Composition including a polythiol, a polyepoxide, a photolatent base, and an amine and methods relating to the composition

Patent metadata

Field	Value
Publication number	US-11090681-B2
Application number	US-201716347417-A
Country	US
Kind code	B2
Filing date	Nov 2, 2017
Priority date	Nov 3, 2016
Publication date	Aug 17, 2021
Grant date	Aug 17, 2021

Abstract

A composition including a polythiol having more than one thiol groups, a polyepoxide having more than one epoxide group, a photolatent base catalyst that can photochemically generate a first amine, and a second amine phase-separated within the composition. A polymer network preparable from the composition, and a method for making the polymer network are also disclosed.

First claim

What is claimed is:

1. A composition comprising:
a polythiol comprising more than one thiol group,
a polyepoxide comprising more than one epoxide group,
a photolatent base, wherein the photolatent base can photochemically generate a first amine, and
a second amine that is phase-separated within the composition.

2. The composition of claim 1 , wherein the first amine and the second amine are different amines.

3. The composition of claim 1 , further comprising a third amine that is not phase-separated.

4. The composition of claim 3 , wherein the first amine, the second amine, and the third amine are different amines.

5. The composition of claim 1 , wherein the first amine and second amine are each independently a tertiary amine, an amidine, or a guanidine.

6. The composition of claim 1 , wherein at least one of the first amine or second amine comprises at least one of tetramethylguanidine, diphenylguanidine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, or 1,5-diazabicyclo[4.3.0]non-5-ene.

7. The composition of claim 1 , wherein the photolatent base is represented by formula:
N(R 7 )(R 6 )—CH(R 5 )—N(R 4 )—C(R 1 )(R 2 )(R 3 ),

wherein
R 1 is selected from phenyl, naphthyl, phenanthryl, anthryl, pyrenyl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, anthraquinonyl, dibenzofuryl, chromenyl, xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, terphenyl, stilbenyl, fluorenyl, phenoxazinyl, and combinations thereof, wherein any of these are unsubstituted or substituted by one or more alkyl, alkenyl, alkynyl, haloalkyl, —NO 2 , —NR 10 R 11 , —CN, —OR 12 , —SR 12 , —C(O)R 13 , —C(O)OR 14 , or halogen groups, a radical of the formula N(R 7 )(R 6 )—CH(R 5 )—N(R 4 )—C(R 2 )(R 3 )—, or a combination thereof;
R 2 and R 3 each are independently selected from hydrogen, alkyl, or phenyl that is unsubstituted or is substituted by one or more times by alkyl, CN, —OR 12 , —SR 12 , halogen, or haloalkyl;
R 5 is alkyl or —NR 8 R 9 ;
R 4 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently hydrogen or alkyl; or
R 4 and R 6 together form a C 2 -C 6 alkylene bridge that is unsubstituted or substituted by one or more alkyl groups having up to four carbon atoms; or
R 5 and R 7 , independently of R 4 and R 6 , together form a C 2 -C 6 alkylene bridge that is unsubstituted or is substituted by one or more alkyl groups having up to four carbon atoms; or
if R 5 is —NR 8 R 9 , R 7 and R 9 together form a C 2 -C 6 alkylene bridge that is unsubstituted or substituted by one or more alkyl groups having up to four carbon atoms.

8. The composition of claim 1 , wherein the second amine is a solid within the composition.

9. The composition of claim 1 , wherein the second amine is segregated within a solid within the composition.

10. The composition of claim 1 , wherein the polythiol is monomeric.

11. The composition of claim 1 , wherein the polythiol is an oligomeric or polymeric polythioether or polysulfide.

12. The composition of claim 1 , wherein the polyepoxide is an oligomeric or polymeric epoxy resin.

13. The composition of claim 1 , further comprising a photosensitizer.

14. A polymer network preparable from the composition of claim 1 , wherein at least some of the thiol groups and epoxide groups have reacted to form thioether groups and hydroxyl groups.

15. A method of making a polymer network, the method comprising:
providing the composition of claim 1 ;
and at least one of:
exposing the composition to light to generate the first amine to at least partially cure the composition; or
allowing the composition to achieve a temperature sufficient for the second amine to at least partially cure the composition.

16. The composition of claim 11 , wherein the polythiol is an oligomeric or polymeric polythioether prepared from components comprising a dithiol and a diene or divinyl ether.

17. The composition of claim 9 , wherein the solid is a semi-crystalline polymer.

18. The composition of claim 3 , wherein at least one of the first amine or second amine has a higher conjugate acid pKa than the third amine.

19. The composition of claim 3 , wherein the third amine is 1,4-diazabicyclo[2.2.2]octane.

20. The composition of claim 1 , further comprising filler.

Assignees

• 3M Innovative Properties Co

Inventors

• Zook Jonathan D
• Ye Sheng
• Townsend Erik M
• Swan Michael D
• Moser William H

Classifications

• C08K5/5415

  containing at least one Si—O bond · CPC title

• B05D3/06

  by exposure to radiation (B05D3/02 takes precedence {; plasma treatment B05D3/141}) · CPC title

• C08G59/56

  together with other curing agents · CPC title

• C09D5/002 Primary

  Priming paints (C09D5/08 takes precedence) · CPC title

• B05D3/107

  Post-treatment of applied coatings · CPC title