交联水性聚氨酯固-固相变材料的制备及性能

doi:10.16085/j.issn.1000-6613.2021-1281

摘要/Abstract

摘要：

以聚乙二醇2000（PEG2000）为软段，异佛尔酮二异氰酸酯（IPDI）为硬段，丙三醇（GL）为扩链剂，制备了一种交联高分子水性聚氨酯固-固相变材料（WPUPCM）。首先，探讨了单体摩尔比、软段含量对WPUPCM储热性能和相变形态的影响；然后，利用红外光谱仪、原子力显微镜、偏光显微镜-热台系统、热重分析仪和差示扫描量热仪对所制备WPUPCM的化学结构、微观结构、结晶性能、热稳定性和循环稳定性做了测试和分析；最后，探讨了经WPUPCM处理后的蓄热调温纺织品的调温性能。结果表明，单体摩尔比和软段含量对WPUPCM的储热性能和相变形态有很大影响，减少软段含量和增加扩链剂的比例均有利于WPUPCM熔融温度的降低，当PEG、IPDI、GL的单体摩尔比为1∶1.8∶0.5时，所制备WPUPCM的熔融温度为35.52℃，并具有较高的熔融热焓（89.75J/g），可以较好地满足其在纺织服装领域的应用需求。所制备的WPUPCM与纯PEG相比，结晶机理均为均相成核结晶，由于硬段的束缚使得WPUPCM的结晶速率变慢，球晶尺寸变小，球晶稳定性提高。研究同时表明所制备的WPUPCM具有良好的热稳定性、循环使用稳定性和调温性能。

关键词: 乳液, 固-固相变材料, 水性聚氨酯, 相变, 结晶, 交联

Abstract:

A cross-linked waterborne polyurethane solid-solid phase change material (WPUPCM) was prepared with polyethylene glycol 2000 (PEG2000) as the soft segment, isophorone diisocyanate (IPDI) as the hard segment, and glycerol (GL) as the chain extender. Firstly, the effects of monomer molar ratio and soft segment content on thermal storage performance and phase transformation morphology of WPUPCM were discussed. Then, the chemical structure, microstructure, crystallization performance, thermal stability and cycle stability of the prepared WPUPCM were tested and analyzed by infrared spectrometer, atomic force microscope, polarizing microscope-heat table system, thermogravimetric analyzer and differential scanning calorimetry. Finally, the temperature regulation performance of heat storage and temperature regulation textiles after WPUPCM treatment was discussed. The results indicated that the monomer molar ratio and soft segment content had a great influence on the heat storage performance and phase transformation morphology of WPUPCM. Reducing the soft segment content and increasing the proportion of chain extender were conducive to the reduction of the melting temperature of WPUPCM. When the monomer molar ratio of PEG, IPDI and GL was 1∶1.8∶0.5, the melting temperature of the prepared WPUPCM was 35.52℃ with a high melting enthalpy of 89.75J/g, which can well satisfy its application requirements in the textile and clothing field. Compared with pure PEG, the prepared WPUPCM had a homogeneous nucleation crystallization mechanism. Due to the constraint of the hard segment, the crystallization rate of WPUPCM slowed down, the size of the spherulites became smaller, and the stability of the spherulites was improved. The study also showed that the prepared WPUPCM had good thermal stability, cycle stability and good temperature regulation performance.

Key words: emulsions, solid-solid phase change material, waterborne polyurethane, phase change, crystallization, cross-linked

中图分类号:

TQ323.8

陆少锋, 崔杉杉, 师文钊, 李苏松, 谢艳, 杨乾诚. 交联水性聚氨酯固-固相变材料的制备及性能[J]. 化工进展, 2022, 41(5): 2574-2581.

LU Shaofeng, CUI Shanshan, SHI Wenzhao, LI Susong, XIE Yan, YANG Qiancheng. Preparation and properties of cross-linked waterborne polyurethane solid-solid phase change material[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2574-2581.

图/表 12

参考文献 21

1	ZHAO C Y, ZHANG G H. Review on microencapsulated phase change materials(MEPCMs): fabrication, characterization and applications[J]. Renewable and Sustainable Energy Reviews, 2011, 15(8): 3813-3832.
2	IQBAL K, SUN D M. Development of thermo-regulating polypropylene fibre containing microencapsulated phase change materials[J]. Renewable Energy, 2014, 71: 473-479.
3	YU Q, TCHUENBOU-MAGAIA F, AL-DURI B, et al. Thermo-mechanical analysis of microcapsules containing phase change materials for cold storage[J]. Applied Energy, 2018, 211: 1190-1202.
4	FAN Z G, HAN P J, ZHANG Z G, et al. Optimized emulsifier combination based microencapsulated phase change materials（MicroPCMs）: preparation, characterization, and applications[J]. Journal of Renewable and Sustainable Energy, 2020, 12(1): 014102.
5	MA X G, WANG L, LI L, et al. The novel thermochromic and energy-storage microcapsules with significant extension of color change range to different tones[J]. Journal of Macromolecular Science, Part A, 2019, 56(6): 588-596.
6	RAHIMI M, MOKHTARI J. Fabrication of thermo-regulating hexadecane-polyurethane core-shell composite nanofibrous mat as advanced technical layer: effect of coaxial nozzle geometry[J]. Journal of Industrial Textiles, 2018, 47(6): 1134-1151.
7	RAHIMI M, MOKHTARI J. Modeling and optimization of waterproof-breathable thermo-regulating core-shell nanofiber/net structured membrane for protective clothing applications[J]. Polymer Engineering & Science, 2018, 58(10): 1756-1765.
8	CHO J S, KWON A, CHO C G. Microencapsulation of octadecane as a phase-change material by interfacial polymerization in an emulsion system[J]. Colloid and Polymer Science, 2002, 280(3): 260-266.
9	DU X, WANG H, CHENG X, et al. Synthesis and thermal energy storage properties of a solid-solid phase change material with a novel comb-polyurethane block copolymer structure[J]. RSC Advances, 2016, 6(48): 42643-42648.
10	HARLÉ T, NGUYEN T M, LEDESERT B, et al. Cross-linked polyurethane as solid-solid phase change material for low temperature thermal energy storage[J]. Thermochimica Acta, 2020, 685: 178191.
11	MU B Y, LI M. Fabrication and characterization of polyurethane-grafted reduced graphene oxide as solid-solid phase change materials for solar energy conversion and storage[J]. Solar Energy, 2019, 188: 230-238.
12	PAKDEL E, NAEBE M, SUN L, et al. Advanced functional fibrous materials for enhanced thermoregulating performance[J]. ACS Applied Materials & Interfaces, 2019, 11(14): 13039-13057.
13	粟劲苍, 刘朋生. 高分子固-固相变储能材料的研究与应用[J]. 合成树脂及塑料, 2006, 23(2): 77-80.
	SU Jincang, LIU Pengsheng. Studies and applications of polymer solid-solid phase transition materials for thermal energy storage[J]. China Synthetic Resin and Plastics, 2006, 23(2): 77-80.
14	CHEN C Z, CHEN J, JIA Y F, et al. Binary shape-stabilized phase change materials based on poly(ethylene glycol)/polyurethane composite with dual-phase transition[J]. Journal of Materials Science, 2018, 53(24): 16539-16556.
15	王宇, 田春蓉, 芦艾, 等. 聚氨酯固-固相变材料的合成与性能分析[J]. 化工新型材料, 2013, 41(2): 82-84.
	WANG Yu, TIAN Chunrong, LU Ai, et al. Synthesis and properties of polyurethane phase change materials(PUPCMs)[J]. New Chemical Materials, 2013, 41(2): 82-84.
16	WEI K, MA B, DUAN S Y. Preparation and properties of bitumen-modified polyurethane solid-solid phase change materials[J]. Journal of Materials in Civil Engineering, 2019, 31(8): 04019139.
17	DENG Y J, ZHON C, ZHANG Q X, et al. Structure and performance of waterborne polyurethane-acrylate composite emulsions for industrial coatings: effect of preparation methods[J]. Colloid and Polymer Science, 2020, 298(2): 139-149.
18	JIANG W C, HUANG Y G, GU G T, et al. A novel waterborne polyurethane containing short fluoroalkyl chains[J]. Journal of Applied Polymer Science, 2011, 121(3): 1536-1542.
19	EI-MOLLA M M. Synthesis of polyurethane acrylate oligomers as aqueous UV-curable binder for inks of ink jet in textile printing and pigment dyeing[J]. Dyes and Pigments, 2007, 74(2): 371-379.
20	陈荣圻. 水性聚氨酯及其在纺织助剂中的应用[J]. 染料与染色, 2013, 50(6): 40-48.
	CHEN Rongqi. Waterborne polyurethanes and their application in textile auxiliaries[J]. Dyestuffs and Coloration, 2013, 50(6): 40-48.
21	肖超鹏, 陆少锋, 谢艳, 等. 高分子固-固相变储能材料的制备与应用[J]. 印染, 2020, 46(3): 5-9.
	XIAO Chaopeng, LU Shaofeng, XIE Yan, et al. Preparation and application of polymer solid-solid phase change energy storage materials[J]. China Dyeing & Finishing, 2020, 46(3): 5-9.

PEG∶IPDI∶GL	PEG含量/%	T_m/℃	ΔH_m/J·g^-1	相变形态
1∶1.1∶0.067	88.86	53.37	179.53	固-液
1∶1.2∶0.13	87.76	50.19	170.82	固-液
1∶1.3∶0.2	86.69	47.59	158.35	固-固
1∶1.4∶0.27	85.64	44.21	136.51	固-固
1∶1.5∶0.33	84.60	42.63	113.74	固-固
1∶2∶0.67	79.83	35.19	80.10	固-固
1∶3∶1.33	71.72	30.34	32.56	固-固
1∶4∶2	65.10	25.81	20.31	固-固

PEG∶IPDI∶GL	PEG含量/%	T_m/℃	ΔH_m/J·g^-1	相变形态
1∶1.1∶0.067	88.86	53.37	179.53	固-液
1∶1.2∶0.13	87.76	50.19	170.82	固-液
1∶1.3∶0.2	86.69	47.59	158.35	固-固
1∶1.4∶0.27	85.64	44.21	136.51	固-固
1∶1.5∶0.33	84.60	42.63	113.74	固-固
1∶2∶0.67	79.83	35.19	80.10	固-固
1∶3∶1.33	71.72	30.34	32.56	固-固
1∶4∶2	65.10	25.81	20.31	固-固

PEG∶IPDI∶GL	PEG含量/%	T_m/℃	ΔH_m/J·g^-1	相变形态
1∶1.8∶0.5	81.78	35.52	89.75	固-固
1∶1.8∶0.8	80.86	31.08	76.60	固-固
1∶2∶0.67	79.83	35.19	80.10	固-固
1∶2∶1	78.80	32.83	75.60	固-固

PEG∶IPDI∶GL	PEG含量/%	T_m/℃	ΔH_m/J·g^-1	相变形态
1∶1.8∶0.5	81.78	35.52	89.75	固-固
1∶1.8∶0.8	80.86	31.08	76.60	固-固
1∶2∶0.67	79.83	35.19	80.10	固-固
1∶2∶1	78.80	32.83	75.60	固-固

循环次数/次	T_m/℃	ΔH_m/J·g^-1	T_c/℃	ΔH_c/J·g^-1
0	35.52	89.75	3.12	84.92
500	35.08	89.03	2.75	85.67
1000	34.57	88.24	1.98	86.29
2000	32.41	87.66	1.23	86.91
3000	31.98	86.92	0.52	87.24