Polyheptenamer: A chemically recyclable polyolefin enabled by the low strain of seven‐membered cycloheptene

Polyheptenamer: A chemically recyclable polyolefin enabled by the low strain of seven‐membered cycloheptene
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聚庚烯:一种由七元环庚烯的低应变实现的化学可回收聚烯烃

DOI:
10.1002/pol.20240196
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发表时间:
2024
影响因子:
3.4
通讯作者:
Sun, Hao
Sun, Hao
中科院分区:
化学3区
文献类型:
--
作者:
Ibrahim, Tarek;Martindale, Jordan;Ritacco, Angelo;Rodriguez, Mia;Sun, Hao

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低应变环烯烃单体,包括五元环、六元环、八元环和大环,最近已被开发用于经由开环易位聚合(ROMP)合成可解聚聚烯烃。这样的聚烯烃可以经历闭环复分解解聚(RCMD)以再生它们的原始单体。尽管如此,通过七元环烯烃(一类重要的低应变环)的ROMP制备的聚烯烃的解聚行为仍然未得到探索。在这项研究中,我们证明了在标准RCMD条件下,聚庚烯体的化学循环到环庚烯。Grubbs的第二代催化剂在甲苯中实现了聚庚烯聚体的高效解聚。据观察,当解聚温度升高和起始聚合物浓度降低时,单体产率增加。在稀释条件(20 mM烯烃)下在60°C下在1小时内实现接近定量的单体再生(>96%)。此外,聚庚烯聚物表现出高于430°C的分解温度,突出了其作为新型热稳定和化学可回收聚合物材料的潜力。
Low‐strain cyclic olefin monomers, including five‐membered, six‐membered, eight‐membered, and macrocyclic rings, have been recently exploited for the synthesis of depolymerizable polyolefins via ring‐opening metathesis polymerization (ROMP). Such polyolefins can undergo ring‐closing metathesis depolymerization (RCMD) to regenerate their original monomers. Nevertheless, the depolymerization behavior of polyolefins prepared by ROMP of seven‐membered cyclic olefins, an important class of low‐strain rings, still remains unexplored. In this study, we demonstrate the chemical recycling of polyheptenamers to cycloheptene under standard RCMD conditions. Highly efficient depolymerization of polyheptenamer was enabled by Grubbs' second‐generation catalyst in toluene. It was observed that the monomer yields increased when the depolymerization temperature increased and the starting polymer concentration was reduced. A near‐quantitative monomer regeneration (>96%) was achieved within 1 h under dilute conditions (20 mM of olefins) at 60°C. Moreover, polyheptenamer exhibited a decomposition temperature above 430°C, highlighting its potential as a new class of thermally stable and chemically recyclable polymer materials.
DOI: 10.1126/science.aar5498
发表时间: 2018-04-27
期刊: SCIENCE
影响因子: 56.9
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