Fluorine-containing oligomer, nano-silica composite particles using the same, and methods for producing both

Abstract

Disclosed is a fluorine-containing oligomer comprising a copolymer of a fluoroalkyl alcohol (meth)acrylic acid derivative represented by the general formula: C n F 2n+1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OCOCR═CH 2   [I] wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4; b is an integer of 0 to 3; and c is an integer of 1 to 3; and a (meth)acrylic acid derivative represented by the general formula: (CH 2 ═CRCO) m R′  [II] wherein R is a hydrogen atom or a methyl group, m is 1, 2, or 3; and when m is 1, R′ is OH group, NH 2 group that is unsubstituted or mono- or di-substituted with an alkyl group having 1 to 6 carbon atoms, or a monovalent group derived from an alkylene glycol or polyalkylene glycol group containing an alkylene group having 2 or 3 carbon atoms; when m is 2 or 3, R′ is a divalent or trivalent organic group derived from a diol or triol. The copolymerization reaction is performed using a hydrocarbon-based peroxide or azo compound polymerization initiator. Also disclosed are nano-silica composite particles formed as a condensate of the fluorine-containing oligomer and an alkoxysilane with nano-silica particles.

1 : Fluorine-containing oligomer comprising a copolymer of a fluoroalkyl alcohol (meth)acrylic acid derivative represented by the general formula:
   C n F 2n+1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OCOCR═CH 2   [I]
   wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4; b is an integer of 1 to 3; and c is an integer of 1 to 3; and a (meth)acrylic acid derivative represented by the general formula:
   CH 2 ═CRCONR 1 R 2   [II]
 
   wherein R is a hydrogen atom or a methyl group, R 1  and R 2  are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.   
     
     
         2 : (canceled) 
     
     
         3 : Fluorine-containing oligomer according to  claim 1 , which has a number average molecular weight Mn of 5,000 or less. 
     
     
         4 : Fluorine-containing oligomer according to  claim 1 , wherein 0.1 to 50 mol % of fluoroalkyl alcohol (meth)acrylic acid derivative is copolymerized. 
     
     
         5 : Method for producing a fluorine-containing oligomer, comprising copolymerizing a fluoroalkyl alcohol (meth)acrylic acid derivative represented by the general formula:
   C n F 2n+1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OCOCR═CH 2   [I]
   wherein R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, a is an integer of 1 to 4; b is an integer of 1 to 3; and c is an integer of 1 to 3; and a (meth)acrylic acid derivative represented by the general formula:
   CH 2 ═CRCONR 1 R 2   [II]
 
   wherein R is a hydrogen atom or a methyl group, R 1  and R 2  are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; in the presence of a hydrocarbon-based peroxide or azo compound polymerization initiator.   
     
     
         6 . (canceled) 
     
     
         7 : Method for producing a fluorine-containing oligomer according to  claim 5 , wherein 0.1 to 50 wt. % of hydrocarbon-based peroxide or azo compound polymerization initiator is used based on the weight of the monomer mixture. 
     
     
         8 - 11 . (canceled)