Reactive amine accelerator, a reactive resin containing said accelerator, and the use thereof

Patent metadata

Field	Value
Publication number	US-11859069-B2
Application number	US-201917272428-A
Country	US
Kind code	B2
Filing date	Sep 9, 2019
Priority date	Sep 14, 2018
Publication date	Jan 2, 2024
Grant date	Jan 2, 2024

Abstract

A reactive amine accelerator is prepared by reacting a primary or secondary aromatic amine with a diglycidyl ether and an α,β-unsaturated carboxylic acid. The reactive amine accelerator can be used in a reactive resin, in particular based on an epoxy (meth)acrylate resin or a urethane (meth)acrylate resin. A reactive resin composition, in particular based on epoxy (meth)acrylate resin and urethane (meth)acrylate resin, which has an amine accelerator is useful. The amine accelerator is covalently incorporated into the polymer network.

First claim

The invention claimed is:

1. An accelerator for a reactive resin system, prepared by reacting the following components:
(1) an aromatic primary or secondary amine, or a mixture thereof having the structure:

where
R 1 is selected from the group consisting of chlorine, bromine, pseudohalogen, C 1-20 alkyl, hydroxy-C 1-20 alkyl, C 2-20 alkenyl, hydroxyl C 2-20 alkenyl, C 2-20 alkynyl, hydroxy C 2-20 alkynyl and phenyl;
m=0-3; and
R 2 is selected from the group consisting of H, C 1 -C 20 hydroxy-C 1 -C 20 alkyl, C 2 -C 20 alkenyl, hydroxy-C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, hydroxy-C 2 -C 20 alkynyl and aryl;
(2) a diglycidyl ether of a diol or polyol, which has 2 to 20 C atoms; and
(3) an α,β-unsaturated carboxylic acid, selected from the group consisting of branched and unbranched C 2 -C 10 -α,β-unsaturated carboxylic acids,
wherein an opening of the epoxy groups present in the diglycidyl ether leads to formation of glycerol bridges between the amine and the diol and between the α,β-unsaturated carboxylic acid and the diol, which results in a finished accelerator.

2. The accelerator for a reactive resin system according to claim 1 , wherein the aromatic primary or secondary amine is a primary amine which is selected from the group consisting of an unsubstituted toluidine, a toluidine halogenated with at least one of chlorine and bromine at an aromatic group that does not have further substituents, and a toluidine halogenated with at least one of chlorine and bromine at an aromatic group that carries another C 1 -C 4 alkyl group at the aromatic group, and wherein the diglycidyl ether is a diglycidyl ether of a diol.

3. The accelerator for a reactive resin system according to claim 1 , wherein the diol is selected from the group consisting of bisphenols, neopentyl glycol, ethylene glycol, phenol novolac resin, cresol novolac resin, and 1,4-butanediol.

4. The accelerator for a reactive resin system according to claim 1 , wherein the α,β-unsaturated carboxylic acid is selected from the group consisting of tiglic acid, sorbic acid, crotonic acid, methacrylic acid, and acrylic acid.

5. The accelerator for a reactive resin system according to claim 1 , wherein the aromatic amine is a primary aromatic amine, and wherein the equivalent ratio of diglycidyl ether:α,β-unsaturated carboxylic acid:primary aromatic amine is in the range of approximately 1:0.3:0.8 to approximately 1:2.09:0.01.

6. The accelerator for a reactive resin system according to claim 1 , wherein the aromatic amine is a secondary aromatic amine, and wherein the equivalent ratio of diglycidyl ether:α,β-unsaturated carboxylic acid:secondary aromatic amine is in the range of approximately 1:0.1:2 to approximately 1:2.09:0.01.

7. The accelerator for a reactive resin system according to claim 1 , having the formula (I) or (II):

in which
R 1 is selected from the group consisting of chlorine, bromine, pseudohalogen, C 1 -C 20 alkyl, hydroxy-C 1 -C 20 alkyl, C 2 -C 20 alkenyl, hydroxy-C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, hydroxy-C 2 -C 20 alkynyl, and phenyl,
m=0-3;
n is a whole number from 1 to 20; and
A is the functional group of the diol which is comprised in the diglycidyl ether (2);

in which
R 1 is selected from the group consisting of chlorine, bromine, pseudohalogen, C 1 -C 20 alkyl, hydroxy-C 1 -C 20 alkyl, C 2 -C 20 alkenyl, hydroxy-C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, hydroxy-C 2 -C 20 alkynyl, and phenyl;
R 2 is selected from the group consisting of C 1 -C 20 alkyl, hydroxy-C 1 -C 20 alkyl; C 2 -C 20 alkenyl, hydroxy-C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, hydroxy-C 2 -C 20 alkynyl, and aryl;
m=0-3;
n is a whole number from 1 to 20; and
A is the functional group of the diol which is comprised in the diglycidyl ether (2).

8. The accelerator for a reactive resin system according to claim 7 , wherein R 1 is selected from the group consisting of chlorine, bromine, hydroxy-C 1 -C 20 alkyl, and C 1 -C 20 alkyl.

9. The accelerator for a reactive resin system according to claim 8 , wherein R 1 is selected from the group consisting of chlorine, bromine, and C 1 -C 6 alkyl.

10. The accelerator for a reactive resin system according to claim 7 , wherein then of formula (I) is a whole number from 1 to 3.

11. The accelerator for a reactive resin system according to claim 7 , wherein then of formula (II) is a whole number from 1 to 2.

12. The accelerator for a reactive resin system according to claim 1 , wherein the diglycidyl ether is a diglycidyl ether of diols selected from the group consisting of bisphenols, neopentyl glycol, ethylene glycol, phenol novolac resin, cresol novolac resin, and 1,4-butanediol.

13. A reactive resin comprising the accelerator according to claim 1 .

14. A reactive resin component (A) for a reactive resin system, comprising the reactive resin according to claim 13 .

15. A reactive resin system comprising the reactive resin component (A) according to claim 14 , and a hardener component (B) comprising an initiator.

16. The reactive resin system according to claim 15 , wherein at least one of the components (A) or (B) comprises an inorganic filler.

17. A method for chemical fastening anchoring in boreholes or for structural bonding, the method comprising:
applying the reactive resin system according to claim 15 to a borehole or a structure.

18. A reactive resin system comprising a reactive resin component (A) and a hardener component (B), wherein the reactive resin component (A) comprises:
at least one accelerator according to claim 1 ;
at least one backbone resin;
at least one reactive diluent;
at least one inhibitor;
at least one hydraulically setting or polycondensable inorganic compound; and
at least one thixotropic agent,
and the hardener component (B) comprises:
at least one initiator for initiating the polymerization of the reactive resin;
at least one filler; and
water.

19. A method of accelerating the curing of a reactive resin, the method comprising:
curing the reactive resin with the accelerator as defined in claim 1 .

Assignees

• Hilti Ag

Inventors

• Gaefke Gerald
• Gnass Beate

Classifications

• C08K5/18 Primary

  with aromatically bound amino groups · CPC title

• C08G59/686 Primary

  containing nitrogen · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08G59/027

  obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer · CPC title

• C07C219/10

  having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of a carbon skeleton containing rings · CPC title