动态化学交联聚烯烃类弹性体研究进展

doi:10.11949/0438-1157.20231408

化工学报 ›› 2024, Vol. 75 ›› Issue (4): 1394-1413.DOI: 10.11949/0438-1157.20231408

动态化学交联聚烯烃类弹性体研究进展

肖扬可¹^,²(), 常印龙¹^,²(), 李平³^,⁴(), 王文俊¹^,², 李伯耿¹^,², 刘平伟¹^,²()

^1.浙江大学化学工程联合国家重点实验室，化学工程与生物工程学院，浙江杭州 310058
^2.浙江大学衢州研究院，浙江衢州 324000
^3.海南贝欧亿科技有限公司，海南儋州 571700
^4.山东京博石油化工有限公司，山东滨州 256600

收稿日期:2023-12-31 修回日期:2024-01-28 出版日期:2024-04-25 发布日期:2024-06-06
通讯作者: 李平,刘平伟
作者简介:肖扬可（1997—），女，博士研究生，xiaoyangke@zju.edu.cn
常印龙（2000—），男，硕士研究生，ylchang@zju.edu.cn
基金资助:
国家自然科学基金项目(21938010);浙江省自然科学基金项目(D24E030007);浙江省先进化工技术创新中心项目(ACTIC-2022-007);浙江大学化学工程联合国家重点实验室项目(SKL-ChE-22 T01)

Review on polyolefin elastomers with dynamic-chemical cross-linking

Yangke XIAO¹^,²(), Yinlong CHANG¹^,²(), Ping LI³^,⁴(), Wenjun WANG¹^,², Bogeng LI¹^,², Pingwei LIU¹^,²()

^1.State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, Zhejiang, China
^2.Institute of Zhejiang University - Quzhou, Quzhou 324000, Zhejiang, China
^3.Hainan Beyonpoly Technology Company Limited, Danzhou 571700, Hainan, China
^4.Shandong Chambroad Petrochemical Company Limited, Binzhou 256600, Shandong, China

Received:2023-12-31 Revised:2024-01-28 Online:2024-04-25 Published:2024-06-06
Contact: Ping LI, Pingwei LIU

摘要/Abstract

摘要：

聚烯烃类弹性体是由乙烯与丙烯或其他高碳α-烯烃共聚而成的高端聚烯烃材料，具有出色的化学稳定性、耐候性和电绝缘性，广泛应用于光伏、汽车、电缆等领域。通过动态化学交联可在保证其加工性的前提下，进一步提高其力学性能与热稳定性，拓展应用范围。综述了动态化学交联聚烯烃弹性体的制备工艺，包括一步法直接交联和功能化后再交联（多步法）。详细介绍了后功能化、乙烯与功能化单体共聚等功能化方法。讨论了动态化学交联聚烯烃类弹性体的表征手段及其链结构、聚集态结构和性能之间的关系。展望了动态交联聚烯烃类弹性体的未来发展。为动态化学交联聚烯烃类弹性体的可控制备、构效关系研究以及高值应用提供理论指导与技术支持，推动高端聚烯烃材料的创新和发展。

关键词: 聚合物反应工程, 高端聚烯烃, 聚烯烃类弹性体, 动态化学交联, 功能化, 构效关系

Abstract:

Polyolefin elastomer (POE) is a high-end polyolefin material that is copolymerized from ethylene and α-olefin. It has excellent properties such as chemical stability, weather resistance and electrical insulation, and is widely used in various fields such as photovoltaic, automobile and cable. Dynamic-chemical cross-linking (DCC) can further improve its mechanical properties and thermal stability, and expand its application range while ensuring its processability. This paper reviews the preparation methods of DCC POEs, including one-step direct cross-linking and multistep cross-linking after functionalization. The functionalization methods, such as post-functionalization and copolymerization of ethylene and functional monomer, are elaborated. The characterization methods of DCC POEs and the relationship between their chain structure, aggregation structure and properties are discussed. The future prospects of DCC POEs are also presented. This paper aims to provide theoretical guidance and technical support for the controlled synthesis, structure-activity relationship study and high value application of DCC POEs, and to promote the innovation and development of high-end polyolefin materials.

Key words: polymer reaction engineering, high-end polyolefin, polyolefin elastomer, dynamic-chemical cross-linking, functionalization, structure-activity relationship

中图分类号:

TH 3

肖扬可, 常印龙, 李平, 王文俊, 李伯耿, 刘平伟. 动态化学交联聚烯烃类弹性体研究进展[J]. 化工学报, 2024, 75(4): 1394-1413.

Yangke XIAO, Yinlong CHANG, Ping LI, Wenjun WANG, Bogeng LI, Pingwei LIU. Review on polyolefin elastomers with dynamic-chemical cross-linking[J]. CIESC Journal, 2024, 75(4): 1394-1413.

图/表 15

图1 动态交联聚烯烃弹性体的合成方法

Fig.1 Synthesis method of dynamically cross-linked polyolefin elastomers

图2 （a）DCP与OBC的自由基引发反应；（b）双端乙烯基硼酸酯的自由基引发交联OBC；（c）含二硫键小分子交联剂的自由基引发交联OBC；（d）不同DCP用量下硼酸酯动态交联OBC的应力-应变曲线；（e）动态交联剂用量与DCP用量变化下二硫键交联OBC的加工成膜情况[图中数字比例，如3-1，代表3%（质量分数）的交联剂用量与1%（质量分数）的DCP用量]

Fig.2 (a) Free radical initiation reaction of DCP and OBC; (b) Free radical triggering double-ended vinyl boronic ester to cross-link OBC; (c) Free radical initiating small molecule cross-linker with disulfide bond to cross-link OBC; (d) Stress-strain curves of boronic ester dynamically cross-linked OBC using different DCP amount; (e) Processing of disulfide cross-linked OBC films using different dynamic cross-linker and DCP amount [the ratio of numbers in the figures, such as 3-1, represents 3%(mass) cross-linker loading and 1%(mass) DCP loading]

图3 （a）EPR的DASP功能化与交联；（b）环氧化EPDM与生物基癸二酸交联

Fig.3 (a) The DASP functionalization and cross-linking of EPR; (b) Epoxidized EPDM cross-linked with biobased sebacic acid

图4 （a）乙烯/1-十四烯/蒽烯共聚物的合成与硼酸酯交联；（b）乙烯/1-辛烯/5-乙烯基-2-降冰片烯共聚物合成与硼酸酯交联；（c）乙烯/丙烯/8-呋喃-1-辛烯的共聚物合成与DA键或亚胺键交联；（d）采用Pd催化剂合成含支链羧基POE、含乙烯基和极性官能团POE

Fig.4 (a) Synthesis of ethylene/1-tetradecene/9-(but-3-en-1-yl)anthracene copolymers with boronic ester cross-linking; (b) Synthesis of ethylene/1-octene/5-vinyl-2-norbornene copolymer with boronic ester cross-linking; (c) Synthesis of ethylene/propylene /8-furan-1-octene copolymer with DA or imine bond cross-linking; (d) Synthesis of branched POE with carboxyl group and POE with vinyl and polar functional group using Pd catalyst

图5 （a）动态化学组合的方法制备高性能聚烯烃类TPE示意图；（b）新型TPE样品与其他已报道的动态交联弹性体、OBC和CPOE的拉伸性能比较

Fig.5 (a) Preparation of high-performance polyolefin based TPE by dynamic-chemical combination method; (b) Comparison of tensile properties of novel TPE with other dynamically cross-linked elastomers, OBC, and CPOE

图6 不同动态化学交联解离或交换机理

Fig.6 Different dynamic-chemical cross-linking through dissociation or exchange mechanisms

图7 （a）硼酸酯交联PE的介观结构示意图、分形结构、聚集体结构；（b）采用不同链长交联剂的环氧化月桂烯/异戊二烯共聚物的AFM图像；（c）不同分子量PEG动态交联的EPR的TEM图像；（d）石蜡动态交联POE的SEM图像

Fig.7 (a) Schematic of proposed mesostructure, fractal structure, and aggregate structure of boronic ester cross-linked PE; (b) AFM images of epoxidized myrcene and isoprene copolymers using cross-linkers with different chain length; (c) TEM images of dynamically cross-linked EPR with PEG of different number-average molecular weight(Mn); (d) SEM image of paraffin wax dynamically cross-linked POE

表1 动态交联聚烯烃类弹性体的力学性能

Table 1 Mechanical properties of dynamically cross-linked polyolefin based elastomers

样品类型	动态化学键	T_m/℃	杨氏模量/MPa	断裂强度/MPa	断裂伸长/ %	文献
商品EPDM	—	—	—	8.0~17.7	184~324	[11]
商品POE	—	36~104	3.8~5.8	1.4~38	600~1000	[11, 20, 86]
商品OBC	—	120	10.6	3~15	1300	[11, 86]
EPDM	酯键	—	2.5~4.5	19.4~22.7	240~390	[29]
EPR	DA键	—	0.84~26.04	4~6	<380	[45]
EPR	亚胺键	—	0.99~5.41	0.83~1.81	42~135	[40]
EPR	DA键	—	—	0.006~0.01	40~750	[87]
POE	硼酸酯键	—	4.2~12.8	2.5~21.3	250~1950	[39]
POE	硼酸酯键	55~80	14.8~29.0	12.8~23.8	470~630	[37]
POE	硼酸酯键	75.9~79.8	—	27.5~35.3	>800	[38]
OBC	硼酸酯键	—	—	15.3	2375	[46]

图8 （a）不同温度下归一化应力松弛曲线；（b）体积膨胀实验测定Tv；（c）温度的AIE示意图；（d）与频率相关的模量-温度曲线在Tv处重合

Fig.8 (a) Normalized stress relaxation curves at different temperatures; (b) Dilatometry test to determine Tv; (c) Illustration of the temperature-dependent AIE; (d) Coalesce of frequency-dependent material functions at Tv for tanδ

图9 功能化EPDM、DA键交联的EPDM与硫固化或过氧化物固化EPDM的杨氏模量、拉伸断裂强度和断裂伸长率对比（a），以及硬度和压缩比结果（b）；亚胺和二硫键双重动态化学交联PB热压过程照片及再加工机理（c）；亚胺和二硫键双重动态化学交联PB化学回收的照片与反应机理示意图（d）

Fig.9 Comparison of functional EPDM, DA bond cross-linked EPDM, and sulfur-cured or peroxide-cured EPDM in Young’s modulus, tensile strength at break and elongation at break (a), and hardness and compression ratio (b); Hot pressing process and reprocessing mechanism of imide and disulfide dynamic chemical cross-linked PB (c); Photos and reaction mechanism of imide and disulfide dynamic chemical cross-linked PB via chemical recycling (d)

图10 （a）酯键交联EPDM回收过程中交联和交换反应的拓扑重排示意图；（b）多次再加工循环后的典型应力-应变曲线

Fig.10 (a) Schematic illustrating cross-linking reaction and topological rearrangements via exchange reactions in ester bond cross-linked EPDM; (b) Typical stress-strain curves after multiple reprocessing cycles

图11 硼酸酯交联的SBR断裂和修复的照片以及修复的SBR拉伸照片（a）；硼酸酯交联的SBR在80℃下经过不同时间修复后（b）和在不同温度下24 h修复后（c）的典型应力-应变曲线；断裂的EPDM/SiO2复合物以及在外力、加热作用下EPDM/SiO2复合物的自修复（d）

Fig.11 Photos of fractured and repaired boronic ester cross-linked SBR, and photos of stretching repaired SBR (a); The typical stress-strain curves of the boronic ester cross-linked SBR repaired at 80℃ for various time (b) and repaired at different temperatures for 24 h (c); Fractured EPDM/SiO2 composites, and self-healing of EPDM/SiO2 composites under external force and heating (d)

图12 交联的聚环辛烯及自修复后的应力-应变曲线对比（红色曲线为修复后样品，蓝色曲线为原始样品）：含0.5%（摩尔分数）慢速硼酸酯交联样品（a）；含0.5%（摩尔分数）快速硼酸酯交联样品（b）；具有硼酸酯动态化学交联和永久交联的PB样品的黏附性能测试照片与黏附机理图（c）；动态硼酸酯交联SBS（SBS-B）与原始SBS、不可逆交联SBS（SBS-H）的黏附性能对比（d）

Fig.12 Comparison of cross-linked polycycloctene (blue curve) and self-healing samples (red curve): the self-healing sample containing 0.5%(mole fraction) slow boronic ester cross-linking (a), and the self-healing sample containing 0.5%(mole fraction) fast boronic ester cross-linking (b); adhesion test and adhesion mechanism of PB samples with boronic ester cross-linking and permanent cross-linking (c); Adhesion properties of dynamic boronic ester cross-linked SBS (SBS-B) compared with original SBS and irreversible cross-linked SBS (SBS-H) (d)

图13 （a）酯键交联的PEVA可逆形状记忆效应的照片；（b）酯键交联的PEVA在加热和冷却循环中临时形状“V”的角度变化；（c）SBS的热触发形状恢复性能；（d）形状记忆行为的定性和定量表征

Fig.13 (a) Reversible shape memory effects of ester bond cross-linked PEVA; (b) Angular variation in the temporary shape “V” of ester cross-linked PEVA during heating and cooling cycles; (c) Heat-triggered shape recovery performance of SBS; (d) Qualitative and quantitative characterization of shape memory behaviour

图14 硼酸酯交联的POE/石蜡复合材料作为致动器和人工肌肉

Fig.14 Boronic ester cross-linked POE/paraffin wax composites as actuators and artificial muscles

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动态化学交联聚烯烃类弹性体研究进展

Review on polyolefin elastomers with dynamic-chemical cross-linking

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