Curable compositions

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.

What is claimed is: 
     
         1 . A room temperature curable cobalt-free resin composition comprising:
 a) a copper containing complex;   b) a quaternary ammonium or phosphonium salt:   c) a tertiary amine or phosphine;   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) (Cu 2+ )(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) a naphthenate, 
 
       
         
           
           
               
               
           
         
       
       wherein m and n are each independently an integer of 0 or greater, and R′ and R″ are each independently H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted alkylaryl;
 iii) an acetyl acetonate, 
 
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  are each independently 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; and
 iv) a bispidon, 
 
       
         
           
           
               
               
           
         
       
       wherein R 5  and R 6  are each independently: a group containing a heteroatom capable of coordinating to a transition metal; a C 1 -C 22  substituted or unsubstituted alkyl; a C 6 -C 10  aryl, wherein at least one of R 5  and R 6  is a non-aromatic hydrocarbon group, the non-aromatic hydrocarbon group being a C 8 -C 22  alkyl chain, R 7  and R 8  are independently: H; C 1 -C 4  alkyl; phenyl; electron withdrawing groups; and reduced products and derivatives thereof, X is selected from: C═O; a ketal derivative of C═O; a thioketal derivative of C═O; and —[C(R 7 ) 2 ] y —, wherein y is 0 or 1 and R 7  are each independently selected from H, OH, O—C 1 -C 24  alkyl, O-benzyl, O—(C═O)—C 1 -C 24  alkyl and C 1 -C 24  alkyl, and wherein R are each independently C 1 -C 4  alkyl. 
     
     
         3 . The room temperature curable cobalt-free resin composition of  claim 1 , wherein the copper containing complex comprises:
   (Cu 2+ )(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 a naphthenate, 
       
         
           
           
               
               
           
         
       
       wherein m and n are each independently an integer of 0 or greater, and R′ and R″ are each independently 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. 
     
     
         5 . The room temperature curable cobalt-free resin composition of  claim 1 , wherein the copper containing complex comprises an acetyl acetonate, 
       
         
           
           
               
               
           
         
       
       wherein R, R 2 , R 3  and R′ are each independently H, substituted or unsubstituted linear alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted linear alkenyl, substituted or unsubstituted branched alkenyl, substituted or unsubstituted aryl or substituted or unsubstituted alkylaryl. 
     
     
         6 . The room temperature curable cobalt-free resin composition of  claim 1 , wherein the copper containing complex comprises a bispidon, 
       
         
           
           
               
               
           
         
       
       wherein R 5  and R 6  are each independently: a group containing a heteroatom capable of coordinating to a transition metal; a C 1 -C 22  substituted or unsubstituted alkyl; a C 6 -C 10  aryl, wherein at least one of R 5  and R 6  is a non-aromatic hydrocarbon group, the non-aromatic hydrocarbon group being a C 8 -C 22  alkyl chain, R 7  and R 8  are independently: H; C 1 -C 4  alkyl; phenyl; electron withdrawing groups; and reduced products and derivatives thereof, X is selected from: C═O; a ketal derivative of C═O; a thioketal derivative of C═O; and —[C(R 7 ) 2 ] y —, wherein y is 0 or 1 and R 7  are each independently selected from H, OH, O—C 1 -C 24  alkyl, O-benzyl, O—(C═O)—C 1 -C 24  alkyl and C 1 -C 24  alkyl, and wherein R is C 1 -C 4  alkyl. 
     
     
         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)-buty 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 composition further comprises a peroxide initiator. 
     
     
         9 . The room temperature curable cobalt-free resin composition 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 p-toluidine, triethylamine, triethanolamine, and tertiary aromatic amines. 
     
     
         10 . 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. 
     
     
         11 . An accelerator for curing a thermosetting resin comprising:
 a) a copper containing complex,   b) a quaternary ammonium or phosphonium salt,   c) a tertiary amine or phosphine,   d) optionally a transition metal salt, and   e) a peroxide initiator.   
     
     
         12 . A method of curing a thermosetting resin comprising adding the accelerator of  claim 11  to the thermosetting resin. 
     
     
         13 . The method of  claim 12 , wherein the thermosetting resin is selected from the group consisting of a polyester resin, a vinyl ester resin, a urethane acrylate resin, a vinyl hybrid resin, and combinations thereof. 
     
     
         14 . The method of  claim 12 , wherein individual components of the accelerator are pre-mixed to form a metal salt complex prior to being added to the thermosetting resin. 
     
     
         15 . The method of  claim 12 , wherein individual components of the accelerator are added individually to the thermosetting resin to form the metal complex in situ. 
     
     
         16 . The method of  claim 12 , wherein one of more individual components of the accelerator are added individually or added together to the thermosetting resin before use, in which one or more components of the accelerator are already present in the thermosetting resin. 
     
     
         17 . The method of  claim 16 , wherein one component of the accelerator is added to the thermosetting resin before use, and the remaining components of the composition of the accelerator are already present in the thermosetting resin. 
     
     
         18 . The method of  claim 17 , wherein the one component added before use is the peroxide initiator. 
     
     
         19 . A thermosetting resin comprising a polyester, a vinyl ester, a urethane acrylate, a vinyl hybrid resin, or a combination thereof, and
 the accelerator of  claim 11 .   
     
     
         20 . The room temperature curable cobalt-free resin of  claim 1 , further comprising N,N-dimethyl acetoacetamine, a thiourea or a mixture thereof.