ACS Publications. Most Trusted. Most Cited. Most Read
Stoichiometric Compounds of Magnesium Dichloride with Ethanol for the Supported Ziegler−Natta Catalysis:  First Recognition and Multidimensional MAS NMR Study

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2003, 125, 42, 12881-12893
    Article

    Stoichiometric Compounds of Magnesium Dichloride with Ethanol for the Supported Ziegler−Natta Catalysis:  First Recognition and Multidimensional MAS NMR Study
    Click to copy article linkArticle link copied!

    View Author Information
    Contribution from the Department of Materials Science, University of Milano−Bicocca, Via R. Cozzi 53, 20125 Milan, Italy, and Basell Polyolefins Italia, G. Natta Research Center, P.le G. Donegani 12, I-44100 Ferrara, Italy
    Other Access OptionsSupporting Information (2)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2003, 125, 42, 12881–12893
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja034630n
    Published September 30, 2003
    Copyright © 2003 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Ethanol associates easily with MgCl2 to form adducts of complex architecture, but until now available characterization methods have failed to identify the pure stoichiometric compounds and their structures. To remedy this, we set about applying homonuclear and heteronuclear 2D correlated solid-state NMR spectroscopy to identify the pure compounds and the ethanol-to-magnesium coordination pattern. High spinning speed and Lee-Goldburg sequences were able to reduce the hydrogen spin-diffusion and homonuclear coupling in the crystalline solid, thus achieving high resolution also in the hydrogen domain. On this basis, the pure adducts, of interest as catalyst supports for Ziegler−Natta polymerization, were isolated for the first time. Magnesium coordination sites with given numbers of ligands and their multiplicity in the crystal cells were determined in the new-found stoichiometric complexes. Variable temperature and 2D carbon−carbon exchange NMR, as well as relaxation times in the fast motion regime, revealed the disordering phenomena generated by ethanol dynamics in the crystal. Decoding the intriguing polymorphysm of the precursors permits to trace the genealogy of tailored MgCl2 titanate granules, active as highly productive catalysts for the stereospecific polymerization of olefins.

    Copyright © 2003 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

    †

     University of Milano − Bicocca and INSTM UdR Milano.

    ‡

     Basell S.p.a.

    Supporting Information Available

    Click to copy section linkSection link copied!

    The additional information is constituted by a background and pulse sequences for Solid State 2D NMR Experiments (Figure S1); micrograph reporting the microsphere powder morphology (Figure S2); linear correlation of weighed average chemical shift of 13C CP MAS NMR spectra vs composition of samples h−l. (Figure S3); XRD profiles of the pure adducts and mixtures (Figure S4); 13C CP MAS NMR spectra of hydrated samples (Figure S5); XRD profiles of hydrated samples (Figure S6); 2D PMLG NMR spectrum of MgCl2·6EtOH sample (Figure S7); DSC scans of the pure adducts (Figure S8); DSC scans of samples i, j, and k (S9); DSC scans and thermal cycles of 2MgCl2·3EtOH sample (S10). This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 86 publications.

    1. Wei Xu, Cheng Zhang, Hongtao Shen, Xinxia Ma, Zhihai Cheng, Jiang Wu, Qunzhi Zhu, Jia Lin, Zaiguo Fu, Hongying Deng. Surface Oxalate Coordination: Facilitating Basic OER Activity by Regulating the Electronic Structure of Fe–Ni3S2. ACS Sustainable Chemistry & Engineering 2022, 10 (44) , 14396-14406. https://doi.org/10.1021/acssuschemeng.2c02456
    2. Ryan J. Witzke, Alon Chapovetsky, Matthew P. Conley, David M. Kaphan, Massimiliano Delferro. Nontraditional Catalyst Supports in Surface Organometallic Chemistry. ACS Catalysis 2020, 10 (20) , 11822-11840. https://doi.org/10.1021/acscatal.0c03350
    3. Zhen Yue, Ning Wang, Yu Cao, Wei Li, Chuan-ding Dong. Reduced Entanglement Density of Ultrahigh-Molecular-Weight Polyethylene Favored by the Isolated Immobilization on the MgCl2 (110) Plane. Industrial & Engineering Chemistry Research 2020, 59 (8) , 3351-3358. https://doi.org/10.1021/acs.iecr.9b06780
    4. Bing Xue, Lei Hui, Huaqin Yang, Yulai Zhao, Linxi Hou, and Wei Li . Immobilization of Ziegler–Natta Catalyst for Ethylene Polymerization on Macropores SiO2 with an Open-Framework Structure. Industrial & Engineering Chemistry Research 2017, 56 (1) , 135-142. https://doi.org/10.1021/acs.iecr.6b03993
    5. V. D’Anna, S. Norsic, D. Gajan, K. Sanders, A. J. Pell, A. Lesage, V. Monteil, C. Copéret, G. Pintacuda, and P. Sautet . Structural Characterization of the EtOH–TiCl4–MgCl2 Ziegler–Natta Precatalyst. The Journal of Physical Chemistry C 2016, 120 (32) , 18075-18087. https://doi.org/10.1021/acs.jpcc.6b05313
    6. Christophe Copéret, Aleix Comas-Vives, Matthew P. Conley, Deven P. Estes, Alexey Fedorov, Victor Mougel, Haruki Nagae, Francisco Núñez-Zarur, and Pavel A. Zhizhko . Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities. Chemical Reviews 2016, 116 (2) , 323-421. https://doi.org/10.1021/acs.chemrev.5b00373
    7. Irene Bassanetti, Angiolina Comotti, Piero Sozzani, Silvia Bracco, Gianluca Calestani, Francesco Mezzadri, and Luciano Marchiò . Porous Molecular Crystals by Macrocyclic Coordination Supramolecules. Journal of the American Chemical Society 2014, 136 (42) , 14883-14895. https://doi.org/10.1021/ja507555j
    8. K. S. Thushara, T. G. Ajithkumar, P. R. Rajamohanan, and Chinnakonda S. Gopinath . Solid-State NMR Investigations of a MgCl2·4(CH3)2CHCH2OH Molecular Adduct: A Peculiar Case of Reversible Equilibrium between Two Phases. The Journal of Physical Chemistry A 2014, 118 (7) , 1213-1219. https://doi.org/10.1021/jp412331s
    9. Fabio Capone, Luca Rongo, Maddalena D’Amore, Peter H. M. Budzelaar, and Vincenzo Busico . Periodic Hybrid DFT Approach (Including Dispersion) to MgCl2-Supported Ziegler–Natta Catalysts. 2. Model Electron Donor Adsorption on MgCl2 Crystal Surfaces. The Journal of Physical Chemistry C 2013, 117 (46) , 24345-24353. https://doi.org/10.1021/jp406977h
    10. Sami Pirinen, Igor O. Koshevoy, Peter Denifl, and Tuula T. Pakkanen . A Single-Crystal Model for MgCl2–Electron Donor Support Materials: [Mg3Cl5(THF)4Bu]2 (Bu = n-Butyl). Organometallics 2013, 32 (15) , 4208-4213. https://doi.org/10.1021/om400407p
    11. Edwin S. Gnanakumar, Ravikumar R. Gowda, Shrikant Kunjir, T. G. Ajithkumar, P. R. Rajamohanan, Debashis Chakraborty, and Chinnakonda S. Gopinath . MgCl2·6CH3OH: A Simple Molecular Adduct and Its Influence As a Porous Support for Olefin Polymerization. ACS Catalysis 2013, 3 (3) , 303-311. https://doi.org/10.1021/cs300730j
    12. Etienne Grau, Anne Lesage, Sébastien Norsic, Christophe Copéret, Vincent Monteil, and Philippe Sautet . Tetrahydrofuran in TiCl4/THF/MgCl2: a Non-Innocent Ligand for Supported Ziegler–Natta Polymerization Catalysts. ACS Catalysis 2013, 3 (1) , 52-56. https://doi.org/10.1021/cs300764h
    13. Edwin S. Gnanakumar, K. S. Thushara, Ravikumar R. Gowda, Sumesh K. Raman, T. G. Ajithkumar, P. R. Rajamohanan, Debashis Chakraborty, and Chinnakonda S. Gopinath . MgCl2·6C6H11OH: A High Mileage Porous Support for Ziegler–Natta Catalyst. The Journal of Physical Chemistry C 2012, 116 (45) , 24115-24122. https://doi.org/10.1021/jp3074078
    14. Lukáš Kobr, Ke Zhao, Yongqiang Shen, Angiolina Comotti, Silvia Bracco, Richard K. Shoemaker, Piero Sozzani, Noel A. Clark, John C. Price, Charles T. Rogers, and Josef Michl . Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors. A Surface Inclusion. Journal of the American Chemical Society 2012, 134 (24) , 10122-10131. https://doi.org/10.1021/ja302173y
    15. Ajin V. Cheruvathur, Ernie H. G. Langner, J. W. (Hans) Niemantsverdriet, and Peter C. Thüne . In Situ ATR-FTIR Studies on MgCl2-Diisobutyl Phthalate Interactions in Thin Film Ziegler–Natta Catalysts. Langmuir 2012, 28 (5) , 2643-2651. https://doi.org/10.1021/la203972k
    16. Raffaele Credendino, Jochem T. M. Pater, Andrea Correa, Giampiero Morini, and Luigi Cavallo . Thermodynamics of Formation of Uncovered and Dimethyl Ether-Covered MgCl2 Crystallites. Consequences in the Structure of Ziegler–Natta Heterogeneous Catalysts. The Journal of Physical Chemistry C 2011, 115 (27) , 13322-13328. https://doi.org/10.1021/jp201410n
    17. Silvia Bracco, Angiolina Comotti, Lisa Ferretti, and Piero Sozzani . Supramolecular Aggregation of Block Copolymers in the Solid State As Assisted by the Selective Formation of Inclusion Crystals. Journal of the American Chemical Society 2011, 133 (23) , 8982-8994. https://doi.org/10.1021/ja201551n
    18. K. S. Thushara, Edwin S. Gnanakumar, Renny Mathew, Ratnesh K. Jha, T. G. Ajithkumar, P. R. Rajamohanan, Krishna Sarma, Sudhakar Padmanabhan, Sumit Bhaduri, and Chinnakonda S. Gopinath . Toward an Understanding of the Molecular Level Properties of Ziegler−Natta Catalyst Support with and without the Internal Electron Donor. The Journal of Physical Chemistry C 2011, 115 (5) , 1952-1960. https://doi.org/10.1021/jp1078289
    19. K. S. Thushara, Renny Mathew, T. G. Ajithkumar, P. R. Rajamohanan, Sumit Bhaduri and Chinnakonda S. Gopinath . MgCl2·4(CH3)2CHOH: A New Molecular Adduct and Super Active Polymerization Catalyst Support. The Journal of Physical Chemistry C 2009, 113 (20) , 8556-8559. https://doi.org/10.1021/jp9026546
    20. Yu-Chi Pan, Hao-Yiang Wu, Guang-Liang Jheng, Hui-Hsu Gavin Tsai and Hsien-Ming Kao . Ordered and Hydrothermally Stable Cubic Periodic Mesoporous Organosilicas with SBA-1 Mesostructures: Synthesis, Characterization, Solid-State NMR Spectroscopy, and DFT Calculations. The Journal of Physical Chemistry C 2009, 113 (7) , 2690-2698. https://doi.org/10.1021/jp807534m
    21. Hsien-Ming Kao, Chia-Hsiu Liao, Tzu-Ti Hung, Yu-Chi Pan and Anthony S. T. Chiang . Direct Synthesis and Solid-State NMR Characterization of Cubic Mesoporous Silica SBA-1 Functionalized with Phenyl Groups. Chemistry of Materials 2008, 20 (6) , 2412-2422. https://doi.org/10.1021/cm800147z
    22. Bosen Qin, Qiaoyang Sun, Lei Yuan, Tianpeng Wen, Jingkun Yu, Shaowei Zhang. A refractories binder derived from modified magnesium chloride hydrate. Journal of the European Ceramic Society 2025, 45 (2) , 116926. https://doi.org/10.1016/j.jeurceramsoc.2024.116926
    23. Yi Liu. Assessing operational stability in condensed-mode fluidized bed reactor for linear low density polyethylene production: Insights from a thermoregulating water valve malfunction analysis. Journal of Elastomers & Plastics 2024, 56 (5) , 661-674. https://doi.org/10.1177/00952443241258450
    24. Qingtao Niu, Aihua He, Chongdian Si, Guodong Liu, Mingxuan Xiao, Guifan Chen, Manman Jin. Influence of titanium loading of TiCl4/MgCl2 Ziegler-Natta catalyst on Trans-1,4 polymerization of isoprene. Polymer 2024, 307 , 127317. https://doi.org/10.1016/j.polymer.2024.127317
    25. Qiaoyang Sun, Lixin Jiang, Tianpeng Wen, Lei Yuan, Jingkun Yu. Structure–property relations of recrystallized products from magnesium chloride ethanol solution: aiming at recycling magnesium resources from nature. Journal of the Australian Ceramic Society 2024, 60 (2) , 553-561. https://doi.org/10.1007/s41779-023-00936-1
    26. Mohammadreza Mehdizadeh, Fereshteh Karkhaneh, Mehdi Nekoomanesh, Samahe Sadjadi, Mehrsa Emami, HamidReza Teimoury, Mehrdad Salimi, Miquel Solà, Albert Poater, Naeimeh Bahri-Laleh, Sergio Posada-Pérez. Influence of the Ethanol Content of Adduct on the Comonomer Incorporation of Related Ziegler–Natta Catalysts in Propylene (Co)polymerizations. Polymers 2023, 15 (23) , 4476. https://doi.org/10.3390/polym15234476
    27. Reza Bazvand, Naeimeh Bahri-Laleh, Hossein Abedini, Mehdi Nekoomanesh, Albert Poater. Exploring microstructure of MgCl2·nEtOH adducts for Ziegler-Natta catalysts. Journal of Molecular Structure 2023, 1291 , 136098. https://doi.org/10.1016/j.molstruc.2023.136098
    28. Yi Luo, Zhenglin He, Huayan Yang, Yunzhang Li, Dongting Yue, Zehui Zhang, Guosheng Shi. Unexpected higher corrosion in the gas phase region of metals caused by calcium and magnesium ions compared to sodium ions. Physical Chemistry Chemical Physics 2023, 25 (32) , 21428-21435. https://doi.org/10.1039/D3CP01571H
    29. Farshid Nouri‐Ahangarani, Naeimeh Bahri‐Laleh, Hossein Abedini, Mehdi Nekoomanesh. Effect of adduct synthesis parameters on the ethylene polymerization kinetics of Ziegler Natta catalysts. Journal of Applied Polymer Science 2023, 140 (28) https://doi.org/10.1002/app.54053
    30. Xianshu Qiao, Hongjun Kang, Yang Li, Kai Cui, Xin Jia, Xiaohong Wu, Wei Qin. Novel FeNi‐Based Nanowires Network Catalyst Involving Hydrophilic Channel for Oxygen Evolution Reaction. Small 2022, 18 (10) https://doi.org/10.1002/smll.202106378
    31. Jacopo Perego, Silvia Bracco, Angiolina Comotti, Daniele Piga, Irene Bassanetti, Piero Sozzani. Anionic Polymerization in Porous Organic Frameworks: A Strategy to Fabricate Anchored Polymers and Copolymers. Angewandte Chemie 2021, 133 (11) , 6182-6188. https://doi.org/10.1002/ange.202014975
    32. Jacopo Perego, Silvia Bracco, Angiolina Comotti, Daniele Piga, Irene Bassanetti, Piero Sozzani. Anionic Polymerization in Porous Organic Frameworks: A Strategy to Fabricate Anchored Polymers and Copolymers. Angewandte Chemie International Edition 2021, 60 (11) , 6117-6123. https://doi.org/10.1002/anie.202014975
    33. Matthieu Humbert, Sébastien Norsic, Jean Raynaud, Vincent Monteil. Activity Enhancement of MgCl2-supported Ziegler-Natta Catalysts by Lewis-acid Pre-treatment for Ethylene Polymerization. Chinese Journal of Polymer Science 2019, 37 (10) , 1031-1038. https://doi.org/10.1007/s10118-019-2335-8
    34. John R. Severn. Recent Developments in Supported Polyolefin Catalysts: A Review. 2019, 1-53. https://doi.org/10.1007/978-3-030-03476-4_1
    35. Alessandro Piovano, Paul Pletcher, Marjolein E. Z. Velthoen, Silvia Zanoni, Sang‐Ho Chung, Koen Bossers, Maarten K. Jongkind, Gianluca Fiore, Elena Groppo, Bert M. Weckhuysen. Genesis of MgCl 2 ‐based Ziegler‐Natta Catalysts as Probed with Operando Spectroscopy. ChemPhysChem 2018, 19 (20) , 2662-2671. https://doi.org/10.1002/cphc.201800592
    36. Naeimeh Bahri-Laleh, Ahad Hanifpour, Seyed Amin Mirmohammadi, Albert Poater, Mehdi Nekoomanesh-Haghighi, Giovanni Talarico, Luigi Cavallo. Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization. Progress in Polymer Science 2018, 84 , 89-114. https://doi.org/10.1016/j.progpolymsci.2018.06.005
    37. Ziaul Haque Ansari, Yan Zeng, George P. Demopoulos, Zhibao Li. Nucleation kinetics of MgCl 2 –ethanol adduct for the supported Ziegler–Natta catalysts with a thermodynamic approach. Journal of Crystal Growth 2018, 494 , 44-52. https://doi.org/10.1016/j.jcrysgro.2018.05.007
    38. Yury V. Kissin, Thomas E. Nowlin, Robert I. Mink. Supported Titanium/Magnesium Ziegler Catalysts for the Production of Polyethylene. 2018, 189-227. https://doi.org/10.1002/9781119242277.ch8
    39. John Severn, Robert L. Jones. Stereospecific α‐Olefin Polymerization with Heterogeneous Catalysts. 2018, 229-312. https://doi.org/10.1002/9781119242277.ch9
    40. Wei Li, Lei Hui, Bing Xue, Chuanding Dong, Yuming Chen, Linxi Hou, Binbo Jiang, Jingdai Wang, Yongrong Yang. Facile high-temperature synthesis of weakly entangled polyethylene using a highly activated Ziegler-Natta catalyst. Journal of Catalysis 2018, 360 , 145-151. https://doi.org/10.1016/j.jcat.2018.01.024
    41. Yury V. Kissin. Catalysts for the Manufacture of Polyethylene. 2017, 25-60. https://doi.org/10.1002/9781119159797.ch2
    42. K. S. Thushara, Maddalena D'Amore, Alessandro Piovano, Silvia Bordiga, Elena Groppo. The Influence of Alcohols in Driving the Morphology of Magnesium Chloride Nanocrystals. ChemCatChem 2017, 9 (10) , 1782-1787. https://doi.org/10.1002/cctc.201700101
    43. A. Comotti, S. Bracco, P. Sozzani. Solid-State NMR of Supramolecular Materials. 2017, 75-99. https://doi.org/10.1016/B978-0-12-409547-2.12494-1
    44. S. Bracco, T. Miyano, M. Negroni, I. Bassanetti, L. Marchio', P. Sozzani, N. Tohnai, A. Comotti. CO 2 regulates molecular rotor dynamics in porous materials. Chemical Communications 2017, 53 (55) , 7776-7779. https://doi.org/10.1039/C7CC02983G
    45. V. H. Nissinen, I. O. Koshevoy, T. T. Pakkanen. Crystalline magnesium chloride–electron donor complexes: new support materials for Ziegler–Natta catalysts. Dalton Transactions 2017, 46 (13) , 4452-4460. https://doi.org/10.1039/C7DT00193B
    46. Silvia Bracco, Daniele Piga, Irene Bassanetti, Jacopo Perego, Angiolina Comotti, Piero Sozzani. Porous 3D polymers for high pressure methane storage and carbon dioxide capture. Journal of Materials Chemistry A 2017, 5 (21) , 10328-10337. https://doi.org/10.1039/C7TA00934H
    47. Tatiana B. Mikenas, Evgeny I. Koshevoy, Svetlana V. Cherepanova, Vladimir A. Zakharov. Study of the composition and morphology of new modifications of titanium‐magnesium catalysts with improved properties in ethylene polymerization. Journal of Polymer Science Part A: Polymer Chemistry 2016, 54 (16) , 2545-2558. https://doi.org/10.1002/pola.28132
    48. Angiolina Comotti, Silvia Bracco, Mario Beretta, Jacopo Perego, Mauro Gemmi, Piero Sozzani. Confined Polymerization in Highly Ordered Mesoporous Organosilicas. Chemistry – A European Journal 2015, 21 (50) , 18209-18217. https://doi.org/10.1002/chem.201503553
    49. Koen C.H. Tijssen, E.S. (Merijn) Blaakmeer, Arno P.M. Kentgens. Solid-state NMR studies of Ziegler–Natta and metallocene catalysts. Solid State Nuclear Magnetic Resonance 2015, 68-69 , 37-56. https://doi.org/10.1016/j.ssnmr.2015.04.002
    50. Sami Pirinen, Kumudini Jayaratne, Peter Denifl, Tuula T. Pakkanen. Ziegler–Natta catalysts supported on crystalline and amorphous MgCl2/THF complexes. Journal of Molecular Catalysis A: Chemical 2014, 395 , 434-439. https://doi.org/10.1016/j.molcata.2014.09.013
    51. . Polymerization and Selective Oligomerization of Alkenes. 2014, 167-200. https://doi.org/10.1002/9781118872369.ch6
    52. K.S. Thushara, T.G. Ajithkumar, P.R. Rajamohanan, Chinnakonda S. Gopinath. Structural investigations of porous MgCl2–2-butanol molecular adduct as support for olefin polymerization. Applied Catalysis A: General 2014, 469 , 267-274. https://doi.org/10.1016/j.apcata.2013.10.002
    53. Edwin S. Gnanakumar, Eswara Rao Chokkapu, Shrikant Kunjir, T. G. Ajithkumar, P. R. Rajamohanan, Debashis Chakraborty, Chinnakonda S. Gopinath. 9-Fluorenemethanol: an internal electron donor to fine tune olefin polymerization activity. Dalton Transactions 2014, 43 (24) , 9143. https://doi.org/10.1039/c4dt00793j
    54. Anatolii D. Pomogailo, Gulzhian I. Dzhardimalieva. Physical Chemistry of Intercalated System. 2014, 205-286. https://doi.org/10.1007/978-90-481-2567-8_5
    55. Harri Heikkinen, Tiina Liitiä, Ville Virkkunen, Timo Leinonen, Tuulamari Helaja, Peter Denifl. Solid state 13C NMR characterisation study on fourth generation Ziegler–Natta catalysts. Solid State Nuclear Magnetic Resonance 2012, 43-44 , 36-41. https://doi.org/10.1016/j.ssnmr.2012.02.006
    56. Maddalena D’Amore, Raffaele Credendino, Peter H.M. Budzelaar, Mauro Causá, Vincenzo Busico. A periodic hybrid DFT approach (including dispersion) to MgCl2-supported Ziegler–Natta catalysts – 1: TiCl4 adsorption on MgCl2 crystal surfaces. Journal of Catalysis 2012, 286 , 103-110. https://doi.org/10.1016/j.jcat.2011.10.018
    57. K. S. Thushara, Edwin S. Gnanakumar, Renny Mathew, T. G. Ajithkumar, P. R. Rajamohanan, Sumit Bhaduri, Chinnakonda S. Gopinath. MgCl2·4((CH3)2CHCH2OH): A new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization. Dalton Transactions 2012, 41 (37) , 11311. https://doi.org/10.1039/c2dt31211e
    58. Lidiane A. Almeida, Maria de Fátima V. Marques. Synthesis of a TiCl 4 Ziegler‐Natta Catalyst Supported on Spherical MgCl 2  ·  n EtOH for the Polymerization of Ethylene and Propylene. Macromolecular Reaction Engineering 2012, 6 (1) , 57-64. https://doi.org/10.1002/mren.201100049
    59. Federica Malizia, Anna Fait, Giuseppe Cruciani. Crystal Structures of Ziegler–Natta Catalyst Supports. Chemistry – A European Journal 2011, 17 (49) , 13892-13897. https://doi.org/10.1002/chem.201101900
    60. Supanan Patthamasang, Bunjerd Jongsomjit, Piyasan Praserthdam. Effect of EtOH/MgCl2 Molar Ratios on the Catalytic Properties of MgCl2-SiO2/TiCl4 Ziegler-Natta Catalyst for Ethylene Polymerization. Molecules 2011, 16 (10) , 8332-8342. https://doi.org/10.3390/molecules16108332
    61. Hui-Hsu Gavin Tsai, Po-Jui Chiu, Guang-Liang Jheng, Chun-Chiang Ting, Yu-Chi Pan, Hsien-Ming Kao. Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups. Journal of Colloid and Interface Science 2011, 359 (1) , 86-94. https://doi.org/10.1016/j.jcis.2011.03.072
    62. Wen Qing Huang, Xi Zhao, Ying Zhang, Wan Tai Yang. Characterization of MgCl2/Alcohol Based Ziegler−Natta Catalyst and its Precursors. Advanced Materials Research 2011, 233-235 , 1568-1574. https://doi.org/10.4028/www.scientific.net/AMR.233-235.1568
    63. Xiaoheng ZHU, Zifang GUO, Wei CEN, Bingquan MAO. Ethylene Polymerization Using Improved Polyethylene Catalyst. Chinese Journal of Chemical Engineering 2011, 19 (1) , 52-56. https://doi.org/10.1016/S1004-9541(09)60176-2
    64. Edwin S. Gnanakumar, K. S. Thushara, Deu S. Bhange, Renny Mathew, T. G. Ajithkumar, P. R. Rajamohanan, Sumit Bhaduri, Chinnakonda S. Gopinath. MgCl2.6PhCH2OH – A new molecular adduct as support material for Ziegler–Natta catalyst: synthesis, characterization and catalytic activity. Dalton Transactions 2011, 40 (41) , 10936. https://doi.org/10.1039/c1dt10786k
    65. , Maria de Fatima Marques, Lidiane Almeida, , Kamilla Cruz, . Influence of the Preparation Technique of MgCl2/TiCl4 Ziegler-Natta Catalyst on the Performance in Ethylene and Propylene Polymerization. Chemistry & Chemical Technology 2010, 4 (4) , 291-296. https://doi.org/10.23939/chcht04.04.291
    66. . Ziegler‐Natta Polymerization. 2010, 3144-3157. https://doi.org/10.1002/9780470638859.conrr695
    67. Ebrahim Jalali Dil, Saeed Pourmahdian, Mohammad Vatankhah, Faramarz Afshar Taromi. Effect of dealcoholation of support in MgCl2-supported Ziegler–Natta catalysts on catalyst activity and polypropylene powder morphology. Polymer Bulletin 2010, 64 (5) , 445-457. https://doi.org/10.1007/s00289-009-0156-6
    68. John Severn, Robert L. Jones. Stereospecific α‐Olefin Polymerization with Heterogeneous Catalysts. 2010, 157-230. https://doi.org/10.1002/9780470504437.ch7
    69. Rubin Huang, Federica Malizia, Gianni Pennini, Cor E. Koning, John C. Chadwick. Effects of MgCl 2 Crystallographic Structure on Active Centre Formation in Immobilized Single‐Centre and Ziegler–Natta Catalysts for Ethylene Polymerization. Macromolecular Rapid Communications 2008, 29 (21) , 1732-1738. https://doi.org/10.1002/marc.200800456
    70. Angiolina Comotti, Silvia Bracco, Piero Sozzani, Satoshi Horike, Ryotaro Matsuda, Jinxi Chen, Masaki Takata, Yoshiki Kubota, Susumu Kitagawa. Nanochannels of Two Distinct Cross-Sections in a Porous Al-Based Coordination Polymer. Journal of the American Chemical Society 2008, 130 (41) , 13664-13672. https://doi.org/10.1021/ja802589u
    71. Cristina Coelho, João Rocha, P.K. Madhu, Luís Mafra. Practical aspects of Lee–Goldburg based CRAMPS techniques for high-resolution 1H NMR spectroscopy in solids: Implementation and applications. Journal of Magnetic Resonance 2008, 194 (2) , 264-282. https://doi.org/10.1016/j.jmr.2008.07.019
    72. Xue Jiang, Xiuzhi Tian, Zhiqiang Fan. Crystal structure of ball-milled mixture of sodium chloride and magnesium chloride–ethanol adduct. Materials Research Bulletin 2008, 43 (2) , 343-352. https://doi.org/10.1016/j.materresbull.2007.03.007
    73. Angiolina Comotti, Silvia Bracco, Patrizia Valsesia, Lisa Ferretti, Piero Sozzani. 2D Multinuclear NMR, Hyperpolarized Xenon and Gas Storage in Organosilica Nanochannels with Crystalline Order in the Walls. Journal of the American Chemical Society 2007, 129 (27) , 8566-8576. https://doi.org/10.1021/ja071348y
    74. L. Resconi, J.C. Chadwick, L. Cavallo. Olefin Polymerizations with Group IV Metal Catalysts. 2007, 1005-1166. https://doi.org/10.1016/B0-08-045047-4/00065-0
    75. Yury Kissin. Chapter 4 Synthesis, Chemical Composition, and Structure of Transition Metal Components and Cocatalysts in Catalyst Systems for Alkene Polymerization. 2007, 207-290. https://doi.org/10.1016/S0167-2991(07)00004-3
    76. Yury Kissin. Chapter 5 Kinetics of Alkene Polymerization Reactions with Transition Metal Catalysts. 2007, 291-417. https://doi.org/10.1016/S0167-2991(07)00005-5
    77. L. A. Utracki, M. Sepehr, E. Boccaleri. Synthetic, layered nanoparticles for polymeric nanocomposites (PNCs). Polymers for Advanced Technologies 2007, 18 (1) , 1-37. https://doi.org/10.1002/pat.852
    78. Junxian Hou, Suyun Jie, Wenjuan Zhang, Wen‐Hua Sun. Vinyl polymerization of norbornene over supported nickel catalyst. Journal of Applied Polymer Science 2006, 102 (3) , 2233-2240. https://doi.org/10.1002/app.24391
    79. Junxian Hou, Wenjuan Zhang, Suyun Jie, Wen-Hua Sun. Vinyl Polymerization of Norbornene over Supported Nickel Catalyst. 2006, 209-212. https://doi.org/10.1016/S0167-2991(06)80459-3
    80. Zhenli Ma, Li Wang, Wenqin Wang, Jianfeng Wang, Haojie Yu. Study of Propylene Polymerization Catalyzed by Spherical MgCl 2 -Supported Ziegler-Natta Catalyst System: Preparation of Spherical Support. Polymer-Plastics Technology and Engineering 2005, 44 (8-9) , 1475-1483. https://doi.org/10.1081/200065168
    81. Rubin Huang, Dongbing Liu, Shibo Wang, Bingquan Mao. Preparation of spherical MgCl2 supported bis(imino)pyridyl iron(II) precatalyst for ethylene polymerization. Journal of Molecular Catalysis A: Chemical 2005, 233 (1-2) , 91-97. https://doi.org/10.1016/j.molcata.2005.02.004
    82. P. Sozzani, S. Bracco, A. Comotti, R. Simonutti. Motional Phase Disorder of Polymer Chains as Crystallized to Hexagonal Lattices. 2005, 153-177. https://doi.org/10.1007/b107180
    83. Piotr Sobota. Metal-assembled compounds: precursors of polymerization catalysts and new materials. Coordination Chemistry Reviews 2004, 248 (11-12) , 1047-1060. https://doi.org/10.1016/j.ccr.2004.06.002
    84. Piero Sozzani, Angiolina Comotti, Silvia Bracco, Roberto Simonutti. A Family of Supramolecular Frameworks of Polyconjugated Molecules Hosted in Aromatic Nanochannels. Angewandte Chemie International Edition 2004, 43 (21) , 2792-2797. https://doi.org/10.1002/anie.200353479
    85. Piero Sozzani, Angiolina Comotti, Silvia Bracco, Roberto Simonutti. A Family of Supramolecular Frameworks of Polyconjugated Molecules Hosted in Aromatic Nanochannels. Angewandte Chemie 2004, 116 (21) , 2852-2857. https://doi.org/10.1002/ange.200353479
    86. I. B. Gorrell. 3  Alkali and alkaline-earth metals. Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem. 2004, 100 , 15-33. https://doi.org/10.1039/B311776F
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2003, 125, 42, 12881–12893
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja034630n
    Published September 30, 2003
    Copyright © 2003 American Chemical Society
    Request reuse permissions

    Article Views

    1030

    Altmetric

    -

    Citations

    86
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.