Polyamides:

1. Introduction:
A polyamide is a macromolecule with repeating units linked by amide bonds. They can occur
both naturally and artificially. Examples of naturally occurring polyamides are proteins, such as
wool and silk. Artificially made polyamides can be made through step-growth polymerization or
solid-phase synthesis, examples being nylons, aramids, and sodium poly (aspartate). Synthetic
polyamides are commonly used in textiles, automotives, carpet and sportswear due to their
extreme durability and strength. Transportation is the major consumer, accounting for 35% of
polyamide (PA) consumption.
Polyamides are polymers which contain repeating amide, -CO-NH-, linkages. Proteins are
examples of naturally occurring polyamides.

The best known manufactured polyamides are often called nylons (the trade name given by the
manufacturer, DuPont) and these are aliphatic polyamides. However, other manufactured
polyamides are also important and these include an aromatic polyamide, Kevlar and plastics
produced from carbamide (urea). The nomenclature for describing the linear, aliphatic
polyamides (the nylons) is based on the number of carbon atoms in the repeating unit.
Nylon (Polyamide) - The generic name for all long-chain fiber-forming polyamides with
recurring amide groups. Polyamides (Nylon) comprise the largest family of engineering plastics
with a very wide range of applications. Polyamides (Nylons) are often formed into fibers and are
used for monofilaments and yarns. Characteristically polyamides (Nylons) are very resistant to
wear and abrasion, have good mechanical properties even at elevated temperatures, have low
permeability to gases and have good chemical resistance.

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2. History & Background:

Polyamide (Nylon) polymer was first commercially introduced by DuPont as a result of the
significant research work of W. H. Carothers in the 1930s, who was conducting early extensive
research efforts in polyesters and polyamides. The first important polyamide was Nylon 66
produced by the reaction of adipic acid (a 6-carbon dibasic acid) and hexamethylene diamine (a
6-carbon aliphatic diamine). Several structural modifications with differing temperature
capabilities have become commercially available including Nylon 46, 610, 612, 6, 11, etc.
Nylon is a thermoplastic, silky material, first used commercially in a nylon-bristled toothbrush
(1938), followed more famously by women's stockings ("nylons"; 1940) after being introduced
as a fabric at the 1939 New York World's Fair. Nylon is made of repeating units linked by amide
bonds and is frequently referred to as polyamide (PA). Nylon was the first commercially
successful synthetic thermoplastic polymer. There are two common ways of making nylon for
fiber applications. In one approach, molecules with an acid (-COOH) group on each end are
reacted with molecules containing amine (-NH2) groups on each end. The resulting nylon is
named on the basis of the number of carbon atoms separating the two acid groups and the two
amines. These are formed into monomers of intermediate molecular weight, which are then
reacted to form long polymer chains.
Nylon was intended to be a synthetic replacement for silk and substituted for it in many different
products after silk became scarce during World War II. It replaced silk in military applications
such as parachutes and flak vests, and was used in many types of vehicle tires.
Nylon fibers are used in many applications, including clothes fabrics, bridal veils, package paper,
carpets, musical strings, pipes, tents, and rope.
Solid nylon is used in hair combs and mechanical parts such as machine screws, gears and other
low- to medium-stress components previously cast in metal. Engineering-grade nylon is
processed by extrusion, casting, and injection molding. Type 6,6 Nylon 101 is the most common
commercial grade of nylon, and Nylon 6 is the most common commercial grade of molded
nylon. For use in tools such as spudgers, nylon is available in glass-filled variants which increase
structural and impact strength and rigidity, and molybdenum sulfide-filled variants which
increase lubricity. Its various properties also make it very useful as a material in additive
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manufacturing; specifically as a filament in consumer and professional grade fused deposition

modeling 3D printers.

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3. Physical and Chemical Properties:

3.1 Physical properties:
1. Tenacity: 6.0 8.5 gm/den 1.
2. Density: 1.14 gm/cc
3. Elongation at break: 15 45%
4. Elasticity: Very good
5. Moisture Regain (MR%): 3.5 5%
6. Resiliency: Good
7. Melting point: 215C
8. Ability to protest friction: Excellent
9. Color: White
10. Light reflection ability: Not good
11. Ability to protect heat: Up to 1500
12. Lusture: Bright to light
3.2 Chemical Properties:
1. Acids: Like nylon 6.6, nylon 6 has not enough ability against acidic action.
2. Basic: Basic does not cause harm to the nylon 6. Nylon 6 has enough ability against
alkali.
3. Effect of bleaching: Strong oxidizing agent is harmful for the nylon 6.
4. Organic solvent: It becomes soluble in any dense acid or phenol.
5. Protection ability against mildew: Mildew cannot cause harm to the nylon 6.
6. Protection ability against insects: Insects cause harm to the nylon 6. 6.
7. Dyes: Nylon 6 could be dye by Direct dyes, Acid dyes and vat dyes.

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4. Uses of polyamides:
1. Polyamide is a high strength fibre. It is used for making fishing nets, ropes, parachutes and
type cords.
2. It is used for making fabrics in textile industry.
3. Crinkled nylon fibres are used for making elastic hosiery.
4. Polyamide is widely used as plastic for making machine parts.
5. It is blended with wool to increase the strength.
6. The properties of the polyamides (nylons), which include high strength, abrasion resistance,
and resilience, make them very important in the manufacture of clothing and carpets. Although
these polyamides account for 95% of the material used in women's hosiery, this still only
accounts for about 5% of the total fibres used to make clothing. Nevertheless this is more than
either the polypropenoates (acrylics) or wool but it is substantially less than either cotton or
polyesters.
7. The children's clothing is made of polyamide 6, impregnated with nanoparticles of titanium
dioxide which gives protection against UV radiation, a very effective way of having a sunscreen.
8. The polyamides (nylons) are also used in engineering plastics, for example, in cars, and for
making films for food packaging. They are used in films for their good balance between
mechanical strength and barrier properties against oxygen, smells and oils.
9. An important development is the use of polyamides to make safety airbags.
10. Polyamides 6 and 6,6 are the most widely used polyamides for fibres and for engineering
materials. The remaining commercial polyamides, for example, polyamides 11 and 12, and 6,10,
are most used as engineering plastics.
11. Ropes made from polyamides are used by rock and ice climbers. They are not only very
strong but they are also stretchy and thus reduce forces in the event of a fall, by spreading the
duration of loading transmitted to anchors and to the body via the harness. Tony Moody is
climbing ice on Heninger, near Cogne in northern Italy.
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5. Manufacture of polyamide 6 and 6,6:

Both polyamides are manufactured from benzene via cyclohexane. Hydrogen is passed through
liquid benzene in the presence of a nickel catalyst under pressure:

Cyclohexane is oxidized by passing air through the liquid under pressure in the presence of a
catalyst (often a cobalt salt) to yield two products:

The mixture of cyclohexanol and cyclohexanone is known as "mixed oil" or KA

(ketone/alcohol).
An alternative route to cyclohexanol is via the hydrogenation of phenol using a nickel catalyst at
ca 400 K and 5 atm:

A more recent route to cyclohexanol is the Asahi process from benzene via its hydrogenation to
cyclohexene and subsequent hydration to alcohol. This is more energy efficient than the other
processes.
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To make polyamide 6, pure cyclohexanone is required. When the mixed oil is heated under
pressure with copper(ll) and chromium(lll) oxides, the cyclohexanol, which is a secondary
alcohol, is dehydrogenated to the corresponding ketone, cyclohexanone:

Cyclohexanone is then converted into caprolactam via the oxime (produced by the reaction of the
ketone with hydroxylamine - in the form of the salt, hydroxylamine hydrogensulfate):

The isomerisation of the oxime to caprolactam by sulfuric acid is an example of the Beckmann
rearrangement in which an oxime is transformed into an amide in the presence of acid.
A zeolite, with acidic sites, is also being used to effect the rearrangement. The zeolite is
regenerated and saves the use of sulfuric acid.
To produce the polymer, the caprolactam, water (acting as a catalyst) and a molecular mass
regulator, e.g. ethanoic acid, are poured into a reaction vessel and heated under nitrogen at 500 K
for about 12 hours:

This is an example of a batch process .

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Polyamide 6,6 is produced by reacting 1,6-diaminohexane (hexamethylenediamine) with

hexanedioic acid (adipic acid) by condensation polymerization.
One of the monomers, hexanedioic acid is also produced from KA mixed oil (cyclohexanol and
cyclohexanone). The mixed oil is oxidized in the liquid phase using moderately concentrated
(60%) nitric acid and a copper(II) nitrate and ammonium vanadate(V) catalyst, at 330 K to form
hexanedioic acid:

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This process has a considerable disadvantage. A side-product is nitrogen(I) oxide (nitrous

oxide), N2O, a powerful greenhouse gas but it is carefully removed by thermal or catalytic
treatment units.
The second monomer, 1,6-diaminohexane, is produced from buta-1,3-diene and from
propenonitrile (polyacrylonitrile).
To form the polymer, the acid and the diamine are then heated together to form a salt.
The chemical reaction for aliphatic dicarboxylic acids and aliphatic diamines to yield an aliphatic
polyamide via a condensation polymerization process can be represented, thus:
The chain length is regulated by controlling process conditions, such as reaction time,
temperature and pressure. An aqueous solution of the salt is heated, in the absence of air, to
500K. A pressure develops in the vessel. The temperature is then raised to 540 K, and the steam
is bled off to keep the pressure constant. Eventually, the pressure is reduced and the polymer is
extruded under nitrogen to yield a lace which is then granulated

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