自组装法制备磺化聚苯乙烯@Fe<sub>3</sub>O<sub>4</sub>磁性复合颗粒及其磁性能

宋月英; 韩丁; 关晓琳; 雷西萍

doi:10.13801/j.cnki.fhclxb.20191014.003

自组装法制备磺化聚苯乙烯@Fe₃O₄磁性复合颗粒及其磁性能

doi: 10.13801/j.cnki.fhclxb.20191014.003

1.
西安建筑科技大学　材料科学与工程学院，西安 710055
2.
西北师范大学　化学化工学院，兰州 730070

基金项目: 陕西省教育厅重点实验室科研计划项目（16JS054）；生态环境高分子材料教育部重点实验室（开放）基金（No.KF-18-01）

详细信息

通讯作者:
雷西萍，博士，教授，研究方向为高分子基复合材料的制备及性能　E-mail：leixiping123456@163.com

中图分类号: TB332
计量
- 文章访问数: 740
- HTML全文浏览量: 130
- PDF下载量: 48
- 被引次数: 0
出版历程
- 收稿日期: 2019-07-01
- 录用日期: 2019-09-28
- 网络出版日期: 2019-10-15
- 刊出日期: 2020-06-15

Preparation and magnetic properties of sulfonated polystyrene @Fe₃O₄ magnetic composite particles by self-assembly method

1.
School of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi′an 710055, China
2.
School of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

摘要

摘要: 实现结构可控、均匀包覆是制备核-壳复合材料的关键。采用离子交换法完成了磺化聚苯乙烯(PSS)表面Na⁺与溶液中Fe²⁺和Fe³⁺的交换，于碱性条件下制备了PSS表面负载Fe₃O₄(PSS@Fe₃O₄)的磁性复合颗粒。通过称重法计算了Fe₃O₄最大包覆率；通过振动样品磁强计(VSM)测试了不同负载含量下PSS@Fe₃O₄复合颗粒的磁性能；通过XRD、衰减全反射-FTIR (ATR-FTIR)、SEM-EDS分析了PSS@Fe₃O₄磁性复合颗粒的化学组成和微观结构。结果表明，随着Fe²⁺/Fe³⁺浓度增加，PSS@Fe₃O₄磁性颗粒的饱和磁化强度也随之增大，最大饱和磁化强度为7.51 emu/g，并具有明显的磁响应性；Fe₃O₄均匀包覆在PSS表面，最大包覆率为8.3 wt%。PSS@Fe₃O₄磁性复合颗粒有望用于磁流变、医学及水处理领域。
- 自组装法 /
- 磺化聚苯乙烯 /
- Fe₃O₄ /
- 磁性能 /
- 复合颗粒
Abstract: Achieving controllable structure and uniform coating is the key for the preparation of core-shell magnetic composite materials. The exchange of Na⁺ with Fe²⁺ and Fe³⁺ on the surface of sulfonic polystyrene (PSS) was completed by ion exchange method. The PSS surface loaded Fe₃O₄(PSS@Fe₃O₄) magnetic composite particles was obtained with alkaline existed. The maximum encapsulation rate of Fe₃O₄ was calculated by weighing method. The magnetic properties were analyzed by vibrating sample magnetometer (VSM). The chemical composition and microstructure of PSS@ Fe₃O₄ magnetic composite particles were analyzed by XRD, ATR-FTIR and SEM-EDS. The results show that the saturation magnetization of PSS@Fe₃O₄ magnetic particles increases with the increase of Fe²⁺/Fe³⁺ concentration. The maximum saturation magnetization of PSS@Fe₃O₄ magnetic particles is 7.51 emu/g which owned the obvious magnetic response. Fe₃O₄ is evenly coated on the surface of PSS, and the maximum coating rate is 8.3 wt%. The PSS@Fe₃O₄ composite particles are expected to be applied in magnetorheological, medical and waste water treatment fields.
- self-assemble method /
- sulfonic polystyrene /
- Fe₃O₄ /
- magnetic properties /
- composite particle

HTML全文

图 1 磺化聚苯乙烯(PSS)@Fe₃O₄磁性复合颗粒制备过程示意图

Figure 1. Schematic diagram of preparation process of sulfonic polystyrene(PSS)@Fe₃O₄ magnetic composite particles

下载: 全尺寸图片幻灯片

图 2 300 K下PSS@Fe₃O₄磁性复合颗粒的磁滞回线

Figure 2. Magnetization curves of PSS@Fe₃O₄ magnetic composite particles at 300 K

下载: 全尺寸图片幻灯片

图 3 外加磁场对PSS@Fe₃O₄磁性复合颗粒（(a)、(c)）和Fe₃O₄（(b)、(d)）的作用

Figure 3. Effect of external magnetic field on PSS@Fe₃O₄magnetic composite particles((a),(c)) and Fe₃O₄((b),(d))

下载: 全尺寸图片幻灯片

图 4 PSS、PSS@Fe₃O₄磁性复合颗粒和Fe₃O₄的XRD图谱

Figure 4. XRD spectra of PSS, PSS@Fe₃O₄ magnetic composite particles and Fe₃O₄

下载: 全尺寸图片幻灯片

图 5 Fe₃O₄和PSS@Fe₃O₄磁性复合颗粒的ATR-FTIR图谱

Figure 5. ATR-FTIR spectra of Fe₃O₄ and PSS@Fe₃O₄ magnetic composite particles

下载: 全尺寸图片幻灯片

图 6 PSS和PSS@Fe₃O₄磁性复合颗粒的SEM图像和EDS图谱

Figure 6. SEM images and EDS spectra of PSS and PSS@Fe₃O₄magnetic composite particles

下载: 全尺寸图片幻灯片

表 1 制备PSS@Fe₃O₄磁性复合颗粒的反应物比例

Table 1. Reaction recipes of the preparation of PSS@Fe₃O₄ magnetic composite particles

Sample	FeCl₂·4H₂O/g	FeCl₃·6H₂O/g	PSS/g	NaOH/(mol·L⁻¹)	Cladding mass fraction/wt%
1	0.30	0.2	5.82	1.25	1.3
2	0.60	0.4	5.82	1.25	2.5
3	0.90	0.6	5.82	1.25	4.3
4	1.20	0.8	5.82	1.25	5.4
5	1.50	1.0	5.82	1.25	6.8
6	2.25	1.5	5.82	1.25	7.7
7	3.00	2.0	5.82	1.25	8.3
8	4.50	3.0	5.82	1.25	8.3
9	7.50	5.0	5.82	1.25	8.3

下载: 导出CSV

参考文献(20)

[1]	杨琥, 袁博, 卢耀柏, 等. 壳聚糖磁性微球的制备及在水处理中的应用[J]. 中国科学, 2008, 38(9):755-761. YANG Hu, YUAN Bo, LU Yaobai, et al. Preparation of magnetic PAA/chitosan microspheres and its application in wastewater treatment[J]. Science in China Press,2008,38(9):755-761(in Chinese).
[2]	徐雅雯, 徐宏, 丁玮杰, 等. 高Fe₃O₄含量微米尺寸磁性复合微球的合成及其在化学发光免疫检测中应用初探[J]. 高分子学报, 2010(11):1341-1345. XU Yawen, XU Hong, DING Weijie, et al. Preparation and bio-application of monodisperse composite microspheres with high Fe₃O₄ content[J]. Acta Polymerica Sinica,2010(11):1341-1345(in Chinese).
[3]	LIANG X, XI B, XIONG S. Porous soft magnetic material: The maghemite microsphere with hierarchical nanoarchitecture and its application in water purification[J]. Materials Research Bulletin,2009,44(12):2233-2239. doi: 10.1016/j.materresbull.2009.08.003
[4]	HATO M J, CHOI H J, SIM H H, et al. Magnetic carbonyl iron suspension with organoclay additive and its magnetorheological properties[J]. Colloids & Surfaces A: Physicochemical & Engineering Aspects,2011,377(1-3):103-109.
[5]	SEDLACIK M, PAVLINEK V, LEHOCKY M. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids[J]. Colloids & Surfaces A: Physicochemical & Engineering Aspects,2011,387(1-3):99-103.
[6]	LIU Y D, HONG C H, CHOI H J. Polymeric colloidal magnetic composite microspheres and their magneto-responsive characteristics[J]. Macromolecular Research,2012,20(12):1211-1218. doi: 10.1007/s13233-012-0198-8
[7]	GOSWAMI M M, DEY C, SARKAR D, et al. Micelles driven magnetite (Fe₃O₄) hollow spheres and a study on AC magnetic properties for hyperthermia application[J]. Journal of Magnetism & Magnetic Materials,2016,417:376-381.
[8]	PARK D E, CHAE H S, CHOI H J, et al. Magnetite-polypyrrole core-shell structured microspheres and their dual stimuli-response under electric and magnetic fields[J]. Journal of Materials Chemistry,2015,3(13):3150-3158.
[9]	盖青青, 曲锋, 梅芳. 磁性粒子在蛋白质分离纯化中的应用[J]. 化学通报, 2010(2):99-105. GAI Qingqing, QU Feng, MEI Fang. Applications of magnetic particles in proteins separation and purification[J]. Chemical Bulletin,2010(2):99-105(in Chinese).
[10]	ALVER E, METIN A Ü. Anionic dye removal from aqueous solutions using modified zeolite: Adsorption kinetics and isotherm studies[J]. Chemical Engineering Journal,2012,200-202:59-67. doi: 10.1016/j.cej.2012.06.038
[11]	TOOR M, JIN B. Adsorption characteristics, isotherm, kinetics, and diffusion of modified natural bentonite for removing diazo dye[J]. Chemical Engineering Journal,2012,187(2):79-88.
[12]	PAPAGEORGIOU G Z, BIKIARIS D N. Crystallization and melting behavior of three biodegradable poly(alkylene succinates). A comparative study[J]. Polymer,2005,46(26):12081-12092. doi: 10.1016/j.polymer.2005.10.073
[13]	CRINI G, PEINDY H N, GIMBERT F. Basic green 4(malachite green) from aqueous solutions by adsorption using cyclodextrin-based adsorbent: Kinetic and equilibrium studies[J]. Removal of C: Separation & Purification Technology,2007,53(1):97-110.
[14]	COTORUELO L M, MARQUÉS M D, DÍAZ F J. Adsorbent ability of lignin-based activated carbons for the removal of p-nitrophenol from aqueous solutions[J]. Chemical Engineering Journal,2012,184(3):176-183.
[15]	HE Ping, CUI Longlan, QIANG Weili, et al. Preparation and characterization of monodisperse P(St/AA) composite microspheres with high Fe₃O₄ content[J]. Acta Polymerica Sinica,2007(8):732-736.
[16]	余智军, 钱浩, 林志勇, 等. 磁性磺酸阳离子交换树脂微球的制备与表征[J]. 化学工程与设备, 2012(6):8-9. YU Zhijun, QIAN Hao, LIN Zhiyong, et al. Preparation and characterization of magnetic sulfonic acid cation exchange resin microspheres[J]. Chemical Engineering & Equipment,2012(6):8-9(in Chinese).
[17]	XU Z, XIA A, WANG C, et al. Synthesis of raspberry-like magnetic polystyrene microspheres[J]. Materials Chemistry & Physics,2007,103(2-3):494-499.
[18]	邓建国, 贺传兰, 龙新平, 等. 磁性Fe₃O₄-聚吡咯纳米微球的合成与表征[J]. 高分子学报, 2003(3):393-397. doi: 10.3321/j.issn:1000-3304.2003.03.013 DENG Jianguo, HE Chuanlan, LONG Xinping, et al. Preparation and characterization of magnetic Fe₃O₄-polypyrrole nanoparticles[J]. Acta Polymerica Sinica,2003(3):393-397(in Chinese). doi: 10.3321/j.issn:1000-3304.2003.03.013
[19]	SINGH K, OHLAN A, PHAM V H. Nanostructured graphene/Fe₃O₄ incorporated polyaniline as a high performance shield against electromagnetic pollution[J]. Nanoscale,2013,5(6):2411-2420. doi: 10.1039/c3nr33962a
[20]	MOHAMMADI A, BARIKANI M, LAKOURAJ M M. Biocompatible polyurethane/thiacalix[4] arenes functionalized Fe₃O₄ magnetic nanocomposites: Synthesis and properties[J]. Materials Science & Engineering C,2016,66:106-118.