氮杂环烯基膦/三乙基硼协同催化环氧烷烃与苯酐交替共聚

韩帅; 温朗奇; 乐天俊; 周辉; 吕小兵

doi:10.11777/j.issn1000-3304.2025.25243

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氮杂环烯基膦/三乙基硼协同催化环氧烷烃与苯酐交替共聚

研究论文 | 更新时间：2026-01-16

- 氮杂环烯基膦/三乙基硼协同催化环氧烷烃与苯酐交替共聚
- N-heterocyclic Olefin-phosphines/Triethylboron Synergisticly Catalytic Copolymerization of Epoxides and Phthalic Anhydride
- 高分子学报 2026年57卷第1期页码：259-267
- 作者机构：
  
  大连理工大学精细化工全国重点实验室大连 116024
- 作者简介：
  
  E-mail: zhouhui@dlut.edu.cn
  xblu@dlut.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 21920102006)
- DOI：10.11777/j.issn1000-3304.2025.25243
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7506
- 收稿：2025-09-16，
  
  录用：2025-10-24，
  
  网络出版：2025-12-18，
  
  纸质出版：2026-01-20
- 稿件说明：
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韩帅, 温朗奇, 乐天俊, 周辉, 吕小兵. 氮杂环烯基膦/三乙基硼协同催化环氧烷烃与苯酐交替共聚. 高分子学报, 2026, 57(1), 259-267.

Han, S.; Wen, L. Q.; Yue, T. J.; Zhou, H.; Lu, X. B. N-heterocyclic olefin-phosphines/triethylboron synergisticly catalytic copolymerization of epoxides and phthalic anhydride. Acta Polymerica Sinica (in Chinese), 2026, 57(1), 259-267.
韩帅, 温朗奇, 乐天俊, 周辉, 吕小兵. 氮杂环烯基膦/三乙基硼协同催化环氧烷烃与苯酐交替共聚. 高分子学报, 2026, 57(1), 259-267. DOI： 10.11777/j.issn1000-3304.2025.25243. CSTR： 32057.14.GFZXB.2025.7506.

Han, S.; Wen, L. Q.; Yue, T. J.; Zhou, H.; Lu, X. B. N-heterocyclic olefin-phosphines/triethylboron synergisticly catalytic copolymerization of epoxides and phthalic anhydride. Acta Polymerica Sinica (in Chinese), 2026, 57(1), 259-267. DOI： 10.11777/j.issn1000-3304.2025.25243. CSTR： 32057.14.GFZXB.2025.7506.

摘要

设计并合成一系列新型氮杂环烯功能化有机膦试剂(NHO-P)，并通过

H-、

C-、

P-核磁共振波谱及高分辨质谱进行结构表征. 构建NHO-P/三乙基硼(Et

B)双组份有机催化聚合体系，用于环氧丙烷(PO)或环氧环己烷(CHO)与邻苯二甲酸酐(苯酐，PA)开环交替共聚反应. 实验结果表明，在PO:PA:NHO-P:Et

B = 2000:800:1:1 (摩尔比)、60 ℃条件下，富电子

NHO-P4

可定量转化酸酐，所制备聚酯数均分子量可达126.3 kg·mol

-1

(聚合物分散度=1.25)，呈完全交替结构. 进一步，通过核磁共振波谱和基质辅助激光解吸电离飞行时间质谱对共聚反应机理进行深入研究，证明了NHO-P作为有机碱经历离子对聚合路径引发开环交替聚合反应，高效制备完全交替结构聚酯材料.

Abstract

A series of novel

-heterocyclic olefin-functionalized phosphines (NHO-P) were successfully designed and synthesized. The chemical structures of NHO-P were thoroughly characterized using

H-

C-

and

P-nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Binary organic systems consisting of NHO-P and triethyl boron (Et

B) were constructed to catalyze the ring-opening alternating copolymerization of propylene oxide (PO) and phthalic anhydride (PA). The results showed that under the conditions of PO:PA:NHO-P:Et

B = 2000:800:1:1 (molar ratio)

at 60 ℃

the electron-rich

NHO-P4

could quantitatively convert the anhydride. The resulting polyester exhibited a high molecular weight of up to 126.3 kg·mol

-1

a polymer dispersity index of 1.25

and more than 99% ester units. Furthermore

the alternating copolymerization reaction mechanism was thoroughly investigated using NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The results demonstrated that NHO-P

acting as an organic base

followed an anionic polymerization pathway to initiate the ring-opening alternating copolymerization reaction

enabling the efficient preparation of polyester materials with a perfectly alternating structure.

关键词

Keywords

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