基于纳米氢氧化镁稳定的Pickering乳液悬浮聚合制备盔甲结构聚苯乙烯@氢氧化镁复合微球

doi:10.7503/cjcu20190462

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 556.doi: 10.7503/cjcu20190462

基于纳米氢氧化镁稳定的Pickering乳液悬浮聚合制备盔甲结构聚苯乙烯@氢氧化镁复合微球

朱佩^1,²,王峰^1,^*,陈哲明^1,²,李根^1,²,高冲¹,刘鹏¹,丁艳芬¹,张世民¹,陈娟^1,²,阳明书^1,^2,^*

^1. 中国科学院化学研究所, 工程塑料院重点实验室, 北京 100190
^2. 中国科学院大学, 北京 100049

收稿日期:2019-08-22 出版日期:2020-02-26 发布日期:2020-02-07
通讯作者: 王峰,阳明书
作者简介:王峰, 男, 博士, 副研究员, 主要从事无卤阻燃高分子材料研究. E-mail: wangfeng0822@iccas.ac.cn|阳明书, 男, 博士, 研究员, 博士生导师, 主要从事聚合物杂化和纳米复合材料研究. E-mail: yms@iccas.ac.cn
基金资助:
国家自然科学基金资助(No.51534007)

Preparation of Armor Structure Polystyrene@Magnesium Hydroxide Composite Microspheres by Pickering Suspension Polymerization with Nano-magnesium Hydroxide as Pickering Stabilizer ^†

ZHU Pei^1,²,WANG Feng^1,^*,CHEN Zheming^1,²,LI Gen^1,²,GAO Chong¹,LIU Peng¹,DING Yanfen¹,ZHANG Shimin¹,CHEN Juan^1,²,YANG Mingshu^1,^2,^*

^1. CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
^2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-08-22 Online:2020-02-26 Published:2020-02-07
Contact: Feng WANG,Mingshu YANG
Supported by:
† Supported by the National NaturaL Science Foundation of China(No.51534007)

摘要/Abstract

摘要：

以苯乙烯为单体、偶氮二异丁腈(AIBN)为引发剂、片状纳米氢氧化镁(MH)为Pickering稳定剂, 采用悬浮聚合法制备盔甲结构的聚苯烯@氢氧化镁(PS@MH)复合微球. 采用扫描电子显微镜(SEM)、能谱分析(EDS)、傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)、热失重分析(TGA)和微型燃烧量热分析(MCC)等对PS@MH复合微球进行表征, 确认了其形貌和结构: 纳米氢氧化镁紧密包覆在聚苯乙烯微球表面, 形成了以纳米氢氧化镁为外层、聚苯乙烯为内球的盔甲结构复合微球; 同时证明了具有盔甲结构的PS@MH复合微球能降低热释放速率, 抑制聚合物的降解. 该方法操作简单, 成本低廉, 制得的盔甲结构PS@MH复合微球粒径尺寸小、分布窄, 球形度较高.

关键词: 盔甲结构, 片状纳米氢氧化镁, Pickering稳定剂, 复合微球

Abstract:

The unique properties of organic-inorganic composite microspheres with armor structure have aroused great interest. Armor structure organic-inorganic composite microspheres were prepared by Pickering suspension polymerization using styrene as monomer, azobisisobutyronitrile(AIBN) as initiator, magnesium hydroxide nanosheets as Pickering stabilizer. The composite microspheres were characterized by scanning election microscopy(SEM), transmission electron microscopy(TEM), energy dispersive spectroscopy(EDS), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), thermal gravimetric analysis(TGA) and micro-scale combustion calorimetry(MCC). The morphology and structure of the composite microspheres were confirmed. Magnesium hydroxide was tightly coated on the surface of the polystyrene microspheres to form the armor structure composite microspheres with magnesium hydroxide as the outer layer and polystyrene as the inner sphere. When magnesium hydroxide content was 2%, the average particle size of the microspheres was 25 μm, much lower than that of pure PS microspheres, 760 μm. It was also proved that the composite microspheres with armor structure could reduce the heat release rate and inhibit the cracking of polymers. And the acid etching of microspheres could remove completely the outer layer of magnesium hydroxide. This Pickering suspension polymerization is simple to operate, low cost, and the prepared armor composite microspheres have small particle size, narrow distribution and high sphericity. Moreover, the armor structure endows the material with a certain degree of flame retardant performance.

Key words: Armor structure, Magnesium hydroxide nanosheet, Pickering stabilizer, Composite microsphere

中图分类号:

O631
O647

TrendMD:

朱佩,王峰,陈哲明,李根,高冲,刘鹏,丁艳芬,张世民,陈娟,阳明书. 基于纳米氢氧化镁稳定的Pickering乳液悬浮聚合制备盔甲结构聚苯乙烯@氢氧化镁复合微球. 高等学校化学学报, 2020, 41(3): 556.

ZHU Pei,WANG Feng,CHEN Zheming,LI Gen,GAO Chong,LIU Peng,DING Yanfen,ZHANG Shimin,CHEN Juan,YANG Mingshu. Preparation of Armor Structure Polystyrene@Magnesium Hydroxide Composite Microspheres by Pickering Suspension Polymerization with Nano-magnesium Hydroxide as Pickering Stabilizer ^†. Chem. J. Chinese Universities, 2020, 41(3): 556.

图/表 14

Fig.1 TEM(A), SEM(B) images and size distribution(C) of the synthesized MH nanosheets

Fig.2 XRD patterns of the synthetic synthetic MH(a) and stardard MH(b)

Fig.3 Confocal fluorescence microscope images of Pickering emulsion stabilized by dyed 2% MH

Fig.4 Optical microscopy images of Pickering emulsions stabilized by different content of MH Mass fraction MH(%): (A) 0.5; (B) 1; (C) 2; (D) 4.

Fig.5 FTIR spectra of MH(a), PS(b), PS@MH-0.5%(c), PS@MH-1%(d), PS@MH-2%(e) and PS@MH-4%(f) microspheres

Fig.6 SEM images of PS(A, B), PS@MH-0.5%(C, D), PS@MH-1%(E, F) and PS@MH-4% micropheres(G, H) (B), (D), (F), (H) are high magnification of the rectangles in (A), (C), (E), (G), respectively.

Table 1 Mean diameters, standard deviation, distribution coefficient and coverage of PS and PS@MH microspheres

Sample	D/μm	δ/μm	ε	Coverage	Sample	D/μm	δ/μm	ε	Coverage
PS	760	208	0.273	0	PS@MH-2%	25	5	0.215	4.06
PS@MH-0.5%	256	243	0.949	10.40	PS@MH-4%	27	11	0.411	9.10
PS@MH-1%	35	14	0.402	2.84

Fig.7 SEM image(A) and EDS patterns(B—D) of PS@MH-0.5% microspheres (B) C element;(C) Mg element; (D) O element.

Fig.8 XRD patterns of MH(a) and PS@MH microspheres(b—d) b. PS@MH-1%; c. PS@MH-2%; d. PS@MH-4%.

Fig.9 SEM images of PS@MH-2%(A, B) and PS@MH-2%-Etch microspheres(C, D) with different magnifications

Fig.10 TGA curves for PS@MH-2%(a) and PS@MH-2%-Etch(b) microspheres

Table 2 MCC data of PS, PS/MH-2% and PS@MH-2%

Sample	HRC/(J·g^-1·K^-1)	HRR/(W·g^-1)	THR/(kJ·g^-1)	T_max/℃
PS	772	822.9	35.2	443.6
PS/MH-2%	781	831.3	35.5	442.3
PS@MH-2%	612	624.1	34.3	436.8

Fig.11 Heat release rate curves of PS(a), PS/MH-2%(b) and PS@MH-2%(c)

Fig.12 Mechanism of armor structure composite microspheres by Pickering suspension polymerizations for emulsion stabilized by MH nanosheets

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基于纳米氢氧化镁稳定的Pickering乳液悬浮聚合制备盔甲结构聚苯乙烯@氢氧化镁复合微球

Preparation of Armor Structure Polystyrene@Magnesium Hydroxide Composite Microspheres by Pickering Suspension Polymerization with Nano-magnesium Hydroxide as Pickering Stabilizer ^†

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