Development of a H3PW12O40/CeO2 catalyst for bulk ring-opening polymerization of a cyclic carbonate,Green Chemistry

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Development of a H3PW12O40/CeO2 catalyst for bulk ring-opening polymerization of a cyclic carbonate
Green Chemistry ( IF 9.3 ) Pub Date : 2018-10-01 , DOI: 10.1039/c8gc01909f
Masayoshi Honda _{1,

2,

3,

4} , Hideki Abe _{1,

2,

3,

4}

Affiliation

A new reaction system involving a heterogeneous H₃PW₁₂O₄₀/CeO₂ catalyst and methyl iodide initiator was developed for bulk ring-opening polymerization (ROP) of trimethylene carbonate (TMC). Combination of a Brønsted acid (H₃PW₁₂O₄₀) and Lewis base (CeO₂) had a synergic effect on a well-controlled ROP without decarboxylation, which gave poly(TMC) of molecular weight (M_n) 30 000 and Polydispersity Index (PDI) of 1.80 at 60 °C and 24 h. Fourier transform infrared (FTIR) spectroscopy elucidated a reaction mechanism in which H₃PW₁₂O₄₀ promoted the initiation reaction and CeO₂ activated TMC, and the interface of these two components was an active site for ROP. The catalyst was removed readily by filtrating a dimethyl carbonate solution of poly(TMC), which was confirmed by inductively coupled plasma-atomic emission spectroscopy. In addition, various kinds of biomass-derived poly(aliphatic carbonate)s were synthesized and thermal properties were investigated by differential scanning calorimetry and thermogravimetry-differential thermal analysis. In particular, pyrolysis-gas chromatography mass spectrometry of these polymers revealed that the degradation mechanism was highly dependent upon a small amount of ether linkages and a pendant methyl group.

中文翻译：

用于环状碳酸酯本体开环聚合的H ₃ PW ₁₂ O ₄₀ / CeO ₂催化剂的开发

开发了一种新的反应体系，该体系包括多相H ₃ PW ₁₂ O ₄₀ / CeO ₂催化剂和甲基碘引发剂，用于碳酸三亚甲基酯（TMC）的本体开环聚合（ROP）。布朗斯台德酸（H ₃ PW ₁₂ O ₄₀）和路易斯碱（CeO ₂）的结合对良好控制的ROP没有脱羧作用具有协同作用，从而得到分子量（M _n）为30 000的聚（TMC）和多分散性在60°C和24 h下的指数（PDI）为1.80。傅里叶变换红外（FTIR）光谱阐明了H ₃ PW ₁₂ O ₄₀的反应机理促进了起始反应和CeO ₂活化的TMC，这两个组分的界面是ROP的活性位点。通过过滤聚（TMC）的碳酸二甲酯溶液可轻松除去催化剂，这已通过电感耦合等离子体原子发射光谱法确认。此外，合成了各种生物质衍生的聚脂族碳酸酯，并通过差示扫描量热法和热重分析-差热分析法研究了其热性能。尤其是，这些聚合物的热解-气相色谱质谱分析表明，降解机理高度依赖于少量的醚键和甲基侧基。

更新日期：2018-10-30

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