Curable compositions

• US 10,000,602 B2
• Filed: 09/18/2015
• Issued: 06/19/2018
• Est. Priority Date: 10/02/2014
• Status: Active Grant

• Current Assignee: Reichhold LLC 2 (DIC Corporation)
• Original Assignee: Reichhold LLC 2 (DIC Corporation)
• Inventors: Nava, Hildeberto, Schramm, William A., Skrobacki, James Anthony
• Primary Examiner(s): Rodd, Christopher M
• Application Number:
  US14/858,604
• Publication Number:
  US 20160096918A1
• Time in Patent Office: 1,005 Days
• Field of Search: None
• CPC Class Codes: C08G 63/16 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/183 Terephthalic acids
• CPC Class Codes: C08G 63/685 containing nitrogen
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/098 Metal salts of carboxylic acids
• CPC Class Codes: C08K 5/14 Peroxides
• CPC Class Codes: C08K 5/17 Amines; Quaternary ammonium compounds
• CPC Class Codes: C08K 5/19 Quaternary ammonium compounds
• CPC Class Codes: C08K 5/50 Phosphorus bound to carbon only

Abstract

The present invention relates generally to accelerators for the curing of thermosetting resins in the presence of metal compounds, quaternary ammonium and/or phosphonium salts, tertiary amines and/or phosphines and peroxide initiators, and methods of curing thermosetting resins using these accelerators.

Claims

1. A room temperature curable cobalt-free resin composition comprising:

a) a copper containing complex;

b) a quaternary ammonium or phosphonium salt;

c) an arylalkyl tertiary amine;

d) optionally a transition metal salt; and

e) an uncured thermosetting resin.

2. The room temperature curable cobalt-free resin composition of claim 1, wherein the copper containing complex is selected from the group consisting of one or more of:

i)

(Cu²⁺)(RCOO⁻

)₂

wherein R is H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted linear alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkylaryl;

ii)

3. The room temperature curable cobalt-free resin composition of claim 1, wherein the copper containing complex comprises:

(Cu²⁺)(RCOO⁻

)₂

wherein R is H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted linear alkynyl, substituted or unsubstituted branched alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkylarl.

4. The room temperature curable cobalt-free resin composition of claim 1, wherein the copper containing complex comprises:

5. The room temperature curable cobalt-free resin composition of claim 1, wherein the copper containing complex comprises:

6. The room temperature curable cobalt-free resin composition of claim 1, wherein the copper containing complex comprises:

7. The room temperature curable cobalt-free resin composition of claim 1, further comprising a peroxide initiator, wherein the peroxide initiator is selected from the group consisting of cumene hydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, tert-butyl peroxybenzoate, di-tert-butyl perphthalate, dicumyl peroxide, 2,5-dimethyl-2,5-bix (tert-buty peroxide)hexane, 2,5-dimethyl-2,5-bis (tert-butylperoxy)hexyne, bis (tert-butylperoxyisopropyl) benzene, ditert-butyl peroxide, 1,1-di (tert-amylperoxy)-cyclohexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, 2,2-di-(tert-butylperoxy)butane;

n-butyl-4,4-di(tert-butyl peroxy)valerate, ethyl-3,3-di-(tert-amylperoxy)butyrate, ethyl-3,3-di(tert-butylperoxy)-bury rate, t-butyl peroxy-neodecanoate, di-(4-5 butyl-cyclohexyl)-peroxydicarbonate, lauryl peroxide, 2,5-dimethyl-2,5-bis(2-ethyl-hexanoyl peroxy) hexane, t-amyl peroxy-2-ethylhexanoate;

2,2′

-azobis(2-methylpropionitrile), 2,2′

-azobis(2,4-methylbutanenitrile), and mixtures of any thereof.

8. The room temperature curable cobalt-free resin composition of claim 1, wherein the quaternary ammonium or phosphonium salt is selected from the group consisting of tetramethylammonium chloride, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium hydrogensulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydrogen sulfate, benzyltributylammonium chloride, benzyltributyl ammonium bromide, tetrabutylphosphonium acetate, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium fluoride, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium acetate.

9. The room temperature curable cobalt-free resin composition of claim 1, wherein the uncured thermosetting resin is selected from the group consisting of a polyester resin, a vinyl ester resin, a urethane acrylate resin, and a vinyl hybrid resin.

10. The composition of claim 1, wherein the composition comprises the transition metal salt.