Porous/nanoporous PHT

Patent metadata

Field	Value
Publication number	US-11098159-B2
Application number	US-201916355075-A
Country	US
Kind code	B2
Filing date	Mar 15, 2019
Priority date	Oct 16, 2014
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

In an embodiment, a polymeric material includes a plurality of hemiaminal units bonded together by a first linkage and a second linkage, wherein the first linkage is thermally stable and resistant to bases and the second linkage is thermally degradable and degradable by a base. In another embodiment, a method of forming nanoporous materials includes forming a polymer network with a chemically removable portion. The chemically removable portion may be polycarbonate polymer that is removable on application of heat or exposure to a base, or a polyhexahydrotriazine (PHT) or polyhemiaminal (PHA) polymer that is removable on exposure to an acid. Removing any portion of the polymer results in formation of nanoscopic pores as polymer chains are decomposed, leaving pores in the polymer matrix.

First claim

What is claimed is:

1. A polymeric material comprising a plurality of hemiaminal units bonded together by a first linkage and a second linkage, wherein the first linkage is thermally stable and resistant to bases and the second linkage is thermally degradable and degradable by a base.

2. The polymeric material of claim 1 , wherein the second linkage is a polycarbonate or polyester linkage.

3. The polymeric material of claim 2 , wherein the first linkage is a dianiline linkage.

4. The polymeric material of claim 1 , wherein each hemiaminal unit has the general structure

the first linkage has the general structure
K′ *) y′ ,

wherein y′ is 2 or 3, and K′ is a divalent or trivalent bridging group, and the second linkage has the general structure

wherein R is a substituted or unsubstituted alkyl, aryl, or alkoxy group having 1 to 50 carbon atoms, R′ is a substituted or unsubstituted alkyl or aryl group having 1 to 50 carbon atoms, and n is 1 to 1,000.

5. The polymeric material of claim 4 , wherein R includes an aromatic diamine.

6. The polymeric material of claim 5 , wherein the aromatic diamine is paraphenylenedianiline.

7. The polymeric material of claim 4 , wherein the second linkage has the structure

wherein R″ is a hydrocarbyl chain, a low molecular weight polyolefin polymer, a polyester, or a polymer unit having pore formation properties similar to the main chain of the second linkage.

8. The polymeric material of claim 4 , wherein each divalent bridging group has the structure

wherein L′ is a divalent linking group selected from the group consisting of —O—, —S—, —N(R″′)—, —N(H)—, —R″″—, and a combination thereof, wherein R″′ and R″″ independently comprise at least 1 carbon, and each starred bond of each divalent bridging group is covalently bonded to a respective starred bond of a hemiaminal unit.

9. The polymeric material of claim 4 , wherein each divalent bridging group is selected from the group consisting of

and a combination thereof.

10. The polymeric material of claim 4 , wherein each trivalent bridging group has a structure selected from the group consisting of

and a combination thereof.

11. A polymeric material comprising a plurality of hemiaminal units bonded together by a first linkage and a second linkage, wherein the first linkage is thermally stable and resistant to bases and the second linkage is thermally degradable and degradable by a base, wherein each hemiaminal unit has the general structure

the first linkage has the general structure
K′ *) y′ ,

wherein y′ is 2 or 3, and K′ is a divalent bridging group, having the structure

wherein L′ is a divalent linking group selected from the group consisting of —O—, —S—, —N(R″′K—N(HK—R″″—, and a combination thereof, wherein R″″ and R″″ are independently selected from the group consisting of methyl, ethyl, propyl, iospropyl, phenyl, and combinations thereof, and each started bond of each divalent bridging group is covalently bonded to a respective starred bond of a hemiaminal unit, and the second linkage has the general structure

wherein R is a substituted or unsubstituted alkyl, aryl, or alkoxy group having 1 to 50 carbon atoms, R′ is a substituted or unsubstituted alkyl or aryl group having 1 to 50 carbon atoms, and n is 1 to 1,000.

12. The polymeric material of claim 11 , wherein the first linkage is a dianiline linkage.

13. The polymeric material of claim 11 , wherein R includes an aromatic diamine.

14. The polymeric material of claim 13 , wherein the aromatic diamine is paraphenylenedianiline.

15. A polymeric material comprising a plurality of hemiaminal units bonded together by a first linkage and a second linkage, wherein the first linkage is thermally stable and resistant to bases and the second linkage is thermally degradable and degradable by a base, wherein each hemiaminal unit has the general structure

the first linkage is a dianiline linkage having the general structure
K′ *) y′ ,

wherein y′ is 2 or 3, and K′ is a divalent or trivalent bridging group, and the second linkage polyacetals, polyaminals, polythioacetals, polyphosphates, and aliphatic polysulfones.

Assignees

• IBM

Inventors

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

Classifications

• C08J2201/042

  Elimination of an organic solid phase · CPC title

• C08J2205/042

  Nanopores, i.e. the average diameter being smaller than 0,1 micrometer · CPC title

• C08G73/065

  Preparatory processes · CPC title

• C08G73/0638

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

• C08J9/26

  by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out · CPC title