Addition Polymers
Molly Powell
Yifeng Yang
December 2023
1 Scientific Background
An addition polymer is constructed through chain
addition reactions between alkene monomers. Un-
like condensation polymerisation, addition polymeri-
sation only produces one product. Given by the gen- generates a free radical on one of its carbon atoms,
eral formula: and the other carbon atom bonds with the initiator.
n CH2 −CH2 −−→ (CH2 CH2 )n (1)
Where n represents the number of monomers joined
in the given polymer.
Figure 1: Representation of the process in which rad-
icalisation occurs in an ethene molecule with an ini-
tiator ‘X’. Termination is not shown in the figure
Addition polymers can be generated when the
monomer undergoes free radical substitution from
an initiator or catalyst, such as Hydrogen Peroxide
(H2 O2 ) [1]. The monomer, Ethene in this example,
1
H H
C C (2)
H H
H (3)
⊕
X H
Where X represents the initiator, and ⊕ represents
the free carbon radical.
These radicals undergo propagation, reacting with
other Ethene molecules and creating more free car-
bon radicals before termination halts the reaction,
resulting in an addition polymer formed of ethene
monomers [Fig. 1]
2 Disposal of Polymers
Addition polymers are non-biodegradable because:
• They contain multiple C-H covalent bonds that
are very strong
• The regularity and symmetrical nature of the
structure leads to a non-polar molecule
– If there is polarity within a molecule, the
molecule can therefore be hydrolysed by
 and acid or a base and be broken apart and • σ bonds are formed from the overlap of two sep-
decomposed. arate S-orbitals [Fig. 3]
– Unlike polyalkenes, other polymers such as – This can be described as head-on, end-to-
ester groups and amide groups contain an end or axial overlap
uneven C=O branch, leading to a polarity
which creates dicarboxylic acids and diols – The electron density is concentrated be-
(Acid + Ester) or dicarboxylic acid and di- tween the two nuclei
amine salts (Acid + Polyamide) – Also forms from the head on overlap of an
S-orbital and a P-orbital and two P-orbitals
These factors all lead to the compound to be inert. overlapping as well
This leads to a lack of biodegradability and therefore
a greater difficulty to recycle (Photo-degradable poly-
mers are a different type of polymer which synthetic
that have been developed to break down under the
exposure of UV light), and addition polymers are also
unable to be broken down organically by enzymes and
microorganisms which makes it even more difficult to
dispose the excess/waste.
This has allowed for polymers to be used most
commonly in material applications, such as plastics
(PVC, Polystyrene, Kevlar), which result in a greater
accessibility for most products as well as a more cost-
effective method of production.
Figure 3: The varying types of formations of a sigma
bond
3 Polymer Stability
• π bonds are formed from the sideways overlap of
The individual components of an addition polymer
two P-orbitals
are alkenes. Alkenes are comprised of C=C double
bonds, which are in essence π and σ bonds. These – This results in the electron density to be
bonds are created through orbital overlap and in above and below the nucleus, instead of be-
alkenes from the hybridisation of SP2 orbitals into tween the nuclei.
SP3. S-orbitals adopt a spherical shape, and P-
orbitals adopt a dumbbell/hourglass shape[Fig. 2].
References
1. Walbridge, D. J. in Comprehensive Polymer Sci-
ence and Supplements (eds Allen, G. & Bev-
ington, J. C.) 197–200 (Pergamon, Amsterdam,
1989). isbn: 978-0-08-096701-1. https : / / www .
sciencedirect . com / science / article / pii /
B9780080967011001531.

Figure 2: Hybridisation of S and P orbitals