1.

Explain the types of condensation polymers ( functional group, mechanism,

application )
A condensation polymer is a polymer formed by condensation reactions.
Monomers of condensation polymers must contain two functional groups so that
each monomer can link up with two other monomers. One type of condensation
polymer is called a polyamide. An amide is characterized by the functional group
shown below wherein the carbon of a carbonyl group is bonded to the nitrogen of
an amine.

Figure 25.20.1: Amide.

One pair of monomers that can form a polyamide is adipic acid and
hexanediamine. Adipic acid is a carboxylic acid with two carboxyl groups on
either end of the molecule. Hexanediamine has amino groups on either end of a
six-carbon chain. When these molecules react with each other, a molecule of
water is eliminated, classifying it as a condensation reaction (see figure below).

Figure
25.20.2: Nylon synthesis.
The polymer that results from the repetition of the condensation reaction is a
polyamide called nylon-66. Nylon-66 was first invented in 1935 and has been
used in all sorts of products. It and other polyamides are commonly found in
fibers and clothing, cooking utensils, fishing line, and carpeting, among many
other applications.
 Figure 25.20.3: Nylon spatula.
Polyester is another common type of condensation polymer. Recall that esters are
formed from the reaction of an alcohol with a carboxylic acid. When both the acid
and alcohol have two functional groups, the ester is capable of being polymerized.
One such polyester is called polyethylene terephthalate (PET) and is formed from
the reaction of ethylene glycol with terephthalic acid. The structure of PET is
shown below.

PET is used in tires, photographic film, food packaging, and clothing. Polyester
fabric is used in permanent-press clothing. Its resistance to wrinkling comes from
the cross-linking of the polymer strands.

Polyfunctional monomers, with more than two functional groups per molecule,
give branched or crosslinked (three-dimensional) polymers The properties of the
linear and the three-dimensional polymers differ widely The mechanism of' step-
reaction polymerization is discussed in this section, following the classification
scheme of Lenz (1967)
Carbonyl Addition-Elimination Mechanism
The most important reaction that has been used fbr the preparation of
condensation polymers is that of addition and elimination at the carbonyl double
bond of' car- boxylic acids and their derivatives. The generalized reaction is

NHR', OCR', ox Cl; and Y may be RfO- , R'OH, RINH,, 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 The following paragraphs provide some typical examples of this
reaction
Direct Reaction. The direct reaction of a dibasic acid and a glycol to form a
polyestex, or a dibasic acid and a diamine to form a polyamide, works well and
is widely used in practice 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 p~eparation of
poly(hexamethy1ene adipamide) (66-nylon) by heating the hexa- methylene
diamine salt of adipic acid above the melting point in an inert atmosphere. The
stringent requirement of stoichiometric equivalence to obtain high molecular
weight is easily met by purifying the salt by recrystallization

is often used to produce polyesters, especially where the dibasic acid has low
solubility. Frequently the methyl ester is used, as in the production of
poly(ethy1ene terephthalate) from ethylene glycol and dimethyl terephthalate.
The reaction between a carboxyl and an ester link is much slower, but other
interchange reactions, such as amine-amide, amine-ester, and acetal-alcohol, are
well known
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, but 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' car~ied out at the
interface between two liquid phases, each containing one of the reactants
(Morgan 1965). Very-high-molecular-weight polymer can be formed. Typically,
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 fbrmed at the interface can be pulled off as a continuous film or filament
The method has been applied to the fbrmation of' polyamides, polyurethanes,
polyureas, polysulfbnamides, and polyphenyl esters. It is particularly useful for
preparing polymers that are unstable at the higher temperatures usual in
stepreaction polyrnerization
Ring Versus Chain Formation. In addition to polymer fbrmation, bifunctional
monomers may react intramolecularly to produce a cyclic product. Thus hydroxy
acids may give either lactones or polymers on heating,

amino acids may give lactams or linear polyamides, and so on.. The chief hctor
governing the type of' product is the size of' the ring that can be formed. If' the
ring contains less than five atoms or more than seven, the product is usually linear
polymer. If a ring of five atoms can fbrm, it will do so to the
exclusion of linear chains If six-. or seven-membered rings can form, either type
of product can result. Larger rings can sometimes be formed under special
conditions The lack of fbrmation of' rings with less than five atoms is explained
by the strain imposed by the valence angles of' the ring atoms Five-membered
rings are virtually strain free, and all larger rings can be strain fiee if' nonplanar
forms are possible.. As the ring size increases, the statistical probability of
forming rings becomes smaller. The formation of five-membered rings to the
complete exclusion of' linear polymer is not thoroughly understood
Carbonyl Addition-Substitution Reactions. The reaction of aldehydes with
alcohols, involving first addition and then substitution at the cabonyl groups, is
of great practical and historic importance in stepwise polymerization. The general
reaction, leading to acetal formation, is

In addition to polyacetals, important polymers formed in this way include those

of formaldehyde and phenol, urea, or melamine
Nucleophilic Substitution Reactions. These reactions are important from the
standpoint of commercial organic polymers, primarily because of their use in the
polymerization of epoxides The most common epoxide monomer is epichlorohy-
drin, which reacts with a nucleophile N: as follows:

Typically, the nucleophile is a bifunctional hydroxy compound such as bisphenol

A
A second nucleophilic substitution reaction of historic interest in polymer chem-
isQy is that used for the production of the early polysulfide rubbers from aliphatic
dichlorides and sodium sulfide:

This type of' reaction can be used for the production of' semi organic and
inorganic polymers, and is probably also the basis for the formation of' natural
polysaccharides and polynucleotides by polymerization in living organisms
catalyzed by enzymes
Double-Bond Addition Reactions. Although addition reactions at double bonds
are often associated with polymerization by chain mechanisms
this is not necessarily the case, and many important stepwise polymerizations are
based on this reaction. Of' major interest among these is the ionic addition of diols
to diisocyanates in the production of' polyurethanes
Free-Radical Coupling. These reactions lead to several polymerization schemes
of interest, including the preparation of arylene ether polymers, polymers
containing acetylene units, and arylene alkylidene polymers If [Ox] is an
oxidizing agent, the first of these can be written as

Aromatic Electrophilic-Substitution Reactions. Reactions of this type, using

standard Friedel-Crafts catalysts, produce polymers by a step-growth mechanism
A typical example is the production of poly(p-phenylene):

Condensation polymerization is the process whereby two or more monomers link

together to form the polymer with the elimination of a small molecule.

In esterification reaction, the acid and the alkanol condense to give a dimer with
the elimination of a water molecule. Since each monomer has only one active
functional group, i.e a hydroxyl group, -OH, and a carboxylate group, -COOH,
the reaction stops once the ester is formed.

For further condensation to occur, each monomer must have at least two active
functional groups. Examples of such monomers are dicarboxylic acids and diols.
Reactions between two such monomers results in a dimer with two reaction sites,
one at each end of the molecule. This dimer is able to undergo further
condensation with more monomers to give rise to a longer chain polymer.

In condensation polymerization, the relative molecular mass of a condensation

polymer is not an exact multiple of the monomers as in an addition polymer. This
is because there is a loss in mass during the condensation process.

The two most important condensation polymers are

 Nylon and
 Terylene
Nylon is a Polyamide while Terylene is a Polyester.

Nylon

This is a general term that refers to a group of synthetic fibres. There are many
types of nylon. In nylon 6.6, the two monomers are hexane-1.6 diamine, H2N –
(CH2)6 – NH2, and hexanedioic acid (adipic acid), COOH – (CH2)4 – COOH.
Both monomers are bifunctional. In the initial condensation, the –COOH group
of the acid reacts with the –NH2 group of the amine, with the elimination of
water, to form the amide linkage group, -CO-NH-.

Nylon 6.6 can be prepared by mixing an aqueous solution of hexane-1,6-diamine

to hexanediolic acid in tetrachloromethane.

Nylon is extensively used as a synthetic fibre because of its very high tensile
strength. Thus nylon fibres are ideal for making ropes, fishing lines nets and
racquet strings. Nylon is also used to replace many steel parts in machines like
gears and bearings. These parts are not only hard but also smooth so that they do
not need lubrication.

Nylon is used for making all kinds of clothing. Such clothing drip-dry easily, and
are crease-free and resistant to fungal and moth attacks. However, nylon clothing
do not absorb moisture and are uncomfortable to wear in warm weather. This
property is common to clothing made of other synthetic fibres as well. Nowadays,
most clothing made of nylon and other synthetic fibres contain a certain amount
of natural fibres like cotton which can absorb moisture.
 Terylene

This is a polyster that is also known as Dacron in the U.S.A. it is formed by the
condensation of benzene-1,4-dicarboxylic acid (terephthalic acid) and ethane-
1,2-diol, using an acid catalyst.

Terylene is another synthetic fibre which is mainly used in the manufacture of

synthetic textiles. It is soft and is capable of retaining an almost permanent crease.
Woven terylene is used for making the sails of boats where a strong rot-proof
material is required.

Phenol-methanal, urea-methanal and melamine-methanal

Phenol-methanal is commonly known as Bakelite. This is a hard plastic or resin.

It is formed by condensing hydroxybenze (phenol), and methanol in the presence
of an acid or an alkali as catalyst.

Various other synthetic resins may be produced using compounds other than
phenols. For example,

 Urea condenses with methanal to form urea-methanal resins, and

 Melamine condenses with methanal to form melamine-methanal resins.
 Phenol-methanal is a dark-brown polymer which is often used to make plugs,
switches, utensile handles, telephone casings, radio housing and sockets. Its
excellent electrical insulating property, together with its non-combustible quality,
makes it an ideal material for the electrical industry.

Urea-methanal is similar to phenol-methanal except that it is transparent and

easily be coloured with pigments. It is used for making electrical fittings and
kitchenware. This plastic is also prepared as a foam, which is commonly used as
a heat insulator.
Melamine-methanal is similar to urea-methanal. It can be produced in attractive
colours and is used mainly to make unbreakable, heat-resistant cups, plates and
bowls.

RUBBER

Rubber is another group of important polymers. Both natural rubber and synthetic
rubber are now available.

Natural Rubber

Rubber is obtained from the rubber tree, Hevea brasiliensis. When the bark of the
tree is cut, a thick white liquid called latex oozes out. If the latex is collected and
heated, it changes into an elastic solid called rubber. This rubber is of little use
because it is soft and sticky. Chemically, it consists of 2-methyl buta-1,3diene
monomers known previously as isoprene.

During condensation polymerization when the monomers polymerize, they form

long polymeric chains which have only a limited number of cross-links between
them. By adding sulphur and heating, the soft rubber becomes hard. This process
is known as vulcanization. The sulphur atoms form strong cross-linkages which
hold the long rubber chains together. This gives greater tensile strength, durability
and elasticity over a wide range of temperatures.

Synthetic Rubber

The first synthetic rubber was poly(2-chlorobuta1,3-diene) or neoprene. Later,

styrenebutadiene rubber (SBR), Thiokol, poly(but-1,3-diene) and poly(2-methyl
propene) were invented. Of these, SBR is the most useful all-purpose synthetic
rubber.

SBR is obtained by the copolymerization of phenylethene (styrene) with three

parts of aqueous buta-1,3-diene. It is vulcanized by carefully heating it with about
3% by mass of sulphur. As a result, bridges of sulphur atoms are formed between
adjacent polymeric chains at the double bond positions. This gives SBR and
synthetic rubber its elasticity and hardness.

SBR rubber is often used in making vehicle tyres and foot ware because of its
high resistance to abrasion.

Polymers in Living Systems

Condensation polymerization can also occur in nature. Natural polymers are

found widely in living things where they play important structural and functional
roles. The main polymers are carbohydrates and proteins. Carbohydrates and
proteins, together with fats and oils, are the main classes of foods that are
necessary to sustain life.