Soluble, processable polyhemiaminals and polyhexahydrotriazines

Patent metadata

Field	Value
Publication number	US-9512332-B2
Application number	US-201414317468-A
Country	US
Kind code	B2
Filing date	Jun 27, 2014
Priority date	Jun 27, 2014
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

Polyhexahydrotriazine (PHT) and polyhemiaminal (PHA) materials incorporating divalent or trivalent bridging groups tend to form highly cross-linked polymers. While highly cross-linked polymers have certain advantageous with respect to stability and various physical characteristics, they are difficult to process once formed. PHA and PHT materials incorporating a plurality of trivalent PHA/PHT groups, a plurality of divalent bridging groups, and a plurality of monovalent end groups are disclosed. According to an embodiment, the cross-link density and molecular weight can be controlled by the inclusion of the end groups. Lower cross-link density and molecular weight give PHA and PHT materials improved characteristics with respect to film and fiber formation methods. A method of coating a component or substrate with a polymer is also disclosed. Embodiments of the method can be used to form either a PHA or PHT film on a substrate, such as microelectronic component.

First claim

What is claimed is:

1. A polyhexahydrotriazine (PHT), comprising: a plurality of trivalent hexahydrotriazine groups having the structure:

a plurality of divalent and/or trivalent bridging groups having the structure:
K ′ *) y′ ,

wherein K′ comprises at least one 6-carbon aromatic ring; and a plurality of monovalent end groups having the structure:
K″—*,

wherein K″ comprises at least one carbon atom, and each nitrogen in the plurality of trivalent hexahydrotriazine groups is directly covalently linked to a starred bond of one of the plurality of bridging groups or a starred bond of one of the plurality of end groups, wherein a ratio of bridging groups to end groups in the PHT is less than 3:1 and greater than or equal to 1:2.

2. The PHT of claim 1 , wherein the PHT has a number average molecular weight (Mn) of about 1000 to about 20000.

3. The PHT of claim 1 , wherein each of the bridging groups has the structure:

4. The PHT of claim 3 , wherein each of the end groups has the structure:

5. The PHT of claim 1 , wherein each of the bridging groups is:

wherein L′ is a divalent linking group selected from the group consisting of O, S, N(R′), N(H), R″, P(R″′), wherein R′, R″, and R″′ independently comprise at least 1 carbon atom.

6. The PHT of claim 1 , wherein each of the bridging groups is:

7. The PHT of claim 1 , wherein at least one bridging group in the plurality of bridging groups is a trivalent bridging group.

8. The PHT of claim 1 , wherein the ratio of bridging groups to end groups is 2:1.

9. The PHT of claim 1 , wherein at least one end group is selected from the group consisting of:

and combinations thereof, wherein W is selected from the group consisting of:
H, NH(R 1 ), N(R 2 )(R 3 ), OH, O(R 4 ), S(R 5 ), P(R 6 ), R 7 , CF 3 , and combinations thereof, wherein R 1 -R 7 each comprise at least 1 carbon atom, and each of R 1 -R 7 may be the same or different.

10. A polyhemiaminal (PHA), comprising:
a plurality of trivalent hemiaminal groups having the structure:

a plurality of divalent and/or trivalent bridging groups having the structure:
K ′ *) y′ ,

wherein K′ comprises at least one 6-carbon aromatic ring; and
a plurality of monovalent end groups having the structure:
K″—*,

wherein K″ comprises at least one carbon atom, and each nitrogen in the plurality of trivalent hemiaminal groups is directly covalently linked to a starred bond of one of the plurality of bridging groups or a starred bond of one of the plurality of end groups, wherein a ratio of bridging groups to end groups in the PHA is less than 3:1 and greater than or equal to 1:2.

11. The PHA of claim 10 , wherein
each of the bridging groups has the structure:

 and
each of the end groups has the structure:

12. The PHA of claim 10 , wherein each of the bridging groups is:

wherein L′ is a divalent linking group selected from the group consisting of O, S, N(R′), N(H), R″, P(R″′), wherein R′, R″, and R″′ independently comprise at least 1 carbon atom.

13. The PHA of claim 10 , wherein at least one end group is selected from the group consisting of:

and combinations thereof, wherein W is selected from the group consisting of:
H, NH(R 1 ), N(R 2 )(R 3 ), OH, O(R 4 ), S(R 5 ), P(R 6 ), R 7 , CF 3 , and combinations thereof, wherein R 1 -R 7 each comprise at least 1 carbon atom, and each of R 1 -R 7 may be the same or different.

14. The PHA of claim 10 , wherein a glass transition temperature of the PHA is below 185° C.

15. The PHA of claim 10 , wherein the ratio of bridging groups to end groups is 2:1.

16. A polyhexahydrotriazine (PHT), comprising: a plurality of trivalent hexahydrotriazine groups having the structure:

a plurality of bridging groups having the structure:

 and
a plurality of monovalent end groups having the structure:
K″—*,

wherein K″ comprises at least one carbon atom, and each nitrogen in the plurality of trivalent hexahydrotriazine groups is directly covalently linked to a starred bond of one of the plurality of bridging groups or a starred bond of one of the plurality of end groups.

17. The PHT of claim 16 , wherein the PHT has a number average molecular weight (Mn) of about 1000 to about 20000.

18. The PHT of claim 16 , wherein a ratio of bridging groups to end groups is 2:1.

19. The PHT of claim 16 , wherein each of the end groups has the structure:

20. The PHT of claim 16 , wherein at least one end group is selected from the group consisting of:

and combinations thereof, wherein W′ is selected from the group consisting of:
H, NH(R 1 ), N(R 2 )(R 3 ), OH, O(R 4 ), S(R 5 ), P(R 6 ), R 7 , CF 3 , and combinations thereof,
wherein R 1 -R 7 each comprise at least 1 carbon atom, and each of R 1 -R 7 may be the same or different.

Assignees

• IBM
• Int Busuiness Machines Corp

Inventors

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

Classifications

• C08G73/0273

  Polyamines containing heterocyclic moieties in the main chain · CPC title

• C08G73/0638

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

• C09D161/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title

• B05D1/30

  performed by gravity only, i.e. flow coating · CPC title

• C08G12/08

  aromatic · CPC title