Progress in Organic Coatings 105 (2017) 303–309

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Synthesis and characterization of a novel internal emulsifier derived

from sunflower oil for the preparation of waterborne polyurethane
and their application in coatings
Hasan Kashef Shendi, Ismail Omrani, Abbas Ahmadi, Abdolreza Farhadian,
Niloofar Babanejad, Mohammad Reza Nabid ∗
Department of polymer and material chemistry, faculty of chemistry and petroleum science, Shahid Beheshti University, G.C, 1983963411, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: A renewable, green and scalable dihydroxy acid was synthesized from sunflower oil and applied as a chain
Received 12 August 2016 extender in the preparation of waterborne polyurethanes. In order to prepare dihydroxy acid, epoxidized
Received in revised form 25 October 2016 sunflower oil was ring-opened with methanol followed by saponification. Chemical structure of dihy-
Accepted 26 November 2016
droxy acid verified by FT-IR and 1 H NMR spectroscopies. Acetone process was used as a main method for
Available online 7 February 2017
the synthesis of waterborne polyurethane nanoparticles from Poly(1,4-butylene adipate) (PBA) and dihy-
droxy acid. Particle size and morphology of nanoparticles were investigated by Dynamic Light Scattering
Keywords:
(DLS) and Scanning Electron Microscopy (SEM), respectively and confirmed the narrow distribution with
Sunflower oil
Waterborne polyurethane
small particle diameters of nanoparticles (50–100 nm). The stable dispersion of nanoparticles applied
Nanoparticles for the preparation of films and subsequent characterizations of their thermal and mechanical proper-
Coating ties. The obtained results corroborated that these kinds of novel waterborne polyurethane nanoparticles
would be extensively efficient and applicable in coatings.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction metals, caulking materials, adhesives for alternative substrates,

emulsion polymerization media for different monomers, associate
Nowadays polyurethanes (PUs) are one of the prominent poly- thickeners, pigment pastes, paint additives and textile dyes should
mers due to their versatility and unique characteristics and produce environmentally friendly products. Considering this issue,
attracted attention of scientists all over the world. PUs are synthe- synthesis of waterborne PUs containing carboxylic acid, sulfonic
sized via polyaddition reaction between isocyanates and polyols acid, and tertiary amine groups in the presence of environmen-
and as they are an essential part of modern life and their dif- tally friendly solvent, water, are extremely preeminent in many
ferent applications in plastics, construction industry, automotive, industries [5–8] that results in decreasing air pollution, improving
medicinal science, synthetic leather, furniture, coatings, etc. [1–3]. the aspects of occupational health and lower energy consump-
Synthesis of PUs from bio-based materials is of highly impor- tion. Additionally, in the procedure of synthesis of waterborne PUs
tance. Solventborn PUs that are widely used in many industrial the viscosity is controllable and adjusted [9–13]. The anionic col-
fields including coationg, ink, and adhesive, typically are formu- loidal PUs are synthesized from various polyols, diisocyanates and
lated as a 25% solution. One of the huge defects of these systems a dihydroxy acid as a chain extender, which contains an anionic
is the toxic solvents such as dimethylfromamide (DMF), toluene, group. Among the well-known dihydroxy acids, dimethylolpropi-
methyl ethyl ketone (MEK) that are used in the process of their onic acid (DMPA) is the one that is used in most reports and leads
preparation and the deleterious effects of these solvents, because to stabilization of polyurethane colloids in the water phase [14];
they are volatile and enter the atmosphere as soon as possible nonetheless, DMPA is synthesized from formaldehyde through the
[4]. In The United States and European countries, stricter legis- complex pathway and is considered an expensive material in the
lation has been imposed to eliminate or decrease the amounts industry. Recently, scientists are interested in synthesis of bio-
of organic volatile solvents released into the atmosphere; there- based PUs from the vegetable oils, for they eliminate any concern
fore, paint and coating industries for various fibers, primers for regarding extensive petroleum resources causing environmental
issues [15–20]. Vegetable oils are an excellent raw material for
preparation of a range of polymers because they are inexpensive,
∗ Corresponding author. readily available, and renewable resources [21–23]. These bene-
E-mail address: m-nabid@sbu.ac.ir (M.R. Nabid). ficial biomaterials are triglycerides of saturated and unsaturated

http://dx.doi.org/10.1016/j.porgcoat.2016.11.033
0300-9440/© 2016 Elsevier B.V. All rights reserved.
304 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309

fatty acids [24]. In this study, we designed and synthesized a dihy- excess acid and dissolved in dichloromethane to simplify separa-
droxy acid from vegetable oils that can be used as a chain extender tion of organic phases. The organic layer was dried with manganese
in the preparation of waterborne polyurethanes containing (PBA) sulfate and filtered. Finally, the clear viscous product was obtained
as polyol. PBA is a biodegradable aliphatic polyester with excellent after evaporation of dichloromethane using a rotary evaporator.
tensile property and is extensively used as a polyol in polyurethane
1
industry [25–28]. The PBA with high molecular weight is used HNMR(300 MHz, CDCl3 ) : ␦(ppm) = 5.32(m, 1H, OCOCH),
in polyurethane films and highly expanded foams, while the one 4-4.3(m, 4H, OCH2 -), 2.9-3.16(m, 2H, O-CH),
with relatively low molecular weight is a basic raw material in
polyurethane hot melt adhesives [29]. Herein the sunflower oil 2.3(t, 2H, CH2 -CO), 1–2(m, 5 h, CH2 , CH3 )
(SFO) was epoxidized to prepare diol using methanolysis process
and the saponification of diol led to dihydroxy acid. The obtained
dihydroxy acid was used as an internal emulsifier in the synthesis
2.4. Methoxylated sunflower oil (MSFO)
of waterborne polyurethane.
The methoxylated sunflower oil was obtained by the ring open-
2. Experimental ing of epoxide ring with methanol. ESFO (50 g) with p-toluene
sulfonic acid as a catalyst were mixed with methanol and refluxed
2.1. Materials under vigorously stirring at 70 ◦ C for 12 h. The same method used
in the separation of ESFO, was used in the purification of MSFO as
Sunflower oil (SFO) was purchased from local supermarket a product.
and used without purification, hydrogen peroxide 35%(H2 O2 ), 1
formic acid, p-toluene sulfonic acid, methanol, anhydrous HNMR(300 MHz, CDCl3 ) : ␦(ppm) = 5.32(m, 1H, OCOCH),
manganese sulfate (MnSO4 ), isophorone diisocyanate (IPDI), 4-4.3(m, 4H, OCH2 -), 3.5–4(m, 2H, O-CH, 3H, O-CH3 ),
4,4 -diphenylmethane diisocyanate (MDI), hexamethylene diiso-
cyanate (HDI), 1, 4-diazobicyclo[2.2.2] octance (DABCO), dibutyltin 2.3(t, 2H, CH2 -CO), 1–2(m, 5 h, CH2 , CH3 )
dilaurate (DBTL), methyl ethyl ketone (MEK), triethylamine (TEA),
adipic acid, Titanium isopropoxide (Ti (i-Pr)4 ) and 1, 4-butanediol
(BDO) were purchased from Merck Co. All materials were used
2.5. Preparation of dihydroxy acid (DHA)
without further purification.
Saponification of methoxylated sunflower oil was carried
2.2. Synthesis of PBA out in sodium hydroxide solution. Briefly, 100 g MSFO, 50 g
sodium hydroxide and 200 mL ethanol were added into 0.5 Liter
The polyester polyols, PBA 1000, was prepared using adipic acid two-necked round bottom flask equipped with condenser and
and 1,4-butanediol in the presence of Ti (i-Pr) 4 as a catalyst [30]. refluxed for 5 h and the product was neutralized by the addi-
A 1 l three-necked round bottom flask equipped with a mechanical tion of hydrochloric acid. Then organic phase was extracted by
stirrer, thermometer, and Dean & Stark trap connected to a con- dichloromethane and washed with saturated sodium chloride
denser was charged with 204 g (2.27 mol) 1, 4-butanediol and 300 g solution. After drying over manganese sulfate, DHA with yellowish
(2.06 mol) adipic acid (AA) and Ti(i-Pr)4 heated to 120 ◦ C, while vig- color was obtained via removal of organic solvent using rotary
orously stirring in order to achieve a clear liquid. Then, by collection evaporator.
of 20, 60 and 68 mL of water as a byproduct in the Dean & Stark trap 1
HNMR(300 MHz, CDCl3 ) : ␦(ppm) = 3.5−4(m, 2H, O CH, 3H,
at 190, 200 and 215 ◦ C after 0.5, 1 and 1.5 h, respectively, the PBA
synthesis was monitored. Finally, the acid value was determined O CH3 ), 2.3(t, 2H, CH2 CO), 1–2(m, 5 h, CH2 , CH3 )
according standard titration and reached 3. After slowly reduction
of pressure to below 100 mm Hg and increase of temperature to
220 ◦ C and 3 h reaction, 72 mL water was collected and acid value
reached to 0.5 by which reaction termination was determined. The 2.6. Synthesis of waterborne polyurethane (WPU)
resulting transparent liquid was cooled down to room temperature
Waterborne polyurethanes were synthesized by acetone pro-
and analyzed by 1 HNMR and the average molecular weight of 1000
cess. The reaction for WPU-3 carried out in three-necked flask
was obtained. 1 H NMR (300 MHz, CDCl3 ): ␦ (ppm) = 4.12 (s, 4H, (CO)
equipped with a mechanical stirrer, nitrogen inlet, condenser, and
OCH2-integration 1), 3.6 (t, 4H, CH2 OH-integration 0.2), 2.53 (s, 4H,
thermometer.100 g of PBA (0.1 mol, Mn = 1000 g/mol), 62.7 g of IPDI
CH2 CO-integration 1.01), 1.67 (m, 8H, CH2 CH2 −integration 2.01).
(0.3 mol), 75.5 g of DHA (0.2 mol) and one drop DBTDL as a catalyst
were heated at 80 ◦ C for 2 h. Then, 50 mL methyl ethyl ketone (MEK)
2.3. Epoxidation of sunflower oil (ESFO) was added to reaction mixture for decrease of viscosity and elimi-
nation of gelation process and the reaction was continued for 2 h at
Epoxidized Sunflower oil (ESFO) have been prepared by the 80 ◦ C. Then, reaction system was cooled to room temperature, and
reaction of the carbon double bond (C C) of sunflower oil and a solution neutralized by TEA (0.24 mol) for 0.5 h. Subsequently, dis-
mixture of formic acid and hydrogen peroxide. Briefly, the sun- tilled water was added slowly to reaction mixture and was stirred
flower oil (100 g) and formic acid (52 mL) were added to reaction vigorously for 0.5 h. Finally, waterborne polyurethane dispersion
vessel that equipped with a mechanical stirrer and thermometer. was obtained by removal of MEK with rotary evaporator at 50 ◦ C
The mixture was vigorously stirred for 10 min at 50 ◦ C. Then 115 mL for 0.5 h. Other WPUs have been synthesized in same conditions
hydrogen peroxide was added dropwise to reaction mixture for
more than 1 h for epoxidation of sunflower oil. (Note: 1:2 molar 2.7. Characterization
ratio of the hydrogen peroxide: SFO, and 1:1.1 molar ratio of the
hydrogen peroxide: formic acid were used). The reaction was con- 1 HNMR
spectra were recorded on Bruker Avance operating at a
tinued for 5 h at 50 ◦ C. Subsequently, the mixture was cooled down frequency of 300 MHz using tetramethylsilane (TMS) as an inter-
to room temperature and washed with distilled water to eliminated nal standard and CDCl3 as solvents. Infrared spectra from 400
 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309 305

Scheme 1. Synthesis route of DHA from sunflower.

to 4000 cm−1 were recorded on a Shimadzu 470 FT-IR instru- 3. Results and discussion
ment, using potassium bromide pellets. Thermal analysis on the
samples was determined with Diamond TGA/DTA (Perkin–Elmer 3.1. FT-IR analysis of SFO, ESFO, MSFO, DHA
Pyris, America) from room temperature to 700 ◦ C at heating rate of
20 ◦ C min −1 under air atmosphere. Dynamic Light Scattering (DLS) The synthesis of DHA was carried out using epoxidation of SFO
was performed using a Nano-ZS ZEN3600 device using 633 nm followed through ring-opening of ESFO by methanol and saponifi-
red laser (at 90◦ angle) from Malvern Instruments. SEM image of cation into fatty acid chains as indicated in Scheme 1. The successful
nanoparticles were recorded using a Philips CM-30 with accel- preparation of products were confirmed by FT-IR (Fig. 1). As shown
erating voltages of 150 and 250 kV instrument by drop casting in Fig. 1b, the new peak at 835 cm−1 belonged to C O bond in
the sample on Formvar-coated copper grid. Differential scanning epoxied group was raised and the peak at 3010 cm−1 related to
calorimetry (DSC) experiments were performed using a DSC 1 MET- vinyl C H bond (Fig. 1a) was almost disappeared [31]. When ring
TLER under N2 atmosphere. The tensile strength and elongation at opening reaction was initiated by methanol, the epoxy groups in
break were determined using Universal Testing Machine (Santam ESFO decreased, while a new broad peak at 3392 cm−1 appeared
− 20) with a crosshead speed of 10 mm/min for samples. Rectangle in MSFO (Fig. 1c) and confirmed that the epoxy rings in ESFO oil
specimens of 5 cm × 1 cm (length × width) were used. An average were opened and hydroxyl groups formed. After the saponifica-
value of at least five replicates of each material was taken. tion, carbonyl absorption peak at 1740 cm−1 in MSFO was shifted to

Fig. 1. FT-IR Analysis of SFO (a), ESFO (b), MSFO (c), DHA (d).
306 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309

Fig. 2. FT-IR spectra of WPUs.

1725 cm−1 in DHA and a broad peak at 2500–3500 cm−1 was raised
(Fig. 1d). The MSFO was liquid at room temperature, whereas DHA
was a waxy solid. The WPUs FT-IR spectra were shown in Fig. 1. The
band at 3200–3500 cm−1 delineated the overlapping of OH and NH
stretching vibrations in WPU. The absorption bands at 1735 cm−1
and 1535 cm−1 correspond to the C O, and C N stretching vibra-
tion, respectively, showing the formation of urethane groups. The
bands around 1735 cm−1 were highly sharp, mainly owning to the
presence of C O in the urethane and polyester segments. Two
bands were appeared at 2900–2945 cm−1 and 2800–2830 cm−1 for
symmetric and asymmetric vibration of CH2 , respectively (Fig. 2).

3.2. 1 HNMR analysis

1 HNMR spectra of SFO, ESFO, MSFO and DHA were shown in

Fig. 3. The integration ratio of raised peaks around 4.1-4.3 ppm to

5.3 ppm was employed for double bond calculation. The results
1
Fig. 3. H NMR spectra of SFO (a), ESFO (b), MSFO (c), DHA (d).
indicated that the SFO used in this work has five carbon-carbon
double bonds per triglyceride (Fig. 3a). The 1 HNMR of ESFO proved
that the C C bonds (peaks between 5.3 and 5.6 ppm) in SFO dis- and WPU-7 was poor due to their large particle size. Particle size
appeared after epoxidation, and epoxy groups (peaks between 2.8 distribution is important parameter to evaluate WPU dispersions’
and 3.2 ppm in spectrum of ESFO) were formed (Fig. 3b). Due to the stability. In general, the dispersions whose particle sizes are larger
ring opening reaction between ESFO and methanol, the number of than 1 ␮m are unstable due to inclination of the large particles to
epoxy groups decreased. The disappearance of epoxy groups (peaks precipitation. The particle size distribution of synthesized WPUs
between 2.8 and 3.2 ppm) and appearance of new peak at 3.4 ppm and their average diameter measured using DLS. As shown in Fig. 4,
in the 1 HNMR spectrum of MSFO (Fig. 3c) indicates that the epoxy the average particle sizes of WPU-1 and WPU-2 dispersions are
rings were opened by methanol. 1 HNMR of DHA is shown in Fig. 3d. 125, 90 nm respectively and the size of other WPUs were listed in
Both signals CH2 -O (4.0–4.4 ppm) and CH-O (5.2 ppm) demon- Table 2. The size distributions of WPUs were between 0.13–0.36.
strates that the backbone glyceride structure disappeared. These The WPUs made from IPDI are more hydrophobic in comparison to
evidence confirm the cleavage of the MSFO structure into fatty acid
chains, containing two hydroxyl groups during the saponification
step. Table 1
The molar composition of WPUs nanoparticles.

3.3. DLS and SEM characterization Molar composition

Sample DHA Isocyante Isocyante (type)

The Synthesis route of waterborne polyurethane prepared from
PBA 1000 , DHA and IPDI are shown in Scheme 2. PBA based water- WPU-1 1 2 IPDI
WPU-2 1.5 2.5 IPDI
borne PU was synthesized by neutralizing prepolymer with TEA WPU-3 2 3 IPDI
and dispersing it in distillated water. Seven type WPUs having WPU-4 1 2 HDI
different mole ratio of chain extender and different type of diiso- WPU-5 1.5 2.5 HDI
cyante were prepared and listed in Table 1.The samples of WPU-1 to WPU-6 1 2 MDI
WPU-7 2 3 MDI
WPU-5 showed good stability; however, the stability of the WPU-6
 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309 307

Scheme 2. The synthesis route of WPUs prepared from PBA 1000 , DHA and IPDI.

the ones made from HDI, because the large amount of DHA as an 3.4. Thermal and mechanical analysis
internal emulsifier is consumed for the water dispersion. In addi-
tion, the mobility of the chains of ionic groups of DHA influence the WPU films were obtained by casting the waterborne
stability of dispersions that leads to smaller nanoparticles. The SEM polyurethane into a Teflon mold and allowing it to dry out at
images of WPU-1and WPU-2 nanoparticles (Fig. 5) show spherical ambient temperature. Thermal stability of WPU films were studied
structures with good agreement with DLS results. using TGA (Fig. 6) and DTA (Fig. 7) and results were summarized in
Table 3. The thermogram of WPUs showed three stages of thermal
decomposition in air atmosphere [32,33]. In the first stage, the
degradation is attributed to urethane linkage decomposition,
which results in the formation of isocyanate, primary or secondary
amine and olefin, and carbon dioxide. The second stages corre-
sponds to decomposition of soft segment (chain scission of polyol)
and the third stage, above 450 ◦ C, was attributed to further oxida-
tion of the WPUs in air. The results show that the thermal stability
of WPU-2 film decreased due to increase of urethane linkage in its
structure. There was no obvious trend in the range of 340–500 ◦ C,

Table 2
Particle size, PDI and solid content of prepared WPUs.

Sample Diameter(nm) PDI Solid Content (%)

WPU-1 125 0.18 30

WPU-2 90 0.22 30
WPU-3 85 0.13 30
WPU-4 95 0.24 30
WPU-5 91 0.36 27
Fig. 4. DLS histogram of WPU-2(a) and WPU-1(b).
308 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309

Fig. 5. SEM images of WPU-1 and WPU-2.

Table 3
Termal properties of WPUs.

TGA in air (◦ C)
◦ ◦
Samples Tg ( C) Tm ( C) T10 T50

WPU-1 −28.7 48.2 307 386

WPU-2 −35.2 41.01 302 398
WPU-3 −38.4 52.9 291 391
WPU-4 −44.6 44.34 317 403
WPU-5 −46.05 29.4 319 400

T10 : 10% weight loss temperature, T50 : 50% weight loss temperature.

because the structure of PBA has not changed dramatically. In

addition, the DTA results confirm three degradation stages in TGA.
As it is shown in Fig. 7, the first, second and third decomposition
stages are 300–400 ◦ C, 400–500 ◦ C, and 500–600 ◦ C, respectively.
It is notable that DHA increase in the WPU structures has a
Fig. 6. TGA thermograms of the WPUs. negative effect on both degradation and stability of WPUs. The
glass transition temperature (Tg ) of WPUs were investigated by
DSC at the heating rate of 10 ◦ C/min in a nitrogen atmosphere for
the temperature range of −100 to +100 ◦ C and are shown in Fig. 8
and it reveals that the Tg of WPUs were close together and were

Fig. 7. DTA thermograms of WPUs.

Table 4
Mechanical properties of WPUs.

sample Tensile strength (MPa) Elongation at break (%) Young’s modulus (MPa) Toughness (MPa)

WPU-1 1.1 ± 0.03 547 ± 7 11.2 ± 0.4 5.5 ± 1

WPU-2 1.85 ± 0.04 324 ± 5 12 ± 0.5 3.25 ± 0.7
WPU-3 4.7 ± 0.06 391 ± 7 130 ± 0.4 16 ± 2
WPU-4 0.95 ± 0.02 29.2 ± 4 9.8 ± 0.3 1.5 ± 0.1
WPU-5 3.5 ± 0.05 355 ± 4 85 ± 0.6 10.2 ± 5
 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309 309

around 80–130 nm and spherical morphology. The film prepared

from WPU-2 showed excellent thermal and mechanical properties
in comparison to the film prepared from WPU-3 and had the high-
est hardness and tensile strength. In general, sunflower oil based
dihydroxy fatty acids were successfully incorporated into anionic
polyurethane systems as internal emulsifier. It should be concluded
that DHA can be produced industrially owing to the inexpensive
and facile methods used in their synthesis and they can be used in
the production of WPUs that are suitable to be coated on poly (vinyl
chloride) surfaces and synthetic leather.

Acknowledgements

Fig. 8. DSC thermograms (10 ◦ C/min) of WPUs. We are grateful to Shahid Beheshti University Research Council
for partial support of this study. The authors give special thanks to
Prof. Abloghasem Moghimi from The Sabzavar Chemical Co for her
valuable discussions and suggestions.

References

[1] Y.T. Kark, Y. Qian, C.I. Lindsay, C. Nijs, R.E. Camargo, A. Stein, C.W. Macosko,
ACS Appl. Mater. Interfaces 5 (2013) 3054–3062.
[2] H. Chung, N.R. Washburn, ACS Appl. Mater. Interfaces 4 (2012) 2840–2846.
[3] W. Xu, C. Ma, J. Ma, T. Gan, G. Zhang, ACS Appl. Mater. Interfaces 6 (2014)
4017–4024.
[4] S. Madbouly, Y. Xia, M.R. Kessler, Macromolecules 46 (2013) 4606–4616.
[5] C.W. Ou, C.H. Su, U.S. Jeng, S. Hsu, ACS Appl. Mater. Interfaces 6 (2014)
5685–5694.
[6] S. Gogoi, N. Karak, ACS Sustain. Chem. Eng. 2 (2014) 2730–2738.
[7] J. Li, W. Zheng, W. Zeng, D. Zhang, X. Peng, Appl. Surf. Sci. 307 (2014) 255–262.
[8] Y. Lu, R.C. Larock, Biomacromolecules 9 (2008) 3332–3340.
[9] M. Ding, J. Li, X. Fu, J. Zhou, H. Tan, Q. Gu, Q. Fu, Biomacromolecules 10 (2009)
2857–2865.
[10] E. Koh, N.-K. Kim, J. Shin, Y.-W. Kim, RSC Adv. 4 (2014) 16214–16223.
[11] C.V. Chang, K. Lu, Prog. Org. Coat. 75 (2012) 435–443.
Fig. 9. Stress–strain profiles of WPUs. [12] D. Pfister, Y. Xia, R.C. Larock, ChemSusChem 4 (2011) 703–717.
[13] X. Liu, K. Xu, H. Liu, H. Cai, J. Su, J. Fu, Y. Guo, M. Chen, Prog. Org. Coat. 72
(2011) 612–620.
around −47 to −28 ◦ C and the peak at about 40–50 ◦ C for WPUs [14] R. Chen, C. Zhang, M.R. Kessler, RSC Adv. 4 (2014) 35476–35483.
is related to melting point of soft segment of WPU (PBA). Tg for [15] H. Lijie, D. Yongtao, Z. Zhiliang, S. Zhongsheng, S. Zhihua, Colloids Surf. A:
WPUs decreased with increasing the DHA amount due to dangling Physicochem. Eng. Aspects 467 (2015) 46–56.
[16] D.V. Palaskar, A. Boyer, E. Cloutet, C. Alfos, H. Cramail, Biomacromolecules 11
chains of DHA that act as plasticizer. Moreover, many factors such (2010) 1202–1211.
as presence of hydrogen bonding, polar groups, and interactions [17] Y. Xia, R.C. Larock, Green Chem. 12 (2010) 1893–1909.
of the hard segments in the structure of WPUs along with the [18] C. Zhang, Y. Xia, R. Chen, S. Huh, P.A. Johnston, M.R. Kessler, Green Chem. 15
(2013) 1477–1484.
molecular weight of them control the mechanical properties of [19] K. Noble, Prog. Org. Coat. 32 (1997) 131–136.
WPUs [34]. The stress–strain profiles for WPUs were provided in [20] S. Rajput, D. Hundiwale, P. Mahulikar, V. Gite, Prog. Org. Coat. 77 (2014)
Fig. 9. Tensile strength at break, elongation at break, toughness 1360–1368.
[21] Y.T. Park, Y. Qian, C.I. Lindsay, C. Nijs, R.E. Camargo, A. Stein, C.W. Macosko,
and Young’s modulus were summarized in Table 4. The WPU-3 ACS Appl. Mater. Interfaces 5 (2013) 3054–3062.
prepared from IPDI has higher tensile strength (4.7 MPa), higher [22] H. Chung, N.R. Washburn, ACS Appl. Mater. Interfaces 4 (2012) 2840–2846.
Young’s modulus (130 MPa) and higher toughness than the WPU-5 [23] P. Sun, J. Wang, X. Yao, Y. Peng, X. Tu, P. Du, Z. Zheng, X. Wang, ACS Appl.
Mater. Interfaces 6 (2014) 12495–12504.
prepared from HDI. Furthermore, an excellent performance of [24] B. De, K. Gupta, M. Mandal, N. Karak, ACS Sustain. Chem. Eng. 2 (2014)
both WPUs in coating is owing to the presence of long alkyl chain 445–453.
of DHA, crystallinity and ester linkages of PBA along with polar [25] Y. Chen, T. Wu, Ind. Eng. Chem. Res. 53 (2014) 16689–16695.
[26] X. Zeng, B. Wu, L. Wu, J. Hu, Z. Bu, B. Li, Ind. Eng. Chem. Res. 53 (2014)
urethane linkages.
3550–3558.
[27] Y. Zhao, Z. Qiu, Cryst. Eng. Comm. 13 (2011) 7129–7134.
4. Conclusion [28] C. Liu, Z. Zhang, K. Liu, X. Ni, J. Li, Soft Matter 9 (2013) 787–794.
[29] Z. Zeng, L. Sun, W. Xue, N. Yin, W. Zhu, Polym. Test. 29 (2010) 66–71.
[30] A. Moghimi, I. Omrani, M.R. Nabid, M. Mahmodi, Eur. Polym. J. 49 (2013)
A green and renewable dihydroxy acid from sunflower oil was 228–234.
synthesized by epoxidiation, ring-opening and saponification reac- [31] C. Zhang, S. Madbouly, M.R. Kessler, ACS Appl. Mater. Interfaces 7 (2015)
tions. The chemical structures of DHA was successfully verified by 1226–1233.
[32] Z. Zhang, Y. Li, R. Chen, M.R. Kessler, ACS Sustain. Chem. Eng 2 (2014)
FTIR and 1 HNMR. It was obtained that DHA can be replaced with 2465–2476.
DMPA and served as both chain extender and internal emulsifier [33] B.-L. Xue, J.-L. Wen, R.-C. Sun, ACS Sustain. Chem. Eng. 2 (2014) 1474–1480.
in the preparation of WPU dispersions. The WPUs had particle size [34] B. Das, U. Konwar, M. Mandal, N. Karak, Ind. Crops Prod. 44 (2013) 396–404.