Intrinsically microporous ladder-type Tröger's base polymers

Patent metadata

Field	Value
Publication number	US-11850557-B2
Application number	US-201917273950-A
Country	US
Kind code	B2
Filing date	Sep 17, 2019
Priority date	Sep 17, 2018
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

Embodiments of the present disclosure feature an intrinsically microporous ladder-type Tröger's base polymer including a repeat unit based on a combination of W-shaped CANAL-type and V-shaped Tröger's base building blocks, methods of making the intrinsically microporous ladder-type Tröger's base polymer, and methods of using the intrinsically microporous ladder-type Tröger's base polymer to separate a chemical species from a fluid composition including a mixture of chemical species. Embodiments of the present disclosure further include ladder-type diamine monomers for reacting to form a Tröger's base in situ, and methods of making the ladder-type diamine monomers using catalytic arene-norbornene annulation.

First claim

What is claimed is:

1. A composition comprising an intrinsically microporous ladder-type Tröger's base polymer comprising a repeat unit represented by formula (I):

wherein each Ar is independently selected from an unsubstituted or substituted aryl group; X is a carbon or heteroatom bridging moiety selected from —[O]—, —[S]—, —[B(O)R a ]—, —[NR a ]—, —[P(O)R a ]—, —[(PO)(O)R a ]—, —[CO]—, —[—CR a R b ]—, —[C(O)R a (O)R b ]—, or —[Si(O)R a (O)R b ]—, and R a and R b are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and heterocyclic groups; R 1 and R 2 are independently selected from the group consisting of hydrogen, linear unsubstituted and substituted alkyl groups, branched unsubstituted and substituted alkyl groups, unsubstituted and substituted alkoxy groups, unsubstituted and substituted aryl groups, heterocyclic groups, halogen groups, —CHO, groups having an —O— moiety, groups having an —O(CO)— moiety, groups having an —O(CO)O— moiety, groups having an —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO 2 , groups having a —N< moiety, groups having a —P< moiety, groups having a —(PO)< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety and groups having a —Si═ moiety; and n is an integer greater than 1.

2. The composition of claim 1 , wherein the intrinsically microporous ladder-type Tröger's base polymer has a BET surface area greater than about 600 m 2 g −1 .

3. The composition of claim 1 , wherein X is a carbon, R 1 and R 2 are hydrogen, and each Ar is independently selected from the group consisting of:

wherein R 3 , R 4 , and R 5 are each independently selected from the group consisting of linear unsubstituted or substituted alkyl groups, branched unsubstituted or substituted alkyl groups, unsubstituted or substituted alkoxy groups, unsubstituted or substituted unsaturated aliphatic groups, unsubstituted or substituted cycloalkyl groups, unsubstituted or substituted aryl groups, unsubstituted or substituted heterocyclic groups, —CHO, groups having a —O— moiety, groups having a —O(CO)— moiety, groups having a —O(CO)O— moiety), groups having a —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO 2 , groups having a —N< moiety, groups having a —P< moiety, groups having a —PO< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety, and groups having a —Si≡ moiety.

4. The composition of claim 1 , wherein n is greater than 5.

5. The composition of claim 1 , wherein the repeat unit has the following structure:

6. The composition of claim 1 , wherein the repeat unit has the following structure:

7. The composition of claim 1 , wherein the composition is configured as a flat sheet membrane, a rolled flat sheet membrane, a supported membrane, a cylinder, a tube, a capillary, a hollow fiber, or a powder.

8. The composition of claim 7 , wherein the composition has a thickness of about 1 to 30 μm.

9. The composition of claim 1 , wherein the intrinsically microporous ladder-type Tröger's base polymer has a bimodal pore size distribution comprising ultramicropores.

10. A method of synthesizing an intrinsically microporous ladder-type Tröger's base polymer comprising:
(a) forming a ladder-type diamine monomer by catalytic arene-norbornene annulation (CANAL) polymerization of a halogenated arylamine and norbornadiene or a derivative thereof, wherein the molar ratio of the halogenated arylamine to norbornadiene or the derivative thereof is 2:1, or
(a1) forming a first intermediate ladder-type compound by CANAL polymerization of a halogenated arene and norbornadiene or a derivative thereof, wherein the ratio of the halogenated arene to norbornadiene or the derivative thereof is 2:1; and
(a2) nitrating the first intermediate ladder-type compound to form an intermediate ladder-type dinitro compound; and
(a3) reducing the two nitro groups of the intermediate ladder-type dinitro compound to form a ladder-type diamine monomer; and
(b) reacting at least two of the ladder-type diamine monomers to form the intrinsically microporous ladder-type Tröger's base polymer comprising a repeat unit represented by formula (I):

wherein each Ar is independently selected from an unsubstituted or substituted aryl group; X is a carbon or heteroatom bridging moiety selected from —[O]—, —[S]—, —[B(O)R a ]—, —[NR a ]—, —[P(O)R a ]—, —[(PO)(O)R a ]—, —[CO]—, —[—CR a R b ]—, —[C(O)R a (O)R b ]—, or —[Si(O)R a (O)R b ]—, and R a and R b are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and heterocyclic groups; R 1 and R 2 are independently selected from the group consisting of hydrogen, linear unsubstituted and substituted alkyl groups, branched unsubstituted and substituted alkyl groups, unsubstituted and substituted alkoxy groups, unsubstituted and substituted aryl groups, heterocyclic groups, halogen groups, —CHO, groups having an —O— moiety, groups having an —O(CO)— moiety, groups having an —O(CO)O— moiety, groups having an —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO 2 , groups having a —N< moiety, groups having a —P< moiety, groups having a —(PO)< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety and groups having a —Si═ moiety; and n is an integer greater than 1.

11. The method of claim 10 , comprising performing step (a), wherein the halogenated arylamine has the following structure:

wherein Y is a chloro, bromo, or iodo group; and R 3 is selected from the group consisting of linear unsubstituted or substituted alkyl groups, branched unsubstituted or substituted alkyl groups, unsubstituted or substituted unsaturated aliphatic groups, unsubstituted or substituted cycloalkyl groups, unsubstituted or substituted aryl groups, unsubstituted or substituted heterocyclic groups, unsubstituted or substituted alkoxy groups, —CHO, groups having a —O— moiety, groups having a —O(CO)— moiety, groups having a —O(CO)O— moiety), groups having a —O(CO)N< moiety, groups having a —S— moiety, groups having a —B< moiety, —NO 2 , groups having a —N< moiety, groups having a —P< moiety, groups having a —PO< moiety, groups having a —(CO)— moiety, groups having a —(CO)O— moiety, groups having a —(CO)N< moiety, and groups having a —Si≡ moiety.

12. The method of claim 10 , comprising performing steps (a1)-(a3), wherein the halogenated arene has the following structure:

wherein Y is a chloro, bromo, or iodo group; and R 4 and R 5 are independently selected from the group consisting of linear unsubstituted or substituted alkyl groups, branched unsubstituted or substituted alkyl groups, unsubstituted or substituted unsaturated aliphatic groups, unsubstituted or substituted cycloalkyl groups, unsubstituted or substituted aryl groups, unsubstituted or substituted heterocyclic groups, li

Assignees

• Univ King Abdullah Sci & Tech
• Univ Leland Stanford Junior

Inventors

• Ma Xiaohua
• Pinnau Ingo
• Lai Holden W H
• Xia Yan

Classifications

• B01D2325/0283

  Pore size · CPC title

• B01D71/44

  Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42 · CPC title

• B01D71/62 Primary

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain · CPC title

• B01D53/228

  characterised by specific membranes · CPC title

• B01D69/02

  characterised by their properties · CPC title