Addition Polymerization

Think of the various materials you've used in the last day. Did you use a plastic bottle, a plastic
bag, a blanket, a toy, a basketball, a toothbrush, a lunch box, a rope, a shopping cart or a non-
stick pan?
What do these have in common? Well, all these materials are known as polymers, and more
specifically, addition polymers. But what are those?
Just like the beaded necklace which is made by joining beads, a polymer is a giant molecule
made by assembling many smaller molecules known as monomers. Recall that in an addition
reaction, two or more molecules join together to give a single product.
Addition polymerization takes place when the monomer molecule contains double carbon
bonds, as in alkenes, or triple carbon bonds, as in alkynes. In this lesson we will consider alkene
monomers.

Poly(alkene)
Under suitable conditions, usually between 2,000 to 100,000 alkene monomers are joined
together to make a variety of addition polymers. During addition polymerization process, the Pi
bonds of the double bonds in each alkene molecule sort of break open, thereby allowing the free
bonds to join with one another to form a chain known as poly(alkene) or polythene. This chain
contains units that repeat themselves, known as repeating units.

Addition polymerization of an alkene. n is usually between 2,000 and 100,000 units.

The brackets contain the repeating unit.
Addition polymerization results in the formation of poly(alkenes) that contain single bonds holding
the carbon. This makes them generally unreactive and chemically inert.
These properties make their usage safe and durable, but this durability also means that they are
not biodegradable when left in the environment. This makes them a pollution hazard.
Now we turn to more specific addition polymers, poly(ethene) and poly(propene).

Poly(ethene)
During the polymerization of ethene, thousands of ethene molecules join together to
make poly(ethene) (aka polyethylene or polythene). Poly(ethene) is by far the most popular
addition polymer.

Addition polymerization of ethene.

By altering the conditions under which polymerization of ethene is done, we can obtain low
density polyethylene or high density polyethylene.
Low density polyethylene (LDPE) is obtained when ethene is subjected to a temperature of
about 200° C, a pressure of 2,000 atmospheres and a small amount of oxygen as an impurity,
which also acts as an initiator.
In low density polyethylene, the chains are highly branched and this results in much lower Van
Der Waals dispersion forces. This makes LDPE soft and flexible, useful in making plastic carrier
bags, squeeze bottles, toys, general packaging, and gas and water pipes.
On the other hand, high density polyethylene (HDPE) is obtained when ethene is exposed to
the Ziegler-Natta catalyst (mixtures of titanium and aluminum compounds) under a temperature
of about 60° C.
Here also the polymeric chains are held by Van Der Waals dispersion forces, but the forces are
stronger than in LDPE because the chains have very little branching. This renders high density
polyethylene a tough, hard and strong product used to make things like plastic milk bottles,
plastic pipes, dust bins and crates.

Poly(propene)
Poly(propene) (aka polypropylene or PP) is formed by repetition of one structural unit of
propene several times using Ziegler-Natta catalyst. The propene molecules are bonded with
each other by covalent bonds.

Addition polymerization of propene.

Poly(propene) has a higher melting point when compared to similarly weighted plastics, making it
good for making food containers subject to high temperatures like in microwaves and
dishwashers.
Poly(propene) shows strong resistance towards cracking and stress, even when flexed. This
makes it useful for use in hinges, water pipes and washing-machine parts.

Poly(propene)
Poly(propene) (aka polypropylene or PP) is formed by repetition of one structural unit of
propene several times using Ziegler-Natta catalyst. The propene molecules are bonded with
each other by covalent bonds.

Addition polymerization of propene.

Poly(propene) has a higher melting point when compared to similarly weighted plastics, making it
good for making food containers subject to high temperatures like in microwaves and
dishwashers.
Poly(propene) shows strong resistance towards cracking and stress, even when flexed. This
makes it useful for use in hinges, water pipes and washing-machine parts.
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