聚苯乙烯磺酸钠掺杂正渗透膜的制备及其性能

doi:10.16085/j.issn.1000-6613.2019-0133

摘要/Abstract

摘要：

通过两步无皂乳液聚合法，改变第二步对苯乙烯磺酸钠的加入量，制备表面携带磺酸根基团量不同的纳米粒子（PSS），并将其应用于正渗透（FO）膜的制备。采用红外光谱仪（FTIR）和光电子能谱仪（XPS）表征粒子组成，通过扫描电子显微镜（SEM）表征膜的表面和断面形貌，测定膜孔隙率和亲水性，考察表面磺酸根量不同的聚合物粒子对膜结构性能的影响。结果表明，PSS的引入能提高膜的孔隙率，改善膜的亲水性，且随着粒子表面携带的磺酸根基团量增多，膜的孔隙率与亲水性也随之提高。这是因为PSS粒子可以支撑内部孔道，且表面携带的亲水基团-SO3Na可以提高膜的亲水性，影响活性层的形成。所制备的FO膜性能也得到相应改善，水通量达到了61.1L/(m²·h)，为纯聚砜膜的2.8倍，盐截留率达到93.2%，J_s/J_v值仅为0.31g/L，性能得到极大提升。

关键词: 无皂乳液聚合, 纳米粒子, 正渗透, 磺酸钠, 膜, 表面

Abstract:

The two step surfactant-free emulsion polymerization method was used to synthesis nanoparticles (PSS) with different sulfonic acid groups by changing the amount of sodium styrene sulfonate added in the second step. The particles were applied to prepare forward osmosis (FO) membranes. The particles compositions were characterized by FTIR and XPS. The morphology of the surface and inner structure, porosity, water contact angle of the synthesized FO membranes were characterized. The effects of polymer particles with different sulfonic radicals on the structure and properties of the membranes were investigated. The results showed that the introduction of PSS can improve the porosity and hydrophilicity of the membranes, and the more sulfonic acid contents were carried on the surface of the particles, the higher the porosity and hydrophilicity of the membranes were. This is because PSS particles can support the internal channels, and the hydrophilic groups -SO₃Na carried on the surface can improve the hydrophilicity of the membrane, affecting the formation of the active layer. The performances of the prepared FO membrane were also improved. The water flux of the membranes reached 61.1 L/(m²·h) with the salt rejection of 93.2%, and the J_s/J_v value was only 0.31g/L.

Key words: surfactant-free emulsion polymerization, nanoparticles, forward osmosis, sodium sulfonate, membranes, surface

中图分类号:

TQ 028.8

方丽瑶,吕慧,付佳蓓,左浩然,刘慧清,曹贵平. 聚苯乙烯磺酸钠掺杂正渗透膜的制备及其性能[J]. 化工进展, 2019, 38(10): 4684-4692.

Liyao FANG,Hui LÜ,Jiabei FU,Haoran ZUO,Huiqing LIU,Guiping CAO. Preparation and characterization of sodium polystyrene sulfonate particle doped FO membranes[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4684-4692.

图/表 11

表1 无皂乳液聚合配方

粒子名称	第一步投料			第二步投料
粒子名称	St/g	NaSS/g	DVB/g	St/g	NaSS/g	DVB/g
PSS1	12.8	0.11	0.45	2.56	0.42	0.09
PSS2	12.8	0.11	0.45	2.56	0.63	0.09
PSS3	12.8	0.11	0.45	2.56	0.84	0.09

表2 不同掺杂量的铸膜液配制

正渗透膜名称	支撑层名称	PSS质量分数/ %	PSF溶液质量分数/ %
PSF-T	PSF-S	0	100
PSS1_2.5T	PSS1_2.5S	2.5	97.5
PSS1_5.0T	PSS1_5.0S	5.0	95.0
PSS2_2.5 T	PSS2_2.5S	2.5	97.5
PSS2_5.0 T	PSS2_5.0S	5.0	95.0
PSS3_2.5 T	PSS3_2.5S	2.5	97.5
PSS3_5.0 T	PSS3_5.0S	5.0	95.0

图1 PSS粒子表面SEM形貌

表3 聚合物粒子PSS数均粒径(Dn)，重均粒径(Dw)及聚合分散指数(PDI)

PSS	D_n/nm	D_w/nm	PDI
PSS1	115.19	117.54	1.0204
PSS2	117.78	120.21	1.0207
PSS3	114.85	117.10	1.0198

图2 PSS2聚合物粒子的红外谱图

表4 聚合物PSS元素组成及表面磺酸根量

PSS	$x C$ /%	$x O$ /%	$x S$ /%	$x N a$ /%	$η S O 3 N a$ /%
PSS1_a	96.27	2.52	0.59	0.61	0.22
PSS1_t	92.60	3.43	2.29	1.68	0.88
PSS2_a	94.14	3.87	0.89	1.10	0.34
PSS2_t	89.64	4.81	3.20	2.35	1.26
PSS3_a	92.61	4.82	1.09	1.48	0.42
PSS3_t	87.05	6.01	4.00	2.94	1.59

表4 聚合物PSS元素组成及表面磺酸根量

PSS	$x C$ /%	$x O$ /%	$x S$ /%	$x N a$ /%	$η S O 3 N a$ /%
PSS1_a	96.27	2.52	0.59	0.61	0.22
PSS1_t	92.60	3.43	2.29	1.68	0.88
PSS2_a	94.14	3.87	0.89	1.10	0.34
PSS2_t	89.64	4.81	3.20	2.35	1.26
PSS3_a	92.61	4.82	1.09	1.48	0.42
PSS3_t	87.05	6.01	4.00	2.94	1.59

表5 AL-FS和AL-DS模式下正渗透膜性能

膜名称	AL-FS			AL-DS
膜名称	J_v /L·m^–2 ·h^–1	J_s /g·m^–2 ·h^–1	J_s·J_v^-1 /g·L^-1	J_v /L·m^–2 ·h^–1	J_s /g·m^–2 ·h^–1	J_s·J_v^-1 /g·L^-1
PSF-T	9.6	5.5	0.58	22.0	12.7	0.58
PSS1_2.5T	26.4	4.0	0.15	48.6	10.7	0.22
PSS1_5.0T	14.3	17.2	1.20	30.5	27.4	0.90
PSS2_2.5 T	30.6	18.7	0.61	61.1	18.8	0.31
PSS2_5.0 T	16.8	22.2	1.32	31.7	32.5	1.02
PSS3_2.5 T	25.3	14.7	0.58	50.6	22.3	0.44
PSS3_5.0 T	17.1	24.7	1.44	32.0	32.8	1.03

表6 不同FO膜孔隙率，水接触角及盐截留率

支撑层掺杂的粒子种类	孔隙率ε /%	水接触角 / (°)	盐截留率R /%
PSF	82.18	71	98.2
PSS1	89.10	70	98.8
PSS2	90.25	68	93.2
PSS3	90.82	65	87.2

图3 支撑层膜上表面的SEM形貌

图4 支撑层膜断面不同放大倍数的SEM形貌图

图5 正渗透膜的活性层截面和活性层上表面SEM形貌图

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