Facile Synthesis of a Hydroxyl-Functionalized Tröger's Base Diamine: A New Building Block for High-Performance Polyimide Gas Separation Membranes

Xiaohua Ma; Mahmoud Abdulhamid; Xiaohe Miao; Ingo Pinnau

doi:10.1021/acs.macromol.7b02301

Facile Synthesis of a Hydroxyl-Functionalized Tröger's Base Diamine: A New Building Block for High-Performance Polyimide Gas Separation Membranes

Xiaohua Ma, Mahmoud Abdulhamid, Xiaohe Miao, Ingo Pinnau^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

82 Scopus citations

Abstract

Two intrinsically microporous polyimides (PIM-PIs) were synthesized by the polycondensation reaction of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3,3′,3′-tetramethylspirobisindane-6,7,6′,7′-tetracarboxylic dianhydride (SBI) with a newly designed o-hydroxyl-functionalized Tröger's base diamine, 1,7-diamino-6H,12H-5,11-methanodibenzo[1,5]diazocine-2,8-diol (HTB). Both amorphous PIM-PIs were soluble in aprotic solvents and showed excellent thermal stability with onset decomposition temperature of ∼380 °C. SBI-HTB displayed a higher CO₂ permeability (466 vs 67 barrer) than 6FDA-HTB but a significantly lower selectivity for CO₂/CH₄ (29 vs 73), H₂/CH₄ (29 vs 181), O₂/N₂ (4.6 vs 6.0), and N₂/CH₄ (1 vs 2.5). 6FDA-HTB displayed the highest gas-pair permselectivity values of all reported OH-functionalized PIM-PIs to date. The high permselectivity of 6FDA-HTB resulted primarily from exceptional diffusion selectivity due to strong size-sieving properties caused by hydrogen bonding between the proton of the hydroxyl group and the nitrogen atoms in the tertiary amine of the Tröger's base (O-H···N).

Original language	English (US)
Pages (from-to)	9569-9576
Number of pages	8
Journal	Macromolecules
Volume	50
Issue number	24
DOIs	https://doi.org/10.1021/acs.macromol.7b02301
State	Published - Dec 26 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

ASJC Scopus subject areas

Materials Chemistry
Polymers and Plastics
Inorganic Chemistry
Organic Chemistry

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10.1021/acs.macromol.7b02301

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title = "Facile Synthesis of a Hydroxyl-Functionalized Tr{\"o}ger's Base Diamine: A New Building Block for High-Performance Polyimide Gas Separation Membranes",

abstract = "Two intrinsically microporous polyimides (PIM-PIs) were synthesized by the polycondensation reaction of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3,3′,3′-tetramethylspirobisindane-6,7,6′,7′-tetracarboxylic dianhydride (SBI) with a newly designed o-hydroxyl-functionalized Tr{\"o}ger's base diamine, 1,7-diamino-6H,12H-5,11-methanodibenzo[1,5]diazocine-2,8-diol (HTB). Both amorphous PIM-PIs were soluble in aprotic solvents and showed excellent thermal stability with onset decomposition temperature of ∼380 °C. SBI-HTB displayed a higher CO2 permeability (466 vs 67 barrer) than 6FDA-HTB but a significantly lower selectivity for CO2/CH4 (29 vs 73), H2/CH4 (29 vs 181), O2/N2 (4.6 vs 6.0), and N2/CH4 (1 vs 2.5). 6FDA-HTB displayed the highest gas-pair permselectivity values of all reported OH-functionalized PIM-PIs to date. The high permselectivity of 6FDA-HTB resulted primarily from exceptional diffusion selectivity due to strong size-sieving properties caused by hydrogen bonding between the proton of the hydroxyl group and the nitrogen atoms in the tertiary amine of the Tr{\"o}ger's base (O-H···N).",

author = "Xiaohua Ma and Mahmoud Abdulhamid and Xiaohe Miao and Ingo Pinnau",

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T2 - A New Building Block for High-Performance Polyimide Gas Separation Membranes

AU - Ma, Xiaohua

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AU - Miao, Xiaohe

AU - Pinnau, Ingo

PY - 2017/12/26

Y1 - 2017/12/26

N2 - Two intrinsically microporous polyimides (PIM-PIs) were synthesized by the polycondensation reaction of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3,3′,3′-tetramethylspirobisindane-6,7,6′,7′-tetracarboxylic dianhydride (SBI) with a newly designed o-hydroxyl-functionalized Tröger's base diamine, 1,7-diamino-6H,12H-5,11-methanodibenzo[1,5]diazocine-2,8-diol (HTB). Both amorphous PIM-PIs were soluble in aprotic solvents and showed excellent thermal stability with onset decomposition temperature of ∼380 °C. SBI-HTB displayed a higher CO2 permeability (466 vs 67 barrer) than 6FDA-HTB but a significantly lower selectivity for CO2/CH4 (29 vs 73), H2/CH4 (29 vs 181), O2/N2 (4.6 vs 6.0), and N2/CH4 (1 vs 2.5). 6FDA-HTB displayed the highest gas-pair permselectivity values of all reported OH-functionalized PIM-PIs to date. The high permselectivity of 6FDA-HTB resulted primarily from exceptional diffusion selectivity due to strong size-sieving properties caused by hydrogen bonding between the proton of the hydroxyl group and the nitrogen atoms in the tertiary amine of the Tröger's base (O-H···N).

AB - Two intrinsically microporous polyimides (PIM-PIs) were synthesized by the polycondensation reaction of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3,3′,3′-tetramethylspirobisindane-6,7,6′,7′-tetracarboxylic dianhydride (SBI) with a newly designed o-hydroxyl-functionalized Tröger's base diamine, 1,7-diamino-6H,12H-5,11-methanodibenzo[1,5]diazocine-2,8-diol (HTB). Both amorphous PIM-PIs were soluble in aprotic solvents and showed excellent thermal stability with onset decomposition temperature of ∼380 °C. SBI-HTB displayed a higher CO2 permeability (466 vs 67 barrer) than 6FDA-HTB but a significantly lower selectivity for CO2/CH4 (29 vs 73), H2/CH4 (29 vs 181), O2/N2 (4.6 vs 6.0), and N2/CH4 (1 vs 2.5). 6FDA-HTB displayed the highest gas-pair permselectivity values of all reported OH-functionalized PIM-PIs to date. The high permselectivity of 6FDA-HTB resulted primarily from exceptional diffusion selectivity due to strong size-sieving properties caused by hydrogen bonding between the proton of the hydroxyl group and the nitrogen atoms in the tertiary amine of the Tröger's base (O-H···N).

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ER -

Facile Synthesis of a Hydroxyl-Functionalized Tröger's Base Diamine: A New Building Block for High-Performance Polyimide Gas Separation Membranes

Abstract

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