Synthesis of high-molecular weight isosorbide-based polycarbonates through efficient activation of endo-hydroxyl groups by an ionic liquid

doi:10.1039/c9gc01500k

	Synthesis of high-molecular weight isosorbide-based polycarbonates through efficient activation of endo-hydroxyl groups by an ionic liquid
	Zhang, Zhencai 1,2; Xu, Fei 1,3; He, Hongyan 1; Ding, Weilu 1; Fang, Wenjuan 1; Sun, Wei 1; Li, Zengxi 1,2; Zhang, Suojiang 2
刊名	GREEN CHEMISTRY
	2019-07-21
卷号	21 期号:14 页码:3891-3901
ISSN号	1463-9262
DOI	10.1039/c9gc01500k
英文摘要	The utilization of renewable resources and carbon dioxide (CO2) has attracted extensive attention due to global warming and continuously declining petroleum-based resources. Herein, a novel synthetic approach of bio-based polycarbonates using isosorbide (ISB) and diphenyl carbonate (DPC), derived from the renewable resources glucose and CO2, respectively, was proposed, where an ionic liquid (IL) was used as a promising green catalyst; to overcome the poor activity of the endo-hydroxyl group (endo-OH) of ISB and achieve high-molecular weight polycarbonates, a new strategy was revealed that involved the activation of the endo-OH group via a series of efficient tetrabutylphosphonium-based IL catalysts. By designing the structures of cations and anions, most of the endo-OH groups have been activated and incorporated into the polymer chain, and the ratio of endo-OH/exo-OH at the end group of the polymer chain has been decreased to 0.25, which, to the best of our knowledge, is the lowest value reported to date. Among the prepared ILs, tetrabutylphosphonium acetate in a trace amount (1.5 x 10(-6) mol) exhibited highest catalytic performance, and poly(isosorbide carbonates) (PICs) with the molecular weight of up to 66 900 g mol(-1), T-g of 169 degrees C and better thermal stability than conventional polycarbonates were achieved. Mass spectrometry and density functional theory calculations provided a deeper understanding of the underlying cation-anion synergistic catalytic mechanism. Furthermore, copolymerization of ISB, diols and DPC was performed to modify the flexibility of PIC, resulting in copolycarbonates with the high molecular weight of 110 000 using 1,10-decanediol as a copolymer monomer.
资助项目	National Key R&D Program of China[2016YFB0600903] ; National Natural Science Foundation of China[21878316] ; National Natural Science Foundation of China[21890762] ; "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences[XDA21031000]
WOS关键词	BISPHENOL-A ; ALIPHATIC POLYCARBONATES ; DIPHENYL CARBONATE ; DIOLS ; CO2 ; POLYCONDENSATION ; POLYESTER ; CATALYST ; ACID
WOS研究方向	Chemistry ; Science & Technology - Other Topics
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000475506200016
资助机构	National Key R&D Program of China ; National Natural Science Foundation of China ; "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/30458]
专题	中国科学院过程工程研究所
通讯作者	Li, Zengxi; Zhang, Suojiang
作者单位	1.Chinese Acad Sci, Beijing Key Lab Ion Liquids Clean Proc, State Key Lab Multiphase Complex Syst, Key Lab Green Proc & Engn,Inst Proc Engn, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Sch Chem Engn, Beijing 100049, Peoples R China 3.Zhongke Langfang Inst Proc Engn, Langfang 065000, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Zhencai,Xu, Fei,He, Hongyan,et al. Synthesis of high-molecular weight isosorbide-based polycarbonates through efficient activation of endo-hydroxyl groups by an ionic liquid[J]. GREEN CHEMISTRY,2019,21(14):3891-3901.
APA	Zhang, Zhencai.,Xu, Fei.,He, Hongyan.,Ding, Weilu.,Fang, Wenjuan.,...&Zhang, Suojiang.(2019).Synthesis of high-molecular weight isosorbide-based polycarbonates through efficient activation of endo-hydroxyl groups by an ionic liquid.GREEN CHEMISTRY,21(14),3891-3901.
MLA	Zhang, Zhencai,et al."Synthesis of high-molecular weight isosorbide-based polycarbonates through efficient activation of endo-hydroxyl groups by an ionic liquid".GREEN CHEMISTRY 21.14(2019):3891-3901.