使用 PMDETA 作为配体的聚（丙烯酸甲酯）大分子引发剂的 Cu(0) 介导合成和扩链的有效方法,Macromolecular Chemistry and Physics

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使用 PMDETA 作为配体的聚（丙烯酸甲酯）大分子引发剂的 Cu(0) 介导合成和扩链的有效方法
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2021-06-10 , DOI: 10.1002/macp.202100120
Morgan J. Cooze ₁ , Nathaniel R. Barr ₁ , Robin A. Hutchinson ₁

Affiliation

Me ₆ TREN（三[2-（二甲氨基）乙基]胺）通常用于 Cu(0) 介导的丙烯酸酯聚合，因为它能够促进高反应速率，同时保持对链增长的出色控制。然而，其成本是商业化的一大障碍。因此，使用 PMDETA（N , N , N ʹ, N ʹʹ, N ʹʹ-五甲基二亚乙基三胺），一种比 Me ₆便宜得多的配体正在探索 TREN 但已知会降低聚合速率以及控制。证明了在铜管式反应器中使用 PMDETA 配体连续生产低分子量 (MW) 聚(丙烯酸甲酯)，在 70°C 下停留时间为 32 分钟，转化率 >70%。所得大分子引发剂溶液可以储存并用丙烯酸甲酯 (MA) 扩链以在半间歇式反应器中使用 PMDETA 或 Me ₆ TREN 作为附加配体实现高转化率，从而提高了新开发的工艺的多功能性，以使用任一配体有效生产嵌段共聚物，或两者的结合。初步结果表明，两步法也可用于用甲基丙烯酸酯链延长大分子引发剂，从而扩大可生产的材料范围。

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Toward an Efficient Process for the Cu(0)-Mediated Synthesis and Chain Extension of Poly(methyl acrylate) Macroinitiator Using PMDETA as Ligand

Me₆TREN (tris[2-(dimethylamino)ethyl]amine) is commonly used in Cu(0)-mediated polymerization of acrylates due to its ability to promote high reaction rates while maintaining excellent control of chain growth. However, its cost presents a significant barrier to commercialization. Thus, the use of PMDETA (N,N,Nʹ,Nʹʹ,Nʹʹ-pentamethyldiethylenetriamine), a ligand that is significantly less expensive than Me₆TREN but is known to reduce the polymerization rate as well as control, is explored. The continuous production of low molecular weight (MW) poly(methyl acrylate) using PMDETA ligand in a copper tubular reactor is demonstrated, with conversions >70% achieved with a residence time of 32 min at 70 °C. The resulting macroinitiator solution can be stored and chain extended with methyl acrylate (MA) to high conversion in a semibatch reactor using either PMDETA or Me₆TREN as additional ligand, increasing the versatility of a newly developed process to efficiently produce block copolymers using either ligand, or a combination of the two. First results suggest that the two-step process can also be used to chain extend the macroinitiator with methacrylates, thus extending the range of materials that can be produced.

更新日期：2021-08-07

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