Polymerization of Olefin

The word ‘polymer’ is coined from two Greek words: poly means many and mer means unit
or part. The term polymer is defined as very large molecules having high molecular mass (103-
107u). These are also referred to as macromolecules, which are formed by joining of repeating
structural units on a large scale. The repeating structural units are derived from some simple
and reactive molecules known as monomers and are linked to each other by covalent bonds.
This process of formation of polymers from respective monomers is called polymerisation.
This part will focus on the polymerisation of alkenes to produce polymers like poly(ethene)
(usually known as polythene, and sometimes as polyethylene), poly(propene) (old name:
polypropylene), PVC and PTFE.

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.

Every polymer has very distinct characteristics, but most polymers have the following general
attributes.

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.

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.

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.

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, polyurethane and polyethylene.

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.

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.

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.
Polymers can also be classified on the basis of mode of polymerisation into two sub groups.

1. Addition polymers

The addition polymers are formed by the repeated addition of monomer molecules possessing
double or triple bonds, e.g., the formation of polythene from ethene and polypropene from
propene. However, the addition polymers formed by the polymerisation of a single monomeric
species are known as homopolymers, e.g., polythene.

The polymers made by addition polymerisation from two different monomers are termed as
copolymers, e.g., Buna-S, Buna-N, etc.

2. Condensation polymers

The condensation polymers are formed by repeated condensation reaction between two
different bi-functional or tri-functional monomeric units. In these polymerisation reactions, the
elimination of small molecules such as water, alcohol, hydrogen chloride, etc. take place. The
examples are terylene (dacron), nylon 6, 6, nylon 6, etc. For example, nylon 6, 6 is formed by
the condensation of hexamethylene diamine with adipic acid.

1) Polythene
There are two types of polythene as given below:

a) Low density polythene:

An addition reaction is one in which two or more molecules join together to give a
single product. During the polymerisation of ethene, thousands of ethene molecules join
together to make poly(ethene) - commonly called polythene.
Ethene is known as the monomer. Poly(ethene) is the polymer.
 The number of molecules joining up is very variable, but is in the region of 2000 to
20000.
Conditions
Temperature: about 200°C
Pressure: about 2000 atmospheres
Initiator: presence of traces of dioxygen or a peroxide initiator (catalyst).

The low density polythene (LDP) obtained through the free radical addition and H-atom
abstraction has highly branched structure. Low density polythene is chemically inert and tough
but flexible and a poor conductor of electricity. Hence, it is used in the insulation of electricity
carrying wires and manufacture of squeeze bottles, toys and flexible pipes.

Properties and uses

Low density poly(ethene) has quite a lot of branching along the hydrocarbon chains, and this
prevents the chains from lying tidily close to each other. Those regions of the poly(ethene)
where the chains lie close to each other and are regularly packed are said to be crystalline.
Where the chains are a random jumble, it is said to be amorphous. Low density poly(ethene)
has a significant proportion of amorphous regions.

One chain is held to its neighbours in the structure by van der Waals dispersion forces. Those
attractions will be greater if the chains are close to each other. The amorphous regions where
the chains are inefficiently packed lower the effectiveness of the van der Waals attractions and
so lower the melting point and strength of the polymer. They also lower the density of the
polymer (hence: "low density poly(ethene)").

Low density poly(ethene) is used for familiar things like plastic carrier bags and other similar
low strength and flexible sheet materials.

a) High density polythene: It is formed when addition polymerisation of ethene takes place
in a hydrocarbon solvent in the presence of a catalyst such as triethylaluminium and titanium
tetrachloride (Ziegler-Natta catalyst) at a temperature of 333 K to 343 K and under a
pressure of 6-7 atmospheres. Ziegler-Natta catalysts are mixtures of titanium compounds
like titanium(III) chloride, TiCl3, or titanium(IV) chloride, TiCl4, and compounds of
aluminium like aluminium triethyl, Al(C2H5)3.
 High density poly(ethene) has very little branching along the hydrocarbon chains - the
crystallinity is 95% or better. This better packing means that van der Waals attractions
between the chains are greater and so the plastic is stronger and has a higher melting point.
Its density is also higher because of the better packing and smaller amount of wasted space
in the structure. High density poly(ethene) is used to make things like plastic milk bottles
and similar containers, washing up bowls, plastic pipes and so on.

2) Poly(propene)/(polypropylene):
3) Propene undergoes addition polymerization to produce poly(propene), often known as
polypropylene, which is one of the most versatile thermoplastic polymers available
commercially. Poly(propene) is manufactured using Ziegler-Natta and other modern
catalysts. There are three variants on the structure of poly(propene) which you may need to
know about, but we'll start from the beginning with a general structure which fits all of
them.

Structure of the poly(propene)

The propene molecule is asymmetrical, and, when polymerized, can form three basic chain
structures dependent on the position of the methyl groups: two are stereoregular (isotactic and
syndiotactic) and the third does not have a regular structure and is termed atactic as shown
diagrammatically below:

Isotactic: All of the -CH3 have the same orientation along the chain. This very regular
arrangement of the CH3 groups makes it possible for the chains to pack close together and
so maximise the amount of van der Waals bonding between them. That means that isotactic
poly(propene) is quite strong either as a solid object or when it is drawn into fibres. This is
the common form of poly(propene) which is used to make plastic crates and ropes amongst
many other things. The 'one handed' structure of isotactic poly(propene) causes the
molecules to form helices. This regular form permits the molecules to crystallize to a hard,
relatively rigid material, which, in its pure form, melts at 440 K. Commercial poly(propene)
is a predominantly isotactic polymer containing 1-5% by mass of atactic material.
Syndiotactic : Syndiotactic poly(propene) is a relatively new material and is another
regularly arranged version of poly(propene). In this case, every alternate CH3 group is
orientated in the same way. The syndiotactic polymer, because of its regular structure, is
also crystalline. This regularity means that the chains can pack closely, and van der Waals
attractions will be fairly strong. However, the attractions aren't as strong as in isotactic
poly(propene). This makes syndiotactic poly(propene) softer and gives it a lower melting
point. Because syndiotactic poly(propene) is relatively new, at the time of writing uses were
still being developed. It has uses in packaging - for example, in plastic film for shrink
wrapping food. There are also medical uses - for example, in medical tubing and for medical
bags and pouches.

Figure : Molecular structures of poly(propene).

Atactic: In atactic poly(propene) the -CH3 groups are orientated randomly along the chain.
Atactic chains are completely random in structure and consequently they do not crystallize.
High molecular mass atactic poly(propene) is a rubber-like material. This lack of regularity
 makes it impossible for the chains to lie closely together and so the van der Waals attractions
between them are weaker. Atactic poly(propene) is much softer with a lower melting point.
It is formed as a waste product during the manufacture of isotactic poly(propene) and its
uses are limited. It is used, for example, in road paint, in making roofing materials like
"roofing felt", and in some sealants and adhesives.

3) Poly(chloroethene) (polyvinyl chloride): PVC

Poly(chloroethene) is commonly known by the initials of its old name, PVC.

Structure

Poly(chloroethene) is made by polymerising chloroethene, CH2=CHCl. Working out its

structure is no different from working out the structure of poly(propene) (see above). As long
as you draw the chloroethene molecule in the right way, the structure is pretty obvious.

The equation is usually written:

It doesn't matter which carbon you attach the chlorine to in the original molecule. Just be
consistent on both sides of the equation. The polymerisation process produces mainly atactic
polymer molecules - with the chlorines orientated randomly along the chain. The structure is
no different from atactic poly(propene) - just replace the CH3 groups by chlorine atoms.
Because of the way the chlorine atoms stick out from the chain at random, and because of their
large size, it is difficult for the chains to lie close together. Poly(chloroethene) is mainly
amorphous with only small areas of crystallinity.

Properties and uses

You normally expect amorphous polymers to be more flexible than crystalline ones because
the forces of attraction between the chains tend to be weaker. However, pure
poly(chloroethene) tends to be rather hard and rigid. This is because of the presence of
additional dipole-dipole interactions due to the polarity of the carbon-chlorine bonds. Chlorine
is more electronegative than carbon, and so attracts the electrons in the bond towards itself.
That makes the chlorine atoms slightly negative and the carbons slightly positive.These
permanent dipoles add to the attractions due to the temporary dipoles which produce the
dispersion forces.

4) Poly(tetrafluoroethene): PTFE

You may have come across this under the brand names of Teflon or Fluon. Teflon is
manufactured by heating tetrafluoroethene with a free radical or persulphate catalyst at high
pressures. It is chemically inert and resistant to attack by corrosive reagents. It is used in making
oil seals and gaskets and also used for non – stick surface coated utensils.

Structure:

Structurally, PTFE is just like poly(ethene) except that each hydrogen in the structure is
replaced by a fluorine atom.
The PTFE chains tend to pack well and PTFE is fairly crystalline. The chains are rather rod-
like, and can lie closely together rather like pencils in a box.

Properties and uses:

PTFE has a relatively high melting point of 327°C and is very resistant to chemical attack. The
carbon chain is so wrapped up in fluorine atoms that nothing can get at it to react with it. This
makes it useful in the chemical and food industries to coat vessels and make them resistant to
almost everything which might otherwise corrode them.

Equally important is that PTFE has remarkable non-stick properties - which is the basis for its
most familiar uses in non-stick kitchen and garden tools. It also has a very low coefficient of
friction and is used in things like low-friction bearings.

5) Polyacrylonitrile

The addition polymerisation of acrylonitrile in presence of a peroxide catalyst leads to the

formation of polyacrylonitrile.
Polyacrylonitrile is used as a substitute for wool in making commercial fibres as orlon or
acrilan.