Polymers including a methylene beta-ketoester and products formed therefrom

Abstract

The present invention provides methylene beta-ketoester monomers, methods for producing the same, and compositions and products formed therefrom. In the method for producing the methylene beta-ketoesters of the invention, a beta-ketoester is reacted with a source of formaldehyde in a modified Knoevenagel reaction optionally in the presence of an acidic or basic catalyst, and optionally in the presence of an acidic or non-acidic solvent, to form reaction complex. The reaction complex may be an oligomeric complex. The reaction complex is subjected to further processing, which may be vaporization by contact with an energy transfer means in order to isolate the beta-ketoester monomer. The present invention further compositions and products formed from methylene beta-ketoester monomers of the invention, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

What is claimed is: 
     
         1 . A polymer having repeat units of the formula: 
       
         
           
           
               
               
           
         
         wherein R and R′ are independently C 1 -C 15  alkyl, C 2 -C 15  alkenyl, halo-(C 1 -C 15  alkyl), C 3 -C 6  cycloalkyl, halo-(C 3 -C 6  cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15  alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15  alkyl), or alkoxy-(C1-15 alkyl), each of which may be optionally substituted by C 1 -C 15  alkyl, halo-(C 1 -C 15  alkyl), C 3 -C 6  cycloalkyl, halo-(C 3 -C 6  cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15  alkyl), aryl, aryl —(C 1 -C 15  alkyl), heteroaryl, C 1 -C 15  alkoxy, C 1 -C 15  alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. 
       
     
     
         2 . The polymer of  claim 1 , wherein the polymer includes a difunctional monomeric cross-linking agent. 
     
     
         3 . The polymer of  claim 1 , wherein the polymer includes a methylene beta-ketoester monomer being formed as a product of a reaction between
 i) formaldehyde; and   ii) ethyl 4,4-dimethyl-3-oxopenanoate, ethyl 3-oxo-3-phenylpropanoate, ethyl 3-oxohexanoate, ethyl 3-oxobutanoate, methyl 3-oxobutanoate, ethyl 4-methyl-3-oxopentanoate, or ethyl 3-oxopentanoate.   
     
     
         4 . A polymeric composition comprising
 i) the polymer of  claim 1 , and   ii) a rheology modifier, a plasticizing agent, or a thixotropic agent.   
     
     
         5 . A polymeric composition comprising:
 i) the polymer of  claim 1 , and   ii) a natural rubber or a synthetic rubber.   
     
     
         6 . A polymeric composition comprising:
 i) the polymer of  claim 1 , and   ii) a filler agent or a reinforcing agent.   
     
     
         7 . A coating including the polymer of  claim 1 . 
     
     
         8 . The coating of  claim 7 , wherein the polymer includes a difunctional monomeric cross-linking agent 
     
     
         8 . The coating of  claim 8 , wherein the coating includes a filler agent or a reinforcing agent. 
     
     
         9 . The coating of  claim 8 , wherein the coating includes a natural rubber or a synthetic rubber. 
     
     
         10 . The coating of  claim 8 , wherein the coating includes a rheology modifier, a plasticizer agent, or a thixotropic agent. 
     
     
         11 . The coating of  claim 8 , wherein R 1  is C 1 -C 15  alkyl or C 2 -C 15  alkenyl. 
     
     
         12 . The coating of  claim 8 , wherein R 1  is halo-(C 1 -C 15  alkyl), halo-(C 3 -C 6  cycloalkyl), or alkoxy-(C1-15 alkyl). 
     
     
         13 . The coating of  claim 8 , wherein R 1  is heterocyclyl, heterocyclyl-(C 1 -C 15  alkyl), aryl, aryl-(C1-C15 alkyl), or heteroaryl. 
     
     
         14 . An article including an adhesive, wherein the adhesive including the polymer of  claim 1 . 
     
     
         15 . The article of  claim 14 , wherein the polymer includes a difunctional monomeric cross-linking agent 
     
     
         16 . The article of  claim 15 , wherein the adhesive includes a filler agent or a reinforcing agent. 
     
     
         17 . The article of  claim 15 , wherein the adhesive includes a rheology modifier, a plasticizer agent, or a thixotropic agent. 
     
     
         18 . The article of  claim 15 , wherein R 1  is C 1 -C 15  alkyl or C 2 -C 15  alkenyl. 
     
     
         19 . The article of  claim 15 , wherein R 1  is halo-(C 1 -C 15  alkyl), halo-(C 3 -C 6  cycloalkyl), or alkoxy-(C1-15 alkyl). 
     
     
         20 . The article of  claim 15 , wherein R 1  is heterocyclyl, heterocyclyl-(C 1 -C 15  alkyl), aryl, aryl-(C1-C15 alkyl), or heteroaryl.