Electron deficient olefins

Abstract

This invention relates to novel electron deficient olefins, such as certain 2-cyanoacrylates and methylidene malonates, prepared using an imine or an iminium salt.

1 . Compounds embraced by structure I 
     
       
         
         
             
             
         
       
     
     wherein X is (a) an electron withdrawing group, or (b) Y;
 Y is 
 
     
       
         
         
             
             
         
       
       wherein D is a member selected from the group consisting of H, alkyl and aryl,
 Z is either
 (i) 
 
 
     
     
       
         
         
             
             
         
       
       
         wherein Q is
 a. an electron withdrawing group or 
 b. a first reactive functionality, or 
 (ii) a second reactive functionality, g is 1-10; and 
 
       
       n is 0 or 1. 
     
   
   
       2 . Compounds according to  claim 1 , wherein X is an electron withdrawing group selected from the group consisting of CN, CO 2 R, CO 2 H, COCl, COR, COPO(OR) 2 , COPOR 2 , SO 2 R, SO 3 R and NO 2 , wherein R is C 1-4 . 
   
   
       3 . Compounds according to  claim 1 , wherein Y is 
     
       
         
         
             
             
         
       
     
     wherein D is a member selected from the group consisting of H, alkyl and aryl, Z is 
     
       
         
         
             
             
         
       
       wherein Q is an electron withdrawing group selected from the group consisting of CN, CO 2 R, CO 2 H, COCl, COR, COPO(OR) 2 , COPOR 2 , SO 2 R, SO 3 R and NO 2 , wherein R is C 1-4 , and g is 1. 
     
   
   
       4 . Compounds according to  claim 1 , wherein Y is 
     
       
         
         
             
             
         
       
     
     wherein D is a member selected from the group consisting of H, alkyl and aryl, Z is 
     
       
         
         
             
             
         
       
       wherein Q is a first reactive functionality selected from the group consisting of amides and thioamides and g is 1. 
     
   
   
       5 . Compounds according to  claim 1 , wherein Y is 
     
       
         
         
             
             
         
       
     
     wherein D is a member selected from the group consisting of H, alkyl and aryl, Z is a second reactive functionality selected from the group consisting of epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, succinimides, 2-cyanoacrylates, methylidene malonates, acrylonitrile, (meth)acrylates, carboxylic acids and derivatives thereof, cyanoacetates, methylene malonates, hydroxyls, silanes, siloxanes, titanates, and zirconates, and g is 1. 
   
   
       6 . Compounds according to  claim 1 , embraced by structure II 
     
       
         
         
             
             
         
       
     
     wherein X is an electron withdrawing group or E, E is as shown, 
     
       
         
         
             
             
         
       
     
     is a reactive functionality, D is a member selected from the group consisting of H, alkyl and aryl, n is 0 or 1, g is 1, and A, B, 1, 2, 3, 4, 5, and 6 are each references to bond designations. 
   
   
       7 . Compounds according to  claim 1 , embraced by structure III 
     
       
         
         
             
             
         
       
     
     wherein X is an electron withdrawing group or F, D is a member selected from the group consisting of H, alkyl and aryl, Z is a reactive functionality, n is 0 or 1 and g is 1. 
   
   
       8 . Compounds according to  claim 7 , wherein Z is a second reactive, functionality selected from the group consisting of epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, succinimides, 2-cyanoacrylates, methylidene malonates, acrylonitrile, (meth)acrylates, carboxylic acids and derivatives thereof, cyanoacetates, methylene malonates, hydroxyls, silanes, siloxanes, titanates, and zirconates. 
   
   
       9 . Compounds according to  claim 1 , selected from the group consisting of 
     
       
         
         
             
             
         
       
     
   
   
       10 . A composition comprising:
 (a) one or more compounds of  claim 1 ;   (b) a stabilizer package comprising at least one of a free radical stabilizer and an anionic stabilizer; and   (c) optionally, one or more additives selected from the group consisting of cure accelerators, thickeners, thixotropes, tougheners, thermal resistance-conferring agents, and plasticizers.   
   
   
       11 . The composition of  claim 10 , further comprising a cyanoacrylate within structure IV: 
     
       
         
         
             
             
         
       
     
     wherein R 1  is selected from C 1-16  alkyl, alkoxyalkyl, cycloalkyl, alkenyl, alkynyl, arylalkyl, aryl, allyl and haloalkyl groups. 
   
   
       12 . The composition of  claim 11 , wherein the cyanoacrylate is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate and combinations thereof. 
   
   
       13 . The composition of  claim 10 , further comprising a methylidene malonate within structure V: 
     
       
         
         
             
             
         
       
     
     wherein R 2  and R 3  are each independently selected from C 1-16  alkyl, alkoxyalkyl, cycloalkyl, alkenyl, alkynyl, arylalkyl, aryl, allyl and haloalkyl groups. 
   
   
       14 . A composition comprising:
 (a) one or more compounds of  claim 9 ;   (b) a stabilizer package comprising at least one of a free radical stabilizer and an anionic stabilizer; and   (c) optionally, one or more additives selected from the group consisting of cure accelerators, thickeners, thixotropes, tougheners, thermal resistance-conferring agents, and plasticizers.   
   
   
       15 . The composition of  claim 14 , further comprising a coreactant. 
   
   
       16 . The composition of  claim 15 , wherein the coreactant is a member selected from the group consisting of epoxides, episulfides, oxetanes, thioxetanes, dioxolanes, dioxanes, isocyanates, maleimides, oxazolines, (meth)acrylates, acrylamides, cyanoacrylates, methylidene malonates, and vinyl ethers. 
   
   
       17 . Compounds according to  claim 4 , wherein the amides or thioamides of Q are embraced by
   C(T)NUV,   
     wherein T is O or S and U or V are each independently selected from H or R, wherein R is C 1-4 .