长链烷酸接枝羟丙基纤维素相变材料的制备及其性能

doi:10.11944/j.issn.1000-0518.2015.05.140303

摘要/Abstract

摘要：

采用酯化的方法将具有相变特征的长链脂肪酸接枝到羟丙基纤维素主链上, 得到了一系列性能稳定, 温度范围适宜的高分子固-固相变材料, 并利用傅里叶红外光谱(FT-IR)、核磁共振(NMR)、差示扫描量热仪(DSC)、热失重分析仪(TGA)和X射线散射等技术手段对其化学结构及相变行为进行了研究。结果表明, 该材料呈现出可逆的固-固相转变特性, 相变温度范围可通过改变脂肪酸的长度调节。利用棕榈酸、硬脂酸和花生酸获得的相变材料焓值达到60 J/g, 所获得的材料在250 ℃以内不发生热分解。通过将两种长链脂肪酸混合同时接枝到羟丙基纤维素主链上, 所得产物的吸/放热温度随着混合脂肪酸组分含量的变化而变化, 同时X射线散射的结果也证明羟丙基纤维素混合酯的分子间距是位于其两种单一酯之间的。这一结果为制备一定温度范围内任意相变温度的高分子固-固相变材料提供了简便的方法。

关键词: 羟丙基纤维素, 长链脂肪酸, 相变材料

Abstract:

A serials of hydroxypropyl cellulose esters graft copolymers with different phase change temperature was prepared. In these materials, semi-flexible hydroxypropyl celluloses serve as skeleton, and flexible alkanoic acid molecules serve as functional branch chains. The structures of the copolymers were characterized using FT-IR and NMR techniques. Their phase change properties and crystallization behavior were analyzed by DSC, TGA and X-ray scattering techniques. The results show that the temperatures at which the products absorb or release heat(melting or crystallization of the side chains) increase with the increase of side chain length. The phase change temperature of the materials can be adjusted by varying the length of the side chain. The fusion enthalpy reaches 60 J/g in case palmitic acid, stearic acid and eicosanoic acid are used. Furthermore, it is found that when mixed long-chain alkanoic acids are used as the reactant, the phase change temperatures of the products can be easily adjusted by changing the ratio of components in the mixture. This result are also proven by X-ray scattering results, the d-Spacing of hydroxypropyl cellulose mixed esters falls in between two single hydroxypropyl cellulose esters indicating that an effective grafting of both kinds of alkanoic acids on to the same hydroxypropyl cellulose chains. The results provide a facile method in preparing phase change temperature tunable polymer based solid-state phase change materials within certain temperature range.

Key words: hydroxypropyl cellulose, alkanoic acid, phase change material

中图分类号:

陈曦, 郑楠, 刘凌志, 门永锋. 长链烷酸接枝羟丙基纤维素相变材料的制备及其性能[J]. 应用化学, 2015, 32(5): 535-541.

CHEN Xi, ZHANG Nan, LIU Lingzhi, MEN Yongfeng. Preparation and Characterization of Alkanoic Acid Grafted Hydroxypropyl Cellulose Phase Change Materials[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 535-541.

参考文献

[1]	Belen Z, Marin J M, Luisa F. Review on Thermal Eenergy Storage with Phase Change Materials:Heat Transfer Analysis and Applications[J]. Appl Therm Eng, 2003, 23:251-283.
[2]	Mondal S. Phase Change Materials for Smart Textiles-An Overview[J]. Appl Therm Eng, 2008, 28:1536-1550.
[3]	Babaev B D, Gasanaliev A M. Phase Diagram of the System LiF-NaF-CaF2-BaF2- BaMoO4[ J ].Inorg Mater, 2003, 39:1203-1207.
[4]	Nagano K, Ogawa K, Mochida T, et al.Thermal Characteristics of Magnesium Nitrate Hexahydrate and Magnesium Chloride Hexahydrate Mixture as a Phase Change Material for Effective Utilization of Urban Waste Heat[J]. Appl Therm Eng, 2004, 24:221-232.
[5]	Ahmet S, Kamil K. Thermal Energy Storage System Using Stearic Acid as a Phase Change Material[J]. Solar Energy, 2001, 71:365-376.
[6]	Li W D, Ding E Y. Preparation and Characterization of a Novel Solid-liquid PCM:Butanediol Di-stearate[J]. Mater Lett, 2000, 61:1526-1528.
[7]	JIANG Yong, DING Enyong, LI Guokang. Progress in Studies of Phase Change Materials for Heat Energy Storage[J]. Guangzhou Chem, 1999, 3:48-54(in Chinese). 姜勇, 丁恩勇, 黎国康. 相变储能材料的研究进展[J]. 广州化学, 1999, 3:48-54.
[8]	He B, Martin V, Setterwall F. Phase Transition Temperature Ranges and Storage Density of Paraffin Wax Phase Change Materials[J]. Energy, 2004, 29:1785-1804.
[9]	Sharma S D, Iwata T, Kitano H, et al.Thermal Performance of a Solar Cooker Based on an Evacuated Tube Solar Collector with a PCM Storage Unit[J]. Solar Energy, 2005, 78:416-426.
[10]	Sari A. Thermal Characteristics of a Eutectic Mixture of Myristic and Palmitic Acids as Phase Change Material for Heating Applications[J]. Appl Therm Eng, 2003, 23:1005-1017.
[11]	Hawes D W, Feldman D, Banu D. Latent Heat Storage in Building Materials[J]. Energy Build, 1993, 20:77-86.
[12]	Nelson G. Application of Microencapsulation in Textiles[J]. Int J Pharmaceut, 2002, 242:55-62.
[13]	Vigo T L, Bruno J S. Temperature-Adaptable Textiles Containing Durably Bound Polyethylene Glycols[J]. Text Res J, 1987, 7:427-429.
[14]	Yuan X P, Ding E Y. Synthesis and Characterization of Storage Energy Materials Prepared from Nano-crystalline Cellulose Polyethylene Glycol[J]. Chinese Chem Lett, 2006, 17:1129-1132.
[15]	Han S O, Woo S K, Lee D W, et al.High Density Polyethylene as a Thermal Energy Storage Material[J]. Polym Mater Sci Eng, 1997, 77:525-526.
[16]	Guo Y Q, Liang X H. Phase Transition Properties of PEG-Cellulose Blends and Their Miscibility in Mixed Solvent[J]. J Macromol Sci-Phys, 1999, 38:449-459.
[17]	Jiang Y, Ding E Y, Li G K. Study on Transition Characteristics of PEG/CDA Solid-solid Phase Change Materials[J]. Polymer, 2002, 43:117-122.
[18]	Ival O S. Phase Change Materials Incorporated Throughout the Structure of Polymer Fibers:USP, 5885475[P], 1999-03-23.
[19]	LIU Xianzhi, LIU Lingzhi, MEN Yongfeng. Synthesis and Characterization of Chitosan/Paraffin PCM Microcapsules[J]. Chinese J Appl Chem, 2012, 29:7-13(in Chinese). 刘先之, 刘凌志, 门永锋. 石蜡相变微胶囊的制备与表征[J]. 应用化学, 2012, 29:7-13.
[20]	ZHANG Mei, NA Ying, JIANG Zhenhua. Preparation and Properties of Polymeric Solid-solid Phase Change Materials of Polyethylene Glycol(PEG)/Poly(vinyl alcohol)(PVA) Copolymers by Graft Copolymerization[J]. Chem J Chinese Univ, 2005, 26:170-174(in Chinese). 张梅, 那莹, 姜振华. 接枝共聚法制备聚乙二醇(PEG)/聚乙烯醇(PVA)高分子固-固相变材料性能研究[J]. 高等学校化学学报, 2005, 26:170-174.
[21]	Chen X, Liu L Z, Men Y F, et al.Effect of Synthetic Pathways on the Phase Transition and Side-chain Crystallization Behavior of Alkyl-substituted Cellulose Ethers[J]. Polym Chem, 2014, 5:4105-4114
[22]	Son C H, Morehouse J H. Thermal Conductivity Enhancement of Solid-solid Phase Materials for Thermal Storage[J]. J Thermophys Heat Transfer, 1991, 5:122-124.
[23]	Jiang Y, Ding E Y, Li G K. Study on Transition Characteristics of PEG/CDA Solid solid Phase Change Materials[J]. Polymer, 2002, 43:117-122.