Isocyanate-Free Polyurea Synthesis via Ru-Catalyzed Carbene Insertion into the N-H Bonds of Urea

被引：9

作者：

de Zwart, Felix J. ^{[1
]}

Laan, Petrus C. M. ^{[1
]}

van Leeuwen, Nicole S. ^{[1
]}

Bobylev, Eduard O. ^{[1
]}

van Hove, Erika R. Amstalden ^{[2
]}

Mathew, Simon ^{[1
]}

Yan, Ning ^{[1
]}

Flapper, Jitte ^{[3
]}

van den Berg, Keimpe J. ^{[3
]}

Reek, Joost N. H. ^{[1
]}

de Bruin, Bas ^{[1
]}

机构：

[1] Univ Amsterdam, Vant Hoff Inst Mol Sci HIMS, Homogeneous Supramol & Bioinspired Catalysis Grp, NL-1098 XH Amsterdam, Netherlands

[2] Free Univ Amsterdam, Amsterdam Inst Life & Environm, Environm & Hlth, NL-1081 HV Amsterdam, Netherlands

[3] Akzo Nobel Decorat Coatings BV, NL-2171 AJ Sassenheim, Netherlands

来源：

MACROMOLECULES | 2021年 / 55卷 / 21期

关键词：

POLYCONDENSATION; NITROGEN;

D O I：

10.1021/acs.macromol.2c01457

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Polyureas have widespread applications due to their unique material properties. Because of the toxicity of isocyanates, sustainable isocyanate-free routes to prepare polyureas are a field of active research. Current routes to isocyanate-free polyureas focus on constructing the urea moiety in the final polymerizing step. In this study we present a new isocyanate-free method to produce polyureas by Ru-catalyzed carbene insertion into the N- H bonds of urea itself in combination with a series of bis-diazo compounds as carbene precursors. The mechanism was inves-tigated by kinetics and DFT studies, revealing the rate-determining step to be nucleophilic attack on a Ru-carbene moiety by urea. This study paves the way to use transition-metal-catalyzed reactions in alternative routes to polyureas.

引用

页码：9690 / 9696

页数：7

共 41 条

[1]

Anslyn Eric V, 2005, Modern Physical Organic Chemistry

[2] Diastereomeric half-sandwich Ru(II) cationic complexes containing amino amide ligands. Synthesis, solution properties, crystal structure and catalytic activity in transfer hydrogenation of acetophenone [J].