基于醛或酮基咔唑超交联多孔聚合物的合成、 表征与气体吸附性能

doi:10.7503/cjcu20170823

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 2105.doi: 10.7503/cjcu20170823

• 高分子化学 • 上一篇

基于醛或酮基咔唑超交联多孔聚合物的合成、表征与气体吸附性能

张荣荣¹, 袁光明^1,², 罗卫华^1,²()

1. 中南林业科技大学材料科学与工程学院, 2. 木竹资源高效利用湖南省协同创新中心, 长沙 410004

收稿日期:2017-12-15 出版日期:2018-09-07 发布日期:2018-06-26
作者简介:
联系人简介: 罗卫华, 男, 博士, 教授, 主要从事功能高分子材料研究. E-mail: lwh6803@163.com
基金资助:
国家自然科学基金(批准号: 31770606)、国家林业公益性行业科研专项(批准号: 201504503)和湖南省自然科学基金(批准号: 2015JJ2200)资助.

Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups^†

ZHANG Rongrong¹, YUAN Guangming^1,², LUO Weihua^1,^2,^*()

1. College of Material Science and Engineering, 2. Hunan Provincial Collaborative Innovation Center for High-efficiency Utilization of Wood and Bamboo Resources, Central South University of Forestry and Technology, Changsha 410004, China

Received:2017-12-15 Online:2018-09-07 Published:2018-06-26
Contact: LUO Weihua E-mail:lwh6803@163.com
Supported by:
† Supported by the National Nature Science Foundation of China(No.31770606), the Special Fund for Forest Scientific Research in the Public Welfare of China(No.201504503) and the Hunan Provincial Natural Science Foundation, China(No.2015JJ2200).

摘要/Abstract

摘要：

设计合成了醛基或酮基功能化的咔唑9-(4-联苯)-3-甲醛基咔唑(CM-2)、 9-(4-联苯)-4-乙酮基咔唑(CM-3)和9-(4-联苯)-2,6-二氟-3-乙酮基咔唑(CM-4). 分别以CM-2, CM-3和CM-4为单体, 以FeCl₃为催化剂, 采用一步法制备了超交联多孔聚咔唑: 聚[9-(4-联苯)-3-甲醛基咔唑](HPP-2)、聚[9-(4-联苯)-4-乙酮基咔唑](HPP-3)和聚[9-(4-联苯)-2,6-二氟-3-乙酮基咔唑](HPP-4). 反应中间体和聚咔唑的结构由核磁共振波谱(¹H NMR, ¹³C NMR)、魔角旋转交叉固体核磁共振波谱(¹³C CP/MAS NMR)、红外光谱(IR)和质谱(MS)进行表征, 研究了聚咔唑的热稳定性及气体(氮气、二氧化碳和甲烷)吸附性能. 结果表明, 3种聚咔唑在400 ℃左右开始分解, 450~550 ℃出现明显失重, 然后逐渐趋于平缓, 800 ℃时的热失重均小于25%, 表明材料有很好的热稳定性; HPP-2, HPP-3和HPP-4的BET比表面积分别为330, 420和660 m²/g, 孔径分别为0.98, 0.96和1.07 nm, 对二氧化碳的吸附质量分数分别为6.90%, 8.30%和9.80%, 对甲烷的吸附质量分数分别为1.10%, 1.30%和1.60%, 表明所得聚合物的孔主要为微孔, 且对二氧化碳和甲烷气体有良好的吸附能力.

关键词: 醛基咔唑, 酮基咔唑, 超交联聚合物, 多孔性, 气体吸附

Abstract:

Three novel carbazoles CM-2, CM-3 and CM-4 were designed and synthesized by ketone- or aldehyde-functionalization of carbazole. Then a series of hypercrosslinked porous polycarbazoles(HPP-2, HPP-3 and HPP-4) was prepared using CM-2, CM-3 and CM-4 as monomers under the catalysis of FeCl₃. The structures of the novel carbazoles and the hypercrosslinked porous polycarbazoles(HPPs) were characterized by nuclear magnetic resonance(¹H NMR, ¹³C NMR), magic angle spinning nuclear magnetic resonance(MAS NMR), infrared(IR) and mass spectrometry(MS). The thermal stability and the gas(nitrogen, carbon dioxide and methane) adsorption properties of the obtained HPPs were also investigated. The results show that the structures of the novel carbazoles and the polymers are consistent with the molecular design. Three kinds of HPPs begin to degrade around 400 ℃ and render a mass loss less than 25% at 800 ℃, denoting that these materials have a good thermal stability. HPP-2, HPP-3 and HPP-4 present BET specific surface areas of 330, 420 and 660 m²/g, with pore sizes mainly distributed at 0.98, 0.96 and 1.07 nm, respectively. The adsorption capacities of CO₂ on HPP-2, HPP-3 and HPP-4 are 6.90%, 8.30% and 9.80%, while those of CH₄ on HPP-2, HPP-3 and HPP-4 are 1.10%, 1.30% and 1.60%, respectively. The results show that the obtained polymers possess mainly micropores and present high adsorption capacity for CO₂ and CH₄. This work provides a new approach for the synthesis of hypercrosslinked porous polycarbazoles.

Key words: Aldehyde-modified carbazole, Ketone-modified carbazole, Hypercrosslinked polymer, Porosity, Gas adsorption

中图分类号:

O631
O626

TrendMD:

张荣荣, 袁光明, 罗卫华. 基于醛或酮基咔唑超交联多孔聚合物的合成、表征与气体吸附性能. 高等学校化学学报, 2018, 39(9): 2105.

ZHANG Rongrong,YUAN Guangming,LUO Weihua. Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups^†. Chem. J. Chinese Universities, 2018, 39(9): 2105.

图/表 11

Scheme 1 Synthesis of aldehyde- or ketone-modified carbazoles CM-2, CM-3 and CM-4

Scheme 2 Synthesis of hypercrosslinked polymers HPP-2 and HPP-4

Scheme 3 Synthesis of hypercrosslinked polymer HPP-3

Fig.1 1H NMR spectrum of CM-3

Fig.2 13C CP/MAS NMR spectra of HPP-2(a), HPP-3(b) and HPP-4(c)

Fig.3 FTIR spectra of HPP-2 and corresponding monomer CM-2(A), HPP-3 and CM-3(B), and HPP-4 and CM-4(C)

Fig.4 TG curves of HPP-2(a), HPP-3(b) and HPP-4(c)

Fig.5 SEM images of polymers HPP-2(A), HPP-3(B) and HPP-4(C)

Fig.6 Nitrogen adsorption-desorption isotherms of HPP-2(a), HPP-3(b) and HPP-4(c) measured at 77 K(A) and the PSD profiles of HPP-2(a), HPP-3(b) and HPP-4(c) calculated by NLDFT(B)The adsorption and desorption branches are labeled with solid and open symbols, respectively.

Fig.7 Gravimetric CO2(A) and CH4(B) adsorption-desorption isotherms for HPP-2(a), HPP-3(b) and HPP-4(c) at 273 K

Table 1 Porosity properties and gas uptake capacities of polymers HPP-2—HPP-4

Polymer	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$D pore d$ /nm	CO₂ uptake^e(%)	CH₄ uptake^e(%)
HPP-2	330	200	0.21	0.98	6.90	1.10
HPP-3	420	250	0.39	0.96	8.30	1.30
HPP-4	660	470	0.68	1.07	9.80	1.60

Table 1 Porosity properties and gas uptake capacities of polymers HPP-2—HPP-4

Polymer	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$D pore d$ /nm	CO₂ uptake^e(%)	CH₄ uptake^e(%)
HPP-2	330	200	0.21	0.98	6.90	1.10
HPP-3	420	250	0.39	0.96	8.30	1.30
HPP-4	660	470	0.68	1.07	9.80	1.60

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基于醛或酮基咔唑超交联多孔聚合物的合成、表征与气体吸附性能

Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups^†

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基于醛或酮基咔唑超交联多孔聚合物的合成、 表征与气体吸附性能

Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups†

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基于醛或酮基咔唑超交联多孔聚合物的合成、表征与气体吸附性能

Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups^†