Method for preparing a polyorganosiloxane and a polyorganosiloxane

Abstract

A method for preparing a polyorganosiloxane represented by the following general formula (1): (R 3 SiO 1/2 ) l (R 2 SiO 2/2 ) m (RSiO 3/2 ) n (SiO 4/2 ) o (1) wherein the method includes a step of condensation reacting at least one organic silicon compound having at least one hydrogen atom and at least one —OX′ group in the molecule, wherein X′ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, in the presence of a catalyst, wherein the catalyst is at least one selected from the group consisting of hydroxides of elements in Group 2 of the periodic table, hydrates of hydroxides of elements in Group 2 of the periodic table, oxides of elements in Group 2 of the periodic table, and hydroxides and oxides of metal elements in Groups 3-15 of the periodic table.

1 . A method for preparing a polyorganosiloxane represented by the following general formula (1):
   (R 3 SiO 1/2 ) l (R 2 SiO 2/2 ) m (RSiO 3/2 ) n (SiO 4/2 ) o   (1)
   wherein R is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom; l, m, n, and o are, independently of each other, an integer of from 0 to 10,000, and a total of 1, m and n is from 2 to 30,000; and at least one R is a hydrogen atom and at least one R is an —OX group in the molecule, wherein X is an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms,   wherein the method comprises a step of condensation reacting at least one organic silicon compound having at least one hydrogen atom and at least one —OX′ group in the molecule, wherein X′ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, in the presence of a catalyst, wherein the catalyst is at least one selected from the group consisting of hydroxides of elements in Group 2 of the periodic table, hydrates of hydroxides of elements in Group 2 of the periodic table, oxides of elements in Group 2 of the periodic table, and hydroxides and oxides of metal elements in Groups 3-15 of the periodic table.   
     
     
         2 . The method according to  claim 1 , wherein the polyorganosiloxane has, on at least one silicon atom, both of at least one hydrogen atom and at least one —OX group, wherein X is an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms. 
     
     
         3 . The method according to  claim 1 , wherein an amount of the catalyst is 0.0001 to 20 mol %, relative to a total molar amount of the organic silicon compound subjected to the condensation reaction. 
     
     
         4 . The method according to  claim 1 , wherein the organic silicon compound as the raw material is represented by the following general formula (2):
   (HR 1   a SiO (4-a-b)/2 (OX′) b ) n   (2)
   
       wherein R 1  is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom, X′ is as defined above, a and b are independent among the parenthesized repeating units, a is an integer of from 0 to 2 and b is an integer of from 1 to 3, provided that a total of a and b is from 0 to 3, and n is an integer of from 1 to 10,000. 
     
     
         5 . The method according to  claim 1 , wherein the condensation reaction is carried out in the presence of at least one solvent. 
     
     
         6 . The method according to  claim 5 , wherein the solvent is at least one selected from the group consisting of hydrocarbons, aromatic hydrocarbons, water, alcohols, alcohol esters, ketones, ethers, esters, cyano group-substituted hydrocarbons, amines, amides, halogenated hydrocarbons and sulfur-containing compounds. 
     
     
         7 . The method according to  claim 1 , wherein the method comprises a step of surface treating the catalyst with a silane coupling agent before used in the condensation reaction. 
     
     
         8 . The method according to  claim 1 , wherein the —OX group accounts for 0.2% or more, in number, of R. 
     
     
         9 . A polyorganosiloxane resin represented by the following general formula (5):
   (R 3 SiO 1/2 ) l′ (R 2 SiO 2/2 ) m′ (RSiO 3/2 ) n′ (SiO 4/2 ) o′   (5)
   wherein R is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom; l′, m′ and o′ are, independently of each other, an integer of from 0 to 10,000; n′ is an integer of from 1 to 10,000; a total of l′, m′ and n′ is from 2 to 30,000; and at least one R is a hydrogen atom and at least one R is an —OX group in the molecule, wherein X is an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; and at least one hydrogen atom and at least one —OX group bond to one and the same silicon atom.   
     
     
         10 . The polyorganosiloxane resin according to  claim 9 , wherein the —OX group accounts for 0.2% or more, in number, of R. 
     
     
         11 . A polyorganosiloxane represented by the following formula (6): 
       
         
           
           
               
               
           
         
       
       wherein R 1  is, independently of each other, a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom; R 2  is, independently of each other, a hydrogen atom or R 1 ; R 3  is, independently of each other, R 1  or an —OX group; X is, independently of each other, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; e is 0 or 1; when e is 0, d is an integer of from 4 to 20 and d′ is 0; when e is 1, d is an integer of from 1 to 20 and d′ is d; p is an integer of 1 or more; and the siloxane units in the square brackets may form a block structure or a random structure. 
     
     
         12 . A polyorganosiloxane represented by the following formula (7): 
       
         
           
           
               
               
           
         
       
       wherein R 1  is, independently of each other, a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom, R 2  is, independently of each other, a hydrogen atom or R 1 ; R 3  is, independently of each other, R 1  or an —OX group; Q is, independently of each other, R 1 , an —OX group or a group represented by the following (8): 
       
         
           
           
               
               
           
         
       
       provided that at least one of Q is the group represented by the aforesaid (8); X is, independently of each other, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; d 1  and d 2  are, independently of each other, an integer of from 1 to 20; e 1  is 1; e 2  is 0 or 1; d 3  is d 1 ; p and p′ are, independently of each other, an integer of 1 or more; and the siloxane units in the square brackets may form a block structure or a random structure. 
     
     
         13 . A polyorganosiloxane represented by the following formula (9): 
       
         
           
           
               
               
           
         
       
       wherein R 1  is, independently of each other, a monovalent hydrocarbon group having 1 to 18 carbon atoms, and optionally having an oxygen, halogen, nitrogen or sulfur atom; R 2  is, independently of each other, a hydrogen atom or R 1 ; R 3  is, independently of each other, R 1  or an —OX group; R 5  is, independently of each other, a hydrogen atom, an alkenyl group having 2 to 10 carbon atoms, or 3-glycidyloxypropyl group, provided that, when at least one R 3  bonding to the silicon atom at the end is an —OX group, R 5  bonding to this silicon atom is not a hydrogen atom; X is, independently of each other, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; t is 0 or 1; s is an integer of from 1 to 20; when t is 0, s′ is 0; when t is 1, s′ is s; q is an integer of 1 or more; and the siloxane units in the square brackets may form a block structure or a random structure. 
     
     
         14 . The polyorganosiloxane according  claim 11 , wherein R 1  is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. 
     
     
         15 . The polyorganosiloxane according to  claim 11 , wherein e is 0 and p is 1 in said formula (6). 
     
     
         16 . The polyorganosiloxane according to  claim 12 , wherein p and p′ are 1 in said formulas (7) and (8). 
     
     
         17 . The polyorganosiloxane according to  claim 13 , wherein t is 0 and q is 1 in said formula (9). 
     
     
         18 . The polyorganosiloxane according to  claim 14 , wherein R 1  and R 2  are, independently of each other, a group selected from phenyl, benzyl, 2-phenylethyl, 2-phenylpropyl and tolyl groups. 
     
     
         19 . The polyorganosiloxane according to  claim 9 , wherein said —OX group is selected from methoxy, ethoxy, isopropoxy, t-butoxy and phenoxy groups. 
     
     
         20 . The polyorganosiloxane according to  claim 11 , selected from compounds represented by the following formulas: 
       
         
           
           
               
               
           
         
       
       wherein d is an integer of from 4 to 20, 
       
         
           
           
               
               
           
         
       
       wherein d is an integer of from 4 to 20, 
       
         
           
           
               
               
           
         
       
       wherein d is an integer of from 4 to 20, 
       
         
           
           
               
               
           
         
       
       wherein d is an integer of from 1 to 20, d′ is d, and p is an integer of 1 or more, and 
       
         
           
           
               
               
           
         
       
       wherein d is an integer of from 1 to 20, d′ is d, and p is an integer of 1 or more. 
     
     
         21 . The polyorganosiloxane according to  claim 12 , represented by the following formula: 
       
         
           
           
               
               
           
         
       
     
     
         22 . The polyorganosiloxane according to  claim 13 , represented by the following formula,