Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer

Abstract

Monofunctional polyfluorooxetane oligomers and polymers are prepared by the cationic polymerization of fluorooxetane monomers with a monoalcohol. The fluorooxetane oligomers or polymers can be copolymerized with generally cyclic ethers. Alternatively, the polyfluorooxetane oligomer or polymer having a single hydroxyl end group can be functionalized with a variety of compounds so as to yield a functional end group such as an acrylate, a methacrylate, an allylic, an amine, etc., with the functionalized oligomer or polymer being suitable for use in radiation curable or thermal curable coating compositions. These functionalized polymers can be copolymerized and cured to provide improvements in wetting and surface properties that have previously been provided by migratory chemicals such as waxes and oils. The partially or fully fluorinated side groups of the fluorooxetanes are believed to be disproportionately present at the interfaces between the coating and the substrate and between the coating and the atmosphere.

What is claimed is:  
     
         1 . A monohydric polyfluorooxetane oligomer or polymer, comprising: 
 the formula                        or combinations thereof, where OR 1  is derived from a monoalcohol, where DP is from 2 to about 150, where each n is the same or different and independent is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms.      
     
     
         2 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 1 , wherein R 1  is a aliphatic group, an alicyclic group, an aromatic group, a heterocyclic group, or a halogenated organic group, or combinations thereof, having a total of from 1 to about 40 carbon atoms, and wherein said DP is from 2 to about 150.  
     
     
         3 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 2 , wherein R 1  has a total of from 1 to 18 carbon atoms, 
 wherein said DP is from about 3 to about 50, and    wherein each Rf is the same or different and independently is a linear or branched fluoronated alkyl having from 1 to about 15 carbon atoms.    
     
     
         4 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 3 , wherein OR 1  is derived from benzyl alcohol, trifluoroethanol, allylic alcohol, or heptafluorobutanol, or combinations thereof.  
     
     
         5 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 1 , wherein said oligomer or polymer is said  
       
         
           
           
               
               
           
         
       
     
     
         6 . A process for forming a monohydric polyfluorooxetane oligomer or polymer, comprising the steps of: 
 reacting a monoalcohol with a fluorooxetane monomer in the presence of a cationic initiator.    
     
     
         7 . A process according to  claim 6 , wherein said monoalcohol is an aliphatic alcohol, an alicyclic alcohol, an aromatic alcohol, a heterocyclic alcohol, a halogenated alcohol, or combinations thereof, wherein the total number of carbons in said monoalcohol is from 1 to about 40 carbon atoms, and 
 wherein said fluorooxetane monomer has the formula                        or combinations thereof, where each n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluoronated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms.      
     
     
         8 . A process according to  claim 7 , wherein said monoalcohol has a total of from 1 to 18 carbon atoms, and wherein the number of repeat units in said polymer is from 2 to about 150.  
     
     
         9 . A process according to  claim 8 , wherein the number of repeat units in said polymer is from about 3 to about 50, wherein each Rf is the same or different and independently is a linear or branch fluoronated alkyl having from 1 to about 15 carbon atoms, wherein said fluorooxetane monomers are polymerized at a temperature of from about 0° C. to about 100° C., wherein in said cationic catalyst is a complex of boron trifluoride-tetrahydrofuran, and wherein said alcohol is benzyl alcohol, trifluoroethanol, allylic alcohol, or heptafluorobutanol, or combinations thereof.  
     
     
         10 . A process according to  claim 7 , wherein said fluorooxetane monomer is said  
       
         
           
           
               
               
           
         
       
     
     
         11 . A monohydric polyfluorooxetane oligomer or polymer comprising: 
 repeat units of the formula                        or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms.      
     
     
         12 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 11 , wherein the number of said repeat groups is from 2 to about 150, and wherein Rf is a perfluoronated alkyl group.  
     
     
         13 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 12 , wherein the number of said repeat units is from about 12 to about 25.  
     
     
         14 . A monohydric polyfluorooxetane oligomer or polymer according to  claim 11 , wherein said repeat unit is said  
       
         
           
           
               
               
           
         
       
     
     
         15 . A functionalized oligomer or polymer, comprising: 
 a monohydric polyfluorooxetane oligomer or polymer having one functional end group thereon, and said oligomer or polymer containing repeat units of the formula                        or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms.      
     
     
         16 . A functionalized oligomer or polymer according to  claim 15 , wherein said functional group is a melamine, an amine, an acetylacetate, an epoxide, a silyl, or an isocyanate, an acrylate, a methacrylate, or an allylic, and wherein the number of repeat units is from 2 to about 150.  
     
     
         17 . A functionalized oligomer or polymer according to  claim 16 , wherein said terminated functional group is an acrylate, a methacrylate, or an allylic.  
     
     
         18 . A functionalized oligomer or polymer according to  claim 17 , wherein the number of repeat units is from 3 to about 50, and wherein Rf is a perfluoronated alkyl group.  
     
     
         19 . A functionalized oligomer or polymer according to  claim 18 , wherein said repeat unit is said  
       
         
           
           
               
               
           
         
       
     
     
         20 . A copolymer, comprising: 
 repeat units of the formula                        or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms, and      repeat units derived from a monomer containing an epoxy (oxirane) functionality, a monomer having a 4-membered cyclic either group (oxetane); a monomer having a 5-membered cyclic ether group, 1,4-dioxane, 1,3-dioxane and 1,3-dioxalane, trioxane, or caprolactone; or combinations thereof.    
     
     
         21 . A copolymer according to  claim 20 , wherein said derived repeat units are derived from monomers of epichlorohydrin, propylene oxide, ethylene oxide, butyl glycidylether, and perfluorooctyl propylene oxide, trimethylene oxide, 3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl) oxetane, 3,3-bromomethyl(methyl)oxetane, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxane, or 1,3-dioxalane, or combinations thereof.  
     
     
         22 . A copolymer according to  claim 21 , wherein Rf is a perfluoronated alkyl group.  
     
     
         23 . A copolymer according to  claim 21 , wherein said copolymer is a random copolymer.  
     
     
         24 . A copolymer according to  claim 20 , wherein said repeat unit is said  
       
         
           
           
               
               
           
         
       
     
     
         25 . A copolymer, comprising: 
 repeat units of the formula                        or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms, and      repeat units derived from one or more unsaturated monomers.    
     
     
         26 . A copolymer according to  claim 25 , wherein said comonomer is a vinyl aromatic monomer having from 8 to 12 carbon atoms; an ethylenically unsaturated monomer free of acid groups having from 4 to 30 carbon atoms; a (cyclo)alkyl ester of maleic acid, fumaric acid or itaconic acid; a (meth)acrylate containing ether groups; a hydroxyalkyl (meth)acrylate; a hydroxypolypropylene glycol(meth)acrylate; or N-vinyl pyrrolidone, and combinations thereof.  
     
     
         27 . A copolymer according to  claim 26 , wherein said comonomer is styrene, alphamethylstyrene, vinyltoluene, methyl(meth)acrylate, ethyl(meth)acrylate, propyl (meth)acrylate, dimethyl maleate, diethyl maleate, diethyl fumarate, dipropyl maleate, dibutyl maleate, dibutyl fumarate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate, and N-vinyl pyrrolidone, and combinations thereof, and wherein (meth) indicates that the use of a methyl group is optional.  
     
     
         28 . A copolymer according to  claim 27 , further including as a crosslinking agent an acrylated, or methacrylated, or allylic functionalized polyester oligomer; an acrylated, or methacrylated, or allylic functionalized urethane acrylic; an acrylated, or methacrylated, or allylic functionalized urethane polyester; an acrylated, or methacrylated, or allylic functionalized expoxy; or an acrylated, or methacrylated, or allylic functionalized epoxy polyester.  
     
     
         29 . A copolymer according to  claim 25 , wherein said repeat group is  
       
         
           
           
               
               
           
         
       
     
     
         30 . A copolymer according to  claim 28 , wherein said repeat group is  
       
         
           
           
               
               
           
         
       
     
     
         31 . A copolymer according to  claim 28 , wherein said copolymer is cured.  
     
     
         32 . A copolymer according to  claim 30 , wherein said copolymer is cured.  
     
     
         33 . A process for forming a partially fluorinated functionalized oligomer or polymer comprising: 
 reacting a partially fluorinated monohydric polyoxetane containing alcohol, optionally including non-oxetane repeating units, either a) sequentially with a di or polyisocyanate forming an isocyanate terminated oligomer or polymer and then reacting said isocyanate terminated oligomer or polymer with a functionalizing compound forming a functionalized polyoxetane oligomer, or polymer or b) in a single step with an isocyanate functionalized compound and forming a functionalized polyoxetane oligomer or polymer.    
     
     
         34 . A process according to  claim 33  wherein said monohydric polyoxetane containing alcohol comprises repeating units of the formula  
       
         
           
           
               
               
           
         
         or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms, and  
         wherein said functionalized group is an acrylate, a methacrylate, an allylic, a melamine, an amine, an acetylacetate, an epoxide, a silyl, or an isocyanate, or combinations thereof.  
       
     
     
         35 . A process according to  claim 34 , wherein said monohydric polyoxetane containing alcohol is reacted with a diisocyanate forming said isocyanate terminated polyoxetane oligomer or polymer which is then reacted with said functionalizing compound.  
     
     
         36 . A process according to  claim 33 , wherein said repeat group is said  
       
         
           
           
               
               
           
         
       
     
     
         37 . A process for forming a partially fluorinated functionized oligomer or polymer comprising; 
 reacting a partially fluorinated polyoxetane containing monohydric alcohol, optionally including non-oxetane repeating units either a) sequentially with a di or polyepoxy compound forming an epoxy terminated oligomer or polymer and then reacting that epoxy terminated oligomer or polymer with a functionalizing compound forming functionalized polyoxetane oligomer or polymer, or b) in a single step reacting said monohydric alcohol with an epoxy functionalized compound and forming an functionized polyoxetane oligomer or polymer.    
     
     
         38 . A process according to  claim 37 , wherein said monohydric polyoxetane containing alcohol comprises repeating units of the formula  
       
         
           
           
               
               
           
         
         or combinations thereof, where n is the same or different and independently is an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms, and  
         wherein said functionalized group is an acrylate, a methacrylate, an allylic, a melamine, an amine, an acetylacetate, an epoxide, a silyl, or an isocyanate, or combinations thereof.  
       
     
     
         39 . A process according to  claim 38 , wherein said monohydric polyoxertane containing alcohol is reacted with a diepoxy forming said isocyanate terminated polyoxetane oligomer or polymer which is then reacted with said functionalizing compound.  
     
     
         40 . A process according to  claim 37 , wherein said repeat unit is said  
       
         
           
           
               
               
           
         
       
     
     
         41 . A coating composition comprising; 
 a functionalized polyfluorooxetane oligomer or polymer with at least 10 weight percent repeating units of the formula                        or combinations thereof, where n is the same or different and independently an integer between 1 and 5, R is hydrogen or an alkyl of 1 to 6 carbon atoms, and each Rf is the same or different and independently on each repeat unit is a linear or branched fluorinated alkyl of 1 to 20 carbon atoms, a minimum of 75 percent of the non-carbon atoms of the alkyl being fluorine atoms and optionally the remaining non-carbon atoms being H, I, Cl, or Br; or each Rf is the same or different and independently is an oxaperfluorinated polyether having from 4 to 60 carbon atoms      at least one unsaturated comonomer copolymerizable with said functionalized oligomer or polymer,    optionally a free radical initiator which is activated by ultraviolet radiation, and    optionally a crosslinking agent.    
     
     
         42 . A coating composition according to  claim 41 , wherein said functional group is a melamine, an amine, an acetylacetate, an epoxide, a silyl, or an isocyanate, an acrylate, a methacrylate, or an allylic, and wherein the number of repeat units is from 2 to about 150.  
     
     
         43 . A coating composition according to  claim 42 , wherein said comonomer is a vinyl aromatic monomer having from 8 to 1 2 carbon atoms; an ethylenically unsaturated monomer free of acid groups having from 4 to 30 carbon atoms; a (cyclo)alkyl ester of maleic acid, fumaric acid or itaconic acid; a (meth)acrylate containing ether groups; a hydroxyalkyl(meth)acrylate; a hydroxypolypropylene glycol(meth)acrylate; or a N-vinyl pyrrolidone, and combinations thereof.  
     
     
         44 . A coating composition according to  claim 43 , wherein the amount of said polyfluorooxetane oligomer or polymer is from about 0.1 to about 20% by weight of said coating composition.  
     
     
         45 . A coating composition according to  claim 44 , wherein said comonomers are styrene, alphamethylstyrene, vinyltoluene, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, dimethyl maleate, diethyl maleate, diethyl fumarate, dipropyl maleate, dibutyl maleate, dibutyl fumarate, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate, and N-vinyl pyrrolidone, and combinations thereof, and wherein (meth) indicates that the use of a methyl group is optional.  
     
     
         46 . A coating composition according to  claim 44 , wherein said polyfluorooxetane functional group is an acrylate, a methacrylate, an epoxide or an allylic group, or combinations thereof, and including as a crosslinking agent, tripropylene glycol diacrylate, trimethylolpropane triacrylate, an acrylated, or methacrylated, or allylic functionalized polyester oligomer; an acrylated, or methacrylated, or allylic functionalized urethane acrylic; an acrylated, or methacrylated, or allylic functionalized urethane polyester; an acrylated, or methacrylated, or allylic functionalized expoxy; or an acrylated, or methacrylated, or allylic functionalized epoxy polyester; and wherein said coating composition is U.V. cured.  
     
     
         47 . A coating composition according to  claim 41 , including crosslinking agents, and wherein said coating is cured.  
     
     
         48 . A coating composition according to  claim 44 , wherein said functional group is acrylate, methacrylate, allylic, or epoxy, including crosslinking agents, and wherein said coating is cured.  
     
     
         49 . A coating composition according to  claim 44 , wherein said polyfluorooxetane functional group is melamine, amine, an epoxide acetylacetate, epoxide, silyl, isocyanate, and combinations thereof including crosslinking agents, and wherein said coating is thermally cured.  
     
     
         50 . A coating composition according to  claim 46 , wherein said oligomer or polymer repeat group is said  
       
         
           
           
               
               
           
         
       
     
     
         51 . A coating composition according to  claim 47 , wherein said oligomer or polymer repeat group is said  
       
         
           
           
               
               
           
         
       
     
     
         52 . A coating composition according to  claim 48 , wherein said oligomer or polymer repeat group is said  
       
         
           
           
               
               
           
         
       
     
     
         53 . A coating composition according to claim  50 , wherein said oligomer or polymer repeat group is said