The Basics of...

Resin Technology
L A Fisher FTSC
G R Hayward CCHEM MRSC MIOSH ATSC

OCCA Student Monograph No. 10

Oil & Colour Chemists’Association

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The Basics of...
Resin Technology
L A Fisher FTSC
G R Hayward CCHEM MRSC MIOSH ATSC

OCCA Student Monograph No. 10

Oil & Colour Chemists’Association

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

ISBN 0 903809 38 9
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 the second in a new series of Student Monographs published by the Oil & Colour
Chemists’ Association, and is part of a collaborative project with its South African Division.
The objective for these new Monographs is to provide a series of basic primers for newcomers to the
surface coatings industry and, specifically, for operatives and trainees in Southern Africa and the Indian
Sub-Continent. Companies, Trade Associations, Professional Bodies and the Authorities have identified
this sector as lacking educational resources and the Oil & Colour Chemists’ Association is pleased to
respond to this need.
The series has been published with the assistance of a grant by the Trustees of the Ellinger-Gardonyi
Fund, an educational trust, administered by the Oil & Colour Chemists’ Association and is supported
from resources provided by its South African Division from the funds generated by SURFEX – Southern
Africa.
The Basics of...
Resin Technology
L A Fisher FTSC
G R Hayward CCHEM MRSC MIOSH ATSC
Introduction
Working in the so called third world countries is an education in itself. One of the things I came to realize
was that, due to lack of opportunity, there were many more people of high intelligence in the working
class than there are in the first world. The reason is due to the fact that in the developed nations
anybody with the brains and/or gumption can get an education. Hence by a natural selection system
there is a stratification. At the same time the type of education is also at variance; going from the farm
school with 30 pupils in 10 grades and one teacher, to the specialised schools with the capacity and
the staff to provide a broad curriculum. A further problem is that, as we develop, the basic qualifications
required also change – 50 years ago a matric was a good starting point whereas industry can, and
does, now require a degree for the same job, that’s progress. The result of this is that the first – third
world gap is increasing.
In South Africa, as is also the case in Latin American and Asian countries, we have a strange mixture of
first and third world. This means that the education tends to be fairly rudimentary for the less privileged
and the Ox Wagon, Porsche gap has to be bridged. This means that industry must fill in the gaps
themselves. The result of this is that, because the demand is relatively low for such disciplines as paint
technology, the technical colleges cannot assist and the paint industry must provide its own education.
Unfortunately the courses available from the UK assume a basic school leaving certificate with maths,
physics and chemistry. To this can be added the language problems. Following on the results of the last
National Matric exams, the first post-apartheid ones in which students all wrote the same exam, one
official comment was to the effect that a greater emphasis on the Sciences will be required.
So, we have some very bright people out there with a basic education and they need only a little help.
We could throw them in the deep end, but it would be better to teach them to float first. The object of
these monographs is to help our students to bridge the gap. It is hoped that, by explaining the basic
concepts, in the least complicated manner, emphasising only the points they really need to know, they
will have a better understanding of what is going on and be less confused. We are not targeting the
higher modules of the course but only the beginners.
As someone once told me ‘When you are up to your neck in crocodiles it can be difficult to remember
that the objective was to drain the swamp’. At least let us attempt to extract some of the crocodiles’
teeth.
Contents

Introduction 1
History 1
Synthetic Resins 1
Vegetable Oils 2
Basic Chemistry 2
Fatty Acids 5
Glycerides 5
Polyols 7
Alkyds 8
The Acid Component 9
Variations 10
Saturated Polyesters 11
Unsaturated Polyesters 12
Processing 13
Heat 14
Heat and Chemical Reaction 15
Azeotropic Distillation 15
Alkyd Manufacture 15
Polyester Process 17
Finishing and Adjusting the Batch 18
The End Use of Alkyd Resins 18
Oil-Modified Alkyds 18
Applications 19
Conclusions 20

The Basics of... Resin Technology
Introduction
One of the problems facing us today is that of
communication. In order to communicate it is
necessary to have a common language.
Unfortunately each field of endeavour has its own
particular terminology and so we tend to grow in
our own environment and begin to speak in
technical terms. In day to day contact within
industry this jargon builds up. People use
abbreviations and terminology with very little idea
of what it means. Some people are quite happy to
go along with this but others would like to know
what is going on. This monograph is intended as a
general guide for those with little scientific
training. This has, by necessity, resulted in
oversimplification which it is hoped the experts in
this technology will overlook.
History
Primitive man painted both his body and the walls
of his home. This was partly decorative and partly
for symbolic or religious reasons. He found all
sorts of substances at hand to help him – iron
oxides, carbon black, chalks and other minerals
to use as pigments along with such things as
grease, oil, rosin, wax, blood, egg, milk and
bitumen for binders. It is interesting to note that
variations of many of these are still in use today. A
considerable amount of credit must therefore be
given to the efforts of the early artists in their
search for better and more durable pigments and
media for their paintings.
The technological demands, with regard to
application, drying time and durability, were such
that a considerable amount of time and effort
went into the development of suitable materials.
As an example, the requirements of the artist
tended to centre upon application characteristics
and durability. Relatively long drying times are
often acceptable and even desirable as this
permitted easy removal and modification. The
great masters were complete self starters and
were required to formulate and compound their
own paints. In this way apprenticeship included a
course in paint technology. In the case of
varnishes, a great deal of the technology and
earlier development was stimulated by the search
1
for better finishes for musical instruments such as
the violin. When a violin is varnished the degree of
hardness becomes important as this contributes
to the resonance of the instrument. As in the case
of the early painters, the manufacture of the
coating was part and parcel of the job.
As time went by the need for coatings to decorate
and protect manufactured articles increased as
did the need for decorative paints of all types. To
bring this about paint manufacturers built upon the
technology of these earlier artists and violin
makers. Even the anti corrosion and construction
industry drew heavily on a similar technology with
the use of white lead, red lead and colours in oil
as protective coatings. There was also a
challenge to produce finishes equal to those
obtained with Chinese and Japanese lacquers and
with vitreous enamel.
At this time the chemical industry was also
growing and by end of the nineteenth century saw
the early development of plastics such as Bakelite
and nitro-cellulose, along with the development of
other synthetic resins by the modification of
natural ones.
Long before synthetic resins were developed,
most paints and varnishes were based upon
vegetable oils such as linseed, pure or modified.
When oils alone were used the resultant products
tended to take a very long time to dry and the
films remained relatively soft for long times. In
addition, they were not always easy to apply being
low in viscosity and the films, by remaining soft
and/or sticky, retained dirt, tended to discolour
and suffered mechanical damage easily. Thus, in
order to produce better and more durable films,
these oils required modification with natural or
fossil resins or other substances. At the same
time methods of modifying and thickening the oils
by heat treatment and the use of reactive
pigments were also devised.
Synthetic Resins
Alkyd resins first came into use in the 1920s
when a plastic material was prepared by the
reaction of glycerine with phthalic anhydride.
These were made and used by the General
Electrical Company of USA for electrical
2
applications, particularly wire insulating varnishes.
“Glyptal” was a registered trade mark and so the
term “alkyd” came to be generally used. This was
derived from the chemical terms for the reacting
products. “Al” was from alcohol and “kyd” (i.e. cid)
from acid. This is explained from the fact that in
chemical technology, glycerine is an alcohol. The
acid refers to the phthalic component referred to
as phthalic anhydride; this, in effect, is phthalic
acid with water removed.
It was not long before methods of modifying these
alkyd resins with oil were found and so gave us
the oil modified alkyds as we know them today.
The term “alkyd” is now used to cover all similar
resins where other alcohol types similar to
glycerine are reacted with other organic acids
similar to phthalic.
As the terms can be, and often are, used loosely,
perhaps further definitions are necessary. In
technical terms a true alkyd is also a polyester
but in trade terms “alkyd” is mostly used to
describe the oil modified material and “polyester”
is generally used to describe what are in technical
terms, unsaturated polyesters in styrene or
similar reactive solvents, or saturated polyesters
either as solutions in organic solvents or in solid
form. Unsaturated polyester resins are cured by
the use of suitable catalysts e.g. organic
peroxides at ambient temperatures; saturated
polyesters are either cured by reaction with amino
or isocyanate containing resins or applied as dry
powders. These types are usually cured by heat at
100–180°C.
Unsaturated polyester resins are used with glass
fibre to make such things as roof sheets, boats
and other plastic objects. The relations of the
early alkyds can be found today in fabrics, threads
and films which are called polyesters. These are
based on similar polymers but which are
thermoplastic and can be moulded and formed
using the property of being softened by heating
and hardening again on cooling.
In some parts of the world, when coatings refer to
“an alkyd” they generally mean the oil modified
resin; however, when resin technologists refer to
“the alkyd” they generally mean the polyester
component.
Vegetable Oils
To obtain a better understanding of oil modified
alkyds, we need to have some knowledge of the
oils used. In the coatings industry they are all of
vegetable or animal type, and they are divided into
the three broad categories:
a) Drying or oxidising;
b) Semi-drying or semi-oxidising;
c) Non-drying or non-oxidising oils.
If an oil can be oxidised it has drying properties.
Oxygen in the air solidifies suitable oils by reacting
with them and converting them from a liquid to a
solid form. Thin films of these oils spread on a
surface can thus act as varnishes, although the
drying would be very slow, the surface tacky and
the film soft. Semi-drying oils are used to impart
special properties to other oils while non-drying
oils are used to produce special paints which are
prepared by mixing with other materials. To make
these oils suitable for use in paints and varnishes
they need to be suitably modified. This was the
basis for the development of oil modified alkyds.
The different oils are used or blended to maximise
their potential and obtain optimum properties. As
is often the case in the surface coating industry, it
is a question of compromising and balancing to
optimise the end results. Thus, for example,
properties such as yellowing tendencies are
traded for hardness and speed of drying.
Chemists also refer to these oils as unsaturated
or non-saturated, partially saturated and saturated
in the same order as above, so these terms will
also be encountered.
What is an oil? Chemically, it is known as a
triglyceride and is considered to be the result of
combining one molecule of glycerine with three
molecules of what are known as “fatty acids”. As
this, again, is a term which will be used often,
some understanding of what is meant will be
useful. To achieve this, some understanding of
organic chemical reactions is required.
Basic Chemistry
There is no need to worry! The chemistry required
involves only three elements, carbon, hydrogen
and oxygen. It is only the permutations and
combinations of these three elements that make
the differences in most of the chemicals which
concern us for the moment. The construction of
these chemicals can be looked upon as having the
same attributes as toy building blocks which can
be linked together with sticks, each block having
a distinct number of holes or connections.
 3

To begin, an understanding of what is meant by a Butane is C4H10

molecule is required. First a definition of an atom
is required. An atom is the smallest particle of any
single element found in nature which can be H H H H
identified as forming part of any substance and
H C C C C H
taking part in a chemical reaction. When several
atoms join together chemically, either with like
H H H H
atoms or those of other elements, to form
another stable substance or compound, this is
called a molecule. Formic acid (found in the stings of ants) is
H2CO2 or (HCOOH) or
For example water is often referred to as H2O,
that is, it is made up from two atoms of hydrogen
– chemical symbol “H”, combining with one atom H
of oxygen – chemical symbol “O”.
H O C O
It has the chemical structural formula:
Counting up the valency bonds on all these
H O H structural formulas will show that the bonds are all
used up or satisfied.
As can be seen, two hydrogen atoms are
connected to one oxygen atom. It is found that various specific arrangements
keep appearing and repeating and it is these
It will be noted that an oxygen atom has two arrangements which are used to typify the various
points at which other atoms can be attached while compounds into special categories.
hydrogen has only one. These points are called
“valency bonds” and so it can be seen that Looking at some examples:
oxygen has a valency of two while hydrogen has a Ethyl alcohol is C2H60 , (C2H5OH)
valency of one.
There is one other element of concern and that is H H
carbon. This has a valency of four – that is it can
join up with four other valency bonds from other H O C C H
elements.
A look at some compounds will illustrate this H H
further.
Carbon dioxide consists of one atom of carbon
Glycerol (glycerine) is C3H8O3
and two atoms of oxygen; this formula is written
CO2 and shown structurally as:
H
O C O H C OH
Again each bar in this example represents a
valency bond. H C OH
Similarly methane (marsh gas) is made up of one H C OH
atom of carbon and four atoms of hydrogen i.e.
CH4, or, when shown structurally:
H

H A check of the valency bonds shows that the rule

holds.
H C H
Glycerol, also known as glycerine, has more than
H one hydroxyl (OH) group and so glycerine and
compounds like it are known in general as
4
“glycols” or in other words “glycerine like
alcohols”. As they have more than one hydroxyl
group they are also referred to as “polyols”
In the above formulae it should be noted that
there is no longer a line (bond) between the O and
the H atoms; they have just been written –OH.
This is a simplification but, at the same time, it
indicates to a chemist what is known as an
“alcohol” or “hydroxyl” group. Chemists know that
if this group is present then it can be expected to
react with other chemicals in certain ways and the
end result of any reactions can generally be
predicted.
This, it is hoped, also explains the formula given in
the brackets above in which the –OH is treated as
if it were a separate entity.
There are other groupings which can be similarly
interpreted.
Looking at organic acids, formic acid, shown
earlier, is the simplest with the structural formula.
H
H O C O
For the sake of simplicity it is usually written
H–COOH
The –COOH group is known as an acidic or
carboxylic group.
The following are other examples of acidic
substances.
Acetic acid: CH3COOH
H nature and effect of the double bond must be
or H C COOH
H have had the carbon atoms joined to each other
Butyric acid: C3H7–COOH
H H H
or H C C C COOH
H H H
Note that the number of carbon atoms combined
with the appropriate number of hydrogen atoms is
increasing. In other words, the compounds are
different only because of the number of –CH2
groups, They have a general formula of:
H–(CH2)n–COOH
where “n” is the number of –CH2 groups in the
chain.
Another form of chemical shorthand can be used
to show these types of acids in a general way.
The part containing the main carbon-hydrogen
groups is given the shorthand form “R”. In this
way these acids can be written down as
R–COOH.
If, in a reaction, other groups need to be
designated and/or it is necessary to indicate
differences but not in precise detail, then these
additional groups can be designated R1, R2, R3
and so on.
In the case of the fatty acids, the number of
carbon atoms in the chain is quite large, for
example lauric acid (C11H23)COOH, myristic acid
(C13H27)COOH and palmitic acid (C15H31)COOH.
The fatty acids of most interest are usually around
C18 but the number of hydrogen atoms now starts
to vary and some more chemistry is needed to
see how this affects the issue.
It is interesting to digress for a moment and
remark on the fact that in nature these acids
always occur with an even number of carbon
atoms in total, one in the acid group and the
remainder in the radical.
In order to examine the chemistry of fatty acids a
little more closely, another division based on their
structure needs to be made. To deal with this, the
introduced.
It has been established that carbon has four
valency links. All the compounds so far discussed
by one bond, They can, however, join together
with two bonds (double bonds). The simplest
example of this is ethylene, C2H4
H H
or C C
H H
Perhaps, showing the four bonds coming out of
the carbon at sharp angles to each other will give
 5

a better concept. The bonds would then look like There is another variation in unsaturated fatty
this: acids which must be mentioned – they can be
either conjugated or non-conjugated. In the
H H conjugated form two double bond linkages are
separated by one single bond link e.g.
C C
H H
H H H H H H H H
This illustrates a system under tension and so
etc C C C C C C C C etc
serves as a reminder that when the double bond
is shown, it can be equated with an instability or a H H H H
greater readiness to react, given the right
conditions, than the much more stable single conjugated
bond linkage. It should now be apparent as to why
the differences in the number of hydrogen atoms When they are separated by more than one single
mentioned above comes about. As the double bond linkage they are non-conjugated e.g.
bonds satisfy their valency requirements there are
no sites for the hydrogen atoms to attach
themselves. H H H H H H H H H
etc C C C C C C C C C etc
Fatty Acids
H H H H H
These are divided into two main categories
“saturated” and “unsaturated”. There is no
“partially saturated” group; this only refers to the non-conjugated
unsaturation in the oil arising from mixtures of Oils containing conjugated fatty acids are more
saturated and unsaturated fatty acids. What is reactive towards oxygen and therefore tend to dry
meant here is that the main chain of the fatty acid better and faster than do non-conjugated fatty
has either got double bonds in its backbone acid containing oils. Conjugated oils also tend to
(unsaturated), or it has not (saturated). react under heat more easily. In other words,
For example, following earlier comments on the double bond
being under stress, when they are in close
juxtaposition, the tension, as might be expected,
H H H H H H H H H
increases and the system becomes more
etc C C C C C C C C C etc reactive. This ties in with the previous comments,
as the more reactive resins can also yellow more
H H H H H than the less reactive ones and thus careful
choice is needed to optimise the properties.
which is unsaturated, or
Glycerides
H H H H H H H H H Having discussed fatty acids and glycerine, an
explanation of what constitutes an oil can be
etc C C C C C C C C C etc
made. Chemically these oils are referred to as
triglycerides and occur naturally. They can be
H H H H H H H H H
synthesised in the laboratory or industrially but
with difficulty hence there is little incentive for
which is saturated. anyone to do so. Certain fatty acids can be
References are often made to the degree of synthesised and modified but these have special
unsaturation. This refers, in this context, to the uses and are not converted into oils as we
number of double bonds in each fatty acid chain; normally know them. The processes used in
these are classified as high, medium or low. With industry are usually the reverse of this; the oil is
edible oils the term “poly-unsaturated” is also being chemically split to produce glycerine and
used to describe oils with several double bonds. fatty acids.
6

For a better understanding of the process, we will eleostearic acid being conjugated is much more
consider the reaction where three molecules of reactive than linolenic acid.
fatty acid join with one molecule of glycerine and
split off water to form one molecule of oil. Typical analysis for various oils and fats is given
below:
The reaction is as shown below:
Table 2: Fatty acids in oils/fats
H Fat/Oil A B C D E F G H Others
O (see Table 1 for names of fatty acids)
H C OH HOOC (R) H C O C (R)
O Olive oil – – 14 2 64 16 2 – 2
H C OH + HOOC (R) H C O C (R) +3H20
Peanut oil – – 6 5 61 22 – – 6
O
H C OH HOOC (R) H C O C (R) Soya bean
oil – – 11 4 25 51 9 – –
H H
Sunflower oil – – 11 6 29 52 2 – –
glycerine fatty acids triglyceride water Corn oil – – 10 4 34 48 – – 3
(1 mol) (3 mols) (oil) (1 mol) (3 mols)
Linseed oil – – 6 4 22 16 52 – –
Tung oil – – 4 1 8 4 3 80 –
The oil formula shown is a general one where (R) Palm oil – 1 48 4 38 9 – – –
is any fatty acid chain with around 7 to 21 carbon
Palm kernel
atoms as normally encountered in the coatings
oil 51 17 8 2 13 2 – – 7
industry. The fatty acid chains do not have to be
the same, and rarely are in nature, thus the Coconut oil 44 18 11 6 7 2 – – 12
formation of an infinite number of different oil Rubber seed
molecules or triglycerides is possible. oil – – 8 9 30 33 20 – –

A definition based upon the composition of an oil Beef tallow – 2 32 25 38 3 – – –

is difficult and for this reason an oil is usually Lard – 1 30 18 41 6 – – 4
defined chemically on the basis of the fatty acid Human fat – 3 25 8 46 10 – – 8
components. In the case of the natural oils, the
fatty acids found in them, although of similar type,
vary in quantities depending upon factors such as This table gives a comparison of the various oils,
as climate, fertilisers used and soil types. many of which are commonly used in coatings.
Three fats have been included as a matter of
Table 1: Typical fatty acids
interest. The difference between fats and oils is,
Key Formula Unsaturated Name as can be seen, very small; most fats tend to be
A C11H23COOH Lauric acid solid while oils tend to be liquid. Saturated oils
also tend to be solid. In industry unsaturated oils
B C13H27COOH Mystistic acid
are reacted with hydrogen to remove the double
C C15H31COOH Palmitic acid bonds and so “harden” them. This is how
D C17H35COOH Stearic acid vegetable oils are made into solid cooking fats
and margarine.
E C17H33COOH – 2H Oleic acid
The compositions of the oils given above are
F C17H31COOH – 4H Linoleic acid
called “typical” due to the differences, sometimes
G C17H29COOH – 6H Linolenic acid quite wide, between different crops of oils, hence
H C17H29COOH – 6H Eleostearic the figures can only be averages. As quite often
(conj) acid happens with vegetable and other natural
agricultural products, the quantity and
composition varies, not only in crops from various
The entries under unsaturated means that for parts of the world, but also in the same location
every two hydrogen atoms less as shown, there is due to climatic and soil effects. Oils with
one double bond. Fatty acids G and H have the unsaturation can be checked for the amount of
same basic formula but the structure is different – unsaturation by reacting them with iodine. Iodine
 7

has the property of reacting with the double bond H H

as oxygen would. By analysis the chemist can
easily determine this quantity and give a result H C OOC(R1) H C OOC(R1)
known as the “iodine number”. This “iodine
number” is therefore used as a measure of the H C OOC(R2) H C OOH
drying potential as well as providing a quality
standard for each batch of oil. With conjugated H C OOH H C OOH
oils this value is not reliable as an indication of
unsaturation. H H

di-glyceride mono-glyceride
Polyols
Next we consider the role of glycerol and other Other alcohols in addition to glycerol are often
alcohols in the alkyd process. You remember used; one of these is pentaerythritol. This, as can
initially it was stated that a true “alkyd” is a be seen from the structural formula, is similar to
reaction between an alcohol and an acid to give a glycerol but has four –OH or hydroxyl groups.
polyester. For many coatings, in order to produce
a suitable product it has to be modified with an H H
oil. The difficulty is that the oils will not react with
the alkyd or polyester itself so a different OH C H H C OH
approach is needed. The acid will react with the
–OH groups of the glycerol but as there are no C
suitable groups on most oils to react these have
to be provided.
This is done by reacting the oil with some extra OH C H H C OH
glycerine to form a monoglyceride or partial ester.
When a molecule of glycerine reacts with a H H
molecule of oil a fatty acid group changes places
i.e. one fatty acid group will leave the oil and pentaerythritol
attach itself to the glycerine. The result is a
mixture of a molecule of glycerine with one or two This will give reactions very similar to glycerine
fatty acids attached. The first is a true but because of the structure, generally tends to
monoglyceride and the second a diglyceride. give resins with improved properties.
There is also some unreacted triglyceride and
glycerol. It is often used in conjunction with ethylene glycol
which has a structure:
In spite of the existence of diglycerides and other
components the reaction product is called a
H
monoglyceride or partial ester.
OH C H

H H OH C H

H C OH H C OOC(R1) H
Ethylene glycol is similar to glycerol but with only
H C OH H C OOC(R2) two –OH groups. Alkyds using a mixture of
pentaerithrytol and ethylene glycol are usually
H C OH H C OOC(R3) referred to as penta-glycol alkyds. This blend is
often used to replace glycerol when the price
H H relationship allows. Processing can be more
complicated due to the lower boiling point of the
glycerine triglyceride (oil) ethylene glycol which can lead to additional
losses.
8

Alkyds to give:
The Monoglyceride Process
In the manufacture of an alkyd by the
monoglyceride process the mixture of oil and
polyol is heated together with a catalyst. A H H H H H H
O O
catalyst is defined as a substance which, while it C C
does not take part in the reaction itself, helps the H C C C O O C C C H
reaction to proceed more quickly in the required O O H H O OH
direction. Catalysts are often compounds
containing such metals as lead, sodium, calcium O C C O C O
or zinc. Lead containing catalysts, although very
efficient, are now replaced by catalysts involving (R1) (R2) (R3)
less toxic metals.
Further reaction
Some of these catalysts e.g. lead can later react possible
with phthalic anhydride giving a hazy product
which is difficult to filter clear. Most catalysts are Water is split off in the reaction.
poisoned by pththalic acid left in the reactor, The above is a simplified representation of the
resulting in inefficient conversion to the basic component of an alkyd polymer.
monoglyceride. To prevent catalyst poisoning it is
The compound shown above still has an
necessary to ensure that the reactor is thoroughly
unreacted hydroxyl group. It is possible for this
drained of the previous batch of resin; in some
group to react with another acidic group e.g.
instances a wash out may be required.
phthalic anhydride and in this way two of these
Having made a monoglyceride this can now be groups could join together with another molecule
reacted with phthalic anhydride to get our finished of phthalic anhydride to form one polymer.
alkyd.
If the two glycerides were both monoglycerides
As previously mentioned, phthalic anhydride is an which is more usual, and not monoglyceride and
acid from which water has been removed thus: diglyceride as shown, it is possible for the
reaction to go on indefinitely. Unless this is
avoided, by careful formulation and good
C O C O operating control on the plant, gelation could
C C C C C C occur, referred to as a ‘gel’.
OH
O
C C C OH C C C
C O C O The Fatty Acid Process
Another way of making an alkyd resin is known as
the fatty acid process. In this case the fatty acids,
This will react with the glyceride mixture: glycerol and/or pentaerythritol, and phthalic
anhydride can be added together. There is no
need to first produce a monoglyceride. As fatty
acids are mostly made by splitting oils in the first
H H place, this could entail extra processing by the
fatty acid manufacturer. Fatty acids are generally
H C OOC(R1) H C OOH more expensive than oils – this increase raw
material cost is offset to some extent by shorter
H C OOC(R2) H C OOC(R3) processing time and a one-stage process.
H C OOH H C OOH However, a considerable quantity of fatty acids
are produced in the refining of oils for edible and
H H other purposes and so are often available at
competitive rates. This process has its place
where special resins have to be made or where
di-glyceride mono-glyceride the processing time needs to be shortened. Also
 9

the resin does not contain additional glycerol However, in the case of xylene there are three
which may be a disadvantage in some possible combinations:
formulations. There is one exception which is tall
oil fatty acids. This material comes from pine CH3
trees used in pulp and paper making and is only
available in the form of fatty acid and never as a
triglyceride. CH3 CH3
CH3
The Acid Component
In the case of acids the most commonly used is CH3 CH3
phthalic acid which is used in the anhydride form.
This in chemical terms is ortho-phthalic anhydride. ortho- meta- para-
There are three types of phthalic acid and to xylene xylene xylene
understand the difference the structures of these
molecule must be considered.
The fundamental or basic part of the phthalic acid
It should be noted that in the ortho form the –CH3
molecule is the benzene ring which has six carbon
groups are attached to carbon atoms adjacent to
atoms and six hydrogen atoms arranged in a
each other in the ring, in the meta form there is
hexagon arrangement.
one atom between the groups and in the para
form two.

Although they all have the same number of carbon

or and hydrogen atoms they have differences,
especially when reacted further to make the
phthalic acids, and we get:

benzene
The second version shown is the shorthand form
often favoured by chemists. It indicates the fact
that it is not known where the double bonds really
are. It might be expected that with all these
double bonds, this would be a very reactive
substance. This is not the case, and in the ring
structure we have a very stable condition.
From benzene, the next product which can be
derived is toluene (sometimes called toluol) –
where one –CH3 group replaces one of the
hydrogen atoms. The next in the series is xylene
(or xylol) which has –CH3 groups replacing two of
the hydrogen atoms. It should be obvious in the
case of toluene that it is immaterial to which
carbon atom the –CH3 group is attached – there is
only one form it can take.
CH3
toluene
COOH
COOH COOH
COOH
COOH COOH
ortho- meta- para-
phthalic acids
This difference in structure is called isomerism
and the chemicals are referred to as isomers of
each other. From this it should be apparent that
as we add monoglycerides to the acid groups
they will all point out in different ways resulting in
different products which will perform differently.
If the previous explanation of the formation of the
anhydride from the acid given earlier is
considered it is fairly obvious now why only the
ortho version can be made into an anhydride. This
can only be done with acid radicals which are on
10
adjacent carbon atoms. Thus neither the para or
the meta forms can be made into an anhydride.
The mechanism, as shown earlier, is:
O O
C C
OH – H2O
O
C OH C very stable but those in maleic are readily
O O
So far as the commercial availability of phthalic
acid is concerned, the ortho isomer is
commercially available in the form of phthalic
anhydride, iso-phthalic acid, which is mainly meta
isomer and tere-phthalic acid, which is essentially
the para-isomer, and are used to make special
polymers for plastics, coatings, powder coatings,
packaging films and polyester textiles.
Without delving too deeply into the subject it
should be noted that phthalic anhydride reacts
more easily and faster as it gives off less water of
reaction than the phthalic acids which require
more water removal. This results in a slower,
more difficult reaction with a lower final yield of
product. The structure of the final polymers tend
to be different and the resins using iso-phthalic
materials have specific properties.
There are two other acids which are isomers of
each other and which are of interest. These are
maleic and fumaric acids. These do not have a
benzene ring but have a double bond between the
two carbons atoms in their back-bone.
H C COOH COOH C H
H C COOH H C COOH
maleic acid fumaric acid
As with ortho-phthalic acid, maleic acid can be
dehydrated to form an anhydride. This does not
happen with fumaric acid due to the position of
the two acid groups.
O O
H C C H C C
OH
O present. Short is greater than 36%, medium has
H C C OH H C C 27–36% and long has less than 27%. As the
O O
maleic acid maleic anhydride
Again the prior removal of part of the water
makes maleic anhydride a much more reactive
form than either of the acids.
By combining these acids into a resin a reactive
double bond can be introduced into the system.
The double bond in the benzene ring of phthalic is
available for further reactions. The use of these
acids is limited in oil modified systems but used
extensively in unsaturated polyester formulation.
Variations
Having covered the essential chemistry
background of the oil modified alkyds,
consideration must now be given to the possible
variations.
Whilst it is possible to use acids other than
phthalic this is less common and so far as the
simpler forms of phthalic based resins are
concerned, the variations are usually confined to
changes in the ratio and the type of oil and polyol
used.
Other acids such as adipic are used when special
flexibilising or other characteristic are required.
Generally, the less oil used in an alkyd the higher
the viscosity and, depending upon the kind of oil
chosen, variations in the hardness or toughness
and drying characteristics of the film are
produced. The proportion of acid to total polyol,
which includes that contained in the oil, is in a
fixed proportion (in a true “alkyd”), but the ratio of
oil can be varied. The amount of excess polyol
over the theoretical amount is increased as the
amount of oil or fatty acid is decreased.
The amount of oil contained in an alkyd is called
the oil length. As the oil length is decreased it
gives changes in the solubility of the resin in
solvents, and stronger solvents are usually
needed.
Oil modified phthalic based alkyds are generally
classified into the broad categories of short,
medium or long oil. Because of the differences in
the size of the oil molecules and therefore the
number of molecules in a given weight, the
definition is often based on the amount of phthalic
quantity of polyol is constant in relation to the
amount of phthalic used, the phthalic quantity
gives an excellent definition.

The choice of the type of oil in the alkyd has a
considerable affect. Those made with drying or
semi-drying oils are used to make the usual
household and industrial air drying coatings.
Those formulated on non-drying oils will not dry on
their own and must be blended with other film
formers or cross linking agents. They are usually
mixed with other types of resins such as
melamine or urea formaldehyde and baked in an
oven when the two resins react together. These
are the basis of baking or stoving enamels which
are used on such things as industrial light fittings,
filing cabinets, type-writers and tools where long
air drying times in the manufacturing process are
not desirable.
Special resins from both categories are used with
nitro-cellulose as are similar resins for automotive
and industrial coatings. It is not possible to go
into the end uses of alkyds in detail as this is
another complex topic.
There are other alkyd resin variations known as
modified alkyds. These are alkyds which are
reacted or modified with rosin, phenolic resins or
other special substances. Other resins for more
sophisticated uses are also being made using
epoxy and other copolymers but discussion on
these is outside the scope of this work.
Earlier, the way the alkyds and polymers were
formed has been outlined and how this is
controlled by correct formulations was discussed.
These reactions must always be taken to the point
where most of the acid has reacted. This is known
as the acid value and is determined as the
reaction proceeds. The formulation gives a
viscosity specification at a given acid value.
Usually the reaction is monitored by determination
of acid value and viscosity values with time – the
acid value decreases and the viscosity increases
with reaction time. This will vary with the amount
of oil present and will also vary with the type of oil
used. Some of the more reactive oils, those with
unsaturation in particular, cross link on their own
and so contribute to the viscosity. In the case of
H H
H C C H
etc O C C C
O O
11
china wood oil (tung oil) this reaction can be very
fast and special care is required whenever they
are used to prevent gelation.
Although these resins are often made in the 100%
form, sometimes known as base resin or solid
forms, for most purposes they are supplied
thinned in solvents. Usually the resin is poured,
once it is in specification, into an appropriate
solvent often contained an an ancillary kettle or
reactor. For most paint manufacture it is easier to
handle resins as a pourable or pumpable liquid.
Saturated Polyesters
Polyester resins used in surface coatings may be
saturated or unsaturated types. The reaction is
similar to that of the alkyds but without the oil;
sometimes the saturated polyesters are known as
oil free alkyds. Similar acids and polyols may be
used and the resins formulated to give either
excess hydroxyl or acid groups which may be
crosslinked, often with suitable curing agents.
We first look at the saturated resin types. This
introduces the principles and should help avoid
possible confusion between saturated and
unsaturated resin types.
The simplest saturated polyester is used for
polyester plastic materials such as Terylene. In
this we react a glycol with tere-phthalic acid. This
is a true direct descendent of the original alkyd.
e.g.
H H
C C tere-phthalic acid
H H
OH OH
OH C C OH
ethylene glycol
O O
This splits off water and gives the polymer:
H H H H
H C C H H C C H
C C C C C C etc
O O O
12

Here only two phthalic units and three glycol units earlier, unsaturation is built into the system by the
are shown reacted together. The resultant use of acids such as maleic anhydride.
polymer can go on increasing in length indefinitely
An unsaturated polyester resin will result if some
providing as there are both acid and alcohol
of the phthalic acid is substituted with maleic acid.
groups available and that the reaction conditions
Mainly because of cost and simplicity, most of the
are maintained. It must be appreciated that this is
general purpose polyester resins use phthalic
an over simplification and is intended only to show
anhydride and maleic anhydride. As both
the principle.
substances are anhydrides and already
Reducing this reaction to its simplest terms – if dehydrated, there is less water of reaction to be
there is an excess of glycol or an excess of acid removed.
the reaction will stop. The reaction is also
With these materials, the result would be as
dependent upon heat to split off molecules of
follows:
water which must be removed from the reacting
mass to maintain the process.
This resultant product is a true thermoplastic, i.e.
ethylene glycol
it softens when heated and hardens again on
cooling – this can be done repeatedly. H H
Variations on this type of formulation, as
previously stated, are thinned in suitable solvents H C C H
and cured by the addition of amino resins or other
curing agents . These now find applications in OH OH
many areas of the coatings industry, typical end
uses being for can coatings, domestic appliances, O
O O O O O
light fittings, etc. One reason why saturated
polyesters are increasing in use is that without the C C C C
addition of oil, the initial colour and colour
retention is much better than with conventional C C
alkyds. These are sometimes referred to as oil-
free alkyds. H H

maleic anhydride phthalic anhydride

Unsaturated Polyesters
In the case of unsaturated polyesters, the acids
are chosen so that there are reactive points on
the chain and so that degrees of flexibility and Which, after splitting off water gives the polymer
chemical resistance can be built in. As mentioned below:

H H H H H H H H

H C C H H C C H H C C H H C C H

OH O OO O O O O OO O O OH
C C C C C C C C
O O O O
C C C C

H H H H
 13

Note: The polymer shown has an acid group on control of the temperature must be kept during
one end and a hydroxyl group on the other and this operation and the very hot resin poured slowly
can therefore react with other groups or similar into the styrene. The base resin can only be partly
polymers at either end. The result can be very cooled before pouring into the styrene due to the
long chains of the structure: increasing viscosity as it cools down. These
resins are normally solid at room temperatures.
– (acid) – (glycol) – (acid) – (glycol) – (acid)
Polystyrene itself is made by polymerising
The actual acids in the chain have not been
molecules of styrene with each other to form long
defined; this depends entirely on the ratios put in
chains; this process is known as co-
by the formulator. All that has to be done is to
polymerisation. Unsaturated polyester resins in
ensure the relative number of molecules of glycol
general use in the glass reinforced plastics (GRP)
and acid required are present. In actual fact an
industry are generally supplied as described
excess of glycol helps to avoid ending up with
above dissolved in styrene monomer, in a similar
several very big molecules and an unstable
way that alkyds are diluted with solvents. With
product. Thus the formulator balances the acid-to-
unsaturated polyesters special catalysts
glycol ratio to obtain the desired polymer. This is
(peroxides) are added to the resin solution just
indicated by the viscosity/acidity relationship after
before use – this polymerises the styrene
most of the acid has reacted, as previously
monomer and resin together to form a solid
described for alkyd resins.
plastic. Because of this crosslinking and chemical
Having decided on how many molecules of acid bonding these plastics are not thermoplastic and
and how many molecules of glycol are needed, the heat will not cause them to soften.
formulator must also decide how many molecules
To sum up, saturated polyesters are unreactive
of each acid, such as phthalic and maleic, are
compounds which can be heated until they
needed. The higher the proportion of unsaturated
become liquid, then mixed with other ingredients
acid used the higher the reactivity of the resin. The
such as fillers, fibres, pigments etc. then extruded
terms “high”, “medium” or “low” reactivity indicate
or moulded while hot. Upon cooling they hold the
the proportion of acid such as maleic used in the
shape of the moulded article. They thus fall in the
formulation, and thus the number of double bonds
same category as other thermoplastics such as
in the polymer chain which can be crosslinked to
nylon, polyethylene, polypropylene and
produce the final end product. In order to give
polystyrene.
special properties to the final resin, which will in
turn give special properties such as flexibility to Unsaturated polyesters are supplied in a liquid
the cured plastic, other acids and glycols may be form and can be mixed with fillers, glass fibre and
used in a formulation. pigments. By adding a suitable catalyst and using
special moulding techniques they are made to
Once the basic unsaturated polyester has been
cure and form solid plastic shapes which are not
made, it is dissolved in what is called a reactive
softened by heat. In actual fact the curing action
diluent, or reactive solvent, such as styrene,
of the catalyst does produce some heat. Heat is
methyl methacrylate or vinyl toluene. A reactive
often used to speed up the curing of unsaturated
diluent is a solvent but it will not evaporate to any
polyesters. In addition to the catalyst other
great extent; it will, instead, cure or crosslink with
chemicals called accelerators are added which
itself and the resin to form the final plastic
initiate the polymerisation process and speed up
moulding or shape. It must be noted that at this
the rate of cure. The most common accelerators
stage of the process this procedure must be
are compounds based upon cobalt metal.
carried out with extreme care and control of
temperature. If the temperature of the resin and
reactive diluent blend during the thinning stage Processing
exceeds 70°C and continues to rise there is a In the manufacture of alkyd and polyesters resins,
very grave danger the blend will polymerise to the same broad principles apply for both types of
form a solid mass. In addition the resultant resins. The ingredients are heated up and the
mixture generates an increasing amount of heat, water of reaction extracted. This reaction is called
termed an exotherm, and can lead to a very esterification. The reaction will not proceed rapidly
dangerous incident. Because of this very careful unless the water is removed and will in fact tend
14
to go backwards if water is allowed to return into
the reacting mass.
In all cases certain of the reactants tend to boil
out of the batch and suitable precautions have to
be taken. In addition oxygen has to be kept out of
contact with the reactants as this tends to cause
yellowing of the product. In cases where oxidising
oils are present, oxygen will react with the oil,
causing thickening and at the same time altering
the drying characteristics of the resin. In order to
ensure that oxygen is excluded, an inert gas such
as nitrogen or carbon dioxide is passed through
the reactor. This also has an advantage in that it
assists in removing the water out of the reaction
and reduces the risk of fire.
Before proceeding further with a consideration
and explanation of the mechanism of the
manufacturing process, an understanding of the
effect of heat and the distillation process is
necessary.
Heat
Heat is a form of energy; when something is
heated energy is put into the system. Applying
heat to most things usually means that some form
of change will take place.
There are three basic states of matter – solid,
liquid and gas. In the chemical world, as a matter
of interest, there are only two elements which
exist in the liquid form under normal conditions,
bromine and mercury. All the other liquids are
compounds (combined elements). Water, under
normal conditions, is a liquid; however if heat is
removed – i.e. if it is frozen – it turns into ice, a
solid. If heat is put into it it will eventually boil and
turn into steam – a gas. Heating the ice or cooling
the steam will change it back into water.
When water is boiling the energy going into the
system is used up in converting the liquid into a
gas i.e. the temperature of the liquid will rise to
100°C (the boiling point of water under normal
open conditions at sea level) when it will then stop
rising. Increasing the heat input will not cause the
temperature to rise any further; extra energy will
speed up the process and the water will boil away
more quickly. The steam which is produced can
be carried over and converted ( condensed) back
into water when it gives up its energy to the air or
other coolant around the condenser as it
becomes a liquid once more. This is illustrated by
a simple apparatus in the laboratory:
Condensation
Vapours
Boiling
liquid
Distilled
Heat liquid
source
Simple condensation apparatus
One aspect of the boiling of liquids which is
utilized in processing is the effect of changing the
pressure on the surface either by increasing
(compressing) it or reducing it (applying a
vacuum). If pressure is applied it has the effect of
raising the temperature at which a liquid boils.
Conversely a reduction of pressure will reduce the
boiling point. In the first instance this means that
very high temperatures can be achieved and in
the second water can also be made to boil at low
temperatures e.g. 370° at 218 atmospheres and
20°C at 17.4 mm mercury). Having witnessed
incidents with disastrous consequences,
especially where a faulty thermometer reading
was concerned, a warning that not all liquids boil
or have a boiling point is worthy of note. Some
substances, if heated to excess, will start to
decompose and may react on their own e.g. base
resins or oils.
This pressure effect is utilised in the case of a
boiler. If generated steam is contained, the
pressure builds up which causes a rise in the
temperature at boiling point of the water. Consider
a car radiator – if too much energy is put into the
system and not removed by the fan, then the
system will boil, build up pressure and escape via
the pressure cap or burst the hose! The radiator
on a car is a pressure controlled system and the
pressure cap on the radiator ensures that the
water does not boil at the operating temperature
of the system. Similarly when a liquid boils under
reduced pressure, the temperature at boiling point
will be lower. It boils at a lower temperature and
thus requires less energy. This means that the
energy input to a reaction can be controlled both

by adjusting the heat input and also by controlling
the pressure. It is therefore imperative that during
any of these processes due consideration is given
to both the temperature and the pressure.
Heat and Chemical Reaction
There are two kinds of chemical reaction involving
heat. One which requires heat to be applied to
cause the reaction to take place is called
“endothermic”. A reaction which gives out heat is
called “exothermic”. In certain cases heat is
required to start the reaction after which it will
become exothermic and continue by itself. This
reaction can sometimes be weak – for example,
when reacting phthalic and maleic anhydride with
polyols a certain temperature must first be
reached before the reaction will start. Once
started, the heat input is controlled to maintain
the reaction and various techniques are used to
maintain the balance so ensuring that the reaction
proceeds in the required manner.
Azeotropic Distillation
If a mixture of two different liquids is boiled it is
found that the vapours will mix and distil over
together. The temperature of this vapour will give
an indication of the ratio of the two substances in
the vapour. Thus knowing the temperature of
given mixtures of two vapours, we can, by
controlling that temperature, obtain the required
proportions of the two liquids. This is known as
azeotropic distillation.
Alkyd Manufacture
When the alkyds were first produced
commercially, this was carried out in what were
known as varnish kettles. They consisted of open
vessels of around 500 litres capacity made of
steel, often with a copper bottom, which were
moved on wheels and placed over an open burner.
They were covered with hoods, a thermometer
clamped onto the edge was used to measure the
temperature and stirring was usually done
manually by the operator. All that was required
was to boil off the water and allow the reaction to
proceed; as can be appreciated, this was
accompanied by large quantities of fumes and
vapourised substances – the whole process was
rather crude.
This soon gave way to the use of larger, closed
reactors with electric or hydraulic powered
15
stirrers, which were totally enclosed with the
fumes conducted away to scrubbers. To improve
colour and avoid viscosity increases due to the
presence of oxygen, as mentioned earlier, an inert
gas such as carbon dioxide or nitrogen is passed
through the vessel. If this gas is blown through the
reacting mixture the water of reaction is removed
more rapidly and the process speeded up.
Blowing the gas through the batch however
removes not only the water, but also some of the
polyols and phthalic which are volatile at the
reaction temperature. This can be compensated
for by the formulator by adjusting the proportions
of the ingredients to compensate for the loss.
This method of processing, rarely used these
days, is known as the “fusion” or “paste” process.
In order to remove the water of reaction we can
also add another liquid, which, when it boils off as
vapour, also carries off the water as mentioned
above (see azeotropic distillation). These mixed
vapours can then be condensed and collected. By
choosing the correct liquid – one that does not
mix with water in the liquid state – the mixture can
now be separated into two layers, the lower water
layer decanted off and the original entraining
liquid returned to the kettle. This allows the use of
a closed system as oxygen is excluded due to the
reactor always being full of vapour. By using this
system we can considerably reduce the amount of
inert gas needed. In practice the most suitable
solvent for this process has been found to be
xylene as it has a suitable boiling point and low
water solubility. Other liquids can and have been
used but this is rare. In the case of this process,
whilst it is often referred to as the “azeotropic
process” due to the actual conditions, it is unlikely
that a true azeotropic state is achieved and so it
is probably more correct to use the name “solvent
process”. To process alkyds in this way we need a
reactor similar to that used for the fusion
processes but fitted with a condenser and
separator system (see diagram on page 16).
It is recommended that some inert gas is used, by
passing it through the batch “sparging” or over
the batch “blanketing”. Sparging helps, as in the
fusion process, to remove volatile components;
this flow of gas through the batch can be helped
by blanket gas which creates a flow through the
condenser system, which further assists in
speeding up the process. The use of some inert
gas also provides an insurance against oxidation
due to oxygen entering the system, as it helps
16
Vapour riser
To scrubber
Inert gas
Blanket
Stirrer
Reactor
Sparge
Simple alkyd reactor
maintain a positive pressure within the reactor.
When there is solvent present, sparging can cause
excessive foaming and careful control must be
exercised.
As with the fusion process there is some
volatilisation of components of the batch. During
the monoglyceride or alcoholysis stage, there is
some decomposition of the oil. In the fusion
process these products, along with some polyols,
are carried away through ducting and removed
with a scrubber (water sprays through the vapours
in a specially designed tank). Even with the
solvent process these products are soluble in the
solvent or condense in the condenser or
separator and cause fouling. The polyols are
usually soluble in the water and the formulation
needs to be adjusted to compensate for these
losses.
Phthalic anhydride can also be carried into the
condenser system as a dust during charging in
addition to its distilling over during the process.
Some of this separates out in the condenser and
stays there, especially as it can convert to the
acid due to the water present. While the anhydride
itself dissolves in the xylol and returns to the
Condenser
Separator
Solvent
Xylene
return
Water
To effluent
batch, the acid is insoluble in xylol and so can be
retained. The collection of phthalic in the
separator can be minimised by running the
separator at a controlled temperature. Generally
speaking phthalic losses in the solvent process
are lower than those in the paste process by
something in the order of 4 to 5% but polyol
losses are higher. The design and configuration of
the vapour riser can almost be considered as an
art in itself and many designs are employed in an
effort to minimise problems with foam and
phthalic contamination.
For alkyds the oil, polyol and catalyst are charged
to the reactor with a flow of inert gas and the
system ventilated to a scrubbing system. After
the alcoholysis stage, the phthalic is added. Up to
this point conditions for both the fusion and the
solvent system are the same. From here on the
fusion process would continue vented to the
scrubber and gas flow would be increased as
required. In the solvent system, after the phthalic
addition, the condenser system would be opened,
the scrubber vent closed and the required amount
of xylol added. Part of the xylol is added and the
temperature raised, then more is added until the
required distillation and solvent return is

Temperature
control
Reflux
condenser
Packed column
Inert gas
Blanket
Stirrer
Reactor
Sparge
Simple polyester reactor
satisfactory. Some adjustment of the quantity of
xylol, which may be either addition or subtraction,
is often needed during the running of the batch to
maintain the required temperatures. Both fusion
and solvent processes are controlled by observing
the relationship between viscosity and acidity. As
the quantity of water which will be released is
dependent upon the quantity of acidic
components (phthalic, fatty acids, etc.) reacted, a
measurement of the quantity of water removed via
the separator is a further guide to the stage
reached in the process.
Polyester Processing
In the case or polyester manufacture, there is no
complication from the oil. The greatest problem is
that of losing the glycol(s) along with the water
during the process . To overcome this, a special
type of vertical condenser system is used in place
of the vapour riser and the azeotropic principle
used. The reactor can otherwise be identical to
that used for the processing alkyds. The first part
of this special distillation column is filled with
special rings called packing and is jacketed to
provide both heating and cooling with
steam/water. Surmounting this is a small tubed
17
Condenser
Water/glycol
collection
condenser with water cooling. During the process
a mixture of glycol and water vapours will rise up
this column, and so by controlling the heating or
cooling on the jacket we can ensure that the
temperature of the mix which reaches the top of
the column is controlled. Using the azeotropic
principal and controlling the temperature of the
glycol/water vapour mix at the top of the column,
water can be removed via the condenser and the
majority of the glycol returned down the column to
the batch in the reactor. Measuring the amount of
water removed and the quantity of glycol it
contains gives valuable information for controlling
the glycol losses and ensuring consistent batches
(see diagram above).
Common types of unsaturated polyesters may be
based upon anhydrides such as phthalic and
maleic or acids such as isophthalic and adipic.
When the acids are used a two-stage process is
employed as they are less reactive. First the acids
are reacted with the glycol; once this has been
accomplished more reactive components such as
the maleic can be introduced. When using phthalic
anhydride the simpler one-stage process can be
used as it reacts easily with both the glycol and
the maleic. In the latter stages both these
18
reactions are continued until the majority of the
acid has reacted and the correct viscosity acid
value relationship achieved. Some manufacturing
processes involve the use of solvent processing
once the major part of the components have
reacted.
Finishing and Adjusting the Batch
Both alkyds and polyesters are generally
dissolved in a solvent on the completion of the
process. In the case of the alkyd, it can be
dropped into the solvent at a fairly high
temperature and,as this may cause the solvent to
boil, the thinning tank is usually closed and fitted
with a condenser. In the case of unsaturated
polyesters these are usually mixed with styrene,
and as styrene can polymerise on its own at
elevated temperatures, control of the temperature
during the addition of the resin is critical. The
resin is therefore cooled to some extent before
being poured at a controlled rate so as to ensure
that the thinning tank temperature does not rise
above 60°C. This minimises the possibility that
the material will gel and become solid in the
thinning tank .
Due consideration must always be given to
chemical reaction taking place in the reactor.
Reactors have different geometry – that is size,
heating, cooling, agitation, height and design of
vapour risers and condensers and other factors
such as the temperature of cooling water are all
important. In taking a formulation and process
from another plant it is best to think in basic
principles and re-establish the best conditions. It
is most unwise to take any formulation from one
operation and try to slavishly follow it. Even if it
prolongs the process time initially, go back to
basics – experience is the best way to find the
optimum conditions and all process variations
must be carefully controlled. Most people are
aware of the difficulties encountered in scale up
from laboratory batches – problems even arise
changing from kettle to kettle in the same plant
where the geometry of the units is known.
It must be emphasised that some complex
reactions are possible and an understanding of
the methods used for control must be
understood. Luckily it is not a very frequent
situation where a reaction gets out of control, but
it has happened and will happen again. Runaway
situations have been known to be caused by faulty
thermometers or temperature controllers as well
as by poor operating procedures. Reliance must
never be placed on one single control, and if
things are not going the way they should or
usually do, operators must be trained to stop,
think and take action; if they cannot rectify the
problem or are in doubt they must call for help.
There is one thing however of which you can be
certain in resin processing – it is usually less
costly and much safer to make haste slowly.
If you are unsure or do not understand anything –
ask.
The End Use of Alkyd Resins
General Considerations
Because of their versatility alkyds have become
the workhorse of the solvent-based coating field.
This is demonstrated by the drying mechanism.
Whilst some coatings can be very high in solids
the general rule is that the viscosity of the resins
as supplied is such that they cannot be applied by
normal methods, e.g. brush, spray, roller, dipping,
or flow coating, unless the viscosity is reduced.
For this reason the initial part of the drying
process is solvent loss (evaporation or absorption
into the substrate) – known as ‘lacquer dry’. The
next stage with an alkyd is a chemical change or
conversion of the resin component(s).
These mechanisms are:
● Oxidation – adsorption of oxygen from the air
to polymerise the oil component;
● Elevated temperature cure – cross-linking
when film is baked/stoved;
● Two-pack cure – room temperature curing of
two components mixed prior to application;
● Catalytic cure – addition of a component in a
very small quantity which will stimulate cross
linking.
It will be noted that the first two are single pack
coatings.
Oil-Modified Alkyds
Choice of Oil
Consideration must first be given to the type of oil
used for the modification and then to the oil itself.

The exposure conditions as well as the application
requirements dictate the choices.
A quick resume of oil types gives us:
● Tung, Oiticica – good drying oils but tend to
be too reactive for alkyds except as modifiers
in small quantities. Yellow on exposure.
● Linseed Oil – good drying but tends to yellow,
especially in interior paints.
● Dehydrated Castor (DCO) – drying oil with good
colour retention/ non-yellowing. Generally
expensive. (Better in medium/short oil length).
● Safflower, Sunflower, Soya – semi-drying oils,
generally very similar. Generally flavoured for
decorative/industrial coatings. Choice usually
a question of price/availability.
● Corn, Tobacco Seed, Grape, Poppy – similar
to above, generally a question of
price/availability.
● Fish Oil – drying oil; selection of
grades/qualities available. Can be very
reactive, use with caution.
● Tall Oil – semi drying; selection of grades/
qualities available. Low rosin grades best for
decorative alkyds. Useful for primers.
● Castor, Coconut, Palm, Peanut – non drying,
used in baking coatings and in plasticising role.
The above list is generalized; there are many
other options, especially when fatty acids are
considered.
Oil Length
The oil length defines the ratio of the oil to
polyester. Remember that the polyester has, in
effect, a fixed glycol/acid ratio determined by the
choice of polyol and acid that has reacted
stoichiometrically (fixed ratio). In general the
shorter the oil length the higher the viscosity and
the greater the need for stronger solvents.
The degree of polymerisation can also have an
effect and in this way we can have two alkyds which
differ in viscosity but have the same oil length.
The oil has a plasticising effect – the longer the oil
length the softer the finish.
Modifications
Further modifications of alkyds are also possible.
Common modifications include using styrene/
vinyls, phenolics and isocyanate as well as cold
19
cut mixtures with other resin systems such as
epoxies, isoprene and chlorinated rubber.
Applications
Decorative Applications
Generally these will employ drying oil modified
alkyd. Wood finishing calls for long oil while metal
finishing can utilise medium oil length. In the
domestic market it is not unknown for
manufacturers to use high viscosity, medium
length alkyds in order to keep down the price.
While some may consider such a trick as sharp
practice consider the fact that the customer will
probably not prepare the surface properly and so
the coating will prove adequate.
Industrial Air Dried
Here the medium length alkyd probably comes
into its own. Such coatings, when properly
applied, can have a life expectancy of upwards of
ten years. They can also be supplied in a suitable
brushing consistency but with thinners available to
allow spray application. Machinery enamels as
well as industrial and marine maintenance fall into
this category. Note that in all these cases we
assume proper choice of primer, build coats or
undercoats (usually alkyd-based).
Industrial Baking
The reactions of alkyds with such modifiers as
amine aldehyde give a comprehensive range of
options. While drying oil may be used in specific
cases, the choice of oil is generally non-drying.
The selection tends to be based upon such
properties as colour retention on baking or
exposure, heat resistance and chemical
resistance. An alternative here is the use of oil-
free alkyds.
Speed and temperature of cure, as well as gloss
and hardness, are mostly catered for by the
choice of amine resin.
End uses include can coatings, appliance and
office equipment finishes and coil coatings.
Industrial Two-pack
Two particular finishes come to mind here and
these are cold-cured wood finishes and two-pack
automotive finishes.
The wood finish is essentially a urea resin cured
with an acid such as phosphoric or sulphonic, the
20
alkyd component being more in the role of
plasticiser. These give excellent speed of dry and
are used both as floor finishes and furniture
finishes.
In the case of the automotive industry both
original equipment and repair shops now use two-
pack urethane systems based on an alkyd reacted
with an isocyanate. The quality and speed of
finishing is excellent.
The speed of dry is often improved by force
drying (in a low temperature oven).
Polyesters
Other than in the field of car patching compounds
the use of styrene modified polyesters for surface
coatings has fallen away. The main setbacks are
short pot-life during application coupled with poor
adhesive properties, especially on metals. There
are also problems with gloss caused by the use of
wax to get tack-free finishes, although formulations
have been devised to get around this. Their use in
the reinforced plastic industry is still their main role.
Conclusions
In this short monograph we have attempted to
cover, in simple terms, the broad and complex
subject of resins, their chemistry, applications and
production. We hope you have found this
approach interesting and that it has stimulated
your interest in this most important component of
surface coatings. ■
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22

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
Internet: www.occa.org.uk