α-甲基苯乙烯马来酸酐共聚物微球固载β-环糊精的制备及应用

doi:10.16085/j.issn.1000-6613.2022-1452

化工进展 ›› 2023, Vol. 42 ›› Issue (4): 2038-2046.DOI: 10.16085/j.issn.1000-6613.2022-1452

α-甲基苯乙烯马来酸酐共聚物微球固载β-环糊精的制备及应用

赖槐东¹^,²(), 程德书²^,³^,⁴, 王坚¹, 罗菊香¹^,²()

^1.福州大学环境与安全工程学院，福建福州 350108
^2.三明学院资源与化工学院，福建三明 365004
^3.福建省氟化工科技经济融合服务平台，福建三明 365004
^4.三明市氟化工产业技术研究院，福建三明 365004

收稿日期:2022-08-03 修回日期:2022-09-20 出版日期:2023-04-25 发布日期:2023-05-08
通讯作者: 罗菊香
作者简介:赖槐东（1998—），男，硕士研究生。E-mail: Lai_Huaidong@126.com。
基金资助:
福建省自然科学基金(2020J01378);国家自然科学基金(51703120);三明市科技局引导性项目(2021-G-5);福建省科技创新重点项目(2021G02012)

Preparation and application of α-methyl styrene maleic anhydride copolymer microspheres immobilized β-cyclodextrin

LAI Huaidong¹^,²(), CHENG Deshu²^,³^,⁴, WANG Jian¹, LUO Juxiang¹^,²()

^1.College of Environment and Safety Engineering, Fuzhou University, Fuzhou, 350108, Fujian, China
^2.School of Resourses and Chemical Engineering, Sanming University, Sanming, 365004, Fujian, China
^3.Fujian Fluorochemical Technology and Economic Integration Service Platform, Sanming, 365004, Fujian, China
^4.Sanming Institute of Fluorochemmical Industry, Sanming, 365004, Fujian, China

Received:2022-08-03 Revised:2022-09-20 Online:2023-04-25 Published:2023-05-08
Contact: LUO Juxiang

摘要/Abstract

摘要：

以α-甲基苯乙烯和马来酸酐为共聚物单体，二乙烯基苯为交联剂，通过自稳定沉淀聚合制备交联α-甲基苯乙烯马来酸酐共聚物微球（PAMSM）；用对甲苯磺酰氯对β-环糊精（β-CD）进行单磺酰化得到单-6-对甲苯磺酰基-β-环糊精（mono-6-OTs-β-CD），其与过量的1,2-丙二氨反应制备得到1,2-丙二胺基-β-环糊精（PDM-β-CD）；通过PDM-β-CD的伯氨与PAMSM的酸酐开环酰胺化反应，将β-CD固载在PAMSM上制备微球β-CD-PDM-PAMSM。采用傅里叶红外光谱（FTIR）、扫描电子显微镜（SEM）、元素分析对β-CD-PDM-PAMSM的结构、表面形貌和组成进行表征。结果表明，β-CD-PDM-PAMSM具有良好的球形度，平均粒径在1.08µm；β-CD固载率高，通过元素分析计算得β-CD固载率为53.1%。将PAMSM、β-CD-PDM-PAMSM、水解PAMSM（H-PAMSM）和水解β-CD-PDM-PAMSM（H-β-CD-PDM-PAMSM）作为吸附剂，研究其对亚甲基蓝溶液（MB）的吸附性能。研究表明，PAMSM对MB的吸附能力为25.3mg/g，β-CD-PDM-PAMSM对MB的吸附能力比PAMSM提高了615.8%，水解后的H-β-CD-PDM-PAMSM和H-PAMSM对MB的吸附能力较PAMSM分别提高了1043.5%和860.8%。

关键词: β-环糊精, PAMSM微球, 1,2-丙二胺基-β-环糊精, 亚甲基蓝, 吸附

Abstract:

Cross-linked α‍-methylstyrene maleic anhydride copolymer microspheres (PAMSM) were prepared by self-stable precipitation polymerization with α‍-methylstyrene and maleic anhydride as copolymer monomers and divinylbenzene as crosslinking agent. Firstly, mono-6-p-toluenesulfonyl-β- cyclodextrin (mono-6-OTs-β-CD) was obtained by the monosulfonylation of β-cyclodextrin (β-CD) with p-toluenesulfonyl chloride, and then 1,2-propylenediamine-‍β‍-cyclodextrin (PDM-‍β‍-CD) was achieved by the ammoniating of mono-6-OTs-β-CD with excess 1,2-propylenediamine. The microspheres of β-CD-PDM-PAMSM were prepared though immobilizing PDM-β-CD to the PAMSM by ringing-open amidation reaction of PDM-β-CD with the primary amines and PAMSM with the anhydride groups. The composition, surface morphology, particle size and distribution of the β-CD-PDM-PAMSM were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and elemental analysis. The results showed that the β-CD-PDM-PAMSM maintained good sphericity and the average particle size was 1.08μm. The immobilization yield of β-CD on PAMSM was high, and the grafting rate of β-CD was 53.1% calculated by the elemental analysis. Then, the adsorption properties for methylene blue solution (MB) of PAMSM, β-CD-PDM-PAMSM, hydrolyzed PAMSM (H-PAMSM) and hydrolyzed β-CD-PDM-PAMSM (H-β-CD-PDM-PAMSM) were investigated. Research suggested that the adsorption capacity of PAMSM for MB was 25.3mg/g, and the adsorption capacity of β-CD-PDM-PAMSM for MB was 615.8% higher than that of PAMSM. The adsorption capacity of H-β-CD-PDM-PAMSM and H-PAMSM for MB was 1043.5% and 860.8% higher than that of PAMSM, respectively.

Key words: β-cyclodextrin, PAMSM microspheres, 1,2-propylenediamine-β-cyclodextrin, methylene blue, absorb

中图分类号:

O631

赖槐东, 程德书, 王坚, 罗菊香. α-甲基苯乙烯马来酸酐共聚物微球固载β-环糊精的制备及应用[J]. 化工进展, 2023, 42(4): 2038-2046.

LAI Huaidong, CHENG Deshu, WANG Jian, LUO Juxiang. Preparation and application of α-methyl styrene maleic anhydride copolymer microspheres immobilized β-cyclodextrin[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2038-2046.

图/表 10

图1 β-CD-PDM-PAMSM微球制备流程图

图2 PAMSM改性前后以及水解前后的SEM图

表1 PAMSM改性前后和水解前后的数均粒径、重均粒径、分散系数

微球	数均粒径D_n/μm	重均粒径D_w/μm	分散系数U
PAMSM	0.96	0.97	1.01
β-CD-PDM-PAMSM	1.08	1.09	1.01
H-PAMSM	1.19	1.22	1.02
H-β-CD-PDM-PAMSM	1.20	1.20	1.00

图3 PAMSM改性前后以及水解前后粒径分布图

图4 样品的FTIR谱图

图5 β-CD、H-PAMSM、H-β-CD-PDM-PAMSM微球的TG曲线

表2 β-CD-PDM-PAMSM的元素分析 (质量分数)

微球	C/%	H/%	O/%	N/%	CD固载率/%
β-CD-PDM-PAMSM	59.1	6.21	32.9	1.33	53.1
H-β-CD-PDM-PAMSM	59.0	6.14	33.4	1.27	50.7

图6 微球的N2吸附-脱附等温线

表3 微球孔结构分析

微球	比表面积/m²·g^-1	总孔容/cm³·g^-1	平均孔径/nm
PAMSM	1.97	0.00243	37.5
β-CD-PDM-PAMSM	4.33	0.00779	8.37
H-PAMSM	3.44	0.0209	26.8
H-β-CD-PDM-PAMSM	4.88	0.0122	4.66

图7 不同吸附剂对MB的吸附效果图

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α-甲基苯乙烯马来酸酐共聚物微球固载β-环糊精的制备及应用

Preparation and application of α-methyl styrene maleic anhydride copolymer microspheres immobilized β-cyclodextrin

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