Sticky Rouse 模型及分子模拟在缔合高分子线性粘弹性行为中的研究进展

张璐; 蒋诺斐; 邵靖宇; 崔翔; 张红东; 杨玉良; 唐萍

doi:10.14028/j.cnki.1003-3726.2024.24.289

您当前的位置：

首页 >

文章列表页 >

Sticky Rouse 模型及分子模拟在缔合高分子线性粘弹性行为中的研究进展

专论 | 更新时间：2025-01-23

- Sticky Rouse 模型及分子模拟在缔合高分子线性粘弹性行为中的研究进展
- Advances in the Sticky Rouse Model and Molecular Simulation for Linear Viscoelasticity of Associative Polymers
- 高分子通报 2025年38卷第2期页码：284-297
- 作者机构：
  
  聚合物分子工程国家重点实验室，复旦大学高分子科学系，上海 200433
- 作者简介：
  
  *唐萍，E-mail: pingtang@fudan.edu.cn
- 基金信息：
  
  国家自然科学基金(21973017;22373023)
- DOI：10.14028/j.cnki.1003-3726.2024.24.289
  中图分类号：
- 收稿日期：2024-09-28，
  
  录用日期：2024-11-04，
  
  网络出版日期：2024-11-27，
  
  纸质出版日期：2025-02-20
- 稿件说明：
移动端阅览
张璐, 蒋诺斐, 邵靖宇, 崔翔, 张红东, 杨玉良, 唐萍. Sticky Rouse 模型及分子模拟在缔合高分子线性粘弹性行为中的研究进展. 高分子通报, 2025, 38(2), 285–298

Zhang, L.; Jiang, N. F.; Shao, J. Y.; Cui, X.; Zhang, H. D.; Yang, Y. L.; Tang, P. Advances in the sticky rouse model and molecular simulation for linear viscoelasticity of associative polymers. Polym. Bull. (in Chinese),2025, 38(2), 285–298
张璐, 蒋诺斐, 邵靖宇, 崔翔, 张红东, 杨玉良, 唐萍. Sticky Rouse 模型及分子模拟在缔合高分子线性粘弹性行为中的研究进展. 高分子通报, 2025, 38(2), 285–298 DOI： 10.14028/j.cnki.1003-3726.2024.24.289.

Zhang, L.; Jiang, N. F.; Shao, J. Y.; Cui, X.; Zhang, H. D.; Yang, Y. L.; Tang, P. Advances in the sticky rouse model and molecular simulation for linear viscoelasticity of associative polymers. Polym. Bull. (in Chinese),2025, 38(2), 285–298 DOI： 10.14028/j.cnki.1003-3726.2024.24.289.

摘要

缔合高分子(associative polymers

APs)因其独特的动力学行为，在自修复、形状记忆、流变改性等多个生产生活领域中得到广泛应用。由于缔合相互作用的存在，高分子链运动与缔合反应发生耦合，这不仅赋予缔合高分子丰富的应用前景，也增加了其材料加工过程的复杂性。发展缔合高分子流变理论对于从分子层面理解其粘弹性质至关重要，不仅能够为其加工及应用条件提供指导，同时也有助于发掘缔合高分子的潜在应用，进一步拓展其应用领域。本文总结并分析了近年来国内外关于缔合高分子流变学理论的主要研究进展，重点介绍了从最基本的Rouse模型出发，基于平均场假设将缔合相互作用视为表观摩擦力的sticky Rouse模型(SRM)。结合分子模拟及相关的实验结果，验证了SRM的平均场假设的适用范围及局限性，并基于现有研究成果对缔合高分子体系流变理论的未来发展方向进行了展望。

Abstract

Associative polymers (APs)

due to their unique dynamic behaviors

show significant potential in fields such as self-healing

shape memory

and rheological modification. The presence of associative interactions leads to a coupling between strand motion and associative reactions

which not only broadens the application of APs

but also adds complexity to their processing. Developing a rheological theory for APs is essential for understanding their viscoelastic properties at the molecular level. Such insights not only guide processing and application conditions

but also help explore new applications

thereby further expanding the utility of APs across various fields. This paper reviews and analyzes recent advances in the rheological theories of APs

particularly focusing on the sticky Rouse model (SRM). The SRM extends the fundamental Rouse model by incorporating associative interactions as an apparent friction coefficient based on the mean-field assumption. Through molecular simulations and relevant experimental results

we validate the applicability and limitations of the mean-field assumption in the SRM. Future directions for rheological theories concerning APs are also discussed in light of current research.

关键词

Keywords

references

Montarnal, D. ; Capelot, M. ; Tournilhac, F. ; Leibler, L . Silica-like malleable materials from permanent organic networks . Science , 2011 , 334 ( 6058 ), 965 − 968 .

Krishnakumar, B. ; Sanka, R. V. S. P. ; Binder, W. H. ; Parthasarthy, V. ; Rana, S. ; Karak, N . Vitrimers: associative dynamic covalent adaptive networks in thermoset polymers . Chem. Eng. J. , 2020 , 385 , 123820 .

Cui, X. ; Jiang, N. F. ; Shao, J. Y. ; Zhang, H. D. ; Yang, Y. L. ; Tang, P . Linear and nonlinear viscoelasticities of dissociative and associative covalent adaptable networks: discrepancies and limits . Macromolecules , 2023 , 56 ( 3 ), 772 − 784 .

Seiffert, S. ; Sprakel, J . Physical chemistry of supramolecular polymer networks . Chem. Soc. Rev. , 2012 , 41 ( 2 ), 909 − 930 .

Wu, S. L. ; Chen, Q . Advances and new opportunities in the rheology of physically and chemically reversible polymers . Macromolecules , 2022 , 55 ( 3 ), 697 − 714 .

Dolog, R. ; Weiss, R. A . Shape memory behavior of a polyethylene-based carboxylate ionomer . Macromolecules , 2013 , 46 ( 19 ), 7845 − 7852 .

Miyamae, K. ; Nakahata, M. ; Takashima, Y. ; Harada, A . Self-healing, expansion-contraction, and shape-memory properties of a preorganized supramolecular hydrogel through host-guest interactions . Angew. Chem. Int. Ed. , 2015 , 54 ( 31 ), 8984 − 8987 .

Wang, Y. H. ; He, J. ; Aktas, S. ; Sukhishvili, S. A. ; Kalyon, D. M . Rheological behavior and self-healing of hydrogen-bonded complexes of a triblock Pluronic copolymer with a weak polyacid . J. Rheology , 2017 , 61 , 1103 − 1119 .

Cui, X. ; Zhang, L. ; Yang, Y. L. ; Tang, P . Understanding the application of covalent adaptable networks in self-repair materials based on molecular simulation . Soft Matter , 2024 , 20 ( 7 ), 1486 − 1498 .

Chen, J. Y. ; Wang, Z. F. ; Yao, B. W. ; Geng, Y. H. ; Wang, C. ; Xu, J. H. ; Chen, T. ; Jing, J. J. ; Fu, J. J . Ultra-highly stiff and tough shape memory polyurea with unprecedented energy density by precise slight cross-linking . Adv. Mater. , 2024 , 36 ( 27 ), e2401178 .

Yang, H. H. ; Wu, S. L. ; Chen, Q . How to choose a secondary interaction to improve stretchability of associative polymers ? Macromolecules , 2021 , 54 ( 17 ), 8112 − 8121 .

Qin, B. ; Zhang, S. ; Sun, P. ; Tang, B. H. ; Yin, Z. H. ; Cao, X. ; Chen, Q. ; Xu, J. F. ; Zhang, X . Tough and multi-recyclable cross-linked supramolecular polyureas via incorporating noncovalent bonds into main-chains . Adv. Mater. , 2020 , 32 ( 36 ), e2000096 .

Hawke, L. G. D. ; Ahmadi, M. ; Goldansaz, H. ; van Ruymbeke, E . Viscoelastic properties of linear associating poly(n-butyl acrylate) chains . J. Rheol. , 2016 , 60 ( 2 ), 297 − 310 .

Zhang, Z. J. ; Huang, C. W. ; Weiss, R. A. ; Chen, Q . Association energy in strongly associative polymers . J. Rheol. , 2017 , 61 ( 6 ), 1199 − 1207 .

Suzuki, S. ; Uneyama, T. ; Inoue, T. ; Watanabe, H . Non-linear rheology of telechelic associative polymer networks: shear thickening and thinning behavior of hydrophobically modified ethoxylated urethane (HEUR) in aqueous solution . Macromolecules , 2012 , 45 ( 2 ), 888 − 898 .

Reutenauer, P. ; Buhler, E. ; Boul, P. ; Candau, S. ; Lehn, J. M . Room temperature dynamic polymers based on Diels-Alder chemistry . Chem. , 2009 , 15 ( 8 ), 1893 − 1900 .

Inglis, A. J. ; Nebhani, L. ; Altintas, O. ; Schmidt, F. G. ; Barner-Kowollik, C . Rapid bonding/debonding on demand: reversibly cross-linked functional polymers via Diels-Alder chemistry . Macromolecules , 2010 , 43 ( 13 ), 5515 − 5520 .

Billiet, S. ; De Bruycker, K. ; Driessen, F. ; Goossens, H. ; Van Speybroeck, V. ; Winne, J. M. ; Du Prez, F. E . Triazolinediones enable ultrafast and reversible click chemistry for the design of dynamic polymer systems . Nat. Chem. , 2014 , 6 ( 9 ), 815 − 821 .

Röttger, M. ; Domenech, T. ; van der Weegen, R. ; Breuillac, A. ; Nicolaÿ, R. ; Leibler, L . High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis . Science , 2017 , 356 ( 6333 ), 62 − 65 .

Denissen, W. ; Rivero, G. ; Nicolaÿ, R. ; Leibler, L. ; Winne, J. M. ; Du Prez, F. E . Vinylogous urethane vitrimers . Adv Funct Mater , 2015 , 25 , 2451 − 2457 .

Worrell, B. T. ; McBride, M. K. ; Lyon, G. B. ; Cox, L. M. ; Wang, C. ; Mavila, S. ; Lim, C. H. ; Coley, H. M. ; Musgrave, C. B. ; Ding, Y. F. ; Bowman, C. N . Bistable and photoswitchable states of matter . Nat. Commun. , 2018 , 9 ( 1 ), 2804 .

Green, M. S. ; Tobolsky, A. V . A new approach to the theory of relaxing polymeric media . J. Chem. Phys. , 1946 , 14 ( 2 ), 80 − 92 .

Lodge, A. S . A network theory of flow birefringence and stress in concentrated polymer solutions . Trans. Faraday Soc. , 1956 , 52 ( 0 ), 120 − 130 .

Zhang, Z. J. ; Chen, Q. ; Colby, R. H . Dynamics of assoc-iative polymers . Soft Matter , 2018 , 14 ( 16 ), 2961 − 2977 .

Semenov, A. N. ; Rubinstein, M . Thermoreversible gelation in solutions of associative polymers. 1. Statics . Macromolecules , 1998 , 31 ( 4 ), 1373 − 1385 .

Chen, Q. ; Colby, R. H . Linear viscoelasticity of sulfonated styrene oligomers near the sol-gel transition . Korea Aust. Rheol. J. , 2014 , 26 ( 3 ), 257 − 261 .

Chen, Q. ; Huang, C. W. ; Weiss, R. A. ; Colby, R. H . Viscoelasticity of reversible gelation for ionomers . Macromolecules , 2015 , 48 ( 4 ), 1221 − 1230 .

Tanaka, F. ; Edwards, S. F . Viscoelastic properties of physically crosslinked networks. 1. Transient network theory . Macromolecules , 1992 , 25 ( 5 ), 1516 − 1523 .

Tanaka, F. ; Edwards, S. F . Viscoelastic properties of physically crosslinked networks. Part 1. Non-linear stationary viscoelasticity . J. Non Newton. Fluid Mech. , 1992 , 43 ( 2-3 ), 247 − 271 .

Tanaka, F. ; Edwards, S. F . Viscoelastic properties of physically crosslinked networks Part 2. Dynamic mechanical moduli . J. Non Newton. Fluid Mech. , 1992 , 43 ( 2-3 ), 273 − 288 .

Tanaka, F. ; Edwards, S. F . Viscoelastic properties of physically crosslinked networks. Part 3. Time-dependent phenomena . J. Non Newton. Fluid Mech. , 1992 , 43 ( 2-3 ), 289 − 309 .

Mendes, A. C. ; Baran, E. T. ; Reis, R. L. ; Azevedo, H. S . Self-assembly in nature: using the principles of nature to create complex nanobiomaterials . Wiley Interdiscip. Rev. Nanomed. Nanobiotechnol. , 2013 , 5 ( 6 ), 582 − 612 .

Semenov, A. N. ; Rubinstein, M . Thermoreversible gelation in solutions of associative polymers. 1. Statics . Macromolecules , 1998 , 31 ( 4 ), 1373 − 1385 .

Rubinstein, M. ; Colby, R. H . Elastic modulus and equilibrium swelling of near-critical gels . Macromolecules , 1994 , 27 ( 12 ), 3184 − 3190 .

Lusignan, C. P. ; Mourey, T. H. ; Wilson, J. C. ; Colby, R. H . Viscoelasticity of randomly branched polymers in the critical percolation class . Int. J. Mol. Sci. , 1995 , 52 ( 6 ), 6271 − 6280 .

Cao, X. ; Yu, X. Y. ; Qin, J. ; Chen, Q . Reversible gelation of entangled ionomers . Macromolecules , 2019 , 52 ( 22 ), 8771 − 8780 .

阮永金 , 王振华 , 卢宇源 , 安立佳 . 高分子动力学的单链模型 . 高分子学报 , 2017 , 48 ( 5 ), 727 − 743 .

Doi, M. ; Edwards, S. F . The Theory of Polymer Dynamics , Oxford University Press , 1988 .

Hansen, D. R. ; Shen, M . Viscoelastic retardation time computations for homogeneous block copolymers . Macromolecules , 1975 , 8 ( 3 ), 343 − 348 .

Wang, F. W. ; DiMarzio, E. A . The dynamics of block-copolymer molecules in solution. the free-draining limit . Macromolecules , 1975 , 8 ( 3 ), 356 − 360 .

Stockmayer, W. H. ; Kennedy, J. W . Viscoelastic spectrum of free-draining block copolymers . Macromolecules , 1975 , 8 ( 3 ), 351 − 355 .

Baxandall, L. G . Dynamics of reversibly crosslinked chains . Macromolecules , 1989 , 22 ( 4 ), 1982 − 1988 .

Chen, Q. ; Tudryn, G. J. ; Colby, R. H . Ionomer dynamics and the sticky Rouse model . J. Rheol. , 2013 , 57 ( 5 ), 1441 − 1462 .

Jiang, N. F. ; Zhang, H. D. ; Yang, Y. L. ; Tang, P . Molecular dynamics simulation of associative polymers: understanding linear viscoelasticity from the sticky rouse model . J. Rheol. , 2021 , 65 ( 4 ), 527 − 547 .

Jiang, N. F. ; Zhang, H. D. ; Tang, P. ; Yang, Y. L . Linear viscoelasticity of associative polymers: sticky Rouse model and the role of bridges . Macromolecules , 2020 , 53 ( 9 ), 3438 − 3451 .

Yang, Y. L. ; Yu, T. Y . Graph theory of configurational and viscoelastic properties of polymers, 2. Linear polymer chains containing small copolymer blocks . Die Makromol. Chem. , 1986 , 187 ( 2 ), 441 − 454 .

Yang, Y. L . Graph theory of viscoelastic and configurational properties of Gaussian chains . Macromol. Theory Simul. , 1998 , 7 ( 5 ), 521 − 549 .

Leibler, L. ; Rubinstein, M. ; Colby, R. H . Dynamics of reversible networks . Macromolecules , 1991 , 24 ( 16 ), 4701 − 4707 .

Rubinstein, M. ; Semenov, A. N . Dynamics of entangled solutions of associating polymers . Macromolecules , 2001 , 34 ( 4 ), 1058 − 1068 .

Semenov, A. N. ; Rubinstein, M . Dynamics of entangled associating polymers with large aggregates . Macromolecules , 2002 , 35 ( 12 ), 4821 − 4837 .

Chen, Q. ; Zhang, Z. J. ; Colby, R. H . Viscoelasticity of entangled random polystyrene ionomers . J. Rheol. , 2016 , 60 ( 6 ), 1031 − 1040 .

Ahmadi, M. ; Hawke, L. G. D. ; Goldansaz, H. ; van Ruymbeke, E . Dynamics of entangled linear supramolecular chains with sticky side groups: influence of hindered fluctuations . Macromolecules , 2015 , 48 ( 19 ), 7300 − 7310 .

Mateyisi, M. J. ; Sommer, J. U. ; Müller-Nedebock, K. K. ; Heinrich, G . Influence of weak reversible cross-linkers on entangled polymer melt dynamics . J. Chem. Phys. , 2018 , 148 ( 24 ), 244901 .

Saalwächter, K. ; Seiffert, S . Dynamics-based assessment of nanoscopic polymer-network mesh structures and their defects . Soft Matter , 2018 , 14 ( 11 ), 1976 − 1991 .

Zhong, M. J. ; Wang, R. ; Kawamoto, K. ; Olsen, B. D. ; Johnson, J. A . Quantifying the impact of molecular defects on polymer network elasticity . Science , 2016 , 353 ( 6305 ), 1264 − 1268 .

Xia, J. S. ; Kalow, J. A. ; Olvera de la Cruz, M . Structure, dynamics, and rheology of vitrimers . Macromolecules , 2023 , 56 ( 19 ), 8080 − 8093 .

Shao, J. Y. ; Jiang, N. F. ; Zhang, H. D. ; Yang, Y. L. ; Tang, P . Sticky rouse model and molecular dynamics simulation for dual polymer networks . Macromolecules , 2022 , 55 ( 2 ), 535 − 549 .

Ricarte, R. G. ; Shanbhag, S . Unentangled vitrimer melts: interplay between chain relaxation and cross-link exchange controls linear rheology . Macromolecules , 2021 , 54 ( 7 ), 3304 − 3320 .

Marrucci, G. ; Bhargava, S. ; Cooper, S. L . Models of shear-thickening behavior in physically crosslinked networks . Macromolecules , 1993 , 26 ( 24 ), 6483 − 6488 .

Vaccaro, A. ; Marrucci, G . A model for the nonlinear rheology of associating polymers . J. Non Newton. Fluid Mech. , 2000 , 92 ( 2-3 ), 261 − 273 .

Uneyama, T. ; Suzuki, S. ; Watanabe, H . Concentration dependence of rheological properties of telechelic associative polymer solutions . Phys. Rev. E Stat. Nonlin. Soft Matter Phys. , 2012 , 86 ( 3 Pt 1 ), 031802 .

Koga, T. ; Tanaka, F. ; Kaneda, I. ; Winnik, F. M . Stress buildup under start-up shear flows in self-assembled transient networks of telechelic associating polymers . Langmuir , 2009 , 25 ( 15 ), 8626 − 8638 .

Sing, M. K. ; Wang, Z. G. ; McKinley, G. H. ; Olsen, B. D . Celebrating soft matter’s 10th anniversary: chain configuration and rate-dependent mechanical properties in transient networks . Soft Matter , 2015 , 11 ( 11 ), 2085 − 2096 .

Tanaka, F. ; Koga, T . Intramolecular and intermolecular association in thermoreversible gelation of hydro-phobically modified associating polymers . Comput. Theor. Polym. Sci. , 2000 , 10 ( 3-4 ), 259 − 267 .

Tanaka, F . Polymer Physics: Applications to Molecular Association and Thermoreversible Gelation. , Cambridge University Press , 2011 .

Martinetti, L. ; Carey-De La Torre, O. ; Schweizer, K. S. ; Ewoldt, R. H . Inferring the nonlinear mechanisms of a reversible network . Macromolecules , 2018 , 51 ( 21 ), 8772 − 8789 .

Ahn, K. H. ; Osaki, K . Mechanism of shear thickening investigated by a network model . J. Non Newton. Fluid Mech. , 1995 , 56 ( 3 ), 267 − 288 .

Wang, S. Q . Transient network theory for shear-thickening fluids and physically crosslinked networks . Macromolecules , 1992 , 25 ( 25 ), 7003 − 7010 .

Vrahopoulou, E. P. ; McHugh, A. J . A consideration of the Yamamoto network theory with non-Gaussian chain segments . J. Rheol. , 1987 , 31 ( 5 ), 371 − 384 .

Tripathi, A. ; Tam, K. C. ; McKinley, G. H . Rheology and dynamics of associative polymers in shear and extension: theory and experiments . Macromolecules , 2006 , 39 ( 5 ), 1981 − 1999 .

Indei, T . Necessary conditions for shear thickening in associating polymer networks . J. Non Newton. Fluid Mech. , 2007 , 141 ( 1 ), 18 − 42 .

邵靖宇 . 复杂缔合体系及刚柔嵌段高分子相变及动力学——平均场理论和分子模拟 . 博士学位论文 , 上海：复旦大学 , 2022 .

Watanabe, H. ; Matsumiya, Y. ; Sato, T . Revisiting nonlinear flow behavior of rouse chain: Roles of FENE, friction-reduction, and Brownian force intensity variation . Macromolecules , 2021 , 54 ( 8 ), 3700 − 3715 .

Jiang, N. F. ; van Ruymbeke, E . Variation of spring stiffness, monomeric friction, and Brownian intensity in the simulation system of unentangled melt under steady flow . Macromolecules , 2023 , 56 ( 8 ), 2911 − 2929 .

Kwon, Y . Nonlinear modification of the Rouse model constraining volume conservation of deforming chains . Rheol. Acta , 2024 , 63 ( 1 ), 79 − 91 .

浏览量

106

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

分子模拟技术在高分子科学实验中的应用