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Industrial Crops and Products 50 (2013) 550– 556

Contents lists available at ScienceDirect

Industrial Crops and Products

journa l h om epa ge: www.elsev ier .com/ locate / indcrop

evelopment of eco-friendly polyurethane coatings based on neemil polyetheramide

shok Chaudharia, Vikas Gitea,∗, Sandip Rajputa, Pramod Mahulikara, Ravindra Kulkarnib

Department of Polymer Chemistry, School of Chemical Sciences, North Maharashtra University, Jalgaon 425001, Maharashtra, IndiaSchool of Chemical Technology, North Maharashtra University, Jalgaon 425001, Maharashtra, India

r t i c l e i n f o

rticle history:eceived 24 May 2013eceived in revised form 23 July 2013ccepted 4 August 2013

eywords:eem oil polyetheramideco-friendly polyurethane coatings

a b s t r a c t

Renewable sources like vegetable oils have been used to prepare many polymeric resins and the topic isgaining more importance due to the functional attributes to structure of oils. In the regard, renewablesource based polyurethane coatings have been prepared from polyetheramide of neem oil in the labo-ratory. In the preparation of polyetheramide, first neem oil was allowed to react with diethanol amine.Obtained fatty amide was modified to the polyetheramide by reacting it with bisphenol-A. Spectroscopictechniques such as FT-IR and 1H NMR confirmed the structures of fatty amide and polyetheramide.Polyurethane coatings were prepared from the polyetheramide by treating it with methylene diphenyl

iO2 nano particlesenewable sources

diisocyanate.Coating properties such as gloss, scratch hardness, adhesion, flexibility, thermal stability, impact and

chemical resistances were evaluated using standard methods. The influence of surface modified TiO2

nano particles on the properties of the neem oil based polyurethane coatings was examined by loadingnano TiO2 from 0 to 4%. The overall performance of coatings revealed that neem oil based polymericcoatings can be successfully used as coatings in industrial applications.

. Introduction

The demand for polymers prepared from renewable sources isn the increase because of a number of reasons notably environ-ental concern, abundant availability and low price of renewable

ources (Anand et al., 2012; Guner et al., 2006; Lligadas et al., 2012).ellulose and vegetable oils are two major renewable sourcesresent on the earth in large quantities. Applications of cellulose inolymeric coatings is limited while vegetable oils have been usedost of the time to prepare polymeric binders for coatings formu-

ations, flooring materials and resin applications (Gu et al., 2012;pera, 2010). Vegetable oils obtained from different sources havelso been widely used in preparation of inks, diluents, plasticizers,

ubricants, agrochemicals, food industries, composite materials,tc. (Derksen et al., 1996; Kashif et al., 2011; Khot et al., 2001;harmin et al., 2006). Vegetable oils can be commonly converted

Abbreviations: IPDI, Isophorone diisocyanate; MDI, Methylene diphenyl diiso-yanate; PEthA, Polyetheramide; PEA, Polyesteramide; TTIP, Titanium isopropoxide;HF, Tetrahydrofuran; TEVS, Vinyltriethoxysilane; DBTDL, Dibutyltin dilaurate; MS,ild steel; AIJFA, Azadirachta indica juss fattyamide; PU, Polyurethane.∗ Corresponding author. Tel.: +91 257 2257431; fax: +91 257 2258403.

E-mail addresses: vikasgite123@gmail.com, vikasgite2000@yahoo.com (V. Gite).

926-6690/$ – see front matter. Crown Copyright © 2013 Published by Elsevier B.V. All rittp://dx.doi.org/10.1016/j.indcrop.2013.08.018

Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.

into derivatives such as alkyd resins and polyols based on alkyds(Nimbalkar and Athawale, 2010). Polyols are low molecular weightpolymers that may be reacted with different diisocyanates such asisophorone diisocyanate (IPDI), methylene diphenyl diisocyanate(MDI) or others, to obtain polyurethane (PU) coatings (Gite et al.,2010). A number of reports have described the preparation of poly-ols from different vegetable oils such as jatropha, soya, cottonseed,linseed, neem oils and their subsequent use in the preparation ofPU (Chaudhari et al., 2013a,b; Gite et al., 2006; Jaliliana et al., 2010;Meshram et al., 2013a,b; Zlantanic et al., 2004). PU of the kind ofinterpenetrating polymer networks have also been prepared usingcastor oil with styrenic-acrylic polymers and these have gainedmuch attention due to their interesting properties (Meier et al.,2007). Epoxidized soybean oil has been studied by curing with var-ious cyclic acid anhydrides in presence of tertiary amines (Gerbaseet al., 2002). Recent routes explored utilization of vegetable oilsin coatings by preparing polyetheramides (PEthA) (Akintayo andAkintayo, 2010; Alam et al., 2004) and polyesteramides (PEA)(Dutta and Karak, 2005; Shende et al., 2004; Zafar et al., 2004).

Azadirachta indica juss can be said to be underutilized when

its available production potential is compared to its presentlimited applications in pharmaceuticals (Biswas et al., 2002) andagrochemicals sector as medicinal compound and bio pesticide(Bagle et al., 2013) respectively. Neem seed oil contains three

ghts reserved.

A. Chaudhari et al. / Industrial Crops and Products 50 (2013) 550– 556 551

CH2

OH CH2

N

CH2

CH2

OH

CO

R

CH2

O C

O

R

CH

CH2

O

O C

O

R

C

O

R

CH2

CH2

OH

NH

CH2

CH2

OH CH2

OH

CH

CH2

OH

OH+

120 0C

Neem oil Diethanol amine

+

Diethanol amide (AIJFA) Glycerol

NaOCH3

thesi

saa2Iln2n

apdEfiu

2

2

atCdf

2

(

2

0Dmtoacwou

Fig. 1. Syn

aturated fatty acids including palmitic (11.90%), stearic (29.96%)nd arachidic (2.94%) acids. It also contains two unsaturated fattycids viz. oleic (50.04%) and linoleic (5.15%) acids (Chaudhari et al.,013a). Although neem plant is widely cultivated in arid zones ofndia with annual neem oil production rate of 18,000 ton, the uti-ization of the seed oil in the development of polymeric resins hasot been investigated except our earlier report (Chaudhari et al.,013a). Our previous report claims preparation of PU coatings fromeem oil fatty amide using diisocyanate.

In the present work, further chemical modification of fattymide (AIJFA) prepared from neem oil has been carried to obtainolyetheramide (PEthA). The synthesized PEthA was treated withiisocyanate at room temperature to prepare the PU coatings.ffects of percent loading of silane modified nano TiO2 on the per-ormance of pristine neem oil PEthA based PU coatings have beennvestigated first time. Performance of PU coatings was evaluatedsing standard methods.

. Experimental

.1. Chemicals and materials

Neem seed oil was purchased from local supplier and useds it is. MDI, bisphenol-A, titanium isopropoxide (TTIP), vinyl-riethoxysilane (TEVS) and dibutyltin dilaurate (DBTDL) (Aldrichhemicals, UK) were of laboratory grade. Cylcohexanone, tetrahy-rofuran and diethanolamine of analytical grade were obtainedrom s.d. fine-chemicals Ltd., India.

.2. Synthesis of A. indica juss fatty amide (AIJFA)

AIJFA was synthesized (Fig. 1) according to our earlier reportChaudhari et al., 2013a).

.3. Synthesis of polyetheramide (PEthA)

Mixture of AIJFA (20 g, 0.10 M) and bisphenol-A (16.65 g,.073 M) were reacted (Fig. 2) in round bottom flask equipped withean and Stark trap, nitrogen inlet tube, thermometer and rotaental. The mixture was allowed to react by dissolving it in a mix-

ure of solvents (80:20 parts of xylene and n-butanone) in presencef dilute sulfuric acid as a catalyst. The reaction mixture was heatedt 175 ± 5 ◦C and refluxed until the theoretical amount of water was

ollected in Dean and Stark trap. Once the theoretical amount ofater removed, reaction was allowed to stop. After the completion

f reaction, solvent was evaporated in a rotary vacuum evaporatornder reduced pressure to obtain PEthA.

s of AIJFA.

2.4. Synthesis of nano TiO2 and their modification by silanecoupling agent

Nano TiO2 was synthesized (Mahshid et al., 2006) and modifiedby using vinyltriethoxysilane (TEVS) coupling agent as reported inthe literature (Chaudhari et al., 2013b; Sabzi et al., 2009).

2.5. Preparation of PU coatings based on PEthA

PU coatings were obtained (Fig. 3) by reacting PEthA at roomtemperature with MDI using NCO/OH ratio 1.1:1 in the presenceof a catalyst DBTDL (0.5%). In a typical process 50% solid contentsolution of PEthA was prepared in cyclohexanone and THF (80:20)mixture. PU were coded as PU0, PU1, PU2, PU3 and PU4 where suffix0–4 indicated the percentage of modified nano TiO2 ranging from0 to 4% (based on amount of PEthA) in PU coatings.

After addition of nano TiO2, reaction mixtures were sonicatedon a sonicator for the proper dispersion of modified nano TiO2 andthen mixture was treated with MDI. The entire reaction mixturewas stirred for next 5 min at room temperature to attain pourableviscosity. This mixture was applied as a coating by using bar appli-cator on MS steel panels of 4 × 6 in. dimensions. The preparedcoating panels were allowed curing at room temperature undervisual examination. Prior to application of the coatings, the steelpanels were pretreated by sand paper and washed with acetone.

3. Characterization

3.1. Chemical analysis

Neem oil, AIJFA and PEthA were characterized for specific gravity(ASTM D5355 - 95), refractive index (ASTM D1747 - 09), saponifi-cation (ASTM D464 - 05), acid (ASTM D5768 - 02), hydroxyl (ASTMD1957-86) and iodine values (ASTM D5768-02).

3.2. Spectroscopic analysis

The FT-IR spectra of the prepared resins were recorded on FTIRspectrophotometer (Shimadzu, Japan, Model No. 8400) from therange of 4000–500 cm−1 as KBr pellets. Homogenous mixture ofsample in KBr was prepared by grinding in mortar and by theaction of 12 ton lab press to diminish moisture present in the sam-ple. 1HNMR spectra of samples were recorded on Varian Mercury300 MHz spectrometer using TMS as an internal standard in pres-ence of CDCl3 as a solvent.

3.3. Transmission electron microscopy (TEM)

The synthesized nano titanium dioxide particles were studiedfor their size by using TEM (TEM, Philips, CM-200, Holland). Theanalysis was carried out by accelerating voltage in the range of

552 A. Chaudhari et al. / Industrial Crops and Products 50 (2013) 550– 556

C

CH3

CH3

OH OH

CH2

OH CH2

N

CH2

CH2

OH

CO

R

CH2

O CH2

N

CH2

CH2

O

CO

C

CH3

CH3

O CH2

CH2

N

CH2

CH2

OH

CO

RR

H n

Polyethe ramide (PEthA)

(AIJFA)

+

Diethanol amide Bispheno l - A

R = Fatty acid chain

Dil. H2SO4

polye

2wo

3

ngJ

3

A6ctbhaD

Fig. 2. Synthesis of

0–200 kV with resolution of 2.4 A by dispersing TiO2 in acetoneith ultrasonic wave for sufficient time. Samples were deposited

n Cu grid and viewed at high magnification.

.4. Field emission scanning electron microscopy (FE-SEM)

Morphologies of TiO2 nano particles and silane modified TiO2ano particles were studied using thin layer of samples coated withold on a FESEM (FE-SEM, HITAHCI High Technologies Corporation,apan, Model No. S-4800) with voltage range from 0.5 to 30 kV.

.5. PU coatings characterizations

The PU coating panels were tested for the gloss (Model BYKdditive & Instruments, Germany) measurement at an angle of0◦ on the calibrated digital gloss meter. Elasticity of the preparedoatings was measured in the range of 45–180◦ angles by usinghe conical mandrel instrument (Raj Scientific Company, Mum-

ai). Pencil hardness of the coatings was measured with the pencilardness tester (Model BYK Additive & Instruments, Germany)ccording to ASTM D-3363 standards. Adhesion of coatings (ASTM-3359-02) was tested on the cross cut adhesion tester (model

CH2

O CH2

N

CH2

CH2

O

CO

C

CH3

CH3

O CH2

C

O

R

H n

CH2

CH2

N

CH2CH

2O

CO

C

CH3

CH3

O CH2

CH2

N

C

CO

RR

DBTD

PU coatin

PEthA

Fig. 3. Preparation o

theramide (PEthA).

no 107, Elcometer, U.K.) consisting of a die with 11 number ofclosed set of parallel blades. For measurement of impact resis-tance, PU coated panels were deformed rapidly by application of theweighted indenter (1.818 lb) from variable heights starting from 5to 40 in. of the tubular impact tester. After falling weighted indenterpeeling and cracking of the coatings from substrate was examined.

3.6. Chemical resistance

For estimating chemical resistance (ASTM D 543-67/1972) ofcoatings, sample panels were dipped in 5% alkali solutions (NaOHand NH4OH), 25% acid solutions (H2SO4 and CH3COOH) and a sol-vent (xylene) for 7 days. During the test, the panels were taken outevery day for once from solutions. Softness, loss in gloss, loss inadhesion, blister and rupture were examined during the test.

3.7. Thermal analysis of PU coatings

Thermal behavior of the prepared PU coatings was studied bythe thermo gravimetric analysis (Model - TGA 4000, PerkinElmer,USA) in the range of 30–600 ◦C temperature at heating rate of20 ◦C/min in presence of N2 as an inert atmosphere.

CH2

NCOOCNH2

N

CH2

CH2

OH

C

R

H2

CH2

O C

O

NH CH2

NH C

O

On

+

L

MDI

gs

f PU coatings.

A. Chaudhari et al. / Industrial Crops a

4006008001200160020002800360020

25

30

35

40

45

50

55

60

65

70

75

%T

33

00

.31

29

29

.97

28

58

.60

23

33

.94

18

86

.44

16

10

.61

14

60

.16

13

63

.72

12

46

.06

10

64

.74

93

9.3

6

83

1.3

5

64

2.3

2

56

3.2

3

4

4

a

PTmP

4

s2

4

g

p1fbatocbo

4

smfia1tbfiaa

1/cmLiqu id

Fig. 4. FTIR spectral analysis of neem oil based PEthA.

. Results and discussion

.1. Characteristic properties of neem oil, AIJFA and PEthA

Specific gravity, refractive index, saponification, acid, hydroxylnd iodine values of raw materials are given in the Table 1.

Specific gravity increased in the sequence of neem oil, AIJFA andEthA, while iodine value was decreased for the same sequence.he hydroxyl value also decreased from AIJFA to PEthA. The trenday be due to increase in molar masses from neem oil to AIJFA and

EthA.

.2. Spectroscopic analysis of AIJFA

The formation of AIJFA was confirmed by FT-IR and 1H NMRpectral analysis according to our earlier report (Chaudhari et al.,013a).

.3. FTIR of PEthA

Fig. 4 is a FTIR spectrum presenting the frequencies of functionalroups of PEthA prepared from neem oil.

The spectrum showed a broad band at 3300 cm−1 indicatingresence of OH stretching of PEthA. The characteristic bands at246 cm−1 and 1064 cm−1 were due to aryl alkyl ether linkagesor C O C asymmetrical and symmetrical stretchings. Absorptionands at 2859 and 2930 cm −1 were attributed to symmetricalnd asymmetrical stretchings of CH2 and CH3 groups respec-ively. The characteristic band at 1611 cm−1 indicated the presencef C O stretching of amide carbonyl group and 1460 cm−1 indi-ated the C N stretching vibrations. The characteristic absorptionands at 831–939 cm−1 represented the presence of aromatic ringf bisphenol-A in PEthA.

.4. 1H NMR spectra of PEthA

1H NMR spectra of PEthA is shown in Fig. 5. The 1H NMRpectra revealed peaks for protons of aromatic ring (bisphenol-Aoiety) around 7.12–6.62 ppm, which was shifted to the down-

eld because aromatic ring is attached to electron donating oxygentom. A proton of geminal dimethyl group was found around.23 ppm. The formation of ether linkages ( CH2 group attachedo electron donating oxygen) through the reaction of AIJFA with

isphenol-A were confirmed by the appearance of peaks at down-eld i.e. 4.01–4.28 ppm. Peaks in the range of 0.90–0.81 ppm weressigned to terminal CH3 of long fatty chain. Downfield peakst 3.31–3.40 ppm were assigned to the CH2 attached to amide

nd Products 50 (2013) 550– 556 553

nitrogen as it is less electronegative, while peaks at 2.21–2.40 ppmwere assigned to CH2 linked to amide carbonyl. Peaks seen at2.01–2.15 ppm were of CH2 attached to olefinic double bondsand peak at 1.35 ppm was of internal CH2 of fatty amide chain.Methylene protons attached to the hydroxyl OH were seen at3.40–3.45 ppm. Proton of OH occurred at 5.91 ppm. Characteristicpeak of olefinic unsaturation occurred at 5.11 ppm. From 1H NMRdata we confirmed the structure of PEthA as proposed in the Fig. 5.

4.5. TEM images of nano TiO2

The particle size of the TiO2 nano particles was found to be inthe range of 100–150 nm, as confirmed by transmission electronmicroscopy and it is shown in Fig. 6.

4.6. SEM images of nano TiO2

The morphology of nano and silane modified nano TiO2 wereinvestigated by FE-SEM images. SEM image of unmodified TiO2 par-ticles showed aggregates and sharp edges (Fig. 7a), while silanemodified nano TiO2 (Fig. 7b) particles were spherical in shape andwithout sharp edges. The modification of TiO2 may have resultedinto the minimum agglomeration of nano particles. These modi-fied individual particles may have good tendency to disperse in anorganic media like PU coatings because of hydrophobic nature ofmodified nano TiO2 particles. SEM images of the modified nanoTiO2 showed upto 200 nm.

4.7. Coating properties

The polyetheramide based polyurethane coatings containingnano TiO2 were applied on the MS panels using the bar coater andthe evaluated coating properties are given in Table 2. Surface drytime of PU-0, PU-1 PU-2, PU-3 and PU-4 coatings were found to be27, 21, 20, 19 and 20 min respectively. This indicated that increasein the % of TiO2 decreased the curing time of coatings upto 3% nanoTiO2. Scratch hardness and cross cut adhesion of coatings wereincreased in PU-0, PU-1 and PU-2 while it decreased in the caseof PU-3 and PU-4. This may be due to poor dispersion of the nanoTiO2 at higher loadings. In the case of gloss, it was observed that asamount of modified nano TiO2 in PU coatings increased, gloss wasalso increased from 92 to 98. Impact resistance and pensile hard-ness of the coatings were found to increase upto 3% nano TiO2 andthen decreased. All PU samples passed the mandrell flexibility testand no kind of failure was observed.

It was found that the prepared PU samples displayed good resis-tance to acids, alkalis and solvent. Chemical resistance test showedno significant changes in the appearance of coatings, after exposingthem to acids, alkalis and solvent. In acid specimens, slight loss ingloss was found after drying the panels. In general we can say the PUprepared from neem oil polyetheramide showed good resistancetoward acids, alkalis and solvent.

4.8. Thermo gravimetric analysis (TGA)

Thermograms of the PU samples prepared from PEthA and effectof percent of nano TiO2 on PU are given in Fig. 8. TGA curves ofall the coating samples showed three steps degradation. First stepdegradation was started in the range of 220–247 ◦C and degradationresulted into 07–14% weight losses for all PEthA based PU coatingswhich was attributed to the decomposition of urethane moieties.Second step degradation started in between 313 and 316 ◦C tem-

perature and degradation resulted in 28–35% weight losses. Thissecond stage degradation may be due to the decomposition of partscontributed by polyol (soft segment). Last or third step degradationtook place in the range of 433–451 ◦C and resulted in 52–75% weight

554 A. Chaudhari et al. / Industrial Crops and Products 50 (2013) 550– 556

Table 1Characteristic properties of neem oil, AIJFA and PEthA.

Properties Specific gravity Refractive index Sap value Acid value OH value Iodine value

Neem oil 0.920 1.503 186 1.3 000 64.55AIJFA 0.927 1.542 – 00 205 59.82PEthA 0.929 1.495 – 00 190 54.46

Fig. 5. 1H NMR spectra of PEthA of neem oil.

Fig. 6. TEM images of nano TiO2 particles.

Table 2PU coatings properties.

Sample/properties Dry to touch (min) Scratch hardness (kg) Cross cut adhesion (%) Gloss 60◦ Impact resistance (lb in.) Pencil hardness

PU-0 27 1.5 96 92 58.18 2HPU-1 21 1.6 97 93 61.81 2HPU-2 20 1.8 98 95 65.45 3HPU-3 19 1.7 97 96 67.27 4HPU-4 20 1.7 96 98 63.63 3H

A. Chaudhari et al. / Industrial Crops and Products 50 (2013) 550– 556 555

Fig. 7. SEM images of unmodifie

100 20 0 30 0 40 0 50 0 60 00

20

40

60

80

100

% w

t los

s

Temp (OC)

PU0

PU1

PU2

PU3

PU4

lhPic

mstitPt

5

sinppcup

A

Ct

of modified cottonseed oil based polyesteramide for coating applications. Prog.Org. Coat. 76, 1144–1150.

Fig. 8. TGA curve of PEthA based polyurethanes.

osses. Third step degradation may be a result of decomposition ofydrocarbon chains. Highest thermal stability was observed for theU-2 sample at the second and last step, while least thermal stabil-ty was observed to the pristine PU-0 amongst all PEthA based PUoatings.

All modified nano TiO2 loaded PU coatings showed better ther-al stability than the pristine PU-0 sample. In the series thermal

tability increased in the trend PU-0, PU-1, PU-3, PU-4 and PU-2. Ini-ially thermal stability of the PU coatings increased with increasen amount of nano filler from 0 to 1 weight percent loading andhen it increased for 3 and 4 weight percents. From the TGA ofU coatings, we can conclude that the PU-2 sample had superiorhermal stability compared to all other samples.

. Conclusions

Neem oil based polyetheramide for PU coatings were prepareduccessfully. The neem oil fatty amide based polyetheramide andts intermediate were characterized by the proper techniques. Theano TiO2 were synthesized and modified by using the silane cou-ling agent. The presence of nano TiO2 significantly increased gloss,encil hardness, chemical resistance and thermal stability of theoatings. The neem oil based resins have good potential to besed as eco-friendly resins in surface coatings or can substitute toetroleum based binders.

cknowledgement

The authors would like to acknowledge to University Grantsommission (UGC), Govt. of India, New Delhi for financial supporto the present work.

d and modified nano TiO2.

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