Linear Rheological Study of Tetra-poly(ethylene glycol) Transient Networks

Jian Tang; Quan Chen

doi:10.11777/j.issn1000-3304.2024.24184

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Linear Rheological Study of Tetra-poly(ethylene glycol) Transient Networks

Research Article | 更新时间：2025-01-24

- Linear Rheological Study of Tetra-poly(ethylene glycol) Transient Networks
- Acta Polymerica Sinica Vol. 56, Issue 2, Pages: 278-285(2025)
- 作者机构：
  
  中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022
- 作者简介：
  
  Jian Tang, E-mail: tangjian@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24184
  CLC：
- CSTR：32057.14.GFZXB.2024.7288
- Published：20 February 2025，
  
  Published Online：01 November 2024，
  
  Received：25 June 2024，
  
  Accepted：2024-08-07
- 稿件说明：
移动端阅览
JIAN TANG, QUAN CHEN. Linear Rheological Study of Tetra-poly(ethylene glycol) Transient Networks. [J]. Acta polymerica sinica, 2025, 56(2): 278-285.
DOI：

JIAN TANG, QUAN CHEN. Linear Rheological Study of Tetra-poly(ethylene glycol) Transient Networks. [J]. Acta polymerica sinica, 2025, 56(2): 278-285. DOI： 10.11777/j.issn1000-3304.2024.24184. CSTR： 32057.14.GFZXB.2024.7288.

摘要

传统缔合高分子体系中往往存在环状链和悬挂链等缺陷结构，这些非均匀性显著阻碍了缔合高分子内部结构参数与其物理性质之间构效关系的定量构筑，并影响了针对这些性质的材料设计开发. 为了解决模型体系缺失的问题，基于四臂聚乙二醇前驱体和锆离子构筑了物理凝胶模型体系，该体系的内部凝胶化程度可以通过调控锆离子与四臂聚乙二醇前驱体的摩尔配比精准调控. 线性流变学测试结果显示，凝胶内部的非均匀性被高度抑制.本文提出了通过凝胶平台模量和松弛时间分别计算前驱体末端连接率的方法，2种方法得到的结果定量吻合，进一步讨论了松弛模式分布变化与超桥结构含量之间的关系，明确了凝胶网络结构演化过程.

Abstract

Transient networks are three-dimensional networks formed by reversible crosslinks. The reversibility is critical to realize functions of novel materials including self-healing

stimuli-responsive and shape memory materials. The design

development

and application of these materials are all dependent on a precise understanding of molecular mechanisms of viscoelasticity. However

defects such as loops and dangling chains are common in conventional associative polymer systems

which significantly impedes the quantitative establishment of relationship between structural parameters and physical properties of associative polymers

thereby hindering the target performance-oriented material design. To address the lack of model systems

this study designs and fabricates a model physical gel system utilizing tetra-poly(ethylene glycol) precursors and zirconium ions. The degree of gelation within this system can be precisely controlled by adjusting the molar ratio of zirconium ions to tetra-poly(ethylene glycol) precursors. By selecting a precursor concentration between the overlap concentration and the entanglement concentration

defects such as loop and entanglement structures are significantly suppressed. This suppression is verified by the correspondence between the experimental plateau modulus and the predictions from phantom network model. By analyzing the thermos-rheological behavior of the transient network

the evolution on the temperature-dependent structure is revealed. Specifically

examining the high-frequency moduli related to the ion dissociation process reveals that the failure of time temperature superposition is due to a decrease in the degree of gelation as the temperature increases. Agreement has been achieved in the degree of association calculated from the plateau modulus and that from the relaxation time. Further discussion is given on a relationship between a content of superbridges and the relaxation mode distribution.

关键词

缔合高分子线性黏弹性松弛时间平台模量超桥

Keywords

Associative polymerLinear viscoelasticityRelaxation timePlateau modulusSuperbridge

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