Silicic Acid (Hetero) Polycondensates Comprising Organically Polymerisable Groups and Either Sulphonate Groups or Sulphate Groups, Organic Polymerisates Produced therefrom, and a Method for Producing said Polycondensates

Abstract

The invention relates to silicic acid (hetero) polycondensates consisting of at least one silane that has a group bonded to silicon by a carbon atom and that carries an organically polymerisable C═C double bond, and at least one silane that has a group bonded to silicon by a carbon atom and that carries a sulphonate group or a sulphate group of the formula —(O) d -SO 3 M wherein d=0 or 1 and M=hydrogen, or a monovalent metal cation, or the corresponding quantity of a polyvalent metal cation, yet not including polycondensates in which the C═C double bonds are formed exclusively by methacrylic esters that are bound, in the form of a methylene acryl ester group, to the groups bonded to silicon by carbon. The invention also relates to composites that consist of such silicic acid (hetero) polycondensates in combination with fillers, and to polymers produced by organically polymerising the C═C double bonds in the polycondensates or composites. Moreover, the invention relates to different possibilities for producing the claimed silicic acid (hetero) polycondensates.

What is claimed is: 
     
         1 . to  16 . (canceled) 
     
     
         17 . A silicic acid (hetero) polycondensate of:
 at least one silane with a first residue bonded by a carbon atom to silicon and carrying an organically polymerizable C═C double bond;   at least one silane with a second residue bonded by a carbon atom to silicon and carrying a sulfonate group or sulfate group of the formula —(O) d —SO 3 M with d=0 or 1 and with M=hydrogen or a monovalent metal cation or the corresponding portion of a multi-valent metal cation;   with the proviso that polycondensates in which the C═C double bonds are formed exclusively by methacrylic esters attached in the form of a methylene acrylic ester group to the groups that are bonded by a carbon to silicon are excluded.   
     
     
         18 . The silicic acid (hetero) polycondensate according to  claim 17 , wherein the organically polymerizable C═C double bond is a vinyl group or is a part of an allyl group, an acryl group, a methacryl group, an optionally substituted bicyclo[2.2.1] heptene group, an optionally substituted bicyclo[2.2.2]octene group, or an optionally substituted oxabicyclo[2.2.1]heptene group. 
     
     
         19 . The silicic acid (hetero) polycondensate according to  claim 17 , further comprising third residues bonded by a carbon atom to silicon and each carrying at least one carboxylic acid group or an ester derived from the least one carboxylic acid group or a corresponding salt of the least one carboxylic acid group or a hydroxyl group, wherein said third residues can be identical with the first and second residues as defined in  claim 1  or can be different. 
     
     
         20 . The silicic acid (hetero) polycondensate according to  claim 19 , wherein the third residues, carrying at least one carboxylic acid group or a hydroxyl group, carry additionally either an organically polymerizable C═C double bond or a sulfonate group or a sulfate group, but not a combination thereof. 
     
     
         21 . The silicic acid (hetero) polycondensate according  claim 20 , wherein the third residues bonded by a carbon atom to silicon are at least partially an alkylene group, an arylene group or an alkylaryl group, wherein the alkylene group, the arylene group, and the alkylaryl group each can be interrupted optionally by one or several groups selected from —O—, —S—, —NH—, —S(O)—, C(O)NH—, —NHC(O)—, —C(O)O—, —C(O)S, —NHC(O)NH—, and —C(O)NHC(O)—. 
     
     
         22 . The silicic acid (hetero) polycondensate according to  claim 17 , wherein the first and second residues bonded by a carbon atom to silicon are at least partially an alkylene group, an arylene group or an alkylaryl group, wherein the alkylene group, the arylene group, and the alkylaryl group each can be interrupted optionally by one or several groups selected from —O—, —S—, —NH—, S(O)—, —C(O)NH—, —NHC(O)—, —C(O)O—, —C(O)S, —NHC(O)NH—, and C(O)NHC(O)—. 
     
     
         23 . The silicic acid (hetero) polycondensate according to  claim 17 , further comprising a silane with a fourth residue bonded by a carbon atom to silicon and carrying an organically polymerizable C═C double bond and further carrying a sulfonate group or a sulfate group. 
     
     
         24 . The silicic acid (hetero) polycondensate according to  claim 23 , wherein the first and second residues bonded by a carbon atom to silicon are at least partially an alkylene group, an arylene group or an alkylaryl group, wherein the alkylene group, the arylene group, and the alkylaryl group each can be interrupted optionally by one or several groups selected from —O—, —S—, —NH—, —S(O)—, —C(O)NH—, —NHC(O)—, —C(O)O—, —C(O)S, —NHC(O)NH—, and —C(O)NHC(O)—. 
     
     
         25 . The silicic acid (hetero) polycondensate according to  claim 17 , made by using additionally at least one hydrolytically condensable metal compound of a metal, selected from metals of the main groups Ill and IV and metals of the transition metal groups III to VI. 
     
     
         26 . The silicic acid (hetero) polycondensate according to  claim 17 , wherein the silicic acid (hetero) polycondensate is water-soluble. 
     
     
         27 . The silicic acid (hetero) polycondensate according to  claim 17  as a dental material or dental adhesive. 
     
     
         28 . A composite, comprising a silicic acid (hetero) polycondensate according to  claim 17  and a filler incorporated into the silicic acid (hetero) polycondensate. 
     
     
         29 . The composite according to  claim 28  as a dental material or dental adhesive. 
     
     
         30 . A polymerisate obtained from a silicic acid (hetero) polycondensate of  claim 17  by polymerization of at least some (meth)acryl groups contained in said silicic acid (hetero) polycondensate. 
     
     
         31 . The polymerisate according to  claim 30  as a dental material or dental adhesive. 
     
     
         32 . A method for preparing a silicic acid (hetero) polycondensate according to  claim 17 , comprising the steps of:
 providing at least one silane with a first residue that is bonded by a carbon atom to silicon and that carries an organically polymerizable C═C double bond, wherein the at least one silane with the first residue is hydrolytically condensable, with the proviso that no silanes in which the C═C double bonds are formed exclusively by methacrylic esters which are attached in the form of a methylene acrylic ester group to the groups that are bonded by a carbon to silicon, are provided;   providing at least one silane with a second residue that is bonded by a carbon atom to silicon and that carries a sulfonate group or sulfate group of the formula —(O) d —SO 3 M with d=0 or 1 and with M=hydrogen or a monovalent metal cation or a corresponding portion of a multi-valent metal cation, wherein the at least one silane with the second residue is hydrolytically condensable; and   co-condensing the at least one silane with the first residue and the at least one silane with the second residue under hydrolytic conditions.   
     
     
         33 . The method according to  claim 32 , carrying out the step of co-condensing by a sol gel process. 
     
     
         34 . A method for preparing a silicic acid (hetero) polycondensate according to  claim 17 , comprising the steps of:
 generating or providing a silicic acid polycondensate of at least one silane with a first residue bonded by a carbon atom to silicon and carrying an organically polymerizable C═C double bond, with the proviso that no silanes in which the C═C double bonds are formed exclusively by methylene acrylic esters are generated or provided; and   reacting only a portion of the at least one silane with said first residue with a compound which carries a sulf(on)ate group and can attack at the organically polymerizable C═C double bond so that some of the groups containing the organically polymerizable C═C double bond are reacted to a sulf(on)ate-containing group.   
     
     
         35 . The method according to  claim 34 , wherein the organically polymerizable C═C double bond is a vinyl group or is a part of an allyl group, an acryl group, a methacryl group, an optionally substituted bicyclo[2.2.1] heptene group, an optionally substituted bicyclo[2.2.2]octene group, or an optionally substituted oxabicyclo[2.2.1]heptene group, and wherein the compound which carries a sulf(on)ate group and can attack the C═C double bond is a thioalkane sulfonate or an aminoalkane sulfonate. 
     
     
         36 . A method for preparing a silicic acid (hetero) polycondensate according to  claim 17 , comprising the steps of:
 generating or providing a silicic acid polycondensate from at least two different silanes, including a silane with a first residue bonded by a carbon atom to silicon and carrying at least one organically polymerizable C═C double bond, with the proviso that no silanes in which the C═C double bonds are formed exclusively by methylene acrylic esters are generated or provided, and further including a silane with a reactive residue bonded by a carbon atom to silicon and carrying a reactive group; and   reacting said reactive group of said silane with said reactive residue with a compound, said compound containing a sulf(on)ate group and further containing a residue which can attack said reactive group and form a link, so that the sulf(on)ate group is introduced into said reactive residue.   
     
     
         37 . The method according to  claim 36 , wherein said reactive group is a strained hetero ring. 
     
     
         38 . The method according to  claim 37 , wherein the strained hetero ring is an epoxy group. 
     
     
         39 . The method according to  claim 37 , wherein said compound is sodium sulfate, sodium sulfite, a primary aminoalkane sulf(on)ate, or a secondary aminoalkane sulf(on)ate. 
     
     
         40 . The method according to  claim 36 , wherein said compound is sodium sulfate, sodium sulfite, a primary aminoalkane sulf(on)ate, or a secondary aminoalkane sulf(on)ate.