开环易位烯烃聚合物的动态交联改性研究进展

doi:10.11949/0438-1157.20231396

摘要/Abstract

摘要：

开环易位聚合（ROMP）为烯烃聚合物的制备提供了一种精确而高效的方法，可制备不同拓扑结构的功能性热塑性烯烃聚合物材料。热塑性烯烃聚合物尽管可以在高温下熔融再加工，但其较低的力学性能和耐热性能限制了其在极端条件下的使用寿命。通过固化交联改性则可以大大改善材料的力学性能等，但也为废旧材料的回收再利用带来了困难。为克服上述局限，构建含有动态键的烯烃聚合物交联网络引起了广泛关注，该类聚合物在提升力学等性能的同时也赋予了其可重复加工的能力。本文聚焦于通过开环易位聚合合成不同拓扑结构的烯烃聚合物，并利用不同类型动态键对其进行动态交联改性的最新研究进展。并对该领域的发展现状和未来研究方向进行了总结。

关键词: 烯烃聚合物, 开环易位聚合, 动态交联, 可逆交联, 自修复, 重加工

Abstract:

Ring-opening metathesis polymerization (ROMP) provides a precise and efficient way to prepare polyolefins, which enables the preparation of functional polymer materials with different topological structures. Although thermoplastic olefin polymers can be melted and reprocessed at high temperatures, their low mechanical properties and heat resistance limit their service life under extreme conditions. In general, the thermomechanical properties of polyolefin materials can be greatly improved by crosslinking modification, but it also brings difficulties to the recycling of waste materials. To address above limitations, fabricating dynamically crosslinked polyolefins with dynamic bonds has attracted extensive attentions. These polymers enhance mechanical properties while retaining the ability to be reprocessed. This review article focuses on the recent progress of polyolefins that are synthesized via ring-opening metathesis polymerization and followed by dynamically crosslinking modification. Finally, the development status and future research of this field are summarized.

Key words: polyolefins, ring-opening metathesis polymerization, dynamic crosslinking, reversible crosslinking, self-healing, reprocessable

中图分类号:

TQ 028.8

吴立盛, 刘杰, 王添添, 罗正鸿, 周寅宁. 开环易位烯烃聚合物的动态交联改性研究进展[J]. 化工学报, 2024, 75(4): 1118-1136.

Lisheng WU, Jie LIU, Tiantian WANG, Zhenghong LUO, Yinning ZHOU. Progress in dynamically crosslinked polyolefins derived from ring-opening metathesis polymerization[J]. CIESC Journal, 2024, 75(4): 1118-1136.

图/表 10

图1 环戊烯与降冰片烯开环易位聚合反应示意图以及Grubbs催化剂结构式

Fig.1 Schematic representation of ROMP of cyclopentene and norbornene, and Grubbs catalysts

图2 氢键动态交联烯烃聚合物的合成途径和性质[20, 62-63]：(a)六点和三点氢键络合物；(b)牺牲氢键的可逆能量耗散和G2催化剂介导的烯烃复分解自愈合网络；(c)含酰胺氢键网络(ACON)和氢键阻断网络(BACON)的合成；(d) ABA型三嵌段环烯烃共聚物（A嵌段：2-脲基-4[1H]-嘧啶酮官能化的降冰片烯的均聚物；B嵌段：2-脲基-4[1H]-嘧啶酮官能化的降冰片烯和含柔性十二烷基酯侧链的降冰片烯的无规共聚物）；(e) 拉伸时聚合物网络能量耗散过程机理

Fig.2 Synthetic pathways and properties of polyolefins dynamically crosslinked by hydrogen bonded[20, 62-63]: (a) six-point and three-point hydrogen bonded complexes; (b) reversible energy dissipative rupture of sacrificial hydrogen bonds in a G2-mediated self-healing olefin-containing network; (c) synthesis of the amid-containing CO network (ACON) and hydrogen-bond-blocked control network (BACON); (d) ABA type block cyclic olefin copolymer （A block: 2-ureido-4[1H]-pyrimidinone (UPy)-functionalized norbornene homopolymer； B block: 2-ureido-4[1H]-pyrimidinone (UPy)-functionalized norbornene random copolymer）; (e) schematic graph for energy dissipative rupture of polymer network

图3 离子相互作用动态交联环烯烃聚合物的合成途径和性质[67-69]：（a）负载不同反离子的基于咪唑基团的降冰片烯共聚物；（b）样品自愈性能测试过程及机理示意图；（c）梯度共聚物的化学结构和拉伸弹性响应机理；（d）具有不同间隔段和尾部段长度的咪唑基降冰片烯共聚物的合成路线

Fig.3 Synthetic pathways and properties of cyclic olefin polymer dynamically crosslinked by ionic interaction[67-69]: (a) imidazolium-based norbornene copolymer with different counterions; (b) photographs showing the self-healing properties of samples and its mechanism under the testing process; (c) chemical structures of gradient copolymers and the mechanism for elastic response; (d) synthetic route of the imidazolium-based norbornene copolymers with different spacer and tail lengths

图4 主客体相互作用动态交联环烯烃聚合物的合成途径和性质[70]：(a) 超分子聚合物；(b) 共价聚合物；(c) 协同共价和超分子聚合物；(d) 三种聚合物的力学性能和动态性能对比

Fig.4 Synthetic pathways and properties of cyclic olefin polymer dynamically crosslinked by host-guest interaction[70]: (a) supramolecular polymers; (b) covalent polymers; (c) synergistic covalent and supramolecular polymers; (d) comparison of mechanical and dynamic properties of three polymers above

图5 双重分子间作用力动态交联环烯烃聚合物的合成途径和性质[72]：(a)双动态交联聚合物的合成路线；(b)拉伸时离子聚集体和稀疏UPy段耗散能量以及密集UPy段限制形变的机制；(c)近红外触发愈合过程的示意图

Fig.5 Synthetic pathways and properties of cyclic olefin polymer dynamically crosslinked by dual-molecular interaction[72]: (a) synthetic route of dual-cross-linked polymer; (b) schematic graph of dense UPy region limited deformation, while UPy dimers in sparse regions with weak ionic interaction can act as sacrificial bonds for energy dissipation; (c) schematic illustration of the NIR triggered healing process

图6 烯烃复分解动态交联烯烃聚合物的合成途径和性质[73]：(a)基于开环易位聚合的聚合物网络的解聚-再聚合循环示意图；(b)解聚温度与两种共聚单体比例的线性关系；(c)聚合物网络在25~55℃之间循环的储能模量

Fig.6 Synthetic pathways and properties of polyolefin dynamically crosslinked by olefin metathesis[73]: (a) schematic of the depolymerization-repolymerization cycle of network polymers based on ROMP; (b) depolymerization temperatures of copolymers depending on the ratios of two comonomers; (c) the storage modulus of sample which were first initiated at 55℃ and cycled between 25℃ and 55℃

图7 硼酸酯键动态交联烯烃聚合物的合成途径和性质[74-75]：(a) 改变邻位基团以调控硼酸酯交换动力学；(b) 硼酸酯动态交联烯烃聚合物的示意图；(c) 基于PE骨架的DCNA的合成；(d) 不同PE-AB掺入量的蠕变对比；(e) 动态共价网络可重加工示意图

Fig.7 Synthetic pathways and properties of polyolefins dynamically crosslinked by boronic ester[74-75]: (a) tuning neighboring group to control the exchange kinetics of boronic ester; (b) dynamic exchange of boronic ester crosslinkers affords olefin polymer; (c) synthesis of a DCNA based on the PE backbone; (d) creep tests of PE with different mass fractions of PE-AB; (e) schematic representation of dynamic covalent networks with reprocessability

图8 酯键和硅醚键动态交联环烯烃聚合物的合成途径和性质[22, 76]：(a) 基于酯交换的动态瓶刷聚合物的合成方案；(b) 含双官能硅醚的聚双环戊二烯的制备；(c) EtSi7与双环戊二烯共聚物在有无辛酸作用下的应力松弛曲线对比；(d) iPrSi7与双环戊二烯共聚物在有无辛酸作用下的应力松弛曲线对比；(e) 上述两种样品的应力松弛的Arrhenius关系图

Fig.8 Synthetic pathways and properties of cyclic olefin polymer dynamically crosslinked by ester bond and siloxane bond[22, 76]: (a) synthetic scheme for generating dynamic bottlebrush polymer networks that undergo transesterification; (b) preparation of polydicyclopentadiene (pDCPD) with bifunctional silyl ether; (c) stress relaxation curves of EtSi7 and pDCPD copolymer cured with and without octanoic acid; (d) stress-relaxation curves of iPrSi7 and pDCPD copolymer cured with and without octanoic acid; (e) Arrhenius plots of stress relaxation for these two samples

图9 乙烯胺酯键动态交联烯烃共聚物的化学途径和性质[77]：(a) 通过ROMP将两端为乙酰乙酸基团的CTA与COE共聚制备遥爪聚合物; (b) 利用遥爪聚合物与TREN合成动态交联网络

Fig.9 Synthetic pathways and properties of polyolefin dynamically crosslinked by vinylogous urethane bond[77]: (a) telechelic polymers by ROMP of COE in the presence of CTA bearing acetoacetate groups; (b) synthesis of dynamic crosslinked network using telechelic polymer and TREN

图10 双动态共价键交联环烯烃聚合物的合成途径和性质[78]：(a) 双动态共价交联网络的合成路线；(b) 两种可独立控制的拓扑变化路线示意图；(c) 羟基化合物与聚己内酯侧链酯交换的模型实验；(d) 不同紫外照射时长下异构化材料的DSC曲线；(e) 异构化材料的应力-应变曲线对比

Fig.10 Synthetic pathways and properties of cyclic olefin polymer dynamically crosslinked by dual-dynamic covalent bonds[78]: (a) synthetic scheme for the network crosslinked by dual-dynamic covalent bonds; (b) schematic illustration of the two independently controllable topological transformations; (c) transesterification between hydroxyl groups and polycaprolactone side chains; (d) DSC curves for the isomerized materials obtained with different UV irradiation time; (e) stress-strain curves of the isomerized materials

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