双马来酰亚胺交联剂的设计及其在聚己内酯辐照交联中的应用

钱翠珊; 徐睿杰; 雷彩红; 谢嘉宜

doi:10.11777/j.issn1000-3304.2026.25323

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双马来酰亚胺交联剂的设计及其在聚己内酯辐照交联中的应用

研究论文 | 更新时间：2026-04-11

- 双马来酰亚胺交联剂的设计及其在聚己内酯辐照交联中的应用
- Design of Bismaleimide Crosslinking Agent and Its Application in PCL Irradiation Crosslinking
- 高分子学报 2026年页码：1-11
- 作者机构：
  
  1.广东工业大学材料与能源学院广州 510006
  2.韶关学院化学与土木工程学院韶关 512005
- 作者简介：
  
  E-mail: xuruijie@gdut.edu.cn
  Lch528@gdut.edu.cn
  xiejy710@sgu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52473031);52503040┫
- DOI：10.11777/j.issn1000-3304.2026.25323
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7568
- 收稿：2025-12-28，
  
  录用：2026-03-03，
  
  网络首发：2026-04-11，
- 稿件说明：
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钱翠珊, 徐睿杰, 雷彩红, 谢嘉宜. 双马来酰亚胺交联剂的设计及其在聚己内酯辐照交联中的应用. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.25323.

Qian, C. S.; Xu, R. J.; Lei, C. H.; Xie, J. Y. Design of bismaleimide crosslinking agent and its application in PCL irradiation crosslinking. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.25323.
钱翠珊, 徐睿杰, 雷彩红, 谢嘉宜. 双马来酰亚胺交联剂的设计及其在聚己内酯辐照交联中的应用. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.25323. DOI： CSTR： 32057.14.GFZXB.2026.7568.

Qian, C. S.; Xu, R. J.; Lei, C. H.; Xie, J. Y. Design of bismaleimide crosslinking agent and its application in PCL irradiation crosslinking. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.25323. DOI： CSTR： 32057.14.GFZXB.2026.7568.

摘要

设计合成了1

3-丙烷双马来酰亚胺(PBMI)和4

4'-(二氨基二苯砜)双马来酰亚胺(DBMI) 2种交联剂，系统研究了5~50 kGy辐照剂量范围内两种合成交联剂和传统交联剂三烯丙基异氰脲酸酯(TAIC)对聚己内酯(PCL)交联性能的影响. 结果表明，合成的双马来酰亚胺型交联剂耐热性优异，DBMI热分解起始温度达到480 ℃，远高于TAIC和PBMI. 在辐照下3种交联剂都能使PCL有效交联，其中DBMI的每摩尔双键交联效率是TAIC的2.4倍，所形成的交联网络在高强度电子束辐照下不易被破坏. 交联后PCL的结晶度略有下降，但屈服强度随凝胶含量增加而增加，其中DBMI形成的交联网络刚性最强，屈服强度高于TAIC和PBMI交联的样品. 辐照后，交联的PCL出现形状记忆功能，形状回复率主要受交联点间分子量影响，当凝胶含量超55%时形状回复率达93%以上.

Abstract

In this study

two types of crosslinking agents

3-propane bismaleimide (PBMI) and 4

4′-(diaminodiphenyl sulfone) bismaleimide (DBMI)

were designed and synthesized. The effects of two types of synthetic crosslinking agents and a traditional crosslinking agent

triallyl isocyanurate (TAIC)

on the crosslinking properties of PCL in the irradiation dose range of 5-50 kGy were systematically studied. The results show that the synthesized bismaleimide crosslinking agent has excellent heat resistance

and the initial temperature of thermal decomposition of DBMI reaches 480 ℃. The crosslinking efficiency of DBMI per molar of double bond is 2.4 times that of TAIC

and the crosslinked network is not easily destroyed under high-intensity electron-beam irradiation. The crystallinity of PCL decreased slightly after crosslinking; however

the yield strength increased with increasing gel content. The crosslinking network formed by DBMI exhibited the strongest rigidity

and its yield strength was higher than those of the TAIC and PBMI crosslinked samples. After irradiation

the crosslinked PCL exhibited a shape memory function. The shape recovery rate is primarily affected by the molecular weight between crosslinking points. When the gel content exceeded 55%

the shape recovery rate was more than 93%.

关键词

Keywords

references

王佳 . 电子束辐照法制备交联PCL/SAN共混物的结晶动力学研究 . 中国科学技术大学博士学位论文 , 2020 .

Prajapati S. ; Gogoi R. ; Tyagi V. K. ; Talwar M. ; Kumar M. ; Chaudhari C. V. Effect of gamma irradiation on shape memory, thermal and mechanical properties of polycaprolactone . Radiat. Phys. Chem. , 2023 , 204 , 110671 . doi: 10.1016/j.radphyschem.2022.110671 http://dx.doi.org/10.1016/j.radphyschem.2022.110671

Sedov I. ; Magsumov T. ; Abdullin A. ; Yarko E. ; Mukhametzyanov T. ; Klimovitsky A. ; Schick C. Influence of the cross-link density on the rate of crystallization of poly( ε -caprolactone) . Polymers , 2018 , 10 ( 8 ), 902 . doi: 10.3390/polym10080902 http://dx.doi.org/10.3390/polym10080902

Li H. L. ; Li W. Z. ; Wu H. T. ; Jiang D. B. ; Yuan M. W. ; Yuan M. L. Synthesis and application of a thermoplastic plate of poly(lactide-ε-caprolactone) for radiation therapy . Biomolecules , 2020 , 10 ( 1 ), 27 . doi: 10.3390/biom10010027 http://dx.doi.org/10.3390/biom10010027

Inverardi N. ; Pandini S. ; Gemmo G. ; Toselli M. ; Messori M. ; Scalet G. ; Auricchio F. Reversible stress-driven and stress-free two-way shape memory effect in a sol-gel crosslinked polycaprolactone . Macromol. Symp. , 2022 , 405 , 2100254 . doi: 10.1002/masy.202100254 http://dx.doi.org/10.1002/masy.202100254

Wang L. J. ; Wang Y. Y. ; Wang Y. F. ; Zhao D. ; Zhou Q. Dynamic disulfide cross-linked polycaprolactone grafted CO 2 -based poly(ester- co -carbonate): effective crystallinity, enhanced mechanical performance, reversible de-crosslinking, and degradability . Eur. Polym. J. , 2025 , 234 , 114026 . doi: 10.1016/j.eurpolymj.2025.114026 http://dx.doi.org/10.1016/j.eurpolymj.2025.114026

Salvekar A. V. ; Zhou Y. ; Huang W. M. ; Wong Y. S. ; Venkatraman S. S. ; Shen Z. X. ; Zhu G. M. ; Cui H. P. Shape/temperature memory phenomena in un-crosslinked poly- ɛ -caprolactone (PCL) . Eur. Polym. J. , 2015 , 72 , 282 - 295 . doi: 10.1016/j.eurpolymj.2015.09.027 http://dx.doi.org/10.1016/j.eurpolymj.2015.09.027

Huang M. J. ; Zhou C. ; Ling Y. ; Zhao G. C. ; Dong L. C. ; Shi J. M. ; Chen J. Preparation and characterization of PCL s hape-memory films via photo-crosslinking . Plast. Rubber Compos. , 2022 , 51 ( 1 ), 47 - 54 . doi: 10.1080/14658011.2021.1949534 http://dx.doi.org/10.1080/14658011.2021.1949534

Malinowski R. Mechanical properties of PLA/PCL blends crosslinked by electron beam and TAIC additive . Chem. Phys. Lett. , 2016 , 662 , 91 - 96 . doi: 10.1016/j.cplett.2016.09.022 http://dx.doi.org/10.1016/j.cplett.2016.09.022

Rytlewski P. ; Stepczyńska M. ; Moraczewski K. ; Malinowski R. ; Karasiewicz T. ; Sikorska W. ; Żenkiewicz M. Flax fibers reinforced polycaprolactone modified by triallyl isocyanurate and electron radiation . Polym. Compos. , 2019 , 40 ( 2 ), 481 - 488 . doi: 10.1002/pc.24672 http://dx.doi.org/10.1002/pc.24672

Huang Y. ; Gohs U. ; Müller M. T. ; Zschech C. ; Wiessner S. Evaluation of electron beam-induced crosslinking of poly(ε-caprolactone): effect of elevated temperatures . J. Appl. Polym. Sci. , 2019 , 136 ( 33 ), 47866 . doi: 10.1002/app.47866 http://dx.doi.org/10.1002/app.47866

Navarro R. ; Burillo G. ; Adem E. ; Marcos-Fernández A. Effect of ionizing radiation on the chemical structure and the physical properties of polycaprolactones of different molecular weight . Polymers , 2018 , 10 ( 4 ), 397 . doi: 10.3390/polym10040397 http://dx.doi.org/10.3390/polym10040397

Flory P. J. ; Rehner , J. Jr . Statistical mechanics of cross-linked polymer networks II. swelling . J. Chem. Phys. , 1943 , 11 ( 11 ), 521 - 526 . doi: 10.1063/1.1723792 http://dx.doi.org/10.1063/1.1723792

Barton A.F.M. Handbook of Solubility Parameters and Other Cohesion Parameters , 2nd Ed .; Boca Raton, FL , CRC Press , 1991 ; ISBN 978 - 0 - 8493 - 0176 - 6 .

Scherrer P. Bestimmung der inneren struktur und der größe von kolloidteilchen mittels röntgenstrahlen . Kolloidchemie Ein Lehrbuch. Berlin, Heidelberg : Springer , 1912 , 387 - 409 . doi: 10.1007/978-3-662-33915-2_7 http://dx.doi.org/10.1007/978-3-662-33915-2_7

Chapelle C. ; Quienne B. ; Bonneaud C. ; David G. ; Caillol S. Diels-Alder-Chitosan based dissociative covalent adaptable networks . Carbohydr. Polym. , 2021 , 253 , 117222 . doi: 10.1016/j.carbpol.2020.117222 http://dx.doi.org/10.1016/j.carbpol.2020.117222

张万喜 , 何天白 , 孙家珍 . 聚合物辐射交联中溶胶分数与剂量间的关系通式 . 科学通报 , 1986 , ( 03 ), 189 - 193 . doi: 10.1360/csb1986-31-3-189 http://dx.doi.org/10.1360/csb1986-31-3-189

孙家珍 . 高分子的结构对辐射交联反应中裂解度的影响——论Charlesby-Pinner和陈-刘-唐关系式的适用性 . 辐射研究与辐射工艺学报 , 1983 , 8 - 16 .

陈欣方 , 刘克静 , 唐敖庆 . 聚乙烯的辐射交联 . 吉林大学学报(自然科学版) , 1977 , ( 4 ), 39 - 55+61 .

朱光明 . 聚己内酯的辐射交联与形状记忆效应研究 . 西北工业大学博士学位论文 , 2003 .

Tabata Y. Radiation-induced crosslinking . Radiat. Phys. Chem. 1977 , 1979 , 14 ( 1-2 ), 235 - 243 .

Filipczak K. ; Wozniak M. ; Ulanski P. ; Olah L. ; Przybytniak G. ; Olkowski R. M. ; Lewandowska-Szumiel M. ; Rosiak J. M. Poly( ε -caprolactone) biomaterial sterilized by E-beam irradiation . Macromol. Biosci. , 2006 , 6 ( 4 ), 261 - 273 . doi: 10.1002/mabi.200500215 http://dx.doi.org/10.1002/mabi.200500215

Tabata Y. Cross-linking of hydrocarbon polymers and their model compounds- linear-energy-transfer effects . ACS Symp. Ser . 1991 , 475 , 31 - 43 . doi: 10.1021/BK-1991-0475.CH002 http://dx.doi.org/10.1021/BK-1991-0475.CH002

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