Recent Progress on the Non-phosgene Synthesis of Polyisocyanates

YANG Xiang-dong; YANG Jing-jing; HUANG Mu-hua

doi:10.14028/j.cnki.1003-3726.2024.24.055

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Recent Progress on the Non-phosgene Synthesis of Polyisocyanates

更新时间：2024-09-10

- Recent Progress on the Non-phosgene Synthesis of Polyisocyanates
- Polymer Bulletin Vol. 37, Issue 9, Pages: 1190-1209(2024)
- 作者机构：
  
  1..中海油石化工程有限公司，济南 250101
  2..北京理工大学材料学院，北京 100081
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2024.24.055
  CLC：
- Published：20 September 2024，
  
  Published Online：20 June 2024，
  
  Received：02 February 2024，
  
  Accepted：17 April 2024
- 稿件说明：
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杨向东, 杨晶晶, 黄木华. 非光气途径合成多异氰酸酯的研究进展. 高分子通报, 2024, 37(9), 1190–1209

Yang, X. D.; Yang, J. J.; Huang, M. H. Recent progress on the non-phosgene synthesis of polyisocyanates. Polym. Bull. (in Chinese), 2024, 37(9), 1190–1209
杨向东, 杨晶晶, 黄木华. 非光气途径合成多异氰酸酯的研究进展. 高分子通报, 2024, 37(9), 1190–1209 DOI： 10.14028/j.cnki.1003-3726.2024.24.055.

Yang, X. D.; Yang, J. J.; Huang, M. H. Recent progress on the non-phosgene synthesis of polyisocyanates. Polym. Bull. (in Chinese), 2024, 37(9), 1190–1209 DOI： 10.14028/j.cnki.1003-3726.2024.24.055.

摘要

多异氰酸酯为聚氨酯弹性体、固体推进剂、胶黏剂、涂料、医药化工中间体等军民两用产品提供重要原料，支撑着现代工业文明的长足进步，改善着人类健康福祉。然而，多异氰酸酯的传统合成方法主要是通过多氨基化合物与光气反应转化而来，剧毒性光气的大量使用给环境造成了危害。为了从源头上实现绿色低碳的生产方式，促进人与自然和谐共生，迫切需要从本质上创新合成路径，发展多异氰酸酯的绿色制备技术。近年来，通过非光气途径合成异氰酸酯，或者通过非异氰酸酯途径制备高性能聚合物材料，已经成为研究的前沿方向之一。本文从氨基甲酸酯热分解脱醇反应、酰胺化合物的Hofmann重排反应、叠氮酰基化合物的Curtius重排反应、羟肟酸的Lossen重排反应、氰酸盐的

-取代反应以及硝基化合物的还原羰基化反应等途径概括了非光气法合成多异氰酸酯的最新进展情况。随着科学技术的不断进步和循环经济对可持续发展的要求不断提高，非光气途径制备多异氰酸酯及其聚氨酯将成为未来发展的潮流和趋势。

Abstract

Polyisocyanates are important raw materials for milit

ary and civilian products such as solid propellants

adhesives

and coatings

supporting the rapid progress of modern industrial civilization. They are also important intermediates for drug synthesis

improving human health and well-being. However

the traditional syntheses of polyisocyanate are mainly through the reactions of polyamines with phosgene

which is highly toxic and harmful to the environment. In order to improve the green and low-carbon production from the source

promote harmonious coexistence between humans and nature

it is urgently necessary to innovate the synthesis path and develop green preparation technology for polyisocyanate. In recent years

the synthesis of isocyanates through non-phosgene methods has become a research frontier as an active intermediate for the synthesis of high-value-added derivatives. The latest progress in the non-phosgene synthesis of polyisocyanate is summarized through pathways such as dealchoholysis of carbonates through pyrolysis

Hofmann rearrangement of amides

Curtius rearrangement on acyl azides

Lossen rearrangement of hydroxamic acid

reductive carbonylation reaction on nitro compounds

-substitution of cyanates

and so on. With the increasing requirements of circular economy for sustainable development

the syntheses of polyisocyanates and their corresponding polyurethanes through non-phosgene pathways will attract more attention in the future.

关键词

多异氰酸酯非光气途径聚氨酯氨基甲酸酯循环经济

Keywords

PolyisocyanateNon-phosgene processPolyurethaneCarbamateCircular economy

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