Polymeric Aluminum Porphyrin Systems: Efficient and Controllable Synthesis of Carbon Dioxide-based Polyols

Chun-wei Zhuo; Han Cao; Zhen-zhen Zhou; Shun-jie Liu; Xian-hong Wang

doi:10.11777/j.issn1000-3304.2022.22349

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Polymeric Aluminum Porphyrin Systems: Efficient and Controllable Synthesis of Carbon Dioxide-based Polyols

Research Article | 更新时间：2024-01-18

- Polymeric Aluminum Porphyrin Systems: Efficient and Controllable Synthesis of Carbon Dioxide-based Polyols
  增强出版
- ACTA POLYMERICA SINICA Vol. 54, Issue 5, Pages: 601-611(2023)
- 作者机构：
  
  1.中国科学院长春应用化学研究所中国科学院生态环境高分子材料重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
- 作者简介：
  
  Shun-jie Liu, E-mail: sjliu@ciac.ac.cn
  Xian-hong Wang, E-mail: xhwang@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2022.22349
  CLC：
- Published：20 May 2023，
  
  Published Online：02 December 2022，
  
  Received：17 October 2022，
  
  Accepted：18 November 2022
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卓春伟,曹瀚,周振震等.高分子铝卟啉体系：二氧化碳基多元醇的高效可控合成[J].高分子学报,2023,54(05):601-611.

Zhuo Chun-wei,Cao Han,Zhou Zhen-zhen,et al.Polymeric Aluminum Porphyrin Systems: Efficient and Controllable Synthesis of Carbon Dioxide-based Polyols[J].ACTA POLYMERICA SINICA,2023,54(05):601-611.
卓春伟,曹瀚,周振震等.高分子铝卟啉体系：二氧化碳基多元醇的高效可控合成[J].高分子学报,2023,54(05):601-611. DOI： 10.11777/j.issn1000-3304.2022.22349.

Zhuo Chun-wei,Cao Han,Zhou Zhen-zhen,et al.Polymeric Aluminum Porphyrin Systems: Efficient and Controllable Synthesis of Carbon Dioxide-based Polyols[J].ACTA POLYMERICA SINICA,2023,54(05):601-611. DOI： 10.11777/j.issn1000-3304.2022.22349.

摘要

二氧化碳基多元醇(CO

-polyol)是一种具有经济、环境双效益的聚氨酯前体材料，然而高效催化体系的缺乏制约着该领域的发展. 本文将新型高分子铝卟啉(PCAT-Al)催化体系应用于CO

与环氧丙烷的调节聚合反应，采用癸二酸、均苯三甲酸、均苯四甲酸和二季戊四醇作为链转移剂，实现CO

-polyol的可控合成. 在不同链转移剂条件下，PCAT-Al的催化效率均大于3.6 kg/g，可高效地制备分子量为470~5600 g/mol的CO

-polyol. 以癸二酸制备二元醇时，PCAT-Al的催化效率可达到6.3 kg/g，并保持高产物选择性(

polyol

= 98.9 wt%，100 ℃). 值得注意的是，PCAT-Al在制备支化多元醇时展现出比传统DMC催化剂更优异的催化性能. 在三元醇、四元醇及六元醇合成中的产物选择性分别达到99.3 wt%，98.2 wt%及95.1 wt%，显著高于DMC体系的88.8 wt%，83.0 wt%及75.8 wt%，表明PCAT-Al体系具有优异的聚合反应可控性. 此外，鉴于优异的质子耐受性，PCAT-Al在高链转移剂负载量下可有效地制备超低分子量CO

-二元醇(

= 470 g/mol). 在CO

与PO的调节聚合反应中，PCAT-Al表现出高活性、高选择性和优异质子耐受性的催化优势，这对CO

-polyol的持续发展具有重要意义.

Abstract

Carbon dioxide-based polyols (CO

-polyol) are emerging polyurethane precursors with economical and environmental benefits

however

the limited efficient catalytic systems restrict the sustainable development of this field. In this work

the novel catalytic system of polymeric aluminum porphyrin (PCAT-Al) was applied to the telomerization of CO

and propylene oxide

where the sebacic acid

trimesic acid

pyromellitic acid

and dipentaerythritol were used as the chain transfer agent (CTA) to achieve the controllable synthesis of CO

-polyols. The catalytic efficiency of PCAT-Al was greater than 3.6 kg/g under different chain transfer agents

and the CO

-polyol with molecular weights ranging from 470 g/mol to 5600 g/mol can be perpared efficiently. Meanwhile

the catalytic efficiency of PCAT-Al reached 6.3 kg/g with high product selectivity (

polyol

= 98.9 wt% at 100 ℃) for the preparation of CO

-diols with sebacic acid. Notably

PCAT-Al exhibited higher catalytic performance than conventional DMC catalysts in the preparation of branched polyols. The product selectivity in the synthesis of tertiary alcohols

tetrahydric alcohols

and hexahydric alcohols reached 99.3 wt%

98.2 wt%

and 95.1 wt%

respectively

which were significantly higher than those of the DMC system at 88.8 wt%

83.0 wt%

and 75.8 wt%

indicating that the PCAT-Al system had excellent controllability of the polymerization reaction. Moreover

PCAT-Al can be used to effectively prepare CO

-diols with ultra-low molecular weight (

= 470 g/mol) under high-loading chain transfer due to the excellent proton tolerance. PCAT-Al exhibits catalytic advantages of high activity

high selectivity and excellent proton tolerance in the CO

-polymerization reaction with PO

which is of great importance for the continued development of CO

-polyol.

关键词

高分子催化剂二氧化碳基多元醇铝卟啉高选择性结构调控

Keywords

Polymeric catalystCO2-polyolAluminum porphyrinHigh selectivityStructural regulation

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