Chain Length Dependence of Glass Transition in Polymers

Jin-tian Luo; Quan-yin Xu; Wen-sheng Xu; Biao Zuo

doi:10.11777/j.issn1000-3304.2024.24218

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Chain Length Dependence of Glass Transition in Polymers

Review | 更新时间：2025-04-01

- Chain Length Dependence of Glass Transition in Polymers
- Acta Polymerica Sinica Vol. 56, Issue 4, Pages: 539-550(2025)
- 作者机构：
  
  1.浙江理工大学化学与化工学院浙江省高分子材料表界面科学重点实验室杭州 310018
  2.中国科学院长春应用化学研究所长春 130022
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24218
  CLC：
- CSTR：32057.14.GFZXB.2024.7306
- Received：31 August 2024，
  
  Accepted：2024-10-23，
  
  Published：20 April 2025
- 稿件说明：
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罗锦添, 徐全印, 徐文生, 左彪. 高分子玻璃化转变的链长依赖性. 高分子学报, 2025, 56(4), 539-550

Luo, J. T.; Xu, Q. Y.; Xu, W. S.; Zuo, B. Chain length dependence of glass transition in polymers. Acta Polymerica Sinica, 2025, 56(4), 539-550
罗锦添, 徐全印, 徐文生, 左彪. 高分子玻璃化转变的链长依赖性. 高分子学报, 2025, 56(4), 539-550 DOI： 10.11777/j.issn1000-3304.2024.24218. CSTR： 32057.14.GFZXB.2024.7306.

Luo, J. T.; Xu, Q. Y.; Xu, W. S.; Zuo, B. Chain length dependence of glass transition in polymers. Acta Polymerica Sinica, 2025, 56(4), 539-550 DOI： 10.11777/j.issn1000-3304.2024.24218. CSTR： 32057.14.GFZXB.2024.7306.

摘要

玻璃化转变的微观机制是凝聚态物理最重要的科学问题之一. 由于链的连通性，高分子表现比小分子物质更复杂的玻璃化行为. 本综述对半个多世纪以来，科学家对高分子玻璃化转变链长依赖性的研究进行了总结. 介绍了高分子玻璃化温度(

)和脆度指数(

)等性质随链长增加而增大并趋于饱和的普遍现象；总结了解释和描述

和

随链长变化的3种主要机制：即高运动活性链末端促进高分子协同运动，从而降低

和

；局部链刚性随链长增加而增大从而减弱链段运动能力，使

升高；分子链内次级松弛单元的耦合和动态促进激活链段松弛，造成

随链长增大而增大. 希望通过对高分子玻璃化现象和机理的总结与讨论帮助读者加深对长链大分子玻璃化转变的认识和理解.

Abstract

Glass transition is one of the most important properties of condensed matter. Chain connectivity endows polymers with complex glass transition behaviour that varies with the chain length. We have summarized more than half a century of research on the chain length dependence of glass transition of polymers. In the first part

we discussed the general phenomenon of the increase in glass transition temperature (

) and dynamical fragility (

) with increasing chain length until they reach saturation values. In the second part

the mechanisms proposed in the past decades to explain the general behaviour of the polymer glass transition were reviewed

including (1) the chain end effect

i.e.

the chain ends associated with extra mobility and excess conformational freedom play a role in accelerating segmental movement and lowering polymer

; (2) the chain stiffness effect

i.e.

the polymer chains stiffened as the molecular weight in

creased

leading to an increase in

with chain length before reaching the thresholds; (3) intramolecular coupling effect

i.e.

dynamic couplings of secondary relaxations along the chains facilitate the segmental relaxation

leading to an increase of

with the chain length. We hope this review helps the readers gain a deeper understanding of the glass transition of polymers and the associated molecular mechanisms.

关键词

Keywords

references

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