Polyhemiaminal and polyhexahydrotriazine materials from 1,4 conjugate addition reactions

Patent metadata

Field	Value
Publication number	US-2019177481-A1
Application number	US-201916274809-A
Country	US
Kind code	A1
Filing date	Feb 13, 2019
Priority date	Mar 10, 2015
Publication date	Jun 13, 2019
Grant date	—

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

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 E on 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 moeity.

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

• C08G16/0231

  containing nitrogen · CPC title

• C09D179/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C09D161/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title

• C08G12/08

  aromatic · CPC title

• C08G73/0638

  with at least three nitrogen atoms in the ring · CPC title