Progress in Organic Coatings 156 (2021) 106267

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Progress in Organic Coatings

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Review

Vegetable oil based polyurethane coatings – A sustainable approach:

A review
Pavan M. Paraskar, Mayur S. Prabhudesai, Vinod M. Hatkar, Ravindra D. Kulkarni *
Department of Oils, Oleochemicals and Surfactants Technology, Institute of Chemical Technology, Matunga (E), Mumbai, 400019, India

A R T I C L E I N F O A B S T R A C T

Keywords: The scientific community has been pooling all its resources, for the past decade, towards the development of
Environment friendly “sustainable development” to usher into an eternally green and sustainable tomorrow. As part of this endeavor,
Vegetable oil the conventional petroleum-based polyurethane (PU) coatings have been replaced by their green counterparts, i.
Polyurethane coating
e., bio-based polyurethane coatings. These green alternatives provide a suitable replacement for the coating
Bio-based materials
industry due to their easy availability, biodegradability, low cost, and lesser environmental impact. The pro­
duction of such green PU coatings is further facilitated by the utilization of bio-based materials, including
vegetable oils and their derivatives such as methyl ester, fatty acid, and other bio-renewable sources. This review
discusses the different chemical modifications used to convert these bio-based precursors into desired polyols and
isocyanates. Furthermore, the formulation of different PU coatings and their subsequent potential applications
are also elaborated on in this review. The coatings sector has already been introduced to the notion of eco-
friendly technologies such as UV-curable, less or zero solvent, waterborne, hyperbranched, and high solids
coatings, complemented by the incorporation of renewable feedstock in monomer synthesis. The review ex­
amines the future hurdles that hinder the utilization of these materials in a wide range of applications and
presents technologies that facilitate potential solutions and mention key players in the coating sectors that are at
the forefront of bringing these revolutionary changes.

1. Introduction 8], carbohydrates [9], proteins [10], starch [11], cellulose [12], poly­
saccharides [13], and many other agricultural products and byproducts.
The industrial revolution brought with it extravagant innovations The utilization of such renewable resources for polyurethane synthesis
that have shaped every aspect of our life today. However, as the saying leads to a drop in environmental impacts such as greenhouse gas emis­
goes, "the bill always comes dues," the toll of industrialization has been sions and non-renewable resource consumption [14,15].
on nature. The world has seen a massive rise in population, which led to Among the broad spectrum of renewable feedstock research, vege­
the depletion of natural resources and a rise in environmental pollution table oil is indisputably the most advantageous and promising alterna­
when combined with higher living standards [1,2]. The fear of petro­ tive to petrochemical resources. Vegetable oil is a triglyceride;
leum reserve depletion and the capricious petroleum feedstock rate has comprising three fatty acids attached to glycerol via ester linkage
motivated researchers to explore new avenues in different chemical (structure depicted in Fig. 2).
industries [3–5]. The bio-based feature also augments the polymer ap­ The fatty acid chains contain 8–24 carbons with carbon-carbon
peal due to copious availability, economical and eco-friendliness. double bonds ranging from 0 to 5, most of which are of cis, non-
Polyurethane (PU), although discovered only 80 years ago, has conjugated configuration. Table 1 gives the fatty acid composition of
become one of the most versatile groups of polymers used in the market. selected vegetable oils and number of carbon-carbon double bonds per
The urethane linkage comprises the reaction product between molecules triglyceride. Vegetable oil provides a wide range of chemical structures
containing multiple hydroxyl moieties with molecules containing mul­ and various reactive sites (epoxy, unsaturation and ester groups) that
tiple isocyanate functionalities (Fig. 1). The polyurethane has seen a can be chemically altered into various customized polyols and their
comprehensive shift from conventional petro-based raw feedstock to application in polyurethanes [16]. Polyurethanes are prepared from
various renewable alternatives, such as vegetable oils [6], fatty acids [7, vegetable oils produced from different plant seeds such as soybean [17],

* Corresponding author.
E-mail address: [email protected] (R.D. Kulkarni).

https://doi.org/10.1016/j.porgcoat.2021.106267
Received 16 December 2020; Received in revised form 3 March 2021; Accepted 29 March 2021
Available online 6 April 2021
0300-9440/© 2021 Elsevier B.V. All rights reserved.
P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

palm [18], neem [19], Karanja [20] castor [21], rapeseed [22], cot­ 2. Vegetable oil-derived monomers
tonseed [23], jatropha [24], etc.
Vegetable oil-based polyurethane coatings has proved their mettle 2.1. Vegetable oil-derived polyols
by showcasing superior properties such as excellent toughness [6],
abrasion resistance [29], corrosion and chemical resistance [30], Excluding castor and Lesquerella oils, most vegetable oils do not
low-temperature flexibility [31], and thriving industrial applications, possess inherent hydroxyl functionality that are utilized in polyurethane
and also decreasing or eliminating the utilization of volatile organic synthesis, but the unsaturation and ester linkages present in tri­
compounds (VOCs) [32]. To mitigate losses from degradative corrosion, glycerides allow for the introduction of such groups. All synthetic
the suitable utilization of domestically surplus resources such as vege­ methods for producing vegetable oil-based polyols practically start from
table oils is a sustainable alternative [33,34]. Extensive research has one of these two functional groups. There are many chemical trans­
been done on polyols derived from vegetable oils [35,36]. Different formation routes to functionalize vegetable oils to develop the desired
reaction pathways have been employed to achieve this, such as material. The main transformation routes are summarized in this review
amidation-esterification [37], hydroformylation [38], epoxidation-ring (Fig. 3). The majority of vegetable oil-based polyols are obtained from
opening [39], ozonolysis [40], and metathesis [41] and coupling of the epoxidation route and then the epoxy’s ring-opening reaction to
thiol-ene with mercaptoethanol [42], all of which have successfully integrate hydroxyl groups. Furthermore, several synthesis routes for
provided polyol with anticipated properties. Derivatives of vegetable developing functional hydroxyl moieties for coatings are also pointed
oils have also been researched exhaustively in the past decade. Unlike out, such as hydroformylation, ozonolysis, thiol-ene coupling reaction,
vegetable oils, their derivatives do not give superior properties as the and transesterification. This segment specializes in the wide variety of
original vegetable oil, but they still meet industrial standards, making polyols presently being made out of vegetable oils and utilized in
them desired for various applications [43]. Fatty acids, methyl esters, polyurethane coatings.
mono and diglycerides, and dimer acids are a few examples of renewable
feedstock used for PU synthesis [16]. Another exciting avenue of 2.1.1. Castor oil
research has been of synthesizing isocyanates using vegetable oil de­ Castor oil is identified as a superior alternative among all the vege­
rivatives. This methodology avoids the hazards of synthesizing and table oils due to its inherently present hydroxyl groups, low toxicity,
handling conventional isocyanates [44]. The most prominently used biodegradability, low cost, favorable to industry, and easy availability
derivatives are fatty acids and dimer fatty acids [45]. Polyurethane [48,49]. Castor oil is comprised primarily of ricinoleic acid (>89 %),
coating types depending on the curing technique used and the type of which is a mono-unsaturated 18-carbon fatty acid with a hydroxyl group
solvent used. Other than the conventional polyurethane that uses on its 12th carbon (Fig. 4). Various studies suggested using castor oil as a
petrochemical solvents, extensive research is also being done on polyol source, replacing petro-derived products such as coatings, foams,
waterborne polyurethane dispersions that use water as the solvent me­ sealants, adhesives, and encapsulating material [50]. Therefore castor
dium. Waterborne polyurethane dispersions have an intrinsic advantage oil obtained significant interest for the synthesis of polyurethanes prior
over conventional polyurethane being eco-friendly and safe for usage to the synthesis of polyol from other vegetable oils was developed.
[46]. PU curing can occur at room temperature or under heat. An Castor oil possesses three hydroxyl groups and approximately 3.04
alternative to thermal curing is UV curing, which involves supplying the unsaturation/triglycerides; thus, it is a suitable candidate for utilizing a
energy needed for curing action in UV radiation [47]. To enhance cross-linking monomer to synthesize polyurethane materials [51,52].
conventional PU coating properties to meet industrial standards, thor­ Above all, the structural factors of castor oil make it suitable for
ough research has also been conducted on nanocomposites, high-solid usage as polyol to prepare PU coating with appropriate properties.
contents, and hyperbranched PU coatings, which depend on the indi­ Moreover, the long-chain fatty acid improves the resultant coatings’
vidual properties and compatibility of discrete components. This hydrophobicity, impact, and flexibility properties. However, castor oil
method has proven efficient compared to other techniques due to a short has less functionality and less reactivity because of the secondary hy­
time, less energy, and better curing action. This review aims at articu­ droxyl groups in the fatty acid chains. Chemical modification routes
lating the development seen by the PU field of research in the past 10–15 were extensively used to enhance castor oil-based polyols’ properties
years and, in doing so, covers topics of importance to different extents and suitability for developing polyurethanes with upgraded properties
depending on their emphasis on the eco-friendly character of the final and broader applications [53]. The castor oil is transesterified through
PU coating. The latest developments in the transformation and appli­ the ester group, and hydroxyl numbers are regulated by different polyols
cations of vegetable oil-based PU coatings, the importance of vegetable like pentaerythritol, glycerol, sorbitol, or amidation [33]. Bakhshi et al.
oil-based polyols in deciding the properties of such coatings, and using prepared antibacterial polyurethane coating through bio-based castor
underutilized natural resources have been explained in detail. oil polyol, polyethylene glycol, benzyl triethanol ammonium chloride
(BTEAC) and TDI. The prepared polyurethane shows a good balance

Fig. 1. Reaction of a diol with a diisocyanate to form polyurethane linkages.

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

between soft and hard segments, which improved the thermal, me­ performance [33,51]. Moreover, a higher residue of unsaturation results
chanical properties, and antibacterial activity of polyurethane coatings in polyurethane coatings with higher tensile strength, tensile modulus,
[54]. Castor oil-based hybrid polyurethane-urea/silica coatings were and toughness. When mono-alcohols are utilized for ring-opening, each
prepared via free radical copolymerization. The castor oil-modified epoxy group produces an additional hydroxyl group with less reactivity
silane-based hybrid PU coatings exhibited better thermal stability, than the primary hydroxyl groups and constrained mechanical and
increased hydrophobicity, reduced swelling, and showed superior thermal applications [43,67,68]. To overcome the problem of low
anti-corrosive properties than castor oil-based PU-urea coatings [55]. reactivity, blends of epoxidized soybean oil (ESO) and other commer­
Sardari and co-workers synthesized castor oil-based waterborne soft cially available epoxies are used to produce materials with the required
polyurethane coatings. In these studies, they prepared saponified castor properties and decrease the cost. The diols comprising two hydroxyl
oil-based polyols through epoxidation followed by a ring-opening groups per epoxy group were used to produce vegetable oil-based pol­
method to synthesize water-based polyurethane. The waterborne poly­ yols with higher hydroxyl functionality. Ethylene glycol and 1,2-pro­
urethane with 40 wt% polyol exhibited reduced particle size and mini­ panediol have also been used for epoxy ring-opening reactions to
mum polydispersity index, and waterborne polyurethane with 60 wt% obtain polyols with primary hydroxyl groups with higher functionality.
polyol showed the lowest viscosity, hardness, adhesion, and glossiness Zhang et al. successfully prepared polyols from ring-opening epoxidized
[56]. The structural modification of castor oil by reaction with succinic soybean oil through castor oil fatty diol; the newly formed hydroxyl
anhydride is followed by reaction with hydroxyl group moieties like group in epoxides has involvement in the ring-opening, which results in
bio-based glycerol and petrochemical-based trimethylolpropane, and oligomerization [69]. Bio-based carboxylic acids, such as oleic acid, was
pentaerythritol has also been studied [57]. The modified branched utilized for ring-opening of epoxidized soybean oil to prepare polyester
castor polyol-based PU coating exhibits better viscoelastic and polyol, which shows the potential application as an anti-corrosion
thermo-mechanical properties. Zaimahwati et al. fabricated castor coating [60]. Hussain et al. prepared polyurethane coatings from
oil-based Polyurethane/MMT nanocomposites coating through the so­ epoxidized soybean oil (ESBO). The Soy-polyol was obtained through an
lution blending method [58]. The nanocomposite PU coating with 5 wt alcoholysis reaction of ESBO with glycerol, and different PU coatings
% montmorillonite showed a better flat and smooth surface. The main were fabricated with a different molar ratios of isocyanate. The gel
advantage of using castor PU nanocomposites in the coating was its content and hardness of the PU coatings prepared increased with an
better adhesive strength and high heat resistance. Panda et al. prepared increased molar ratio of hardener [70]. The reaction of epoxidized oil
castor oil-derived waterborne polyurethane dispersion with different with acrylic acid produces acrylated epoxidized oil, which can be
NCO/OH molar ratios using isophorone diisocyanate (IPDI) and dime­ modified and react under UV radiation to form highly cross-linked
thylol propionic acid (DMPA) as an internal emulsifier [59]. The molar polymer networks within a few seconds. In the report of Li et al., acry­
ratios used in the formulation dictated waterborne polyurethanes’ lated epoxidized soybean oil (AESO) and pentaerythritol triacrylate
structural property; for instance, higher hard segment content led to (PETA) were introduced to a UV-curable waterborne polyurethane
enhanced physicomechanical and abrasion resistance. acrylate (PUA) resin and then used for waterborne wood coating [71]. It
revealed that acrylated epoxidized soybean oil could improve the
2.1.2. Epoxidation/oxirane ring-opening cross-linking density and form more robust networks within the curing
The most utilized route for the preparation of polyols is epoxidation action. These could be attributed to the acrylated epoxidized soybean
of carbon-carbon double bonds of vegetable oils, followed by oxirane oil, which consists of two forms of functional groups: carbon-carbon
ring-opening with proton donors like alcohols, carboxylic acids, and double bonds that can be UV-cured and hydroxyl groups that
amines [60–62]. A schematic description of polyol synthesis via epoxi­ contribute to intermolecular chain formation by hydrogen bonding.
dation of vegetable oil and subsequent oxirane ring-opening is presented
in Fig. 3. Vegetable oils are generally epoxidized by preparing in situ 2.1.3. Transesterification
peracids from hydrogen peroxide and acetic or formic acid [35,63]. The transesterification route utilizes the ester functionality in vege­
However, substantial research has been conducted on epoxidation-ring table oils/triglyceride structures to prepare polyols. The primarily used
opening routes to prepare bio-based polyols by sunflower, linseed, polyol for vegetable oil transesterification is glycerol, but other polyols
soybean, cottonseed oils, and so on. These bio-based polyols could be like pentaerythritol [72] and trimethylolpropane [73] have also been
utilized to produce suitable polyurethane coatings for industrial appli­ researched. Many researchers have reported the synthesis of mono­
cations [25,39]. The properties of polyols prepared from epoxidized glycerides from vegetable oils such as castor, Nahar, soybean, linseed,
vegetable oils and following ring-opening rely on the nature of the and neem for polyurethane production. Transesterification reactions are
starting oil and the fatty acid composition. Additionally, the types of mostly catalyzed by organic and inorganic bases such as methoxides of
ring-opening agents, the count and position of the hydroxyl moieties, calcium, sodium, and potassium [74–76], sodium hydroxide; and cal­
and residual degree of unsaturation in the final product also influence cium hydroxide [77], and metal oxides such as lead and calcium oxides.
final polyols’ properties [64–66]. The polyol’s hydroxyl number and The transesterification of vegetable oils with glycerol, in the presence of
functionality directly correlate to the cross-linking density, glass tran­ a catalyst (metal oxide), produces a mixture of polyols consisting of
sition temperature, and the polyurethane coatings’ mechanical mono-, di-, triglycerides, and residual glycerol [78]. Amongst all the

Fig. 2. Triglyceride structure and its reactive sites.

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

constituents, monoglyceride, which carries two hydroxyl moieties per were enhanced by incorporating silane-modified nano TiO2 in the resin.
molecule, plays a vital role in polyurethane synthesis. These mono­ The coatings were subjected to various property evaluation tests such as
glycerides are converted into alkyds by reacting with polybasic acids flexibility, impact resistance, chemical resistance, gloss, scratch resis­
such as maleic acid, phthalic anhydride, fumaric acid, etc. tance, cross-cut adhesion, and thermal stability.

2.1.4. Synthesis of monoglyceride 2.1.5. Synthesis of alkyd

Monoglycerides have proven to be reliable polyols for polyurethane A modification of the transesterification route involves introducing
synthesis, and their use has been well documented. Monoglyceride can alkyd functionality in the monoglyceride-based polyol (Fig. 5 (b)). A
be obtained using transesterification of vegetable oil with excess glyc­ dehydration reaction between the monoglyceride’s hydroxyl group and
erol in a single step, adding to the route’s economic advantage [25]. A carboxyl groups of difunctional acid yields alkyd functional polyol.
schematic description of polyol synthesis from vegetable oils via the Chaudhari et al. have presented extensive work encompassing four
monoglyceride route is shown in Fig. 5 (a). Gite et al. use four vegetable different types of dibasic acids: maleic anhydride, itaconic acid, phthalic
oils, namely soybean, sesame, castor, and linseed oils, to synthesize anhydride, and dimer fatty acid with catalyst CaO used in conjunction
monoglyceride, which was later cross-linked with a trimer isophorone with monoglyceride of neem oil and toluene 2,4-diisocyanate to
diisocyanate (IPDI) to formulate polyurethane coatings. The thin film formulate PU coatings [83]. It was confirmed that neem oil was added to
coatings were subjected to various property evaluation tests such as the anti-corrosive coating aspect, and all the alkyd-based PU coatings
scratch hardness, gloss, flexibility, and physicochemical stability [31]. showed excellent coating properties. The use of different types of oils in
Thakur et al. explored the use of castor oil monoglyceride in the syn­ the alkyd-urethane formulation has been demonstrated by the work of
thesis of hyper-branched polyurethane coatings via cross-linking with Ling et al., who prepared alkyd-diols from phthalic anhydride and
toluene diisocyanate (TDI), along with poly(ε-caprolactone) diol (PCL) monoglyceride of palm oil, soy oil, and sunflower oil [84]. These
and 1,4-butanediol (BD) used as a macroglycol and chain extender, alkyd-diols were then used in different permutations with 4,4-methylene
respectively [79]. They adopted a ‘high dilution and slow addition’ diphenyl diisocyanate to form 5 different poly (alkyd-urethane). The
technique that provided hyper-branched polymers with good solubility poly (alkyd-urethane) displayed overall good mechanical properties and
in most polar aprotic solvents and high yield. The evaluation of dielec­ chemical resistance and revealed an improvement in coating perfor­
tric constant and loss factor displayed the dielectric properties for PU mance brought about by soy oil or sunflower oil-based alkyd-diols
coatings. blending. Palm oil poly (alkyd-urethane) presented good thermal sta­
Das et al. used monoglyceride as polyol and reacted with toluene bility. Ismail et al. worked on formulating polyester polyols from
diisocyanate, butanediol, and poly (ε-caprolactone) pentaerythritol to monoglycerides of soybean oil and phthalic anhydride taken in different
provide a hyper-branched structure [80]. The hyper-branched poly­ ratios of 20 %, 40 %, and 60 %. Various characterizations such as pencil
urethane film with the multifunctional unit of pentaerythritol and hardness, chemical resistance, flexibility, and impact resistance revealed
confined globular structure had structural and compositional superiority improved coating properties, increasing the polyurethane formulation’s
over its’ linear counterpart, corroborated from the results of tensile hard segment [85].
strength, elongation at break, impact resistance, scratch hardness,
biodegradability test, and thermal stability. The incorporation of 2.1.6. Transamidation
monoglyceride as a polyol unit in different polyurethane coatings has Amide functionality in the polyol structure confers several advan­
also been well documented, such as the work presented by Chang et al. tageous properties to the final polyurethane coating. The amide func­
in which monoglycerides of linseed oil have been used to formulate tionality is responsible for thermal stability, curing time, cross-linking
waterborne urethane oil wood coatings [81]. The waterborne urethane density, flexibility, and adhesion. Hence the introduction of the amide
dispersion was also evaluated for various properties such as dispersion group is highly sought after in polyol synthesis [33]. These are achieved
stability, particle size, solid content, and polydispersity index, all of by the catalyzed amidation reaction between a vegetable oil/­
which showed promising results from an application point of view. triglyceride molecule and diethanolamine, yielding diethanolamide
Linseed, castor, coconut, sunflower, mustard, and rice bran oils were (Fig. 6 (a)). Diethanolamide has two hydroxyl groups and a long fatty
used in the synthesis of low molecular weight monoglyceride polyols for acid chain, making it ideal for use as a polyol in polyurethane synthesis.
polyurethane formulations with MDI [82]. The properties of the coating The chain length of the fatty acid group attached to the amide group

Table 1
Degree of unsaturation and fatty acid composition of common vegetable oils.
Fatty acid composition [%] References

Vegetable oil Double bondsc C16:0 C18:0 C18:1 C18:2 C18:3

Castora 3.0 1.2 0.7 4.5 4.7 0.4

Linseed 6.6 5.8 3.7 18.9 16.1 57.4
Soybean 4.6 9.4 4.2 23.5 56.2 6.5
Sunflower 4.7 6.2 2.5 25.7 61.1 0.08
Palm 1.7 43.8 4.3 40.2 10.1 0.2
Cottonseed 3.9 22.5 3.5 17.7 55.8 0.5
[25]
Olive 2.8 13.7 2.5 69.8 10.0 0.4
Canola 3.9 4.0 1.3 62.3 20.2 9.1
Rapeseed 3.8 4.1 1.8 56.4 24.3 10.1
Peanut 3.4 10.5 2.6 47.2 30.2 0.34
Sesame 3.9 8.9 6.1 40.9 42.6 0.8
Corn 4.5 9.3 2.5 23.5 59.6 1.3
Rubber seed 4.3 3.4 8.3 32.0 37.0 16.4 [26]
Karanja 2.4 11.5 7.9 51.5 16.6 2.6 [27]
Mustardb 3.3 3.4 1.3 12.2 16.3 8.9 [28]
a
Composed of 88.6 % ricinoleic acid.
b
Composed of 46.7 % erucic acid.
c
Number of C–
–C bonds per triglyceride.

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

Fig. 3. General synthesis pathways to vegetable oil-based polyols.

from diethanolamide can be varied depending on the vegetable oil used

[86]. However, further modifications of diethanolamide enhance its
properties as a viable polyol. Modifications such as esterification with a
polybasic acid or dehydration with a diol, yielding polyesteramide
polyol (Fig. 6 (b)) and polyetheramide polyol (Fig. 6 (c)), respectively,
are the most commonly researched routes. These modifications allow
the introduction of long fatty chains, unsaturation, and ester linkage in
Fig. 4. Chemical structure of castor oil.
the polyol structure, contributing to the final polyurethane coatings’

Fig. 5. (a) Preparation of vegetable oil-based monoglycerides (b) Preparation of alkyd.

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

Fig. 6. (a) Preparation of vegetable oil-based diethanolamide (b) Preparation of polyesteramide polyol (c) Preparation of polyetheramide polyol.

performance. microcapsules loading presented the highest thermal stability [89].

Another extensive study was conducted by Patil et al., which utilized
2.1.7. Diethanolamide different dicarboxylic acids and anhydrides to prepare polyesteramide
The displacement reaction between diethanolamine and triglyceride polyols from cottonseed oil. The employed acid components were se­
leads to the coupling of a fatty acid chain to the nitrogen group of bacic, suberic, succinic, tartaric, phthalic, maleic, and azelaic acids and
diethanolamine, converting it into a diethanolamide having a newly the isocyanate component was MDI [4]. The use of vegetable oil and
formed amide functionality (Fig. 6 (a)). Plenty of research work focuses dicarboxylic acids contributes to PU coatings’ bio-based content by
on diethanolamides as only an intermediate product for subsequent increasing it to 65 %. The synthesized polyurethane coating showed
polyesteramide polyol or polyetheramide polyol [87]. However, from a faster curing, excellent mechanical/chemical performances, alkali/acid
structural requirements perspective, the diethanolamide has two hy­ resistance, hydrophobicity, superior gloss, adhesion, and pencil hard­
droxyl groups qualifying it as a polyol. Raychura and the team prepared ness as compared to the petroleum-based polyurethane. Polyurethane
mahua oil-based fatty amide and cross-linked it with IPDI and HDI to dispersion was also prepared from polyesteramide polyols, as presented
formulate two-pack wood coatings [88]. The prepared coating was then by More et al., who utilized mustard oil as the feedstock for polyol
subjected to a comparative study using different testing parameters such synthesis. The polyol was cross-linked with isophorone diisocyanate to
as thermal stability, chemical resistance to acid, alkali, salt, beverage form the polyurethane prepolymer, and upon reacting with DMPA to
stain resistance, cigarette ignition resistance, surface morphology study, bring dispersion in water and hydroxyl ethyl methacrylate to introduce
antibacterial and antifungal activity. unsaturation in the polyurethane backbone [90]. The UV cured coating
retained flexibility due to fatty amide aliphatic linkage while presenting
2.1.8. Polyesteramide polyol excellent hardness properties due to the amide group. Siyanbola et al.
Polyesteramide polyols can be considered to be the most widely used prepared a hybrid coating to comprise Thevetia peruviana seed
polyols in polyurethane synthesis. The ease of synthesis, the versatile oil-based polyesteramide polyol-urethane, modified with silica–zinc
final products, and the commercially inexpensive synthesis route oxide (ZnO). The reaction of a prepared polyol and 4,4’- diisocyanato­
contribute to polyesteramide polyol’s popularity. Polyesteramide poly­ dicyclohexylmethane was carried out in siloxane-modified zinc oxide to
ols are synthesized by an esterification reaction between a fatty amide obtain –NCO-terminated prepolymer. The study showed that properties
and polybasic acid (Fig. 6 (b)) [87]. The versatility of final polyol arises like thermal stability, glass transition temperature, antibacterial activ­
due to the wide variety of polybasic acids that can be employed. The ity, and corrosion resistance of the coatings improved with increased
effect of fatty acid composition on the properties of final polyurethane siloxane modified ZnO content [91].
coatings was conducted by Paraskar et.al. They reported a comparative
study showcasing the use of three different vegetable oils, namely 2.1.9. Polyetheramide polyol
linseed oil, Karanja oil, and castor oil, with itaconic acid in the synthesis Polyetheramide polyol is another variation carried out on dieth­
of polyesteramide polyol. The fabricated polyurethane coatings showed anolamide, which involves the dehydration reaction between the hy­
excellent physicomechanical, thermal, chemical resistance, and droxyl groups of fatty amide and a diol (Fig. 6 (c)). Like polyesteramide
anti-corrosive properties. The castor oil-based polyurethane coating has polyols, a wide variety of polyetheramide polyols are available for
superior thermal stability, fast drying time than linseed oil-based poly­ synthesis due to the permutation and combinations between different
urethane coating [33]. Chaudhari et al.; synthesized anti-corrosive fatty amides and diols. Raychura et al. formulated wood protective
polyurethane coatings from neem oil with phthalic anhydride as the polyurethane coatings from polyetheramide polyol of mahua oil, which
polybasic acid component. Dispersed polyamido-amine based polyurea was synthesized via catalytic aminolysis with diethanolamine and sub­
microcapsules were used to incorporate the coating’s self-healing abil­ sequent etherification with diglycidyl ether of bisphenol-A [92]. The
ity, and the extent of loading played a role in the final coating properties. wood protective coating showed good resistance to solvent and house­
Amongst all samples, the coating with 4 wt% microcapsules loading hold chemicals such as acid, alkali, salt, and beverages stain, while
showed the best anti-corrosive properties, while the coating with 3 wt% cigarette ignition caused no damage to the coating, justifying suitability

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

for the household applications. Another work by Raychura et al. pre­ reducing an aldehyde into polyols in the presence of Raney nickel
sents bisphenol C in synthesizing polyetheramide polyols from fatty catalyst [40]. The sodium borohydride reaction with ozonide in a
amides of mahua oil. The thermal analysis of the coatings indicated the mixture of solvents such as dichloromethane and methanol directly of­
coating’s stability up to the temperature of 180 ◦ C. Coating performance fers primary alcohol. Narine et al. reported the successful synthesis of
analysis showed good mechanical properties with low surface wetta­ polyols from unsaturated canola oil followed by ozonolysis and hydro­
bility, which can add to the wood substrate’s shelf-life [93]. Chaudhari genation reactions [103]. Due to the effect of vegetable oils’ fatty acid
et al. utilized neem oil and bisphenol-A to synthesize polyetheramide composition, the ozonolysis-based polyols aggregate various constitu­
polyol-based polyurethane coatings. The effect of surface-modified TiO2 ents of mono, diol, and triols with triglyceride structures and saturated
nanoparticles on enhancing the formulated polyurethane coatings’ triglycerides [40]. The ozonolysis process eliminated half of every fatty
properties was assessed by varying the loading amount of nano TiO2 acid chain and prohibited the inclusion of dangling chains into the
from 0 to 4%. It was observed that nano TiO2 significantly enhanced polyurethane, which is beneficial because the dangling chains can act as
coating properties like thermal stability, pencil hardness, gloss, and plasticizers to soften the materials. Therefore, ozonolysis-based polyols
chemical resistance [94]. The use of virgin olive oil and a possess faster curing rates than isocyanates. The polyols obtained from
microwave-assisted synthesis approach was presented by Alam et al. The the ozonolysis process show nearly 40 % lower molecular weight than
olive oil was converted to N-N’-bis (2-hydroxyl ethyl) olive fatty amide the previous processes comprising the carbon-carbon double bonds
through condensation polymerization reaction with orcinol. The polyol (hydroformylation/reduction and epoxidation/oxirane ring-opening)
was cross-linked with TDI to form polyurethane resin, which was used as and which shows a low viscosity upon melting [40,68].
an anti-corrosive polymeric coating [95]. The coatings showed good Ozonolysis-based polyols have also been prepared by hydrogenation
thermal stability, corrosion resistance, and physicomechanical proper­ free one-step reaction. Generally, polyols like glycerol and ethylene
ties. Alam et al. also showed the use of soybean oil in polyurethane glycol have been reacting with vegetable oil in the presence of a catalyst
synthesis via the reaction of N, N-bis (2-hydroxy ethyl) soybean oil fatty (e.g., calcium carbonate, sodium hydroxide) to produce a mixture of
amide with bisphenol-A to yield polyetheramide polyol. The corrosion primary and secondary alcohols, respectively [104]. Fig. 7 shows the
resistance study supported the applicability of developed polyurethane ozonide intermediates produced from vegetable oil’s ozonolysis, which
resin as an anti-corrosive coating. The presented modification was found reacted with ethylene glycol’s hydroxyl moieties to create ester linkages
to be an excellent unification of combined properties of fatty amide, and terminal hydroxyl.
urethane moiety, and bisphenol-A [96]. Benecke et al. produced polyurethane coatings with low VOC from
soybean oil glyceride polyols, which was synthesis via one-step ozo­
2.2. Hydroformylation/reduction nolysis with glycerol and it showed excellent gloss, hardness, along with
good adhesion to a metal substrate [105].
Another significant route for preparing vegetable oil-based polyols is
hydroformylation, followed by hydrogenation (Fig. 3). The hydro­ 2.2.2. Thiol-ene coupling
formylation of vegetable oils implies the conversion of carbon-carbon Thiol-ene chemistry is extensively utilized for various coatings ap­
double bonds in fatty acid chains to aldehydes at 70–130 ◦ C with plications because of its versatile nature and mild reaction conditions.
rhodium or cobalt catalyst and syngas (a mixture of H2 and CO), and The incorporation of thiols to carbon-carbon double bonds has multiple
then hydrogenation of aldehyde to lead primary hydroxyl groups [97]. benefits against the conventional acrylate system, such as insensitivity
During hydroformylation, the vegetable oil-based polyol’s hydroxyl to oxygen, delayed gelation, and reduced shrinkage stress [106].
functionality relies on the number of unsaturation present in the vege­ Thiol-ene coupling is a single-step reaction that involves a free radical
table oil. Linseed and soybean oils are mostly utilized as initial feed­ chain mechanism in which the double bonds of unsaturated fatty acids
stock, but other oils, along with sunflower and safflower, have also been are reactive towards thiols (2-mercaptoethanol, 3-mercaptopropionate,
used [98,99]. The hydroformylation pathway gives a polyol with pri­ and glyceryl dimercaptoacetate) and produce primary hydroxyl groups
mary hydroxyl groups that are more reactive towards isocyanate than (Fig. 3). Thiol-ene polymerization is of particular importance because it
secondary hydroxyl groups produced by the epoxide consists of a photoreaction, having a fast reaction rate and high con­
ring-opening/methanolysis route [38]. The cross-linking density, glass version [107]. Caillol et al. prepared soybean oil-based polyols through
transition temperature, and mechanical properties of the derived poly­ the thermally initiated thiol-ene coupling, which was slower than
urethanes mostly rely on polyol’s hydroxyl functionality and iso­ UV-initiated thiol-ene coupling. A series of UV-curable thiol-ene coating
cyanates’ character. Therefore, hydroformylated polyols exhibit higher systems based on castor oil has been developed [42]. Black and Rawlins
curing ability and lower gel time during the reaction with isocyanates prepare thiol-ene UV-curable coatings from vinyl ether derivatives of
for polyurethanes than epoxidized polyol [100]. To improve the struc­ castor oil and allyl, acrylate, and combined with multifunctional thiols.
ture and performance of polyols, other structural transformations were Auto-oxidation of double bonds residue of triglycerides helped increase
investigated, such as methanolysis and polycondensation, in which the cross-link density of PU coating and improved chemical resistance,
hyperbranched polyols with enhanced functionalities and molecular hardness, and solvent resistance [108]. Wang et al. developed
weights [101] and triols with increased molecular weights [99] were cardanol-based polyol with increase hydroxyl numbers through
formulated. The negative effect on waterborne PU coatings’ properties thiol-ene coupling and prepared polyurethanes with improved tensile
has been shown due to the variety of hydroxyl functionality distribution strength, elastic modulus, and hardness properties [109]. Additionally,
of hydroformylated polyester polyols. Polyols of narrower functionality cardanol-based polyurethane’s thermal stability has been increased
distribution produced coatings having excellent balance of flexibility, after converting the phenolic hydroxyl to aliphatic hydroxyl. Fu et al.
abrasion resistance, and hardness, while polyols of broad functionality developed another useful strategy, in which castor oil-based undecyle­
distribution resulted in smoothing coatings with lower abrasion resis­ nic acid was converted into a diisocyanate through Curtius’s rear­
tance [102]. The bio-based RENUVATM polyols prepared from soybean rangement of thiol-ene coupling 3-mercaptopropionic acid. The
oil by Dow Chemical Co. are also utilized as monomers for coatings, prepared diisocyanate was utilized for waterborne polyurethane dis­
adhesives, sealants, flexible foams, and elastomers. persions [110]. The polyurethane coatings prepared from the thiol-ene
coupling reaction showed high gloss and excellent adhesion to the
2.2.1. Ozonolysis/reduction metal surface. Additionally, the fatty acid chains from vegetable oils
Polyol preparation from vegetable oils via ozonolysis generally in­ increased coating flexibility and showed low tensile strength, tensile
volves two stages, shown in Fig. 3. The process involves forming ozonide modulus, and chemical resistance properties.
at the carbon-carbon double bonds of vegetable oils, followed by

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

Fig. 7. Ozonolysis route with the reaction of ethylene glycol (R1 and R2 are fatty acid chains of vegetable oil; R1′′ , R2′′ are modified fatty acid chains of vegetable oil).

2.3. Vegetable oil-derived isocyanate textile, and automotive adhesives applications [45]. Moreover, Zhang
et al. produced polyurethane dispersions from castor oil (CO), dimer
Vegetable oils and their derived fatty acids are also important acid diisocyanate (DDI), and alkoxysilane-modified castor oil (MCO),
renewable materials for the synthesis of isocyanate. In industry, iso­ and the coatings exhibited high thermal stability, excellent corrosion
cyanates are produced from primary amine and gaseous phosgene resistance, and mechanical properties [114].
(highly toxic) routes. There is an urgent need to explore phosgene-free
routes for diisocyanate development because of safety and health 3. Vegetable oil based polyurethane coatings
problem related to this route. The uses of aliphatic diisocyanates are
restricted to flexible coatings in which the absence of unsaturation is 3.1. High solids PU coatings
advantageous. Additionally, few widely known lab-scale processes, such
as Curtius rearrangement, Lossen rearrangements, and Hofmann’s re­ Due to concern of environmental regulations, high-solids coatings
action, are accessible [37]. Using this strategy, oleic acid-based linear have gained attention in the coating industry. Currently, polyurethane-
saturated terminal diisocyanate was prepared through Curtius rear­ derived coatings represent the most high-solids coatings in the protec­
rangement [111]. Initially, oleic acid was transformed to diacid and tive and marine coatings market. Generally, high solids coatings have a
then converted to acyl azides by the reaction with sodium azide, and, higher content of solids in paints (70–80 % solids) and less VOC content
upon heating, it had decomposed to isocyanates (Fig. 8). The study than traditional solvent-based coatings [15]. Moreover, researchers are
shows that polyurethane’s physical properties based on aliphatic diiso­ also trying to develop 100 % solids polyurethanes. High solids coatings
cyanate (bio-derived) possess similar results to those of petroleum-based have lower solvent emissions and narrow molecular weight distribution,
1,6-hexamethylene diisocyanate polyurethane [112]. and other advantages as similar to traditional systems with better
More et al. used the Curtius rearrangement through acyl hydrazide properties and durability; thus, it can be applied in the coating industry.
fatty acid-based derivatives to synthesize fatty acid-based diisocyanates An excellent high solids coating material must have adequate spray
without harmful sodium azide (Fig. 9) [113]. A variety of partially and viscosity without compromising the material’s performance character­
fully vegetable oil-derived thermoplastic polyurethanes were prepared, istics. However, a detrimental effect of viscosity and lower molecular
and good mechanical and thermal properties were obtained. Compara­ weight of high solids coatings is coatings’ drying behavior and low
tively, good thermal stability was noticed with 230− 280 ◦ C decompo­ stability [115]. Polyols derived from vegetable oil have relatively high
sition temperatures at 5 wt% loss. molecular mobility and carry pendant dangling chains responsible for a
Numerous global polymer manufacturers are engaged in the indus­ low modulus and low glass transition temperatures (Tg). Kong et al.
trial synthesis of bio-based isocyanates; few of them manufacture com­ prepared polyols through epoxidation/hydroxylation of vegetable oils
mercial bio-based isocyanate, such as 2-heptyl-3,4-bis(9- (sunflower, Camelina, Linola flax, NuLin flax, and Canola) followed by
isocyanatononyl)-1-pentylcyclohexane produced by Cognis (BASF-Ger­ esterification reactions with various diols (1,3 propanediol and 1,2
many) from a dimer fatty acid. Another example is of aliphatic poly­ propanediol). Polyurethane coatings with high solids were produced by
isocyanate commercialized by Vencorex (Joint Venture between PTT the reaction of such polyols and isocyanate [116]. All polyurethane
Global Chemical, Thailand, and the Perstorp Group) under the trade coatings showed a bio-based content of about 60 % and exhibited good
name of Tolonate. According to the literature, Henkel Corporation adhesion due to chemical interaction. Low molecular weight, few
Company or General Mills Co. commercialized fatty acid-derived dii­ pendant chains, and higher functionality also play a crucial role in
socyanate known as dimer acid diisocyanate (DDI) use to produce improving these coatings’ properties. Additionally, the solvent-free
polyurethanes. This diisocyanate is based on a fatty acid’s dimer and has strategy also increased coatings hydrophobicity by increasing of
36 carbon atoms in the chain. Charlon et al. prepared a fully bio-based cross-linking density of the coating. Somani et al. developed low vis­
thermoplastic polyurethane through a one-step bulk process from dimer cosity castor oil derivatives and produced high solids PU coatings from
acid diisocyanate and different renewable polyols suitable for coatings, different aromatic and aliphatic isocyanates to improve flexibility and

Fig. 8. Preparation of fatty acid-based aliphatic diisocyanate [112].

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

Fig. 9. Synthesis of fatty acid-based diisocyanate [113].

impact strength [117]. One of the appealing strategies for preparing favored over dendrimers because of their one-step synthesis process and
high solids coating is utilizing reactive diluents in the coating system. reduction of purification steps during the synthesis [119]. The hyper­
Mannari and co-workers developed soy polyols for two-component high branched structures have better properties than their linear counterparts
solids polyurethane coating. The study shows that soybean oil phos­ [80]. The structures and properties of hyperbranched polyols, poly­
phate ester polyols can act as hydroxyl components and a reactive esters, and polyurethanes are reported by Chattopadhyay and Raju
diluent for polyurethane coating systems [118]. [120]. Vegetable oil based hyperbranched PU coatings (Fig. 10) have
been reported by Deka et al. [121]. They first synthesized vegetable
oil-based monoglycerides and utilized glycerol chain extender with poly
3.2. Hyperbranched PU coatings
(ε-caprolactone) diol to prepare hyperbranched polyol and produced
hyperbranched polyurethanes with varying segmental ratios. The
The dendritic polymers comprise three important sub-groups: den­
segmental ratios produced a substantial impact on coating performance
drimers, hyperbranched polymers, and dendrigrafts. Due to the unique
concerning thermal-mechanical and physical properties.
structural features such as high surface functionalities and no entan­
Vegetable oil contributed to decreased resin’s viscosity and
glement, hyperbranched polymers and dendrimers have become an
improved hardness of the coatings, which exhibited excellent adhesion
important class of polymeric material in the past several years. Addi­
to the substrate, flexibility, and good gloss [122]. Wei and co-workers
tionally, they possess high reactivity, high solubility, low viscosity, and
synthesized waterborne hyperbranched polyurethane UV curable
improved cross-link density. However, hyperbranched polymers are

Fig. 10. Synthesis of hyperbranched polyurethane [121].

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

coatings from a hyperbranched polyester polyol produced from castor 3.3. Waterborne PU coatings
oil and 2,2-bis (hydroxymethyl) propionic acid. Subsequently, a water­
borne hyperbranched polyurethane acrylate emulsion was prepared Waterborne polyurethane dispersions (WPUDs) are gaining impor­
through the reaction of hyperbranched polyester polyol with maleic tance as coatings materials due to increasing environmental concerns
anhydride and isocyanate-bearing semi adduct (IPDI-HEA) taken at a about volatile organic chemicals (VOCs) and hazardous air pollutants.
different molar ratio using an emulsifier free process. The prepared They are categorized as water-dispersible/colloidal (dispersions), water-
coatings exhibited excellent transparency and outstanding adhesion soluble/water–reducible (solutions), and emulsions (latex) paints.
properties [123]. Moreover, advanced surface coating material has also Waterborne PUs offers numerous benefits compared to traditional
been prepared from castor oil-based hyperbranched poly (ester amide), solvent-borne PUs, comprising low VOCs emission, high molecular
and the coating exhibited high thermal stability concerning the degree weight with low viscosity, and good spreading ability during application
of branching. Additionally, hyperbranched poly (ester amide) showed [127]. Recently, vegetable oil gaining attention in the WPUDs industry
biodegradability properties, which can be considered a green advantage due to its reactive functionalities such as carboxyl groups, hydroxyl
in advanced surface coating technology [124]. The soy oil-derived groups, unsaturation, and reactive phenolic structures. Polyols based on
hyperbranched PU prepared through thiol-ene reactions exhibits good vegetable oil (soybean oil, rapeseed oil, and castor oil) have been
transparency and high tensile strength, promoting the bio-based mate­ employed with diisocyanates, dimethylol propionic acid, and chain
rial for high-performance coating application [125]. The bio-based extender to prepare environmentally friendly anionic WPUDs (Fig. 11)
hyperbranched polyurethane and polystyrene with a very minimum with uniform particle sizes [30,128,129].
amount (0.01− 0.1 wt%) of Silica/Reduced graphene oxide (RGO) The hydrophobic nature of vegetable oil triglyceride chains provides
nanohybrid loading were used to fabricate effective anti-corrosive some challenges for the synthesis of WPUDs. Additionally, triglycerides’
coating nanocomposites. The prepared nanocomposites coating exhibi­ hydrophobic nature improves the physical and chemical properties of
ted excellent thermal stability, surface hydrophobicity, and mechanical WPUDs with increased thermal and hydrolytic stability [6,130].
property upon a significantly less amount of nanohybrid loading [126]. Recently, Gogoi and co-workers reported that fatty acid-based WPUDs
Overall, hyperbranched polyurethane performance relies on vegetable based on dimer technology improve the hydrolytic and storage stability
oil class as the precursor, isocyanate, chain extender, and type of of polyurethane dispersions and shows improvement in adhesion, gloss,
nano-filler used. mechanical strength, hydrophobicity, and chemical resistance proper­
ties [131]. The properties of WPUDs primarily depend on the type of

Fig. 11. Synthesis of waterborne polyurethane dispersions [127].

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

triglyceride or polyol, nature of isocyanate, type of chain extender and oligomer. The general reaction scheme for vegetable oil-based PUA is
emulsifier, and polymerization techniques [30]. The various features of shown in Fig. 12. Bastürk et al. prepared soybean oil-based methacry­
WPUDs are internal or external emulsifiers that produce stability to the lated urethane acrylate oligomer through a two-stage process; in the first
hydrophobic polyurethane dispersed in the water phase. Due to the stage, methacrylated epoxidized soybean oil (MSO) monomer was pre­
addition of internal emulsifiers such as dimethylol propionic acid pared and further react with isophorone diisocyanate to produce an
(DMPA) and dimethylol butanoic acid (DMBA) into the polymer struc­ isocyanate-terminated oligomer. The second stage involved the prepa­
ture, the particle sizes in the resulting PUDs are smaller, which leads to ration of isocyanate-terminated oligomer and its reaction with 2-hydrox­
excellent stability. DMPA is generally utilized as an internal emulsifier yl ethyl methacrylate (HEMA) to produce methacrylated urethane
for anionic WPUDs [132]. However, DMPA is not bio-renewable; acrylate [65]. Liu and the research group developed polyfunctional
therefore, the bio-based content of the WPUD system is bounded; polyurethane acrylate from cardanol with polyfunctional acrylate pre­
therefore, to eliminate these drawbacks, few researchers have tried to cursor prepared through reacting isophorone diisocyanate with pen­
prepare DMPA-free anionic WPUDs by incorporating vegetable-oil. taerythritol triacrylate, and the prepared coating exhibits increased
Recently, Gaddam et al. prepared DMPA-free vegetable-oil-based thermal and mechanical performance, excellent adhesion and flexibility
WPUDs with an ionic soft segment such as phosphorylated polyol. properties [146]. Moreover, the unsaturation present in vegetable oil
Phosphorylated polyol (both ionizable phosphoryl and hydroxyl groups) plays a vital role in the UV-curable cross-linking process. Su et al. pre­
were prepared from epoxidized cottonseed oil via pared a series of vegetable oil (grapeseed oil, canola oil, corn oil,
ring-opening/hydrolysis with ortho-phosphoric acid. The developed rapeseed oil, peanut oil, olive oil, and palm oil) based acrylate prepol­
coating (phosphol-P5) exhibited high thermal stability, tensile strength, ymers by a one-step acrylation process. They investigated the effect of
excellent hydrophobicity, and good corrosion resistance properties [23]. unsaturation contents on the grafting rate and product properties [140].
The bio-based chain extenders were also used in WPUDs. It is prepared The study revealed an increased number of unsaturation in vegetable oil
through the esterification reaction of glycerol and citric acid (CA) and attributes to speed up the reaction rate and increased grafting number of
utilized with macroglycol (dimer acid and polyethylene glycol) and poly products, which increased the functionality and cross-linking density of
(ε-caprolactone) diol for the synthesis of biodegradable water dispersion UV-curable coating.
thermoplastic polyurethanes. The resulting coatings exhibited excellent Furthermore, increased unsaturation could also improve the me­
self-healing capability, high tensile and impact strength, and superior chanical, thermal, and physical properties of UV-curable films. Alter­
scratch resistance [133]. Linseed monoglyceride-based waterborne natively, some researchers add various reactive diluents
polyurethane-silica (LMGWPU-Si) composites exhibited better perfor­ (trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate
mance compared to conventional polyurethane dispersion. The addition (TPGDA), 1,6-hexanediol diacrylate (HDDA)) into UV-curing systems,
of aminosiloxane increased the cross-link density of LMGWPU-Si com­ which helps to reduce the viscosity of the curing system as well as
posite, and the prepared film showed good water-resistance and high increasing the cross-linking density of the coating [147]. Recently,
contact value, which reflects good hydrolysis resistance [10]. Overall, vegetable oil (castor oil, tung oil, and cardanol) derived reactive diluents
WPUDs coatings have exhibited low costing, excellent stability, are also used in the UV curing system, which shows the potential to
eco-friendly approach, and biodegradation ability. replace conventional reactive diluents in the UV curing system [142,
148,149]. Hu and co-workers developed a cardanol-based monomer
3.4. UV curable PU coatings through epoxidation of the unsaturated alkyl side chains of cardanol
segments and used it as a reactive diluent to copolymerize with castor
Typically conventional PU coatings are cured via thermal curing and oil-derived polyurethane acrylate and prepared various UV-curable
polymerization processes, usually with catalysts and solvents. In com­ coatings. The cardanol-based UV-curable coatings exhibited superior
parison with thermal curing, UV-curing technology is noticed as 5E, adhesion, excellent flexibility, hardness, and increased thermal stability
which stands for Economical, Environmental friendly, Efficiency, En­ [150].
ergy saving, and, Enabling; therefore, the process can be considered
"clean and green" [17,134]. Generally, UV-curing systems comprise 3.5. Nanocomposites PU coatings
three building blocks: i) Oligomer (mono or multifunctional acrylated
terminated prepolymer), ii) Monomers (reactive diluents), iii) Photo­ Bio-based PU nanocomposites are advanced materials formed by the
initiators. To date, different types of additives are consistently used in right combination of suitable nanomaterials and a bio-based PU matrix
such systems [135–137]. The polyurethane acrylate (PUA) molecular with hyperbranched structural architecture. Nanomaterials enhance
structure primarily comprises the polyols chain, urethane segments, and interaction between coating-surface interaction and increase coating
acrylate hydroxyalkyl ester segments. The acrylate functionality in­ durability and opacity [151]. Due to the small particle size of 100 nm or
troduces more enhance properties to the PU coating as compared to the less, some nanomaterials are suitable for transparent coating systems.
conventional PU. Properties such as excellent flexibility and outstanding One of the most important and widely accepted polyurethane applica­
adhesion on different substrates (metal, wood, and plastic) demon­ tions, especially bio-based PU and nanocomposites, is binders for paints
strated by PUA have made it a popular coating choice in the UV-curable and surface coatings [152]. Nanocomposites comprising of two different
coatings segment [138]. Additionally, PUA-based UV-curable coatings materials present a very high interfacial contact. For example, inorganic
exhibited good impact resistance, abrasion resistance, optical trans­ material with spherical and uniform morphology is dispersed into an
parency and scratch resistance, and so on [139]. Vegetable oil is an organic coating [153]. In each case, there is an interfacial region where
essential feedstock for preparing polyurethane acrylate (PUA) oligomer several molecular or atomic layers of the two phases behave differently
and reactive diluents because vegetable oil possesses diverse function­ from bulk. Instead of larger particles, dispersing nanoparticles allows a
alities such as hydroxyl and unsaturation carboxyl, and epoxy, therefore, coating formulator to increase the "interfacial material" content signif­
can be used for various chemical transformation [140,141]. There was icantly. The formation of such advanced nanocomposites has an enor­
already research on vegetable oil (soybean, linseed, castor, tung oil and mous significance related to the tremendous improvement in
cardanol) based PUA, which has utilized in UV curable coatings and performance in the mechanical, barrier, and flame retardancy, thermal,
coatings exhibited excellent adhesion substrates, low volumetric optical, electrical, and biological properties, which are poor in pristine
shrinkage, high gloss, and hardness [142–145]. Furthermore, hydroxyl PU [154,155]. The most outstanding significance of PU nanocomposites
groups can also be introduced in vegetable oil through several methods, coating is retaining its lightweight characteristics and transparency,
as discussed above, and the prepared polyol reacts with diisocyanate and something not possible to achieve employing conventional systems
acrylate functionality (mono, di, and tri) to the preparation of PUA [156]. Recent advancement in the field of coating technologies is the

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

Fig. 12. General reaction scheme for vegetable oil-based polyurethane acrylate.

design and development of functional nanocomposite coatings by and mechanical properties of UA nanocomposites [168]. These coatings
incorporation of nanoparticles used in organic coatings are CaCO3 showed substantial enhancement in nanocomposites’ mechanical
[157], Fe2O3 [158], Al2O3 [159], ZnO [160], TiO2 [161], SiO2 [162] properties and thermal performance by incorporating 3 or 5 wt% clay
and clay [163]. Predominantly, the size, shape, and concentration of nanoparticles to polymer-matrix with improved nanocomposites’ ther­
these nanomaterials determine the type of coatings they provide. The mal conductivity. The incorporation of nanoclay enhanced the phys­
use of vegetable oils in the fabrication of organic nanocomposite coat­ icomechanical performance of nanocomposite coatings. Alam and
ings enhances the biodegradability, thermal and mechanical stabilities, co-workers developed eco-friendly polyurethane-TiO2 nanocomposite
anticorrosion property, adhesion and flexibility of the products [155]. coatings using sunflower oil-based amide diol as a soft segment, toluene
Gurunathan and Chung prepared a sequence of cottonseed oil-derived diisocyanate and TiO2 nanoparticles. The performance of nano­
waterborne polyurethane–silica hybrid coatings by creating a chemi­ composite coatings with nano TiO2 shows improved corrosion, me­
cally modified interface between NCO groups of polyurethane oligomers chanical, and thermal stability behavior compared to virgin
and the surface of 3-aminopropyl trimethoxysilane (APTMS). Cotton­ polyurethane coatings [169]. Kashif et al. prepared polyorthotoluidine
seed oil was used to prepare modified APTMS PU composites. The (POT)/castor oil polyurethane (COPU) nanocomposite coatings by a
APTMS acts as a bifunctional chain extender/filler and acts as a rein­ solution blending technique and investigated its anticorrosion proper­
forcing agent in the hybrid coatings [164]. Patil et al. reported two types ties. The anticorrosive properties of COPU coatings in saline and acid
of bio-based hyperbranched polyester polyols (HyBPs) prepared by conditions were found to be inferior compared to the POT/COPU coat­
reacting castor oil-based polyols (monoglyceride and fatty amide) with ings. A low dispersion level of POT in COPU is found to enhance these
2,2-bis (hydroxymethyl) propionic acid. Subsequently, they prepared coatings’ thermal stability and physicomechanical properties [170].
nanocomposites coatings of HyBPs filled by graphene oxide nano­
particles in 3 different weight percentages variation (0, 0.1, and 0.5 % of
graphene oxide for HyBPs weight) [165]. Madhi and co-workers pre­ 3.6. Non-isocyanate polyurethane (NIPU) coatings
pared environmentally friendly and bio-based UV-curable urethane
acrylate-filled with graphene at loads varying from 0 wt% to 3 wt% Due to the new European regulations imposed since January 2009,
[166]. The incorporation of graphene oxide nanoparticles demonstrated free isocyanate content is strictly monitoring and regulating. Polymer
a reduction of surface roughness of coatings and increment of thermo­ researchers have also been comprehensively exploring the synthesis of
mechanical properties of the resultant nanocomposite coating film to bio-based isocyanates in recent years. Traditionally, most commercial
increase graphene oxide loading. Azemati et al. investigated nano­ processes for manufacturing diisocyanate monomer are based on
particles’ effect on coatings and heat transfer using various wt% of nano noxious substances such as phosgene. Therefore, vegetable oil-derived
zirconium oxide (1, 3, and 5%) on metallic plates [167]. Besides, zir­ non-isocyanate polyurethanes (NIPUs) raised industrial and academic
conium oxide nanoparticles enhanced the coating’s emissivity coeffi­ research curiosity and research hotspot in polyurethane applications in
cient and absorption in all samples. Amoozadeh and co-workers the coatings industry [171–173]. NIPU based coatings are generally a
prepared UV-curable urethane acrylate-Clay nanocomposites (UA/Clay) two-pack system that is safe-to-handle, moisture insensitive and have
to study the nanoparticles’ effects on the thermal conductivity, stability little-to-no use of the volatile organic compound (VOC) [174]. The
coatings held excellent adhesion, chemical, and abrasive resistance,

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P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

high hydrolytic stability than traditional PU systems [175]. Numerous NIPU based coatings through sunflower oil with a solvent and
methods have been investigated to synthesize NIPUs, including catalysts-free approach. The prepared sunflower oil-based cyclic car­
step-growth polyaddition, polycondensation, ring-opening polymeriza­ bonate was reacted with aliphatic and aromatic amines with different
tion (ROP), and rearrangement reactions [176]. To summarize, among molar ratios. The NIPU coatings prepared from IPDA exhibited superior
the numerous routes leading to NIPUs, the polyaddition of cyclic car­ anti-corrosive and physicochemical properties than EDA and DETA
bonates prepared from renewable feedstocks with diamines seems to be [175]. Das et al. prepared the eco-friendly polyurethane resin systems
the most exciting pathways. The synthetic strategy is outlined in via bulk polyaddition reaction of natural amine-containing poly­
(Fig. 13) [177]. saccharide, chitosan with carbonated soybean oil (CSBO) to produce the
Among these, the chemical interactions between CO2 and corre­ NIPUs. They successfully synthesized CSBO by reacting epoxidized
sponding epoxy precursors have been widely researched. The epoxy soybean oil with carbon dioxide. Overall, the higher cross-link networks
groups can be developed from unsaturated vegetable oil (soybean oil, produced by the stoichiometric carbonate-to-amine ratio and prepared
linseed oil, sunflower oil, mustard oil, etc.). The epoxy moieties can be coatings show the highest density, thermal stability, and mechanical
reacted with the CO2 at a higher temperatures and in the presence of an properties [184]. The short-chain diamines (ethylenediamine) showed
organo-catalyst (Tetrabutylammonium halide) to prepared cyclic car­ the maximum tensile strength and hardness, and long-chain diamines
bonate. The prepared cyclic carbonate group provides favorable reac­ (hexamethylenediamine) showed minimum tensile strength and hard­
tion conditions to synthesized cross-linked or linear NIPU networks ness properties variation in hydrogen bonding and cross-linking density.
[177–179]. The cyclic carbonates are non-toxic, biodegradable, and can The NIPU system cannot achieve curing at ambient temperature due to
be used as solvents with high boiling and flashpoints. Cyclic the low reactivity of the cyclic carbonates compared to the hydroxyl and
carbonate-containing oligomers form NIPU with aliphatic amines isocyanate reactions of conventional PU; thus, curing at high tempera­
(Hexamethylenediamine, diethyltriamine ethylenediamine, tris (2-ami­ tures is favored. These restrict NIPU systems’ application for room
noethyl) amine) or aromatic amines (isophorone diamine, m-xylenedi­ temperature coatings such as furniture, floor, automotive, and industrial
amine, and p-xylenediamine) or polyamines (polyoxypropylene adhesives [185,186].
diamines, polyoxypropylene triamine) through a simple ring-opening
addition reaction [180,181]. Pathak et al. invented a novel synthesis 4. Conclusion and future perspective
route of NIPUs coating via dehydrated castor oil fatty acid, using a
three-step process comprising esterification and epoxidation, followed This article provides a modernized viewpoint on polyurethane
by carbonation using CO2. The presence of hydroxyl-urethane groups in coatings research, which encompasses advances in various synthesis
the final coating enhanced the coating’s overall properties [182]. Soy­ schemes and coating techniques, having industrial significance. Vege­
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cure [183]. Doley et al. produced environmentally friendly, low-cost primary and most widely applied route for synthesizing polyols from

Fig. 13. Synthesis route for vegetable oil-based non-isocyanate polyurethane.

13
P.M. Paraskar et al. Progress in Organic Coatings 156 (2021) 106267

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Declaration of Competing Interest oil-based polyurethane for potential application as host in polymer electrolytes,
Bull. Mater. Sci. 38 (2015) 1155–1161, https://doi.org/10.1007/s12034-015-
0995-8.
The authors report no declarations of interest. [22] U. Stirna, A. Fridrihsone, B. Lazdiņa, M. Misāne, D. Vilsone, Biobased
polyurethanes from rapeseed oil polyols: structure, mechanical and thermal
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Acknowledgments s10924-012-0560-0.
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The authors thank the Department of Science and Technology (DST- waterborne polyurethane–Silanol dispersions from cottonseed-oil-Based
phosphorylated polyol as ionic Soft segment, ACS Sustainable. Chem. Eng. 5
Inspire), Delhi, India, for the funding. (2017) 6447–6455, https://doi.org/10.1021/acssuschemeng.7b00327.
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