Polymers based on diisoalkenylarenes and uses thereof

Patent metadata

Field	Value
Publication number	US-11873369-B2
Application number	US-202117644146-A
Country	US
Kind code	B2
Filing date	Dec 14, 2021
Priority date	Dec 23, 2020
Publication date	Jan 16, 2024
Grant date	Jan 16, 2024

Abstract

Polymers are obtained by polymerizing in the presence of a Bronsted acid or a Lewis acid catalyst, a monomer comprising a 1,3-diisoalkenylarene, a 1,4-diisoalkenylarene, or mixtures thereof. The polymer comprises at least one of repeat units (A), (B), (C), and (D); wherein R 1 is H or a C1-C8 alkyl group.

The polymers have high T g and exhibit good solubility in non-polar solvents, forming substantially gel-free solutions. The polymers are useful for producing crosslinked materials having good physical properties. The crosslinked materials are valuable for further downstream uses, such as copper clad laminates.

First claim

The invention claimed is:

1. A polymer comprising a combination of repeat units (A), (B), (C) and (D):

wherein R 1 is a H, C1-C8 alkyl group;
wherein Ar is an arene ring;
wherein the polymer has a solubility in a hydrocarbon solvent at 25° C. of at least 10 wt. °;
wherein the polymer has a T g of from 50° C. to 300° C., measured using DSC according to ASTM D3418;
wherein the polymer forms a substantially gel-free solution in a hydrocarbon solvent; and
wherein the polymer has a weight average molecular weight of 8,000 to 70,000 Dalton, measured according to ASTM D5296.

2. The polymer of claim 1 , wherein R 1 is methyl, ethyl, isopropyl, or n-butyl.

3. The polymer of claim 1 , wherein said polymer comprises at least one terminal group selected from structures (F), (F), (G) and (H):

wherein R 1 is H or a C1-C8 alkyl group, and
wherein Ar is an arene ring.

4. The polymer of claim 1 , having one or more of
a viscosity of 3,000 to 15,000 cP, measured on a 50 wt. % solution in cyclohexane at 25° C.;
a viscosity of 50 to 1200 cP, measured on a 50 wt. % solution in toluene at 25° C.;
a viscosity of 5 to 100 cP, measured on a 15 wt. % solution in toluene at 25° C.;
a Tg of 50-300° C. measured using DSC according to ASTM D341;
a moisture absorption coefficient of less than 0.05, measured at 25° C. according to ASTM D570;
a permittivity (Dk) of 2-2.5, according to ASTM D2520; and
a loss tangent (Df) of 0.0001-0.002, according to ASTM D2520.

5. The polymer of claim 1 , further comprising structural units derived from a comonomer selected from:
(i) a cyclodiene or a dimer thereof;
(ii) a divinylarene other than the diisoalkenylarene of formulas (I (ii) or combinations thereof;
(iii) an adduct of a cyclodiene and an acyclic diene;
(iv) an allyl compound having two or more allyl groups;
(v) a vinyl compound other than the divinylarene (ii) and having two or more vinyl groups;
and any combination thereof.

6. The polymer of claim 1 , wherein said polymer is obtained by electrophilically polymerizing in the presence of a Bronsted acid or a Lewis acid catalyst, a monomer comprising any of a 1,3-diisoalkenylarene (I), a 1,4-diisoalkenylarene (II), or mixtures thereof

wherein R 1 is H or a C1-C8 alkyl group, and
wherein Ar is an arene ring.

7. The polymer of claim 5 , wherein the cyclodiene is a 1,3-cyclohexadiene.

8. The polymer of claim 5 , wherein the cyclodiene is a 1,3-cyclodiene dimer comprising vinyl norbornene.

9. The polymer of claim 6 , wherein the polymerizing is conducted in a hydrocarbon solvent selected from an aliphatic hydrocarbon, an aromatic hydrocarbon, and combinations thereof.

10. The polymer of claim 6 , wherein said polymerizing comprises adding the monomer to a solution of the Bronsted acid or Lewis acid catalyst in the hydrocarbon solvent, at a reaction temperature of −100° C. to 120° C.

11. The polymer of claim 10 , wherein the Bronsted acid or Lewis acid catalyst is present in an amount of <0.7 wt. % of the weight of the monomer.

12. The polymer of claim 10 , wherein the Bronsted acid or Lewis acid catalyst is mixed with at least an electron donating additive at a 1:10 to 10:1 mole ratio to form complexes.

13. The polymer of claim 12 , wherein the electron donating additive is any of an organic ether, water and alcohol, and mixtures thereof.

14. The polymer of claim 13 , wherein the electron donating additive is selected from ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), 1,2-diethoxypropane, 2-(ethoxymethyl)tetrahydrofuran, 2,2’-(propane-2,2-diyl)bis(tetrahydrofuran), (methylsulfinyl)methane (dimethyl sulfoxide, DMSO), 2-aminoethanesulfonic acid (taurine), water, ethanol, isopropanol, butanol, hexanol, octanol, ethylene glycol butyl ether (EGBE), diethylene glycol butyl ether (DEGBE), diethylene glycol dibutyl ether (DEGDBE), tetraethylen glycol dimethylether, dipropylene glycol dimethylether, polyethylene glycol (PEG), polypropylene glycol (PPG), ethyl acetate, and mixtures thereof.

15. The polymer of claim 6 , wherein said polymerizing comprises controlling the monomer addition rate to maintain an unreacted monomer concentration of no more than 5 wt. %, relative to the total weight of the monomer.

16. A curable composition comprising the polymer of claim 1 , one or more rubbery polymers, one or more crosslinking agents, and optionally one or more curing initiators.

17. A cured composition obtained from the curable composition of claim 16 , wherein the cured composition has one or more of:
a 180° peel strength to copper of from 0.1 to 1.0 N/m,
a dissipation factor (Df) of from 0.0005 to 0.005, according to ASTM D2520,
a dielectric constant (Dk) of from 2.2 to 2.8, according to ASTM D2520,
a UL94 fire retardance of V0 or V1,
a coefficient of thermal expansion of from 5-25 ppm/° C. in the XY plane, and from 30-100 ppm/° C. in the Z direction, measured with DMA over a temperature range of from −50° C. to 300° C.; and
a moisture absorption of 0.02% to 0.2%, measured according to ASTM D570.

18. A prepreg comprising the cured composition of claim 17 .

19. A polymer composition obtained by electrophilically polymerizing in the presence of a Bronsted acid or a Lewis acid catalyst, a monomer comprising any of a 1,3-diisoalkenylarene (I), a 1,4-diisoalkenylarene (H), or mixtures thereof:

wherein R 1 is H or a C1-C8 alkyl group;
wherein Ar is an arene ring;
wherein the polymer has a solubility in a hydrocarbon solvent at 25° C. of at least 10 wt. and forms a substantially gel-free solution in a hydrocarbon solvent;
wherein the polymer has a T g of 50° C. to 300° C., measured using DSC according to ASTM D3418; and
wherein the polymer has a weight average molecular weight Mw of 8,000 to 70,000 Dalton, measured according to ASTM D5296.

20. The polymer composition of claim 19 , wherein said composition comprises a polymer comprising a combination of repeat units (A), (B), (C) and (D

wherein R 1 is H or a C1-C8 alkyl group, and
wherein Ar is an arene ring.

Assignees

• Kraton Polymers Llc
• Kraton Corp

Inventors

• Tian Jason
• Ding Ruidong
• Reiter Chad

Classifications

• C08G61/02 Primary

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• C08J5/24

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title

• C08G2261/12

  Copolymers · CPC title

• C08G2261/1412

  Saturated aliphatic units · CPC title

• C08G2261/1642

  comprising reactive double bonds or triple bonds · CPC title