The Influence of Ziegler-Natta and Metallocene Catalysts on Polyolefin Structure, Properties, and Processing Ability
Abstract
:1. Introduction
- (i)
- (ii)
- Homogeneous catalysts: These are the second broad class of catalysts and are based on complexes of Ti, Zr, or Hf. They are generally used in combination with a range of different organo-aluminum co-catalysts known as metallocene/methylaluminoxane (MAO). Traditionally, they include metallocenes but also feature multi-dentate oxygen- and nitrogen-based ligands [14,15].
No. | Properties | Polyethylene | Polypropylene |
---|---|---|---|
1 | Density | 0.92–0.95 | 0.9–0.91 |
2 | Young Modulus (GPa) | 0.3–1.0 | 1.4 |
3 | Glass Transition Temperature (°C) | −125–−80 | −20 |
4 | Limiting oxygen index (LOI) (%) | 18 | 17 |
5 | Melting temperature (°C) | 112–134 | 160 |
6 | Specific Heat Capacity: Conventional (J/kg·K) | 1750–2400 | 1900 |
7 | Specific Heat Capacity: Volumetric (10 J/m·K) | 1600–2200 | 1700 |
8 | Speed of sound (10 m/s) | 18–32 | 34–39 |
9 | Stiffness to weight ratio: Tensile (MN-m/kg) | 0.32–1.0 | 1.2–1.5 |
10 | Stiffness to weight ratio: Tensile, Ultimate (KN-m/kg) | 7.6–52 | 25–39 |
11 | Tensile Strength: Ultimate (MPa) | 7–49 | 23–36 |
12 | Thermal Conductivity Ambient (W/m·K) | 0.36–0.45 | 0.15 |
2. Polyethylene and Polypropylene
Year | Progress in olefin polymerization process |
---|---|
1951 | Hogan and Banks synthesizes crystalline polypropylene using chromium-NiO catalyst supported on silica alumina. (Subsequently, in 1983, the US patent office awards the patent to them for having substantial crystalline polypropylene content.) |
1953 | Karl Ziegler polymerizes ethene into high MW-HDPE (high density polyethylene) with the discovery of the catalyst based on titanium tetrachloride, and diethylaluminium chloride as co-catalyst. |
1954 | Giulio Natta, utilizes the catalyst suggested by Ziegler to produce PP. Ziegler and Natta are both awarded the Nobel Prize for Chemistry 1963 in recognition of their work on the Ziegler-Natta catalyst. |
1957 | Commercial production of PP commence in Italy, Germany, and USA. Natta and Breslow, independently discover metallocene catalyst to catalyze olefin polymerization with conventional co-catalyst (Al alkyls). |
1961–1980 | PP is used for manufacturing various products like fibers, fabrics, upholstery, nonwoven fabrics, and others on a commercial scale. |
1973 | 2nd generation Ziegler Natta catalysts introduced with TiCl3 purple phases at lower temperatures. |
1975–1978 | 3rd generation catalysts supported on MgCl2 commercialized by many companies. |
1977–1980 | Kaminsky and Sinn discover high activity metallocene single-site catalysts (SSCs) using methylaluminoxane (MAO) as co-catalyst. |
1984 | Ewen at the Exxon Company (USA) demonstrate that appropriate titanocenes render partially isotactic polypropylene. |
1991 | Fourth generation Ziegler Natta catalysts based on aluminium-oxane activated metallocene complexes used. |
1995–1998 | Brookhart and co-workers discover non-metallocene SSC based primarily on chelated late transition metals. Brintzinger and co-workers report on the synthesis of chiral bridged (“ansa”) metallocenes for homogeneous stereospecific 1-olefin polymerization [59]. Exxon Mobil and other companies commercialize PP using SSC. |
1997 | Montel (or Lyondell Basell) commercialize PP based on 5th generation Ziegler-Natta catalyst that use 1.3-diethers, and succinated as donors. |
3. Role and Type of Catalysts
3.1. Kinetic Study of Olefin Polymerization in General
(1) Elementary chemical reactions of olefin homopolymerization system. | |||
Initiation | (1) | ||
Propagation | (2) | ||
Transfer | β-hydride | (3) | |
to hydrogen | (4) | ||
to monomer | (5) | ||
to cocatalyst | (6) | ||
Deactivation | (7) | ||
(8) | |||
Poisoning | (9) | ||
(2) Elementary chemical reactions of olefin copolymerization system. | |||
Initiation | (10) | ||
(11) | |||
Propagation | (12) | ||
(13) | |||
(14) | |||
(15) | |||
Transfer | β-hydride | (16) | |
β-hydride | (17) | ||
to hydrogen | (18) | ||
to hydrogen | (19) | ||
to monomer | (20) | ||
to monomer | (21) | ||
to monomer | (22) | ||
to monomer | (23) | ||
to cocatalyst | (24) | ||
to cocatalyst | (25) | ||
Deactivation | Deactivation | (26) | |
Deactivation | (27) | ||
Deactivation | (28) | ||
Poisoning | Poisoning | (29) | |
Poisoning | (30) |
3.2. Electron Donors
3.3. The Contribution of Metallocene-Related and Group 4 Ziegler-Natta Catalysts to the Advancement in Olefin Polymerization Processes
3.4. Olefin Polymerization by Half-Titanocenes Containing Aryloxy Ligands
Cp' (μmol) | Olefin | Activity b | TON c | 10−4Mw d | Mw/Mn d |
---|---|---|---|---|---|
Cp (18.3) | Ethylene | 77 | 2,750 | – | – |
Cp (5.0) | 1-Hexene | 62 | 370 | 0.68 | – |
tBuC5H4 (15.1) | Ethylene | 258 | 9,200 | 5.99 | 2.1 |
tBuC5H4 (5.0) | 1-Hexene | 90 | 532 | 8.04 | 1.6 |
tBuC5H4 (5.0) | 1-Octene | 125 | 558 | 8.25 | 1.9 |
1,3-Me2C5H2 (24.2) | Ethylene | 215 | 7,660 | 1.75 | 2.5 |
1,3-Me2C5H2 (5.0) | 1-Hexene | 184 | 1,090 | 8.73 | 1.9 |
1,3-tBu2C5H2 (5.0) | Ethylene | 653 | 23,300 | 64.9 | 6.8 |
1,3-tBu2C5H2 (5.0) | 1-Hexene | 26 | 152 | 2.16 | 1.6 |
1,3-tBu2C5H2 (5.0) | 1-octene | 38 | 168 | 1.75 | 1.5 |
Cp* (6.5) | Ethylene | 2,220 | 79,100 | 45.9 | 5.0 |
Cp* (1.0) | 1-Hexene | 728 | 4,330 | 69.4 | 1.6 |
Cp* (1.0) | 1-Octene | 970 | 4,320 | 49.5 | 1.8 |
Cp* (1.0) | 1-Decene | 1036 | 3,690 | 41.7 | 1.7 |
R1, R2, R3 (μmol) | Activity b | TON c | 10−4Mw d | Mw/Mn d |
---|---|---|---|---|
iPr, H, iPr (4.2) | 1,240 | 43,100 | 64.9 | 4.7 |
H, Me, H (13.0) | 25 | 890 | – | – |
Me, H, Me (4.0) | 1,000 | 35,700 | 123 | 4.5 |
tBu, Me, Me (13.0) | 446 | 15,900 | – | – |
Me, Me, Me (8.4) | 369 | 13,200 | – | – |
Complex | Co-Catalyst | Activity b | 10−4Mw c | Mw/Mn c |
---|---|---|---|---|
CpTiCl2(N=PCy3) | MAO | 42 | 0.36 d | 1.8 |
33.6 | 2.2 | |||
CpTiCl2(N=PiPr3) | MAO | 49 | 1.87 d | 2.8 |
57.9 | 2.4 | |||
CpTiCl2(N=PtBu3) | MAO | 500 | 8.99 | 2.4 |
CpTiMe2(N=PCy3) | Ph3CB(C6F5)4 | 231 | 13.5 | 2.8 |
CpTiMe2(N=PiPr3) | Ph3CB(C6F5)4 | 225 | 16.4 | 3.4 |
CpTiMe2(N=PtBu3) | Ph3CB(C6F5)4 | 401 | 16.6 | 3.4 |
tBuCpTiCl2(N=PCy3) | MAO | 46 | 0.74 d | 2.1 |
89.4 | 3.4 | |||
tBuCpTiCl2(N=PiPr3) | MAO | 16 | 0.76 d | 1.9 |
91 | 2.5 | |||
tBuCpTiCl2(N=PtBu3) | MAO | 881 | 6.54 | 2.4 |
tBuCpTiMe2(N=PCy3) | Ph3CB(C6F5)4 | 1807 | 31 | 7.5 |
tBuCpTiMe2(N=PiPr3) | Ph3CB(C6F5)4 | 1193 | 25.9 | 9.9 |
tBuCpTiMe2(N=PtBu3) | Ph3CB(C6F5)4 | 1296 | 32.1 | 12.3 |
[Me2Si(C5Me4)(NtBu)]TiCl2 | MAO | 630 | – | – |
Pre-catalyst (μmol·L−1) | Co-Catalyst | t/min | Activity b | 10−4Mn c | Mw/Mn c |
---|---|---|---|---|---|
Cp*TiCl2[N=P(NMe2)3] (100) | MAO | 30 | 21 | 82.6 | 1.72 |
Cp*TiCl2[N=P(NEt2)3] (100) | MAO | 30 | 39 | 9.01 | 1.65 |
Cp*TiCl2[N=P{N(Me)iPr}3] (50) | MAO | 30 | 56 | 12.78 | 2.76 |
Cp*TiCl2[N=P{N(Et)Ph}3] (50) | MAO | 30 | 200 | 12.61 | 4.02 |
CpTiMe2[N=P(NMe2)3] (4) | Al/B d | 10 | 2,200 | 31.5 | 2.05 |
CpTiMe2[N=P(NEt2)3] (4) | Al/B d | 10 | 3,500 | 39.4 | 1.91 |
CpTiMe2[N=P(NPr2)3] (4) | Al/B d | 10 | 5,500 | – | – |
CpTiMe2[N=P(NBu2)3] (4) | Al/B d | 10 | 3,600 | – | – |
CpTiMe2[N=P{N(Me)iPr}3] (4) | Al/B d | 10 | 3,600 | 38.86 | 1.85 |
CpTiMe2[N=P{N(Et)Ph}3] (4) | Al/B d | 10 | 4,200 | 43.25 | 1.92 |
Cp*TiMe2[N=P(NMe2)3] (4) | Al/B d | 10 | 4,200 | 14.08 | 4.92 |
Cp*TiMe2[N=P(NEt2)3] (4) | Al/B d | 10 | 4,700 | – | – |
Cp*TiMe2[N=P(NPr2)3] (4) | Al/B d | 10 | 10,000 | – | – |
Cp*TiMe2[N=P(NBu2)3] (4) | Al/B d | 10 | 6,100 | – | – |
Cp*TiMe2[N=P{N(Me)iPr}3] (4) | Al/B d | 10 | 4,900 | 28.81 | 2.14 |
Cp*TiMe2[N=P{N(Et)Ph}3] (4) | Al/B d | 10 | 4,200 | 32.46 | 2.03 |
Cp*TiMe2[N=PiPr3] (4) | Al/B d | 10 | 5,200 | 49.34 | 2.05 |
CpTiMe2[N=PtBu3] (4) | Al/B d | 10 | 5,600 | 43.78 | 1.8 |
Cp2ZrMe2 (4) | Al/B d | 10 | 16,000 | 17.5 | 1.89 |
4. Conclusions and Future Perspective
Nomenclature
C* | active site |
Cd | deactivated site |
Dr | dead polymer of chain length r |
H2 hydrogen | the most common chain transfer agent for these systems, except for Phillips catalysts |
M | monomer |
Al | cocatalyst |
I | impurities |
Pr | living polymer chain of length r |
Acknowledgments
Author Contributions
Conflicts of Interest
References
- McNaught, A.D.; Wilkinson, A. Compendium of Chemical Terminology; IUPAC Nomenclature Books Series; Blackwell: Oxford, UK, 1997. [Google Scholar]
- Chung, T.C.M. Functional Polyolefins for Energy Applications. Macromolecules 2013, 46, 6671–6698. [Google Scholar] [CrossRef]
- Mandal, B.M. Fundamentals of Polymerization; World Scientific: Hackensack, NJ, USA, 2013. [Google Scholar]
- Albizzati, E.; Galimberti, M. Catalysts for olefins polymerization. Catal. Today 1998, 41, 415–421. [Google Scholar]
- Ziegler, K. Organometallic Chemistry; Zeiss, H., Ed.; ACS Monograph 147; Reinhold Publishing Corp.: New York, NY, USA, 1960; Volume 194. [Google Scholar]
- Gambarotta, S. Vanadium-based Ziegler–Natta: Challenges, promises, problems. Coord. Chem. Rev. 2003, 237, 229–243. [Google Scholar] [CrossRef]
- Kaminsky, W. New polymers by metallocene catalysis. Macromol. Chem. Phys. 1996, 197, 3907–3945. [Google Scholar] [CrossRef]
- Natta, G. Kinetic studies of α-olefin polymerization. J. Polym. Sci. 1959, 34, 21–48. [Google Scholar] [CrossRef]
- Claverie, J.P.; Schaper, F. Ziegler-Natta catalysis: 50 years after the Nobel Prize. MRS Bull. 2013, 38, 213–218. [Google Scholar] [CrossRef]
- Torres, W.; Donini, J.C.; Vlcek, A.A.; Lever, A.B.P. Polymer Films with Tunable Surface Properties: Separation of an Oil-in-Water Emulsion at Poly(3-methylthiophene). Langmuir 1995, 11, 2920–2925. [Google Scholar] [CrossRef]
- Fregonese, D.; Mortara, S.; Bresadola, S. Ziegler-Natta MgCl2-supported catalysts: Relationship between titanium oxidation states distribution and activity in olefin polymerization. J. Mol. Catal. A Chem. 2001, 172, 89–95. [Google Scholar] [CrossRef]
- Kashiwa, N.J. The discovery and progress of MgCl2-supported TiCl4 catalysts. Polym. Sci. A Polym. Chem. 2004, 42, 1–8. [Google Scholar] [CrossRef]
- Natta, G.; Pino, P.; Mazzanti, P. Regular linear head-to-tail polymerizates of certain unsaturated hydrocarbons and filaments comprising said polymerizates. U.S. Patent 3,715,344, 6 February 1973. [Google Scholar]
- Kesti, M.R.; Coates, G.W.; Waymouth, R.M. Homogeneous Ziegler-Natta polymerization of functionalized monomers catalyzed by cationic Group IV metallocenes. J. Am. Chem. Soc. 1992, 114, 9679–9680. [Google Scholar] [CrossRef]
- Klimke, K.; Parkinson, M.; Piel, C.; Kaminsky, W.; Spiess, H.W.; Wilhelm, M. Optimisation and Application of Polyolefin Branch Quantification by Melt-State 13C-NMR Spectroscopy. Macromol. Chem. Phys. 2006, 207, 382–395. [Google Scholar] [CrossRef]
- Kaminsky, W.; Funck, A.; Hähnsen, H. New application for metallocene catalysts in olefin polymerization. Dalton Trans. 2009, 8803–8810. [Google Scholar] [CrossRef]
- Santos, L.S. What do We Know about Reaction Mechanism? The Electrospray Ionization Mass Spectrometry Approach. J. Braz. Chem. Soc. 2011, 22, 1827–1840. [Google Scholar] [CrossRef]
- Sagel, E. Polyethylene Global Overview. Available online: http://www.ptq.pemex.com/productosyservicios/eventosdescargas/Documents/Foro%20PEMEX%20Petroqu%C3%ADmica/2012/PEMEX%20PE.pdf (accessed on 25 April 2013).
- Shiga, A. Theoretical study of heterogeneous Ziegler-Natta catalysts: A comparison between TiCl3 catalysts and MgCl2 supported catalysts by using paired interacting orbitals (PIO) analysis. Macromol. Res. 2010, 18, 956–959. [Google Scholar] [CrossRef]
- Ahmad, N.; Mahmood, K. Preparation and distribution measurements for polyethylene single-crystals for various type of sizes. J. Chem. Soc. Pak. 1993, 15, 105–109. [Google Scholar]
- Zhang, W.-H.; Chien, S.W.; Hor, T.S.A. Recent advances in metal catalysts with hybrid ligands. Coord. Chem. Rev. 2011, 255, 1991–2024. [Google Scholar] [CrossRef]
- Ghasem, N.M.; Ang, W.L.; Hussain, M.A. Dynamics and stability of ethylene polymerization in multizone circulating reactors. Korean J. Chem. Eng. 2009, 26, 603–611. [Google Scholar] [CrossRef]
- Cho, K.; Lee, B.H.; Hwang, K.-M.; Lee, H.; Choe, S. Rheological and mechanical properties in polyethylene blends. Polym. Eng. Sci. 1998, 38, 1969–1975. [Google Scholar] [CrossRef]
- Aida, T.; Meijer, E.W. Functional Supramolecular Polymers. Science 2012, 335, 813–817. [Google Scholar] [CrossRef]
- Korevaar, P.A.; George, S.J.; Markvoort, A.J.; Smulders, M.M.J.; Hilbers, P.A.J.; Schenning, A.P.H.J.; de Greef, T.F.A.; Meijer, E.W. Pathway complexity in supramolecular polymerization. Nature 2012, 481, 492–496. [Google Scholar] [CrossRef]
- Kitamaru, R.; Horii, F.; Murayama, K. Phase Structure of Lamellar Crystalline Polyethylene by Solid-state High-Resolution 13C-NMR: Detection of the Crystalline-Amorphous Interphase. Macromolecules 1986, 19, 636–643. [Google Scholar] [CrossRef]
- Miroslav, J.; Roman, C.; Petr, P. Morphology of Polyethylene with Regular Side Chains Distribution. In Proceedings of the 4th WSEAS International Conference on Engineering Mechanics, Structures, Engineering Geology, Corfu Island, Greece, 14–16 July 2011.
- Janicek, M.; Cermak, R.; Obadal, M.; Piel, C.; Ponizil, P. Ethylene Copolymers with Crystallizable Side Chains. Macromolecules 2011, 44, 6759–6766. [Google Scholar] [CrossRef]
- Kaminsky, W.; Piel, C. Tailoring polyolefins by metallocene catalysis: Kinetic and mechanistic aspects. J. Mol. Catal. A Chem. 2004, 213, 15–19. [Google Scholar] [CrossRef]
- MAG Recycling Services. Available online: http://www.magrecycling.com.au/RecycledProducts/HDPE.aspx (accessed on 15 January 2013).
- University of Southern Mississippi. Available online: http://www.pslc.ws/macrog/pe.htm (accessed on 15 January 2013).
- Zhang, J.; Wang, X.; Jin, G.-X. Polymerized metallocene catalysts and late transition metal catalysts for ethylene polymerization. Coord. Chem. Rev. 2006, 250, 95–109. [Google Scholar] [CrossRef]
- Piel, C.; Starck, P.; Seppälä, J.V.; Kaminsky, W. Thermal and mechanical analysis of metallocene-catalyzed ethene–α-olefin copolymers: The influence of the length and number of the crystallizing side chains. J. Polym. Sci. A Polym. Chem. 2006, 44, 1600–1612. [Google Scholar] [CrossRef]
- Starck, P. Dynamic mechanical thermal analysis on Ziegler-Natta and metallocene type ethylene copolymers. Eur. Polym. J. 1997, 33, 339–348. [Google Scholar] [CrossRef]
- Natta, G.; Mazzanti, G.; Valvassori, A.; Sartori, G.; Fiumani, D. Ethylene–propylene copolymerization in the presence of catalysts prepared from vanadium triacetylacetonate. J. Polym. Sci. 1961, 51, 411–427. [Google Scholar] [CrossRef]
- Debras, G. Process for Producing Polyethylene Having a Broad Molecular Weight Distribution. WO1995010548 A1, 2 February 1993. [Google Scholar]
- Dammert, R.; Heino, E.-L.; Korvenoja, T.; Martinsson, H.-B. A Multimodal Polymer Composition. WO2000037556 A1, 15 May 2000. [Google Scholar]
- Zapata, P.A.; Quijada, R.; Lieberwirth, I.; Benavente, R. Polyethylene Nanocomposites Obtained by in Situ Polymerization via a Metallocene Catalyst Supported on Silica Nanospheres. Macromol. React. Eng. 2011, 5, 294–302. [Google Scholar] [CrossRef]
- Bianchini, C.; Giambastiani, G.; Rios, I.G.; Mantovani, G.; Meli, A.; Segarra, A.M. Ethylene oligomerization, homopolymerization and copolymerization by iron and cobalt catalysts with 2,6-(bis-organylimino)pyridyl ligands. Coord. Chem. Rev. 2006, 250, 1391–1418. [Google Scholar] [CrossRef]
- Kukalyekar, N.; Balzano, L.; Peters, G.W.M.; Rastogi, S.; Chadwick, J.C. Characteristics of Bimodal Polyethylene Prepared via Co-Immobilization of Chromium and Iron Catalysts on an MgCl2-Based Support. Macromol. React. Eng. 2009, 3, 448–454. [Google Scholar] [CrossRef]
- Bianchini, C.; Giambastiani, G.; Luconi, L.; Meli, A. Olefin oligomerization, homopolymerization and copolymerization by late transition metals supported by (imino)pyridine ligands. Coord. Chem. Rev. 2010, 254, 431–455. [Google Scholar] [CrossRef]
- Alt, F.; Böhm, L.; Enderle, H.; Berthold, J. Bimodal polyethylene—Interplay of catalyst and process. Macromol. Symp. 2001, 163, 135–144. [Google Scholar] [CrossRef]
- Chen, X.; Liu, D.; Wang, H. Synthesis of Bimodal Polyethylene Using Ziegler-Natta Catalysts by Multiple H2 Concentration Switching in a Single Slurry Reactor. Macromol. React. Eng. 2010, 4, 342–346. [Google Scholar] [CrossRef]
- Fernandes, F.A.N.; Lona, L.M.F. Multizone circulating reactor modeling for gas-phase polymerization.I. Reactor modeling. J. Appl. Polym. Sci. 2004, 93, 1042–1052. [Google Scholar] [CrossRef]
- Ruff, M.; Paulik, C. Controlling Polyolefin Properties by In-Reactor Blending, 1–Polymerization Process, Precise Kinetics, and Molecular Properties of UHMW-PE Polymers. Macromol. React. Eng. 2012, 6, 302–317. [Google Scholar] [CrossRef]
- Small, B.L.; Brookhart, M.; Bennett, A.M.A. Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene. J. Am. Chem. Soc. 1998, 120, 4049–4050. [Google Scholar] [CrossRef]
- Wang, Q.; Li, L.; Fan, Z. Polyethylene with bimodal molecular weight distribution synthesized by 2,6-bis(imino)pyridyl complexes of Fe(II) activated with various activators. Eur. Polym. J. 2004, 40, 1881–1886. [Google Scholar] [CrossRef]
- Czaja, K.; Król, B. Two-step polymerization of propylene over MgCl2-supported titanium catalyst. Macromol. Chem. Phys. 1998, 199, 451–455. [Google Scholar] [CrossRef]
- Pater, J.; Weickert, G.; van Swaaij, W. Propene bulk polymerization kinetics: Role of prepolymerization and hydrogen. AIChE J. 2003, 49, 180–193. [Google Scholar] [CrossRef]
- Ibrehem, A.S.; Hussain, M.A.; Ghasem, N.M. Modified mathematical model for gas phase olefin polymerization in fluidized-bed catalytic reactor. Chem. Eng. J. 2009, 149, 353–362. [Google Scholar] [CrossRef]
- Monji, M.; Abedi, S.; Pourmahdian, S.; Taromi, F.A. Effect of prepolymerization on propylene polymerization. J. Appl. Polym. Sci. 2009, 112, 1863–1867. [Google Scholar] [CrossRef]
- Shan, C.L.P.; Soares, J.B.P.; Penlidis, A. HDPE/LLDPE reactor blends with bimodal microstructures—Part II: Rheological properties. Polymer 2003, 44, 177–185. [Google Scholar] [CrossRef]
- Hutchinson, R.A.; Chen, C.M.; Ray, W.H. Polymerization of olefins through heterogeneous catalysis X: Modeling of particle growth and morphology. J. Appl. Polym. Sci. 1992, 44, 1389–1414. [Google Scholar] [CrossRef]
- Meier, G.B.; Weickert, G.; van Swaaij, W.P.M. FBR for catalytic propylene polymerization: Controlled mixing and reactor modelling. AIChE J. 2002, 6, 1268–1283. [Google Scholar]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Moustavi, N. Kinetic modeling of propylene homopolymerization in a gas-phase fluidized-bed reactor. Chem. Eng. J. 2010, 161, 240–249. [Google Scholar] [CrossRef]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Moustavi, N. Improved single phase modeling of propylene polymerization in a fluidized bed reactor. Comput. Chem. Eng. 2012, 36, 35–47. [Google Scholar] [CrossRef]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Shafeeyan, M.S.; Mostoufi, N. Experimental and Modeling Analysis of Propylene Polymerization in a Pilot-Scale Fluidized Bed Reactor. Ind. Eng. Chem. Res. 2014, 53, 8694–8705. [Google Scholar] [CrossRef]
- Kaminsky, W. Highly active metallocene catalysts for olefin polymerization. J. Chem. Soc. Dalton Trans. 1998, 1413–1418. [Google Scholar] [CrossRef]
- Brintzinger, H.H.; Fischer, D.; Mulhaupt, R.; Rieger, B.; Waymouth, R.M. Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts. Angew. Chem. Int. Ed. Engl. 1995, 34, 1143–1170. [Google Scholar] [CrossRef]
- Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Selectivity in Propene Polymerization with Metallocene Catalysts. Chem. Rev. 2000, 100, 1253–1345. [Google Scholar] [CrossRef]
- Razavi, A.; Thewalt, U. Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts. Coord. Chem. Rev. 2006, 250, 155–169. [Google Scholar] [CrossRef]
- Chen, E.Y.-X. Coordination Polymerization of Polar Vinyl Monomers by Single-Site Metal Catalysts. Chem. Rev. 2009, 109, 5157–5214. [Google Scholar] [CrossRef]
- Kaminsky, W.; Kuelper, K.; Brintzinger, H.H.; Wild, F.R.W.P. Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst. Angew. Chem. Int. Ed. Engl. 1985, 24, 507–508. [Google Scholar] [CrossRef]
- Kaminsky, W.; Sinn, H. Methylaluminoxane: Key Component for New Polymerization Catalysts. Adv. Polym. Sci. 2013, 258, 1–28. [Google Scholar] [CrossRef]
- Makio, H.; Prasad, A.V.; Terao, H.; Saito, J.; Fujita, T. Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts. Dalton Trans. 2013, 42, 9112–9119. [Google Scholar]
- Press, K.; Venditto, V.; Goldberg, I.; Kol, M. Zirconium and hafnium Salalen complexes in isospecific polymerisation of propylene. Dalton Trans. 2013, 42, 9096–9103. [Google Scholar] [CrossRef]
- Karger-Kocsis, J. Polypropylene. 2. Copolymers and Blends; Chapman & Hall: London, UK, 1995. [Google Scholar]
- Ge, Z.; Chen, T.; Song, Z. Quality prediction for polypropylene production process based on CLGPR model. Control Eng. Pract. 2011, 19, 423–432. [Google Scholar] [CrossRef] [Green Version]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Mostoufi, N.; Hajimolana, S. Dynamics and Predictive Control of Gas Phase Propylene Polymerization in Fluidized Bed Reactors. Chin. J. Chem. Eng. 2013, 21, 1015–1029. [Google Scholar] [CrossRef]
- Gómez-Elvira, J.M.; Tiemblo, P.; Elvira, M.; Matisova-Rychla, L.; Rychly, J. Relaxations and thermal stability of low molecular weight predominantly isotactic metallocene and Ziegler-Natta polypropylene. Polym. Degrad. Stab. 2004, 85, 873–882. [Google Scholar] [CrossRef]
- Datta, S.; Sahnoune, A. Transparent and Translucent Crosslinked Propylenebased Elastomers, and Their Production and Use. WO2005049672A1, 19 May 2005. [Google Scholar]
- Kaminsky, W.; Laban, A. Metallocene catalysis. Appl. Catal. A 2001, 222, 47–61. [Google Scholar] [CrossRef]
- Nie, Y.; Sun, J.; Yin, W.; Wang, L.; Shi, Z.; Schumann, H. Novel diphenyl thioether-bridged binuclear metallocenes of Ti and Zr for synthesis of polyethylene with broad molecular weight distribution. J. Appl. Polym. Sci. 2011, 120, 3530–3535. [Google Scholar] [CrossRef]
- Ronkko, H.-L.; Korpela, T.; Knuuttila, H.; Pakkanen, T.T.; Denifl, P.; Leinonen, T.; Kemell, M.; Leskela, M. Particle growth and fragmentation of solid self-supported Ziegler–Natta-type catalysts in propylene polymerization. J. Mol. Catal. A Chem. 2009, 309, 40–49. [Google Scholar] [CrossRef]
- Vyas, P.B.; Kaur, S.; Patil, H.R.; Gupta, V.K. Synthesis of polypropylene with varied microstructure and molecular weights characteristics using supported titanium catalyst system. J. Polym. Res. 2011, 18, 235–239. [Google Scholar] [CrossRef]
- Pater, J.T.M.; Weickert, G.; Loos, J.; van Swaaij, W.P.M. High precision prepolymerization of propylene at extremely low reaction rates—Kinetics and morphology. Chem. Eng. Sci. 2001, 56, 4107–4120. [Google Scholar] [CrossRef]
- Mayrhofer, L.; Paulik, C. Growth Kinetics Obtained from Single Particle Gas-Phase Ethene Homopolymerization with a Ziegler-Natta Catalyst. Macromol. React. Eng. 2013, 8, 194–200. [Google Scholar] [CrossRef]
- Najafi, M.; Parvazinia, M.; Ghoreishy, M.H.R.; Kiparissides, G. Development of a 2D Single Particle Model to Analyze the Effect of Initial Particle Shape and Breakage in Olefin Polymerization. Macromol. React. Eng. 2013, 8, 29–45. [Google Scholar]
- Tregubov, A.A.; Zakharov, V.A.; Mikenas, T.B. Supported titanium-magnesium catalysts for ethylene polymerization: A comparative study of catalysts containing isolated and clustered titanium ions in different oxidation states. J. Polym. Sci. A Polym. Chem. 2009, 47, 6362–6372. [Google Scholar] [CrossRef]
- Damavandi, S.; Galland, G.B.; Zohuri, G.H.; Sandaroos, R. FI Zr-type catalysts for ethylene polymerization. J. Polym. Res. 2011, 18, 1059–1065. [Google Scholar] [CrossRef]
- Dashti, A.; Ramazani, S.A.; Hiraoka, Y.; Kim, S.Y.; Taniike, T.; Terano, M. Kinetic and morphological study of a magnesium ethoxide-based Ziegler-Natta catalyst for propylene polymerization. Polym. Int. 2009, 58, 40–45. [Google Scholar] [CrossRef]
- Yang, G.; Hong, M.; Li, Y.; Yu, S. Synthesis of Novel Bis (β-enaminoketonato) titanium Catalyst with High Activity and Excellent Ability to Copolymerize Olefins. Macromol. Chem. Phys. 2012, 213, 2311–2318. [Google Scholar] [CrossRef]
- Busico, V. Metal-catalysed olefin polymerisation into the new millennium: A perspective outlook. Dalton Trans. 2009, 41, 8794–8802. [Google Scholar] [CrossRef]
- Quadrelli, E.A.; Basset, J.M. On silsesquioxanes’ accuracy as molecular models for silica-grafted complexes in heterogeneous catalysis. Coord. Chem. Rev. 2010, 254, 707–728. [Google Scholar] [CrossRef]
- Yu, Y.; Fu, Z.; Fan, Z. Chain transfer reactions of propylene polymerization catalyzed by AlEt3 activated TiCl4/MgCl2 catalyst under very low monomer addition rate. J. Mol. Catal. A Chem. 2012, 363–364, 134–139. [Google Scholar] [CrossRef]
- Arlman, E.J.; Cossee, P. Ziegler-Natta catalysis III. Stereospecific polymerization of propene with the catalyst system TiCl3-AlEt3. J. Catal. 1964, 3, 99–104. [Google Scholar] [CrossRef]
- Seppälä, J.; Kokko, E.; Lehmus, P.; née Malmberg, A.P.; Hakala, K.; Lipponen, S.; Löfgren, B. Functional Polyolefins through Polymerizations by Using Bis(indenyl) Zirconium Catalysts. Adv. Polym. Sci. 2013, 258, 179–232. [Google Scholar] [CrossRef]
- Doi, Y.; Suzuki, S.; Soga, K. Living coordination polymerization of propene with a highly active vanadium-based catalyst. Macromolecules 1986, 19, 2896–2900. [Google Scholar] [CrossRef]
- Piers, W.E.; Marwitz, A.J.V.; Mercier, L.G. Mechanistic Aspects of Bond Activation with Perfluoroarylboranes. Inorg. Chem. 2011, 50, 12252–12262. [Google Scholar] [CrossRef]
- Pater, J.T.M.; Weickert, G.; van Swaaij, W.P.M. Polymerization of liquid propylene with a fourth-generation Ziegler-Natta catalyst: Influence of temperature, hydrogen, monomer concentration, and prepolymerization method on powder morphology. J. Appl. Polym. Sci. 2003, 87, 1421–1435. [Google Scholar] [CrossRef]
- Weickert, G.; Meier, G.B.; Pater, J.T.M.; Westerterp, K.R. The particle as microreactor: Catalytic propylene polymerizations with supported metallocenes and Ziegler-Natta catalysts. Chem. Eng. Sci. 1999, 54, 3291–3296. [Google Scholar] [CrossRef]
- Abu-Sharkh, B.; Hussein, I.H. MD simulation of the influence of branch content on collapse and conformation of LLDPE chains crystallizing from highly dilute solutions. Polymer 2002, 43, 6333–6340. [Google Scholar] [CrossRef]
- Kaminsky, W.; Sperber, O.; Werner, R. Pentalene substituted metallocene complexes for olefin polymerization. Coord. Chem. Rev. 2006, 250, 110–117. [Google Scholar] [CrossRef]
- Kaminsky, W. Zirconocene catalysts for olefin polymerization. Catal. Today 1994, 20, 257–271. [Google Scholar] [CrossRef]
- Wang, B. Ansa-metallocene polymerization catalysts: Effects of the bridges on the catalytic activities. Coord. Chem. Rev. 2006, 250, 242–258. [Google Scholar] [CrossRef]
- Kaminsky, W. Trends in Polyolefin Chemistry. Macromol. Chem. Phys. 2008, 209, 459–466. [Google Scholar] [CrossRef]
- Kaminsky, W.; Hopf, A.; Piel, C. Cs-symmetric hafnocene complexes for synthesis of syndiotactic polypropene. J. Organometal. Chem. 2003, 684, 200–205. [Google Scholar] [CrossRef]
- Stadler, F.J.; Piel, C.; Klimke, K.; Kaschta, J.; Parkinson, M.; Wilhelm, M.; Kaminsky, W.; Münstedt, H. Influence of Type and Content of Various Comonomers on Long-Chain Branching of Ethene/α-Olefin Copolymers. Macromolecules 2006, 39, 1474–1482. [Google Scholar] [CrossRef]
- Piel, C.; Stadler, F.J.; Kaschta, J.; Rulhoff, S.; Münstedt, H.; Kaminsky, W. Structure-Property Relationships of Linear and Long-Chain Branched Metallocene High-Density Polyethylenes Characterized by Shear Rheology and SEC-MALLS. Macromol. Chem. Phys. 2006, 207, 26–38. [Google Scholar] [CrossRef]
- Kakinuki, K.; Fujiki, M.; Nomura, K. Copolymerization of Ethylene with α-Olefins Containing Various Substituents Catalyzed by Half-Titanocenes: Factors Affecting the Monomer Reactivities. Macromolecules 2009, 42, 4585–4595. [Google Scholar] [CrossRef]
- Suhm, J.; Heinemann, J.; Wörner, C.; Müller, P.; Stricker, F.; Kressler, J.; Okuda, J.; Mülhaupt, R. Novel polyolefin materials via catalysis and reactive processing. Macromol. Symp. 1998, 129, 1–28. [Google Scholar] [CrossRef]
- Soga, K.; Uozumi, T.; Nakamura, S.; Toneri, T.; Teranishi, T.; Sano, T.; Arai, T.; Shiono, T. Structures of polyethylene and copolymers of ethylene with 1-octene and oligoethylene produced with the Cp2ZrCl2 and [(C5Me4)SiMe2N(t-Bu)]TiCl2 catalysts. Macromol. Chem. Phys. 1996, 197, 4237–4251. [Google Scholar] [CrossRef]
- Leone, G.; Losio, S.; Piovani, D.; Sommazzi, A.; Ricci, G. Living copolymerization of ethylene with 4-methyl-1-pentene by an α-diimine Ni(II)/Et2AlCl catalyst: Synthesis of diblock copolymers via sequential monomer addition. Polym. Chem. 2012, 3, 1987–1990. [Google Scholar] [CrossRef]
- Lee, J.; Kim, Y. Preparation of polyethylene with controlled bimodal molecular weight distribution using zirconium complexes. J. Ind. Eng. Chem. 2012, 18, 429–432. [Google Scholar] [CrossRef]
- Nakayama, Y.; Sogo, Y.; Cai, Z.; Shiono, T. Copolymerization of ethylene with 1,1-disubstituted olefins catalyzed by ansa-(fluorenyl)(cyclododecylamido)dimethyltitanium complexes. J. Polym. Sci. A Polym. Chem. 2013, 51, 1223–1229. [Google Scholar] [CrossRef]
- Shapiro, P.J.; Cotter, W.D.; Schaefer, W.P.; Labinger, J.A.; Bercaw, J.E. Model Ziegler-Natta alpha-Olefin Polymerization Catalysts Derived from[{(η5-C5Me4)SiMe2(η1-NCMe3)}(PMe3)Sc(µ2-H)]2 and[{(η5-C5Me4)SiMe2(η1-NCMe3)}Sc(µ2-CH2CH2CH3)]2, Synthesis, Structures, and Kinetic and Equilibrium Investigations of the Catalytically Active Species in Solution. J. Am. Chem. Soc. 1994, 116, 4623–4640. [Google Scholar]
- Cano, J.; Kunz, K.; Organometal, J. How to synthesize a constrained geometry catalyst (CGC)—A survey. J. Organomet. Chem. 2007, 692, 4411–4423. [Google Scholar] [CrossRef]
- Unverhau, K.; Kehr, G.; Fröhlich, R.; Erker, G. Synthesis of [3]ferrocenophane-bridged Cp–amido zirconium complexes and ansa-zirconocene complexes and their use in catalytic polymerisation reactions. Dalton Trans. 2011, 40, 3724–3736. [Google Scholar] [CrossRef]
- Stevens, J.C.; Wilson, D.R. Olefin Polymerization Process Using Supported Constrained Geometry Catalysts. U.S. Patent 6,884,857 B1, 26 April 2005. [Google Scholar]
- Okuda, J.; Schattenmann, F.J.; Wocadlo, S.; Massa, W. Synthesis and Characterization of Zirconium Complexes Containing a Linked Amido-Fluorenyl Ligand. Organometallics 1995, 14, 789–795. [Google Scholar] [CrossRef]
- Spaleck, W.; Aulbach, M.; Bachmann, B.; Küber, F.; Winter, A. Stereospecific metallocene catalysts: Scope and limits of rational catalyst design. Macromol. Symp. 1995, 89, 237–247. [Google Scholar] [CrossRef]
- Kaminsky, W. Discovery of Methylaluminoxane as Cocatalyst for Olefin Polymerization. Macromolecules 2012, 45, 3289–3297. [Google Scholar] [CrossRef]
- Chien, J.C.W.; Wang, B.P. Metallocene–methylaluminoxane catalysts for olefin polymerizations. IV. Active site determinations and limitation of the 14CO radiolabeling technique. J. Polym. Sci. A Polym. Chem. 1989, 27, 1539–1557. [Google Scholar] [CrossRef]
- Kaminsky, W.; Ahlers, A.; Moeller-Lindenhof, N. Asymmetrische Oligomerisation von Propen und 1-Buten mit einem Zirconocen/Aluminoxan-Katalysator. Angew. Chem. 1989, 101, 1304–1306. (in German). [Google Scholar] [CrossRef]
- Ewen, J.A.; Amer, J. Mechanisms of stereochemical control in propylene polymerizations with soluble Group 4B metallocene/methylalumoxane catalysts. Chem. Soc. 1984, 106, 6355–6364. [Google Scholar] [CrossRef]
- Natta, G.; Corradini, P.; Allegra, G. The different crystalline modifications of TiCl3, a catalyst component for the polymerization of α-olefins. I: α-, β-, γ-TiCl3. II: δ-TiCl3. J. Polym. Sci. 1961, 51, 399–410. [Google Scholar] [CrossRef]
- Trementozzi, Q.; Geymer, D.O.; Boyd, T.; Dietrich, H.J. Polymerization of Alpha-Olefins Using a Delta TiCL3 Catalyst. U.S. Patent 3573270 A, 30 March 1971. [Google Scholar]
- Boor, J., Jr. Ziegler-Natta Catalysts and Polymerization; Academic Press: New York, NY, USA, 1979. [Google Scholar]
- Keii, T. Kinetics of Ziegler-Natta Polymerization; Kodansha: Tokyo, Japan, 1972. [Google Scholar]
- Soares, J.B.P. Mathematical modelling of the microstructure of polyolefins made by coordination polymerization: A review. Chem. Eng. Sci. 2001, 56, 4131–4153. [Google Scholar] [CrossRef]
- Zhang, H.X.; Lee, Y.J.; Park, J.R.; Lee, D.H.; Yoon, K.B. Control of molecular weight distribution for polypropylene obtained by a commercial Ziegler-Natta catalyst: Effect of a cocatalyst and hydrogen. J. Appl. Polym. Sci. 2011, 120, 101–108. [Google Scholar] [CrossRef]
- Lou, J.Q.; Tu, S.T.; Fan, Z.Q. Polypropylene Chain Structure Regulation by Alkoxysilane and Ether Type External Donors in TiCl4/DIBP/MgCl2-AlEt3 Ziegler-Natta Catalyst. Iran. Polym. J. 2010, 19, 927–936. [Google Scholar]
- Shen, X.-R.; Fu, Z.-S.; Hu, J.; Wang, Q.; Fan, Z.-Q. Mechanism of Propylene Polymerization with MgCl2-Supported Ziegler-Natta Catalysts Based on Counting of Active Centers: The Role of External Electron Donor. Phys. Chem. C 2013, 117, 15174–15182. [Google Scholar] [CrossRef]
- Chadwick, J.C. Polyolefins—Catalyst and Process Innovations and their Impact on Polymer Properties. Macromol. React. Eng. 2009, 3, 428–432. [Google Scholar] [CrossRef]
- Andoni, A.; Chadwick, J.C.; Niemantsverdriet, H.J.W.; Thune, P.C. The role of electron donors on lateral surfaces of MgCl2-supported Ziegler-Natta catalysts: Observation by AFM and SEM. J. Catal. 2008, 257, 81–86. [Google Scholar] [CrossRef]
- Singh, G.; Kaur, S.; Makwana, U.; Patankar, R.B.; Gupta, V.K. Influence of Internal Donors on the Performance and Structure of MgCl2 Supported Titanium Catalysts for Propylene Polymerization. Macromol. Chem. Phys. 2009, 210, 69–76. [Google Scholar]
- Makwana, U.; Naik, D.G.; Singh, G.; Patel, V.; Patil, H.R.; Gupta, V.K. Nature of Phthalates as Internal Donors in High Performance MgCl2 Supported Titanium Catalysts. Catal. Lett. 2009, 131, 624–631. [Google Scholar] [CrossRef]
- Kissin, Y.V.; Liu, X.S.; Pollick, D.J.; Brungard, N.L.; Chang, M. Ziegler-Natta catalysts for propylene polymerization: Chemistry of reactions leading to the formation of active centers. J. Mol. Catal. A Chem. 2008, 287, 45–52. [Google Scholar] [CrossRef]
- Heikkinen, H.; Liitia, T.; Virkkunen, V.; Leinonen, T.; Helaja, T.; Denifl, P. Solid state 13C-NMR characterisation study on fourth generation Ziegler-Natta catalysts. Solid State Nucl Magn. Reson. 2012, 43–44, 36–41. [Google Scholar]
- Lu, L.; Niu, H.; Dong, J.Y. Propylene polymerization over MgCl2-supported TiCl4 catalysts bearing different amounts of a diether internal electron donor: Extrapolation to the role of internal electron donor on active site. J. Appl. Polym. Sci. 2012, 124, 1265–1270. [Google Scholar] [CrossRef]
- Alshaiban, A.; Soares, J.B.P. Effect of Hydrogen and External Donor on Propylene Polymerization Kinetics with a 4th-Generation Ziegler-Natta Catalyst. Macromol. React. Eng. 2012, 6, 265–274. [Google Scholar] [CrossRef]
- Marques, M.F.V.; da Silva Cardoso, R.; da Silva, M.G. Preparation of MgCl2-supported Ziegler-Natta catalyst systems with new electron donors. Appl. Catal. A 2010, 374, 65–70. [Google Scholar] [CrossRef]
- Harding, G.W.; van Reenen, A.J. Polymerisation and structure–property relationships of Ziegler-Natta catalysed isotactic polypropylenes. Eur. Polym. J. 2011, 47, 70–77. [Google Scholar] [CrossRef]
- Vestberg, T.; Denifl, P.; Parkinson, M.; Wilen, C.E. Effects of external donors and hydrogen concentration on oligomer formation and chain end distribution in propylene polymerization with Ziegler-Natta catalysts. J. Polym. Sci. Part A Polym. Chem. 2010, 48, 351–358. [Google Scholar]
- Thushara, K.S.; Gnanakumar, E.S.; Mathew, R.; Jha, R.K.; Ajithkumar, T.G.; Rajamohanan, P.R.; Sarma, K.; Padmanabhan, S.; Bhaduri, S.; Gopinath, C.S. Toward an Understanding of the Molecular Level Properties of Ziegler-Natta Catalyst Support with and without the Internal Electron Donor. J. Phys. Chem. C 2011, 115, 1952–1960. [Google Scholar] [CrossRef]
- Brambilla, L.; Zerbi, G.; Piemontesi, F.; Nascetti, S.; Morini, G. Structure of Donor Molecule 9,9-Bis(Methoxymethyl)-Fluorene in Ziegler-Natta Catalyst by Infrared Spectroscopy and Quantum Chemical Calculation. J. Phys. Chem. C 2010, 114, 11475–11484. [Google Scholar]
- Busico, V.; Cipullo, R.; Monaco, G.; Talarico, G.; Vacatello, M.; Chadwick, J.C.; Segre, A.L.; Sudmeijer, O. High-Resolution 13C-NMR Configurational Analysis of Polypropylene Made with MgCl2-Supported Ziegler-Natta Catalysts. 1. The “Model” System MgCl2/TiCl4–2,6-Dimethylpyridine/Al(C2H5)3. Macromolecules 1999, 32, 4173–4182. [Google Scholar] [CrossRef]
- Liu, B.P.; Nitta, T.; Nakatani, H.; Terano, M. Precise arguments on the distribution of stereospecific active sites on MgCl2-supported Ziegler-Natta catalysts. Macromol. Symp. 2004, 213, 7–18. [Google Scholar] [CrossRef]
- Wang, Q.; Murayama, N.; Liu, B.P.; Terano, M. Effects of Electron Donors on Active Sites Distribution of MgCl2-Supported Ziegler-Natta Catalysts Investigated by Multiple Active Sites Model. Macromol. Chem. Phys. 2005, 206, 961–966. [Google Scholar] [CrossRef]
- Bukatov, G.D.; Zakharov, V.A.; Barabanov, A.A. Mechanism of olefin polymerization on supported Ziegler-Natta catalysts based on data on the number of active centers and propagation rate constants. Kinet. Catal. 2005, 46, 166–176. [Google Scholar]
- Vanka, K.; Singh, G.; Iyer, D.; Gupta, V.K. DFT Study of Lewis Base Interactions with the MgCl2 Surface in the Ziegler-Natta Catalytic System: Expanding the Role of the Donors. J. Phys. Chem. C 2010, 114, 15771–15781. [Google Scholar] [CrossRef]
- Stukalov, D.V.; Zakharov, V.A.; Zilberberg, I.L. Adsorption Species of Ethyl Benzoate in MgCl2-Supported Ziegler-Natta Catalysts. A Density Functional Theory Study. J. Phys. Chem. C 2010, 114, 429–435. [Google Scholar]
- Taniike, T.; Terano, M. Coadsorption model for first-principle description of roles of donors in heterogeneous Ziegler-Natta propylene polymerization. J. Catal. 2012, 293, 39–50. [Google Scholar] [CrossRef]
- Credendino, R.; Pater, J.T.M.; Liguori, D.; Morini, G.; Cavallo, L. Investigating Alkoxysilane Coverage and Dynamics on the (104) and (110) Surfaces of MgCl2-Supported Ziegler-Natta Catalysts. J. Phys. Chem. C 2012, 116, 22980–22986. [Google Scholar] [CrossRef]
- Wondimagegn, T.; Ziegler, T. The Role of External Alkoxysilane Donors on Stereoselectivity and Molecular Weight in MgCl2-Supported Ziegler-Natta Propylene Polymerization: A Density Functional Theory Study. J. Phys. Chem. C 2012, 116, 1027–1033. [Google Scholar] [CrossRef]
- Cheng, R.H.; Luo, J.; Liu, Z.; Sun, J.W.; Huang, W.H.; Zhang, M.G.; Yi, J.J.; Liu, B.P. Adsorption of TiCl4 and electron donor on defective MgCl2 surfaces and propylene polymerization over Ziegler-Natta catalyst: A DFT study. Chin. J. Polym. Sci. 2013, 31, 591–600. [Google Scholar] [CrossRef]
- Shen, X.R.; Hu, J.; Fu, Z.S.; Lou, J.Q.; Fan, Z.Q. Counting the number of active centers in MgCl2-supported Ziegler-Natta catalysts by quenching with 2-thiophenecarbonyl chloride and study on the initial kinetics of propylene polymerization. Catal. Commun. 2013, 30, 66–69. [Google Scholar] [CrossRef]
- Xia, S.J.; Fu, Z.S.; Liu, X.Y.; Fan, Z.Q. Copolymerization of ethylene and 1-hexene with TiCl4/MgCl2 catalysts modified by 2,6-diisopropylphenol. Chin. J. Polym. Sci. 2013, 31, 110–121. [Google Scholar] [CrossRef]
- Hu, J.; Han, B.; Shen, X.R.; Fu, Z.S.; Fan, Z.Q. Probing the roles of diethylaluminum chloride in propylene polymerization with MgCl2-supported Ziegler-Natta catalysts. Chin. J. Polym. Sci. 2013, 31, 583–590. [Google Scholar] [CrossRef]
- Li, J.; Gao, W.; Wu, Q.; Li, H.; Mu, Y. Synthesis and structures of adamantyl-substituted constrained geometry cyclopentadienyl–phenoxytitanium complexes and their catalytic properties for olefin polymerization. J. Organomet. Chem. 2011, 696, 2499–2506. [Google Scholar] [CrossRef]
- Sinn, H.; Kaminsky, W.; Vollmer, H.J.; Woldt, R. “Living Polymers” on Polymerization with Extremely Productive Ziegler Catalysts. Angew. Chem. Int. Ed. Engl. 1980, 19, 390–392. [Google Scholar] [CrossRef]
- Grubbs, R.H.; Coates, G.W. α-Agostic Interactions and Olefin Insertion in Metallocene Polymerization Catalysts. Acc. Chem. Res. 1996, 29, 85–93. [Google Scholar] [CrossRef]
- Lee, I.M.; Gauthier, W.J.; Ball, J.M.; Iyengar, B.; Collins, S. Electronic effects of Ziegler-Natta polymerization of propylene and ethylene using soluble metallocene catalysts. Organometallics 1992, 11, 2115–2122. [Google Scholar] [CrossRef]
- Chapman, A.M.; Haddow, M.F.; Wass, D.F. Cationic Group 4 Metallocene–(o-Phosphanylaryl)oxido Complexes: Synthetic Routes to Transition-Metal Frustrated Lewis Pairs. Eur. J. Inorg. Chem. 2012, 1546–1554. [Google Scholar] [CrossRef]
- Berg, D.J.; Barclay, T.; Fei, X. Trivalent lanthanide–alkene complexes: Crystallographic and NMR evidence for coordination of tethered alkenes in the solid state and solution. J. Organomet. Chem. 2010, 695, 2703–2712. [Google Scholar] [CrossRef]
- Rocchigiani, L.; Ciancaleoni, G.; Zuccaccia, C.; Macchioni, A. An Integrated NMR and DFT Study on the Single Insertion of α-Olefins into the M[BOND]C Bond of Group 4 Metallaaziridinium Ion Pairs. ChemCatChem. 2013, 5, 519–528. [Google Scholar] [CrossRef]
- Rowley, C.N.; Woo, T.K. Counteranion Effects on the Zirconocene Polymerization Catalyst Olefin Complex from QM/MM Molecular Dynamics Simulations. Organometallics 2011, 30, 2071–2074. [Google Scholar] [CrossRef]
- Bahri-Laleh, N.; Nekoomanesh-Haghighi, M.; Mirmohammadi, S.A. A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler-Natta catalyst. J. Organomet. Chem. 2012, 719, 74–79. [Google Scholar] [CrossRef]
- Kawamura-Kuribayashi, H.; Koga, N.; Morokuma, K. An ab initio MO and MM study of homogeneous olefin polymerization with silylene-bridged zirconocene catalyst and its regio- and stereoselectivity. J. Am. Chem. Soc. 1992, 114, 8687–8694. [Google Scholar] [CrossRef]
- Hustad, P.D.; Tian, J.; Coates, G.W. Mechanism of Propylene Insertion Using Bis(phenoxyimine)-Based Titanium Catalysts: An Unusual Secondary Insertion of Propylene in a Group IV Catalyst System. J. Am. Chem. Soc. 2002, 124, 3614–3621. [Google Scholar] [CrossRef]
- Cohen, A.; Coates, G.W.; Kol, M. polymerization by C1-symmetric {ONNO'}-type salan zirconium complexes. J. Polym. Sci. A Polym. Chem. 2013, 51, 593–600. [Google Scholar] [CrossRef]
- Resconi, L.; Camurati, I.; Sudmeijer, O. Chain transfer reactions in propylene polymerization with zirconocene catalysts. Top. Catal. 1999, 7, 145–163. [Google Scholar] [CrossRef]
- Ray, G.J.; Johnson, P.E.; Knox, J.R. Carbon-13 Nuclear Magnetic Resonance Determination of Monomer Composition and Sequence Distribution in Ethylene-Propylene Copolymers Prepared with a Stereoregular Catalyst System. Macromolecules 1977, 10, 773–778. [Google Scholar] [CrossRef]
- Lu, L.; Niu, H.; Dong, J.-Y.; Zhao, X.; Hu, X. Ethylene/propylene copolymerization over three conventional C2-symmetric metallocene catalysts: Correlation between catalyst configuration and copolymer microstructure. J. Appl. Polym. Sci. 2010, 118, 3218–3226. [Google Scholar] [CrossRef]
- Nekoomanesh, M.; Zohuri, G.H.; Mortazavi, M.M.; Jamjah, R.; Ahmadjo, S. Structural Analysis of Ethylene/Propylene Copolymer Synthesized Using High Activity Bi-supported Ziegler-Natta Catalyst. Iran. Polym. J. 2005, 14, 793–798. [Google Scholar]
- Razavi, A. Syndiotactic Polypropylene: Discovery, Development, and Industrialization via Bridged Metallocene Catalysts. Adv. Polym. Sci. 2013, 258, 43–116. [Google Scholar] [CrossRef]
- Vestberg, T.; Parkinson, M.; Fonseca, I.; Wilén, C.-E. Poly (propylene-co-ethylene) produced with a conventional and a self-supported Ziegler-Natta catalyst: Effect of ethylene and hydrogen concentration on activity and polymer structure. J. Appl. Polym. Sci. 2012, 124, 4889–4896. [Google Scholar]
- Randall, J.C. Methylene Sequence Distributions and Number Average Sequence Lengths in Ethylene-Propylene Copolymers. Macromolecules 1978, 11, 33–36. [Google Scholar] [CrossRef]
- Cheng, H.N. Carbon-13 NMR analysis of ethylene-propylene rubbers. Macromolecules 1984, 17, 1950–1955. [Google Scholar] [CrossRef]
- Natta, G.; Pasquon, I.; Zambelli, A. Stereospecific Catalysts for the Head-To-Tail Polymerization of Propylene to a Crystalline Syndiotactic Polymer. J. Am. Chem. Soc. 1962, 84, 1488–1490. [Google Scholar] [CrossRef]
- Wu, J.Q.; Li, Y.S. Well-defined vanadium complexes as the catalysts for olefin polymerization. Coord. Chem. Rev. 2011, 255, 2303–2314. [Google Scholar] [CrossRef]
- Pellecchia, C.; Zambelli, A.; Mazzeo, M.; Pappalardo, D. Syndiotactic-specific polymerization of propene with Nickel-based catalysts. 3. Polymer end-groups and regiochemistry of propagation. J. Mol. Catal. A Chem. 1998, 128, 229–237. [Google Scholar] [CrossRef]
- Makio, H.; Terao, H.A.; Iwashita, T. Fujita, FI Catalysts for Olefin Polymerization—A Comprehensive Treatment. Chem. Rev. 2011, 111, 2363–2449. [Google Scholar] [CrossRef]
- Takeuchi, D. Recent progress in olefin polymerization catalyzed by transition metal complexes: New catalysts and new reactions. Dalton Trans. 2010, 39, 311–328. [Google Scholar]
- Small, B.L.; Brookhart, M. Polymerization of propylene by a new generation of iron catalysts: Mechanisms of chain initiation, propagation, and termination. Macromolecules 1999, 32, 2120–2130. [Google Scholar]
- Britovsek, G.J.P.; Gibson, V.C.; Kimberley, B.S.; Maddox, P.J.; McTavish, S.J.; Solan, G.A.; White, A.J.P.; Williams, D.J. Novel olefin polymerization catalysts based on iron and cobalt. Chem. Commun. 1998, 849–850. [Google Scholar]
- Britovsek, G.J.P.; Gibson, V.C.; Wass, D.F. The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes. Angew. Chem. Int. Ed. 1999, 38, 428–447. [Google Scholar] [CrossRef]
- Tian, J.; Coates, G.W. Development of a Diversity-Based Approach for the Discovery of Stereoselective Polymerization Catalysts: Identification of a Catalyst for the Synthesis of Syndiotactic Polypropylene. Angew. Chem. Int. Ed. 2000, 39, 3626–3629. [Google Scholar] [CrossRef]
- Tian, J.; Hustad, P.D.; Coates, G.W. A New Catalyst for Highly Syndiospecific Living Olefin Polymerization: Homopolymers and Block Copolymers from Ethylene and Propylene. J. Am. Chem. Soc. 2001, 123, 5134–5135. [Google Scholar] [CrossRef]
- Heurtefeu, B.; Bouilhac, C.; Cloutet, É.; Taton, D.; Deffieux, A.; Cramail, H. Polymer support of “single-site” catalysts for heterogeneous olefin polymerization. Prog. Polym. Sci. 2011, 36, 89–126. [Google Scholar] [CrossRef]
- Caporaso, L.; de Rosa, C.; Talarico, G. The relationship between catalyst precursors and chain end groups in homogeneous propene polymerization catalysis. J. Polym. Sci. A Polym. Chem. 2010, 48, 699–708. [Google Scholar] [CrossRef]
- Bochmann, M. The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts. Organometallics 2010, 29, 4711–4740. [Google Scholar] [CrossRef]
- Alley, W.M.; Hamdemir, I.K.; Johnson, K.A.; Finke, R.G. Ziegler-type hydrogenation catalysts made from Group 8–10 transition metal precatalysts and AlR3 cocatalysts: A critical review of the literature. J. Mol. Catal. A Chem. 2010, 315, 1–27. [Google Scholar] [CrossRef]
- Laine, A.; Linnolahti, M.; Pakkanen, T.A.; Severn, J.R.; Kokko, E.; Pakkanen, A. Comparative Theoretical Study on Homopolymerization of α-Olefins by Bis(cyclopentadienyl) Zirconocene and Hafnocene: Elemental Propagation and Termination Reactions between Monomers and Metals. Organometallics 2010, 29, 1541–1550. [Google Scholar] [CrossRef]
- Nomura, K.; Zhang, S. Design of Vanadium Complex Catalysts for Precise Olefin Polymerization. Chem. Rev. 2011, 111, 2342–2362. [Google Scholar] [CrossRef]
- Nomura, K.; Liu, J. Half-titanocenes for precise olefin polymerisation: Effects of ligand substituents and some mechanistic aspects. Dalton Trans. 2011, 40, 7666–7682. [Google Scholar] [CrossRef]
- Nomura, K.; Fukuda, H.; Katao, S.; Fujiki, M.; Kim, H.J.; Kim, D.-H.; Saeed, I. Olefin Polymerization by Half-Titanocenes Containing η2-Pyrazolato Ligands–MAO Catalyst Systems. Macromolecules 2011, 44, 1986–1998. [Google Scholar] [CrossRef]
- Tomotsu, N.; Ishihara, N.; Newman, T.H.; Malanga, M.T. Syndiospecific polymerization of styrene. J. Mol. Catal. A Chem. 1998, 128, 167–190. [Google Scholar] [CrossRef]
- Schellenberg, J.J. Recent transition metal catalysts for syndiotactic polystyrene. Prog. Polym. Sci. 2009, 34, 688–718. [Google Scholar] [CrossRef]
- Guo, F.; Nishiura, M.; Koshino, H.; Hou, Z. Cycloterpolymerization of 1,6-Heptadiene with Ethylene and Styrene Catalyzed by a THF-Free Half-Sandwich Scandium Complex. Macromolecules 2011, 44, 6335–6344. [Google Scholar] [CrossRef]
- Liu, K.; Wu, Q.; Gao, W.; Mu, Y.; Ye, L. Half-Titanocence Anilide Complexes Cp'TiCl2[N(2,6-R12C6H3)R2]: Synthesis, Structures and Catalytic Properties for Ethylene Polymerization and Copolymerization with 1-Hexene. Eur. J. Inorg. Chem. 2011, 1901–1909. [Google Scholar]
- Nomura, K.; Fukuda, H.; Katao, S.; Fujiki, M.; Kim, H.J.; Kim, D.-H.; Zhang, S. Effect of ligand substituents in olefin polymerisation by half-sandwich titanium complexes containing monoanionic iminoimidazolidide ligands–MAO catalyst systems. Dalton Trans. 2011, 40, 7842–7849. [Google Scholar]
- Redshaw, C.; Tang, Y. Tridentate ligands and beyond in group IV metal α-olefin homo-/co-polymerization catalysis. Chem. Soc. Rev. 2012, 41, 4484–4510. [Google Scholar]
- Delferro, M.; Marks, T.J. Multinuclear Olefin Polymerization Catalysts. Chem. Rev. 2011, 111, 2450–2485. [Google Scholar]
- Fink, G. Contributions to the Ziegler-Natta Catalysis: An Anthology. Adv. Polym. Sci. 2013, 257, 1–35. [Google Scholar] [CrossRef]
- Beddie, C.; Hollink, E.; Wei, P.; Gauld, J.; Stephan, D.W. Use of Computational and Synthetic Chemistry in Catalyst Design: A New Family of High-Activity Ethylene Polymerization CatalystsBased on Titanium Tris(amino)phosphinimide Complexes. Organometallics 2004, 23, 5240–5251. [Google Scholar] [CrossRef]
- Galeski, A.; Bartczak, Z.; Kazmierczak, T.; Slouf, M. Morphology of undeformed and deformed polyethylene lamellar crystals. Polymer 2010, 51, 5780–5787. [Google Scholar] [CrossRef]
- Gokmen, M.T.; Du Prez, F.E. Porous polymer particles—A comprehensive guide to synthesis, characterization, functionalization and applications. Prog. Polym. Sci. 2012, 37, 365–405. [Google Scholar] [CrossRef] [Green Version]
- Callais, P. Outlook for PE and PP Resins. 16th Annual Canadian Plastics Resin Outlook Conference. Available online: http://www.canplastics.com/conference/2011Presentations/5._Peter_Callais (accessed on 6 October 2011).
- Arriola, D.J.; Carnahan, E.M.; Hustad, P.D.; Kuhlman, R.L.; Wenzel, TT. Catalytic Production of Olefin Block Copolymers via Chain Shuttling Polymerization. Science 2006, 312, 714–719. [Google Scholar] [CrossRef]
- Yoon, J.; Mathers, R.T.; Coates, G.W.; Thomas, E.L. Optically Transparent and High Molecular Weight Polyolefin Block Copolymers toward Self-Assembled Photonic Band Gap Materials. Macromolecules 2006, 39, 1913–1919. [Google Scholar] [CrossRef]
- Domski, G.J.; Rose, J.M.; Coates, G.W.; Bolig, A.D.; Brookhart, M. Living alkene polymerization: New methods for the precision synthesis of polyolefins. Prog. Polym. Sci. 2007, 32, 30–92. [Google Scholar] [CrossRef]
- Hustad, P.D.; Coates, G.W. Insertion/Isomerization Polymerization of 1,5-Hexadiene: Synthesis of Functional Propylene Copolymers and Block Copolymers. J. Am. Chem. Soc. 2002, 124, 11578–11579. [Google Scholar] [CrossRef]
- Mathers, R.T.; Coates, G.W. Cross metathesis functionalization of polyolefins. Chem. Commun. 2004, 422–423. [Google Scholar] [CrossRef]
- Funck, A.; Kaminsky, W. Polypropylene carbon nanotube composites by in situ polymerization. Compos. Sci. Technol. 2007, 67, 906–915. [Google Scholar] [CrossRef]
- Kaminsky, W. Metallocene Based Polyolefin Nanocomposites. Materials 2014, 7, 1995–2013. [Google Scholar] [CrossRef]
- Collins, S. Polymerization catalysis with transition metal amidinate and related complexes. Coord. Chem. Rev. 2011, 255, 118–138. [Google Scholar] [CrossRef]
- Chakrabarti, M.H.; Brandon, N.P.; Hashim, M.A.; Mjalli, F.S.; AlNashef, I.M.; Bahadori, L.; Abdul Manan, N.S.; Hussain, M.A.; Yufit, V. Cyclic Voltammetry of Iron (III) Acetylacetonate in Quaternary Ammonium and Phosphonium Based Deep Eutectic Solvents. Int. J. Electrochem. Sci. 2013, 8, 9652–9676. [Google Scholar]
- Yusoff, R.; Aroua, M.K.; Shamiri, A.; Ahmady, A.; Jusoh, N.S.; Asmuni, N.F.; Bong, L.C.; Thee, S.H. Density and Viscosity of Aqueous Mixtures of N-Methyldiethanolamines (MDEA) and Ionic Liquids. J. Chem. Eng. Data 2013, 58, 240–247. [Google Scholar] [CrossRef]
- Chakrabarti, M.H.; Mjalli, F.S.; AlNashef, I.M.; Hashim, M.A.; Hussain, M.A.; Bahadori, L.; Low, C.T.J. Prospects of applying ionic liquids and deep eutectic solvents for renewable energy storage by means of redox flow batteries. Renew. Sustain. Energy Rev. 2014, 30, 254–270. [Google Scholar] [CrossRef]
- Chakrabarti, M.H.; Brandon, N.P.; Mjalli, F.S.; Bahadori, L.; Al Nashef, I.M.; Hashim, M.A.; Hussain, M.A.; Low, C.T.J.; Yufit, V. Cyclic Voltammetry of Metallic Acetylacetonate Salts in Quaternary Ammonium and Phosphonium Based Deep Eutectic Solvents. J. Solut. Chem. 2013, 42, 2329–2341. [Google Scholar] [CrossRef]
- Bahadori, L.; Chakrabarti, M.H.; Mjalli, F.S.; AlNashef, I.M.; Abdul Manan, N.S.; Hashim, M.A. Physicochemical properties of ammonium-based deep eutectic solvents and their electrochemical evaluation using organometallic reference redox systems. Electrochim. Acta 2013, 113, 205–211. [Google Scholar] [CrossRef]
- Lu, J.; Yan, F.; Texter, J. Advanced applications of ionic liquids in polymer science. Prog. Polym. Sci. 2009, 34, 431–448. [Google Scholar]
- Ibrehem, A.S.; Hussain, M.A.; Ghasem, N.M. Decentralized advanced model predictive controller of fluidized-bed for polymerization process. Iran. J. Chem. Eng. 2012, 31, 91–117. [Google Scholar]
- Ho, Y.K.; Shamiri, A.; Mjalli, F.S.; Hussain, M.A. Control of industrial gas phase propylene polymerization in fluidized bed reactors. J. Proc. Control 2012, 22, 947–958. [Google Scholar] [CrossRef]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Moustofi, N.; Shafeeyan, M.S. Dynamic modeling of gas phase propylene homopolymerization in fluidized bed reactors. Chem. Eng. Sci. 2011, 66, 1189–1199. [Google Scholar] [CrossRef]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S.; Moustofi, N. Comparative simulation study of gas-phase propylene polymerization in fluidized bed reactors using Aspen polymers and two phase models. Chem. Ind. Chem. Eng. Q. 2013, 19, 13–24. [Google Scholar] [CrossRef]
- Shamiri, A.; Hussain, M.A.; Mjalli, F.S. Two phase dynamic model for gas phase propylene copolymerization in fluidized bed reactor. Defect. Diffus. Forum 2011, 312–315, 1079–1084. [Google Scholar] [CrossRef]
- Huang, R.; Xu, X.; Lee, S.; Zhang, Y.; Kim, B.J.; Wu, Q. High Density Polyethylene Composites Reinforced with Hybrid Inorganic Fillers: Morphology, Mechanical and Thermal Expansion Performance. Materials 2013, 6, 4122–4138. [Google Scholar] [CrossRef] [Green Version]
© 2014 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/).
Share and Cite
Shamiri, A.; Chakrabarti, M.H.; Jahan, S.; Hussain, M.A.; Kaminsky, W.; Aravind, P.V.; Yehye, W.A. The Influence of Ziegler-Natta and Metallocene Catalysts on Polyolefin Structure, Properties, and Processing Ability. Materials 2014, 7, 5069-5108. https://doi.org/10.3390/ma7075069
Shamiri A, Chakrabarti MH, Jahan S, Hussain MA, Kaminsky W, Aravind PV, Yehye WA. The Influence of Ziegler-Natta and Metallocene Catalysts on Polyolefin Structure, Properties, and Processing Ability. Materials. 2014; 7(7):5069-5108. https://doi.org/10.3390/ma7075069
Chicago/Turabian StyleShamiri, Ahmad, Mohammed H. Chakrabarti, Shah Jahan, Mohd Azlan Hussain, Walter Kaminsky, Purushothaman V. Aravind, and Wageeh A. Yehye. 2014. "The Influence of Ziegler-Natta and Metallocene Catalysts on Polyolefin Structure, Properties, and Processing Ability" Materials 7, no. 7: 5069-5108. https://doi.org/10.3390/ma7075069