Lecture 1

Polymer Reaction Engineering

By Muhammad Zafar Iqbal

Contents

Chain Reactions in Liquid Phase

These may be initiated by thermal, photochemical or any of radiation induction source In some respects, Liquid phase chain reaction resembles Gaseous phase chain reaction But in many respects, these two are different as the effect of non-ideality associated with solvents. The solvent also plays important role in chain length and structure of the final polymer. There is little difference in all types of chain reactions.

Free Radical Solution Polymerization

Rule of Thumb: If a single radical is involved in each step reaction, then linear chain reaction will occur. Of all the chain reactions, free radical reactions are the most extensively studied. From kinetic point of view, there is great similarity between gas phase FRP and liquid phase FRP. The initiation is very dependent on temp. and environment. Temperature may change the nature and type of reacting radicals. Most important example: Benzoyl Peroxide

 Main drawback:

Azo- compounds are free from such complications like side reactions:

This is known to be free from side reactions but the complication lies again in the kinetics of cyano-isopropyl radical as ketene imino radical:

 The free radicals may be generated by some other modes but the actions series is same for all of them like:

Autoacceleration during solution polymerization

Degree of Polymerization and Chain Transfer

This definition is very sensitive to the reaction chemistry In simple words, it is defined as the avg. no. of monomer units per polymer chain. For termination via disproportionation, This is equal to the kinetic chain length. For termination via chain combination, this is equal to the twice the kinetic chain length. Where kinetic chain length is defined as the avg. no. of monomer units reacting with a given radical centre from its initiation to its termination.

Kinetics of Chain Transfer Processes

Chain transfer process is defined as the process whereby a growing polymer radical transfers its activity to an adjacent monomer, initiator, solvent or any other polymer radical or terminated polymer molecule. The net effect of this termination process is that the original polymer radical loses its capacity for further growth and the second molecule called the transfer agent becomes the free radical capable of adding monomer units.

So the final equation becomes:

General relationship for chain transfer in radical chain reactions in solution

Transfer to monomer and Initiator

Transfer to the Solvent