Polymers
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Polymer
A polymer is a large molecule made by linking together repeating
units of small molecules called monomers. The process of linking
them together is called polymerization.
Polymers can be
divided into two
broad groups:
synthetic polymers
and biopolymers
(natural polymers).
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Classes of Synthetic Polymers
Synthetic polymers can be divided into two major classes,
depending on their method of preparation. Chain-growth
polymers, also known as addition polymers, are made
by chain reactions—the addition of monomers to the end of a
growing chain.
Polystyrene—used for disposable food containers, insulation,
and toothbrush handles, among other things—is an example
of a chain-growth polymer.
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Classes of Synthetic Polymers
Step-growth polymers, also called condensation polymers, are
made by combining two molecules while, in most cases,
removing a small molecule, generally water or an alcohol.
Dacron® is the most common of the group of polymers known
as polyesters—polymers with many ester groups. Polyesters
are used for clothing and are responsible for the wrinkle-
resistant behavior of many fabrics.
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Chain-Growth Polymers
Chain-growth polymerization proceeds by one of three
mechanisms: radical polymerization, cationic polymerization, or
anionic polymerization.
For chain-growth polymerization to occur by a radical
mechanism, a radical initiator must be added to the monomer
to convert some of the monomer molecules into radicals.
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Chain-Growth Polymers
This process is repeated over and over. Hundreds or even
thousands of alkene monomers can add one at a time to the
growing chain. Eventually, the chain reaction stops because the
propagating sites are destroyed.
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Chain-Growth Polymers
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Chain-Growth Polymers
Chain-growth polymerization of monosubstituted ethylenes
exhibits a marked preference for head-to-tail addition, where
the head of one monomer is attached to the tail of another.
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Ring-Opening Polymerizations
Polymerization reactions that involve ring-opening reactions,
such as the polymerization of propylene oxide, are called ring-
opening polymerizations.
Nylon-6 is obtained by heating caprolactum with water at a
high temperature.
Nylon 6 is used for the manufacture of tyre cords, fabrics and
ropes.
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Stereochemistry of Polymerization
An efficient and stereospecific catalytic polymerization procedure
was developed by Karl Ziegler and Giulio Natta in the 1950's.
The catalyst formed by reaction of triethylaluminum with
titanium tetrachloride has been widely studied, but other metals
(e.g. V & Zr) have also proven effective.
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Copolymers
The polymers we have discussed so far are formed from only
one type of monomer and are called homopolymers. Often,
two or more different monomers are used to form a polymer.
The resulting product is called a copolymer.
Even if only two kinds of monomers are used, copolymers with
very different properties can be prepared by varying the
amounts of each monomer. Both chain-growth polymers and
step-growth polymers can be copolymers.
Copolymers have properties quite different from homopolymers.
For example, butadiene - styrene copolymer is quite tough and is
a good substitute for natural rubber. It is used for the autotyres,
floortiles, footwear components, cable insulation, etc.
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Important
constitutions
for synthetic
copolymers
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14
Polyamides
Nylon is the common name of a synthetic polyamide.
Nylon first found wide use in textiles and carpets. Because it is
resistant to stress, it is now used in many other applications,
such as mountaineering ropes, tire cords and fishing lines, and
as a substitute for metal in bearings and gears.
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Polyamides
Kevlar® is an aramide with a tensile strength greater than that of
steel. Army helmets are made of Kevlar®, which is also used for
lightweight bulletproof vests and high-performance skis. Because
it is stable at very high temperatures, it is used in the protective
clothing worn by firefighters.
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Polyesters
Polyesters are step-growth polymers in which the monomer
units are joined together by ester groups.
The most common polyester is known by the trade name
Dacron®. High resilience, durability, and moisture resistance are
the properties of this polymer that contribute to its “wash-and-
wear” characteristics.
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Polyesters
Kodel® polyester is formed by the transesterification of dimethyl
terephthalate with 1,4-di(hydroxymethyl)cyclohexane. The stiff
polyester chain causes the fiber to have a harsh feel that can be
softened by blending it with wool or cotton and blend is known
as Terecott
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Polyurethanes
A urethane—also called a carbamate—is a compound that has
an OR group and an NHR group bonded to the same carbonyl
carbon. Urethanes can be prepared by treating an isocyanate
with an alcohol.
If the reaction is carried out in the presence of a blowing
agent, the product is a polyurethane foam. Blowing agents
are gases such as nitrogen or carbon dioxide.
Polyurethane foams are used for furniture stuffing, carpet
backings, and insulation.
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Polyurethanes
Notice that polyurethanes prepared from diisocyanates and
diols are the only step-growth polymers that we have seen in
which a small molecule is not lost during polymerization.
One of the most important uses of polyurethanes is in fabrics
with elastic properties, such as spandex (Lycra®).
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Natural Rubber
When the bark of a rubber tree is cut, a sticky white liquid
oozes out. This is the same liquid found inside the stalks of
dandelions and milkweed.
Natural rubber is a polymer isoprene. All the double bonds in
natural rubber are cis. Rubber is a waterproof material because
it consists of a tangle of hydrocarbon chains that have no affinity
for water.
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Synthetic Rubber
Neoprene is a synthetic rubber made by polymerizing 2-chloro-
1,3-butadiene in the presence of a Ziegler–Natta catalyst that
causes all the double bonds in the polymer to have the trans
configuration.
Neoprene is used to make wet suits, shoe soles, tires, hoses
and coated fabrics.
A problem common to both natural and most synthetic rubbers
is that the polymers are very soft and sticky. They can be
hardened by a process known as vulcanization.
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Synthetic Rubber
Buna - N (NBR Rubber) is obtained by polymerization of 1,3-
butadiene & acrylonitrile in the presence of sodium .It is used
for making oil seels, manufacturing of tank linings, protective
gloves etc.
Buna - S (SBR Rubber) is obtained by polymerization of 1,3-
Butadiene & styrene. It is resistant to the action of petrol,
lubricating oil and organic solvents. It is used in making oil
seals, tank lining, etc.
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Thermosetting Polymers
Very strong and rigid materials can be obtained if polymer
chains are cross-linked. The greater the degree of cross-linking,
the more rigid is the polymer. Such cross-linked polymers are
called thermosetting polymers. After they are hardened, they
cannot be remelted by heating.
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Bakelite
Phenol - formaldehyde polymers are the oldest synthetic
polymers. These are obtained by the condensation reaction of
phenol with formaldehyde in the presence of either an acid or a
base catalyst.
The initial product could be a linear product – Novolac used in
paints.
Novolac on heating with formaldehyde undergoes cross
linking to form an infusible solid mass called bakelite. It is used
for making combs, phonograph records, electrical switches
and handles of various utensils.
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Bakelite
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Biodegradable Polymers
These are those polymers which get decomposed under aerobic
or anaerobic conditions, as a result of the action of enzymes.
Most biodegradable polymers exhibit ester or amide groups,
which can be hydrolyzed by enzymes. Some examples are
given as follows:
Nylon 2-Nylon-6 is a Biodegradable polymer. It is an alternating
copolymer of glycine(H2N-CH2-COOH) and amino caproic acid
[H2N(CH2)5COOH] and hence copolymer and polyamide
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Biodegradable Polymers
PHVB, Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) is obtained by
the copolymerisation of 3-hydroxybutanoic acid and 3 – hydroxy-
pentanoic acid.
It is used in speciality packaging, orthopaedic devices and in
controlled release of drugs.
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