The Degree of polymerization (DP or Xn) is defined as number of repeating monomer units in the polymers.
The Degree of a polymerization is calculated by taking ratio of molecular weight of the polymer and molecular weight of the repeat unit.
What is Polymerization?
Polymers derived from word “poly” means many and “mers” mean parts, are long-chain molecules formed by repetition of many small simple chemical repeating units.
The repeating units are termed monomers. These monomers can either repeat linearly or in the form of chains that are connected as branches to form a three-dimensional network. The monomers are linked with one another via chemical reactions by a process called polymerization.
Types of Polymerization
In 1953, Paul Flory classified polymerization reactions in two groups; step-growth polymerization (also called condensation reactions) and chain polymerization (also known as addition reactions).
Step Polymerization
In Step Growth Polymerization, bi-functional or multifunctional monomers react to first form dimers, then trimers, longer oligomers and then long-chain polymers.
The mechanism of step polymerization is just like a group of people reaching out each other with their hands to form a human chain, in case of polymers the reactive sites act as two hands which join with one another to form a polymer chain.
As there can be more than one reactive site on a monomer so there is a high extent of polymerization resulting in a high molecular chain. Polyesters, polyamides, polyurethanes etc. are few common examples of step polymerization.
Chain Polymerization
In Chain polymerization, the reaction takes place by an active center which is a free radical or ion to form a macromolecule. The polymer growth takes place at the endpoints of the chains hence it is also termed as addition polymerization.
The mechanism of reaction involves three steps, initiation, propagation and termination.
Many common polymers are formed by chain polymerization such as polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polyimide (PI), polymethyl methacrylate, polyvinyl acetate.
How to Calculate Degree of Polymerization
Degree of polymerization can be calculated by dividing polymer’s molecular weight to repeating unit’s molecular weight.
Classification of Degree of Polymerization
The Degree of Polymerization is classified in two forms, the number-average degree of polymerization and weight-average degree of polymerization.
The number-average degree of polymerization is the weighted mean of degrees of polymerization, weighted by the mole fractions (or the number of molecules) of the polymer. It is experimentally determined by measurements of the osmotic pressure of the polymer.
The weight-average degree of polymerization is the weighted mean of degrees of polymerization, weighted by the weight fractions (or the overall weight of the molecules) of polymer. It is experimentally determined by measurements of Rayleigh light scattering by the polymer.
Degree of polymerization (DP) of Step-growth polymerization
In step-growth polymerization, the DP is calculated by Carothers’ equation which is defined for linear and branched molecules. For linear polymer formed by the reaction (usually by condensation) of two monomers in equimolar quantities, the equation of DP is:
In Linear polymerization where one monomer is in excess quality the equation is modified as:
Where, r is the stoichiometric ratio of reactants, as the excess reactant is generally placed in the denominator so r < 1 always.
The excess reactant is generally added to control the DP of polymers for a given value of p. When the limiting reagent monomer is added in the limit of complete conversion, p → 1 and
When a monomer has functionality greater than one, it results in branching of polymer. In this case, the DP of polymers will depend on the average functionality of the monomer fav. The fav for a given reaction can be calculated as:
The modified Carothers equation for branched step polymerization will be:
Degree of polymerization (DP) of Chain-growth polymerization
The degree of polymerization of chain-growth polymerization, cannot be calculated by Carothers.
At the beginning of the reaction, long chains are formed and longer reaction times have little effect on the average molecular weight it only increases the polymer yield. Hence, the DP of polymers given by the formula below is associated with the kinetic chain length, which is the average number of monomers polymerized for each chain initiated.
