Industrial Crops and Products -...

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Industrial Crops and Products 76 (2015) 215–229 Contents lists available at ScienceDirect Industrial Crops and Products journal homepage: www.elsevier.com/locate/indcrop Recent advances in vegetable oils based environment friendly coatings: A review Eram Sharmin a,b,, Fahmina Zafar a,c , Deewan Akram a,d , Manawwer Alam e , Sharif Ahmad a a Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110 025, India b Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955, Saudi Arabia c Inorganic Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia,New Delhi 110 025, India d Department of Chemistry, Faculty of Science, Jazan University, P.O. Box 2097, Jazan, Saudi Arabia e Research Centre–College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia a r t i c l e i n f o Article history: Received 17 January 2015 Received in revised form 6 June 2015 Accepted 9 June 2015 Keywords: Vegetable oils Coatings Environment friendly High solids Waterborne Hyperbranched UV curable a b s t r a c t The overarching goal worldwide for the scientific community is “sustainable development” today, for an everlasting sustainable and green tomorrow. The strategy includes (i) harvesting renewable resources instead of fossil fuels, (ii) using environment friendly routes, and (iii) engineering material degradation pathways operating under reasonable time frames. The concept revolves around the focal point of “Green” or “Sustainable” Chemistry. In the world of coatings, the idea has already made its debut in the form of environment friendly technologies-low or no solvent, high solids, hyperbranched, water borne and UV curable coatings, utilising monomers/polymers derived from renewable resources. Vegetable oils [VEGO] constitute Mother Nature’s most abundant, cost-effective, non toxic, and biodegradable resource. They have been traditionally used for several non-food applications mainly coatings since primitive times. Today, the implementation of the modern technologies coupled with the full fledged use of VEGO based monomers or polymers in the field as raw materials, is an excellent effort toward sustainable future in the world of coatings globally. The review highlights some state-of-the art-modifications of VEGO as environment friendly-low or no solvent, high solids, hyperbranched, water borne and UV curable coatings. The article provides a handy overall vision of VEGO based environment friendly coatings on a single platform. These approaches can be well employed on those oils that are non-edible, non-medicinal and are left unexplored, unutilised or underutilised to date, thus adding value to an unutilised or underutilised sustainable resource. © 2015 Elsevier B.V. All rights reserved. Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 2. VEGO and their chemical transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 3. Low solvent or “zero solvent” coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 4. High solids [HS] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 5. Hyperbranched [HYP] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220 Abbreviations: BMF, butylated melamine formaldehyde; CasO, castor oil; DGEBA, diglycidyl epoxy of bisphenol A; DMPA, dimethylol propionic acid; DPE, dipentaerythritol; FAD, fatty amide diol; HS, high solids; HYP, hyperbranched; HBPA, HYP polyamine; HPU, HYP polyurethane; LinO, linseed oil; MFO, Mesua ferrea oil; MG, monoglycerides; MMT, montmorillonite; MWCNT, multiwalled carbon nanotubes; NC, nanocomposites; HEFA, N,N’-bis(2-hydroxyethyl)fatty amide; PAA, poly(amido amine); PANI, polyaniline; PCD, poly(-caprolactone) diol; PEsterA, polyesteramide; PU, polyurethanes; RSO, rubberseed oil; SoyO, soybean oil; SunFO, sunflower oil; TDI, toluene-2,4-diisocyanate; TO, tung oil; UV, ultra violet; VEGO, vegetable oils; VOC, volatile organic compounds; VOMM, VO macro-monomer; WB, waterborne; WPU, waterborne polyurethane. Corresponding author at: Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110025, India. Fax: +91 11 26981717/Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955, Saudi Arabia. E-mail address: [email protected] (E. Sharmin). http://dx.doi.org/10.1016/j.indcrop.2015.06.022 0926-6690/© 2015 Elsevier B.V. All rights reserved.

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Industrial Crops and Products 76 (2015) 215–229

Contents lists available at ScienceDirect

Industrial Crops and Products

journa l homepage: www.e lsev ier .com/ locate / indcrop

ecent advances in vegetable oils based environment friendlyoatings: A review

ram Sharmin a,b,∗, Fahmina Zafar a,c, Deewan Akram a,d, Manawwer Alam e,harif Ahmad a

Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110 025, IndiaDepartment of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,audi ArabiaInorganic Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia,New Delhi 110 025, IndiaDepartment of Chemistry, Faculty of Science, Jazan University, P.O. Box 2097, Jazan, Saudi ArabiaResearch Centre–College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia

r t i c l e i n f o

rticle history:eceived 17 January 2015eceived in revised form 6 June 2015ccepted 9 June 2015

eywords:egetable oilsoatingsnvironment friendlyigh solidsaterborne

yperbranchedV curable

a b s t r a c t

The overarching goal worldwide for the scientific community is “sustainable development” today, for aneverlasting sustainable and green tomorrow. The strategy includes (i) harvesting renewable resourcesinstead of fossil fuels, (ii) using environment friendly routes, and (iii) engineering material degradationpathways operating under reasonable time frames. The concept revolves around the focal point of “Green”or “Sustainable” Chemistry. In the world of coatings, the idea has already made its debut in the form ofenvironment friendly technologies-low or no solvent, high solids, hyperbranched, water borne and UVcurable coatings, utilising monomers/polymers derived from renewable resources. Vegetable oils [VEGO]constitute Mother Nature’s most abundant, cost-effective, non toxic, and biodegradable resource. Theyhave been traditionally used for several non-food applications mainly coatings since primitive times.Today, the implementation of the modern technologies coupled with the full fledged use of VEGO basedmonomers or polymers in the field as raw materials, is an excellent effort toward sustainable futurein the world of coatings globally. The review highlights some state-of-the art-modifications of VEGO as

environment friendly-low or no solvent, high solids, hyperbranched, water borne and UV curable coatings.The article provides a handy overall vision of VEGO based environment friendly coatings on a singleplatform. These approaches can be well employed on those oils that are non-edible, non-medicinal andare left unexplored, unutilised or underutilised to date, thus adding value to an unutilised or underutilisedsustainable resource.

© 2015 Elsevier B.V. All rights reserved.

ontents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2162. VEGO and their chemical transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216

3. Low solvent or “zero solvent” coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4. High solids [HS] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5. Hyperbranched [HYP] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Abbreviations: BMF, butylated melamine formaldehyde; CasO, castor oil; DGEBA, diglycAD, fatty amide diol; HS, high solids; HYP, hyperbranched; HBPA, HYP polyamine; HPU, HYontmorillonite; MWCNT, multiwalled carbon nanotubes; NC, nanocomposites; HEFA,

CD, poly(�-caprolactone) diol; PEsterA, polyesteramide; PU, polyurethanes; RSO, rubbeO, tung oil; UV, ultra violet; VEGO, vegetable oils; VOC, volatile organic compounds; VO∗ Corresponding author at: Materials Research Laboratory, Department of Chem

ax: +91 11 26981717/Department of Pharmaceutical Chemistry, College of Pharmacy, Uaudi Arabia.

E-mail address: [email protected] (E. Sharmin).

ttp://dx.doi.org/10.1016/j.indcrop.2015.06.022926-6690/© 2015 Elsevier B.V. All rights reserved.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .220

idyl epoxy of bisphenol A; DMPA, dimethylol propionic acid; DPE, dipentaerythritol;P polyurethane; LinO, linseed oil; MFO, Mesua ferrea oil; MG, monoglycerides; MMT,

N,N’-bis(2-hydroxyethyl)fatty amide; PAA, poly(amido amine); PANI, polyaniline;rseed oil; SoyO, soybean oil; SunFO, sunflower oil; TDI, toluene-2,4-diisocyanate;

MM, VO macro-monomer; WB, waterborne; WPU, waterborne polyurethane.istry, Jamia Millia Islamia (A Central University), New Delhi 110025, India.

mm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,

216 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229

6. WB coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2227. Radiation curable coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2258. Future perspectives and summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

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References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. Introduction

In the past two decades, research and development efforts havendergone vast changes globally, due to the ever growing con-umer expectations of good quality and performance coupled withower cost, escalating prices of petro-based chemicals due to theear of depleting stocks by the end of twenty first century, concernselated to energy consumption and environmental contaminationimproper waste management, greenhouse effect, health prob-ems), regulations such as Clean Air Act Ammendment, 1990 andapid innovations. These challenges related to predictions, regula-ions and innovations have forced the coatings industry to changets gears worldwide and resulted in the exploration and utilizationf sustainable alternatives to chemicals derived from petro-basedroducts (Lochab et al., 2014). The researchers in industry andcademia are actively engaged to explore and formulate new strate-ies to meet the mandatory limits through the “tapping of our greenold-the naturally available resources” primarily:-

(i) to cut off the increasing raw material costs of the petro-basedproducts

(ii) to develop environmentally benign formulationsiii) to expedite their post-service degradationiv) to add value to an otherwise waste material

As a consequence, some “environmentally friendly” or “green”echnologies have evolved, with special emphasis being laid on thexcessive utilization of renewable resources such as vegetable oilsVEGO] and also reducing or eliminating the use of volatile organicompounds [VOC]. Considering the vast amount spent on corro-ion and its mitigation programs worldwide, we understand thathe proper utilization of our domestically abundant sustainableesources such as VEGO thriving on our acres of agricultural lands

ay prove as silver lining, in this regard (Balachandran et al., 2013;iller, 2014). This review article describes the recent advances

n the modifications and applications of VEGO as environmentriendly protective coatings, role of VEGO based components inoverning the properties of these coatings, and further encourageshe application of these approaches on non-edible and non-

edicinal VEGO, adding value to a waste or unutilized sustainableesource.

. VEGO and their chemical transformations

VEGO constitute a broad class of sustainable resources render-ng a plethora of value added functional materials. They comprisene of the most important components of biomass. They are tri-sters of glycerol and fatty acids (saturated and unsaturated).EGO mainly consist of triglycerides as major (93–98 wt%) andiglycerides, monoglycerides and phosphoglycerides as minoromponents. VEGO and their derivatives find applications in coat-ngs owing to their unique structural attributes and tendency toorm films (depending upon their unsaturated portion). Consider-

ng their degree of unsaturation, described by their iodine value,EGO are classified as “drying” (iodine value > 130), “semi-drying”

100 < iodine value < 130) and “non-drying” (iodine value < 100)asn linseed oil [LinO], soybean oil [SoyO] and palm kernel oil,

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

respectively (Alam et al., 2014; Xia and Larock, 2010). Usually, dry-ing or semi-drying oils are used in surface coatings. Non-dryingoils may also be utilized for the purpose by the incorporationof suitable entities (e.g., hydroxyls) or modifiers (vinyls, acrylics,acrylic co-polymers) in oil backbone, through chemical reactionsto transform them as film formers. In virgin oils, longer dryingtimes are required while the films formed do not meet the desir-able physico-mechanical and corrosion resistance performance.Consequently, several chemical transformations are carried outthrough the important functionalities and active sites of VEGOsuch as hydroxyls, oxiranes, double bonds, allylic carbons, esters,alpha carbon to the ester group and others. About 90% reactionsoccur at carboxyl functionality while the rest involve unsatura-tion sites (Gunstone, 2001). Some of them have been exemplifiedin Fig. 1. VEGO undergo glycerolysis reaction resulting in the for-mation of monoglycerides or diglycerides that are used as rawmaterials in the production of alkyds. Amidation (base catalysed)is carried out at carboxyl functionality, producing fatty amidediols/polyols that serve as starting material for the developmentof polyesteramides [PEsterA] and polyetheramides. Another muchexplored important reaction is transesterification reaction alsooccurring at carboxyl functionality. Epoxidation and hydroxylationreactions occurring at double bonds of VEGO produce epoxies andpoyols, respectively. The former render strong thermosets whencured by suitable curing agents such as amines, acids, amides,while the latter yield polyester and polyurethane [PU] coatingson treatment with acid/anhydride or isocyanates. Maleinization,acrylation, vinylation, hydrohalogenation are few other examplesinvolving reactions at double bonds of VEGO (Ahmad et al., 2004;Lligadas et al., 2013; Maisonneuve et al., 2013; Miao et al., 2014;Montero de Espinosa and Meier, 2011; Mosiewicki and Aranguren,2013).

The coatings obtained from fossil fuel derived petro-basedchemicals such as vinyls, acrylics, epoxies, PU, polyesters andothers, are often (i) costly, (ii) toxic, (iii) hazardous after use (non-biodegradable), and (iv) may require ample of hazardous solventsduring processing and coating applications, thus causing envi-ronmental contamination and health hazards on exposure. VEGOderivatives are generally devoid of these drawbacks bearing advan-tages of cost effectiveness, non-toxicity, biodegradability, requiringno or low solvents due to their inherent fluidity characteristic.VEGO coatings are available for specific uses as antimicrobial,biocompatible, biodegradable, corrosion protective, architectural,decorative, electrical insulating, paper packaging, and self-healingcoatings. However, due to long aliphatic hydrophoebic chains, theyare often low on mechanical strength, lack toughness and are waterinsoluble (Bordes et al., 2009; Lligadas et al., 2010). Thus to fur-ther augment the performance of VEGO coatings, and to competewith their petro-based counterparts, several innovative and state-of-the-art modifications have been accomplished in the field.

3. Low solvent or “zero solvent” coatings

VEGO chains are flexible due to the the presence of long aliphaticfatty acid chains. VEGO derivatives generally serve as solvents orreactive diluents in coatings, often in combination with commercialresins, and themselves participate in chemical reactions occurring

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229 217

l reac

dpK2

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Fig. 1. Chemica

uring drying or curing or crosslinking reactions forming inherentart of the final material (Ahmad et al., 2011; Czub, 2006; Das andarak, 2009; Ghosal et al., 2013; Muturi et al., 1994; Sharmin et al.,011, 2010).

The research is focused on the development of VEGO based coat-ngs using “zero solvent” or “low solvent” approach. This meansuring synthesis and coating formulation, either completely elim-

nating the use of solvent or introducing only minimum amountf solvent for dilution, to offset the effect of high viscosity oftenchieved in due course of chemical reactions, as a result of increasen crosslinking and viscosity, which restricts the free mobility ofolymer chains, during polymerisation.

Ahmad et al. and Zafar et al., prepared solventless PEsterA andetal containing PEsterA from Linum ussiatatissimum or Linseed Oil

LinO], taking advantage of inherent fluidity of VEGO chains (Fig. 2).he synthesis of PEsterA is generally accomplished by chemicaleaction between N,N’-bis(2-hydroxyethyl) fatty amide (obtainedy base catalysed amidation of VEGO) and phthalic anhydride orhthalic acid as raw materials, in presence of on organic solvente.g., xylene). However, during synthesis of PEsterA under solventree conditions, self catalysed direct esterification reaction takeslace at temperature lower than the melting points of both theonomers used as raw materials, owing to (i) good fluidity of N,N’-

is(2-hydroxyethyl) fatty amide in which phthalic anhydride isissolved, and (ii) solvent free condition allowing better proximityf the reactants with each other facilitating the reaction to occurt relatively lower temperature (Ahmad et al., 2007; Zafar et al.,011). In solvent free synthesis of metal [Zn (II), Mn (II), Co (II), CuII)] containing PEsterA, the mechanism involved (self catalysed)

ddition–elimination mechanism at the carbonyl double bond ofhe carboxylic acid group of PEsterA chain. The presence and con-ent of metal also governed the synthesis reaction time due to theatalytic effect of the metal itself. The results obtained were based

tions of VEGO.

on the extent of occupancy of d orbitals of the metals. Co (II) and Cu(II) containing PEsterA were prepared in lower reaction time due totheir partially filled d orbitals (d7 and d9) which conferred higherreactivity as compared to Mn(II) having half filled (d5) d orbitals,associated with higher stability and lower reactivity. Similar resultswere also observed in drying times/curing behavior of coatings.PEsterA containing Co (II) and Cu (II) metals (with higher number ofunfilled d orbitals) were cured faster compared to Mn (II) containingPEsterA (half filled d orbitals) due to higher reactivity of the former.The curing behavior in metal containing solvent free PEsterA wasa result of cross-linking of polymeric chains through coordinationof metals with donor groups of the polymer such as oxygen, nitro-gen and double bond, contrary to the curing mechanism of plainVEGO based PEsterA which involves slow lipid autoxidation pro-cess that further requires driers to accelerate the curing process(Ahmad et al., 2007; Zafar et al., 2007, 2011). Akram et al. (2008,2010a,b) developed LinO and castor oil [CasO] based boron contain-ing PU coatings for corrosion protection using minimum amount ofsolvent (used in the second step of reaction, i.e., PU formation, onlyto offset the effect of high viscosity and complexity of the inherentPU structures) with good physico-mechanical and chemical resis-tance against alkali, acid, tap water and xylene, and also thermalstability upto 220 ◦C.

Karak and Das prepared nanocomposite blends of Mesua fer-rea oil [MFO] based epoxy and commercial epoxy with nanoclayas modifier cured with poly(amido amine) hardener for useas coatings. The combination produced miscible system withgood compatibility of either matrix. The hardener simultaneouslyreacted with oxirane rings present in either epoxy resin, allowing

for better compatibility of the two matrices, and proper interac-tion of nanoclay. The cumulative effect of commercial and VEGOepoxies, respectively, as well as nanoclay, can be observed inthe improved scratch hardness, impact resistance, flexibility and

218 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229

O (in

aIaeiwapcarhiupeg

Fig. 2. Synthesis of PEsterA from VEG

dhesion of the nanocomposite coatings (Das and Karak, 2009).t can be seen that MFO epoxy served as the binder, diluent andlso modifier to offset the brittleness (drawback) of commercialpoxy, owing to its long (flexible) aliphatic alkyl chains render-ng toughness. Thus, MFO based epoxy acted as an ingredient as

ell as reactive diluent in nanocomposite preparation. Sharminnd coworkers described the in situ preparation of LinO basedolyol nanocomposite as a raw material for polyester and PUoatings, with LinO polyol as organic matrix and metal acetates inorganic precursor by facile “solventless, one-pot” chemicaleaction (Sharmin et al., 2013). LinO polyol is formed by theydroxylation reaction of LinO; it bears hydroxyl groups chemically

nserted (via epoxidation followed by hydroxylation) at unsat-

ration sites of LinO (Sharmin et al., 2007). Thus, LinO basedolyol not only served the purpose of solvent due to its inher-nt fluidity characteristic, but also as matrix providing functionalroups for the chemical reaction), and also as stabilizer (prevent-

the absence and presence of solvent).

ing agglomeration of nanoparticles) for the preparation of metaloxide nanoparticles from metal acetate and hydroxyls of LinOpolyol, resulting in the formation of nano-sized metal oxide parti-cles producing nanocomposite (Sharmin et al., 2015, 2013). In situpreparation of SiO2 nanoparticles was carried out in polyol matrixusing tetraethoxyorthosilane as inorganic precursor and CasO andLinO based polyols as organic matrices, respectively, by “zero sol-vent” approach (Akram et al., 2010a,b; Sharmin et al., 2011). Theprepared coatings were scratch resistant, impact resistant, glossyand flexibility retentive (Akram et al., 2008, 2010a,b; Sharmin et al.,2011).

4. High solids [HS] coatings

The drive towards HS coatings is initiated and fostered byenvironmental regulations. Epoxy, alkyd and PU based coatingsare currently representing the major part of HS coatings in the

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229 219

ased H

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Fig. 3. VEGO b

rotective coatings market. Paints with more than 80% solidsontent by volume are generally referred to as HS paints; thoseith 60–70% solids content can also be called HS paints. These sys-

ems contain a higher percentage of solids paints and lower solventontent than conventional solvent-borne coatings (Chattha and vanene, 1982; Haseebuddin et al., 2009). Efforts are also being made

o develop 100% solids PU and PU urea coatings.HS coatings have lower solvent emissions as well as other tech-

ical benefits besides bearing closer resemblance to conventional

ystems with improved performance and durability, making themeadily acceptable in applications. In HS coatings, narrow molecu-ar weight distribution is attained to lower solution viscosity with

more homogeneously cross-linked network (Lindeboom, 1997).

YP polyester.

The lowering of viscosity can be achieved by increasing oil chainlength (of binder) that lowers the molecular weight and also intro-duces more unsaturation content (due to C C of oil). However, anadverse consequence of lowering the molecular weight and vis-cosity of HS coatings is poor stabilization properties and dryingbehavior of coatings (Zabel et al., 1999). To overcome this prob-lem, conventional solvents in HS coatings are partially replaced byreactive diluents that function as diluents during the formulationof coatings and during curing, form an integral part of the coating.

Often driers are used to promote drying in thick films (Bhabhe andAthawale, 1997; Das and Karak, 2009; Lindeboom, 1997).

HS alkyds from Glycine max or SoyO and dehydratedCasO fatty acid combinations with varying percentage of

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20 E. Sharmin et al. / Industrial Cr

ipentaerythritol [DPE] (as multi-functional polyol to introduceranching) have been synthesized with 80% solids in mineral tur-entine oil and characterized for their physicochemical, optical,hermal and mechanical properties. The increased DPE contentntroduced good branching, cross linking, and increased the corro-ion protection performance, improved gloss and thermal stabilityf the alkyd coating (Haseebuddin et al., 2009).

Air drying HS alkyd paints provide environmental as well as eco-omical benefits (Lindeboom, 1997). Alkyd–acrylic hybrids havingnal solids content of 75–80% were prepared by dropping alkydesin into an acrylic dispersion (Jowkar-Deriss and Karlsson, 2004).ifferent liquid structures were produced depending on the modef addition of the surfactant to the system. To improve upon therying characteristics of HS alkyd paints, thiol–ene reaction wasarried out, which can assist their oxidative drying. Fast drying HSlkyd paints were thus obtained by using visible light photoinitia-ors and/or cobalt free metal catalysts (Klaasen and van der Leeuw,006).

VEGO polyols have relatively high molecular mobility, containendant dangling chains, which lead to relatively low glass tran-ition temperatures (Tg) and a low modulus. Kong and coworkersroduced polyols, Liprols, by epoxidation/hydroxylation of VEGOCanola, Helianthus annuus L. or Sunflower oil [SunFO], Camelina,inola® 2090 flax and NuLin® 50 flax crude oils) followed by trans-sterification reactions of the glycerides with diols (1,2 propaneiol and 1,3 propane diol). Such polyols on treatment with an

socyanate produced PU coatings which were HS in nature. Suchoatings showed good adhesion due to chemical interaction andechanical interlocking at the interface. Also, few pendant chains,

ow molecular weight and high functionality are another importantactors contributing to good performance of these coatings. The sol-ent free approach also improved hydrophobicity of coatings byncreasing of cross-linking density (Kong et al., 2013).

A good HS coating material should have acceptably low viscos-ty without compromising on performance characteristics of the

aterial. This is achieved by the use of reactive diluents, increas-ng oil chain length, and narrower molecular weight distribution.

diluent decreases the viscosity of the material and eventuallyecomes an integral part of the coating after drying (since itarticipates in drying reactions). The lowering of molecular weight

s achieved by increasing of fatty acids contents or increasing theatio of OH/COOH groups. However, a homogenous network cannote formed and overall coating properties are deteriorated. Increas-

ng oil chain length often results in loose packing of molecules (dueo unsaturation). Low molecular weight resins often exhibit slowrying and sagging. So, to overcome these drawbacks, along withhe reduction of molecular weights in the resins, a simultaneousncrease in molecular branching was performed; it was preferredo obtain resins with well-defined highly branched structure.

. Hyperbranched [HYP] coatings

The dendritic polymers–dendrimers, HYP polymers and den-rigrafts are preferred over HS resins. The dendrimers involve

solation and purification steps and are costly relative to HYPolymers, which combine lower manufacturing costs and sin-le step polymerization. The principal concept of HYP polymerseports back to the works of Flory and Kienle past several decades,hich later on graduated to more elaborated building blocks (van

enthem, 2000).Star and HYP polymers show improved drying and performance

haracteristics over HS alkyds; these are synthesized in single step

nd are less costly than their other counterparts. The low viscositiesf the final product allow for easier film formation and the low VOContent attribute to the environment friendliness (Bat et al., 2006;indeboom, 1997; Manczyk and Szewczyk, 2002).

d Products 76 (2015) 215–229

HYP polymers have many advantages over their linear analogs.HYP polymers have higher solubility, lower hydrodynamic diam-eter and lower melt as well as solution viscosity, and highreactivity compared to their linear counterparts owing to theircompact, non-entangled and highly branched structures withlarge numbers of active functional groups on the periphery(Deka and Karak, 2009a,b). Due to their highly functionalizedthree-dimensional globular non-entangled inimitable architecturalfeatures and unique properties coupled with their single-steppreparative techniques, these macromolecules are considered asadvanced polymeric materials. Chattopadhyay and Raju (2007)have described the structures and properties of HYP polyols,polyesters, PU, and others. Bat and coworkers prepared HYPpolyester using DPE as core molecule and dimethylol propionicacid [DMPA] twice, as chain extender, to obtain HYP derivativewith peripheral hydroxyl groups. The latter was further reactedwith CasO fatty acid, LinO fatty acid and benzoic acid, to obtainHYP of second, third and fourth generation (Fig. 3). VEGO contentprovided reduced viscosity and increased hardness to the coat-ings, which showed good abrasion resistance, adherence to thesubstrate, excellent gloss and flexibility (Bat et al., 2006). Radia-tion curable material was synthesized by Samuelsson et al. (2004),from a hydroxy functional HYP polyether onto which an epoxyfunctional fatty acid, vernolic acid, was attached, polymerized withvernolic acid methyl ester as reactive diluents; the results werecompared with a model oil based trimethylol propane [TMP] films(structurally similar but with no polyether core), which showedlower Tg value and softness after polymerization. In anotherpublication by Karakaya et al. (2007) DPE (core molecule) wastransesterified with CasO and a mixture of CasO and LinO andesterified with DMPA. The obtained HYP resin was treated withmelamine formaldehyde; the coatings prepared therefrom showedexcellent adhesion, gloss, flexibility, impact and abrasion resis-tance.

Urethane acrylates with different degrees of acrylation wereobtained by the reaction of partially modified HYP polyesters anddifferent amounts of acrylate-isocyanate adduct from equimolaramounts of isophorone diisocyanate and 2-hydroxyethyl acrylate.Here, HYP of the second and the third pseudo-generation weresynthesized from DMPA and TMP; the modification of the OH end-groups was carried out with isononanoic acid and SoyO fatty acidsin separate reports by Dzunuzovic et al. (2006). Tall oil fatty acidsbased HYP alkyd resin prepared from fourth generation hydrox-ylated HYP polyester through acid catalysis exhibited excellentadhesion, flexibility, drying time, gloss and chemical resistance(Murillo et al., 2010, 2011).

In a recent work, the drawbacks of epoxy resins such as brit-tleness or low toughness and nonbiodegradability were overcomeby preparing a HYP epoxy from CasO modified HYP polyesterpolyol and in situ-generated diglycidyl ether of bisphenol A[DGEBA]. Here, biodegradation and flexibility were conferred bythe VEGO chains. HYP structure as well as the aromatic (epoxy) andaliphatic (VEGO chains) constituents collectively imparted goodtoughness to the coatings, increasing the free volume betweenmolecules (due to steric effect) in the three-dimensional network(De et al., 2014). Hyperbranched polyurethane [HPU], polyester,alkyd and hyperbranched polyesteramide [HPEsterA] coatingswere produced from MFO, CasO, and SunFO. A VEGO deriva-tive as biobased chain extender is treated with another chainextender, isocyanate and a multi-functional amine by A2 + B3approach (Fig. 4; Kalita and Karak, 2014). The produced materialsshowed good thermostability, flame retardancy, hardness, chem-

ical resistance, higher tensile strength, impact resistance, scratchhardness, flexibility retention than their linear counterpart owingto the stronger intra- and intermolecular secondary interactions,hydrogen bonding, chain entanglements and compact confined

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229 221

s of VE[ brancS

gtsic2aKePtptbstmg

Fig. 4. SynthesiReprinted (adapted) with permission from Kalita and Karak (2014). Biobased hyperci. 131, 39579–39586.]. Copyright 2013. John Wiley and Sons.

eometry, collectively. Good flexibility retention was offered byhe fatty chains of the parent VEGO, within the highly branchedtructure and the presence of larger void spaces which offer eas-er movement of chains in HYP material relative to the linearounterpart (Bao et al., 2013; Das et al., 2013; Deka and Karak,009a,b; Karak et al., 2009; Konwar and Karak, 2009; Mahapatrand Karak, 2007; Pramanik et al., 2013a,b,c; Rana et al., 2013;alita and Karak, 2014). SunFO based HPU were prepared by Dast al. (2013) by following A2 + B2 + B4 approach. SunFO based MG,CD, and butanediol were treated with TDI such that hydroxylerminated prepolymer (A2) was formed. In the next step this pre-olymer or diol was treated with pentaerythritol (B4) and TDIo produce HPU. Similarly, a linear PU analog was also preparedy the addition of BD in place of PE. HPU showed higher tensile

trength, impact resistance, scratch hardness, flexibility retentionhan its linear counterpart owing to the stronger intra- and inter-

olecular secondary interactions, hydrogen bonding, chain entan-lements and compact confined geometry of HPU, collectively

GO based HPU.hed shape-memory polyurethanes: effect of different vegetable oils. J. Appl. Polym.

Good flexibility retention was offered by PC component andMG chains of SunFO within the highly branched structure andthe presence of larger void spaces which offer easier move-ment of chains in HPU relative to the linear PU (Das et al.,2013).

Nanocomposites [NC] of VEGO based HYP polymers have beenprepared for some advanced applications demanding high mechan-ical strength, good adhesion, chemical resistance, thermostability,low water vapor permeability and others, with different nanore-inforcements such as Octadecylamine-modified montmorilloniteclay (MMT) nanoclay, silver nanoparticles, Multiwalled Carbonnanotubes (MWCNT), polyaniline [PANI] nano fibres, Function-alised reduced graphene oxide (f-RGO), and others. It can be wellinterpreted that the properties of HYP depend upon the type ofVEGO as parent precursor, chain extender, isocyanate, and the type

of nano-reinforcement employed. HYP are much sought after mate-rials for surface coating applications due to their unique propertiesand reduced viscosity (Table 1 and Fig. 5 ).

222 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229

Table 1Environment friendly nanocomposite coatings from VEGO.

S.No. Type Modifiers Properties References

1. HPU from MFO MMT nanoclay Light weight, transparency,flexibility characteristic, goodtensile strength, scratchhardness, impact resistance,low water vapor loss, higherthermal stability

Deka and Karak (2010, 2011)De and Karak (2014) De et al.(2014)

2. HPU from MFO Silver nanoparticles and clay Good thermal stability andmechanical properties, longdispersion stability, smallparticle size, narrow sizedistribution along with goodantimicrobial efficacy againstE. coli, S. aureus, P. aeruginosaand C. albicans producingantimicrobial coatings

Deka et al. (2010a) Karak et al.(2010) Konwar et al. (2010)

3. HPEsterA from CasO (Fig. 5) MWCNT Improved tensile strength,shape memory, enhancedbiodegradability, and nocytotoxicity; with goodantimicrobial efficacy against S.aureus and B. subtilis

Deka et al. (2010b) Pramaniket al. (2013a,b,c) (Fig. 5)

4. HPEsterA from CasO PANI nano fibres Mechanically strong, thermallystable, antistatic materials dueto the interfacial interaction ofPANI nanofibers with the HYPPEA matrix

Pramanik et al. (2014,2013a,b,c)

5. HPU from CasO f-RGO Improved tensile strength andtoughness, good thermalstability and electricalconductivity

Thakur and Karak (2014b,a)

6. WPU from CasO: Organoclay Enhanced mechanical andthermal performance due tostrong interfacial interactionsbetween filler and matrix

Gurunathan et al. (2015)

7. WPEsterA from LinO MMT nanoclay Improved scratch hardness,impact resistance, flexibility,chemical resistance (in acid,alkali, salt and water, andthermal stability)

Zafar et al. (2015)

8. UV curable Acrylated LinO TiO2 nanoparticles Improved hardness, impactresistance, glass transition

Diez-Pascual and Diez-Vicente,(2015)

6

mwTwpmhmabItnect

sdob

. WB coatings

The term WB is applied to those coating systems that pri-arily use water as the solvent or sometimes upto 80% waterith small amount of other solvents such as glycol ethers.

hey are classified as: water–soluble/water–reducible (solutions),ater–dispersible/colloidal (dispersions) and emulsions (latex)

aints. The physical properties and performances of each typeentioned above depend upon the choice of the resin. Generally,

ydrophilic groups are inserted in oil chains that yield the poly-er water dispersible. The polymer derivatives commonly used

re vinyls, two-component acrylics, epoxies, polyesters, styrene-utadiene, amine-solubilized, carboxyl-terminated alkyd and PU.

nterest in WB materials arises due to their non-polluting, easyo handle, quick drying, economic and environmentally friendlyature (Athawale and Nimbalkar, 2011; Dara et al., 2009; Gündüzt al., 2002, 2004; Shah and Ahmad, 2012). The synthesis of WBoatings is a challenging task due to hydrophoebic nature of VEGOriglyceride chains.

WB alkyds based on non or semi-drying VEGO generally do nothow good drying tendency at room temperature. Consequently,

riers are added to achieve drying of coatings. However, in mostf the cases, proper drying and good performance is achieved onlyy baking the coatings at elevated temperatures. Aigbodion et al.

temperature, thermal stability,and bactericidal effect againstS. aureus and E. coli

have synthesized WB alkyds based on Rubberseed oil [RSO] forcoating applications (Aigbodion et al., 2003a,b; Aigbodion andPillai, 2001). RSO was first maleinated or fumarized and thentreated with glycerol to yield its monoglyceride derivative; the lat-ter was chemically reacted with phthalic anhydride and the acidfunctionalities of the final product were neutralised with amine.The modified alkyd resins had lower VOC than their correspondingvirgin counterparts. They showed good water, brine and acid resis-tance while fair alkali resistance attributed to the presence of esterlinkages. Heated RSO and alkyd resins were evaluated as binders inair drying solvent and WB coatings.

WB alkyds are more chemical resistant than their solvent-bornecounterparts (Aigbodion and Pillai, 2000). To further improve theperformance of WB alkyds, Saravari et al. prepared alkyds frommonoglycerides derived from interesterified product of palm andtung oil [TO], along with carboxyl functionalized acrylic copoly-mers (butyl methacrylate and maleic anhydride) in place of di- orpolybasic acids; the unreacted carboxyl groups could be neutralizedby a base to give water reducible alkyds. Films were obtained bybaking at 190 ◦C; these showed good water, acid and alkali resis-tance (Saravari et al., 2005). In some instances, proper air-dried

films could not be obtained, thus, driers were added and filmswith good flexibility, adhesion, impact strength, water, acid andalkali resistance were obtained by baking at elevated temperatures

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229 223

sis of

[ d muh hem.

(e

Rif(baW2cprtMdCtbs(b

Fig. 5. SyntheReprinted (adapted) with permission from Pramanik et al. (2013). Biofunctionalizeyperbranched poly(ester amide) and its biophysico interfacial properties. J. Phys. C

Aigbodion et al., 2003a,b; Aigbodion and Pillai, 2000, 2001; Wut al., 2004).

In another example by Kamani and research group, maleinatedice bran oil fatty acids were used for curing of DGEBA epoxy

n presence of co-solvents and additives. These could be utilizedor varnishes suitable for electrophoretic deposition and dippingShikha et al., 2003). An excellent review has appeared on VEGOased WB coatings by Nimbalakar and Athawale wherein theuthors provided a brief overview of WB alkyds, alkyd emulsions,

B urethanes and hybrid dispersions (Athawale and Nimbalkar,011). Water reducible Canola oil alkyd has shown better thermal,hemical and coating properties relative to its pristine counter-art (Nimbalkar and Athawale, 2010). Pathan and Ahmad (2013a,b)ecently prepared WB alkyd from SoyO and CasO. They followedraditional method of glycerolysis of SoyO and CasO, forming

G, followed by esterification of MG with phthalic acid pro-ucing alkyd resin, and simultaneously treatment of SoyO andasO alkyd with triethylamine, rendering WB alkyd. It was furtherreated with butylated melamine formaldehyde [BMF], which acted

oth as crosslinker and modifier because curing with BMF led toimultaneous inclusion of s-triazine ring into WB alkyd backboneFig. 6). The latter drastically improved the corrosion resistanceehaviour of modified alkyd coatings. The coatings showed good

FAD-MWCNT.ltiwalled carbon nanotube: a reactive component for the in situ polymerization of

C. 117, 25097–25107.]. Copyright 2013. American Chemical Society

hydrophobicity as investigated by contact angle measurements(contact angle values ranging from 83–95

◦). The coatings also

showed good scratch hardness, impact resistance and flexibilityretention characteristic because of good crosslinking of chains,excellent adhesion with the substrate and hardness conferredby the s-triazine ring. The latter also improved the antibacte-rial behaviour of WB alkyd relative to plain alkyd against bothStaphylococcus aureus and Escherichia coli, though slightly bet-ter against S. aureus because in the latter the polyglycogen outerlayer is sufficiently loosely packed and allows for the deep pen-etration of the polymer, while the cell wall of Gram negativebacteria is surrounded by an additional outer membrane with abilayer phospholipids structure, which offers a supplementary bar-rier and obstructs the penetration of a wide range of antimicrobialagents into the cell. They also investigated the corrosion resistancebehavior of VEGO based WB alkyd by potentiodynamic polarisa-tion and electrochemical measurements techniques for the firsttime. The mechanism of corrosion protection involved the for-mation of highly crosslinked hydrophobic surface which repelled

the corrosive media and prevented corrosion of the underlyingsubstrate. The polar groups of WB alkyd oriented towards thesubstrate promoted adhesion and also facilitated the protectionphenomenon.

224 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229

ed wa

peWhfewtebag

Fig. 6. VEGO bas

New chlorinated rapeseed oil polyol based waterborneolyurethane [WPU] was synthesized and used to modify glyc-rol plasticized starch films. Plasticized starch was miscible with

PU only below 20 wt% of WPU, attributed to the intermolecularydrogen bonding interactions between starch and WPU. The films

ormed were biodegradable with improved physical properties (Lut al., 2005). In a report by Mohamed et al. (2001) epoxidized SoyOas treated with methyl amine; the formed adduct was charac-

erized by FTIR analysis, further emulsified and added to differentmulsion paint formulations using styrene/acrylic copolymer as

inder for emulsion paint. The role of soy epoxy-methyl aminedduct as corrosion inhibitor for carbon steel was also investi-ated and compared with the results obtained with lead chromate.

terborne alkyd.

It was found that paint containing 0.5% of methylamine adductprovided better protection to carbon steel than those containing25% of lead chromate with good flexibility and chemical resistance(Mohamed et al., 2001). In another report, Aglan et al. used the sameinhibitor with different binders, i.e., Styrene [ST]/acrylic copolymerand water soluble alkyd resin and also investigated their corrosioninhibition mechanism (Badran et al., 2002). All the systems showedgood adhesion, hardness, ductility, acid and alkali resistance. ST/acrylic copolymer films showed lower water uptake values thanalkyds. These paints were free from any heavy metal or VOC.

Polymeric dispersants have been prepared from CasO fatty acidsfor WB paint applications (Dara et al., 2009). In another publication,SoyO was treated with phosphoric acid, hydrolysed, neutralized

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E. Sharmin et al. / Industrial Cro

ith organic base to obtain aqueous dispersions. The phosphory-ated polyols obtained were used as a component in WB coatings

ith superior corrosion resistance performance (Guo et al., 2006).PU and waterborne polyesteramide [WPEsterA] are preparedith VEGO based diol/polyol, chain extenders such as dimethylol

ropionic acid, N-methyl diethanolamine, a diisocyanate, phthalicnhydride, and an amine for further neutralization (Gurunathant al., 2015; Ren et al., 2015; Zafar et al., 2015). WPU coatings havehown good storage ability, low cost, and potential biodegradabilityNi et al., 2010). Another approach involve macro or miniemulsionolymerization of acrylic monomers in presence of VEGO poly-ers (Hu et al. 2015; Lu and Larock, 2007, 2008, 2010; Wang and

ones, 2000; Akbarinezhad et al., 2009; Quintero et al., 2006). Tourther improve the performance WB nanocomposites have alsoeen developed (Table 1).

. Radiation curable coatings

Conventional thermoset coating formulations are generallyured through thermal crosslinking and polymerization processes,ften in presence of catalysts (to initiate curing reactions), and sol-ents or water. Radiation curable coating formulations are free ofolvents or water; curing is initiated by a catalyst or photoini-iator by irradiation with ultra violet [UV] or visible light. Theyequire low curing energy, show high curing efficiency and arecologically compliant as no VOC or water are required for suchormulations. The process involved is considered “clean and green”V curing technology is applicable at ambient temperature, thus,

t can be applied to thermally sensitive molecules. The photopoly-erisation can be accomplished by polyaddition of double bonds

nder radical or cationic initiation or by cycloaddition of photo-ensitive molecules or chromophores (Fig. 7) (Fertier et al., 2013).ypical raw materials used in UV curing are (i) oligomers (e.g.,crylates, unsaturated polyesters), (ii) monomers (reactive dilu-nts), (iii) photoinitiators, and (iv) additives. Acrylated oligomersre generally used in UV-cure coatings owing to their relativelyigher reactivity and lower volatility. Styrene due to its volatility iseplaced with higher molecular weight and functionality reactiveiluents to increase reactivity, line speed, and mechanical proper-ies. Acrylated resins such as epoxy acrylates, polyether acrylates,rethane acrylates, polyester acrylates, and silicone acrylates areenerally preferred over methacrylated ones due to higher cureates and lower oxygen inhibition. An optimum composition ofoating material as well as UV curing time is required to obtainoatings of desirable performance, e.g., good adhesion, scratchesistance, impact resistance, abrasion resistance, flexibility, opti-al transparency, and others (Chen et al., 2010; Fertier et al., 2013;ianni et al., 2009; Han et al., 2007; Nebioglu and Soucek, 2007;engasamy and Mannari, 2014; Smitha et al., 2013; Wan Rosli et al.,003; Wouters et al., 2004).

One of the most important VEGO derivative used for UV cur-ble coatings are epoxies, both naturally available such as in oilsf Vernonia galamensis, Euphorbia lagascae, and chemically syn-hesized from various oils, e.g., LinO, SoyO, palm and other oilsZovi et al., 2011). VEGO derivatives such as CasO, Lesquerelland Vernonia oil macromonomers have been used in radiationurable architectural coatings, which were glossy, hard and well-dherent to substrates (Kolot and Grinberg, 2004; Soucek et al.,004; Thames and Yu, 1999; Thames et al., 1996). VEGO epoxiesure by cationic polymerization in presence of suitable photoinitia-ors as reported by Crivello and Thames et al. The coatings obtained

ossess good adhesion, impact resistance, UV stability, gloss reten-ion, and corrosion resistance (Thames and Yu, 1999; Thames et al.,996). Soucek and Crivello have carried out synthesis and pho-opolymerization of epoxidized oil (Crivello and Narayan, 1992;

d Products 76 (2015) 215–229 225

Wu et al., 1999; Zou and Soucek, 2004, 2005). Similarly, radia-tion curable HYP resin based on epoxy functional fatty acids wasreported by Johansson and coworkers (Samuelsson et al., 2004).Acrylated LSO coatings have shown good flexibility and adhesionon metal substrates (Thames et al., 1996). Thiol–ene UV curablecoatings have been prepared by Rawlins et al. (Black and Rawlins,2009). The alcoholysis of tobacco seed oil in combination with poly-hydroxyl compounds gave polyols. PU from the resulting polyolswere further reacted with hydroxyethyl methacrylate to produceUV urethane acrylate coatings with excellent performance (Patelet al., 2008). The influence of cashew nut shell oil, epoxidized SoyO,CasO, and dioctyl phthalate on the photocrosslinking kinetics of UVcurable mixtures containing an o-cresol novolac epoxy resin, a bis-cycloaliphatic diepoxide monomer, and a triarylsulfonium salt as acationic photoinitiator has been studied by Hien et al. (2011). Theyhave also carried out the cationic photopolymerization of a mixtureof epoxy resin modified by TO in the presence of a triarylsulfoniumsalt after 1.2 s of exposure under a light intensity of 250 mW/cm2

and storage in the dark for a few hours. UV cured coatings con-taining the optimum amount of the VEGO or VEGO epoxy showedthe best performance. These may find applications as adhesivesas well as decorative and protective coatings (Hien et al., 2011).Decker et al. (2001) have studied the cationic photocrosslinkingof DGEBA resin with epoxidized SoyO. In their investigation, theyfound that the formulation with an optimum content of the com-ponents proceeded substantially with faster curing than that of theneat DGEBA.

UV cured HYP coatings showed good mechanical and thermalproperties; the former were more dependent on the degree of acry-lation than molar mass (Dzunuzovic et al., 2006). Chen et al. havereported the coating performance of acrylated epoxidized SoyObased UV curable coating material prepared by the inclusion ofacrylated sucrose and commercial HYP acrylates. The coatings con-taining both the modifiers showed good performance; those withHYP acrylates showed good hardness, adhesion, solvent resistanceand glass transition temperature, while the ones with acrylatedsucrose exhibited improved toughness, but reduced water resis-tivity and thermal stability of the coatings (Chen et al., 2011; Wuet al., 2011). Acrylated SoyO epoxy based UV curable coatings,with biobased gallic acid cross linking agent have shown highlyimproved coating properties in terms of pencil hardness, wearresistance and adhesion (Ma et al., 2014). Recently, to further aug-ment the performance, UV curable nanocomposites have also beendeveloped as antimicrobial coatings (Table 1).

8. Future perspectives and summary

VEGO are abundantly available, easy to procure and cost effec-tive sources of nature. These hone unique natural functionalattributes and potential biodegradability that symbolize theminevitably as established raw materials toward renewable feed-stocks for environment friendly materials. Although the use ofVEGO in paints and coatings is decades old and well studied,today emphasis is being laid on research pertaining to modifica-tions of these materials to introduce novel properties for improvedperformance, environment friendliness at affordable costs. Themulti-step reactions are involved in the synthesis of VEGO basedmonomers/polymers at elevated temperatures and times, consum-ing ample of solvents. The coatings obtained also consist of complexsynthesis and cure schedules with longer curing times and temper-atures. The long drying times and high curing temperatures often

impair the quality of the final product and yield. Thus, efforts mustbe taken toward the development of low or solvent free materialsrendering VOC free coatings, i.e., cutting off the use of solvents dur-ing processing, formulation and application of coatings. The solvent

226 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215–229

UV cu

ftntImtstegsmaapadeatu

Fig. 7. VEGO based

ree reactions under microwave irradiations may provide remedieso some of the drawbacks such as poor yield due to inhomoge-ous heating (under conventional conditions) and longer synthesisimes. Another alternate may be the enzymatic synthesis approach.n HYP polymers, it is proposed that as a green material, the core

olecule should also be biobased in origin, unlike the present syn-hetic ones. If an oil based core molecule is well developed, it willurely be of advantageously reduced viscosity, which will facilitatehe complete elimination of the use of solvents and reactive dilu-nts in HYP coatings. WB coatings have been developed from VEGOenerally prepared in water along with some co-solvent. Effortshould be directed to achieve 100% water solubility of VEGO poly-ers, offering several advantages especially towards applications

s “green” VEGO coatings. To improve upon the performance char-cteristic of VEGO coatings blending with commercially availableolymers is the simplest method to reach a synergistic platformt both cost and performance levels. Conventional curing agents,rying agents, diluents and modifiers must be replaced by theirnvironment friendly renewable resource based counterparts. The

pproach presented in the article must be employed on those oilshat are non-edible and non-medicinal to add value to a waste ornutilized material.

rable acrylic polyol.

The manuscript provides an insight into the world of VEGOas potential candidates for environment friendly materials. Theyyield value added materials by simple chemical reactions, whichfind plethora of applications, especially as protective coatings. Thegreater utilization of the aforementioned non-depletable, domesti-cally abundant and reliable resources over conventional resourcesof energy is expected to have less deleterious/hazardous impact onenvironment at a stable price and may cut off the annual expensesincurred on processing and purchase of materials. The state-ofthe-art-modifications in the field are expected to promote both aca-demic and industrial research on industrial (non-food) applicationsof VEGO, focussing on both crop-oriented and product-orientedresearch and to further establish VEGO as workhorses of polymermaterials, particularly the coatings industry. Thus followed andimplemented, we are sure to enter the promising era of 100% greencoatings.

Acknowledgements

Dr. Eram Sharmin is thankful to the Council of Scientific andIndustrial Research, New Delhi, India, for Senior Research Asso-ciateship against Grant No. 13(8464-A)/2011-Pool. Dr. Fahmina

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afar is thankful to the University Grants Commission, India forr. D. S. Kothari Post Doctoral Fellowship, Ref. # F.4/2006(BSR)/13-86/2013(BSR) with Prof. Nahid Nishat. Dr Deewan Akram ishankful to the Council of Scientific and Industrial Research,ew Delhi, India for Senior Research Fellowship against Granto.9/466(0122) 2K10-EMR-I.

ppendix A. Supplementary data

Supplementary data associated with this article can be found, inhe online version, at http://dx.doi.org/10.1016/j.indcrop.2015.06.22

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