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杂环 - 酮亚胺锌酚盐配合物作为丙交酯开环聚合的高效催化剂。

Heterolepic -Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide.

作者信息

Ghosh Swarup, Schäfer Pascal M, Dittrich Dennis, Scheiper Christoph, Steiniger Phillip, Fink Gerhard, Ksiazkiewicz Agnieszka N, Tjaberings Alexander, Wölper Christoph, Gröschel André H, Pich Andrij, Herres-Pawlis Sonja, Schulz Stephan

机构信息

Faculty of Chemistry University of Duisburg-Essen and Center for Nanointegration Duisburg-Essen (CENIDE) Universitätsstr. 7, S07 S03 C30 D-45141 Essen.

Institute of Inorganic Chemistry RWTH Aachen University Landoltweg 1 52074 Aachen Germany.

出版信息

ChemistryOpen. 2019 Jul 4;8(7):951-960. doi: 10.1002/open.201900203. eCollection 2019 Jul.

DOI:10.1002/open.201900203
PMID:31338277
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6625107/
Abstract

Zinc phenoxide complexes LZnOAr - (L=MeNCHNC(Me)CHC(Me)O) and LZnOAr - (L=MeNCHNC(Me)CHC(Me)O) with donor-functionalized -ketoiminate ligands (L) and OAr substituents (Ar=Ph , ; 2,6-Me-CH , ; 3,5-Me-CH , ; 4-Bu-CH , ) with tuneable electronic and steric properties were synthesized and characterized. - adopt binuclear structures in the solid state except for , while they are monomeric in CDCl solution. - are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CHCl at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight ( ) and moderately controlled molecular weight distribution (MWDs). and showed a living polymerization character and kinetic studies on the ROP of -LA with and proved first order dependencies on the monomer concentration. Homonuclear decoupled H-NMR analyses of polylactic acid (PLA) formed with -LA proved isotactic enrichment of the PLA microstructure.

摘要

合成并表征了具有供体官能化的β-酮亚胺配体（L）和OAr取代基（Ar = Ph、2,6-Me₂C₆H₃、3,5-Me₂C₆H₃、4-BuₜC₆H₃）且具有可调节电子和空间性质的苯氧基锌配合物LZnOAr（L = MeNCHNC(Me)CHC(Me)O）和LZnOAr（L = MeNCHNC(Me)CHC(Me)O）。除了[具体某种情况未明确写出]外，[配合物名称未明确写出]在固态时采用双核结构，而它们在CDCl₃溶液中为单体。[配合物名称未明确写出]是在CHCl₃中于室温下催化丙交酯（LA）开环聚合（ROP）的活性催化剂，催化活性由OAr取代基的电子和空间性质控制，得到具有高平均分子量（[具体数值未明确写出]）和适度可控分子量分布（MWDs）的聚合物。[配合物名称未明确写出]和[配合物名称未明确写出]表现出活性聚合特征，并且对用[配合物名称未明确写出]和[配合物名称未明确写出]进行的丙交酯（-LA）ROP的动力学研究证明对单体浓度呈一级依赖性。用丙交酯（-LA）形成的聚乳酸（PLA）的同核去耦¹H-NMR分析证明了PLA微观结构的全同立构富集。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/68310ae6b821/OPEN-8-951-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/e82bd6a515b1/OPEN-8-951-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/4bf7e43a34cb/OPEN-8-951-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/6e0919b1fbff/OPEN-8-951-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/9b9364da06a8/OPEN-8-951-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/95e6c0ba0973/OPEN-8-951-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/68310ae6b821/OPEN-8-951-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/e82bd6a515b1/OPEN-8-951-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/4bf7e43a34cb/OPEN-8-951-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/6e0919b1fbff/OPEN-8-951-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/9b9364da06a8/OPEN-8-951-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/95e6c0ba0973/OPEN-8-951-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/17c4/6625107/68310ae6b821/OPEN-8-951-g005.jpg

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