Curing of liquid thermosetting resins

• US 9,068,045 B2
• Filed: 03/28/2014
• Issued: 06/30/2015
• Est. Priority Date: 04/05/2013
• Status: Active Grant

• Current Assignee: Reichhold LLC 2 (DIC Corporation)
• Original Assignee: Reichhold Incorporated
• Inventors: Nava, Hildeberto, Skrobacki, Anthony
• Primary Examiner(s): LEE, DORIS L
• Application Number:
  US14/229,517
• Publication Number:
  US 20140303315A1
• Time in Patent Office: 459 Days
• Field of Search: 524/555, 524/437, 524/556
• US Class Current: 1/1
• CPC Class Codes: C08G 63/914 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08L 67/06 Unsaturated polyesters

Abstract

The compositions of the present invention for accelerating the curing of thermosetting resins, including a) an organophosphine metal complex, optionally with a transition metal salt essentially free of cobalt; b) a tertiary amine, optionally with a quaternary ammonium or phosphonium salt; and c) a peroxide initiator.

Claims

1. A composition for the curing of thermosetting resins, wherein said composition comprises:

a) an organophosphine metal complex;

b) a tertiary amine;

c) a peroxide initiator;

d) optionally a transition metal salt essentially free of cobalt; and

e) optionally a quaternary ammonium or phosphonium salt.

2. The composition of claim 1, wherein the phosphine compound of the organometal phosphine metal complex containing compound comprises a phosphine compound with the structure of Formula I:

3. The composition of claim 1, wherein the metal of the metal salt comprises a metal selected from the group consisting of lithium, calcium, copper, vanadium, zirconium, titanium, zinc, iron, sodium, potassium, magnesium, manganese and barium and the salt comprises chlorides, bromides, iodides, nitrates, sulfates, phosphates, oxalates, salicylates, acetonates, alkyl organic acids, carboxylates, and naphthenates, and the like.

4. The composition of claim 1, wherein the phosphine compound of the organophosphine metal complex containing compound comprises a phosphine compound with the structure of Formula III:

5. The composition of claim 1, wherein the organophosphine metal complex containing compound comprises a phosphine selected from the group consisting of (2,4)-Bis(di-tert-butylphosphino)pentane, 1,4-Bis(di-tert-butylphosphino)butane, 1,2-Bis(di-tert-butylphosphino)ethane, Bis(di-tert-butylphosphino)methane, Bis(di-tert-butylphosphino)pentane, 1,3-Bis(di-tert-butylphosphino)propane, 1,2-Bis(dicyclohexylphosphino)ethane, 1,3-Bis(dicyclohexylphosphino)propane, 1,4-Bis(dimethylphosphino)butane, 1,2-Bis(dimethylphosphino)ethane, 1,3-Bis(dimethylphosphino)propane, Bis(dimethylamino)methylphosphine, di-tert-butylmethylphosphine, di-tert-butylneopentylphosphine, di-tert-butylphenylphosphine, dicyclohexylnorbornylphosphine, dripropylphosphine, triisopropylphosphine, tri-tert-butylphosphine, triisobutylphosphine, tricyclohexylphosphine, tris(2-furyl)phosphine, tris(3-methoxypropyl)phosphine, tris(1-naphthyl)phosphine, trimethylphosphine, triethylphosphine, diethylphenylphosphine, triphenylphosphine, ortho-phenylene bis(diphenylphosphine), ortho-phenylene bis(dimethylphosphine), ortho-phenylene bis(diethylphosphine), ortho-phenylene bis(ethylphenylphosphine), tris(diphenylphosphinoethyl)phosphine, tris(diethylphosphinoethyl)phosphine, tris(dimethylphosphinoethyl)phosphine, tris(ethylphenylphosphinoethyl)phosphine, (2-methoxyphenyl)methylphenylphosphine, 1-Bromo-2-diphenylphosphinobenzene, dimethyl(phenyl)phosphine, cyclohexyldiphenylphosphine, cicyclohexylphenylphosphine, Bis(3,5-ditrifluoromethylphenyl)phenylphosphine, di-tert-butyl(4-dimethylaminophenyl)phosphine, (4-dimethylaminophenyl)diphenylphosphine, Bis(2-(bis(diethylamido)phosphino)phenyl)ether, Bis(2-diphenylphosphinoethyl)phenylphosphine, 2,6-Bis(diphenylphosphinomethyl)pyridine, 2,6-Bis[bis(3,5-dimethylphenyl)phosphinomethyl]pyridine, 2-(diphenylphosphino)pyridine, Bis(2-diphenylphosphinophenyl)ether, diphenylphosphinostyrene, ethyldiphenylphosphine, methyldiphenylphosphine, 2,2′

-Bis(diphenylphosphino)-1,1′

-binaphthyl, (2,3)-Bis(diphenylphosphino)butane, (2,5)-Bis(diphenylphosphino)hexane, 1,2-Bis(diphenylphosphino)propane, (1,2)-Bis[(2-methoxyphenyl)phenylphosphino]ethane, 2,2′

-Bis[bis(3,5-dimethylphenyl)phosphino]-1,1′

-binaphthyl, 1,4-Bis[bis(3,5-dimethylphenyl)phosphino]butane, 1,2-Bis[bis(3,5-dimethylphenyl)phosphino]ethane, Bis[bis(3,5-dimethylphenyl)phosphino]methane, 1,5-Bis[bis(3,5-dimethylphenyl)phosphino]pentane, 1,3-Bis[bis(3,5-dimethylphenyl)phosphino]propane, 2,2′

-Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]-1,1′

-binaphthyl, 2,2′

-Bis(di-p-tolylphosphino)-1,1′

-binaphthyl, (1,2)-Bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,3-Bis[bis(o-methoxyphenyl)phosphino]propane, 1,4-Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]butane, 1,2-Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]ethane, Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]methane, 1,3-Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]propane, Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]methane, 1,2-Bis(di-tert-butylphosphino)benzene, 2,2′

-Bis(di-tert-butylphosphino)biphenyl, 1,2-Bis(di-tert-butylphosphinomethyl)benzene, 1,3-Bis(di-tert-butylphosphinomethyl)benzene, 1,2-Bis(dicyclohexylphosphino)benzene, 2,2′

-Bis(dicyclohexylphosphino)-1,1′

-binaphthyl, 2,2′

-Bis(dicyclohexylphosphino)biphenyl, 1,2-Bis(diphenylphosphino)benzene, 2,2′

-Bis(diphenylphosphino)-1,1′

-binaphthyl, 2,2′

-Bis(diphenylphosphino)-1,1′

-biphenyl, 1,4-Bis(diphenylphosphino)butane, 1,2-Bis(diphenylphosphino)ethane, Bis(2-diphenylphosphino)ethyl ether, Bis(2-diphenylphosphinoethyl)phenylphosphine, 1,6-Bis(diphenylphosphino)hexane, Bis(diphenylphosphino)methane, 1,5-Bis(diphenylphosphino)pentane, Bis(2-diphenylphosphinophenyl)ether, 1,3-Bis(diphenylphosphino)propane, 2,2′

-Bis[bis(3,5-dimethylphenyl)phosphino]-1,1′

-binaphthyl, 2,2′

-Bis[bis(3,5-ditrifluoromethylphenyl)phosphino]-1,1′

-binaphthyl, 2,2′

-Bis[bis(4-methylphenyl)phosphino]-5,5′

,6,6′

,7,7′

,8,8′

-octahydro-1,1′

-binaphthyl, (1R,2R)-Bis[(2-methoxyphenyl)phenylphosphino]ethane, 1,1′

-Bis[bis(diethylamino)phosphino]ferrocene, 1,1′

-Bis(di-tert-butylphosphino)ferrocene, 1,1′

-Bis(dicyclohexylphosphino)ferrocene, 2-tert-Butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine, tert-Butylimino-tri(pyrrolidino)phosphorane, Hexaethylphosphorous triamide, Hexaisopropylphosphorus triamide, Tris(4-morpholino)phosphine, and any combination thereof.

6. The composition of claim 1, 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-butylperoxide)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-butylperoxy)valerate, ethyl-3,3-di-(tert-amylperoxy)butyrate, ethyl-3,3-di(tert-butylperoxy)-butyrate, 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.

7. The composition of claim 1, wherein the tertiary amine is a thiourea.

8. The thermosetting resin of claim 1, wherein the tertiary amine is selected from the group consisting of N,N-dimethyl aniline, N,N-diethyl aniline, N,N-dimethyl acetoacetamide, N,N-dimethyl p-toluidine, trithylamine, triethanolamine, and tertiary aromatic amines.

9. The composition of claim 1, wherein the metal of the organophosphine metal complex comprises a metal selected from the group consisting of lithium, calcium, copper, vanadium, zirconium, titanium, zinc, iron, sodium, potassium, magnesium, manganese and barium.

10. The composition of claim 9, wherein the metal complex is ferrous chloride or copper bromide.

11. The composition of claim 1, wherein the organophosphine metal complex containing compound comprises a phosphine compound with the structure of Formula II:

12. The composition of claim 11, wherein the metal of the organophosphine metal complex comprises a metal selected from the group consisting of lithium, calcium, copper, vanadium, zirconium, titanium, zinc, iron, sodium, potassium, magnesium, manganese and barium.

13. The composition of claim 1, wherein the phosphine compound of the organophosphine metal complex containing compound comprises a phosphine compound with the structure of Formula IV:

14. The composition of claim 13, wherein the metal of the organophosphine metal complex comprises a metal selected from the group consisting of lithium, calcium, copper, vanadium, zirconium, titanium, zinc, iron, sodium, potassium, magnesium, manganese and barium.

15. A thermosetting resin comprising a polyester, vinyl ester, urethane acrylate, or a vinyl hybrid resin and the accelerator of claim 1.

16. The thermosetting resin of claim 15, further comprising a component selected from the group consisting of free radical scavengers, antioxidants, and any combination thereof.

17. The thermosetting resin of claim 15, further comprising an additional curing accelerator or promoter.

18. The thermosetting resin of claim 17, wherein the additional curing accelerator or promoter is a quaternary ammonium or phosphonium salt selected from the group consisting of tetramethylammonium chloride, tetramethylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium hydrogensulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydrogen sulfate, benzyltributylammonium chloride, benzyltributylammonium bromide, tetrabutylphosphonium acetate, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium fluoride, tetrabutylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium acetate.

19. The thermosetting resin of claim 15, further comprising a polymerization inhibitor.

20. The thermosetting resin of claim 19, wherein the polymerization inhibitor is selected from the group consisting of phenothiazine, phenol, 2,6-di-tert-butyl-4-methyl phenol, hydroquinone (HQ), toluhydroquinone (THQ), bisphenol “

A”

(BPA), triphenyl antimony, naphthoquinone (NQ), p-benzoquinone (p-BQ), butylated hydroxy toluene (BHT), hydroquinone monomethyl ether (HQMME), 4-ethoxyphenol, 4-propoxyphenol, and propyl isomers thereof, monotertiary butyl hydroquinone (MTBHQ), ditertiary Butyl hydroquinone (DTBHQ), tertiary butyl catechol (TBC), 1,2-dihydroxybenzene, 2,5-dichlorohydroquinone, 2-acetylhydroquinone, 1,4-dimercaptobenzene, 2,3,5-trimethylhydroquinone, 2-aminophenol, 2-N,N,-dimethylaminophenol, catechol, 2,3-dihydroxyacetrophenone, pyrogallol, 2-methylthiophenol, and mixtures of any thereof.

21. The thermosetting resin of claim 19, wherein the polymerization inhibitor is selected from the group consisting of N,N-di-tert-butylnitroxide;

N,N-di-tert-amylnitroxide;

N-tert-butyl-2-methyl-1-phenyl-propylnitroxide;

N-tert-butyl-1-diethyl phosphono-2,2-dimethyl propyl nitroxide;

2,2,6,6-tetramethyl-piperidinyloxy;

4-amino-2,2,6,6-tetramethyl-piperidinyloxy;

4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;

4-oxo-2,2,6,6-tetramethyl-piperidinyloxy;

4-dimethylamino-2,2,6,6-tetramethyl-piperidinyloxy;

4-ethanoyloxy-2,2,6,6-tetramethyl-piperidinyloxy;

2,2,5,5-tetramethylpyrrolidinyloxy;

3-amino-2,2,5,5-tetramethylpyrrolidinyloxy;

2,2,4,4-tetramethyl-1-oxa-3-azacyclopcntyl-3-oxy;

2,2,4,4-tetramethyl-1-oxa-3-pyrrolinyl-1-oxy-3-carboxylic acid;

2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy;

4-bromo-2,2,6,6-tetramethyl-piperidinyloxy;

4-chloro-2,2,6,6-tetramethyl-piperidinyloxy;

4-iodo-2,2,6,6-tetramethyl-piperidinyloxy;

4-fluoro-2,2,6,6-tetramethyl-piperidinyloxy;

4-cyano-2,2,6,6-tetramethyl-piperidinyloxy;

4-carboxy-2,2,6,6-tetramethyl-piperidinyloxy;

4-carbomethoxy-2,2,6,6-tetramethyl-1-piperidinyloxy;

4-carbethoxy-2,2,6,6-tetramethyl-piperidinyloxy;

4-cyano-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;

4-methyl-2,2,6,6-tetramethyl-1-piperidinyloxy;

4-carbethoxy-4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy;

4-hydroxy-4-(1-hydroxypropyl)-2,2,6,6-tetramethy 1-piperidinyloxy;

4-methyl-2,2,6,6-tetranlcthyl-1,2,5,6-tetrahydropyridinyloxyl, and mixtures of any thereof.