赤藓糖醇与共价交联网络复合材料的制备与可控相变性质

Preparation and Controllable Phase Change Properties of Composites Between Erythritol and Covalent Cross-linking Network

摘要

构建了一种基于聚乙烯亚胺（PEI）与丙三醇三缩水甘油醚（GTE）的化学交联聚合物网络体系， 并以此为载体制备了释热过程可控的赤藓糖醇（ERY）相变复合材料， 系统探究了该聚合物网络对ERY过冷稳定性及结晶行为的调控机制. 结果表明， 聚合物网络通过物理相互作用与ERY结合， ERY能够在网络中保持原有晶体结构. 值得注意的是， 聚合物网络交联度的增加导致冷结晶温度降低， 这一现象与传统理论预期相悖， 因为交联度增加意味着网络中-OH基团增多， 本应增强与ERY的相互作用， 从而提高冷结晶温度. 进一步分析发现， 聚合物网络中-OH 基团之间形成的分子内氢键竞争性地削弱了网络与ERY 分子的有效相互作用， 从而促进了其本征结晶行为. 本研究为深入理解ERY基复合相变材料中分子间相互作用对相变热力学行为的调控规律提供了新的视角和实验依据.

Abstract

A chemically cross-linked polymer network system based on polyethyleneimine（PEI） and glycerol triglycidyl ether（GTE） was constructed. Using this system as a matrix， erythritol（ERY） phase change composites with controllable heat release behavior were prepared， and the regulatory mechanism of the polymer network on the supercooling stability and crystallization behavior of ERY was systematically investigated. The results show that the polymer network interacts with ERY through physical interactions， and ERY maintains its original crystal structure within the network. Notably， the increase in cross-linking density of the polymer network leads to a decrease in the cold crystallization temperature， which contradicts conventional theoretical expectations， as a higher cross-linking density implies an increase in -OH groups within the network that should enhance interactions with ERY and thereby increase the cold crystallization temperature. Further analysis reveals that intramolecular hydrogen bonds formed among the -OH groups within the polymer network competitively weaken the effective interactions between the network and ERY molecules， thereby promoting its intrinsic crystallization behavior. This study provides a new perspective and experimental basis for in-depth understanding of the regulation of intermolecular interactions on the phase change thermodynamic behavior in ERY-based composite phase change materials.

关键词

赤藓糖醇 / 相变材料 / 可控相变材料 / 分子间相互作用 / 聚合物网络

Key words

Erythritol / Phase change material / Controllable phase change material / Molecular interactions / Polymer network

参考文献

[1] Cai L., Li L. Z., Li H., Cai C., Li T. H. , Chem. J. Chinese Universities, 2025, 46(10), 20250035

[2] (蔡磊, 李立哲, 李昊, 蔡畅, 李铁虎 . 高等学校化学学报, 2025, 46(10), 20250035)

[3] Xie Z. X., Kou Y., Shi Q., Tian Y. , Chem. J. Chinese Universities, 2025, 46(2), 20240372

[4] (解卓学, 寇艳, 史全, 田颖 . 高等学校化学学报, 2025, 46(2), 20240372)

[5] Geng L., Cui J., Zhang C., Yan Y., Zhao J., Liu C. , Chem. Eng. J., 2024, 495, 153359

[6] Chen S., Long Z., Jia L., Wang Y., Zhao G. , J. Energy Storage, 2026, 166, 122352

[7] Zhang H., van Wissen R., Nedea S., Rindt C. , In Proceedings of the Advances in Thermal Energy Storage, Eurotherm Seminar 99, Lleida, 2014, 1-11

[8] Diarce G., Gandarias I., Campos-Celador A., García-Romero A., Griesser U. J. , Sol. Energy Mater. Sol. Cells, 2015, 134, 215-226

[9] Zhang H., Nedea S., Rindt C. , The 13th International Conference on Energy Storage-Greenstock 2015, Beijing, 2015, 19-21

[10] Hua W., Lv X., Zhang X., Ji Z., Zhu J. , J. Energy Storage, 2023, 67, 107378

[11] Li X., Zhang J., Liu Y., Xu Y., Cui K., Yao Z., Fu B., Song C., Shang W., Tao P., Deng T. , Chem. Eng. J., 2023, 452, 139328

[12] Suzuki M., Machida H., Satomi H., Hirasawa I ., Kagaku Kogaku Ronbunshu, 2018, 44(1), 12-17

[13] Pan M., Wang D., Wang L., Dong N., Xie H., Yu W. , Chem. Eng. J., 2024, 499, 156058

[14] Nakano K., Masuda Y., Daiguji H. , J. Phys. Chem. C, 2015, 119(9), 4769-4777

[15] Shao X., Chenxu Y., Wang B., Zhang N., Yuan Y. , Sol. Energy Mater. Sol. Cells, 2023, 256, 112335

[16] Puupponen S., Seppälä A. , Sol. Energy Mater. Sol. Cells, 2018, 180, 59-66

[17] Turunen K., Yazdani M. R., Puupponen S., Santasalo-Aarnio A., Seppälä A. , Appl. Energy, 2020, 266, 114890

[18] Turunen K., Mikkola V., Laukkanen T., Seppälä A. , Appl. Energy, 2023, 332, 120530

[19] Turunen K., Yazdani M. R., Santasalo-Aarnio A., Seppälä A. , Sol. Energy Mater. Sol. Cells, 2021, 230, 111273

[20] Turunen K., Santasalo-Aarnio A., Seppälä A.; Ed: Droege P., Stadler I., Trimborn C. , Proceedings of the 14th International Renewable Energy Storage Conference 2020(IRES 2020), Atlantis Press, Paris, 2021, Vol. 6, 186-192

[21] Yuan M., Cao D., Liu C., Xu C., Liao Z. , Chem. Eng. J., 2023, 469, 143743

[22] Yang S., Shi H. Y., Liu J., Lai Y. Y., Bayer Ö., Fan L. W. , Nat. Commun., 2024, 15(1), 4948

[23] Li Y., Kou Y., Sun K., Chen J., Deng C., Fang C., Shi Q. , J. Energy Chem., 2023, 80, 228-236

[24] Chen J., Kou Y., Sun K., Liu H., Zhang X., Fang C., Shi Q. , Mater. Today Sustain., 2023, 22, 100398

[25] Chen J., Kou Y., Zhang S., Zhang X., Liu H., Yan H., Shi Q. , Angew. Chem. Int. Ed., 2024, 63(16), e202400759

[26] Smith B. C. , Spectrosc.(Santa Monica), 2022, 37(3), 17-19

[27] Yan H., Kou Y., Zhang S., Liu H., Yin N., Xu Y., Shi Q. , Chem. Eng. J., 2025, 522(3), 167630

[28] Gou D., Qiu P., Hong F., Wang Y., Ren P., Cheng X., Wang L., Liu T., Liu J., Zhao J. , Int. J. Biol. Macromol., 2024, 274, 132917

基金资助

国网陕西省电力有限公司科技项目(5226KY250018)