This is an open access article published under an ACS AuthorChoice License, which permits

copying and redistribution of the article or any adaptations for non-commercial purposes.

Article

Cite This: ACS Omega 2019, 4, 12505−12511 http://pubs.acs.org/journal/acsodf

Synthesis and Properties of UV-Curable Polyfunctional Polyurethane

Acrylate Resins from Cardanol
Yun Hu,† Qianqian Shang,† Caiying Bo,† Puyou Jia,† Guodong Feng,† Fei Zhang,‡ Chengguo Liu,*,†
and Yonghong Zhou*,†
†
Institute of Chemical Industry of Forest Products; Key Laboratory of Biomass Energy and Material, Jiangsu Province;
Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Jiangsu Province; Key Laboratory of Chemical
Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Laboratory for Biomass
Chemical Utilization, Chinese Academy of Forestry, Nanjing 210042, P. R. China
‡
Jiangsu Police Institute, Nanjing 210031, P. R. China
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: A novel UV-curable polyurethane acrylate

(PUA) oligomer was synthesized by modifying cardanol
with a polyfunctional acrylate precursor obtained through
Downloaded via 91.243.191.232 on July 25, 2019 at 04:46:01 (UTC).

reacting pentaerythritol triacrylate with isophoronediisocya-

nate. Chemical structures of the obtained cardanol-based PUA
(C-PUA) oligomer were confirmed by Fourier transform
infrared and 1H NMR. Subsequently, viscosity and gel content
of the C-PUA resins containing different quantities of
hydroxymethyl methacrylate (HEMA) were characterized.
The C-PUA oligomer possessed a viscosity of 8360 mPa s,
which reduced to 115 mPa s when 40% of the HEMA diluent
was added. Furthermore, thermal, mechanical, coating, and
swelling properties of the resulting UV-cured C-PUA/HEMA materials were investigated. The ultimate biomaterials showed
excellent performance, including a glass transition temperature (Tg) of 74−123 °C, maximum thermal degradation temperature
of 437−441 °C, tensile strength of 12.4−32.0 MPa, tensile modulus of 107.2−782.7 MPa, and coating adhesion of 1−2. In
conclusion, the developed C-PUA resins show great potential to be applied in UV-curable materials like coatings.

■ INTRODUCTION
UV-curing technology has attracted much attention because of
its various advantages such as high efficiency, mild curing
conditions, low capital spending, low energy consumption, and
low volatile organic chemical.1 Therefore, UV-curing materials
are considered “clean and green” and have been widely used in
modern industry like coatings, adhesives, drug delivery
systems, etc.2 In recent years, due to the scarcity of fossil
feedstock and concern on environmental pollution, there is a
growing interest in developing polymeric materials from
renewable resources, such as carbohydrates, proteins, and
plant oils.3,4 The incorporation of UV-curing technology into
biobased polymeric materials may provide a “greener” strategy
for the polymer industry.
Cardanol is an agricultural byproduct obtained from cashew
nut shell liquid (CNSL).5−7 Although the total production of
CNSL is only around 1 million tons annually in the world, it is
one of the few major sources of naturally occurring phenols.8
Cardanol contains an aromatic ring with an unsaturated long
C15 chain at the meta-position and a polar hydroxyl group,
which may endow the resulting products with many desirable
properties like flexibility, hydrophobicity, thermal resistance,
acid/alkali resistance, etc. As a result, cardanol and its
derivatives have been widely used in industrial fields9,10 such
as coatings,11−15 polybenzoxazine,16 plasticizers,17 antioxi-
dants,18 surfactants,19 and polymeric materials.20−22 Cardanol
has also been involved in the preparation of UV-curable
materials. Rekha et al.23 reported the synthesis of a telechelic
urethane−methacrylate cross-linkers based on cardanol, and
their curing process and double-bond conversion upon UV
irradiation was studied. Chen et al.24 investigated the cationic
photopolymerization, thermal, and mechanical properties of
thin-film materials containing epoxidized cardanol. It was
found that epoxidized cardanol imparted balanced physi-
ochemical properties to the cationic UV-curable materials, thus
demonstrating a great potential to be utilized as a reactive
ingredient in cationic UV-curable systems. Li et al.25 reported
the synthesis of a cardanol-based UV-curable vinyl ester
monomer and its copolymerization with maleic anhydride
modified dimer fatty acids polymerized glycidyl methacrylate
to form rigid biobased materials. The resulting materials
showed good mechanical and thermal properties, all them to
be used as eco-friendly materials in coatings. In our group, we
developed several new cardanol-based diluents, including
cardanyl acrylate, epoxidized cardanyl acrylate, and epoxidized
cardanol glycidyl ether.26−28 When these diluents were
Received: April 23, 2019
Accepted: July 15, 2019
Published: July 23, 2019

© 2019 American Chemical Society 12505 DOI: 10.1021/acsomega.9b01174

ACS Omega 2019, 4, 12505−12511
ACS Omega
employed to modify a castor oil-based polyfunctional polyur-
ethane acrylate (PUA) oligomer, they demonstrated good
ability in reducing viscosity and volumetric shrinkage as well as
improving the biobased content of the obtained bioresins.
Compared with the many cases related to cardanol-based
diluents or biomodifiers for UV-curable resins, examples of
cardanol-based oligomers as main ingredient are few. Liu and
his coauthors reported the synthesis of a series of novel
hyperbranched UV-curable oligomers from cardanol.7,13−15
The resultant oligomers contained rigid carbon rings as “hard
cores” and high acrylic CC functionality, thus leading to
enhanced thermal, mechanical, and coating properties, as well
as reasonably high biorenewable contents for the UV-cured
biomaterials. However, the synthesis of these oligomers
generally involved four steps, which may clearly increase the
cost of products. Besides, high viscosities (>12 000 mPa s)
were observed for the oligomers,12,14 which could also be
attributed to the long route of synthesis. All these
disadvantages may greatly limit their real application in the
industry of UV-curable materials.
In this paper, we developed a cardanol-based polyurethane
acrylate (C-PUA) resin via a two-step procedure. To improve
the active CC functionality of the C-PUA product, cardanol
was capped with a polyfunctional acrylate precursor obtained
by reacting pentaerythritol triacrylate (PETA) with isophor-
onediisocyanate (IPDI). The structure of C-PUA was
characterized by Fourier transform infrared (FT-IR) and 1H
NMR. Moreover, UV-curable resins were formulated using
hydroxyethyl methacylate (HEMA) as diluent and ultimate
physicochemical, mechanical, and thermal properties of the
resulting materials were investigated in detail. The aim of this
research is to develop a cardanol-based oligomer with low
viscosity through a simple chemical route while possessing
high performance (e.g., stiffness) after UV curing.
■ RESULTS AND DISCUSSION
Structural Characterization of C-PUA. Chemical
structures of cardanol, intermediate of IPDI−PETA, and C-
PUA were determined by FT-IR and 1H NMR, respectively.
Figure 1 depicts the FT-IR spectra of cardanol, IPDI−PETA,
Figure 1. FT-IR spectra of cardanol, IPDI−PETA, and C-PUA.
and C-PUA. In the spectrum of cardanol, the strong absorption
at 3352 cm−1 corresponded to the hydroxyl group. The
absorption at 3008 cm−1 was assigned to the CC−H on the
unsaturated alkyl chains. The characteristic peaks at 2925 and
2854 cm−1 were assigned to the C−H stretching on methylene
and methyl groups.29 The peaks at 1594, 1490, and 1457 cm−1
12506
Article
corresponded to the vibration absorption of benzene ring.25 In
the spectrum of IPDI−PETA, the characteristic absorption
peaks at 3359 and 2267 cm−1 represented the groups of −NH
and −NCO, respectively. Moreover, the characteristic
absorption of the CC groups and ester carbonyl from
PETA are observed at 1635, 808, and 1726 cm−1, respectively.
In the spectrum of C-PUA, several characteristic peaks were
shown: −NH group (3359 cm−1), ester carbonyl (1726 cm−1),
and CC groups (1635 and 808 cm−1).29,30 These peaks are
new compared to the spectrum of cardanol. Moreover, the
peak at 2267 cm−1 representing the −NCO group almost
diminished. All these results indicated that the target
compound of C-PUA was synthesized successfully.
1
H NMR spectra of cardanol, IPDI−PETA, and C-PUA are
shown in Figure 2. In the spectrum of cardanol, the peaks at
Figure 2. 1H NMR spectra of (a) cardanol, (b) IPDI−PETA, and (c)
C-PUA.
6.8−7.3 ppm can be attributed to the protons on the benzene
ring and the peaks at 5.1−5.7 ppm were ascribed to the
protons on the CC groups of the aliphatic segment.31 In the
spectrum of IPDI−PETA, the characteristic peaks of IPDI
(0.9−1.4 ppm corresponding to the protons on the hexatomic
ring) and PETA (6.0−6.6 ppm representing the protons from
CC groups) were evident. In the spectrum of C-PUA, the
characteristic peak at 7.4 ppm, belonging to the protons at the
−NH− from −NCO, confirmed the successful reaction
between IPDI, PETA, and cardanol.32 Compared with the
spectrum of cardanol C-PUA, the peak at 5.9 ppm
corresponding to the −OH disappeared, reflecting that the
phenolic hydroxyl group was consumed completely. All these
changes indicated the successful synthesis of C-PUA.
Physical Properties of UV-Curable C-PUA Resins.
Viscosity. Figure 3 indicates the variation of viscosity of the
DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511
ACS Omega
Figure 3. Effect of HEMA on viscosity and gel content of the C-PUA/
HEMA resins.
C-PUA resin with the content of the HEMA diluent. It can be
seen that the pure C-PUA resin showed a viscosity value of
8360 mPa s at 25 °C. Notably, the viscosity of the C-PUA/
HEMA resin dropped from 8360 to 115 mPa s with the
increase of HEMA concentration from 0 to 40%.33 To provide
an efficient flow to facilitate good processability, the favored
viscosity for liquid resins is controlled commonly in the range
of 200−1000 mPa s at ambient temperature.34 Therefore, the
viscosity of the C-PUA/HEMA systems can be adjusted to
meet the requirements of the UV-curable techniques.
Photopolymerization Kinetics of the C-PUA/HEMA Resins.
Photopolymerization kinetics of the C-PUA/HEMA resins was
studied by real-time infrared (RT-IR) technique. The CC
conversion curves of the resins are depicted in Figure 4, and
the values of final CC conversion are listed in Table 1. The
initial CC conversion of the resins generally increased when
the content of HEMA rose from 0 to 40%. The reason for this
change may lie in the fact that the addition of more HEMA
diluent decreases the viscosity of resin, which promotes the
motion of radical groups during the UV-curing process. The
final CC conversion of the bioresins dropped from 52.0 to
46.0% as the HEMA content increased to 10% and then grew
gradually to 70.5% as the content of HEMA increased from 10
to 40%. The reason was that as the content of HEMA
increased, the CC concentration of C-PUA/HEMA system
was increased. At the same time, the viscosity of the system
was lowered and the diffusion ability of the free radicals
increased, and the final CC conversion of the C-PUA/
HEMA system showed an increasing trend. In general, a higher
Figure 4. (a) Double-bond conversions and (b) conversion rate of the C-PUA/HEMA resins measured by FT-IR.
12507
Article
concentration of diluent favored the growth of the final CC
conversion of the C-PUA resins.
Gel Content. The Cgel of the cured C-PUA/HEMA resins
were determined by Soxhlet extraction, and the corresponding
results are shown in Figure 3. First, all of the cured C-PUA/
HEMA presented high gel contents, with values ranging from
93.3 to 97.9%, suggesting that the C-PUA resins were well
cross-linked. As the content of HEMA increased, the Cgel of the
cured C-PUA biomaterial increased gradually, indicating that
the employment of HEMA diluent can improve the cross-link
extent of the C-PUA resin.
Properties of the UV-Cured C-PUA Resins. Dynamic
Mechanical Analysis. Figure 5 presents changes of the storage
modulus (E′) and the loss factor (tan δ) with temperature for
the cured C-PUA resins, and the related data are shown in
Table 1. The glass transmission temperature (Tg) was
determined from the peak temperatures of the tan δ curves.
First, the pure C-PUA material demonstrated a E′ at 25 °C
(E′25) of 708.6 MPa and Tg of 74 °C, both of which were
much higher than those of the pure cardanol-based multiarmed
oligomers.13 Furthermore, as the HEMA content grew from 0
to 40%, E′ at 25 °C (E′25) increased from 708.6 to 1578.8
MPa. Meanwhile, the Tg value increased apparently from 74 to
123 °C as the content of HEMA increased. These results
indicated that the incorporation of the HEMA dilute could
improve the thermomechanical properties of the resulting UV-
cured bioresins. The thermomechanical properties of the
thermosets usually have close correlation with the structural
factors, such as cross-link density (νe).30 According to the
kinetic theory of rubber elasticity, the νe of the cured
copolymers could be determined with the following
formula35,36
E′
νe =
3RT
where E′ is the storage modulus of the cross-linked copolymers
in the rubbery plateau region, R is the universal gas constant,
and T is the absolute temperature. In this study, the rubber
modulus at the temperature of Tg + 60 °C was employed for
the calculation of νe. The calculated νe data are presented in
Table 1. The νe value increased with the growth of HEMA,
which was one of the possible reasons for the increase of both
E′25 and Tg.30 Besides, the incorporation of HEMA could bring
DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511
ACS Omega Article

Table 1. Thermomechanical, Thermal Properties, and Final CC Conversions of the UV-Cured C-PUA Resins
samples E′25a (MPa) Tgb (°C) νec (103 mol m−3) T5d (°C) Tpe (°C) wcharf (%) final CC conversion (%)
C-PUA 708.6 74 7.05 247 441 9.3 52.0
C-PUA/10%HEMA 1268.2 83 7.54 254 443 7.6 46.0
C-PUA/20%HEMA 1410.3 113 7.64 255 438 7.2 55.9
C-PUA/30%HEMA 1470.2 123 9.13 262 436 7.0 62.7
C-PUA/40%HEMA 1578.8 123 9.93 263 437 6.1 70.5
a
Storage modulus at 25 °C. bGlass-transition temperature. cCross-link density. d5% Weight-loss temperature. eMaximum thermal degradation
temperature. fChar yield.

Figure 5. (a) Storage modulus and (b) loss factor of the UV-cured C-
PUA/HEMA materials. Figure 6. (a) TGA curves and (b) their derivatives of the UV-cured
C-PUA/HEMA materials.
steric hindrance into the cross-linked structures, which is
another possible reason for the growth of E′25 and Tg.
Thermogravimetric Analysis (TGA). TGA thermograms and
their derivative curves of the UV-cured C-PUA/HEMA resins
are shown in Figure 6. The relevant results are summarized in
Table 1. The degradation process of UV-cured C-PUA/HEMA
can be divided into four stages. The first stage (<240 °C) was
slowest, which is due to the removal of residual low-molecular-
weight ingredients.15 The second stage at 240−380 °C can be
assigned to the decomposition of hard segment in the urethane
structures connecting with cardanol or PETA.37 The third
stage at 380−510 °C was quickest and can be ascribed to the
degradation of the cross-linked bonds and char formation,
while the last stage (>510 °C) corresponded to the gradual
degradation of char residue. Furthermore, when the content of Figure 7. Typical tensile−strain curves of the UV-cured C-PUA/
HEMA increased from 0 to 40%, the 5% weight-loss HEMA resins.
temperature (T5) increased from 247 to 263 °C, while the
maximum thermal degradation temperature (Tp) and char MPa. The large increase may also be attributed to the growing
yield (wchar) slightly decreased, indicating that the incorpo- cross-link density of the obtained materials and the
ration of the HEMA diluent did not influence the thermal incorporation of the HEMA diluent with steric hindrance.38
stability of the new bioresins too much. Coating Properties. The coating properties of the UV-cured
Mechanical Properties. The typical tensile stress−strain C-PUA/HEMA materials including adhesion, pencil hardness,
curves of the UV-cured C-PUA/HEMA reins are shown in and flexibility were investigated, and the data are listed in
Figure 7, and the corresponding data are listed in Table 2. It Table 2. Obviously, as the HEMA concentration grew from 0
can be seen that all the biobased materials fractured without to 40%, the adhesion grew from 2 to 1, the pencil hardness
reaching a yield point, indicating the rigid characteristic of the changed gradually from B to HB, while the flexibility was
materials.30,38 When the content of HEMA grew from 0 to maintained at the minimum value of 2 mm. The improvement
40%, the tensile strength increased significantly from 12.4 to of adhesion is probably attributed to the increase of the
31.9 MPa, and Young’s modulus increased from 107.2 to 782.7 hydroxyl concentration provided by HEMA, while the growth
12508 DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511
ACS Omega Article

Table 2. Mechanical and Coating Properties of the UV-Cured C-PUA/HEMA Resins

samples σa (MPa) Eb (MPa) εc (%) Ad.d P.H.e Fl.f (mm)
C-PUA 12.4 ± 2.4 107.2 ± 14.5 7.3 ± 1.1 2 B 2
C-PUA/10%HEMA 19.9 ± 1.2 283.0 ± 34.0 5.4 ± 0.9 1 B 2
C-PUA/20%HEMA 23.8 ± 2.1 331.7 ± 21.9 5.4 ± 0.5 1 HB 2
C-PUA/30%HEMA 27.9 ± 4.6 595.7 ± 17.1 5.2 ± 0.3 1 HB 2
C-PUA/40%HEMA 32.0 ± 7.7 782.7 ± 54.2 4.8 ± 2.5 1 HB 2
a
Tensile strength. bYoung’s modulus. cTensile breaking strain. dAdhesion of coatings. ePencil hardness of coatings. fFlexibility of coatings.

Table 3. Swelling Properties of the UV-Cured C-PUA/HEMA Resins

samples water ethanol acetone toluene
C-PUA 0.2 ± 0.1 3.8 ± 1.4 5.4 ± 0.2 9.3 ± 1.3
C-PUA/10%HEMA 0.9 ± 0.1 3.3 ± 0.6 7.5 ± 0.8 5.7 ± 1.1
C-PUA/20%HEMA 0.7 ± 0.1 2.9 ± 0.6 8.9 ± 1.1 5.2 ± 1.7
C-PUA/30%HEMA 0.7 ± 0.1 2.6 ± 0.9 8.8 ± 1.3 2.5 ± 0.6
C-PUA/40%HEMA 1.5 ± 0.2 2.7 ± 0.1 6.6 ± 0.1 2.9 ± 0.5

of hardness can be ascribed to both the growth of νe and the Synthesis of Cardanol-Based Polyurethane Acrylate.
incorporation of steric structure too.38,39 The synthetic route for the C-PUA product is outlined in
Swelling Properties. The solvent resistance of the cured C- Scheme 1. IPDI (19.98 g, 0.09 mol), 0.30 g of 4-
PUA/HEMA resins was examined, and the results are listed in
Table 3. In general, all the cured materials exhibited better Scheme 1. Synthesis Route for C-PUA and Chemical
resistance to water than to organic solvents. As the Structure of HEMA
concentration of HEMA rose from 0 to 40%, the uptake of
water increased basically from 0.2 to 1.5%, which is possibly
because of the growing content of hydroxyl groups from
HEMA. Meanwhile, the uptake of ethanol and toluene
dropped gradually from 3.8 to 2.7% and from 9.3 to 2.9%,
respectively, while the absorbed amounts of acetone grew first
from 5.4 to 8.9% and then dropped to 6.6%. The improvement
of resistance to ethanol and toluene may be attributed to the
growing cross-link density of the cured materials when the
HEMA content increased.35,40

■ CONCLUSIONS
In this work a novel cardanol-based polyfunctional PUA
oligomer was successfully synthesized by a simple two-step
procedure. The viscosity of oligomer was obviously lower than
those of the hyperbranched cardanol-based oligomers shown in
previous works. Moreover, the resulting UV-cured biomaterials
containing the HEMA diluent demonstrated excellent ultimate methoxyphenol, 30 mL of hexane, and 0.25 g of catalyst
properties such as storage modulus, Tg, maximum thermal DBTDL were placed together into a four-neck round-bottom
degradation temperature, tensile strength and modulus, and flask equipped with a mechanical stirrer, refluxing condenser,
adhesion and flexibility of coatings, mainly due to the high C dropping funnel, and an inlet for nitrogen (N2) gas. Under the
C functionality of oligomer and the special structures (e.g., atmosphere of N2, the reaction mixture was agitated and
benzene ring) involved in cardanol. Therefore, the developed heated to 45 °C and then 29.8 g (0.10 mol) of PETA was
cardanol-based PUA resins show promise to be used in UV- slowly added. After that the mixture was heated to 60 °C and
curable materials like coatings. agitated at this temperature for 6 h. Subsequently, 27.45 g

■
EXPERIMENTAL SECTION
Materials. Cardanol (MD5036) was purchased from
Shanghai Meidong Biological Materials Co., Ltd. (China).
Isophoronediisocyanate (IPDI, 99%) was supplied by Nine
Ding Chemistry Co., Ltd. (China). Dibutyltin dilaurate
(DBTDL) was obtained from Shanghai Titan Scientific Co.,
Ltd. (China). 2-Hydroxy-2-methylpropiophenone (Darocur
1173, 98%), pentaerythritol triacrylate (PETA, 96%), and 4-
methoxyphenol (98%) were bought from Sahn Chemical
Technology Co., Ltd. (China). HEMA (97%) was purchased
from Adamas Reagent Co., Ltd. (China).
12509
(0.09 mol) of cardanol was used to react with the remaining
isocyanate at 60 °C. The reaction did not stop until the
concentration of free isocyanate (determined by the method of
n-butyl amine reverse titration41) dropped to ∼0%. Finally, the
hexane solvent was evaporated via rotary evaporation and the
C-PUA product as a light yellow transparent viscous liquid was
obtained.
Curing of the C-PUA Resins. The UV-curable samples
were formulated by mixing the obtained oligomer, HEMA
diluent, and Darocur 1173 (3% of the total weight of C-PUA
and HEMA) for 20 min, followed by centrifuged to remove air
bubbles. After that the mixture was poured into homemade
poly(tetrafluoroethylene) molds or spread on tinplates, which
DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511
ACS Omega
were polished and cleaned with acetone. At last, all of the
samples were cured by an Intelli-Ray 400 W UV light-curing
microprocessor (Uvitron International Corporation) with an
UV light intensity of 100 mW cm−2 for 4 min. The cured
samples were stored in a glass desiccator for 7 days before
further evaluation.
■ CHARACTERIZATION
FT-IR spectra of the samples were recorded on a Nicolet iS10
IR spectrometer (Thermo-Fisher) with a scanning range from
4000 to 500 cm−1. 1H NMR spectra of the samples were
performed on a DRX-300 spectrometer (Bruker, Germany)
with deuterated chloroform as the solvent.
Viscosity (Vs) of the UV-curable resins was tested by a DVS
+ digital-display viscometer (Brookfield Corporation) with a
small sample adapter at 25 °C.
Gel content (Cgel) of the UV-cured samples was determined
via Soxhlet extraction. Typically, an UV-cured specimen with a
mass of about 0.5 g was weighted and extracted by acetone
using the Soxhlet extractor for 24 h. Then, the specimen was
dried in oven at 60 °C to give a constant weight and weighed
again. The Cgel values were determined from the weight ratio of
the specimen after and before extraction.
The measurement of volumetric shrinkage (ΔV) was
performed on a ZMD-2 electronic automatic density meter
(Fangrui Instrument Corporation, China). The ΔV value was
calculated via the determined densities of the samples before
and after UV curing. The ΔV values were calculated by the
following formula
ρs − ρl
ΔV = × 100%
ρs
where ρS and ρl are the densities of the UV-cured samples and
the uncured liquid resins, respectively.
Dynamic mechanical analysis of the UV-cured samples was
carried out on a Q800 solids analyzer (TA Corporation) with
an oscillating frequency of 1 Hz in double cantilever mode.
The cured samples with a size of 40 × 6 × 1 mm3 were
examined from −80 to 200 °C and a heating rate of 3 °C
min−1.
Thermogravimetric analysis (TGA) of the UV-cured
samples was performed on an STA 409PC thermogravimetry
instrument (Netzsch Corporation, Germany) with a Nicolet
iS10 FT-IR. The samples were heated from 40 to 800 °C at a
heating rate of 10 °C min−1 under N2 as the purge gas.
Mechanical properties of the UV-cured samples were carried
out on a SANS7 CMT-4304 Universal tester (Shenzhen
Xinsansi Jiliang Instrument Corporation, China) with a cross-
head speed of 5 mm min−1. Dumbbell specimens with a size of
62 × 10 × 3 mm3 were measured. The tensile properties for
each sample were determined from an average value of five
specimens.
Coating properties of the UV-cured samples including
adhesion, pencil hardness, and flexibility were evaluated
according to GB 1720-79(89), GB/T 6739-2006, and GB/T
6739-1996, respectively. Detailed procedures are reported in
our previous works.27,30
Swelling properties of the UV-cured samples were
determined using water, ethanol, acetone, and toluene as
solvents. Specimens were weighed and immersed ion different
solvents for 48 h at ambient temperatures, then dried, and
12510
Article
weighed again. The swelling properties with various solvents
were calculated by the following formula
W1 − W0
S= × 100%
W1
where W0 and W1 are the masses of the cured sample before
and after immersion in the solvent, respectively.
UV-curing behaviors of the biobased resins were studied by
a modified Nicolet 5700 spectrometer from Thermo-Nicolet
Instrument. The conversion of double bond (CC) was
determined by monitoring the change of absorption at about
810 cm−1.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: liuchengguo@icifp.cn. Tel/Fax: +86-25-85482520
(C.L.).
*E-mail: zyh@icifp.cn. Tel/Fax: +86-25-854825777 (Y.Z.).
ORCID
Puyou Jia: 0000-0002-3372-9135
Chengguo Liu: 0000-0001-5768-5184
Yonghong Zhou: 0000-0001-5385-5414
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We greatly thank the Fundamental Research Funds of CAF
(No. CAFYBB2017QB006) and the Natural Science Founda-
tion of Jiangsu Province (BK20161122) for financial support.
■
REFERENCES
(1) Takeuchi, H.; Konno, T.; Mori, H. Synthesis of Multifunctional
Silsesquioxane Nanoparticles with Hydroxyl and Polymerizable
Groups for UV-Curable Hybrid Coating. React. Funct. Polym. 2017,
115, 43−52.
(2) Sharmin, E.; Zafar, F.; Akram, D.; Alam, M.; Ahmad, S. Recent
Advances in Vegetable Oils Based Environment Friendly Coatings: A
Review. Ind. Crops Prod. 2015, 76, 215−229.
(3) Das, S.; Pandey, P.; Mohanty, S.; Nayak, S. K. Insight on Castor
Oil Based Polyurethane and Nanocomposites: Recent Trends and
Development. Polym.-Plast. Technol. Eng. 2017, 56, 1556−1585.
(4) Yan, R.; Yang, D.; Zhang, N.; Zhao, Q.; Liu, B.; Xiang, W.; Sun,
Z.; Xu, R.; Zhang, M.; Hu, W. Performance of UV Curable Lignin
Based Epoxy Acrylate Coatings. Prog. Org. Coat. 2018, 116, 83−89.
(5) Kathalewar, M.; Sabnis, A.; D’Mello, D. Isocyanate Free
Polyurethanes from New CNSL Based Bis-Cyclic Carbonate and Its
Application in Coatings. Eur. Polym. J. 2014, 57, 99−108.
(6) Kathalewar, M.; Sabnis, A.; D’Melo, D. Polyurethane Coatings
Prepared from CNSL Based Polyols: Synthesis, Characterization and
Properties. Prog. Org. Coat. 2014, 77, 616−626.
(7) Liu, R.; Luo, J.; Ariyasivam, S.; Liu, X.; Chen, Z. High
Biocontent Natural Plant Oil Based UV-Curable Branched Oligomers.
Prog. Org. Coat. 2017, 105, 143−148.
(8) Campaner, P.; D’Amico, D.; Longo, L.; Stifani, C.; Tarzia, A.
Cardanol-Based Novolac Resins as Curing Agents of Epoxy Resins. J.
Appl. Polym. Sci. 2009, 114, 3585−3591.
(9) Voirin, C.; Caillol, S.; Sadavarte, N. V.; Tawade, B. V.; Boutevin,
B.; Wadgaonkar, P. P. Functionalization of Cardanol: Towards
Biobased Polymers and Additives. Polym. Chem. 2014, 5, 3142−3162.
(10) Caillol, S. Cardanol: A Promising Building Block for Biobased
Polymers and Additives. Curr. Opin. Green Sustainable Chem. 2018,
14, 26−32.
(11) Choi, Y.-S.; Kang, H.; Kim, D.-G.; Cha, S.-H.; Lee, J.-C.
Mussel-Inspired Dopamine- and Plant-Based Cardanol-Containing
DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511
ACS Omega
Polymer Coatings for Multifunctional Filtration Membranes. ACS
Appl. Mater. Interfaces 2014, 6, 21297−21307.
(12) Lalitha, K.; Sandeep, M.; Prasad, Y. S.; Sridharan, V.;
Maheswari, C. U.; Srinandan, C. S.; Nagarajan, S. Intrinsic
Hydrophobic Antibacterial Thin Film from Renewable Resources:
Application in the Development of Anti-Biofilm Urinary Catheters.
ACS Sustainable Chem. Eng. 2017, 5, 436−449.
(13) Liu, R.; Zhang, X.; Zhu, J.; Liu, X.; Wang, Z.; Yan, J. UV-
Curable Coatings from Multiarmed Cardanol-Based Acrylate
Oligomers. ACS Sustainable Chem. Eng. 2015, 3, 1313−1320.
(14) Liu, R.; Zhu, G.; Li, Z.; Liu, X.; Chen, Z.; Ariyasivam, S.
Cardanol-Based Oligomers with “Hard Core, Flexible Shell”
Structures: From Synthesis to UV Curing Applications. Green Chem.
2015, 17, 3319−3325.
(15) Liu, J.; Liu, R.; Zhang, X.; Li, Z.; Tang, H.; Liu, X. Preparation
and Properties of UV-Curable Multi-Arms Cardanol-Based Acrylates.
Prog. Org. Coat. 2016, 90, 126−131.
(16) Amarnath, N.; Appavoo, D.; Lochab, B. Eco-Friendly Halogen-
Free Flame Retardant Cardanol Polyphosphazene Polybenzoxazine
Networks. ACS Sustainable Chem. Eng. 2018, 6, 389−402.
(17) Jia, P.; Hu, L.; Shang, Q.; Wang, R.; Zhang, M.; Zhou, Y. Self-
Plasticization of PVC Materials Via Chemical Modification of
Mannich Base of Cardanol Butyl Ether. ACS Sustainable Chem. Eng.
2017, 5, 6665−6673.
(18) Liu, Z.; Chen, J.; Knothe, G.; Nie, X.; Jiang, J. Synthesis of
Epoxidized Cardanol and Its Antioxidative Properties for Vegetable
Oils and Biodiesel. ACS Sustainable Chem. Eng. 2016, 4, 901−906.
(19) Wang, X.; Kalali, E. N.; Wang, D.-Y. Renewable Cardanol-
Based Surfactant Modified Layered Double Hydroxide as a Flame
Retardant for Epoxy Resin. ACS Sustainable Chem. Eng. 2015, 3,
3281−3290.
(20) Fouquet, T.; Fetzer, L.; Mertz, G.; Puchot, L.; Verge, P.
Photoageing of Cardanol: Characterization, Circumvention by Side
Chain Methoxylation and Application for Photocrosslinkable
Polymers. RSC Adv. 2015, 5, 54899−54912.
(21) Fu, C.; Liu, J.; Xia, H.; Shen, L. Effect of Structure on the
Properties of Polyurethanes Based on Aromatic Cardanol-Based
Polyols Prepared by Thiol-Ene Coupling. Prog. Org. Coat. 2015, 83,
19−25.
(22) Bo, C.; Wei, S.; Hu, L.; Jia, P.; Liang, B.; Zhou, J.; Zhou, Y.
Synthesis of a Cardanol-Based Phosphorus-Containing Polyurethane
Prepolymer and Its Application in Phenolic Foams. RSC Adv. 2016, 6,
62999−63005.
(23) Rekha, N.; Asha, S. Synthesis and FTIR Spectroscopic
Investigation of the UV Curing Kinetics of Telechelic Urethane
Methacrylate Crosslinkers Based on the Renewable Resource-
Cardanol. J. Appl. Polym. Sci. 2008, 109, 2781−2790.
(24) Chen, Z.; Chisholm, B. J.; Webster, D. C.; Zhang, Y.; Patel, S.
Study of Epoxidized-Cardanol Containing Cationic UV Curable
Materials. Prog. Org. Coat. 2009, 65, 246−250.
(25) Li, S.; Yang, X.; Huang, K.; Li, M.; Xia, J. Design, Preparation
and Properties of Novel Renewable UV-Curable Copolymers Based
on Cardanol and Dimer Fatty Acids. Prog. Org. Coat. 2014, 77, 388−
394.
(26) Hu, Y.; Feng, G.; Shang, Q.; Bo, C.; Jia, P.; Liu, C.; Xu, F.;
Zhou, Y. Bio-Based Reactive Diluent Derived from Cardanol and Its
Application in Polyurethane Acrylate (PUA) Coatings with High
Performance. J. Coat. Technol. Res. 2019, 16, 499−509.
(27) Hu, Y.; et al. Use of Cardanol-Based Acrylate as Reactive
Diluent in UV-Curable Castor Oil-Based Polyurethane Acrylate
Resins. Ind. Crops Prod. 2018, 117, 295−302.
(28) Hu, Y.; Shang, Q.; Wang, C.; Feng, G.; Liu, C.; Xu, F.; Zhou, Y.
Renewable Epoxidized Cardanol-Based Acrylate as a Reactive Diluent
for UV-Curable Resins. Polym. Adv. Technol. 2018, 29, 1852−1860.
(29) Hu, Y.; Liu, C.; Shang, Q.; Zhou, Y. Synthesis and
Characterization of Novel Renewable Castor Oil-Based UV-Curable
Polyfunctional Polyurethane Acrylate. J. Coat. Technol. Res. 2018, 15,
77−85.
12511
Article
(30) Wu, Q.; Hu, Y.; Tang, J.; Zhang, J.; Wang, C.; Shang, Q.; Feng,
G.; Liu, C.; Zhou, Y.; Lei, W. High-Performance Soybean-Oil-Based
Epoxy Acrylate Resins: “Green” Synthesis and Application in UV-
Curable Coatings. ACS Sustainable Chem. Eng. 2018, 6, 8340−8349.
(31) Mishra, V.; Desai, J.; Patel, K. I. (UV/Oxidative) Dual Curing
Polyurethane Dispersion from Cardanol Based Polyol: Synthesis and
Characterization. Ind. Crops Prod. 2018, 111, 165−178.
(32) Ma, H.-X.; Li, J.-J.; Qiu, J.-J.; Liu, Y.; Liu, C.-M. Renewable
Cardanol-Based Star-Shaped Prepolymer Containing a Phosphazene
Core as a Potential Biobased Green Fire-Retardant Coating. ACS
Sustainable Chem. Eng. 2017, 5, 350−359.
(33) Li, K.; Shen, Y.; Fei, G.; Wang, H.; Li, J. Preparation and
Properties of Castor Oil/Pentaerythritol Triacrylate-Based UV
Curable Waterborne Polyurethane Acrylate. Prog. Org. Coat. 2015,
78, 146−154.
(34) Phalak, G.; Patil, D.; Vignesh, V.; Mhaske, S. Development of
Tri-Functional Biobased Reactive Diluent from Ricinoleic Acid for
UV Curable Coating Application. Ind. Crops Prod. 2018, 119, 9−21.
(35) Zhang, Y.; Li, Y.; Wang, L.; Gao, Z.; Kessler, M. R. Synthesis
and Characterization of Methacrylated Eugenol as a Sustainable
Reactive Diluent for a Maleinated Acrylated Epoxidized Soybean Oil
Resin. ACS Sustainable Chem. Eng. 2017, 5, 8876−8883.
(36) Dai, J.; Ma, S.; Liu, X.; Han, L.; Wu, Y.; Dai, X.; Zhu, J.
Synthesis of Bio-Based Unsaturated Polyester Resins and Their
Application in Waterborne UV-Curable Coatings. Prog. Org. Coat.
2015, 78, 49−54.
(37) Dai, J.; Ma, S.; Teng, N.; Dai, X.; Shen, X.; Wang, S.; Liu, X.;
Zhu, J. 2,5-Furandicarboxylic Acid- and Itaconic Acid-Derived Fully
Biobased Unsaturated Polyesters and Their Cross-Linked Networks.
Ind. Eng. Chem. Res. 2017, 56, 2650−2657.
(38) Qian, X.; Song, L.; Hu, Y.; Yuen, R. K. K.; Chen, L.; Guo, Y.;
Hong, N.; Jiang, S. Combustion and Thermal Degradation
Mechanism of a Novel Intumescent Flame Retardant for Epoxy
Acrylate Containing Phosphorus and Nitrogen. Ind. Eng. Chem. Res.
2011, 50, 1881−1892.
(39) Dai, J.; Liu, X.; Ma, S.; Wang, J.; Shen, X.; You, S.; Zhu, J.
Soybean Oil-Based UV-Curable Coatings Strengthened by Crosslink
Agent Derived from Itaconic Acid Together with 2-Hydroxyethyl
Methacrylate Phosphate. Prog. Org. Coat. 2016, 97, 210−215.
(40) Liu, C.; Wang, C.; Hu, Y.; Zhang, F.; Shang, Q.; Lei, W.; Zhou,
Y.; Cai, Z. Castor Oil-Based Polyfunctional Acrylate Monomers:
Synthesis and Utilization in UV-Curable Materials. Prog. Org. Coat.
2018, 121, 236−246.
(41) Dai, J.; Ma, S.; Wu, Y.; Zhu, J.; Liu, X. High Bio-Based Content
Waterborne UV-Curable Coatings with Excellent Adhesion and
Flexibility. Prog. Org. Coat. 2015, 87, 197−203.
DOI: 10.1021/acsomega.9b01174
ACS Omega 2019, 4, 12505−12511