Polymers, processes for producing the same, and curable compositions produced therefrom

Abstract

An alkenyl- or crosslinkable silyl-terminated vinyl polymer is provided. Such a functional group is introduced into its terminus at a high ratio, not via sulfur atoms. Those polymers can be prepared by polymerizing a vinyl monomer for obtaining a halogen-terminated vinyl polymer, and then substituting an oxy anion or carbanion having such a functional group for the terminal halogen of said polymer.

1 . A vinyl polymer having an alkenyl group of the following general formula (1) at at least one terminus of its main chain:  
       —CH 2 —C(R 1 )(R 2 )—O—R 3 —C(R 4 )═CH 2   (1)  
       (wherein R 1 and R 2 are the same or different, and each represents a univalent organic group; R 3  represents a divalent organic group having 1 to 20 carbon atoms and optionally containing one or more ether or ester bonds; R 4  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms).  
     
     
         2 . The polymer according to  claim 1  wherein the group R 3  is a divalent organic group represented by the following general formula (2):  
       —C 6 H 4 —(CH 2 ) n —  (2)  
       (wherein C 6 H 4  represents phenylene, and n represents an integer of 0 to 14).  
     
     
         3 . The polymer according to  claim 1  wherein the group R 3  is a divalent organic group represented by the following general formula (3):  
       —C(O)—R 5 —  (3)  
       (wherein R 5  represents a direct bond or a divalent organic group having 1 to 19 carbon atoms and optionally containing one or more ether or ester bonds).  
     
     
         4 . The polymer according to  claim 3  wherein the group R 5  is a direct bond or a divalent organic group represented by the following general formula (4):  
       —(CH 2 ) n —  (4)  
       (wherein n represents an integer of 1 to 19).  
     
     
         5 . The polymer according to  claim 1 ,  2 ,  3  or  4 , wherein its main chain is prepared by polymerizing a (meth)acrylic acid type monomer.  
     
     
         6 . The polymer according to  claim 5  wherein the (meth)acrylic acid type monomer is an acrylic ester monomer.  
     
     
         7 . The polymer according to  claim 5  wherein the (meth) acrylic acid type monomer is a methacrylic ester monomer.  
     
     
         8 . The polymer according to  claim 6  wherein the acrylic ester is butyl acrylate.  
     
     
         9 . The polymer according to  claim 1 , 2 ,  3  or  4  wherein its main chain is prepared by polymerizing a styrene type monomer.  
     
     
         10 . The polymer according to any one of  claims 1  to  9 , wherein a ratio (Mw/Mn) of its weight average molecular weight (Mw) to number average molecular weight (Mn) as determined by gel permeation chromatography is not over 1.8.  
     
     
         11 . The polymer according to any one of  claims 1  to  10 , wherein its number average molecular weight ranges from 500 to 100000.  
     
     
         12 . A vinyl polymer having a crosslinkable silyl group at at, least one terminus of its main chain, which is prepared by adding a hydrosilane compound having a crosslinkable silyl group to the polymer according to any one of  claims 1  to  11 .  
     
     
         13 . A vinyl polymer having an alkenyl group of the following general formula (5) at at least one terminus of its main chain:  
       —CH 2 —C(R 1 )(R 2 )—C(R 6 )(R 7 )—R 8 —C(R 9 )═CH 2   (5)  
       (wherein R 1  and R 2  are the same or different, and each represents a univalent organic group; R 6  and R 7  are the same or different, and each represents an electron-withdrawing group or one of them represents an electron-withdrawing group with the other representing hydrogen, an alkyl group having 1 to 10 carbon atoms, or phenyl; R 8  represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and optionally containing one or more ether bonds; R 9  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms).  
     
     
         14 . The polymer according to  claim 13  wherein an electron-withdrawing group represents one group selected from the group consisting of —CO 2 R (in which R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms), —C(O)R(R represents the same as mentioned above), and —CN.  
     
     
         15 . The polymer according to  claim 13  or  14  wherein its main chain is prepared by polymerizing a (meth) acrylic acid type co monomer.  
     
     
         16 . The polymer according to  claim 15  wherein the (meth)acrylic acid type monomer is an acrylic ester monomer.  
     
     
         17 . The polymer according to  claim 15  wherein the (meth)acrylic acid type monomer is a methacrylic ester monomer.  
     
     
         18 . The polymer according to  claim 16  wherein the acrylic ester is butyl acrylate.  
     
     
         19 . The polymer according to  claim 13  or  14  wherein its main chain is prepared by polymerizing a styrene type monomer.  
     
     
         20 . The polymer according to any one of  claims 13  to  19 , wherein a ratio (Mw/Mn) of its weight average molecular weight (Mw) to number average molecular weight (Mn) as determined by gel permeation chromatography is not over 1.8.  
     
     
         21 . The polymer according to any one of  claims 13  to  20 , wherein its number average molecular weight ranges from 500 to 100000.  
     
     
         22 . A vinyl polymer having an crosslinkable silyl group of the following general formula (6) at at least one terminus of its main chain:  
       —CH 2 —C(R 1 )(R 2 )—C(R 6 )(R 7 )—R 8 —C(R 9 )—CH 2 —[Si(R 10 ) 2-b (Y) b O] m —Si(R 11 ) 3-a (Y) a   (6)  
       [wherein R 1  and R 2  are the same or different, each represents a univalent organic group; R 6  and R 7  are the same or different, each represents an electron-withdrawing group or one of them represents an electron-withdrawing group with the other representing hydrogen, an alkyl group having 1 to 10 carbon atoms, or phenyl; R 8  represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and optionally containing one or more ether bonds; R 9  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; R 10  and R 11  are the same or different, each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′) 3 SiO— (R′ represents a univalent hydrocarbon group of 1 to 20 carbon atoms and three Rs are the same or different) and when two or more R 10  or R 11  occur, they are the same or different; Y represents hydroxyl or a hydrolyzable group and when two or more Y occur, they are the same or different; a represents 0, 1, 2, or 3; b represents 0, 1, or 2; m represents an integer of 0 to 19, provided that a+mb≧1].  
     
     
         23 . The polymer according to  claim 22  wherein the electron-withdrawing group represents one group selected from the group consisting of —CO 2 R (in which R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms), —C(O)R(R represents the same as described above), and —CN.  
     
     
         24 . The polymer according to  claim 22  or  23  wherein its main chain is prepared by polymerizing a (meth)acrylic acid type monomer.  
     
     
         25 . The polymer according to  claim 24  wherein the (meth)acrylic acid type monomer is an acrylic ester monomer.  
     
     
         26 . The polymer according to  claim 24  wherein the (meth)acrylic acid type monomer is a methacrylic ester monomer.  
     
     
         27 . The polymer according to  claim 25  wherein the acrylic ester monomer is butyl acrylate.  
     
     
         28 . The polymer according to  claim 22  or  23  wherein its main chain is prepared by polymerizing a styrene type monomer.  
     
     
         29 . The polymer according to any one of  claims 22  to  28 , wherein a ratio (Mw/Mn) of its weight average molecular weight (Mw) to number average molecular weight (Mn) as determined by gel permeation chromatography is not over 1.8.  
     
     
         30 . The polymer according to any one of  claims 22  to  29 , wherein its number average molecular weight ranges from 500 to 100000.  
     
     
         31 . A method for preparing the vinyl polymer having an alkenyl group at a terminus of its main chain according to  claims 1  to  11 , which comprises polymerizing a vinyl monomer to obtain a vinyl polymer having a group of the following general formula (7) at at least one terminus of its main chain, and substituting an alkenyl-containing oxy anion of the following general formula (8) for the terminal halogen of said polymer:  
       —CH 2 —C(R 1 )(R 2 )(X)  (7)  
       (wherein R 1 and R 2  are the same or different, each represents a univalent organic group and X represents chlorine, bromine, or iodine);  
       M + O − —R 3 —C(R 4 )═CH 2   (8)  
       (wherein R 3  represents a divalent organic group having 1 to 20 carbon atoms and optionally containing one or more ether or ester bonds; R 4  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; M +  represents an alkali metal ion or a quaternary ammonium ion).  
     
     
         32 . The method according to  claim 31  wherein M+represents sodium ion or potassium ion.  
     
     
         33 . The method according to  claim 31  or  32  wherein said vinyl monomer is polymerized using an organohalogen compound or a sulfonyl halide compound as an initiator and a transition metal complex as an catalyst.  
     
     
         34 . The method according to  claim 33  wherein the transition metal complex is a complex of one metal selected from the group consisting of copper, nickel, ruthenium and iron.  
     
     
         35 . The method according to  claim 34  wherein the transition metal complex is a complex of copper.  
     
     
         36 . The method according to  claim 31  or  32  wherein said vinyl monomer is polymerized using a chain transfer agent.  
     
     
         37 . A method for preparing the vinyl polymer having a crosslinkable silyl group at a terminus of its main chain according to claims  12 , which comprises adding a hydrosilane compound having a crosslinkable silyl group of the following general formula (9);  
       H—[Si(R 10 ) 2-b (Y) b O]m—Si(R 11 ) 3-a (Y) a   (9)  [wherein R 10  and R 11  are the same or different, each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′) 3 SiO— (wherein R′ represents a univalent hydrocarbon group of 1 to 20 carbon atoms and three R's are the same or different) and when two or more R 10  or R 11  occur, they are the same or different; Y represents hydroxyl or a hydrolyzable group and when two or more Y occur, they are the same or different; a represents 0, 1, 2, or 3; b represents 0, 1, or 2; m represents an integer of 0 to 19, provided that a+mb≧1]   to the vinyl polymer having an alkenyl group at at least one terminus of its main chain according to any one of  claims 1  to  11 .    
     
     
         38 . A method for preparing the vinyl polymer having an alkenyl group at a terminus of its main chain according to any one of  claims 13  to  21 , which comprises polymerizing a vinyl monomer to obtain a vinyl polymer having a group of the following general formula (7) at at least one terminus of its main chain, and substituting an alkenyl-containing carbanion of the following general formula (10) for the terminal halogen of said polymer:  
       —CH 2 —C(R 1 )(R 2 )(X)  (7)  
       (wherein R 1  and R 2  are same or different, and each represents a univalent organic group and X represents chlorine, bromine, or iodine);  
       M + C + (R 6 )(R 7 )—R 8 —C(R 9 )═CH 2   (10)  
       (wherein R 6  and R 7 each represents an electron-withdrawing group or one of them represents an electron-withdrawing group with the other representing hydrogen, an alkyl group having 1 to 10 carbon atoms, or phenyl; R 8  represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and optionally containing one or more ether bonds; R 9  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; M +  represents an alkali metal ion or a quaternary ammonium ion).  
     
     
         39 . The method according to  claim 38  wherein M +  represents sodium ion or potassium ion.  
     
     
         40 . The method according to  claim 38  or  39  wherein said vinyl monomer is polymerized using an organohalogen compound or a sulfonyl halide compound as an initiator and a transition metal complex as an catalyst.  
     
     
         41 . The method according to  claim 40  wherein the transition metal complex is a complex of one metal selected from the group consisting of copper, nickel, ruthenium and iron.  
     
     
         42 . The method according to  claim 41  wherein the transition metal complex is a complex of copper.  
     
     
         43 . The method according to  claim 38  or  39  wherein said vinyl monomer is polymerized using a chain transfer agent.  
     
     
         44 . A method for preparing the vinyl polymer having a crosslinkable silyl group at a terminus of its main chain according to any one of  claims 22  to  30 , which comprises polymerizing a vinyl monomer to obtain a vinyl polymer having a group of the following general formula (7) at at least one terminus of its main chain, and substituting a crosslinkable silyl-containing carbanion of the following general formula (11) for a terminal halogen of said polymer:  
       —CH 2 —C(R 1 )(R 2 )(X)  (7)  
       (wherein R 1  and R 2  are the same or different, and each represents a univalent organic group and X represents chlorine, bromine, or iodine);  
       M + C − (R 6 )(R 7 )—R 8 —CH(R 9 )—CH 2—[Si(R   10 ) 2-b (Y) b O] m —Si(R 11  ) 3-a (Y) a   (11)  
       [wherein R 6  and R 7  are the same or different, and each represents an electron-withdrawing group or one of them represents an electron-withdrawing group with the other representing hydrogen, an alkyl group having 1 to 10 carbon atoms, or phenyl; R 8  represents a direct bond or a divalent organic group having 1 to 10 carbon atoms and optionally containing one or more ether bonds; R 9  represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; R 10  and R 1  are the same or different, and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′) 3 SiO—(R′ represents a univalent hydrocarbon group of 1 to 20 carbon atoms and three R's are the same or different) and when two or more R 10  or R 11  occur, they are the same or different; Y represents hydroxyl or a hydrolyzable group and when two or more Y occur, they are the same or different; a represents 0, 1, 2, or 3; b represents 0, 1, or 2; m represents an integer of 0 to 19, provided that a+mb≧1; M +  represents an alkali metal ion or a quaternary ammonium ion].  
     
     
         45 . The method according to  claim 44  wherein M +  represents sodium ion or potassium ion.  
     
     
         46 . The method according to  claim 44  or  45  wherein said vinyl monomer is polymerized using an organohalogen compound or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst.  
     
     
         47 . The method according to  claim 46  wherein the transition metal complex is a complex of one metal selected from the group consisting of copper, nickel, ruthenium and iron.  
     
     
         48 . The method according to  claim 47  wherein the transition metal complex is a complex of copper.  
     
     
         49 . The method according to  claim 44  or  45  wherein said vinyl monomer is polymerized using a chain transfer agent.  
     
     
         50 . A method for preparing the vinyl polymer having a crosslinkable silyl group at a terminus of its main chain according to any one of  claims 22  to  30 , which comprises adding a hydrosilane compound having a closslinkable silyl group of the following general formula (9):  
       H—[Si(R 10  ) 2-b (Y) b O] m —Si(R 11 ) 3-a   (9)  
       [wherein R 10  and R 11  are the same or different, and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′) 3 SiO— (R′ represents a univalent hydrocarbon group of 1 to 20 carbon atoms and three R's are the same or different) and when two or more R 10  or R 11  occur, they are the same or different; Y represents hydroxyl or a hydrolyzable group and when two or more Y occur, they are the same or different; a represents 0, 1, 2 or 3; b represents 0, 1 or 2; m represents an integer of 0 to 19, provided that a+mb≧1]
 to the vinyl polymer having an alkenyl group at at least one terminus of its main chain according to any one of  claims 13  to  21 .  
 
     
     
         51 . A curable composition comprising (a) the vinyl polymer having an alkenyl group at a terminus of its main chain according to any one of  claims 1  to  11  and (b) a hydrosilyl-containing compound.  
     
     
         52 . A curable composition comprising, as a principal component, the vinyl polymer having a crosslinkable silyl group at a terminus of its main chain according to  claim 12 .  
     
     
         53 . A curable composition comprising (a) the vinyl polymer having an alkenyl group at a terminus of its main chain according to any one of  claims 13  to  21  and (b) a hydrosilyl-containing compound.  
     
     
         54 . A curable composition comprising, as a principal component, the vinyl polymer having a crosslinkable silyl group at a terminus of its main chain according to any one of  claims 22  to  30 .