Basic Science for Students of

Paint Technology
R Stanfield FTSC

OCCA Student Monograph No. 1

Oil & Colour Chemists’Association

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Basic Science for Students
of Paint Technology
R Stanfield FTSC

OCCA Student Monograph No. 1

Oil & Colour Chemists’Association

B CF
Published by the Oil & Colour Chemists’ Association,
Priory House, 967 Harrow Road, Wembley HA0 2SF, United Kingdom
© OCCA 1998
First Published 1993
Second Edition 1998

ISBN 0 903809 01 4
Printed by The Burlington Press, Foxton, Cambridge CB2 6SW, United Kingdom
Typeset by My Word!, 138 Railway Terrace, Rugby, CV21 3HN, United Kingdom

Foreword
This monograph is part of a series of Student Monographs published by the Oil and Colour Chemists’
Association, and is part of a collaborative project with the British Coatings Federation to produce
additional reading material for students wishing to take up studies on the Federation’s distance learning
programme – the Open Tech. The monographs are also suitable for those persons seeking basic
background information on aspects of the science and technology of surface coatings.
The monographs have been written by authors nominated by the British Coatings Federation and
approved by that Federation’s Tutors and Assessment Boards. The series has been published with the
help of a grant by the Trustees of the Ellinger-Gardonyi Fund, an educational trust administered by the Oil
and Colour Chemists’ Association and established to enhance education and training in surface coatings
technology
Basic Science for Students
of Paint Technology
R Stanfield FTSC
General Introduction
Technical developments in the Paint Industry over the last 70 years or so have made it essential for
students in this field to have a sound understanding of basic scientific principles.
This monograph is directed towards those students who have had limited opportunities to acquire such
an understanding.
In selecting the subject matter for this work, two main problems were anticipated – which subjects to
include and in how much detail should each be covered.
On the first point, the greatest problem proved to be what to leave out rather than what to put in.
On the second point, an attempt has been made to go into each topic in just sufficient depth to provide
students with a good understanding on which they can build by further reading.
The object has been to familiarise the reader with the important basic scientific principles and then
develop just some of these along selected areas of paint technology.
By taking this approach, I have tried to meet the needs of as many students of paint technology as
possible, and hope that you find most, if not all, of this monograph both useful and interesting.
Some additions have been made to this latest edition of the Monograph, including some material on
pigments, colour and energy.
This project could not have been completed without the help of others, and I wish to record my
appreciation to Alan Vickers and Ken Arbuckle, who kindly read through my draft text, pointed out errors
and made valuable suggestions which have greatly improved the final version.
Ron Stanfield
September, 1998
Contents

Introduction 1
The nature of matter 1
The states of matter 3
Energy 7
Compounds 7
Organic compounds 10
Organic and inorganic pigments 19
Inorganic compounds 20
Organic polymers 24
Properties of organic polymers 28
Colour 33
Further reading 33

Basic Science for Students of Paint
Technology
Introduction
The monograph begins by introducing the primary
particles from which all matter is formed and
goes on to explain the structure of atoms and
molecules. The way that the elements have been
classified to form the Periodic Table is then
illustrated and an indication given as to how this
table can be used to identify properties of the
elements.
After this, the gaseous, liquid and solid states of
matter are reviewed with reference to the mobility
of the atoms and molecules present in them.
The relationship between the arrangement of
atoms and molecules within a material in the solid
state and its properties is introduced with
reference to pigments.
The nature of energy is discussed before moving
on to an explanation of how individual elements
combine to form compounds. The nature of the
bonds within this formation is given and reference
is also made to the secondary bonding forces
between individual molecules.
This is followed by a short historical review of the
division of compounds into organic and inorganic
classifications and a look at the structure of the
carbon atom and its importance in organic
compounds. The methods used to name organic
compounds generally is explained and each of the
most important classes of organic compound is
considered. Particular emphasis is placed on
organic compounds containing functional groups.
The last part of the section deals with organic and
inorganic pigments and how their composition
influences their colour and other properties.
A section on inorganic compounds reviews the
types of bonding involved and the varying valency
of some of the elements which they contain. An
explanation of isotopes, a study of acids and
bases, hydrogen ion concentration and electro-
negativity then follows. The last part of this
section deals with oxidation and reduction
reactions.
1
The next sections of the monograph utilise some
of the earlier work to explain both the formation
and properties of organic polymers. The
mechanism of addition and condensation
polymerisation is shown and the difference
between linear, branched and network polymer
molecules illustrated. Functionality and its
importance in determining the type of polymer
produced and the properties of the polymer is
discussed.
The section on the properties of the polymers
relates their component parts, their structure,
their size and their functionality to the
characteristics they exhibit as film formers.
To complete the monograph there is a short
section in which the subject of colour is
introduced.
The nature of matter
We will start by considering the “building blocks”
of matter, the composition of these building
blocks and how their structure influences the
materials which they can produce.
All matter is made up of tiny separate particles
called atoms and molecules.
The simplest forms of matter are referred to as
elements, and elements contain only one sort of
matter.
Atoms
Atoms are very minute particles. Some indication
of their size is shown by the weight of one atom
of hydrogen, which is 1.673 x 10–24 grams. They
contain within their structure three types of
particles. (In fact there are also some other
particles present which we need not concern
ourselves with in this paper.)
The three particles in the atom are protons,
neutrons and electrons.
The arrangement of these in the atom can be
illustrated as in Figure 1.
2

Figure 1 The Atomic Number is often given the symbol Z in

chemistry.

Electrons Atomic weight

N
+
Nucleus
P protons in a specific atom is constant, but the
(neutrons and
protons)
Notes
● The electrons, which are negatively charged,
orbit at high speed around the nucleus.
● The neutrons, as their name implies, are
electrically neutral.
● The protons each have a positive charge.
● There are always an equal number of protons
and electrons, so that the atom is electrically
neutral.
● The neutrons and protons are relatively much
heavier than the electrons.
This is a simple illustration of atomic structure
which we will enlarge upon to help us understand
how atoms join together.
But first we need to define two further terms used
in referring to atoms.
Atomic number
This refers to the number of protons in the atom.
(As the number of electrons is equal to the
number of protons, we can also say the Atomic
Number is the number of electrons in the atom).
This refers to the number of protons plus the
number of neutrons in the atom. The number of
number of neutrons may vary.
We should also note that the size of the particles
within an atom are minute when compared with
the overall size of the atom. In fact, atoms consist
mainly of a lot of space!
The arrangement of electrons orbiting the atomic
nucleus needs to be considered to enable us to
understand how atoms can link up to form larger
pieces of matter. These electrons are arranged in
shells or groups around the nucleus, these being
referred to as quantum groups. These shells may
be numbered 1, 2, 3, 4 and so on, but the usual
convention is to describe them as the K, L, M, N
etc shells.
The two examples in Figure 2 will help to explain
this.
The location of the electrons around the nucleus
of the atom has been the subject of extensive
studies and it has been shown that there is a
maximum number for each group. This maximum
is 2 for the first group and then 8, 8, 18, 18 and
32 in each successive group. Electrons fill up
each inner group to its maximum before starting
to fill the next outer group. (This statement is not

Figure 2

Carbon atom Chlorine atom

6P 6P 17P 17P
+ + + +
6N 6N 18N 18N

Nucleus Protons 6 17
Neutrons 6 18
Electrons 1st group (K shell) 2 2
2nd group (L shell) 4 8
3rd group (M shell) – 7
Atomic Number 6 17
Atomic Weight 12 35

completely correct, but it helps us in our basic
understanding of this subject.)
When the outermost quantum group of an atom
has its full complement of electrons then that
atom is very stable.
If you refer back to Figure 1 you will see that this
atom has 2 electrons in its outer group (in this
case its only group). It has the maximum for this
group and so we would expect it to be stable with
regard to reacting with other atoms. This is in fact
the case, as this figure shows the structure of
Helium, one of a group of atoms known as the
inert gases.
Now refer to the carbon atom in Figure 2 and you
will see that whilst the first group has its full
complement of 2 electrons, its second group has
only 4 electrons, whereas the maximum is 8.
The fact that carbon has a valency of 4 results
from this electron arrangement, but we will
discuss this later.
The chlorine atom in Figure 2 has the full
complement of electrons in the first and second
groups (ie 2 and 8), but the third group is one
short, having only 7. Again, this arrangement of
electrons determines how chlorine behaves in its
reaction with other atoms.
Molecules
Molecules are created by the linking together of
two or more atoms. This is an important
definition, because all the materials around us are
the result of atoms linking or combining together.
We need to differentiate between molecules
formed by the linking together of like atoms and
those created by the combination of two or more
different atoms.
In the first case, the molecule formed is still
referred to as an element and, for example,
oxygen exists in nature as the molecule O2, an
element.
When the molecule contains atoms of at least
two different elements it is defined as a
compound.
For example, a molecule of water contains 2
atoms of hydrogen and 1 atom of oxygen and is,
therefore, a compound. Similarly, ethyl alcohol,
whose molecule is formed from 2 carbon atoms,
6 hydrogen atoms and 1 oxygen atom (C2H5OH),
is a compound.
3
Elements
Our basic building blocks for all matter are,
therefore, atoms plus the simplest molecules,
those formed from like atoms. The overall terms
for these are the elements, which contain only one
sort of matter.
In nature, there are 92 of these elements and all
matter which exists is built up from combinations
of these 92 elements. (There are some additional
elements which do not occur naturally, but we will
not concern ourselves with these).
Periodic table
The 92 elements have been classified into the
Periodic Table, which is based on the electron
arrangement within each element. These are
listed in order of their atomic number and a new
line is started from each element which has all its
groups filled with electrons and none partly filled.
That is to say, there are 2, 8, 8, 18, 18, and 32
electrons in each group.
The Periodic Table is shown in Table 1, and it
provides a remarkable guide to the properties and
behaviours of elements.
Note that in each vertical column of the Table,
elements which are very much alike in their
behaviour are listed. For example, under Group 0
you will see helium, neon, argon, krypton, xenon
and radon. All of these, known as the inert gases,
have all their electron groups filled. In Group VII
are listed fluorine, chlorine, bromine, iodine and
astatine. All these have one electron deficient in
their outer group. These elements, known as the
halides, all behave in a similar manner in their
reactions with other atoms and molecules.
The states of matter
Every substance is a mass of separate atoms or
molecules. These atoms or molecules are in
constant motion and the hotter they are, the
quicker they move. As they approach each other,
their atomic structure results in a strong
repulsion. When they are some distance apart
there is a weak attraction between them. At a
certain point, there is a balance between
attractive and repulsive forces. If we consider the
physical state, at normal temperature, of the
elements in the Periodic Table, we will see that
some exist as gases, some as liquids and others
as solids. For example, in Group VII both fluorine
and chlorine are gases, bromine is a liquid, whilst
4

Table 1: Periodic table of elements

Group Group
I
1
II Periodic table of Group Group Group Group Group Group
III IV V VI VII 0
2
H
1,008
3 4
elements 5 6 7 8 9
He
4.003
10
Li Be B C N O F Ne
6,940 9.02 10.82 12.010 14.008 16.000 19.00 20.183
11 12 Transition elements 13 14 15 16 17 18
Na Mg Al Si P S CI A
22.997 24.32 26.97 28.06 30.98 32.06 35.457 39.944
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.096 40.08 45.10 47.90 50.95 52.01 54.93 55.85 58.94 58.69 63.57 65.38 69.72 72.59 74.91 78.96 79.916 83.7
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.48 87.63 88.92 91.22 92.91 95.95 (99) 101.7 102.91 106.7 107.88 112.41 114.76 118.70 121.76 127.61 126.92 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
132.91 137.36 138.9 178.6 180.88 183.92 186.31 190.2 193.1 195.23 197.2 200.6 204.39 207.2 209.00 (210) (210) (222)
87 88 89 58 – 71
Fr Ra Ac 90 – 103
(223) 226.05 (227)

Lanthanide 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
series 138.92 140.13 140.92 144.27 (145) 150.43 152.0 156.9 159.2 162.46 163.5 167.2 169.4 173.04 174.99

Actinide 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
series (227) 232.12 231 238.07 237 (242) (243) (243) (245) (246) (254) (255) (256) (253) (257)

Rare earth elements

iodine and astatine are solids at room
temperature.
The gaseous state
In a gas, the atoms are a long way apart and we
can illustrate this by reference to the conversion
of water (a liquid) to steam or water vapour (a
gas). One cubic centimetre of water makes 1700
cubic centimetres of steam – so there is clearly a
lot of empty space between the molecules of a
gas!
The atoms or molecules in a gas are not arranged
in any order and they are moving randomly at
speeds of several hundred miles an hour. The only
constraint on their movements is the wall of the
containing vessel.
As the temperature is increased, the energy
possessed by the atoms or molecules increases,
the faster they move and the greater the impact
with the vessel. The end result is gas pressure
which increases with temperature.
If the lid of the container is removed, the gas will
start to escape. In fact, a gas has normally no
boundary surface and completely fills any
available space. We will note how liquids and
solids differ in this respect in a moment.
We have made reference to the volume, the
temperature, and the pressure of a gas and the
general relationship between them is given by
Boyle’s Law. This states that the volume of a
given mass of gas is directly proportional to its
temperature and inversely proportional to its
pressure, or simply:
V is proportional T / P or PV = RT
where P = pressure
T = temperature (absolute)
V = volume
R = a constant
The liquid state
Now, if we decrease the temperature of a gas, the
energy of the molecules is reduced and their
speed of movement slows down. Instead of
travelling at high speed, colliding with the walls of
the vessel and with each other, they move more
slowly and tend to remain close together. As their
speed decreases, the attractive forces referred to
earlier will begin to operate and these will further
restrict their movement.
At a suitably low temperature, there will be a
jostling mass of molecules, in constant motion,
but held together by the attractive forces between

them. The gas will have changed into a liquid, and
as the molecules are much closer together, the
overall volume will have been greatly reduced.
It is these forces of attraction or cohesion,
operating when the molecules are relatively close
together, which are responsible for matter
existing as a liquid.
Like a gas, a liquid has no definite shape and will
take up the form of the vessel it is in. However,
the space it occupies has a limit shown by the
surface of the liquid.
Within the bulk of the liquid, each molecule is
surrounded by other molecules so, on average,
irrespective of their movement, each molecule is
attracted equally in all directions – see A and B in
Figure 3 below. However, on the surface there is a
resultant downward attraction, as there are no
liquid molecules above the surface, which is
illustrated by C in Figure 3.
Figure 3. If circles indicate spheres of
attraction between molecules then in C
attraction only occurs on that part of the
sphere beneath the liquid surface
C
B be reduced, and so more will be lost to the
A
As a consequence of this downward pull, the
concentration of molecules at the surface is
greater than in the bulk of the liquid and the
surface is in a state of tension. This surface
tension has a specific value which can be
determined for each liquid. This surface tension
also gives rise to the spherical shape of drops of
liquid as the tension at the surface of the drop
causes it to contract to give the minimum volume,
namely a sphere.
The surface tension of a liquid is a vital factor in
preparing surfaces for painting and in formulating
paints, with regard to how effectively they can wet
the surface.
Two simple examples will illustrate surface tension
and wetting.
5
First, it is possible to carefully place a needle on
the surface of water where it will float. The “skin”
on the surface, which is really a higher
concentration of water molecules, will enable the
“heavier than water” needle to float.
Secondly, if we drop water onto a greasy surface
it will not flow out and wet the surface but will
remain as tiny drops of water. Grease molecules
do not attract water molecules, so the surface
tension of the water pulls it into small drops.
These drops will not be spherical as another
force, gravity, tries to flatten the drops.
Another phenomenon which occurs on liquid
surfaces is that of evaporation. As we have
discussed, the molecules in a liquid are in
constant motion and inevitably some will travel
upward and move into the space above the
surface. These molecules will escape the
attractive forces within the liquid and act as
gaseous molecules. This loss of liquid at the
surface is referred to as evaporation.
The rate of evaporation will be decided by the
specific liquid we are dealing with and also its
temperature. In addition, the pressure of the air
above the liquid will affect the rate at which the
liquid evaporates.
If we increase the temperature of the liquid, the
rate of evaporation will increase and the
molecules will move faster, attractive forces will
atmosphere.
When a specific temperature is reached by the
liquid, the forces of attraction will be completely
eliminated and the molecules will act like a gas
again. In other words, the liquid will boil. The
temperature at which this occurs for each liquid,
the boiling point, will be influenced by the
atmospheric pressure, or by a pressure which is
applied. (For example, liquids will boil at a lower
temperature when a vacuum is applied).
Before we move on to solid matter, please note
that, in addition to defining gases and liquids, we
have made reference to surface tension, wetting,
evaporation and boiling point.
The solid state
Solids are quite different from gases and liquids in
that they possess rigidity and a tendency to
maintain both their shape and volume. The
molecules in solids, though always in motion,
6
remain in a fixed pattern. The forces of attraction
are strong enough to overcome the main motion
of the molecules, which are close packed in a
regular pattern.
In some materials, which are apparently solid, the
distribution of atoms or molecules is not
altogether regular. Such materials, like glass or
bitumen, are said to be amorphous, that is without
shape.
The regular form of the solid state is called the
crystalline state.
Crystalline solids consist of atoms set in a regular
pattern within a specific geometric shape. One
example of this is the cubic shape of the common
salt (sodium chloride) crystal.
Figure 4: Crystal structure of
sodium chloride
= sodium
= chlorine
There are many other shapes including diamond,
octahedron etc. Within these crystal structures,
the individual atoms are vibrating very rapidly,
rather like a pendulum, but the overall positioning
remains the same.
If the solid is heated, the energy introduced into
the crystal by this heat causes the molecules to
speed up and the vibrations to become longer,
until the atoms swing out so far that no pattern
remains. The pattern is destroyed, the solid has
melted and has changed into the liquid state. The
temperature at which the solid changes into a
liquid is the melting point of that substance.
Some substances exist in more than one
crystalline form, a phenomenon known as
polymorphism. Polymorphism occurs in both
elements and compounds, and among elements it
is referred to as allotropy.
One example of allotropy is carbon which exists in
the diamond shape (as diamonds) and the planar
hexagonal shape (as graphite). These crystals of
the same atom have very different physical
properties.
A form of polymorphism which is relevant to the
paint industry is that of titanium dioxide, which
may be used as a pigment in two crystalline
forms, anatase and rutile. Both of these are
identical in chemical composition but differ in
crystal structure and in some of their properties.
Pigments generally are discussed later in the
monograph but it is useful to make reference to
them here as they come within the category of the
solid state of matter. The pigments used in paints
are normally supplied as a fine powder – although
in some cases they are supplied already
dispersed in a liquid of some kind. They are, in
fact, chemical compounds with a crystalline
structure and these compounds contain various
combinations of atoms held within this crystalline
structure. The properties of each type of
compound is determined by:
● the specific type of atoms in the molecule of
the compound
● the numbers of atoms in the molecule of the
compound
● how these atoms arranged in the crystal
structure.
A simple illustration of this is shown by the
properties of various iron oxides. “Red iron oxide”
is essentially two atoms of iron combined with 3
atoms of oxygen (Fe2O3) whereas magnetite,
which is black, has 3 atoms of iron combined with
4 atoms of oxygen (Fe3O4). The iron oxides found
in nature usually contain a mixture of several
compounds and the properties are determined by
the ratios of these different compounds. In
addition, they often contain impurities which will
affect their colour.
It is not only the overall arrangement of the atoms
which is important but also the presence of
certain groups of atoms in a molecule that can
influence the colour of the pigments. This is of
particular significance when dealing with pigments
which come under the heading of “organic”, a
term which is explained later. Certain chemical
groupings known as chromophores contribute to
the colour of the pigment.
To summarise, in the solid state it is the atoms
and the manner by which they are held together in
crystalline structures which largely determines the
properties of the material. Some of the factors
 7

which influence the properties include
polymorphism, allotropy, general crystal structure
and the presence of specific groupings referred to
as chromophores.
Energy
The next important topic to look at in this study of
basic science is energy. Matter may be defined as
“that which has mass and inertia”, while energy
may be roughly described as “forces” of one kind
or another. By saying that a piece of matter has
inertia we mean that it takes some force to get it
moving. Energy is a capacity for doing work and
may appear in a number of different forms but all
energy is either potential or kinetic. A simple
illustration of this is a steel ball resting on a
bench. The ball is a piece of matter at rest but it
has potential energy due to its height above the
floor and the force of gravity. It also has inertia. If
it is given a gentle tap so that it rolls off the edge
of the bench it will drop down and hit the floor with
some force. The gentle tap is the force required
to overcome inertia. The force of its impact with
the floor is kinetic energy – the energy of motion.
Potential energy is the capacity for doing work
which a piece of matter possesses because of its
position. Water at the top of a waterfall is a good
example of having potential energy. Kinetic energy
is the energy of motion. A bullet, a moving train,
the water pouring from the top of a waterfall, a
particle of paint being moved around in a paint
mill – all have kinetic energy.
The steel ball on a bench is one example of
mechanical energy, but energy may also exist as
every way. One way that it affects paints is the
tendency for heavy pigments to be “pulled down”
and settle in a can of paint.
Finally, mass is energy. All matter can be
destroyed and can become another form of
energy. For example coal can be burnt and
becomes heat and light (radiation) energy. In fact
energy can never be destroyed but can be
changed from one form to another. This is the
Law of Conservation of Energy.
Compounds
We have examined the building blocks of matter
and referred to these as atoms and molecules of
a single substance, and we grouped these
together as elements. Now we need to start
looking at the buildings we can form, or
compound, from these elements.
A compound is matter which has been formed
from two or more different elements.
Many compounds occur naturally on Earth, whilst
others can be prepared by chemical reactions. A
study of chemistry includes the numerous
procedures which may be used to make different
compounds. This study revolves around the types
of linkages required to join one element to another
and we will now consider these linkages.
Below is a table showing a few of the elements
with their electron configuration.
Table 2: Electron configuration of some elements
Quantum group
_ ____________________________________________________________________________________

heat energy, electrical energy, radiation and Element Symbol Atomic K(1) L(2) M(3)
chemical energy, and all these forms of energy number
occur in areas of paint technology. Hydrogen H 1 (1) – –
Mechanical energy is involved in the refining of Helium He 2 (2) – –
earth pigments and in paint manufacturing Lithium Li 3 2 (1) –
processes. Manufacturing resins requires both
Carbon C 6 2 (4) –
heat energy (a basically kinetic energy) and
chemical energy (potential energy) and both of Nitrogen N 7 2 (5) –
these forms are required to cure stoving paints. Oxygen O 8 2 (6) –
Radiation energy covers visible light, ultra-violet Fluorine F 9 2 (7) –
(UV) and infra-red (IR) radiation, all of which are Neon Ne 10 2 (8) –
important to the paint technologist. UV and IR
Sodium Na 11 2 8 (1)
radiation are used to cure certain types of coating
and visible light is one of the elements of colour Chlorine Cl 17 2 8 (7)
perception.
The force of gravity, mentioned above when The bracketed figures we refer to as the valence
describing potential energy, influences our lives in electrons.
8
Let us first consider sodium (Na), which has a
single electron in its outer quantum group. To
achieve the optimum number of electrons in its
outer group, the sodium atom requires to either
gain 7 electrons, or to lose one electron. If we
consider chlorine (Cl), this needs to either lose 7
or gain 1. The loss or gain of 7 electrons requires
considerable energy and is unlikely to take place.
However, the loss or gain of 1 electron from an
atom is relatively simple.
If we draw the sodium and chlorine atoms with
their outer electron shells we have:
Na CI
Now if sodium loses one electron and chlorine
takes this electron, then both atoms have a stable
situation in their outer shells. But neither of them
are electrically neutral. The sodium will now have
a positive charge, with more protons than
electrons, while the chlorine has a negative
charge, with more electrons than protons.
We can show this as:
Na + CI + _
Na CI
This type of linkage or valency is electrovalency.
Electrovalency involves the transfer of electrons
to form an electrovalent or ionic bond.
In this type of valency, the molecule formed will,
overall, be electrically neutral, the optimum level
of electrons in the outer groups will have been
achieved but the molecules will have a small
positive charge at one end and a small negative
one at the other end.
The second form of linkage we will examine is the
covalent link.
Covalency – instead of the transfer of electrons
which occurs in electrovalent links, covalency
involves the sharing of electrons. Each atom
contributes one electron to form a shared pair.
We can illustrate this by the covalent bonds
between carbon and hydrogen. Carbon has 4
electrons in its outer group and hydrogen has 1
electron.
C H
By linking 4 hydrogen atoms to 1 carbon atom we
obtain methane CH4.
H
4H + C H C H
H
The carbon atom then has 8 electrons in its outer
orbit – a stable level. Similarly, each of the 4
hydrogen atoms has 2 electrons in its outer
group, which is again a stable state. The carbon
has formed 4 linkages and is said to be
tetravalent – it has a valency of 4. The hydrogen
atom is monovalent. Carbon almost invariably
forms covalent compounds and is almost always
tetravalent. Hydrogen is usually monovalent.
Some atoms are capable of exhibiting more than
one valency and, for example, sulphur can be 2, 4
or 6 covalent, as it is possible for 1, 2 or 3 pairs
of electrons in the outer group to be involved in
the valency bonds. This is why compounds such
as sulphur dioxide and sulphur trioxide exist.
We need to make brief reference to a special type
of covalency known as co-ordinating valency
and its special feature is that both of the shared
electrons are provided by one of the atoms.
Dipoles and dipole moments
The existence of dipoles in molecules, and the
general effects of electron displacement when
atoms link together, are important indicators to
the behaviour of compounds and groups within
the compounds.
By comparing molecules formed by covalent
bonding between like atoms and between unlike
atoms, we can further explain what we mean by
dipoles.
A covalent link between two like atoms, for
instance hydrogen, will result in a symmetrical
arrangement of the bonding pair of electrons:
H H

This is because the electron affinity – the power
to attract electrons – of both atoms is identical.
Now, if we look at a covalent bond between two
unlike atoms, for instance hydrogen and chlorine,
we find that the electron affinity of chlorine is
much greater than that of hydrogen.
H + CI H CI
The covalent bonding pair of electrons are pulled
towards the chlorine atom. The hydrogen will be
slightly positive and the chlorine slightly negative
which we can depict as:
δ+ δ– δ+ δ–
H—Cl or as H → Cl
This arrangement, somewhat analogous to the
poles of a magnet, is called a dipole and the
molecule of HCl is said to have a dipole moment.
Dipole moment is defined as the product of the
electron charges (e) and the distance (d) between
the charges.
Note that in the HCl molecule above there is no
separation of the H and Cl atoms and they remain
joined together, as with the poles of a magnet. It
is the distribution of the electrons which result in
the formation of the dipole.
(Mention should be made of the fact that in certain
circumstances the H and Cl atom will not remain
joined together, for example if the HCl is in
aqueous solution. At this point we want to
concentrate on the covalent bond between
molecules and will deal with solutions at a later
stage).
There are other forms of electron displacement in
addition to that described above and we will
consider one of these.
If we take a molecule which contains a chain of
atoms such as:
4 3 2 1
—C—C—C—C—Cl
then the strong electron affinity of the chlorine
atom will attract the electron pair away from the
adjacent carbon atom (C-1). However, this
electron shift will make C-1 slightly positive and it
will cause an electron shift from C-2 to C-1,
9
although this effect will be less than the shift
between C-1 and Cl. As C-2 is now slightly
positive, it will attract the electron pair away from
C-3, and so on.
The overall effect (called the inductive effect) will
be a small negative charge in the chlorine atom
and a small positive charge towards C-4. The
molecule will have a dipole and a measurable
dipole moment.
Polar and non-polar compounds
The existence and strength of a dipole moment
will tell us whether a molecule is polar or non-
polar and how strong is its polarity.
Examination of two compounds, which happen to
have solvent properties, will illustrate polarity.
Octane
H H H H H H H H
H C C C C C C C C H
H H H H H H H H
The symmetry of the octane molecule means that
any electron affinity differences between C and H
atoms is equalised. There is no electron shift
towards either end of the molecule. It has no
dipole and is non-polar.
Butyl alcohol
H H H H
H C C C C OH
H H H H
We have referred to the different electron affinity
between different atoms, but we can also refer to
the different electron affinity between specific
groups of atoms.
In the butyl alcohol molecule above, the “OH”
group has a greater affinity for electrons than
carbon and so it will attract the bonding pair away
from the adjacent atom of carbon. The inductive
effect referred to earlier will come into play and
the whole molecule will have a dipole. Butyl
alcohol is a polar compound and has a significant
dipole moment.
In this section we have considered the methods
by which atoms may link up to form large
10
molecules or compounds. The type of bonds or
valency links have been explained as
electrovalent, covalent and co-ordinating.
The electron affinity of specific atoms and
chemical groups, and the effect that this has on
the electron displacement which occurs, has been
discussed, together with the resultant polar or
non-polar character of a molecule.
We will use this background of the bonding of
atoms to form compounds in subsequent sections
of this monograph.
Secondary valency forces
Before we leave this section, we need to refer to
forces which attract molecules to each other. The
type of bonds already discussed are referred to
as primary valency bonds and the forces which
they exert in holding atoms together are quite
strong.
In addition to these primary valency forces, there
also exists some much weaker ones which attract
whole molecules to each other. These are known
as secondary valency forces or intermolecular
forces. They are also called van der Waals
forces, after the man who carried out a detailed
study of them.
The explanation of van der Waals forces is quite
complex, as they depend not only on the
existence of dipoles within polar molecules, but
also on dipoles which are induced in non-polar
molecules by the motion of electrons.
For the purposes of this monograph, an
awareness of the existence of these secondary
valence forces is more important than a detailed
understanding of what causes them.
We will be referring to these forces when we
discuss the properties of polymers used in paints.
Hydrogen bonding
We have referred to hydrogen and its
monovalency. With its single electron, the
formation of a single bond would be expected, but
properties such as boiling points and evaporation
rates of some liquids indicate that more than one
linkage may occur.
In a polar –O– –H+ bond, the difference in
electron affinity (electro-negativity) results in a
shift of the hydrogen electron towards the oxygen
atom.
Now, if this polar OH group approaches another
electro-negative atom, there will be attraction
between the positive and negative charges. This
attraction is, in some cases, sufficient to form a
weak chemical bond between the two groups.
Using water as an example:
+ –
H O
+ – +
H O H
+
H
where the dotted line denotes a hydrogen bond.
This association of molecules created by
hydrogen bonding results in changes in the
properties of some materials. For example, the
rate at which some solvents evaporate is much
slower than would be expected for the simple
unassociated molecule.
Hydrogen bonding occurs in some polar organic
compounds as well as inorganic compounds such
as water and ammonia.
Organic compounds
Division of organic and inorganic
compounds
The study of chemistry is usually classified into
two sections, organic compounds and inorganic
compounds.
An understanding of both classes is necessary in
the study of paint technology, and in this section
we will deal with the organic compounds.
Before doing so, we will spend a few moments
discussing the difference between an organic and
an inorganic substance.
A brief historical background may help us to
appreciate how this division of chemistry came
about.
An early classification of substances from natural
sources was that of Lemery in 1675, who stated
that there were three groups which he called:
● mineral
● vegetable
● animal.
This was widely accepted until Lavoisier, in 1784,
demonstrated that all compounds from both
vegetable and animal sources always contained
carbon and hydrogen.
 11

Then, as analytical methods improved, it was been found since that carbon can, in special
found that the same compound could sometimes cases, exhibit other valencies, but for most
be obtained from both animal and vegetable purposes we may consider that Kekulé’s views
sources. As it became difficult to justify the still hold good.
difference between compounds from animal and
Carbon invariably uses its valency electrons to
vegetable sources, substances from nature were
form covalent bonding, and between carbon
called either “organic” – from living organisms (ie
atoms either a single, a double or a triple covalent
animal and vegetable), or “inorganic” – from non-
bond is possible.
living organisms.
We can illustrate this by considering three
Until the early 1800s, there was a widely held
compounds which all contain two carbon atoms.
belief that organic compounds could only be
produced under the influence of some “vital force” Ethane (C2H6)
or “life force”. The idea of a “vital force” began to
be eroded when Wöhler, in 1828, prepared urea H H
from ammonium cyanate. Up to this time urea had
only been obtained from animal sources. H C C H

The “vital force” theorists took some time to H H

convince but, as methods of syntheses
progressed, many so-called organic compounds
Single bond between carbons
were made from inorganic sources. However, the
terms inorganic and organic were retained and Ethylene (C2H4)
chemical substances continue to be studied under (or ethene)
the two different headings.
H H
Today we understand organic chemistry as the
chemistry of carbon compounds, and all organic
C C
compounds contain carbon. The compounds of
carbon are far more numerous than the H H
compounds of all the other elements put together.
The ability of carbon to combine with other carbon Double bond between C atoms
atoms to form long chains is another factor in
classifying compounds as organic. Acetylene (C2H2)
(or ethyne)
There are some carbon containing compounds
which are not classified as organic mainly
because their origins were from inorganic H C C H
sources. Examples are carbon monoxide, carbon
dioxide and calcium carbonate, all of which Triple bond between C atoms
contain carbon but are called inorganic.
In each of the examples above, the tetravalency
To summarise, the division of chemistry into of carbon is satisfied, with 4 covalent bonds being
organic and inorganic is not a precise one but it formed.
has proved useful for the purposes of study.
The ethane molecule is said to be saturated, and
Carbon compounds both the ethylene and acetylene molecules are
All organic compounds contain carbon, so we will unsaturated.
start by reviewing this element.
Unsaturation
Carbon has an atomic number of 6, with The term unsaturation refers to the presence of
2 electrons in its inner quantum group and multiple bonds between adjacent carbon atoms of
4 electrons in its outer group. a molecule. A molecule which contains one or
These 4 valency electrons were referred to earlier more double or triple bonds in its carbon chain is
and it was Kekulé, in 1857, who first postulated said to be unsaturated. One that has no multiple
that carbon always exhibits tetravalency. It has carbon/carbon bonds is described as saturated.
12

Organic molecules with long carbon chains may If we consider the compound butane, then a
contain a number of unsaturated bonds. This is a problem does arise. To write C4H10 does not
feature of, for example, the drying oils used in differentiate between possible chemical
airdrying paints. structures, where we can have:
(i)
Conjugation H H H H
Where these unsaturated bonds are positioned
between alternate carbon atoms as in: H C C C C H

H H H H H H H H H H

C C C C C C
or (ii)
then the compound is said to be conjugated and
to possess conjugated double bonds. H H H
The term unsaturation is only applicable to
adjacent carbon atoms, and the double bond H C C C H
–C=O in ethanal (acetaldehyde):
H H
H H H C H

H C C O H

H
is not unsaturation.
The double and triple bonds in an organic
compound are very reactive and this reactivity is
utilised in a number of processes used in paint
technology. For example, some polymerisation
reactions in paint resins depend on the existence
of double bonds. The existence of conjugated
double bonds impart special properties to
compounds enabling them to readily polymerise
and form larger molecules.
Nomenclature of organic compounds
Early chemists named a compound on the basis
of its history. For example, methyl alcohol was
called wood spirit as it was obtained by the
destructive distillation of wood. Later the term
methyl was used from the Latin methu (wine) and
hule (wood). But as the number of organic
compounds increased, more specific names
became necessary. For a simple compound such
as methane we can refer to its name, its chemical
formula CH4, or to its chemical structure.
H (iii) The “IUPAC” system developed by the
H C H longest chain possible is chosen and the
H n-hydrocarbon.
Both (i) and (ii) contain the same number of C and
H atoms but they exhibit different properties.
Three systems of naming organic compounds
exist and an outline of each system is given
below:
(i) Trivial System – the straight chain compounds
are called normal or n- and so (a) above is
n-butane. If the compound contains the group:
CH3
CH
CH3
it is known as the iso-compound and (b) above is,
therefore, iso-butane.
(ii) A system which regards, for example, a
hydrocarbon as a substitution product of
methane. The simplest compounds retain their
trivial name but longer chains as in the “iso-
pentane” example following can adopt this
system.
International Union of Chemists. In this, the
compound is named as a derivative of the
 13

Examples of the three systems for naming Paraffins range from gases, with methane boiling
hydrocarbon are as follows: at –161°C, to liquids and solids, with octadecane
melting at 28°C.
(i) (ii) (iii)
The liquid paraffins are used as solvents in the
CH3CH2CH2CH3 n-butane n-butane n-butane
paint industry, generally as mixtures rather than
CH3–CH–CH2–CH3 iso- dimethyl 2-methyl specific compounds. For example, white spirit,
pentane ethyl butane obtained by fractional distillation of petroleum, has
–

CH3 methane a boiling range between 150 and 190°C. White

It is important to be aware of the various systems
of naming compounds although we will use
descriptions in common use by the paint industry
wherever possible in this monograph.
Isomers
The ability of a compound to exist in more than
one form, that is to have more than one chemical
structure, is called isomerism.
The normal and iso-forms of butane shown earlier
is an example of a compound having more than
one isomer.
Classification of organic compounds
Organic compounds have been classified into
specific groups based on:
● the elements they contain
● the arrangement of these elements within the
compound
● the type of valency bonds holding the
elements together.
Aliphatic or open-chain compounds
These contain only carbon and hydrogen with the
carbon chains being open – as opposed to being
closed and forming rings.
These aliphatic compounds may be further sub-
divided into saturated and unsaturated
hydrocarbons.
Saturated hydrocarbons or paraffins
Saturated hydrocarbons are called the paraffins,
and the chief source of these compounds is
mineral oil, petroleum or natural gas.
Their general formula is CnH2n+2 and examples are:
Methane CH4
Ethane C2H6
Propane C3H8
Butane C4H10
Octadecane C18H38
spirit also normally contains some non-aliphatic
compounds.
Some points to note regarding the paraffins is
that all the valency bonds are single links and that
the existence of isomers becomes possible when
there are more than two carbon atoms in the
molecular chain.
The fact that each paraffin differs from its
neighbour by –CH2 leads to the definition of a
homologous series.
Homologous series
A series of compounds in which each differ from
its immediate neighbour by –CH2.
We will see that homologous series exist in other
classes of organic compound, and within each of
these series patterns of chemical behaviour are
similar. However, it should be noted that quite
often the first member of a homologous series is
not typical of the series as a whole.
Alkyl groups
If we remove one hydrogen from methane we get
a CH3– group, and similarly with ethane we get a
C2H5– group. CH3 is called the methyl group or
radical and C2H5 the ethyl group. Other common
ones are C3H7, propyl, and C4H9, butyl.
These univalent radicals formed by the removal of
one hydrogen from a paraffin are known as the
alkyl radical or group, a terminology which we
need to utilise in later sections of this paper.
Unsaturated hydrocarbons or olefins
These are also referred to as alkenes. These
contain only carbon and hydrogen atoms but they
also contain a double bond. Again these form a
homologous series starting with ethylene –
CH2=CH2
or H H
C C
H H
14

A list of the first 3 olefins or alkenes in the For example:

homologous series together with their chemical
Cyclo pentene (C5H8) CH
formula and description is shown below:
CH CH2
Ethylene CH2=CH2
CH2 CH2
Propylene CH2=CH–CH3
Butylene CH3CH2CH=CH2 1-Butylene* (the -ene ending indicating the olefin
classification).
CH3CH=CH–CH3 2-Butylene*
A number of alicyclic compounds occur in
* Note that two isomers of butylene can exist and
petroleum and some of these are used by the
that the -ene ending denotes an olefin or alkene.
paint industry as solvents.
Some olefins find a place in the paint industry in
The solvency power of these alicyclic
the preparation of resins and in the syntheses of
hydrocarbons is generally slightly higher than the
raw materials for later use in resins.
corresponding aliphatic equivalents and the ring
There is a further group of unsaturated compounds usually boil at a higher temperature.
hydrocarbons which contain a triple bond and
these are called the acetylenes or alkynes. Terpenes
Examples are: A special group of ring compounds we need to
mention are the cylcic terpenes.
Acetylene HC CH
These contain 6 carbon atoms and one
Methyl acetylene CH3C CH unsaturated bond in the ring, and members of this
group have been used as solvents in paints for
The triple bond makes these compounds very many years. These solvents are, in fact, a mixture
reactive. of terpenes but some of the main ingredients are:

Alicyclic hydrocarbons CH3 CH3

Up until now we have discussed organic
compounds with an open chain structure, but C C
there are many compounds which contain closed CH CH3 CH CH2 CH
rings. C CH
3
One group of closed ring carbon compounds is CH2 CH2 CH2 CH2
the aliphatic cyclic or alicyclic type. CH
CH
Examples of these are:
C
Cyclo butane (C4H8) CH2 CH2 CH3 CH2
CH2 CH2
α pinene limonene
Note that the tetravalency of the carbon atom is (turpentine) (di-pentene)
satisfied but the molecule contains 2 hydrogen As the ring contains 6 carbon atoms these are
atoms less than the aliphatic, open chain butane. sometimes referred to as the hydroaromatic
Cyclo hexane (C6H12) compounds, but their properties are quite
CH2 different to the true aromatic compounds we will
CH2 CH2 discuss shortly. (There are also some non-cyclic
or linear terpene compounds but we will not deal
CH2 CH2
with these.)
CH2
Again this has 2 hydrogen atoms less than the Heterocyclic compounds
aliphatic hexanes. Some alicyclic hydrocarbons Alicyclic and cyclic terpenes contain only carbon
contain unsaturated bonds and may be atoms in their rings. There are some ring
considered as cyclic olefins. compounds which contain other elements as well

as carbon, and these are named the
heterocyclics. The most common elements, other
than carbon, in these compounds are oxygen,
nitrogen and sulphur.
Examples of heterocyclic compounds are:
Furan (furfuran)
CH CH
CH CH
O
Furan is a low boiling liquid (BPt 32°C). Furan has
no field of application in paints but two of its
derivatives, tetrohydrofuran and furfuraldehyde,
are strong solvents which may be used in oil
extraction.
Pyrazole
CH CH
CH
N
NH
(The azoles as a group are 5 membered rings,
with at least 2 hetero atoms, one of which is
nitrogen.)
Pyridine
CH
CH CH
CH CH
N in place of hydrogen atoms, it is very difficult
Pyridine, a liquid with an unpleasant odour, is of
no specific interest in paint formulation, but its
structure is worth noting. It has a six membered
ring with alternate double bonds and, as we will
see in a moment, this structure is similar to that
of benzene. Pyridine has properties similar to
benzene and is a good example of how the
structure of a compound influences its properties.
Aromatic hydrocarbons
All the compounds in this group have, within their
structure, one or more 6 membered carbon rings
with alternate double bonds. That is, they contain
the benzene ring, usually shown as:
15
CH
CH CH
CH CH
CH
or sometimes as
or
The early aromatic compounds obtained from
natural sources were termed “aromatic” because
they had a pleasant odour (for example, the
balsams and natural resins). Later it was shown
that these compounds contained the benzene
ring, and the current definition is based on this
fact and not on the aroma of the substance.
The structure and the electron configuration of the
benzene (C6H6) molecule has been the subject of
much study, but there are some points which we
should note to help our understanding of the
behaviour of aromatic compounds.
● Although benzene can be shown as having 3
double bonds, in fact each of its carbon
atoms has identical properties.
● The double bonds do not behave in the same
way as the alternate double bonds in a
conjugated aliphatic molecule.
● The benzene ring is extremely stable and
while it is possible to substitute other groups
to break the ring.
One theory is that benzene is in a continuous
state of oscillation between two isomeric forms,
as:
For our purposes the stability of the benzene ring
and the comparatively strong solvent power of
aromatic based solvents are points to note.
16

The hydrogen atoms in benzene can be Alcohols

substituted and when more than one substitution An alcohol is a compound that contains one or
occurs then isomers are obtained. more hydroxyl (–OH) group in its carbon chain.
Example of mono substitution:
Monohydric alcohols
CH3 OH These contain one –OH group and have the
general formula CnH2n+1OH.
They form a homologous series, which are named
after the alkyl radicals referred to earlier.
Methyl alcohol CH3OH
Ethyl alcohol C2H5OH
Propyl alcohol C3H7OH
Toluene (C6H5CH3) Phenol (C6H5OH) Note that from propyl alcohol onwards, there will
be more than one isomer for each compound.
There are no isomers, as each of the 6 carbon There are three types of alcohol as follows:
atoms is identical.
(i) primary
Example of di-substitution: –CH2OH eg CH3CH2CH2CH2–OH
CH3 CH3 CH3
(ii) secondary
CH3
CH3CH2
CH3 CH OH eg C OH
CH3
CH3

ortho-xylene meta-xylene para-xylene (iii) tertiary

or or or
1,2 dimethyl 1,3 dimethyl 1,4 dimethyl
benzene benzene benzene
In this section we have referred to aromatic
compounds with single benzene rings. More
complex structures with multiple benzene rings
occur, for example in some of the naptha solvents
used in paints and also in many organic pigments.
Organic compounds containing
functional groups
The classes of organic compounds we now need
to consider may be regarded as being based on
the hydrocarbons but which also have a functional
group in their structure.
Functional groups
These are chemical groups within a molecule
which are capable of reacting with functional
groups in other molecules. Many such groups can
exist but we will restrict our work to those which
are important in paint technology.
CH3
C OH eg CH3 C OH
CH3
(i) is named butyl alcohol or butan-1-ol
(ii) is secondary butyl alcohol or butan-2-ol
(iii) is tertiary butyl alcohol or butan 1:1 dimethyl
ethanol.
The hydroxyl group has a strong electron
affinity compared with the carbon atom, with the
result that alcohols have a dipole and are quite
strongly polar. The strength of the dipole
decreases with the increase in the number of
carbon atoms in the carbon chain of the
molecules.
One important property of solvents which are
highly polar is that they will dissolve polar
materials but not non-polar substances. Also, the
hydroxyl group is reactive and is capable of
chemical reaction with other suitable groups.
 17

The presence of more than one hydroxyl group in and if R1 and R2 are CH3 we have:
a molecule gives rise to other types of compound
as follows: CH3
C O
Glycols CH3
Glycols contain two –OH groups
acetone
eg ethylene glycol CH2OH–CH2OH
Both ketones and aldehydes are polar and the
H H –C=O group is reactive. In general, the ketones
have a role as paint solvents whilst the aldehydes
HO C C OH are used for their reactivity in the production of
paint resins.
H H
Carboxylic acids
Trithydric alcohols The carboxyl group has the formula –CO2H and its
These have three –OH groups structure is written as:

eg glycerine (or glycerol) O

C or CO.OH
CH2 OH
OH
CH2 OH
Organic compounds containing the carboxyl group
are classified as carboxylic acids.
CH2 OH
The term “acid” is found in both organic and
inorganic chemistry and it can sometimes be
Tetrahydric alcohols difficult to relate the properties of acids from the
These contain four –OH groups two groups. The inorganic sulphuric acid is an oily
eg pentaerythritol liquid which will attack metals and destroy skin
and tissues, whilst the organic citric acid is
CH2OH consumed as lemonade powder.

HOCH2 C CH2OH One definition of an acid is a substance which

yields hydrogen ions. The hydrogen atom contains
CH2OH 1 electron and 1 proton and if the electron is lost
we are left with a single proton, which is the
positively charged hydrogen ion written as H+.
Aldehydes and ketones
Organic compounds containing the general group It is better to regard an acid as a substance which
has a tendency to lose a proton or hydrogen ion.
R1 This tendency varies with different acids and, for
C O example, the strong inorganic acids such as
R2 hydrochloric, nitric and sulphuric have a very
strong tendency to lose protons. In aqueous
are classified as ketones or aldehydes. solution these acids will completely separate or
If R1 is a hydrogen atom, the compound is an dissociate into their hydrogen ions and their
aldehyde. For example, when R1 is H and R2 is negative radicals.
CH3 we have: HCl → H+ + Cl–
H This degree of separation, normally referred to as
C O the dissociation constant, is the explanation of
the strength or weakness of an acid.
CH3
As a general guide, inorganic acids have a high
acetaldehyde dissociation constant and are referred to as
18

strong acids. The organic acids are generally
weak with a low dissociation constant.
There is a large family of carboxylic acids in
existence, starting with formic acid HCOOH and
then acetic acid CH3COOH.
The monobasic acids can be written as:
O manufacture of paint resins.
R C
OH
where “R” is an alkyl radical,
and the dibasic acids as:
COOH
R H
COOH
The alkyl radical may be large and contain a long
chain of carbon atoms. This chain may be fully
saturated or it may contain double or triple bonds
and so be unsaturated.
When the carboxylic acids dissociate they behave
like other acids to form:
CH3COO– + H+
but as they are weak acids, their tendency to
dissociate is small.
It is possible to produce strong acids by
substitution of the alkyl hydrogen atoms by
halides. For example, trichloracetic acid
(CCl3COOH) is a very strong acid.
The most common monobasic acids used in the
paint industry are, in fact, those derived from
vegetable oils.
These oils are esters of the trihydric alcohol,
glycerol and long chain monobasic carboxylic
acids.
CH2OH CH2OOCR
CHOH + 3R–COOH → CHOOCR
CH2OH CH2OOCR
glycerol + monobasic triglyceride
acid (vegetable oil)
The acids derived from these oils invariably have
18 carbon atoms in their molecular chain and they
are known as the fatty acids. Typical examples of
these fatty acids are oleic, linoleic, and linolenic
acids, all of which can be obtained from both soya
bean oil and linseed oil. These three fatty acids
differ in the numbers of double bonds they have in
their carbon chains.
Before leaving this section on we will look at two
dibasic carboxylic acids which are used in the
Maleic acid is an unsaturated dibasic acid.
H
C COOH
C COOH
maleic acid
Ortho-phthalic acid, which is normally used in the
anhydride form.
COOH CO
→ O + H20
COOH CO
dehydration
o-phthalic acid phthalic anhydride + water
or
benzene 1.2.
dicarboxylic acid
The term anhydride refers to the compound
formed when a molecule, or molecules, of water
are removed.
In addition to the ortho form, two other isomers of
phthalic acid exist, these being iso-phthalic acid
(benzene 1.3. dicarboxylic acid) and tere-phthalic
acid (benzene 1.4. dicarboxylic acid). Both of
these isomers are used in modern paint resins.
Esters
We referred to this class of compound above,
when we described oils as being esters of
glycerol and fatty acids.
Any reaction between a carboxylic acid and an
alcohol results in the formation of an ester, the
general formula for which is:
R1COO R2
where R represents alkyl radicals.

To complete our classification of organic
compounds, the list below shows the
characteristic grouping of the remaining relevant
types. In each of the below, R represents an alkyl
radical.
Class Characteristic group
Ethers –C–O–C–
Epoxides
O
R CH CH2
Amines R–NH2 primary amine
R very much based on the chemistry of dyestuffs
NH secondary amine
R synthetically manufactured. The structure of these
R and physical chemistry. Their chemistry involves
teritiary amine
R NH
R including benzene rings. The physical chemistry is
Amides –CONH2
Organic and inorganic pigments
We referred to pigments when we dealt with the
solid state of matter. Pigments are insoluble
powders which, when dispersed in the film-former,
contribute important properties to the dried
coating of the paint. One of the most important of
these properties is colour but they can also
contribute other properties including opacity,
viscosity control, gloss control, and corrosion
resistance. Extenders are also insoluble powders
but they are virtually transparent when dispersed
in the film-former and make little or no
contribution to colour and opacity. They are
included to modify certain physical properties
such as flow and degree of gloss.
The difference between the chemical structure of
organic and inorganic compounds, described
earlier, applies to pigments which are classified as
being organic or inorganic.
The earliest paints used pigments which were
obtained by digging certain minerals out of the
earth and grinding them to a fine powder. These
natural pigments are all inorganic compounds,
19
typical examples being the oxide of iron called
“red oxide”, and ultramarine blue from lapis lazuli.
Natural extenders include whiting (chalk), barytes
(barium sulphate) and numerous metal silicates
which exist as clays. The colour and other
properties of these pigments and extenders is
dependent upon their molecular composition and
atomic structure. The natural earth pigments are
not usually pure chemical compounds but tend to
contain contaminants and these also have an
effect on the colour. The methods of refining
and/or producing these inorganic pigments
synthetically has provided better quality and more
consistent products.
The chemistry of the early organic pigments was
derived from natural plants but they are now all
pigments is based on a combination of organic
reactions which produce compounds with a high
proportion of carbon to carbon bonds, and usually
related to the way they adsorb and transmit light
to produce the colours required. Their formulation
may also include the incorporation of
chromophores, such as >C=C< , –N=N– , NO2 ,
>C=O , –N=NO , as part of their colour
constitution.
This phenomena has resulted in a very great
number of organic pigments being developed
based on chemical compounds whose structure
incorporates these chromophores.
The presence of long –C–C– bonds in organic
pigments means that they have generally poorer
resistance to high temperatures than the inorganic
pigments. The C–C bond is more easily broken
down under the influence of high temperatures.
However, advances in organic pigment chemistry
has resulted in pigments with heat resistance
properties being available to the paint industry
which are suitable for many applications.
Some pigments which come within the organic
category because of their numerous –C–C– bonds
also contain a metal within their structure.
Important examples of this group are the
“phthalocyanine” pigments which contain a copper
atom in the centre of their structure. Such
compounds tend to have superior heat resistance
than organic pigments not containing a metal.
20
Inorganic compounds
Apart from the few exceptions referred to earlier,
we can regard inorganic chemistry as that area
which deals with compounds formed from
elements other than carbon.
Early research work which led to the theory of
atomic structure was carried out on inorganic
compounds, probably because of their simple
structure when compared with the complex
organic substances then available.
Inorganic compounds may be formed as a result
of electro-valent or co-valent bonding which has
been explained earlier.
This is a convenient point at which to stress the
differences between compounds and mixtures.
Compounds
Compounds are pure substances made up of
elements which are chemically combined.
Compounds are homogenous and have a specific
composition, for example H2SO4, KOH, or
Na2CO3.
Mixtures
Mixtures, as the name implies, are mixtures of
pure substances obtained by physical processes.
Their composition may vary widely and the
individual components may be separated by
physical means (for example, by distillation or the
use of magnetism).
Spacial structure of inorganic
compounds
The arrangement of the elements in an inorganic
compound will be dictated by the types of bond
and the nature of the elements present. We should
note that the structure will be 3-dimensional and
that for each single compound the spacial
arrangement is fairly specific.
Metallic bonding
Simple ionic or covalent bonding does not explain
the special properties exhibited by the metallic
elements. These metallic elements readily lose
their valency electrons and these electrons
become delocalised with no underlying directional
bonds. Although the whole system remains
electrically neutral, the valency electrons may be
regarded as existing as a swarm around the
positively charged atoms.
This delocalised swarm of electrons, referred to
as metallic bonding, results in typical properties of
metals such as high electrical and thermal
conductivity.
This metallic bonding behaviour is observed in
compounds other than metals and alloys, for
example in tungsten carbide (W2C).
Formulae and valence
Many elements exhibit more than one valency; for
example iron may be divalent as in ferrous oxide
(FeO) or trivalent as in ferric oxide (Fe2O3). (Note
that the modern terminology for these is iron (II)
oxide and iron (III) oxide).
Valence numbers, also known as oxidation
numbers, of elements refer to the number of
electrons of an element which are involved in the
formation of a compound.
Some indication of valence numbers is provided
by referring to the Periodic Classification of
elements (Table 1).
Group 1 elements normally have a valency of +1.
Group II elements normally have a valency of +2.
Group VII elements normally have a valency of –1.
(This provides only a general indication and there
are exceptions.)
The net sum of valence numbers in a compound is
zero, which will result in an electrically neutral
compound.
So if we combine magnesium with its valence
number of +2 with chlorine, which has a valence
number of –1, we will get magnesium chloride
(MgCl2) with a net sum of zero.
Radicals
In many chemical compounds, there are clusters
of elements which behave as if they were a single
element. We referred earlier to the alkyl radicals
such as methyl (CH3), ethyl (C2H5) and so on.
If we consider the inorganic compounds:
sodium chloride NaCl
sodium hydroxide NaOH
sodium nitrate NaNO3
we can see that the hydroxide (OH) radical and the
nitrate (NO3) radical have behaved in the same
way towards sodium as the single chlorine atom.
The atoms in a radical are held together by
covalent bonds, but the radical contains either an

excess or a deficiency of electrons, and so has an
electrical charge.
In the examples above, the hydroxide and nitrate
radicals, like the chlorine, contain an excess of
electrons and have a single negative charge.
Other examples of radicals are:
ammonium (NH4)+1 1 positive charge
carbonate (CO3) –2
2 negative charges
phosphate (PO4)–3 3 negative charges.
Isotopes
In the section on the Nature of Matter, we defined
the atomic weight of an atom as the sum of its
protons and neutrons. For each element, the
number of protons is constant but the number of
neutrons may vary.
Chlorine, for example, can exist in nature in two
isotopic forms with its atoms containing either 18
or 20 neutrons.
Not all elements exist in more than one isotopic
form, but where isotopes do occur the proportion
of each may vary depending on the source of the
element.
The proportions of the two chlorine isotopes
normally occur in nature as:
● 75.4% of isotope with 17 protons and
18 neutrons giving an atomic weight of 35
● 24.6% of isotope with 17 protons and
20 neutrons giving an atomic weight of 37
From this, the average atomic weight or relative
atomic mass can be calculated as 35.46.
For most purposes the relative atomic mass
quoted in text books is perfectly adequate for
chemical calculations.
Acids and bases
We discussed acids earlier when dealing with the
carboxylic acids and we stated that an acid is a
substance with a tendency to lose protons or
hydrogen ions.
A base may be defined as a substance with a
tendency to gain a proton.
Simpler definitions of acids and bases are:
+
acid – a substance which yields hydrogen ions (H )
base – a substance which yields hydroxyl ions (OH–)
21
and these simple definitions are adequate when
dealing with aqueous solutions.
Before expanding on these definitions we should
remind ourselves of what we mean by:
ions – these are electrically charged atoms or
groups of atoms
electron affinity – the ability of an atom or group
of atoms to attract electrons.
Atoms or groups have differing abilities to attract
electrons, and this difference has been
determined and listed as the electro-negative
series.
If we consider the strong inorganic acid
hydrochloric, we know that there is an
electrovalent or ionic bond between the H and Cl
atoms and that the Cl has a stronger electron
affinity than the H atom. The molecule exists as Cl
with an extra electron in its shell and H with an
electron deficit. However, the strong ionic bond
holds these two oppositely charged ions together.
If this hydrochloric acid is dissolved in water then
the ions dissociate and exist as separate ions in
the water. We can illustrate this separation by
passing a small direct current from a battery
across two electrodes placed in the water. The
process, known as electrolysis, will result in
hydrogen bubbles which appear at the negative
electrode (the cathode).
If we repeat the electrolysis with a basic
substance then oxygen bubbles will form at the
anode – the positive electrode.
This type of experiment is, of course, not possible
with those acids or bases which are not soluble in
water and that is why there is a need to use the
proton donor and proton acceptor definition of
acids and bases.
The degree of dissociation of the positive and
negative ions is an indication of the strengths of
different acids and bases. Most of the inorganic
acids such as hydrochloric, nitric and sulphuric
have high degrees of dissociation and are strong
acids.
There are some weak inorganic acids such as
nitrous acid (HNO2) and carbonic acid (H2CO3).
The strong bases are called the alkalis and these
include sodium hydroxide (NaOH) and potassium
hydroxide (KOH). Ammonia (NH3) when dissolved
in water becomes a base (NH4OH) which is
22

relatively weak. In aqueous solution, these bases An excess of either KOH or HNO3 will ensure that
ionise to form separate particles of, for example, the “left to right” reaction predominates.
the Na4+ ion and the –OH– ion.
Measurement of acidity or basicity
Salts It is often necessary to measure whether a
When an acid and a base are mixed a chemical substance in solution has an excess of acid or
reaction occurs, which is not surprising in view of base or whether it is neutral.
the opposing definition of these two types of
substance. As our definitions of acids or bases refer to their
ability to lose or gain hydrogen ions, a
For example: measurement of hydrogen ion concentration
NaOH + HCI → NaCl + H20 provides a valuable method of assessment.

Sodium Hydrochloric Sodium Water Hydrogen ion concentration or pH can be

hydroxide acid chloride determined by using a specifically designed glass
probe which is immersed in the solution being
The product formed from the reaction between an tested, and is connected to a meter. The meter
acid and a base is called a salt. In the example, measures the pH on a scale from O to 14, where
above, sodium chloride or “common salt” is readings towards zero indicate a strong acid and
formed, but the term salt is applied generally to readings towards 14, a strong base. Neutrality is
the products formed. (When acids and alkalis shown as a pH of 7.
react with each other they give out heat and the
reaction is said to be exothermic). An alternative method of measuring acidity is to
use certain organic compounds called indicators
Salts are named from the acids involved and so, which change colour depending on whether they
for example, a nitrate will be formed from nitric are in an acid or basic solution. For example,
acid. litmus changes from red in acid solution to blue in
KOH + HNO3 → KNO3 + H2O a basic solution and vice versa.
Potassium Nitric Potassium Water By using a known strength solution of a base and
hydroxide acid nitrate titrating this into an acid solution containing one of
these compounds known as indicators, the
With some acids, more than one salt is possible.
strength of the acid can be determined.
An example of this is ortho phosphoric acid
(H3PO4) which is capable of using one, two or all These indicators do not change colour at
three of its H atoms to produce: precisely pH7. The point at which colour changes
occur varies for each of these indicators and
NaH2PO4 mono sodium phosphate
usually occurs over a range of pH. For example,
Na2HPO4 di sodium phosphate cresol red changes from yellow to red over a pH
range of 7.2 to 8.8.
Na3PO4 tri sodium phosphate
with sodium hydroxide.
Acidic and basic oxides
The salt produced by the reaction between an In addition to those substances which are
acid and base will dissociate in water to form obviously acidic or basic from their chemical
ions. structure, there are other compounds which act in
an acidic or basic manner.
KNO3 → K+ + NO3–
The oxides of non-metals such as boric acid
If the water is evaporated we will get solid
(B2O3) are acidic whilst oxides of metals are often
crystals of the salt, in this case potassium nitrate.
basic or amphoteric.
In solution, it is possible for the salt forming
reaction to go in reverse. By amphoteric we mean that the substance can
exhibit both acidic and basic characteristics.
KNO3+ H20 → KOH + HNO3
Aluminium oxide is amphoteric and will react with
and such reversible reactions are shown as:
hydrochloric acid to form aluminium chloride or
KOH + HNO3 KNO3 + H2O with sodium hydroxide to form sodium aluminate.
 23

Neutrality where the iron atom has changed from being

In a reaction between an acid and a base where divalent to being trivalent, is an oxidation reaction.
there is no excess of either reactant, we can To complete our definition we must add that an
expect to obtain a solution of pH7, that is, it is element which is caused to increase its valency
neither acidic nor basic. has been oxidised, while an element which is
For example: caused to reduce its valency is said to be
reduced.
2KOH + H2SO4 → K2SO4 + 2 H2O
A more precise definition of oxidation of an atom
Potassium Sulphuric Potassium Water
is when, in the course of a chemical reaction, the
hydroxide acid sulphate
atom loses control over one of more of its valency
Note that the proportions of the reactants are electrons.
based on the atomic weights.
If you refer back to the copper oxide example you
should note that while the copper oxide has been
Atomic Number Atomic weight
reduced, the hydrogen has been oxidised. In fact,
Potassium 19 39.1 oxidation and reduction reactions always
Hydrogen 1 1 occur together.
Oxygen 8 16
A good example of oxidation which has to be dealt
Sulphur 16 32
with in the coatings industry is the oxidation of
Potassium hydroxide Molecular Wt. = 56.1 iron to form rust.
Sulphuric acid Molecular Wt. = 98.0
Electronegativity
So in the example above, we would require 2 × We have made frequent reference to the differing
56.1 gms of KOH and 98 gms of sulphuric acid. electron affinity of elements, the stronger ability of
Caution: The reaction between a strong acid and some atoms to attract electrons compared with
a strong base or alkali is exothermic – it other atoms.
generates a lot of heat. Unless both the acid and Elements with a strong electron affinity are said to
alkali are used in a diluted form in water, this type be highly electronegative, and a chemist named
of reaction is highly dangerous. Pauling determined the eletronegativity values
of all the elements. Some of these are shown
Oxidation and reduction below.
The simplest definition of oxidation is the addition
of oxygen to an element or compound or the Values of electronegativity of some elements
(Pauling)
removal of hydrogen. So if aluminium reacts with
oxygen H 2.1 K 0.8
4Al + 302 → 2Al2O3 C 2.5 Ca 1.0
to form aluminium oxide, an oxidation reaction has N 3.0 Ti 1.5
taken place.
O 3.5 Fe 1.8
Similarly, reduction can be the removal of oxygen
Na 0.9 Z 1.6
from a compound such as:
Al 1.5 S 1.8
CuO + H2 → Cu + H2O
Cl 3.0 Pb 1.9
Copper oxide
– the copper oxide has been reduced to copper. These values are a useful guide to the electron
distribution in a bond and the degree of polarity
The simple definitions are unfortunately
which exists. A large electronegativity difference
incomplete, as the reaction:
favours the formation of ions – for example in the
2FeCl2 + Cl2 → 2FeCl3 sodium and chlorine bond.
Ferrous Chlorine Ferric In addition, the electronegativity of an element
chloride chloride increases with its oxidation state. For example,
24
the ferric ion Fe3+ is more electronegative (i.e. it
has a stronger affinity for electrons) that the
ferrous ion Fe2+.
Organic polymers
A polymer is a large molecule made up of similar
or dissimilar molecules joined together.
To join these molecules together chemical
reactions have to take place. So before we
consider the types of polymeric reactions involved
in the preparation of synthetic resins we need to
examine what occurs when a chemical reaction
takes place.
We can illustrate a chemical reaction by a simple
equation. For example, the reaction between a
carboxylic acid and an alcohol to form an ester
may be shown as :
R1COOH + R2OH R1COOR2 + H2O
or, to take a specific case:
C2H5OH + CH3COOH C2H5OOC.CH3 + H2O
Ethyl Acetic Ethyl Water
alcohol acid acetate
This simple equation does not give the full picture
of what is occurring in a chemical reaction and we
need to consider the following factors:
● When a chemical reaction takes place bonds
between atoms of the molecules involved are
broken and formed. In the reaction above the
points of breakage and formation may be
shown by dotted lines:
C2H5 OH + CH3COO H C2H5 OOC.CH3 + O OH
● Energy is involved in the breaking and forming
of bonds. This energy, known as the “energy
of activation”, is related to the atoms involved
and the velocity of their electrons. In many of
the reactions concerning polymerisation the
energy required is provided by heat. As
temperature increases the velocity of the
electrons increases and the rate of the
reaction increases.
Arrhenius, in 1889, calculated that the rate of
a reaction approximately doubles for each
10°C rise in temperature.
● In the equation above we have shown the sign
which indicates that the reaction is
reversible. An excess of acetic acid or an
added acid will encourage ester formation but
a deficiency of acid or an excess of water will
result in the reaction going in reverse (from
right to left). In the latter case hydrolysis of
the ester occurs to form ethyl alcohol and
acetic acid. Hydrolysis will also take place if
an alkali is present.
Many organic reactions are reversible and
appropriate steps need to be taken to ensure
that the maximum yield of the desired
products is achieved.
An example of this is in the preparation of oil
modified alkyds, which involves the formation
of many ester linkages. The water formed by
the reaction is continuously removed in a
separator which minimises the reverse
reaction of hydrolysis of these esters.
● The equation indicates the initial and final
products of the reaction but does not tell us
how the reaction proceeds. Most chemical
reactions go through successive steps before
the end products are reached. (The
esterification reaction is no exception and it is
thought that an intermediate step involving
the formation of an addition compound of
acid and alcohol first occurs).
The rate of the overall reaction is controlled
by the slowest step – known as the “rate
determining step”.
A knowledge of the mechanism of a reaction –
how it proceeds – is useful in determining the
optimum conditions for achieving the maximum
yield of the desired end product. Before we study
these reaction mechanisms it needs to be pointed
out that organic reactions are often slow and the
maximum theoretical yield is rarely achieved.
Functional groups (also referred to as
reactive groups)
In the simple esterification reaction we have
discussed each of the two reactants has only one
reactive group – the carboxylic acid group
(–COOH) and the hydroxyl group (–OH). This
means that only one new linkage can be formed
and although we achieve a larger ester molecule,
we cannot produce a polymer.
The number of reactive groups in molecules
taking part in a reaction will determine the size
and structure of the resulting molecule.
 25

This can be illustrated by the following: contain such reactive groups which are then
capable of cross-linking in the paint film after it
No. of reactive groups has been applied. We will refer back to this aspect
Molecule Molecule Resulting after we have looked at the reactions involved in
A B molecule polymerisation.
(i) 1 1 A–B
Definition of polymerisation
(ii) 1 2 A–B–A “Intermolecular combinations that are functionally
(iii) 1 3 A–B–A capable of proceeding indefinitely.”
A Although the above statement is correct, in
practice other factors prevent the reaction
(iv) 2 2 –A–B–A–B–A–B– proceeding indefinitely and producing polymers of
infinite size.
(v) 2 3 –A–B–A–B–A Such factors include the increase in viscosity as
A A B–A– the polymer becomes larger, thus reducing its
mobility and the opportunities for reactive groups
A–B B–A
to come together.
In addition, our objective is to obtain a polymer
In (i), the resulting molecule will be a relatively suitable for paint formulations, therefore we plan
simple one with a finite size. It will certainly not be our process to give polymers within a specific
a polymer. range of molecular size.
Even in (ii) and (iii), where only one of the reacting Mechanism of polymerisation
molecules is monofunctional, the molecule formed There are two distinct mechanisms used to
will have a small and a finite size. produce polymers, addition and condensation.
However, in the case of (iv) and (v) it is possible to
form very large molecules which, in theory, could Addition polymerisation
grow to an infinite size. This occurs mainly between molecules containing
double or triple bonds, and in addition
With the reactants shown in (iv), this large
polymerisation there is no liberation of small
molecule would be a linear polymer whilst the
molecules.
reactants in (v) would normally give a three
dimensional network polymer. If, however, the tri- Example – Polymerisation of vinyl chloride
functional molecule B in (v) is present in only small
quantities, the polymer formed will be mainly
H H
linear but with some branched chains.
This may be summarised as: CH2 C → CH2 C
● When each of the two reacting molecules Cl Cl
have 2 reactive groups then a linear polymer n
can be formed.
● When one of the reactants has at least 2 vinyl chloride polyvinyl chloride
reactive groups and the other has at least 3, monomer
then a three dimensional polymer can be The principal steps in this type of polymerisation
formed. are:
● When the tri-functional molecule is present in (i) Initiation of the reaction (or activation)
only very small amounts a branched chain (ii) Growth or progression
polymer can be formed. (iii) Termination
It is useful to note that in examples (iv) and (v) we
have shown some unlinked reactive groups in the (i) Initiation or activation
resultant molecule or polymer. When polymers are Often the monomer is liquid and can be
prepared it is possible to design them so that they polymerised in bulk. Alternatively a solution of the
26

monomer is prepared and polymerisation carried The foreign molecule supplying the hydrogen
out in this solution. A third method is to emulsify atom can be a chain transfer agent, sometimes
the polymer and carry out emulsion polymerisation. called a chain stopper, which is introduced into
The initiator used is one that can generate free the system. The chain transfer agent is designed
radicals. Usually these are organic peroxides to absorb its free radicals within itself and so
which decompose to give free radicals on heating. prevents them from taking part in further
polymerisation.
Organic peroxide e.g. Benozoyl peroxide
The polymer molecules produced are vary large
(RCO2)2 C6H5COO.OCO C6H5 but they will not all be of the same size. Some
(RCO2)2 → 2RCO 2 free radicals → 2R•+ CO2
• polymer chains will be terminated early in the
reaction whilst others will continue to grow. It is
possible to achieve some control of the average
H H H H
size of polymer chains by the amounts of initiator
R• + C C → R C C• and chain transfer agents used and the practical
conditions employed.
H Cl H Cl The polymer molecule size is defined by its
molecular weight which is arrived at by adding
Vinyl Monomer
together the atomic weights of all the atoms in
chloride free radical
the molecule.
(ii) Growth or progression When only one type of monomer molecule is
If M represents the free radical of the monomer involved in the polymerisation reaction this is
then the series of growth can be represented as: referred to as homopolymerisation.
● M → M• It is possible to use more than one type of
(Monomer Monomer free radical) monomer, and the reaction is then referred to as
copolymerisation or interpolymerisation.
● M + M• → MM•
Many of the resins used in emulsion paints use
● M + MM• → MMM• combinations of monomers with the objective of
(Polymer free radical) achieving optimum coating properties.
and so on to Mn•, where n represents the number Copolymers of, for example, vinyl acetate and
of monomer units in the polymer. ethyl acrylate or other acrylates have largely
superseded the homopolymer of vinyl acetate
(iii) Termination alone in this field of coatings.
There are several ways in which the growth of the Although the preparation of addition polymers is
polymer chain may be stopped, all of which carried out with the aid of initiators like the
involve the removal of the free radicals: organic peroxide, the reaction can occur at a
● Two free radical units may combine slower rate without such “catalysts”.
M• + MM• → MMM In storage, the monomers can slowly form free
radicals by a dimerisation process:
● One free radical removes a hydrogen atom
from another free radical to become an
unsaturated compound.

2 C C → •C C C C•
R1 CH CH2• + R• → R1 CH CH2 + RH

H
and this can lead to a slow polymerisation of the
● Transfer of a hydrogen atom from a “foreign”
monomer. To prevent this, a small addition of chain
molecule.
transfer agent is usually made to the stored
M• + R1H → MH + R1• monomer.
 27

Condensation polymerisation Glycerol CH2 OH a trifunctional

In the definition of addition polymerisation, alcohol
the point was made that no small molecules CH2 OH
are liberated in this process.
With condensation polymerisation the process does CH2 OH
involve the liberation of small molecules. Although
the small molecules concerned are often water, the Phthalic anhydride
term condensation polymerisation covers reactions
where other small molecules such as ammonia and CO
O
hydrogen chloride are freed. CO
A definition of condensation polymerisation
reactions is the condensation of bi- or which behaves as a dibasic acid
polyfunctional molecules to form linkages with the
elimination of small molecules. COOH
A good example, and one which occurs frequently COOH
in the preparation of resin polymers for paints, is
polyesterification. Fatty acids such as linoleic acids
Earlier, we examined the esterification between a CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
mono functional acid and alcohol.
a monobasic acid derived from linseed oil where it
Now, if we consider difunctional molecules we can exists as the trigyceride.
illustrate a condensation polymerisation reaction.
If linoleic acid is written R COOH then the
HOOC–R–COOH + HO–R1–OH → triglyceride which occurs in linseed oil is:
dibasic acid dihydric alcohol
HOOC–RCOOR1–OH + H2O CH2 OOCR

One ester linkage has been formed together with CH OOCR

one molecule of water. The molecule formed still
contains functional groups capable of further
esterification reactions, as shown at the foot of
this page*.
Each reaction produces a further ester group and
a molecule of water and, in theory, the length of
the polymer chain can increase until all the
functional groups present have esterified.
Polymers formed by multiple esterifcation
reactions are called polyesters.
Some of the earliest synthetic resins developed
for use in surface coatings were the oil modified
alkyds.
These are products formed by polyesterification
from polyhydric alcohols, polybasic acids and
monobasic acids. Examples of the reactants used
in alkyd preparations are:
CH2 OOCR
Using such a combination of multi functional
groups can result in a series of esterification
reactions leading to cross-linked, three
dimensional polymers and the liberation of water.
Suitable conditions have to be provided and the
energy of activation for these chemical reactions
is achieved by carrying out the process at an
elevated temperature.
Also, the water produced is continuously removed
which assists the progress of polymerisation.
If we used equal ratios of acid and alcohol
functional groups at the start of the process, we
should in theory be able to continue
polymerisation until no functional groups are left.
This does not happen.

* HOOC–RCOOR1–OH + HOOC–R–COOH → HOOC–R–COOR1–OOC–R–COOH + H2O

and
HO–R1–OH + HOOC–RCOOR1–OOC–R–COOH → HO–R1–OOCR–COOR1–OOC–R–COOH + H2O
28
With addition polymerisation, we noted that
polymer growth proceeds primarily by the
continuous addition of the small monomer
molecules. This progressive growth continues, at
a very fast rate, until termination occurs.
In contrast, the ordinary chemical reactions in the
condensation polymerisation process result in the
original molecules joining together and effectively
doubling their size. Then these larger molecules
join together and so on until very large and very
viscous polymer molecules are formed.
At this rate, the numbers of remaining functional
groups will have fallen steeply and it becomes
difficult for them to locate each other and react.
The rate of reaction will become very slow.
In practice the whole polymerisation process is
normally controlled by checking the viscosity and
stopping the reaction at a specified point.
The final product from the condensation poly-
merisation process will contain polymers of differing
sizes and molecular weight. By careful selection of
the type of reactant, the relative quantities of
reactant and the process conditions, the properties
of the polymer resin can be predetermined.
Some factors involved in the design of
condensation resin polymers are:
● Functionality of reactants
By including some mono-functional material (eg a
fatty acid) we can control the size of the polymer.
Once the fatty acid carboxylic acid group reacts
with a hydroxyl group it effectively acts as a
“chain stopper”. Using tri or tetra functional
reactants will lead to rapid polymerisation and
high molecular weight.
● Ratios of reactants
To ensure that the final polymer has few
unreacted carboxylic acid groups (ie a low acid
value) we can use an excess of the polyol in the
process. This excess of functional hydroxyl
groups increases the odds of the remaining
carboxylic acid groups being esterified.
Most alkyd or polyester resins are designed to have
a low acid value, as any free acidity may impair the
performance of the coating produced from it.
For most polyesters, however, an excess of
hydroxyl groups is designed into the polymer, as
these functional groups are required for cross
linking reactions after the coating has been applied.
● Process conditions
The temperature of the condensation process will
have an effect not only on the rate at which
polymerisation proceeds but also on the average
size of the polymer formed.
● Addition of reactants
A late addition of one or more of the reacting
materials or a steady feed of one of them into the
reaction vessel can give closer control of average
molecular weight or polymer size.
There are many other factors involved in the
formulation and manufacture of synthetic resin
polymers but the above are useful general points.
Properties of organic polymers
In the previous section of this Monograph we
described how relatively small molecules or
monomers can, by a series of chemical reactions,
link together to form the large molecules we refer
to as polymers.
All the resins or binders used in paint formulations
are organic polymers and the properties of these
polymers play a vital role in the performance of
the coating systems in which they are used.
Choosing the most suitable binder for a particular
type of paint from the wide range of commercially
available resins is an essential part of the paint
formulating process. To do this, it is necessary to
understand the composition, the structure and the
chemical and physical properties of the various
types of polymer.
An in-depth study of polymer chemistry is not
required at this stage, but it will be useful to look
at types of polymer and to consider some of the
parameters which determine their properties.
Before doing this there are two points we need to
clarify.
● Our earlier discussions on the polymerisation
process were concentrated on the initial
manufacture of polymers. We will see that
many resin systems are designed to undergo
a further polymerisation process after the
paint has been applied.
● The viscosity of these resin polymers is
usually very high and they are often solid at
room temperature. After manufacture they
are generally thinned with a suitable solvent
to make them easier to handle.

When discussing the properties of a resin polymer
we will be referring to it in its solvent free form.
The major factors which determine the chemical
and physical properties of a polymer may be
listed as:
● The arrangement or geometry of the
chemical groups within the final polymer.
● The total number of small molecules or
monomer units linked together to from the
polymer.
● The type and chemical composition of these
units.
● The presence or absence of functional groups
in the manufactured polymer molecule.
We shall now look at these in more detail.
The geometry of polymer molecules
If we refer back to the addition polymerisation of
the unsaturated monomer vinyl chloride, we will
note that the monomer molecules join together to
from a long chain. This long chain consists of a
series of repeating identical units which may be
represented as:
CH2 CH CH2 CH CH2 CH
Cl Cl Cl
the identical repeating units being:
CH2 CH
Cl
The linear or chain structure of polyvinyl chloride
is just one of three possible geometric
arrangements found in polymer molecules.
We can distinguish these arrangements as:
A linear chain structure as above:
Branched polymers
29
Network or cross-linked polymers.
Each of these three forms of polymer are created
by chemical reactions which, you will recall,
involve the breaking and formation of bonds.
The bonds which are formed to link the monomer
units together are electron sharing or covalent
bonds. These covalent links are most often single
bonds although double bonds may be formed.
Polymer chains do not have a stiff, rigid form
because there is some freedom of movement of
the atoms forming a bond. This movement will be
greatest with a single bond, less with a double
bond and if a triple bond is present it will have
considerable rigidity.
The movement of atoms around a single bond
results in the chain being flexible – rather like a
CH2 metal
CH link chain or telephone cord. The chain will
have a crinkled shape, somewhat like the
illustration
Cl below, and it will be three dimensional
and may be crumpled into a coil shape.
Each of these linear chains is one molecule of the
polymer and its size may be measured by its
molecular weight. In a synthetic polymeric resin
there will be a very large number of these chain
molecules but they will not all be of the same
length and will not all have the same molecular
weight. Individual chains may contain just a few
monomer units or many hundreds of monomer
units linked together.
In a chain polymer resin, the individual chains will
intertwine and be attracted to each other by
secondary valency forces. These secondary
forces, also known as van der Waals or
intermolecular forces, play an important role in
giving the polymer its mechanical strength.
Although these forces are relatively weak, the
30
attraction between polymer molecules is
significant at low temperatures.
However, because these secondary
intermolecular forces are weak, they are easily
broken by the action of suitable solvents or by the
application of heat. This results in some specific
properties of linear molecules which we will
explain in a moment.
The next type of polymer geometry is the
branched chain pattern. These have similarities
with the simpler chain polymers but the chains
have “branches” from which side chains grown. As
stated earlier, the presence of only a small
quantity of a tri-functional component will enable
these branched chains to form on a linear
polymer. Again these branched chain polymers
will be three dimensional in space and will not
have a rigid structure.
The third type is the network or cross-linked
configuration which may be considered as linear
chains which have become linked by the formation
of covalent bonds across the chains. This cross-
linking results in three dimensional structures with
greatly increased rigidity.
The strength of the covalent bonds in the network
polymer means that it is less affected by solvents
and does not soften and melt on heating.
There are a great number of network polymers in
use in the coatings industry including those
polymers known as oil modified alkyds. For
example, one type of alkyd can be produced from
the chemical reactions between:
Phthalic anhydride – 2 reactive carboxylic
acid groups
Glycerol – 3 reactive hydroxyl
groups
Linseed oil fatty acids – 1 reactive carboxylic
acid group
This combination of reactants satisfies the
parameters for a network polymer and in addition
the unsaturated bonds in the linseed oil fatty acids
provide reactive points for further cross-linking.
Alkyds of this kind, prepared from unsaturated
fatty acids, are used as the resins in many
domestic air-drying paints. After these paints are
applied, further chemical reactions take place
involving atmospheric oxygen. These reactions,
which result in further cross-linking and growth in
polymer size, convert the coating to a dry tough
film.
Number of units in the polymer
The size of a polymer molecule is determined by
the number of small molecules which go into its
creation. The polymerisation process will produce
a large number of polymer molecules which will
not all be of the same size.
If we start with chain polymers, the size is
determined by the number of monomer units
which it contains, rather like the number of links in
a metal chain.
It is the convention that the molecule must contain
at least 10 monomer units for it to be called a
polymer. In practice, organic polymers contain
very large numbers of these units.
The term “degree of polymerisation” refers to
the number of units which link together to form a
polymer. When manufacturing a resin, the degree
of polymerisation is controlled to give polymer
molecules which have an average size capable of
giving the properties we need in a particular paint
formulation.
Ideal polymers are those with a small size
distribution and not those which contain polymer
molecules with sizes ranging from very small to
very large.
Small polymer molecules exhibit poor solvent
resistance and poor resistance to mechanical
wear. Very large molecules have very high
viscosities and will need to be thinned with a lot of
solvent to enable then to be used in paint
production and application.
(Large molecular sized polymers are used in
certain types of paint systems. For example,
water based emulsion paints use very large
polymers but instead of dissolving them in large
quantities of solvent, they are dispersed in water
to form an emulsion. This technique gives
handleable products without the need for
excessive amounts of solvent).
The average polymer size may be expressed in
terms of the molecular weight, and this may be

given as either “number average molecular
weight” or the “weight average molecular
weight”.
For chain polymers, there is a third method of
measuring average polymer size called the melt
flow index which we will explain in a moment.
As the size of the polymer molecule grows, the
forces of attraction within the molecule become
stronger and the viscosity increases until eventually
the polymer becomes solid at ambient temperatures.
For chain polymers there is a relationship between
the viscosity and the length of the polymer chain.
However, the secondary valence forces which
attract these chains to one another also influence
the viscosity and the softening properties of the
polymer.
These secondary valence forces are greatly
weakened at higher temperatures and the
application of heat allows the polymer chains to
move relative to one another. The viscosity of the
melt will then depend on the average length of the
polymer chains and not be influenced by the
secondary valence forces. This is the basis of the
melt flow index method of measuring average
molecular weights of chain polymers.
Type and chemical composition of
molecules used to build polymers
The nature of the monomers or small molecules
which form a polymer not only give the polymer its
name but also give it many of its properties. Both
polyvinyl chloride and polyvinyl acetate are chain
polymers but they have quite different properties.
*
CH3
CH2 CH CH2 O C O CH2 CH
O O
CH3 OH
Notes:
● Absence of ester groups
Only –C–C– and –C–O–C– linkages
● Presence of polar groups – hydroxyl (–OH) and epoxy
● Aromatic (benzene) rings along molecule
aids mechanical strength
● Chains of 5 single bonds between hydroxyl groups
31
Polyvinyl chloride is a hard stiff polymer resin with
good resistance to water, whereas polyvinyl
acetate is a somewhat brittle plastic polymer with
relatively poor water resistance. Polyvinyl acetate
was one of the first polymers to be used in
emulsion paints but because of its sensitivity to
water, modern paints use a copolymer resin
produced by copolymerisation of vinyl acetate
with, for example, an acrylic monomer.
There are many types of monomer used to produce
addition homo-polymers and co-polymers, the
choice of monomer used depending on the type of
paint in which the final resin is to be used.
When we come to the polymers produced by
condensation reactions we find that there is an
even larger range of starting point materials.
The manner in which these starting point
materials influence the properties of the final
polymer can be illustrated by considering two
typical paint resins.
Airdrying decorative paints use oil modified alkyd
resins as the medium or binder. These alkyd resins
are condensation polymers produced from reactions
between monobasic acids, polybasic acids and
polyalcohols. The polymerisation of these raw
materials results in the formation of multiple ester
groups in the polymer molecule. Ester linkages are
susceptible to attack by alkalis and so this type of
polymer is not good for alkali resistance.
Epoxy resin molecule
In contrast, epoxy resin polymers (see formula
below*) contain only carbon-carbon and ether
linkages, both of which remain strong in the
CH3
CH2 O C O CH2 CH CH2
CH3
Good alkali
resistance
C C Good adhesion
O
Aids flexibility
32
presence of alkalis, and this explains their
excellent alkali resistance.
Epoxy resins also have excellent adhesion
properties which is due to the presence of
hydroxyl and epoxide groups. These are polar
groups and they provide “anchor” points to the
substrate.
Finally epoxy resins exhibit good hardness and
flexibility, which is explained by the presence of
specific chemical groupings in the polymer
molecule. Each molecule contains a large number
of aromatic rings and these strongly stable
groups contribute to the hardness of epoxies.
The epoxy polymer also contains chains of five
single bonds. Rotation of the atoms about these
single bonds give the polymer its good flexibility.
Functional groups – convertible and
non-convertible polymers
The process of polymerisation proceeds until, for
reasons explained earlier, polymer growth comes
to a halt.
Once the polymerisaton process is completed,
linear polymers do not possess any functional
groups and so these linear polymers lack the
facility to crosslink across their chains. They are
incapable of undergoing further chemical
reactions with other functional groups to form
larger polymer molecules.
When such polymers are incorporated into a paint
and applied, the paint dries by solvent evaporation
alone. After the solvent has been removed no
chemical reactions are possible within the polymer
and no cross-linking can occur.
The strength of these linear polymers depends on
their high molecular weight and the interchain
attraction provided by the secondary valence
forces.
Polymers of this type, which cannot be converted
to a higher polymeric state and dry by solvent
evaporation alone, are described as non-
convertible polymers.
Non-convertible polymers
When paints based on such non-convertible
polymers are applied and allowed to dry, they can
be easily re-dissolved in the type of solvent used
to prepare the resin solution in the first place. A
simple example of a non-convertible polymer is
shellac solution (French polish).
A different situation exists with condensation
polymers such as the oil modified alkyds and
epoxy resins. This type of resin will still have
functional groups in its molecules when the
polymerisation process has finished. The alkyd
polymer molecules may contain reactive double
bonds and unreacted hydroxyl and carboxlic acid
groups. These remaining functional groups enable
the polymer to undergo further chemical
reactions, to cross-link and so become converted
to a higher polymeric state.
Polymers of this type are called convertible
polymers.
The cross-linking occurs either between different
functional groups in the original polymer, or
between groups in the original polymer and
groups in another, added, polymer or chemical.
For example, the polymer added to an epoxy resin
could be an amino resin such as a butylated urea
formaldehyde resin. In this case the hydroxyl and
epoxy functional groups in the epoxy resin are
capable of reacting with the functional groups in
the amino resin. (The amino resin will have
reactive hydroxyl groups, methylol groups and
some reactive hydrogen groups in its molecule.)
After blending the epoxy resin with the amino resin
in suitable proportions, applying the coating and
allowing the solvents to evaporate, cross-linking
reactions can take place.
To effect this cross-linking of convertible coatings
some form of energy has to be introduced into the
system. This “energy of activation” is often
supplied in the form of heat by stoving the paint,
but the conversion may also take place at ambient
or only slightly elevated temperatures.
For example, the epoxy/amino combination
referred to above will require the action of heat to
effect cross-linking but an airdrying alkyd will
polymerise at ambient temperatures by an
oxidation process involving atmospheric oxygen.
Such “post application” polymerisation results in
the applied film being converted to a highly cross-
linked structure with extremely high molecular
weights. Once it has cross-linked the paint film will
be resistant to the solvents in which it was
originally dissolved and it will not soften on
heating.
There are two more terms applied to organic
polymers which need to be defined before we

close this section. These are “thermoplastic” and
“thermosetting”.
Thermoplastic polymers fall into the same
category as non-convertible polymers as they
have no reactive or functional groups in their
polymer molecules and so cannot undergo further
chemical cross-linking.
They are linear polymers and as their name
implies they soften on heating. On cooling they
return to their original hardness and this softening
and rehardening can be repeated many times.
Their hardness at ambient temperature is partly
due to the molecular size and its viscosity and
partly due to the van der Waals forces.
Thermoplastic polymers are used in many
applications today and include “plastics” such as
polyproplene, nylon and polythylene.
Thermosetting polymers are convertible polymers
which require the action of heat to provide the
energy of activation necessary for the functional
groups present to react and crosslink. Once heat
has been applied and cross-linking has occurred
the polymer cannot be softened by reheating but
becomes permanently converted to a hard tough
and solvent resistant material.
Colour
This monograph would not complete without
some reference to “Colour”, a topic already
mentioned earlier when matter in the solid state
was discussed and also in the section on organic
and inorganic compounds.
The perceived colour of an article derives from
the chemical structure of the colorant it contains.
It is this chemical structure that determines the
colour which appears as a result of the interaction
of light and matter. This subject, colour physics, is
introduced here but is dealt with in more detail in
OCCA Student Monograph No 4.
Goethe wrote, in 1810, “The theory of colours, in
particular, has suffered much, and its progress
incalculably retarded by having been mixed up
with optics generally, a science with cannot
dispense with mathematics; whereas the theory of
colour, in strictness, may be investigated quite
independently of optics” (Faber Birren – History of
Painting).
This is certainly not the case nowadays when
colour physics is used to explain, define and
33
measure colour precisely using optics, science
and mathematics. Although the aesthetics of
colour preference and appreciation remain,
science has provided us with a very
comprehensive understanding of colour.
Colour is defined as a sensation produced in the
human brain by the inter-action of light on an
object, and the three essential requirements for
producing a colour sensation are a source of light,
an object and an observer. If any one of these
three is taken away, the colour sensation is taken
away. If any one of these three essentials are
altered then the colour sensation will alter.
The radiant energy in the form of visible light
directed at the object may differ in its composition
over the range of 400 nanometres (violet) to 700
nanometres (red) depending on its source. The
most common form of light is daylight, provided
by the sun, but other sources of light may be
used including artificial ones. Some of the
wavelenghs of this radiant energy will be
absorbed by the object while some will be
reflected.
The composition and structure of the compounds
which make up the dye or pigment are the main
factors which determine what light is absorbed
and which is reflected. As a result of the radiant
energy exciting groups of atoms in the crystal
structure of the pigment molecule, the object
selectively absorbs some of the incident light and
reflects the remainder, which is then perceived by
an observer.
Although colour is defined as a sensation
produced in the human brain, measurement of
colour is increasingly carried out instrumentally.
The “observer” is a colour computer containing a
spectrophotometer which measures the colour
and a computer which calculates the data
required to define the colour.
For a more detailed explanation of Colour Physics
the reader is referred to OCCA Monograph No.4.
Further reading
There are so many textbooks on chemistry and
physics, ranging from elementary to advanced,
that it is not easy to provide a reading list to suit
all students.
However, the following suggestions may be of
value.
34
1. Principles of organic chemistry,
Murray PRS, Heinemann
2. Success in organic chemistry. Hawkins MD,
John Murray 1981
3. A guide to modern organic chemistry. Owen
SM and Brooker AT, Longman,1991
The above three titles are examples of the many
good textbooks on basic chemistry.
4. Introduction to paint chemistry.
Turner GPA. Chapman and Hall, 1988
This contains a useful section on general science.
5. Introduction to paint technology. OCCA
Useful all round introduction
6. Modern surface coatings. Nylen P and
Sutherland E. J Wiley and Sons 1975
This is a comprehensive and advanced book on
surface coatings.
7. Alkyd resins. Martens R. Rheinhold Publishing
Co, 1961.
Useful as a guide to one important type of
convertible polymer.
8. Colour physics. OCCA Student Monograph
No.4
9. The basics of resin technology. OCCA
Student Monograph No.10
10. The basics of solvents and thinners. OCCA
Student Monograph No.9
■
35
36
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Titles in the Student Monograph Series

No. 1 Basic Science for Students of Paint Technology

No. 2 Corrosion
No. 3 Water-borne Resins
No. 4 Colour Physics
No. 5 Dispersion and Dispersion Equipment
No. 6 Additives for Water-borne Coatings
No. 7 Standards
No. 8 Water-borne Coatings
No. 9 The Basics of … Solvents and Thinners
No. 10 The Basics of … Resin Technology

Honorary Technical Education Officer: A T Hopgood FTSC

Honorary Editor: P S Thukral PhD CChem FTSC
Chairman Special Publications Committee: R H E Munn BSc LRSC FTSC

Oil & Colour Chemists’ Association

Priory House, 967 Harrow Road, Wembley HA0 2SF, England
Tel: +44 (0)181 908 1086 Fax: +44 (0)181 908 1219
Email: publications@occa.org.uk
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