A solvent-less green synthetic route toward a sustainable bio-based elastomer: design, synthesis, and characterization of poly(dibutyl itaconate-co-butadiene),Polymer Chemistry

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A solvent-less green synthetic route toward a sustainable bio-based elastomer: design, synthesis, and characterization of poly(dibutyl itaconate-co-butadiene)
Polymer Chemistry ( IF 4.1 ) Pub Date : 2019-10-21 , DOI: 10.1039/c9py01393h
Xinxin Zhou _{1,

2,

3,

4} , Haijun Ji _{1,

2,

3,

4} , Guo-Hua Hu _{5,

6,

7,

8,

9} , Runguo Wang _{1,

2,

3,

4} , Liqun Zhang _{1,

2,

3,

4}

Affiliation

A sustainable poly(dibutyl itaconate-co-butadiene) (PDIB) elastomer with curable double bonds was synthesized by environmentally benign emulsion polymerization of bio-based dibutyl itaconate with butadiene. The microstructure of the PDIB elastomer was confirmed by FTIR and NMR. The resulting copolymers had predominately trans- and vinyl-polybutadiene in their chains, a molecular weight from 236 000 to 392 000 Da, and a glass transition temperature from −42 to −72 °C, depending on the feed weight percentage of butadiene. The reactivity ratios of dibutyl itaconate and butadiene determined by the classical Fineman–Ross method and Kelen–Tüdös one indicated a non-ideal copolymerization behavior with an azeotropic point at 0.383. The monomer sequence distribution indicated that butadiene could undergo self-propagation to form long flexible segments while dibutyl itaconate preferred to form short sequences with isolated, diad or triad moieties. The mechanical properties of PDIB could compete with or even surpass those of traditional synthetic rubbers. The stress and the elongation at break of unfilled PDIB40 (40 wt% butadiene) were over 2 MPa and 600%, respectively, indicating that PDIB elastomers could be good candidates for the replacement of traditional synthetic rubbers based on fossil resources.

中文翻译：

迈向可持续生物基弹性体的无溶剂绿色合成路线：聚衣康酸二丁酯-共-丁二烯的设计，合成和表征

可持续的聚（二丁基itaconate-共丁二烯）（PDIB）弹性体与固化性双键通过用丁二烯的生物基衣康酸二丁酯对环境无害的乳液聚合合成。通过FTIR和NMR确认了PDIB弹性体的微观结构。所得的共聚物主要具有反式和乙烯基-聚丁二烯在链中的分子量，取决于丁二烯的进料重量百分比，分子量为236 000至392 000 Da，玻璃化转变温度为-42至-72°C。用经典的Fineman-Ross法和Kelen-Tüdös法测定的衣康酸二丁酯和丁二烯的反应率表明共沸点为0.383，这是不理想的共聚行为。单体序列分布表明丁二烯可进行自我繁殖以形成长的柔性链段，而衣康酸二丁酯优选形成具有分离的，二单元或三单元部分的短序列。PDIB的机械性能可以与传统合成橡胶相媲美甚至超越。未填充的PDIB40（40 wt％丁二烯）的应力和断裂伸长率分别超过2 MPa和600％。

更新日期：2019-10-21

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