Curable resin compositions and process for preparing oligomers and polymers having acryloyl groups, substituted methacrylate groups and beta-dicarbonyl groups

Abstract

A curable resin composition which exhibits no drawbacks such as yellowing and exhibits excellent hydrolysis sensitivity is provided, and a process for preparing curable oligomers and polymers which has foregoing properties is provided. The composition comprises a curable oligomer or polymer, wherein the oligomer or polymer has an acryloyl group, a β-dicarbonyl group having a chemical structure part represented by any of the following structures, and a substituted methacrylate group represented by the following structure. The process comprises a reaction step of reacting at least one multifunctional monomeric acrylate with at least one compound having at least one β-dicarbonyl group in the presence of a tertiary organic phosphine.

1 . A process for preparing a curable oligomer or polymer, having an acryloyl group, a β-dicarbonyl group having a chemical structure part represented by any of the following structures,  
       
         
           
           
               
               
           
         
       
       and a substituted methacrylate group represented by the following structure,  
       
         
           
           
               
               
           
         
       
       comprising a reaction step of reacting at least one multifunctional monomeric acrylate with at least one compound having at least one β-dicarbonyl group in the presence of a tertiary organic phosphine.  
     
     
         2 . A process according to  claim 1 , characterized in that the multifunctional monomeric acrylate is a di-, tri-, tetra-, penta-, or hexaacrylate.  
     
     
         3 . A process according to  claim 1 , wherein the compound having a β-dicarbonyl group is an acetoacetate, malonate or β-diketone.  
     
     
         4 . A process according to  claim 1 , wherein a mixture of monomeric multifunctional acrylates and a mixture of β-dicarbonyl compounds are used.  
     
     
         5 . A process according to  claim 1 , wherein the amount of added tertiary phosphine is within the range of 0.2 to 10% by weight.  
     
     
         6 . A process according to  claim 1 , wherein the reaction temperature is within the range of 25 to 125° C.  
     
     
         7 . A process according to  claim 1 , wherein the tertiary organic phosphine is selected from the group consisting of tripropylphosphine, triisopropylphosphine, trivinylphosphine, tributylphosphine, triisobutylphosphine, tri-tert.-butylphosphine, triallylphosphine, tris(2,4,4-trimethylpentyl)phosphine, tricyclopentylphosphine, tricyclohexylphosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, triphenylphosphine, tri-n-octylphosphine, tri-n-dodecylphosphine, tribenzylphosphine, dimethylphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, diphenyl(2-methoxphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(4-dimethylaminophenyl)phosphine, hexamethylene triaminophosphine and hexaethylene triaminophosphine.