EG-M106 Lecture2

Polymer Processing EG-M106
Polymerisation and Biopolymers

Learning outcomes
- Overview of polymerisation
- How it can fix the polymer structure
- Importance of molecular weight
- What are biopolymers
- Possible benefits and drawbacks of
biopolymers
Polymer terminology
Monomer
Polymer
Polymerisation
H H H H H H H H H
C C +C C C C C C C
H H H H H H H H H
ethylene Polyethylene
Monomer -
Single repeat
Unreacted
unit polymer
single molecule
Polymerisation
Polymers are synthesized from monomers via a

chemical process
This process is known as polymerisation

Polymerisation
There are mainly two types of polymerisation
processes:
- addition: involves a double-bond
- condensation: involves reacting groups,

normally losing water
Polymerisation
In addition polymerisation
- A catalyst initiates the polymerisation reaction

whereby each monomer adds onto the next monomer
until all the monomers are polymerised.
Polymerisation
In condensation polymerisation
- Each monomer adds on to the next monomer,

but this time the chemical reaction also produces a
low molecular weight byproduct that has to be
continually removed. Condensation polymers are
usually polymerised from two or more families of
monomers. Example would be nylon (chemical name
polyamide)
Byproduct
Polymerisation
Polymerisation
We can use reactive ends to make thermosets
• If we have reactive groups just at ends, we’ll make

a linear polymer – thermoplastic
• If we have more reactive groups, can make
crosslinks - thermoset
Polymerisation
Degree of polymerisation (n)
H H H H H H
C C C C C C
H H H H H H
n
The degree of polymerisation
could be in excess of 100,000
The higher the number of repeat units (n) the higher

the molecular weight
Molecular Weight
Most commercial polymers have a number average

molecular weight between 40,000 and 200,000
Some ultra high molecular weight polyethylene

(UHMWPE) have a molecular weight from 1 to 6
million.
The number of average molecular weight is the

addition of the molecules divided by the number of
molecules
Molecular Weight
Some polymers such as polyamides and polyesters
have strong intermolecular forces.
These plastics can posses sufficient mechanical

properties even though they have low molecular
weight
In materials such as polyethylene, intermolecular
forces are low, therefore high molecular weights are
required for this material to have the appropriate
mechanical properties for practical applications.
Molecular Weight
If molecular weight is too low, the mechanical
properties will generally be too low for the polymer
material to have any commercial application.
Molecular Weight
Polymer molecular weight is important because it
determines many physical properties. Examples
include:
- temperatures for transitions from liquids to
solids
- stiffness
- strength
- viscoelasticity
- toughness
- viscosity
Molecular Weight
However, if the molecular weight is too high then
processing is very difficult as the melt viscosity*
increases.
* Viscosity in a fluid is a measure of its resistance to deformation

Molecular Weight
Therefore, to process polymers (injection
mould/extrusion) requires a comprise between a
molecular weight that is low enough for reasonably
easy processing but high enough for application
purposes.
Molecular Weight
The addition of monomers during polymerisation
(both addition and condensation), is completely
random.
The growth of the molecules is difficult to control

This results in
molecules of various
lengths being
generated with
different molecular
weights
Therefore the molecular weight
distribution becomes relevant
Molecular Weight Distribution
The MWD is very important factor in processing
• Lower molecular weight
units melt faster than
higher molecular weight
units
• In IM plastic needs to be
injected into a mould as
quick as possible
• If you have a narrow
MWD the plastic is
molten at the same time
which reduces melt
strength
Molecular Weight Distribution
The MWD is very important factor in processing
• If you have a broader
MWD this gives the
plastic more melt strength
which is superior for
processing with extrusion
• The difference in MWD is

a decisive factor in
determining whether a
plastic is used for
extrusion or IM
Molecular Weight Characterisation
End Group Analysis
• Direct method
Take a known mass of polymer and dissolve it in a suitable
solvent.
Analyse the solution chemically to determine the number of
end groups present.
Divide the total polymer mass by the number of end groups
(chains) to give the average weight per chain.
Gel Permeation Chromatography(GPC)
• Indirect method
• The polymer is dissolved in a suitable solvent.
• The polymer solution is fed at a controlled rate through a
column of porous material (often silica gel).
• Different sized polymer molecules take different times to
travel through the column.
Solvent
Resevoir
Gel
column
Pump
Detector
Sample
injected
Viscometry
• Viscosity depends very strongly on molecular
weight.
• Can use this as a method of measurement.
• Simple version is Melt Flow Index (MFI) – a
measure of processability.
• MFI = amount of molten polymer (per minute)
going through a tube under certain force at
certain temperature.
Biopolymers (bio-based) and Biodegradables
Need for clear distinction:

Biopolymers are those derived from natural sources
Biodegradable polymers break down biologically under action
of natural environment
• Separation between compostable (normal conditions)
• and biodegradable (which may need industrial conditions)
Bio-based polymers
Polymers that are produced from natural pre-cursors (normally

plant based or bacteria based oils or sugars).
Advantages – lower environmental impacts of production, long

term sustainability
Disadvantage – may be higher environmental impact due to

land use (farming), more expensive
Bio-based polymers
Specific environmental considerations
Requires the cutting down of rainforest to permit growing crops

for polymer (e.g. soya-based polymers)
Can use existing waste product to convert into polymers (e.g.

cashew-nut oil polymer to replace epoxy resins)
Biopolymers
Produced from plant material (oils, sugars, cellulose)

• or algae
• or bacteria
We can produce many synthetic* polymers from these sources
*imitate a natural product

Biodegradable Polymers
Will breakdown to molecules that can be absorbed naturally

into the environment.
Degradation maybe possible in normal composting

environment (compostable) or may need specific
temps/enzymes.
Advantages – reduces problem of long-term littering
Disadvantage – limits useable lifetime, disrupts recycling

processes, may cause methane generation in landfill.
Biodegradable polymers
Specific environmental considerations
A single-use product from PLA (only biodegradable in

industrial conditions), which adversely affects existing
recycling systems
The polymer can be used when incorporation into the natural

environment is the easiest option (e.g. starch-based polymers
used for crop mulch film
Biodegradable Polymers
Some examples of suitable use

• Crop film
• Tree shelters
• Biodegradable
microbeads &
glitter

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Polymer Processing EG-M106

Polymerisation and Biopolymers

Polymers are synthesized from monomers via a

This process is known as polymerisation

- addition: involves a double-bond

- condensation: involves reacting groups,

- A catalyst initiates the polymerisation reaction

- Each monomer adds on to the next monomer,

• If we have reactive groups just at ends, we’ll make

The higher the number of repeat units (n) the higher

Most commercial polymers have a number average

Some ultra high molecular weight polyethylene

The number of average molecular weight is the

These plastics can posses sufficient mechanical

* Viscosity in a fluid is a measure of its resistance to deformation

The growth of the molecules is difficult to control

• The difference in MWD is

Need for clear distinction:

Polymers that are produced from natural pre-cursors (normally

Advantages – lower environmental impacts of production, long

Disadvantage – may be higher environmental impact due to

Specific environmental considerations

Requires the cutting down of rainforest to permit growing crops

Can use existing waste product to convert into polymers (e.g.

Produced from plant material (oils, sugars, cellulose)

*imitate a natural product

Will breakdown to molecules that can be absorbed naturally

Degradation maybe possible in normal composting

Advantages – reduces problem of long-term littering

Disadvantage – limits useable lifetime, disrupts recycling

Specific environmental considerations

A single-use product from PLA (only biodegradable in

The polymer can be used when incorporation into the natural

Some examples of suitable use

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