Storage stable heat activated quaternary ammonium catalysts for epoxy cure

Patent metadata

Field	Value
Publication number	US-10179832-B2
Application number	US-201615293864-A
Country	US
Kind code	B2
Filing date	Oct 14, 2016
Priority date	Apr 15, 2014
Publication date	Jan 15, 2019
Grant date	Jan 15, 2019

Abstract

The present invention relates to a catalyst composition for curing epoxy group containing compounds comprising a base and a quaternary ammonium salt, of Formula (I):

with R 1 , R 2 , R 3 , R 4 , R 5 , Y, A and X being as defined herein. Also encompassed are adhesive compositions containing said catalyst composition and the use of the catalyst composition.

First claim

What is claimed is:

1. Catalyst composition comprising:
(a) a base; and
(b) a quaternary ammonium salt represented by Formula (I):

wherein
R 1 , R 2 and R 3 are independently from each other selected from the group consisting of linear or branched, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkenyl with 3 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms and substituted or unsubstituted aryl with 6 to 20 carbon atoms; two of R 1 , R 2 and R 3 may combine to form together with the nitrogen atom to which they are attached a substituted or unsubstituted 5-to 10-membered ring;
R 4 is selected from the group consisting of hydrogen, linear or branched, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkenyl with 3 to 20 carbon atoms and substituted or unsubstituted aryl with 6 to 20 carbon atoms;
Y is C or N + , provided that if Y is N + , A is O and R 5 is O − ;
A is O or CR 6 R 7 ;
R 5 is selected from the group consisting of hydrogen, —OH, linear or branched, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkenyl with 3 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, and substituted or unsubstituted aryl with 6 to 20 carbon atoms, or, if Y is N + and A is O, R 5 is O − ;
R 6 and R 7 are independently from each other selected from the group consisting of hydrogen, halogen, nitro, —NRR′, cyano, —C(O)R, —C(O)OR, —(CO)NRR′, —NR′C(O)R, —OC(O)R, linear or branched, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkenyl with 3 to 20 carbon atoms, linear or branched, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, and substituted or unsubstituted aryl with 6 to 20 carbon atoms; or
R 5 and R 6 may combine to form together with the carbon atoms to which they are attached a substituted or unsubstituted 5- to 10-membered cycloalkenyl, heteroalicyclic or heteroaryl ring;
R and R′ are independently selected from H, alkyl with 1 to 20 carbon atoms, alkenyl with 2 to 20 carbon atoms, alkynyl with 2 to 20 carbon atoms, aryl with 6 to 14 carbon atoms, cycloalk(en)yl with 3 to 8 carbon atoms, 5- to 14-membered heteroaryl, comprising 1 to 4 heteroatoms selected from N, O, and S, and 5- to 14-membered heterocycloalk(en)yl, comprising 1 to 4 heteroatoms selected from N, O, and S; and
X is an anion.

2. The catalyst composition according to claim 1 , wherein the quaternary ammonium salt is represented by Formula (II)

wherein R 1 , R 2 , R 3 , R 5 , R 6 , R 7 and X are as defined in claim 1 .

3. The catalyst composition according to claim 1 , wherein the quaternary ammonium salt is represented by Formula (III):

wherein R 1 , R 2 , R 3 , R 5 and X are as defined above.

4. The catalyst composition according to claim 1 , wherein R 1 , R 2 and/or R 3 are methyl or ethyl.

5. The catalyst composition according to claim 1 , wherein the anion X is selected from the group consisting of dicyandiamide-anion, F − , Cl − , Br − , I − ,OH − , HSO 3 − , SO 3 2 − , SO 4 2− , NO 2 − , NO 3 − , PO 4 3− , BF 4 − , SbF 6 − , PF 6 − , ClO 4 − , acetate, citrate, formate, glutarate, lactate, maleate, malonate, oxalate, pyruvate, and tartrate.

6. The catalyst composition according to claim 2 or 3 , wherein
(a) the ammonium compound is a compound represented by Formula (II) wherein R 5 , R 6 and R 7 are hydrogen, or R 5 and R 7 are hydrogen and R 6 is —C(O)OR, with R being C 1 -C 20 alkyl;
(b) the ammonium compound is a compound represented by Formula (III) and R 5 is independently selected from the group consisting of substituted or unsubstituted phenyl or C 1-20 alkoxy; or
(c) the ammonium compound is selected from the group consisting triethylallyl ammonium, triethyl (4-crotonic acid ethyl ester)ammonium, triethyl (2-phenylethan-2-one) ammonium, triethyl (4-nitro-2-phenylethan-2-one) ammonium, triethyl (4-chloro-2-phenylethan-2-one) ammonium, and triethyl (2-acetic acid ethyl ester)ammonium, with X being an anion.

7. The catalyst composition according to claim 1 , wherein the base is a liquid base and is selected from the group consisting of metal alkoxides, aqueous NaOH, KOH, Ca(OH) 2 , Na 2 CO 3 , Na 3 PO 4 and combinations thereof.

8. The catalyst composition according to claim 1 , wherein a combination of base and ammonium compound is selected from the group consisting of: triethylallyl ammonium bromide and titanium tetrabutoxide; triethylallyl ammonium bromide and titanium tetraisopropoxide; triethylallyl ammonium bromide and Na methoxylate; triethyl-(2-phenylethan-2-one) ammonium bromide and titanium tetraisopropoxide; triethyl-(4-chloro-2-phenylethan-2-one) ammonium bromide and titanium tetraisopropoxide; triethylallyl ammonium hexafluoroantimonate and titanium tetraisopropoxide; triethyl-(4-chloro-2-phenylethan-2-one) ammonium hexafluoroantimonate and titanium tetraisopropoxide; triethyl-(4-nitro-2-phenylethan-2-one) ammonium hexafluoroantimonate and titanium tetraisopropoxide; triethyl (2-acetic acid ethyl ester)ammonium bromide and titanium tetraisopropoxide; triethyl (2-acetic acid ethyl ester)ammonium hexafluoroantimonate and titanium tetraisopropoxide; triethyl (4-crotonic acid ethyl ester) ammonium bromide and titanium tetraisopropoxide; and triethyl (4-crotonic acid ethyl ester)ammonium hexafluoroantimonate and titanium tetraisopropoxide.

9. The catalyst composition according to claim 1 , wherein the catalyst composition further comprises a second curing agent.

10. The catalyst composition according to claim 9 , wherein the catalyst composition further comprises an accelerator selected from the group consisting of urea derivatives, imidazole derivatives, and mixtures thereof.

11. A method of curing epoxy resins comprising curing epoxy resins with the catalyst composition according to claim 1 , wherein the epoxy resins are selected from the group consisting of diglycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, bisphenol S, tetramethylbiphenol; diglycidyl ethers of alkylene glycols with 2 to 20 carbon atoms and poly(ethylene oxide) or poly(propylene oxide) glycols; polyglycidyl ethers of phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins (epoxy novalac resins), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins and dicyclopentadiene-substituted phenol resins, and any combination thereof.

12. The method of curing epoxy resins according to claim 11 , wherein the epoxy resins are cured at a temperature from about 50 to about 180° C.

13. Adhesive composition comprising the catalyst composition according to claim 1 and at least one epoxy resin, wherein the at least one epoxy resin is selected from the group consisting of diglycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, bisphenol K, bisphenol M, bisphenol S, tetramethylbiphenol; diglycidyl e

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Holtgrewe Christian
• Walter Pablo
• Bachon Thomas
• Schoenfeld Rainer

Classifications

• C08G59/245

  aromatic · CPC title

• C08G59/4092

  titanium containing compounds · CPC title

• C08G59/686 Primary

  containing nitrogen · CPC title

• C08G59/184

  with amines · CPC title

• C08G59/182

  using pre-adducts of epoxy compounds with curing agents · CPC title