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Progress in Organic Coatings 76 (2013) 1144– 1150

Contents lists available at SciVerse ScienceDirect

Progress in Organic Coatings

j our nal homep age: www.elsev ier .com/ locate /porg coat

ynthesis and characterization of modified cottonseed oil based polyesteramideor coating applications

awan D. Meshrama,∗, Ravindra G. Puria,1, Amol L. Patil a,2, Vikas V. Giteb,3

University Institute of Chemical Technology, North Maharashtra University, Jalgaon, Maharashtra 425 001, IndiaDepartment of Polymer Chemistry, School of Chemical Sciences, North Maharashtra University, Jalgaon, Maharashtra 425 001, India

a r t i c l e i n f o

rticle history:eceived 17 October 2012eceived in revised form 20 February 2013ccepted 22 March 2013vailable online 8 May 2013

eywords:

a b s t r a c t

Cottonseed oil fatty amide (CFA) was prepared in the laboratory by base catalyzed aminolysis of cot-tonseed oil. Further it was reacted with phthalic acid to obtain polyesteramide (CPEA) and modified bypost reacting with vinyl acetate monomer in varying ratios of 4:1, 3:1 and 2:1 in the presence of t-butylhydroperoxide as an initiator. The incorporation of vinyl acetate in CPEA was analyzed using FTIR, 1HNMR and 13C NMR spectral techniques. The physico-chemical properties such as iodine value, specificgravity and refractive index were determined by standard laboratory test methods. Mechanical, chem-

olyesteramideoatinginylationenewable sourceottonseed oil

ical resistance and other coating properties of the coatings synthesized from CPEA and modified CPEAapplied on mild steel substrates were also studied by standard methods. Thermal stability and curingbehavior of modified CPEA were determined by thermo gravimetric analysis (TGA) and differential scan-ning calorimetric (DSC) techniques. It was observed that modification of polyesteramide improved thecuring, mechanical and chemical performance of CPEA films. It was found that among the CPEA:vinylacetate ratios, 2:1 ratio exhibited the best results.

© 2013 Elsevier B.V. All rights reserved.

. Introduction

In recent years, manufacturing of polymers using petroleumased raw materials is declined due to the depletion of fossil stocksnd with rising prices of crude oil. Moreover, the growing con-ern toward environmental protection and energy conservationlso driven the coating technologists to substitute conventionaletroleum based polymeric binders with renewable resources1–3]. Polymeric resins derived from vegetable oils provided anpportunity to utilize eco-friendly and sustainable resource foranufacturing of polymeric binders [4–6]. Vegetable seed oils have

een actively used to develop different polymeric binders such aslkyds, polyurethanes, epoxies, polyesteramides, polyetheramides,

∗ Corresponding author. Tel.: +91 0257 2257442;ax: +91 0257 2258403/2258406; mobile: +91 8087276922.

E-mail addresses: pawan.dm@gmail.com (P.D. Meshram),avigpuri@rediffmail.com (R.G. Puri), amolpatil.12d@gmail.com (A.L. Patil),ikasgite123@gmail.com (V.V. Gite).1 Tel.: +91 0257 2257442; fax: +91 0257 2258403/2258406;obile: +91 9960411814.2 Tel.: +91 0257 2257442; fax: +91 0257 2258403/2258406;obile: +91 7350182942.3 Tel.: +91 0257 2257432; fax: +91 0257 2258403/2258406;obile: +91 9420067321.

300-9440/$ – see front matter © 2013 Elsevier B.V. All rights reserved.ttp://dx.doi.org/10.1016/j.porgcoat.2013.03.014

etc. [7–11]. These resins have various fields of applications such ascoatings, adhesives, binders, composites, etc. [12].

N,N-bis(2-hydroxyethyl) vegetable oil fatty amides obtained bybase catalyzed aminolysis of various vegetable oils are excellentexample of polyesteramides used in coatings [13]. Vegetable oilbased polyesteramides are regular copolymers and has combina-tion of good properties of polyesters and polyamides [14]. Presenceof ester ( COOR) and amide ( NH COR) functional groups in thebackbone of polymeric chain of oil based polyesteramide (PEA)improve the quality of coatings in terms of ease of applications,thermal stability, resistance against chemicals and water, fasterdrying and enhanced hardness over normal alkyds [15]. Althoughpolyesteramides have attracted great attention because of their sta-bility at high temperature, some limitations such as high curingtemperature, high melting point and slightly poor chemical resis-tance restrict their application in coatings [14]. These drawbackscan be overcome by modification of polyesteramides using vinylmonomers and peroxide as an initiator [16,17]. Vegetable oils suchas castor, nahar seed, neem, soybean and karanja oils are reportedfor their use in the preparation of polyesteramides [8,18–21]. Indiais an agrarian country and the second largest producer of cotton-seed in the world [22]. Considering the availability of cottonseed oil

in India, it may be a more viable and cheap source for the produc-tion of resins for surface coating applications. Our earlier researchon utilization of cottonseed oil for synthesizing moisture curedpolyether urethane coating focused on feasibility of cottonseed

P.D. Meshram et al. / Progress in Organic Coatings 76 (2013) 1144– 1150 1145

CH2

N

CH2

CH2 OH

CH2 OH

CR

OCH2

NH

CH2

CH2 OH

CH2 OH

3

CH2

CH

CH2

O

O CO RO CO R

CO R CH2

CH

CH2

OH

OH

OH

3+ +CH3ONa

120 oC

roxye

oc

pawbwmmi

2

2

puardvI

2a

ci(rawriaa

Triglycerides Diethanolamine

Scheme 1. Synthesis of N,N-bis(2-hyd

ils as a potential renewable source for preparation of polymericoatings [23].

The present work investigated synthesis of cottonseed oil basedolyesteramide, its modification with vinyl acetate which was useds a polymeric binder in coating application. The synthesized resinsere characterized by FTIR, 1H NMR and 13C NMR techniques and

y physico-chemical properties. Thermal behavior of these resinsas studied using DSC and TGA techniques. Coatings based on theodified and unmodified polyesteramide resins were applied onild steel strips and evaluated for their physico-mechanical, coat-

ng and chemical resistance properties.

. Materials and methods

.1. Materials

Cottonseed oil of RBD grade (refined, bleached, deodorized) wasrocured from Kamani Oil Industries, Mumbai, India. The chemicalssed for analysis were of analytical grade, while remainingll chemicals used were of synthetic grade. Other supportingeagents viz. phthalic acid, sodium methoxide (Merck, India),iethanolamine, diethyl ether, t-butyl hydroperoxide (TBP) andinyl acetate were of analytical grade (S.D. Fine-Chem Ltd., Mumbai,ndia).

.2. Synthesis of N,N-bis(2-hydroxyethyl) cottonseed oil fattymide (CFA)

Synthesis of CFA was carried by base catalyzed aminolysis ofottonseed oil (Scheme 1) [24]. Typical reaction was carried outn a glass reactor consisting of a four-necked round bottom flask1000 mL). The reactor was equipped with a motor driven speedegulator for stirring and temperature sensor to control the temper-ture throughout the reaction. Additionally, the reactor was fittedith a condenser and the entry neck which was used for dropping

aw materials as well as to maintain inert atmosphere by pass-ng N2 gas as per requirement. The whole assembly was placed in

thermostatic oil bath with special arrangement for smooth andccurate control of the temperature within ±5 ◦C of the desired

145 ± 5 oC

- nH2O

C

C

O-Phtalic Acid

+N

CH2

CH2

C

O

R

CH2

CH2

OH

OH

Fatty amide

O

HO

O

HO

wherePart of - R ma

Palmitic acid

Oleic acid

Linoleic acid

Scheme 2. Synthesis of cottonseed

GlycerolFatty amide

thyl) cottonseed oil fatty amide (CFA).

temperature. A calculated amount of diethanolamine (0.32 mol)and sodium methoxide (0.007 mol) were charged into the reactorand heated up to 80 ◦C for 15 min with constant stirring. Cotton-seed oil (0.1 mol) was added drop wise into the reaction mixtureover a period of 60 min under constant stirring with gradual risein temperature up to 120 ◦C. The reaction was continued for next3 h under controlled stirring at 120 ◦C. The progress of reactionwas monitored using TLC along with determination of solubility ofthe reaction mixture in methanol. After attaining the solubility inmethanol, the product was dissolved in diethyl ether, followed bywashing in 15% aq. NaCl solution and dried over anhydrous sodiumsulfate. The upper ethereal layer was separated and the solvent wasevaporated in rotary vacuum evaporator to obtain CFA.

2.3. Synthesis of cottonseed oil polyesteramide (CPEA)

The CPEA was synthesized (Scheme 2) in the laboratory usingfollowing steps [14]. Equimolar amount of CFA (0.54 mol) andphthalic acid (0.54 mol) were dissolved in xylene (50 mL) in a four-necked round bottom flask equipped with Dean and Stark trap,nitrogen inlet, thermometer and mechanical stirrer. The reactionmixture was heated at 145 ± 5 ◦C under continuous stirring in aninert atmosphere. Progress of the reaction was monitored by deter-mining acid value at regular intervals. Simultaneously, amount ofwater collected in Dean Stark trap was also considered as a tool tomonitor the reaction. The reaction was stopped after the desiredacid value reached and calculated amount of water collected inDean Stark trap. CPEA in purified form was obtained after removalof excess xylene using vacuum rotary evaporator under reducedpressure.

2.4. Modification of cottonseed oil polyesteramide

The proposed reaction route for synthesis of modified cot-

tonseed oil polyesteramide (MCPEA) is shown in Scheme 3.Modification of CPEA (Scheme 3) involved three MCPEA which arebased on the ratios (weight basis) selected 4:1, 3:1 and 2:1 for CPEAto vinyl acetate (containing 0.5 wt% TBP initiator).

N CH2CH2

C

RO

CH2 CH2O OH C

Polyesteramide

O

C OH

n

O

y be represented for

CH2 CH2 CH313

CH2 CH2 CH3CH CH77

CH2 CH CH7

CH2 CH CH CH2 CH34

oil polyesteramide (CPEA).

1146 P.D. Meshram et al. / Progress in Organic Coatings 76 (2013) 1144– 1150

N CH2CH2

CRO

CH2 CH2O OH C

O

C

O

OH

CH2

CH

CH

CH2

CH2

CH2

CH2

CH2

CH

CH2

CH

CH

CH

1 2 3

wherePart of - R may be represented for

CH2 CH2 CH313

1. Palmitic acid

2. Oleic acid

3. Linoleic acid

CH2 CH2 CH3CH CH77

CH2 CH CH7

CH2 CH CH CH2 CH34

CPEA

CH2

CH

CH

CH2

H2C CH90-100 oC

Xylene, TBP

CH2

CH

CH

CH2

CH2 CH

CH2

CH

CH

CH2

CPEA Vinyl acetate Copolymer of CPEA

OC CH3

O

OC CH3

O

CH2

CH

O

C

CH3

O

otton

ihrviru

2

iC8oTwdatsFusaSiJ

The physical properties of cottonseed oil were studiedand given below: specific gravity = 0.918 (at 25 ◦C), acid value

( Oleic acid )

Scheme 3. Synthesis of modified c

In actual process CPEA and vinyl acetate were mixed with xylenen a four-necked round bottom flask under inert atmosphere andeated in the range of 90–100 ◦C temperature with constant stir-ing. The progress of the reaction was monitored with increase iniscosity of the reaction product. After attaining pourable viscos-ty to the product, reaction was stopped. The excess solvent wasemoved from modified resin under reduced pressure using vac-um rotary evaporator to obtain MCPEA.

.5. Methods of analysis

Acid value, saponification value, iodine value and specific grav-ty of cottonseed oil were determined according to AOCS Methodd 3d-63, AOCS Method Cd 3-25, AOCS Method Cd 1b-87 and MS17:1989 respectively. The fatty acid composition of cottonseedil was determined by gas chromatography of methyl esters usinghermo Scientific GC-8610 Microprocessor Controlled GC equippedith capillary column (BP1 30 m × 0.53 mm ID × 1.0 �m) and FIDetector. An injector temperature was 250 ◦C, while oven temper-ture was maintained at 220 ◦C. Nitrogen was used as carrier gas athe flow rate of 10 mL/min. MCPEA samples were characterized bypectrophotometric techniques such as FTIR, 1H NMR and 13C NMR.TIR spectra were recorded on Shimazdu FTIR-8400 spectrometersing NaCl cell into the range of 4000–400 cm−1. The absorbancepectra for each analysis were averaged over 32 scans. The 1H NMR

nd 13C NMR spectra were recorded on Varian Mercury YH-300pectrometer. Thermal stability and curing behavior were stud-ed by thermo gravimetric analysis (TGA) (Shimadzu TG-50, Tokyo,apan) and differential scanning calorimetry (Shimadzu DSC-60,

seed oil polyesteramide (MCPEA).

Tokyo, Japan) under N2 atmosphere (20 mL/min) at a heating rateof 10 ◦C/min.

2.6. Evaluation of coating properties

Prior to coatings both CPEA and MCPEA samples were diluted to65% in xylene. The prepared solutions were applied with brush onseparate clean mild steel panels (50 mm × 20 mm × 1 mm) as per IS101 (Part 1/Sec 3)-1986. Curing of CPEA and MCPEA coated sampleswere performed at 200 and 180 ◦C for 20 and 15 min respectively.The gloss meter (model BYK Instruments, Germany) was used todetermine the gloss of coatings at an angle of 60◦. Dry film thicknessof the applied coatings was determined using ultrasonic thicknessgauge (ASTM D-6132-04). Mechanical properties such as scratchhardness (IS 101 Part 5/Sec 2-1988), impact resistance (IS 101 Part5/Sec 3-1988) and flexibility (ASTM D 3281-84) of coated films werealso determined. Besides this, the chemical resistance test was per-formed according to ASTM 1308-02 in water, acid (1 wt% HCl), alkali(1 wt% NaOH), salt (3.5 wt% NaCl) and xylene.

3. Results and discussion

(mg KOH/g) = 0.12, iodine value (g I2/100 g) = 106, saponificationvalue (mg KOH/g) = 195. Fatty acid composition of cottonseedoil was found to be: palmitic acid, C16:0 = 21.6%; stearic acid,C18:0 = 3.3%; oleic acid, C18:1 = 20.8%; linoleic acid, C18:2 = 54.3%.

P.D. Meshram et al. / Progress in Organic Coatings 76 (2013) 1144– 1150 1147

F fatty

o

3

aisbim2a

ora

cbpbao

1atccs2

3

i

ig. 1. FTIR spectra of (A) cottonseed oil, (B) N,N-bis(2-hydroxyethyl) cottonseed oilil polyesteramide (MCPEA).

.1. FTIR spectral analysis

Fig. 1 shows the FTIR spectra of cottonseed oil, CFA, CPEAnd MCPEA. In case of IR spectra of cottonseed oil the character-stic peaks at 3007 cm−1 and 1650 cm−1 were attributed to thetretching vibrations of C H and C C respectively. The broadand at 3325 cm−1 was due to the presence of O H stretching

n CFA. The absorption bands for CH2 symmetrical and asym-etrical stretchings of fatty amide chains appeared at 2924 and

854 cm−1 respectively. The peak at 1737 cm−1 showed the char-cteristic absorption band for stretching vibration of C O. TheC C stretching of fatty acid constituents in fatty amide wasbserved at 1622 cm−1. The absorption band at 1057 cm−1 rep-esented presence of C N stretching, while the CH2 bendingppeared at 1462 cm−1.

The synthesis of CPEA can be supported by the presence of theharacteristic peaks in IR spectra: CH2 asymmetrical stretchingand at 2854 cm−1 and symmetrical stretching at 2924 cm−1. Theeaks at 1730 and 1284 cm−1 showed the characteristic absorptionand for stretching vibration of C O and C O groups function-lity due to ester linkages. The C N stretching of amide groupsccurred at 1458 cm−1.

It was observed that the FTIR spectra of MCPEA at 1732 and599 cm−1 were characteristics of 〉C O ester of vinyl acetate/estermide and unsaturation present in the polyesteramide respec-ively. A new characteristic peak appeared at 796 cm−1 may beorrelated to the C H vibrations of vinyl groups. Asymmetri-al stretching of CH2 observed at 2862 cm−1, while symmetricaltretching of CH2 present in the polyesteramide observed at926 cm−1.

.2. NMR spectral analysis

The 1H NMR spectra of MCPEA (Fig. 2) showed character-stic peaks at ı = 1.25 and ı = 7.10–7.29 ppm for gem dimethyl

amide (CFA), (C) cottonseed oil polyesteramide (CPEA) and (D) modified cottonseed

protons and for aromatic ring protons from phthalic acid com-ponent present in resin respectively. Appearance of peak atı = 3.88–3.94 ppm assigned to CH linked with O CO group. Achemical shift at ı = 1.60 ppm was due to methine protons of fattyalkyl chain modified by vinyl acetate. The terminal aliphatic CH3of fatty acid chain was observed at ı = 0.87 ppm. The characteris-tic peaks at ı = 3.43–3.52 and ı = 2.76 ppm were of CH2 attachedto amide nitrogen and that of amide carbonyl respectively. Protonresonance of carboxylic acid group was present at ı = 8.01 ppm. Theother chemical shifts at ı = 4.38 and 5.34 ppm were characteristicchemical shifts of methine proton attached to ester and olefinicprotons of fatty acid chain respectively. These spectral results con-firmed that modification has occurred on fatty acid chain of CPEA.

The 13C NMR spectra of MCPEA (Fig. 3) revealed peaks of CH3(fatty amide chain), CH3 and CH2 of acetate portion at ı = 14.0,19.6 and 25.5 ppm respectively. The peaks of internal CH2 offatty amide chain and CH2 attached to double bond occurredat ı = 33–25 and 27.1 ppm, respectively, and CH2 attached toamide carbonyl appeared at ı = 33.9. The characteristic peak atı = 58–60 ppm were due to CH2 attached to N atom of fattyamide. The peaks at ı = 127–125 ppm were assigned for unsatu-ration of fatty amide chain of fatty acid. The small peaks appearedbetween ı = 136–129 ppm were assigned to the aromatic ring car-bons of phthalic acid part present in the resin. Peak at ı = 171.5 ppmwas due to C of phthalic carbonyl attached to fatty amide whilepeaks at ı = 174 and 178 ppm were attributed to the free end andfatty amide carbonyl respectively. 13C NMR spectral data also con-firmed modification of fatty acid chain of CPEA.

3.3. Thermal analysis

Fig. 4 shows the TGA thermogram of the MCPEA resin. Initiallydegradation of resin found at 166 ◦C and 10% weight loss occurredat 209 ◦C, while 20% weight loss at 234 ◦C. Beyond this temperature

1148 P.D. Meshram et al. / Progress in Organic Coatings 76 (2013) 1144– 1150

Fig. 2. 1H NMR spectra of MCPEA.

R spec

sw

ptis

Fig. 3. 13C NM

low decomposition took place and as a result, about 50 and 80%eight losses occurred at 375 and 459 ◦C respectively.

The DSC of MCPEA is given in Fig. 5. The first endothermic◦

eak starting from 47 to 86 C can be correlated to the curing of

he resin through unsaturation present in the resin because dur-ng this temperature range TGA thermogram does not showed anyignificant weight loss. The actual decomposition of the resin was

Fig. 4. TGA curve for MCPEA.

tra of MCPEA.

found at comparatively higher temperature. Beyond 235 ◦C theresin had undergone severe deformation and afterward degrada-tion as clearly seen in TGA. Considering the thermal stability of

MCPEA, coating prepared from MCPEA could be safely used up to200 ◦C.

Fig. 5. DSC curve for MCPEA.

P.D. Meshram et al. / Progress in Organic Coatings 76 (2013) 1144– 1150 1149

Table 1Physico-chemical characterization of CPEA and MCPEA.

Sample Iodine value(mg I2/g)

Specific gravity(g/mL 25 ◦C)

Refractiveindex (at 25 ◦C)

CPEA 25.92 0.986 1.520MCPEA 4:1 19.46 0.988 1.525MCPEA 3:1 18.25 0.994 1.531MCPEA 2:1 16.11 1.008 1.542

Table 2Coating properties of CPEA and MCPEA.

Sample Scratchhardness (kg)

Impact resistance(lb/in.)

Bending test(1/8 in. mandrel)

Gloss at 60◦

CPEA 1.8 100 Passes 70MCPEA 4:1 2.1 100 Passes 74MCPEA 3:1 2.3 100 Passes 77MCPEA 2:1 2.6 100 Passes 80

Table 3Chemical resistance performance of CPEA and MCPEA.

Sample Water resistance (7days)

Alkali resistance(1% NaOH, 1 day)

Acid resistance(1% HCl, 7 days)

Salt resistance(3.5% NaCl, 7 days)

Xyleneresistance (1 h)

CPEA a f f b fMCPEA 4:1 a f c b eMCPEA 3:1 a f c b eMCPEA 2:1 a e b a d

a swell

3

ipswtbos

3

TtoMioo1taiTbHrpittii

[[

[[[

– not affected; b – discoloration; c – loss of gloss; d – blistering; e – softening and

.4. Physico-chemical characterization

The physico-chemical properties of CPEA and MCPEA are givenn Table 1. From the data it was observed that physico-chemicalroperties of CPEA were different than MCPEA copolymers. Morepecifically the specific gravity and refractive index were increased,hile the iodine value decreased from CPEA to MCPEA. A similar

rend was found when vinyl acetate loading was increased. This cane attributed to the increase in molecular weight by modificationf CPEA with vinyl acetate and conversion of some double bonds toingle bonds during addition of vinyl acetate groups.

.5. Coating properties

Coating properties of CPEA and MCPEA are shown in Table 2.he scratch hardness values of MCPEA were found to be higherhan that of CPEA. It was also observed that the scratch hardnessf coatings increased with increase in the vinyl acetate content ofCPEA. This may be because of increase in the cross-linking density

n MCPEA with increase in vinyl acetate content. The baked coatingsf CPEA were obtained at 200 ◦C for 20 min whereas baked coatingsf MCPEA were obtained at relatively lower temperature, i.e. near to80 ◦C in about 15 min. Decrease in baking temperature from CPEAo MCPEA can be correlated to increase in cross-linking by vinylcetate. The chemical resistance test indicated slight improvementn chemical resistance properties for MCPEA than CPEA (Table 3).he resistance of coating prepared from 2:1 composition showedetter chemical resistance in alkali (1% NaOH; 1 day), acid (1%Cl; 7 days), water (7 days) and salt (3.5% NaCl; 7 days). Chemical

esistance of coatings prepared from CPEA was poor than all com-ositions of MCPEA and it increased with increase in vinyl acetate

n MCPEA up to 2:1 composition. Again increase in chemical resis-ance for MCPEA may be because of higher cross-linking densityhan CPEA cured resin as penetration of chemicals inside the resins restricted by cross-links which may be increased with increasen vinyl monomer content.

[[

[

[

ing; f – loss of adhesion, film completely removed.

4. Conclusions

The CPEA was modified by vinyl acetate and evaluated fortheir physico-mechanical and chemical resistance performance.The modified CPEA (MCPEA) showed better physico-chemical andcoating properties as compared to CPEA resin. Due to modificationof CPEA baking temperature of MCPEA coatings reduced com-pared to temperature required for baking to CPEA. The coatingsof 2:1 compositions have superior physico-chemical and coatingfilm properties among all the compositions and can be safely usedup to 200 ◦C.

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