Industrial Crops and Products 76 (2015) 215229

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Industrial Crops and Products

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Recent advances in vegetable oils based environment friendlycoatings: A review

Eram Sharmina,b,, Fahmina Zafara,c, Deewan Akrama,d, Manawwer Alame,Sharif Ahmada

a Materials Resb Department oSaudi Arabiac Inorganic Mad Department oe Research Cen

a r t i c l e i n f o

Article history:Received 17 January 2015Received in reAccepted 9 Jun

Keywords:Vegetable oilsCoatingsEnvironment fHigh solidsWaterborneHyperbrancheUV curable

a b s t r a c t

The overarching goal worldwide for the scientic community is sustainable development today, for an

Contents

1. Introd2. VEGO3. Low s4. High s5. Hyper

AbbreviatioFAD, fatty amidmontmorillonPCD, poly(-caTO, tung oil; U Correspon

Fax: +91 11 26Saudi Arabia.

E-mail add

http://dx.doi.o0926-6690/ vised form 6 June 2015e 2015

riendly

d

everlasting 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 Greenor 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 Natures 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 edged use of VEGO basedmonomers or polymers in the eld as raw materials, is an excellent effort toward sustainable futurein the world of coatings globally. The review highlights some state-of-the art-modications of VEGO asenvironment 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.

uction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 and their chemical transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216olvent or zero solvent coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216olids [HS] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218branched [HYP] coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .220

ns: BMF, butylated melamine formaldehyde; CasO, castor oil; DGEBA, diglycidyl epoxy of bisphenol A; DMPA, dimethylol propionic acid; DPE, dipentaerythritol;e diol; HS, high solids; HYP, hyperbranched; HBPA, HYP polyamine; HPU, HYP polyurethane; LinO, linseed oil; MFO, Mesua ferrea oil; MG, monoglycerides; MMT,

ite; MWCNT, multiwalled carbon nanotubes; NC, nanocomposites; HEFA, N,N-bis(2-hydroxyethyl)fatty amide; PAA, poly(amido amine); PANI, polyaniline;prolactone) diol; PEsterA, polyesteramide; PU, polyurethanes; RSO, rubberseed oil; SoyO, soybean oil; SunFO, sunower oil; TDI, toluene-2,4-diisocyanate;V, ultra violet; VEGO, vegetable oils; VOC, volatile organic compounds; VOMM, VO macro-monomer; WB, waterborne; WPU, waterborne polyurethane.ding author at: Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110025, India.981717/Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,

ress: eramsharmin@gmail.com (E. Sharmin).

rg/10.1016/j.indcrop.2015.06.0222015 Elsevier B.V. All rights reserved.earch Laboratory, Department of Chemistry, Jamia Millia Islamia (A Central University), New Delhi 110 025, Indiaf Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah Al-Mukarramah, PO Box 715, Postal Code: 21955,

terials Research Laboratory, Department of Chemistry, Jamia Millia Islamia,New Delhi 110 025, Indiaf Chemistry, Faculty of Science, Jazan University, P.O. Box 2097, Jazan, Saudi ArabiatreCollege of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia

216 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

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

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226Appe . . . . . . Refer . . . . . .

1. Introdu

In the paundergone sumer expelower cost,fear of deplrelated to e(improper lems), regurapid innovtions and inits gears woof sustainabproducts (Lacademia argies to meetgold-the na

(i) to cut oproduc

(ii) to deve(iii) to expe(iv) to add

As a contechnologieexcessive u[VEGO] andcompoundssion and itsthe proper resources smay prove aMiller, 201in the modfriendly progoverning tthe applicamedicinal Vresource.

2. VEGO an

VEGO coing a plethoone of the esters of gVEGO maindiglyceridecomponentings owingform lms ing their deVEGO are c(100 < iodinin linseed

tivelsemay aable

co-psfor

are rhysicuenh ths hydcarboat cates (G1. VE

of als inied oolyoesteed iming ans o, respby sthe latmeion, ing res et ro de

coaals

, are rada

prontal tivesf coslow coatpatitive,s. Ho

en lole (Bgmeeir part m

solndix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

ction

st two decades, research and development efforts havevast changes globally, due to the ever growing con-ctations of good quality and performance coupled with

escalating prices of petro-based chemicals due to theeting stocks by the end of twenty rst century, concernsnergy consumption and environmental contaminationwaste management, greenhouse effect, health prob-lations such as Clean Air Act Ammendment, 1990 andations. These challenges related to predictions, regula-novations have forced the coatings industry to changerldwide and resulted in the exploration and utilizationle alternatives to chemicals derived from petro-basedochab et al., 2014). The researchers in industry ande actively engaged to explore and formulate new strate-

the mandatory limits through the tapping of our greenturally available resources primarily:-

ff the increasing raw material costs of the petro-basedtslop environmentally benign formulationsdite their post-service degradationvalue to an otherwise waste material

sequence, some environmentally friendly or greens have evolved, with special emphasis being laid on thetilization of renewable resources such as vegetable oils

also reducing or eliminating the use of volatile organic [VOC]. Considering the vast amount spent on corro-

mitigation programs worldwide, we understand thatutilization of our domestically abundant sustainableuch as VEGO thriving on our acres of agricultural landss silver lining, in this regard (Balachandran et al., 2013;

4). This review article describes the recent advancesications and applications of VEGO as environmenttective coatings, role of VEGO based components inhe properties of these coatings, and further encouragestion of these approaches on non-edible and non-EGO, adding value to a waste or unutilized sustainable

d their chemical transformations

nstitute a broad class of sustainable resources render-ra of value added functional materials. They comprisemost important components of biomass. They are tri-lycerol and fatty acids (saturated and unsaturated).ly consist of triglycerides as major (9398 wt%) ands, monoglycerides and phosphoglycerides as minors. VEGO and their derivatives nd applications in coat-

to their unique structural attributes and tendency to

respecing or oils mof suitacrylicto trantimes able pConseqthrougsuch aalpha occur tion siin Fig. mationmateriis carrdiols/pof polyexploroccurrreactiopoyolscured while on treacrylatinvolvLligadaMonte2013).

Thechemicothersbiodegduringronmederivatages ono or VEGO biocomdecoracoatingare oftinsolubther auwith thof-the-

3. Low

(depending upon their unsaturated portion). Consider-gree of unsaturation, described by their iodine value,

lassied as drying (iodine value > 130), semi-dryinge value < 130) and non-drying (iodine value < 100)asoil [LinO], soybean oil [SoyO] and palm kernel oil,

VEGO chfatty acid creactive dilresins, and . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

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

y (Alam et al., 2014; Xia and Larock, 2010). Usually, dry-i-drying oils are used in surface coatings. Non-dryinglso be utilized for the purpose by the incorporationentities (e.g., hydroxyls) or modiers (vinyls, acrylics,olymers) in oil backbone, through chemical reactions

m them as lm formers. In virgin oils, longer dryingequired while the lms formed do not meet the desir-o-mechanical and corrosion resistance performance.tly, several chemical transformations are carried oute important functionalities and active sites of VEGOroxyls, oxiranes, double bonds, allylic carbons, esters,n to the ester group and others. About 90% reactionsrboxyl functionality while the rest involve unsatura-unstone, 2001). Some of them have been exempliedGO undergo glycerolysis reaction resulting in the for-

monoglycerides or diglycerides that are used as raw the production of alkyds. Amidation (base catalysed)ut at carboxyl functionality, producing fatty amide

ls that serve as starting material for the developmentramides [PEsterA] and polyetheramides. Another much

portant reaction is transesterication reaction alsot carboxyl functionality. Epoxidation and hydroxylationccurring at double bonds of VEGO produce epoxies andectively. The former render strong thermosets when

uitable curing agents such as amines, acids, amides,atter yield polyester and polyurethane [PU] coatingsnt with acid/anhydride or isocyanates. Maleinization,vinylation, hydrohalogenation are few other examplesactions at double bonds of VEGO (Ahmad et al., 2004;al., 2013; Maisonneuve et al., 2013; Miao et al., 2014;

Espinosa and Meier, 2011; Mosiewicki and Aranguren,

tings obtained from fossil fuel derived petro-basedsuch as vinyls, acrylics, epoxies, PU, polyesters andoften (i) costly, (ii) toxic, (iii) hazardous after use (non-ble), and (iv) may require ample of hazardous solventscessing and coating applications, thus causing envi-contamination and health hazards on exposure. VEGO

are generally devoid of these drawbacks bearing advan-t effectiveness, non-toxicity, biodegradability, requiringsolvents due to their inherent uidity characteristic.ings are available for specic uses as antimicrobial,ble, biodegradable, corrosion protective, architectural,

electrical insulating, paper packaging, and self-healingwever, due to long aliphatic hydrophoebic chains, they

w on mechanical strength, lack toughness and are waterordes et al., 2009; Lligadas et al., 2010). Thus to fur-nt the performance of VEGO coatings, and to competeetro-based counterparts, several innovative and state-odications have been accomplished in the eld.

vent or zero solvent coatingsains are exible due to the the presence of long aliphatichains. VEGO derivatives generally serve as solvents oruents in coatings, often in combination with commercialthemselves participate in chemical reactions occurring

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 217

VEGO

during dryipart of the Karak, 20092011, 2010

The reseings using during syntinating theof solvent fachieved inin crosslinkpolymer ch

Ahmad emetal conta[LinO], takinThe synthereaction beby base catphthalic ac(e.g., xylenefree conditiplace at temmonomers bis(2-hydrodissolved, aof the reactat relatively2011). In so(II)] containadditionelthe carboxytent of metcatalytic eff

extetainiartiaity ated wFig. 1. Chemical reactions of

ng or curing or crosslinking reactions forming inherentnal material (Ahmad et al., 2011; Czub, 2006; Das and; Ghosal et al., 2013; Muturi et al., 1994; Sharmin et al.,).arch is focused on the development of VEGO based coat-

on the(II) contheir preactivassociazero solvent or low solvent approach. This meanshesis and coating formulation, either completely elim-

use of solvent or introducing only minimum amountor dilution, to offset the effect of high viscosity often

due course of chemical reactions, as a result of increaseing and viscosity, which restricts the free mobility ofains, during polymerisation.t al. and Zafar et al., prepared solventless PEsterA andining PEsterA from Linum ussiatatissimum or Linseed Oilg advantage of inherent uidity of VEGO chains (Fig. 2).

sis of PEsterA is generally accomplished by chemicaltween N,N-bis(2-hydroxyethyl) fatty amide (obtainedalysed amidation of VEGO) and phthalic anhydride orid as raw materials, in presence of on organic solvent). However, during synthesis of PEsterA under solventons, self catalysed direct esterication reaction takesperature lower than the melting points of both the

used as raw materials, owing to (i) good uidity of N,N-xyethyl) fatty amide in which phthalic anhydride isnd (ii) solvent free condition allowing better proximityants with each other facilitating the reaction to occur

lower temperature (Ahmad et al., 2007; Zafar et al.,lvent free synthesis of metal [Zn (II), Mn (II), Co (II), Cuing PEsterA, the mechanism involved (self catalysed)imination mechanism at the carbonyl double bond oflic acid group of PEsterA chain. The presence and con-al also governed the synthesis reaction time due to theect of the metal itself. The results obtained were based

were also oPEsterA conunlled d orPEsterA (haThe curing a result of cof metals wgen and doVEGO basecess that fu(Ahmad et 2010a,b) deing PU coatsolvent (useto offset thePU structurtance againstability up

Karak anrea oil [MFas modieas coatingsgood compreacted witfor better ction of nanepoxies, rethe improv.

nt of occupancy of d orbitals of the metals. Co (II) and Cung PEsterA were prepared in lower reaction time due tolly lled d orbitals (d7 and d9) which conferred highers compared to Mn(II) having half lled (d5) d orbitals,ith higher stability and lower reactivity. Similar results

bserved in drying times/curing behavior of coatings.taining Co (II) and Cu (II) metals (with higher number ofbitals) were cured faster compared to Mn (II) containinglf lled d orbitals) due to higher reactivity of the former.behavior in metal containing solvent free PEsterA wasross-linking of polymeric chains through coordinationith donor groups of the polymer such as oxygen, nitro-uble bond, contrary to the curing mechanism of plaind PEsterA which involves slow lipid autoxidation pro-rther requires driers to accelerate the curing processal., 2007; Zafar et al., 2007, 2011). Akram et al. (2008,veloped LinO and castor oil [CasO] based boron contain-ings for corrosion protection using minimum amount ofd in the second step of reaction, i.e., PU formation, only

effect of high viscosity and complexity of the inherentes) with good physico-mechanical and chemical resis-st alkali, acid, tap water and xylene, and also thermalto 220 C.d Das prepared nanocomposite blends of Mesua fer-

O] based epoxy and commercial epoxy with nanoclayr cured with poly(amido amine) hardener for use. The combination produced miscible system withatibility of either matrix. The hardener simultaneouslyh oxirane rings present in either epoxy resin, allowingompatibility of the two matrices, and proper interac-oclay. The cumulative effect of commercial and VEGOspectively, as well as nanoclay, can be observed ined scratch hardness, impact resistance, exibility and

218 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

adhesion oIt can be sealso modiepoxy, owiing toughnwell as reaand coworkpolyol nancoatings, was inorganireaction (Shydroxylatiinserted (vuration sitepolyol not ent uiditygroups for Fig. 2. Synthesis of PEsterA from VEGO (in the absence an

f the nanocomposite coatings (Das and Karak, 2009).en that MFO epoxy served as the binder, diluent ander to offset the brittleness (drawback) of commercialng to its long (exible) aliphatic alkyl chains render-ess. Thus, MFO based epoxy acted as an ingredient asctive diluent in nanocomposite preparation. Sharminers described the in situ preparation of LinO based

ocomposite as a raw material for polyester and PUith LinO polyol as organic matrix and metal acetatec precursor by facile solventless, one-pot chemicalharmin et al., 2013). LinO polyol is formed by theon reaction of LinO; it bears hydroxyl groups chemicallyia epoxidation followed by hydroxylation) at unsat-s of LinO (Sharmin et al., 2007). Thus, LinO basedonly served the purpose of solvent due to its inher-

characteristic, but also as matrix providing functionalthe chemical reaction), and also as stabilizer (prevent-

ing agglomoxide nanopolyol, resucles producpreparationusing tetraeLinO basedvent approprepared coand exibil2011).

4. High so

The drivenvironmenare currentd presence of solvent).

eration of nanoparticles) for the preparation of metalparticles from metal acetate and hydroxyls of LinOlting in the formation of nano-sized metal oxide parti-ing nanocomposite (Sharmin et al., 2015, 2013). In situ

of SiO2 nanoparticles was carried out in polyol matrixthoxyorthosilane as inorganic precursor and CasO and

polyols as organic matrices, respectively, by zero sol-ach (Akram et al., 2010a,b; Sharmin et al., 2011). Theatings were scratch resistant, impact resistant, glossy

ity retentive (Akram et al., 2008, 2010a,b; Sharmin et al.,

lids [HS] coatings

e towards HS coatings is initiated and fostered bytal regulations. Epoxy, alkyd and PU based coatingsly representing the major part of HS coatings in the

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 219

protective content by with 6070tems contaicontent thaOene, 1982to develop 1

HS coatinical benesystems wireadily accelar weight da more homFig. 3. VEGO based HYP polyester

coatings market. Paints with more than 80% solidsvolume are generally referred to as HS paints; those% solids content can also be called HS paints. These sys-n a higher percentage of solids paints and lower solventn conventional solvent-borne coatings (Chattha and van; Haseebuddin et al., 2009). Efforts are also being made00% solids PU and PU urea coatings.

ngs have lower solvent emissions as well as other tech-ts besides bearing closer resemblance to conventionalth improved performance and durability, making themptable in applications. In HS coatings, narrow molecu-istribution is attained to lower solution viscosity withogeneously cross-linked network (Lindeboom, 1997).

The lowerinlength (of bduces moreadverse concosity of Hbehavior oflem, convenreactive dilof coatings Often driersAthawale, 1

HS alkyCasO fatty.

g of viscosity can be achieved by increasing oil chaininder) that lowers the molecular weight and also intro-

unsaturation content (due to C C of oil). However, ansequence of lowering the molecular weight and vis-

S coatings is poor stabilization properties and drying coatings (Zabel et al., 1999). To overcome this prob-tional solvents in HS coatings are partially replaced byuents that function as diluents during the formulationand during curing, form an integral part of the coating.

are used to promote drying in thick lms (Bhabhe and997; Das and Karak, 2009; Lindeboom, 1997).ds from Glycine max or SoyO and dehydrated

acid combinations with varying percentage of

220 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

dipentaerythritol [DPE] (as multi-functional polyol to introducebranching) have been synthesized with 80% solids in mineral tur-pentine oil and characterized for their physicochemical, optical,thermal and mechanical properties. The increased DPE contentintroduced sion protecof the alkyd

Air dryinnomical bennal solids resin into anDifferent liqof additiondrying charcarried out,alkyd painttors and/or 2006).

VEGO popendant dasition tempproduced p(Canola, HeLinola 209estericatiodiol and 1,isocyanate coatings shmechanicallow molecufactors contvent free aincreasing o

A good Hity withoutmaterial. Thing oil chaiA diluent dbecomes aparticipatesis achievedratio of OH/be formed aing oil chainto unsaturadrying and the reductiincrease in to obtain re

5. Hyperbr

The dendrigrafts arisolation anpolymers, gle step poreports bacwhich laterBenthem, 2

Star andcharacteristand are lessof the nal pcontent attrLindeboom

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 their

ct, nnumand dimes anativeed pescr

ters, ter uMPAeriphasO

secoed rehich

ate, erable

hydnal fic acred wurallTg v

ationsteried wine fnt a

thaned bynt amts ofHYP sized

wasrateHYP

HYPon, lo et

rece or loparin

andA]. HGO chic (Vess les (

al., 2and prod

bioer, ich (Fd gosistanss, stronen bgood branching, cross linking, and increased the corro-tion performance, improved gloss and thermal stability

coating (Haseebuddin et al., 2009).g HS alkyd paints provide environmental as well as eco-ets (Lindeboom, 1997). Alkydacrylic hybrids havingcontent of 7580% were prepared by dropping alkyd

acrylic dispersion (Jowkar-Deriss and Karlsson, 2004).uid structures were produced depending on the mode

of the surfactant to the system. To improve upon theacteristics of HS alkyd paints, thiolene reaction was

which can assist their oxidative drying. Fast drying HSs were thus obtained by using visible light photoinitia-cobalt free metal catalysts (Klaasen and van der Leeuw,

lyols have relatively high molecular mobility, containngling chains, which lead to relatively low glass tran-eratures (Tg) and a low modulus. Kong and coworkersolyols, Liprols, by epoxidation/hydroxylation of VEGOlianthus annuus L. or Sunower oil [SunFO], Camelina,0 ax and NuLin 50 ax crude oils) followed by trans-n reactions of the glycerides with diols (1,2 propane3 propane diol). Such polyols on treatment with anproduced PU coatings which were HS in nature. Suchowed good adhesion due to chemical interaction and

interlocking at the interface. Also, few pendant chains,lar weight and high functionality are another importantributing to good performance of these coatings. The sol-pproach also improved hydrophobicity of coatings byf cross-linking density (Kong et al., 2013).S coating material should have acceptably low viscos-

compromising on performance characteristics of theis is achieved by the use of reactive diluents, increas-

n length, and narrower molecular weight distribution.ecreases the viscosity of the material and eventuallyn integral part of the coating after drying (since it

in drying reactions). The lowering of molecular weight by increasing of fatty acids contents or increasing theCOOH groups. However, a homogenous network cannotnd overall coating properties are deteriorated. Increas-

length often results in loose packing of molecules (duetion). Low molecular weight resins often exhibit slowsagging. So, to overcome these drawbacks, along withon of molecular weights in the resins, a simultaneousmolecular branching was performed; it was preferredsins with well-dened highly branched structure.

anched [HYP] coatings

dritic polymersdendrimers, HYP polymers and den-e preferred over HS resins. The dendrimers involved purication steps and are costly relative to HYP

which combine lower manufacturing costs and sin-lymerization. The principal concept of HYP polymersk to the works of Flory and Kienle past several decades,

on graduated to more elaborated building blocks (van000).

HYP polymers show improved drying and performanceics over HS alkyds; these are synthesized in single step

costly than their other counterparts. The low viscositiesroduct allow for easier lm formation and the low VOCibute to the environment friendliness (Bat et al., 2006;, 1997; Manczyk and Szewczyk, 2002).

compalarge (Deka three-featurepreparadvanchave dpolyespolyesacid [Dwith pwith CHYP ofprovidings, wsubstrtion cufrom afunctiovernolcompa(structlower publictranseesterimelamexcelletance.

UreobtaindiffereamounHere, synthegroupsin sepabased ylatedadhesi(Muril

In atlenessby prepolyol[DGEBthe VEaliphattoughnmolecu(De etalkyd were tive asextendapproashoweical rehardneto the hydrogon-entangled and highly branched structures withbers of active functional groups on the peripheryKarak, 2009a,b). Due to their highly functionalizednsional globular non-entangled inimitable architecturald unique properties coupled with their single-step

techniques, these macromolecules are considered asolymeric materials. Chattopadhyay and Raju (2007)ibed the structures and properties of HYP polyols,PU, and others. Bat and coworkers prepared HYPsing DPE as core molecule and dimethylol propionic] twice, as chain extender, to obtain HYP derivativeeral hydroxyl groups. The latter was further reacted

fatty acid, LinO fatty acid and benzoic acid, to obtainnd, third and fourth generation (Fig. 3). VEGO contentduced viscosity and increased hardness to the coat-

showed good abrasion resistance, adherence to thexcellent gloss and exibility (Bat et al., 2006). Radia-

material was synthesized by Samuelsson et al. (2004),roxy functional HYP polyether onto which an epoxyatty acid, vernolic acid, was attached, polymerized withid methyl ester as reactive diluents; the results wereith a model oil based trimethylol propane [TMP] lms

y similar but with no polyether core), which showedalue and softness after polymerization. In another

by Karakaya et al. (2007) DPE (core molecule) wased with CasO and a mixture of CasO and LinO andith DMPA. The obtained HYP resin was treated with

ormaldehyde; the coatings prepared therefrom showeddhesion, gloss, exibility, impact and abrasion resis-

e acrylates with different degrees of acrylation were the reaction of partially modied HYP polyesters andounts of acrylate-isocyanate adduct from equimolar

isophorone diisocyanate and 2-hydroxyethyl acrylate.of the second and the third pseudo-generation were

from DMPA and TMP; the modication of the OH end- carried out with isononanoic acid and SoyO fatty acids

reports by Dzunuzovic et al. (2006). Tall oil fatty acidsalkyd resin prepared from fourth generation hydrox-

polyester through acid catalysis exhibited excellentexibility, drying time, gloss and chemical resistanceal., 2010, 2011).nt work, the drawbacks of epoxy resins such as brit-w toughness and nonbiodegradability were overcomeg a HYP epoxy from CasO modied HYP polyester

in situ-generated diglycidyl ether of bisphenol Aere, biodegradation and exibility were conferred byains. HYP structure as well as the aromatic (epoxy) andEGO chains) constituents collectively imparted goodto the coatings, increasing the free volume betweendue to steric effect) in the three-dimensional network014). Hyperbranched polyurethane [HPU], polyester,hyperbranched polyesteramide [HPEsterA] coatings

uced from MFO, CasO, and SunFO. A VEGO deriva-based chain extender is treated with another chainsocyanate and a multi-functional amine by A2 + B3ig. 4; Kalita and Karak, 2014). The produced materials

od thermostability, ame retardancy, hardness, chem-ce, higher tensile strength, impact resistance, scratchexibility retention than their linear counterpart owingger intra- and intermolecular secondary interactions,onding, chain entanglements and compact conned

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 221

[Reprinted (adSci. 131, 39579

geometry, cthe fatty chstructure anier movemcounterpart2009a,b; Kaand Karak, Kalita and Ket al. (2013PCD, and bterminatedpolymer orto produce by the addistrength, imthan its linemolecular sglements aFig. 4. Synthesis of VEGO based HPUapted) with permission from Kalita and Karak (2014). Biobased hyperbranched shape-me39586.]. Copyright 2013. John Wiley and Sons.

ollectively. Good exibility retention was offered byains of the parent VEGO, within the highly branchedd the presence of larger void spaces which offer eas-

ent of chains in HYP material relative to the linear (Bao et al., 2013; Das et al., 2013; Deka and Karak,rak et al., 2009; Konwar and Karak, 2009; Mahapatra2007; Pramanik et al., 2013a,b,c; Rana et al., 2013;arak, 2014). SunFO based HPU were prepared by Das

) by following A2 + B2 + B4 approach. SunFO based MG,utanediol were treated with TDI such that hydroxyl

prepolymer (A2) was formed. In the next step this pre- diol was treated with pentaerythritol (B4) and TDIHPU. Similarly, a linear PU analog was also preparedtion of BD in place of PE. HPU showed higher tensilepact resistance, scratch hardness, exibility retentionar counterpart owing to the stronger intra- and inter-econdary interactions, hydrogen bonding, chain entan-nd compact conned geometry of HPU, collectively

Good exiMG chainsthe presenment of ch2013).

Nanocomprepared foical strengtlow water inforcemenclay (MMTnanotubes alised reduinterpretedVEGO as paof nano-reinrials for surand reduce.mory polyurethanes: effect of different vegetable oils. J. Appl. Polym.

bility retention was offered by PC component and of SunFO within the highly branched structure andce of larger void spaces which offer easier move-ains in HPU relative to the linear PU (Das et al.,

posites [NC] of VEGO based HYP polymers have beenr some advanced applications demanding high mechan-h, good adhesion, chemical resistance, thermostability,vapor permeability and others, with different nanore-ts such as Octadecylamine-modied montmorillonite) nanoclay, silver nanoparticles, Multiwalled Carbon(MWCNT), polyaniline [PANI] nano bres, Function-ced graphene oxide (f-RGO), and others. It can be well

that the properties of HYP depend upon the type ofrent precursor, chain extender, isocyanate, and the typeforcement employed. HYP are much sought after mate-

face coating applications due to their unique propertiesd viscosity (Table 1 and Fig. 5 ).

222 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

Table 1Environment friendly nanocomposite coatings from VEGO.

S.No. Type Modiers Properties References

1. HPU from MFO MMT nanoclay Light weight, transparency,exibilensileardnew wa

herma

Deka and Karak (2010, 2011)

2. ood techaispersarticleistribuntimi. coli, nd C. ntimi

3. mprovhape miodegytotoxntimiureus

4. echatable, o the iANI nEA ma

5. mprovoughntabilitonduc

6. nhanc

7.

8.

6. WB coat

The termmarily use with smallThey are clawaterdisppaints. Thementioned hydrophilicmer water are vinyls, butadiene, Interest in to handle, nature (Athet al., 2002coatings is atriglyceride

WB alkyshow gooddriers are aof the casesby baking tthlot

HPU from MFO Silver nanoparticles and clay GmdpdaEaa

HPEsterA from CasO (Fig. 5) MWCNT Isbcaa

HPEsterA from CasO PANI nano bres MstPP

HPU from CasO f-RGO Itsc

WPU from CasO: Organoclay E

thermastrong betwee

WPEsterA from LinO MMT nanoclay Improvimpactchemicalkali, stherma

UV curable Acrylated LinO TiO2 nanoparticles Improvresistantemperand baS. aureu

ings

WB is applied to those coating systems that pri-water as the solvent or sometimes upto 80% water

amount of other solvents such as glycol ethers.ssied as: watersoluble/waterreducible (solutions),ersible/colloidal (dispersions) and emulsions (latex)

physical properties and performances of each typeabove depend upon the choice of the resin. Generally,

groups are inserted in oil chains that yield the poly-dispersible. The polymer derivatives commonly usedtwo-component acrylics, epoxies, polyesters, styrene-amine-solubilized, carboxyl-terminated alkyd and PU.WB materials arises due to their non-polluting, easyquick drying, economic and environmentally friendlyawale and Nimbalkar, 2011; Dara et al., 2009; Gndz, 2004; Shah and Ahmad, 2012). The synthesis of WB

challenging task due to hydrophoebic nature of VEGO chains.ds based on non or semi-drying VEGO generally do not

drying tendency at room temperature. Consequently,dded to achieve drying of coatings. However, in most, proper drying and good performance is achieved onlyhe coatings at elevated temperatures. Aigbodion et al.

have synthcoating apPillai, 2001treated witter was chefunctionalitThe modievirgin countance whilelinkages. Heair drying s

WB alkycounterparperformancmonoglycetung oil [TOmers (butypolybasic acby a base tbaking at 1tance (Saralms couldwith good alkali resistity characteristic, good strength, scratchss, impact resistance,ter vapor loss, higherl stability

De and Karak (2014) De et al.(2014)

hermal stability andnical properties, longion stability, small

size, narrow sizetion along with good

crobial efcacy againstS. aureus, P. aeruginosaalbicans producingcrobial coatings

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

ed tensile strength,emory, enhanced

radability, and noicity; with good

crobial efcacy against S.and B. subtilis

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

nically strong, thermallyantistatic materials duenterfacial interaction ofanobers with the HYPtrix

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

ed tensile strength andess, good thermaly and electricaltivity

Thakur and Karak (2014b,a)

ed mechanical and Gurunathan et al. (2015)

l performance due tointerfacial interactionsn ller and matrixed scratch hardness,

resistance, exibility,al resistance (in acid,alt and water, andl stability)

Zafar et al. (2015)

ed hardness, impactce, glass transitionature, thermal stability,ctericidal effect againsts and E. coli

Diez-Pascual and Diez-Vicente,(2015)

esized WB alkyds based on Rubberseed oil [RSO] forplications (Aigbodion et al., 2003a,b; Aigbodion and). RSO was rst maleinated or fumarized and thenh glycerol to yield its monoglyceride derivative; the lat-mically reacted with phthalic anhydride and the acidies of the nal product were neutralised with amine.d alkyd resins had lower VOC than their correspondingterparts. They showed good water, brine and acid resis-

fair alkali resistance attributed to the presence of esterated RSO and alkyd resins were evaluated as binders inolvent and WB coatings.ds are more chemical resistant than their solvent-bornets (Aigbodion and Pillai, 2000). To further improve thee of WB alkyds, Saravari et al. prepared alkyds fromrides derived from interesteried product of palm and], along with carboxyl functionalized acrylic copoly-

l methacrylate and maleic anhydride) in place of di- orids; the unreacted carboxyl groups could be neutralized

o give water reducible alkyds. Films were obtained by90 C; these showed good water, acid and alkali resis-vari et al., 2005). In some instances, proper air-dried

not be obtained, thus, driers were added and lmsexibility, adhesion, impact strength, water, acid andance were obtained by baking at elevated temperatures

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 223

[Reprinted (adhyperbranche

(Aigbodion et al., 2004)

In anothRice bran oin presencefor varnishe(Shikha et abased WB authors proWB urethan2011). Watechemical anpart (Nimbarecently prtraditional MG, followducing alkyCasO alkyd treated withboth as crosimultaneo(Fig. 6). Thbehaviour oFig. 5. Synthesis of FAD-MWCNT.apted) with permission from Pramanik et al. (2013). Biofunctionalized multiwalled carbd poly(ester amide) and its biophysico interfacial properties. J. Phys. Chem. C. 117, 25097

et al., 2003a,b; Aigbodion and Pillai, 2000, 2001; Wu.er example by Kamani and research group, maleinatedil fatty acids were used for curing of DGEBA epoxy

of co-solvents and additives. These could be utilizeds suitable for electrophoretic deposition and dippingl., 2003). An excellent review has appeared on VEGOcoatings by Nimbalakar and Athawale wherein thevided a brief overview of WB alkyds, alkyd emulsions,es and hybrid dispersions (Athawale and Nimbalkar,r reducible Canola oil alkyd has shown better thermal,d coating properties relative to its pristine counter-lkar and Athawale, 2010). Pathan and Ahmad (2013a,b)

epared WB alkyd from SoyO and CasO. They followedmethod of glycerolysis of SoyO and CasO, forminged by esterication of MG with phthalic acid pro-d resin, and simultaneously treatment of SoyO andwith triethylamine, rendering WB alkyd. It was further

butylated melamine formaldehyde [BMF], which actedsslinker and modier because curing with BMF led tous inclusion of s-triazine ring into WB alkyd backbonee latter drastically improved the corrosion resistancef modied alkyd coatings. The coatings showed good

hydrophob(contact anshowed goretention cexcellent aby the s-trrial behavioStaphylococter against layer is sufetration ofbacteria is bilayer phorier and obsagents intobehavior oftion and eltime. The mmation of hthe corrosisubstrate. Tsubstrate pphenomenoon nanotube: a reactive component for the in situ polymerization of25107.]. Copyright 2013. American Chemical Society

icity as investigated by contact angle measurementsgle values ranging from 8395

). The coatings also

od scratch hardness, impact resistance and exibilityharacteristic because of good crosslinking of chains,dhesion with the substrate and hardness conferrediazine ring. The latter also improved the antibacte-ur of WB alkyd relative to plain alkyd against bothcus aureus and Escherichia coli, though slightly bet-S. aureus because in the latter the polyglycogen outerciently loosely packed and allows for the deep pen-

the polymer, while the cell wall of Gram negativesurrounded by an additional outer membrane with aspholipids structure, which offers a supplementary bar-tructs the penetration of a wide range of antimicrobial

the cell. They also investigated the corrosion resistance VEGO based WB alkyd by potentiodynamic polarisa-ectrochemical measurements techniques for the rstechanism of corrosion protection involved the for-

ighly crosslinked hydrophobic surface which repelledve media and prevented corrosion of the underlyinghe polar groups of WB alkyd oriented towards theromoted adhesion and also facilitated the protectionn.

224 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

New chpolyurethanerol plasticWPU only bhydrogen bformed weret al., 2005)was treatedterized by Femulsion pbinder for adduct as cgated and cFig. 6. VEGO based waterborne alky

lorinated rapeseed oil polyol based waterbornee [WPU] was synthesized and used to modify glyc-

ized starch lms. Plasticized starch was miscible withelow 20 wt% of WPU, attributed to the intermolecularonding interactions between starch and WPU. The lmse biodegradable with improved physical properties (Lu. In a report by Mohamed et al. (2001) epoxidized SoyO

with methyl amine; the formed adduct was charac-TIR analysis, further emulsied and added to differentaint formulations using styrene/acrylic copolymer asemulsion paint. The role of soy epoxy-methyl amineorrosion inhibitor for carbon steel was also investi-ompared with the results obtained with lead chromate.

It was founprovided b25% of lead(Mohamedinhibitor wand water sinhibition mgood adhesacrylic copalkyds. The

Polymerfor WB painSoyO was td.

d that paint containing 0.5% of methylamine adductetter protection to carbon steel than those containing

chromate with good exibility and chemical resistance et al., 2001). In another report, Aglan et al. used the sameith different binders, i.e., Styrene [ST]/acrylic copolymeroluble alkyd resin and also investigated their corrosionechanism (Badran et al., 2002). All the systems showedion, hardness, ductility, acid and alkali resistance. ST/olymer lms showed lower water uptake values thanse paints were free from any heavy metal or VOC.ic dispersants have been prepared from CasO fatty acidst applications (Dara et al., 2009). In another publication,reated with phosphoric acid, hydrolysed, neutralized

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 225

with organic base to obtain aqueous dispersions. The phosphory-lated polyols obtained were used as a component in WB coatingswith superior corrosion resistance performance (Guo et al., 2006).WPU and waterborne polyesteramide [WPEsterA] are preparedwith VEGO propionic aanhydride, et al., 2015;shown good(Ni et al., 20polymerizamers (Hu eJones, 2000further impbeen develo

7. Radiatio

Conventcured throuoften in prevents or wasolvents ortiator by irrequire lowecologicallyformulationUV curing tit can be apmerisation under radicsensitive mTypical rawacrylates, uents), (iii) pare generalhigher reacreplaced wdiluents to ties. Acrylaturethane acgenerally prates and lcoating macoatings ofresistance, cal transparGianni et aRengasamy2003; Wou

One of table coatinof Vernoniathesized fro(Zovi et al.and Vernoncurable arcadherent to2004; Thamcure by catitors as repopossess gootion, and co1996). Souctopolymeri

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 exibility and adhesion

tal sus ha

The ayl courthethan008)nd de mixliphac phlso cay reer 1.orage

the st pel as d

et aBA rthat ts proGEBAcureties;thaned thUV ced su

botrylatass te exhnd t2011iobaed cnce ahe peped a

ure p

O arurcetes bly afor in pemphf theanc

step ers/

ple osis an. The

the qn toing Vcessbased diol/polyol, chain extenders such as dimethylolcid, N-methyl diethanolamine, a diisocyanate, phthalicand an amine for further neutralization (Gurunathan

Ren et al., 2015; Zafar et al., 2015). WPU coatings have storage ability, low cost, and potential biodegradability10). Another approach involve macro or miniemulsiontion of acrylic monomers in presence of VEGO poly-t al. 2015; Lu and Larock, 2007, 2008, 2010; Wang and; Akbarinezhad et al., 2009; Quintero et al., 2006). Torove the performance WB nanocomposites have alsoped (Table 1).

n curable coatings

ional thermoset coating formulations are generallygh thermal crosslinking and polymerization processes,sence of catalysts (to initiate curing reactions), and sol-ter. Radiation curable coating formulations are free of

water; curing is initiated by a catalyst or photoini-radiation with ultra violet [UV] or visible light. They

curing energy, show high curing efciency and are compliant as no VOC or water are required for suchs. The process involved is considered clean and greenechnology is applicable at ambient temperature, thus,plied to thermally sensitive molecules. The photopoly-can be accomplished by polyaddition of double bondsal or cationic initiation or by cycloaddition of photo-olecules or chromophores (Fig. 7) (Fertier et al., 2013).

materials used in UV curing are (i) oligomers (e.g.,nsaturated polyesters), (ii) monomers (reactive dilu-hotoinitiators, and (iv) additives. Acrylated oligomersly used in UV-cure coatings owing to their relativelytivity and lower volatility. Styrene due to its volatility isith higher molecular weight and functionality reactiveincrease reactivity, line speed, and mechanical proper-ed resins such as epoxy acrylates, polyether acrylates,rylates, polyester acrylates, and silicone acrylates arereferred over methacrylated ones due to higher cureower oxygen inhibition. An optimum composition ofterial as well as UV curing time is required to obtain

desirable performance, e.g., good adhesion, scratchimpact resistance, abrasion resistance, exibility, opti-ency, and others (Chen et al., 2010; Fertier et al., 2013;l., 2009; Han et al., 2007; Nebioglu and Soucek, 2007;

and Mannari, 2014; Smitha et al., 2013; Wan Rosli et al.,ters et al., 2004).he most important VEGO derivative used for UV cur-gs are epoxies, both naturally available such as in oils

galamensis, Euphorbia lagascae, and chemically syn-m various oils, e.g., LinO, SoyO, palm and other oils, 2011). VEGO derivatives such as CasO, Lesquerellaia oil macromonomers have been used in radiation

hitectural coatings, which were glossy, hard and well- substrates (Kolot and Grinberg, 2004; Soucek et al.,es and Yu, 1999; Thames et al., 1996). VEGO epoxies

onic polymerization in presence of suitable photoinitia-rted by Crivello and Thames et al. The coatings obtainedd adhesion, impact resistance, UV stability, gloss reten-rrosion resistance (Thames and Yu, 1999; Thames et al.,ek and Crivello have carried out synthesis and pho-

zation of epoxidized oil (Crivello and Narayan, 1992;

on mecoating2009).hydroxwere fUV ureet al., 2CasO, acurablcycloacationihave aof epoxsalt aftand sttainingthe beas welDeckerof DGEfound ponenneat D

UV properlation reportbased acrylattainingHYP acand glsucrostivity aet al., with bimprovresistament tdevelo

8. Fut

VEGtive soattribuinevitastocks VEGO today tions operformmulti-monoming amsyntheaturesimpairbe takerendering probstrates (Thames et al., 1996). Thiolene UV curableve been prepared by Rawlins et al. (Black and Rawlins,lcoholysis of tobacco seed oil in combination with poly-mpounds gave polyols. PU from the resulting polyolsr reacted with hydroxyethyl methacrylate to producee acrylate coatings with excellent performance (Patel. The inuence of cashew nut shell oil, epoxidized SoyO,ioctyl phthalate on the photocrosslinking kinetics of UVtures containing an o-cresol novolac epoxy resin, a bis-tic diepoxide monomer, and a triarylsulfonium salt as aotoinitiator has been studied by Hien et al. (2011). Theyrried out the cationic photopolymerization of a mixturesin modied by TO in the presence of a triarylsulfonium2 s of exposure under a light intensity of 250 mW/cm2

in the dark for a few hours. UV cured coatings con-optimum amount of the VEGO or VEGO epoxy showedrformance. These may nd applications as adhesivesecorative and protective coatings (Hien et al., 2011).l. (2001) have studied the cationic photocrosslinkingesin with epoxidized SoyO. In their investigation, theythe formulation with an optimum content of the com-ceeded substantially with faster curing than that of the.d HYP coatings showed good mechanical and thermal

the former were more dependent on the degree of acry- molar mass (Dzunuzovic et al., 2006). Chen et al. havee coating performance of acrylated epoxidized SoyOurable coating material prepared by the inclusion ofcrose and commercial HYP acrylates. The coatings con-

h the modiers showed good performance; those withes showed good hardness, adhesion, solvent resistanceransition temperature, while the ones with acrylatedibited improved toughness, but reduced water resis-

hermal stability of the coatings (Chen et al., 2011; Wu). Acrylated SoyO epoxy based UV curable coatings,sed gallic acid cross linking agent have shown highlyoating properties in terms of pencil hardness, wearnd adhesion (Ma et al., 2014). Recently, to further aug-rformance, UV curable nanocomposites have also beens antimicrobial coatings (Table 1).

erspectives and summary

e abundantly available, easy to procure and cost effec-s of nature. These hone unique natural functionaland potential biodegradability that symbolize thems established raw materials toward renewable feed-

environment friendly materials. Although the use ofaints and coatings is decades old and well studied,asis is being laid on research pertaining to modica-

se materials to introduce novel properties for improvede, environment friendliness at affordable costs. Thereactions are involved in the synthesis of VEGO basedpolymers at elevated temperatures and times, consum-f solvents. The coatings obtained also consist of complexd cure schedules with longer curing times and temper-

long drying times and high curing temperatures oftenuality of the nal product and yield. Thus, efforts must

ward the development of low or solvent free materialsOC free coatings, i.e., cutting off the use of solvents dur-ing, formulation and application of coatings. The solvent

226 E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229

free reactioto some ofnous heatintimes. AnotIn HYP polymolecule shthetic onessurely be ofthe compleents in HYPgenerally pshould be dmers, offerias green Vacteristic opolymers isat both cosdrying agenenvironmenapproach pthat are nounutilized mFig. 7. VEGO based UV curable acrylic p

ns under microwave irradiations may provide remedies the drawbacks such as poor yield due to inhomoge-g (under conventional conditions) and longer synthesisher alternate may be the enzymatic synthesis approach.mers, it is proposed that as a green material, the coreould also be biobased in origin, unlike the present syn-

. If an oil based core molecule is well developed, it will advantageously reduced viscosity, which will facilitatete elimination of the use of solvents and reactive dilu-

coatings. WB coatings have been developed from VEGOrepared in water along with some co-solvent. Effortsirected to achieve 100% water solubility of VEGO poly-ng several advantages especially towards applicationsEGO coatings. To improve upon the performance char-

f VEGO coatings blending with commercially available the simplest method to reach a synergistic platformt and performance levels. Conventional curing agents,ts, diluents and modiers must be replaced by theirt friendly renewable resource based counterparts. The

resented in the article must be employed on those oilsn-edible and non-medicinal to add value to a waste or

aterial.

The maas potentiayield valuend plethogreater utilcally abundof energy isenvironmenincurred onthe-art-modemic and iof VEGO, foresearch anmaterials, pimplementcoatings.

Acknowled

Dr. EramIndustrial Rciateship aolyol.

nuscript provides an insight into the world of VEGOl candidates for environment friendly materials. They

added materials by simple chemical reactions, whichra of applications, especially as protective coatings. Theization of the aforementioned non-depletable, domesti-ant and reliable resources over conventional resources

expected to have less deleterious/hazardous impact ont at a stable price and may cut off the annual expenses

processing and purchase of materials. The state-ofdications in the eld are expected to promote both aca-ndustrial research on industrial (non-food) applicationscussing on both crop-oriented and product-orientedd to further establish VEGO as workhorses of polymerarticularly the coatings industry. Thus followed and

ed, we are sure to enter the promising era of 100% green

gements

Sharmin is thankful to the Council of Scientic andesearch, New Delhi, India, for Senior Research Asso-gainst Grant No. 13(8464-A)/2011-Pool. Dr. Fahmina

E. Sharmin et al. / Industrial Crops and Products 76 (2015) 215229 227

Zafar is thankful to the University Grants Commission, India forDr. D. S. Kothari Post Doctoral Fellowship, Ref. # F.4/2006(BSR)/13-986/2013(BSR) with Prof. Nahid Nishat. Dr Deewan Akram isthankful to the Council of Scientic and Industrial Research,New Delhi,No.9/466(0

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Recent advances in vegetable oils based environment friendly coatings: A review1 Introduction2 VEGO and their chemical transformations3 Low solvent or zero solvent coatings4 High solids [HS] coatings5 Hyperbranched [HYP] coatings6 WB coatings7 Radiation curable coatings8 Future perspectives and summaryAcknowledgementsAppendix A Supplementary dataAppendix A Supplementary data