Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition

Hui Li; Bing-Bing Pan; Yi-Yi Zhang; Wen Li; Zi-Jian Xue; Zhen-Bin Chen; Hong Liu

doi:10.1007/s10118-026-3636-3

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Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition

RESEARCH ARTICLE | Updated：2026-07-02

- Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition
- Chinese Journal of Polymer Science Vol. 44, Issue 8, Pages: 2691-2703(2026)
- Affiliations：
  
  a.School of Material Science and Engineering, LanZhou University of Technology, Lanzhou 730050, China
  b.Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Environment, South China Normal University, Guangzhou 510006, China
- Author bio：
  
  lihuidhg@lut.edu.cn
- Funds：
- DOI：10.1007/s10118-026-3636-3
  CLC：
- Received：31 January 2026，
  
  Accepted：26 February 2026，
  
  Online First：01 July 2026，
  
  Published：15 August 2026
- Accepted：
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Li, H.; Pan, B. B.; Zhang, Y. Y.; Li, W.; Xue, Z. J.; Chen, Z. B.; Liu, H. Evolutionary characteristics of linear free-radical polymerization behavior under gradient condition. Chinese J. Polym. Sci. 2026, 44, 2691–2703

Hui Li, Bing-Bing Pan, Yi-Yi Zhang, et al. Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2691-2703.
Li, H.; Pan, B. B.; Zhang, Y. Y.; Li, W.; Xue, Z. J.; Chen, Z. B.; Liu, H. Evolutionary characteristics of linear free-radical polymerization behavior under gradient condition. Chinese J. Polym. Sci. 2026, 44, 2691–2703 DOI： 10.1007/s10118-026-3636-3.

Hui Li, Bing-Bing Pan, Yi-Yi Zhang, et al. Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition[J]. Chinese Journal of Polymer Science, 2026, 44(8): 2691-2703. DOI： 10.1007/s10118-026-3636-3.

摘要

Increasing Δ

intensifies spatial heterogeneity in free-radical polymerization. High-temperature regions promote rapid initiation and termination

yielding lower

and

whereas low-temperature regions produce higher molecular weights

large

$$\langle R_{\mathrm{g}}^2 \rangle $$

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https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113713798&type=small

http://notExist.jpg

and slower porosity reduction.

Abstract

This study investigates the evolution of free-radical polymerization under spatially graded conditions by constructing a position-dependent reaction probability model. Given the strong temperature dependence of thermal initiators

spatial temperature variations significantly affect both local monomer reactivity and the macroscopic evolution of polymer st

ructures. Understanding this coupling is crucial for designing gradient-controlled synthesis strategies. The dissipative particle dynamics (DPD) method was employed to investigate free radical polymerization under gradient temperature conditions. Increasing Δ

enhances spatial heterogeneity: high-temperature regions form dense networks with lower molecular weights (

and

) due to rapid initiation and frequent termination. In contrast

low-temperature regions yield higher molecular weights and expanded chain conformations (

$$R_{\mathrm{g}}^2 $$

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113713784&type=

https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113713784&type=small

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) resulting from longer radical lifetimes. These structural differences further govern pore evolution: porosity decreases rapidly and reaches lower final values in high-temperature zones

while low-temperature regions exhibit delayed evolution but higher final porosity. This study demonstrates that the precise control of polymer growth orientation

molecular weight distribution

and porous morphology can be achieved by incorporating gradient conditions

thereby establishing a new paradigm for the targeted synthesis of gradient functional materials.

关键词

Keywords

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