聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

doi:10.11949/0438-1157.20220715

摘要/Abstract

摘要：

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料，氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂，通过非溶剂诱导相转化法制备了PMIA平板膜，系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明，聚合物浓度和LiCl含量增加，铸膜液黏度增大，导致膜孔径减小，纯水通量降低。而PEG含量的增加，使得聚合物链呈现舒展状态，膜孔径增大，纯水通量升高，亲水性增强。随着PVP含量的增加，膜的纯水通量先升高后降低，膜的亲水性变差。当PMIA的质量分数为9%，LiCl的质量分数为2.8%，PVP的质量分数为1.2%时，膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1，对牛血清蛋白（BSA）的截留率为80%，展现出较高的渗透性，为制备高性能膜材料提供了新的思路。

关键词: 平板膜, 废水, 分离, 聚合物, 聚间苯二甲酰间苯二胺, 添加剂, 孔结构

Abstract:

PMIA flat-sheet membranes were prepared by non-solvent induced phase inversion method. Specifically, poly(m-phenylene isophthalamide) (PMIA) as polymer materials, lithium chloride (LiCl), polyethylene glycol (PEG-400) and polyvinyl pyrrolidone (PVP) as additives were blended to form casting solution. The effects of polymer concentration, additive type and content on the structures and properties of PMIA membranes were systematically investigated. The results exhibited that with the increase of polymer concentration and LiCl content, the viscosity of the casting solution was enhanced, resulting in the decrease of pore size and pure water flux. While the polymer chains were stretched with the increasing content of PEG, which made pore size and water flux of membranes improved. Then, with increasing PVP additive, the pure water flux of the membrane was increased firstly and then decreased, and the hydrophilicity of the membrane became worse. When the mass fraction of PMIA was 9%, LiCl was 2.8% and PVP was 1.2%, the pure water flux of the membrane was as high as 1421.55 L·m^-2·h^-1·bar^-1 with 80% rejection of bovine serum albumin (BSA) maintained. The high permeability provided a new idea for the preparation of high-performance membrane materials.

Key words: flat-sheet membrane, waste water, separation, polymers, PMIA, additives, pore structure

中图分类号:

TQ 028.8

郑喜, 王涛, 任永胜, 赵珍珍, 王雪琪, 赵之平. 聚间苯二甲酰间苯二胺平板膜的制备及其性能研究[J]. 化工学报, 2022, 73(10): 4707-4721.

Xi ZHENG, Tao WANG, Yongsheng REN, Zhenzhen ZHAO, Xueqi WANG, Zhiping ZHAO. Preparation and properties research of poly(m-phenylene isophthalamide) flat-sheet membrane[J]. CIESC Journal, 2022, 73(10): 4707-4721.

图/表 24

图1 PMIA的分子式和化学结构及膜制备过程示意图

Fig.1 Molecular formula and chemical structure diagram of PMIA and schematic diagram of membrane preparation process

表1 不同聚合物浓度的铸膜液

Table 1 Casting solution of different polymer concentration

膜	PMIA/g	LiCl/g	PVP-K15/g	DMAc/g	总计/g
A1	9	3.8	1.2	86	100
A2	10	3.8	1.2	85	100
A3	11	3.8	1.2	84	100
A4	12	3.8	1.2	83	100

图2 不同聚合物浓度下膜的SEM图

Fig.2 SEM images of membrane with different polymer concentrations

图3 不同聚合物浓度下膜的孔径

Fig.3 Pore diameter of membranes at different polymer concentrations

表2 不同聚合物浓度下膜的孔径和孔隙率数据

Table 2 Pore diameter and porosity data of membranes at different polymer concentrations

膜	平均孔径/μm	最可几孔径/μm	孔隙率/%
A1	0.2375	0.2203	71.98±3.84
A2	0.1145	0.1022	61.78±4.74
A3	0.0947	0.0918	56.11±3.27
A4	0.0379	0.0355	63.39±1.28

图4 不同聚合物浓度下膜的AFM图和平均粗糙度

Fig.4 AFM pictures and average roughness of different polymer concentrations membranes

图5 不同聚合物浓度下膜的渗透通量和水接触角

Fig.5 Permeation flux and water contact angle of membranes at different polymer concentrations

图6 PMIA/DMAc/LiCl溶解体系

Fig.6 Dissolved system of PMIA/DMAc/LiCl

表3 不同无机添加剂浓度的铸膜液

Table 3 Casting solutions with different concentrations of inorganic additives

膜	LiCl/g	PMIA/g	PVP-K15/g	DMAc/g	总计/g
B1	2.8	9	1.2	87	100
B2	3.8	9	1.2	86	100
B3	4.8	9	1.2	85	100
B4	5.8	9	1.2	84	100

图7 不同无机添加剂浓度下膜的SEM图

Fig.7 SEM images of membrane at different concentrations of inorganic additives

图8 不同无机添加剂浓度下膜的孔径

Fig.8 Pore diameter of membrane at different concentrations of inorganic additives

表4 不同无机添加剂浓度下膜的孔径和孔隙率数据

Table 4 Pore diameter and porosity data of membranes at different concentrations of inorganic additives

膜	平均孔径/μm	最可几孔径/μm	孔隙率/%
B1	0.2247	0.2232	78.87±5.66
B2	0.1768	0.1718	76.39±2.31
B3	0.1113	0.1057	70.56±4.75
B4	0.0913	0.0847	66.27±2.84

图9 不同无机添加剂浓度下膜的渗透通量和水接触角

Fig.9 Permeation flux and water contact angle of membranes at different concentrations of inorganic additives

图10 牛血清蛋白溶液标准曲线

Fig.10 The standard curve of BSA solution

表5 不同小分子有机添加剂的铸膜液

Table 5 Casting solution of different organic additive with small molecule

膜	PEG/g	PMIA/g	LiCl/g	PVP-K15/g	DMAc/g	总计/g
C1	2	10	3.8	1.2	83	100
C2	4	10	3.8	1.2	81	100
C3	6	10	3.8	1.2	79	100
C4	8	10	3.8	1.2	77	100

图11 不同小分子有机添加剂浓度下膜的SEM图

Fig.11 SEM images of membrane at different concentrations of organic additives with small molecule

图12 不同小分子有机添加剂浓度下膜的孔径

Fig.12 Pore diameter of membrane at different concentrations of organic additives with small molecule

表6 不同小分子有机添加剂浓度下膜的孔径和孔隙率数据

Table 6 Pore diameter and porosity data of membrane at different concentrations of organic additives with small molecule

膜	平均孔径/μm	最可几孔径/μm	孔隙率/%
C1	0.0618	0.0483	69.58±0.68
C2	0.0571	0.0537	80.09±1.72
C3	0.0797	0.0783	79.67±0.80
C4	0.1050	0.0774	76.11±3.35

图13 不同小分子有机添加剂浓度下膜的渗透通量和水接触角

Fig.13 Permeation flux and water contact angle of membranes at different concentrations of organic additives with small molecule

表7 不同大分子有机添加剂的铸膜液

Table 7 Casting solution of different organic additives with macromolecular

膜	PVP-K15/g	PMIA/g	LiCl/g	DMAc/g	总计/g
D1	1.2	10	3.8	85	100
D2	3.2	10	3.8	83	100
D3	5.2	10	3.8	81	100
D4	7.2	10	3.8	79	100

图14 不同大分子有机添加剂浓度下膜的SEM图

Fig.14 SEM images of membrane at different concentrations of organic additives with macromolecule

图15 不同大分子有机添加剂浓度下膜的孔径

Fig.15 Pore diameter of membranes at different concentrations of organic additives with macromolecule

表8 不同大分子有机添加剂浓度下膜的孔径和孔隙率数据

Table 8 Pore diameter and porosity data of membranes at different concentrations of organic additives with macromolecule

膜	平均孔径/μm	最可几孔径/μm	孔隙率/%
D1	0.1250	0.1176	73.31±0.71
D2	0.1522	0.1807	78.28±0.20
D3	0.0613	0.0566	84.80±1.52
D4	0.1354	0.0676	76.05±0.86

图16 不同大分子有机添加剂浓度下膜的渗透通量和水接触角

Fig.16 Permeation flux and water contact angle of membranes at different concentrations of organic additives with macromolecule

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