Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites

Sheng-Chao Chai; Tian-Yang Xu; Xiao Cao; Gang Wang; Quan Chen; Hao-Long Li

doi:10.1007/s10118-019-2262-8

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Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites

ARTICLE | Updated：2021-02-18

- Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites
- Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites
- Chinese Journal of Polymer Science 2019年37卷第8期页码：797-805
- Affiliations：
  
  a.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
  b.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  qchen@ciac.ac.cn (Q.C.)
  hl_li@jlu.edu.cn (H.L.L.)
- Funds：
  
  HL thanks support by the National Natural Science Foundation of China (Nos. 21622403 and 21474039); QC thanks support by the National Natural Science Foundation of China (No. 21722407).
- DOI：10.1007/s10118-019-2262-8
  中图分类号：
- 收稿：2019-02-01，
  
  修回：2019-3-12，
  
  录用：2019-3-25，
  
  网络首发：2019-04-25，
  
  纸质出版：2019-08
- Accepted：
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Citation: Chai, S. C.; Xu, T. Y.; Cao, X.; Wang, G.; Chen, Q.; Li, H. L. Ultrasmall nanoparticles diluted chain entanglement in polymer nanocomposites. Chinese J. Polym. Sci. 2019, 37, 797–805

Sheng-Chao Chai, Tian-Yang Xu, Xiao Cao, et al. Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites[J]. Chinese Journal of Polymer Science, 2019, 37(8): 797-805.
Citation: Chai, S. C.; Xu, T. Y.; Cao, X.; Wang, G.; Chen, Q.; Li, H. L. Ultrasmall nanoparticles diluted chain entanglement in polymer nanocomposites. Chinese J. Polym. Sci. 2019, 37, 797–805 DOI： 10.1007/s10118-019-2262-8.

Sheng-Chao Chai, Tian-Yang Xu, Xiao Cao, et al. Ultrasmall Nanoparticles Diluted Chain Entanglement in Polymer Nanocomposites[J]. Chinese Journal of Polymer Science, 2019, 37(8): 797-805. DOI： 10.1007/s10118-019-2262-8.

摘要

Abstract

Nanoparticle-polymer composites exhibit unusual mechanical properties and chain dynamics when the nanoparticle size is smaller than the entanglement mesh size of the matrix polymer chains

corresponding to the ultrasmall regime defined by de Gennes. However

the mechanism is still ambiguous due to the lack of suitable model systems. Here

we develop an ultrasmall nanoparticle system by using a bimodal grafting strategy to graft both short alkyl chains and long polystyrene chains onto the polyoxometalate molecular nanoparticles with a tunable repulsive potential between the nanoparticles

thus facilitating their uniform dispersion in polystyrene matrices. Linear viscoelasticity of the resultant nanocomposites changes with increasing the filler content

which shows a decrease in both plateau modulus and terminal relaxation time

indicative of a dilution effect of the nanoparticles. Namely

the entanglement network becomes sparser with increasing the filler content.

关键词

Keywords

references

Balazs, A. C.; Emrick, T.; Russell, T. P . Nanoparticle polymer composites: Where two small worlds meet . Science , 2006 . 314 1107 - 1110 . DOI: 10.1126/science.1130557 http://doi.org/10.1126/science.1130557 .

Kumar, S. K.; Benicewicz, B. C.; Vaia, R. A.; Winey, K. I . 50 th Anniversary perspective: Are polymer nanocomposites practical for applications? . Macromolecules , 2017 . 50 714 - 731 . DOI: 10.1021/acs.macromol.6b02330 http://doi.org/10.1021/acs.macromol.6b02330 .

Raftopoulos, K. N.; Pielichowski, K . Segmental dynamics in hybrid polymer/POSS nanomaterials . Prog. Polym. Sci. , 2016 . 52 136 - 187 . DOI: 10.1016/j.progpolymsci.2015.01.003 http://doi.org/10.1016/j.progpolymsci.2015.01.003 .

Einstein, A . On the theory of Brownian movement . Ann. Phys. , 1906 . 19 371 - 381 . .

Batchelor, G. K . The effect of Brownian motion on the bulk stress in a suspension of spherical particles . J. Fluid Mech. , 1977 . 83 97 - 117 . DOI: 10.1017/S0022112077001062 http://doi.org/10.1017/S0022112077001062 .

Mackay, M. E.; Dao, T. T.; Tuteja, A.; Ho, D. L.; Horn, B. V.; Kim, H. C.; Hawker, C. J . Nanoscale effects leading to non-Einstein-like decrease in viscosity . Nat. Mater. , 2003 . 2 762 - 766 . DOI: 10.1038/nmat999 http://doi.org/10.1038/nmat999 .

Tuteja, A.; Mackay, M. E.; Hawker, C. J.; Horn, B. V . Effect of ideal, organic nanoparticles on the flow properties of linear polymers: Non-Einstein-like behavior . Macromolecules , 2005 . 38 8000 - 8011 . DOI: 10.1021/ma050974h http://doi.org/10.1021/ma050974h .

Nusser, K.; Schneider, G. J.; Pyckhout-Hintzen, W.; Richter, D . Viscosity decrease and reinforcement in polymer-silsesquioxane composites . Macromolecules , 2011 . 44 7820 - 7830 . DOI: 10.1021/ma201585v http://doi.org/10.1021/ma201585v .

Goldansaz, H.; Goharpey, F.; Afshar-Taromi, F.; Kim, I.; Stadler, F. J.; Ruymbeke, E. V.; Karimkhani, V . Anomalous rheological behavior of dendritic nanoparticle/linear polymer nanocomposites . Macromolecules , 2015 . 48 3368 - 3375 . DOI: 10.1021/acs.macromol.5b00390 http://doi.org/10.1021/acs.macromol.5b00390 .

Mangal, R.; Srivastava, S.; Archer, L. A . Phase stability and dynamics of entangled polymer-nanoparticle composites . Nat. Commun. , 2015 . 6 7198 DOI: 10.1038/ncomms8198 http://doi.org/10.1038/ncomms8198 .

Wyart, F. B.; de Gennes, P. G . Viscosity at small scales in polymer melts . Eur. Phys. J. E , 2000 . 1 93 - 97 . DOI: 10.1007/s101890050011 http://doi.org/10.1007/s101890050011 .

Cai, L. H.; Panyukov, S.; Rubinstein, M . Mobility of nonsticky nanoparticles in polymer liquids . Macromolecules , 2011 . 44 7853 - 7863 . DOI: 10.1021/ma201583q http://doi.org/10.1021/ma201583q .

Yamamoto, U.; Schweizer, K. S . Theory of nanoparticle diffusion in unentangled and entangled polymer melts . J. Chem. Phys. , 2011 . 135 224902 DOI: 10.1063/1.3664863 http://doi.org/10.1063/1.3664863 .

Kalathi, J. T.; Yamamoto, U.; Schweizer, K. S.; Grest, G. S.; Kumar, S. K . Nanoparticle diffusion in polymer nanocomposites . Phys. Rev. Lett. , 2014 . 112 108301 DOI: 10.1103/PhysRevLett.112.108301 http://doi.org/10.1103/PhysRevLett.112.108301 .

Yamamoto, U.; Schweizer, K. S . Microscopic theory of the long-time diffusivity and intermediate-time anomalous transport of a nanoparticle in polymer melts . Macromolecules , 2014 . 48 152 - 163 . .

Chen, T.; Qian, H. J.; Lu, Z. Y . Note: Chain length dependent nanoparticle diffusion in polymer melt: Effect of nanoparticle softness . J. Chem. Phys. , 2016 . 145 106101 DOI: 10.1063/1.4962370 http://doi.org/10.1063/1.4962370 .

Frischknecht, A. L.; McGarrity, E. S.; Mackay, M. E . Expanded chain dimensions in polymer melts with nanoparticle fillers . J. Chem. Phys. , 2010 . 132 204901 DOI: 10.1063/1.3428760 http://doi.org/10.1063/1.3428760 .

Li, Y.; Kroger, M.; Liu, W. K . Nanoparticle effect on the dynamics of polymer chains and their entanglement network . Phys. Rev. Lett. , 2012 . 109 118001 DOI: 10.1103/PhysRevLett.109.118001 http://doi.org/10.1103/PhysRevLett.109.118001 .

Kalathi, J. T.; Grest, G. S.; Kumar, S. K . Universal viscosity behavior of polymer nanocomposites . Phys. Rev. Lett. , 2012 . 109 198301 DOI: 10.1103/PhysRevLett.109.198301 http://doi.org/10.1103/PhysRevLett.109.198301 .

Senses, E.; Ansar, S. M.; Kitchens, C. L.; Mao, Y.; Narayanan, S.; Natarajan, B.; Faraone, A . Small particle driven chain disentanglements in polymer nanocomposites . Phys. Rev. Lett. , 2017 . 118 147801 DOI: 10.1103/PhysRevLett.118.147801 http://doi.org/10.1103/PhysRevLett.118.147801 .

Long, D. L.; Tsunashima, R.; Cronin, L . Polyoxometalates: Building blocks for functional nanoscale systems . Angew. Chem. Int. Ed. , 2010 . 49 1736 - 1758 . DOI: 10.1002/anie.v49:10 http://doi.org/10.1002/anie.v49:10 .

Zhang, J.; Liu, Y.; Li, Y.; Zhao, H.; Wan, X . Hybrid assemblies of Eu-containing polyoxometalates and hydrophilic block copolymers with enhanced emission in aqueous solution . Angew. Chem. Int. Ed. , 2012 . 124 4676 - 4680 . DOI: 10.1002/ange.201107481 http://doi.org/10.1002/ange.201107481 .

Liao, Y.; Liu, N.; Zhang, Q.; Bu, W . Self-assembly of polyoxometalate-based starlike polymers in solvents of variable quality: From free-standing sheet to vesicle . Macromolecules , 2014 . 47 7158 - 7168 . DOI: 10.1021/ma501343s http://doi.org/10.1021/ma501343s .

Tan, C.; Liu, N.; Yu, B.; Zhang, C.; Bu, W.; Liu, X.; Song, Y. F . Organic-inorganic hybrids formed by polyoxometalate-based surfactants with cationic polyelectrolytes and block copolymers . J. Mater. Chem. C , 2015 . 3 2450 - 2454 . DOI: 10.1039/C4TC02971B http://doi.org/10.1039/C4TC02971B .

Ma, C.; Wu, H.; Huang, Z. H.; Guo, R. H.; Hu, M. B.; Kubel, C.; Yan, L. T.; Wang, W . A Filled-honeycomb-structured crystal formed by self-assembly of a Janus polyoxometalate-silsesquioxane (POM-POSS) co-cluster . Angew. Chem. Int. Ed. , 2015 . 54 15699 - 15704 . DOI: 10.1002/anie.201507237 http://doi.org/10.1002/anie.201507237 .

Hou, X. S.; Zhu, G. L.; Ren, L. J.; Huang, Z.; Zhang, R. B.; Ungar, G.; Yan, L. T.; Wang, W . Mesoscale graphene-like honeycomb mono- and multi-layers constructed via self-assembly of co-clusters . J. Am. Chem. Soc. , 2017 . 140 1805 - 1811 . .

Li, D.; Jia, X.; Cao, X.; Xu, T.; Li, H.; Qian, H.; Wu, L . Controllable nanostructure formation through enthalpy-driven assembly of polyoxometalate clusters and block copolymers . Macromolecules , 2015 . 48 4104 - 4114 . DOI: 10.1021/acs.macromol.5b00712 http://doi.org/10.1021/acs.macromol.5b00712 .

Wang, S.; Li, H.; Li, D.; Xu, T.; Zhang, S.; Dou, X.; Wu, L . Noncovalent functionalization of graphene nanosheets with cluster-cored star polymers and their reinforced polymer coating . ACS Macro Lett. , 2015 . 4 974 - 978 . DOI: 10.1021/acsmacrolett.5b00287 http://doi.org/10.1021/acsmacrolett.5b00287 .

Zhang, L.; Cui, T.; Cao, X.; Zhao, C.; Chen, Q.; Wu, L.; Li, H . Inorganic-macroion-induced formation of bicontinuous block copolymer nanocomposites with enhanced conductivity and modulus . Angew. Chem. Int. Ed. , 2017 . 56 9013 - 9017 . DOI: 10.1002/anie.201702785 http://doi.org/10.1002/anie.201702785 .

Zhang, W. B.; Yu, X.; Wang, C. L.; Sun, H. J.; Hsieh, I. F.; Li, Y.; Dong, X. H.; Yue, K.; Horn, R. V.; Cheng, S. Z. D . Molecular nanoparticles are unique elements for macromolecular science: From " nanoatoms” to giant molecules . Macromolecules , 2014 . 47 1221 - 1239 . DOI: 10.1021/ma401724p http://doi.org/10.1021/ma401724p .

Zhang, W. B.; Cheng, S. Z. D . Toward rational and modular molecular design in soft matter engineering . Chinese J. Polym. Sci. , 2015 . 33 797 - 814 . DOI: 10.1007/s10118-015-1653-8 http://doi.org/10.1007/s10118-015-1653-8 .

Li, H.; Qi, W.; Li, W.; Sun, H.; Bu, W.; Wu, L . A highly transparent and luminescent hybrid based on the copolymerization of surfactant-encapsulated polyoxometalate and methyl methacrylate . Adv. Mater. , 2005 . 17 2688 - 2692 . DOI: 10.1002/(ISSN)1521-4095 http://doi.org/10.1002/(ISSN)1521-4095 .

Baker, L. C. W.; McCutcheon, T. P . Heteropoly salts containing cobalt and hexavalent tungsten in the anion . J. Am. Chem. Soc. , 1956 . 78 4503 - 4510 . DOI: 10.1021/ja01599a001 http://doi.org/10.1021/ja01599a001 .

Li, D.; Li, H.; Wu, L . Structurally dependent self-assembly and luminescence of polyoxometalate-cored supramolecular star polymers . Polym. Chem. , 2014 . 5 1930 - 1937 . DOI: 10.1039/C3PY01349A http://doi.org/10.1039/C3PY01349A .

Judeinstein, P . Synthesis and properties of polyoxometalates based inorganic-organic polymers . Chem. Mater. , 1992 . 4 4 - 7 . DOI: 10.1021/cm00019a002 http://doi.org/10.1021/cm00019a002 .

Moore, A. R.; Kwen, H.; Beatty, A. M.; Maatta, E. A . Organoimido-polyoxometalates as polymer pendants . Chem. Commun. , 2000 . 18 1793 - 1794 . .

Han, Y.; Xiao, Y.; Zhang, Z.; Liu, Bo.; Zheng, P.; He, S.; Wang, W . Synthesis of polyoxometalate-polymer hybrid polymers and their hybrid vesicular assembly . Macromolecules , 2009 . 42 6543 - 6548 . DOI: 10.1021/ma9011686 http://doi.org/10.1021/ma9011686 .

Miao, W. K.; Yan, Y. K.; Wang, X. L.; Xiao, Y.; Ren, L. J.; Zheng, P.; Wang, C. H.; Ren, L. X.; Wang, W . Incorporation of polyoxometalates into polymers to create linear poly(polyoxometalate)s with catalytic function . ACS Macro Lett. , 2014 . 3 211 - 215 . DOI: 10.1021/mz5000202 http://doi.org/10.1021/mz5000202 .

Tang, J.; Yu, W.; Hu, M. B.; Xiao, Y.; Wang, X. G.; Ren, L. J.; Zheng, P.; Zhu, W.; Chen, Y.; Wang, W . Bottom-up hybridization: A strategy for the preparation of a thermostable polyoxometalate-polymer hybrid with hierarchical hybrid structures . ChemPlusChem , 2014 . 79 1455 - 1462 . DOI: 10.1002/cplu.201402092 http://doi.org/10.1002/cplu.201402092 .

Tang, J.; Ma, C.; Li, X. Y.; Ren, L. J.; Wu, H.; Zheng, P.; Wang W . Self-assembling a polyoxometalate-PEG hybrid into a nanoenhancer to tailor PEG properties . Macromolecules , 2015 . 48 2723 - 2730 . DOI: 10.1021/acs.macromol.5b00214 http://doi.org/10.1021/acs.macromol.5b00214 .

Tang, J.; Li, X. Y.; Wu, H.; Ren, L. J.; Zhang, Y. Q.; Yao, H. X.; Hu, M. B.; Wang, W . Tube-graft-sheet nano-objects created by a stepwise self-assembly of polymer-polyoxometalate hybrids . Langmuir , 2016 . 32 460 - 467 . DOI: 10.1021/acs.langmuir.5b04504 http://doi.org/10.1021/acs.langmuir.5b04504 .

Qi, W.; Wu, L . Polyoxometalate/polymer hybrid materials: Fabrication and properties . Polym. Int. , 2009 . 58 1217 - 1225 . DOI: 10.1002/pi.v58:11 http://doi.org/10.1002/pi.v58:11 .

Wu, H.; Yang, H. K.; Wang, W . Covalently-linked polyoxometalate-polymer hybrids: Optimizing synthesis, appealing structures and prospective applications . New J. Chem. , 2016 . 40 886 - 897 . DOI: 10.1039/C5NJ01257K http://doi.org/10.1039/C5NJ01257K .

Yan, J.; Zheng, X.; Yao, J.; Xu, P.; Miao, Z.; Li, J.; Lv, Z.; Zhang, Q.; Yan, Y . Metallopolymers from organically modified polyoxometalates (MOMPs): A review . J. Organomet. Chem. , 2019 . 884 1 - 16 . DOI: 10.1016/j.jorganchem.2019.01.012 http://doi.org/10.1016/j.jorganchem.2019.01.012 .

Zhang, S.; Xu, T.; Chai, S.; Zhang, L.; Wu, L.; Li, H . Supramolecular star polymer films with tunable honeycomb . Polymer , 2017 . 117 306 - 314 . DOI: 10.1016/j.polymer.2017.04.048 http://doi.org/10.1016/j.polymer.2017.04.048 .

Rubinstein, M.; Colby, R. H. Polymer physics , Oxford University Press, Oxford, 2003 , p. 362

Chen, Q.; Uno, A.; Matsumiya, Y.; Watanabe, H . Viscoelastic mode distribution of moderately entangled linear polymers . Nihon Reoroji Gakk. , 2010 . 38 187 - 193 . .

Ferry, J. D. Viscoelastic properties of polymers , Wiley, New York, 1980 , p. 264−320

Chen, Q.; Matsumiya, Y.; Masubuchi, Y.; Watanabe, H.; Inoue, T . Component dynamics in polyisoprene/poly(4- tert -butylstyrene) miscible blends . Macromolecules , 2008 . 41 8694 - 8711 . DOI: 10.1021/ma8013417 http://doi.org/10.1021/ma8013417 .

Chen, Q.; Matsumiya, Y.; Watanabe, H . Dynamics in miscible blends of polyisoprene and poly( p - tert -butyl styrene): Thermo-rheological behavior of components . Polym. J. , 2012 . 44 102 - 114 . DOI: 10.1038/pj.2011.33 http://doi.org/10.1038/pj.2011.33 .

Leblanc, J. L . Rubber-filler interactions and rheological properties in filled compounds . Prog. Polym. Sci. , 2002 . 27 627 - 687 . DOI: 10.1016/S0079-6700(01)00040-5 http://doi.org/10.1016/S0079-6700(01)00040-5 .

Jancar, J.; Douglas, J. F.; Starr, F. W.; Kumar, S. K.; Cassagnau, P.; Lesser, A. J.; Sternstein, S. S.; Buehler, M. J . Current issues in research on structure-property relationships in polymer nanocomposites . Polymer , 2010 . 51 3321 - 3343 . DOI: 10.1016/j.polymer.2010.04.074 http://doi.org/10.1016/j.polymer.2010.04.074 .

Jouault, N.; Moll, J. F.; Meng, D.; Windsor, K.; Ramcharan, S.; Kearney, C.; Kumar, S. K . Bound polymer layer in nanocomposites . ACS Macro Lett. , 2013 . 2 371 - 374 . DOI: 10.1021/mz300646a http://doi.org/10.1021/mz300646a .

Gong, S. S.; Chen, Q.; Moll, J.; Kumar S. K.; Colby, R. H . Segmental dynamics of polymer melts with spherical nanoparticles . ACS Macro Lett. , 2014 . 3 773 - 777 . DOI: 10.1021/mz500252f http://doi.org/10.1021/mz500252f .

Chen, Q.; Gong, S. S.; Moll, J.; Zhao, D.; Kumar S. K.; Colby, R. H . Mechanical reinforcement of polymer nanocomposites from percolation of a nanoparticle network . ACS Macro Lett. , 2015 . 4 398 - 402 . DOI: 10.1021/acsmacrolett.5b00002 http://doi.org/10.1021/acsmacrolett.5b00002 .

Inoue, T.; Nirihisa, Y.; Katashima, T.; Kawasaki, S.; Tada, T. A . Rheo-optical study on reinforcement effect of silica particle filled rubber . Macromolecules , 2017 . 50 8072 - 8082 . DOI: 10.1021/acs.macromol.7b01361 http://doi.org/10.1021/acs.macromol.7b01361 .

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