Polyhemiaminal and polyhexahydrotriazine materials from 1,4 conjugate addition reactions

Patent metadata

Field	Value
Publication number	US-11041048-B2
Application number	US-201916274809-A
Country	US
Kind code	B2
Filing date	Feb 13, 2019
Priority date	Mar 10, 2015
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

Polyhemiaminal (PHA) and polyhexahydrotriazine (PHT) materials are modified by 1,4 conjugate addition chemical reactions to produce a variety of molecular architectures comprising pendant groups and bridging segments. The materials are formed by a method that includes heating a mixture comprising solvent(s), paraformaldehyde, aromatic amine groups, aliphatic amine Michael donors, and Michael acceptors, such as acrylates. The reaction mixtures may be used to prepare polymer pre-impregnated materials and composites containing PHT matrix resin.

First claim

The invention claimed is:

1. A polymeric material, comprising:
a first trivalent hemiaminal group having the structure:

and
a first, second, and third phenyl group each having the structure:

wherein:
each wavy bond site of the first trivalent hemiaminal group is covalently attached to a respective one of the first, second, and third phenyl groups at a wavy bond site of the respective one of the first, second, and third phenyl groups;
at least one of B, C, or D on at least one of the first, second, or third phenyl groups has the structure:

and B, C, and D are hydrogen (H) otherwise;
at least one of R1 and R2 has the structure:

and
R3 includes at least one carbon.

2. The polymeric material of claim 1 , wherein A, B, D, and Eon each of the first, second, and third phenyl groups are hydrogens (H).

3. The polymeric material of claim 2 , wherein at least one of the first, second, and third phenyl groups has a C group having the structure:

wherein R1 and R2 both have the structure:

4. The polymeric material of claim 3 , wherein R3 in each instance is:
—(CH 2 ) 11 CH 3 .

5. The polymeric material of claim 3 , wherein R3 in each instance is:
—(CH 2 )N(CH 3 ) 2 (H 3 C + Cl − ).

6. The polymeric material of claim 1 , wherein R1 in each instance is hydrogen (H).

7. The polymeric material of claim 6 , wherein R3 in at least one instance has the structure:

wherein R4 comprises a methylene unit, and R5 comprises a second trivalent hemiaminal group.

8. The polymeric material of claim 7 , wherein R4 is a polymeric moiety.

9. The polymeric material of claim 8 , wherein R4 comprises a poly(ether) segment.

10. The polymeric material of claim 8 , wherein R4 comprises a poly(butadiene) segment.

11. The polymeric material of claim 8 , wherein R4 comprises a poly(amino ester) segment.

12. The polymeric material of claim 1 , wherein
A, C, and E are hydrogen (H) on at least one of the first, second, and third phenyl groups, and
B and D, on at least one of the first, second, and third phenyl groups, each have the structure:

13. The polymeric material of claim 12 , wherein R2 in each instance is hydrogen (H).

14. The polymeric material of claim 13 , wherein R3 in each instance comprises a poly(butadiene) segment.

15. The polymeric material of claim 13 , wherein R3 in each instance comprises a poly(amino ester) segment.

16. The polymeric material of claim 1 , wherein at least one instance of R3 is:
—(CH 2 ) 11 CH 3 .

17. The polymeric material of claim 1 , wherein at least one instance of R3 is:
—(CH 2 )N(CH 3 ) 2 (H 3 C + Cl − ).

18. A polymeric material, comprising:
a first trivalent hemiaminal group having the structure:

and
a first, second, and third phenyl group each having the structure:

wherein:
each wavy bond site of the first trivalent hemiaminal group is covalently attached to a respective one of the first, second, and third phenyl groups at a wavy bond site of the respective one of the first, second, and third phenyl groups;
at least one of B, C, or D on at least one of the first, second, or third phenyl groups has the structure:

and B, C, and D are hydrogen (H) otherwise;
R1 in at least one instance is hydrogen (H);
R2 has the structure:

and
R3 includes at least one carbon.

19. The polymeric material of claim 18 , wherein
R3 in each instance is —(CH 2 ) 11 CH 3 ; or
R1 in each instance is hydrogen (H) and R3 in at least one instance has the structure:

wherein R4 comprises a methylene unit, and R5 comprises a second trivalent hemiaminal group.

20. A polymeric material, comprising:
a first trivalent hemiaminal group having the structure:

and
a first, second, and third phenyl group each having the structure:

wherein:
each wavy bond site of the first trivalent hemiaminal group is covalently attached to a respective one of the first, second, and third phenyl groups at a wavy bond site of the respective one of the first, second, and third phenyl groups;
at least one of B, C, or D on at least one of the first, second, or third phenyl groups has the structure:

and B, C, and D are hydrogen (H) otherwise;
R1 in each instance is hydrogen (H);
R2 has the structure:

and
R3 in at least one instance has the structure:

wherein R4 comprises a methylene unit, and R5 comprises a second trivalent hemiaminal group.

Assignees

• IBM

Inventors

• Boday Dylan J
• Fevre Mareva
• Garcia Jeannette M
• Hedrick James L
• Wojtecki Rudy J

Classifications

• C08G73/0273 Primary

  Polyamines containing heterocyclic moieties in the main chain · CPC title

• C08F12/28

  Amines · CPC title

• C08F8/32

  by reaction with amines · CPC title

• C09D161/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title

• C08G12/08

  aromatic · CPC title