Process for the continuous production of epoxylated addition polymers, and powder and liquid coating applications containing epoxylated addition polymers

Abstract

A process is disclosed for a continuous, high temperature polymerization process for preparing a free radically polymerized epoxy-functional polymeric product. The process comprises continuously charging into a reactor at least one epoxy-functional acrylic monomer, and optionally at least one non-functional free radical polymerizable monomer. An optional free radical polymerization initiator may also be added. The reactor is maintained at an effective temperature for an effective period of time to cause polymerization of the monomers into a polymeric product, such that the polymeric product is formed substantially free of gel particles. A clear coating is also disclosed incorporating polymers of the present invention, such that the clear coating has a low Delta b value at standard conditions.

What is claimed is:  
     
         1 . A continuous, high temperature polymerization process for preparing a free radically polymerized epoxy-functional polymeric product comprising: 
 (a) continuously charging into a reactor monomer(s) consisting essentially of: 
 (i) at least one epoxy-functional acrylic monomer;  
 (ii) optionally at least one non-functional monomer which is a non-functional free radical polymerizable monomer; and  
   (b) maintaining an effective temperature in the reactor for an effective period of time to cause polymerization of the monomers to produce a polymeric product, such that the polymeric product is formed substantially free of gel particles.    
     
     
         2 . The continuous, high temperature polymerization process of  claim 1 , wherein (a) further comprises continuously charging into the reactor: 
 (i) from about 1 percent to 100 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;    (ii) from 0 percent to about 99 percent by weight of at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers, non-functional styrenic monomers and combinations thereof based on the total weight of the monomers; and    (iii) at least one free radical polymerization initiator.    
     
     
         3 . The continuous, high temperature polymerization process of  claim 2 , wherein (a) further comprises continuously charging into the reactor a solvent in an amount up to 40 percent by weight of the total weight of the monomers.  
     
     
         4 . The continuous, high temperature polymerization process of  claim 1 , wherein the effective temperature is from about 160° to about 270° C., and the effective period of time for residence of the monomers within the reactor is less than 60 minutes.  
     
     
         5 . The continuous, high temperature polymerization process of  claim 1 , wherein the epoxy-functional acrylic monomer is glycidyl methacrylate.  
     
     
         6 . The continuous, high temperature polymerization process of  claim 1 , wherein the monomers further comprise at least one non-functional methacrylate monomer, at least one non-functional acrylate monomer, and at least one non-functional styrenic monomer.  
     
     
         7 . The continuous, high temperature polymerization process of  claim 1 , wherein the monomers further comprise at least two different non-functional methacrylate monomers and at least one non-functional acrylate monomer.  
     
     
         8 . The continuous, high temperature polymerization process of  claim 1 , wherein the monomers further comprise at least two different non-functional methacrylate monomers, at least one non-functional acrylate monomer, and at least one non-functional styrenic monomer.  
     
     
         9 . The continuous, high temperature polymerization process of  claim 1 , wherein the monomers consist essentially of epoxy-functional acrylic monomer(s) and non-functional styrenic monomer(s).  
     
     
         10 . The continuous, high temperature polymerization process of  claim 2 , wherein the free radical polymerization initiator is di-t-amyl peroxide.  
     
     
         11 . A continuous, high temperature polymerization process for preparing a free radically polymerized epoxy-functional polymeric product comprising; 
 (a) continuously charging into a reactor monomer(s) consisting essentially of: 
 (i) at least one epoxy-functional acrylic monomer;  
 (ii) at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers, and combinations thereof; and  
   (b) maintaining an effective temperature in the reactor for an effective period of time to cause polymerization of the monomers to produce a polymeric product, such that the polymeric product is formed substantially free of gel particles.    
     
     
         12 . The continuous, high temperature polymerization process of  claim 11 , wherein (a) further comprises continuously charging into the reactor at least one solvent.  
     
     
         13 . The continuous, high temperature polymerization process of  claim 11 , wherein (a) further comprises continuously charging into the reactor at least one free radical polymerization initiator.  
     
     
         14 . The continuous, high temperature polymerization process of  claim 11 , wherein the effective temperature is from about 175° C. to about 250° C., and wherein the effective period of time for residence of the monomers within the reactor is less than 15 minutes.  
     
     
         15 . The continuous, high temperature polymerization process of  claim 11 , wherein (a) further comprises continuously charging into the reactor at least one non-functional styrenic monomer.  
     
     
         16 . The continuous, high temperature polymerization process of  claim 11 , wherein the monomers further comprise at least two different non-functional acrylate monomers or nonfunctional methacrylate monomers.  
     
     
         17 . The continuous, high temperature polymerization process of  claim 16 , wherein the monomers further comprise at least two different non-functional methacrylate monomers and at least one non-functional acrylate monomer.  
     
     
         18 . The continuous, high temperature polymerization process of  claim 11 , wherein the monomers further comprise at least three non-functional methacrylate monomers.  
     
     
         19 . The continuous, high temperature polymerization process of  claim 11 , wherein (a) further comprises continuously charging into the reactor: 
 (i) about 15 percent to about 60 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;    (ii) up to about 85 percent by weight of at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers, and combinations thereof based on the total weight of the monomers;    (iii) about 0.0005 to about 0.06 moles of at least one free radical polymerization initiator per mole of monomers;    (iv) 0 percent to about 25 percent by weight of at least one non-functional styrenic monomer based on the total weight of the monomers; and    (v) 0 percent to about 15 percent by weight of solvent based on the total weight of the monomers.    
     
     
         20 . The continuous, high temperature polymerization process of  claim 11 , wherein the epoxy-functional acrylic monomer is glycidyl methacrylate.  
     
     
         21 . The continuous, high temperature polymerization process of  claim 19 , wherein the non-functional methacrylate and non-functional acrylate monomers are selected from the group consisting of methyl methacrylate, butyl methacrylate, butyl acrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and combinations thereof.  
     
     
         22 . The continuous, high temperature polymerization process of  claim 21 , further comprising at least one non-functional styrenic monomer.  
     
     
         23 . A powder coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 1;  and    (b) other materials sufficient to form a powder coating composition when combined with the polymeric product.    
     
     
         24 . A powder coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 11;  and    (b) other materials sufficient to form a powder coating when combined with the polymeric product.    
     
     
         25 . A powder coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 1 percent to 100 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;  
 (ii) optionally From 0 percent to about 99 percent by weight of a at least one non-functional monomer which is a non-functional free radical polymerizable monomer, such that the monomers are polymerized into the polymeric product, such that the polymeric product comprises at least 40 percent by weight of polymerized epoxy-functional monomers;  
   (b) other materials sufficient to form a powder clear coating when combined with the polymeric product, wherein the powder clear coating composition exhibits a Delta b value of 1.2 or less at standard conditions.    
     
     
         26 . A powder coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 15 percent to about 60 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;  
 (ii) up to 85 percent by weight of at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers and combinations thereof based on the total weight of the monomers, such that the monomers are polymerized into the polymeric product; and  
 (iii) 0 to about 25 percent by weight of at least one non-functional styrenic monomer based on the total weight of the monomers, such that the polymeric product comprises at least 40 percent by weight of polymerized epoxy-functional monomers;  
   (b) other materials sufficient to form a powder clear coating when combined with the polymeric product, wherein the powder clear coating composition exhibits a Delta b value of 1.2 or less at standard conditions.    
     
     
         27 . A liquid coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 1;  and    (b) other materials sufficient to form a liquid coating composition when combined with the polymeric product.    
     
     
         28 . A liquid coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 11;  and    (b) other materials sufficient to form a liquid coating composition when combined with the polymeric product.    
     
     
         29 . A liquid coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 1 percent to 100 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of (he monomers;  
 (ii) optionally from 0 percent to about 99 percent by weight of at least one non-functional monomer which is a non-functional free radical polymerizable monomer, such that the monomers are polymerized into the polymeric product; and  
   (b) other materials sufficient to form a liquid clearcoating when combined with the polymeric product, wherein the liquid coating composition exhibits a Delta b value of 1.2 or less at standard conditions.    
     
     
         30 . A liquid clear coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 15 percent to about 60 percent by weight at least one epoxy-functional acrylic monomer based on the total weight of the monomers;  
 (ii) up to 85 percent by weight of at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers and combinations thereof based on the total weight of the monomers;  
 (iii) 0 to about 25 percent by weight of at least one non-functional styrenic monomer based on the total weight of the monomers, such that the monomers are polymerized into the polymeric product; and  
   (b) other materials sufficient to form a liquid clear coating when combined with the polymeric product, wherein the liquid coating composition exhibits a Delta b value of 1.2 or less at standard conditions.    
     
     
         31 . A continuous, high temperature polymerization process for preparing a free radically polymerized epoxy-functional polymeric product comprising: 
 (a) continuously changing into a reactor monomers consisting essentially of: 
 (i) at least one epoxy-functional acrylic monomer;  
 (ii) at least one non-functional methacrylate monomer;  
 (iii) at least one non-functional acrylate monomer; and  
   (b) maintaining an effective temperature in the reactor for an effective period of time to cause polymerization of the monomers to produce a polymeric product, wherein the acrylate monomer is added in a sufficient amount such that at least 60 percent of the total functional and non-functional methacrylate monomers are incorporated into the polymeric product.    
     
     
         32 . The continuous, high temperature polymerization process of  claim 31 , wherein (a) further comprises continuously charging into the reactor at least one free radical polymerization initiator.  
     
     
         33 . The continuous, high temperature polymerization process of  claim 31 , wherein (a) further comprises continuously charging into the reactor at least one non-functional styrenic monomer.  
     
     
         34 . The continuous, high temperature polymerization process of  claim 31 , wherein (a) further comprises continuously charging into the reactor at least one solvent.  
     
     
         35 . The continuous, high temperature polymerization process of  claim 31 , wherein a homopolymer of each nonfunctional acrylate monomer has a T g  of less than or equal to 30° C.  
     
     
         36 . The continuous, high temperature polymerization process of  claim 31 , wherein a homopolymer of each non-functional acrylate monomer has a T g  of greater than 30° C.  
     
     
         37 . The continuous, high temperature polymerization process of  claim 31 , wherein (a) further comprises continuously charging into the reactor: 
 (i) about 15% to about 60% by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;    (ii) up to about 60% by weight of at least one non-functional methacrylate monomer based on the total weight of the monomers;    (iii) tip to about 25% by weight of at least one non-functional acrylate monomer based on the total weight of the monomers;    (iv) about 0.0005 to about 0.06 moles of at least one free radical polymerization initiator per mole of monomers;    (v) up to about 25% by weight of at least one non-functional styrenic monomer based on the total weight of the monomers; and    (vi) up to about 15% by weight of solvent based on the total weight of the monomers.    
     
     
         38 . The continuous, high temperature polymerization process of  claim 37 , wherein the epoxy-functional acrylic monomer is glycidyl methacrylate.  
     
     
         39 . The continuous, high temperature polymerization process of  claim 38 , wherein the non-functional acrylate monomer is selected from the group consisting of cyclohexyl acrylate, isoborynl acrylate, and combinations thereof.  
     
     
         40 . The continuous, high temperature polymerization process of  claim 38 , wherein the non-functional methacrylate monomers are selected from the group consisting of methyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and combinations thereof.  
     
     
         41 . The continuous, high temperature polymerization process of  claim 37 , further comprising at least one non-functional styrenic monomer.  
     
     
         42 . A powder coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 31;  and    (b) other materials sufficient to form a powder coating composition when combined with the polymeric product.    
     
     
         43 . A liquid coating composition, comprising: 
 (a) the polymeric product made according to the process of  claim 31;  and    (b) other materials sufficient to form a liquid coating composition when combined with the polymeric product.    
     
     
         44 . A powder clear coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 15 percent to about 60 percent by weight of at least one epoxy-functional acrylic monomer based on the total weight of the monomers;  
 (ii) up to 60 percent by weight of at least one non-functional methacrylate monomer based on the total weight of the monomers;  
 (iii) up to 25 percent by weight of at least one non-functional acrylate monomer, such that the monomers are polymerized into the polymeric product such that the polymeric product comprises at least 40 percent by weight of polymerized epoxy-functional monomers;  
   (b) other materials sufficient to form a powder clear coating composition when combined with the polymeric product, wherein the powder clear coating composition exhibits a Delta b value of 1.2 or less at standard conditions.    
     
     
         45 . A liquid coating composition, comprising: 
 (a) a polymeric product, the polymeric product consisting essentially of: 
 (i) about 15% to about 60% by weight at least one epoxy-functional acrylic monomer based on the total weight of the monomers;  
 (ii) tip to 85% by weight of at least one non-functional monomer selected from the group consisting of non-functional acrylate monomers, non-functional methacrylate monomers and combinations thereof based on the total weight of the monomers; and  
 (iii) tip to 25% by weight of at least one non-functional acrylate monomer, such that the monomers are polymerized into the polymeric product;  
   (b) other materials sufficient to form a liquid clear coating composition when combined with the polymeric product, wherein the liquid clear coating composition exhibits a Delta b value of 1.2 or less at standard conditions.