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
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
收藏
页码:3097 / 3106
页数:10
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