Study on Catalytic Behavior of Iron-based Catalyst with IITP as Electron Donor in the Polymerization of Butadiene

Shi-Liang Xu; Ying-Nan Zhao; Yao Yu; Qi Yang; Li-Hua Na; Heng Liu; Chun-Yu Zhang; Xue-Quan Zhang

doi:10.1007/s10118-024-3078-8

Your Location：

Home >

Browse articles >

Study on Catalytic Behavior of Iron-based Catalyst with IITP as Electron Donor in the Polymerization of Butadiene

RESEARCH ARTICLE | Updated：2024-04-12

- Study on Catalytic Behavior of Iron-based Catalyst with IITP as Electron Donor in the Polymerization of Butadiene
- Chinese Journal of Polymer Science Vol. 42, Issue 5, Pages: 612-619(2024)
- Affiliations：
  
  a.Key Laboratory of Advanced Rubber Material, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
  b.Shandong Provincial College Laboratory of Rubber Material and Engineering, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
  c.Key Lab of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Lab of Rubber-plastics, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
- Author bio：
  
  lhna@qust.edu.cn (L.H.N.)
  cyzhang@qust.edu.cn (C.Y.Z.)
- Funds：
- DOI：10.1007/s10118-024-3078-8
  CLC：
- Received：24 October 2023，
  
  Revised：2023-11-24，
  
  Accepted：06 December 2023，
  
  Online First：26 January 2024，
  
  Published：01 May 2024
- Accepted：
Scan QR Code
Xu, S. L.; Zhao, Y. N.; Yu, Y.; Yang, Q.; Na, L. H.; Liu, H.; Zhang, C. Y.; Zhang, X. Q. Study on catalytic behavior of iron-based catalyst with IITP as electron donor in the polymerization of butadiene. Chinese J. Polym. Sci. 2024, 42, 612–619

Shi-Liang Xu, Ying-Nan Zhao, Yao Yu, et al. Study on Catalytic Behavior of Iron-based Catalyst with IITP as Electron Donor in the Polymerization of Butadiene[J]. Chinese Journal of Polymer Science, 2024, 42(5): 612-619.
Xu, S. L.; Zhao, Y. N.; Yu, Y.; Yang, Q.; Na, L. H.; Liu, H.; Zhang, C. Y.; Zhang, X. Q. Study on catalytic behavior of iron-based catalyst with IITP as electron donor in the polymerization of butadiene. Chinese J. Polym. Sci. 2024, 42, 612–619 DOI： 10.1007/s10118-024-3078-8.

Shi-Liang Xu, Ying-Nan Zhao, Yao Yu, et al. Study on Catalytic Behavior of Iron-based Catalyst with IITP as Electron Donor in the Polymerization of Butadiene[J]. Chinese Journal of Polymer Science, 2024, 42(5): 612-619. DOI： 10.1007/s10118-024-3078-8.

摘要

By employing electron donor compounds as an innovative approach

the synthesis of low melting point syndiotactic 1

2-polybutadiene was successfully achieved utilizing an iron-based catalyst. This catalytic system exhibits remarkable advantages in terms of high activity and thermal stability

while simultaneously demonstrating the characteristics of a controlled/living polymerization process.

Abstract

In this study

a novel iron-based catalyst system

Fe(acac)

/(isocyanoimino) triptenylphosphorane (IITP)/AlR

was employed for the synthesis of syndiotactic 1

2-polybutadiene in hexane. This catalyst system exhibits remarkably high catalytic activity

achieving a polymerization activity of 762 kg

polymer

·mol

catalyst

−1

·h

−1

at 50 °C with a [BD]/[Fe]

molar ratio of 20000. Furthermore

living polymerization characteristic were observed during the investigation of the polymerization kinetics of 1

3-butadiene polymerization. These characteristics were well demonstrated by a narrow molecular weight distribution (PDI≈2.0) of the resulting polybutadiene and a linear relationship between −ln(1 −

) and polymerization time as well as number average molecular weight and polymer yield. The resultant polymer showed a 1

2-selectivity of approximately 76% and stereoregularity ranging from 62% to 73%(

rrrr

). Additionally

through kinetic studies on polymerization reaction

an apparent activation energy

value of this catalytic system was calculated to be 84.98 kJ·mol

−1

which suggests that high polymerization temperature favors efficient polymerization.

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. Springer Berlin Heidelberg 2006 , 204 , 1−154..

Gao, W.; Cui, D. Highly cis -1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichloride precursors. J. Am. Chem. Soc. 2008 , 130 , 4984−4991..

Kaita, S.; Hou, Z.; Wakatsuki, Y. Stereospecific polymerization of 1,3-butadiene with samarocene-based catalysts 1. Macromolecules 1999 , 32 , 9078−9079..

Kaita, S.; Takeguchi, Y.; Hou, Z.; Nishiura, M.; Doi, Y.; Wakatsuki, Y. Pronounced enhancement brought in by substituents on the cyclopentadienyl ligand: catalyst system (C 5 Me 4 R) 2 Sm(THF) x /MMAO (R = Et, i Pr, n Bu, TMS; MMAO = modified methylaluminoxane) for 1,4- cis stereospecific polymerization of 1,3-butadiene in cyclohexane solvent. Macromolecules 2003 , 36 , 7923−926..

Jenkins, D. K. Butadiene polymerization with a rare earth compound using a magnesium alkyl cocatalyst: 1. Polymer 1985 , 26 , 147−151..

Kaita, S.; Yamanaka, M.; Horiuchi, A. C.; Wakatsuki, Y. Butadiene polymerization catalyzed by lanthanide metallocene-alkylaluminum complexes with cocatalysts: metal-dependent control of 1,4- cis / trans stereoselectivity and molecular weight. Macromolecules 2006 , 39 , 1359−1363..

Cariou, R.; Chirinos, J.; Gibson, V. C.; Jacobsen, G.; Tomov, A. K.; Elsegood, M. R. J. 1,3-Butadiene polymerization by bis(benzimidazolyl)aminemetal complexes: remarkable microstructural control and a protocol for in-reactor blending of trans -1,4-, cis -1,4-, and cis -1,4- co -1,2-vinylpolybutadiene. Macromolecules 2009 , 42 , 1443−1444..

Taube, R.; Maiwald, S.; Sieler, J. Komplexkatalyse: LVII. Vereinfachte Synthese des Nd( π -C 3 H 5 ) 3 ·C 4 H 8 O 2 nach der Grignard-Methode und Darstellung der neuen Allylneodym(III)-Komplexe [Nd( π -C 5 Me 5 )( π -C 3 H 5 ) 2 ·C 4 H 8 O 2 ]und [Nd( π -C 3 H 5 )Cl(THF) 5 ]B(C 6 H 5 ) 4 ·THF als Präkatalysatoren für die stereospezifische Butadienpolymerisation. J. Organomet. Chem. 2001 , 621 , 327−336..

Nakayama, Y.; Baba, Y.; Yasuda, H.; Kawakita, K.; Ueyama, N. Stereospecific polymerizations of conjugated dienes by single site iron complexes having chelating N,N,N -donor ligands. Macromolecules 2003 , 36 , 7953−7958..

Thiele, S. K. H.; Wilson, D. R. Alternate transition metal complex based diene polymerization. J. Macromol. Sci., Part C 2003 , 43 , 581−628..

Francois, D.; Philippe, T. π -Allyl type polymerization. Ind. Eng. Chem. Prod. Res. Dev . 1971 , 10 , 261−269..

Ricci, G.; Forni, A.; Boglia, A.; Motta, T.; Zannoni, G.; Canetti, M.; Bertini, F. Synthesis and X-ray Structure of CoCl 2 (P i PrPh 2 ) 2 . A new highly active and stereospecific catalyst for 1,2 polymerization of conjugated dienes when used in association with MAO. Macromolecules 2005 , 38 , 1064−1070..

Jang, Y.; Kim, P.; Lee, H. Electronic and steric effects of phosphineligand on the polymerization of 1,3-butadiene using co-based cata. Macromolecules 2002 , 35 , 1477−1480..

Monteil, V.; Bastero, A.; Mecking, S. 1,2-Polybutadiene latices by catalytic polymerization in aqueous emulsion. Macromolecules 2005 , 38 , 5393−5399..

Zheng, W.; Wang, F.; Bi, J.; Zhang, H.; Zhang, C.; Hu, Y.; Bai, C.; Zhang, X. Synthesis and characterization of soft-hard stereoblock polybutadiene with Fe(2-EHA) 3 /Al( i -Bu) 3 /DEP catalyst system. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53 , 1182−1188..

Lu, J.; Hu, Y.; Zhang, X.; Bi, J.; Dong, W.; Jiang, L.; Huang, B. Fe(2-EHA) 3 /Al( i -Bu) 3 /hydrogen phosphite catalyst for preparing syndiotactic 1,2-polybutadiene. J. Appl. Polym. Sci. 2006 , 100 , 4265−4269..

Ashitaka, H.; Ishikawa, H.; Ueno, H.; Nagasaka, A. Syndiotactic 1,2-polybutadiene with Co-CS 2 catalyst system. I. Preparation, properties, and application of highly crystalline syndiotactic 1,2-polybutadiene. J. Polym. Sci. Polym. Chem. Ed. 1983 , 21 , 1853−1860..

Fang, L.; Zhao, W.; Zhang, C.; Zhang, X.; Shen, X.; Liu, H.; Kakuchi, T. Highly Efficient and thermal robust cobalt complexes for 1,3-butadiene polymerization. Chinese J. Polym. Sci. 2022 , 40 , 1369−1379..

Natta, C. Stereospecific polymerizations. J. Polym. Sci. 1960 , 48 , 219−239..

Endo, K.; Uchida, Y. 1,2-Polymerization of 1,3-butadiene with Cr(acac) 3 -alkylaluminum catalysts. J. Appl. Polym. Sci . 2000 , 78 , 1621−1627..

Ricci, G.; Battistella, M.; Porri, L. Chemoselectivity and stereospecificity of chromium(II) catalysts for 1,3-diene polymerization. Macromolecules 2001 , 34 , 5766−5769..

Korthals, B.; Berkefeld, A.; Ahlmann, M.; Mecking, S. Catalytic polymerization of butadiene in aqueous systems with cationic nickel(II) complexes. Macromolecules 2008 , 41 , 8332−8338..

Jang, Y.; Choi, D. S.; Han, S. Effects of tris(pentafluorophenyl)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..

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..

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..

Hua, J.; Liu, K.; Wang, Z.; Geng, J.; Wang, X. Effect of vinyl and phenyl group content on the physical and dynamic mechanical properties of HVBR and SSBR. J. Appl. Polym. Sci. 2018 , 135 , 45975−4983..

Hua, J. Study on dynamic properties of molybdenum-catalyzed branched HVPBR. China Rubber Ind. 2011 , 58 , 466−470..

David, R. L. A.; Kornfield, J. A. Facile, efficient routes to diverse protected thiols and to their deprotection and addition to create functional polymers by thiol-ene coupling. Macromolecules 2008 , 41 , 1151−1161..

Brummelhuis, N. t.; Diehl, C.; Schlaad, H. Thiol-ene modification of 1,2-polybutadiene using UV light or sunlight. Macromolecules 2008 , 41 , 9946−9947..

Carey, D. H.; Ferguson, G. S. Synthesis and characterization of surface-functionalized 1,2-polybutadiene bearing hydroxyl or carboxylic acid groups. Macromolecules 1994 , 27 , 7254−7266..

Ajjou, A. N.; Alper, H. Catalytic Hydrocarboxylation and hydroesterification reactions of 1,2-polybutadiene. Macromolecules 1996 , 29 , 1784−1788..

Coates, G. W.; Grubbs, R. H. Quantitative ring-closing metathesis of polyolefins. J. Am. Chem. Soc. 1996 , 118 , 229−230..

Pan, W.; Chen, H.; Mu, J.; Li, W.; Jiang, F.; Weng, G.; Hu, Y.; Gong, D.; Zhang, X. Synthesis of high crystalline syndiotactic 1,2-polybutadienes and study ontheir reinforcing effect on cis -1,4 polybutadiene. Polymer 2017 , 111 , 20−26..

Xie, T.; Tang, J.; Geng, J.; Wang, X.; Hua, J. Balance of the steric hindrance and solubility of alkoxy ligands for ultrahigh-activity molybdenum-based butadiene coordination polymerization. Polym. Chem. 2022 , 13 , 1712−1718..

Li, P.; Liu, K.; Zhang, B.; Liu, J.; Hua, J. m -Cresol-substituted triethyl aluminum/MoCl 5 /TBP catalytic system for coordination polymerization of butadiene. Iran. Polym. J . 2018, 27 , 537−544..

Bazzini, C.; Giarrusso, A.; Porri, L. Diethylbis(2,2′-bipyridine)iron/MAO. A very active and stereospecific catalyst for 1,3-diene polymerization. Macromol. Rapid Commun. 2002 , 23 , 922−927..

Luo, S.; Akron, O. H. Bridgestone Corporation. 2003 , U.S. Pat., 6528588 B2.

Gong, D.; Dong, W.; Hu, J.; Zhang, X.; Jiang, L. Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite. Polymer 2009 , 50 , 2826−2829..

Throckmorton, M. C.; Akron; Ohio. The Goodyear Tire & amp; Rubber Company, 1976 , U.S. Pat., 3936432.

Hsu, L., H.; F., Halasa, A., F. Preparation and characterization of crystalline 3,4-polyisoprene. Rubber Chem. Technol. 1994 , 67 , 865−870..

Swift, H. E.; Bozik, J. E.; Wu, C. Y. Specific catalysis with iron coordination complexes. J. Catal. 1970 , 17 , 331−340..

Sun, Q.; Wang, F. Synthesis of crystalline 3,4-polyisoperne with Fe-based catalyst system. Acta Polymerica Sinica (in Chinese) 1988 , 145−148..

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..

Gong, D.; Dong, W.; Hu, Y.; Bi, J.; Zhan, X.; Jiang, L. Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors. Polymer 2009 , 50 , 5980−5986..

Gong, D.; Pan, W.; Zhu, T.; Chen, H.; Zhou, Z.; Jiang, F.; Hu, Y.; Zhang, X. Polymerization of 1,3-butadiene catalyzed by a thermal robust, high selective and active iron catalyst: an applicable recipe for producing syndiotactic 1,2-polybutadiene. Polymer 2016 , 98 , 136−142..

Jing, C.; Wang, L.; Zhu, G.; Hou, H.; Zhou, L.; Wang, Q. Enhancing thermal stability in aminopyridine iron(II)-catalyzed polymerization of conjugated dienes. Organometallics 2020 , 39 , 4019−4026..

Hu, Z.; Xu, Y.; Hu, W.; Luo, W.; Zhao, Y.; Huang, W.; Gong, D. Synthesis and properties of syndiotactic 1,2-polybutadiene catalyzed by iron catalyst with phosphate as additive. J. Appl. Polym. Sci. 2020 , 138 , 49686−49694..

Fischbach, A.; Anwander, R. Rare-earth metals and aluminum getting close in Ziegler-type organometallics. in Neodymium based Ziegler catalysts fundamental chemistry . Springer Berlin Heidelberg, 2006 , 204 , 155−281..

Gong, D.; Liu, W.; Pan, W.; Chen, T.; Jia, X.; Huang, K.-W.; Zhang, X. Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts. J. Mol. Catal. A: Chem. 2015 , 406 , 78−84..

Yuan, Y.; Chen, B.; Zhang, X. Study on the formation of β -crystal during the crystallization process of polypropylene reactor granule. Polymer 2007 , 48 , 5480−5483..

Liu, J.; Li, Y.; Liu, J.; Li, Z. Ethylene polymerization with a highly active and long-lifetime macrocycle trinuclear 2,6-bis(imino)pyridyliron. Macromolecules 2005 , 38 , 2559−2563..

Yu, J.; Liu, H.; Zhang, W.; Hao, X.; Sun, W. H. Access to highly active and thermally stable iron procatalysts using bulky 2-[1-(2,6-dibenzhydryl-4-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl] pyridine ligands. Chem. Commun. 2011 , 47 , 3257−3259..

Burcher, B.; Breuil, P.-A. R.; Magna, L.; Olivier-Bourbigou, H. In Iron Catalysis II , Topics in Organometallic Chemistry. Iron-Catalyzed Oligomerization and Polymerization Reactions. Springer Cham , 2015 , 50 , 217−257..

Gong, D.; Ying, W.; Zhao, J.; Li, W.; Xu, Y.; Luo, Y.; Zhang, X.; Capacchione, C.; Grassi, A. Controlling external diphenylcyclohexylphosphine feeding to achieve cis -1,4-syn-1,2 sequence controlled polybutadienes via cobalt catalyzed 1,3-butadiene polymerization. J. Catal. 2019 , 377 , 367−377..

Dong, B.; Zhuang, R.; Zhang, C.; Zheng, W.; Zhang, H.; Hu, Y.; Sun, G.; Zhang, X. Living polymerization of 1,3-butadiene catalyzed by half-titanocene complex bearing dibenzhydryl-substituted aryloxide ligand. Chinese J. Polym. Sci. 2017 , 35 , 721−727..

Views

218

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Synergistic Spring-entanglement Network Design of High-modulus and Low-hysteresis Ionic Elastomers for High-fidelity Sensing

Dynamic Structural Colors in Helical Superstructures: from Supramolecules to Polymers

High Temperature Iron Ethylene Polymerization Catalysts Bearing N,N,N'-2-(1-(2,4-Dibenzhydryl-6-fluorophenylimino)ethyl)-6-(1-(arylphenylimino)ethyl)pyridines

Upgrading Commercially Available Polyethylene to High-value Materials with Strong Mechanical Performance and Hydrophilicity by Blending with Ethylene/meta-Methoxystyrene Copolymers

Sequence-encoded Conformation Pathways in Viscoelastic Microphase Separation of Multiblock Copolymers

Related Author

Pei-Yi Wu

Ting Cui

Jing-Ming Cai

Cun-Yi Li

Zhou-Yue Lei

Bo Ji

Lang Qin

Yan-Lei Yu

Related Institution

Department of Civil Engineering, Aalto University

State Key Laboratory of Advanced Fiber Materials, College of Chemistry and Chemical Engineering, Center for Advanced Low-Dimension Materials, Donghua University

State Key Laboratory of Digital Medical Engineering, School of Biological Science and Medical Engineering, Southeast University

School of Civil Engineering, Southeast University

School of Mechanical and Mechatronic Engineering, University of Technology Sydney, 817 Broadway, Ultimo

⁰