Acetoacetylated polyvinyl polymers

Abstract

The present invention relates compositions containing acetoacetylated polyvinyl polymers obtained from polyvinyl polymers, such as polyvinyl butyrals. These coating compositions are especially suitable for use as wash primers in automotive OEM and refinish coating applications.

1 . A composition comprising: 
 (a) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent and (q) ranges from about 1 mole percent to about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo;    (b) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent, (q) ranges from about 1 mole percent to about 88 mole percent and (x) ranges from about 0.5 to about 6 mole percent, sum of (m), (n), (p), (q) and (x) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, and wherein Z is H, or —COOH and Y is —COOH, halo, unsubstituted phenyl or a combination thereof; said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or    (c) a combination thereof.    
   
   
       2 . The coating composition of  claim 1  wherein in said acetoacetylated polyvinyl polymer R 1  is propyl and R 2  is methyl.  
   
   
       3 . The coating composition of  claim 1  wherein GPC weight average molecular weight of said acetoacetylated polyvinyl polymer ranges from about 20,000 to about 300,000.  
   
   
       4 . The coating composition of  claim 1  wherein Tg of the acetoacetylated polyvinyl polymer ranges from about 40° C. to about 60° C.  
   
   
       5 . The coating composition of  claim 1  wherein said acetoacetylated polyvinyl polymer is solubilized in one or more solvents.  
   
   
       6 . The coating composition of  claim 1  wherein VOC of said composition ranges from 0.1 to 0.72 kilograms per liter of said composition.  
   
   
       7 . The curable coating composition of  claim 1  wherein said acetoacetylated polyvinyl polymer is produced by the steps comprising: 
 (i) dissolving in one or more solvents:    (a) a polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent and (o) ranges from about 13 mole percent to about 98.5 mole percent, sum of (m), (n) and (o) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14 alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo;    (b) a polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent and (o) ranges from about 13 mole percent to about 98.5 mole percent and (x) ranges from about 0.5 to about 6 mole percent, sum of (m), (n), (o) and (x) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, and wherein Z is H, or —COOH and Y is —COOH, halo, unsubstituted phenyl or a combination thereof; said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or    (c) a combination of thereof to form a solution;    (ii) contacting said solution with C 1  to C 12  alkyl acetoacetate to produce said acetoacetylated polyvinyl polymer.    
   
   
       8 . The composition of  claim 7  wherein said R 1  is propyl and said R 2  is methyl.  
   
   
       9 . The coating composition of  claim 1  formulated as automotive refinish or OEM wash primer composition.  
   
   
       10 . A method of producing a coating on a substrate comprising: 
 (i) applying a layer over a substrate surface of a coating composition comprising:    (a) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent and (q) ranges from about 1 mole percent to about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo;    (b) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to 85 mole percent, (n) ranges from about 0 mole percent to 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent, (q) ranges from about 1 mole percent to about 88 mole percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and (x) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, and wherein Z is H, or —COOH and Y is —COOH, halo, unsubstituted phenyl or a combination thereof; said substituents being independently selected from the group consisting of C 1  to C 12 alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or    (c) a combination thereof; and    (ii) drying said layer under ambient conditions or at elevated cure temperatures to form said coating on said substrate.    
   
   
       11 . The method of  claim 10  wherein said wherein said R 1  is propyl and said R 2  is methyl.  
   
   
       12 . The method of  claim 10  or  11  further comprising applying a layer of base coating composition on said layer before said drying step.  
   
   
       13 . The method of  claim 12  further comprising applying a layer of clear coating composition on said layer of base coating composition before said drying step.  
   
   
       14 . The method of  claim 13  wherein said coating composition is a wash primer composition.  
   
   
       15 . The method of  claim 14  wherein said substrate is an automotive body.  
   
   
       16 . A method of producing a multi-coat system on a substrate comprising: 
 (i) applying a layer over a substrate surface of a coating composition comprising:    (a) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent and (q) ranges from about 1 mole percent to about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14 alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo;    (b) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to 85 mole percent, (n) ranges from about 0 mole percent to 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent, (q) ranges from about 1 mole percent to about 88 mole percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and (x) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, and wherein Z is H, or —COOH and Y is —COOH, halo, unsubstituted phenyl or a combination thereof; said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or    (c) a combination thereof;    (ii) applying a layer of a base coating composition on said composition layer;    (iii) applying a layer of a clear coating composition on said layer of base coating composition to form a multi-layer system on said substrate; and    (iv) drying said multi-layer system under ambient conditions or at elevated cure temperatures to form said multi-coat system on said substrate.    
   
   
       17 . The method of  claim 16  wherein said substrate is an automotive body.  
   
   
       18 . A method of producing a molded article comprising: 
 (i) mixing fibrids, floc, pulp, micropulp or a combination thereof with a composition to form a moldable component, said composition comprising:    (a) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to about 85 mole percent, (n) ranges from about 0 mole percent to about 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent and (q) ranges from about 1 mole percent to about 88 mole percent, sum of (m), (n), (p) and (q) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo;    (b) an acetoacetylated polyvinyl polymer having the formula:                          wherein (m) ranges from about 1.5 mole percent to 85 mole percent, (n) ranges from about 0 mole percent to 20.5 mole percent, (p) ranges from about 12 mole percent to about 87 mole percent, (q) ranges from about 1 mole percent to about 88 mole percent and (x) ranges from 0.5 to 6 mole percent, sum of (m), (n), (p), (q) and (x) being 100 and wherein R 1  and R 2  are independently H, substituted or unsubstituted C 1  to C 12  alkyl, substituted or unsubstituted C 6  to C 14  aryl, substituted or unsubstituted C 7  to C 22  aralkyl, substituted or unsubstituted C 6  to C 14  alkaryl, substituted, unsubstituted C 4  to C 14  carbocyclyl or a combination thereof, and wherein Z is H, or —COOH and Y is —COOH, halo, unsubstituted phenyl or a combination thereof; said substituents being independently selected from the group consisting of C 1  to C 12  alkoxy, acyl, carboxyl, derivative of carboxyl, sulfonyl, derivative of sulfonyl, cyano, and halo; or    (c) a combination thereof;    (ii) heating said moldable component into a melt;    (iii) conveying a desired amount of said melt into a cavity of an article mold;    (iv) cooling said desired amount of melt to form said article; and    (v) removing said article from said cavity.    
   
   
       19 . The method of  claim 18  wherein said molded article is a safety helmet.