丙烯酸酯大分子引发剂铜介导的扩链在半间歇反应器中合成甲基丙烯酸酯和苯乙烯嵌段共聚物,Macromolecular Reaction Engineering

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丙烯酸酯大分子引发剂铜介导的扩链在半间歇反应器中合成甲基丙烯酸酯和苯乙烯嵌段共聚物
Macromolecular Reaction Engineering ( IF 1.8 ) Pub Date : 2021-12-10 , DOI: 10.1002/mren.202100043
Morgan J. Cooze ₁ , Hayden M. Deacon ₁ , Katrina Phe ₁ , Robin A. Hutchinson ₁

Affiliation

已经开发了一种通过铜介导的聚合控制丙烯酸酯生长的工艺，在铜管式反应器中连续合成大分子引发剂，随后在不添加铜的半间歇式反应器中进行扩链。然而，由于反应速率显着降低，已证明将该方法扩展到甲基丙烯酸酯和苯乙烯是很困难的。通过^使用PMDETA ( N , _N , N ' , N " , N'-五甲基二亚乙基三胺）作为配体。在 4 小时内实现了 70 °C 下 > 80% 的甲基丙烯酸甲酯转化率和室温下 > 90% 的二甘醇甲基丙烯酸酯转化率，同样的室温条件成功地应用于甲基丙烯酸丁酯的可控扩链。尽管在 85 °C 下 4 小时内苯乙烯的转化率略低（60-70%），但实现的转化率远高于其他研究中的转化率。疏水-亲水三嵌段结构是通过将单体连续进料到半间歇式反应器中产生的，使总反应时间小于 5 小时。将甲基丙烯酸酯和/或苯乙烯结合到结构化嵌段聚合物中的能力极大地扩展了可以通过该工艺以低铜含量有效合成的产品范围。

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Methacrylate and Styrene Block Copolymer Synthesis by Cu-Mediated Chain Extension of Acrylate Macroinitiator in a Semibatch Reactor

A process for the well-controlled growth of acrylates by Cu-mediated polymerization has been developed, with macroinitiator synthesized continuously in a copper tubular reactor and subsequently chain-extended in a semibatch reactor without additional copper. Extending this process to methacrylates and styrene, however, has proven difficult due to a significant reduction in reaction rate. This barrier has been overcome by chain-extending the low molecular weight (M_n of 760 g mol^–1) poly(methyl acrylate) macroinitiator with methacrylates and styrene using PMDETA (N,N,N′,N″,N″-pentamethyldiethylenetriamine) as ligand. Methyl methacrylate conversions of >80% at 70 °C and diethylene glycol methyl ether methacrylate conversions of >90% at room temperature are achieved in 4 h, with the same room temperature conditions successfully applied for controlled chain extensions with butyl methacrylate. Although styrene conversions are slightly lower (60–70%) over 4 h at 85 °C, the rates achieved are substantially higher than achieved in other studies. Hydrophobic–hydrophilic triblock structures are produced through sequential monomer feeds to the semibatch reactor, keeping total reaction time to less than 5 h. The ability to incorporate methacrylates and/or styrene into structured block polymers greatly extends the range of products that can be efficiently synthesized with low copper levels by this process.

更新日期：2021-12-10

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