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,
Nilofar babnejad, 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
the synthesis of waterborne polyurethane nanoparticles from Poly(1,4-butylene adipate) (PBA) and dihy-
Keywords:
droxy acid. Particle size and morphology of nanoparticles were investigated by Dynamic Light Scattering
Sunflower oil
(DLS) and Scanning Electron Microscopy (SEM), respectively and confirmed the narrow distribution with
Waterborne polyurethane
Nanoparticles
small particle diameters of nanoparticles (50–100 nm). The stable dispersion of nanoparticles applied
Coating for the preparation of films and subsequent characterizations of their thermal and mechanical proper-
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 of organic volatile solvents released into the atmosphere; there-

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

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

issues [15–20]. Vegetable oils are an excellent raw material for hydrogen peroxide: formic acid were used). The reaction was con-
preparation of a range of polymers because they are inexpensive, tinued for 5 h at 50 ◦ C. Subsequently, the mixture was cooled down
readily available, and renewable resources [21–23]. These bene- to room temperature and washed with distilled water to eliminated
ficial biomaterials are triglycerides of saturated and unsaturated excess acid and dissolved in dichloromethane to simplify separa-
fatty acids [24]. In this study, we designed and synthesized a dihy- tion of organic phases. The organic layer was dried with manganese
droxy acid from vegetable oils that can be used as a chain extender sulfate and filtered. Finally, the clear viscous product was obtained
in the preparation of waterborne polyurethanes containing (PBA) after evaporation of dichloromethane using a rotary evaporator.
as polyol. PBA is a biodegradable aliphatic polyester with excellent
1
tensile property and is extensively used as a polyol in polyurethane HNMR(300 MHz, CDCl3 ) : ␦(ppm) = 5.32(m, 1H, OCOCH),
industry [25–28]. The PBA with high molecular weight is used 4-4.3(m, 4H, OCH2 -), 2.9-3.16(m, 2H, O-CH),
in polyurethane films and highly expanded foams, while the one
with relatively low molecular weight is a basic raw material in 2.3(t, 2H, CH2 -CO), 1–2(m, 5 h, CH2 , CH3 )
polyurethane hot melt adhesives [29]. Herein the sunflower oil
(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
without further purification. 2.5. Preparation of dihydroxy acid (DHA)

2.2. Synthesis of PBA Saponification of methoxylated sunflower oil was carried

out in sodium hydroxide solution. Briefly, 100 g MSFO, 50 g
The polyester polyols, PBA 1000, was prepared using adipic acid sodium hydroxide and 200 mL ethanol were added into 0.5 Liter
and 1,4-butanediol in the presence of Ti (i-Pr) 4 as a catalyst [30]. two-necked round bottom flask equipped with condenser and
A 1 l three-necked round bottom flask equipped with a mechanical refluxed for 5 h and the product was neutralized by the addi-
stirrer, thermometer, and Dean & Stark trap connected to a con- tion of hydrochloric acid. Then organic phase was extracted by
denser was charged with 204 g (2.27 mol) 1, 4-butanediol and 300 g dichloromethane and washed with saturated sodium chloride solu-
(2.06 mol) adipic acid (AA) and Ti(i-Pr)4 heated to 120 ◦ C, while vig- tion. After drying over manganese sulfate, DHA with yellowish color
orously stirring in order to achieve a clear liquid. Then, by collection was obtained via removal of organic solvent using rotary evapora-
of 20, 60 and 68 mL of water as a byproduct in the Dean & Stark trap tor.
at 190, 200 and 215 ◦ C after 0.5, 1 and 1.5 h, respectively, the PBA
1
synthesis was monitored. Finally, the acid value was determined HNMR(300 MHz, CDCl3 ) : ␦(ppm) = 3.5−4(m, 2H, O CH, 3H,
according standard titration and reached 3. After slowly reduction
of pressure to below 100 mm Hg and increase of temperature to O CH3 ), 2.3(t, 2H, CH2 CO), 1–2(m, 5 h, CH2 , CH3 )
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
resulting transparent liquid was cooled down to room temperature
and analyzed by 1 HNMR and the average molecular weight of 1000 2.6. Synthesis of waterborne polyurethane (WPU)
was obtained. 1 H NMR (300 MHz, CDCl3 ): ␦ (ppm) = 4.12 (s, 4H, (CO)
OCH2-integration 1), 3.6 (t, 4H, CH2 OH-integration 0.2), 2.53 (s, 4H, Waterborne polyurethanes were synthesized by acetone pro-
CH2 CO-integration 1.01), 1.67 (m, 8H, CH2 CH2 −integration 2.01). cess. The reaction for WPU-3 carried out in three-necked flask
equipped with a mechanical stirrer, nitrogen inlet, condenser, and
2.3. Epoxidation of sunflower oil (ESFO) thermometer.100 g of PBA (0.1 mol, Mn = 1000 g/mol), 62.7 g of IPDI
(0.3 mol), 75.5 g of DHA (0.2 mol) and one drop DBTDL as a catalyst
Epoxidized Sunflower oil (ESFO) have been prepared by the were heated at 80 ◦ C for 2 h. Then, 50 mL methyl ethyl ketone (MEK)
reaction of the carbon double bond (C C) of sunflower oil and a was added to reaction mixture for decrease of viscosity and elimi-
mixture of formic acid and hydrogen peroxide. Briefly, the sun- nation of gelation process and the reaction was continued for 2 h at
flower oil (100 g) and formic acid (52 mL) were added to reaction 80 ◦ C. Then, reaction system was cooled to room temperature, and
vessel that equipped with a mechanical stirrer and thermometer. solution neutralized by TEA (0.24 mol) for 0.5 h. Subsequently, dis-
The mixture was vigorously stirred for 10 min at 50 ◦ C. Then 115 mL tilled water was added slowly to reaction mixture and was stirred
hydrogen peroxide was added dropwise to reaction mixture for vigorously for 0.5 h. Finally, waterborne polyurethane dispersion
more than 1 h for epoxidation of sunflower oil. (Note: 1:2 molar was obtained by removal of MEK with rotary evaporator at 50 ◦ C
ratio of the hydrogen peroxide: SFO, and 1:1.1 molar ratio of the for 0.5 h. Other WPUs have been synthesized in same conditions
 H.K. Shendi et al. / Progress in Organic Coatings 105 (2017) 303–309 305

Scheme 1. Synthesis route of DHA from sunflower.

2.7. Characterization TLER under N2 atmosphere. The tensile strength and elongation at
break were determined using Universal Testing Machine (Santam
1 HNMR spectra were recorded on Bruker Avance operating at a − 20) with a crosshead speed of 10 mm/min for samples. Rectangle
frequency of 300 MHz using tetramethylsilane (TMS) as an inter- specimens of 5 cm × 1 cm (length × width) were used. An average
nal standard and CDCl3 as solvents. Infrared spectra from 400 value of at least five replicates of each material was taken.
to 4000 cm−1 were recorded on a Shimadzu 470 FT-IR instru-
ment, using potassium bromide pellets. Thermal analysis on the
3. Results and discussion
samples was determined with Diamond TGA/DTA (Perkin–Elmer
Pyris, America) from room temperature to 700 ◦ C at heating rate of
3.1. FT-IR analysis of SFO, ESFO, MSFO, DHA
20 ◦ C min −1 under air atmosphere. Dynamic Light Scattering (DLS)
was performed using a Nano-ZS ZEN3600 device using 633 nm
The synthesis of DHA was carried out using epoxidation of SFO
red laser (at 90◦ angle) from Malvern Instruments. SEM image of
followed through ring-opening of ESFO by methanol and saponifi-
nanoparticles were recorded using a Philips CM-30 with accel-
cation into fatty acid chains as indicated in Scheme 1. The successful
erating voltages of 150 and 250 kV instrument by drop casting
preparation of products were confirmed by FT-IR (Fig. 1). As shown
the sample on Formvar-coated copper grid. Differential scanning
in Fig. 1b, the new peak at 835 cm−1 belonged to C O bond in
calorimetry (DSC) experiments were performed using a DSC 1 MET-
epoxied group was raised and the peak at 3010 cm−1 related 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.

vinyl C H bond (Fig. 1a) was almost disappeared [31]. When ring
opening reaction was initiated by methanol, the epoxy groups in
ESFO decreased, while a new broad peak at 3392 cm−1 appeared
in MSFO (Fig. 1c) and confirmed that the epoxy rings in ESFO oil
were opened and hydroxyl groups formed. After the saponifica-
tion, carbonyl absorption peak at 1740 cm−1 in MSFO was shifted to
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 1
Fig. 3. H NMR spectra of SFO (a), ESFO (b), MSFO (c), DHA (d).
bands were appeared at 2900–2945 cm−1 and 2800–2830 cm−1 for
symmetric and asymmetric vibration of CH2 , respectively (Fig. 2).
3.3. DLS and SEM characterization

1 HNMR
The Synthesis route of waterborne polyurethane prepared from
3.2. analysis
PBA 1000 , DHA and IPDI are shown in Scheme 2. PBA based water-
1 HNMR spectra of SFO, ESFO, MSFO and DHA were shown in
borne PU was synthesized by neutralizing prepolymer with TEA
and dispersing it in distillated water. Seven type WPUs having
Fig. 3. The integration ratio of raised peaks around 4.1-4.3 ppm to
different mole ratio of chain extender and different type of diiso-
5.3 ppm was employed for double bond calculation. The results
cyante were prepared and listed in Table 1.The samples of WPU-1 to
indicated that the SFO used in this work has five carbon-carbon
WPU-5 showed good stability; however, the stability of the WPU-6
double bonds per triglyceride (Fig. 3a). The 1 HNMR of ESFO proved
and WPU-7 was poor due to their large particle size. Particle size
that the C C bonds (peaks between 5.3 and 5.6 ppm) in SFO dis-
appeared after epoxidation, and epoxy groups (peaks between 2.8
and 3.2 ppm in spectrum of ESFO) were formed (Fig. 3b). Due to the Table 1
ring opening reaction between ESFO and methanol, the number of The molar composition of WPUs nanoparticles.
epoxy groups decreased. The disappearance of epoxy groups (peaks Molar composition
between 2.8 and 3.2 ppm) and appearance of new peak at 3.4 ppm
Sample DHA Isocyante Isocyante (type)
in the 1 HNMR spectrum of MSFO (Fig. 3c) indicates that the epoxy
rings were opened by methanol. 1 HNMR of DHA is shown in Fig. 3d. WPU-1 1 2 IPDI
WPU-2 1.5 2.5 IPDI
Both signals CH2 -O (4.0–4.4 ppm) and CH-O (5.2 ppm) demon-
WPU-3 2 3 IPDI
strates that the backbone glyceride structure disappeared. These WPU-4 1 2 HDI
evidence confirm the cleavage of the MSFO structure into fatty acid WPU-5 1.5 2.5 HDI
chains, containing two hydroxyl groups during the saponification WPU-6 1 2 MDI
step. WPU-7 2 3 MDI
 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.

distribution is important parameter to evaluate WPU dispersions’ 125, 90 nm respectively and the size of other WPUs were listed in
stability. In general, the dispersions whose particle sizes are larger Table 2. The size distributions of WPUs were between 0.13–0.36.
than 1 ␮m are unstable due to inclination of the large particles to The WPUs made from IPDI are more hydrophobic in comparison to
precipitation. The particle size distribution of synthesized WPUs the ones made from HDI, because the large amount of DHA as an
and their average diameter measured using DLS. As shown in Fig. 4, internal emulsifier is consumed for the water dispersion. In addi-
the average particle sizes of WPU-1 and WPU-2 dispersions are tion, the mobility of the chains of ionic groups of DHA influence the
stability of dispersions that leads to smaller nanoparticles. The SEM
images of WPU-1and WPU-2 nanoparticles (Fig. 5) show spherical
structures with good agreement with DLS results.

3.4. Thermal and mechanical analysis

WPU films were obtained by casting the waterborne

polyurethane into a Teflon mold and allowing it to dry out at
ambient temperature. Thermal stability of WPU films were studied
using TGA (Fig. 6) and DTA (Fig. 7) and results were summarized in

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.

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-
Fig. 6. TGA thermograms of the WPUs. 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 3. The thermogram of WPUs showed three stages of thermal because the structure of PBA has not changed dramatically. In
decomposition in air atmosphere [32,33]. In the first stage, the addition, the DTA results confirm three degradation stages in TGA.

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

FTIR and 1 HNMR. It was obtained that DHA can be replaced with
DMPA and served as both chain extender and internal emulsifier
in the preparation of WPU dispersions. The WPUs had particle size
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.
Fig. 8. DSC thermograms (10 ◦ C/min) of WPUs.
Acknowledgements

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.

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