Chemistry Africa

https://doi.org/10.1007/s42250-022-00318-3

REVIEW

Review on Solvents Based Alkyd Resins and Water Borne Alkyd Resins:
Impacts of Modification on Their Coating Properties
Ikhazuagbe H. Ifijen1 · Muniratu Maliki2 · Ifeanyi J. Odiachi3 · Oscar N. Aghedo4 · Ewanole B. Ohiocheoya5

Received: 26 November 2021 / Accepted: 13 January 2022

© The Tunisian Chemical Society and Springer Nature Switzerland AG 2022

Abstract
In recent times, attempts have been made to produce eco-friendly sound exceptional resin compounds from natural renewable
resources. Among the diverse renewable available sources, vegetable oils obtained from various seeds are considered the
best natural sources, due to their novel characteristics, worldwide abundance and functionalities. However, the alkyd resins
synthesized from available vegetable oils are still limited in properties. This review focused on the several modification routes
that have been utilized in the synthesis of solvents and water based alkyd resins, the impacts on their coating properties and
challenges of using alkyd coatings. Literature analysis reveals that modifications of solvents based alkyd resins and water-
borne alkyd resins have immensely improved their potential applications in the field of paints and coatings. Properties like
adhesion, drying time, gloss retention, resistance to scratch, chemical resistance capability in various corrosive environments,
thermal stability, flexibility, roughness, hardness, abrasion resistance, mechanical properties, etc., were improved by modify-
ing solvent based alkyd resin and water based alkyd resin with gum rosin, acrylate, n-butyl methacrylate, maleican hydride,
silicon oxide (­ SiO2), titanium oxide (­ TiO2), etc. Also, waterborne coatings have been shown to be a more environmentally
friendly coating when compared to solvent based coatings. However, water based alkyd resin is more eco-friendly than the
solvent based alkyd resin; as a consequence, they emit little or no contaminant that can be detrimental to the environment.

Keywords Renewable resource · Coating performance · Eco-friendly

1 Introduction
The interests of eco-friendly materials by consumer and
industries have increased the usage of environmentally
favourable agricultural sources as feedstock for the gen-
eration of valuable polymers [1–4]. The design of eco-
friendly chemicals has been made from a spectrum of
* Ikhazuagbe H. Ifijen
larylans4u@yahoo.com
1
Department of Research Operations, Rubber Research
Institute of Nigeria, Iyanomo, Benin City, Nigeria
2
Department of Industrial Chemistry, Edo University,
Iyamho, Edo State, Nigeria
3
Department of Science Laboratory Technology, Delta State
Polytechnic, Ogwashi‑Uku, Nigeria
4
Department of Science Laboratory Technology, Faculty
of Life Sciences, University of Benin, P.M.B. 1154,
Benin City, Nigeria
5
Division of Plant Protection, Rubber Research Institute
of Nigeria, Iyanomo, Benin City, Nigeria
natural renewable resources over the years [5, 6]. The earth
is endowed with diverse herbs and plants, lavishly yielding
a variety of bio-based feedstock’s that can be tailor-made to
multiple invaluable materials [7].
Infinite polymeric materials have been prepared from
renewable means such as lignin, starch, wool fibre, vegeta-
ble oils and several others [8]. They can be used in countless
practical functions such as plasticizer, biomedical engineer-
ing, biodegradable packaging materials, adhesives, coatings,
biological appliances and binder for paints [8]. Among sev-
eral renewable resources, vegetable oils extracted from vari-
ous seeds may be the perfect option for chemical industries
[6]. Seed oils are cost-effective, eco-friendly, less toxic to
human beings and biodegradable and occur in the form of
triglyceride of unsaturated and saturated fatty acids [6].
Copious polymeric materials, with immense potentials, have
also been synthesized from vegetable oils [9].
One of the most traditional polymers developed from tri-
glyceride oils is a polyester resin; conventionally known as
alkyd resin [1–4]. Alkyd resins have earned a noticeable
position in the paints and coating industries, because of

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their low cost of production, simplicity in applications and
reliable protection of materials from environmental attacks
[5–7]. Furthermore, they are also known as biologically
degradable polymers, as they have repeating ester moieties
[7, 8]. Dry and semi-dry oils, such as sunflower, coconut,
castor, soybean, Jatropha curcas and linseed oils, are gener-
ally favoured to non-dry oil in the development of oil-modi-
fied polyesters [9–11], because the aim is always to produce
alkyd resin with good drying properties [12]. In addition to
the aforementioned non-conventional vegetable oils, semi-
drying oils have also been extracted from orange seed, soy-
bean, rubber seed, Jatropha curcas Albiziabenth and tomato
seed for the syntheses of polyester resins [13–15].
The levels of volatile organic compounds (VOCs) in
solvent-based alkyd resins are higher than that in water-
based alkyd resins [13]. Although, the use of solvents in
synthesizing alkyd resin help to facilitate the drying prop-
erties, coating application, the generation of a durable and
regular film of the coating application. On the downside,
when these compounds evaporate, they emit VOCs into the
environment resulting in ecological pollution. Hence, stricter
environmental policies have mandated paint manufacturers
to significantly decrease the levels of VOCs in their paints.
These days, progresses in paint industry suggest that
water-based resins are in several ways equivalent, or better
to their solvent-based counterparts. As a consequence, the
prospect of generating environmentally friendly industrial-
ized organic coating has attracted so much attention. The
use of natural renewable resources for extraction and design
of eco-friendly ingredients for synthesis of coatings can be
used to achieve the fabrication of solvent free coatings par-
ticularly, water-borne alkyd resins [14]. The advantages of
these coatings over solvent based coatings are lower volatile
organic content (VOC), excellent durability, low odor, easy
and safer cleanup, lower or no risk of fire from handling
flammable solvents, proven performance in residential and
industrial applications and less hazardous disposal [16].
Waterborne alkyd resins are derivatives of polymers with
an high acid number that is higher than 50 which gives it
the necessary water solubility on neutralization or during
the development of salt with aliphatic amines, particularly
dimethylethanolamine and trimethylamine for oven-drying
and air-drying alkyd resins respectively [17]. Unlike solvent
based coatings, waterborne coatings are environmentally
friendly because the main solvent is water. This means that
the utilized binder must be dispersible or emulsified in water.
The preparation of this kind of water-based alkyd resin is
primarily achieved using short oil resins with less than 40%
oil content and medium with 40–60% oil content modified
with semidrying and drying fatty acids/oils. In view of the
fact that the reaction with aromatic isocyanates or oligo-
meric aliphatic can results in short-oil, means that there is
a possibility of producing a two-pack systems that quickly
give rise to cross linking when mixed instantly before use
[18]. The development of paint films with the most favora-
ble properties are usually achieved when the NCO/OH ratio
equal to 1. On the other hand, it may be beneficial to diverge
a little from this ratio. Coatings with good substrate flex-
ibility and adhesion is obtained when the ratio is less than
1 (undercross-linking) as some of the OH moieties remain
unreacted, however, the resistance of the coatings to chemi-
cals and solvents tends to be low [18]. The coating displays
enhanced hardness, improved chemical resistance and longer
drying time but the adhesion to the substrate becomes lower
when the ratio is greater than 1 (over-cross linking) [18–21].
Table 1 reports some relevant earlier published reviews

Table 1  Scope of some relevant previously published reviews

Running title Scope of the review Year of References
publica-
tion

Advances in Waterborne Acrylic Resins Jiao et al. (2020) carried out detailed synthetic techniques that have been
Hybrid alkyds, the glowing route to
reach cutting-edge properties?
Recent Advances in Environment-
Friendly Alkyd Nanocomposites
2021 [22]
exploited by various researchers in synthesizing waterborne acrylic resins,
the composition of the resin and the fundamental characteristics of each
monomer. The modification mechanism and methods of the resin including
corrosion resistance, thermal performance; water resistance and mechani-
cal property was also highlighted. Lastly, The applications and prospect of
waterborne acrylic resin were also discussed
This review highlights several research works in literature that are associated 2021 [23]
with grafting of polymers such as epoxy, acrylic or polyurethane to alkyd
resins and the diverse approaches that were employed in synthesizing these
alkyd hybrids. In addition, the perspectives about the future advancements of
alkyd hybrids and the most significant hybrids are reported
Sharmin et al. (2016) described a concise summary of the up to date progress 2016 [24]
in eco-friendly alkyd nanocomposite coatings and the effects of nanofillers
on their coating properties. This review is slightly similar to this present
study

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Chemistry Africa
Scheme 1  General scope of this
review
Alkyd resins
Alkyd resins preparation and synthesis
Solvents based
alkyd resins
Modification of solvent based resins
to other derivatives
and their most important content. However, reference [22]
focuses specifically on waterborne acrylic resin whereas ours
focuses on varying modifications that have been carried out
on solvent and water borne alkyd resins including acrylic
resin. The review by the team of Sylvain Caillol [23] is quite
different from this account because it focused on the grafting
of polymeric materials with alkyd resin. Finally, Sharmin
et al. [24] did not only concentrate on modifications car-
ried out on alkyd resins by the incorporation of nanomate-
rials but also on modifications with other materials. Also,
their review is focused on modifications carried out on sol-
vent- and alkyd-based resins. Since the above review was
published in the year 2016, there is information gaps from
several studies carried out from 2017 to until now.
Despite, the fact that water-based coatings account for
about 80% of paint sold in the residential marketplace when
compared to their solvent based counterparts [25]. The coat-
ing applications of both alkyd resins are still limited in some
aspects of their properties. For example, the application con-
ditions of water-based alkyd resin scan affect the appearance
Coating properties of alkyd resins
Alkyd resins
Water-borne
alkyd resins
Modification waterborne alkyd resins to
other derivatives
Challenges of using Alkyd Coatings
and performance of the coatings as the drying time becomes
longer when the coating is carried out in lower temperatures
and high humidity condition. Also, their resistance to some
chemicals is also very low. These and other disadvantages
have led to several modifications of solvents based and water
based alkyd resins by research scientists. As a consequence,
this review focused on the several modification routes that
have been utilized in the synthesis of solvents and water
based alkyd resins and the impacts on their coating proper-
ties. Reviews on alkyd resins in literature are very limited
and there are currently no review on alkyd resins that is spe-
cifically about solvent borne and water borne alkyd resins.
The general scope of this review is depicted in Scheme 1.
2 Alkyd Resins
Alkyd resins are the main product of poly (condensation)
reaction between polyalcohols, polycarboxylic acids or
their anhydrides in presence of fatty acids or vegetable oils
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[2]. In the mid-1920s, polyesters modified with unsaturated
fatty acids, identified as alkyd resins, were polymerized
by a scientist known as Kienle for the very first time [12,
13, 15]. Since the 1930s, alkyd resins have been employed
essentially as coatings or binders in the paints industries
due to their diverse benefits, which include excellent gloss,
low cost and good heat resistance over other resins [16].
Industrial production of this resin began in 1933 before
other companies started producing it [12, 26]. Admittedly,
the economic benefit of the alkyd resins has been sustained
by their exceptional characteristics, which can be altered by
modifying the oil length, and their adaptability with several
polymers, which makes them very versatile polymers to offer
a broad range of coating materials for diverse uses [12].
Nevertheless, in the 1950s, the production of water-based
paints, which captured the majority of the coatings market,
made possible by the emergence of emulsion polymerization
technology, was driven by acrylic and vinyl polymer [18, 27,
28]. Certainly, water-based coatings are more straightfor-
ward to clean, and less expensive to fabricate. Furthermore,
the emergence of synthetic polymers and resins, particu-
larly acrylic, for the coating sector considerably under-
mined the position of the alkyd resins [15, 29]; although,
a current drive in research on alkyd resins commenced in
the 1980s due to environmental concerns. Certainly, alkyd
resins are essentially made up of biobased raw materials.
But, organic solvents such as xylene or white spirit, derived
from petroleum sources have been employed in dissolving
alkyd resins [30, 31].Those organic solvents used in paint or
ink formulations are known as volatile organic compounds
(VOC), because they can be released into the atmosphere as
a result of their volatility [15, 25, 29]. Therefore, their use
is restricted by European regulations to circumvent adverse
environmental impact, such as air pollution.
To formulate zero VOC paints, several investigations have
centered on the development of water-based alkyd coatings
[18, 27, 28], regrettably, the performances of solvent-based
alkyd coatings are still better than water-based alkyd coat-
ings [18, 27, 28]. Certainly, the resulting coatings from
water-based alkyd coatings produced an unacceptable yel-
lowing effect with a long drying time. Moreover, alkyd res-
ins experience low hardness and poor chemical resistance
[27, 30–33]. Alkyd resins are usually blended or chemically
modified with other polymers to obtain hybrid polymers that
combine the best properties of both polymers, since alkyd
coatings are no longer adequate on their own to meet both
environmental hurdles and property requirements [34–36].
Consequently, a hybrid polymer is composed of at least two
varieties of polymers that can be bonded by strong physical
intermolecular interactions or chemical covalent bonds [16,
21, 27].
Depending on their applicability, coatings need varying
characteristics, so alkyd resins can be blended with various
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Chemistry Africa
polymers to incorporate a broad range of coatings. Admit-
tedly, a low volume of VOC is needed for interior purposes;
whereas water and ultraviolet (UV) light resistances are
mostly needed for exterior purposes [16, 27, 37]. Typical
examples of hybrid alkyds involve epoxy-alkyd, urethane-
alkyd, silicone-alkyd, amide-alkyd and acrylic-alkyd [15,
29]. The synthesis of silicone-alkyd resin, which is one
of the first investigated alkyd hybrid systems, was carried
out in 1947 [23, 34, 38]. The modification of alkyd resins
with polyamide resins usually has impacts on its viscosity,
yielding thixotropic alkyd resins [24, 35]. It has been estab-
lished by several studies that hybridization with urethane
can enhance the toughness, drying time, chemical, abrasion
resistance and UV resistance of alkyd resins [26, 34, 36, 39].
Properties such as pendulum hardness, viscosity, morphol-
ogy, adhesion and impact strength are enhanced by blends
between alkyds and epoxy resins enhanced [21, 30, 37–39].
The drying time of alkyd emulsion can be improved by the
addition of acrylic latexes [27]. Acrylic-alkyd hybrid sys-
tems realized an encouraging strategy for merging the most
desirable characteristics of both acrylics and alkyds in a low
VOC water-based system [28, 40].
2.1 Alkyd Resins Preparation and Synthesis
The three well-known methods used in the synthesis of
alkyd are the alcoholysis process, the acidolysis process and
the fatty acid process [29, 41]. These techniques depend on
the starting materials that are used in the formation of the
alkyd resin. The first synthesis of alkyd resin was carried
out by a process known as the alcoholysis process or mono-
glyceride process (Fig.1). This method was invented by a
scientist named Kienle [12, 29]. This technique is still the
most commonly used process today. The first stage of the
two-stage process usually starts with a transesterification
reaction between triglycerides and polyol, which are the
principal components of vegetable oils [9, 10]. Glycerol is
the most commonly utilized polyol in the synthesis of alkyd
resins. This polyol is made up of three hydroxyl groups,
two secondary and two primaries; although, Trimethylol-
propane, which is a molecule with three alcohol functions,
has a better reactivity when compared to glycerol, because
all the hydroxyl groups are in a primary position [29]. How-
ever, glycerol is still preferred in the synthesis of alkyd resin
because it is less expensive.
Another alcohol that is widely used is Pentaerythritol,
with four primary hydroxyl functions. It is widely utilized
because it permits the generation of highly branched poly-
mers [30, 39]. Speedy elevation in molecular weight, as well
as viscosity is brought about by its high functionality; which
allows faster chain growth. This first step allows the forma-
tion of a monoglyceride, which confers miscibility between
Chemistry Africa

the reactants (Scheme 2) [7, 31]. This reaction is done in the
presence of basic catalysts such as lead oxide and lithium
hydroxide at 240 °C.
Solubility test in methanol is used to confirm the for-
mation of a mixture mainly containing monoglycerides [2,
31–33]. The formation and presence of monoglyceride are
examined by dissolving the reaction mixture in methanol
with a ratio of 1:3. The complete dissolution, which is sig-
nified by a clear liquid solution, is an indication of major-
ity monoglyceride formation [2, 31, 34, 35]. Nevertheless,
unreacted glycerol, diglycerides and unconverted triglycer-
ides are also usually present in the mixture.
Next, a (protected) polyacid such as phthalic anhydride,
of petrochemical origin, is transferred to the reaction mix-
ture containing monoglyceride and the following step, the
polycondensation, occurs (Scheme 3) [2, 31].
Triglycerides are firstly reacted with polyacids at high
temperature (about 280–300 °C), to form fatty acids and an
acidolysis product in the two-step acidolysis reaction pro-
cess (Scheme 4) [38]. The completion of acidolysis can be
estimated by the analysis of the fatty acid content through

Fig. 1  Procedure for alkyd resin

synthesis [2, 31]

Scheme 2  Transesterification
reaction of glycerol and triglyc-
eride to form monoglyceride

Scheme 3  Polycondensation
of monoglyceride with phthalic
anhydride to form alkyd resin
[2, 31]

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Scheme 4  Acidolysis reac-
tion to modify triglyceride oil
with isophthalic acid and then
polycondensation [23]
Scheme 5  Polymerization of
alkyd resin using fatty acids
[23]
titration. Ordinarily, the reaction gets to completion in
approximately 1 h, when the mixture is transparent [23].
The occurrence of reactivity problems or solubility of
polyacids is one of the major reasons for acidolysis [23].
This is the reason why this process is usually utilized with
terephthalic acids or isophthalic. Besides, even with the
presence of a catalyst, this process takes a much more pro-
longed time and a higher temperature than the monoglyc-
eride process. As a result, the acidolysis process is rarely
employed in alkyd resin synthesis.
The next stage is the polycondensation reaction between
the carboxylic groups and a polyol; and the acidolysis prod-
uct, which enables the formation of an alkyd resin [29, 38].
The formation of alkyds in one step is allowed by the third
process, which uses fatty acid instead of triglycerides [29,
38]. Indeed, fatty acids can easily react with polyol since
they contain a carboxylic group. Consequently, a first mis-
cibility step for the monoglyceride or acidolysis process is
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Chemistry Africa
not necessary. Thereby, polyacids, polyols and fatty acids
are dispersed together to react via the esterification pathway
(Scheme 5).
The use of fatty acids in the synthesis of alkyd resin is
more favourable, allowing shorter process time and better
products [23]. However, it is more costly than oils. For this
reason, a mixture of fatty acids and oil is frequently used in
order to make the final product cost effective.
The polycondensation reaction usually takes place
between a carboxylic acid and an alcohol in all the afore-
mentioned processes. There is the existence of a ther-
modynamic equilibrium during the reaction, which can
be shifted by removing water from the reaction mixture.
This principle is the bed rock of this reaction [35, 42,
43]. The first step, also known as the fusion process, is
carried out at an elevated temperature by mixing of the
reactant components, at a temperature range of around
230–240 °C [2, 20, 44, 45]. Moreover, for prevention of
Chemistry Africa
harmful oxygen action and advancement of polyconden-
sation, the inert gas (nitrogen gas) is passed through the
reaction mixture to remove water. In most cases, there is
a reasonable loss of volatile reactants due to the fact that
this process occurs at elevated temperature. This proce-
dure is generally used where the loss of volatile reactants
has less impact on process control parameters to produce
long oil alkyd resins.
To subdue these issues, a second technique called solvent
process or azeotrope process, which involves the addition of
small quantities of a hydrocarbon solvent such as xylene into
the reaction mixture, is widely used [1, 2]. In this process,
reactants are heated together at temperatures between 200
and 240 °C, to form a water/solvent azeotrope. The removed
water and solvent are recovered and re-injected into the reac-
tor, thus enabling considerably more reliable control of the
process parameters [1, 2]. Only one water molecule rather
than two anhydride acid compounds are released in the mix-
ture, during polycondensation when diacids are employed
[21, 46]. Thus, phthalic anhydride is more favourable in the
polymerization of alkyd. The polymerization reaction is con-
trolled by estimating the viscosity and the acid value. This
estimation is discontinued when these parameters reach the
earlier established values. The number of free acid groups
in the alkyd resin corresponds to its acid value [37, 47]. The
acid value decreases during the polymerization, because of
the consumption of the acid groups leads to the extension
of the polymer chains causing an elevation in viscosity and
molar mass.
2.2 Coating Properties of Alkyd Resins
Since the 1930s, alkyd-based paints have been a prevailing
product in the coating industry [17, 19]. Though, they com-
pete with water-based coatings such as acrylics and latex,
their exceptional features still make them a more preferable
coating for numerous utilizations. The coating applications
of alkyd resin usually produce a tough, durable, superb fin-
ish with outstanding water resistance and barrier properties
[17, 19]. Their resistance to environmental factors and their
strong adhesion to practically every surface make them a
preferred coating for architectural, machinery, wood and
industrial applications.
Studies have established that the thermal stability of these
resins can get to as high as 105 °C [24]. Better coating proper-
ties are obtained from using drying oil (oil with better drying
properties) when compared to non-drying oil (oil with lesser
drying capability) [2]. Generally, the properties of alkyd resin
can be influenced by the degree and type of unsaturation in the
fatty acids present in the drying oil. The use of drying oil to
obtain drying alkyds with sufficient unsaturated fatty acids that
permit oxygen-curing in the air has been established by several
studies. In the synthesis of alkyd resin, the use of non-drying
oil is not always a good choice because of the formation of
a non-drying alkyd with less improved properties (An alkyd
that does not allow curing in the air due to lower contents of
unsaturated fatty acids) [24]. However, the drying properties
of this resin can be improved upon by blending with drying
oil or incorporating other materials into it [31]. Apart from
the drying properties, modifications of drying and non-drying
oil-based alkyd resins are constantly carried out to enhance
their mechanical, physico-chemical, and chemical resistance
properties [25]. The properties of resin such as drying time,
color, moisture resistivity, hardness, etc. depend on the extent
of unsaturation of the utilized oil [24]. The curing of alkyd
resins through auto-oxidation process is made possible by
the presence of these unsaturation sites. The method forms
the active free radicals leading to the development of a three-
dimensional cross-linked network [48].
The environmental limitations placed on the unique
solvent-borne formulations have made their marketability
challenging. These limitations have given birth to the unique
waterborne alkyd coatings and modified alkyd coatings
which provided a superior performance than the solvent-
borne products with greatly decreased solvent content. The
utilization of vegetable oils instead of petroleum-based oils
also provides alkyds with a unique prospect as a green prod-
uct. Although, it once seems like the environmental issues
of solvent-based alkyds would greatly hinder the utilization
and marketable feasibility of alkyd coatings, the industry
has reacted with more recent waterborne, low-VOC deriva-
tives that provide oil-based paints with high performance
while handling the environmental problems of conventional
solvent-borne coatings.
2.3 Solvents Based Alkyd Resins
The economic and industrial advantages of the solvents
based modified alkyd resins have made it one of the most
essentially used binders for stains and paints for many years.
However, interest in the utilization of biodegradable, eco-
friendly binders has grown due to worries about the poten-
tially hazardous nature of the solvents to the environment
and painters. Despite these concerns, solvent-based alkyd
coatings are still widely been used in paint preparation and
other possible applications. Myriads of vegetable oil types
have been employed in the synthesis of unmodified solvent
based alkyd resins, which have been widely utilized as
coatings and binder for making paints [2, 20, 49]. However,
when expose to thermal fluctuation, UV radiation, salty con-
ditions and high humid, the performance of these coatings
and paints are inferior when compared to modified alkyds.
Within few months of exposures to these conditions, unmod-
ified solvent based alkyd resin paints show colour fading,
loss of gloss and considerable chalking [14].
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Scheme 6  Reaction schemes
for synthesis of acrylic copoly-
mer and methacrylated A. benth
alkyd resin [14]
2.3.1 Modification of Solvent Based Resins to Other
Derivatives
In an attempt to arrive at a more practical and feasible appli-
cation to solvent-based alkyd resins, several studies have
introduced chemical modifications to its structure to give
properties ranging from fast hard-drying, soft, flexible films,
etc. [7]. Dizman et al. [50] modified an alkyd resin with
Gum rosin, using phthalic anhydride, soybean oil, gum rosin
acid and glycerin. The obtained gum rosin modified resin
(RA-GR) alkyd resin showed better properties, in compari-
son with benzoic acid modified resin (RA-BA) with a better
adhesion to metals, and short drying times without loss in
the glosses. The obtained properties were also better than
the rubber-soybean seed oil-based alkyd resin and rubber-
linseed seed oil based alkyd resin synthesized by Otabor
et al. [31] and Ifijen et al. [2] respectively.
Several studies have improved the properties of alkyd
resins by the introduction of acrylic monomers [14, 27,
51]. Investigations of the modification of diverse vegetable
oil-based alkyds by the introduction of acrylate have been
carried out by earlier workers [14, 27, 51]. The acrylation
procedure is achieved via monoglyceride or post-acrylation
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methods. Akintayo and Adebowale investigated the prepa-
ration and properties of acrylate Albiziabenth medium oil
alkyds [14], following the chemical reaction route illustrated
in Schemes 6 and 7. Improved performances in terms of
resistance to scratch, drying time, adhesion and chemical
resistance capability in various corrosive environments,
were observed by the acrylate alkyd resin synthesized by
introducing a copolymer of n-butyl methacrylate and malei-
canhydride (n-BMA-CO-MA) into the other alkyd reactants.
Grozdanov et al. synthesized alkyd resin based nano-
composite coatings, filled with different content of silicon
oxide ­(SiO2) and titanium oxide (­ TiO2) nanoparticles (2 and
4 wt%) via a solvent casting method [52]. The experimental
analysis of the synthesised alkyd revealed that the presence
of the ­TiO2 and ­SiO2 nanoparticles generally improved the
thermal, drying, flexibility, roughness, hardness, abrasion
resistance and mechanical properties of the as-synthesized
resins.
Naik et al. synthesised a hyperbranched polyol
(HBP) using dipentaerythritol as a core material; and 2,
2-bis(methylol) propionic acid as a chain extender [53]. The
concentrations of soya (Glycine max) fatty acid were var-
ied to produce hyperbranched alkyd (HBA) resins. To make
Chemistry Africa
Scheme 7  Synthetic pathway of epoxy-modified waterborne alkyd resin based on ZSO [58]
high solid hyperbranched urethane alkyd (HBUA) resins,
the group reacted HBA resins containing unreacted hydroxyl
groups (OH) with isophorone diisocyanate (NCO) at ratio of
1.6:1. The unique features of this hyperbranched polyester-
based –NCO-terminated urethane alkyd is that it can gener-
ate moisture cured polyurethane coatings when cured under
atmospheric moisture. The mechanical and gloss retention
coatings properties of the alkyd synthesized by Naik et al.
showed properties with improvement, when compared to
the conventional alkyds due to compact structure and higher
degree of cross linking [53]. These coatings should be espe-
cially beneficial in the areas where surface development and
moisture elimination are strenuous and the coating must be
used under humid conditions, for instance, naval utilization.
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The monoglyceride can then be further reacted with
acrylic copolymer to yield the resin (Scheme 6) [14].
Ikhuoria et al. post-polymerized Rubber seed oil (RSO)
alkyd resin with styrene monomer at variable ratios at
100 °C for 3 and 6 h, to obtain two sets of styrenated alkyds
[54]. Physico-chemical properties of the styrenated alkyds
showed a better improved drying time, even in the absence
of a drier compared to styrenated alkyd. Although, it has
been established that most conventional alkyd get attacked
when subjected to alkali, the styrenated modified alkyds
synthesized by Ikhuoria et al. is resistant to alkali [54]. This
investigation revealed that the post-polymerization of alkyd
with styrene is a one route that should be taken in order to
obtain an alkyd resin with improved properties. They also
established that the drying properties of the styrenated modi-
fied alkyds increased with a longer reaction time during its
synthetic procedure.
The incorporation of varying types of materials such as
gum rosin, acrylate, n-butyl methacrylate, maleicanhydride,
silicon oxide ­(SiO2) and titanium oxide ­(TiO2), into solvent
based alkyd matrix during or after the synthetic stages,
have been shown by the aforementioned studies to improve
properties such as adhesion, drying time, gloss retention,
resistance to scratch, chemical resistance capability in vari-
ous corrosive environments, thermal stability, flexibility,
roughness, hardness, abrasion resistance and mechanical
properties. However, the use of volatile organic solvents as
diluents in organic coatings formulations has contributed
to the increasing atmospheric pollution over the years [20].
2.4 Water‑Borne Alkyd Resins
Waterborne coatings make use of water as the solvent to
disperse or emulsify resin. As a consequence, these coat-
ings are easily applicable and environmentally friendly
[55]. Waterborne coatings usually contain up to 80% water
mixed with small amounts of additional solvents, such as
glycol ethers [17]. These coatings are also known to be envi-
ronment-friendly. Waterborne alkyd coatings tend to take
an extended time to dry when compared to solvent-borne
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Chemistry Africa
coatings; nevertheless, the application outcome has compa-
rable flow, leveling, gloss characteristics. They are excep-
tionally adaptable because they can be thinned with water to
practically any viscosity. Water-borne alkyd resins are more
economical and environment-friendly, when compared to sol-
vents based modified alkyds [17, 55]. Moreover, research-
ers were directed by environmental legislation on volatile
organic solvents utilization, to produce coating materials with
environmental friendly nature [17, 55]. Some of the advan-
tages of water-borne resins over solvent-borne coatings are
listed as follows [56]: lower toxicity and flammability due
to lower VOC levels, superior adhesion, lower air emis-
sions, satisfactory resistance to abrasion and heat, covering
the same surface area using lesser coating, the paint guns
can be cleansed readily with water or water-based solutions
without the use of acetone, paint thinner or methyl acetate,
utilization of conventional application techniques and usage
of waterborne primer where the solvent primer would react
with existing substrate materials or coatings. In most circum-
stances, these coatings are less expensive than solvent-borne
coatings. Despite the numerous advantages mentioned above,
waterborne resins also have flaws such as long drying times,
low coating hardness, short shelf stability due to poor hydro-
lytic stability, limited water resistance, etc. [57].
2.4.1 Modification of Waterborne Alkyd Resins to Other
Derivatives
Waterborne alkyd resins needs to be modified to alleviate the
aforementioned challenges. To rectify the aforementioned
flaws and other flaws which are not listed above, several
researchers have modified waterborne alkyd resins by incor-
porating polymeric and metallic materials at the nano-scale
or micro-scale level into their structures. Ma et al. syn-
thesized waterborne alkyd resins based on Zanthoxylum
bungeanum seed oil (ZSO) modified with epoxy resin via
polyesterification reaction [58]. The epoxy-modified water-
borne alkyd resins displayed better properties in terms of
hardness, drying time, adhesion, flexibility, chemical resist-
ance and thermal stability. The epoxy-modified waterborne
Chemistry Africa
alkyd resin based on ZSO synthetic pathway is depicted by
the reaction Scheme 7. The investigation of Ma et al. showed
that ZSO can be used as a possible source of natural material
for alkyd coating application [58].
Aigbodion et al. modified RSO alkyds (50% oil length)
with various amounts of maleic anhydride and fumaric acid,
separately to study their water-reducible alkyd resins binding
capability [59]. For comparative purposes, Rubber seed oil
(RSO), was also modified with different amounts of maleic
anhydride [59]. Reduction in the iodine value and increment
in the acid/saponification values of the RSO, were observed
after modification with maleic anhydride. The volatile
organic compounds exhibited by the RSO modified with
maleic anhydride, exhibited lower amounts of (˂20 g ­L−1)
when compared to the corresponding RSO alkyds (34–87 g
­L−1). However, the alkyd samples were superior to the modi-
fied RSO in chemical resistance. The research of Aigbodion
et al. was able to establish the quality improvement caused
by the addition of maleic anhydride to RSO and RSO alkyds
by considerably improving their quality as binders in low-
VOC, nonpolluting, and eco-friendly coatings [59].
Naik et al. [53] employ dipentaerythritol as a core mate-
rial, 2,2-bis(methylol) propionic acid as a chain extender,
and varying concentrations of soya fatty acid in the synthesis
of hyper-branched polyol (HBP). The unreacted hydroxyl
groups present in the HBA resins were reacted with iso-
phorone diisocyanate, at an NCO/ OH ratio of 1.6:1 to pro-
duce high solid hyper-branched urethane alkyd (HBUA)
resins [53]. The excess NCO content in the HBUA resins
was cured with atmospheric moisture, forming moisture-
cured HBUA coatings. Experimental analysis from this
study shows that gloss retention and mechanical properties
of the synthesized HBUA coatings are more reliable than the
traditional alkyds, due to the compact nature of the HBUA
coatings structure and a greater degree of cross linking. This
study developed HBUA resins coatings at higher solids than
when compared to the traditional linear alkyds. The unique-
ness of the synthesized moisture-cured HBUA resins is that
they can be utilized as a binder material, even in an envi-
ronment where there are low pollution weather-resistance
coatings. These coatings should be, especially beneficial in
the fields where moisture evacuation and surface preparation
are challenging.
Water reducible alkyd resin, composed of varying
amounts of colloidal silica, was prepared by Kurt et al.
[60]. Their findings revealed that the coatings have unique
salt water resistance, acid and water. The introduction of
new composite acrylic resins such as addition of styrene,
silanes, different acrylic polymer blends or alkyd polymers
to interior paints have been done in recent times [22, 61].
Two-pack system waterborne urethane dispersions, which
are usually mixed together before usage, have also been
used as coatings in resins. The two-pack system is made
up of an easily dispersible hydrophilically modified poly-
isocyanate and polyurethane polyol dispersion in water
[22, 61]. The vehicle for the two-pack system waterborne
urethane dispersions are the aforementioned solvent and
the resin.
Pathan and Ahmad synthesised butylated melamine–for-
maldehyde (BMF) cured waterborne castor alkyd (WCA-
BMF), using eco-friendly solvent (s-triazine ring) and
investigated the anticorrosion properties of the synthesized
alkyd [63]. The reaction scheme of the synthesis of BMF
cured waterborne castor alkyd is depicted in Scheme 8.
Analytical results revealed that the presence of BMF in the
castor alkyd resin improved its adhesion, impact resistance
(> 100 cm), bending capacity (1/8 inch bend test), thermal
stability, scratch hardness (7.50 kg) and corrosion proper-
ties. They attributed the improvement in the aforementioned
characteristics to the extra cross-linking reaction caused by
the butoxy groups and hydroxyl group of ricinoleic acid of
the BMF. Therefore, this study was able to establish that the
modification of castor oil-based water-born alkyd resins with
an s-triazine ring can generate a high-performance corrosion
protection coating material via a green route.
Enhancements in coatings performance was also estab-
lished by modifying waterborne alkyd coatings with nano-
Fe2O3 [64]. The corrosion process was delayed even when
the nano-Fe2O3 was loaded at very low concentrations (0.05,
0.1 and 0.2%). An even better coating performance was
achieved when the loading was increased to 0.3% [64]. The
addition of nano-silica to waterborne alkyd resins has been
revealed to improve the thermal stability, abrasion resist-
ance, adhesion properties, scratch resistance, glass transi-
tion temperature and impact resistance [64]. Dhoke et al.
introduced ZnO nanoparticles to waterborne alkyd resin
and discovered improvement in the abrasion resistance and
film compactness [64]. The modification had facilitated the
formation of hard and complex network due to the catalytic
influence the ZnO nanoparticles had on the curing reaction.
The mechanical properties of the alkyd drastically improved
due to the stronger interactions between the alkyd matrix and
the nanoparticles.
The incorporation of nano-ZnO also improves the UV
resistance of coatings due to the established UV blocking
properties of nano-ZnO [65]. The blending of poly (meth-
ylmethacrylate-butylacrylate)/nanocalcium carbonate with
alkyd coating and 50 wt% water as solvent was successfully
carried out by a previous study [65]. An examination of the
coating application showed improvement in the mechani-
cal, thermal properties and gloss of the coating. However,
the impact resistance property was observed to be low. The
impact strength of the coatings was deteriorated by the
highly crystalline calcium carbonate nanoparticles at loca-
tions where there was occurrence of aggregation of particles,
thereby, generating stress at these specific sites [65].
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Scheme 8  Reaction scheme of the synthesis of BMF cured waterborne castor alkyd [63]

13
Chemistry Africa
Waste polyethylene terephthalate (PET), known polyester,
which is naturally difficult to decompose; have been used in
waterborne alkyd-amino baking coatings. Xia et al. (2020)
synthesized and investigated waterborne alkyd-amino baking
coating by using amino resin, waterborne alkyd resin based
on waste polyethylene terephthalate (PET). To improve its
solubility, surfactants were also added. The waterborne
alkyd-amino resin films showed, water dispersibility, excel-
lent adhesion, balanced hardness and flexibility, high gloss
and outstanding chemical resistance except for alkali resist-
ance owing to hydrolysis of ester bonds [66].
2.5 Challenges of Using Alkyd Coatings
Alkyd coatings and coating systems are comparatively simple
to mix together and apply by spray, brush or other methods.
Due to this implicity in utilization and their reasonably low
cost, moisture, corrosion resistance and good color retention,
alkyd coatings have been extensively utilized as architectural,
marine, industrial and household coatings. Nonetheless, there
are several concerns that should be made available to indus-
tries before using alkyd coatings [67]. These include:
• Pigments often settle to the bottom of the container
because they are heavier than the resins and oils con-
stituting the paint. The pigment particles may be quite
solid and not easy to disperse by standard mixing if such
settling has been for an extended time.
• It’s not unusual for alkyd paints to “skin over” at some
point in storage container, generating a semi-oxidized
layer on the surface that is partly dried. The paint under-
neath the skin is still fluid in nature.
• Alkyd coatings with longer oil may possibly take a sub-
stantial period of time to get hardened and dry. Alkyd
primers with longer oil coatings applied on bridges have
been known not dry for several years, staying as a semi
liquid after application. The top coats might separate
from the primer layer on application of pressure; inti-
mating that the surface of the coating isn’t appropriate for
walking over. On the other hand, oxidation and progres-
sion to a hardened state of shorter oil alkyds continue to
occur all through their lives, and cracking and brittleness
may take place if they are exposed to humid temperatures
and sunlight.
• Gloss and colour retention are not as high-quality as
those of several other coatings, mostly polysiloxanes,
acrylics, and polyurethanes.
• Water immersion service isn't recommended for alkyds
due to the carbonyl-ester groups (–COO–) in constituent
oils and the alkyd resin.
• Oil and alkyd abased paints aren’t suitable for coating
mortar, concrete or the majority of cementitious masonry.
Degrading of the oil constituent in the paints may occur
due to attack from the alkalis in the cement causing the
paints to be softened and tacky after application.
• Likewise, the use of alkyds and oil-modified coatings
are not appropriate for a zinc-rich primer because during
the corrosion of zinc, the formation of zinc hydroxide
and other alkaline corrosion products may saponify and
attack the alkyd resin or oil in the coating.
3 Conclusions
Several modification routes that have been utilized in syn-
thesizing solvents and water based alkyd and the impacts
on their coating properties are reviewed. The application of
alkyd resins for coatings has been recognized for more than
100 years but recent environmental hurdles make alkyds
promising polymers for coating manufacturing. Admittedly,
even though alkyds manifests superb coating properties, they
undergo attacks from external aggressions such as chemi-
cals, mechanical, leaching and abrasion. The modification
performed on solvent-based alkyd resins and water-borne
alkyd resins over the years engineered overcoming the afore-
mentioned deficiencies possible. Physical–chemical proper-
ties like coating performances, drying properties, thermal
stability, anticorrosive properties and chemical properties of
the currently synthesised alkyds have also experienced dras-
tic improvements in recent times. Nevertheless, some of the
reactants used in obtaining some of the existing alkyd resins
need to be changed to a more eco-friendly compound e.g.
the use of isocyanate compounds in the synthesis of polyu-
rethane should be discouraged because it is harmful to the
environment and human health. Acceptance of the existing
initiatives towards eco-friendly coatings, the advancement of
low solvent or solvent-free alkyd coatings should be encour-
aged to decrease the usage of toxic solvents during the pro-
duction, processing, formulation, and utilization of coatings.
More importance should be placed on the production of high
solids, waterborne, UV curable alkyd and hyperbranched
using different economic materials. Blending with cost-
effective reinforcing components will also definitely lessen
expenses and enhance performance properties. The addition
of value to underexploited oil should be encouraged by the
greater utilization of non edible and non medicinal oils in the
development of alkyds. In addition, water-borne alkyd resin
should be considered as a possible replacement for solvent-
based and other types of alkyd resin that are associated with
environmental pollution.
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