyclo[2.2.1]hepta-2,5-diene (NBD);
and
3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3);
b) an organopalladium compound selected from the group consisting of:
palladium (II) bis(tricyclohexylphosphine) dichloride;
palladium (II) bis(tricyclohexylphosphine) dibromide;
palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785); and
palladium (II) bis(tricyclohexylphosphine) bis(trifluoroacetate); and
c) an activator selected from the group consisting of:
tolylcumyliodonium-tetrakis pentafluorophenylborate;
4,4′-di-(C10-C13)alkyldiphenyl iodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate;
lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); and
dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and
d) a solvent selected from the group consisting of water, toluene, trifluorotoluene, tetrahydrofuran, ethyl acetate, cyclohexane, methylcyclohexane, and a mixture in any combination thereof; and
wherein the composition exhibits shelf life stability from about one hour up to seven weeks at about 25° C. and undergoes mass polymerization only when subjected to a suitable temperature above 100° C.

### Claim 9 (depends on 8)

The kit according to claim 8, wherein the monomer is selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD);
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD);
and
3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3).

### Claim 10 (depends on 8)

The kit according to claim 8, which further comprises:
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 R9R10SiOSiR11R12, where each of R9, R10, R11 and R12 are the same or different and each independently of one another selected from the group consisting of methyl, ethyl and linear or branched (C3-C6)alkyl;
R5, R6, R7 and R8 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C16) alkyl; and
a compound of formula (A2):
wherein
R13, R14, R15 and R16 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl and linear or branched (C3-C16)alkyl.

### Claim 11 (depends on 10)

The kit according to claim 10, wherein the compound of formula (A1) is selected from the group consisting of:
1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB); and
1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBC4NB).

### Claim 12 (depends on 10)

The kit according to claim 10, wherein the compound of formula (A2) is:
1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethanobiphenylene ((NBD)2).

### Claim 13 (depends on 8)

The kit according to claim 8, which further comprises an inorganic filler.

### Claim 14 (depends on 8)

The kit according to claim 8, which is selected from the group consisting of:
2-hexyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (HexTD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA);
2,2′-bi(bicyclo[2.2.1]heptan-5-ene (NBANB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA);
5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and tolylcumyliodonium-tetrakis pentafluorophenylborate;
5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and 4,4′-di-(C10-C13)alkyldiphenyl iodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate;
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA);
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and
5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a, 9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium (II) bis(tricyclohexylphosphine) diacetate (Pd785) and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).