Polymer Science and

Technology-CHT411
Step-growth/Condensation
Polymerization

Lecture 7: 13-10-2020
 Condensation Polymerization
• Condensation polymers are those in which the molecular formula of the
repeat unit of the polymer chain lacks certain atoms present in the
monomer from which it is formed (or to which it can be degraded)

• Condensation polymers are usually formed by the stepwise intermolecular

condensation of reactive groups
Distinguishing features of Chain and
Step growth polymerization
Types of Condensation Polymerization
• The type of products formed in a condensation reaction is determined by
the functionality of the monomers, that is, by the average number of
reactive functional groups per monomer molecule
– Monofunctional monomers give only low-molecular-weight products
– Bifunctional monomers give linear polymers
– Polyfunctional monomers, with more than two functional groups per
molecule, give branched or crosslinked (three-dimensional) polymers
 Carbonyl Addition-Elimination
Mechanism
• The most important reaction that has been used for the preparation of
condensation polymers
• Addition and elimination at the carbonyl double bond of carboxylic acids and
their derivatives

where R and R' (below) may be alkyl or aryl groups,

X may be OH, OR', NH2, NHR', OC(O)R', or Cl
Y may be R’O-, R'OH, R’NH2, or R'COO-

• The species in the bracket is considered to be a metastable intermediate, which

can either return to the original state by eliminating Y or proceed to the final state
by eliminating X
 Direct Reaction
• The direct reaction of a dibasic acid and a glycol to form a polyester
• The direct reaction of a dibasic acid and a diamine to form a polyamide
• In esterification, a strong acid or acidic salt often serves as a catalyst
• The reaction may be carried out by heating the reactants together and
removing water, usually applying vacuum in the later stages
• An important modification of the direct reaction is the use of a salt, as in
the preparation of poly(hexamethy1ene adipamide) (nylon 6,6) by heating
the hexamethylene diamine salt of adipic acid above the melting point in an
inert atmosphere
 Interchange
• Reaction between glycol and ester

• often used to produce polyesters, especially where the dibasic acid has low
solubility
• Methyl ester is used for production of poly(ethy1eneterephthalate), PET
from ethylene glycol and dimethyl terephthalate
• Reaction between carboxyl and ester is much slower
• Other interchange reactions: amine-amide, amine-ester, acetal-alcohol
 Acid chloride or Anhydride
• Either of these species can be reacted with a glycol or an amine to give a
polymer
• The anhydride reaction is widely used to form an alkyd resin from phthalic
anhydride and a glycol

• The condensation in bulk of an acid chloride with a glycol is not useful

because of side reactions leading to low-molecular-weight products
• the reaction of an acid chloride with a diamine is a valuable means of
preparing polyamides..
 Interfacial Condensation
• The reaction of an acid halide with a glycol or a diamine proceeds rapidly
to high-molecular-weight polymer if carried out at the interface between
two liquid phases, each containing one of the reactants
• Very-high-molecular-weight polymer can be formed
• An aqueous phase containing the diamine or glycol and an acid acceptor is
layered at room temperature over an organic phase containing the acid
chloride
• The polymer formed at the interface can be pulled off as a continuous film
or filament
• Used for polyamides, polyurethanes, polyureas, polysulfonamides, and
polyphenyl esters
• It is particularly useful for preparing polymers that are unstable at the
higher temperatures usual in step reaction polymerization
 Kinetics of Stepwise Polymerization
• Linear AB step polymerization (ARB polymerization)
• Liner A2+B2 step polymerization
 Linear AB step polymerization
•
 Kinetic solution
•
 Rate of disappearance
•
 Rate of disappearance
•
 Rate of appearance
•
 For example
• For i =2
• Rate of appearance of 2-mer is half
of the rate of disappearance of monomer in reaction with another monomer
as one 2-mer appears for two 1-mer disappearance

• For i=3

or
 Kinetic equation
• The overall reaction kinetics can be written as

• For i=1
 Solution for the kinetic equation
Kinetic Equation
• Direct Sequential solution
• Discrete transformation methods
• Direct solutions of moments
• Moment integration
• From Generating functions
Statistical solutions
• Combinatorial methods
• Recursive methods