Methods for Making Functionalized Fluorinated Monomers, Fluorinated Monomers, and Compositions for Making the Same

Abstract

A method of making a functionalized fluorinated monomer for use in making oligomers and polymers that can be used to improve surface properties of polymer-derived systems, such as coatings. The method of making a functionalized fluorinated monomer includes reacting at least one fluorinated nucleophilic reactant, such as a fluorinated alcohol, with at least one compound containing at least one epoxide group. Other methods include reaction of a fluorinated alcohol with a cyclic carboxylic anhydride. In another embodiment, a method includes reacting a fluorinated mesylate, tosylate or triflate with an amine, alkoxide or phenoxide. In other embodiments, the method includes reacting a fluorinated alcohol with an alkyl halide, or reacting a fluorinated alkyl halide with an amine. The functionalized fluorinated monomers may be used as intermediates and reacted to modify the functional groups thereon. Further, the functionalized fluorinated monomers may be reacted to form polymers or oligomers, or with polymers or oligomers having functional groups to modify the polymer or oligomer through the functional group thereon.

1 - 118 . (canceled) 
     
     
         119 . A method for making a functionalized fluorinated monomer, comprising:
 forming the functionalized fluorinated monomer by reacting at least one fluorinated nucleophilic reactant having one functional reactant group with at least one compound comprising at least two epoxide groups,   wherein the functionalized fluorinated monomer formed has at least two hydroxyl groups,   wherein each hydroxyl group on the functionalized fluorinated monomer formed is derived from an epoxide group, and   wherein the functionalized fluorinated monomer formed is useful as a reactant in formation of a fluorinated polymer, a fluorinated oligomer or a chain-extended functionalized fluorinated monomer.   
     
     
         120 . The method of  claim 119 , wherein the at least one fluorinated nucleophilic reactant is selected from the group consisting of a fluorinated alcohol, a fluorinated carboxylic acid, a fluorinated organic acid anhydride, a fluorinated amine, a fluorinated thiol, a fluorinated amide, a fluorinated sulfonamide, and combinations thereof. 
     
     
         121 . The method of  claim 120 , wherein the at least one fluorinated nucleophilic reactant is a mixture of at least two of the fluorinated alcohol, the fluorinated carboxylic acid, the fluorinated organic acid anhydride, the fluorinated amine, the fluorinated thiol, the fluorinated amide, and the fluorinated sulfonamide. 
     
     
         122 . The method of  claim 119 , wherein the at least one compound comprising at least two epoxide groups is selected from the group consisting of 1,4-butanediol diglycidyl ether; 1,4-cyclohexanedimethanol diglycidyl ether; 1,6-hexanediol diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; bis(3,4-epoxycyclohexylmethyl)adipate; trimethylolpropane triglycidyl ether; sorbitol polyglycidyl ether; and pentaerythritol tetraglycidyl ether. 
     
     
         123 . The method of  claim 119 , wherein the at least one fluorinated nucleophilic reactant is a fluorinated alcohol comprising either a partially or fully fluorinated, branched or unbranched, substituted or unsubstituted alkyl group having one to about eighteen carbon atoms, and having 0 to 6 ether linkages, and when substituted includes an aromatic group, a sulfur pentafluoride group, a halogen, or a combination thereof; or is a partially or fully fluorinated, substituted or unsubstituted aryl group, wherein when substituted includes a sulfur pentafluoride group, a halogen atom, or a combination thereof. 
     
     
         124 . The method of  claim 119 , wherein the at least one fluorinated nucleophilic reactant is a fluorinated alcohol selected from the group of 2,2,2,-trifluoroethanol; 2,2,3,3,3-pentafluoro-1-propanol; 1,1,1,3,3,3-hexafluoro-2-propanol; 4-hydroxyphenylsulfur pentafluoride; 2-perfluoropropoxy-2,3,3,3-tetrafluoropropanol; and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol. 
     
     
         125 . The method of  claim 119 , wherein reaction of the at least one fluorinated nucleophilic reactant is a fluorinated alcohol and the at least one compound comprising at least two epoxide groups takes place in the presence of a base catalyst. 
     
     
         126 . The method of  claim 125 , wherein each of the at least two hydroxyl groups of the functionalized fluorinated monomer is a secondary hydroxyl group. 
     
     
         127 . The method of  claim 125 , wherein the at least one fluorinated nucleophilic reactant is a fluorinated alcohol and the functionalized fluorinated monomer has a structure according to formula (I): 
       
         
           
           
               
               
           
         
         wherein R f  is a partially or fully fluorinated, branched or unbranched, substituted or unsubstituted alkyl group having one to about eighteen carbon atoms, and having 0 to 6 ether linkages, and when substituted includes a group selected from an aromatic group, a sulfur pentafluoride group, a halogen atom, and a combination thereof; or is a partially or fully fluorinated, substituted or unsubstituted aryl group, that when substituted includes a sulfur pentafluoride group, a halogen atom, or a combination thereof; 
         wherein R 1  is R f , or a saturated or unsaturated, branched or unbranched, substituted or unsubstituted alkyl group, cyclic alkyl group or heterocyclic group having 1 to about 24 carbon atoms, wherein when R 1  is an alkyl group, a cyclic alkyl group, or a heterocyclic group, R 1  comprises 0 to 6 ether linkages, ester linkages, or aryl groups; and
 wherein n is 2 to about 4. 
 
       
     
     
         128 . The method of  claim 127 , wherein R 1  is substituted with one or more functional groups selected from the group of an epoxide, a carboxylic acid, a carboxylic acid ester, a carboxylate salt, an amine, and a thiol. 
     
     
         129 . The method of  claim 119 , wherein the functionalized fluorinated monomer is a fluorinated polyol. 
     
     
         130 . The method of  claim 119 , wherein the at least one fluorinated nucleophilic reactant is a fluorinated alcohol, and the fluorinated alcohol and the at least one compound comprising at least two epoxide groups are reacted in the presence of an acid catalyst. 
     
     
         131 . The method of  claim 130 , wherein each of the at least two hydroxyl groups of the functionalized fluorinated monomer is a primary hydroxyl group. 
     
     
         132 . The method of  claim 130 , wherein the at least one fluorinated nucleophilic reactant is a fluorinated alcohol and the functionalized fluorinated monomer has a structure according to formula (II): 
       
         
           
           
               
               
           
         
         wherein R f  is a partially or fully fluorinated, branched or unbranched, substituted or unsubstituted alkyl group having one to about eighteen carbon atoms, and having 0 to 6 ether linkages, and when substituted includes a group selected from an aromatic group, a sulfur pentafluoride group, a halogen atom, and a combination thereof; or is a partially or fully fluorinated, substituted or unsubstituted aryl group, that when substituted includes a sulfur pentafluoride group, a halogen atom, or a combination thereof; 
         wherein R 1  is R f , or a saturated or unsaturated, branched or unbranched, substituted or unsubstituted alkyl group, cyclic alkyl group or heterocyclic group having 1 to about 24 carbon atoms, wherein when R 1  is an alkyl group, a cyclic alkyl group, or a heterocyclic group, R 1  comprises 0 to 6 ether linkages, ester linkages, or aryl groups; and 
         wherein n is 2 to about 4. 
       
     
     
         133 . The method of  claim 119 , further comprising polymerizing the functionalized fluorinated monomer having the at least one hydroxyl group to form a fluorinated polyester via condensation polymerization or ring opening polymerization to form a polymer or oligomer. 
     
     
         134 . The method of  claim 119 , further comprising polymerizing the functionalized fluorinated monomer having at least one hydroxyl group to form a fluorinated polycarbonate via condensation polymerization or ring opening polymerization to form a polymer or oligomer. 
     
     
         135 . The method of  claim 119 , further comprising reacting the functionalized fluorinated monomer with a cyclic reactant selected from one or more of a cyclic carboxylic acid anhydride, a cyclic ether, a cyclic carbonate, and a cyclic ester to form a chain extended fluorinated monomer or a chain-extended fluorinated oligomer. 
     
     
         136 . The method of  claim 135 , wherein the functionalized fluorinated monomer is a fluorinated diol having at least one ether linkage and the chain-extended fluorinated monomer is a fluorinated dicarboxylic acid. 
     
     
         137 . The method of  claim 136  further comprising polymerizing the chain extended functionalized fluorinated monomer via condensation polymerization to form a fluorinated polyester. 
     
     
         138 . A chain-extended fluorinated monomer made by the method of  claim 135 . 
     
     
         139 . A functionalized fluorinated monomer made by the method of  claim 119 . 
     
     
         140 . A method for making a polymer or oligomer, comprising reacting a first reactant having at least one hydroxyl group with a cyclic ester, a cyclic carbonate, or a cyclic ether via ring opening polymerization to form a fluorine-containing polyester polyol, a fluorine-containing polycarbonate polyol, or a fluorine-containing polyether polyol, respectively, wherein the first reactant having the at least one hydroxyl group is selected from (i) a functionalized fluorinated monomer made by the method of  claim 119  or (ii) a chain extended fluorinated monomer or a chain extended fluorinated oligomer, which is made by reacting a functionalized fluorinated monomer made by the method of  claim 119  with a cyclic reactant selected from the group of a cyclic carbonate, a cyclic ether, and a cyclic ester.