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    Ionic Polymerization: Dr. Saima Shabbir, MS&E

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    Tayyab Ahsan
    Ionic polymerization uses ionic charges as active centers rather than free radicals. It is more specific to monomers that can stabilize positive or negative charges. Cationic polymerization uses initiators like protons or Lewis acids to generate positively charged active centers on the monomer. Anionic polymerization avoids termination because ion pairs cannot recombine, allowing for living polymerization and well-defined polymers. Both require anhydrous conditions due to reactive active centers.

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    Ionic Polymerization: Dr. Saima Shabbir, MS&E

    Uploaded by

    Tayyab Ahsan
    69 views19 pages
    Ionic polymerization uses ionic charges as active centers rather than free radicals. It is more specific to monomers that can stabilize positive or negative charges. Cationic polymerization uses initiators like protons or Lewis acids to generate positively charged active centers on the monomer. Anionic polymerization avoids termination because ion pairs cannot recombine, allowing for living polymerization and well-defined polymers. Both require anhydrous conditions due to reactive active centers.

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    Polymers Lecture 22

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    Ionic polymerization uses ionic charges as active centers rather than free radicals. It is more specific to monomers that can stabilize positive or negative charges. Cationic polymerization uses initiators like protons or Lewis acids to generate positively charged active centers on the monomer. Anionic polymerization avoids termination because ion pairs cannot recombine, allowing for living polymerization and well-defined polymers. Both require anhydrous conditions due to reactive active centers.

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    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    69 views19 pages

    Ionic Polymerization: Dr. Saima Shabbir, MS&E

    Uploaded by

    Tayyab Ahsan
    Ionic polymerization uses ionic charges as active centers rather than free radicals. It is more specific to monomers that can stabilize positive or negative charges. Cationic polymerization uses initiators like protons or Lewis acids to generate positively charged active centers on the monomer. Anionic polymerization avoids termination because ion pairs cannot recombine, allowing for living polymerization and well-defined polymers. Both require anhydrous conditions due to reactive active centers.

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    © All Rights Reserved
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    of 19

    Ionic Polymerization

    Dr. Saima Shabbir, MS&E


    Ionic Polymerization
    Active center is ionic charge instead of free radical.
    Therefore, ionic polymerization is more monomer
    specific than free radical.
    Only monomers that can sufficiently stabilize positive
    or negative charge will undergo ionic polymerization.
    Cationic Polymerization

    Anionic Polymerization
    Therefore, most monomers cannot be polymerized
    by ionic polymerization.

    Dr. Saima Shabbir, MS&E


    Characteristics of Ionic Polymerization
    i) Ionic polymerization is faster than free radical
    polymerization (generally)
    - [M*] = concentration of propagating chain is
    higher
    - [M+], [M-] = 104 - 106 [M]
    ii) Counter ion of opposite charge
    - Degree of association (Xn) influences rate of
    propagation (kp)
    - Polarity of solvent, ability to solvate counter ion
    significantly affect

    Dr. Saima Shabbir, MS&E


    Characteristics of Ionic Polymerization
    iii) Termination cannot occur between two
    growing chains
    - Active centers are of the same charge and
    the same charge repel each other
    so that coupling cannot take place

    Dr. Saima Shabbir, MS&E


    A. Cationic Polymerization

    Dr. Saima Shabbir, MS&E


    Cationic Polymerization
    I. Initiation
    Creation of +ve active centers:
    Monomer + Electrophiles, R+
    a) Protonic acids, H2SO4, HClO4
    involve addition of H+ to monomer
    b) Hydrogen halide acids, HCl ------ not suitable
    because Cl- recombines.
    c) Lewis acids + co-catalyst such as water, acid,
    organic halide

    Dr. Saima Shabbir, MS&E


    Cationic Polymerization
    Lewis acids: Boron trifluoride BF3, Aluminum
    chloride AlCl3, Tin tetrachloride SnCl4
    First step
    BF3 + H2O (trace) H+ (BF3OH)-
    AlCl3 + RCl R+ (AlCl4)-

    Dr. Saima Shabbir, MS&E


    Cationic Polymerization
    Second Step
    H+(BF3OH)- + CH2=CR1R2 CH3-C+R1R2 (BF3OH)-
    R+A- + CH2=CR1R2 R-CH2-C+R1R2A-

    Initiator Electrophile, R+ Counter ion, A-

    Dr. Saima Shabbir, MS&E


    Cationic Polymerization
    II. Propagation

    Propagation step is similar to free radical


    Predominantly head-to-tail
    Used for making stereospecific polymers

    Dr. Saima Shabbir, MS&E


    Cationic Polymerization
    III. Termination
    a) Unimolecular rearrangement of ion pair:

    b) Chain transfer to monomer is usual

    Terminated polymer New chain


    Chain transfer to solvent, impurities, H2O,
    polymer (branching) are all common.
    Dr. Saima Shabbir, MS&E
    Kinetics of Cationic Polymerization
    Specific to actual monomer, solvent, initiator
    Side reactions are many, and likely.
    Sub-zero temperatures are often necessary for high
    molecular weight polymers
    If water is co-catalyst, it must by stoichiometric
    H2O is good charge transfer agent
    Rapid; complete conversion in seconds
    Problem: heat transfer
    non-steady state conditions!

    Dr. Saima Shabbir, MS&E


    Kinetics of Cationic Polymerization
    Only Commercially Noteworthy Example:
    Synthesis of butyl rubber by copolymerization of
    isobutylene with small amount of isoprene
    At -90oC using Lewis acid initiator (AlCl3) in chlorinated
    solvents such as chloromethane.
    Solvent/ Counter Ion Effects:

    Very polar solvents (dichloromethane) separate ions and


    large, bulky counter ions (SbCl6 weakly associated-----
    faster
    Dr. Saima Shabbir, MS&E
    B. Anionic Polymerization

    Dr. Saima Shabbir, MS&E


    Anionic Polymerization
    Absence of an inherent termination process
    - Ion pair rearrangement involves elimination of a hydride
    ion, H-.....highly unfavorable.
    - Alkali metal counter ions, +, have no tendency to
    recombine with active growing centers to form dead
    polymer.
    Thus, without chain transfer, there is no tendency to
    create unreactive polymer
    Polymer chains that permanently retain their active
    centers and grow as long as there is monomer ----- Living
    Polymerization
    Dr. Saima Shabbir, MS&E
    Anionic Polymerization
    Example: Polymerization of styrene in liquid
    ammonia (one of first examples of anionic
    polymerization)
    I. Initiation
    KNH2 K+ + NH2-
    potassium amide amide ion

    Dr. Saima Shabbir, MS&E


    Anionic Polymerization
    II. Propagation

    III. Chain Transfer


    2

    Dr. Saima Shabbir, MS&E


    Anionic Polymerization
    Common Initiator Systems
    - Organolithium compounds: Butyl lithium
    Very reactive
    Used with non-polar hydrocarbon solvents
    With low Cs constants ----- living polymerization

    Dr. Saima Shabbir, MS&E


    Anionic Polymerization
    Solvent/ Counter Ion Effects
    M+ counter ions are smaller than A-
    - tightly bound
    - Propagation 102 - 104 times slower than cationic
    - Using polar solvents help solvate and activate ion
    pairs

    Dr. Saima Shabbir, MS&E


    Anionic Polymerization
    Practical Considerations
    High reactivity
    Low concentration of reacting species
    - Purity, dryness, inert gases needed
    - H2O, CO2, O2 all kill growing chains
    - Despite difficulties: very narrow PDIs
    Block copolymers of defined length

    Dr. Saima Shabbir, MS&E

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