O. R.

OBANLA
CHE417, CU

DEPARTMENT OF CHEMICAL ENGINEERING,

COVENANT UNIVERSITY, OGUN STATE

CHE417: POLYMER PROCESS ENGINEERING

Lectures 6 and 7

CONDENSATION POLYMERIZATION (Step-Reaction Polymerization)

Condensation polymerization produces important polymers such as polyesters, polyamides

(nylons), polycarbonates, polyurethanes, and phenol-formaldehyde resins.

It is a reaction between two different monomers, with each monomer possessing at least two
similar functional groups that can react with the functional groups of the other monomer. The
polymer chains grow stepwise by the reactions occurring between the two molecular species.

Example

(i) Reaction of a dicarboxylic acid and a dialcohol (diol) to produce polyesters:

A similar reaction between a diamine and a diacid can also produce polyamides.

(ii) Reactions between one monomer species with two different functional groups:

One functional group of one molecule reacts with the other functional group of the
second molecule.

For example, polymerization of an amino acid starts with condensation of two

monomer molecules:

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In these two examples, a small molecule (water) results from the condensation reaction.

Ring opening polymerization can also be considered a condensation reaction, although a small
molecule is not eliminated. Example, opening of lactam ring

Caprolactam polycaprolactam

Condensation polymerization is also known as step-reaction polymerization because the

reactions occur in steps. First, a dimer forms, then a trimer, next a tetramer, and so on until
the polymer terminates.

Although step polymerizations are generally slower than addition polymerizations, with long
reaction times required for high conversions, the monomers disappear fast. The reaction
medium contains only dimers, trimers, tetramers, and so on.

For example, the dimer formed from the condensation of a dicarboxylic acid and a diol has
hydroxyl and carboxyl endings that can react with either a dicarboxylic acid or a diol to form
a trimer:

The compounds formed continue condensation as long as the species present have different
endings. The polymer terminates by having one of the monomers in excess. This produces a
polymer with similar endings.

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For example, a polyester formed with excess diol could be represented:

In these reactions, the monomers have two functional groups (whether one or two monomers
are used), and a linear polymer results. With more than two functional groups present,
crosslinking occurs and a thermosetting polymer results. Example of this type are
polyurethanes and urea formaldehyde resins.

Acid catalysts, such as metal oxides and sulfonic acids, generally catalyze condensation
polymerizations. However, some condensation polymers form under alkaline conditions. For
example, the reaction of formaldehyde with phenol under alkaline conditions produces
methylolphenols, which further condense to a thermosetting polymer.

Kinetics of Chain Polymerization

Typical radical polymerization starts with thermal decomposition of a radical initiator. The
rate of decomposition depends on rate constant and the concentration in the initiator.

𝑘𝑑
𝐼 → 2𝑅 ∗

𝑑[𝐼] 1 𝑑[𝑅∗]
− = = 𝑘𝑑[𝐼]
𝑑𝑡 2 𝑑𝑡

The radical generated can undergo radical addition to a monomer. This generated radicals of
the monomer and the process is the initiation step

𝑘𝑖
𝑅∗ + 𝑀 → 𝑀∗

𝑑[𝑀] 𝑑[𝑀∗]
− = = 𝑘𝑖[𝑀][𝑅∗]
𝑑𝑡 𝑑𝑡

Where kd is initiator dissociation rate constant and ki is initiation rate constant

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Assuming that the ki >> kd

𝑑[𝑀∗] 𝑑[𝑅∗]
= = 2𝑘𝑑[𝐼]
𝑑𝑡 𝑑𝑡

Since it is only some of the radicals that reacts with the monomers to initiate the growing
chains, factor f is introduced. Ususally, factor ‘f’ is assumed to be 0.5 thus,

𝑑[𝑀∗]
= 2𝑓𝑘𝑑[𝐼]
𝑑𝑡

f = 0.3 to 0.8

The continuous monomer addition to the the growing chain proceeds at similar rate with
same kprop but different from the ki

𝑘𝑝𝑟𝑜𝑝
𝑀∗ + 𝑀 →−−→ 𝑀 − 𝑀∗

𝑑[𝑀] [𝑀][𝑀∗]
− =𝑘
𝑝𝑟𝑜𝑝
𝑑𝑡

Final step in radical polymerization is termination step. Assuming it is by coupling of two

radicals, then,

𝑘𝑡
𝑀∗ + 𝑀∗ → 𝑀 − 𝑀

𝑑[𝑀∗] 2𝑑[𝑀 − 𝑀]
− = = 2𝑘𝑡[𝑀∗]2
𝑑𝑡 𝑑𝑡

The rate depends on the termination rate constant and the concentration of both growing
chains.

Both the termination and propagation rates depends on the concentration of the reactive
intermediates which are usually unknown. For steady state approximation, it is usually
assumed that the concentration of the reactive intermediates do not change, i.e. zero change
in concentration of the reactive intermediate.

Thus, the sum of all rates generating the intermediate equal the sum of all the rates
consuming the intermediate. Or the rate of appearance of the radical in the first place equals
its rate of disapearance. That is,

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Ratetermination = Rate initiation

2𝑘𝑡[𝑀∗]2 = 2𝑓𝑘𝑑[𝐼]

𝑓𝑘 𝑑[𝐼] 1/2
[𝑀∗] = ( )
𝑘𝑡

Recall that
𝑑[𝑀] [𝑀][𝑀∗]
− =𝑘
𝑝𝑟𝑜𝑝
𝑑𝑡

𝑑[𝑀] 𝑓𝑘 [𝐼] 1/2

− = 𝑘𝑝𝑟𝑜𝑝 [ 𝑀] ( 𝑑 )
𝑑𝑡 𝑘𝑡

Thus, the growth rate increases with concentration of monomer and as square root of the
initiator concentration. The equation can then the simplified to

𝑑[𝑀]
− = 𝑘 ′[𝑀][𝐼]1/2
𝑑𝑡 𝑔

Where 𝑘 , = 𝑘 𝑓𝑘𝑑 1/2

𝑔 𝑝𝑟𝑜𝑝 ( )
𝑘𝑡

There could be a considerable increase in both the reaction rate and the molecular weight
during polymerization. This situation is called auto acceleration or gel effect or Trommsdorff
effect. It occurs when there is a decrease in the termination rate due to the increase of
medium viscosity.

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Kinetics of Condensation Polymerization

Condensation polymers grow via a step-growth process.

In formation of polyester, it involves substitution of an alcohol functional group at a carboxylic

acid to form an ester.

HO-R-OH + HOOC-R’-COOH → -COR’COO-R-O- + H2O

M1 + M2 → P
As monomer disappears, the polymer appears. The reaction mechanism is elementary
reaction and the rate law is given by the rate constant and the concentration of the reactants
so

𝒅[𝑷]
𝑹𝒂𝒕𝒆 = = 𝒌 [𝑴𝟏][𝑴𝟐]
𝒅𝒕

Let [M1] = [M2] =[M]

Then,
𝑹𝒂𝒕𝒆 = 𝒌 [𝑴]𝟐

This is a simple second-order rate equation. It is differential rate law, because it is expressed
in terms of the rate of change of one material to change of the other.

The integrated form of the rate law

𝒅[𝑴]
𝑹𝒂𝒕𝒆 = − = 𝒌 [𝑴]𝟐
𝒅𝒕

𝒅[𝑴]
− = 𝒌 𝒅𝒕
[𝑴]𝟐

Integrating

𝒄𝒕 𝒅[𝑴] 𝒕
∫ − =∫ 𝒌 𝒅𝒕
𝒄𝟎 [𝑴] 𝟐 𝒕=𝟎

𝟏 𝟏
− [𝑴] = 𝒌𝒕
[𝑴] 𝟎

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In step-growth polymerization, the molecules probably rect at similar rates. Two monomers
combined to form dimers, dimers forming tetramers, two tetramers forming octamers etc..
the monomers [M] actually refers to the functional froups. In this case, [OH] and [COOH]. The
rate of disapparence of the functional groups of the reactants is therefore the rate of forimng
the polymer molecules.

̅𝑛
One important parameter is the degree of polymerization Dp or 𝑋

𝑰𝒏𝒊𝒕𝒊𝒂𝒍 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒏𝒐𝒎𝒆𝒓𝒔

𝑫𝑷 = ̅𝑿̅=
𝒏
𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒄𝒖𝒍𝒆𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒔𝒚𝒔𝒕𝒆𝒎

[𝑴]𝟎
𝑫 = ̅𝑿̅=
𝑷 𝒏
[𝑴]

This is the inverse of fraction of monomer functional groups remaining in the system

Fraction of the functional group already converted to the polymer therefore will be

[𝑴]
𝒑 = 𝟏 − [𝑴]
𝟎

Or

[𝑴]
𝟏 − 𝒑 = [𝑴]
𝟎

Or
𝟏 [𝑴]𝟎
= = 𝑫 = ̅𝑿̅(𝑪𝒂𝒓𝒐𝒕𝒉𝒆𝒓𝒔 𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏)
𝒑 𝒏
𝟏− 𝒑 [𝑴]

This last equation is the Carothers’s equation.