Sulfonic acid esters as regulators in radical polymerization reactions

Patent metadata

Field	Value
Publication number	US-10982071-B2
Application number	US-201615571949-A
Country	US
Kind code	B2
Filing date	May 2, 2016
Priority date	May 7, 2015
Publication date	Apr 20, 2021
Grant date	Apr 20, 2021

Abstract

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.

First claim

The invention claimed is:

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.

Assignees

• Ivoclar Vivadent Ag
• Univ Wien Tech

Inventors

• Liska Robert
• Gorsche Christian
• Seidler Konstanze
• Moszner Norbert

Classifications

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08K5/42 Primary

  Sulfonic acids; Derivatives thereof · CPC title

• C08L57/00

  Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title