含氯化锌的聚吡咯微胶囊的制备与性能表征

doi:10.7503/cjcu20160400

摘要/Abstract

摘要：

以油包水(W/O)乳液作为软模板, 十二烷基苯磺酸钠(DBSNa)和对甲苯磺酸(TsOH)作为掺杂剂, 过氧化苯甲酰(BPO)作为氧化剂, 采用原位聚合法制备了聚吡咯微胶囊, 形成以氯化锌水溶液为芯材, 聚吡咯为壁材的核-壳结构的微米材料. 表征结果发现, 当包覆氯化锌水溶液浓度为20%(质量分数), 十二烷基苯磺酸钠、对甲苯磺酸和过氧化苯甲酰含量占单体的质量分数分别为1.27%, 4.12%和123.71%时, 形成的聚吡咯微胶囊大小均一, 粒径在50 μm左右, 微胶囊表面形貌饱满光滑. 有望拓展水性药物和全固态离子选择电极的应用领域.

关键词: 导电聚合物, 聚吡咯, 微胶囊, 油包水乳液

Abstract:

Conductive polymer microcapsules have become a new research highlight because of its properties of both conductivity and micro/nano structure. Polypyrrole microcapsules containing ZnCl₂ solution were chemically synthesized by in-situ polymerization method with water-in-oil emulsion as soft template, sodium dodecylbenzenesulfonate(DBSNa) and p-toluene sulphonic acid(TsOH) as dopants, benzoyl peroxide(BPO) as oxidant. Characterization results show that the polypyrrole microcapcules are regular core-shell structure when the concentration of ZnCl₂ is 20%(mass fraction), the mass fractions of DBSNa, TsOH, BPO to the monomer are 1.27%, 4.12%, 123.71%, respectively. And the microcapcules have a fullness and smooth surface and the particle size of about 50 μm. This study is expected to expand the application of water-soluble drugs and all-solid-state ion selective electrode.

Key words: Conductive polymer, Polypyrrole, Microcapsule, Water-in-oil emulsion

中图分类号:

O632.6
O642

TrendMD:

药健, 王建平, 魏尧, 王学晨, 李伟, 张兴祥. 含氯化锌的聚吡咯微胶囊的制备与性能表征. 高等学校化学学报, 2016, 37(10): 1907.

YAO Jian, WANG Jianping, WEI Yao, WANG Xuechen, LI Wei, ZHANG Xingxiang. Synthesis and Characterization of Polyprrole Microcapcule Containing ZnCl₂ Solution^†. Chem. J. Chinese Universities, 2016, 37(10): 1907.

图/表 16

Scheme 1 Structures of typical conductive polymer

Scheme 2 Reaction processes of PPy microcapsules containing ZnCl2

Table 1 Recipes for the fabrication of microcapsules

Sample	m_BPO/g	Mass fraction of the monomer(%)	$m ZnC l 2$ /g	Concentration(%)	m_TsOH/g	Mass fraction of TSOH(%)	m_Emulsifier/g
S1	6	123.71	0.1	1			2.0
S2	6	123.71	0.5	5			2.0
S3	6	123.71	1	10			2.0
S4	6	123.71	2	20			2.5
S5	6	123.71	3	30			3.0
S6	1	20.61	2	20			2.5
S7	4	82.47	2	20			2.5
S8	8	164.95	2	20			2.5
S9	6	123.71	2	20	0.05	1.03	2.5
S10	6	123.71	2	20	0.10	2.06	2.5
S11	6	123.71	2	20	0.20	4.12	2.5
S12	6	123.71	2	20	0.30	6.18	2.5

Table 1 Recipes for the fabrication of microcapsules

Sample	m_BPO/g	Mass fraction of the monomer(%)	$m ZnC l 2$ /g	Concentration(%)	m_TsOH/g	Mass fraction of TSOH(%)	m_Emulsifier/g
S1	6	123.71	0.1	1			2.0
S2	6	123.71	0.5	5			2.0
S3	6	123.71	1	10			2.0
S4	6	123.71	2	20			2.5
S5	6	123.71	3	30			3.0
S6	1	20.61	2	20			2.5
S7	4	82.47	2	20			2.5
S8	8	164.95	2	20			2.5
S9	6	123.71	2	20	0.05	1.03	2.5
S10	6	123.71	2	20	0.10	2.06	2.5
S11	6	123.71	2	20	0.20	4.12	2.5
S12	6	123.71	2	20	0.30	6.18	2.5

Fig.1 ESEM images of microcapsules with different concentrations of ZnCl2Mass fraction of ZnCl2: (A) 1%; (B) 5%; (C) 10%; (D) 20%; (E) 30%.

Fig.2 Optical microscope images of microcapsules with different concentrations of ZnCl2 Mass fraction of ZnCl2: (A) 1%; (B) 5%; (C) 10%; (D) 20%; (E) 30%.

Fig.3 Particle size distribution of sample S4

Fig.4 ESEM images of microcapsules with different contents of BPOMass fraction of BPO: (A) 20.61%; (B) 82.47%; (C) 123.71%; (D) 164.95%.

Fig.5 Optical microscope images of microcapsules with different contents of BPOMass fraction of BPO: (A) 20.61%; (B) 82.47%; (C) 123.71%; (D) 164.95%.

Fig.6 Particle size distribution of sample S8

Fig.7 ESEM images of microcapsules with different contents of TsOHMass fraction of TsOH: (A)1.03%; (B) 2.06%; (C) 4.12%; (D) 6.18%.

Fig.8 Optical microscope images of microcapsules with different contents of TsOHMass fraction of TsOH: (A)1.03%; (B) 2.06%; (C) 4.12%; (D) 6.18%.

Fig.9 Particle size distribution of sample S11

Fig.10 SEM images of cross section of microcapsules

Fig.11 FTIR spectra of ZnCl2-PPy microcapsules a. S4; b. S8; c. S11.

Fig.12 XPS spectra of ZnCl2-PPy microcapsules(A) Ungrinded; (B) grinded.

Fig.13 Raman spectrum of PPy microcapcules

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