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
- Evolutionary Characteristics of Linear Free-radical Polymerization Behavior under Gradient Condition
- Chinese Journal of Polymer Science 2026年44卷第8期页码：2691-2703
- 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：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 22463006); Qinzhou District Science and Technology Major Special Project in Tianshui City (No. 2024-NCKJG-4929).;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3636-3.The data that support the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3636-3
  中图分类号：
- 收稿：2026-01-31，
  
  录用：2026-02-26，
  
  网络首发：2026-07-01，
  
  纸质出版：2026-08-15
- 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

http://notExist.jpg

) 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

references

Liu, S. The future of free radical polymerizations. Chem. Mater. 2024 , 36 , 1779−1780..

Truong, N. P.; Jones, G. R.; Bradford, K. G. E.; Konkolewicz, D.; Anastasaki, A. A comparison of raft and atrp methods for controlled radical polymerization. Nat. Rev. Chem. 2021 , 5 , 859−869..

[Nesvadba, P. in Encyclopedia of radicals in chemistry, biology and materials , John Wiley & Sons, Bologna, 2012 , p. 2099.

Zhang, Z.; Krajniak, J.; Dookhith, A. Z.; Tian, Y.; Sachar, H. S.; Marioni, N.; Duncan, T. J.; Liu, J.; Sanoja, G. E.; Ganesan, V. Topology and mechanical properties of polymer networks formed under free radical and atom transfer radical polymerizations. Macromolecules 2025 , 58 , 3168−3187..

Mantzara, D.; Whitfield, R.; Wang, H. S.; Truong, N. P.; Anastasaki, A. Ultrafast thermal raft depolymerization at higher solid contents. ACS Macro Lett. 2025 , 14 , 235−240..

Kayanuma, M. A theoretical study of radical formation mechanisms in pet-raft polymerization using porphyrins as photoredox catalysts. J. Phys. Chem. A 2025 , 129 , 2718−2724..

Li, X.; Shi, J.; Kong, C.; Li, C.; Wang, H.; Jiang, S.; Li, Y. Photoinitiator-grafted polymer coating enable various hydrogels with strong resistance to both drying and swelling. Chem. Eng. J. 2024 , 480 , 147937..

Zhang, Y.; Xie, Q.; Pan, J.; Ma, C.; Zhang, G. Strong-adhesion and nonfouling self-generating zwitterionic janus hydrogel paint. Chem. Eng. J. 2024 , 485 , 149959..

Wen, S.; Xu, Y.; Fan, L.; Peng, B.; Zhang, J.; Zhang, Q.; Pang, Y.; Deng, Y.; Zou, Y. Hydrophilic coating of membrane by uv-induced radical and cationic curing of photosensitive resins: lower shrinkage, smoother surface and better anti-fouling performance. Prog. Org. Coat. 2024 , 195 , 108666..

Yao, M.; Wei, Z.; Li, J.; Guo, Z.; Yan, Z.; Sun, X.; Yu, Q.; Wu, X.; Yu, C.; Yao, F.; Feng, S.; Zhang, H.; Li, J. Microgel reinforced zwitterionic hydrogel coating for blood-contacting biomedical devices. Nat. Commun. 2022 , 13 , 5339..

Wei, M.; Wang, H.; Chen, C.; Fei, G.; Yang, D.; Li, K.; Wang, M.; Yang, X.; Li, N.; Song, L.; Yang, M.; Wang, Z. Conductive, adhesive, and biocompatible hydrogel sensor based on zwitterionic for effective wound healing and monitoring. Chem. Eng. J. 2025 , 506 , 160235. .

Zhu, H.; Wang, C.; Yang, Y.; Ma, H.; Fan, X.; Zhang, Y.; Dai, Z.; Cai, R.; Qian, K. High-strength mechanically gradient hydrogels via physical crosslinking for tendon-mimetic tissue repair. npj Flex Electron. 2025 , 9 , 53..

Quan, Z.; Wang, X.; Zheng, K.; Wen, Y.; Lin, J.; Cui, M. Synthesis of novel composite hydrogel based on Carboxymethyl Cellulose/Acrylamide/β-Cyclodextrin for drug delivery. Int. J. Biol. Macromol. 2025 , 287 , 138387..

Hashem, M. S.; Sobh, R. A.; Fahim, A. M.; Elsayed, G. H. Alginate sulfonamide hydrogel beads for 5-fluorouracil delivery: antitumor activity, cytotoxicity assessment, and theoretical investigation. Int. J. Biol. Macromol. 2024 , 282 , 136573..

Makhado, E. Preparation of carboxymethyl cellulose-based silica hydrogel nanocomposite for methylene blue and malachite green dyes adsorption from aqueous solution. Surf. Interfaces 2025 , 56 , 105699..

Lakshmi Priya, A.; Subhapriya, P.; Jenisha, S.; Murali Krishnan, M.; Dhanapal,V. Experimental and theoretical investigation of allylated chitosan and acrylic acid-based smart polymer hydrogel for the removal of brilliant green from aqueous media. Int. J. Biol. Macromol. 2025 , 289 , 138814..

Chaurasiya, A.; Pande, P. P.; Shankar, R.; Khare, P.; Kumar, P.; Yadav, N. K.; Dey, K. K. Synthesis and characterization of chemically functionalized novel smart guar gum xanthate based hydrogel: swelling, isotherm, kinetics, thermodynamic and reusability studies. J. Phys. Chem. Solids 2025 , 200 , 112584..

Nair, A.; Kumawat, Y. K.; Choudhary, S.; Nath, J.; Sharma, K.; Rasool, T.; Sharma, V.; Kumar, V. Malachite green dye adsorption from wastewater using pine gum-based hydrogel: kinetic and thermodynamic studies. J. Mol. Struct. 2024 , 1295 , 136671..

Song, L.; Wang, Z.; Chen, S.; Shen, Y.; Yin, J.; Wang, R. Phytic acid-induced gradient hydrogels for highly sensitive and broad range pressure sensing. Adv. Mater. 2025 , 37 , 2417978..

Zhang, X.; Aziz, S.; Zhu, Z. Tough and fast thermoresponsive hydrogel soft actuators. Adv. Mater. Technol. 2025 , 10 , 2401920..

Farooq, A.; Wanyan, H.; Li, Q.; Lu, S.; Huang, W.; Waqas, M.; Hong, B.; Huang, L.; Chen, L.; Zhou, X.; Wu, H. An adhesive, antibacterial, conductive zwitterionic cellulose nanofibers-containing hydrogel for flexible strain sensors and super-capacitors. Carbohydr. Polym. 2025 , 358 , 123534..

Luo, Y.; Yang, Q.; Chen, M.; Long, K.; Su, C.; Li, J.; Huang, M.; Lu, A.; Guo, S. Stretchable, adhesive, conductive hydrogel initiated by liquid metal complex for multi-functional sensing. Chem. Eng. J. 2024 , 496 , 153674..

Luo, J.; Hu, Y.; Luo, S.; Wang, X.; Chen, S.; Zhang, M.; Jiang, J.; Liu, L.; Qin, H. Strong and multifunctional lignin/liquid metal hydrogel composite as flexible strain sensors. ACS Sustain. Chem. Eng. 2024 , 12 , 7105−7114..

Rao, Z.; Takayanagi, M.; Nagaoka, M. Verification for temperature dependence of tacticity in polystyrene radical polymerization with the combination of reaction pathway analysis and red moon methodology. J. Phys. Chem. B 2022 , 126 , 5343−5350..

Zhang, Y.; Wei, H.; Hua, B.; Hu, C.; Zhang, W. Preparation and application of the thermo-/pH−/ Ion-Sensitive Semi-IPN hydrogel based on chitosan. Int. J. Biol. Macromol. 2024 , 258 , 128968..

Yang, L.; Bao, L.; Zhong, Y.; Hao, C.; Chen, J.; Wu, J.; Wang, X. Fabrication of in situ metal-organic framework grown on sodium lignosulphonate hydrogel for removal of Pb2+, methylene blue and crystal violet from aqueous solution. J. Cleaner Prod. 2024 , 434 , 139831..

Wu, Y.; He, G.; Liu, M.; Huang, L.; Xiang, Y. Epoxy-functionalized coatings via free radical polymerization: spray-drying enabled interfacial engineering for high-performance SBR/Kaolin composites. Prog. Org. Coat. 2025 , 208 , 109529..

Zhang, Y.; Wang, H.; Song, Z.; Wang, C.; Hou, J.; Sui, K.; Qi, P. Directed selective transport and enrichment of micropollutants by gradient hydrogels. J. Hazard. Mater. 2025 , 486 , 136929..

Jiang, P.; Zhang, Y.; Mu, X.; Liu, D.; Liu, Y.; Guo, R.; Ji, Z.; Wang, X.; Wang, X. Grayscale stereolithography of gradient hydrogel with site-selective shape deformation. Adv. Mater. Technol. 2022 , 7 , 2101288..

Liu, X.; Liu, S.; Yang, R.; Wang, P.; Zhang, W.; Tan, X.; Ren, Y.; Chi, B. Gradient chondroitin sulfate/poly( γ -glutamic acid) hydrogels inducing differentiation of stem cells for cartilage tissue engineering. Carbohydr. Polym. 2021 , 270 , 118330..

Jiang, Q.; Shang, Y.; Cheng, H.; Zhao, J.; Yang, L.; He, Z.; Wei, J.; Liang, R.; Su, W.; Zheng, L.; Liao, C. Bioadhesive and antioxidant hydrogel by MoS 2 -TA dual-catalytic system initiated free radical polymerization combined with phototherapy for cartilage regeneration. Mater. Today Bio 2025 , 33 , 102056..

Wang, J. T.; Pei, Y. Y.; Han, B. J.; Sun, R. S.; Zuo, R. T.; Cui, G. X.; Zhang, H.; Cao, Z. Z.; Jin, L.; Li, Q. F. Multifunctional chitosan-based lanthanide luminescent hydrogel with stretchability, adhesion, self-healing, color tunability and antibacterial ability. Int. J. Biol. Macromol. 2024 , 264 , 130768..

Jia, Z.; Lv, X.; Hou, Y.; Wang, K.; Ren, F.; Xu, D.; Wang, Q.; Fan, K.; Xie, C.; Lu, X. Mussel-inspired nanozyme catalyzed conductive and self-setting hydrogel for adhesive and antibacterial bioelectronics. Bioact. Mater. 2021 , 6 , 2676−2687..

[Rudin, A.; Choi, P., In The Elements of Polymer Science & Engineering ; Elsevier, Waterloo, 2013 , p. 341.

Viciosa, M. T.; Quiles Hoyo, J.; Dionísio, M.; Gómez Ribelles, J. L. Temperature modulated DSC study of the kinetics of free radical isothermal network polymerization. J. Therm. Anal. Calorim. 2007 , 90 , 407−414..

Lloyd, E. M.; Feinberg, E. C.; Gao, Y.; Peterson, S. R.; Soman, B.; Hemmer, J.; Dean, L. M.; Wu, Q.; Geubelle, P. H.; Sottos, N. R.; Moore, J. S. Spontaneous patterning during frontal polymerization. ACS Cent. Sci. 2021 , 7 , 603−612..

Ye, S.; Yong, W.; Xu, J.; Fu, G. Oxygen- Co -Thermal driver for constructing integrated anisotropic hydrogels with programmable shape deformation, superior self-healing, and mechanical performance. Chem. Mater. 2023 , 35 , 8170−8180..

Kinoshita, K.; Takano, Y.; Ohkouchi, N.; Deguchi, S. Free-radical polymerization of acrylic acid under extreme reaction conditions mimicking deep-sea hydrothermal vents. ACS Omega 2017 , 2 , 2765−2769..

Furuya, T.; Koga, T. Molecular simulation of effects of network structure on fracture behavior of gels synthesized by radical polymerization. Macromolecules 2025 , 58 , 3359−3368..

Kuang, Y.; Dormidontova, E. E. Pearl-necklace to unimolecular micelle formation by heterograft bottlebrush polymers in solution. Macromolecules 2025 , 58 , 1470−1480..

Li, H.; Xue, Z. J.; Xue, Y.-H.; Li, Y.; Liu, H. Topological structure evolution of polymer network based on star-shaped multi-armed precursors. Chinese J. Polym. Sci. 2025 , 43 , 1240−1252..

Hoogerbrugge, P. J.; Koelman, J. M. V. A. Simulating microscopic hydrodynamic phenomena with dissipative particle dynamics. EPL 1992 , 19 , 155..

Groot, R. D.; Warren, P. B. Dissipative particle dynamics: bridging the gap between atomistic and mesoscopic simulation. J. Chem. Phys. 1997 , 107 , 4423−4435..

[Müller, M.; Katsov, K.; Schick, M. Biological and synthetic membranes: what can be learned from a coarse-grained desc ription Physics Reports 2006 , 434 , 113–176..

Español, P.; Warren, P. Statistical mechanics of dissipative particle dynamics. EPL 1995 , 30 , 191..

[Warren, P. Dissipative particle dynamics. Curr. Opin. Colloid In . 1998 , 3 , 620−624..

Groot, R. D.; Madden, T. J. Dynamic simulation of diblock copolymer microphase separation. J. Chem. Phys. 1998 , 108 , 8713−8724..

Kröger M. Simple models for complex nonequilibrium fluids. Physics Reports 2004 , 390 , 453−551..

Yue, L.; Zhang, X.; Li, W.; Tang, Y.; Bai, Y. Quickly self-healing hydrogel at room temperature with high conductivity synthesized through simple free radical polymerization. J. Appl. Polym. Sci. 2019 , 136 , 47379..

Das, D.; Pham, T, T, H.; Noh, I. Characterizations of hyaluronate-based terpolymeric hydrogel synthesized via free radical polymerization mechanism for biomedical applications. Colloid Surface B 2018 , 170 , 64−75..

Monteferrante, M.; Tiribocchi, A.; Succi, S.; Pisignano, D.; Lauricella, M. Capturing free-radical polymerization by synergetic Ab initio calculations and topological reactive molecular dynamics. Macromolecules 2022 , 55 , 1474−1486..

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