Fast-curing epoxy systems

Patent metadata

Field	Value
Publication number	US-11359048-B2
Application number	US-201916408725-A
Country	US
Kind code	B2
Filing date	May 10, 2019
Priority date	May 17, 2018
Publication date	Jun 14, 2022
Grant date	Jun 14, 2022

Abstract

The present invention provides a composition comprisinga) at least one epoxy resin,b) at least one cyclic amine of the formula (I)in whichR1 to R4 is H or an organic radical,with the proviso that at least one of the R1, R2, R3 and R4 radicals ═H, andX═—(Y1)m-(A1)n-(Y2)o-(A2)p-(Y3)q-(A3)r-(Y4)s—  (II)where, independently of one another,m, n, o, p, q, r and s=0 or 1,A1, A2, A3=alkylene or alkenylene radical andY1, Y2, Y3, Y4═NR5, PR5, O or S, where R5 independently=organic radical,where any two organic radicals selected from R1 to R5 and any radicals present in the alkylene and/or alkenylene radicals A1, A2, A3 may also form one or more further rings,with the proviso that at least one of the radicals selected from R1 to R5 present and any radicals present in the alkylene and/or alkenylene radicals A1, A2, A3 is substituted by at least one —NHR6 or —NH2 group, where R6=organic radical, andc) at least one salt of a strong Brønsted acid with a counterion selected from metal ions, metal-containing ions, phosphonium ions and unsubstituted ammonium ions,where the ratio of the epoxy groups in the epoxy resin to the sum total of all NH groups in all amines is 0.5:1 to 1.5:1,and to processes for production thereof and use thereof.

First claim

The invention claimed is:

1. A composition comprising
a) an epoxy resin selected from bisphenol A diglycidyl ether or bisphenol F diglycidyl ether,
b) a cyclic amine of the formula (I)

in which
wherein R 1 , R 2 , R 3 and R 4 ═H, and
X═—(Y 1 ) m -(A 1 ) n -(Y 2 ) o -(A 2 ) p -(Y 3 ) q -(A 3 ) r -(Y 4 ) s —  (II)

wherein,
m, n, o, p, q, r and s=0 or 1, provided that at least one of m, n, o, p, q, r, and s is 1
A 1 , A 2 , A 3 have the formula (III))
—(CR 7 R 8 ) x —(CR 9 ═CR 10 ) y —(CR 11 R 12 ) z —  (III)

wherein
R 7 , R 8 , R 9 , R 10 , R 11 and R 12 ═H or organic radical and
1≤x+y+z≤7 and
Y 1 , Y 2 , Y 3 , Y 4 ═NR 5 , PR 5 , O or S, where R 5 independently=organic radical,
where any two organic radicals R 5 , R 7 , R 8 , R 9 , R 10 , R 11 or R 12 optionally form one or more further rings,
wherein at least one radical present as R 5 , R 7 , R 8 , R 9 , R 10 , R 11 or R 12 is present and is substituted by a —NHR 6 or —NH 2 group, where R 6 =organic radical,
c) a salt of a Brønsted acid having a pKa of between 2 and −9.0, selected from the group consisting of calcium nitrate, magnesium bromide, zirconium(IV) chloride, indium chloride, bismuth chloride, copper tetrafluoroborate, calcium oxalate, lithium bromide and magnesium nitrate, and
d) an amine not covered by the part b), wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 10% by weight, and
wherein the ratio of the epoxy groups in the epoxy resin to the sum total of all NH groups in all amines is 0.5:1 to 1.5:1.

2. The composition according to claim 1 , wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 30% by weight.

3. The composition according to claim 2 , wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 50% by weight.

4. The composition according to claim 1 , wherein
R 7 , R 8 , R 11 and R 12 ═H
and the sum total of x, 0.5 y, z, m, o, q, and s is from 2 to 8, and
wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 70% by weight, and
X in formula (II) has a chain length of from 2 to 15 atoms.

5. The composition according to claim 1 , wherein X in formula (II) has a chain length of 2 to 15 atoms.

6. The composition according to claim 1 , wherein X has the formula (IIa)
X═—(CR 7 R 8 x —(Y) o —(CR 11 R 12 ) z —  (IIa)

wherein
x and z=0, 1, 2, 3, 4, 5, 6 or 7,
o=0 or 1,
2≤x+o+z≤15
R 7 , R 8 , R 11 , R 12 ═H or organic radical and
Y═NR 5 , PR 5 , O or S, where R 5 =organic radical
wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 50% by weight.

7. The composition according to claim 6 , wherein x=1, 2, 3 or 4, o=0 or 1 and z=0, 1 or 2
wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 50% by weight.

8. The composition according to claim 1 , further comprising
e) auxiliaries or additives.

9. The composition according to claim 8 , wherein the amine d) is selected from the group consisting of
aliphatic amines,
oxyalkylenepolyamines
cycloaliphatic amines,
araliphatic amines,
aromatic amines
adduct hardeners,
polyamidoamine hardeners
Mannich base hardeners and
Mannich bases.

10. The composition according to claim 8 , wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 30% by weight.

11. The composition as claimed in claim 1 , wherein
component a) is present in an amount from 30 to 95% by weight based on the total weight of the composition; wherein component b) is present in an amount from 1 to 50% by weight based on the total weight of the composition; wherein component c) is present in an amount of from 0.001 to 5% by weight based on the total weight of the composition; wherein the composition optionally further comprises e) auxiliaries or additives in an amount of up to 48% by weight based on the total weight of the composition; and wherein the percentage of b) based on total weight of b) and d) is from 70 to 98% by weight.

12. A process for producing a composition according to claim 1 , wherein the epoxy resin a), the cyclic amine b) the salt of a Brønsted acid c) and the amine d) are mixed with one another, wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 50% by weight.

13. A process for producing a composition according to claim 12 , wherein X in formula (II) has a chain length of 2 to 15 atoms.

14. A composite comprising the composition according to claim 1 .

15. A casting resin comprising the composition according to claim 1 .

16. A coating composition comprising the composition according to claim 1 .

17. An adhesive comprising the composition according to claim 1 .

18. A composition comprising
a) an epoxy resin selected from bisphenol A diglycidyl ether or bisphenol F diglycidyl ether,
b) a cyclic amine selected from the group consisting of aminoethylpiperazine (AEP, 1-(2-aminoethyl)piperazine), 1-(3-aminopropyl)piperazine, 1-imidazolidinoethanamine, imidazolidino-N-propanamine, .alpha.-methyl-l-piperazinethanamine, 2,6-dimethyl-1-piperazinoethanamine, 2-amino-1-(piperazin-1-yl)ethanone, 4-(2-aminoethyl)piperidine, 3-(2-aminoethyl)piperidine, 2-(2-aminoethyl)piperidine, and triazinane,
c) a salt of a Brønsted acid having a pKa of between 2 and −9 selected from the group consisting of calcium nitrate, magnesium bromide, zirconium(IV) chloride, indium chloride, bismuth chloride, copper tetrafluoroborate, calcium oxalate, lithium bromide and magnesium nitrate, and
d) an amine not covered by the part b), wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 50% by weight, and
wherein the ratio of the epoxy groups in the epoxy resin to the sum total of all NH groups in all amines is 0.9:1 to 1.1:1.

19. A composition comprising
a) an epoxy resin selected from bisphenol A diglycidyl ether or bisphenol F diglycidyl ether,
b) a cyclic amine selected from the group consisting of aminoethylpiperazine (AEP, 1-(2-aminoethyl)piperazine), 1-(3-aminopropyl)piperazine, 1-imidazolidinoethanamine, imidazolidino-N-propanamine, .alpha.-methyl-1-piperazinethanamine, 2,6-dimethyl-1-piperazinoethanamine, 2-amino-1-(piperazin-1-yl)ethanone, 4-(2-aminoethyl)piperidine, 3-(2-aminoethyl)piperidine and 2-(2-aminoethyl)piperidine,
c) a salt of a Brønsted acid selected from the group consisting of calcium nitrate, magnesium bromide, zirconium(IV) chloride, indium chloride, bismuth chloride, copper tetrafluoroborate, calcium oxalate, lithium bromide and magnesium nitrate,
d) an amine not covered by the part b), wherein the percentage by weight of the cyclic amine b) based on the total weight of the amines b) and d) is at least 10% by weight, where the ratio of the epoxy groups in the epoxy resin to the sum total of all NH groups in all amines is 0.5:1 to 1.5:1.

Assignees

• Evonik Operations Gmbh

Inventors

• Spyrou Emmanouil
• Fuchsmann Dirk
• Kohlstruk Britta
• Sandkühler Annette

Classifications

• C08G59/28

  containing acyclic nitrogen atoms · CPC title

• C08G59/245

  aromatic · CPC title

• C08G59/68

  characterised by the catalysts used · CPC title

• C08G59/5073

  having two nitrogen atoms in the ring · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title