Synthesis and properties of siloxane-

crosslinked polyurethane-urea/silica hybrid

films from castor oil

Allauddin Shaik, Ramanuj Narayan &

K. V. S. N. Raju

Journal of Coatings Technology and

Research

ISSN 1547-0091
Volume 11
Number 3

J Coat Technol Res (2014) 11:397-407

DOI 10.1007/s11998-013-9548-5

1 23
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1 23
 Author's personal copy
J. Coat. Technol. Res., 11 (3) 397–407, 2014
DOI 10.1007/s11998-013-9548-5
Synthesis and properties of siloxane-crosslinked polyurethane-
urea/silica hybrid films from castor oil
Allauddin Shaik, Ramanuj Narayan, K. V. S. N. Raju
 American Coatings Association & Oil and Colour Chemists’ Association 2014
Abstract A novel hybrid diol (HD) crosslinker has
been synthesized with hydrolyzable –Si–OR groups
from 3-amino propyl trimethoxy silane and 3-glycidoxy
propyl trimethoxy silane. Its chemical structure was
confirmed by Fourier transform infrared spectroscopy,
1
H and 13C nuclear magnetic resonance spectroscopy
to introduce it as a crosslinker in the castor oil, a
renewable resource, to develop functional organic
inorganic hybrid coatings. A series of castor oil-based
organic–inorganic hybrid materials were prepared
from castor oil, isophorone diisocyanate, and the
different weight percentages of synthesized HD.
Dynamic mechanical thermal analysis, thermogravi-
metric analysis, differential scanning calorimetry, and
the universal testing machine were employed to
characterize the hybrid films. The measured properties
were found to be strongly influenced by the weight
ratio of HD to the castor oil-based polyurethanes. The
glass transition temperatures (Tg) for the cured hybrid
films were found to be 26–72C. Antibacterial activity,
in vitro hydrolytic degradation, and swelling properties
of the hybrid films have been studied. The cured hybrid
films exhibited excellent antibacterial activity, which
was enhanced with addition of the HD. The alkoxy
silane-crosslinked castor oil-based coatings have shown
better mechanical and viscoelastic properties in com-
parison to the control (uncrosslinked castor oil-based
polyurethane-urea) coatings. The results showed that
the weight percent of the HD is the main factor that
controls the thermal, antimicrobial, mechanical, swell-
ing, and degradation properties of these hybrid films.
Keywords Castor oil, Antibacterial, Degradation,
Glass transition, Hybrid diol
A. Shaik, R. Narayan, K. V. S. N. Raju (&)
Polymers & Functional Materials Division, Indian Institute
of Chemical Technology, Hyderabad 500007, India
e-mail: kvsnraju@iict.res.in; drkvsnraju@gmail.com
Introduction
Renewable resources can provide an interesting sus-
tainable platform to substitute partially, and to some
extent totally, petroleum-based polymers through the
design of bio-based polymers that can compete or even
surpass the existing petroleum-based materials on a
cost-performance basis with high eco-friendly values.1,2
The increasing importance of polymeric materials from
renewable resources has put polyols and polyurethanes
(PUs) derived from vegetable oils in the spotlight,
especially due to their simple preparation yet greatly
promising applications such as bone regeneration,
flexible foam, to rigid foam as insulation in walls,
medical devices and footwear, adhesives, sealants, and
elastomers used on floors and automotive interiors.3–6
Vegetable oils such as soybean, cotton seed, linseed,
and castor are available on a global basis in very large
quantities at affordable costs and also have a number
of excellent properties, which could be utilized in
producing bio-renewable feedstock for PU. Hydroxyl
functionality occurs naturally in castor oil and it
consists of a mixture of about 70% pure glycerol
triricinoleate and about 30% glyceryl diricinoleate/
monooleate or monolinoleate and has an average
hydroxyl functionality of 2.7.7,8 Because of its hydroxyl
functionality, castor oil (CO) is suitable in isocyanate
reactions to make PU, so CO acts as a polyol which
reacts with polyfunctional isocyanates to form PUs
whose properties range from rigid polymers to elasto-
mers.9,10 Also, the multifunctional nature of CO may
contribute toughness to the PU, and provides flexibility
due to the long fatty acid chain in CO. It has
advantages like water resistance and flexibility as well
as some disadvantages, such as low functionality and
low reactivity due to the secondary hydroxyl groups,
thus leading to semiflexible and semirigid materials.11
However, these oil-based materials have relatively low
thermal stability, primarily due to the presence of
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urethane bonds and they are soft in nature. In order to
overcome these problems, organic and inorganic mate-
rials have been combined into hybrid forms using the
sol–gel process to improve the properties of the vege-
table oils. The crosslinking reactions that occur during
formation of organic inorganic hybrid (OIH) materials
can increase the chemical stability or resistance to
swelling of the organic component and the covalent
linkages between the organic and inorganic components
improve the homogeneity of the silica network within
the organic matrix with excellent film properties,
hydrophobicity, good biodegradability12 and also im-
prove the processing properties, like dispersion behavior
or viscosity by supplying compatibility between filler
and polymer.13 After moisture cure hydrolized silanols
are able to undergo condensation with other silanols in
the medium, thus leading to crosslinks.14 Composites
with good mechanical properties have been prepared
from acrylate-modified soybean oil and natural fibers.15
OIH films have been developed with plant oils and
metal (Ti and Zr) oxides.16–18 Galià and co-workers19
synthesized silicon-containing polyurethanes with en-
hanced flame-retardant properties and polyurethane
networks with potential applications in biomedicine.
Jiménez-Gallegos et al.20 have developed hybrid poly-
urethane for calcified tissues repairing. In addition,
several hybrid polymeric membranes have been inves-
tigated.21,22 Lligadas et al.23 have prepared a new class
of bionanocomposites materials from linseed oil. Hiro-
shi et al.24 have developed green nanocomposites by an
acid-catalyzed curing of epoxidized plant oils in the
presence of organophilic clay. In all these materials
silicones play an important role among polymers with
special properties, because they possess many unusual
properties; even an addition of a very small amount of
silicones causes a crucial improvement of properties of
modified materials. We observe a continuously growing
interest in applications of reactive silanes and renewable
resources in many different fields of materials science
and chemical technology.
In an attempt to find new hybrid materials and uses
for the novel crosslinker, we have investigated the
synthesis of new organo-silane functional material
using 3-amino propyl trimethoxy silane (APTMS)
and 3-glycidoxy propyl trimethoxy silane (GPTMS).
APTMS is able to react with both the active sites of
GPTMS and it may catalyze the hydrolysis of the
Si(OR)3 groups by hydroxyl anions,25 alternatively
easily reacting with the epoxide ring leading to the
formation of secondary or tertiary amines. Cardiano
et al.26 reported room temperature reaction of GPTMS
and APTMS. They performed this reaction in an open
system to form a high viscosity mixture with a rubbery
consistency. Our group has studied the same procedure
method, but we performed the reaction in nitrogen
atmosphere to obtain a hydroxyl functional group.
The objective of this work was to obtain OIH
materials from castor oil. We have investigated the
preparation of hybrid diol (HD) from APTMS and
GPTMS and used it as a crosslinker to develop OIH
398
materials from CO. Thermal and mechanical properties
of these hybrid films were investigated by differential
scanning calorimetry (DSC), dynamic mechanical ther-
mal analysis (DMTA), thermogravimetric analysis
(TGA), and the universal testing machine (UTM). The
effect of the HD crosslinker on the thermal, mechanical,
hydrolytic degradation, swelling, and antibacterial prop-
erties of the resulting crosslinked silica hybrid polyure-
thane-urea coating films was studied.
Experimental section
Materials
Castor oil was obtained from the local market. Its
characteristic properties are hydroxyl no. 160–165 mg
KOH/g and acid value 3 mg KOH/g. Isophorone
diisocyanate (IPDI) was supplied by Alfa Aesar
(MA, USA), APTMS, GPTMS were supplied by
Dynasilan, Germany. Dibutyltin dilaurate (DBTDL)
was obtained from Aldrich (Milwaukee, WI). All other
chemicals were analytical grade and were used without
further purification.
Synthesis of HD
APTMS (10 g, 0.055 mol) was introduced into a
100 mL three-neck flask equipped with a mechanical
stirrer, a droping funnel and a nitrogen inlet. GPTMS
(26.35 g, 0.11 mol) was added into the flask drop by
drop and the mixture was stirred vigorously for 36 h at
room temperature. A light yellow liquid resulted. The
reaction scheme for the synthesis of the HD is shown in
Scheme 1. IR: 3500 (–OH bond), 3050–2995 (–C–H
stretching), 1630 (bending –OH bond), 1490 (bending
vibrations of the –C–H bonds), 1369 (–C–N–C bond),
1090 (strong peak, Si–O–C unit), 1190 (Si–O–CH3),
1085 (–OCH3 bond); 1H NMR (CDCl3, 500 MHz): d
(ppm) = 3.81 (m, Hf), 3.57 (d, He), 3.56 (s, Ha, Si–
OCH3), 3.41 (t, Hd), 1.65 (q, Hc), 1.45 (q, Hi), 0.65 (t,
Hb); 13C NMR (CDCl3, 125 MHz): d (ppm) = 72.8
(CH2OCH2CH(OH)), 72 (–CH2OCH2CH(OH)), 70.8
(–CH2OCH2CH(OH)), 62.06 (–CH2N–CH(OH)), 59.8
(–NCH2CH2CH2), 50.5 (Si(OCH3)3), 23.7 (–SiCH2CH2
CH2N–), 22.55 (–SiCH2CH2CH2O–), 9.52 (–SiCH2CH2
CH2N–), 4.9 (SiCH2CH2CH2O–).
Synthesis of hybrid polyurethane films
The hybrid composites were prepared using HD and
the formulations are shown in Table 1. The HD was
added based on weight percentage of the overall
weight of CO. The CO was added at fixed amount
while HD was varied at 5, 10, and 20 wt%. The blend
(CO and HD) reacted with IPDI at a ratio of 1:1.6 (CO
to IPDI) using 0.1 wt% of DBTL as catalyst for 6 h at
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J. Coat. Technol. Res., 11 (3) 397–407, 2014

O
H2N Si(OCH3)
O Si(OCH3)3 +

GPTMS APTMS

Si(OCH3)3
Si(OCH3)3 Si(OCH3)3

O N O

OH OH

Scheme 1: Synthetic route for hybrid diol preparation

Table 1: Formulations and mole ratios of the obtained
hybrid films
Symbol of sample CO/IPDI HD/IPDI
COPU 1/1.6 1/1
COPUHD5 1/1.6 1/1
COPUHD10 1/1.6 1/1
COPUHD20 1/1.6 1/1
80C, to get NCO-terminated hybrid prepolymers and
was used further for the preparation of the final coatings.
The hybrid NCO-terminated prepolymer films were
cast on tin foil supported on a glass plate using a manual
driven square applicator. The films were kept in an
atmospheric moisture and laboratory humidity condition
for 40 days for moisture curing and also to carry out the
hydrolysis reactions of the alkoxy silane groups of HD.
Thus, the silanol groups condensed to form Si–O–Si
crosslinks. They were removed from the glass plate, and
the free films of the coatings were obtained by amal-
gamation technique. The disappearance of –NCO peak
at 2270 cm1 from Fourier transform infrared (FTIR)
spectroscopy was taken as a measure of complete cure.
The compositions of the different hybrid composites and
mole ratios are shown in Table 1.
Characterization
The structures of HD and hybrid materials were char-
acterized by using FTIR spectroscopy on a Thermo
Nicolet Nexus 670 spectrometer. Each sample was
scanned within the range 400–4000 cm1 for 128 times
with resolution, 4 cm1 and averaged to obtain the
spectrum. The 1H and 13C nuclear magnetic resonance
(NMR) spectra were recorded in CDCl3 solution using a
Varian-Inova-500 MHz spectrometer. Chemical shifts
(d) are given in ppm with tetramethylsilane as a standard.
A DMTA IV instrument (Rheometric Scientific, Piscat-
away, NJ, USA) in tensile mode at a frequency of 1 Hz
with a heating rate of 3C/min and scanning the films from
70 to 150C has been used to study the viscoelastic
HD properties of the films. TGA Q500 (TA Instruments, Inc.,
New Castle, DE, USA) with a heating rate of 10C/min
0
under a N2 atmosphere has been carried out to study the
0.05
0.1
thermal properties. The DSC analysis was recorded on a
Mettler Toledo DSC 821 (Columbus, OH, USA). The
0.2
samples were heated from 70 to 150C at a heating rate
of 20C/min under nitrogen atmosphere at a flow rate of
30 mL/min. Contact angle was measured by G10
(KRUSS) instrument through sessile drop method.
Stress–strain measurements were performed on dumb-
bell-shaped samples cut from the cured free films using a
UTM AGS-10k NG (Shimadzu, Japan). At least five
identical dumbbell-shaped specimens were tested for
each sample, and their average mechanical properties
were reported. Antibacterial behavior of cured films was
investigated by agar diffusion method27 by pouring the
medium into sterile petri dishes under aseptic conditions
in a laminar air flow chamber. When the medium in the
plates solidified, 0.5 mL (approx. 106 CFU/ml) of culture
of test organism was inoculated and uniformly spread
over the agar surface with a sterile L-shaped rod.
Embedded polymer samples with 2 9 2 cm (approx.)
samples were washed with double distilled water and
placed on the medium and incubated at 37C (bacteria)
for 24 h. The activity was performed based on the
formation of an inhibition zone and loss of growth of
organism beneath and surrounding the films placed on the
agar medium. Three replicates were maintained for each
treatment.
Results and discussion
Characterization of hybrid diol
1
H and 13C NMR spectra of synthesized hybrid diol are
shown in Figs. 1 and 2, respectively. The exact resonance

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d a
J b
c
3.70 3.60 3.50 3.40 3.30
a
e
f
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0
ppm
1
Fig. 1: H NMR spectrum of the hybrid diol
positions have been reported from the expanded spec-
trum for each resonance area. The 1H NMR spectrum of
HD was recorded and the signals were not observed at
d = 3.86 ppm, d = 2.82 ppm, and d = 2.68 ppm due to
the methylene group and the two diastereotopic protons
of the glycidyl ether group means –OCH2 (glycidyl),
–OCH2 (epoxy ring), and –OCH2 (epoxy ring).28,29 The
chemical shifts appearing at 3.56 ppm are associated
with methyl protons of (a) Si–OCH3, indicating that
methoxysilyl moieties of APTMS and GPTMS did not
participate in hydrolysis and condensation of the final
product. The multiplet signals at d 0.65(b) ppm, 1.65(c)
ppm, and 3.41(d) ppm with intensity characterize the
protons of the first, second, and third methylene groups
related to the silicon atom in the –SiCH2CH2CH2O–
fragment. Several multiplets at d 2.3–2.5 ppm corre-
spond to protons of various groups bound to the nitrogen
atom (CH2)2NCH2–. The broad peak in the d 3.41–
3.43 ppm interval corresponds to the –OH groups. The
peaks at 1.45(i) ppm due to–CH2CH2–Si–, 3.57(e) ppm
(–O–CH2–CH(OH)–), and 3.81(f) ppm (–O–CH2–
CH(OH)–) indicate the reaction of APTMS and
GPTMS results in the formation of a silane hydroxyl
terminated liquid. The chemical shifts appearing at
d = 3.56 ppm are associated with methyl protons of
Si–OCH3, indicating that methoxysilyl moieties of
APTMS and GPTMS did not participate in hydrolysis
and condensation of the final product. Similar conclu-
sions can be drawn for the assignment of peaks in the 13C
NMR spectrum (Fig. 2) of the same sample which shows
the complete disappearance of the CH and CH2 ring
400
a
a
b b Si(OCH3)3
Si(OCH3)3 Si(OCH3)3
h i d
g e c
O N O
d f f
e g
OH OH
J J
d
g b
c
h
i
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
signals, clearly indicating that no epoxide ring was
present. The spectra of the HD show the disappearance
of the resonances associated with the methylenic group
of the epoxy fragment peaks at 45 and 52 ppm because
the epoxy ring carbons have not been observed and the
methylene neighbor to the –NH2 groups 44.63 ppm.
This suggests that the epoxy rings have opened with
–NH2 functional groups in APTMS. The signals of the
Si(OCH3)3 fragments at 50.5 (1) ppm appear in the
final product. Also, we found that no signals attribut-
able in 51–55 ppm region were detected, indicating that
the RSi(OCH3)3 is not involved in hydrolysis and the
epoxide ring is not involved in secondary reactions such
as homopolymerization or hydrolytic cleavage.26,28,30
Thus the analysis of the 1H and 13C NMR spectra shows
that the two hydrogen atoms in the amino function of
an APTMS molecule are substituted for the epoxide
group to form the hydroxyl moieties. The reaction
between GPTMS and APTMS is studied by FTIR
spectroscopy and the resulting spectrum is shown in
Fig. 3. FTIR spectra were not very helpful for obtaining
information on the cleavage of the epoxy ring with
–NH2. In fact the absorptions due to residual silanol
groups and uncleaved epoxide ring cannot be confi-
dently assigned due to several medium and weak
intensity bands in the range 900–980 cm1. In our
work, the bands around 1654 and 1600 cm1 corre-
sponding to d NH2 and d NH vibration modes were used
as a reference for the evaluation of the spectrum of the
HD and the progress of reaction through the opening of
the epoxy rings and can be monitored following the
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1
1 Si(OCH3)3 1
2 3
Si(OCH3)3 Si(OCH3)3
9 10 5 2
4
4
8 6
O N O
5 7 7
3
6 8
OH OH 10
1
2

5
6 4
7 8
9

90 80 70 60 50 40 30 20 10 0
ppm
13
Fig. 2: C NMR spectrum of the hybrid diol
% Transmitance

OCH3
CH2 Stretching
Symmetric and C–N–C
Stretching Si(OCH3) Stretching
asymmetric stretching

4500 4000 3500 3000 2500 2000 1500 1000 500

Wave numbers(Cm–1)

Fig. 3: The FTIR spectra of hybrid diol

decrease of the IR absorption bands associated with DMTA analysis

–C–H stretching (–C–H stretch in the epoxide), at
3050–2995 cm1 and the disappearance of bands of
epoxide at 1260–1240 cm1 (ring breathing). A strong
peak near 1090 cm1 is commonly present in the IR
spectrum of compounds with an Si–O–C unit, whereas
a 1190 cm1 band is typical for Si–O–CH3 com-
pounds.31,32 The absorption with strongest intensity
vibration at 1085 cm1 was also observed in HD which
was an indication that available –OCH3 groups of
precursors had not condensed each other through sol–
gel condensation.
DMTA measures the deformation of a material in
response to oscillating forces. The DMTA technique is
used to detect the viscoelastic behavior of polymeric
materials and yields quantitative results for the tensile
storage modulus E¢ and the corresponding loss mod-
ulus E†. The loss factor tan d can then be expressed as
the quotient of loss and storage, E†/E¢. E¢ and E†
characterize the elastic and viscous component of a
material under deformation, and E¢ is a measure of the
mechanical energy stored under load. The tan d

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compares the amounts of dissipated and stored energy. To observe the effect of crosslinker weight ratio on
The Tg values of hybrid films are obtained from the dynamic mechanical properties, the E¢ and tan d
peaks of tan d curves. The crosslink density (te) of temperature curves for the representative coating films
hybrid films was calculated by using equation (1) are shown in Figs. 4a and 4b, while the data is reported
in Table 2. The viscoelastic behavior of the hybrid
te ¼ E0 =3RT; ð1Þ films was studied by the DMTA instrument and the
results are shown in Fig. 4. The Tg values of COPU,
where R is the universal gas constant and T the COPUHD5, COPUHD10, and COPUHD20 are 31.5,
temperature in K. E¢ values in the rubbery region at 38.3, 53.1, and 72.4C, respectively. The E¢ values (Pa)
T > Tg were taken to calculate te by using equation (1). of COPU, COPUHD5, COPUHD10, and COPU-
HD20 hybrid coating are 1.1 9 108, 2.51 9 108,
4.52 9 108, and 5.8 9 108, respectively, at 30C, which
indicates good mechanical integrity of the hybrid films.
The increase in E¢ at 30C and Tg with increasing HD
content suggests that the hybrid films became increas-
(a) 1 2 ingly the harder due to increase in crosslink density.
1. COPU 3
1.0 The addition of HD leads to a significant increase in Tg
2. COPUHD5 4
and storage modulus due to Si–O–Si network and
3. COPUHD10
0.75 crosslinked structures, which retard segmental motion
4. COPUHD20
of the polymer32–34 and increase the glass transition
temperature and storage modulus.
Tan δ

0.5

0.25
TGA analysis

0.0 TGA is used to measure a variety of polymeric

–60.0 –25.0 10.0 45.0 80.0 115.0 150.0
phenomenon involving weight changes, sorption of
Temperature, °C
gases, desorption of contaminant, and degradation.
(b) The thermal degradation studies of different synthe-
1 × 109 sized hybrid films was done in an N2 environment at a
4 heating rate of 10C/min and are shown in Fig. 5. Two
3
step decomposition profiles were observed for hybrid
1. COIP films. It was noticed from the TGA profile that the
5 × 108 2. COIPHD5%
thermal stability of the hybrid films is higher than the
3. COIPHD10%
E (Pa)

2 COPU. The difference between the two can be

4. COIPHD20%
¯ 1 explained by the difference in urethane and HD
content in these hybrid films. The initial decomposition
2 × 108
located between 100 and 150C was due to the
volatilization of the residual solvent as well as the
entrapped moisture present in the cured films. There
were two distinct stages of decomposition in the curves.
–20.0 40.0 100.0 In the first stage, polyurethane decomposed slowly
Temperature (°C) until 300C, which accounted for the first 15–25% of
the weight loss. Weight loss was very rapid in the
Fig. 4: (a) Tan d vs temperature curves of hybrid films. (b) temperature range of 300–500C. The main degrada-
E¢ vs temperature curves of hybrid films tion process can be observed at temperatures around
310–340C. The thermal properties of hybrid films
depend on the network structure and the stability is a
function of more than one variable such as: polar
Table 2: DMTA data of hybrid films groups, cohesive energy between molecular chains,
molecular chain rigidity, and other chemical structural
Sample E¢ at 30C E¢ at Crosslink factors such as, for example, steric strain and confor-
code (Pa) Tg + 5C density (t) mational arrangements of groups. All these factors
(Pa) (Tg + 5C) complicated the understanding of the relationship
(mole/cm3) between crosslinking density and thermal stability of
COPU 1.1 9 108 9.1 9 107 1.17 9 102
the hybrid films. In the present study, the crosslink
COPUHD5 2.51 9 108 1.12 9 108 1.42 9 102
densities were changed by varying the HD concentra-
COPUHD10 4.52 9 108 2.43 9 108 2.94 9 102
tion to study the effect of crosslink density on the
COPUHD20 5.8 9 108 3.44 9 108 3.93 9 102
thermal properties. The early stage of weight loss is
determined by the concentration of urethane groups,

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the main degradation product being carbon dioxide.
The thermal stability of COPU, COPUHD5, COPU-
HD10, and COPUHD20 hybrid films was evaluated
from the TGA data derived from the thermo gravi-
metric analysis in N2 environment. The TGA curves of
hybrid films are shown in Fig. 5. The relative thermal
stability of various hybrid films was evaluated from
TGA data. The values of TON (initial decomposition
temperature for degradation step), TEND (final decom-
position temperature for degradation step) and %
weight remaining at 350, 450, and 550C are summa-
rized in Table 3. All the hybrid samples show a three-
step degradation profile. The data in the table show
that the thermal stability of the hybrid films increased
with increasing the HD weight percent. The TON and
TEND temperature of the hybrid films COPU, COPU-
HD5, COPUHD10, and COPUHD20 are 310.2, 369.6;
323.6, 384.2; 330.6, 416.1; and 338.2, 432.5C, respec-
tively. The above behavior might be observed due to
the formation of more crosslinking structures with
increasing the HD weight. The addition of crosslinker
leads to a significant increase in thermal stability due to
the formed Si–O–Si linkages.
Contact angle
water contact angle was in the range of 82–65. The
contact angle data of the hybrid films are reported in
Table 4. The improvement of the hydrophobic capacity
of hybrid films can be confirmed by addition of novel
crosslinker due to the increasing the siloxane content.
Table 4 shows that the higher contact angle observed
for the formulation COPUHD20 hybrid film among all
hybrid films.
Swelling properties
The water resistance of the films was measured by
calculating the percentage swelling by weight. To do
this, preweighed dry films were immersed in deionized
water for 50 h to study the water resistance at room
temperature. After removing the samples from the
immersion bath, they were blotted with soft tissue
paper and weighed to calculate the swelling ratio (Q%)
using following equation35:
Swelling ratio ðQÞ% ¼ ½ðWs  Wd Þ=Wd   100;
where Wd is the weight of the dry sample and Ws is the
weight of the swollen sample.

The hydrophobic nature of the COPU, COPUHD5, Toluene swollen

COPUHD10, and COPUHD20 different hybrid films
was evaluated by measuring the contact angle. The A known weight (W0) of cured hybrid films was
immersed in a toluene bath for 48 h. The toweled down
110 dry sample weight (W1) and the oven-dried sample
weight (W2) were obtained. Toluene swollen (wt%)
90 and the weight loss (WL%) of hybrid films in toluene
COPUHD20 were calculated according to the following equations.
70 COPUHD10
COPU wt% ¼ ½ðW1 W2 Þ=W2   100
Weight (%)

COPUHD5 wt: amounts of toluene absorption by hybrid film

50
WL ð%Þ ¼ ½ðW0 W2 Þ=W0   100
30
WL : amounts of hybrid films dissolved into the
toluene solution
10

–10 Volume swelling ratio of hybrid films was calculated

0 100 200 300 400 500 600
Temperature (°C)
by using following equation
ðQv Þ ¼ Vsw =Vdr ;
Fig. 5: TGA thermograms of hybrid films

where Vsw and Vdr are the volume of the swollen and
Table 3: Thermal analysis data of hybrid coatings
dried sample, respectively.
Sample name Ton Tend % weight remaining at Table 4 shows the water and toluene swelling as a
function of immersion time of the hybrid films of
350 (C) 450 (C) 550 (C) COPU, COPUHD5, COPUHD10, and COPUHD20.
The swelling ratio measurements of the cured films can
COPU 310.2 369.6 42.3 0.8 0
COPUHD5 323.6 384.2 44.6 1.9 0.4
be used to observe water resistance and hydrophobic-
COPUHD10 330.6 416.1 45.5 2.3 0.9
ity. This suggests that there exists sufficiently high
crosslink density in these films, which enables the
COPUHD20 338.2 432.5 47.8 2.9 1.2
swelling behavior to outweigh the weight loss caused

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J. Coat. Technol. Res., 11 (3) 397–407, 2014

Table 4: Contact angle and swelling data of the hybrid films

Sample code Contact wt% Toluene WL (%) weight loss Qv volume Q (%) swelling
angle (h) swollen of Toluene swelling ratio ratio of water

COPU 66 ± 1.3 130.38 2.07 1.64 1.65

COPUHD5 69 ± 0.92 90.84 1.73 1.24 0.98
COPUHD10 74 ± 1.4 71.62 1.21 1.13 0.64
COPUHD20 79 ± 1.23 42.56 0.69 1.06 0.23

by water soluble oil segments or only slightly cross- COPU

linked ones. All of the hybrid films exhibited significant 6 COPUHD5
swelling in toluene, and this varied with HD weight COPUHD10

Weight loss (%)

5
ratio, as shown in Table 4. The addition of HD COPUHD20
typically decreased the degree of swelling, indicating 4
the formation of more crosslinked networks. This is 3
expected because the concentration of Si–O–Si net-
2
work increases drastically with the addition of HD.
1

0
In vitro degradation of hybrid films 0 20 40 60 80 100 120 140
Time (Day)
The degradation tests were performed in compliance
with the standard ASTM F1635-04a.36 The in vitro Fig. 6: Weight loss curves of hybrid films in PBS at 37°C as
hydrolysis was evaluated by placing rectangular sam- a function of time
ples of polymers in 10 mL of 0.1 M phosphate buffer
pH 7.4 at 37C with constant shaking (100 REV).
Samples of each formulation were removed from
Table 5: Tensile properties data of hybrid films
buffer after 7, 14, 30, 45, 60, 75, and 95 days. The
degradation media were refreshed every week. At each Sample code Max. stress (N/mm2) Elongation break (%)
time point, the polymer sample was taken out of the
buffer and dried at room temperature for 2 h and the COPU 7.5 ± 2.12 95.98
hydrolysis of the polymer was monitored by weight loss COPUHD5 6.21 ± 1.27 54.23
of the sample. For the calculation of mass loss, the COPUHD10 5.6 ± 1.1 32.12
samples were weighed before and after the test. The COPUHD20 3.4 ± 1.18 16.81
calculation was performed using the final mass of dry
specimen, as follows:
% of mass loss ¼ ½ðinitial mass  final massÞ= expected for these materials. As shown in Fig. 6, the
initial mass  100: HD crosslinker has some influence on the hydrolytic
degradation rate. With the increase of the HD weight
percent, the degradation rate decreased, which is in
The in vitro degradation experiments of the hybrid agreement with the hydrophobicity of the films. The
films were carried out by immersion of the samples in degradation rate of COPU film corresponds to the
PBS (pH 7.4, 0.1 M) at 37C, and the results are water absorption ability, with faster degradation found
plotted in Fig. 6. The amount of penetrated water in the more absorbent films. COPUHD20 sample
molecules in the films plays an important role in their shows lowest degradation rate. This is due to the
hydrolytic degradation. The degradation rate was hydrophobic nature of this polymer network that arises
evaluated by the weight loss of the polymers over from long aliphatic hydrocarbon chains of fatty acid
predetermined time intervals. Thus, the evaluation of part of castor oil chemical structure and also Si–O–Si
the effect of HD crosslinking on the degradation network. Water molecules cannot penetrate into poly-
behavior of the castor oil-based films was performed by mer network and reach hydrolytically labile ester
measuring the mass loss of cured films that had been groups of castor oil.37,38 This phenomenon of degra-
crosslinked with different amounts of HD (0, 5, 10, and dation: unreacted methoxy groups constitute defect
20%) upon immersion in PBS for different time sites that can be first attacked by water, thus breaking
periods. After 90 days of degradation, the weight the order of the film and also occurs by uptake of water
losses of hybrid films were all below 6%. Because of followed by the hydrolysis of ester bonds and gener-
the inherent hydrophobicity of vegetable oil-based ation of hydrophilic hydroxyl, amine, and carboxylic
polyurethanes, a low rate of hydrolytic degradation is groups at the surface during degradation process.

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S. aureus
Fig. 7: Antibacterial activity of hybrid films
Table 6: Antibacterial activity of hybrid films
Antibacterial COPU COPUHD5 COPUHD10 COPUHD20
activity
E. coli + ++ ++ ++
S. aureus + ++ ++ ++
+ Moderately active (8–12 mm); ++ highly active (14–18 mm)
Mechanical properties
The tensile strength and elongation at break data of
COPU, COPUHD5, COPUHD10, and COPUHD20
hybrid films are summarized in Table 5. The mechan-
ical behavior of the crosslinked polyurethane hybrids is
dependent on the HD weight percent. It is caused by
changing the hard segment content, crosslinking den-
sity, and intermolecular interactions between their
hard segments. Elongation decreases dramatically
along with increasing molar ratio of HD. In the case
of polyurethanes obtained only with castor oil, it shows
more elongation. The elongation at break values
continuously decreased with the addition of HD. This
is an expected situation due to the increase in the
amount of the inorganic content.
Antibacterial activity
All cured films show moderate and mild antibacterial
activity behavior against bacteria E. coli, S. aureus as
shown in Fig. 7 and Table 6. The systems reveal an
excellent combination of hydroxyls, urethane, and Si
component, which gives synergistic effect to denatur-
ation of bacterial proteins, disruption of cell membranes,
and decomposition of essential metabolites resulting in
overall cessation of cellular activities showing good
antibacterial behavior toward S. aureus. Another reason
may be the small size and large surface area of silica,
which makes the antibacterial action more effective.39,40
J. Coat. Technol. Res., 11 (3) 397–407, 2014
E. coli
Conclusions
An attempt has been made to develop renewable
resource-based polyurethane silica hybrid coatings
using castor oil. For this purpose, a novel crosslinker
has been used for the synthesis of HD that was further
reacted with different weight ratios of castor oil and
isophorone diisocyanate to get isocyanate-terminated
silica hybrid polyurethane prepolymer. The excess
isocyanate of the prepolymers was cured under atmo-
spheric moisture to get polyurethane/urea–silica hybrid
coatings. A detailed spectroscopic investigation has
been carried out to confirm the structures of HD and
coatings. Coatings were studied for thermal, tensile,
and viscoelastic properties using different techniques.
The coating properties such as swelling, hydrolytic
degradation, antibacterial activity, and contact angle
were also measured. The swelling properties and
contact angle were directly dependent on the weight
ratio of HD. The hydrophobic character of the hybrid
coating films was found to increase with an increasing
HD ratio. The silane-crosslinked castor oil-based
coatings show better mechanical and viscoelastic
properties in comparison to the control (uncrosslinked
COPU) coatings. The oil chains are chemically con-
nected to the silica functional group, and the incorpo-
ration of silica not only works as a reinforcement filler
but also increases the crosslink density and thermal
properties of the castor oil. This is evidenced by the
higher thermo-mechanical properties measured by
DMTA. Incorporating more weight percent of HD to
the castor oil, it was seen that the films were very
brittle due to high portion of the inorganic domain.
Therefore, the film properties of these samples could
not be investigated above 20%. The accurate control of
the modification of polyurethane with latent crosslink-
ing group, and thus control over the structure cross-
linking, is a critical consideration for materials
intended for medical or biological applications. Hybrid
films showed mild to moderate antibacterial activity
against E. coli and S. aureus which gradually improved
with HD. These materials exhibit fairly good thermal
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J. Coat. Technol. Res., 11 (3) 397–407, 2014
stability and find use in the field of thermal and
antibacterial protective applications. Hence, a new
modification done on the CO in order to increase
thermal, mechanical, biocompatibility, and reduce the
use of petroleum raw materials and these materials
constitute a potential for replacing petroleum-based
polyurethanes.
Acknowledgments Shaik Allauddin would like to
thank the Council of Scientific and Industrial Research
(CSIR), New Delhi, India for the research fellowship.
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