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Preparation of Thermally Rearranged Poly(benzoxazole-
co -imide) Membranes Containing Tröger's Base Structure and Their Gas Separation Performances- Acta Polymerica Sinica Vol. 56, Issue 8, Pages: 1358-1368(2025)
- 作者机构：
东华大学材料科学与工程学院 先进纤维材料全国重点实验室 上海 201620
- 作者简介：
Jie Dong, E-mail: dj01@dhu.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2025.25045
CLC：- CSTR：32057.14.GFZXB.2025.7392
Received：14 March 2025，
Accepted：25 April 2025，
Published Online：30 June 2025，
Published：20 August 2025
- 稿件说明：
移动端阅览
宋映晓, 唐傲, 张家霖, 董杰, 赵昕, 张清华. 含Tröger’s base结构聚(苯并噁唑-酰亚胺)热重排分离膜的制备与其气体分离特性研究. 高分子学报, 2025, 56(8), 1358-1368
Song, Y. X.; Tang, A.; Zhang, J. L.; Dong, J.; Zhao, X.; Zhang, Q. H. Preparation of thermally rearranged poly(benzoxazole-co-imide) membranes containing tröger’s base structure and their gas separation performances. Acta Polymerica Sinica, 2025, 56(8), 1358-1368
宋映晓, 唐傲, 张家霖, 董杰, 赵昕, 张清华. 含Tröger’s base结构聚(苯并噁唑-酰亚胺)热重排分离膜的制备与其气体分离特性研究. 高分子学报, 2025, 56(8), 1358-1368 DOI： 10.11777/j.issn1000-3304.2025.25045. CSTR： 32057.14.GFZXB.2025.7392.
Song, Y. X.; Tang, A.; Zhang, J. L.; Dong, J.; Zhao, X.; Zhang, Q. H. Preparation of thermally rearranged poly(benzoxazole-co-imide) membranes containing tröger’s base structure and their gas separation performances. Acta Polymerica Sinica, 2025, 56(8), 1358-1368 DOI： 10.11777/j.issn1000-3304.2025.25045. CSTR： 32057.14.GFZXB.2025.7392.
摘要
设计合成了一种新型含Tröger’s base (TB)结构的二胺单体—2
8-二氨基-4
10-二甲基-6
12-氢-5
11-亚甲二苯并[1
5
]
二氮辛(TBDA)，并将其与2
2′-双(3
4-二羧酸)六氟丙烷二酐(6FDA)和2
2-双(3-氨基-4-羟基苯基)六氟丙烷(APAF)共聚反应，合成了一系列含邻羟基酰亚胺单元的聚酰亚胺(HPI). 在高温下对HPI膜进行热重排处理，获得了兼具TB自聚微孔结构和热重排结构的聚(苯并噁唑-酰亚胺)气体分离膜. 研究结果显示，TB自具微孔结构和热重排结构的协同作用抑制了分子链的规整堆砌，使分离膜自由体积增加，从而赋予其优异的气体分离特性. 经430 ℃热重排反应的6FTB1-TR430膜表现出最优异的综合气体分离性能，对CO
2
、CH
4
、O
2
和N
2
的渗透系数分别为267.6、7.0、57.2和12.5 Barrer (1 Barrer = 7.5×10
-14
cm
3
(STP)/(cm
2
·s·Pa)，STP表示标准状态，即0 ℃，1.01×10
5
Pa)，同时，选择性分别达到
α
(CO
2
/CH
4
)=38.2及
α
(O
2
/N
2
)=4.6. 此外，该类分离膜的热分解温度为530~560 ℃，玻璃化转变温度(
T
g
)超过400 ℃，显示出优异的热稳定性. 该研究为设计和开发聚酰亚胺类高效气体分离膜提供了新的思路.
Abstract
A novel diamine monomer containing a Tröger's base (TB) structure
2
8-diamino-4
10-dimethyl-6
12-hydrogen-5
11 methylene dibenzo [1
5
]
diazo octane (TBDA)
was designed and synthesized. This monomer was then copolymerized with 4
4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2
2′-bis(3-amino-4-hydroxyl-phenyl) hexafluoropropane (APAF) to synthesize a series of polyimides (HPI) containing
ortho
-hydroxyamide units. The HPI membranes underwent thermal rearrangement (TR) at high temperatures to yield poly(benzoxazole-
co
-imide) (PBO-PI) gas separation membranes by the thermal rearrangement containing the TB structure and the thermally rearranged benzoxazole units. The results demonstrated that the synergistic effect of the inherent microporosity of TB moieties and thermal rearrangement inhibited the dense packing of molecular chains
providing the membrane with a rich free volume
thus imparting excellent gas separation properties. The gas permeation coefficients of the 6FTB1-TR membrane containing 10 mol% of TBDA and thermally rearranged at 430 ℃ demonstrated excellent gas separation performance with CO
2
CH
4
O
2
and N
2
permeation coefficients of 267.6
7.0
57.2
and 12.5 Barrer
respectively
with the ideal selectivities of
α
(CO
2
/CH
4
) and
α
(O
2
/N
2
) being 38.2 and 4.6
respectively. Moreover
its thermal degradation temperature is over 530 ℃ and glass transition temperature (
T
g
) exceedes 400 ℃
demonstrating excellent thermal stability. This study provides new insights into the design and development of novel high-performance gas separation membranes.
关键词
Keywords
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