The surface properties and corrosion resistance of fluorinated polyurethane coatings

Article abstract of DOI:10.1016/j.jfluchem.2015.04.002

Fluorine-containing epoxy (FO) compounds were synthesized through a one-step process from 2,2,3,3-tetrafluoro-1-propanol (TFP) and epichlorohydrin (ECH). Cationic polymerization was adopted to prepare fluorinated polyglycol with controllable molecular weight. The structure of FO and FPO were studied by FTIR, NMR and GPC and a two-component fluorinated polyurethane coating was synthesized using FPO and methyl diphenylenediisocyanate (MDI) with a room temperature curing method. We characterized the contact angle of the surface of the coating. The water resistance and resistance to salt spray as well as SEM imaging of the film surface indicates that hydrophobicity, water resistance, and corrosion resistance are improved due to surface migration of the fluorine element.

Full text of DOI:10.1016/j.jfluchem.2015.04.002

Accepted Manuscript
Title: The Surface Properties and Corrosion Resistance of
Fluorinated Polyurethane Coatings
Author: Xia Wang Jiaojiao Hu Ying Li Jinrui Zhang
Yuanyuan Ding
PII:
S0022-1139(15)00098-6
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2015.04.002
FLUOR 8540
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Received date:
Revised date:
Accepted date:
30-10-2014
6-3-2015
7-4-2015
Pleasecitethisarticleas:X. Wang, J. Hu, Y. Li, J. Zhang, Y. Ding, TheSurfaceProperties
and Corrosion Resistance of Fluorinated Polyurethane Coatings, Journal of Fluorine
Chemistry (2015), http://dx.doi.org/10.1016/j.jfluchem.2015.04.002
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The Surface Properties and Corrosion Resistance of Fluorinated Polyurethane
Coatings
Xia Wang*, Jiaojiao Hu, Ying Li*, Jinrui Zhang, Yuanyuan Ding
*School of Materials Science and Engineering, University of Shanghai for Science
and Technology, Shanghai 200093, China.
To whom the correspondence should be addressed:
Professor. Xia Wang
School of Materials Science and Engineering, University of Shanghai for Science and
Technology
516 Jungong Road, Shanghai 200093, China
E-mail: liying@usst.edu.cn
Fax: +86-21-55270632. Phone: +86-21-55274069.
Page 1 of 21

Abstract
Fluorine-containing epoxy (FO) compounds were synthesized through a one-step
process from 2,2,3,3-tetrafluoro-1-propanol (TFP) and epichlorohydrin (ECH).
Cationic polymerization was adopted to prepare fluorinated polyglycol with
controllable molecular weight. The structure of FO and FPO were studied by FTIR,
NMR and GPC and a two-component fluorinated polyurethane coating was
synthesized using FPO and methyl diphenylenediisocyanate (MDI) with a room
temperature curing method. We characterized the contact angle of the surface of the
coating. The water resistance and resistance to salt spray as well as SEM imaging of
the film surface indicates that hydrophobicity, water resistance, and corrosion
resistance are improved due to surface migration of the fluorine element.
Keywords: fluorinated polyglycol; fluorinated polyurethane coating; hydrophobic;
corrosion resistance
Page 2 of 21

1. Introduction
Corrosion is material deterioration due to reactions between the material and the
environment. According to the American Association of Corrosion Engineers (NACE),
annual losses caused by corrosion account for 3%-5% of GDP [1-3]. Therefore,
finding the right way to prevent material corrosion has profound importance. In many
corrosion prevention schemes, the use of anti-corrosion coatings is proposed due to
their cost and convenience [4]. Of these, polyurethane coatings are a very versatile
class. They are second only to alkyd painting [5]. Because of a large number of
hydrogen bonds, large intermolecular forces, and chemical stability, polyurethane
anti-corrosion coatings have excellent chemical resistance [6-8]. However, single
polyurethane coating cannot sustain very harsh corrosive environments such as high
salt spray, high heat, chemicals, sewage, and other harsh conditions. These prevent its
widespread deployment [9].
For high-solid fluorinated heavy-duty polyurethane coatings, fluorinated blocks
were introduced into the molecular chains of polyurethane elastomer (PU) [10-13].
The resulting fluorinated polyurethane elastomers (FPU) not only maintain most of
the outstanding properties of PU such as high strength, high toughness, and high
damping properties, but also offer improved solvent and chemical resistance, a lower
surface tension, and a low coefficient of friction [14-16]. This results in wide
applications in the areas of heavy duty coatings, which have important theoretical and
practical significance.
In this work, solvent-based fluorinated polyurethane coatings were prepared by
Page 3 of 21

controlling the introduction of the fluorine-containing segment to modulate the
surface enrichment effect of the fluorinated segment [17-19]. For environmental
reasons, this paper uses cyclohexanone, butyl acetate—a xylene mixed solvent system
to minimize the amount of xylene. Via solubility parameter principles, the molar ratio
of cyclohexanone, butyl acetate, and xylene is 1: 1: 1. To further enhance the
corrosion resistance of FPU coating, we also added two anticorrosive
pigments—aluminum tripolyphosphate and mica flakes. The common feature of
aluminum tripolyphosphate and mica flakes is that they are flake pigments, and they
easily form a "labyrinth effect" in the painting that can improve impermeability. They
form solid complexion on the surface of the metal and also complex hydroxyl and
carboxy groups in the coating. Consequently, the adhesion of the coating has been
improved. In this work, the NCO / OH molar ratio is set to 1.05:1. This is because the
water in environment and on the surface of the substrate has a negative influence on
–OH and -NCO reactions. Finally, the surface properties, water resistance and salt
spray corrosion of FPU coatings were studied. The results indicate that the surface
migration of fluorine gives the fluorinated polyurethane coatings excellent chemical
stability, salt spray resistance, and low surface energy.
2. Experimental
2.1 Materials
Tetrafluoropropanol (TFP) and diphenyl-methane-diisocyanate (MDI) were
purchased from Sigma, USA. The fluorinated epoxy compound (FO), fluorinated
polyether polyol (FPO) were prepared according to the literature. The
Page 4 of 21

1,2-epichlorohydrin, cyclohexane, tetrahydrofuran, sodium hydroxide,
methylenechloride, ethylene glycol, a boron trifluoride diethyl ether, dibutyl tin
dilaurate, cyclohexanone, butyl acetate, and ditoluene were purchased from China
Medicine, Shanghai Chemical Reagent Corporation. The mica flakes and aluminum
tripolyphosphate were supplied by Shijiazhuang tuomalin minerals Co. Ltd. The billi-
on positive anti-corrosion Material Co. Ltd. in the new Music City.
2.2 Synthesis of fluorinated epoxy compounds (FO)
The molar ratio of epichlorohydrin and tetrafluoropropanol is 7:1. FPO was
prepared by a two-step solution polymerization method. The synthesis process is
described as follows: excess ECH and cyclohexane (as water-carrying agent) were
added in a three-neck glass flask equipped with a magnetic rotor and water separator.
This was placed in a constant temperature oil bath. When the solvent began to reflux,
the 40% sodium hydroxide and TFP were slowly added into glass flask. The solution
was stirred for 6 h at 100°C. The reaction was stopped upon reaching an anhydrous
state. The resulting product was subjected to distillation under reduced pressure to
obtain the pure fluorinated epoxy compound. The reaction formula and synthesis of
the fluorinated epoxy is shown in Scheme. 1.
Scheme. 1. Reaction scheme of FO.
2.3 Synthesis of fluorinated polyether polyol (FPO)
This study used a controlled cationic polymerization method to synthesize
fluorinated polyether polyol. The molar ratio of fluorinated epoxy compound and
Page 5 of 21

tetrahydrofuran was between 1.5:1—1:1.5.
The methylene chloride and tetrahydrofuran were first added into a reactor equipped
with a stirrer and a thermometer in a three-necked flask at 0°C under nitrogen.
Cationic copolymerization of FO with THF was performed by slowly adding FO to
3 2
the reaction mixture containing bulk THF, EG, and BF OEt . After 6 h, distilled water
was added and stirred for 5 min to stop the reaction. The product was then washed
with distilled water 5-6 times to neutrality. After vacuum dehydration for 2-3 h, a
colorless, transparent, and sticky fluorinated glycol was collected (Scheme. 2.).
F2
C
O
O
+
m +m
O
1 2
FPO
n1+n2 HF2C
Scheme. 2. Reaction scheme of FPO
2.4 Film preparation
The fluorinated polyurethane coating was prepared by two components. One
component was prepared by mixing 15 parts of fluorine-containing polyether polyol
FPO) and 0.01 parts of dibutyltindilaurate. These were added sequentially to a
(
three-necked flask equipped with a stirring bar and then stirred for 30 min. The other
component was prepared by mixing 10 parts of MDI, 5 parts of aluminum
tripolyphosphate and mica flakes that were stirred to dissolution in the mixed solvent
system. To remove moisture, the anticorrosive pigments and mixed solvents were
dehydrated before use. The two mixed components in the three-neck flask were stirred
8
-10 min. The samples were coated on to tinplate sheets after grinding the mixed
material to a fineness of 40 ~ 50 μm. The applied wet coatings were hardened after
4-h of curing at room temperature.
2
Page 6 of 21

2.5 Preparation of comparative polyurethane coating
The contrast coating in this paper is a polyurethane coating. It has the same
formulation and preparation as fluorinated polyurethane coatings except there is
replacement of the raw materials. The tetrafluoropropanol was replaced with
n-propanol. The epoxy compound and the polyether polyol were prepared first
followed by the polyurethane coating.
2
2
.6 Characterization
.6.1 FT-IR, NMR, and GPC
An Fourier transform infrared (FT-IR, America Perkin Elmer Instrument Co. Ltd.,
China) was used to identify FO and FPO structures. The samples for FT-IR analysis
were prepared by solution casting of 1% (W/V) polymer in THF directly onto KBr
plates and dried at 70°C. Four scans were averaged for each sample in the range of
-1
4
000 to 600 cm .
Bruker DMX400 H-NMR and Bruker AV 300 C-NMR at 400 MHz were used to
further determine the FO and FPO structure, respectively, using deuterated chloroform
CDCl ) as the solvent.
The average molar mass of the polyether polyol (hereinafter referred to as
1
13
(
3
molecular weight) was determined by gel permeation chromatography (GPC; Perkin
Elmer). Tetrahydrofuran was the eluent, polystyrene (PS) was the standard sample,
flow rate was 1 mL/min at 35℃. The theoretical molecular weight of the polyether
polyol was dominated by controlling the amount of the initiator ethylene glycol (EG)
and the catalyst boron trifluoride diethyl ether, which was calculated as follows:
Page 7 of 21

[
m(FO)+m(THF)]/n(EG) = M
V(EG orboron trifluoride diethyl ether)= m(EG or boron trifluoride diethyl ether) /ρ
1.2)
(1.1)
(
2.6.2 Contact angle
Contact angle (CA, DSA30, KRUSS) measurements were used as a measure of
the hydrophobicity of the material surface. The contact angles were measured by the
sessile drop method using telescoping goniometers at room temperature. Then, 510
µL of distilled water was pumped from a micro-syringe onto the surface of the FPU
films, and an image was captured by a telescope fitted with a video camera. All results
were expressed as the average value of at least five independent measurements. These
were collected within the first 10 s after application of droplets.
2.6.3 Water resistance test
The FPU coating on the tin is applied and cured. Then, two-thirds of the tinplate
samples were placed in a water bath at 25°C for 24 h. Finally, they were removed and
dried by filter paper to observe whether the coating surface modified changes such as
blistering, loss, and rust.
2.6.4 Anti-corrosion test
The FPU coating and PU coating were cured and placed simultaneously in a
closed F-90 resistant to salt spray machine. The salt concentration was 50±10 g/L; salt
settlement was 1 mL/h; spray chamber temperature was 35±2°C for 72 h. After a
predetermined period, the samples were removed from the chamber, rinsed with clean
water to remove the remaining solution on the surface of the testing samples and then
Page 8 of 21

immediately studied for blistering, rust and cracking. Finally, scanning electron
microscopy (SEM; model QuantaFEG450) was used to observe the surface
morphology.
3. Results and discussion
In this paper, an important reactant was FPO, which was synthesized by FO and
THF in a controlled cationic ring-opening copolymerization reaction. What’s more, FO
was obtained through the preparation of ECH and TFP. Thus, the structural
1
13
confirmations of FO and FPO were characterized by FT-IR, H-NMR, and C-NMR
(Figs. 1 and 2).
743
1465
3470
1404
3008
764
2933
679
1455
902
1353
1231
833
1205
1230
2935
832
1203
2876
1101
1107
4000
3500
3000
2500
2000
1500
1000
500
4000
3500
3000
2500
2000
1500
1000
500
-1
-1
Wavenumber(cm)
Wavenumber/cm
Fig. 1. FT-IR spectra of FO.
Fig. 3. FT-IR spectra of FPO.
In the spectrum, there are stretching vibration absorption peaks of C-O (1107 and
-1
-1
-1
7
64 cm ), C-F (1231 and 1205 cm ) [20], three-ring (1404 and 833 cm ) and methyl
-1
(
3008 and 2933 cm ). Through the analysis of the infrared spectrum, fluorine was
introduced into the epoxy chloropropane. It retained the three-ring structure. In
1
addition, the H-NMR spectrum of FO（Fig.2.） was also observed.
Page 9 of 21

1
Fig. 2. H-NMR spectra of FO
The 1H-NMR spectra of FO is shown in fig. 2. It is evident that the peak appears
at 5.76-6.06 ppm, which is assigned to the proton in -CF2H. The peaks at 3.81-3.89
ppm are attributed to –CH2 in OCH2CF2H, and the peaks assigned to the protons of
-OCH2CH appear at 2.54-2.77 ppm. Besides, the peaks at 3.77 ppm corresponding to
the CH in the epoxy group are also observed in the 1H-NMR spectra of FO.
Fig. 3. presents the FTIR spectrum of FPO. There was an O–H stretching vibration
-1
absorption peak at 3470 cm , and C-H stretching vibration absorption peak at 2935
-1
-1
and 2876 cm ; its bending vibration absorption peak was observed at 1455 cm . This
proved that –OH and -CH were in the compounds. The peak at 1203, 1230, and 1353
2
-1
cm were assigned to the C–O stretching vibration absorption and O-H plane bending,
vibration, and absorption. This indicates that the compound belongs to a primary
-1
alcohol. A C-C frame stretching peak was observed at 693 and 743 cm which shows
that the compound contains -(CH . The value of n is not less than 4. From the
spectrum, we conclude that that the stronger characteristic absorption bands locating at
2 n
)
-1
1
101 cm can be attributed to stretching vibrations of C-F.
Page 10 of 21

The fluorine-containing group was completely consumed in the reaction, which
13
can also conclude in C-NMR of FPO. It is evident that the peak appears at 27 and 70
ppm, which is assigned to THF. Two peaks at 65-80 ppm and 105-120 ppm are relative
to the fluorinated epoxy compound. Thus, we conclude that the fluorinated polyether
polyol is polymerization of fluorinated epoxy compound and tetrahydrofuran. Besides,
13
the peaks of C-NMR assigned to the random copolymer of polyether polyol mainly
13
appear at 70-80 ppm [21]. This is the same as C-NMR of the random copolymer of
polyether polyol shown here.
3.1 Contact angle
Variation of roughness, and chemical composition can change the water contact
angle. Samples’ surfaces prepared in this paper are smooth that have no defects and
bubbles, and are placed under constant temperature and humidity of the environment,
so the surfaces which we take to CA measurement are the same batch, the same lab
environment. This paper uses three different molecular weights of FPO (1300, 1500,
and 2000 g/mol) for the FPU coatings. These are termed: FPU (FPO1300), FPU
(FPO1500), and FPU (FPO2000). The coating of different surfaces was measured with
contact angles and surface energy (Table 1) by the contact angle meter.
#
Table 1. Surface properties of the FPU coatings.
Coating system
FPU (FPO1300)
FPU (FPO1500)
FPU (FPO2000)
Contact angle (°)
130.0
Surface energy (mN/m)
6.86
8.30
126.7
110.7
16.69
Page 11 of 21

PU (HPO1300)*
Theoretical body fluorine content is 14.34%.
Using the same method of FPO synthesis to prepare HPO with 1300 g/mol
103.8
20.76
#
*
molecular weight and further prepared with PU coating.
Fluorinated polyurethane (FPU) showed significantly higher contact angle values
versus the polyurethane (PU). Table 1 shows the PU (HPO1300) after the introduction
of fluorine coating, its contact angle changes from 103.8 ° to 130.0 °. This clearly
indicates the generation of a more hydrophobic surface as a result of introducing the
fluorinated groups. Because of low surface energy of fluorine atoms, it can migrate to
the surface of the material spontaneously. Fluorinated groups exhibit hydrophobic and
unique low surface energy. In general, a lower surface free energy component is
enriched on the surface to minimize the polymer-air surface tension. It is believed that
the lower surface energy of fluorine atoms provides a thermodynamic driving force for
the migration of fluorine to the free surface. We observed that the contact angle
increased with decreasing molecular weight of FPO in Table 1. The smaller molecular
weight of FPO is the shorter molecular chain. Thus, the interaction between the
molecular chains is reduced, and it is easier for fluorinated side chains to migrate to the
surface. Fluorine migrates to the top of surface and creates a low surface energy on the
upper surface. This results in a higher contact angle and lower surface energy, and thus
the coatings have improved hydrophobicity.
3.2 Water resistance
The fluorinated polyurethane coatings are applied on tinplate to cure resulting in
Page 12 of 21

FPU coating samples. In the test, two-thirds of the tinplate samples were placed into a
water bath at 25°C for 24 h. They were imaged after removal and drying with filter
paper (Fig. 4).
A
B
C
Fig. 4. Surfaces of FPU coatings after the water resistance test.
Here, A, B, and C represent FPU (FPO1300), FPU (FPO1500), and FPU
FPO2000) coating systems, respectively.
(
After the water resistance test, FPU (FPO2000) films have serious rust spots (Fig.
3
C.). The FPU (FPO1300) film rusted only slightly (Fig. 3A.). This can be explained
according to Table 1. Comparing FPU (FPO1500) and FPU (FPO2000), FPU
FPO1300) underwater contact angle is the largest. Thus, it had the lowest surface
(
energy. For hydrophobic properties, FPU (FPO1300) is the best. FPU (FPO1300) has
higher water penetration than FPU (FPO1500) and FPU (FPO2000) coating, FPU
(FPO1500) in the second best.
3.3 Anti-corrosion test
Stain testing has little influence on the performance of the surface of the FPU
coating (Table 2). This reflects that the surface enrichment of F improves the chemical
resistance. Furthermore, the effect of F on FPU coating corrosion resistance is also
Page 13 of 21

fully reflected in the state of the surface coating after being subjected to the salt spray
test (Fig.5.). Figure 5 shows the surface state of the FPU (FPO1300) and PU
(HPO1300) coating after the salt spray test. The FPU (FPO1300) coating’s surface did
not change after the salt spray test, but the PU (HPO1300) film has a serious crack.
Table 2. Impacts of salt spray on the surface properties of fluorinated polyurethane
coatings.
Coating system
Contact angle (°)
Surface energy (mN/m)
Before test After test
Before test
6.86
After test
7.93
FPU (FPO1300)
FPU (FPO1500)
FPU (FPO2000)
130.0
126.7
110.7
128.3
122.4
102.5
8.30
10.38
16.69
21.53
PU (HPO1300)
FPU (FPO1300)
Fig. 5. The surface of PU (HPO1300) and FPU (FPO1300) after the anti-corrosion test.
To further analyze the protective effect of the F element on the FPU coating, FPU
(FPO2000) coating’s surface morphology before and after the salt spray test was also
observed by SEM (Fig. 6.). It shows that the surface morphology of the coating has not
obviously changed. This proves that due to the protective effect of the F element on the
surface, there is no structural damage caused by the corrosion test after 72 h. The FPU
Page 14 of 21

(FPO2000) coating still has a complete state.
A
B
Fig. 6. SEM images of FPU (FPO2000) coating’s surface
A, B represent SEM photographs of FPU (FPO2000) coating’s surface before
and after anti-corrosion test).
(
4. Conclusions
In this paper, FO was one-step synthesized from 2,2,3,3-tetrafluoro-1-propanol
(TFP) and epichlorohydrin (ECH). Cationic polymerization was adopted to prepare
fluorinated polyglycol with controllable molecular weight. The structures of FO and
FPO were characterized by FTIR and NMR. Finally, a two-component fluorinated
polyurethane coating was successfully prepared by using FPO and methyl
diphenylenediisocyanate (MDI) with a room temperature curing method. The
incorporation of fluorinated polyether glycol in the polyurethane showed a significant
effect on the hydrophobic and anti-corrosion resistance of PU. The contact angle of
PU (HPO1300) was 103.8 °. This increased to 130.0 ° when introducing fluorine into
the coating. The salt spray test suggested that FPU (FPO1300) coating surface
Page 15 of 21

changed little, while PU (HPO1300) coating surface had severe cracking. These
results indicate that there was an obvious migration of fluorinated groups to the
surface of the fluorinated polyurethane films. Furthermore, the fluorinated
polyurethane had outstanding anti-corrosion resistance versus the conventional PU.
Also the contact angle of the coating, water resistance, and resistance to salt spray
performance illustrates that along with the lower molecular weight FPO, the resulting
FPU coatings have better hydrophobic, water resistance, and anti-corrosion
performance.
Acknowledgements
This work was supported by the National Natural Science Foundation of China
(21101107，51173107) and the Hujiang Foundation of China(B14006).
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Page 18 of 21

Fluorine-containing epoxy (FO) compounds were synthesized through a one-step process
from 2,2,3,3-tetrafluoro-1-propanol (TFP) and epichlorohydrin (ECH). Cationic polymerization
was adopted to prepare fluorinated polyglycol with controllable molecular weight. And a
two-component fluorinated polyurethane coating was synthesized using FPO and methyl
diphenylenediisocyanate (MDI) with a room temperature curing method. The hydrophobicity,
water resistance, and corrosion resistance of coating are improved due to surface migration of the
fluorine element.
Page 19 of 21

1. Fluorine migrates to the top of surface and creates a low surface energy.
2. Fluorinated polyurethane showed higher contact angle versus polyurethane.
3. FPU coating has outstanding anti-corrosion resistance versus PU coating.
4. The lower molecular weight FPO, the FPU coatings have better water resistance.
22.
Page 20 of 21

*Graphical Abstract - Pictogram
Page 21 of 21