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    Ch5 CoordinationPolymerization Daly

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    Sudsiri Hemsri
    The document summarizes the history and development of coordination polymerization processes, including Ziegler-Natta catalyst systems. It describes early discoveries in the stereoregular polymerization of olefins using titanium and vanadium catalysts. Subsequent work led to the development of heterogeneous Ziegler-Natta catalysts using titanium compounds and aluminum alkyls that allow for the production of isotactic polypropylene. Later improvements involved single-site metallocene catalysts that provide highly stereoregular polymers like isotactic polypropylene and syndiotactic polystyrene.

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    Ch5 CoordinationPolymerization Daly

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    Sudsiri Hemsri
    111 views31 pages
    The document summarizes the history and development of coordination polymerization processes, including Ziegler-Natta catalyst systems. It describes early discoveries in the stereoregular polymerization of olefins using titanium and vanadium catalysts. Subsequent work led to the development of heterogeneous Ziegler-Natta catalysts using titanium compounds and aluminum alkyls that allow for the production of isotactic polypropylene. Later improvements involved single-site metallocene catalysts that provide highly stereoregular polymers like isotactic polypropylene and syndiotactic polystyrene.

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    The document summarizes the history and development of coordination polymerization processes, including Ziegler-Natta catalyst systems. It describes early discoveries in the stereoregular polymerization of olefins using titanium and vanadium catalysts. Subsequent work led to the development of heterogeneous Ziegler-Natta catalysts using titanium compounds and aluminum alkyls that allow for the production of isotactic polypropylene. Later improvements involved single-site metallocene catalysts that provide highly stereoregular polymers like isotactic polypropylene and syndiotactic polystyrene.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    111 views31 pages

    Ch5 CoordinationPolymerization Daly

    Uploaded by

    Sudsiri Hemsri
    The document summarizes the history and development of coordination polymerization processes, including Ziegler-Natta catalyst systems. It describes early discoveries in the stereoregular polymerization of olefins using titanium and vanadium catalysts. Subsequent work led to the development of heterogeneous Ziegler-Natta catalysts using titanium compounds and aluminum alkyls that allow for the production of isotactic polypropylene. Later improvements involved single-site metallocene catalysts that provide highly stereoregular polymers like isotactic polypropylene and syndiotactic polystyrene.

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    Coordination Polymerization

    Ziegler Natta Processes

    Stereoregular Polymerization
    Cationic Initiation of Vinyl Ethers Schildknecht et al. Ind. Eng. Chem. 39, 180, (1947)
    BF3.Et2O Propane - 80-60 C
    OR OR OR OR

    O CH2 H3C CH3

    Isotactic vinyl ether

    Stereoregular Polymerization
    Anionic Polymerization of Methyl Methacrylate, H. Yuki, K. Hatada, K.Ohta, and Y. Okamoto, J. Macromol. Sci. A9, 983 (1975)
    CH3 O O BuLi or MgBr Toluene -78-0 C BuLi THF -78 C
    H3C OR
    OR OR OR

    Isotactic
    H3C OR OR
    OR OR

    Syndiotactic

    POLYETHYLENE (LDPE)
    R H2C CH2 20-40,000 psi 150-325 C H2C CH2 x

    Molecular Weights: 20,000-100,000; MWD = 3-20 density = 0.91-0.93 g/cm3 H3C

    Highly branched structureboth long and short chain branches


    Tm ~ 105 C, Xlinity ~ 40%

    H3C

    CH3

    H3C

    H3C C H2 H3C H3C CH3 CH3

    15-30 Methyl groups/1000 C atoms Applications: Packaging Film, wire and cable coating, toys, flexible bottles, housewares, coatings

    Zieglers Discovery
    1953 K. Ziegler, E. Holzkamp, H. Breil and H. Martin Angew. Chemie 67, 426, 541 (1955); 76, 545 (1964).

    Al(Et)3 + NiCl2

    CH3CH2CH=CH2 + Ni + AlCl(Et)2 100 atm 110 C


    Same result
    White Ppt. (Not reported by Holzkamp) White Ppt. (Eureka! reported by Breil)

    + Ni(AcAc)
    + Cr(AcAc) + Zr(AcAc)

    Al(Et)3 + TiCl4

    CH2CH2 1 atm "linear" 20-70 C Mw = 10,000 - 2,000,000

    Polypropylene (atactic)
    CH3 R * CH2 CH3 n Low molecular weight oils

    Formation of allyl radicals via chain transfer limits achievable molecular weights for all a-olefins

    Nattas Discovery
    1954 Guilio Natta, P. Pino, P. Corradini, and F. Danusso
    J. Am. Chem. Soc. 77, 1708 (1955) Crystallographic Data on PP J. Polym. Sci. 16, 143 (1955) Polymerization described in French

    CH3

    TiCl3 Al(Et)2Cl

    CH3

    CH3

    CH3

    CH3

    Isotactic
    VCl4 - 78 C Al(iBu)2Cl
    O in CH3 CH3 CH3 CH3

    CH3

    CH3

    Syndiotactic

    Ziegler and Natta awarded Nobel Prize in 1963

    Polypropylene (isotactic)
    CH3 TiCl3 Al(Et)2Cl
    Density ~ 0.9-0.91 g/cm3very high strength to weight ratio Tm = 165-175C: Use temperature up to 120 C Copolymers with 2-5% ethyleneincreases clarity and toughness of films Applications: dishwasher safe plastic ware, carpet yarn, fibers and ropes, webbing, auto parts
    CH3 CH3 CH3 CH3

    Polyethylene (HDPE)
    CH3

    Essentially linear structure Few long chain branches, 0.5-3 methyl groups/ 1000 C atoms

    Molecular Weights: 50,000-250,000 for molding compounds 250,000-1,500,000 for pipe compounds >1,500,000 super abrasion resistancemedical implants MWD = 3-20 density = 0.94-0.96 g/cm3 Tm ~ 133-138 C, Xlinity ~ 80% Generally opaque Applications: Bottles, drums, pipe, conduit, sheet, film

    Polyethylene (LLDPE)
    Copolymer of ethylene with a-olefin
    CH3 CH3 CH3 CH3 CH3

    Density controlled by co-monomer concentration; 1-butene (ethyl), or 1-hexene (butyl), or 1-octene (hexyl) (branch structure)

    Applications: Shirt bags, high strength films

    UNIPOL Process
    N. F. Brockman and J. B. Rogan, Ind. Eng. Chem. Prod. Res. Dev. 24, 278 (1985)

    Temp ~ 70-105C, Pressure ~ 2-3 MPa

    CATALYST PREPARATION
    Ball mill MgCl2 (support) with TiCl4 to produce maximum surface area and incorporate Ti atoms in MgCl2 crystals Add Al(Et)3 along with Lewis base like ethyl benzoate Al(Et)3 reduces TiCl4 to form active complex Ethyl Benzoate modifies active sites to enhance stereoselectivity Catalyst activity 50-2000 kg polypropylene/g Ti with isospecificity of > 90%

    Catalyst Formation
    AlEt3 + TiCl4 EtTiCl3 + Et2AlCl

    Et2AlCl + TiCl4 EtTiCl3 + EtAlCl2 EtTiCl3 + AlEt3 Et2TiCl2 + EtAlCl2 EtTiCl3 TiCl3 + Et. (source of radical products) Et. + TiCl4 EtCl + TiCl3 TiCl3 + AlEt3 EtTiCl2 + Et2AlCl

    General Composition of Catalyst System


    Group I III Metals AlEt3 Et2AlCl EtAlCl2 i-Bu3Al Et2Mg Et2Zn Et4Pb Transition Metals TiCl4 a,g, d TiCl3 MgCl2 Support VCl3, VoCL3, V(AcAc)3 Titanocene dichloride Ti(OiBu)4 (Mo, Cr, Zr, W, Mn, Ni) Additives H2 O2, H2O
    R C CH

    R-OH Phenols R3N, R2O, R3P Aryl esters HMPA, DMF

    Adjuvants used to control Stereochemistry

    O O CH2CH3 N H

    Si O

    O O

    Ethyl benzoate 2,2,6,6-tetramethylpiperidine

    Phenyl trimethoxy silane

    Hindered amine (also antioxidant)

    Nature of Active Sites


    R Al R Cl Cl Ti Cl Cl
    Monometallic site

    H3C

    Cl d Ti Cl Cl

    d CH2

    Al

    R R

    Bimetallic site

    Active sites at the surface of a TiClx crystal on catalyst surface.

    Monometallic Mechanism for Propagation


    Monomer forms -complex with vacant d-orbital

    CH2 Cl Ti Cl Cl Cl

    CH3

    CH2 Cl Ti Cl Cl Cl

    CH3

    Alkyl chain end migrates to -complex to form new -bond to metal

    H2C CH3 Cl Ti Cl Cl Cl CH2

    CH2 Cl Ti Cl Cl Cl

    CH3

    Monometallic Mechanism for Propagation


    Chain must migrate to original site to assure formation of isotactic structure

    H2C CH3 Cl Ti Cl Cl Cl CH2

    H3C CH2 Cl Ti Cl Cl Cl

    If no migration occurs, syndiotactic placements will form.

    Enantiomorphic Site Control Model for Isospecific Polymerization


    Stereocontrol is imposed by initiator active site alone with no influence from the propagating chain end, i.e. no penultimate effect Demonstrated by: 13C analysis of isotactic structures

    not
    Stereochemistry can be controlled by catalyst enantiomers

    Modes of Termination
    1. -hydride shift
    C H CH2 Ti R Al Ti CH2 CH2 H Al R Ti CH2 R Al

    2. Reaction with H2 (Molecular weight control!)


    C H H H CH2 Al Ti R CH2 CH3 H Ti Al R Ti CH2 R Al

    Types Of Monomers Accessible for ZN Processes


    1. a-Olefins

    H2C CH2 CH3 CH2CH3 R


    2. Dienes, (Butadiene, Isoprene, CH2=C=CH2)

    trans-1,4

    cis-1,4

    iso- and syndio-1,2

    1.2 Disubstituted double bonds do not polymerize

    Ethylene-Propylene Diene Rubber (EPDM)


    S. Cesca, Macromolecular Reviews, 10, 1-231 (1975)
    + + CH3 VOCl3 Et AlCl V(AcAc)3 2

    Catalyst soluble in hydrocarbons Continuous catalyst addition required to maintain activity

    .4-.8 .5-.1 0.05

    Rigid control of monomer feed ratio required to assure incorporation of propylene and diene monomers

    Development of Single Site Catalysts

    R Cl Cl Ti Cl Cl
    Z-N multisited catalyst, multiple site reactivities depending upon specific electronic and steric environments

    Me

    Single site catalyst every site has same chemical environment

    Kaminsky Catalyst System


    W. Kaminsky et.al. Angew. Chem. Eng. Ed. 19, 390, (1980); Angew. Chem. 97, 507 (1985)
    Me X + X CH3 * Al O * n

    Al:Zr = 1000

    Linear HD PE Activity = 107 g/mol Zr

    Me = Tl, Zr, Hf

    CH3
    Atactic polypropylene, Mw/Mn = 1.5-2.5 Activity = 106 g/mol Zr

    Methylalumoxane: the Key Cocatalyst


    toluene Al(CH3)3 + H2O
    CH3 Al O O Al Al O O Al CH3 CH3

    CH3 * Al O * n

    0C

    n = 10-20

    MAO
    Proposed structure

    Al O O Al Al

    Nature of active catalyst


    X Cp2Me X CH3 + * Al O * n

    MAO
    CH3 X CH3 + Al O X Al m

    Transition metal alkylation

    Cp2Me

    CH3 Cp2Me CH2 +

    X X Al O Al O m

    Ionization to form active sites

    Noncoordinating Anion, NCA

    Homogeneous Z-N Polymerization


    Advantages: High Catalytic Activity Impressive control of stereochemistry Well defined catalyst precursors

    Design of Polymer microstructures, including chiral polymers Disadvantages:


    Requires large excess of Aluminoxane (counter-ion) Higher tendency for chain termination: -H elimination, etc. Limited control of molecular weight distribution

    Evolution of single site catalysts


    Date Metallocene Stereo control Performance

    1950s

    None

    Moderate Mw PE
    Some comonomer incorporation

    Me

    Early 1980s
    Me

    None

    High MW PE Better comonomer incorporation

    Synthesis of Syndiotactic Polystyrene


    N. Ishihara et.al. Macromolecules 21, 3356 (1988); 19, 2462 (1986)
    Cl Cl * Al O * + n

    Styrene
    44.1%

    Ti

    CH3

    Ti Cl Cl Cl

    99.2%

    Ti

    Cl Cl 1.0%

    syndiotactic polystyrene

    m.p. = 265C

    Evolution of single site catalysts


    Date Metallocene Late 1980s
    N Me R

    Stereo control Slight Highly Syndiotactic

    Performance Very High Mw PE, excellent comonomer incorporation Used commercially for PP

    Late 1980s

    R R Me

    Early 1990s
    Me

    Highly Used commercially Isotactic for PP

    Technology S-curves for polyolefin production

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