Amine-Containing Polymers, Dispersions Thereof and Methods of Making and Using the Same

Abstract

Described herein is a polymer comprising: interpolymerized units of (i) a fluorinated terminal alkene monomer and (ii) a tertiary amine-containing fluorinated monomer comprising at least one of a vinyl amine, a substituted vinyl amine, an allyl amine, a substituted allyl amine, and combinations thereof, wherein the polymer can be amorphous or semi-crystalline with a melting point no greater than 325° C. Dispersions thereof and methods of making and using the same are also described.

What is claimed is: 
     
         1 . An aqueous dispersion comprising a fluorinated polymer comprising:
 (a) an aqueous continuous phase;   (b) a plurality of fluorinated polymer particles, wherein the fluorinated polymer particle comprises interpolymerized units of (i) a fluorinated terminal alkene monomer and (ii) a tertiary amine-containing fluorinated monomer wherein the tertiary amine-containing fluorinated monomer is selected from at least one of the following formulas:   
       
         
           
           
               
               
           
         
       
       where X 1  is selected from H or F; X 2  is selected from H or F; X 3  is selected from H or F; and each R f  group are (i) independently selected from a linear or branched perfluorinated alkyl group comprising 1 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or (ii) bonded together to form a ring structure comprising 4 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or 
       
         
           
           
               
               
           
         
       
       where X 1 , X 2 , and X 3  are independently selected from H, or F; 
       Y 1  is H or F; Y 2  is For CF 3 ; and each R f  group are (i) independently selected from a linear or branched perfluorinated alkyl group comprising 1 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or (ii) bonded together to form a ring structure comprising 4 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; and
 (c) a hydrocarbon surfactant. 
 
     
     
         2 . The aqueous dispersion of  claim 1 , wherein the hydrocarbon surfactant is non-ionic. 
     
     
         3 . The aqueous dispersion of  claim 1 , wherein the aqueous dispersion comprises at least 2 wt % and at most 10 wt % of the hydrocarbon surfactant. 
     
     
         4 . The aqueous dispersion of  claim 1 , wherein the aqueous dispersion comprises 5 to 60% by weight of the plurality of fluorinated polymer particles. 
     
     
         5 . The aqueous dispersion of  claim 1 , wherein the fluorinated terminal alkene monomer is tetrafluoroethylene. 
     
     
         6 . The aqueous dispersion of  claim 1 , wherein the fluorinated terminal alkene monomer comprises at least one of tetrafluoroethylene; vinylidene fluoride; hexafluoropropylene; chlorotrifluoroethylene; 2,3,3,3-tetrafluoropropene; and combinations thereof. 
     
     
         7 . The aqueous dispersion of  claim 1 , wherein the tertiary amine-containing fluorinated monomer comprises at least one of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         and combinations thereof. 
       
     
     
         8 . The aqueous dispersion of  claim 1 , wherein the tertiary amine-containing fluorinated monomer comprises at least one of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         and combinations thereof. 
       
     
     
         9 . The aqueous dispersion of  claim 1 , wherein the hydrocarbon surfactant is non-ionic or anionic. 
     
     
         10 . The aqueous dispersion of  claim 1 , wherein the fluorinated polymer particles of the plurality of fluorinated polymer particles have an average particle diameter of 30 to 400 nm. 
     
     
         11 . The aqueous dispersion of  claim 1 , further comprising a fluorinated liquid. 
     
     
         12 . The aqueous dispersion of  claim 1 , wherein the fluorinated polymer particle comprises a cure-site selected from Br, I, nitrile, and combinations thereof. 
     
     
         13 . The aqueous dispersion of  claim 1 , wherein the fluorinated polymer particle is semi-crystalline. 
     
     
         14 . The aqueous dispersion of  claim 13 , wherein the fluorinated polymer particle has a melting point no greater than 325° C. 
     
     
         15 . The aqueous dispersion of  claim 1 , wherein the fluorinated polymer particle is amorphous. 
     
     
         16 . A coating composition comprising the dispersion of  claim 1 . 
     
     
         17 . A method of coating a substrate comprising: contacting the aqueous dispersion of  claim 1  onto a substrate. 
     
     
         18 . The method of coating a substrate of  claim 17 , wherein the substrate comprises at least one of metal, glass, wood, ceramic, fabric, plastic, and combinations thereof. 
     
     
         19 . A method of making a fluoropolymer comprising:
 (a) polymerizing in an aqueous continuous phase, (i) a fluorinated terminal alkene monomer and (ii) a tertiary amine-containing fluorinated monomer wherein the tertiary amine-containing fluorinated monomer is selected from at least one of the following formulas:   
       
         
           
           
               
               
           
         
       
       where X 1  is selected from H or F; X 2  is selected from H or F; X 3  is selected from H or F; and each R f  group are (i) independently selected from a linear or branched perfluorinated alkyl group comprising 1 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or (ii) bonded together to form a ring structure comprising 4 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or 
       
         
           
           
               
               
           
         
       
       where X 1 , X 2 , and X 3  are independently selected from H, or F;
 Y 1  is H or F; Y 2  is For CF 3 ; and each R f  group are (i) independently selected from a linear or branched perfluorinated alkyl group comprising 1 to 8 carbon atoms and optionally comprising at least one catenated O or N atom; or (ii) bonded together to form a ring structure comprising 4 to 8 carbon atoms and optionally comprising at least one catenated O or N atom.