Pyrazolylimine Ni(Ⅱ) Complexes: Synthesis, Characterization, and Catalytic Behaviors for 1, 3-Butadiene Polymerization

doi:10.11944/j.issn.1000-0518.2015.08.140425

Chinese Journal of Applied Chemistry ›› 2015, Vol. 32 ›› Issue (8): 909-915.DOI: 10.11944/j.issn.1000-0518.2015.08.140425

• Full Papers • Previous Articles Next Articles

Pyrazolylimine Ni(Ⅱ) Complexes: Synthesis, Characterization, and Catalytic Behaviors for 1, 3-Butadiene Polymerization

HAN Chao^a,LIU Heng^b,YANG Feng^a^*(),HU Yanming^b,ZHANG Xuequan^b^*

^a School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
^b Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Received:2014-12-12 Accepted:2015-04-02 Published:2015-08-08 Online:2015-08-08
Contact: YANG Feng,ZHANG Xuequan
Supported by:
Supported by National Natural Science Foundation of China(No.51203092)

Abstract

Abstract:

A series of NN-bidentate nickel(Ⅱ) complexes bearing pyrazolylimine ligands(4a~4e) was synthesized and characterized by FTIR and elemental analysis. Determined by X-ray single crystal diffraction, complex 4b adopted distorted trigonal bipyramidal geometry around the central metal. Activated by ethylaluminum sesquichloride(EASC), all complexes exhibited high cis-1, 4 selectivity towards 1, 3-butadiene polymerization to afford liquid polybutadienes(PB) with relative molecular mass of 4500~9000 and 91% cis-1, 4 content. The catalytic activity of the complex decreased as the hindrance of the substituent on the ligand increased. The effects of Al/Ni molar ratio and polymerization temperature on the polymerization were further investigated in details. The catalytic activity increased with the increase of polymerization temperature from 20 ℃ to 60 ℃, and the polymer yield only slightly decreased even at a high temperature of 80 ℃, indicating high thermal stability of the active species generated by the present catalytic system.

Key words: pyrazolylimine, nickle complex, liquid polybutadiene, coordination polymerization

CLC Number:

HAN Chao, LIU Heng, YANG Feng, HU Yanming, ZHANG Xuequan. Pyrazolylimine Ni(Ⅱ) Complexes: Synthesis, Characterization, and Catalytic Behaviors for 1, 3-Butadiene Polymerization[J]. Chinese Journal of Applied Chemistry, 2015, 32(8): 909-915.

References

[1]	Barcia F L, Soares B G, Sampaio E. Adhesive Properties of Epoxy Resin Modified by End-Functionalized Liquid Polybutadiene[J]. J Appl Polym Sci, 2004, 93: 2370-2378.
[2]	Barcia F L, Amaral T P, Soares B G. Synthesis and Properties of Epoxy Resin Modified with Epoxy-Terminated Liquid Polybutadiene[J]. Polymer, 2003, 14: 5811-5819.
[3]	REN Wentan, ZHANG Yong, PENG Zonglin, et al.Characteristics of Liquid Rubber and It's Application in Rubber Industry[J]. China Rubber Sci Technol Market, 2006, 6: 16-20(in Chinese). 任文坛, 张勇等, 彭宗林, 等. 液体橡胶的特性及其在橡胶工业中的应用[J]. 橡胶科技市场, 2006, 6: 16-20.
[4]	LIANG Tao, WEI Xuling, ZHANG Huiyi, et al.Progress in Research and Development of Diene Liquid Rubber[J]. Polym Bull, 2012, (4): 11-16(in Chinese). 梁滔, 魏绪玲, 张惠怡, 等. 双烯类液体橡胶的研究进展[J]. 高分子通报, 2012, (4): 11-16.
[5]	CHENG Qian, LIANG Jizhao. Progress in Research and Development of Polybutadiene Liquid Rubber[J]. Special Purpose Rubber Prod, 2013, 34: 72-76(in Chinese). 程倩, 梁基照. 聚丁二烯液体橡胶及其研究进展[J]. 特种橡胶制品, 2013, 34: 72-76.
[6]	LIANG Tao, WANG Hongshan, GAO Yangguang, et al.Research Progress in Liquid Rubber[J]. China Synthetic Rubber Ind, 2010, 33: 482-487(in Chinese). 梁滔, 王洪山, 高阳光, 等. 液体橡胶的研究进展[J]. 合成橡胶工业, 2010, 33: 482-487.
[7]	Lotti L, Coiai S, Ciardelli F, et al.Thiol-Ene Radical Addition of L-Cysteine Derivatives to Low Molecular Weight Polybutadiene[J]. Macromol Chem Phys, 2009, 210: 1471-1483.
[8]	LIU Heng, WANG Feng, ZHANG Xuequan, et al.Synthesis, Characterization of Bis(arylcarboximidoyl -chloride)pyridine Ni(Ⅱ) Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene[J]. Chem J Chinese Univ, 2014, 35: 1336-1342(in Chinese). 刘恒, 王凤, 张学全, 等. 吡啶双亚胺酰氯Ni(Ⅱ) 配合物的合成、表征及催化合成液体聚丁二烯[J]. 高等学校化学学报, 2014, 35: 1336-1342.
[9]	Wang F, Liu H, Zheng W J, et al.Fully-Reversible and Semi-Reversible Coordinative Chain Transfer Polymerizations of 1, 3-Butadiene with Neodymium-Based Catalytic Systems[J]. Polymer, 2013, 54: 6716-6724.
[10]	Wang Y Y, Lin S A, Zhu F M, et al.Nickel(Ⅱ) Complexes Bearing Pyrazolylimine Ligands: Synthesis, Characterization, and Catalytic Properties for Ethylene Oligomerization[J]. Inorg Chim Acta, 2009, 362: 166-172.
[11]	Gong D R, Wang F, Wang B L, et al.Highly Trans-1, 4 Selective Polymerization of 1, 3-Butadiene Initiated by Iron(Ⅲ) Bis(imino)pyridyl Complexes[J]. Inorg Chim Acta, 2011, 373: 47-53.
[12]	Liu H, Jia X Y, Wang F, et al.Synthesis of Bis(N-arylcarboximidoyl-chloride)pyridine Cobalt(Ⅱ) Complexes and Their Catalytic Behavior for 1, 3-Butadiene Polymerization[J]. Dalton Trans, 2013, 42: 13723-13732.
[13]	Porri L, Giarrusso A, Ricci G. Recent Views on the Mechanism of Diolefin Polymerization with Transition Metal Initiator Systems[J]. Prog Polym Sci, 1991, 16: 405-441.

Pyrazolylimine Ni(Ⅱ) Complexes: Synthesis, Characterization, and Catalytic Behaviors for 1, 3-Butadiene Polymerization

RichHTML

PDF

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 7

Recommended Articles

Metrics

Comments

[1]	ZHUANG Rui, DONG Bo, ZHAO Wenpeng, HU Yanming, ZHANG Xuequan. Pyridyl/Quinolyl-imine Ni(Ⅱ) Complexes:Synthesis and Application for Preparation of Liquid Polybutadiene [J]. Chinese Journal of Applied Chemistry, 2017, 34(11): 1259-1264.
[2]	Qu Yahuan, Yu Wei, Li Yuliang, Yu Guangqian . Synthesis of Propionamide Complexes with Lanthanide Chloride and Catalytic Activity of Its NdCl₃ Complex in Butadiene Polymerization [J]. Chinese Journal of Applied Chemistry, 1998, 0(5): 21-23.
[3]	Ren Jingsong, Hu Jingyu, Shen Qi. Polymerization of Acrylonitrile Catalyzed by[(t-BuCp)₂NdCH₃]₂ [J]. Chinese Journal of Applied Chemistry, 1995, 0(3): 105-106.
[4]	Sun Junquan, Wang Guangming, Shen Zhiquan. COORDINATION POLYMERIZATION OF BUTYL METHACRYLATE WITH Nd(Oct)₃-Al(i-Bu)₃ [J]. Chinese Journal of Applied Chemistry, 1993, 0(4): 1-4.
[5]	Hu Jingyu, Shen Qi, Zhao Liqun. A NOVEL BINARY IRON CATALYST FOR BUTADIENE POLYMERIZATION [J]. Chinese Journal of Applied Chemistry, 1991, 0(1): 42-45.
[6]	Liao Yuzhen, Zhao Liqun, Liu Xichun . BULK POLYMERIZATION OF BUTADIENE WITH RARE EARTH CATALYST [J]. Chinese Journal of Applied Chemistry, 1988, 0(2): 34-37.
[7]	Wang Fengjiang, Liu Guozhi, Qian Baogong. STUDIES ON THE POLYMERIZATION OF BUTADIENE IN THE PRESENSE OF IRON CATALYST Ⅵ.EFFECTS OF NITROGENCONTAINING LIGANDS ON THE POLYMERIZATION AND THE MICROSTRUCTURE OF POLYMER [J]. Chinese Journal of Applied Chemistry, 1988, 0(1): 15-20.