Coordination Polymerization of α,ω-Diolefin: the Regulation of Polymer Microstructure by Catalyst

doi:10.6023/A21080377

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (11): 1320-1330.DOI: 10.6023/A21080377 Previous Articles Next Articles

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α,ω-双烯烃的配位聚合: 催化剂对聚合物微观结构的调控

李勇, 王晓艳^*(), 唐勇

中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2021-08-12 发布日期:2021-09-24
通讯作者: 王晓艳

作者简介:

李勇, 中国科学院上海有机化学研究所2018级硕士研究生. 2018年本科毕业于中南大学. 目前研究方向为新型烯烃配位聚合催化剂的设计合成.

王晓艳, 中国科学院上海有机化学研究所副研究员. 2010年本科毕业于东北林业大学. 2015年在中国科学院长春应用化学研究所取得博士学位. 随后在中国科学院上海有机化学研究所金属有机化学实验室/南开大学化学系进行博士后的研究工作. 2017年正式加入上海有机化学研究所金属有机化学国家重点实验室, 开展新型过渡金属催化剂、“活性”自由基聚合及可控烯烃配位聚合等方面的研究.

唐勇, 中国科学院上海有机化学研究所研究员. 1986年本科毕业于四川师范学院; 1992年和1996年先后在中国科学院上海有机化学研究所获得硕士和博士学位. 1996年至1999年先后在美国科罗拉多州立大学和美国乔治城大学从事博士后研究; 1999年5月入职上海有机化学研究所, 2000年1月, 担任上海有机化学研究所“百人计划”项目研究员, 2015年当选中国科学院院士. 主要从事金属有机化学研究, 包括: 不对称催化, 烯烃聚合催化剂的设计、合成与应用, 叶立德化学以及天然产物全合成等.

基金资助:
中国科学院青年创新促进会(2020259); 国家自然科学基金(21901253); 国家自然科学基金(21690072); 上海市青年科技英才启明星计划(21QA1411200)

Coordination Polymerization of α,ω-Diolefin: the Regulation of Polymer Microstructure by Catalyst

Yong Li, Xiao-Yan Wang(), Yong Tang

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2021-08-12 Published:2021-09-24
Contact: Xiao-Yan Wang
Supported by:
Youth Innovation Promotion Association CAS(2020259); National Natural Science Foundation of China(21901253); National Natural Science Foundation of China(21690072); Shanghai Rising-Star Program(21QA1411200)

In the past decades, the polyolefin industry has been booming, and the synthesis of polyolefin with unique structure and property has been the constant pursuit of polymer chemists. Until now, scientists have been able to synthesize various polyolefins by regulating monomer structure, catalyst central metal, ligand structure and polymerization conditions. Among the various polyolefins, those with aliphatic rings in the main chain have been widely concerned because of their excellent thermal stability and transparency. The coordination polymerization of α,ω-diolefin is a very efficient approach to obtain polymers containing aliphatic rings in backbone. This method has some advantages, such as easy availability and modification of monomers, and the effective regulation of polymer microstructure by catalysts. Polymers with pendant double bonds or aliphatic rings or crosslinked gel can be obtained according to the different double bond that inserts into the intermediate generating after the first insertion reaction. According to the relative orientation of two branched chains in the ring, the polymers are divided into cis and trans isomers. By the relative configuration of the rings, there are isotactic and syndiotactic structures. Due to the 1,2-insertion or 2,1-insertion of the first insertion reaction between the catalyst and the monomer, the resultant polymers contain ring units with monomethylene or dimethylene. Under the catalyzation of complexes with different absolute configurations, chiral polymers with the same optical rotation and opposite direction can be obtained. The microstructure of these polymers should have a significant influence on their aggregation state, thermodynamics and mechanical properties, which can be finely regulated by changing the central metal and ligand structure of the catalyst. This review focuses on the microstructure of polymers of α,ω-diolefins, and emphatically introduces how to regulate the polymer structure by varying the catalyst structure. Besides, the possible development direction of this field is predicted, so as to promote the rapid development of structure-performance relationship and practical application of these polymers.

Key words: α,ω-diolefin, coordination polymerization, catalyst, microstructure, cyclopolymer

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Yong Li, Xiao-Yan Wang, Yong Tang. Coordination Polymerization of α,ω-Diolefin: the Regulation of Polymer Microstructure by Catalyst[J]. Acta Chimica Sinica, 2021, 79(11): 1320-1330.

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Fig. & Tab. 29

Figure 1. Stereoregular poly(1,5-hexadiene)s

Figure 2. Insertion reactions of α,ω-diolefin coordination polymerization intermediate with different double bonds

Figure 3. Cyclopolymerization of 1,6-heptyldiene and the following dehydrogenation

Figure 4. “One-step addition” mechanism

Figure 5. “Two-step addition” mechanism

Figure 6. Zirconium metallocene catalysts used by Waymouth et al.

Figure 7. Schematic diagram of transition states by different metallocene catalysts

Figure 8. Influence of transition states (chair and twist boat) on cis-trans configuration of rings

Figure 9. Homopolymerization of 1,5-hexadiene by chiral zirconium metallocene catalyst

Figure 10. Effect of catalyst configuration on polymer structure

Figure 11. Polymers of type I and II

Figure 12. Amidine-zirconium metal catalyst

Figure 13. Homopolymerization of 1,5-hexadiene by Fujita catalyst

Figure 14. The polymerization of 1,7-octandiene by Nomura group's catalysts

Run	Cat. (μmol)	OD/ hexane/mL	Yield/ mg	Act.^b	M_n/ ×10⁴	M_w/M_n
1	1 (0.3)	15.0/—	160	1.6	76.3	1.86
2	1 (0.3)	15.0/—	160	1.6	66.4	1.89
3	1 (0.1)	15.0/—	120	3.6	81.1	1.63
4	1 (0.1)	10.0/5.0	104	3.1	61.2	1.66
5	1 (1.0)	7.5/7.5	227	6.8	37.8	2.00
6	1 (0.1)	7.5/7.5	66.4	2.0	46.5	1.69
7	1 (1.0)	5.0/10.0	79	2.4	17.4	1.89
8	2 (0.1)	15.0/—	39.0	1.2	65.1	1.70
9	2 (0.1)	15.0/—	39.0	1.2	65.6	1.76

Table 1. The polymerization of 1,7-octandiene by Nomura group's catalystsa

Figure 15. Copolymerization of 1,7-octandiene with 1-octene and subsequent functionalization

Figure 16. Formation of cis-isotactic cyclopolymers catalyzed by bulky hafnium complex

Figure 17. The mechanism of producing cyclopolymers dominated by cis-configuration

Figure 18. Polymerization of α,ω-diolefins containing silicon substituents

Figure 19. Homopolymerization of substituted 1,6-heptadiene catalyzed by palladium complexes

Figure 20. Effect of steric hindrance of substituents in ligand on polymer structure

Figure 21. The mechanism for the regulation of polymer structure by steric hindrance of ligand

Figure 22. The regulation of polymer configuration by switching the central metal

Figure 23. Mechanism of regulating polymer configuration by switching central metal

Figure 24. Effect of catalyst symmetry on the stereoscopic regularity of polymers

Figure 25. Copolymerization of ethylene with 1,6-heptadiene derivatives catalyzed by palladium(II) phosphinesulfonato complex

Figure 26. Copolymerization of 1,6-heptadiene with ethylene and styrene catalyzed by half-sandwich scandium alkyl complexes

Figure 27. Homopolymerization of 1,6-heptadiene derivatives with polar substituents at the 4-position

Figure 28. Mechanism for polymerization of 1,6-heptadiene derivatives with (a) polar substituent containing oxygen atom or (b) polar substituent containing sulfur atom at the 4-position

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α,ω-双烯烃的配位聚合: 催化剂对聚合物微观结构的调控

Coordination Polymerization of α,ω-Diolefin: the Regulation of Polymer Microstructure by Catalyst

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