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Synthesis and properties of multi-block thermoplastic polyurethanes constructed with polystyrene and poly(butylene adipate) sequences

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Abstract

A simple route is established to synthesize segmented polyurethanes constructed mainly with polystyrene and poly(butylene adipate) sequences. A long dihydroxyl terminated polystyrene (HO-PS-OH) was synthesized through the radical polymerization of styrene with 4.4′-azobis(4-cyanopentanol) as initiator. The HO-PS-OH, HO-terminated poly(butylene adipate) (HO-PBA-OH), and 4,4′-methylenediphenyl diisocyanate (MDI) were polymerized further in a one-step solution process, and a series of multi-block polystyrene-block-poly(butylene adipate) TPUs (PS–b-PBA TPUs) was prepared. Meanwhile, five two-step PS–b-PBA TPUs (ts- PS–b-PBA TPUs) were also prepared; that is, the HO-PBA-OH was first reacted with excessive MDI to obtain long OCN-terminated PBA-methylenediphenyl diurethane (PBA-MDU) prepolymers, and then it was polymerized with HO-PS-OH to form ts-PS–b-PBA TPUs. PS–b-PBA TPUs and ts-PS–b-PBA TPUs all showed two glass transition temperatures. Phase separation occurred between their hard and soft phases. Different from amorphous ts-PS–b-PBA TPUs that were constructed with long PBA-MDU soft segments (SSs) and PS-MDU hard segments (HSs), short and scattered PBA-MDU SSs and PS-MDU HSs led to crystallized PS–b-PBA TPUs that showed better mechanical property than ts-PS–b-PBA TPUs. Long amorphous PS and crystallizable PBA sequences provided the PS–b-PBA TPUs with high Tg and good thermal and mechanical properties.

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Funding

This work was financially supported by the Beijing Natural Science Foundation (nos. 2222070 and 2182056).

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Authors and Affiliations

  1. Key Laboratory of Carbon Fiber and Functional Polymers (BUCT), Ministry of Education; College of Materials Science and Engineering, Beijing University of Chemical Technology, 100029, Beijing, China

    Haonan Dong, Yuanmeng Wang, Min Fan, Jingbo Zhao, Zhiyuan Zhang & Junying Zhang

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  1. Haonan Dong
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  2. Yuanmeng Wang
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  3. Min Fan
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Correspondence to Jingbo Zhao or Junying Zhang.

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Dong, H., Wang, Y., Fan, M. et al. Synthesis and properties of multi-block thermoplastic polyurethanes constructed with polystyrene and poly(butylene adipate) sequences. J Polym Res 29, 413 (2022). https://doi.org/10.1007/s10965-022-03271-4

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