Kinetic Studies of Copolymerization of Cyclohexene Oxide with CO2 by a Diamino-bis(phenolate) Chromium(III) Complex

被引：30

作者：

Ni, Kaijie ^{[1
]}

Kozak, Christopher M. ^{[1
]}

机构：

[1] Mem Univ Newfoundland, Dept Chem, St John, NF A1B 3X7, Canada

来源：

INORGANIC CHEMISTRY | 2018年 / 57卷 / 06期

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会;

关键词：

BINARY CATALYST SYSTEMS; COBALT-SALEN COMPLEXES; TOF MS ANALYSIS; CARBON-DIOXIDE; ALTERNATING COPOLYMERIZATION; PROPYLENE-OXIDE; CO2/EPOXIDE COPOLYMERIZATION; STEREOCHEMISTRY CONTROL; POLY(PROPYLENE CARBONATE); MECHANISTIC INSIGHT;

D O I：

10.1021/acs.inorgchem.7b02952

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A diamino-bis(phenolate) chromium(III) complex, CrCl(THF)[L], 1, where [L] = dimethylaminoethylamino-N,N-bis(2-methylene-4,6-tert-butylphenolate), has been synthesized in high yield and characterized by MALDI-TOF mass spectrometry, elemental analysis, UV-vis spectroscopy and single crystal X-ray diffraction. This complex combined with 4-dimethylaminopyridine (DMAP) or bis(triphenylphosphoranylidene)ammonium chloride or azide salts (PPNCl or PPNN3) shows improved activity over previously reported amine-bis(phenolate) chromium(III) complexes for copolymerization of cyclohexene oxide (CHO) and CO2 to yield poly(cyclohexene) carbonate (PCHC). Kinetic studies of the complex/DMAP system showed the activation energy for polycarbonate formation to be 62 kJ/mol. End group analysis of resulting polycarbonates by MALDI-TOF MS reveals either the chloride of the Cr(III) complex or the external nucleophile initiates the copolymerization reaction.

引用

页码：3097 / 3106

页数：10

共 50 条

[1] Effect of Azide and Chloride Binding to Diamino-bis(phenolate) Chromium Complexes on CO2/Cyclohexene Oxide Copolymerization
Ni, Kaijie
Paniez-Grave, Valentine
Kozak, Christopher M.
[J]. ORGANOMETALLICS, 2018, 37 (15) : 2507 - 2518
[2] Mechanistic Studies of Cyclohexene Oxide/CO2 Copolymerization by a Chromium(III) Pyridylamine-Bis(Phenolate) Complex
Devaine-Pressing, Katalin
Kozak, Christopher M.
[J]. CHEMSUSCHEM, 2017, 10 (06) : 1266 - 1273
[3] Chromium Diamino-bis(phenolate) Complexes as Catalysts for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide
Ambrose, Kenson
Murphy, Jennifer N.
Kozak, Christopher M.
[J]. INORGANIC CHEMISTRY, 2020, 59 (20) : 15375 - 15383
[4] Chromium(III) amine-bis(phenolate) complexes as catalysts for copolymerization of cyclohexene oxide and CO2
Chen, Hua
Dawe, Louise N.
Kozak, Christopher M.
[J]. CATALYSIS SCIENCE & TECHNOLOGY, 2014, 4 (06) : 1547 - 1555
[5] Copolymerization of Cyclohexene Oxide and CO2 with a Chromium Diamine-bis(phenolate) Catalyst
Dean, Rebecca K.
Dawe, Louise N.
Kozak, Christopher M.
[J]. INORGANIC CHEMISTRY, 2012, 51 (16) : 9095 - 9103
[6] Ring opening polymerization and copolymerization for polyester and polycarbonate formation by a diamino-bis(phenolate) chromium(<sc>iii</sc>) catalyst
Vos, Cyler W.
Beament, James
Kozak, Christopher M.
[J]. POLYMER CHEMISTRY, 2023, 14 (45) : 5083 - 5093
[7] Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis-(phenolate) complex
Dean, Rebecca K.
Devaine-Pressing, Katalin
Dawe, Louise N.
Kozak, Christopher M.
[J]. DALTON TRANSACTIONS, 2013, 42 (25) : 9233 - 9244
[8] Copolymerization of CO2 and cyclohexene oxide
Super, M
Beckman, EJ
[J]. MACROMOLECULAR SYMPOSIA, 1998, 127 : 89 - 108
[9] Role of the cocatalyst in the copolymerization of CO2 and cyclohexene oxide utilizing chromium salen complexes
Darensbourg, DJ
Mackiewicz, RM
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (40) : 14026 - 14038
[10] Kinetic and mechanistic investigation for the copolymerization of CO2 and cyclohexene oxide catalyzed by trizinc complexes
Xu, Yonghang
Lin, Limiao
He, Chun-Ting
Qin, Jiaxiang
Li, Zhong
Wang, Shuanjin
Xiao, Min
Meng, Yuezhong
[J]. POLYMER CHEMISTRY, 2017, 8 (23) : 3632 - 3640

← 1 2 3 4 5 →