Activity Enhancement of MgCl<sub>2</sub>-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization

Matthieu Humbert; Sébastien Norsic; Jean Raynaud; Vincent Monteil

doi:10.1007/s10118-019-2335-8

Your Location：

Home >

Browse articles >

Activity Enhancement of MgCl₂-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization

ARTICLE | Updated：2021-02-18

- Activity Enhancement of MgCl₂-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization
- Chinese Journal of Polymer Science Vol. 37, Issue 10, Pages: 1031-1038(2019)
- Affiliations：
  
  UMR 5265 Laboratoire de Chimie Catalyse Polymères et Procédés (C2P2), Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS, Bat 308F, 43 Bd du 11 novembre 1918, Villeurbanne F-69616, France
- Author bio：
  
  jean.raynaud@univ-lyon1.fr (J.R.)
  vincent.monteil@univ-lyon1.fr (V.M.)
- Funds：
- DOI：10.1007/s10118-019-2335-8
  CLC：
- Received：23 May 2019，
  
  Revised：2019-7-16，
  
  Accepted：19 July 2019，
  
  Online First：23 August 2019，
  
  Published：2019-10
- Accepted：
Scan QR Code
Citation: Humbert, M.; Norsic, S.; Raynaud, J.; Monteil, V. Activity enhancement of MgCl₂-supported Ziegler-Natta catalysts by Lewis-acid pre-treatment for ethylene polymerization. Chinese J. Polym. Sci. 2019, 37, 1031–1038 DOI: 10.1007/s10118-019-2335-8.

Matthieu Humbert, Sébastien Norsic, Jean Raynaud, et al. Activity Enhancement of MgCl₂-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(10): 1031-1038. DOI: 10.1007/s10118-019-2335-8.
Citation: Humbert, M.; Norsic, S.; Raynaud, J.; Monteil, V. Activity enhancement of MgCl₂-supported Ziegler-Natta catalysts by Lewis-acid pre-treatment for ethylene polymerization. Chinese J. Polym. Sci. 2019, 37, 1031–1038 DOI: 10.1007/s10118-019-2335-8. DOI：

Matthieu Humbert, Sébastien Norsic, Jean Raynaud, et al. Activity Enhancement of MgCl₂-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(10): 1031-1038. DOI: 10.1007/s10118-019-2335-8. DOI：

摘要

Abstract

Ziegler-Natta precatalysts were synthetized from Lewis-base-modified-MgCl

supports and treated by various Lewis acids

prior to activation by triethylaluminum

in order to increase their activity in ethylene polymerization. BCl

provided the highest increase in activity. Interestingly

polymerization results showed no substantial modification of polymer properties

which is consistent with that Lewis acid only promotes the creation of new active sites

after activation by TEA

possessing very similar features to the original ones achievable with conventional precatalysts (

i.e

. without Lewis-acid treatment).

关键词

Keywords

references

Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H . Polymerisation von Äthylen und Anderen olefinen . Angew. Chem. , 1955 . 67 ( 16 ): 426 - 426 . .

Natta, G . Macromolecular chemistry: From sereospecific polymerization to asymmetric autocatalytic synthesis of macromolecules . Science , 1965 . 147 261 - 272 . DOI: 10.1126/science.147.3655.261 http://doi.org/10.1126/science.147.3655.261 .

Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G . Crystalline high polymers of α -olefins . J. Am. Chem. Soc. , 1955 . 77 ( 6 ): 1708 - 1710 . .

Kashiwa, N . The discovery and progress of MgCl 2 -supported TiCl 4 catalysts . J. Polym. Sci., Part A: Polym. Chem. , 2004 . 42 ( 1 ): 1 - 8 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

Böhm, L. L. in Polyolefins: 50 Years after Ziegler and Natta I . Kaminsky, W., Ed., Springer Berlin Heidelberg: Berlin, Heidelberg, 2013 , 257, pp. 59−79.

Moore, E. P. Jr. in Polypropylene handbook: Polymerization, characterization, properties, processing, applications . Hanser Gardner Publications, Munich; New York, Cincinnati, 1996 .

Grau, E.; Lesage, A.; Norsic, S.; Copéret, C.; Monteil, V.; Sautet, P . Tetrahydrofuran in TiCl 4 /THF/MgCl 2 : A non-innocent ligand for supported Ziegler-Natta polymerization catalysts . ACS Catal. , 2013 . 3 ( 1 ): 52 - 56 . DOI: 10.1021/cs300764h http://doi.org/10.1021/cs300764h .

Kim, I.; Kim, J. H.; Choi, H. K.; Chung, M. C.; Woo, S. I . Comonomer enhancement effect of 1-hexene in ethylene copolymerization catalyzed over MgCl 2 /THF/TiCl 4 catalysts . J. Appl. Polym. Sci. , 1993 . 48 ( 4 ): 721 - 730 . DOI: 10.1002/app.1993.070480414 http://doi.org/10.1002/app.1993.070480414 .

Czaja, K.; Białek, M . Microstructure of ethylene-1-hexene and ethylene-1-octene copolymers obtained over Ziegler-Natta catalysts supported on MgCl 2 (THF) 2 . Polymer , 2001 . 42 ( 6 ): 2289 - 2297 . DOI: 10.1016/S0032-3861(00)00621-2 http://doi.org/10.1016/S0032-3861(00)00621-2 .

Sobota, P . Metal-assembled compounds: Precursors of polymerization catalysts and new materials . Coord. Chem. Rev. , 2004 . 248 ( 11 ): 1047 - 1060 . .

Seenivasan, K.; Sommazzi, A.; Bonino, F.; Bordiga, S.; Groppo, E . Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator . Chem. Eur. J. , 2011 . 17 ( 31 ): 8648 - 8656 . DOI: 10.1002/chem.201100804 http://doi.org/10.1002/chem.201100804 .

Pirinen, S.; Koshevoy, I. O.; Denifl, P.; Pakkanen, T. T . A single-crystal model for MgCl 2 -electron donor support materials: [Mg 3 Cl 5 (THF) 4 Bu] 2 (Bu = n -Butyl) . Organometallics , 2013 . 32 ( 15 ): 4208 - 4213 . DOI: 10.1021/om400407p http://doi.org/10.1021/om400407p .

Pirinen, S.; Jayaratne, K.; Denifl, P.; Pakkanen, T. T . Ziegler-Natta catalysts supported on crystalline and amorphous MgCl 2 /THF complexes . J. Mol. Catal. A: Chem. , 2014 . 395 434 - 439 . DOI: 10.1016/j.molcata.2014.09.013 http://doi.org/10.1016/j.molcata.2014.09.013 .

Noto, V. D.; Marigo, A.; Viviani, M.; Marega, C.; Bresadola, S.; Zannetti, R . MgCl 2 -supported Ziegler-Natta catalysts: Synthesis and X-ray diffraction characterization of some MgCl 2 -Lewis base adducts . Makromol. Chem. , 1992 . 193 ( 1 ): 123 - 131 . DOI: 10.1002/macp.1992.021930112 http://doi.org/10.1002/macp.1992.021930112 .

Forte, M. C.; Coutinho, F. M. B . Highly active magnesium chloride supported Ziegler-Natta catalysts with controlled morphology . Eur. Polym. J. , 1996 . 32 ( 2 ): 223 - 231 . DOI: 10.1016/0014-3057(95)00124-7 http://doi.org/10.1016/0014-3057(95)00124-7 .

Sozzani, P.; Bracco, S.; Comotti, A.; Simonutti, R.; Camurati, I . Stoichiometric compounds of magnesium dichloride with ethanol for the supported Ziegler-Natta catalysis: First recognition and multidimensional MAS NMR study . J. Am. Chem. Soc. , 2003 . 125 ( 42 ): 12881 - 12893 . DOI: 10.1021/ja034630n http://doi.org/10.1021/ja034630n .

Thushara, K. S.; Mathew, R.; Ajithkumar, T. G.; Rajamohanan, P. R.; Bhaduri, S.; Gopinath, C. S . MgCl 2 ·4(CH 3 ) 2 CHOH: A new molecular adduct and super active polymerization catalyst support . J. Phys. Chem. C , 2009 . 113 ( 20 ): 8556 - 8559 . DOI: 10.1021/jp9026546 http://doi.org/10.1021/jp9026546 .

Malizia, F.; Fait, A.; Cruciani, G . Crystal structures of Ziegler-Natta catalyst supports . Chem. Eur. J. , 2011 . 17 ( 49 ): 13892 - 13897 . DOI: 10.1002/chem.v17.49 http://doi.org/10.1002/chem.v17.49 .

Thushara, K. S.; Gnanakumar, E. S.; Mathew, R.; Ajithkumar, T. G.; Rajamohanan, P. R.; Bhaduri, S.; Gopinath, C. S . MgCl 2 ·4((CH 3 ) 2 CHCH 2 OH): A new molecular adduct for the preparation of TiCl x /MgCl 2 catalyst for olefin polymerization . Dalton Trans. , 2012 . 41 ( 37 ): 11311 - 11318 . DOI: 10.1039/c2dt31211e http://doi.org/10.1039/c2dt31211e .

D’Anna, V.; Norsic, S.; Gajan, D.; Sanders, K.; Pell, A. J.; Lesage, A.; Monteil, V.; Copéret, C.; Pintacuda, G.; Sautet, P . Structural characterization of the EtOH-TiCl 4 -MgCl 2 Ziegler-Natta precatalyst . J. Phys. Chem. C , 2016 . 120 18075 DOI: 10.1021/acs.jpcc.6b05313 http://doi.org/10.1021/acs.jpcc.6b05313 .

Credendino, R.; Liguori, D.; Fan, Z.; Morini, G.; Cavallo, L . Toward a unified model explaining heterogeneous Ziegler-Natta catalysis . ACS Catal. , 2015 . 5 ( 9 ): 5431 - 5435 . DOI: 10.1021/acscatal.5b01076 http://doi.org/10.1021/acscatal.5b01076 .

Blaakmeer, E. S. (Merijn); Antinucci, G.; Busico, V.; van Eck, E. R. H.; Kentgens, A. P. M . Solid-state NMR investigations of MgCl 2 catalyst support . J. Phys. Chem. C , 2016 . 120 ( 11 ): 6063 - 6074 . DOI: 10.1021/acs.jpcc.5b12606 http://doi.org/10.1021/acs.jpcc.5b12606 .

Philippaerts, A.; Ensinck, R.; Baulu, N.; Cordier, A.; Woike, K.; Berthoud, R.; De Cremer, G.; Severn, J. R . Influence of the particle size of the MgCl 2 support on the performance of Ziegler catalysts in the polymerization of ethylene to ultra‐high molecular weight polyethylene and the resulting polymer properties . J. Polym. Sci., Part A: Polym. Chem. , 2017 . 55 2679 DOI: 10.1002/pola.v55.16 http://doi.org/10.1002/pola.v55.16 .

Ribour, D.; Monteil, V.; Spitz, R . Detitanation of MgCl 2 -supported Ziegler-Natta catalysts for the study of active sites organization . J. Polym. Sci., Part A: Polym. Chem. , 2008 . 46 ( 16 ): 5461 - 5470 . DOI: 10.1002/pola.v46:16 http://doi.org/10.1002/pola.v46:16 .

Ribour, D.; Monteil, V.; Spitz, R . Strong activation of MgCl 2 -supported Ziegler-Natta catalysts by treatments with BCl 3 : Evidence and application of the " cluster” model of active sites . J. Polym. Sci., Part A: Polym. Chem. , 2009 . 47 ( 21 ): 5784 - 5791 . DOI: 10.1002/pola.v47:21 http://doi.org/10.1002/pola.v47:21 .

Ribour, D.; Spitz, R.; Monteil, V . Modifications of the active sites distribution in the Ziegler-Natta polymerization of propylene using Lewis acids . J. Polym. Sci., Part A: Polym. Chem. , 2010 . 48 2631 - 2635 . DOI: 10.1002/pola.v48:12 http://doi.org/10.1002/pola.v48:12 .

Kobayashi, S.; Busujima, T.; Nagayama, S . A novel classification of Lewis acids on the basis of activity and selectivity . Chem. Eur. J. , 2000 . 6 ( 19 ): 3491 - 3494 . DOI: 10.1002/1521-3765(20001002)6:19<3491::AID-CHEM3491>3.3.CO;2-G http://doi.org/10.1002/1521-3765(20001002)6:19<3491::AID-CHEM3491>3.3.CO;2-G .

Hilt, G.; Pünner, F.; Möbus, J.; Naseri, V.; Bohn, M. A . A Lewis acidity scale in relation to rate constants of Lewis acid catalyzed organic reactions . Eur. J. Org. Chem. , 2011 . 5962 - 5966 . .

Soares, J. B. P.; McKenna, T. F. L. in Polyolefin reaction engineering, first edition , Wiley-VCH Verlag GmbH & amp; Co., 2012 , p.163.

Kissin, Y. V . Main kinetic features of ethylene polymerization reactions with heterogeneous Ziegler-Natta catalysts in the light of a multicenter reaction mechanism . J. Polym. Sci., Part A: Polym. Chem. , 2001 . 39 ( 10 ): 1681 - 1695 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Alkyl Alcohol Chain-length Mediated Steric Hindrance at Support Surface in Heterogeneous α-Diimine Ni Catalysts for Modulating Ethylene Polymerization

Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization

High-Performance α-Diimine Nickel Complexes for Facile Access of PE Elastomers with Exceptional Material Properties

Peculiarities of Ethylene Polymerization Reactions with Bis(imino)pyridyl Complexes of CoCl2 and FeCl2

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

Related Author

Fan Yu

Bin Dai

Ning Liu

Bin-Yuan Liu

Chen Zou

Ming Zhou

Meng-Yuan Xue

Ping-Zhou Huang

Related Institution

Hebei Key Laboratory of Functional Polymer, School of Chemical Engineering and Technology, Hebei University of Technology

State Key Laboratory of Precision and Intelligent Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China

School of Chemistry and Chemical Engineering/State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, Shihezi University

Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Chemical and Environmental Engineering, Jianghan University

Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central Minzu University

⁰

Activity Enhancement of MgCl2-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization

DOI：10.1007/s10118-019-2335-8

摘要

Abstract

关键词

Keywords

references

Activity Enhancement of MgCl₂-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization