Research Article

Cite This: ACS Sustainable Chem. Eng. 2020, 8, 914−925 pubs.acs.org/journal/ascecg

Tailoring the Performance of Vegetable Oil-Based Waterborne

Polyurethanes through Incorporation of Rigid Cyclic Rings into Soft
Polymer Networks
Haiyan Liang,† Yanchun Li,† Siying Huang,† Kaixi Huang,† Xueyi Zeng,† Qianwen Dong,†
Chengguo Liu,‡ Pengju Feng,*,§ and Chaoqun Zhang*,†
†
College of Materials and Energy, South China Agricultural University, Guangzhou 510642, P. R. China
‡
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry (CAF), National Engineering Laboratory for
Biomass Chemical Utilization, Key Laboratory on Forest Chemical Engineering, National Forestry and Grassland Administration,
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Key Laboratory of Biomass Energy and Material, Jiangsu Province, 16 Suojin Wucun, Nanjing 210042, P. R. China
§
Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, Guangzhou 510632, P. R. China
Downloaded via UNIV OF SAO PAULO on December 16, 2023 at 11:58:40 (UTC).

ABSTRACT: Vegetable oil-based polymeric materials always

suffer from relatively poor performance, such as lower tensile
strength and glass transition temperatures, than petroleum-
based polymeric materials, which greatly limit their practical
applications. In this study, octahydro-2,5-pentalenediol
(OPD) was synthesized from naturally occurring citric acid
and used together with castor oil as the polyol blends for the
production of bio-based waterborne polyurethane (PU)
dispersions (PUDs). The effects of the OPD contents on
the particle size and ζ potential of the resulting polyurethane
dispersion, and the thermal stability, mechanical properties,
and hydrophilicity of the resulting polyurethane films were
systematically investigated. Taking advantage of the rigid
cyclic structures of the OPD and the flexible fatty acid chain of castor oil, waterborne polyurethane (WPU) films with tailorable
mechanical performance ranging from elastomeric polymers to rigid plastics were successfully prepared and characterized. The
tensile strength of the samples increases from 9.5 to 22.3 MPa with the ratio between OPD and castor oil increasing from 0:10
to 5:5, whereas their elongation at break decreases from 192 to 12%. A significant increase in the glass transition temperature,
transparency, and anticorrosive properties was observed for the resulting polyurethane films with increasing the OPD content.
However, the thermal stability of the PU films exhibited a slight decrease as the OPD content increased. Moreover, the water
contact angle exhibited a slight increase for the polyurethane films prepared from polyol blends compared to the WPU film
prepared from pure castor oil. This work provides a novel route to tailor the performance of vegetable oil-based waterborne
polyurethanes through the incorporation of rigid cyclic rings into soft polymer networks.
KEYWORDS: polyols, waterborne polyurethane, octahydro-2,5-pentalenediol, castor oil

■ INTRODUCTION
For decades, polyurethanes (PUs) have been considered to be
one of the most versatile polymers and applied in various
industrial fields, such as ink, adhesives, foams, sealants, and so
on.1,2 However, during the production and application,
conventional solvent-borne PUs always used plenty of volatile
organic compounds (VOCs) and hazardous air pollutants
(HAPs), which are serious environmental and health hazards.3
Therefore, waterborne polyurethanes (WPU) have been
considered as the replacement for traditional solvent-borne
PUs due to the intensive attention toward safety and
environmental issues on a global scale. WPUs exhibit many
outstanding performances, including good applicability,
excellent abrasion resistance, low viscosity at high temper-
atures, etc., which undoubtedly expanded their applications in
medical dressing, drug loading, and other biomedical fields.4
Recently, the raw materials for the preparation of WPU,
including polyols, isocyanates, catalysts, additives, and so on,
are still mainly derived from petroleum resources.5 With the
increasing concern on limited crude oil reserves, research
studies on utilizing bio-based feedstock, including cellulose,
lignin, and vegetable oils as substitutes for petroleum-based
counterparts, are new promising domains.6 Among them,
vegetable oils are one of the most promising options due to
their low cost, renewability, and ready availability.7 There are
three esters and 0−7 carbon−carbon double bonds in the
molecular of vegetable oils, which provides the reactive sites
for chemical modification.8 Castor oil is the only natural
Received: September 15, 2019
Revised: December 5, 2019
Published: December 11, 2019

© 2019 American Chemical Society 914 DOI: 10.1021/acssuschemeng.9b05477

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ACS Sustainable Chemistry & Engineering
vegetable oil that contains hydroxyl groups that can be directly
employed as the polyol in the preparation of WPU without
further modification, whereas other vegetable oils have to be
modified to introduce hydroxyl groups. However, the flexible
long chain of fatty acids and the relatively low OH number
(mostly 70−300 mg KOH/g)9 of vegetable oil-based polyols
led to their resulting WPU films suffering from certain limits of
mechanical and thermal properties, such as relatively low
tensile strength and glass transition temperatures (Tg).10
Much effort has been dedicated to improve the tensile
strength and Tg of the vegetable oil-based WPU films, such as
nanoenhancement, fiber reinforcement, increasing cross-link-
ing density, and so on. Among them, incorporating rigid cyclic
structures in the backbone of polymer chains stands out at the
privileged position for excellent mechanical strength and high
Tg.5 For example, Wang et al. reported that employing
isophorone diamine, containing cyclic structures, as the chain
extender can significantly increase the water resistance and
tensile strength of the resulting WPU films, compared with the
films whose chain extended by diethylene triamine and
ethylenediamine.11 Delpierre et al. have successfully tuned
the tensile strength of the PU films from 0.3 to 11 MPa via
varying the boroxine ring content from 25 to 75% molar, and
the Tg of the films was improved from −11 to 41 °C.12 Xia et
al. incorporated isosorbide into the WPU chains ranging from
0 to 20% of the total diols, and thus obtained significant
improvement in mechanical properties (from 0.69 to 8.15
MPa) and Tg.
In this work, octahydro-2,5-pentalenediol (OPD) was
synthesized from dimethyl-1,3-acetonedicarboxylate (derived
from naturally occurring citric acid) and glyoxal through
Weiss−Cook condensation, decarboxylation under acidic
conditions and reduction with NaBH4. OPD, with two fused
cyclopentane rings, exhibits excellent rigidity and thermal
stability, which envisioned to greatly restrict the motion of the
polymer chain if incorporated in the macromolecular
structures, leading to the high performance of polymers
(high Tg and tensile strength).13−15
Therefore, OPD was used as a partial replacement of castor
oil as the polyol for the preparation of vegetable oil-based
WPUs. The OH group from OPD, castor oil, and emulsifier
[dimethylolbutanoic acid (DMBA)] competitively reacts with
the NCO of isophorone diisocyanate (IPDI) to form the
polymer. To investigate the influence of the OPD content on
the resulting WPU, a series of polyurethane dispersions
(PUDs) are synthesized with different proportions between
OPD and castor oil. The structures of the intermediate
[tetrahydropentalene-2,5(1H,3H)-dione] and OPD were con-
firmed by 1H NMR, 13C NMR, and Fourier transform infrared
(FTIR) spectroscopy. The particle size and ζ potential of the
PUDs were characterized by a zetasizer. Dynamic mechanical
analysis (DMA), thermogravimetric analysis (TGA), and
differential scanning calorimetry (DSC) were performed to
investigate the thermal properties of the resulting PU films, and
the mechanical properties were characterized by tensile testing.
Moreover, the effect of the OPD amount on the pencil
hardness, crosshatch adhesion, and water contact angle of the
PU films are also explored. Taking advantage of the rigid cyclic
structures of the OPD and the flexible fatty acid chain of castor
oil, it was anticipated to obtain WPU films with tailorable
mechanical performance ranging from elastomeric polymers to
rigid plastics.
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■ EXPERIMENTAL SECTION
Materials. Glyoxal (40% aqueous solution) and dimethyl-1,3-
acetonedicarboxylate were purchased from Sigma-Aldrich. Sodium
hydroxide, sodium bicarbonate, and anhydrous MgSO4 were
purchased from Tianjin Damao Chemical Reagent Factory. NaBH4
was provided by Energy Chemical Co. Ltd. Anhydrous methanol and
aqueous hydrochloric acid were purchased from Tianjin Chemical
Reagent Co. Ltd. Dichloromethane (DCM) was purchased from
Guangzhou Chemical Reagents Factory. Castor oil (OH number: 164
mg KOH/g) was supplied by Fuyu Chemical Co. Ltd. Isophorone
diisocyanate was provided by Wengjiang Chemical Reagent Co. Ltd.
Dimethylolbutanoic acid was purchased from Adamas Reagent Co.,
Ltd. Methyl ethyl ketone (MEK), glacial acetic acid, and triethylamine
(TEA) were purchased from Aladdin reagent. Dibutyltin dilaurate
(DBTDL) was purchased from the Fuchen Chemical Reagent
Factory. All materials were used as received without further
purification.
Synthesis of OPD. Under a N2 atmosphere, sodium hydroxide
(1.40 g, 35.0 mmol) was dissolved in anhydrous methanol (25 mL,
1.46 M) at 0 °C to form a milky-white solution. Dimethyl-1,3-
acetonedicarboxylate (6.0 g, 34.4 mmol) was added dropwise over a
period 15 min. A yellow precipitate was formed, and the resulting
mixture was heated to reflux for 3 h at 65 °C under vigorous stirring.
An aqueous solution of 40% glyoxal (1.14 g, 19.7 mmol) was added
dropwise to the stirred hot solution. After addition, the reaction was
moved to room temperature and stirred overnight. The reaction
mixture was filtered and washed with methanol (5.0 mL) to obtain a
light yellow disodium salt that was directly dissolved in a mixture of
aqueous hydrochloric acid (1.0 M, 5.0 mL) and glacial acetic acid
(10.0 mL). After refluxing for 5 h, the reaction mixture was cooled
down to room temperature and extracted with DCM (3 × 15 mL).
The combined organic phase was washed with aqueous sodium
bicarbonate (3 × 20 mL), dried over anhydrous MgSO4, filtered, and
concentrated under vacuum to give tetrahydropentalene-2,5(1H,3H)-
dione as a brown solid (3.95 g, 28.6 mmol, 83%). 1H NMR (300
MHz, CDCl3) δ 2.93−2.90 (m, 2H), 2.46−2.37 (m, 4H), 2.21−1.95
(m, 4H); 13C NMR (75 MHz, CDCl3) 218.0 (CO), 43.4 (CH2),
36.2 (CH).
A solution of tetrahydropentalene-2,5(1H,3H)-dione (4.26 g, 30.0
mmol) in methanol (60.0 mL) was stirred under N2 at 0 °C. NaBH4
(2.27 g, 60.0 mmol) was added portion-wise to the above solution,
along with the generation of lots of bubbles. After stirring at room
temperature overnight, the reaction mixture was poured into ice and
diluted with hydrochloric acid (80 mL, 2.0 mol/L), and extracted
with DCM (3 × 150 mL). The combined organic phase was washed
with aqueous sodium bicarbonate (3 × 20 mL), dried over anhydrous
MgSO4, filtered, and concentrated under vacuum to give diaster-
eoisomers of ocatahydro-2,5-pentalenediol (syn/anti = 1/3) as a
white solid (3.80 g, 26.7 mmol, 89%). 1H NMR (300 MHz,
(CD3)2SO) δ (major isomer) 4.58 (d, J = 4.3 Hz, 2H), 4.01−3.92 (m,
2H), 2.27−2.15 (m, 2H), 1.98−1.85 (m, 4H), 1.44−1.33 (m, 4H); δ
(minor isomer) 4.50 (d, J = 4.3 Hz, 1H), 4.33 (d, J = 4.3 Hz, 1H),
4.24−4.10 (m, 1H), 4.01−3.92 (m, 1H), 2.45−2.30 (m, 2H), 1.98−
1.85 (m, 2H), 1.66−1.46 (m, 4H), 1.14−1.08 (m, 2H); 13C NMR (75
MHz, CDCl3), 13C NMR (75 MHz, (CD3)2SO): δ (major isomer)
74.0 (CH), 42.4 (CH2), 38.3 (CH); δ (minor isomer) 73.4 (CH),
72.5 (CH), 42.31 (CH2), 42.26 (CH2), 38.2 (CH).
Preparation of WPUs from OPD and Castor Oil-Based
Polyols. First, IPDI (3.89 g) and DBTDL (5 μL) were added into an
oven-dried double-necked flask and stirred (240−260 rpm) at 78 °C
for 2 h. Then, the OPD/castor oil/DMBA mixture was added
dropwise to the flask for 30 min, while MEK was added to reduce the
viscosity. The mole ratio among the NCO groups of the IPDI, the
OH groups of the OPD and castor oil, the OH groups of the DMBA
was 1.7:1.0:0.69. The mole ratio between OPD and castor oil in the
OPD/castor oil mixture was varied from 0:10 to 1:9, 2:8, 3:7, 4:6, 5:5,
and 6:4, which were coded as PU-OPD0, PU-OPD10, PU-OPD20,
PU-OPD30, PU-OPD40, PU-OPD50, and PU-OPD60, respectively.
After another 1 h at 78 °C, the reactants were cooled down to room
DOI: 10.1021/acssuschemeng.9b05477
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ACS Sustainable Chemistry & Engineering
Scheme 1. Synthesis Routine of Octahydro-2,5-pentalenediol
Figure 1. (a) 1H NMR and (b) 13C NMR spectrum of tetrahydropentalene-2,5(1H,3H)-dione. (c) 1H NMR spectrum, (d) 13C NMR spectrum,
and (e) FTIR spectra of octahydro-2,5-pentalenediol.
temperature, and the mixture was neutralized with TEA at stirring for
30 min. Finally, deionized water (55−60 mL) was added for
emulsification, followed by vigorous stirring (350 rpm) for 2 h. After
the removal of MEK by rotary evaporator, the waterborne PUDs with
a solid content of 15 wt % were obtained. The corresponding PU
films were first obtained by casting 30 mL PUDs in a silicon mold (6
× 6 cm2), drying at room temperature, and then the films were dried
in a vacuum at 80 °C for 24 h to remove the residual water. The
representative synthesis routine of OPD/castor oil-based waterborne
polyurethane dispersions is shown in Scheme 2.
Characterization. A Bruker AVANCE III NMR spectrometer was
used to record the 1 H NMR and 13 C NMR spectra of
tetrahydropentalene-2,5(1H,3H)-dione and OPD separately operating
at 300 and 100.6 MHz, using dimethyl sulfoxide (DMSO)-d6 as the
solvent at room temperature.
An FTIR spectrum for OPD powder was recorded using a Thermo-
Nicolet Nexus 670 FTIR spectrometer over the wave numbers range
of 400−4000 cm−1 using a KBr pelleting technique. The infrared
spectra of the dried WPU films were recorded on a VERTEX 70
(Germany BRUKER) FTIR spectrometer ranging from 400 to 4000
cm−1.
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The particle size distribution and ζ potential of the PUDs were
determined by a Zetasizer Nano ZSE (Malvern Instruments). The
PUDs were diluted with distilled water to around 0.01 wt % before
conducting the tests.
The transparency of the films was evaluated using an ultraviolet−
visible spectrophotometer (Evolution201) in the range of 200−800
nm. The tensile testing was carried out on an electronic universal
testing machine (UTM-4202) with a crosshead speed of 100 mm/
min. Rectangle sample films with a length of 25 mm and a width of 10
mm were dried at 60 °C for 12 h before use. At least three replicates
of each resulting PU film were taken for the tests.
The pencil hardness and crosshatch adhesion of the sample were
measured according to ASTM D 3363 and ASTM D 3359 at room
temperature, respectively. The thickness of the coatings was measured
using a Yuwen Ec-770 coating thickness gauge at an average of above
five measurements. The coatings used in the tests were obtained by
casting 1 mL PUDs onto tinplate with a coated area of 5 × 10 cm2
and first drying at room temperature for 24 h, followed by drying in a
vacuum at 60 °C for 24 h.
Dynamic mechanical analysis (DMA) of the PU films was
performed on a Netzsch DMA 242C dynamic mechanical analyzer
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Scheme 2. Synthesis of OPD/Castor Oil-Based Waterborne Polyurethane Dispersions
in the tensile mode at 1 Hz, using rectangular specimens of 6 mm ×
25 mm (length × width). The specimens were heated from −60 to
120 °C at a rate of 5 °C min−1. The glass transition temperatures (Tg)
were determined by the peaks of the loss factor curves.
The thermogravimetric analysis of the PU samples was conducted
on a Netzsch-STA 449C thermal analyzer. All of the samples were
weighed between 8 and 14 mg and heated from 30 to 700 °C in a
nitrogen atmosphere with a heating rate of 10 °C/min.
Differential scanning calorimetry (DSC) was carried out on a
thermal analyzer (PE DSC8000). All of the samples were weighed
between 8 and 14 mg. They were first heated from 25 to 100 °C to
erase thermal history, then cooled to −70 °C at a rate of 10 °C/min,
and later heated to 150 °C at a rate of 5 °C/min. The midpoint
temperature in heat capacity change of the second DSC scan is
considered to be Tg.
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The water contact angle of the resulting PU films was measured on
a contact angle goniometer (Powereach JC2000C1) with the sessile-
drop method at room temperature. All of the samples were previously
dried at 60 °C for over 48 h. The scanning electron microscopy
(SEM) imaging of the PU films was performed on a JEOL JSM-
6380LA Quanta 200 microscope.
Tafel analysis of the samples was performed on an electrochemical
working station (Shanghai Chenhua CHI 600E, China) at room
temperature using 3.5 wt % NaCl aqueous solution as the electrolyte.
Potentiodynamic polarization curves were obtained using a three-
electrode system [saturated Ag/AgCl electrode served as the reference
electrode, platinum (Pt) electrode as the counter electrode, and
uncoated or coated tin as the working electrode, respectively] at a
scan rate of 10 mV/s. The samples used in the test possess a coated or
uncoated area of 1 × 1 cm2 with a coating thickness of 60 ± 5 μm.
DOI: 10.1021/acssuschemeng.9b05477
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ACS Sustainable Chemistry & Engineering Research Article

■ RESULTS AND DISCUSSION

Synthesis and Characterization of Octahydro-2,5-
from 2827 to 2986 cm−1 gradually decrease as the OPD ratio
increased, resulting from the decreasing content of castor oil.
Furthermore, the small peak at 1741 cm−1 corresponding to
pentalenediol. As shown in Scheme 1, OPD was prepared
free urethane gradually decreases with the increase of the OPD
from the commercially available dimethyl-1,3-acetonedicarbox-
ratio, indicating the increasing hydrogen bond strength of the
ylate and glyoxal via Weiss−Cook condensation, decarbox-
films.18,19
ylation, and reduction reactions. The molecular structure of the
The PUDs prepared with different OPD contents and their
intermediates [tetrahydropentalene-2,5(1H,3H)-dione] and
particle size distribution are presented in Figure 2. With the
the desired product (OPD) were confirmed by 1H NMR,
13
C NMR, and FTIR, and the results are shown in Figure 1. As
seen in Figure 1a, only three signals were observed in the 1H
NMR spectrum of tetrahydropentalene-2,5(1H,3H)-dione, and
the peaks at δ 2.9, δ 2.4, and δ 2.0 ppm can be attributed to the
protons 1, 2, and 2′, respectively, indicating that the
intermediates have been successfully isolated and purified.
Furthermore, all of the characteristic peaks in the 13C NMR
spectrum of intermediates (Figure 1b) can be correctly
assigned to the various carbon atoms present in the
tetrahydropentalene-2,5(1H,3H)-dione chains, further con-
firming the structure of the intermediates. As shown in Figure
1c,d, the resonances assigned to the tetrahydropentalene-
2,5(1H,3H)-dione cannot be found after reduction reactions,
demonstrating that no intermediates remained in the desired Figure 2. (a) Appearance of PUDs with different OPD ratios in the
product (OPD). Moreover, the desired product is a mixture of polyol blends: (1) 0%, (2) 10%, (3) 20%, (4) 30%, (5) 40%, (6) 50%,
two stereoisomers, endo/endo isomer (identified as A), and and (7) 60%. (b) Particle size distribution of PUDs with different
OPD contents.
endo/exo isomer (identified as A′). The signals at around δ
4.5, δ 4.33, and δ 3.96 ppm can be assigned to the protons,
increase of the OPD contents, the transparency of the resulting
numbered as 3, 7, and 10, on carbons that were linked to
PUDs gradually increases, from milky of PU-OPD0 to visible
hydroxyl groups in isomer A′ and A, respectively, while the
transparency with the yellow light of PU-OPD60, which is
protons (numbered as 1 and 5) on bridged carbons exhibited associated with their particle sizes. As shown in Figure 2 and
overlapped multiplets at around 2.39 and 2.21 ppm, Table 1, the average particle size of the samples gradually
respectively.13 The integral area ratio of proton peaks 3 to 7,
3 to 10, and 1 to 5 are 6.1:1, 5.6:1, and 3.2:1, respectively,
Table 1. Properties of the Resulting PUDs
implying that the molar ratio of A to A′ is around 3:1.14 In the
FTIR spectra of OPD, an identical strong absorption band at hydrophilic Z-
3295 cm−1 can be observed, corresponding to the typical −OH DMBA groups average ζ
contents contents size potential
stretching vibration on the bicycles. In addition, the bands at samples (wt %) (wt %) appearance (nm) (mV)
1109 and 2948 cm−1 were assigned to the stretching of −C−O PU- 8.2 2.5 milky white 615 −50.3
and −CH2, respectively, which further confirmed the structure OPD0
of OPD. PU- 8.6 2.6 milky white 342 −58.4
Preparation and Properties of the PUDs with Differ- OPD10
ent OPD/Castor Oil Ratios. OPD was used together with PU- 9.0 2.7 milky white 255 −60.5
OPD20
castor oil as the polyol blends for the production of bio-based PU- 9.5 2.9 milky white 220 −60.8
waterborne polyurethane dispersions (PUDs). Taking advant- OPD30
age of the rigid cyclic structures of the OPD and the flexible PU- 10.0 3.0 translucent 43.8 −59.8
fatty acid chain of castor oil, WPU with tailorable performance OPD40
should be prepared. The effect of the OPD contents on the PU- 10.6 3.2 transparent 24.4 −45.2
OPD50 with yellow
particle size and ζ potential of the resulting polyurethane light
dispersion, and the thermal stability, mechanical properties, PU- 11.2 3.4 transparent 22.8 −34.8
and hydrophilicity of the resulting polyurethane films were OPD60 with yellow
systematically investigated. light
As shown in Scheme 2, the OH group from OPD, castor oil,
and emulsifier (dimethylolbutanoic acid) competitively reacts decreases as the OPD content increases. The average particle
with the NCO of isophorone diisocyanate (IPDI) to form sizes of PU-OPD0 (OPD ratio of the total diol is 0%) and PU-
carbamate groups. The molecular structures of the WPU films OPD60 (OPD ratio of the total diol is 60%) dispersions are
are confirmed by FTIR spectral analysis, and the FTIR spectra around 615 and 23 nm, respectively. Generally, two factors
are normalized with respect to the CO peak (1700 cm−1). mainly dominate the particle size and its distribution of the
As shown in Figure 3c, the characteristic peaks assigned to the resulting PUDs: hydroxyl numbers of the polyols and the
N−H (3322 cm−1), CH2 (2942 and 2856 cm−1), and CO hydrophilic contents (carboxylate ions).20,21
(1700 cm−1) stretching vibrations are both observed and the It is well known that a higher OH number of the polyol
peak assigned to the OH group (3295 cm−1) of OPD results in a higher cross-linking density of the resulting WPU,
disappeared for the PU films, which suggests the generation of leading to an increasing particle size of the resulting PUD.9,18
WPU.16,17 The peaks attributed to CH2 stretching vibrations Therefore, with the increase of the OPD content, the particle
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Figure 3. (a) Appearance, (b) UV spectrum, (c) FTIR spectra, and (d) stress−strain curves for the PU films.

Table 2. Mechanical Properties of the Resulting PU Films

samples hard segment Content (wt %) tensile strength (MPa) elongation at break (%) toughness (J/mm3) Young’s modulus (MPa)
PU-OPD0 44.4 9.5 ± 2.7 191.7 ± 37.6 15.8 ± 3.1 32.1 ± 6.8
PU-OPD10 47.7 12.7 ± 1.5 168.8 ± 23.1 16.7 ± 7.0 119.9 ± 27.8
PU-OPD20 51.2 16.3 ± 2.2 140.9 ± 92.5 31.3 ± 12.7 172.5 ± 76.6
PU-OPD30 55.2 18.8 ± 1.8 28.6 ± 6.3 41.9 ± 18.5 183.7 ± 12.1
PU-OPD40 59.5 19.6 ± 1.0 14.6 ± 3.0 3.5 ± 0.5 192.2 ± 70.4
PU-OPD50 64.4 22.3 ± 1.1 12.3 ± 1.2 7.8 ± 0.4 382.8 ± 57.7

size of the PUDs theoretically increases, as a result of the
partial replacement of castor oil with high OH number OPD.
However, the use of OPD also leads to an increase of the
DMBA content in the backbone of polymer chains when the
hydroxyl molar ratios between the OPD/castor oil and DMBA
remained constant (see Table 1). The carboxylate ions
provided by DMBA could keep the PUDs electrostatically
stabilized via developing a stable electrical double layer around
the PUD particles. 22 The increasing DMBA content
contributes to the increase in the electric charges, which lead
to the enhancement of the thickness of the electrical double
layer and the electrostatic repulsive forces among the PUD
particles. The aggregation of PUD particles is therefore
hindered, which results in the decreasing particle size and
increasing transparency of the PUDs. With the smallest particle
size and the most transparent appearance among the samples,
PU-OPD60 possesses the highest DMBA content of 11.2 wt %
and the highest hydrophilic group content of 3.4 wt %.
However, the particle size of the PUDs is also influenced by
other factors such as the ionic group position, the viscosity of
the PUDs, process variables, etc.22,23
The absolute value of ζ potential of the PUDs shows a
similar trend with the particle size of the PUDs, and all of the
samples exhibit the absolute value of ζ potential above 35 mV,
indicating the excellent stability of the samples (see Table 1).
For example, the ζ potential of PU-OPD0 is −50.3 mV, while
that of PU-OPD50 is −45.2 mV. Moreover, all of the PUDs
were centrifuged at 3000 rpm for 30 min, and no obvious
919
precipitate or stratification were observed, further confirming
their excellent storage stability.24,25
Properties of the PU Films. As shown in Figure 3a,b, all
of the PU films with ∼0.8 mm thickness exhibited good
transparency. Notably, the incorporation of OPD increases the
transparency of the samples. In detail, with the OPD ratio
increasing from 0 to 50%, the light transmittance value of the
samples increases from 71 to 80%. This may mainly relate to
the light absorption of castor oil,26,27 the ratio of which
gradually decreases with the increase of the OPD ratio. As is
known to all, the transparency of films is also influenced by the
thickness, cross-linking density, film-forming conditions, etc.,
of the samples.28,29
Figure 3d illustrates the tensile stress−strain curves for all
PU films, and tensile strength, elongation at break, toughness,
and the Young’s modulus are summarized in Table 2. The hard
segment (HS) content is calculated based on the fraction of
the total mass of OPD, IPDI, DMBA, and TEA over the total
mass of castor oil, OPD, IPDI, DMBA, and TEA9
hard segment content
= mass(OPD + IPDI + DMBA + TEA)
/mass(castor oil + OPD + IPDI + DMBA + TEA)
× 100% (1)
The resulting PU film with 60% OPD content was found
broken and could not be tensile tested due to its brittle nature
when a high OPD content is incorporated into the backbone of
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Table 3. DMA Data of the Resulting PU Films

Tg obtained from Tg obtained from E′ at 25 °C ve pencil hardness crosshatch adhesion film thickness
samples DSC (°C) DMA (°C) (MPa) (mol/m3) (6B-HB-6H, 6H = best) (5B = best) (μm)
PU- −7.4 35.2 78.3 208.1 2H 2B 32 ± 7
OPD0
PU- 0.05 48.1 315.7 340.3 2H 3B 30 ± 11
OPD10
PU- 4.8 48.0 374.8 304.7 2H 3B 29 ± 3
OPD20
PU- 6.5 68.0 939.4 232.0 5H 4B 27 ± 9
OPD30
PU- 15.4 71.4 1137.8 122.7 6H 4B 30 ± 8
OPD40
PU- 48.8 75.00 1619.7 123.8 6H 4B 28 ± 4
OPD50
PU- 52.6
OPD60

Figure 4. (a) DSC thermograms of the resulting PU films. (b) Dependence of Tg for the PU films. (c) DMA curves for the PU films with different
OPD contents.

the polymer network. Replacement of castor oil by OPD
improves the mechanical properties of the PU films
significantly. In detail, as the OPD amount of total polyol
increases from 0 to 50%, the Young’s modulus and tensile
strength of the resulting PU films increase from 32.1 to 382.8
and 9.5 to 22.3 MPa, respectively, while the elongation at break
of them decreases significantly from 192 to 12%, as expected.
Toughness is considered as the characteristics of a material’s
resistance to fracture, which is obtained from the area below
the stress−strain curves. The toughness of the films increases
from 15.8 to 41.9 J/mm3 with the increase of the OPD amount
from 0 to 30% of total diol but sharply drop to around 8 J/
mm3 as the OPD amount further shifts above 40%. The
increasing hard segment content of the PU films (see Table 2)
induced by the replacement of the castor oil by OPD and the
increasing rigid bicyclic structure from the OPD lead to the
films with tailorable mechanical performance ranging from
ductile plastics to rigid plastics.30
920
The coating properties of the resulting PU films, including
pencil hardness, crosshatch adhesion, and film thickness, were
also studied (see Table 3). The results show that PU films
obtained from higher OPD contents exhibit improved pencil
hardness and crosshatch adhesion. The pencil hardness of the
samples ranges from 2H to 6H. The lowest pencil hardness
was observed in PU-OPD0, and the greatest pencil hardness
was observed in PU-OPD50. All samples show excellent
adhesion, which increases from 2B to 4B as the OPD content
increases. The increase of the OPD content results in a higher
hard segment content of the samples and thus leads to the
improvement in hardness and adhesion of the coatings.31,32
The thermal behaviors of the PU films were determined by
DSC, and their data are shown in Table 3. As shown in Figure
4a,b, only one Tg and no melting or crystallization transition
are observed in all DSC curves, indicating the amorphous
nature of the OPD-based PU films. As the content of OPD
increases from 0 to 60%, the Tg of the PU films increases
steadily from −7.4 to 52.6 °C. On the one hand, the castor oil
DOI: 10.1021/acssuschemeng.9b05477
ACS Sustainable Chem. Eng. 2020, 8, 914−925
ACS Sustainable Chemistry & Engineering
Figure 5. (a) Network of the PU films from castor oil. (b) Network of the PU films from castor oil and OPD. (c) Chemical structure of monomers
for building the WPU network.
with high flexible long chains is gradually replaced by OPD,
resulting in the increase of the hard segment (HS) content of
the PUs from 44 to 64 wt %. On the other hand, incorporation
of OPD in the PU chains would decrease the free volume and
prevent close packing of polymer chains, leading to the
enhancement in Tg of the samples.13
Figure 4c depicts the storage modulus (E′) and tan δ curves
of the PU films prepared with different OPD contents. The E′
of the resulting PU films over the whole temperature range
increases as the content of OPD increases. All of the PU films
are glassy below 0 °C, and the E′ decreases slightly as the
temperature increases. Then, a noticeable decline is observed
in the E′ for all of the samples from 0 to 80 °C, originating
from the primary relaxation process of the films. The energy
dissipation during the relaxation process is shown in the tan δ
curves, where the maximum of the curve was taken as Tg. Only
one Tg could be observed in all of the tan δ curves, which is
consistent with the DSC results, corresponding to the
homogenous nature of the PU films. The E′ at 25 °C, Tg,
and ve of the PU films are summarized in Table 3. In this work,
the cross-linking density (ve) is calculated from the following
equation33
E′ = 3veRT
(2)
R is the universal gas constant, and T = Tg + 30 °C. An
increase of Tg from 35 to 75 °C and a significant enhancement
of E′ at 25 °C from 78.3 to 1619.7 MPa are observed for the
films when the OPD content increases from 0 to 50%. This can
be explained by the increase of hard segment contents in the
samples induced by the replacement of castor oil by OPD with
the rigid bicyclic skeleton.14,34 Additionally, the increase of the
rigid bicyclic diol (OPD) reduces the free volume in the
samples as mentioned above (shown in Figure 5), leading to
the impediment of molecular chain movements, then
improving the stiffness of the films and resulting in increased
E′ and Tg.35,36 Moreover, the ve also plays a vital role in
influencing the thermodynamic properties of the films. The ve
of the PU film without OPD is 208.1 mol/m3, and it reaches
340.3 mol/m3 when 10% of OPD was incorporated. This
increase could be a result of the short molecular chains of
OPD, which leads to a rather short distance between the cross-
linking points in the PU chains. However, the ve of the PU
921
Research Article
films reduces steadily upon further increase in the OPD molar
fraction. This may result from the compensation of the
increased linear structure of OPD for the decreased distance
between the cross-linking points. However, PU-OPD30 also
shows a higher ve of 232 mol/m3 than PU-OPD0. Higher ve of
the films will lower their chain mobility.37 Due to the fact that
higher temperature is required for rigid materials to achieve the
same degree of mobility, the higher the ve is, the lower the
chain mobility is, and Tg will be higher accordingly.
The Tgs, determined by both DMA curves and DSC curves,
show an upward trend (Figure 4b) as the OPD content
increases. However, the Tgs observed from the DMA curves
are higher than the corresponding ones from DSC curves,
which could be explained by the different natures of the two
methods.20 The DSC method is based on the heat capacity
change when the samples are heated from frozen to unfrozen,
which could be highly influenced by the cooling rate, whereas
the DMA method determines Tg by measuring the mechanical
response change of the polymer chains.
TGA curves for PU films prepared from different OPD
contents are shown in Figure 6, and the corresponding data are
summarized in Table 4. Three stages of thermal degradation
could be observed for all of the CO/OPD films. The
dissociation of labile urethane bonds is responsible for the
weight loss in the first stage between 200 and 320 °C, which
leads to the formation of isocyanates, alcohol, primary amines,
secondary amines, and carbon dioxide. The temperature of 5
wt % weight loss (T5) is usually considered as the onset
decomposition temperature. As described in Table 4, there is a
great improvement in T5 when OPD was introduced in the
backbone of the polymer network. Specifically, the T5 of PU
films without OPD is 209.9 °C, and the T5 of PU-OPD10 is
227.7 °C. This could be explained by the increased cross-
linking density of the sample from 208 to 340 mol/m3 when
the OPD contents in the polyol blends increase from 0 to 10%,
which improve the thermal stability of the PU films.38
However, a downward trend is observed when the OPD
contents continue to increase above 10% because the influence
of the increasing urethane bonds takes the dominant position.
As the content of OPD further increases to 50%, the T5 of the
resulting films gradually decreases to 206.6 °C. The
introduction of OPD leads to an increase of the hard segment
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ACS Sustainable Chemistry & Engineering Research Article

shows a declining trend as the OPD contents increase, which

manifests that the thermal stabilities decrease with the
replacement of castor oil by OPD. Generally, the polymers
with a lower molecular weight show poorer thermal stability.39
OPD has a much lower molecular weight than castor oil does,
and the increase of the OPD content would decrease the total
percentage of polyols by weight, thus leading to the decreased
thermal stabilities of the resulting PU films. The decreased
thermal stability, which results from the increasing urethane
content, compensates for the enhanced thermal stability from
the increased OPD content, which leads to the general
reduction of Tmax2 (the maximum degradation temperatures of
the OPD/castor oil chain). Additionally, all of the samples
exhibit similar Tmax1, which represents the maximum
degradation of the urethane/urea groups, whereas a slight
decrease is observed for the Tmax2 of the films with a higher
OPD content, which is attributed to the maximum degradation
of the OPD/castor oil fatty acid chains, originating from the
more thermally unstable OPD than the castor oil. The third
stage is mainly assigned to further thermo-oxidation of the
resulting PU films.
Figure 7a shows the water contact angle curves of PU films
with different OPD contents. It is found that the incorporation
of rigid OPD improves the water contact angles of the PU
Figure 6. (a) TGA curves and (b) their derivative curves of PU films
prepared from different OPD contents. films, indicating the enhancement of surface hydrophobicity.
There are two factors influencing the water contact angles of
Table 4. TGA and Water Contact Angle Data for the the films: the hydrophilic DMBA content and cross-linking
Resulting PU Films density. An obvious upward trend could be noted for the PU
films when the OPD content increases from 0 to 10%. In
water contact detail, the water contact angle of the film without OPD is 66°,
samples T5 T10 T50 Tmax1 Tmax2 angle (deg)
whereas the water contact angle of the film increases to 83°
PU- 209.9 253.7 330.4 305.2 343.4 66.3 ± 1.8 when 10% OPD was incorporated into the backbone of
OPD0
polyurethane chains. As mentioned above, with the introduc-
PU- 227.7 254.8 319.4 303.8 337.1 82.8 ± 3.3
OPD10 tion of 10% OPD, the cross-linking density increases drastically
PU- 218.7 246.6 318 301 340.2 74.5 ± 4.1 and therefore accompanies with a sharp increase of hydro-
OPD20 phobicity. Although the hydrophilic group (provided by
PU- 214 241.7 311.6 299.4 337.1 75.8 ± 1.2 DMBA) also increases with the increasing OPD content, the
OPD30 increase of hydrophobicity dominates the variation of the
70.3 ± 1.2
PU-
OPD40
219.2 250.9 306 301.2 326
water contact angle of the films.40,41 However, the water
PU- 206.6 242.5 304.3 301.8 326.2 72.0 ± 2.2 contact angles show a slight decline as the OPD content
OPD50 continues to increase, but they are still higher than PU-OPD0.
The water contact angle of the PU film with 50% OPD is 72°.
as discussed earlier (see Table 2), resulting in the enhance- This decrease in hydrophobicity can be explained by the
ment of labile urethane bonds in the PUDs, and therefore combination of the decreased cross-linking density and the
exhibits a decrease in thermal stability of the PU films. increased hydrophilic DMBA content of the samples with
The second stage in the range of 320−380 °C is mainly increasing OPD content.17 Besides, the surface roughness of
attributed to the chain scission of the polyols, namely, the the films is also an important factor in influencing the surface
OPD/castor oil fatty acid chains. In this degradation stage, T50 hydrophobicity of the samples. As shown in Figure 7b, the

Figure 7. (a) Water contact angle curves and (b) SEM images for the PU films prepared with different OPD contents.

922 DOI: 10.1021/acssuschemeng.9b05477

ACS Sustainable Chem. Eng. 2020, 8, 914−925
ACS Sustainable Chemistry & Engineering
Table 5. Electrochemical Corrosion Parameters for the PU Films
electrodes bare tin PU-OPD0 PU-OPD10
Ecorr (V) −1.014 −0.891 −0.869
Icorr (A) 3.62 × 10−4 4.76 × 10−5 3.89 × 10−5
IE (%) 86.9 89.3
surfaces of the samples are evenly distributed without an
increase in the large surface or recessed areas and gradually
become neat and smooth with the increase of the OPD ratio,
resulting from the relative increase in the cross-linking
densities.42−44 This may be another reason for the slight
decrease in the water contact angle of the sample as the OPD
ratio increased from 10 to 50%.
The effect of the OPD ratio on the corrosion protection of
the samples is evaluated by the potentiodynamic polarization
method.45 The electrochemical corrosion parameters for the
PU films, including the corrosion potential (Ecorr), corrosion
current (Icorr), and inhibition efficiency (IE), are summarized
in Table 5. The Icorr is obtained by extrapolating the cathodic
and anodic polarization curves of Tafel polarization for the
samples, and the y coordinate of their intersection point is the
Icorr value. IE is calculated by the following equation46
Icorr(0) − Icorr(i)
IE(i)(%) = × 100%
Icorr(0) (3)
where Icorr(0) is the Icorr of bare tin and Icorr(i) is the Icorr of
sample i. It is well known that a lower Icorr or a higher Ecorr
corresponds to the improvement in the anticorrosive proper-
ties for coating.47 As shown in Figure 8 and Table 5, the Ecorr
Figure 8. Tafel polarization curves of the PU films prepared with
different OPD contents after immersion in 3.5 wt % aqueous NaCl
solution for 2 h.
of the coating obviously increases from −0.891 to −0.778 V
with an increase of the OPD ratio from 0 to 50% and both
have more positive values than that of bare tin. Besides, the Icorr
of the samples decreases from 4.76 × 10−5 to 1.92 × 10−5 A as
the OPD ratio increased from 0 to 50%, while the bare tin
exhibits the largest Icorr of 3.62 × 10−4 A. Both these results
demonstrate that the WPU coating provides effective
anticorrosion protection for the bare tin with an IE above
86.9%, resulting from the barrier effect of coating.45 Moreover,
the corrosion protection performance of the coating increases
with the increase of the OPD content. In detail, the IE of the
samples increases from 86.9 to 94.7% as the OPD ratio
increased from 0 to 50%. This can be explained by the fact that
the incorporation of OPD results in the formation of a more
923
Research Article
PU-OPD20 PU-OPD30 PU-OPD40 PU-OPD50
−0.850 −0.801 −0.813 −0.778
2.427 × 10−5 2.21 × 10−5 2.071 × 10−5 1.92 × 10−5
93.3 93.9 94.3 94.7
complex polymer network than the pure WPU network, which
restricts the penetration of corrosive species more.48
■
CONCLUSIONS
In this work, OPD, with two parallel rigid cyclopentane rings,
was applied as the partial replacement of castor oil to prepare
bio-based waterborne polyurethane for enhanced mechanical
properties and Tg. The obtained PUDs exhibit improving
transparency as the OPD content increases, and both the
particle sizes and ζ potential of the PUDs decrease with the
increase of OPD. Experimental results demonstrate a
significant improvement in the mechanical properties of the
PU films via the partial replacement of castor oil by OPD. An
increase of the OPD content from 0 to 50% leads to an
increase of the hard segment in the PUDs, resulting in an
increase of Tg from 35 to 75 °C, Young’s moduli from 32 to
383 MPa, tensile strength from 9.5 to 22.3 MPa, and the water
contact angle from 66 to 72° of the samples. Moreover,
obvious upward trends in pencil hardness, crosshatch adhesion,
and anticorrosive properties are also observed for their films as
the OPD content increases, whereas their thermal stability
decreases slightly. This work provides a new way for the
synthesis of vegetable oil-based waterborne polyurethane with
enhanced performance, which could find wide applications in
ink, adhesives, sealants, and anticorrosion coatings. However,
further optimizations are still needed, such as improving the
toughness while retaining the high tensile strength of the films.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: pfeng@jnu.edu.cn (P.F.).
*E-mail: zhangcq@scau.edu.cn, nwpuzcq@gmail.com (C.Z.).
ORCID
Chengguo Liu: 0000-0001-5768-5184
Pengju Feng: 0000-0002-5470-0403
Chaoqun Zhang: 0000-0001-5754-8729
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was sponsored by the Fundamental Research Funds
of CAF (CAFYBB2017QB006), the National Natural Science
Foundation (51703068 and 21602078), the Guangdong
Province Science & Technology Program (2017A010103015
and 2018B030306016), the Program of the Science,
Technology Department of Guangzhou, China
(201803020039), Key Projects of Basic Research and Applied
Basic Research of the Higher Education Institutions of
Guangdong Province (2018KZDXM014), Guangzhou Munic-
ipal Key Laboratory of Woody Biomass Functional New
Materials (201905010005), and the Open Project of Jiangsu
Key Laboratory for Biomass Energy and Materials
(JSBEM201803).
DOI: 10.1021/acssuschemeng.9b05477
ACS Sustainable Chem. Eng. 2020, 8, 914−925
ACS Sustainable Chemistry & Engineering
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925 DOI: 10.1021/acssuschemeng.9b05477

ACS Sustainable Chem. Eng. 2020, 8, 914−925