Condensation Polymerization

Condensation polymers are formed through a condensation reaction,

releasing a small molecule by-product such as water or methanol.
The type of end product resulting from a condensation polymerization is
dependent on the number of functional end groups of the monomer
which can react.

Monomers with only one reactive group terminate a growing chain, and
thus give end products with a lower molecular weight. Linear polymers
are created using monomers with two reactive end groups and monomers
with more than two end groups give three dimensional polymers which
are crosslinked.
Monomers: bifunctional
HO-CO-(CH2)n-CO-OH, HO-(CH2)n-OH, HO-CO-(CH2)n-OH
Trifunctional: crosslinker

Polymers retain their functionality as end groups at the completion of

polymerization. Can be determined by titration
Many step polymerization reactions are equilibrium
condensation processes: it is necessary to remove
byproducts to drive the reactions to higher conversion.
Step polymerizations are characterized by the
disappearance of monomer very early in the reaction far
before the production of any polymer of sufficiently high
molecular weight.

Equivalence of groups in bifunctional reactants

HO2C-(CH2)X-CO2H + 2C2H5OH C2H5O2C-(CH2)X-CO2C2H5 + 2H2O

Reactivity of one functional group is affected by the other

when x 5, above which they act independently
 Condensation Polymerization in Nature

Proteins are condensation polymers made from amino acid

monomers. Carbohydrates are also condensation polymers made
from sugar monomers such as glucose and galactose.

Condensation Polymers, unlike addition polymers are bio-

degradable. The peptide or ester bonds between monomers can be
hydrolysed by acid catalysts or bacterial enzymes breaking the
polymer chain into smaller pieces.
The most commonly known condensation polymers are proteins,
fabrics such as nylon, silk, or polyester.
Addition
Monomer concentration decreases steadily
throughout reaction
High polymer is formed at once; polymer
mol wt. changes little throughout reaction
Long reaction times hardly affects mol wt
Condensation
Monomer disappears early in reaction
Mol wt rises steadily throughout reaction
Long reaction times are essential to obtain
high molecular weights
Rate constant is independent of chain length. For esterification rate
becomes virtually constant when the chain length reaches 4 carbons.
Rate becomes slower by increase in the viscosity of medium because
it will slow down the diffusion of the monomers

https://www.youtube.com/watch?v=0r2F70_kmUA
O O
OH
n + n HO
HO OH

Ethylene glycol Poly(ethylene terephthalate)

Terephthalic acid
+ 2n H2O

n HO-CO-(CH2)4-CO-OH + n H2N-(CH2)6-NH2 -[CO-(CH2)4-CO-NH-(CH2)6-NH-]n-

Adipic acid hexamethylenediamine Nylon-6,6 + 2nH2O

n HO-(CH2)4-OH + n O=C=N-(CH2)6-N=C=O -[-O-(CH2)4-O-CO-NH-(CH2)6-NH-CO-]n-

1,4-butanediol 1,6-hexane diisocyanate polyurethane
Certain monomers tend to form cyclic compounds.
Reactants of the A-B type may undergo intramolecular
cyclization.
H2N-R-COOH HN-R-CO

Reactants of the A-A type are not likely to undergo

cyclization.
Exception
O

O
HOCH2CH2OH (preferred)
Ethylene glycol
-[OCH2CH2O]-
High concentration of monomers favor linear polymerization.
The concentration factor increases the overall competitive
position of linear polymerization relative to cyclization.
Molecular weight control:
Presence of one monomer in slight excess: The polymerization then
proceeds to a point at which one reactant is completely used up and
all the chain ends possess the same functional group-the group that
is in excess.

Addition of a small amount of monofunctional group: It reacts with

the growing polymer to yield chain ends devoid of a functional group
and therefore incapable of further reaction.
For A-A, B-B type reactions, the number of A and B functional
groups are given by NA and NB. The stoichiometric imbalance
r = NA/NB
and Xn = (1+r)/(1-r)
Ring Opening

O
No leaving group
O

CO-O
Cyclic monomers preferred over linear monomers: No leaving
group
Carothers Equation:
W.H. Carother: related Xn and p(extent of reaction)

When p = 0.95(95%)
conversion xn = 50
When p = 0.99(99%)
conversion xn = 100

The most important result of this equation is that real

polymer does not form except at very high conversions
in step polymerization.
Therefore, one requires very pure ingredients,
absolutely clean reaction chemistry (i.e., no side
reactions), and often prolonged reaction times.
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Suppl
emental_Modules_(Organic_Chemistry)/Polymers/Condensation_
Polymers

https://www.ias.ac.in/article/fulltext/reso/022/04/0355-0368