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6 Polymerization

1 Introduction 1.1 Polyethylene 1.2 Polypropylene 2 Catalysts for Polyethylene 3 Catalysts for Polypropylene 4 Catalytic Cycle for Alkene Polymerization 4.1 Cossee–Arlman Mechanism 4.2 Mechanism of Alkene Insertion 4.3 Mechanistic Evidence 5 Metallocene Catalysts 5.1 Structures of Metallocene Catalysts and the Co-catalysts 5.2 Special Features and Advantages of Metallocene Catalysts 5.3 Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts 6 Chromocene and Heterogeneous Catalysts

6.7 Polymers of Other Alkenes 6.8 Engineering Aspects The two largest production: 1. Polyethylene 2. Polypropylene Mainly by heterogeneous process until the early 1990 (use of homogeneous metallocene catalysts). 1.1 Polyethylene (discovered in 1933 by ICI lab)

1. HDPE: From low temp and pressure (0.96 g/cm3) 2. LDPE: From with high temp and pressure (0.92 g/cm3)

LLDPE Small amount of butane/octene as co-monomers Structural features  physical properties e. elasticity.. 1.3.2 Polypropylene .g. crystallinity…….

the m.or syndiotacticity by 13C NMR 50 MHz: pentad 150 MHz: Nonad Relative intensity  Degree of tacticity Because of its ordered structure. and tensile strength (拉 力 ) than the atactic polymer.171°C atactic polymers = < 0 °C.: isotactic polymers = 165 . Typically. Phillips Catalyst (CrO3 on silica) 2. an isotactic polymer has higher m. 2 CATALYSTS FOR POLYETHYLENE Heterogeneous catalysts 1. Union Carbide Catalyst Silica + chromocene  silica supported catalyst .p.Determination of iso.p.

 Physical properties . and the extent of branching of the polymer chains.3. distribution of the molecular weights. TiCl4 + trialkylaluminum compound in organic solvent (colloidal (膠體的 )  heterogeneous) B. TiCl3 on solid support For both chromium. choice and pretreatment of the supported catalyst as well as other process parameters determine the molecular weights. Ziegler Catalyst A.and titanium-based catalysts.

β.  α. TiCl4/organoaluminum/promoter . the others (brown) are layers. γ. δ give high tacticity. TiCl4/organoaluminum compound TiCl3 from the reduction of TiCl4 by the organoaluminum compound) TiCl3 exists in 4 crystalline forms: α.3 CATALYSTS FOR POLYPROPYLENE Discovered by Natta (TiCl3 + organoaluminum reagent) to produce isotactic polypropylene with high crystallinity Three generations of catalysts 1. β. β does not. γ. δ ( polymorphs) β form (purple) has a chain structure. Reduction of TiCl4 by organoaluminum compound 2.

4.1 Cossee–Arlman Mechanism .000 g of polypropylene per gram of catalyst per hour could be achieved with an isotacticity index of 96–99%. Cossee–Arlman mechanism 2. TiCl3 supported on MgCl2/organoaluminum/promoter  highly effective: 30. Addition of promoters (ether/esters) to destroy AlEtCl2 3.Monoethyl reagent poisons the catalyst by blocking the coordination site. Green–Rooney mechanism. 4 CATALYTIC CYCLE FOR ALKENE POLYMERIZATION 1.

6  three routes 1. direct insertion of alkene into the metal–alkyl bond without the formation of any intermediate. with hydrogen gas . 6.

8 Green-Rooney Mechanism Agostic interaction of α hydrogen: intermediates α hydrogen Which mechanism??? γ hydrogen (Cossee–Arlman mechanisms Mechanism/Green-Rooney Mechanism) is the true . β-elimination 3. The last route is non-catalytic.2. living polymerization Cossee–Arlman Mechanism Direct insertion: transition state 6.

12!! Similar to 6. only difference is agostic interaction .8.Difficult to tell because it is difficult to determine the transition state or intermediates in heterogeneous Ziegler-Natta catalyst!! Indirect evidence from homogeneous metallocene catalyst Does not totally support Green-Rooney Mechanism!! But agostic interaction should present! Transition state 6.

3 Mechanistic Evidence 4f14 A model of metallocene compound for mechanistic studies. .or not!!! Agostic interaction is important for stereoregular polymerization of metallocene catalysts!!! (no consequence in ethylene polymerization) 4.

Metallocene Catalyst Background Homogeneous catalysts discovered in 1980s A milestone in polymer chemistry $5 billions investment + 1500 patent 0.5 tones of polypropylene in 2003 .5.

C.5.1 Structures of Metallocene Catalysts and the CoCatalysts a: part of indenyl ligand possible b: M is Ti(IV) or Zr(IV) c: A is an optional bridging atom eg. . d: X = Cl. Si.g. alkyl e.

26 because of high Lewis acidity of MAO .Metallocene Catalyst/H2O/AlMe3 H2O/AlMe3  MAO (methyl aluminoxanes.27 Abstraction of CH3 from 6. actual cocatalyst) MAO to generate coordinatively unsaturated intermediates 6.

Structural information from crystallography 27 Al NMR and X-ray Advantages of Metallocene catalysts over ZieglarNatta catalysts 1.MAO The general formula of MAO is given by Me2Al-O[AlMe]n-OAlMe2. where n is between 5 and 20. polymerize a very wide variety of vinyl .

2.) 3.3 Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts Cs symmetry C2 symmetry .monomers irrespective of their molecular weights and steric features. The most important feature of the metallocene catalysts is their ability to produce highly stereoregular polymers  choices of ligands 5. and with co-polymers nonidentical around the (Ziegler–Natta coordination environments catalytically active metal centers. This produces a vinyl double bond at the end of each polymer chain. The predominant mechanism for chain termination is by β-hydride elimination. the advantage of single site  produce extremely uniform homopolymers catalyst. give polymers with broad molecular-weight distributions. 4.

Which catalyst is chiral? Chiral catalyst  isotactic polymer Achiral catalyst  syndiotactic polymer .

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Temperature dependence Predict the tacticity of the polymer with temperature! A variety of monomers possible .

Mechanisms 6 CHROMOCENE AND HETEROGENEOUS CATALYSTS .

39 is inactive in the production of HDPE.  The oxidation state should be _______ 7 Polymers of other alkenes . The oxidation state of chromocene on silica = +2 or +3? (see page 4)  Well defined chromocene complexes for HDPE production Practice the electron counts and oxidation states??  6.

8 Engineering Aspects See the textbook .