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化学进展 2023, Vol. 35 Issue (7): 1106-1122 DOI: 10.7536/PC221102 前一篇   

• 综述 •

本征导热聚合物研究:机理、结构与性能及应用

周文英1,*(), 王芳1, 杨亚亭1, 王蕴1, 赵莹莹2, 张亮青2   

  1. 1 西安科技大学化学与化工学院 西安 710054
    2 西安科技大学材料科学与工程学院 西安 710054
  • 收稿日期:2022-06-17 修回日期:2022-09-13 出版日期:2023-07-24 发布日期:2022-10-30
  • 基金资助:
    国家自然科学基金(52277028); 国家自然科学基金(51577154); 陕西省自然科学基础项目(2022-JM186); 陕西省自然科学基础项目(2021JQ-566); 陕西省教育厅科研计划项目(21JK0756)
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Intrinsically Thermal Conductive Polymers: Heat Conduction Mechanism, Structure & Performances and Applications

Wenying Zhou1(), Fang Wang1, Yating Yang1, Yun Wang1, Yingying Zhao2, Liangqing Zhang2   

  1. 1 School of Chemistry & Chemical Engineering, Xi'an University of Science and Technology,Xi'an 710054, China
    2 School of Materials Science and Engineering, Xi'an University of Science and Technology,Xi'an 710054, China
  • Received:2022-06-17 Revised:2022-09-13 Online:2023-07-24 Published:2022-10-30
  • Contact: * e-mail: wyzhou2004@163.com
  • Supported by:
    National Natural Science Foundation of China(52277028); National Natural Science Foundation of China(51577154); Natural Science Basic Research Plan in Shaanxi Province of China(2022-JM186); Natural Science Basic Research Plan in Shaanxi Province of China(2021JQ-566); Scientific Research Program Funded by Shaanxi Provincial Education Department(21JK0756)

散热已成为制约超高频、大功率微电子器件和高电压电气绝缘设备日益微型化的技术瓶颈和发展面临的重要挑战,急需高性能的导热材料实现快速散热。相比导热高分子复合材料,本征结构的导热高分子材料因同步的高导热及高绝缘强度、优异柔韧性、轻质高强等优异的综合性能及优势受到了国内外学者的广泛研究和关注。本文首先讨论了聚合物的本征导热机理,系统深入地分析和评述了单体及分子链结构、结晶、取向、分子链间作用、交联、缺陷等结构因素,以及温度、压力、环境等因素对声子热传递及聚合物导热的影响机理,进一步归纳了本征导热聚合物的制备策略和途径。最后总结了当前本征导热聚合物研究面临的主要问题和挑战,展望了未来发展方向及其在众多领域的重要潜在应用。

关键词： 导热聚合物, 声子传递, 有序结构, 取向, 氢键

Heat dissipation has emerged as a critical challenge and technical bottleneck which is increasingly restricting the continuous miniaturization of large-power and ultrahigh frequency microelectronic devices and high-voltage electrical insulation equipment. High-performance heat conductive materials are highly desirable for effective thermal management. Compared with conventional heat conductive polymeric composites, the intrinsically thermal conductive polymers have gained extensive research and attention from domestic and overseas owing to their integrated excellent overall properties like high thermal conductivity and high dielectric breakdown strength, excellent flexibility, lightweight and high strength, etc. The present paper first discusses the heat conduction mechanisms in intrinsic polymers, and then systematically analyzes and reviews the following factors influencing phonon transport and polymers’ thermal conductivity: the structures from monomers and molecular chains with diverse scales, crystallinity, orientation, inter-chain interactions, crosslinking, structure defects, as well as temperature, pressure, environmental factors, etc. Further, the strategies to prepare high thermal conductivity polymers have been summarized. Finally, this paper sums up the existing questions and challenges ahead in the study of thermal conductive polymers, and points out their future research direction and prospects potential important applications in various industrial occasions.

Contents

1 Introduction

2 Thermal conduction mechanisms in polymers

3 Polymers’ structure and thermal conductivity

3.1 Near-range structures

3.2 Long-range structures

3.3 Aggregation structure

4 Other factors affecting TC

4.1 Density and specific heat capacity

4.2 Electrical conductivity

4.3 Speed of sound

4.4 Temperature

4.5 Pressure

4.6 Environmental factors

5 Strategies for the preparation of ITCP

5.1 Top-down methods

5.2 Bottom-up methods

6 Conclusion and Prospects

Key words: thermally conductive polymers, phonon transport, ordered structure, orientation, hydrogen bond
()
图1 聚合物的热传导机制(a~f: 热能在晶格中逐步传递示意图)
Fig.1 Thermal conduction mechanism in polymers[10]. (Reprinted with permission from Ref.[10]; Copyright (2016) Progress in Polymer Science)
图2 聚电解质(PAR,PVPR)、四个笼状分子[19](DSQ、GHSQ、PC71BM、ADP)、COF、MOF如基于卟啉的反应性金属原(PorV-x)[20]及液晶LC等分子结构
Fig.2 Structures of polyelectrolytes (PAR, PVPR), four caged molecules[19]: DSQ, GHSQ, PC71BM, and ADP, COF and MOF like porphyrin-based reactive metallomesogen (PorV-x)[20], and LC molecules
图3 含不同类型支链结构的PE链的导热[22]
Fig.3 k of PE chains with different types of branching chains[22].(Reprinted with permission from Ref. [22]; Copyright (2019) Advanced Functional Materials)
图4 在380 ~ 410 K范围温度变化诱导链节旋转致使热导率急剧变化
Fig.4 Sharp thermal conductivity changes from 380 to 410 K due to the thermal excitation of segmental rotation[14]. (Reprinted with permission from Ref. [14]; Copyright (2018) Polymer)
图5 链扭结数量对聚合物链导热的影响[52]
Fig.5 Effect of number of kinks on k of a polymer chain[52]. (Reprinted with permission from Ref. [52]; Copyright (2019) Journal of Applied Physics)
图6 (a) 聚合物受到拉伸时内部结构变化的示意图[14]; ( b) k是聚三氟氯乙烯结晶度的函数[62]; (c)不同拉伸比下k随着平行于和垂直于拉伸方向的变化[35,58]; (d) 由分子动力学模拟的PE在不同拉伸比下的导热[15]
Fig.6 (a) Schematic of the internal structure changes when the polymer is subject to drawing[14]; (b) k as a function of crystallinity for polytrifluorochloroethylene[62]; (c) k along the direction parallel and perpendicular to the draw direction at different draw ratios[35,58]; (d) k of PE at different draw ratios from MDS[15]. (Reprinted with permission from Ref. [14] [62] [35] [58] [15]; Copyright (2018) Polymer)
图7 不同聚合物的导热随密度(a)和声速(b)的变化关系[14]
Fig.7 k of different polymers as a function of their densities (a) and sound of speed (b)[14]. (Reprinted with permission from Ref. [14]; Copyright (2018) Polymer)
图8 (a) 未极化和极化后P(VDF-TrFE)薄膜的导热; (b) P(VDF-TrFE)薄膜的电场-极化曲线和矫顽电场; (c) 半结晶PVDF的结构[101]
Fig.8 (a) k of unpoled and poled P(VDF-TrFE) films; (b) The P-E loop and coercive electric field of P(VDF-TrFE) film; (c) Structure of semi-crystalline PVDF[101]. (Reprinted with permission from Ref. [101]; Copyright (2021) Nano Energy)
图9 含氰基联苯致晶基元的液晶单体,通过阴离子开环聚合制备的侧链液晶聚合物[104]
Fig.9 Liquid crystal monomer with cyanobiphenyl mesogen and side-chain liquid crystal polymer prepared through anionic ring-opening polymerization[104]. (Reprinted with permission from Ref. [104]; Copyright (2022) Royal Society of Chemistry)
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