1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands

Liang Fang; Wen-Peng Zhao; Chao Han; Chun-Yu Zhang; Heng Liu; Yan-Ming Hu; Xue-Quan Zhang

doi:10.1007/s10118-019-2198-z

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1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands

ARTICLE | Updated：2021-02-18

- 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands
- Chinese Journal of Polymer Science Vol. 37, Issue 5, Pages: 462-470(2019)
- Affiliations：
  
  a.CAS Key Laboratory of High-Performance Synthetic Rubber and its Composite Materials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.University of Chinese Academy of Sciences, Beijing 100049, China
  c.School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
- Author bio：
  
  cyzhang@ciac.ac.cn (C.Y.Z.)
  hengliu@ciac.ac.cn (H.L.)
- Funds：
- DOI：10.1007/s10118-019-2198-z
  CLC：
- Received：27 September 2018，
  
  Revised：2018-10-30，
  
  Accepted：03 November 2018，
  
  Online First：26 November 2018，
  
  Published：2019-05
- Accepted：
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Citation: Fang, L.; Zhao, W. P.; Han, C.; Zhang, C. Y.; Liu, H.; Hu, Y. M.; Zhang, X. Q. 1,3-Butadiene polymerizations catalyzed by cobalt and iron dichloride complexes bearing pyrazolylimine ligands. Chinese J. Polym. Sci. 2019, 37, 462–470

Liang Fang, Wen-Peng Zhao, Chao Han, et al. 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands[J]. Chinese Journal of Polymer Science, 2019, 37(5): 462-470.
Citation: Fang, L.; Zhao, W. P.; Han, C.; Zhang, C. Y.; Liu, H.; Hu, Y. M.; Zhang, X. Q. 1,3-Butadiene polymerizations catalyzed by cobalt and iron dichloride complexes bearing pyrazolylimine ligands. Chinese J. Polym. Sci. 2019, 37, 462–470 DOI： 10.1007/s10118-019-2198-z.

Liang Fang, Wen-Peng Zhao, Chao Han, et al. 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands[J]. Chinese Journal of Polymer Science, 2019, 37(5): 462-470. DOI： 10.1007/s10118-019-2198-z.

摘要

Abstract

A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of (PhC＝N(C

)

-2

6)(C

)

-3

5)MtCl

= Me

= H

Mt = Co (

)

Fe (

); R

= Me

Mt = Co (

)

Fe (

); R

= H

Mt = Co (

)

Fe (

); R

= Me

Mt = Co (

)

Fe (

); R

= Ph

Mt = Co (

)

Fe (

)) were synthesized and thoroughly characterized. Determined by single crystal X-ray diffraction

complexes

and

revealed dimeric structures

in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride (EASC)

all the cobalt complexes displayed high activities in 1

3-butadiene polymerization

affording polybutadienes with predominant

cis

-1

4 contents (up to 97.0%). Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes

the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex

changing cocatalyst from trialkyl aluminums to methyl aluminoxane (MAO) led to an shift of selectivity from high

cis

-1

4- to

trans

-1

4-/1

2- manner. Being activated by MAO

complexes

and

gave

trans

-1

4-/1

2- binary polybutadienes

while complexes

and

afforded

cis

-1

4- enriched polymers.

关键词

Keywords

references

Friebe, L.; Nuyken, O.; Obrecht, W . Neodymium-based Ziegler/Natta catalysts and their application in diene polymerization . Neodymium Based Ziegler Catalysts Fundamental Chemistry , 2006 . 1 - 154 . .

Zhang, Z.; Cui, D.; Wang, B.; Liu, B.; Yang, Y . Polymerization of 1,3-conjugated dienes with rare-earth metal precursors . Struct. Bond. , 2010 . 137 49 - 108 . DOI: 10.1007/978-3-642-12811-0 http://doi.org/10.1007/978-3-642-12811-0 .

Ricci, G.; Sommazzi, A.; Masi, F.; Ricci, M.; Boglia, A.; Leone, G . Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization . Coord. Chem. Rev. , 2010 . 254 661 - 676 . DOI: 10.1016/j.ccr.2009.09.023 http://doi.org/10.1016/j.ccr.2009.09.023 .

Porri, L.; Giarrusso, A.; Ricci, G . Recent views on the mechanism of diolefin polymerization with transition metal initiator systems . Prog. Polym. Sci. , 1991 . 16 405 - 441 . DOI: 10.1016/0079-6700(91)90024-F http://doi.org/10.1016/0079-6700(91)90024-F .

Thiele, S. K. H.; Wilson, D. R . Alternate transition metal complex based diene polymerization . J. Macromol. Sci. Polym. Rev. , 2003 . C43 581 - 628 . DOI: 10.1081/MC-120025979 http://doi.org/10.1081/MC-120025979 .

Ricci, G.; Panagia, A.; Porri, L . Polymerization of 1,3-dienes with catalysts based on mono- and bis-cyclopentadienyl derivatives of vanadium . Polymer , 1996 . 37 363 - 365 . DOI: 10.1016/0032-3861(96)81112-8 http://doi.org/10.1016/0032-3861(96)81112-8 .

van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G . Polymerization of α -olefins and butadiene and catalytic cyclotrimerization of 1-alkynes by a new class of group IV catalysts. Control of molecular weight and polymer microstructure via ligand tuning in sterically hindered chelating phenoxide titanium and zirconium species . J. Am. Chem. Soc. , 1995 . 117 3008 - 3021 . DOI: 10.1021/ja00116a006 http://doi.org/10.1021/ja00116a006 .

Jang, Y.; Choi, D. S.; Han, S . Effects of tris(pentafluoro phenyl)borane on the activation of a metal alkyl-free Ni-based catalyst in the polymerization of 1,3-butadiene . J. Polym. Sci., Part A: Polym. Chem. , 2004 . 42 1164 - 1173 . DOI: 10.1002/pola.11062 http://doi.org/10.1002/pola.11062 .

Sivaram, S.; Upadhyay, V. K . Synthesis of high cis -polymerization usging cobalt(II) 2-ethylhexoate modified triethylaluminum catalyst . J. Macromol. Sci. Pur. , 1992 . 29 13 - 19 . DOI: 10.1080/10101329208054559 http://doi.org/10.1080/10101329208054559 .

Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A . Syndiotactic 1,2-polybutadiene with Co-CS 2 catalyst system. 1. Preparation, properties, and application of highly crystalline syndiotactic 1,2-polybutadiene . J. Polym. Sci., Part A: Polym. Chem. , 1983 . 21 1853 - 1860 . DOI: 10.1002/pol.1983.170210625 http://doi.org/10.1002/pol.1983.170210625 .

Wang, F.; Liu, H.; Zheng, W.; Guo, J.; Zhang, C.; Zhao, L.; Zhang, H.; Hu, Y.; Bai, C.; Zhang, X . Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems . Polymer , 2013 . 54 6716 - 6724 . DOI: 10.1016/j.polymer.2013.10.031 http://doi.org/10.1016/j.polymer.2013.10.031 .

Nishii, K.; Kang, X.; Nishiura, M.; Luo, Y.; Hou, Z . Regio- and stereospecific living polymerization and copolymerization of ( E )-1,3-pentadiene with 1,3-butadiene by half-sandwich scandium catalysts . Dalton Trans. , 2013 . 42 9030 - 9032 . DOI: 10.1039/c3dt50357g http://doi.org/10.1039/c3dt50357g .

Hu, Y.; Dong, W.; Masuda, T . Novel methylaluminoxane-activated neodymium isopropoxide catalysts for 1,3-butadiene polymerization and 1,3-butadiene/isoprene copolymerization . Macromol. Chem. Phys. , 2013 . 214 2172 - 2180 . DOI: 10.1002/macp.201300383 http://doi.org/10.1002/macp.201300383 .

Gibson, V. C.; Redshaw, C.; Solan, G. A . Bis(imino)pyridines: Surprisingly reactive ligands and a gateway to new families of catalysts . Chem. Rev. , 2007 . 107 1745 - 1776 . DOI: 10.1021/cr068437y http://doi.org/10.1021/cr068437y .

Wang, Z.; Solan, G. A.; Mahmood, Q.; Liu, Q.; Ma, Y.; Hao, X.; Sun, W. H . Bis(imino)pyridines incorporating doubly fused eight-membered rings as conformationally flexible supports for cobalt ethylene polymerization catalysts . Organometallics , 2018 . 37 380 - 389 . DOI: 10.1021/acs.organomet.7b00809 http://doi.org/10.1021/acs.organomet.7b00809 .

Mu, H.; Pan, L.; Song, D.; Li, Y . Neutral nickel catalysts for olefin homo- and copolymerization: Relationships between catalyst structures and catalytic properties . Chem. Rev. , 2015 . 115 12091 - 12137 . DOI: 10.1021/cr500370f http://doi.org/10.1021/cr500370f .

Li, M.; Shu, X.; Cai, Z.; Eisen, M. S . Synthesis, structures, and norbornene polymerization behavior of neutral nickel(II) and palladium(II) complexes bearing aryloxide imidazolidin-2-imine ligands . Organometallics , 2018 . 37 1172 - 1180 . DOI: 10.1021/acs.organomet.8b00059 http://doi.org/10.1021/acs.organomet.8b00059 .

Ricci, G.; Morganti, D.; Sommazzi, A.; Santi, R.; Masi, F . Polymerization of 1,3-dienes with iron complexes based catalysts: Influence of the ligand on catalyst activity and stereospecificity . J. Mol. Catal. A Chem. , 2003 . 204-205 287 - 293 . DOI: 10.1016/S1381-1169(03)00310-8 http://doi.org/10.1016/S1381-1169(03)00310-8 .

Ricci, G.; Forni, A.; Boglia, A.; Motta, T . Synthesis, structure, and butadiene polymerization behavior of alkylphosphine cobalt(II) complexes . J. Mol. Catal. A Chem. , 2005 . 226 235 - 241 . DOI: 10.1016/j.molcata.2004.10.022 http://doi.org/10.1016/j.molcata.2004.10.022 .

Nath, D. C. D.; Shiono, T.; Ikeda, T . Cis -specific living polymerization of 1,3-butadiene with CoCl 2 and methylaluminoxane . Macromol. Chem. Phys. , 2002 . 203 756 - 760 . DOI: 10.1002/(ISSN)1521-3935 http://doi.org/10.1002/(ISSN)1521-3935 .

Endo, K.; Hatakeyama, N . Stereospecific and molecular weight-controlled polymerization of 1,3-butadiene with Co(acac) 3 -MAO catalyst . J. Polym. Sci., Part A: Polym. Chem. , 2001 . 39 2793 - 2798 . DOI: 10.1002/pola.1258 http://doi.org/10.1002/pola.1258 .

Leicht, H.; Göttker-Schnetmann, I.; Mecking, S . Synergetic effect of monomer functional group coordination in catalytic insertion polymerization . J. Am. Chem. Soc. , 2017 . 139 6823 - 6826 . DOI: 10.1021/jacs.7b03087 http://doi.org/10.1021/jacs.7b03087 .

Leicht, H.; Göttker-Schnetmann, I.; Mecking, S . Stereoselective copolymerization of butadiene and functionalized 1,3-dienes . ACS Macro Lett. , 2016 . 5 777 - 780 . DOI: 10.1021/acsmacrolett.6b00321 http://doi.org/10.1021/acsmacrolett.6b00321 .

Gong, D.; Jia, X.; Wang, B.; Wang, F.; Zhang, C.; Zhang, X.; Jiang, L.; Dong, W . Highly trans -1,4 selective polymerization of 1,3-butadiene initiated by iron(III) bis(imino)pyridyl complexes . Inorg. Chim. Acta , 2011 . 373 47 - 53 . DOI: 10.1016/j.ica.2011.03.047 http://doi.org/10.1016/j.ica.2011.03.047 .

Gong, D.; Jia, X.; Wang, B.; Zhang, X.; Huang, K. W . Trans -1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO . J. Organomet. Chem. , 2014 . 766 79 - 85 . DOI: 10.1016/j.jorganchem.2014.05.018 http://doi.org/10.1016/j.jorganchem.2014.05.018 .

Gong, D.; Wang, B.; Cai, H.; Zhang, X.; Jiang, L . Synthesis, characterization and butadiene polymerization studies of cobalt(II) complexes bearing bisiminopyridine ligand . J. Organomet. Chem. , 2011 . 696 1584 - 1590 . DOI: 10.1016/j.jorganchem.2011.01.015 http://doi.org/10.1016/j.jorganchem.2011.01.015 .

Gong, D.; Wang, B.; Bai, C.; Bi, J.; Wang, F.; Dong, W.; Zhang, X.; Jiang, L . Metal dependent control of cis -/ trans -1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine . Polymer , 2009 . 50 6259 - 6264 . DOI: 10.1016/j.polymer.2009.10.054 http://doi.org/10.1016/j.polymer.2009.10.054 .

Jia, X.; Liu, H.; Hu, Y.; Dai, Q.; Bi, J.; Bai, C.; Zhang, X . Highly active and cis -1,4 selective polymerization of 1,3-butadiene catalyzed by cobalt(II) complexes bearing alpha-diimine ligands . Chinese J. Catal. , 2013 . 34 1560 - 1569 . DOI: 10.1016/S1872-2067(12)60625-1 http://doi.org/10.1016/S1872-2067(12)60625-1 .

Alnajrani, M. N.; Mair, F. S . Synthesis and characterization of β -triketimine cobalt complexes and their behaviour in the polymerization of 1,3-butadiene . Dalton Trans. , 2014 . 43 15727 - 15736 . DOI: 10.1039/C4DT02196G http://doi.org/10.1039/C4DT02196G .

Alnajrani, M. N.; Mair, F. S . The behaviour of β -triketimine cobalt complexes in the polymerization of isoprene . RSC Adv. , 2015 . 5 46372 - 46385 . DOI: 10.1039/C5RA06792H http://doi.org/10.1039/C5RA06792H .

Gong, D.; Wang, B.; Jia, X.; Zhang, X . The enhanced catalytic performance of cobalt catalysts towards butadiene polymerization by introducing a labile donor in a salen ligand . Dalton Trans. , 2014 . 43 4169 - 4178 . DOI: 10.1039/c3dt52708e http://doi.org/10.1039/c3dt52708e .

Chandran, D.; Kwak, C. H.; Ha, C. S.; Kim, I . Polymerization of 1,3-butadiene by bis(salicylaldiminate)cobalt(II) catalysts combined with organoaluminium cocatalysts . Catal. Today , 2008 . 131 505 - 512 . DOI: 10.1016/j.cattod.2007.10.068 http://doi.org/10.1016/j.cattod.2007.10.068 .

Guo, J.; Zhang, C.; Bi, J.; Zhang, H.; Bai, C.; Hu, Y.; Zhang, X . Cobalt complexes bearing pyridine-imino ligands with bulky aryl substituents: Synthesis, characterization, and 1,3-butadiene polymerization behaviors . J. Organomet. Chem. , 2015 . 798 414 - 421 . DOI: 10.1016/j.jorganchem.2015.05.004 http://doi.org/10.1016/j.jorganchem.2015.05.004 .

Ai, P.; Chen, L.; Guo, Y.; Jie, S.; Li, B. G . Polymerization of 1,3-butadiene catalyzed by cobalt(II) and nickel(II) complexes bearing imino- or amino-pyridyl alcohol ligands in combination with ethylaluminum sesquichloride . J. Organomet. Chem. , 2012 . 705 51 - 58 . DOI: 10.1016/j.jorganchem.2012.01.013 http://doi.org/10.1016/j.jorganchem.2012.01.013 .

Wang, B.; Gong, D.; Bi, J.; Dai, Q.; Zhang, C.; Hu, Y.; Zhang, X.; Jiang, L . Synthesis, characterization and 1,3-butadiene polymerization behaviors of cobalt complexes bearing 2-pyrazolyl-substituted 1,10-phenanthroline ligands . Appl. Organomet. Chem. , 2013 . 27 245 - 252 . DOI: 10.1002/aoc.v27.4 http://doi.org/10.1002/aoc.v27.4 .

Guo, J.; Liu, H.; Bi, J.; Zhang, C.; Zhang, H.; Bai, C.; Hu, Y.; Zhang, X . Pyridine-oxazoline and quinoline-oxazoline ligated cobalt complexes: Synthesis, characterization, and 1,3-butadiene polymerization behaviors . Inorg. Chim. Acta , 2015 . 435 305 - 312 . DOI: 10.1016/j.ica.2015.07.013 http://doi.org/10.1016/j.ica.2015.07.013 .

Appukuttan, V.; Zhang, L.; Ha, J. Y.; Chandran, D.; Bahuleyan, B. K.; Ha, C. S.; Kim, I . Stereospecific polymerizations of 1,3-butadiene catalyzed by Co(II) complexes ligated by 2,6-bis(benzimidazolyl)pyridines . J. Mol. Catal. A Chem. , 2010 . 325 84 - 90 . DOI: 10.1016/j.molcata.2010.04.002 http://doi.org/10.1016/j.molcata.2010.04.002 .

Wang, G.; Jiang, X.; Zhao, W.; Sun, W.; Yao, W.; He, A . Catalytic behavior of Co(II) complexes with 2-(benzimidazolyl)-6-(1-(arylimino)ethyl)pyridine ligands on isoprene stereospecific polymerization . J. Appl. Polym. Sci. , 2014 . 131 39703 - 39708 . DOI: 10.1002/app.39703 http://doi.org/10.1002/app.39703 .

Appukuttan, V.; Zhang, L.; Ha, C. S.; Kim, I . Highly active and stereospecific polymerizations of 1,3-butadiene by using bis(benzimidazolyl)amine ligands derived Co(II) complexes in combination with ethylaluminum sesquichloride . Polymer , 2009 . 50 1150 - 1158 . DOI: 10.1016/j.polymer.2008.12.047 http://doi.org/10.1016/j.polymer.2008.12.047 .

Liu, H.; Wang, F.; Jia, X.; Liu, L.; Bi, J.; Zhang, C.; Zhao, L.; Bai, C.; Hu, Y.; Zhang, X . Synthesis, characterization, and 1,3-butadiene polymerization studies of Co(II), Ni(II), and Fe(II) complexes bearing 2-( N -arylcarboximidoylchloride)quinoline ligand . J. Mol. Catal. A Chem. , 2014 . 391 25 - 35 . DOI: 10.1016/j.molcata.2014.04.008 http://doi.org/10.1016/j.molcata.2014.04.008 .

Liu, H.; Jia, X.; Wang, F.; Dai, Q.; Wang, B.; Bi, J.; Zhang, C.; Zhao, L.; Bai, C.; Hu, Y.; Zhang, X . Synthesis of bis( N -arylcarboximidoylchloride)pyridine cobalt(II) complexes and their catalytic behavior for 1,3-butadiene polymerization . Dalton Trans. , 2013 . 42 13723 - 13732 . DOI: 10.1039/c3dt51403j http://doi.org/10.1039/c3dt51403j .

Liu, H.; Yang, S. Z.; Wang, F.; Bai, C. X.; Hu, Y. M.; Zhang, X. Q . Polymerization of 1,3-butadiene catalyzed by cobalt(II) and nickel(II) complexes bearing pyridine-2-imidate ligands . Chinese J. Polym. Sci. , 2016 . 34 1060 - 1069 . DOI: 10.1007/s10118-016-1825-1 http://doi.org/10.1007/s10118-016-1825-1 .

Liu, H.; Zhuang, R.; Dong, B.; Wang, F.; Hu, Y. M.; Zhang, X. Q . Mono- and binuclear cobalt(II) complexes supported by quinoline-2-imidate ligands: Synthesis, characterization, and 1,3-butadiene polymerization . Chinese J. Polym. Sci. , 2018 . 36 943 - 952 . DOI: 10.1007/s10118-018-2097-8 http://doi.org/10.1007/s10118-018-2097-8 .

Liu, H.; Wang, F.; Han, C.; Zhang, H.; Bai, C.; Hu, Y.; Zhang, X . Cobalt and nickel complexes supported by 2,6-bis(imidate)pyridyl ligands: Synthesis, characterization, and 1,3-butadiene polymerization studies . Inorg. Chim. Acta , 2015 . 434 135 - 142 . DOI: 10.1016/j.ica.2015.05.022 http://doi.org/10.1016/j.ica.2015.05.022 .

Wang, Y.; Lin, S.; Zhu, F.; Gao, H.; Wu, Q . Dinuclear nickel(II) complexes bearing two pyrazolylimine ligands: Synthesis characterization, and catalytic properties for vinyl-type polymerization of norbornene . Eur. Polym. J. , 2008 . 44 2308 - 2317 . DOI: 10.1016/j.eurpolymj.2008.04.043 http://doi.org/10.1016/j.eurpolymj.2008.04.043 .

Han, C . Pyrazolylimine Ni(II) complexes: Synthesis, characterization, and catalytic behaviors for 1,3-butadiene polymerization . Chinese J. Appl. Chem. , 2015 . 32 909 - 915 . DOI: 10.11944/j.issn.1000-0518.2015.08.140425 http://doi.org/10.11944/j.issn.1000-0518.2015.08.140425 .

Jie, S.; Ai, P.; Li, B . Highly active and stereospecific polymerization of 1,3-butadiene catalyzed by dinuclear cobalt(II) complexes bearing 3-aryliminomethyl-2-hydroxybenzaldehydes . Dalton Trans. , 2011 . 40 10975 - 10982 . DOI: 10.1039/c1dt11073j http://doi.org/10.1039/c1dt11073j .

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