Carothers Equation - Linear Polymers: One Monomer in Excess

Linear Polymers: One Monomer in Excess

If one monomer is present in stoechiometric excess, then the equation becomes

• r is the stoichiometric ratio of reactants, the excess reactant is conventionally the denominator so that r < 1. If neither monomer is in excess, then r = 1 and the equation reduces to the equimolar case above.

The effect of the excess reactant is to reduce the degree of polymerization for a given value of p. In the limit of complete conversion of the limiting reagent monomer, p → 1 and

Thus for a 1% excess of one monomer, r = 0.99 and the limiting degree of polymerization is 199, compared to infinity for the equimolar case. An excess of one reactant can be used to control the degree of polymerization.