Industrial Crops & Products 113 (2018) 249–258

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Industrial Crops & Products

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

Functional soybean oil-based polyols as sustainable feedstocks for T

polyurethane coatings
Prakash Alagia, Ravindra Ghorpadea, Jeong Hyeon Janga, Chandrashekhar Patilb,
⁎
Harishchandra Jirimalib, Vikas Giteb, Sung Chul Honga,
a
Department of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul, 143-747, Republic of Korea
b
Department of Polymer Chemistry, School of Chemical Sciences, North Maharashtra University, Jalgaon, 425001, Maharashtra, India

A R T I C L E I N F O A B S T R A C T

Keywords: The development of renewable and viable alternatives to petroleum-based polymeric materials is a major
Soybean oil challenge to the long-term environmental and waste management issues of the polymer industry. In this study, a
Functional polyol technology platform composed of a series of efficient and quantitative thiol-ene reactions for preparing func-
Thiol-ene reaction tional and sustainable polyols is proposed. First, a soybean oil (SO)-based polyol with two hydroxyl groups
Polyurethane
(MSO) was synthesized through a controlled thiol-ene click reaction between SO and 2-mercaptoethanol.
Coating
Second, other functional groups, such as silane, fluorine or ethylene oxide units, were introduced to the MSO
through another thiol-ene reaction between the MSO and thiol-terminated intermediates to afford SO-based
functionalized polyols. The thiol-terminated intermediates were obtained using a Michael addition reaction
between dithiol- and methacrylate-terminated compounds. Employing silane-modified MSO (SiMSO) as a re-
presentative functionalized polyol, preparation of polyurethane (PU) coatings was demonstrated. For compar-
ison, PU coatings with commercially available poly(propylene glycol) (PPG) and MSO were also prepared. The
thermal, physico-mechanical and anticorrosion properties of the PU coatings clearly demonstrated that coatings
made with the silane groups had a better performance. PU coatings with SiMSO exhibited higher hardness, Tg,
and adhesion strength than the PU coatings with MSO and PPG. Notably, incorporation of SiMSO improved the
anticorrosion properties of the PU coating in a 3.5 wt% aqueous NaCl solution, probably due to the improved
blocking and adhesion properties of the coating on mild steel panel. The present study demonstrates SO-based
functional polyols as promising alternatives to conventional polyols to afford PU coatings with desirable
properties.

1. Introduction unique structure of VO enables it to undergo various chemical trans-

The replacement of petroleum-based raw materials with renewable
resources is a major economic and environmental challenge (Gandini
et al., 2016; Lligadas et al., 2010; Miao et al., 2014; Xia and Larock,
2010). Over the past decades, most of the starting materials for poly-
mers have been derived from petroleum-based resources, which are
widely regarded as unsustainable (Nohra et al., 2013). Environmental
concerns, depleting world crude oil stocks, and increasing oil costs have
triggered efforts to utilize bio-based resources for polymer production,
since it is abundant and inexpensive (Pfister et al., 2011).
Several bio-renewable substances, such as vegetable oil (VO), cel-
lulose, starch, sugar, and proteins have been considered as potential
raw materials (Gandini, 2008; Tanaka et al., 2008; Zhang et al., 2014).
Among them, VOs have gained considerable attention due to their
unique chemical structure with unsaturation sites and ester groups. The
formations to produce materials with many applications (Wang et al.,
2017). Taking advantage of this versatility, increasing efforts are being
focused on the use of VOs as platform chemicals. VOs with hydroxyl,
epoxy, amine, polyacid, isocyanate or silane groups have been prepared
(Ionescu et al., 2015; Jaillet et al., 2013). Among them, the preparation
of VO-based polyols has become attractive in terms of polymer synth-
esis (Alagi et al., 2016a; Alagi et al., 2016b; Alagi et al., 2017; Alagi and
Hong, 2015). Polyols from VOs with hydroxyl functionalities were ty-
pically prepared by epoxidation, hydroformylation, ozonolysis, ami-
dation, and transesterification reactions (Alagi and Hong, 2015;
Desroches et al., 2012; Nohra et al., 2013; Pfister et al., 2011). How-
ever, the VO-based derivatives generally contained only one type of
functionality on the molecule, which often limits the diversity of their
potential applications.
Polyols are essential raw materials for polyurethanes (PUs), which

⁎
Corresponding author.
E-mail address: sunghong@sejong.ac.kr (S.C. Hong).

https://doi.org/10.1016/j.indcrop.2018.01.041
Received 4 September 2017; Received in revised form 13 January 2018; Accepted 16 January 2018
0926-6690/ © 2018 Elsevier B.V. All rights reserved.
P. Alagi et al.
Scheme 1. Reaction scheme for the preparation of functionalized polyols through sequential thiol-ene reactions: First step, the preparation of MSO (a); second step, the preparation of
functionalized polyols containing silane, fluorine or EO (b).
are one of the most important classes of polymer materials. With a
global production of 18 Mt in 2016, PUs have ranked sixth in the annual
worldwide production of polymers (Cornille et al., 2017). The appli-
cations of PUs vary from thermoplastic to thermoset materials, in-
cluding coatings, adhesives, sealants, foams, insulation, and other au-
tomotive parts (Akindoyo et al., 2016; Chattopadhyay and Webster,
2009; Chung et al., 2016; Jin et al., 2016; Nohra et al., 2013). Among
them, PU coatings have received considerable attention because of their
excellent abrasion resistance, chemical resistance, toughness and low
temperature flexibility (Alagi et al., 2017), which made PUs popular
materials for automobile finishing and industrial maintenance
(Chattopadhyay and Raju, 2007).
For coating application, silane is one of the most important and
desirable functional groups. Moisture may hydrolyze the silane groups
to afford silanols, which undergo condensation with other silanols or
with functional groups on the substrate, resulting in efficient cross-
linking and strong adhesion of the coating materials (Chaudhury et al.,
1987; Dumée et al., 2014). Several studies have demonstrated the in-
troduction of alkoxysilanes into VO-based polymers. 3-Aminopropyl-
trialkoxysilane was used as an end-capping reagent for VO-based PUs
(Jena and Raju, 2007; Seeni Meera et al., 2013). Acrylated epoxidized
soybean oil (SO) was shown to react with 3-aminopropyltriethoxysilane
(Çolak and Küsefoğlu, 2007). Probably, castor oil with silane func-
tionality can be a simple target due to its inherent secondary hydroxyl
functionality (Allauddin et al., 2013; Fu et al., 2014). However, the type
and number of hydroxyl functionality of castor oil are not so desirable
for well-defined polymer synthesis.
Thiol-ene chemistry has been receiving increased attention because
of its high efficiency and quantitative controllability (Alagi et al.,
2016a; Alagi et al., 2016b; Hoyle and Bowman, 2010; Lowe, 2010). The
addition of thiol groups to carbon-carbon double bonds (C]Cs) can be
initiated thermally or photochemically by UV light (Caillol et al., 2013;
250
Industrial Crops & Products 113 (2018) 249–258
Desroches et al., 2011; Ionescu et al., 2015). In our previous studies, we
successfully demonstrated the preparation of well-defined SO-based
polyols with a controlled number of primary hydroxyl groups by an
efficient, quantitative and simple photo-initiated thiol-ene reaction
(Alagi et al., 2016a; Alagi et al., 2016b; Alagi and Hong, 2015). The
polyols were then successfully used for preparing thermoplastic PUs. In
this study, we extend our strategy to demonstrate the preparation of the
SO-based polyols with additional functional groups such as silane,
fluorine and ethylene oxide (EO). In particular, the performance of al-
koxysilane-modified SO-based polyol in PU coatings was evaluated.
Through this study, an efficient and simple chemical toolbox is pro-
vided to allow an access to renewable and functional chemical building
blocks for PUs with predetermined characteristics.
2. Experimental
2.1. Materials
SO (analytical standard), 2,2-dimethoxy-2-phenylacetophenone (DMPA,
99%), 2-mercaptoethanol (ME, > 99%), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
heptadecafluorodecyl methacrylate (FMA, 97%), poly(ethylene glycol) me-
thyl ether methacrylate (EOMA, number average molecular weight,
Mn ∼ 500 g/mol), (3-mercaptopropyl)trimethoxysilane (MTS, 95%), 2,2′-
(ethylenedioxy) diethanethiol (DT, 95%), triethylamine (TEA, 99%), poly
(propylene glycol) diol (PPG, Mn ∼ 2000 g/mol), and dibutyltin dilaurate
(DBTDL, 95%) were obtained from Aldrich (St. Louis, MO, USA) and used as
received. Tetrahydrofuran (THF, > 99%, Daejung Chemicals, Seoul, Korea),
dichloromethane (99.5%, Samchun Chemicals, Seoul, Korea), ethyl acetate
(EA, 99%, Samchun Chemicals, Seoul, Korea), and n-hexane (95%, Samchun
Chemicals, Seoul, Korea) were also used without purification.
P. Alagi et al. Industrial Crops & Products 113 (2018) 249–258

Table 1
Preparation and characteristics of the functionalized SO-based polyols.

Experiment Polyol Type and average number of Reaction time Conversiona(%, 1H Hydroxyl valueb Mnc (g/ Mwc (g/ PDIc
number designation functional groups per molecule (h) NMR) (titration, mg KOH/g) mol) mol)

1 MSO 2.0 OH 6.0 41.0 105 1900 2020 1.06

2 SiMSO 2.0 OH + 2.0 Si(OCH3)3 12.0 100 64 2930 3600 1.22
3 EOMSO 2.0 OH + 32.3 EO 12.0 100 32 3960 6390 1.61
4 FMSO 2.0 OH + 19.2 CF2or3 12.0 100 32 4000 5980 1.49

Photoinitiator, DMPA; UV irradiation, 365 nm; [Thiol]/[ene]/[photoinitiator] = 3/1/0.133.

a
The extents of reaction of C]Cs calculated by the intensity changes of the peaks at 5.4 ppm in 1H NMR spectra compared with that of SO.
b
The values were determined by ASTM D 1957–86 through titration.
c
Determined by SEC analyses: number average molecular weight, Mn; weight average molecular weight, Mw.

Scheme 2. Schematic representation of the preparation of PU coatings with MSO (a) and SiMSO (b).

2.2. Preparation of SO-based polyol with two primary hydroxyl groups 2.4. Preparation of polyols with ethylene oxide (EOMSO) and fluorine
(MSO) (FMSO) functionalities

MSO with an average of two primary hydroxyl groups was prepared
by a controlled photo-induced thiol-ene reaction of ME and SO, fol-
lowing the same procedures reported in our previous study (Scheme 1a
and experiment number 1 in Table 1) (Alagi et al., 2016a).
2.3. Preparation of polyol with silane functionality (SiMSO)
The SiMSO was then prepared through subsequent photo-induced thiol-
ene reaction of MTS and MSO (Scheme 1b). MSO (20 g, 0.0193 mol), MTS
(34.11 g, 0.1737 mol), DMPA (0.54 g, 1.0% by weight) and THF (20 mL)
were added to a Schlenk flask equipped with a magnetic stirrer. The reac-
tion was carried out under UV irradiation (365 nm) at −20 °C for 6 h in a
nitrogen atmosphere. The reaction was terminated after the complete
conversion of C]Cs of SO as monitored by 1H NMR spectroscopy. The
reaction mixture was precipitated with n-hexane to remove unreacted MTS.
Finally, SiMSO was recovered as a viscous liquid by drying under a vacuum
at 30 °C for 24 h (yield = 62%).
A base-catalyzed Michael addition reaction between EOMA (20 g,
0.04 mol) and DT (8.02 g, 0.044 mol) was performed in the presence of
TEA (4.04 g, 0.04 mol) in a 100-mL Schlenk flask (Scheme S1a, see
Supporting information). The reaction mixture was stirred at room
temperature for 12 h under a nitrogen atmosphere. The reaction mix-
ture was filtered and extracted in EA and water to remove TEA before
being precipitated in n-hexane to remove unreacted DT. The thiol-ter-
minated intermediates with EO functionality were then recovered by
drying under a vacuum at 40 °C for 12 h (yield = 78%). EOMSO was
prepared through a photo-induced thiol-ene reaction between the thiol-
terminated intermediate and MSO (Scheme 1b). The thiol-terminated
EO intermediate (20 g, 0.0293 mol) was reacted with MSO (3.37 g,
3.25 × 10−3 mol) in the presence of DMPA (0.24 g, 1.0 wt%) and THF
(10 mL) in a 100-mL Schlenk flask equipped with a magnetic stirrer
(experiment number 3 in Table 1). The reaction was carried out under
UV irradiation (365 nm) at −20 °C for 6 h in a nitrogen atmosphere.
The reaction was terminated after the complete conversion of the C]Cs

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P. Alagi et al.
Table 2
Properties of PPG-based, MSO-based, and SiMSO-based PU coatingsa.
PU designation Polyol (g) Diisocyanate (g) Gloss at 60°
PPG-MDI PPG (2.0) MDI (0.376) 90
MSO-MDI MSO (2.0) MDI (0.681) 102
SiMSO-MDI SiMSO (2.0) MDI (0.415) 119
a
Isocyanate content of MDI (27.7%) was determined by titration according to ASTM D 5155-01. [NCO]: [OH] = 1.2: 1.
b
Cross cut adhesion tests for PU coatings were conducted according to ASTM D3359-95A.
c
Hardness of PU coatings were determined according to ASTM D3336 using a pencil hardness tester.
d
Flexibility of PU coatings were investigated according to ASTM D522 using a conical mandrel instrument.
of SO as monitored by 1H NMR spectroscopy. The reaction mixture was
precipitated in a mixture of diethyl ether and n-hexane (80:20) to re-
move any unreacted thiol-terminated intermediate. Finally, EOMSO
was recovered as a viscous liquid by drying under a vacuum at 40 °C for
12 h. FMSO was also prepared following a similar procedure (experi-
ment number 4 in Table 1, see Section 1 of Supporting information).
2.5. Preparation of PU coatings based on MSO and SiMSO
PU coatings were prepared from MSO and SiMSO by reacting the
polyols with 4,4′-diphenylmethane diisocyanate (MDI, 98%, Aldrich,
St. Louis, MO, USA) using a [NCO]: [OH] ratio of 1.2: 1 at room tem-
perature (Scheme 2 and Table 2). In this study, relatively high [NCO]:
[OH] ratio of 1.2:1 was adopted to ensure better mechanical properties
and hydrolysis/corrosion resistances of the coating materials, as sup-
ported by several reports (Lu et al., 2017; de Oliveira et al., 2013;
Rajput et al., 2014). A predetermined quantity of the polyol (2.0 g) and
DBTDL (0.5 wt%, 0.013 g) were dissolved in xylene (2 mL), followed by
the addition of a desired quantity of MDI to react with the polyols. After
2 min, the reaction mixture was coated on a mild steel (MS) panel (V
Panels, Mumbai, India, with the standard size used for physico-me-
chanical testing, i.e., 150 mm × 70 mm × 0.34 mm) with a bar appli-
cator. MS is an alloy of carbon and iron, which may undergo corrosion
under chemical/oxidative environments. In advance, the panels were
polished with fine abrasive papers, followed by consecutive washing
and drying with deionized (DI) water and acetone. The PU-coated pa-
nels were thermally treated at 40 °C for 12 h and 50 °C for 24 h for the
curing of the MSO-based and SiMSO-based PU coatings, respectively.
PU-coated panel with typical PPG was prepared as a reference following
the same procedure.
2.6. Characterization
1
H NMR spectra and 13C NMR were recorded on a Bruker 500 MHz
Avance spectrometer to elucidate the structural characteristics of the
functionalized SO-based polyols. The NMR spectra were obtained at
room temperature in deuterated chloroform with tetramethylsilane as
an internal standard. The molecular weight values of the PU samples
were obtained by using size exclusion chromatography (SEC, Shimadzu
LC-20A) equipped with PSS columns (Styragel HR 2, 4, and 5) and a
Shimadzu RID-10A refractive index detector. THF was used as an eluent
at a flow rate of 1.0 mL/minute. A calibration curve to determine the
molecular weight value was obtained using a polystyrene standard. The
Fourier transform infrared (FT-IR) spectra of the polyols and PU coat-
ings were obtained by using a Thermo Nicolet 380 FT-IR spectrometer
(resolution, 4 cm−1; a wavenumber range, 4000–500 cm−1). The hy-
droxyl values of the polyols (in mg-KOH/g) were determined by volu-
metric titration method (ASTM D1957-86). The hydroxyl values re-
ferred to the weight (mg) of potassium hydroxide (KOH) required to
titrate the free acetic acid generated during the acetylation of the OH
groups (Eq. (1)).
(A − B ) × N × 56.1
Hydroxyl value =
S (1)
Industrial Crops & Products 113 (2018) 249–258
Gel content (wt%) Cross-cut adhesionb (%) Pencil hardnessc Flexibilityd Contact angle (°)
78.2 68 4H Pass 73.7 ± 0.43
86.1 78 4H Pass 76.5 ± 1.65
89.7 100 5H Pass 82.6 ± 2.33
where “A” was the volume (mL) of KOH solution required for the
blank test (without sample). “B” was the volume (mL) of KOH solution
used for the titration of a sample. “N” and “S” were the normality of the
KOH solution and the weight (g) of the sample, respectively. The gloss
values of PU coatings were determined by using an automatic digital
display gloss meter (BYK Additives & Instruments, Germany) at an
angle of 60° after calibration with a standard polished black reference
panel. The cross-cut adhesion test was conducted according to ASTM
D3359-95A by using Elcometer 107 X-hatch type apparatus. A
1 mm × 1 mm sized cross-cut mark was applied over the sample using
the 10-point sharp razor blades. Then, an adhesive tape (Scotch brand
810 Magic Tape) was adhered on the sectional surface, followed by a
sudden stripping-off of the tape after a few minutes. The number of
cubes remained on the surface was compared with the number of cubes
removed from the panel. The hardness values of the PU coatings were
measured by using a pencil hardness tester (BYK Additives &
Instruments, ASTM D3363). Pencils with different grades (6B ∼ 5H)
were moved over the surface of the coated panels at a fixed 45° with a
standard holder. The hardest pencil that did not scratch the film de-
noted its hardness. The flexibility of the PU coatings was verified ac-
cording to ASTM D522 by using a conical mandrel instrument (Raj
Scientific Instruments, Mumbai, India). The sample panel was bent at
different angles between 45° and 180° to observe any peeling or
cracking on the bent portion. The gel content values of the PU coating
films (separately prepared on a glass substrate to determine the gel
content) were determined by immersing the samples in toluene at room
temperature for 24 h. Subsequently, the insoluble part of the samples
was washed with methanol and dried under vacuum at 80 °C for 12 h.
The gel content values (%) were calculated on the basis of the weight
ratio between the insoluble part and the original sample. Differential
scanning calorimetry (DSC; DSC4000, PerkinElmer) was used to de-
termine the glass transition temperature (Tg) of the PUs. The DSC ex-
periments were conducted under a nitrogen atmosphere in the range of
−90 °C to 200 °C at a heating rate of 10 °C/minute. Initially, the sam-
ples were heated to 180 °C to eliminate its thermal history.
Thermogravimetric analyses (TGA) were performed using a TGA4000
analyzer (PerkinElmer) under a nitrogen atmosphere. The samples were
heated from room temperature to 900 °C at a heating rate of 10 °C/
minute. The water contact angles of the PU coatings were determined
using a contact-angle analyzer (Phoenix 450, SEO Co., South Korea) at
room temperature. Water droplets were dropped on PU coating films at
1 μL/s. The contact angles were assessed using image-processing soft-
ware (version 1.46, National Institution of Health, Bethesda, MD, USA).
The electrochemical corrosion resistance of the samples was in-
vestigated through potentiodynamic polarization (PDP). PDP was used
to evaluate the barrier properties of the PU coating against acidic and
saline solutions. For PDP experiments, small MS panels (V Panels,
Mumbai, India, 50 mm × 10 mm × 0.34 mm) were polished with fine
abrasive papers and consecutively washed and dried with DI water and
acetone. The MS panels were then coated with different PU solutions
with a brush. The thicknesses of the coatings were controlled to be
approximately 40 μm, as determined by a digital outside micrometer.
PDP tests of the coated and bare MS panels were performed with a
three-electrode glass cell (Metohm Autolab PGSTAT-101, Netherlands)
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P. Alagi et al.
in 0.5N HCl and 3.5 wt% NaCl aqueous solutions at room temperature.
Ag/AgCl, platinum, and the test specimens were used as the reference,
counter, and working electrodes, respectively. A 1.0 cm2 area of the MS
panel-working electrode was exposed to the corrosive solution. Before
the electrochemical measurements, the working electrode was stabi-
lized for at least 20 min. The PDP tests were conducted in the potential
range of −1 V to +1 V at a scan rate of 0.01 V/s. The electrochemical
corrosion rates were determined using a Tafel extrapolation method.
The corrosion potential (Ecorr) and corrosion current density (Icorr) were
evaluated by extrapolating the linear regions of the cathodic and anodic
curves to the point of intersection (Frankel, 2016). The polarization
resistance (Rp) values were determined from the Tafel plots using
Stearn Geary equation.
ba bc
Rp =
2.3(ba + bc ) Icorr
where ba and bc were determined empirically from the anodic and
cathodic slopes of a Tafel plot, respectively. The corrosion rate (mm/
year) was calculated from Eq. (3) and the corrosion inhibition efficiency
(IE%) was calculated using the Eq. (4).
Icorr M
Corrosion rate (mm / year ) = × 3270
DV
(Corrosion rate (bare) − Corrosion rate (sample) )
Inhibition efficiency (%) =
Corrosion rate (bare)
× 100
where M is the molecular weight of the MS subjected to corrosion (g/
mol), V is the valency (the number of electrons lost during the oxidation
reaction of the metal, i.e., 2 for MS) and D is the density of the corre-
sponding metal (7.85 g/cm3 for MS) (Wei et al., 2013).
3. Results and discussion
Scheme 1 illustrates the strategy used for the preparation of func-
tionalized VO-based polyols with a controlled number of primary hy-
droxyl groups and other functional groups, such as silane, fluorine or
EO. A SO-based polyol was firstly prepared through a thiol-ene reaction
of ME with SO at −20 °C under UV irradiation (365 nm) in the presence
of DMPA (Scheme 1a). The polyols contained an average of two pri-
mary hydroxyl groups. The primary hydroxyl groups were targeted to
ensure high enough reactivity of the polyols. MSO was obtained by
terminating the reaction of ME with SO at ∼40% conversion of the
C]Cs of the SO (Fig. 1b and Fig. S1, see Supporting information).
Subsequently, the MSO was further reacted with MTS to incorporate a
silane group into the polyol, thus affording SiMSO (Scheme 1). The
preparation of SiMSO was also performed at a relatively low tempera-
ture (−20 °C) under a N2 atmosphere to avoid a sol-gel reaction be-
tween the trimethoxysilane groups (Ionescu et al., 2015). The resulting
SiMSO contained two different functional groups, namely reactive
primary hydroxyl groups and hydrolyzable methoxysilane groups that
would become hydroxysilane groups. The methoxysilane groups were
thus capable of self-condensing or reacting with other inorganic sub-
strates that contained hydroxyl functional groups.
Fig. 1 shows the 1H NMR spectra for MTS, MSO and SiMSO. The
progress of the reaction was monitored by the decreased intensity of
signals at 5.4 and 2.0 ppm (Fig. S1 versus Fig. 1b and c; for Fig. S1, see
Supporting information), which represented the disappearance of the
C]Cs in MSO due to the successful photoaddition of ME and MTS.
Simultaneously, the appearance of proton peaks at 3.6 and 0.8 ppm
corresponded to protons in eSie(OCH3)3 and in the eCH2e next to
eSie(OCH3)3, respectively, indicating the successful attachment of
MTS onto the MSO (Fig. 1c).
The successful introduction of MTS into MSO was also confirmed by
13
C NMR analyses of the SiMSO (Fig. 2). Different from the 13C NMR
spectrum of MSO (Fig. 2a), the absence of peaks between 125 and
Industrial Crops & Products 113 (2018) 249–258
135 ppm of 13C NMR spectrum of SiMSO indicated successful conver-
sion of carbon-carbon double bonds (Fig. 2b). The addition of MTS to
MSO was confirmed by the appearance of a peak at 9 ppm, which
corresponded to the carbon attached to the silicon atom in MTS
(Fig. 2b). New peak at 51 ppm of 13C NMR spectrum of SiMSO was
characteristic peak of the carbon atoms next to oxygen atom of MTS.
Furthermore, in the FT-IR spectra (Fig. S2, see Supporting information),
strong peaks near 1090 cm−1 and 1190 cm−1 corresponded to
eSieOeC and eSieOeCH3 units, respectively, and proved the suc-
cessful preparation of silane-functionalized polyols (Allauddin et al.,
2013; Bhosale et al., 2015).
Fig. 3a shows that the SEC traces of MSO and SiMSO exhibit dif-
ferent retention times. SiMSO exhibited a shorter retention time than
MSO, indicating that SiMSO had a larger Mn (2930 g/mol, Table 1)
than MSO (1900 g/mol, Table 1) due to the covalent attachment of MTS
(2)
onto the MSO. Minor amounts of oligomers were observed, as indicated
by shoulder peak observed at a relatively short retention time (Fig. 3a).
The oligomers probably consisted of dimers or trimers of the VOs,
which is consistent with the results reported by Bantchev et al.
(Bantchev et al., 2009). The Si content in SiMSO was determined by the
gravimetric method described in ASTM D 6740-01 (3.49 wt%, see
Section 2 of Supporting information) and by TGA in air (3.50 wt%,
(3)
Fig. 3b, also see Section 2 of Supporting information for the calcula-
tions). The values from both methods agreed well with each other,
suggesting approximately 3.5 wt% of Si in SiMSO.
Employing other thiol-terminated chemicals, the reaction procedure
(4)
can be adopted as a technical platform to afford polyols with other
functional units. To demonstrate this, the preparations of polyols with
EO and fluorine groups were attempted following the same procedures.
Firstly, EO- and fluorine-containing intermediates with primary thiol
groups were prepared through a Michael addition between the corre-
sponding methacrylates (EOMA and FMA) and DT (Scheme S1, see
Supporting information). Secondly, the EOMSO and FMSO were pre-
pared through the thiol-ene reaction of these intermediates with MSO
(Scheme 1b).
The Michael addition of EOMA and DT were monitored by 1H NMR
analysis. The progress of the reaction was indicated by the dis-
appearance of peaks at 5.6 ppm and 6.15 ppm, which correspond to the
C]Cs of the methacrylate groups in EOMA (Fig. S3a and S3b, see
Supporting information). The appearance of new peaks at 2.65 and
2.75 ppm was attributed to the eCH and eCH2 protons of the tertiary
carbon and the thio-ether linkage of the intermediate, respectively (Fig.
S3a and S3b, see Supporting information). The 1H NMR spectrum of
EOMSO demonstrated a successful photo-induced thiol-ene reaction
between the thiol-terminated EO intermediate and MSO, as evidenced
by the decreased intensity of the peaks at 5.4 and 2.0 ppm (Fig. S3c, see
Supporting information). The simultaneous appearance of proton peaks
at 2.6–3.8 ppm indicated the successful attachment of the thiol-termi-
nated EO intermediate onto the MSO. The Mn value of EOMSO (3960 g/
mol, Table 1 and Fig. S4, see Supporting information) was higher than
that of MSO (1900 g/mol, Table 1) due to the incorporation of EO in-
termediate units onto MSO.
The preparation of FMSO was also demonstrated following the same
reaction procedures. Firstly, FMA was reacted with DT to produce thiol-
terminated fluorine intermediate (Scheme S1, see Supporting in-
formation), which was further reacted with MSO in a thiol-ene reaction
to afford FMSO (Scheme 1b). The preparation of the thiol-terminated
fluorine intermediate was also confirmed by 1H NMR spectroscopy and
was indicated by the disappearance of the peaks at 5.6 and 6.2 ppm,
which corresponded to the C]Cs of the methacrylate unit of FMA (Fig.
S5b, see Supporting information). The appearance of new peaks at 2.5
and 2.7–2.8 ppm stemmed from eCH2 protons adjacent to the eCF2
group, the eCH proton of the tertiary carbon of FMA, and eCH2 pro-
tons associated with the thio-ether linkage of the thiol-terminated in-
termediate (Fig. S5a and S5b, see Supporting information). Fig. S5c
shows the 1H NMR spectrum of FMSO, which has decreased peak
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P. Alagi et al.
intensities at 5.4 and 2.0 ppm, representing the disappearance of the
C]Cs from MSO (Fig. 1b and Fig. S5c; for Fig. S5, see Supporting in-
formation). The appearance of proton peaks at 2.5–3.8 ppm indicated
the successful attachment of the thiol-terminated fluorine intermediate
onto MSO to afford FMSO. The Mn value of FMSO (4000 g/mol, Table 1
and Fig. S4, see Supporting information) was also higher than that of
MSO (1900 g/mol, Table 1), clearly suggesting the successful grafting of
the fluorine intermediate onto MSO. Table 1 summarizes the properties
of the functionalized SO-based polyols.
To exemplify the effect of the incorporated functional group on the
characteristics of the PUs, PU coatings with SiMSO were prepared. For
comparison, PU coatings with PPG and MSO were also prepared
(Table 2). In this study, SiMSO was specifically selected as an example
of the functionalized polyol for PU coatings, because the silane units
may afford hydrolyzed silanols that can enhance the performance of
coatings (Chaudhury et al., 1987; Dumée et al., 2014). EOMSO and
FMSO are probably more suitable for PUs in biomedical applications
(Jiang et al., 2009; Ma et al., 2009; Zhou et al., 2011), which will be
topic of our separate study. As a diisocyanate, aromatic diisocyanate
(MDI) was employed for the coating applications in this study due to
their better reactivity and physico-chemical performances than ali-
phatic diisocyanates (Javni et al., 2003; Yilgör et al., 2015).
The PU coatings were prepared through a polyaddition reaction
between the diisocyanate and either PPG, MSO or SiMSO in the pre-
sence of DBTDL as a catalyst. FT-IR spectra of all the PU coatings
254
Industrial Crops & Products 113 (2018) 249–258
Fig 1. 1H NMR spectra of MTS (a), MSO (b) and
SiMSO (c).
demonstrated the disappearance of the isocyanate band at 2270 cm−1
and the appearance of the characteristic stretching bands of urethane at
3330 cm−1 (eNH) and 1740 cm−1 (a combined vibration of the ur-
ethane carbonyl eNHeCOeO and the esteric carbonyl eCOeO), in-
dicating the successful formation of PU coatings (Fig. 4). The dis-
appearance of the large and broad absorption bands at
3400 ∼ 3500 cm−1 confirmed the absence of hydroxyl groups from
polyols in the PU coating films because they had reacted to form ur-
ethane groups (Fig. S2a versus Fig. 4; for Fig. S2, see Supporting in-
formation). Specifically, the FT-IR spectra of the SiMSO-based PU
coating films exhibited broad peaks in the range of 1000–1200 cm−1
that corresponded to the overlapped peaks from eSieOeSie, eCe-
SieOe, and eSieOeCe stretching (Allauddin et al., 2013; Gurunathan
and Chung, 2016).
Table 2 presents the physico-mechanical properties of the PPG-
based, MSO-based and SiMSO-based PU coatings. The relatively high
gloss value of the SiMSO-based PU coating (119 as shown in Table 2)
was attributed to the formation of enhanced cross-linking structures
due to the silane units. The increased cross-link density of SiMSO-MDI
resulted in smooth surfaces, which reflected large amount of light and
thus provided high gloss values (Pathan and Ahmad, 2013). To confirm
this, the degrees of cross-linking were estimated by the gel content of
the films of the PPG-based, MSO-based, and SiMSO-based PU coatings
(gel content values in Table 2) (Balanuca et al., 2017). The film of
SiMSO-based PU coating exhibited higher gel content (89.7%) than
P. Alagi et al.
those of the films of PPG-based (78.2%) and MSO-based (86.1%) PU
coatings, suggesting that the Si-O-Si units in SiMSO acted as cross-lin-
kers that increased the cross-link density of the film (Gurunathan and
Chung, 2016). Scheme S2 (see Supporting information) illustrates the
cross-linking of the silane groups and their adhesion to MS substrates
through covalent and hydrogen bonds (see Section 3 of Supporting
information).
Partly because of the enhanced cross-link density, the SiMSO-based
PU coating exhibited higher Tg value (1 °C) than those of the PPG-based
(−63 °C) and MSO-based (−12 °C) PU coatings (Fig. 5 and Table S1,
see Supporting information). The increased cross-link density of the
SiMSO-based PU coating retarded the segmental mobility of the PU
255
Industrial Crops & Products 113 (2018) 249–258
13
Fig. 2. C NMR spectra of MSO (a) and SiMSO (b).
Fig. 3. SEC traces (a) and TGA curves (b) of MSO and
SiMSO.
chain network, resulting in increased Tg value (Gurunathan and Chung,
2016; Ma et al., 2007; Seeni Meera et al., 2014).
Due to the interaction between the silane units in SiMSO and the MS
substrate, the SiMSO-based PU coating exhibited enhanced cross-cut
adhesion value (100%, Table 2). The SiMSO-based PU coating exhibited
a perfect cross-straight line after the cross-cut adhesion tape test,
without any detachment of squares from the lattice. The enhanced
cross-cut adhesion value of the SiMSO-based PU coating was attributed
to the covalent and hydrogen bonding between the eOeSieOe units of
SiMSO and the eOH groups on the MS (Dumée et al., 2014). The cross-
cut adhesion value of the SiMSO-based PU coating was obviously higher
than those of the PPG-based (68%) and MSO-based (78%) PU coatings.
P. Alagi et al.
Fig. 4. FT-IR spectra of PPG-, MSO-, and SiMSO-based PU coatings.
Both PPG-based and MSO-based PU coatings showed detachment of
squares from the lattice because of low adhesion between the coating
materials and the MS substrate due to the absence of such adhesive
bonds.
Different polyols afforded PU coatings with different hardness va-
lues. The hardness properties of the coatings were assessed by using
pencils with different hardness values (Table 2). The softest pencils
(6B–1B) were firstly used to measure the hardness of the coatings. If it
did not produce any scratch on the coating surface, the pencils of next
hardness (1H–5H) were used for the test, until the coatings became
obviously scratched. SiMSO-based PU coating had a higher pencil
hardness (5H) than the PPG-based and MSO-based PU coatings (4H),
again because of the higher cross-link density arising from the presence
of silane units (Table 2). However, all the coatings were reasonably
flexible, as evidenced by bending tests with a conical mandrel instru-
ment, in which the aliphatic hydrocarbon chain and ether linkages of
the polyols afforded enough of a plasticizing effect to impart flexibility
to the coatings (Table 2) (De and Karak, 2013). These results suggested
that the grafting of MTS onto MSO enhanced the physico-mechanical
performances of the SiMSO-based PU as a coating material.
The contact angle is a useful index to determine the hydrophobicity
of PU coatings (Table 2). The contact angles of the PU coatings with
polyols increased from PPG to MSO and finally to SiMSO. The PU
coating with MSO was more hydrophobic than that with PPG since the
long hydrophobic carbon chains of fatty acids form a hydrophobic in-
terfacial layer (Çolak and Küsefoğlu, 2007). An even larger hydro-
phobicity was observed for the PU coating made with SiMSO. Because
of their low surface energy, the SieOeSi units likely migrated towards
and assembled on the polymer surface, diminishing the interfacial en-
ergy between the polymer surfaces and air (Yuan et al., 2016). Ad-
ditionally, the low standard deviations of the contact angle measure-
ments demonstrated a good surface homogeneity of the coatings since
the measurements were repeated at five different locations across the
surface of the coatings.
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Industrial Crops & Products 113 (2018) 249–258
Fig. 6. PDP curves of PU coatings on MS in a 3.5 wt% NaCl medium.
The MSO- and SiMSO-based PUs exhibited a three-step degradation
process during TGA, while the PPG-based PU exhibited a two-step de-
gradation process (Fig. S6, see Supporting information). The first de-
gradation stage at 250–330 °C was attributed to the degradation of
urethane linkages (Petrović et al., 2007). The second degradation stage
was observed at 390–410 °C and was due to the decomposition of ester
linkages and aromatic moieties. The third degradation stage at
410–500 °C was attributed to the decomposition of the hydrocarbon
chains in the polyol and siloxane components (Ghosal et al., 2015). The
presence of the silane moiety in the SiMSO-based PU afforded thermally
stable components (Gurunathan and Chung, 2016; Seeni Meera et al.,
2014) and also generated more SiO2 residue (18.8%, Table S1, see
Supporting information) than those of the PPG-based and MSO-based
PUs. The silane moiety in the SiMSO-based PU acted as a barrier that
inhibited heat and mass transfer and contributed to the increased
thermal stability (Chattopadhyay and Webster, 2009).
To evaluate the anticorrosion performances of the PPG-based, MSO-
based, and SiMSO-based PU coatings, PU coatings with a thickness of
approximately 40 μm were prepared along with bare MS as a reference.
PDP experiments were then conducted on the coatings in solutions of
3.5 wt% NaCl or 0.5N HCl. Tafel plots for bare MS and MS with the PU
coatings in a 3.5 wt% NaCl solution is shown in Fig. 6. Electrochemical
parameters, such as Icorr, Rp and the corrosion rate are summarized in
Table 3. All the coated MSs exhibited a higher Rp, a lower Icorr, and a
lower corrosion rate than the bare MS, demonstrating the protective
abilities of the PU coatings and their good barrier properties against
diffusive and corrosive ions. The Icorr and corrosion rates decreased in
the order of bare MS, MS with PPG-based, MSO-based, and SiMSO-
based PU coatings.
Corrosion of a steel surface involves several oxidation and reduction
processes that are responsible for the spontaneous dissolution of steel
into a corrosive medium (Pathan and Ahmad, 2013). Corrosive media
penetrate through the porous passive oxide layer of steel surfaces to
further corrode the metal (Luckachan and Mittal, 2015). Thus, the
anticorrosion ability of a coating depends on the accessibility of water
Fig. 5. DSC curves of PPG-based PU coating (a) and
MSO-based/SiMSO-based PU coatings (b).
P. Alagi et al.
Table 3
Electrochemical parameters obtained by PDP studies for bare MS and MS with PU coatings in a 3.5 wt% NaCl solution at room temperature.
Sample Ecorr (mV) Icorr (A cm−2) Rp (Ω)
Bare MS −644.790 9.57 × 10−7 6.693 × 103
PPG-MDI −522.430 6.80 × 10−7 3.273 × 104
MSO-MDI −472.430 2.36 × 10−7 2.279 × 104
SiMSO-MDI −490.030 1.32 × 10−7 5.677 × 104
and corrosive ions to the coating/substrate interface (Weng et al.,
2012). The urethane linkages of PU coatings protected the MS surfaces
via hydrogen bonding. The silane functionality of the SiMSO-based PU
coating afforded additional covalent and hydrogen bonding with the
oxide layer of the MS surface (Scheme S2, see Supporting information)
(Dumée et al., 2014), further inhibiting corrosion. The cross-linked
networks of the SiMSO-based PU coating (from the silane groups) also
afforded a rigid protective layer on the MS surface. The hydrophobic
nature of the SiMSO-based PU coating, as confirmed by the contact
angle measurement, reduced its wettability and prevented the pene-
tration of corrosive aqueous ions.
In acidic media (0.5 N HCl solution), all the PU coatings exhibited
lower corrosion rates than bare MS due to the protective layers of PU
(Table S2, see Supporting information). Interestingly, in this acidic
media, PPG-based PU coatings exhibited better anticorrosion perfor-
mance than the MSO-based and SiMSO-based PU coatings (Table S2 and
Fig. S7, see Supporting information) likely due to the facile hydrolysis
(i.e., decomposition) of the ester units in MSO and SiMSO under acidic
conditions (Brown et al., 1980; Zhang and Madbouly, 2016).
4. Conclusion
In this report, a chemical toolbox for preparing a library of bio-
based functional building blocks for polymers is proposed. Quantitative
and efficient transformations of the C]Cs of SO to hydroxyl and other
functional groups, such as silane, EO or fluorine, were successfully
demonstrated using a series of thiol-ene reactions. PU coating with the
SO-based silane-functionalized polyol exhibited a higher hardness, Tg
and adhesion strength than the MSO-based and PPG-based PU coatings
due to the presence of the rigid silane functional group and its enhanced
cross-linking. In the presence of the SiMSO-based polyol, the PU coating
also exhibited improved anticorrosion characteristics in aqueous NaCl
solutions, as demonstrated by the low Icorr and electrochemical corro-
sion rate. The improved anticorrosion characteristic was attributed to
the robust hydrophobic nature of the SiMSO-based PU coating, sug-
gesting that the incorporation of silane groups into VO-based polyol
improved their thermal, physico-mechanical, and anticorrosion prop-
erties. These examples demonstrate the successful application of this
technology platform to prepare polyols with predetermined function-
alities to produce polymers with desirable performances.
Acknowledgments
This research was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) funded by
the Ministry of Education (2015R1D1A1A09061172).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.indcrop.2018.01.041.
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