Sulfonic acid esters as regulators in radical polymerization reactions
The invention relates to the use of sulfonic acid esters of the following Formula 1 and/or Formula 2, individually or as a mixture of more than one thereof, as regulators in polymerization reactions of radically polymerizable, ethylenically unsaturated monomers: wherein A in each case independently is selected from H, CN, linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues; X in each case independently is —COO— or —CON(R 1 )—, wherein the binding to A occurs via O or N, or is absent if A is an aromatic hydrocarbon residue or CN; B in each case independently is selected from linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues; R 1 in each case independently is selected from hydrogen and linear, branched or cyclic aliphatic or aromatic C 1 -C 10 hydrocarbon residues, which are optionally substituted with one or more OH groups, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more oxygen atoms; and n in each case independently is an integer from 1 to 6.
1. Polymerizable composition comprising a regulator for polymerization reactions of radically polymerizable, ethylenically unsaturated monomers which is selected from sulfonic acid esters of the following Formula 1 and/or Formula 2, individually or as a mixture of more than one thereof:
wherein
A in each case independently is selected from H, CN, linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues, which are optionally substituted with one or more substituents, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more urethane groups, ester groups, O and/or S;
X in each case independently is —COO— or —CON(R 1 )—, wherein the binding to A occurs via O or N, or is absent if A is an aromatic hydrocarbon residue or CN;
B in each case independently is selected from linear, branched or cyclic aliphatic or aromatic C 1 -C 30 hydrocarbon residues, which are optionally substituted with one or more substituents, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more urethane groups, ester groups, O and/or S;
R 1 in each case independently is selected from hydrogen and linear, branched or cyclic aliphatic or aromatic C 1 -C 10 hydrocarbon residues, which are optionally substituted with one or more OH groups, wherein the aliphatic hydrocarbon residues are optionally interrupted by one or more oxygen atoms; and
n in each case independently is an integer from 1 to 6, and
60 to 98 wt.-% of at least one ethylenically unsaturated monomer, based on the total weight of the monomers and regulators.
2. A polymerizable composition according to claim 1 , characterized in that the molar ratio between the ethylenic unsaturations in the radically polymerizable monomers and the sulfonate groupings in the sulfonic acid esters of Formulae 1 and 2 is at least 3:1.
3. A polymerizable composition according to claim 1 , characterized in that the ethylenically unsaturated monomers are selected from (meth)acrylates, vinyl esters and mixtures thereof.
4. A polymerizable composition according to claim 3 , characterized in that the ethylenically unsaturated monomers are selected from multifunctional (meth)acrylates and vinyl esters.
5. A polymerizable composition according to claim 1 , characterized in that the polymerizable composition comprises at least one radical polymerization initiator and optionally at least one solvent.
6. A polymerizable composition according to claim 1 , characterized in that A is selected from hydrocarbon residues with 1 to 20 carbon atoms.
7. A polymerizable composition according to claim 1 , characterized in that A comprises an aliphatic hydrocarbon residue, which is optionally interrupted by 1 to 4 urethane groups, ester groups or oxygen atoms, and is optionally substituted with 1 to 4 OH groups.
8. A polymerizable composition according to claim 1 , characterized in that A and/or B comprise at least one phenyl, phenylene, naphthyl or naphthylene residue, which are in each case optionally substituted with 1 to 3 substituents selected from OH, CH 3 and OCH 3 .
9. A polymerizable composition according to claim 1 , characterized in that R 1 is an aliphatic C 1-6 hydrocarbon residue, which is optionally interrupted by 1 to 2 oxygen atoms and optionally substituted with 1 to 2 OH groups.
10. A polymerizable composition according to claim 1 , characterized in that either
i) X is —COO—, in which case the binding to A occurs via O, or
ii) X is absent, wherein A is an aromatic hydrocarbon residue with 6 carbon atoms, which is optionally substituted with 1 to 3 substituents selected from —CH 3 , —OH and —OCH 3 .
11. A polymerizable composition according to claim 1 , characterized in that n=2 to 4.
12. A polymerizable composition according to claim 1 , characterized in that
a) A for n=1 is selected from optionally branched C 1-10 alkyl, optionally interrupted by oxygen atoms, and phenyl, which for n>1 can be substituted with further vinylsulfonate or sulfonyloxyacryloyloxy or sulfonyloxyacrylamido groupings; and/or
b) B for n=1 is selected from OH, C 1-10 alkyl, phenyl and naphthyl, which are optionally substituted with OH, C 1-6 alkyl or alkoxy, benzyl or phenoxy, and for n>1 can be substituted with further vinyloxysulfonyl groupings; and/or
c) R 1 is selected from C 1-10 alkyl.
13. A polymerizable composition according to claim 1 , characterized in that the sulfonic acid ester or esters of Formula 1 and/or Formula 2 is/are selected from:
14. Polymer, obtained by radical polymerization of a composition as defined in claim 1 .
15. Polymer according to claim 14 , characterized in that the radical polymerization was carried out with ethylenically unsaturated monomers selected from multifunctional (meth)acrylates and vinyl esters and the polymer is a cross-linked polymer.
16. Polymer according to claim 14 for use as a varnish, coating or adhesive or for the production of shaped bodies by casting or 3D printing.
17. A regulator according to claim 1 , characterized in that the molar ratio between the ethylenic unsaturations in the radically polymerizable monomers and the sulfonate groupings in the sulfonic acid esters of Formulae 1 and 2 is at least least 5:1.
18. A regulator according to claim 1 , characterized in that A is selected from hydrocarbon residues with 1 to 12, carbon atoms.
19. A regulator according to claim 1 , characterized in that A and/or B comprise 1 to 4 phenyl or phenylene residues, which are in each case optionally substituted with 1 to 3 substituents selected from OH, CH3 and OCH3.
20. A regulator according to claim 1 , characterized in that
a) 60 to 98 wt.-% of the ethylenically unsaturated monomers, based on the total weight of the monomers and regulators, are used; and/or
b) 0.1 to 3 wt.-%, of at least one radical polymerization initiator is used; and/or
c) at least one solvent, selected from water, dimethyl sulfoxide, ethanol, dimethyl¬formamide, polyethylene glycol and mixtures thereof is used.
21. A regulator according to claim 1 , characterized in that
a) 70 to 95 wt.-%, of the ethylenically unsaturated monomers, based on the total weight of the monomers and regulators, are used; and/or
b) 0.1 to 3 wt.-%, of at least one radical polymerization initiator is used; and/or
c) at least one solvent, selected from water, dimethyl sulfoxide, ethanol, dimethyl¬formamide, polyethylene glycol and mixtures thereof is used.