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Effect of branching architecture on glass transition behavior of hyperbranched copolystyrenes: the experiment and simulation studies

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Abstract

By controlling the feed ratio of CMS/styrene and the polymerization time, a series of hyperbranched copolystyrenes (HBCPS) were synthesized with comparable weight-averaged molecular weights (M w) but different degree of branching (DB) through atom transfer radical self-condensing vinyl copolymerization (ATR-SCVCP) with CuBr/2,2′-bipyridyl as the catalyst. The resulting HBCPS samples were used to investigate the effect of branching architecture on their glass transition behavior. With the DB increased, the glass transition temperatures (T g) of HBCPS samples measured by DMA and DSC both decreased. Their spin-lattice relaxation times (1H T 1r) of protons displayed the same downtrend with increasing DB. Besides, a correlation between the T gs and the DB was well established by all-atom molecular dynamics (MD) simulations. The values of MD-determined T gs are little higher than the corresponding experimental ones. However, the dependence of T gs on DB is in good agreement with the experimental results, i.e., T g decreases both in experiments and simulations with increasing DB.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China

    Xiang Luo, Wei Huang  (黄卫) & De-yue Yan

  2. Institute of Theoretical Chemistry, State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130021, China

    Shi-jie Xie & Zhong-yuan Lu  (吕中元)

  3. Instrumental Analysis Center, Shanghai Jiao Tong University, Shanghai, 200240, China

    Bo-na Dai

Authors
  1. Xiang Luo
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  2. Shi-jie Xie
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  3. Wei Huang  (黄卫)
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  4. Bo-na Dai
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  5. Zhong-yuan Lu  (吕中元)
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  6. De-yue Yan
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Corresponding authors

Correspondence to Wei Huang  (黄卫) or Zhong-yuan Lu  (吕中元).

Additional information

This work was financially supported by the National Basic Research Program (Nos. 2012CB821500 and 2013CB834506), the National Natural Science Foundation of China (Nos.91127047, 21174086 and 21274167).

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Luo, X., Xie, Sj., Huang, W. et al. Effect of branching architecture on glass transition behavior of hyperbranched copolystyrenes: the experiment and simulation studies. Chin J Polym Sci 34, 77–87 (2016). https://doi.org/10.1007/s10118-016-1730-7

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  • DOI: https://doi.org/10.1007/s10118-016-1730-7

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