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Ionic polymerization. Cme / mse 404G polymeric materials. outline. Characteristics Cationic polymerization Propagation reaction Termination reaction Kinetic chain length. characteristics. used for making stereoregular polymers with high tacticity
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Ionic polymerization Cme/mse 404G polymeric materials ionic polymerization
outline Characteristics Cationic polymerization Propagation reaction Termination reaction Kinetic chain length ionic polymerization
characteristics • used for making stereoregular polymers with high tacticity • selectivity is high, and is due to stabilization of the reactive chain site • Table 4.13 gives some typical commercial polymers • initiation of the ion pair has a low activation energy, and the rate is not sensitive to temperature • ion pairs do not reaction with each other: there are few or no termination reactions • solvents should be very pure ionic polymerization
Cationic polymerization • Table 4.14 shows the polarity range over which some catalysts, solvents and monomers are used. • We will review and extend Example Problem 4.9. Cationic Polymerization of Styrene ionic polymerization
initiation • where the term on the far right hand side is the reacting chain site. • If this reaction goes far to the right, almost all of the sulfuric acid will start chains when monomer is present. ionic polymerization
propagation • The reaction center continues to add monomer ionic polymerization
termination • In this case, the reacting center can terminate via a monomolecular reaction ionic polymerization
In-class problem. QUESTION • Can the quasi-steady state assumption apply to this problem? • [are the reactive site production and loss rates in equilibrium?] ionic polymerization
In-class problem. ANSWER • Since the reaction of the acid with monomer is instantaneous and irreversible, the qssa does not apply • we can integrate the termination reaction from the initial condition to the reactive site concentration at time t. • This equation can be substituted into the propagation equation to get the concentration of monomer as a function of time. ionic polymerization
Kinetic chain length • We can estimate the kinetic chain length by taking the ratio of the propagation to the termination step. This is the ratio of the rate of monomer addition to the chain, divided by the ratio of chain loss. ionic polymerization
In-class problem. QUESTION • How can we keep the polymer chain length constant during an ionic polymerization ionic polymerization