UNIVERSITY OF NAIROBI

A TERM PAPER SUBMITTED IN PARTIAL FULFILLMENT OF A

COURSE IN ADVANCED POLYMER CHEMISTRY

TOPIC: AN OVERVIEW OF POLYMERS USED IN PAINT AND

SURFACE COATINGS APPLICATION

By:
NYUMBA ODHIAMBO DAVID
I56/11877/2018
DEPARTMENT OF CHEMISTRY

UNIVERSITY OF NAIROBI

@2018

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I declare that this is my original work and has not been submitted anywhere as per the
DECLARATION and the knowledge of the researchers. Where other people’s work has been
used, this has properly been acknowledged and referenced in accordance with the University of
Nairobi’s requirements”.

NAME
NYUMBA ODHIAMBO DAVID SIGNATURE…………………..DATE……….………..

INSTRUCTOR
PROF. JOHN ONYARI

DEPARTMENT OF CHEMISTRY
UNIVERSITY OF NAIROBI

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CHAPTER 1: OVERVIEW OF THE STUDY
1.1 ABSTRACT
An investigation was carried out to identify the different types of polymers used in paint and
surface coatings and variations of the final products upon modifications of the materials used. The
process of manufacturing paint and surface coatings involves a great deal of understanding various
molecular behavior of paint and surface coatings polymeric matrix. These advance knowledge
helps in developing new and advanced modifications of the super polymers. Every desire of a paint
and surface coating manufacturer is to develop a finished product with a cutting edge technology
capable of meeting and even surpassing the desired objectives and requirements of the final
consumer with little or no additional production costs, there are several processes and material
inputs which accompanies the production of the paint and surface coatings. In contrast to early
man techniques of acquiring paint, the current technological advancement has seen breakthrough
in ways of developing and modifying the final paints and coatings that satisfies the preferences of
the end user. These technological advancement can be attributed to the increase in knowledge of
chemistry behind the properties and factors affecting it thereof at molecular level. Polymer- based
paints and coatings can be considered to be a two-phase composite materials consisting of pigment
and other additives dispersed in a continuous matrix of polymers.

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TABLE CONTENTS

CHAPTER 1.0 OVERVIEW OF THE STUDY….…………………………………….......... 6

1.1 Abstract…...…………………………………………………………….……. 6

CHAPTER 2.0 INTRODUCTION……….………...………………….....……………...…… 10

2.1 Literature Reviews………………….………………………………………... 10

CHAPTER 3 METHODOLOGY…………………………………………………………….. 15

3.1 Study Methodology………………………………………….………………. 15

CHAPTER 4.0 DISCUSSIONS……………………...……………………..………………… 16

4.1.1 Classifications of resins……………….…………………………………… 16

4.1.2 Alkyd resins………………………………………………………………... 16

4.1.3 Polyester resins………………………...…………………………………... 16

4.1.4 Epoxy resin………………………….……………………………………... 16

4.1.5 Acrylic resin………………………………………………………………. 16

4.1.6 Polyurethane resin………………………………………………………... 16

CHAPTER 5.0 CONCLUSION ……………………………...……………………………… 23

5.1 Conclusion…………………………………………………………………… 23

REFERENCES………………………………………………………...……………………… 24

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CHAPTER 2: INTRODUCTION
In the entire history of man, colour has fascinated him regardless of the time or age of his
occupancy on the planet. The clear evidence that colour has been around since time immemorial
is depicted by the prehistoric cave paintings unearthed by archeologists. So it’s true to allude that
the history of paint is as old as the history of mankind.
It’s quite astonishing to note such relationship of mankind with colour yet colour itself is not
the finished product. These products’ main purpose is to enhance the properties of the finished
objects by accentuating its surface features or even by concealing them from view. (V. Mannari,
2015)
It is of great importance to highlight that most surface coatings are based on the synthetic
polymers, which means that they are industrially produced substances which are composed of
extremely large and often interconnected that form tough flexible adhesive films when applied to
surfaces. (Lewarchik, 2016)
Polymers provide the coating film its capacity to adhere to the substrate, its chemical
resistance, and flexibility. In addition, the continuity of the film and in cases of environmental
stresses it gives the coating durability, its gloss properties most of its mechanical and thermal
properties and any chemical reactivity that the film exhibits are dependent on polymer properties.
(Bierwagen, 2014)
These key properties which are exhibited by the polymer are molecular weight, molecular
weight distribution, glass transition temperature (Tg) and solubility. (Bierwagen, 2014)

2.1 LITERATURE REVIEWS

Due to immense advances in knowledge of polymer chemistry, much of the work has often be
geared towards synthesis and developing new polymer matrixes, effects due variations on material
and the characterization pathways. (Derosa, 2008). Just for various reasons such as complex
structures, complex degradation mechanisms and ignorance of polymer science confusion occurs
on polymer basics. (Albertsson, 1995)
Some resins upon oxidative hardening, also release condensation products into the atmosphere
and are as well regarded as volatile part of the paint. As for these reasons paint industry is one of
the most heavily regulated industry in the world due to exposure to volatile emissions in form of
solvents thereby forcing producers to adopt low-solvent and solvent less technologies (Markit,
2017)
The volatile components of the paint constitutes the solvents which are organic in nature, water
and coalescing agents while the non-volatile components comprises of polymeric film forming
agents commonly known as resins, plasticizers, additives, dyes, pigments and extenders.
The huge percentage composition of paint by volume is characterized by solvent and resin. Of
these two, the most important is the resin because it ultimately identifies and determines the

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characteristics and usage of the final product such as the method of application, the drying and
hardening characteristics, mechanical properties and resistance to weathering. (Talbert, 2008)

CHAPTER 3: METHODOLOGY
This article undertakes to review the compositions of different polymers used in paints and
surface coatings and tries to explain the materials input that influences the differences in the final
properties. The study is undertaken under various categories of paints depending on the classes of
material inputs that is used in their manufacture.

4.0 DISCUSSIONS

4.1 COMPOSITION OF PAINTS AND SURFACE COATINGS

To study these amazing facts, it’s important to understand the composition of paints and surface
coatings. Paints are made up of various components which are specifically formulated depending
on the desired properties of the paint, the method of application, the characteristics of the substrate
the paint is to be applied on and economic implications on the production which directly translates
to costs.
4.1.1 CLASSIFICATION OF RESINS
The paint components are classified depending on their volatility. (Lambourne & Strivens, Paint
and Surface Coatings-Theory and Practice, 1999)
To understand the characteristics of the synthetic polymers used in paint and surface coatings, it’s
important to categorize them into six broad groups as follows;
1. Alkyd resins
2. Polyester resins
3. Epoxy resins
4. Acrylic resins
5. Polyurethane resins

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 4.1.2 ALKYD RESINS
These are short –branched polyesters which are products of polycondensation of a polybasic acid
and a polyhydric alcohol reaction in the presence of glycerides oil or oil derived fatty acids. The
wetting properties of the resin is facilitated by the oil and, when unsaturated, it allows coherent
films to be formed on cure but the unsaturation adversely affects hardness, durability color and
gloss retention properties. (Goldschmidt & Streitberger, 2007)
Alkyds synthesis is done from three basic components: Polybasic acids, Polyols and (except
for oil free alkyds) fatty acids. The nature and proportionality of these raw materials in the resin
controls the properties of the resin. (Goldschmidt & Streitberger, 2007)
Alkyds are relatively inexpensive in terms of raw materials and manufacturing costs. They are easy
to pigment and are compatible with most substances used in surface coatings. The alkyds can also be
modified for special purpose applications. (Goldschmidt & Streitberger, 2007)
In comparison with other polymers which may offer individual better properties in some specific
applications, alkyds have widest range of acceptable properties in terms of surface coatings combined
with its costs and versatility.

ALKYD RESIN CLASSIFICATIONS

The various combinations and modifications of raw materials used in the manufacture of alkyd
resins results in different specifications of the resin. However, the following are the ways of classifying
the alkyds.
a) OIL LENGTH
This classification is due to the oil that has been used to manufacture the resin. It depends on
the weight percentage of fatty acid in the resin. The alkyd resin can be referred to as short oil
(<45%), medium oil (<45-55%), or long oil (>55%).
The final properties of the resin is also dependent on the type of the fatty acid used and
determines the classification as either drying, semidrying, and non-drying depending on the
degree of unsaturation in the fatty acid.

b) PHTHALIC ANHYDRIDE PERCENTAGE

The most commonly used raw material in alkyd formulations. There exists an inverse
relationship between the percentage of Phthalic anhydride and the degree of fatty acid
formulation, short oil alkyds have above 35%, medium oil alkyds contain between 20 and 35%
Phthalic anhydride, and long oil alkyds below 20% Phthalic anhydride.

c) ACID VALUE AND HYDOXYL NUMBER

The determination of acid value is based on the milligrams of potassium hydroxide required to
neutralize one gram of resin. In alkyd resin, 0.1 M KOH in ethanol is usually preferred.

ALKYD RESIN RAW MATERIALS

a) Polybasic Acids
There are various dibasic acids which could be used in the manufacture of alkyd resins.
The following are examples.

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 Phthalic Anhydride Isophthalic acid Terephthalic acid

Trimellitic anhydride

The selection of any of the above dibasic acids to be used depend on the desired properties of the
resin. Phthalic anhydride has found wide usage and is a preferred choice because it gives improved
film hardness and chemical resistance than Isophthalic acid or Terephthalic acid. During reaction,
it does not suffer from major solubility problem and reacts at low temperature unlike other
anhydrides.

b) Polyhydric Alcohols

Glycerol Pentaerythritol Trimethylol propane

Glycerol and pentaerythritol are the most widely used polyhydric alcohols. It is important to note
that Glycerol contains two primary and one secondary hydroxyl group and this makes it a choice
in alkyds of all fatty acid and different varieties and modifications based on oil lengths whereas
Pentaerythritol contains four primary hydroxyl groups and this makes it a material of choice in
manufacturing a relatively complex resin with better performance properties like fast drying,
greater hardness, better gloss.
Despite the better properties achieved by pentaerythritol, it is never used in short and medium oil
types because of its rapid gelling properties brought about by its higher functionality.

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 c) Oils or Oils derived fatty acids
It is worth to note at this point that much of the oils used in paint manufacturing comes from
vegetable and to a lesser extent from animals. These are esters of glycerol and fatty acids, they are
non-volatile and unstable at high temperatures.
Fatty acids are large group of compounds consisting of long hydrocarbon chain of above sixteen
carbon atoms and upwards, attached to a carboxyl group and they are present in oil in varying
amounts as glycosides. They are either saturated or unsaturated and in case of unsaturation, they
can be conjugated or non-conjugated.
The oils used vary greatly in properties according to the nature of fatty acids contents present in
their compositions. This is because the degree of unsaturation in the fatty acid determines the
drying properties of a specific alkyd resin.
The fatty acid content of a particular oil is normally referred to as the iodine number and the higher
iodine number of the oil usually translates to the faster drying properties of its resin.
Positioning of the double bonds in the structure of the fatty acid is also of immense importance as
the conjugated bonds results in a much more reactivity in autoxidation than the non-conjugated
ones.
The mostly used among the vegetable oils in alkyd manufacturing is the soya bean oil.Considering
the drying capabilities of the oils, they can be classified as
 Drying oils like Linseed oil, Tung oil
 Semi drying oils like Soya bean oil
 Nondrying oils like Castor oil.

The secret behind the drying nature of oils can be described in comparison between linseed oil and
Tung oil, the difference is that Linseed oil consist of glycerol of fatty acid containing two or three
isolated double bonds whereas Tung oil consists of conjugated unsaturated fatty acid which results
in greater reactivity and drying properties.

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 The Table below from Holmberg, K., High Solids Alkyd Resins. New York: Dekker, 1987
shows vegetable oils and their fatty acid compositions.

Typical Fatty Acid composition(%) of vegetable oils

Vegetable oils

Fatty Acid CAST COCO LINS OLIVE PALM PALM PEA SAFF- SOY- SUN- TALL TUNG
OR NUT EED KERNEL NUT LOWER BEAN FLOWER
C8 Caprylic 6 3
C10 Capric 6 4
C12 Lauric 44 51
C14 Myristic 18 1 17
C16 Palmitic 2 11 6 16 48 8 6 8 11 11 5 4
C18 Stearic 1 6 4 2 4 2 5 3 4 6 3 1
C18 Oleic 7 7 22 64 38 13 61 13 25 29 46 8
C18 Linoleic 87 2 16 16 9 2 22 75 51 52 41 4
C18 Linolenic 3 52 2 9 2 3 3
C18 Eleostearic 80
C18 Ricinoleic
C20 Arachidic 2 2
Source: (Holmberg, 1987)
Nondrying oils contain glycosides from saturated fatty acids which have no drying properties or
may contain small amount of acid with one double bond.
MANUFACTURE OF ALKYD RESIN
The industrial production of alkyds takes place in two stages. Vegetable oil and a polyhydroxy -
alcohol like pentaerythritol are heated first with a catalyst for around two hours at a temperature
of 2700C.
Glycerides oils does not readily react with other raw materials involved in the manufacture of
alkyds since they are tri-glycerides and due to stearic hindrance reactions is greatly affected. Such
hindrances can be overcome by the following technique.
Alcoholysis of oil.
It is a technique where oil is pre-reacted with a polyol to convert tri-glycerides oil into reactive
monoglycerides which can easily take part in polycondensation reaction. This process brings about
an ester interchange between oil and polyol.
Since the vegetable is an ester of glycerol and long chain unsaturated fatty acids, the reaction is a
trans-esterification, the fatty acid forms an ester with the polyhydroxy-alcohol. Di- and tri- esters
of pentaerythritol and di- and monoglycerides are formed in the products.
The mixture is cooled to 1500C and little excess of Phthalic anhydride is added and the mixture is
reheated to 2400C for several hours until the reaction is complete when the alkyd resin is formed.

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Below is a reaction scheme for the Alcoholysis process

The above process is carried out at a temperature range of 2400C-2600C in the presence of a
catalyst like sodium hydroxide. The presence of basic catalyst speeds up the rate of ester
interchange between oil and polyol. The presence of air inside the reactor leads to discoloration of
the final alkyd resin and this problem is solved by conducting the process in an inert atmosphere
of Nitrogen gas.
Acidolysis of oil
This process involves reacting oil with the acid first. It’s normally used only when there is a
problem with reactivity or solubility of dibasic acids. It operates under a higher temperature than
2600C and basic catalyst presence does not affect the reaction rate as would have been expected.
The cycle time is much longer and there is more risk of discoloration and side polymerizations
with process.
Fatty acid process
This process involves the use of fatty acids derived from oils. Fatty acids contain carboxylic groups
which makes them readily react with polyol and dibasic acid, they are all charged directly into the
reactor and the process of polycondensation is begun to produce the resin.
Cost analysis shows that fatty acids are expensive as compared to oils but they have shorter process
cycle time and better alkyds. For a cost effective approach, a combination of fatty acids and oil is
frequently applied.

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 4.1.3 POLYESTER RESIN
A polyester is a polymer compound that has a recurring ester groups (-CO-O-) as an integral part
of the main polymer chain. The polymer forms from the condensation reaction between a polyol
and an acid. When a carboxylic acid with two carboxyl groups is esterified with an alcohol
containing two hydroxyl groups, long chains called polyesters are formed.
A useful and a common type of polyester resin is the unsaturated form although the saturated form
exists as well. The possible acid reactants that are employed in the production of polyester
includes;

 Terephthalic acid
 Isophthalic acid
 Phthalic anhydride
 Adipic acid
And the glycols used include;
 Neopentyl glycol
 Propylene glycol
 Di-ethylene glycol
 Glycerin
a. Saturated Polyester
A saturated polymer is one which has no double or triple bond in its main carbon backbone
chain. The process of obtaining a saturated form polyester resin is by using an excess polyol
(glycol) in the reaction process. They are formulated such that they produce high hydroxyl or
carboxyl contents, as they are mainly used in the production of polyurethanes. The resulting
polymer could be either of a hydroxyl terminated polyester or a carboxyl terminated one. In most
cases the resulting resin is a hydroxyl terminated polyester. (Poilluci & Hansen, 2013)
b. Unsaturated Polyester

This is the most common type of polyester resin. They are referred to as copolyesters, meaning
that they are polyesters prepared from a saturated dicarboxylic acid or its anhydride (usually
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Phthalic anhydride) as well as an unsaturated dicarboxylic acid or anhydride (usually maleic
anhydride). (Ebewele, 2000)
These two acid constituents are reacts with one or more dialcohols, such as ethylene glycol or
propylene glycol to produce the characteristic ester groups that link the precursor molecules
together into long, chainlike, multiple-unit polyester molecules.
The maleic anhydride units of this copolyesters are unsaturated because they contain carbon-
carbon double bonds that are capable of undergoing further polymerization under the proper
conditions. Such conditions are created when the copolyesters is dissolved in a monomer such as
styrene and the two are subjected to the action of free radical initiators. (Ebewele, 2000)

Unsaturated polyester Peroxide

initiator

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 4.1.4 EPOXY RESINS
Epoxy resins are derived from a simple organic compound known as ethylene oxide-oxirane

Most common starting materials for epoxy resins are epichlorohydrin and a diphenol.
Bisphenol A is always the diphenol of choice. This is a base-catalyzed reaction between an epoxide
and a polyhydroxy compound. (Ebewele, 2000)

The reaction is a ring opening polymerization of the epoxide ring, this involves catalysis with a
strong base like sodium hydroxide. The chloride ion is displaced by a nucleophilic attack of the
phenoxy ion and the ring opens. (Ebewele, 2000)

Curing of the linear polymer formed is done by crosslinking either with an acid anhydride in a
reaction with the –OH groups or by an amine, which opens the terminal epoxide rings. (Ebewele,
2000)

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The molar ratio of epichlorohydrin to bisphenol A can range from as high as 10:1 to as low as
1.2:1. This means the resulting resins ranging from liquids to semisolid to solid and varying
molecular weights and softening points (Polymer-science-and-technology.pdf, pg. 69)

4.1.5 ACRYLIC RESINS

Another important category of coating materials is the acrylic polymers. These polymers find
wide use due to their excellence properties of chemical and weather resistance, resistance to
hydrolysis, gloss and colour retention in exterior applications, strength and transparency.
(Lewarchik, 2016)
The word acrylic is used to refer to polymers primarily based on acrylate and methacrylate
esters in their structure as well as with other vinyl unsaturated compounds.

Poly Methacrylate Poly Methyl Methacrylate

(Soft and rubbery) (Hard and brittle)

These polymers are normally used as general purpose coatings, anticorrosive coatings for
metals and as well as wire enamel. Because of their versatility and performance as, they account
for 25% of all coatings and global sales. (Lewarchik, 2016)
There are three broad categories of liquid coatings that utilize acrylic resins in their matrix.
These include, thermoplastic, thermoset and waterborne. These may incorporate other vinyl
monomers in their polymer matrix such as styrene and vinyl acetate in order to reduce cost.
(Lewarchik, 2016)

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Acrylate resins have several advantages over other paint binders:
1. ) Polyacrylates are only slightly attacked by chemicals, and confer a high degree of
resistance to paints
2. ) Polyacrylates are colorless, transparent, and do not yellow, even after prolonged
thermal stress
3. ) Polyacrylates do not absorb above 300 nm and are therefore not degraded by UV
radiation (as long as they do not contain styrene or similar aromatic compounds).
4. ) Polyacrylates do not have unstable double bonds
5. ) Polyacrylates have outstanding gloss and gloss retention
6. ) Acrylates, and especially methacrylates are stable to hydrolysis long as they do
not contain styrene or similar aromatic compounds)
Thermoplastic Acrylic polymers
These polymers generally have excellent properties in exterior durability and therefore found wide
application in automotive exterior coatings. Thermoplastic resins have high level of methyl
methacrylate in their polymer backbone to provide excellent hardness and exterior durability.
Methyl methacrylate as a hard monomer imparts resistance to petrol, UV resistance, and gloss
retention. It is therefore used in copolymers for topcoats, particularly for automotive application.
(Lambourne & Strivens, Paint and Surface Coatings-Theory and Practice, 1999)
Butyl methacrylate is a softer monomer imparting excellent low-bake humidity resistance, but its
plasticizing effect is limited. It gives good undercoat adhesion and solvent resistance and excellent
UV resistance and Ethyl acrylate has good plasticizing properties but as a monomer has a highly
unpleasant and toxic vapour. Its copolymers are fairly resistant to UV and give good gloss
retention. (Lambourne & Strivens, Paint and Surface Coatings-Theory and Practice, 1999)
Thermosetting Acrylic polymers
These types of polymers are specifically designed with functional monomers to either react with
themselves when exposed to heat or moisture, or with that of a cross-linker to form a cross-linked
film. Thermoset resins belong to a group of lower molecular weight and therefore have higher
application solids.
After crosslinking, they offer films with excellent resistance to organic solvents, moisture and UV
light and they do not soften appreciably even when exposed to moderately high temperatures

4.1.6 POLYURETHANE RESINS

Polyurethanes are linear polymers that have a molecular backbone containing a recurring
carbamate groups (-NHCO2). These groups, known as urethane, which is a trade name for ethyl
carbamate, NH2COOC2H5, are produced through a chemical reaction between a diisocyanate and
a polyol. (Bayer, 2014)

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 Ethyl carbamate structure

General polyurethane structure

Synthesis of polyurethanes
Polyurethanes are formed by reaction of polyisocyanates with compounds that have an active
hydrogen:

The following are possible reaction schemes for isocyanate reactions:

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 Equations for preparation, chain extension and curing of polyurethanes
The manufacture of condensed polyurethanes
Urethane oils can be formed by the addition of vegetable oil to the polyurethane. Urethane
alkyds can be formed by reacting isocyanates with alkyds. They cure in the same way as alkyds,
that is, by oxidative crosslinking of the unsaturated groups in the fatty acid portions of the
molecule.
Moisture curing polyurethanes are produced by reaction of isocyanates with polyether or
polyester polyols. Unreacted isocyanate groups are present and these react with atmospheric
moisture to cure the resins by forming cross-linked polyurea- polyurethane structures.

5.0 CONCLUSION
It’s imperative to note from the understanding of the atomic and molecular construction of
polymers gives a lot of information on the various modification that can be undertaken to develop
high performance polymers with super properties.
It is factual that polymer consumption will continue to grow and the range of general purpose
materials will continue to grow hence the demand for cutting edge technologies. This will mean
that sooner the distinction between thermoplastics and thermosets will become gradually thin with
the development of new materials for a more demanding environments than previously witnessed.

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REFERENCES
1. Albertsson, Degradable Polymers, 1995
2. R. Lambourne & T A Strivens: Paint and surface coatings-Theory and Practice,
1999
3. V. Mannari, C.J. Patel: Understanding Raw Materials © Copyright 2015 by
Vincentz Network, Hanover, Germany
4. Ron Lewarchik, Chemical Dynamics: Acrylic Resin Fundamentals, 2016
5. Bierwagen, Gordon P: Surface Coating, 2014
6. Derosa, Thomas F: Advances in Polymer Chemistry and Methods, 2008
7. Bayer, Material Science: Chemistry of Polyurethane Coatings, 2014
8. Ebewele, Robert O: Polymer Science and Technology, 2000
9. Poilluci, Richard A & Hansen, Christian J: Reducing use of Styrene Monomer in
unsaturated polyester resins, 2013

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