Research about

Polymers

Submitted by:

Jael Viktor F. Manangan

July 27, 2011

Polymers

A polymer is a large molecule composed of repeating structural units. Sometimes, people refer to
the term polymer to plastics, but it actually encompasses a large class comprising both natural and
synthetic materials with a wide variety of properties.

The word polymer is derived from the Greek words Poly meaning many and meros
meaning part. The term was coined in 1833 by a Swedish chemist named Jons Jacob Berzelius, who
also worked out the modern technique of chemical formula notation. A polymer is synthesized by
chemically joining together many small molecules into one giant molecule. The small molecules used to
synthesize polymers are called monomers. Synthetic polymers can be classified as addition polymers,
formed from monomer units directly joined together, or condensation polymers, formed from monomer
units combining such that a small molecule, usually water, is produced during each reaction.

The first synthetic polymer, a phenol-formaldehyde polymer, was introduced under the name
Bakelite, by Leo Baekeland in 1909. Its original use was to make billiard balls. Rayon, the first
synthetic fiber was developed as a replacement for silk in 1911.

Although many polymers were made in the following years, the technology to mass produce them
was not developed until World War II, when there was a need to develop synthetic rubber for tires and
other wartime applications and nylon for parachutes. Since that time, the polymer industry has grown and
diversified into one of the fastest growing industries in the world. Today, polymers are commonly used in
thousands of products as plastics, elastomers, coatings, and adhesives. They make up about 80% of the
organic chemical industry with products produced at approximately 150 kg of polymers per person
annually in the United States.

Characteristics of polymers

The majority of manufactured polymers are thermoplastic, meaning that once the polymer is
formed it can be heated and reformed over and over again. This property allows for easy processing and
facilitates recycling. The other group, the thermosets, cannot be remelted. Once these polymers are
formed, reheating will cause the material to ultimately degrade, but not melt.
1. Polymers can be very resistant to chemicals - Consider all the cleaning fluids in your home
that are packaged in plastic. Reading the warning labels that describe what happens when the chemical
comes in contact with skin or eyes or is ingested will emphasize the need for chemical resistance in the
plastic packaging. While solvents easily dissolve some plastics, other plastics provide safe, non-breakable
packages for aggressive solvents.

2. Polymers can be both thermal and electrical insulators - A walk through your house will
reinforce this concept, as you consider all the appliances, cords, electrical outlets and wiring that are made
or covered with polymeric materials. Thermal resistance is evident in the kitchen with pot and pan
handles made of polymers, the coffee pot handles, the foam core of refrigerators and freezers, insulated
cups, coolers, and microwave cookware. The thermal underwear that many skiers wear is made of
polypropylene and the fiberfill in winter jackets is acrylic and polyester.

3. Generally, polymers are very light in weight with significant degrees of strength
- Consider the range of applications, from toys to the frame structure of space stations, or from delicate
nylon fiber in pantyhose to Kevlar, which is used in bulletproof vests. Some polymers float in water while
others sink. But, compared to the density of stone, concrete, steel, copper, or aluminum, all plastics are
lightweight materials.

4. Polymers can be processed in various ways - Extrusion produces thin fibers or heavy pipes
or films or food bottles. Injection molding can produce very intricate parts or large car body panels.
Plastics can be molded into drums or be mixed with solvents to become adhesives or paints. Elastomers
and some plastics stretch and are very flexible. Some plastics are stretched in processing to hold their
shape, such as soft drink bottles. Other polymers can be foamed like polystyrene (Styrofoam),
polyurethane and polyethylene.

5. Polymers are materials with a seemingly limitless range of characteristics and colors
- Polymers have many inherent properties that can be further enhanced by a wide range of additives to
broaden their uses and applications. Polymers can be made to mimic cotton, silk, and wool fibers;
porcelain and marble; and aluminum and zinc. Polymers can also make possible products that do not
readily come from the natural world, such as clear sheets and flexible films.

6. Polymers are usually made of petroleum, but not always - Many polymers are made of
repeat units derived from natural gas or coal or crude oil. But building block repeat units can sometimes
be made from renewable materials such as polylactic acid from corn or cellulosics from cotton linters.
 Some plastics have always been made from renewable materials such as cellulose acetate used for
screwdriver handles and gift ribbon. When the building blocks can be made more economically from
renewable materials than from fossil fuels, either old plastics find new raw materials or new plastics are
introduced.

7. Polymers can be used to make items that have no alternatives from other materials
- Polymers can be made into clear, waterproof films. PVC is used to make medical tubing and blood bags
that extend the shelf life of blood and blood products. PVC safely delivers flammable oxygen in non-
burning flexible tubing. And anti-thrombogenic material, such as heparin, can be incorporated into
flexible PVC catheters for open heart surgery, dialysis, and blood collection. Many medical devices rely
on polymers to permit effective functioning.

Physical properties:

Branching

During the propagation of polymer chains, branching can occur. In free-radical polymerization, this
occurs when a chain curls back and bonds to an earlier part of the chain. When this curl breaks, it leaves
small chains sprouting from the main carbon backbone. Branched carbon chains cannot line up as close to
each other as unbranched chains can. This causes less contact between atoms of different chains, and
fewer opportunities for induced or permanent dipoles to occur. A low density results from the chains
being further apart. Lower melting points and tensile strengths are evident, because the intermolecular
bonds are weaker and require less energy to break.
Besides branching, polymers can have other topologies: linear, network (cross-linked 3D structure), IPN
(integrated polymer network), comb, or star as well as dendrimer and hyperbranched structures.

Stereoregularity

Stereoregularity or tacticity describes the isomeric arrangement of functional groups on the

backbone of carbon chains. Isotactic chains are defined as having substituent groups aligned in one
direction. This enables them to line up close to each other, creating crystalline areas and resulting in
highly rigid polymers.

In contrast, atactic chains have randomly aligned substituent groups. The chains do not fit together
well and the intermolecular forces are low. This leads to a low density and tensile strength, but a high
degree of flexibility.

Syndiotactic substituent groups alternate regularly in opposite directions. Because of this

regularity, syndiotactic chains can position themselves close to each other, though not as close as isotactic
polymers. Syndiotactic polymers have better impact strength than isotactic polymers because of the
higher flexibility resulting from their weaker intermolecular forces.

Constitution of Polymers

Copolymers: Copolymerization with two or more different monomers results in chains with
varied properties. There are twenty amino acid monomers whose sequence results in different shapes and
functions of protein chains. Copolymerising ethene with small amounts of 1-hexene (or 4-methyl-1-
pentene) is one way to form linear low-density polyethene (LLDPE). The C4 branches resulting from the
hexene lower the density and prevent large crystalline regions from forming within the polymer, as they
do in HDPE. This means that LLDPE can withstand strong tearing forces whilst remaining flexible.

A block copolymer is formed when the reaction is carried out in a stepwise manner, leading to a
structure with long sequences or blocks of one monomer alternating with long sequences of the other.
There are also graft copolymers, in which entire chains of one kind (e.g., polystyrene) are made to grow
out of the sides of chains of another kind (e.g., polybutadiene), resulting in a product that is less brittle
and more impact-resistant. Thus, block and graft copolymers can combine the useful properties of both
constituents and often behave as quasi-two-phase systems.

The following is an example of step-growth polymerization, or condensation polymerization, in

which a molecule of water is given off and nylon is formed. The properties of the nylon are determined by
the R and R' groups in the monomers used.
The first commercially successful, completely synthetic polymer was nylon 6,6, with alkane chains R =
4C (adipic acid) and R' = 6C (hexamethylene diamine). Including the two carboxyl carbons, each
monomer donates 6 carbons; hence the name. In naming nylons, the number of carbons from the diamine
is given first and the number from the diacid second. Kevlar is an aromatic nylon in which both R and R'
are benzene rings.

Copolymers illustrate the point that the repeating unit in a polymer, such as a nylon, polyester or
polyurethane, is often made up of two (or more) monomers.
Chemical Properties

Intermolecular Forces

The attractive forces between polymer chains play a large part in determining a polymer's
properties. Because polymer chains are so long, these interchain forces are amplified far beyond the
attractions between conventional molecules. Also, longer chains are more amorphous (randomly
oriented). Polymers can be visualised as tangled spaghetti chains - pulling any one spaghetti strand out is
a lot harder the more tangled the chains are. These stronger forces typically result in high tensile strength
and melting points.

The intermolecular forces in polymers are determined by dipoles in the monomer units. Polymers
containing amide groups can form hydrogen bonds between adjacent chains; the positive hydrogen atoms
in N-H groups of one chain are strongly attracted to the oxygen atoms in C=O groups on another. These
strong hydrogen bonds result in, for example, the high tensile strength and melting point of kevlar.
Polyesters have dipole-dipole bonding between the oxygen atoms in C=O groups and the hydrogen atoms
in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so ethene's melting point and
strength are lower than kevlar's, but polyesters have greater flexibility.
Ethene, however, has no permanent dipole. The attractive forces between polyethene chains arise from
weak van der Waals forces. Molecules can be thought of as being surrounded by a cloud of negative
electrons. As two polymer chains approach, their electron clouds repel one another. This has the effect of
lowering the electron density on one side of a polymer chain, creating a slight positive dipole on this side.
This charge is enough to actually attract the second polymer chain. Van der Waals forces are quite weak,
however, so polyethene melts at low temperatures.
Types of Polymers

Synthetic Polymers

Synthetic polymer is a polymer that is manufactured in industry from chemical substances through
the polymerisation process. Through research, scientists are now able to copy the structure of natural
polymers to produce the synthetic polymers. Plastics, synthetic fibres, and elastomers are examples of
synthetic polymers. The raw materials for the manufacture of synthetic polymers are distillates of
petroleum. There are three classifications of synthetic polymers: Thermo plastics, Fibres, and Elastomers.

Thermoplastics

Is a polymer which, when subjected to heat, becomes soft so they can be moulded into
various shapes. The proper ties of plastics are: light, strong, inert to chemicals such as acids and
alkali, and are insulators of electricity and heat.

Synthetic Fibres

Are longed chained polymers that withstand stretching. Examples of synthetic fibres are
nylon, which are used to make ropes, fishing lines, clothing, etc., and terylene, which are also used
to make clothing, which makes them not crease easily, fishing nets.

Elastomer

Is a polymer that can regain its original shape after being stretched or pressed. Both
natural and synthetic rubber are examples of elastomer.

Natural Polymers

This group consists of naturally occurring polymers and chemical modifications of these polymers.
Cellulose, starch, lignin, chitin, and various polysaccharides are included in this group. These materials
and their derivatives offer a wide range of properties and applications. Natural polymers tend to be readily
biodegradable, although the rate of degradation is generally inversely proportional to the extent of
chemical modification.

Natural polymers include the RNA and DNA that are so important in genes and life processes. In
fact, messenger RNA is what makes possible proteins, peptides, and enzymes. Enzymes help do the
chemistry inside living organisms and peptides make up some of the more interesting structural
components of skin, hair, and even the horns of rhinos. Other natural polymers include polysaccharides
(sugar polymers) and polypeptides like silk, keratin, and hair. Natural rubber is, naturally a natural
polymer also, made from just carbon and hydrogen. Let's look at each of the main families of natural
polymers closely.

Polymerization

Is a chemical process that combines several monomers to form a polymer or polymeric compound.
There are two types of polymerization: polymerization by addition, and polymerization by condensation.

Polymerization by addition

Involves monomers with >C=C< bonding, where the monomers join together to make a
long chain without losing any simple molecules from it. Examples of polymers produced through
this process are polythene, PVC Perspex and other plastics.

Polymerization by condensation

Involves the elimination of small molecules like water, methanol, ammonia, or hydrogen
chloride during the process. Examples of products of this process are terylene and nylon-66.