Curatives for epoxy compositionsers

Abstract

The invention provides epoxy and oxetane compositions including the novel acyloxy and N-acyl curing agents described herein. Use of invention curing agents result in cured adhesive compositions with remarkably increased adhesion and reduced hydrophilicity when compared to resins cured with other types of curing agents. Furthermore, the curatives of this invention do not interfere with free-radical cure and are thus suited for use in hybrid cure thermoset compositions.

1 . A composition, comprising:
 (a) an epoxy resin or oxetane resin; and   (b) a curative having the structure of Formula I or Formula II:   
       
         
           
           
               
               
           
         
         wherein each of R and R 1  is, independently, selected from the group consisting of a substituted or an unsubstituted aliphatic, heteroaliphatic, aromatic, heteroaromatic, siloxane, maleimido, and cinnamyl moieties; 
         Ar is selected from the group consisting of a substituted or an unsubstituted aryl or heteroaryl having between 6 and about 20 carbon atoms; and 
         n is an integer having the value between 1 and about 11. 
       
     
     
         2 . The composition of  claim 1 , wherein each of R and R 1  is, independently, selected from the group consisting of a substituted or an unsubstituted alkyl, cycloalkyl, alkenyl, aryl, and heterocyclic moieties. 
     
     
         3 . The composition of  claim 1 , wherein Ar is a substituted or an unsubstituted C 6  to about C ii  aryl or a substituted or an unsubstituted C 6  to about C 11  heteroaryl. 
     
     
         4 . The composition of  claim 1 , wherein n is 3 to about 11. 
     
     
         5 . (canceled) 
     
     
         6 . The composition of  claim 1 , wherein R 1  is different than at least one R and optionally, the at least one R is a terminal R group. 
     
     
         7 . (canceled) 
     
     
         8 . The composition of  claim 1 , wherein the curative is a liquid at room temperature. 
     
     
         9 . The composition of  claim 1 , wherein the curative is selected from the group of compounds consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein:
 each of n′, x, y and z is an integer, n′, n″ and n″′ independently having the value between 0 and about 10; 
 each of x and y independently having the value between 4 and about 50; and 
 z independently having the value between 2 and about 40. 
 
       
     
     
         10 - 14 . (canceled) 
     
     
         15 . The composition of  claim 1 , wherein the epoxy comprises at least one of a glycidyl ether epoxy compound, a cycloaliphatic epoxy compound, or an aliphatic epoxy compound. 
     
     
         16 . The composition of  claim 15 , wherein the glycidyl ether epoxy compound is selected from the group consisting of:
 (a) a glycidyl ether of a phenol, an amine, an alcohol, or an isocyanurate;   (b) a trisglycidyl ether of a phenolic compound;   (c) a glycidyl ether of a cresol formaldehyde condensate;   (d) a glycidyl ether of a phenol formaldehyde condensate;   (e) a glycidyl ether of a cresol dicyclopentadiene addition compound;   (f) a glycidyl ether of a phenol dicyclopentadiene addition compound;   (g) a glycidyl ether of a fused ring polyaromatic phenol;   (h) diglycidyl ether;   (i) a glycidyl ether of an aliphatic alcohol;   (j) a glycidyl ether of a polyglycol;   (k) a glycidyl derivative of an aromatic amine; and   (l) an ester linked epoxy compound.   
     
     
         17 . The composition of  claim 15 , wherein the glycidyl ether epoxy compound is selected from the group consisting of:
 (a) a phenyl glycidyl ether;   (b) a cresyl glycidyl ether;   (c) a nonylphenyl glycidyl ether;   (d) a p-tert-butylphenyl glycidyl ether;   (e) a diglycidyl ether;   (f) a trisglycidyl ether of bisphenol A, bisphenol F, ethylidinebisphenol, dihydroxydiphenyl ether, N,N′-disalicylal-ethylenediamine, triglycidyl-p-aminophenol, N,N,N′,N′-tetraglycidyl-4,4′-diphenylmethane, triglycidyl isocyanurate, bis(4-hydroxyphenyl)sulfone, bis(hydroxyphenyl)sulfide, 1,1-bis(hydroxyphenyl)cyclohexane, 9,19-bis(4-hydroxyphenyl)fluorene, 1,1,1-tris(hydroxyphenyl)ethane, tetrakis(4-hydroxyphenyl)ethane, trihydroxytritylmethane, 4,4′-(1-alpha-methylbenzylidene)bisphenol, 4,4′-(1,3-componentthylethylene)diphenol, componentthylstilbesterol, 4,4′-dihyroxybenzophenone, resorcinol, catechol, or tetrahydroxydiphenyl sulfide;   (g) a glycidyl ether of a dihydroxy naphthalene, 2,2′-dihydroxy-6,6′-dinaphthyl disulfide, or 1,8,9-trihydroxyanthracene;   (h) a diglycidyl ether of 1,4butanediol;   (i) a diglycidyl ether of diethylene glycol;   (j) a diglycidyl ether of neopentyl glycol; a diglycidyl ether of cyclohexane dimethanol;   (k) a diglycidyl ether of tricyclodecane dimethanol;   (l) a trimethyolethane triglycidyl ether;   (m) a glycidyl ether a trimethyol propane triglycidyl ether;   (n) a glycidyl ether of Heloxy 84™;   (O) a glycidyl ether of Heloxy 32™;   (p) a polyglycidyl ether of castor oil;   (q) polyoxypropylene diglycidyl ether;   (r) Heloxy 71; and   (s) glycidyl methacrylate.   
     
     
         18 . The composition of  claim 15 , wherein the cycloaliphatic epoxy compound is selected from the group consisting of a cyclohexene oxide, a 3-vinylcyclohexene oxide, vinylcyclohexene dioxide, a dicylcopentadiene dioxide, a tricyclopentadiene dioxide, a tetracyclopentadiene dioxide, a norbornadiene dioxide, a bis(2,3-epoxycyclopentyl)ether, a limonene dioxide, a 3′,4′-epoxycyclohexamethyl-3,4-epoxycyclohexanecarboxylate, a 3′,4′-epoxycyclohexyloxirane, a 2(3′,4′-epoxycyclohexyl)-5,1″-spiro-3″,4″-epoxycyclohexane-1,3-dioxane, and a bis(3,4-epoxycyclohexamethyl) adipate; or the aliphatic epoxy compound is selected from the group consisting of an epoxidized polybutadiene, an epoxidized polyisoprene, an epoxidized poly(1,3-butadiene-acrylonitrile), an epoxized soybean oil, an epoxidized castor oil, a dimethylpentane dioxide, a divinylbenzene dioxide, a butadiene dioxide, and a 1,7-octadiene dioxide. 
     
     
         19 . The composition of  claim 15 , wherein the composition is a coating, a matrix resin or a composite resin. 
     
     
         20 . (canceled) 
     
     
         21 . (canceled) 
     
     
         22 . The composition of  claim 1 , wherein the adhesive further comprises at least one compound selected from the group consisting of an acrylate, a methacrylate, a maleimide, a vinyl ether, a vinyl ester, a styrenic compound, an allyl functional compound, a phenol, an anhydride, a benzoxazine, and an oxazoline. 
     
     
         23 . (canceled) 
     
     
         24 . The composition of  claim 1 , wherein the curative comprises at least one phenyl ester moiety. 
     
     
         25 . A composition, comprising:
 (a) an epoxy resin or oxetane resin; and   (b) a curative of  claim 24 ,   wherein the composition is an adhesive, a coating, a matrix resin or a composite resin.   
     
     
         26 . A composition comprising the adhesive of  claim 25 , wherein the composition is a thermal interface material, die attach adhesive, underfill material or mold compound. 
     
     
         27 . The composition of  claim 25 , wherein the composition is a coating, a matrix resin or a composite resin. 
     
     
         28 . The composition of  claim 25 , wherein the composite resin further comprises at least one of carbon fiber, fiberglass or silica. 
     
     
         29 . The composition of  claim 24 , wherein the adhesive further comprises at least one thermally or electrically conductive filler. 
     
     
         30 . The composition of  claim 1 , wherein the adhesive further comprises at least one thermally or electrically conductive filler.