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三齿苯氧基-亚胺和苯氧基-胺配体的钛和钒配合物及其在环状酯开环聚合中的应用

Titanium and Vanadium Complexes of Tridentate Phenoxy-Imine and Phenoxy-Amine Ligands and Their Application in the Ring-Opening Polymerization of Cyclic Esters.

作者信息

Białek Marzena, Klimasińska Alicja, Spaleniak Grzegorz, Dziuk Błażej

机构信息

Institute of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.

Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50370 Wrocław, Poland.

出版信息

Molecules. 2023 Dec 22;29(1):87. doi: 10.3390/molecules29010087.

Abstract

Phenoxy-imine and phenoxy-amine proligands, with the additional OH donor groups 2,4-Bu-6-(2-CH(OH)-CHN=CH)CHOH (), 6-(2-CH(OH)-CHN=CH)CHOH (), and 2,4-Bu-6-(2-CH(OH)-CHNH-CH)CHOH (), were synthesized and their titanium (-) and vanadium (-) complexes were prepared in reactions with Ti(OPr) and VO(OPr), respectively. All new compounds were characterized with the use of FTIR, H, and C NMR spectroscopy; X-ray crystallography was also used to study proligands. All the complexes proved to be active catalysts in the ring-opening polymerization (ROP) of -caprolactone, -lactide, and -lactide in the melt. The effects of the complex structure (transition metal type, presence of Bu substituents, and type of nitrogen donor group), as well as the polymerization time and temperature, on the monomer conversion and polymer properties were investigated in detail.

摘要

合成了带有额外羟基供体基团2,4-二叔丁基-6-(2-羟甲基-乙烯基亚胺基)环己醇()、6-(2-羟甲基-乙烯基亚胺基)环己醇()和2,4-二叔丁基-6-(2-羟甲基-乙胺基)环己醇()的苯氧基-亚胺和苯氧基-胺前体配体,并分别通过与Ti(OPr)₄和VO(OPr)₃反应制备了它们的钛(-)和钒(-)配合物。使用傅里叶变换红外光谱、¹H和¹³C核磁共振光谱对所有新化合物进行了表征;还利用X射线晶体学研究了前体配体。所有配合物在ε-己内酯、丙交酯和乙交酯的熔融开环聚合(ROP)中均为活性催化剂。详细研究了配合物结构(过渡金属类型、叔丁基取代基的存在以及氮供体基团的类型)以及聚合时间和温度对单体转化率和聚合物性能的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/368c/10779786/4aea98801866/molecules-29-00087-sch001.jpg

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