苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用

黄华华; 董金勇

doi:10.3724/SP.J.1105.2010.00087

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苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用

研究论文 | 更新时间：2021-03-19

- 苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用
- SYNTHESIS OF STYRYLCAPPED ISOTACTIC POLYPROPYLENES AND THEIR APPLICATION IN SYNTHESIS OF POLYPROPYLENES WITH TOPOLOGICAL STRUCTURE
- 高分子学报 2010年第1期页码：87-95
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- DOI：10.3724/SP.J.1105.2010.00087
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- 纸质出版日期：2010-1-20，
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黄华华, 董金勇. 苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用[J]. 高分子学报, 2010,(1):87-95.

HUANG Huahua, DONG Jinyong. SYNTHESIS OF STYRYLCAPPED ISOTACTIC POLYPROPYLENES AND THEIR APPLICATION IN SYNTHESIS OF POLYPROPYLENES WITH TOPOLOGICAL STRUCTURE[J]. Acta Polymerica Sinica, 2010,(1):87-95.
黄华华, 董金勇. 苯乙烯基封端反应性等规聚丙烯的催化合成及其在构筑新型拓扑结构聚丙烯高分子中的应用[J]. 高分子学报, 2010,(1):87-95. DOI： 10.3724/SP.J.1105.2010.00087.

HUANG Huahua, DONG Jinyong. SYNTHESIS OF STYRYLCAPPED ISOTACTIC POLYPROPYLENES AND THEIR APPLICATION IN SYNTHESIS OF POLYPROPYLENES WITH TOPOLOGICAL STRUCTURE[J]. Acta Polymerica Sinica, 2010,(1):87-95. DOI： 10.3724/SP.J.1105.2010.00087.

摘要

在具有高度等规定向能力的rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MAO催化体系所催化的丙烯聚合反应中，通过控制聚合条件，实现聚合物链选择性地向对双苯乙烯单体的链转移反应，合成出一种新的苯乙烯基封端的反应性等规聚丙烯.以这种苯乙烯基封端反应性聚丙烯为结构单元，构筑了两种拓扑结构（接枝和星型）的聚丙烯共聚物，一是在CpTiCl3/MAO催化下，与苯乙烯小分子进行配位聚合，合成了以间规聚苯乙烯为主链、等规聚丙烯为侧链的接枝共聚物（sPS-g-iPP）；二是选择性地在链端苯乙烯基上进行氯化和取代反应，定量地将叠氮基团引入等规聚丙烯链端，再与多炔基偶合剂进行点击反应，合成了星型等规聚丙烯.

Abstract

This paper demonstrates the successful synthesis of reactive isotacticpolypropylene terminated with styryl groups.The styryl group was introduced into the iPP chain end via chain transfer reaction to 1

4-divinylbenzene or 1

2-bis(4-vinylphenyl)ethane

during metallocenecatalyzed propylene polymerization by rac-Me2Si［2-Me-4-Ph(Ind)］2ZrCl2/MAO complex in the presence of hydrogen.Although hydrogen does not influence the polymer molecular weight

it greatly affects the catalyst activity.The iPP molecular weight is strongly dependent on the concentration of chain transfer agent.The isotacticity (mmmm) of iPP macromonomers is quite high ( 70%).The polymerization mechanism was also studied by using deuterium as labelled molecule of hydrogen in combination with 13C-NMR technique

and it is clear that the existent double enchainment of chain transfer agent is because the styryl-capped polymer chain would spontaneously insert into ZrH species with the unique 1

2-manner.The reactive iPP obtained was used as building block

and two kinds of topological structural polymers were synthesized.Styryl-capped iPP was copolymerized with styrene using CpTiCl3/MAO complex to produce sPS-g-iPP copolymer.Crude copolymer was subjected to extraction with chloroform which resulted in pure graft copolymer free of styryl-capped iPP.DSC results show thatTm

and Tc of sPS main chains and iPP side chains are all lower than those of the sPS and iPP homopolymers

separately.The appearance of extremely large supercoolings in sPS main chains is attributed to crystallization starting from homogeneous nuclei in isolated microdomains of graft copolymers which are generated by phase segregation.In addition

the terminal styryl groups of iPP were effectively transformed to azido groups through chlorination and substitutional reaction

and azidocapped iPP was obtained.Then

the click reaction between azido-capped iPP and trialkyne-containing couple agent was conducted in the presence of CuBr/PMDETA.1H-NMR results indicated that the click reaction was fast and highly efficient

and star isopolypropylene was synthesized.

关键词

烯烃配位聚合链转移反应反应性等规聚丙烯接枝共聚物星型等规聚丙烯

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