[Ru]催化烯烃的 Metathesis 和 Ethenolysis,用于合成和回收生物基聚碳酸酯和聚氰尿酸酯

IF 4.1 2区 化学 Q2 POLYMER SCIENCE Polymer Chemistry Pub Date : 2024-11-04 DOI:10.1039/d4py00940a
Dana M. Pinson, Francesca D. Eckstrom, Gregory S. Ostrom, K. Randall McClain, Lawrence Baldwin, Benjamin Grant Harvey
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引用次数: 0

摘要

丁香酚是一种天然存在的丰富酚类化合物,通过烯烃偏聚反应转化为热塑性聚碳酸酯,然后与三苯乙烯发生界面聚合反应。聚合物的锰含量为 5300 - 12700 g mol-1,平均玻璃化转变温度(Tg)为 82 ℃。在[Ru]合成催化剂存在下,聚碳酸酯在适度的乙烯压力(150 - 240 psi)下通过乙烯裂解反应解聚,生成离散单体[双(4-烯丙基-2-甲氧基苯酚)碳酸酯,化合物 2]。然后用第二代 Grubbs 催化剂 (M204) 对化合物 2 进行聚合,生成 Mn = 7500 g mol-1 的再生聚合物,其 Tg 为 114 °C。Tg 升高 32 °C 是因为烯丙基向内部位置发生了异构化,从而在芳香基团之间形成了链烯和 3 碳不饱和连接。为了将乙醚溶解再循环方法扩展到交联网络,丁香酚被转化成氰酸酯(3),然后经过热循环三聚生成 2,4,6-三(4-烯丙基-2-甲氧基苯氧基)-1,3,5-三嗪(4),这是一种具有三嗪核心和三个带有甲氧基和烯丙基取代基的下垂芳香环的单体。4 通过烯烃偏聚反应(M204 催化剂)进行交联,生成 Mn = 8600 g mol-1 的网络,Tg 为 180 ℃。与聚碳酸酯类似,聚氰尿酸酯在乙烯存在下可有效解聚,从而再生出 4。化合物 4 随后又进行了两次聚合和解聚,证明了三嗪单体/网络的完全循环性。与原始聚合物相比,再生网络具有相似的 Tgs(167-184 °C)和热稳定性。总之,这项工作表明,在标准乙醚溶解条件下,可以很容易地从丁香酚中制备出热塑性和交联网络,并对其进行催化回收。与许多传统方法不同的是,这项工作中描述的回收聚合物在热机械性能方面没有明显退化。这种方法支持循环生物经济,有助于减少塑料垃圾和环境中微/纳米塑料微粒的积累。
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[Ru]-Catalyzed Olefin Metathesis and Ethenolysis for the Synthesis and Recycling of Bio-Based Polycarbonates and Polycyanurates
Eugenol, an abundant, naturally occurring phenolic compound, was converted into a thermoplastic polycarbonate by olefin metathesis followed by interfacial polymerization with triphosghene. This resulted in polymers with Mn ranging from 5300 – 12700 g mol-1 and an average glass transition temperature (Tg) of 82 °C. The polycarbonates were depolymerized via ethenolysis reactions under modest ethylene pressures (150 – 240 psi) in the presence of [Ru]-metathesis catalysts to yield a discrete monomer [bis(4-allyl-2-methoxyphenol) carbonate, compound 2]. 2 was then polymerized with a second generation Grubbs catalyst (M204) to produce a recycled polymer with Mn = 7500 g mol-1 and a Tg of 114 °C. The 32 °C increase in Tg was due to the isomerization of the allyl group to internal positions, which then allowed for the formation of stilbene and 3-carbon unsaturated linkages between aromatic groups. To expand the ethenolysis recycling approach to cross-linked networks, eugenol was converted into a cyanate ester (3), which was then thermally cyclotrimerized to generate 2,4,6-tris(4-allyl-2-methoxyphenoxy)-1,3,5-triazine (4), a monomer with a triazine core and three pendent aromatic rings with methoxy and allyl substituents. 4 was cross-linked via olefin metathesis (M204 catalyst) to generate a network with Mn = 8600 g mol-1 and a Tg of 180 °C. Similar to the polycarbonate, the polycyanurate was efficiently depolymerized in the presence of ethylene to regenerate 4. Compound 4 was then polymerized and depolymerized two additional times, demonstrating full circularity for the triazine monomer/network. The recycled networks exhibited similar Tgs (167–184 °C) and thermal stability compared to the virgin polymer. Overall, this work demonstrates that both thermoplastic and cross-linked networks can be readily prepared from eugenol and catalytically recycled under standard ethenolysis conditions. Unlike many conventional approaches, the recycled polymers described in this work exhibited no significant degradation in thermomechanical properties. This type of approach supports a circular bioeconomy and may help to reduce plastic waste and the accumulation of micro/nanoplastic particles in the environment.
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来源期刊
Polymer Chemistry
Polymer Chemistry POLYMER SCIENCE-
CiteScore
8.60
自引率
8.70%
发文量
535
审稿时长
1.7 months
期刊介绍: Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.
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