Polymers including a methylene beta-ketoester and products formed therefrom

Abstract

The present teachings are directed at 1,1-di substituted alkene monomers (e.g., methylene beta-ketoester monomers), methods for producing the same, polymerizable compositions including a methylene beta-ketoester monomer, and polymers, compositions and products formed therefrom. The monomer preferably is a high purity monomer. In the method for producing the methylene beta-ketoesters of the invention, a beta-ketoester may be reacted with a source of formaldehyde. The methylene beta-ketoester monomers may be used in 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).

1 . A polymerizable composition comprising:
 at least one methylene beta-ketoester monomer having 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-(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  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 amount of ketals in the polymerizable composition is less than about 10 ppm and the amount of latent acid-forming impurities in the polymerizable composition is less than about 10 ppm. 
     
     
         3 . The polymerizable composition of  claim 1  including a stabilizing amount of at least one stabilizer selected from the group consisting of an acidic stabilizer, a vapor phase stabilizer, and a free radical stabilizer. 
     
     
         4 . The polymerizable composition of  claim 3 , wherein the polymerizable composition is an adhesive, a coating, or a sealant. 
     
     
         5 . The polymerizable composition of  claim 3 , wherein the at least one stabilizer includes the acidic stabilizer selected from trifluoromethane sulfonic acid, maleic acid, methane sulfonic acid, difluoro acetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, and chlorodifluoro acid. 
     
     
         6 . The polymerizable composition of  claim 3 , wherein the at least one stabilizer includes the vapor phase stabilizer selected from hydroquinone, methyl hydroquinone, butylated hydroxytoluene, butylated hydroxyanisole. 
     
     
         7 . (canceled) 
     
     
         8 . (canceled) 
     
     
         9 . A polymerizable composition comprising:
 at least one methylene beta-ketoester monomer having 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-(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  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-ketoester monomer is a high purity monomer having a purity of about 95 weight percent or more. 
       
     
     
         10 . The polymerizable composition of  claim 9 , wherein the amount of any analogous compound having the methylene group of the methylene beta-ketoester replaced by a hydroxyaklyl group is about 3 mole percent or less, based on the total moles of the monomer. 
     
     
         11 . The polymerizable composition of  claim 9 , wherein any impurities in the monomer, if present, includes an analogous 1,1-disubstituted alkane compound in an amount of about 40 mole percent or more of the impurity. 
     
     
         12 . The polymerizable composition of  claim 9 , wherein the concentration of any impurities having a dioxane group is about 2 mole percent or less, based on the total weight of the methylene beta-ketoester. 
     
     
         13 . The polymerizable composition of  claim 9 , wherein the polymerizable composition includes a stabilizing amount of at least one stabilizer selected from the group consisting of an acidic stabilizer, a vapor phase stabilizer, and a free radical stabilizer. 
     
     
         14 . The polymerizable composition of  claim 9 , wherein the polymerizable composition is an adhesive, a coating, or a sealant. 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . The polymerizable composition of  claim 9 , 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 
     
     
         18 . A method of preparing the polymerizable composition of  claim 1  comprising:
 forming a methylene beta-ketoester monomer by reacting 
 i) formaldehyde; and 
 ii) a beta-ketoester; 
 wherein the reaction product has a purity of about 97 percent or more 
 wherein the amount of ketals in the reaction product is less than about 100 ppm and/or the amount of latent acid-forming impurities in the reaction product is less than about 100 ppm. 
 
     
     
         19 . The method of  claim 18 , wherein the beta-ketoester is 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. 
     
     
         20 . A method of preparing the polymerizable composition of  claim 9  comprising:
 forming a methylene beta-ketoester monomer by reacting 
 i) formaldehyde; and 
 ii) a beta-ketoester. 
 wherein the reaction product has a purity of about 97 percent or more. 
 ing: 
 forming a methylene beta-ketoester monomer by reacting 
 i) formaldehyde; and 
 ii) a beta-ketoester. 
 wherein the reaction product has a purity of about 97 percent or more.