Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof

Patent metadata

Field	Value
Publication number	US-11130861-B2
Application number	US-201816498378-A
Country	US
Kind code	B2
Filing date	Mar 29, 2018
Priority date	Mar 30, 2017
Publication date	Sep 28, 2021
Grant date	Sep 28, 2021

Abstract

A novel soluble polyfunctional vinyl aromatic copolymer capable of yielding a cured product or molded body having improved heat resistance, compatibility, dielectric properties, wet heat reliability and resistance to thermal oxidative degradation. Disclosed herein is a soluble polyfunctional vinyl aromatic copolymer containing structural units derived from a divinyl aromatic compound (a), styrene (b), and a monovinyl aromatic compound (c) other than styrene. The copolymer includes structural units made up of an unsaturated hydrocarbon group represented by Formula (a1) and derived from the divinyl aromatic compound (a); and the copolymer includes, at terminals thereof, predetermined amounts of specific terminal groups having a vinyl group or a vinylene bond derived from monomers (a), (b), and (c). Also disclosed is a method for producing the copolymer.

First claim

The invention claimed is:

1. A soluble polyfunctional vinyl aromatic copolymer being a polyfunctional vinyl aromatic copolymer that contains 2 mol % or more and less than 95 mol % of structural units derived from a divinyl aromatic compound (a), and contains 5 mol % or more and less than 98 mol % of structural units derived from styrene (b) and a monovinyl aromatic compound (c) other than styrene,
wherein the copolymer satisfies the following conditions:
the polyfunctional vinyl aromatic copolymer contains structural units represented by Formula (a 1) and derived from the divinyl aromatic compound (a):

in the formula, R 1 represents a C6 to C30 aromatic hydrocarbon group;
the polyfunctional vinyl aromatic copolymer contains, at a terminal thereof, a terminal group represented by Formulae (t1), (t2), and (t3) and derived from the divinyl aromatic compound (a), styrene (b), and the monovinyl aromatic compound (c) other than styrene:

in the formula, R 2 represents a C6 to C30 aromatic hydrocarbon group; Z 1 represents a vinyl group, a hydrogen atom, or a C1 to C18 hydrocarbon group; and * represents a bonding site with a main chain; the same applies hereafter;

in the formula, R 3 and R 4 represent each independently a C6 to C30 aromatic hydrocarbon group; and Z 3 and Z 4 represent each independently a vinyl group, a hydrogen atom or a C1 to C18 hydrocarbon group;

in the formula, R 5 represents a C6 to C30 aromatic hydrocarbon group; and Z 5 represents a vinyl group, a hydrogen atom, or a C1 to C18 hydrocarbon group;
a mole fraction of a sum total of structural units of Formula (a1) and terminal groups of Formulae (t1), (t2), and (t3) with respect to a sum total of the divinyl aromatic compound (a), styrene (b), and the monovinyl aromatic compound (c) other than styrene lies in the range of 0.02 to 0.8;
an introduction amount in the copolymer of a terminal group (tv) having a vinyl group is 0.2 or more per molecule; and
a mole fraction of Formula (t3) with respect to a sum total of terminal groups of Formulae (t1), (t2), and (t3) is 0.7 or less; and wherein
the copolymer has a number-average molecular weight of 300 to 100,000, a molecular weight distribution Mw/Mn, denoted by a ratio of weight-average molecular weight and number-average molecular weight, of 100 or lower, and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

2. A method for producing the soluble polyfunctional vinyl aromatic copolymer of claim 1 , the method being a method for producing a polyfunctional vinyl aromatic copolymer through polymerization of the divinyl aromatic compound (a), the styrene (b), and the monovinyl aromatic compound (c) other than styrene, in the presence of a Lewis acid catalyst (f) and a Lewis base compound (g), wherein
the divinyl aromatic compound (a) is used in an amount of 2 mol % or more and less than 95 mol %, and the styrene (b) and the monovinyl aromatic compound (c) other than styrene are used in an amount of 5 mol % or more and less than 98 mol %, with respect to a sum total of (a), (b), and (c), and polymerization is carried out at a temperature of −20° C. to 120° C.

3. The method for producing the soluble polyfunctional vinyl aromatic copolymer according to claim 2 , wherein the Lewis acid catalyst (0 is a metal fluoride or a complex thereof.

4. The method for producing the soluble polyfunctional vinyl aromatic copolymer according to claim 2 , wherein the Lewis base compound (g) is one or more compound selected from the group consisting of ester-based compounds, ketone-based compounds, and ether-based compounds.

5. A curable resin composition, containing the soluble polyfunctional vinyl aromatic copolymer according to claim 1 , and a radical polymerization initiator (h).

6. The curable resin composition according to claim 5 , further comprising a flame retardant and/or a filler.

7. A cured product, obtained through curing of the curable resin composition of claim 5 .

8. A curable composite material, comprising: the curable resin composition of claim 5 , and a base material, wherein a proportion of a content of the base material is 5 to 90 wt %.

9. A cured composite material, obtained through curing of the curable composite material of claim 8 .

10. A laminate, having a layer of the cured composite material of claim 9 , and a metal foil layer.

11. A metal foil with resin, having a film formed from the curable resin composition of claim 5 , on one side of a metal foil.

12. A varnish for circuit board materials, obtained through dissolution of the curable resin composition of claim 5 in an organic solvent.

13. A curable resin composition, containing the soluble polyfunctional vinyl aromatic copolymer according to claim 1 , and a curable reactive resin or a thermoplastic resin.

14. The curable resin composition according to claim 13 , wherein the curable reactive resin is a modified polyphenylene ether compound terminally modified with a substituent having a carbon-carbon unsaturated double bond, an epoxy resin having two or more epoxy groups per molecule, or a vinyl compound having one or more unsaturated hydrocarbon groups in the molecule.

15. A cured product, obtained through curing of the curable resin composition of claim 13 .

16. A curable composite material, comprising: the curable resin composition of claim 13 , and a base material, wherein a proportion of a content of the base material is 5 to 90 wt %.

17. A cured composite material, obtained through curing of the curable composite material of claim 16 .

18. A laminate, having a layer of the cured composite material of claim 17 , and a metal foil layer.

19. A metal foil with resin, having a film formed from the curable resin composition of claim 13 , on one side of a metal foil.

20. A varnish for circuit board materials, obtained through dissolution of the curable resin composition of claim 13 in an organic solvent.

Assignees

• Nippon Steel Chemical & Mat Co Ltd

Inventors

• Kawabe Masanao
• Iwashita Shinichi

Classifications

• H05K1/0353

  consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement · CPC title

• B32B15/08

  of synthetic resin · CPC title

• C08L71/126

  modified by chemical after-treatment · CPC title

• C08K3/36

  Silica · CPC title

• C08F212/06

  Hydrocarbons · CPC title