Organocatalysts for L-Lactide polymerization: 2-alkyl- and 2-aryl-1,1,3,3-tetramethylguanidines

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2024-09-26 DOI:10.1016/j.mcat.2024.114580

Rajiv Kamaraj , Prasanna Kumar Ganta , Taoufik Ben Halima , Fei Huang , Venkata Sai Sashankh Penki , Hsi-Ching Tseng , Shangwu Ding , Hsuan-Ying Chen , Hsing-Yin Chen

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Abstract

A series of 2-alkyl- and 2-aryl-1,1,3,3-tetramethylguanidine derivatives were synthesized, and their application in L-Lactide (LA) polymerization was studied. Bn-TMG was the best catalyst in LA polymerization ( [Bn-TMG] = 5 mM, conversion = 94 % after 4 h at 25 °C) compared to other monoguanidine derivatives. In addition, the catalytic activities of C2-dTMG exhibited higher catalytic activity than Bn-TMG, ⁿBu-TMG (monoguanidine derivatives), and C3-dTMG (diguanidine derivative). Density functional theory calculations revealed that Bn-TMG deprotonated benzyl alcohol enhanced benzyl alcohol's initiation ability to LA, and the protonated Bn-TMG activated LA ring-opening process by interacting with the ether oxygen atom of LA. Bn-TMG presented excellent catalytic activity and controllability for LA polymerization at 25 °C.

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用于 L-内酯聚合的有机催化剂：2-烷基和 2-芳基-1,1,3,3-四甲基胍

研究人员合成了一系列 2-烷基和 2-芳基-1,1,3,3-四甲基胍衍生物，并研究了它们在 L-内酰胺（LA）聚合中的应用。与其他单胍衍生物相比，Bn-TMG 是 LA 聚合过程中的最佳催化剂（[Bn-TMG] = 5 mM，25 °C 下 4 小时后转化率 = 94 %）。此外，C2-dTMG 的催化活性高于 Bn-TMG、nBu-TMG（单胍衍生物）和 C3-dTMG（二胍衍生物）。密度泛函理论计算表明，Bn-TMG 对苯甲醇的去质子化作用增强了苯甲醇对 LA 的引发能力，质子化的 Bn-TMG 通过与 LA 的醚氧原子相互作用激活了 LA 的开环过程。Bn-TMG 在 25 °C 下对 LA 聚合具有优异的催化活性和可控性。

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods