Methods for preparing polyheterosiloxanes

Abstract

This invention relates to methods for preparing polyheterosiloxane materials having at least two different non-Si metal elements. The polyheterosiloxane materials prepared by these methods are solid materials which can be easily dispersed in a solvent of choice.

1 . A method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising:
 (1) reacting
 (C) a hydrolyzable metal (M2) salt, where (M1) and (M2) are non-Si metal elements and different from each other, and 
 (B) a silicon-containing material having hydrolyzable groups selected from
 (B1) an organosiloxane, or 
 (B2) a silane, and 
 
 with an amount of water to form a reaction product; and 
   (2) further reacting the reaction product of step (1) and (A) a metal (M1) alkoxide, and
 if necessary adding an additional amount of water to form the polyheterosiloxane, such that total amount of the water added is between 50 and 200% of that necessary to hydrolyze and condense the alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C), to form the polyheterosiloxane, and with the proviso that at least two non-Si metal elements are provided by Component (A) and/or (C). 
   
     
     
         2 . The method according to  claim 1  wherein;
 (A) the metal (M1) alkoxide is selected from metal alkoxides having a general formula (I) R 1   m M1O n X p (OR 2 ) v1-m-p-2n , where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R 1  is an alkyl group having from 1 to 18 carbon atoms, each R 2  is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3  is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4  is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, 
 (B) the silicon-containing material is selected from (B1) an organosiloxane having an average formula (II) R 5   b (R 6 O) a SiO (4−(a+b))/2  or (B2) a silane having a general formula (III) R 5   c SiY d , where Y is Cl or OR 6 , each R 5  is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R 6  is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3  is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4  is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4, and 
 (C) the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R 7   e M2(Z) (v2−e)/w  or (C2) a hydrated metal salt having a general formula (V) M2(Z) v2/w .xH 2 O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R 7  is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5-12. 
 
     
     
         3 . The method according to  claim 1 , wherein M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb. 
     
     
         4 . The method according to  claim 3 , where M2 is Al. 
     
     
         5 . The method according to  claim 1  where M1 is Ti. 
     
     
         6 . The method according to  claim 1 , where the total amount of water added is between 70 and 150% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups. 
     
     
         7 . The method according to  claim 6 , where the total amount of water added is between 80 and 120% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups. 
     
     
         8 . A polyheterosiloxane prepared by any of the method of  claim 1 . 
     
     
         9 . A coating composition comprising the polyheterosiloxane of  claim 8 . 
     
     
         10 . A method for preparing a polyheterosiloxane having at least two non-Si metal elements comprising:
 (1) reacting
 (A) a metal (M1) alkoxide, and 
 (B) a silicon-containing material having hydrolyzable groups selected from
 (B1) an organosiloxane, or 
 (B2) a silane, and 
 
 with an amount of water to form a reaction product; and 
   (2) further reacting the reaction product of step (1) and (C) a hydrolyzable metal (M2) salt, where (M1) and (M2) are non-Si metal elements and different from each other, and   if necessary adding an additional amount of water to form the polyheterosiloxane, such that total amount of the water added is between 50 and 200% of that necessary to hydrolyze and condense the alkoxy groups and other hydrolyzable groups on Components (A), (B), and (C), to form the polyheterosiloxane, and with the proviso that at least two non-Si metal elements are provided by Component (A) and/or (C).   
     
     
         11 . The method according to  claim 10  wherein;
 (A) the metal (M1) alkoxide is selected from metal alkoxides having a general formula (I) R 1   m M1O n  X p (OR 2 ) v1-m-p-2n,  where M1 is selected from Ti, Al, Ge, Zr, Sn, Cr, Ca, Ba, Sb, Cu, Ga, Hf, In, Fe, Mg, Mo, Nb, Ce, Er, La, Nd, Pr, Sm, Y, Sr, Ta, Te, W, and V, each X is independently selected from carboxylate ligands, organosulfonate ligands, organophosphate ligands, 3-diketonate ligands, and chloride ligands, v1 is the oxidation state of M1, m is a value from 0 to 3, n is a value from 0 to 2, p is a value from 0 to 3, each R 1  is an alkyl group having from 1 to 18 carbon atoms, each R 2  is an independently selected monovalent alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3  is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4  is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, 
 (B) the silicon-containing material is selected from (B1) an organosiloxane having an average formula (II) R 5   b (R 6 O) a SiO (4−(a+b))/2  or (B2) a silane having a general formula (III) R 5   c SiY d , where Y is Cl or OR 6 , each R 5  is an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group, R 6  is an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) —(R 3 O) q R 4 , where q is a value from 1 to 4, each R 3  is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R 4  is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, a is a value from 0.1 to 3, b is a value from 0.5 to 3, and (a+b) is a value from 0.6 to 3.9, c is a value from 0 to 3, d is a value from 1 to 4 and (c+d) equals 4, and 
 (C) the hydrolyzable metal (M2) salt is selected from (C1) a non-hydrated metal salt having a general formula (IV) R 7   e M2(Z) (v2−e)/w  or (C2) a hydrated metal salt having a general formula (V) M2(Z) v2/w .xH 2 O, where M2 is selected from any of the metal elements in the periodic table, v2 is the oxidation state of M2, w is the oxidation state of ligand Z where Z is independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate, each R 7  is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 8 carbon atoms, or aryl group having from 6 to 8 carbon atoms, e is a value from 0 to 3 and x is a value from 0.5-12. 
 
     
     
         12 . The method according to  claim 10 , wherein M2 is selected from Li, Na, Ca, Mg, Ba, Ti, Zr, Ce, Eu, Nd, Er, Yb, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Ge, and Pb. 
     
     
         13 . The method according to  claim 12 , wherein M2 is Mg. 
     
     
         14 . The method according to  claim 10 , wherein M1 is Ti. 
     
     
         15 . The method according to  claim 10 , wherein the total amount of water added is between 70 and 150% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups. 
     
     
         16 . The method according to  claim 15 , wherein the total amount of water added is between 80 and 120% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups. 
     
     
         17 . A polyheterosiloxane prepared by any of the method of  claim 10 . 
     
     
         18 . A coating composition comprising the polyheterosiloxane of  claim 17 .