A one-pot, solvent-free, and controlled synthetic route for thermoresponsive hyperbranched polyurethanes,Polymer Chemistry

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A one-pot, solvent-free, and controlled synthetic route for thermoresponsive hyperbranched polyurethanes
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-09-02 , DOI: 10.1039/d0py01026j
Lucas Polo Fonseca _{1,

2,

3,

4} , Daniela de Morais Zanata _{1,

2,

3,

4} , Cony Gauche _{1,

2,

3,

4} , Maria Isabel Felisberti _{1,

2,

3,

4}

Affiliation

Hyperbranched polyurethanes (HPUs) are known for their multifunctionality and versatile properties. Despite the importance of this class of polymers, the issues associated with their synthesis remain a challenge, such as the lack of reproducibility, the need for polymerization in diluted solutions to avoid crosslinking, and the need for purification with organic solvents. Here, we report the synthesis of HPUs based on poly(ethylene glycol), polycaprolactone triol, and isophorone diisocyanate by dynamic urea bond-mediated polymerization (DUBMP). This polymerization technique allowed for kinetic control over the molar mass distribution and suppressed the formation of by-products. Besides, gelation was not verified up to 0.91 conversion. Both molar mass and dispersity of the HPUs were precisely tailored by hindered secondary amine/isocyanate molar ratio, time, and temperature of the polymerization. HPUs with molar masses ranging from 4 kDa to 49 kDa, molar mass dispersities ranging from 1.6 to 2.8, and properties varying from viscous liquids to elastomers were obtained by changing the synthetic parameters. Furthermore, amphiphilicity imparted an LCST phase behavior to HPU aqueous solutions, which depends on both their molar mass and composition. Thermoreversible gels were formed at around 30 °C, driven by the macroscopic phase separation of HPU aqueous solutions. Finally, HPUs showed high cell viability against mouse fibroblasts.

中文翻译：

一锅，无溶剂，可控制的合成路线，用于热响应性超支化聚氨酯

超支化聚氨酯（HPU）以其多功能性和多功能性而闻名。尽管这类聚合物很重要，但与其合成相关的问题仍然是一个挑战，例如缺乏可重复性，需要在稀释溶液中进行聚合反应以避免交联以及需要用有机溶剂进行纯化。在这里，我们报告通过动态脲键介导的聚合反应（DUBMP）合成基于聚乙二醇，聚己内酯三醇和异佛尔酮二异氰酸酯的HPU。该聚合技术允许动力学控制摩尔质量分布并抑制副产物的形成。此外，未证实凝胶化至0.91转化率。HPU的摩尔质量和分散度均受阻于仲胺/异氰酸酯的摩尔比，聚合时间和温度而精确调整。通过改变合成参数，可以获得摩尔质量范围为4 kDa至49 kDa，摩尔质量分散度范围为1.6至2.8，性能从粘性液体到弹性体不等的HPU。此外，两亲性赋予HPU水溶液LCST相行为，这取决于它们的摩尔质量和组成。在HPU水溶液的宏观相分离的驱动下，大约30°C时会形成热可逆凝胶。最后，HPU对小鼠成纤维细胞显示出高细胞活力。通过改变合成参数可以获得从粘性液体到弹性体的各种性能。此外，两亲性赋予HPU水溶液LCST相行为，这取决于它们的摩尔质量和组成。在HPU水溶液的宏观相分离的驱动下，大约30°C时会形成热可逆凝胶。最后，HPU对小鼠成纤维细胞显示出高细胞活力。通过改变合成参数可以获得从粘性液体到弹性体的各种性能。此外，两亲性赋予HPU水溶液LCST相行为，这取决于它们的摩尔质量和组成。在HPU水溶液的宏观相分离的驱动下，大约30°C时会形成热可逆凝胶。最后，HPU对小鼠成纤维细胞显示出高细胞活力。

更新日期：2020-10-13

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