Epoxy resin composition

• US 4,189,548 A
• Filed: 04/25/1978
• Issued: 02/19/1980
• Est. Priority Date: 09/13/1977
• Status: Expired due to Term

• Current Assignee: Mitsui Petrochemical Industries, Ltd. (Mitsui Chemicals)
• Original Assignee: Mitsui Petrochemical Industries, Ltd. (Mitsui Chemicals)
• Inventors: Sakashita, Takeshi, Miyamoto, Ryoichi
• Primary Examiner(s): Lieberman, Paul
• Application Number:
  US05/899,967
• Time in Patent Office: 665 Days
• Field of Search: 260/836, 260/837 R
• US Class Current: 525/109
• CPC Class Codes: C08F 12/04 containing one ring
• CPC Class Codes: C08F 240/00 Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
• CPC Class Codes: C08F 32/08 having two condensed rings coumarone-indene polymers C08F244/00

Abstract

An epoxy resin composition comprising

[A] a novel copolymer produced by polymerizing a polymerizable material selected from the group consisting of

(a) substituted or unsubstituted dicyclopentadiene;

(b) a cationically polymerizable unsaturated hydrocarbon-containing fraction obtained by distilling a cracking or reforming product of a petroleum and having a boiling point in the range of -20° C. to 280° C.;

(c) a cationically polymerizable vinyl aromatic hydrocarbon having 8 to 10 carbon atoms;

(d) a mixture of two or three of ingredients (a), (b) and (c); and

(e) a mixture of any one of ingredients (a) to (d) with a cationically polymerizable unsaturated aliphatic hydrocarbon having 4 to 10 carbon atoms in the presence of a cationic polymerization catalyst with a high-boiling product having a boiling point of at least about 150° C. and an oxygen content of at least 0.5% by weight being introduced into the polymerization system at any stage of the polymerization process or into the resulting polymer, the said high-boiling product being obtained as a by-product in a process comprising oxidizing a benzene or naphthalene ring-substituted with at least one isopropyl group to convert it to the corresponding hydroperoxide and then decomposing it with an acid to produce the corresponding phenol or naphthol;

[B] a polyepoxy compound; and

[C] a curing agent.

This epoxy resin composition is useful for paints, adhesives, road-repairing materials, floor coverings, etc.

Claims

1. An epoxy resin composition comprising

(A) a novel copolymer produced by polymerizing a polymerizable material selected from the group consisting of

(a) substituted or unsubstituted dicyclopentadiene,

(b) a cationically polymerizable unsaturated hydrocarbon-containing fraction obtained by distilling a cracking or reforming product of a petroleum and having a boiling point in the range of -20°

C. to 280°

C.,

(c) a cationically polymerizable vinyl aromatic hydrocarbon having 8 to 10 carbon atoms,

(d) a mixture of two or three of ingredients (a), (b) and (c), and

(e) a mixture of any one of ingredients (a) to (d) with a cationically polymerizable unsaturated aliphatic hydrocarbon having 4 to 10 carbon atoms

in the presence of a cationic polymerization catalyst with a high-boiling product having a boiling point of at least about 150°

C. and an oxygen content of at least 0.5% by weight being introduced into the polymerization system at any stage of the polymerization process or into the resulting polymer, the said high-boiling product being obtained as a residue, comprising a mixture of by-products, in a process comprising oxidizing a benzene or naphthalene ring-substituted with at least one isopropyl group to convert it to the corresponding hydroperoxide, decomposing the hydroperoxide with an acid to produce the corresponding phenol or naphthol, and separating the phenol or naphthol from the resultant reaction mixture to obtain said residue comprising a mixture of said by-products;

(B) a polyepoxy compound; and

(C) a curing agent.

2. The composition of claim 1 wherein the substituted or unsubstituted dicyclopentadiene is dicyclopentadiene, methyldicyclopentadiene or dimethyldicyclopentadiene.

3. The composition of claim 1 wherein the substituted or unsubstituted dicyclopentadiene is crude substituted or unsubstituted dicyclopentadiene having a purity of at least 35% by weight and produced by the thermal dimerization of the corresponding substituted or unsubstituted cyclopentadiene.

4. The composition of claim 1 wherein the cationically polymerizable unsaturated hydrocarbon-containing fraction is a fraction composed mainly of C₈ -C₁₂ aromatic unsaturated hydrocarbons having a boiling point in the range of 140°

to 280°

C.

5. The composition of claim 1 wherein the cationically polymerizable unsaturated hydrocarbon-containing fraction is a fraction composed mainly of C₄ -C₅ aliphatic unsaturated hydrocarbons having a boiling point in the range of -20°

C. to +100°

C.

6. The composition of claim 1 wherein the cationically polymerizable unsaturated hydrocarbon-containing fraction is a mixture consisting of (1) a fraction composed mainly of C₄ -C₅ aliphatic unsaturated hydrocarbons having a boiling point in the range of -20°

C. to 100°

C. and (2) a fraction composed mainly of C₈ -C₁₂ aromatic unsaturated hydrocarbons having a boiling point in the range of 140°

to 280°

C.

7. The composition of claim 1 wherein the cationically polymerizable vinyl aromatic hydrocarbon is selected from the group consisting of styrene, α

- and β

-methylstyrenes, o-, m- and p-vinyltoluenes, o-, m- and p-isopropenyl toluenes, and mixtures of these.

8. The composition of claim 1 wherein the cationically polymerizable unsaturated aliphatic hydrocarbon is selected from the group consisting of butadiene, isoprene, piperylene, isobutylene, 2-butene, 2-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene, and mixtures of these.

9. The composition of claim 1 wherein the cationically polymerizable unsaturated aliphatic hydrocarbon is mixed with any one of ingredients (a) to (d) in an amount of at most 80% by weight based on the weight of any one of the ingredients (a) to (d).

10. The composition of claim 1 wherein the high-boiling product has an oxygen content of 1 to 17% by weight.

11. The composition of claim 1 wherein the high-boiling product has a hydroxyl value of at least 10 mg KOH/g.

12. The composition of claim 1 wherein the high-boiling product has a hydroxyl value of 20 to 500 mg KOH/g.

13. The composition of claim 1 wherein the benzene ring-substituted with at least one isopropyl group is cumene, cymene or diisopropylbenzene, and the corresponding phenol is phenol, cresol or dihydroxybenzene.

14. The composition of claim 1 wherein the amount of the high-boiling product introduced is 5 to 200 parts by weight per 100 parts by weight of all the cationically polymerizable ingredients in the polymerizable material.

15. The composition of claim 1 wherein the amount of the high-boiling product introduced is 10 to 100 parts by weight per 100 parts by weight of all the cationically polymerizable ingredients in the polymerizable material.

16. The composition of claim 1 wherein the high-boiling product is introduced into the polymerization system before the initiation of the polymerization.

17. The composition of claim 1 wherein the cationic polymerization catalyst is a Friedel-Crafts catalyst.

18. The composition of claim 1 wherein the cationic polymerizable catalyst is boron trifluoride, a boron trifluoride complex, or aluminum trichloride.

19. The composition of claim 1 wherein the polymerization is carried out at a temperature of 0°

to 200°

C.

20. The composition of claim 1 wherein the polymer is liquid at room temperature, or solid with a softening point of not more than 200°

C.

21. The composition of claim 1 wherein the polymer has an oxygen content of 0.5 to 15% by weight.

22. The composition of claim 1 wherein the polymer has a hydroxyl value of at least 1 mg KOH/g.

23. The composition of claim 1 wherein the polymer has a hydroxyl value of 1 to 400 mg KOH/g.

24. The composition of claim 1 wherein the polyepoxy compound has an epoxy equivalent of at most 5,000.

25. The composition of claim 1 wherein the polyepoxy compound has a molecular weight of 150 to 5,000.

26. The composition of claim 1 wherein the polyepoxy compound is selected from the group consisting of polyglycidyl ethers of polyphenol compounds and novolac-type polyepoxy compounds.

27. The composition of claim 1 wherein the amount of the novel polymer [A] is 5 to 1,500 parts by weight per 100 parts by weight of the polyepoxy compound [B].

28. The composition of claim 1 wherein the curing agent is a polyfunctional compound containing at least two functional groups selected from primary and secondary amino groups, acid anhydride groups, a mercapto group and a phenolic hydroxyl group.

29. The composition of claim 1 wherein the amount of the curing agent [C] is 0.2 to 200 parts by weight per 100 parts by weight of the sum of the novel polymer [A] and the polyepoxy compound [B].

30. The composition of claim 1 wherein the high-boiling product contains up to 10% by weight of said phenol or naphthol.

31. The composition of claim 1 wherein the high-boiling product contains up to 5% by weight of said phenol or naphthol.