Soluble, processable polyhemiaminals and polyhexahydrotriazines

Patent metadata

Field	Value
Publication number	US-9598608-B2
Application number	US-201414571130-A
Country	US
Kind code	B2
Filing date	Dec 15, 2014
Priority date	Jun 27, 2014
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

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 method of coating a component with a polymer, the method comprising: forming a polyhemiaminal (PHA) film on a substrate, the PHA film comprising:
a plurality of trivalent hemiaminal groups having the structure:

a plurality of divalent and/or trivalent bridging groups having the structure:

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 film is less than 3:1 and greater than or equal to 1:2; and
heating the PHA film to a first temperature above a glass transition temperature of the PHA film.

2. The method of claim 1 , further comprising:
molding the PHA film while at or above the first temperature.

3. The method of claim 1 , further comprising:
heating the PHA film to a second temperature that is above the first temperature to convert the PHA film to a polyhexahydrotriazine (PHT).

4. The method of claim 1 , wherein the bridging group has the structure:

and
the end group has the structure:

5. The method of claim 1 , wherein the substrate includes a microelectronic component.

6. The method of claim 1 , wherein the PHA film is formed on the substrate by spin casting.

7. The method of claim 1 , wherein the bridging group 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.

8. The method 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 , 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.

9. The method of claim 1 , wherein a glass transition temperature of the PHA film is below 185° C.

10. A method of forming a polymeric coating, the method comprising: forming a polyhemiaminal (PHA) material comprising:
a plurality of trivalent hemiaminal groups having the structure:

a plurality of divalent and/or trivalent bridging groups having the structure:

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;
heating the PHA material to a first temperature above a glass transition temperature of the PHA material; and
molding the PHA material while at or above the first temperature.

11. The method of claim 10 , wherein a ratio of bridging groups to end groups in the PHA material is less than 3:1 and greater than or equal to 1:2.

12. The method of claim 10 , further comprising:
heating the PHA material to a second temperature that is above the first temperature to convert the PHA material to a polyhexahydrotriazine (PHT) material.

13. The method of claim 10 , wherein the bridging group has the structure:

and
the end group has the structure:

14. The method of claim 10 , wherein the PHA material is formed on a substrate.

15. The method of claim 14 , wherein a microelectronic component is disposed on the substrate.

16. The method of claim 14 , wherein the PHA material is spin cast onto the substrate.

17. The method of claim 10 , wherein the bridging group 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.

18. The method 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.

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

20. A method of coating a component with a polymer, the method comprising: forming a polyhemiaminal (PHA) film on a substrate, the PHA film comprising:
a plurality of trivalent hemiaminal groups having the structure:

a plurality of bridging groups having the structure:

and
a plurality of end groups having the structure:

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; and heating the PHA film to a first temperature above a glass transition temperature of the PHA film.

Assignees

• IBM

Inventors

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

Classifications

• C08G73/0638

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

• B05D1/30

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

• C09D161/22

  of aldehydes with acyclic or carbocyclic compounds · CPC title

• C09D179/04 Primary

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

• C08G12/08

  aromatic · CPC title