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Preparation and Gas Separation Properties of Thermally Rearranged Membranes Containing Spirobisindane Structures
- Acta Polymerica Sinica Vol. 56, Issue 2, Pages: 350-360(2025)
- 作者机构：
1.辽宁科技大学化工学院 鞍山 114051
2.大连理工大学化工学院 精细化工国家重点实验室 碳素实验室 大连 116024
- 作者简介：
Yun-hua Lu, E-mail: luyunhua@ustl.edu.cn
Guo-yong Xiao, E-mail: xiaoguoyong@ustl.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2024.24176
CLC：- CSTR：32057.14.GFZXB.2024.7300
Published：20 February 2025，
Published Online：04 November 2024，
Received：23 July 2024，
Accepted：2024-09-25
- 稿件说明：
移动端阅览
XIAN-ZHI WANG, YUN-HUA LU, GUO-YONG XIAO, MENG-JIE HOU, LIN LI, TONG-HUA WANG. Preparation and Gas Separation Properties of Thermally Rearranged Membranes Containing Spirobisindane Structures. [J]. Acta polymerica sinica, 2025, 56(2): 350-360.
XIAN-ZHI WANG, YUN-HUA LU, GUO-YONG XIAO, MENG-JIE HOU, LIN LI, TONG-HUA WANG. Preparation and Gas Separation Properties of Thermally Rearranged Membranes Containing Spirobisindane Structures. [J]. Acta polymerica sinica, 2025, 56(2): 350-360. DOI： 10.11777/j.issn1000-3304.2024.24176. CSTR： 32057.14.GFZXB.2024.7300.
摘要
合成了一种新型二胺单体3
3
3'
3'-四甲基-6
6'-双(3-氨基-4-羟基苯氧基)-1
1'-螺旋双茚满(TBAHS)，然后分别与等摩尔比的6种二酐单体聚合，涂膜后经300 ℃热酰亚胺化制备出一系列含羟基的聚醚酰亚胺(PEI)膜，再经450 ℃热处理得到相应的热重排(TR)膜. 测试结果表明：由于螺旋双茚满结构的引入，6种PEI膜均表现出优异的力学性能和热性能，玻璃化转变温度在317~352 ℃. 热重排后，TR膜的力学性能显著下降，但气体渗透性能大幅度提高，尤其是基于4
4'-(六氟异丙烯)二酞酸酐(6FDA)的TR(TBAHS-6FDA)膜对CO
2
、H
2
、O
2
和N
2
的气体渗透系数分别达到806.2、869.0、180.7和27.7 Barrer. 同时，O
2
/N
2
的选择性为6.52，分离性能接近2015年上限；CO
2
/N
2
的选择性为29.10，分离性能超越了2008年Robeson上限. 因此，将螺旋双茚满结构引入到聚合物分子链中将有效提高膜材料的气体分离性能.
Abstract
Firstly
a new type of diamine monomer 3
3
3'
3'-tetramethyl-6
6'-bis(3-amino-4-hydroxyphenoxy)- 1
1'-spirobisindane (TBAHS) was synthesized
and then polymerized with six kinds of dianhydride monomers in equal molar ratios. After coating
a series of hydroxyl containing polyetherimide (PEI) membranes were prepared by thermal imidization at 300 ℃. Subsequently
the corresponding thermal rearrangement (TR) membranes were obtained by heat treatment at 450 ℃. The testing results show that due to the introduction of the spirobisindane structure
all the six PEI membranes exhibited excellent mechanical and thermal properties
with glass transition temperatures of 317-352 ℃. After thermal treatment
the mechanical properties of the TR membranes significantly decreased
but the gas permeabilities were greatly improved. In particular
the gas permeabilities of the TR(TBAHS-6FDA) membrane for CO
2
H
2
O
2
and N
2
reached 806.2
869.0
180.7
and 27.
7 Barrers
respectively. Meanwhile
the ideal selectivity of O
2
/N
2
was 6.52
and the separation performance was close to the upper limit of 2015. The selectivity of CO
2
/N
2
was 29.10
exceeding the 2008 Robeson upper limit. Therefore
the introduction of the spirobisindane structure into polymer chains can effectively improve the gas separation performance of membrane materials.
关键词
螺旋双茚满结构聚醚酰亚胺热重排气体分离膜材料
Keywords
Spirobisindane structurePolyetherimideThermal rearrangementGas separationMembrane materials
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