Synthesis and surface properties of novel fluoroalkylsilyl methacrylate copolymers

Article abstract of DOI:10.1016/j.jfluchem.2015.07.026

The syntheses of novel mono(1H,1H,2H,2H-tridecafluorooctyl) dimethylsilylpropyl methacrylate (MFSA), bis(1H,1H,2H,2H-tridecafluorooctyl)methylsilylpropyl methacrylate (BFSA) and tris(1H,1H,2H,2H-tridecafluorooctyl)silylpropyl methacrylate (TFSA) were achieved in two steps each in good yields. These fluoroalkylsilyl methacrylate monomers (MFSA, BFSA and TFSA) readily reacted with methyl methacrylate (MMA), butyl acrylate (BA), hydroxyethyl methacrylate (HEMA) to form their corresponding fluoroalkysilyl methacrylate copolymers via continuous emulsion polymerization. The structures of fluoroalkylsilyl methacrylate monomers and copolymers were characterized by FT-IR, ¹H NMR, ¹³C NMR and ¹⁹F NMR. The stability of copolymer emulsions was determined by measuring their particle size and zeta potential, and the thermal stability of copolymers was also evaluated by using thermo-gravimetric analysis. In addition, it was observed that improving fluorine content, increasing the packing density of fluoroalkylsilyl segments, and annealing process could enhance the excellent water and oil repellency of fluoroalkylsilyl methacrylate copolymers. The surface free energies of copolymer films were calculated. Moreover, an enrichment of fluoroalkyl chains at the copolymer surface was directly verified by measuring contact angles and using atomic force microscopy.

Full text of DOI:10.1016/j.jfluchem.2015.07.026

Journal of Fluorine Chemistry 178 (2015) 187–194
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and surface properties of novel fluoroalkylsilyl methacrylate
copolymers
a
a,b,
Lu Cai , Zhanxiong Li
*
a
College of Textile and Clothing Engineering, Soochow University, Suzhou 215021, China
b
State Key Laboratory of Disaster Prevention & Mitigation of Explosion & Impact, Nanjing 210007, China
A R T I C L E I N F O
A B S T R A C T
Article history:
The syntheses of novel mono(1H,1H,2H,2H-tridecafluorooctyl) dimethylsilylpropyl methacrylate (MFSA),
bis(1H,1H,2H,2H-tridecafluorooctyl)methylsilylpropyl methacrylate (BFSA) and tris(1H,1H,2H,2H-trideca-
fluorooctyl)silylpropyl methacrylate (TFSA) were achieved in two steps each in good yields. These
fluoroalkylsilyl methacrylate monomers (MFSA, BFSA and TFSA) readily reacted with methyl methacrylate
Received 7 February 2015
Received in revised form 20 July 2015
Accepted 24 July 2015
Available online 29 July 2015
(MMA), butyl acrylate (BA), hydroxyethyl methacrylate (HEMA) to form their corresponding fluoroalkysilyl
methacrylate copolymers via continuous emulsion polymerization. The structures of fluoroalkylsilyl
Keywords:
1
13
19
methacrylate monomers and copolymers were characterized by FT-IR, H NMR, C NMR and F NMR. The
stability of copolymer emulsions was determined by measuring their particle size and zeta potential, and
the thermal stability of copolymers was also evaluated by using thermo-gravimetric analysis. In addition, it
was observed that improving fluorine content, increasing the packing density of fluoroalkylsilyl segments,
and annealing process could enhance the excellent water and oil repellency of fluoroalkylsilyl methacrylate
copolymers. The surface free energies of copolymer films were calculated. Moreover, an enrichment of
fluoroalkyl chains at the copolymer surface was directly verified by measuring contact angles and using
atomic force microscopy.
Fluoroalkylsilyl methacrylate
Polymerization
Surface properties
Water and oil repellency
ß 2015 Elsevier B.V. All rights reserved.
1
. Introduction
Fluoropolymers present a number of peculiar and useful
antifouling [17–20]. Currently, the fluorinated polyacrylates with
various structures, such as graft [21], random [22], hybrid
nanocomposites [23] and core-shell [24–26], have been synthe-
sized by emulsion polymerization, solvent polymerization,
controlled radical polymerization, and other polymerization
methods [27,28].
The hydrophobic and oleophobic properties of fluorinated
polyacrylates depend on the length of fluorocarbon chains and the
packing density of fluoroalkyl tails on the surface [29]. The long
perfluoroalkyl side chains (C > 6) in fluorinated copolymers could
reduce the surface energies as low as 8 mN/m and confer the
optical properties [30], but they have been found to cause a series
of problems, such as bioaccumulation, difficult to decomposition,
and environmental unfriendliness [31,32]. On the other hand,
fluoroalkyl segments show a tendency to separate from the carbon
chains under appropriate temperatures. Consequently, the surface
properties, such as high thermal stability, excellent chemical and
weather resistance, low refractive indices, low coefficient of
friction, high optical clarity, and the interesting water and oil
repellency because of the low polarizability and the strong
electronegativity of the fluorine atom [1–7]. These unique
characteristics have led to a growing interest in fluorine chemistry
for a wide range of applications [8]. Among various fluoropoly-
mers, the fluorinated polyacrylates have attracted increasing
interest from basic and applied polymer research communities.
Because fluorinated polyacrylates exhibit unique properties
including good mechanical behavior, excellent chemical and
thermal stability, low refractive index, predominant hydropho-
bicity and oleophobicity [9–16], they have been used progres-
sively in the fields of fabric finishing, leather, coatings and
3
is uniformly covered with trifluoromethyl (–CF ) groups and the
packing density of fluoroalkyl groups on the outermost surface of
the polymer is higher than that in the internal of the polymer
[33,34].
*
Corresponding author at: Soochow University, College of Textile and Clothing
Indeed, many researchers have reported the synthesis and
properties of fluorinated polyacrylates. Recently, Bertolucci and
Yang independently reported the synthesis and characterization of
Engineering, No. 199 Renai Road, Industry Park, Suzhou, China.
Tel.: +86 512 67061190; fax: +86 512 67246786.
E-mail address: lizhanxiong@suda.edu.cn (Z. Li).
http://dx.doi.org/10.1016/j.jfluchem.2015.07.026
0022-1139/ß 2015 Elsevier B.V. All rights reserved.

1
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L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
the fluoroalkyl acrylate block copolymers [35,36]. Castelvetro’s
group examined the thermal degradation behavior of a nearly
alternating copolymer of vinylidene cyanide with 2,2,2,-trifluor-
oethyl methacrylate [37]. In addition, He’s group disclosed a series
of core-shell fluoroalkylsilyl methacrylate copolymers [25,26].
However, little work has been done on fluorinated polyacrylates
with two or more short fluoroalkyl groups attaching to one
structure unit, which could confer a low surface free energy that is
similar to those of long fluoroalkyl chains, and could be considered
as environmental friendly because the short fluoroalkyl chains are
easy to degrade.
Herein, three novel fluorinated polymethacrylates, namely
mono(1H,1H,2H,2H-tridecafluorooctyl) dimethylsilylpropyl meth-
acrylate (MFSA), bis(1H,1H,2H,2H-tridecafluorooctyl)methylsilyl-
propyl
methacrylate
(BFSA)
and
tris(1H,1H,2H,2H-
tridecafluorooctyl)silylpropyl methacrylate (TFSA), were synthe-
sized via hydrosilylation and Grignard reaction. Subsequently, these
monomers reacted with other acrylic monomers via continuous
emulsion polymerization to obtain corresponding copolymers. The
properties of the copolymer films were examined by using thermal
analysis, contact angle measurement, and atomic force microscopy.
Fig. 1. FT-IR spectra of fluoroalkylsilyl methacrylate monomers: (a) MFSA; (b) BFSA;
(c) TFSA.
indicates that all the monomers have reacted in the polymeriza-
ꢀ
1
tion reaction. Generally, the strong peaks at 1235 cm
and
ꢀ1
2
. Results and discussion
1163 cm are assigned to the stretching absorption of C–F bonds,
which are overlapped with the characteristic absorption peaks
of –COO– at 1240 cm and 1160 cm . Moreover, it can be seen
that absorptions at 1235 cm and 1163 cm become stronger as
the amount of BFSA monomer increased, which indicates the
effective incorporation of bisfluoroalkylsilyl methacrylate into
the copolymers.
The structures of the copolymers were further confirmed by H
NMR and F NMR. Fig. 3 presents the H NMR spectrum of
bisfluoroalkylsilyl methacrylate copolymer with 20% fluorine
1
19
ꢀ1 ꢀ1
2
.1. FT-IR, H NMR and F NMR spectroscopy
ꢀ1
ꢀ1
Three novel fluoroalkylsilyl methacrylate monomers were
synthesized via hydrosilylation and Grignard reaction in two
steps (see Scheme 1). The chemical structures of these newly
synthesized monomers were confirmed by FT-IR. As shown in
Fig. 1, all the monomers exhibit the characteristic absorption
1
1
9
1
ꢀ1
ꢀ1
peaks of –CH
3
stretching vibrations at 2954 cm and 2880 cm
,
and the characteristic absorption peak of C 55 O stretching
content. The proton NMR peaks of C CH
1.68 and 0.64 ppm, and the peak of SiCH is observed at
2
0.07 ppm. However, the peaks of SiCH CH CH are observed
6
F
13CH
2
2
appear at
ꢀ
1
ꢀ1
is
vibration at 1726 cm . The absorption peak at 1636 cm
assigned to the C 55 C bond. The asymmetrical and symmetrical
3
2
2
ꢀ
1
ꢀ1
deformation vibrations at 1457 cm and 1384 cm belong to –
at relatively low field, 4.03, 2.00, and 1.25 ppm, due to the
adjacency to electron-withdrawing ester group. The existence of
all characteristic proton peaks confirms the successful synthesis of
ꢀ1
ꢀ1
CH
3
. The absorption peaks at 1240 cm
and 1160 cm are
corresponding to the stretching vibrations of C–F bond. Since the
chemical structures of fluoroalkylsilyl methacrylate monomers
have been demonstrated, they readily reacted with methyl
methacrylate, butyl acrylate and hydroxyethyl methacrylate via
continuous emulsion polymerization to obtain corresponding
copolymers (see Scheme 2). Here, the FT-IR spectra of the
bisfluoroalkylsilyl methacrylate copolymers with different fluo-
rine contents were discussed as a representative, which could be
seen in Fig. 2. As shown in curves a–f, the strong stretching
19
bisfluoroalkylsilyl methacrylate copolymer. Fig. 4 shows the
F
NMR spectrum of bisfluoroalkylsilyl methacrylate copolymer with
20% fluorine content. The signals of fluorine atoms appear from
ꢀ81.15 ppm to ꢀ126.30 ppm, indicating the successful incorpo-
ration of bisfluoroalkylsilyl methacrylate into the copolymer.
2.2. Particle size and zeta potential analysis
ꢀ
1
vibration of C 55 O appears at 1730 cm . The disappearance of
The effect of fluorine content on the particle size was shown in
Fig. 5. It clearly indicates that the particle sizes of these three
ꢀ
1
characteristic absorption peak of the C 55 C bond at 1636 cm
Scheme 1. Synthetic routes to fluoroalkylsilyl methacrylate monomers.

L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
189
Scheme 2. Synthetic route to fluoroalkylsilyl methacrylate copolymers.
copolymers are increased gradually with the increasing fluorine
content. In addition, at the same fluorine content, the increasing
fluoroalkyl chains enlarge the particle size of copolymer. The
hydrophobic interactions around the particles were enhanced by
the increasing fluorine segments, which induced the aggregation of
particles formed at early stage and led to the particle size
enlargement [38].
Zeta potential is another representation of the emulsion
stability. Fig. 5 shows the effect of fluorine content on the zeta
potential. The data in Fig. 5 are the absolute values of tested zeta
potentials. The results show that the zeta potentials of these
copolymers are decreased with the increasing fluorine content,
indicating that the stability of copolymer emulsion is reduced with
the increasing fluorine content. This result is consistent with the
effect of fluorine content on the particle size.
Fig. 2. FT-IR spectra of bisfluoroalkylsilyl methacrylate copolymers: (a) 0 wt% BFSA;
(b) 4 wt% BFSA; (c) 8 wt% BFSA; (d) 12 wt% BFSA; (e) 16 wt% BFSA; (f) 20 wt% BFSA.
1
9
Fig. 4. F NMR spectrum of bisfluoroalkylsilyl methacrylate copolymer.
1
Fig. 3. H NMR spectrum of bisfluoroalkylsilyl methacrylate copolymer.
Fig. 5. Effect of fluorine content on the particle size and zeta potential.

1
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L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
methacrylate copolymer at initial stage. Next, all the copolymers
with and without fluoroalkylsilyl segments undergo the stage of
rapid weight loss when the temperature is around 360 8C, which is
corresponding to the decomposition of carbon chains. At the
complete decomposition stage, the monofluoroalkylsilyl methac-
rylate copolymers exhibit more residue content compared to the
non-fluorinated polyacrylate. Moreover, the residue content
increases with the increment of fluorine content, and the residue
is about 9.49% when the fluorine content of monofluoroalkylsilyl
methacrylate copolymer is 20%. Evidently, the increased residue
content is caused by the incorporation of fluoroalkylsilyl groups
into the copolymers.
2.4. Contact angle analysis
Many properties of materials are dependent on the surface
structure and on the chemical composition of the outermost
surface layer [39,40]. Fluorinated polymers are well known for
their lower surface free energy. When the surface of a material is
Fig. 6. TGA curves of monofluoroalkylsilyl methacrylate copolymer: (a) 0 wt%
2 3
uniformly covered with CF or CF groups, a very low energy
MFSA; (b) 4 wt% MFSA; (c) 8 wt% MFSA; (d) 12 wt% MFSA; (e) 16 wt% MFSA; (f)
surface can be achieved. In the present work, contact angles were
measured to evaluate the surface properties of fluoroalkylsilyl
methacrylate copolymers. Given the fluoroalkyl chains have the
strong tendency to migrate and segregate under high tempera-
tures, we measured the water and hexadecane contact angles of
fluoroalkylsilyl methacrylate copolymers before and after anneal-
ing and summarized these data in Tables 1 and 2. The results
demonstrate that the water and oil repellency of fluoroalkylsilyl
methacrylate copolymers are improved significantly after anneal-
ing, which confirms the migration of fluoralkyl chains. Moreover,
the trisfluoroalkylsilyl methacrylate copolymer exhibits better
water and oil repellency than monofluoroalkylsilyl methacrylate
copolymer and bisfluoroalkylsilyl methacrylate copolymer at the
same fluorine content, indicating that the incorporation of more
fluorinated segments into the monomer molecule can significantly
improve the water and oil repellency of materials [41]. Comparing
the water and oil repellency of trisfluoroalkylsilyl methacrylate
copolymer before and after annealing, we find that the contact
angle is improved slightly when the fluorine content reaches 20%.
In the trisfluoroalkylsilyl methacrylate copolymer, three fluor-
oalkyl groups are attached to the polymer backbone through a
2
0 wt% MFSA;.
2
.3. Thermal stability analysis
The thermal stability of monofluoroalkylsilyl methacrylate
copolymer was evaluated by using TG analysis under
N
2
atmosphere, and the results were included in Fig. 6. It is widely
accepted that the fluorinated polymer has the better thermal
stability than that without fluorine modification. However, in this
study the thermal stability of monofluoroalkylsilyl methacrylate
copolymer decreases with the increment of fluorine content. As
shown in Fig. 6, at initial stage the copolymers containing
fluoroalkylsilyl segments decompose faster than the copolymer
without fluoroalkylsilyl segments, which is attributed to the
polymers with low molecular weight in the monofluoroalkylsilyl
methacrylate copolymer [1]. The illustration of particle size
distribution in Fig. 6 shows that the distribution of latex particles
broadens with the increasing fluorine content, which indicates
more oligomers (particles with small size) in high fluorine content
and results in the poor thermal stability of monofluoroalkylsilyl
Table 1
Water contact angles of fluoroalkylsilyl methacrylate copolymers before and after annealing.
Fluorine content (%)
Monofluoroalkylsilyl methacrylate
Bisfluoroalkylsilyl methacrylate
Trisfluoroalkylsilyl methacrylate
copolymer (8)
copolymer (8)
copolymer (8)
Before annealing
After annealing
Before annealing
After annealing
Before annealing
After annealing
0
4
8
75.6
81.4
83.0
85.1
88.4
88.5
76.2
102.4
106.4
107.5
108.4
108.7
75.6
83.9
85.1
88.0
90.0
90.1
76.2
103.8
106.3
107.4
107.3
108.3
75.6
85.0
76.2
105.8
108.7
109.3
109.4
109.8
87.2
94.1
99.6
103.4
1
1
2
2
6
0
Table 2
Hexadecane contact angles of fluoroalkylsilyl methacrylate copolymers before and after annealing.
Fluorine content (%)
Monofluoroalkylsilyl methacrylate
Bisfluoroalkylsilyl methacrylate
Trisfluoroalkylsilyl methacrylate
copolymer (8)
copolymer (8)
copolymer (8)
Before annealing
After annealing
Before annealing
After annealing
Before annealing
After annealing
0
4
8
37.2
50.2
55.5
57.5
58.5
60.2
40.3
54.4
56.1
60.2
65.0
66.3
37.2
52.7
57.0
56.7
59.7
60.1
40.3
55.1
58.5
62.9
65.3
68.0
37.2
68.4
69.0
71.7
72.5
75.0
40.3
68.9
69.6
72.5
73.2
76.6
1
1
2
2
6
0

L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
191
silicon atom, which can form a relatively denser fluoroalkyl layer
without annealing. This phenomenon further demonstrates the
benefits of the introduction of more fluorinated segments. With
the data of water and oil contact angles in hands, we calculated the
surface free energies of fluoroalkylsilyl methacrylate copolymers
according to the following equations:
qffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffi
d
d
p
p
r
LVð1 þ cos
u
Þ ¼ 2
r
r
þ 2
r
r
(1)
(2)
SV LV
SV LV
P
d
g
gSV
¼
g
þ
SV
SV
In the equations above, p and d are the polar and dispersion
components of each surface free energy; SV and LV are the
interfacial tension at solid–vapor and liquid–vapor interfaces,
respectively; is the contact angle of water or oil. According to
Eq. (2), the surface free energies of fluoroalkylsilyl methacrylate
copolymers SV can be calculated by the dispersion and polar
components. Herein, water and hexadecane contact angles were
taken as the hydrophobic and oleophobic indexes, respectively.
The surface tension, dispersion and polar components for water are
g
g
u
g
Fig. 7. Surface free energies of fluoroalkylsilyl methacrylate copolymers before and
after annealing.
ꢀ
1
ꢀ1
d
ꢀ1
p
LV
7
2.8 mN m
(
g
LV), 21.8 mN m ðr Þ, 51 mN m ðr Þ, and for
LV
ꢀ1 ꢀ1 ꢀ1
d
LV
hexadecane are 27.6 mN m
(
g
LV), 27.6 mN m ðr Þ, 0 mN m
annealing are significantly lower than those without annealing due
to the segregation of fluoroalkyl chains on the outmost surface
during high-temperature treatment. In addition, three adjacent
fluoroalkyl groups in one structure unit might lead to a more
regular and denser arrangement of fluoroalkyl chains at the surface
of the copolymer. This could be an additional favorable factor for
reducing the surface free energy.
p
LV
ðr Þ. The calculated surface free energies were shown in Fig. 7. The
surface free energy of the fluoroalkylsilyl methacrylate copolymer
is much lower than that of non-fluorinated polyacrylate. Moreover,
the surface free energies of three different fluoroalkylsilyl
methacrylate copolymers are reduced with the increment of
fluorine content, and the surface free energies of copolymers after
Fig. 8. AFM images of films: (a) 3D image of unannealed non-fluorinated polyacrylate film; (b) 3D image of annealed trisfluoroalkylsilyl methacrylate copolymer film;
c) height image of (a); (d) height image of (b).
(

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L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
2.5. Atomic force microscopy analysis
methacrylate copolymer film exhibited an obvious roughness
which was resulted from the segregation of fluoroalkyl chains on
the air-polymer interface, driven by the low surface energy of
fluorinated segments and unfavorable interactions between
fluoroalkyl chains and non-fluorinated acrylates.
Atomic force microscopy is widely used to detect the
morphology of polymer films on a nanometer scale [42]. In this
study, the silica wafer was washed successively with acetone and
methanol for 30 min. Then the non-fluorinated polyacrylate latex
and the trisfluoroalkylsilyl methacrylate copolymer latex with a
fluorine content of 20% were spun on silica wafers and dried for
4. Experimental
1
day at room temperature. Next, the silica wafer with a nanometer
scale of trisfluoroalkylsilyl methacrylate copolymer film was
annealed at 120 8C for 60 min before observation. The morphology
of non-fluorinated polyacrylate film and trisfluoroalkylsilyl
methacrylate copolymer film observed by AFM in tapping mode
was shown in Fig. 8. Picture (a) is the 3D morphology image of
unannealed non-fluorinated polyacrylate film, and picture (b) is
the 3D morphology image of annealed trisfluoroalkylsilyl methac-
rylate copolymer film. Pictures (c) and (d) are the height images of
the pictures (a) and (b), respectively. It can be found that there are
many small but conspicuous protruding nodes in picture (b), which
are corresponding to the bright areas on the picture (d) and result
in a hydrophobic surface with the water contact angle of 109.88.
However, the surface is relatively flat in picture (a), which has a
water contact angle of 75.98. As shown in height images (c) and (d),
the dots in height image (d) is obviously distinguishable from the
dark areas, while they are blurred and inconspicuously separated
from dark areas in picture (c). As we all know, the interaction
between fluoroalkyl chains and silica wafer is stronger than that
between acrylate segments and silica wafer. Moreover, the
fluoroalkyl chains have the inherent properties of migration and
segregation under high temperatures. Therefore, the fluoroalkyl
chains prefer to migrate to the air-polymer interface and occupy
the outmost surface during the annealing process [43,44]. Obvi-
ously, these higher protruding nodes and brighter areas in picture
4.1. Materials
Butyl acrylate (BA, purity ꢁ 98%), methyl methacrylate (MMA,
purity ꢁ 98%), hydroxyethyl methacrylate (HEMA, purity = 96%),
ammonium persulfate (AP, purity ꢁ 99%), sodium dodecyl sulfate
(SDS, purity ꢁ 98%), AEO-9 (purity ꢁ 98%), diethyl ether (Et
2
O,
purity ꢁ 99%), and magnesium sulfate (MgSO
4
, purity ꢁ 99%) were
obtained from Qiangsheng Functional Chemicals Co. Ltd and used
without further purification. Tetrahydrofuran (THF) and toluene
offered by Qiangsheng Functional Chemicals Co. Ltd were purified
by distillation. Chlorodimethylsilane (purity ꢁ 99%), methyldi-
chlorosilane (purity ꢁ 99%), trichlorosilane (purity ꢁ 99%) and
allyl methacrylate (purity = 98%) were purchased from Aladdin
Chemistry Co. Ltd. Karsedt’s catalyst, magnesium turnings and
iodine were supplied by Sinopharm Chemical Co. Ltd.
1H,1H,2H,2H-perfluorooctyl bromide (purity ꢁ 99%) was pur-
chased from Fuxin Heng Tong Fluorine Chemicals Co. Ltd.
4.2. Measurements
FT-IR spectra were obtained using a NICOLET 5700 spectrometer
1
on KBr disks. H NMR was recorded on an INOVA-400 spectrometer
1
3
in CDCl
3
with Me
4
Si as an internal standard. C NMR spectra were
with Me Si as
F NMR was obtained on a Bruker DPX
300 spectrometer in CDCl with CFCl as an internal reference.
recorded on an INOVA-400 spectrometer in CDCl
internal standard.
3
4
1
9
(b) and (d) are generated from the thermal migration of fluoroalkyl
chains, and the darker areas are corresponding to the non-
fluorinated acrylate segments. Consequently, these protruding
nodes not only improve the roughness of annealed trisfluoroalk-
ylsilyl methacrylate copolymer film but also generate a hydropho-
bic surface [45].
3
3
All the chemical shifts were expressed in ppm, and coupling
constants (J) were given in Hz. The particle size and zeta potential
were obtained by using a Mastersizer 2000 particle sizer. Thermal
property was tested on a Diamond TG/DTA5700 thermal analyzer.
Water and oil repellency of the fluoroalkylsilyl methacrylate
copolymers were examined by measuring the contact angles of
water and hexadecane, respectively. The contact angles of water
3
. Conclusions
Three novel fluoroalkylsilyl methacrylate monomers were
drops and hexadecane drops (3 mL) were recorded on an OCA40
successfully synthesized by hydrosilylation and Grignard reac-
tions, and fluoroalkylsilyl methacrylate copolymer latexes were
prepared by continuous emulsion polymerization of these
fluorinated monomers. The structures of fluoroalkylsilyl methac-
rylate monomers and their corresponding copolymers were
Micro at 25 8C. The film surface morphology was measured by
Atomic Force Microscope in tapping mode, and the latex was spun
on silica wafers on a desktop spin coater with a speed of 5000 rpm
for 20 s.
1
13
19
confirmed by FT-IR, H NMR, C NMR and F NMR. The particle
sizes of copolymers were increased with the increment of fluorine
content and the incorporation of more fluoroalkyl segments. In
contrast, the zeta potentials of copolymers were decreased with
the increasing fluorine content. TG analysis of monofluoroalkylsilyl
methacrylate copolymer showed that the fluoroalkylsilyl methac-
rylate copolymer decomposed faster at initial stage due to the
presence of oligomers (particles with small size) in the copolymer.
However, after the complete decomposition, the residue content
was increased with the increment of fluorine content. The data of
contact angles showed that increasing fluorine content and
introduction of more fluoroalkyl segments in one structure unit
could reduce the surface free energy of copolymer. Moreover, it
was demonstrated that the annealing process promoted the
segregation of fluoroalkyl chains and reduced the surface free
energy significantly. AFM analysis of annealed trisfluoroalkylsilyl
methacrylate copolymer film and unannealed non-fluorinated
polyacrylate film revealed that the surface of trisfluoroalkylsilyl
4.3. Synthesis of 3-(chlorodimethylsilyl)propyl methacrylate (1a)
To a 100 mL three-necked round bottle, allyl methacrylate
(6.31 g, 0.05 mol) and 10 mL toluene were added successively. One
drop of Karsedt’s catalyst was added when the temperature of the
reaction system reached 70 8C. Then chlorodimethylsilane (5.67 g,
0.06 mol) in 10 mL toluene was added dropwise. After the addition
was finished, the reaction was kept for another 3 h. Next, the
solvent and unreacted chlorodimethylsilane were removed under
reduced pressure. Colorless liquid, 10.61 g (96% yield). FT-IR (KBr):
2956.4, 2892.7, 1720.0, 1635.4, 1453.1, 1256.3, 1166.7, 1055.7,
ꢀ
1 1
842.3 cm . H NMR (400 MHz, CDCl
5.56 (s, 1H, CHH 55 CCH
), 4.15ꢀ4.12 (t, 3H, J = 12.0 Hz,
SiCH CH CH ), 1.94 (s, 3H, CH 55 CCH ), 1.78 (m, 2H, SiCH CH CH ),
0.88 (m, 2H, SiCH CH CH ), 0.43 (s, 3H, SiCH ). C NMR (100 MHz,
CDCl ): 165.90 (COO), 134.95 (CH 55 C), 123.83 (CH 55 C), 64.88
CH ), 21.01 (SiCH CH ), 16.61 (CH 55 CCH ), 13.50
), 0.90 (SiCH ).
3 3
): d 6.10 (s, 1H, CHH 55 CCH ),
3
2
2
2
2
3
2
2
2
1
3
2
2
2
3
3
d
2
2
(SiCH
(SiCH
2
2
CH
2
2
2
2
2
3
3

L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
193
4
.4. Synthesis of 3-(dichloromethylsilyl)propyl methacrylate (1b)
6.10 (s, 1H, CHH 55 CCH
J = 12.0 Hz, SiCH CH CH
SiCH CH CH ), 1.66 (m, 2H, C
0.65 (m, 2H, C CH ), 0.13 (s, 1H, SiCH
CDCl ): 166.30 (COO), 135.80 (CH 55 C), 124.33 (CH
(SiCH CH CH ), 31.21 (C ), 22.16 (SiCH CH
(CH 55 CCH ), 8.11 (SiCH ), 3.22 (C CH
), ꢀ4.10(SiCH
NMR (300 MHz, CDCl ): ), ꢀ114.06 (2F, CF
ꢀ81.15 (3F, CF
ꢀ116.49 (2F, CF CF CF ), ꢀ122.09 (2F, CF (CF CF ), ꢀ123.60 (2F,
CF (CF CF (CF CF ).
), ꢀ126.30 (2F, CF
3
), 5.52 (s, 1H, CHH 55 CCH
3
), 4.11ꢀ4.08 (t, 3H,
2
2
2
), 1.93 (s, 3H, CH
2 3
55 CCH ), 1.86 (m, 2H,
The synthetic procedure was the same as that used for the
2
2
2
6
F
13CH
2
), 1.16 (m, 2H, SiCH
2
CH
). C NMR (100 MHz,
55 C), 65.12
), 17.61
2 2
CH ),
1
3
synthesis of 3-(chlorodimethylsilyl)propyl methacrylate. Colorless
liquid, 11.70 g (97% yield). FT-IR (KBr): 2959.7, 2931.4, 2891.9,
6
F
13CH
2
2
3
3
d
2
2
ꢀ
1
1
1
(
720.0, 1637.1, 1453.1, 1261.1, 1166.6, 799.0 cm
400 MHz, CDCl ): 6.11 (s, 1H, CHH 55 CCH ), 5.57 (s, 1H,
CH CH ), 1.94
), 1.16 (m, 2H,
). C NMR (100 MHz, CDCl ):
55 C), 124.33 (CH 55 C), 64.63
CH ), 17.30 (CH 55 CCH ), 14.10
.
H NMR
2
2
2
6
F
13CH
2
2
2
1
9
3
d
3
2
3
2
6
F
13CH
2
2
3
).
CF
F
CHH 55 CCH
3
), 4.18ꢀ4.15 (t, 3H, J = 12.0 Hz, SiCH
2
2
2
3
d
3
3
2
),
(s, 3H, CH
2
55 CCH
3
), 1.87 (m, 2H, SiCH
2
CH
2
CH
2
3
2
2
3
2
)
2
2
13
SiCH CH CH
1
2
2
2
), 0.76 (s, 3H, SiCH
3
3
d
3
2
)
3
2
3
2
)
4
2
66.31 (COO), 135.34 (CH
2
2
(SiCH
2
2
CH
2
CH
2
), 20.96 (SiCH
).
2
2
2
3
4.8. Synthesis of tris(1H,1H,2H,2H-tridecafluoroocty)silylpropyl
methacrylate (2c)
(SiCH
), 1.50 (SiCH
3
4
.5. Synthesis of 3-(trichlorosilyl)propyl methacrylate (1c)
The synthetic procedure was the same as that used for the
synthesis of mono(1H,1H,2H,2H-tridecafluorooctyl)dimethylsilyl-
propyl methacrylate. Light yellow liquid, 43.15 g (92% yield). FT-IR
(KBr): 2945.6, 2882.4, 1719.4, 1638.8, 1445.9, 1382.1, 1262.1,
The synthetic procedure was the same as that used for the
synthesis of 3-(chlorodimethylsilyl)propyl methacrylate. Colorless
liquid, 12.56 g (96% yield). FT-IR (KBr): 2958.8, 2929.4, 2895.4,
ꢀ1 1
1240.5, 1205.4, 1160.7, 845.2 cm . H NMR (400 MHz, CDCl
6.10 (s, 1H, CHH 55 CCH ), 5.54 (s, 1H, CHH 55 CCH
), 4.10ꢀ4.07 (t, 3H,
J = 12.0 Hz, SiCH CH CH ), 1.92 (s, 3H, CH 55 CCH ), 1.88 (m, 2H,
SiCH CH CH ), 1.65 (m, 2H, C ), 1.18 (m, 2H, SiCH CH CH ),
0.78 (m, 2H, C ). C NMR (100 MHz, CDCl ): 166.29
(COO), 135.61 (CH CH CH ),
31.68 (C ), 22.21 (SiCH 55 CCH ), 5.60
(SiCH ), 3.01 (C
81.15 (3F, CF
ꢀ122.09 (2F, CF
(2F, CF (CF CF
3
): d
ꢀ
1 1
1
720.1, 1636.4, 1452.9, 1262.1, 1167.1, 1043.8, 815.8 cm
NMR (400 MHz, CDCl ): 6.13 (s, 1H, CHH 55 CCH ), 5.59 (s, 1H,
CHH 55 CCH CH CH ), 1.96 (s,
), 4.22ꢀ4.19 (t, 3H, J = 12.0 Hz, SiCH
H, CH 55 CCH ), 1.90 (m, 2H, SiCH CH CH ), 1.49 (m, 2H,
SiCH CH C NMR (100 MHz, CDCl ): 166.50 (COO),
35.90 (CH 55 C), 124.53 (CH 55 C), 65.01 (SiCH CH CH ), 22.03
SiCH CH ), 17.61 (CH 55 CCH ), 17.08 (SiCH ).
.
H
3
3
3
d
3
2
2
2
2
3
3
2
2
2
2
2
2
6
F
13CH
2
2
2
2
1
3
3
2
3
2
2
2
6
F
13CH
2
CH
55 C), 124.42 (CH
2
3
d
13
2
2
CH
2
).
3
d
2
2
55 C), 65.25 (SiCH
2
2
2
1
(
2
2
2
2
2
6
F
13CH
2
2
CH
2
), 17.73 (CH
2
3
1
9
2
2
2
3
2
2
6
F
13CH
2
CH
2
).
F
NMR (300 MHz, CDCl
), ꢀ116.49 (2F, CF CF
), ꢀ123.60 (2F, CF (CF CF
3
):
CF
d
),
ꢀ
3
), ꢀ114.06 (2F, CF
3
CF
2
3
2
2
4
.6. Synthesis of mono(1H,1H,2H,2H-
3
(CF
).
2
)
2
CF
2
3
2
)
3
2
), ꢀ126.30
tridecafluorooctyl)dimethylsilylpropyl methacrylate (2a)
3
2 4
)
2
To a 250 mL three-necked round bottle, magnesium turnings
3.60 g, 0.15 mol), two grains of iodine and 100 mL THF were added
4.9. Preparation of fluoroalkylsilyl methacrylate copolymer (3a-c)
(
successively under nitrogen atmosphere. Then, 1H,1H,2H,2H-
perfluorooctyl bromide (21.35 g, 0.05 mol) with 30 mL THF was
added dropwise in 2 h at 60 8C and the reaction was kept for
another 1 h after the addition. Next, 3-(chlorodimethylsilyl)propyl
methacrylate (8.80 g, 0.04 mol) in 20 mL THF was added dropwise
to the prepared Grignard reagent solution. The reaction was
continued for 3 h. After the reaction was completed, the reaction
was quenched with 100 mL saturated brine, and extracted three
Emulsion copolymerization was carried out with mixed
monomers of methyl methacrylate, butyl acrylate, hydroxyethyl
methacrylate and fluoroalkylsilyl methacrylate. The detailed
recipes were listed in Table 3. The consumption of emulsifiers
namely SDS and AEO-9 was 1% of the total mass of the monomers,
respectively. The monomers and emulsifiers were preemulsified
for 15 min on an emulsification instrument with a speed of
8000 r/min. After the pre-emulsion was transferred into a 250 mL
three-necked round bottle, the pre-emulsion was stirred and
2
times with 30 mL Et O. The combined organic layers were washed
with saturated brine (3 ꢂ 30 mL) and deionized water (3 ꢂ 30 mL),
dried with magnesium sulfate. The pure product was obtained
after the removal of solvent. Light yellow liquid, 19.59 g (92%
yield). FT-IR (KBr): 2954.8, 2880.4, 1722.1, 1641.0, 1451.8, 1384.0,
2
heated to 70 8C under the N atmosphere. Next, a solution of
ammonium persulfate (AP) in 20 mL deionized water was added
into the pre-emulsion solution within 1 h. The polymerization was
kept for 3 h at 70 8C. Then the latex was filtered to remove the
ꢀ1 1
1
262.1, 1243.2, 1200.1, 1160.1, 840.6 cm
CDCl ): 6.10 (s, 1H, CHH 55 CCH ), 5.55 (s, 1H, CHH 55 CCH
.13ꢀ4.10 (t, 3H, J = 12.0 Hz, SiCH CH CH ), 1.93 (s, 3H,
CH 55 CCH ), 1.85 (m, 2H, SiCH CH CH ), 1.70 (m, 2H, C ),
.17 (m, 2H, SiCH CH CH ), 0.59 (m, 2H, C CH ), 0.11 (s, 1H,
C NMR (100 MHz, CDCl ): 166.40 (COO), 135.86
55 C), 65.01 (SiCH CH CH ), 30.09
CH ), 17.52 (CH 55 CCH ), 10.02 (SiCH
), ꢀ1.90 (SiCH ). F NMR (300 MHz, CDCl ):
CF CF CF
), ꢀ114.40 (2F, CF
), ꢀ123.66 (2F, CF (CF CF
.
H NMR (400 MHz,
3
d
3
3
),
4
2
2
2
Table 3
F
13CH
2
Recipes for the syntheses of fluoroalkylsilyl methacrylate copolymers.
2
3
2
2
2
6
1
SiCH
2
2
2
6
F
13CH
2
2
Fluorine content (%)
0
4
8
12
7.40
16
20
13
3
).
3
d
MFSA (g)
BA (g)
0
2.00
4.42
11.16
16.00
4.00
16.06
16.00
4.00
(
(
CH
C
2
55 C), 124.53 (CH
), 22.03 (SiCH
CH
2
2
2
2
16.00
4.00
1.20
0.13
99.25
0
16.00
4.00
16.00
4.00
16.00
4.00
6
F
13CH
2
2
2
2
3
2
),
d
MMA (g)
HEMA (g)
AP (g)
1
9
3
.91 (C
6
F
13CH
2
2
3
3
1.20
1.20
1.20
1.20
1.20
ꢀ
ꢀ
81.10 (3F, CF
122.04 (2F, CF
(CF CF
3
), ꢀ113.88 (2F, CF
3
2
3
2
2
),
0.14
0.15
0.17
0.19
0.22
Conversion (%)
BFSA (g)
BA (g)
99.05
1.59
16.00
4.00
98.76
3.41
16.00
4.00
98.21
5.60
98.05
8.18
97.89
11.43
16.00
4.00
3
(CF
).
2
)
2
CF
2
3
2
)
3
2
), ꢀ126.17
(2F, CF
3
2 4
)
2
16.00
4.00
1.20
0.13
99.31
0
16.00
4.00
16.00
4.00
MMA (g)
HEMA (g)
AP (g)
4.7. Synthesis of bis(1H,1H,2H,2H-
1.20
1.20
1.20
1.20
1.20
0.14
0.15
0.16
0.18
0.20
tridecafluorooctyl)methylsilylpropyl methacrylate (2b)
Conversion (%)
TFSA (g)
BA (g)
98.86
1.46
16.00
4.00
98.65
3.14
16.00
4.00
98.02
5.09
97.88
7.38
97.62
10.11
16.00
4.00
The synthetic procedure was the same as that used for the
synthesis of mono(1H,1H,2H,2H-tridecafluorooctyl)dimethylsilyl-
propyl methacrylate. Light yellow liquid, 31.47 g (91% yield). FT-IR
16.00
4.00
1.20
0.13
99.26
16.00
4.00
16.00
4.00
MMA (g)
HEMA (g)
AP (g)
1.20
1.20
1.20
1.20
1.20
0.14
0.15
0.16
0.17
0.19
(
1
KBr): 2958.1, 2880.4, 1720.3, 1639.5, 1443.3, 1384.0, 1262.1,
ꢀ
1
1
Conversion (%)
98.35
97.83
97.25
96.33
95.87
240.2, 1209.1, 1160.1, 844.5 cm . H NMR (400 MHz, CDCl ): d
3

1
94
L. Cai, Z. Li / Journal of Fluorine Chemistry 178 (2015) 187–194
[
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3
[
The conversions of all the fluoroalkylsilyl methacrylate
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W
W
2
1
ꢀ W
ꢀ W
0
0
Solid content ðwt%Þ ¼
ꢂ 100%
[
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½
W
3
ꢂ solid content%ꢃ ꢀ W
4
1749–1758.
Conversion ðwt%Þ ¼
ꢂ 100%
2
and W are the
[
[
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W
5
Where W
weight of emulsion before and after drying to a constant weight,
is the total weight of all the materials put in glass reactor in
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0
is the weight of the petri dish, W
1
[
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W
3
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[
[
[
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4
5
volatilize when drying, and W is the total weight of monomers,
respectively.
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(
[
[
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Acknowledgements
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We gratefully acknowledge the financial supports by the
National Natural Science Foundation of China (No. 51273140),
the State Key Laboratory of Disaster Prevention & Mitigation of
Explosion & Impact (No. DPMEIKF 201305), and the Project Funded
by the Priority Academic Program Development of Jiangsu Higher
Education Institutions.
1
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Appendix A. Supplementary data
[
[
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.jfluchem.2015.07.
[
[
[
[
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(
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