Department of Chemical Engineering

Polymers and Plastics Engineering (0905553)

Molecular Structure
Homopolymers
A homopolymer is defined as a polymer derived from one type of monomer. The
term homopolymer thus refers to the source of the mers in a polymer and not to the
actual constitutional (‫ )بنيوي‬units.

Copolymers
Copolymers are generated from more than one type of momomers; they are called
biopolymer, terpolymers, quaterpolymers, etc., according to the number of monomer
types.
The copolymerization of ethylene, CH 2  CH 2 , and propylene, CH 2  CH CH 3  ,

thus leads to the biopolymer poly(ethylene-co-propylene).

Linear polymers
A linear polymer is a polymer molecule in which the atoms
are more or less arranged in a long chain. This chain is
called the backbone.

Cyclic polymers
A cyclic polymer consists of linear polymer molecules that
are intramoleculary joined via their own ends; they do not
have endgroups.
Normally, some of these atoms in the chain will have small chains of atoms attached
to them. These small chains are called pendant groups. The chains of pendant groups
are much smaller than the backbone chain. Pendant chains normally have just a few
atoms, but the backbone chain usually has hundreds of thousands of atoms.

Normally, when we talk of polymers, we're not just talking about huge molecules
whose atoms are arranged in chains. We like to think that the atoms that make up the
backbone of a polymer chain come in a regular order, and this order repeats itself all
along the length of the polymer chain.
For example, in polypropylene, the backbone chain is made up of just two carbon
atoms repeated over and over again. One carbon atom has two hydrogen atoms
attached to it, and the other has one hydrogen atom and one pendant methyl group.

This unit of a carbon atom with two hydrogen atoms followed by a carbon atom with
a hydrogen atom and a methyl group repeats itself over and over again along the
backbone chain. This little recurring structure is called the repeat structure or the
repeat unit.

To make things simple, we usually only draw one unit of the repeat structure, like
this:
The repeat unit is put inside brackets, and the subscript n just stands for the number of
repeat units in the polymer chain.

Many polymers are built so their molecules consist of many thousands of atoms
arranged into long linear chains.

But they don't have to be long straight chains. Polymers can be made in a lot of other
arrangements. Let's look at a few of them:

Branching Out

Not all polymers are linear in this way. Sometimes there are chains attached to the
backbone chain which are comparable in length to that backbone chain. This is called
a branched polymer. Some polymers, like polyethylene, can be made in linear or
branched versions.
The branch chains have some strange habits. Sometimes, both ends of the branch
chains are attached to the backbone chains of separate polymer molecules. If enough
branch chains are attached to two polymer molecules, it can happen that all of the
polymer backbone chains in a sample will be attached to each other in a giant
network! When this happens, the sample is in fact one single molecule, a molecule
large enough to pick up in your hands! Polymers like this are called crosslinked
polymers. Many types of rubber, such as polyisoprene and polybutadiene, are
crosslinked. A tire is actually one giant network molecule, a molecule so big it takes
two hands to pick it up.

Sometimes the ends of several polymer chains are joined together at a common
centre. Polymers like this are called star polymers. They're used as additives in motor
oil.
Sometimes there is no backbone chain at all. Sometimes a polymer is built in such a
way that branches just keep growing out of branches and more branches grow out of
those branches. These are called dendrimers, from the ancient Greek word for "tree".

Dendrimers have unusual shapes which make pretty pictures, and really unusual
properties. Drug delivery is one possibility.

Supermolecular Structure

Polymer properties are influenced not only by the chemical structure of

polymers (constitution, molar mass, configuration, and microconformation) but also
by their physical structure. These structures may range from totally irregular
arrangements of chain segments and shorter or longer parallelisations of chains to
voids and other defects in otherwise highly organised assemblies of polymer
molecules.
Two possible ideal structures exist in the solid state: perfect crystals and
totally amorphous polymers. Polymer molecules are perfectly ordered in ideal
crystals. They convert at the thermodynamic melting temperature into melts, which
ideally are totally disordered. Most polymers can only stretch out for a distance
before they fold back on themselves. Very few polymers can stretch out perfectly
straight.
 Folded and stretched polymer chains.
Polymers form stacks of these folded chains. A stack of polymer chains
folded back on themselves is called a lamella. A schematic diagram for polymer
lamellae is shown below.

Schematic diagram of lamellae.

Of course, it is not always as neat as this. Sometimes part of a chain is
included in this crystal, and part of it isn’t. When this happens, the lamella is no
longer neat and tidy, but sloppy, with chains hanging out of it everywhere as in the
following figure.

Sometimes a polymer chain is indecisive and decide to

come back into the lamella after wandering around outside for a
while. The result is what is called the switchboard model of a
polymer crystalline lamella.
 Schematic diagram for the switchboard model of a polymer crystalline lamella.
Some of the polymer is crystalline, and some is not, and most crystalline
polymers are not entirely crystalline. The chains, or parts of chains, that are not in the
crystals have no order to the arrangement of their chains, they are in the amorphous
state. So, a crystalline polymer really has two components: the crystalline portion and
the amorphous portion. The crystalline portion is in the lamella, and the amorphous
portion is outside the lamella.
Lamella grow from a central nucleus in three dimensions, so together they
look like a sphere. The whole sphere is called a spherulite. In a sample of a
crystalline material there are many billions of spherulites. In between the crystalline
lamellae there are regions where there is no order to the arrangement of the polymer
chains. These disordered regions are the amorphous regions.

Presentation of a spherulite showing the tie molecules, the lamellar fibrils, the
amorphous region and the crystal nucleus.
 It can be seen that a single polymer chain may be partly in a crystalline
lamella, and partly in the amorphous state. Some chains even start in one lamella,
cross the amorphous region, and then join another lamella. These chains are called tie
molecules. Crystallinity makes a material strong, but it also makes it brittle. A
completely crystalline polymer would be too brittle to be used as plastic. The
amorphous regions give polymer toughness, that is, the ability to bend without
breaking.

Amorphous and Crystalline Polymers

Many polymers are a mix of amorphous and crystalline regions, but some are
highly crystalline and some are highly amorphous. Polymer structure and
intermolecular forces are important factors affecting polymer crystallinity. If the
structure is regular and orderly, it will pack into crystals easily.
Plastics have a higher density when they crystallise due to the closer packing
of the molecules. Typical characteristics of crystalline and amorphous plastics are
shown in the Table.

Typical characteristics of crystalline and amorphous plastics.

Amorphous
 Broad softening range: thermal
agitation of the molecules breaks
down the weak secondary bonds.
The rate at which this occurs varies
producing broad temperature range
for softening.
 Usually transparent: the looser
structure transmits light so the
material appears transparent.
 Low shrinkage: all thermoplastics
are processed in the amorphous
Crystalline
 Sharp melting point: the regular
close-packed structure results in
most of the secondary bonds being
broken down at the same time.
 Usually opaque: the difference in
refractive indices between the two
phases causes interference so the
material appears translucent or
opaque.
 High shrinkage: as the material
solidifies from the amorphous state
 state. On solidification, the random
arrangement of molecules produces
little volume change and hence low
shrinkage.
 Low chemical resistance: the more
open random structure enables
chemicals to penetrate deep into the
material and to destroy many of the
secondary bonds.
 Poor fatigue and wear resistance: the
random structure contributes little to
fatigue or wear properties.
 Examples: PVC, PS, PC
the polymers take up a closely
packed, highly aligned structure.
This produces a significant volume
change manifested as high
shrinkage.
 High chemical resistance: the tightly
packed structure prevents chemical
attack deep within the material.
 Good fatigue and wear: the uniform
structure is responsible for good
fatigue and wear properties.
 Examples: PE, PP, PA