丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征

doi:10.7503/cjcu20150655

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2557.doi: 10.7503/cjcu20150655

丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征

牟思阳, 郭静(), 齐善威, 张勃, 张鸿, 于跃

大连工业大学纺织与材料工程学院, 辽宁省功能纤维及其复合材料工程技术研究中心, 大连 116034

收稿日期:2015-08-19 出版日期:2015-12-10 发布日期:2015-11-17
作者简介:联系人简介: 郭静, 女, 博士, 教授, 博士生导师, 主要从事高分子材料成型加工与改性研究. E-mail:guojing@dlpu.edu.cn
基金资助:
国家自然科学基金(批准号: 51373027)和辽宁省科学技术基金(批准号: 2015020221)资助

Synthesis and Characterization of Poly(acrylonitrile-co-itaconate)-graft-Poly(ethylene glycol) Copolymers as Novel Solid-Solid Phase Change Materials for Thermal Energy Storage^†

MU Siyang, GUO Jing^*(), QI Shanwei, ZHANG Bo, ZHANG Hong, YU Yue

School of Textile and Material Engineering, Functional Fiber and Its Composite Materials Engineering Technology Research Center in Liaoning Province, Dalian Polytechnic University, Dalian 116034, China

Received:2015-08-19 Online:2015-12-10 Published:2015-11-17
Contact: GUO Jing E-mail:guojing@dlpu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.51373027) and the Liaoning Science and Technology Foundation of China(No.2015020221)

摘要/Abstract

摘要：

将衣康酸与丙烯腈共聚, 构建具有双端羧基活性点的聚合物骨架, 以二苯甲烷二异氰酸酯(MDI)为桥基, 将聚乙二醇(PEG)接枝到聚合物骨架上, 制备了丙烯腈-衣康酸共聚物接枝聚乙二醇(AIPCMs). 采用红外光谱、差示扫描量热、 X射线衍射、偏光显微镜、热失重及水静态接触角等方法研究了其结构、相变潜热性能、结晶性能、结晶形态、热稳定性及亲水性. 结果表明, 合成的AIPCMs具有固-固相变特性及优异的热储能性能, 相变潜热达到70.5 J/g. 化学接枝改变了AIPCMs中PEG的结晶结构及结晶形态. AIPCMs的热稳定性优异, 初始分解温度达 289 ℃, 并且其亲水性较好, 接触角最小可达 33.71°.

关键词: 固-固相变材料, 聚乙二醇, 能量储存与转换, 丙烯腈-衣康酸共聚物

Abstract:

The core of this study firstly synthesizes an “active” matrix materials with the itaconic acid containing double-carboxyl end group and acrylonitrile copolymer through molecular design. Then, the poly(ethy-lene glycol)(PEG) was grafted to the poly(acrylonitrile-co-itaconate)[P(AN-co-IA)] using methylenediphenyl diisocyanate(MDI) as a bridge-base and cross-linking agent. The poly(acrylonitrile-co-itaconate)-graft-poly(ethylene glycol)[P(AN-co-IA)-g-PEG] solid-solid phase change materials(SSPCMs) were obtained in this paper. Furthermore, the chemical structure, crystallization properties, thermal energy storage properties , crystallization process, thermal stabilities, and hydrophilic property of the SSPCMs were investigated using Fourier transform infrared, differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy, thermogravimetric analysis and water contact angle, respectively. The results showed that these SSPCMs had the characteristics of solid-solid phase change, excellent energy storage properties and latent heat of 70 J/g or more. The crystalline morphology and crystal structures of the synthesized SSPCMs are difference from PEG and P(AN-co-IA). Moreover, The SSPCMs have a good thermal stability and the initial decomposition temperature(T_d) is 289 ℃, and the hydrophilic property of the blend membrane were improved, the water contact angle minimum can be achieved at 33.71°.

Key words: Solid-solid phase change material, Poly(ethylene glycol), Energy storage and conversion, Poly(acrylonitrile-co-itaconate)

中图分类号:

O631

TrendMD:

牟思阳, 郭静, 齐善威, 张勃, 张鸿, 于跃. 丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征. 高等学校化学学报, 2015, 36(12): 2557.

MU Siyang, GUO Jing, QI Shanwei, ZHANG Bo, ZHANG Hong, YU Yue. Synthesis and Characterization of Poly(acrylonitrile-co-itaconate)-graft-Poly(ethylene glycol) Copolymers as Novel Solid-Solid Phase Change Materials for Thermal Energy Storage^†. Chem. J. Chinese Universities, 2015, 36(12): 2557.

图/表 9

Scheme 1 Synthetic routes of P(AN-co-IA)-g-PEG

Fig.1 FTIR spectra of PEG(a), P(AN-co-IA)(b) and AIPCMs-2(c)

Fig.2 DSC curves of AIPCMs with different PEG content(A, B) and crystallization curves of AIPCMs(C)

Table 1 Thermal energy storage properties of PEG and AIPCMs

Sample^*	T_c(on) /℃	ΔH_c/(J·g^-1)	T_m(on) /℃	ΔH_m/(J·g^-1)
PEG	44.52	178.3	66.14	184.8
AIPCMs-1	33.1	9.1	48.5	11.2
AIPCMs-2	39.52	32.1	53.43	32.4
AIPCMs-3	38.52	47.1	53.48	49.1
AIPCMs-4	38.57	69.2	53.58	70.5

Fig.3 DSC curves of AIPCMs after 5 cycles

Fig.4 XRD curves of PEG4000 and AIPCMs

Fig.5 POM images of AIPCMs-3(A, B) and PEG(C, D) at 80 ℃(A, C) and 20 ℃(B, D)

Fig.6 TGA curves of P(AN-co-IA)(a), PEG(b) and AIPCMs-2(c)

Fig.7 TGA curves of AIPCMs-1(a), AIPCMs-2(b), AIPCMs-3(c) and AIPCMs-4(d) Temperature range: (A) 0—600 ℃; (B) 230—340 ℃; (C) 380—450 ℃.

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丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征

Synthesis and Characterization of Poly(acrylonitrile-co-itaconate)-graft-Poly(ethylene glycol) Copolymers as Novel Solid-Solid Phase Change Materials for Thermal Energy Storage^†

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丙烯腈-衣康酸共聚物接枝聚乙二醇固-固相变材料的制备及表征

Synthesis and Characterization of Poly(acrylonitrile-co-itaconate)-graft-Poly(ethylene glycol) Copolymers as Novel Solid-Solid Phase Change Materials for Thermal Energy Storage†

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Synthesis and Characterization of Poly(acrylonitrile-co-itaconate)-graft-Poly(ethylene glycol) Copolymers as Novel Solid-Solid Phase Change Materials for Thermal Energy Storage^†