Abstract
A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3·(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate (MMA) polymerization. After 24 hours,more than 95.5% MMA was converted to polymethyl methacrylate (PMMA) with a viscosity average molecular weight (W η) of 416000 g·mol−1 at 60 °C for MMA/Al(i-Bu)3/chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.
Similar content being viewed by others
References
Zhang GS, Zhu SM, Yan DY. Reverse Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by AIBN/FeCl3/Isophthalic Acid System[J]. Chin. Sci. Bull., 2001, 46(13), 1–3
Xue L, Agarwal US, Lemstra PJ. High Molecular Weight PMMA by ATRP[J]. Macromolecules, 2002, 35(22): 8 650–8 652
Singha NK, Rimmer S, Klumperman B. Mass Spectrometry of Poly (Methyl Methacrylate)(PMMA) Prepared by Atom Transfer Radical Ppolymerization (ATRP)[J]. Eur. Polym. J., 2004, 40(1): 159–163
Huang Z, Zhang Y, Li H, et al. A Novel Immobilized Cobalt (II)/Copper (II) Bimetallic Catalyst for Atom Transfer Radical Polymerization (ATRP) of Methyl Methacrylate[J]. Appl. Catal. A-Gen., 2007, 332(2): 192–199
Barrientos-Ramírez S, Montes de Oca-Ramírez G, Ramos-Fernández EV, et al. Influence of the Surface Chemistry of Activated Carbons on the ATRP Catalysis of Methyl Methacrylate Polymerization[J]. Appl. Catal. A-Gen., 2011, 397(1):225–233
Edwards HGM, Johal KS, Johnson A F. FT-Raman Spectroscopic Monitoring of the Group-transfer Polymerisation of Methyl Methacrylate[J]. Vib. Spectrosc, 2006, 41(2): 160–169
Begum F, Simon SL. Modeling Methyl Methacrylate Free Radical Polymerization in Nanoporous Confinement[J]. Polymer, 2011, 52(7):1 539–1 545
Zhao H, Simon SL. Methyl Methacrylate Polymerization in Nanoporous Vonfinement [J]. Polymer, 2011, 52(18): 4 093–4 098
Begum F, Zhao H, Simon SL. Modeling Methyl Methacrylate Free Radical Polymerization: Reaction in Hydrophobic Nanopores[J]. Polymer, 2012,53(15): 3 261–3 268
Ihara E, Amamoto M, Inoue K. Anionic Polymerization of Methyl Methacrylate in the Presence of Chromium Carbonyl [Cr (CO)6][J]. Polym. Bul., 2003, 50(4): 213–218
Yasuda H, Yamamoto H, Yamashita M, et al. Synthesis of High Molecular Weight poly (Methyl Methacrylate) with Extremely Low Polydispersity by the Unique Function of Organolanthanide (III) Complexes[J]. Macromolecules, 1993, 26(26): 7 134–7 143
Yasuda H, Tamai H. Characteristics of Rare Earth Systems as Polymerization Initiators[J]. Prog. Polym. Sci., 1993, 18(6): 1 097–1 139
Ihara E, Morimoto M, Yasuda H. Living Polymerizations and Copolymerizations of Alkyl Acrylates by the Unique Catalysis of Rare Earth Metal Complexes[J]. Macromolecules, 1995, 28(23): 7 886–7 892
Desurmont G, Li Y, Yasuda H, et al. Reaction Pathway for the Formation of Binuclear Samarocene Hydride from Monomeric Alkyl Samarocene Derivative and the Effective Catalysis of Samarocene Hydride for the Block Copolymerization of Ethylene with Polar Monomers[J]. Organometallics, 2000, 19(10): 1 811–1 813
Collins S, Ward DG. Group-transfer Polymerization Using Cationic Zirconocene Compounds[J]. J. Am. Chem. Soc., 1992, 114(13): 5 460–5 462
Collins S, Ward DG, Suddaby K H. Group-transfer Polymerization Using Metallocene Catalysts: Propagation Mechanisms and Control of Polymer Stereochemistry[J]. Macromolecules, 1994, 27(24): 7 222–7 224
Li Y, Ward DG, Reddy SS, et al. Polymerization of Methyl Methacrylate Using Zirconocene Initiators: Polymerization Mechanisms and Applications[J]. Macromolecules, 1997, 30(7): 1 875–1 883
Soga K, Deng H, Yano T, et al. Stereospecific Polymerization of Methyl Methacrylate Initiated by Zirconocene dimethyl/B(C6F5)3 (or Ph3CB(C6F5)4)/Zn (C2H5)2[J]. Macromolecules, 1994, 27(26): 7 938–7 940
Deng H, Shiono T, Soga K. Isospecific Polymerization of Methyl Methacrylate Initiated by Chiral Zirconocenedimethyl/Ph3CB(C6F5)4 in the Presence of Lewis Acid[J]. Macromolecules, 1995, 28(9): 3 067–3 073
Deng H, Soga K. Isotactic Polymerization of Tert-butyl Acrylate with Chiral Zirconocene[J]. Macromolecules, 1996, 29(5): 1 847–1 848
Stuhldreier T, Keul H, Höcker H, et al. Preparation and First X-ray Structure of a Zirconocene β-Keto Ester Enolate[J]. Organometallics, 2000, 19(24): 5 231–5 234.
Frauenrath H, Keul H, Höcker H. Stereospecific Polymerization of Methyl Methacrylate with Single-component Zirconocene Complexes: Control of Stereospecificity via Catalyst Symmetry[J]. Macromolecules, 2001, 34(1): 14–19
Cameron P A, Gibson VC, Graham A J. On the Polymerization of Methyl Methacrylate by Group 4 Metallocenes[J]. Macromolecules, 2000, 33(12): 4 329–4 335
Bolig AD, Chen EYX. Reversal of Polymerization Stereoregulation in Anionic Polymerization of MMA by Chiral Metallocene and Non-Metallocene Initiators: a New Reaction Pathway for Metallocene-initiated MMA Polymerization[J]. J. Am. Chem. Soc., 2001, 123(32):7 943–7 944
Bolig A D, Chen E Y X. Isotactic-b-syndiotactic stereoblock Poly (methyl methacrylate) by Chiral Metallocene/Lewis Acid Hybrid Catalysts[J]. J. Am. Chem. Soc., 2002, 1246](20): 5612–5613
Rodriguez-Delgado A, Mariott W R, Chen E Y X. Synthesis and MMA Polymerization of Chiral Ansa-zirconocene Ester Enolate Complexes with C2-and Cs-ligation[J]. J. Organomet. Chem., 2006, 691(16): 3 490–3 497
Strauch JW, Fauré JL, Bredeau S, et al. (Butadiene) metallocene/B(C6F5)3 Pathway to Catalyst Systems for Stereoselective Methyl Methacrylate Polymerization:Evidence for an Anion Dependent Metallocene Catalyzed Polymerization Process[J]. J. Am. Chem. Soc., 2004, 126(7): 2 089–2 104
Sun JQ, Pan ZD, Hu WQ, et al. Polymerization of Methyl Methacrylate with Ethylene Bridged Heterodinuclear Metallocene of Samarium and Titanium[J]. Eur. Polym. J., 2002, 38(3): 545–549
Qian YL, Bala MD, Yousaf M, et al. Novel 2-propenyl cyclopentadienyl Lanthanide Complexes as Single Component Methyl Methacrylate (MMA) Polymerization Catalysts[J]. J. Mol.Catal. A: Chem., 2002, 188(1): 1–10
Bala M D, Huang J L, Zhang H, et al. Synthesis, Characterization and Application of Organolanthanide Complexes (CH2CHCH2CH2C5H4)2 Ln Cl· 2THF (Ln= Sm, Y, Dy, Er) as methyl methacrylate (MMA) polymerization catalysts[J]. J. Organomet. Chem., 2002, 647(1): 105–113
Stone KJ, Little RD. An Exceptionally Simple and Efficient Method for the Preparation of a Wide Variety of Fulvenes[J]. J. Org. Chem., 1984, 49(11): 1 849–1 853
Herwig W, Zeiss H. Notes: Chromium Trichloride Tetrahydrofuranate[J]. J.Org.Chem., 1958, 23(9): 1 404–1 404
Sheldrick GM. SHELXS-98 Program for the Solution of Crystal Structures[M]. University of Göttingen Press, Göttingen (Germany), 1998
Sheldrick G M. SHELXL-98 Program for the Refinement of Crystal Structures[M].University of Göttingen Press, Göttingen (Germany), 1998
Heinemann O, Jolly P, Krüger C, et al. Bis (indenyl) Chromium Is a Dimer[J]. Organometallics, 1996, 15(26): 5 462–5 463
Döhring A, Göhre J, Jolly P, et al. Donor-Ligand-Substituted Cyclopentadienylchromium (III) Complexes: A New Class of Alkene Polymerization Catalyst. 1. Amino-Substituted Systems[J]. Organometallics, 2000, 19(4): 388–402
Enders M, Fernández P, Ludwig G, et al. New Chromium (III) Complexes as Highly Active Catalysts for Olefin Polymerization[J]. Organometallics, 2001, 20(24): 5 005–5 007
Natta G, Danusso F, Moraglio G. Dilatometrische Eigenschaften und Struktur Isomerer Polymeren des Äthylens und von α-Olefins[J]. Angew.Chem., 1957, 69: 686
Simionescu C, Asandei N, Benedek I, et al. La Copolymerisation du Systeme Binaire Acrylonitrile-methylmethacrylate a l’aide Des Promoteurs du Type Soluble Ziegler-natta Constitues Par le Complexe: Dichlorure du Biscyclopentadienyl-titane-triethyle Aluminium[J]. Eur. Polym. J., 1969, 5(4): 449–462
Hu WQ, Sun JQ, Pan ZD, et al. The Polymerization of Methyl Methacrylate with a New Tin-bridged Yttrocene/Al(i-Bu)3[J]. J. Zhejiang Univ. (Sci.), 2000, 1(2): 157–161
Emmons ED, Kraus RG, Duvvuri SS, et al. High-pressure Infrared Absorption Spectroscopy of Poly (methyl methacrylate)[J]. J. Polym. Sci., Part B: Polym. Phys., 2007, 45(3): 358–367
Kuila T, Bose S, Khanra P, et al. Characterization and Properties of in Situ Emulsion Polymerized Poly (Methyl Methacrylate)/Graphene Nanocomposites[J]. Composites Part A, 2011, 42(11): 1 856–1 861
Wang WP, Liu Y, Li XX, et al. Synthesis and Characteristics of Poly (methyl methacrylate) / Expanded Graphite Nanocomposites[J]. J. Appl. Polym. Sci., 2006, 100(2): 1 427–1 431
Author information
Authors and Affiliations
Corresponding author
Additional information
Funded by the National Natural Science Foundation of China (No. 51204125), the Natural Science Foundation of Hubei Province ( Nos. 2014CFB812 and 2014CFB810) and the Open Fund Project Funded by the Key Laboratory of Coal Conversion and New Carbon Materials of Hubei Province in China (No. WKDM201302)
Rights and permissions
About this article
Cite this article
Cheng, Z., Gong, K., Wang, Y. et al. Synthesis, characterization and application of a novel carbon bridged half-metallocene chromium catalyst for methyl methacrylate polymerization. J. Wuhan Univ. Technol.-Mat. Sci. Edit. 29, 1294–1301 (2014). https://doi.org/10.1007/s11595-014-1084-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11595-014-1084-3