High chemical recyclability of vinyl lactone acrylic bioplastics,Polymer Chemistry

当前位置： X-MOL 学术 › Polym. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

High chemical recyclability of vinyl lactone acrylic bioplastics
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0py00786b
Reid A. Gilsdorf _{1,

2,

3,

4} , Matthew A. Nicki _{1,

2,

3,

4} , Eugene Y.-X. Chen _{1,

2,

3,

4}

Affiliation

The depolymerization selectivity of poly(methyl methacrylate) (PMMA) under thermolysis and dynamic vacuum is inherently limited by the repeat-unit structure, leaving much (∼47%) of PMMA to fragment and carbonize to char. Here we show that renewable, high-performance alternatives to PMMA with vinyl lactone repeat units, poly(α-methylene-γ-butyrolactone) (PMBL) and poly(γ-methyl-α-methylene-γ-butyrolactone) (PγMMBL), unexpectedly depolymerize much more selectively and recover monomers with considerably higher yield and purity than PMMA (76% pure monomer isolated from PγMMBL) and are also devoid of char formation, leaving the residue as only the oligomers with a total mass balance. To uncover the origin of the unexpected high chemical recyclability of P(M)MBL, this study has ascertained their ceiling temperature (T_c) by density functional theory, trapped and analyzed both primary and tertiary macroradicals generated during the depolymerization, and probed the stability of macroradicals using Lewis acid additives and mixed plastic feeds. The evidence obtained through this study suggests that the much enhanced recyclability of P(M)MBL bioplastics relative to PMMA is not due to their differences in T_c values, but rather the linear ester and cyclic ester-imparted difference in stability and monomer-production roles of primary and tertiary macroradicals generated in the random chain scission processes.

中文翻译：

乙烯基内酯丙烯酸生物塑料的高化学可回收性

聚甲基丙烯酸甲酯（PMMA）在热解和动态真空下的解聚选择性固有地受到重复单元结构的限制，剩下大部分（〜47％）的PMMA断裂并碳化成炭。在这里，我们显示了具有乙烯基内酯重复单元，聚（α-亚甲基-γ-丁内酯）（PMBL）和聚（γ-甲基-α-亚甲基-γ-丁内酯）（PγMMBL）的PMMA的可再生，高性能替代品，出乎意料的是，它比PMMA（从PγMMBL分离出的76％的纯单体）具有更高的收率和纯度，并且收率和纯度都高得多，并且没有形成焦炭，只剩下低聚物，总质量平衡。为了揭示P（M）MBL意外的高化学可回收性的根源，本研究确定了其最高温度（T_c）通过密度泛函理论，捕获和分析了在解聚过程中产生的一级和三级大基团，并使用路易斯酸添加剂和混合塑料原料探测了大基团的稳定性。通过这项研究获得的证据表明，P（M）MBL生物塑料相对于PMMA的可回收性大大提高，不是由于它们的T _c值不同，而是由于线性酯和环状酯在稳定性和单体产量方面的差异在随机断链过程中产生的一级和三级宏观自由基的作用。

更新日期：2020-08-06

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11