Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom

Abstract

The present teachings are directed at polymers, polymeric compositions, polymerizable compositions, and articles including a 1,1-disubstituted alkene monomers (e.g., methylene beta-diketone monomers) and one or more formulation materials. The monomer preferably is a high purity monomer. Preferably, the amount of ketals (e.g., in the polymerizable composition) is less than about 100 ppm and/or the amount of latent acid-forming impurities (e.g., in the polymerizable composition) is less than about 100 ppm (e.g., based on the total weight of the monomer). Preferably, the methylene beta-diketone monomer is a high purity monomer having a purity of about 95 weight percent or more. The monomer(s) may be employed in compositions and products, 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 polymerizable composition comprising:
 i) at least one methylene beta-diketone monomer; and   ii) one or more formulation materials selected including an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a toughening agent, a plasticizing agent, a thixotropic agent, a cross-linking agent, a reinforcing agent, a dye, a filler, an opacifier, a thermal degradation reducer, a natural or synthetic rubber, an adhesion promotor, or any combination thereof;   wherein the methylene beta-diketone has the structural formula:   
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  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-(C 1 -C 15  alkyl), heteroaryl or heteroaryl-(C 1 -C 15  alkyl), or alkoxy —(C 1 -C 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  alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; 
         or 
         wherein R 1  and R 2  are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring 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; 
         wherein the amount of ketals in the polymerizable composition is less than about 100 ppm and/or the amount of latent acid-forming impurities in the polymerizable composition is less than about 100 ppm. 
       
     
     
         2 . The polymerizable composition of  claim 1 , wherein the formulation material includes the thixotropic agent. 
     
     
         3 . The polymerizable composition of  claim 1 , wherein the formulation material includes the toughening agent. 
     
     
         4 . The polymerizable composition of  claim 1 , wherein the formulation material includes a natural or synthetic rubber. 
     
     
         5 . The polymerizable composition of  claim 1 , wherein the formulation material includes an acrylic rubber or an ethylene/acrylic elastomer. 
     
     
         6 . The polymerizable composition of  claim 1 , wherein the formulation material includes a cross-linking agent, a cure accelerator, or both. 
     
     
         7 . The polymerizable composition of  claim 1 , wherein the formulation material includes an adhesion promotor. 
     
     
         8 . The polymerizable composition of  claim 1 , wherein the formulation material includes a thixotropic agent. 
     
     
         9 . The polymerizable composition of  claim 1 , wherein the formulation material includes a reinforcing agent, a dye, a filler, or an opacifier. 
     
     
         10 . A polymer prepared from the polymerizable composition of  claim 1 , wherein the polymer includes repeat units formed from the methylene beta-diketone monomer. 
     
     
         11 . A polymerizable composition comprising:
 i) at least one methylene beta-diketone monomer; and   ii) one or more formulation materials selected including an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a toughening agent, a plasticizing agent, a thixotropic agent, a cross-linking agent, a reinforcing agent, a dye, a filler, an opacifier, a thermal degradation reducer, a natural or synthetic rubber, an adhesion promotor, or any combination thereof;   wherein the methylene beta-diketone has the structural formula:   
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  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-(C 1 -C 15  alkyl), heteroaryl or heteroaryl-(C 1 -C 15  alkyl), or alkoxy —(C 1 -C 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  alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester; 
         or 
         wherein R 1  and R 2  are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring 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; 
         wherein the methylene beta-diketone monomer is a high purity monomer having a purity of about 95 weight percent or more. 
       
     
     
         12 . The polymerizable composition of  claim 11 , wherein the formulation material includes the thixotropic agent. 
     
     
         13 . The polymerizable composition of  claim 11 , wherein the formulation material includes the toughening agent. 
     
     
         14 . The polymerizable composition of  claim 11 , wherein the formulation material includes a natural or synthetic rubber. 
     
     
         15 . The polymerizable composition of  claim 11 , wherein the formulation material includes an acrylic rubber or an ethylene/acrylic elastomer. 
     
     
         16 . The polymerizable composition of  claim 11 , wherein the formulation material includes a cross-linking agent, a cure accelerator, or both. 
     
     
         17 . The polymerizable composition of  claim 11 , wherein the formulation material includes an adhesion promotor. 
     
     
         18 . The polymerizable composition of  claim 11 , wherein the formulation material includes a thixotropic agent. 
     
     
         19 . The polymerizable composition of  claim 11 , wherein the formulation material includes a reinforcing agent, a dye, a filler, or an opacifier. 
     
     
         20 . A polymer prepared from the polymerizable composition of  claim 11 , wherein the polymer includes repeat units formed from the methylene beta-diketone monomer.