P[MMA-IL]修饰石墨烯协同调控PVDF复合物结晶与介电行为

胡亚东; 徐佩; 罗霄; 左新钢; 陈放; 丁运生

doi:10.11777/j.issn1000-3304.2017.16231

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P[MMA-IL]修饰石墨烯协同调控PVDF复合物结晶与介电行为

研究论文 | 更新时间：2021-03-19

- P[MMA-IL]修饰石墨烯协同调控PVDF复合物结晶与介电行为
- Effect of Graphene Modified by P[MMA-IL] on the Crystallization and Dielectric Behavior of PVDF Composite Film
- 高分子学报 2017年第5期页码：776-784
- 作者机构：
  
  1.合肥工业大学化学与化工学院合肥 230009
  2.先进功能材料与器件安徽省重点实验室合肥 230009
- 作者简介：
  
  徐佩, E-mail:chxuper@hfut.edu.cn Pei Xu, E-mail:chxuper@hfut.edu.cn
  丁运生, E-mail:dingys@hfut.edu.cn Yun-sheng Ding, E-mail:dingys@hfut.edu.cn
- 基金信息：
  
  国家自然科学基金(51603060);国家自然科学基金(51373045);中央高校基本科研业务费专项(JZ2016HGTB0723)
- DOI：10.11777/j.issn1000-3304.2017.16231
  中图分类号：
- 纸质出版日期：2017-5，
  
  收稿日期：2016-7-18，
  
  修回日期：2016-8-26，
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胡亚东, 徐佩, 罗霄, 左新钢, 陈放, 丁运生. P[MMA-IL]修饰石墨烯协同调控PVDF复合物结晶与介电行为[J]. 高分子学报, 2017,(5):776-784.

Ya-dong Hu, Pei Xu, Xiao Luo, Xin-gang Zuo, Fang Chen, Yun-sheng Ding. Effect of Graphene Modified by P[MMA-IL] on the Crystallization and Dielectric Behavior of PVDF Composite Film[J]. Acta Polymerica Sinica, 2017,(5):776-784.
胡亚东, 徐佩, 罗霄, 左新钢, 陈放, 丁运生. P[MMA-IL]修饰石墨烯协同调控PVDF复合物结晶与介电行为[J]. 高分子学报, 2017,(5):776-784. DOI： 10.11777/j.issn1000-3304.2017.16231.

Ya-dong Hu, Pei Xu, Xiao Luo, Xin-gang Zuo, Fang Chen, Yun-sheng Ding. Effect of Graphene Modified by P[MMA-IL] on the Crystallization and Dielectric Behavior of PVDF Composite Film[J]. Acta Polymerica Sinica, 2017,(5):776-784. DOI： 10.11777/j.issn1000-3304.2017.16231.

摘要

为改善石墨烯（Gra）在聚偏氟乙烯（PVDF）中的分散性和界面性质，以甲基丙烯酸甲酯（MMA）和1-乙烯基-3-乙基咪唑溴盐（IL）为单体合成P[MMA-IL]共聚物，用于修饰石墨烯（Gra），并通过溶液共混、热压法制备PVDF/PMMA、PVDF/P[MMA-IL]

、PVDF/PMMA/Gra和PVDF/P[MMA-IL]/Gra复合薄膜.采用Raman光谱、场发射扫描电子显微镜（FESEM）、傅里叶变换反射红外光谱分析仪（FTIR-ATR）、X射线衍射仪（XRD）、偏光显微镜（POM）、示差扫描量热仪（DSC）和电感电容电阻测试仪（LCR）对复合薄膜的结构形态、结晶与介电行为进行表征和分析. Raman光谱表明P[MMA-IL]

与Gra之间存在强相互作用；FESEM照片显示P[MMAIL]能够促进Gra在基体中的分散；DSC、XRD和FTIR-ATR数据表明PMMA降低PVDF的结晶温度，PMMA和Gra未能诱导出

-PVDF极性晶体，而单独的P[MMA-IL]会通过咪唑阳离子-偶极子作用诱导

-PVDF晶体；通过咪唑阳离子-

强相互作用，P[MMA-IL]在模板剂Gra表面进行修饰，协同诱导作用增强. POM照片表明

-PVDF晶体在生长过程中，MMA链段会嵌入到球晶的晶片空隙中，引起结构疏松；离子-偶极子和IL成核作用导致

-PVDF晶体尺寸较小，结晶较快.介电行为研究表明PMMA及其修饰Gra降低PVDF的结晶度和链浓度，导致界面极化和取向极化较弱，介电响应较弱；而P[MMA-IL]修饰Gra诱导的

-PVDF晶体、以及IL链段在界面的离子极化使得界面极化作用增强，介电响应增强.

Abstract

In order to enhance the dispersion of graphene (Gra) in PVDF matrix and improve the interface properties of the composite materials

a copolymer (P[MMA-IL]) with 1-vinyl-3-ethyl imidazole bromine (IL) and methyl methacrylate (MMA) was synthesized by radical polymerization. A series of PVDF/PMMA

PVDF/PMMA/Gra

PVDF/P[MMA-IL]

and PVDF/P[MMA-IL]/Gra were prepared using a solution-cast and hot pressing method. The morphological structure

crystallization and dielectric behavior were investigated by Raman spectrometer

field emission scanning electron microscope (FESEM)

X-ray diffraction (XRD)

polarized optical microscopy (POM)

differential scanning calorimetry (DSC) and LCR meter

respectively. Raman spectra indicated that strong π interaction between imidazole ring and carbon ring established between P[MMA-IL]

and Gra

and FESEM observation showed the good dispersity of Gra in PVDF matrix due to that interaction. DSC results indicated that

of PVDF was decreased by the presence of PMMA as a diluent

and that

and

of PVDF were promoted by P[MMA-IL] modified Gra because of the presence of

polar crystal. Gra was modified by P[MMA-IL] as a template to increase the degree of crystallinity of PVDF. XRD and FTIR-ATR results confirmed that the

-crystal was not induced by PMMA and Gra

but by P[MMA-IL] due to the electrostatic interaction between the

of the polymer backbone and imidazolium cation

and the strong induction was brought by the template of Gra. POM photos displayed that

-crystal with loose structure were embedded into the chip space of spherulites because the presence of MMA chain segments. The electrostatic interaction and nucleating agents of IL chain segments resulted in

crystal with small size and increased the crystallization rate. Dielectric properties study showed that PMMA and modified Gra reduced the crystallinity and concentration of PVDF chain

leading to weak interface polarization and orientation polarization of PVDF. The dielectric constant is low. While P[MMA-IL]

and modified Gra induced more

crystal

the strong interface polarization was enhanced by

crystal and ion polarization of IL chain segments improved the dielectric constant.

关键词

聚偏氟乙烯甲基丙烯酸甲酯离子液体结晶行为介电行为

Keywords

Polyvinylidene fluorideMethyl methacrylateIonic liquidCrystallization behaviorDielectric behavior

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