Compounds containing (meth)acrylate groups and sulfonate or sulfate groups, polymers and condensates therefrom and use of the polymers and condensates

Abstract

A compound has at least three functionalities, including a first functionality (a) that is a sulfonate group or a sulfate group of the formula —(O).sub.d—SO.sub.3M with d=0 or 1 and with M=hydrogen or a monovalent metal cation or a corresponding portion of a multivalent metal cation; a second functionality (b) that is a (meth)acryl residue; and a third functionality (c) that is a carboxylic acid function and/or a thioether group. When the compound is free of silicon, the sulfonate or sulfate group and the (meth)acryl residue are separated from each other by a hydrocarbon-containing residue having a carbon chain. The carbon chain is interrupted by S or NH, or the carbon chain contains a linking group, selected from C(O)NH, NHC(O), NR.sup.8C(O), NHC(O)O, NR.sup.8C(O)O, NHC(O)NH, C(O)NHC(O) and —C(O)S—, wherein R.sup.8 is alkyl or alkenyl or a (meth)acryl group.

Claims

1. A compound comprising at least three functionalities, including: a first functionality that is a sulfonate group or a sulfate group of the formula —(O).sub.d—SO.sub.3M with d=0 or 1 and with M=hydrogen or a monovalent metal cation or a corresponding portion of a multivalent metal cation; a second functionality that is a (meth)acryl residue; and a third functionality that is a carboxylic acid function and/or a thioether group; with the proviso that, when the compound is free of silicon, the sulfonate group or the sulfate group and the (meth)acryl residue are separated from each other by a hydrocarbon-containing residue having a carbon chain, wherein the carbon chain is interrupted by S or NH, or the carbon chain contains a linking group, selected from the group consisting of C(O)NH, NHC(O), NR.sup.8C(O), NHC(O)O, NR.sup.8C(O)O, NHC(O)NH, C(O)NHC(O) and —C(O)S—, wherein R.sup.8 is alkyl or alkenyl or a (meth)acryl group.

2. The compound according to claim 1 with the formula (II) ##STR00011## wherein R.sup.1 is a bivalent hydrocarbon residue which, when f=1, is bonded by a carbon atom to the silicon atom, R.sup.9 is H or alkyl or, when a=0, f=1, and g=1, a hydrolytically condensable residue or can be ##STR00012## R.sup.3 is an alkylene that is unsubstituted or substituted with a functional group, straight-chain, branched or has at least one cyclic structure, A is a linking group, selected from the group consisting of C(O)NH, NHC(O), NR.sup.8C(O), NHC(O)O, NR.sup.8C(O)O, NHC(O)NH, C(O)NHC(O) and —C(O)S—, R.sup.4 is a hydrocarbon group that is optionally interrupted by O, S, NH or NR.sup.8 and/or optionally functionally substituted, M is hydrogen or a monovalent metal cation or the corresponding portion of a multivalent metal cation, R.sup.5 and R.sup.6, independently of each other, are either residues that are condensable under hydrolysis conditions or alkyl, aryl, arylalkyl, alkylaryl or alkylarylalkyl substituted or unsubstituted, straight-chain, branched or having at least one cyclic structure, alkenyl, arylalkenyl, or alkenylaryl, R.sup.8 is alkyl or alkenyl with 1 to 6 carbon atoms or a (meth)acryl residue, B is vinyl, 2-allyl or, when e>1, an organic residue with e vinyl groups that are present in each case bonded to a group located in the curly brackets, Y is a nitrogen atom, —O—CH═, —S—CH═, or —NH—CH═, wherein in each case the oxygen atom, the sulfur atom or the NH group has a bond to the adjacent C(O) group, a is 0 or 1, b is 0 or 1, c is 0 or 1, d is 0 or 1, e is 1, 2 or 3, f is 0 or 1, and g is 0 or 1, wherein, when f is 1, a and g both are ≠0, and wherein, when f is 0, at least one of the residues R.sup.3 or R.sup.4 carries a functional substituent comprising a (meth)acryl residue or an acidic group, or R.sup.4 is an alkylene that is interrupted at least by S.

3. The compound according to claim 2, wherein at least one of the residues R.sup.3 and R.sup.4 is substituted with at least one hydroxyl group and/or with a residue R.sup.10COOM and/or with a residue SO.sub.3M, wherein R.sup.10 is a chemical bond or a C.sub.1-C.sub.6 alkylene residue.

4. The compound according to claim 2, wherein f=0, g=0, and a=0.

5. The compound according to claim 2, with the proviso that, when Y is a nitrogen atom, b=0 and c=0, the residue R.sup.3 means optionally substituted ethylene, and, when Y is a nitrogen atom, b=0 and c=1, the residue R.sup.4 is an alkylene that is interrupted by O, S, NH or NR.sup.8 and optionally functionally substituted.

6. The compound according to claim 2, wherein the linking group A in the formula (II) is selected from (read from the left to the right in the formula (a) C(O)NH, NHC(O), NR.sup.8C(O), C(O)O, and OC(O), wherein R.sup.8 is alkyl or alkenyl with 1 to 6 carbon atoms or a (meth)acryl residue.

7. A method for preparing a compound with the formula (II) as defined in claim 2, the method comprising the steps of: (a) Providing a hydrocarbon compound which carries at least two functional groups, selected from primary amines, secondary amines, hydroxyl groups and thiol groups; (b) Reacting a first one of the two functional groups with optionally activated (meth)acrylic acid and reacting the second one of the two functional groups with a carboxylic acid that is optionally activated and has a C═C double bond, wherein said carboxylic acid can be (meth)acrylic acid or a different double bond-containing carboxylic acid; and (c) Adding, subsequent to the step (b), a sulfonate group-containing compound or a sulfate group-containing compound or a sulfite to the C═C double bond of the carboxylic acid residue reacted with said second functional group in such a way that on the (meth)acryl residue reacted with said first functional group such an addition does not take place.

8. The method according to claim 7, wherein the sulfonate group-containing compound or the sulfate group-containing compound has an OH-, SH- or NHR.sup.11-group, with R.sup.11=hydrogen or C.sub.1-C.sub.6 alkyl.

9. A method for preparing a compound of the formula (II) of claim 2, the method comprising the steps of: (a) Providing a hydrocarbon compound which carries at least one hetero ring, selected from the group consisting of oxacycyclopropyl, azacyclopropyl, thiocyclopropyl, and a cyclic carbonate, (b) Reacting the hetero ring with a sulfite or a sulfonate group-containing compound or a sulfate group-containing compound, and (c) Reacting at least the OH-, SH- or NH.sub.2-group generated in the step (b) with optionally activated (meth)acrylic acid.

10. The method according to claim 9, wherein the sulfonate group-containing compound or the sulfate group-containing compound has an OH-, SH- or NHR.sup.11-group, with R.sup.11=hydrogen or C.sub.1-C.sub.6 alkyl.

11. A method for preparing a compound of the formula (II) as defined in claim 2, the method comprising the steps of: (a) Providing a hydrocarbon compound comprising an alkylamino group or a mercapto group, (b) Reacting an alkenyl sulfonate with the alkylamino group or the mercapto group, and (c) Reacting the secondary amino group produced in the step (b) with optionally activated (meth)acrylic acid.

12. A method for preparing a compound of the formula (II) of claim 2, the method comprising the steps of: (a) Providing an organic compound with at least three (meth)acryl groups, and (b) Adding a sulfonate group-containing compound or a sulfate group-containing compound or a sulfite in less than stoichiometric quantity to the C═C double bond of one or several of the (meth)acryl groups such that the addition does not take place at least at one (meth)acryl residue.

13. A method for preparing a compound of the formula (II) of claim 2, the method comprising the steps of: (a) providing a (meth)acrylsilane with at least two (meth)acryl groups, which are bonded by a carbon atom of a hydrocarbon group to the silicon atom, and (b) adding a sulfonate group-containing compound or a sulfate group-containing compound or a sulfite in less than stoichiometric quantity to the C═C double bond of one or several of the (meth)acryl residues such that the addition does not take place at least at one (meth)acryl residue.

14. A method for preparing a compound of claim 4, the method comprising: reacting an organic compound, comprising at least one first (meth)acryl residue and at least one alkenylcarboxyl residue, with a sulfonate group-containing compound or a sulfate group-containing compound or a sulfite so that the sulfonate group-containing compound or the sulfate group-containing compound or the sulfite is added to the C═C double bond of the alkenylcarboxyl residue in such a way that at the first (meth)acryl residue no such addition takes place; wherein the at least one alkenylcarboxyl residue can be a second (meth)acryl residue or the residue of another alkenylcarboxylic acid.

15. A polymerisate, obtained from or by use of at least one compound of claim 1 by polymerization of at least some of the (meth)acryl residues.

16. The polymerisate according to claim 15 in the form of a dental material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a shows two REM images at different enlargements of dental enamel roughness produced with a compound according to the invention.

(2) FIG. 1b shows a profilometer image of dental enamel roughness produced with a compound according to the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

(3) Below, preparation methods for the above reactions are provided in an exemplary way.

(4) Reaction 1:

(5) Stage 1: 5.11 g (0.024 mol) N-(2-aminoethyl)-3-aminopropyl methyldimethoxysilane was dissolved in 5.21 g triethylamine and 30 ml toluene and was cooled to 0° C. Afterwards, 5.0 ml (0.051 mol) methacrylic acid chloride in 30 ml toluene were added dropwise. The reaction mixture was stirred for 3 h at room temperature. The mixture was centrifuged and the obtained solution adjusted for hydrolysis and condensation with 1 N hydrochloric acid to pH 1-2. After 24 h the volatile components were removed under vacuum.

(6) Stage 2: 3.92 g (0.013 mol) of the product of stage 1 were dissolved in 30 ml ethanol, the solution adjusted with sodium hydroxide to pH 10, and heated to 60° C. Afterwards 1.93 g (0.015 mol) sodium 2-mercaptoethansulfonate dissolved in 40 ml H.sub.2O were added dropwise, followed by stirring for 4 h. Ethanol was removed under vacuum and the aqueous solution treated with a cation exchanger. The volatile components were removed under vacuum. The end product is redissolvable in water.

(7) Reaction 2:

(8) Stage 1: 8.69 g (0.042 mol) N-(2-aminoethyl)-3-aminopropyl methyldimethoxysilane were dissolved in 50 ml ethyl acetate and heated to 50° C. A solution of 4.23 g (0.043 mol) maleic acid anhydride dissolved in 30 ml ethyl acetate was added dropwise, followed by stirring for 19 h. The mixture was centrifuged and the residual material purified twice with ethyl acetate and dried under vacuum.

(9) Stage 2: 6.06 g (0.021 mol) of the product of stage 1 were dissolved in 5 ml water and 1.72 g NaOH and cooled to 0° C. 2.1 ml (0.021 mol) methacrylic acid chloride were slowly added dropwise with strong stirring action, followed by stirring for 5 h at 50° C. Afterwards, the volatile components were removed under vacuum.

(10) Stage 3: 9.82 g (0.021 mol) of the product of stage 2 were dissolved in 20 ml water and heated to 60°. Afterwards, 2.61 g (0.021 mol) sodium sulfite were added dropwise with stirring action, followed by stirring for 24 h. The aqueous solution was treated with a cation exchanger and the volatile components were removed under vacuum. The product can be redissolved in water.

(11) Reaction 5:

(12) a)

(13) Stage 1: 5.04 g (0.040 □mol) sodium sulfite were dissolved in 30 ml H.sub.2O and heated to 80° C. A solution of 9.96 g (0.040 □mol) 3-glycidoxypropyl methyldiethoxysilane in 10 ml ethanol was added dropwise, followed by stirring under reflux for 3 h.

(14) After evaporation of ethanol, the aqueous phase was purified with ethyl acetate and afterwards the volatile components were removed under vacuum.

(15) Stage 2: 5.04 g (0.016 mol) of the product of the stage 1 were dissolved in 10 ml water and 2.79 g (0.070 □mol) NaOH and cooled to 0° C. Afterwards, 4.0 ml (0.016 mol) methacrylic acid chloride were added dropwise and the reaction mixture stirred for 4 h at 30° C. The solution was purified with ethyl acetate, the aqueous phase treated with a cation exchanger, and the volatile components removed afterwards under vacuum. The product can be redissolved in water.

(16) b)

(17) Stage 1: 3.38 g (0.027 mol) 2-aminoethane sulfonic acid were dissolved in 40 ml H.sub.2O and adjusted with 1 N NaOH solution to pH 14. A solution of 6.81 g (0.027 mol) 3-glycidoxypropyl methyldiethoxysilane in 30 ml ethanol was added dropwise at 50° C., followed by stirring for 3 h. Then ethanol was removed under vacuum and the aqueous solution was purified with ethyl acetate. Afterwards the volatile components were removed under vacuum.

(18) Stage 2: 5.12 g (0.014 mol) of the product of stage 1 were dissolved in 10 ml water and 2.58 g (0.065 mol) NaOH and cooled to 0° C. 1.5 ml (0.016 mol) methacrylic acid chloride were added dropwise and the reaction mixture stirred for 4 h at 30° C. The aqueous solution was purified with ethyl acetate and was treated with a cation exchanger. Afterwards the volatile components were removed under vacuum. The product can be redissolved in water.

(19) Reaction 6:

(20) Stage 1: 5.14 g (0.027 mol) 3-aminopropyl methyldiethoxysilane were dissolved in 30 ml ethanol and 1.65 g (0.016 g) triethylamine and heated to 70° C. Afterwards 14 ml (0.027 mol) aqueous 25% sodium vinylsulfonate solution were added dropwise, followed by stirring for 24 h. Afterwards ethanol was removed under vacuum and the aqueous solution was washed with ethyl acetate. Afterwards the volatile components were removed under vacuum.

(21) Stage 2: 5.73 g (0.018 mol) of the product of stage 1 was dissolved in 10 ml water and 2.92 g (0.075 mol) NaOH and cooled to 0° C. 1.8 ml (0.018 mol) methacrylic acid chloride were added dropwise and the reaction mixture stirred for 5 h at 30°. Afterwards the solvent was removed under vacuum. The aqueous solution was purified with ethyl acetate and was treated with a cation exchanger. Afterwards the volatile components were removed under vacuum. The product can be redissolved in water.

(22) Reaction 4:

(23) 1.50 g (0.005 mol) trimethylpropane triacrylate and 13.9 mg (0.06 wt. %) butylhydroxytoluene were dissolved in 20 ml ethanol and heated to 40° C. 0.87 g (0.005 mol) sodium 2-mercaptoethanesulfonate were dissolved in 20 ml water and added dropwise. The reaction mixture was stirred for 4 h and ethanol was removed afterwards at 40° C. under vacuum. The aqueous solution was purified afterwards with ethyl acetate, treated with a cation exchanger, and the volatile components were removed under vacuum. The product can be redissolved in water.