Process for Amination of Acrylic Macromonomers and Products Therefrom

Abstract

Processes for forming adducts of amines with acrylic macromonomers are provided. Also provided are processes for using ring-closing reactions of the adducts to form lactams. The adducts are useful, for example, for making adhesives, surfactants, viscosity modifiers, processing aids, and other products.

1 . A compound having the structure 
       
         
           
           
               
               
           
         
         wherein each R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 carbon atoms, or substituted aryl; R 3  and R 4  are independently H, alkyl of 1-100 carbon atoms, or substituted alkyl of 1-100 non-hydrogen atoms or R 3  is a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; m=1-100 and is equal to or less than the number of reactive amino groups on R 3 , and R 6  are independently —CN, —CO 2 R 1 , —COR 1 , or —CONR 1 R 1 . 
       
     
     
         2 . A compound having the structure 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 carbon atoms, or substituted aryl; R 3  is H, alkyl of 1-100 carbon atoms, or substituted alkyl or a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; and m+m′=1-100 and is equal to or less than the number of reactive amino groups on R 3 . 
       
     
     
         3 . A compound of  claim 1  or  2  wherein R 3  is derived from a polymeric amine. 
     
     
         4 . The compound of  claim 3  wherein m is 2 and n is between 3 and 50. 
     
     
         5 . The compound of  claim 3  wherein m and n are each independently between 3 and 50. 
     
     
         6 . A compound of  claim 1  or  2  wherein R 3  is derived from a polymeric and polyfunctional amine. 
     
     
         7 . A compound of  claim 1  or  2  wherein R 3  is derived from a bifunctional amine. 
     
     
         8 . A compound of  claim 1  or  2  wherein n is from 1 to 10. 
     
     
         9 . A compound of  claim 1  or  2  wherein m is from 2 to 50. 
     
     
         10 . A compound of  claim 1  or  2  wherein R 3  is derived from an amine-terminated polymer. 
     
     
         11 . A compound of  claim 1  or  2  wherein R 3  is derived from a diamino-terminated polymer or a polymeric polyamine. 
     
     
         12 . A compound of  claim 1  or  2  wherein R 5  is methyl. 
     
     
         13 . A compound of  claim 1  or  2  wherein R 2  is derived from a macromonomer of an alkyl methacrylate. 
     
     
         14 . A process of synthesizing a compound having a formula of: 
       
         
           
           
               
               
           
         
         comprising contacting an amine of formula R 3 R 4 NH, with a macromonomer of formula 
       
       
         
           
           
               
               
           
         
         and allowing the amine and the macromonomer to react; 
         wherein R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 non-hydrogen atoms, or substituted aryl; R 3  and R 4  are independently H, alkyl of 1-20 carbon atoms, or, substituted alkyl of 1-20 non-hydrogen atoms or R 3  is a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; m=1-100 and is equal to or less than the number of reactive amino groups on R 3 , and R 6  are independently —CN, —CO 2 R 1 , —COR 1 , or —CONR 1 R 1 . 
       
     
     
         15 . A process of synthesizing a compound of formula: 
       
         
           
           
               
               
           
         
         comprising contacting an amine of formula R 3 NH 2  with a macromonomer of formula 
       
       
         
           
           
               
               
           
         
         and allowing the amine and the macromonomer to react; 
         wherein R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 nonhydrogen atoms, or substituted aryl; R 3  are independently H, alkyl of 1-20 carbon atoms, substituted alkyl of 1-20 non-hydrogen atoms or a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; m+m′=1-100 and is equal to or less than the number of reactive amino groups on R 3 . 
       
     
     
         16 . A process of  claim 14  or  15  wherein the synthesis is carried out at a temperature from 0 and 200° C. 
     
     
         17 . A process of  claim 14  or  15  wherein the reaction is batch, semibatch or continuous. 
     
     
         18 . A process of  claim 14  or  15  wherein the synthesis is carried out at a pressure of from 1 to 100 atmospheres. 
     
     
         19 . A process of  claim 14  or  15  wherein the reaction is carried out in a solvent. 
     
     
         20 . A process of  claim 14  or  15  wherein the reaction is carried out in the melt. 
     
     
         21 . A product formed by a process comprising reacting a macromonomer of formula 
       
         
           
           
               
               
           
         
         with an amine of formula R 3 R 4 NH; 
         wherein R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 non-hydrogen atoms, or substituted aryl; R 3  and R 4  are independently H, alkyl of 1-20 carbon atoms, or substituted alkyl of 1-20 non-hydrogen atoms or R 3  is a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; m=1-100 and is equal to or less than the number of reactive amino groups on R 3 , and R 6  are independently —CN, —CO 2 R 1 , —COR 1 , or —CONR 1 R 1 . 
       
     
     
         22 . A product comprising a compound having a structure as described in  claim 1  or  2 , said product selected from the group consisting of inks, dispersions, adhesives, resists, and automotive and architectural coatings, paints, or finishes, including high solids, aqueous, or solvent-based finishes. 
     
     
         23 . A product comprising a compound having a structure as described in  claim 1  or  2 , said product selected from the group consisting of dispersants, compatibilizers, adhesives, adhesion promoters, biological agents, compatibilizers, coupling agents, crosslinkers, curing agents, de-foamers, emulsifiers, flocculent, grafting agents, photopolymerizable materials, resists, stabilizers, surface active agents, surfactants, and viscosity modifiers. 
     
     
         24 . A compound having the structure 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are independently H, alkyl of 1-20 carbon atoms, aryl, substituted alkyl of 1-20 carbon atoms, or substituted aryl; R 3  is H, alkyl of 1-100 carbon atoms, or substituted alkyl or a polymer; R 5  is methyl, hydrogen or hydroxymethyl; n=1-100; and m+m′=1-100 and is equal to or less than the number of reactive amino groups on R 3 ; and R 10  and R 11  are independently hydrogen or alkyl and may be combined in a cyclic structure.