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Chain Shuttling Copolymerization for Synthesis of Multi-block Cyclic Olefin Copolymers
- Acta Polymerica Sinica Vol. 54, Issue 11, Pages: 1708-1719(2023)
- 作者机构：
天津大学材料科学与工程学院 天津 300350
- 作者简介：
Li Pan, E-mail: lilypan@tju.edu.cn
- 基金信息：
DOI：10.11777/j.issn1000-3304.2023.23100
CLC：Published：20 November 2023，
Published Online：30 June 2023，
Received：12 April 2023，
Accepted：11 May 2023
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刘炬阳,高欢,王菲等.链穿梭共聚合制备环烯烃多嵌段共聚物[J].高分子学报,2023,54(11):1708-1719.
Liu Ju-yang,Gao Huan,Wang Fei,et al.Chain Shuttling Copolymerization for Synthesis of Multi-block Cyclic Olefin Copolymers[J].Acta Polymerica Sinica,2023,54(11):1708-1719.
刘炬阳,高欢,王菲等.链穿梭共聚合制备环烯烃多嵌段共聚物[J].高分子学报,2023,54(11):1708-1719. DOI： 10.11777/j.issn1000-3304.2023.23100.
Liu Ju-yang,Gao Huan,Wang Fei,et al.Chain Shuttling Copolymerization for Synthesis of Multi-block Cyclic Olefin Copolymers[J].Acta Polymerica Sinica,2023,54(11):1708-1719. DOI： 10.11777/j.issn1000-3304.2023.23100.
摘要
乙烯和降冰片烯(NB)的共聚物是最具代表性的环烯烃共聚物(COC). 更多NB的引入赋予了COC优异的力学强度、透明度和耐热性的同时，也使COC变得更脆. 为了在保持COC高强度、透明度和耐热性的同时改善其脆性，优选了2种聚合活性相近，对NB选择性不同的催化剂Ph
2
C(Cp)(9-Ind)ZrCl
2
和Et(Ind)
2
ZrCl
2
，在相同的条件下可分别合成高降冰片烯插入率COC与低降冰片烯插入率COC，以二乙基锌为链转移剂，实现了降冰片烯与乙烯聚合的链穿梭共聚反应，获得了同时含有高NB插入率的COC链段和低NB插入率的COC链段的多嵌段共聚物. 通过改变二乙基锌用量、初始单体比来实现对多嵌段COC分子量和结构调控. 热力学、拉伸性能和透光性测试证明多嵌段COC与无规COC相比，不仅实现了韧性的明显提升(断裂伸长率从
<
5%提高至10%~11%)，而且保持了高的强度、耐热性和透光度.
Abstract
The copolymer of ethylene and norbornene (NB) is the most representative cyclic olefin copolymer (COC). Introduction of NB imparts excellent strength
transparency
and heat resistance to COC
and it also makes it more brittle
which limits its application in many fields. Therefore
improving the toughness of COC while maintaining its excellent characteristics such as high strength
heat resistance
and transparency is a critical challenge. To address this challenge
this study optimized two catalysts
Ph
2
C(Cp)(9-Ind)ZrCl
2
and Et(Ind)
2
ZrCl
2
which exhibit comparable polymerization activity but different selectivities toward NB in the E/NB copolymerization. We studied the coordination chain transfer polymerization of two catalysts under different polymerization conditions to verify the reversibility of chain transfer of the two catalysts in E/NB copolymerization. Based on this
chain shuttling copolymerization of ethylene and norbornene by adopting a dual-catalyst system and Et
2
Zn as a chain shuttling agent was successfully achieved. The multiblock structure of the chain shuttling copolymers with both high and low NB incorporation in COC segments was further revealed by
13
C-NMR spectra
GPC and DSC analyses. The molecular weight and composition of the multiblock COCs could be easily regulated by varying the amount of Et
2
Zn and initial monomer ratio. Thermodynamic
tensile
and light transmittance tests demonstrated that the multiblock COCs bearing significantly enhanced toughness (
i.e.
elongation at break increases from
<
5% to 10%-11%) compared to those of the random COC by single catalyst
while maintaining high strength
heat resistance
and light transmittance. In summary
a series of multiblock COCs were efficiently prepared
via
chain shuttling copolymerization by using a dual-catalyst system. As expected
these COCs exhibited enhanced toughness while maintaining high thermal resistance
mechanical strength
and transparency. This study offers a new solution for improving tensile performance while maintaining high heat resistance and transparency of COCs.
关键词
环烯烃共聚物链转移聚合多嵌段共聚物链穿梭共聚合
Keywords
Cyclic olefin copolymerChain transfer polymerizationMultiblock copolymerChain shuttling copolymerization
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