Polymer, processes for producing polymer and composition

Abstract

The present invention relates to a vinyl polymer terminated in a silanol group, a hydrolyzable silyl group or an acrylic functional group, to a method of producing a vinyl polymer having a hydrolyzable silyl group at one or more termini thereof which comprises reacting a vinyl polymer having a silanol group at one or more termini thereof with a silicon compound having two or more silicon atom-bound hydrolyzable groups, and a method of producing a vinyl polymer having an acrylic functional group at one or more termini thereof which comprises reacting a vinyl polymer having a silanol group at one or more termini thereof with a silicon compound represented by the general formula (3): XSiR 2 -G-O—C(O)C(L)=CH 2   (3) wherein X is a hydrolyzable group.

1 . A method of producing a vinyl polymer (II) having a hydrolyzable silyl group at one or more termini thereof 
 which comprises reacting a vinyl polymer (I) having a silanol group at one or more termini thereof    with a silicon compound having two or more silicon atom-bound hydrolysable groups.    
   
   
       2 . The method of producing according to  claim 1 , 
 wherein the vinyl polymer (I) has a main chain obtained by polymerizing at least one monomer selected from the group consisting of (meth)acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers.    
   
   
       3 . The method of producing according to  claim 1 , 
 wherein the silanol group of the vinyl polymer (I) is represented by the general formula (1):      —[Si(R 1 ) 2-b (OH) b O] m —Si(R 2 ) 3-a (OH) a   (1)    wherein R 1  and R 2  are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group represented by (R′) 3 SiO—, in which R′ is a monovalent hydrocarbon group containing 1 to 20 carbon atoms and the three R′ groups may be the same or different; when there are two or more R 1  or R 2  groups, they may be the same or different; a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m is an integer of 0 to 19, provided that the relation a+mb≧1 should be satisfied.    
   
   
       4 . The method of producing according to  claim 3 , 
 wherein, the general formula (1), m=0.    
   
   
       5 . The method of producing according to  claim 1 , 
 wherein the vinyl polymer (I) has a ratio (Mw/Mn) of weight average molecular weight (Mw) to a number average molecular weight (Mn) of less than 1.8 as determined by gel permeation chromatography.    
   
   
       6 . The method of producing according to  claim 1 , 
 wherein the vinyl polymer (I) has a main chain obtained by living radical polymerization.    
   
   
       7 . The method of producing according to  claim 6 , 
 wherein the living radical polymerization is carried out in the manner of atom transfer radical polymerization.    
   
   
       8 . The method of producing according to  claim 7 , 
 wherein a metal complex to be used as a catalyst for the atom transfer radical polymerization is a copper, nickel, ruthenium or iron complex.    
   
   
       9 . The method of producing according to  claim 8 , 
 wherein the catalyst for atom transfer radical polymerization is a copper complex.    
   
   
       10 . The method of producing according to  claim 1 , 
 wherein the vinyl polymer (1) is obtainable by carrying out the hydrosilylation reaction of a vinyl polymer having an alkenyl group at one or more one termini thereof with a silicon compound having both a silicon atom-bound hydrolyzable group and a hydrosilyl group    and then converting said hydrolyzable group to a silanol group by hydrolysis.    
   
   
       11 . The method of producing according to  claim 10 , 
 wherein the silicon compound having both a silicon atom-bound hydrolysable group and a hydrosilyl group is chlorodimethylsilane.    
   
   
       12 . The method of producing according to  claim 1 , 
 wherein the silicon compound having two or more silicon atom-bound hydrolyzable groups is represented by the general formula (2):      Z-[Si(R 3 ) 2-b (Y′) b O] m —Si(R 4 ) 3-a (Y′) a   (2)    wherein R 3  and R 4  are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group represented by (R′) 3 SiO—, in which R′ is a monovalent hydrocarbon group containing 1 to 20 carbon atoms and the three R′ groups may be the same or different and, when there are two or more R 3  or R 4  groups, they may be the same or different, Y′ represents a hydrolyzable group other than a hydroxyl group, Z represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms, a triorganosiloxy group represented by (R′) 3 SiO—, in which R′ is as defined above, or a hydrolyzable group other than a hydroxyl group, a represents 0, 1, 2 or 3, b represents 0, 1 or 2 and m is an integer of 0 to 19 provided that when Z is a hydrolyzable group, the relation a+mb≧1 should be satisfied and, when Z is other than a hydrolyzable group, the relation a+mb≧2 should be satisfied.    
   
   
       13 . The method of producing according to  claim 12 , 
 wherein the hydrolyzable groups, namely Y′ and Z, in general formula (2) are each selected from the group consisting of ketoximo, acyloxy, alkoxy, amido, aminoxy, amino and alkenoxy groups.    
   
   
       14 . The method of producing according to  claim 12  wherein, in general formula (2), m=0.  
   
   
       15 . A vinyl polymer having a hydrolyzable silyl group at one or more termini thereof and obtainable by the method of producing according to  claim 1 .  
   
   
       16 . A curable composition 
 which comprises the vinyl polymer having a hydrolyzable silyl group at one or more termini thereof according to  claim 15 .    
   
   
       17 . A method of producing a vinyl polymer (III) having an acrylic functional group at one or more termini thereof 
 which comprises reacting a vinyl polymer (I) having a silanol group at one or more termini thereof    with a silicon compound represented by the general formula (3):      XSiR 2 -G-O—C(O)C(L)=CH 2   (3)    wherein R is a hydrocarbon group containing 1 to 14 carbon atoms or halogenated hydrocarbon group containing 1 to 10 carbon atoms and the two R groups may be the same or different, X is a hydrolyzable group, G is an alkylene group containing 1 to 4 carbon atoms and L is a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms.    
   
   
       18 . The method of producing according to  claim 17 , 
 wherein, in general formula (3), G is a group represented by —CH 2 —, —CH 2 CH 2  or —CH 2 CH(CH 3 )CH 2 —   and L is a hydrogen atom or methyl group.    
   
   
       19 . The method of producing according to  claim 17 , 
 wherein, the vinyl polymer (I) has a main chain obtained by polymerizing at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers.    
   
   
       20 . The method of producing according to  claim 17 , 
 wherein the silanol group of the vinyl polymer (I) is represented by the general formula (1):      —[Si(R 1 ) 2-b (OH) b O] m —Si(R 2 ) 3-a (OH) a   (1)    wherein R 1  and R 2  are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms or an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group represented by (R′) 3 SiO—, in which R′ is a monovalent hydrocarbon group containing 1 to 20 carbon atoms and the three R′ groups may be the same or different; when there are two or more R 1  or R 2  groups, they may be the same or different; a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m is an integer of 0 to 19, provided that the relation a+mb≧1 should be satisfied.    
   
   
       21 . The method of producing according to  claim 20 , 
 wherein, in general formula (1), m=0    
   
   
       22 . The method of producing according to  claim 17 , 
 wherein the vinyl polymer (I) ha a main chain obtained by living radical polymerization.    
   
   
       23 . The method of producing according to  claim 22 , 
 wherein the living radical polymerization is carried out in the manner of atom transfer radical polymerization.    
   
   
       24 . The method of producing according to  claim 22 , 
 wherein a metal complex to be used as a catalyst for the atom transfer radical polymerization is a copper, nickel, ruthenium or iron complex.    
   
   
       25 . The method of producing according to  claim 24 , 
 wherein the catalyst for atom transfer radical polymerization is a copper complex.    
   
   
       26 . The method of producing according to  claim 16 , 
 wherein the vinyl polymer (I) is obtainable by carrying out the hydrosilylation reaction of a vinyl polymer having an alkenyl group at one or more one termini thereof with a silicon compound having both a silicon atom-bound hydrolyzable group and a hydrosilyl group    and then converting said hydrolyzable group to a silanol group by hydrolysis.    
   
   
       27 . The method of producing according to  claim 25 , 
 wherein the silicon compound having both a silicon atom-bound hydrolyzable group and a hydrosilyl group is chlorodimethysilane.    
   
   
       28 . A vinyl polymer having an acrylic functional group at one or more termini thereof and obtainable by the method of producing according to  claim 16 .  
   
   
       29 . The polymer according to  claim 27   which has a ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of less than 1.8 as determined by gel permeation chromatography.    
   
   
       30 . A curable composition 
 which comprises the vinyl polymer having an acrylic functional group at one or more termini thereof according to  claim 27 .    
   
   
       31 . The curable composition according to  claim 30   which comprises a photopolymerization initiator so as to be cured by irradiation of light and/or electron beams.    
   
   
       32 . The curable composition according to  claim 31 . 
 wherein the photopolymerization initiator is a photo radical initiator.    
   
   
       33 . The curable composition according to  claim 31 . 
 wherein the photopolymerization initiator is a photo anion initiator.    
   
   
       34 . The curable composition according to  claim 30 , 
 which comprises a heat polymerization initiator so as to be cured by heating.    
   
   
       35 . The curable composition according to  claim 30   which comprises a radical-polymerizable group-containing monomer and/or oligomer.    
   
   
       36 . The curable composition according to  claim 30   which comprises an anion-polymerizable group.    
   
   
       37 . The curable composition according to  claim 35 , 
 wherein the radical- or anion-polymerizable group is an acrylic functional group.