Synthesis of Free-solvent Liquid Ethylene Propylene Diene Monomer Based on the Efficiently Cycling Between V3+ and V2+ of VOCl3 Catalysts

Yan-long Qi; Chao Yang; Lei Wu; Li Liu; Ming-chao Wang

doi:10.11777/j.issn1000-3304.2025.25185

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Synthesis of Free-solvent Liquid Ethylene Propylene Diene Monomer Based on the Efficiently Cycling Between V³⁺ and V²⁺ of VOCl₃ Catalysts

Research Article | 更新时间：2026-03-23

- Synthesis of Free-solvent Liquid Ethylene Propylene Diene Monomer Based on the Efficiently Cycling Between V³⁺ and V²⁺ of VOCl₃ Catalysts
- Acta Polymerica Sinica Vol. 57, Issue 3, Pages: 754-763(2026)
- 作者机构：
  
  1.西南交通大学化学学院成都 610031
  2.湖北航天化学技术研究所航天化学能源全国重点实验室襄阳 441003
  3.哈尔滨工业大学化学与化工学院哈尔滨 150001
  4.中国科学院长春应用化学研究所长春 130022
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25185
  CLC：
- CSTR：32057.14.GFZXB.2025.7520
- Received：22 October 2025，
  
  Accepted：18 November 2025，
  
  Online First：05 January 2026，
  
  Published：20 March 2026
- 稿件说明：
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祁彦龙, 杨超, 吴磊, 刘丽, 王明超. 基于VOCl₃活性中心的还原-氧化(V³⁺/V²⁺)高效合成无溶剂液体三元乙丙橡胶. 高分子学报, 2026, 57(3), 754-763.

Qi, Y. L.; Yang, C.; Wu, L.; Liu, L.; Wang, M. C. Synthesis of free-solvent liquid ethylene propylene diene monomer based on the efficiently cycling between V³⁺and V²⁺ of VOCl₃ catalysts. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 754-763.
祁彦龙, 杨超, 吴磊, 刘丽, 王明超. 基于VOCl₃活性中心的还原-氧化(V³⁺/V²⁺)高效合成无溶剂液体三元乙丙橡胶. 高分子学报, 2026, 57(3), 754-763. DOI： 10.11777/j.issn1000-3304.2025.25185. CSTR： 32057.14.GFZXB.2025.7520.

Qi, Y. L.; Yang, C.; Wu, L.; Liu, L.; Wang, M. C. Synthesis of free-solvent liquid ethylene propylene diene monomer based on the efficiently cycling between V³⁺and V²⁺ of VOCl₃ catalysts. Acta Polymerica Sinica (in Chinese), 2026, 57(3), 754-763. DOI： 10.11777/j.issn1000-3304.2025.25185. CSTR： 32057.14.GFZXB.2025.7520.

摘要

液体三元乙丙橡胶(EPDM)具有固体EPDM的特性，又具有良好的流动性，可应用于防腐防污涂层、增塑剂、润滑油、黏合剂等. 然而，其合成过程面临诸多挑战，如分子量控制难、合成效率低、金属残留高等. 本研究采用VOCl

催化体系合成无溶剂型液体EPDM，具有优异的流动性和热稳定性，黏度为2469~3546 mPa·s (25 ℃)，聚合物的分子量低至4960 g/mol，最大热失重温度约405 ℃，具有良好的热稳定性. 探讨了聚合反应中助催化剂(Al

，EASC)、活化剂(三氯乙酸乙酯

ETCA)、VOC

之间的相互作用，考察了副反应对聚合反应结果的影响，通过ETCA“少量多次”添加策略，有效抑制了ETCA和EASC之间的副反应，持续构建V

↔V

循环，使聚合物的收率从2.93 g/g

cat

提高至31.26 g/g

cat

. 本研究避免了常规液体胶合成时使用高浓度催化剂的缺点.

Abstract

Liquid ethylene propylene diene monomer (EPDM) possesses the characteristics of solid EPDM and exhibits good fluidity

making it suitable for applications such as anti-corrosion and anti-fouling coatings

plasticizers

lubricants

and adhesives. However

its synthesis process faces numerous challenges

including difficulties in molecular weight control

low synthesis efficiency

and high metal residue. In this study

a solvent-free liquid EPDM which exhibited excellent fluidity and thermal stability was synthesized by using VOCl

catalysts. The viscosity of liquid EPDM ranged from 2469 mPa·s to 3546 mPa·s at 25 ℃. The molecular weight of the polymer was as low as 4960 g/mol. The obtained polymer showed good thermal stability

with the maximum thermal weight loss temperature approximately 405 ℃. The interactions among co-catalyst (Al

EASC)

activator (ethyl trichloroacetate

ETCA)

and VOCl

during the polymerization reaction wer

e explored

and the impact of side reactions on the polymerization results was investigated. By adopting an "add a small amount multiple times" strategy for ETCA

the side reactions between ETCA and EASC were reduced

continuously establishing a cycle of V

and V

. This gives an increase in the polymer yield from 2.93 g/g

cat

to 31.26 g/g

cat

. This study avoids the drawbacks of using high-concentration catalysts in conventional liquid rubber synthesis.

关键词

Keywords

references

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