Controllable Synthesis of Branched CO<sub>2</sub>-based Hexol

Wang Ping; Liu Shun-jie; Qin Yu-sheng; Wang Xian-hong; Wang Fo-song

doi:10.11777/j.issn1000-3304.2017.16210

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Controllable Synthesis of Branched CO₂-based Hexol

Research Article | 更新时间：2021-05-18

- Controllable Synthesis of Branched CO₂-based Hexol
- Acta Polymerica Sinica Issue 2, Pages: 259-265(2017)
- 作者机构：
  
  1.中国科学院长春应用化学研究所长春 130022
  2.中国科学院大学北京 100049
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.16210
  CLC：
- Published：20 February 2017，
  
  Received：24 June 2016，
  
  Revised：1 September 2016，
扫描看全文
Wang Ping, Liu Shun-jie, Qin Yu-sheng, Wang Xian-hong, Wang Fo-song. Controllable Synthesis of Branched CO₂-based Hexol. [J]. Acta Polymerica Sinica (2):259-265(2017)
DOI：

Wang Ping, Liu Shun-jie, Qin Yu-sheng, Wang Xian-hong, Wang Fo-song. Controllable Synthesis of Branched CO₂-based Hexol. [J]. Acta Polymerica Sinica (2):259-265(2017) DOI： 10.11777/j.issn1000-3304.2017.16210.

摘要

利用Zn-Co双金属氰化物为催化剂，疏水性二季戊四醇（DPE）作为起始剂，实现了二氧化碳（CO

）和环氧丙烷（PO）的不死共聚合，高效、高选择性地合成了支化结构CO

基六元醇，且该产物有6个羟基封端.该支化CO

基六元醇的合成路线具有可控的特点，其分子量可通过PO与DPE的摩尔比准确控制（1500~8000），同时分子量分布很窄（最低至1.08）.值得注意的是，降低反应温度可显著改善聚合选择性，例如，当温度为50℃时，产物碳酸酯单元含量高达60%，而反应副产物环状碳酸酯的含量可控制在5.5 wt%以下，但是体系催化活性下降至0.14 kg g

-1

.该支化结构CO

基六元醇有望作为高交联密度的多元醇，用于制备高强硬质聚氨酯泡沫材料.

Abstract

Branched CO

-based oligo (carbonate-ether) hexols were synthesized in high productivity and selectivity by immortal copolymerization of CO

and propylene oxide (PO) in the presence of hydrophobic dipentaerythritol (DPE) using the zinc-cobalt double metal cyanide (Zn-Co-DMC) catalyst. The structure of the CO

-based hexols was confirmed

via

FTIR

H-NMR

C-NMR

DEPT-NMR

MALDI-TOF-MS

GPC and DSC. However

because of the overlap of the proton signals assigned to DPE and CO

-based hexols

respectively

it was hard to make sure the fully conversion of the 6 hydroxyl groups in DPE. By using

C-NMR technique wisely

we confirmed that all the 6 hydroxyl groups participated in the copolymerization due to the chemical shift of characteristic carbon signal of DPE. Moreover

the MALDI-TOF-MS spectrum of the polymer gave a direct visualization of the structure of CO

-based hexols

which contained 6 hydroxyl groups per macromolecule. The number average molecular weight (

) of the CO

-based hexol was in good linear relationship to the molar ratio of PO to DPE (PO/DPE)

and hence could be precisely controlled from 1500 to 8000. Besides

the rapid chain transfer reaction in the immortal copolymerization afforded the CO

-based hexol with a narrow polydispersity index (PDI) of 1.08 at

of 1600

which was reported as one of the narrowest PDI in heterogeneous catalytic systems. Notably

decreasing reaction temperature could substantially improve the catalytic selectivity

e.g.

at copolymerization temperature of 50℃

the carbonate unit (CU) content in the CO

-based hexols could reach as high as 60%

while the weight fraction of the unwanted byproduct propylene carbonate (

) could be controlled to as low as 5.5 wt%

although the catalytic productivity declined to 0.14 kg g

-1

. Unfortunately

the natural hydrophilic polyhydric alcohols

like sucrose and lactose

resulted in uncontrolled reactions and the corresponding CO

-based polyols could not be obtained. These results suggested that the natural polyhydric alcohols could not coordinate to the active center of catalyst.

关键词

二氧化碳环氧丙烷CO2基六元醇支化结构

Keywords

Carbon dioxidePropylene oxideCO2-based hexolsBranched structure

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School of Applied Chemistry and Engineering, University of Science and Technology of China

Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

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China Center of Chemistry for Frontier Technologies, Zhejiang University

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⁰

Controllable Synthesis of Branched CO2-based Hexol

DOI：10.11777/j.issn1000-3304.2017.16210

摘要

Abstract

关键词

Keywords

references

Controllable Synthesis of Branched CO₂-based Hexol