Conventional radical polymerization and iodine-transfer polymerization of 4′-nonafluorobutyl styrene: Surface and thermal characterizations of the resulting poly(fluorostyrene)s

Article abstract of DOI:10.1002/pola.26712

4′-Nonafluorobutylstyrene (3) was synthesized and polymerized by conventional and controlled radical polymerization (iodine transfer polymerization (ITP)). Such an aromatic fluoromonomer was prepared from Ullmann coupling between 1-iodoperfluorobutane and

Full text of DOI:10.1002/pola.26712

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Conventional Radical Polymerization and Iodine-Transfer Polymerization
of 40-Nonafluorobutyl styrene: Surface and Thermal Characterizations of
the Resulting Poly(fluorostyrene)s
Flavio Ceretta,1 Alessandro Zaggia,1 Lino Conte,1 Bruno Ameduri2
1
ꢀ
Fluorine Chemistry Laboratory, Dipartimento di Ingegneria Industriale, Universita degli Studi di Padova, 35031 Padova, Italy
2
ꢁ
ꢁ
Ingenierie & Architectures Macromoleculaires, Institut Charles Gerhardt, UMR 5253, ENSCM, Montpellier Cedex 34296, France
Correspondence to: B. Ameduri (E-mail: bruno.ameduri@enscm.fr)
Received 5 February 2013; accepted 22 March 2013; published online 3 May 2013
DOI: 10.1002/pola.26712
ABSTRACT: 40-Nonafluorobutylstyrene (3) was synthesized and
polymerized by conventional and controlled radical polymer-
ization (iodine transfer polymerization (ITP)). Such an aromatic
fluoromonomer was prepared from Ullmann coupling
between 1-iodoperfluorobutane and 4-bromoacetophenone
followed by a reduction and a dehydration in 50% overall
yield. Two radical polymerizations of (3) were initiated by
AIBN either under conventional or controlled conditions, with
1-iodoperfluorohexane in 84% monomer conversion and in
50% yield. ITP of (3) featured a fast monomer conversion and
a linear evolution of the ln([M]0/[M]) versus time. The kinetics
while it worthed 1.15 when synthesized by ITP. Thermal
stabilities of these oligomers were satisfactory (10% weight
loss under air occurred from 305 ꢁC) whereas the melting
point was 47 ꢁC. Contact angles and surface energies
assessed from spin-coated poly(3) films obtained by conven-
tional (hysteresis 5 18ꢁ, surface energy 18 mN.m21) and ITP
21
(hysteresis 5 47ꢁ, surface energy 15 mN.m ) evidenced D
-
values’ influence onto surface properties of the synthesized
C
V
polymers.
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of radical homopolymerization of (3) enabled one to assess
KEYWORDS: degree of polymerization (DP); fluoropolymers; 40-
nonafluorobutyl styrene; gel permeation chromatography
(GPC); heteroatom-containing polymers; iodine transfer poly-
merization; kinetics; living radical polymerization (LRP); NMR
spectroscopy; surface properties; thermal properties
2
its square of the propagation rate to the termination rate (kp
/
kt) in ITP conditions (36.2ꢀ1022 lꢀmol22ꢀsec22 at 80 ꢁC) from
-
the Tobolsky’s kinetic law. Polydispersity index (D) of the fluo-
ropolymer achieved by conventional polymerization was 1.30
for the formation of stable and highly structured crystalline
phases. Conversely, short perfluoroalkyl chain (less than six
perfluorinated carbon atoms) at room temperature form iso-
tropic phases without any structuration and leads to poor
surface properties.3
INTRODUCTION Fluorinated polymers are attractive materi-
als because of their remarkable properties1,2 such as low
polarizability, strong electronegativity, and small Van der
Waals radius of the fluorine atom (1.32 Å). The strength of
CAF bond (its bond dissociation energy, 485 kJ ꢀ mol21
)
implies high thermal and chemical resistance, resistance to
oxidation and hydrolytic decomposition, low flammability,
low reflective index, and low dielectric constants. One of the
more interesting properties achieved by polymers having
high density of CAF bonds is the simultaneous hydro- and
oleophobicity, low wettability, antisticking properties, low ad-
hesion, and low friction coefficient. When long perfluoroalkyl
pendant side chains (more than eight perfluorinated carbon
atoms) are incorporated into a polymer backbone, they self-
assemble into ordered structures and lead to low-energy
surfaces composed of tightly packed ACF3 groups.3–5 The
marked rigidity of long perfluoroalkyl chain is responsible
Because of these outstanding properties and since mid-1950s,
fluoropolymers containing long perfluoroalkyl side chains
have been extensively used in the synthesis of low surface
energy protective coatings of different materials (metals, pa-
per, stone, wood, leather, and textiles, to name a few). In the
last decade, concerns about these compounds have been
underlined because long-chain perfluorinated telomers2 sat-
isfy the defining characteristics of persistent organic pollu-
tants. They are toxic, persistent, and resistant to
degradation.6,7 This arises from the too stable perfluorinated
chain which cannot degrade under enzymatic or metabolic
Additional Supporting Information may be found in the online version of this article.
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decomposition.8 In addition, they bioaccumulate and have
long half-lives in human blood (3.5 years for perfluorooctanoic
acid [PFOA] and 5.4 years for perfluorooctanesulfonic acids).9
This issue pushed the Environmental Protection Agency to
launch the 2010/2015 PFOA Stewardship Program which
aims to the complete elimination of long-chain perfluorochem-
icals by 2015. Consequently, an urging need to find out alter-
natives has become a real challenge.
EXPERIMENTAL
Materials
2,20-Azobisisobutyronitrile (AIBN), tetrahydrofuran (THF),
methanol, acetonitrile, potassium hydrogen sulfate, sodium
borohydride, diiodomethane, and toluene were purchased
from Aldrich Chemical. 1-Iodoperfluorohexane was a gift
from Elf Atochem. 40-Nonafluorobutylacetophenone (1) was
synthesized as in the previously published study56 from
the crosscoupling reaction of 1-iodoperfluorobutane with 40-
bromoacetophenone. Deuterated solvents were purchased at
Eurisop-Top (Grenoble, France). All the solvents and reac-
tants were used with a purity of 98–99%. AIBN was purified
by recrystallization from methanol and dried under vacuum
prior to use.
The hydrophobicity can be attributable to the tightly packed
structure of the fluorinated side chains both in the bulk and
at the surface of the polymer.3–5 Polymers bearing fluori-
nated substituents that contain aromatic groups in the side
chains are able to improve the surface properties by the
enhanced self-assembly behavior of the semifluorinated side
groups containing phenyl rings.10
Characterization
Among polymers, polystyrenes exhibit several advantages
such as satisfactory light transmittance, easy processing, good
transparency, and low cost.11 For these reasons, polystyrenes
can be appropriate candidates for optical device materials, as
evidenced by Boner and Hagemann12 who reported that the Tg
value is higher for a polystyrene that bears an ortho-substi-
Nuclear magnetic resonance (NMR) spectra were recorded
on a Bruker AC 400 instrument, using deuterated chloroform
as the solvent and tetramethylsilane (or CFCl3) as the refer-
1
ence for H (or 19F) nuclei. Coupling constants and chemical
shifts are given in hertz (Hz) and parts per million (ppm),
respectively. The experimental conditions for recording 1H
19
ꢁ
tuted CF3 group (Tg 5 175 C) than those substituted in meta
(Tg 5 63 ꢁC) and para (Tg 5 101 ꢁC) positions.
(or F) NMR spectra were as follows: flip angle: 90ꢁ (or
30ꢁ), acquisition time: 4.5 s (or 0.7 s), pulse delay: 2 s, num-
ber of scans: 128, and pulse width: 5 ms for 19F NMR. In the
details of NMR characterization, s, d, t, q, and m stand for
singlet, doublet, triplet, quinted, and multiplet, respectively.
Regarding the synthetic aspect, the literature reports only
a few examples of fluoroalkyl-substituted styrene mono-
mers13 and most of them have been polymerized by conven-
tional14–16 or controlled17–21 radical polymerization (Table
1). Indeed, controlled radical polymerization (CRP) has
attracted a growing interest owing to the ability of this pro-
cess to control the polymeric structures and architec-
tures,22,23 to predict molar masses, and to get narrow
polydispersities.22–24 Examples of different methods that
lead to the controlled free-radical polymerization are as fol-
lows: (i) nitroxide-mediated radical polymerization
(NMP),25,26 (ii) atom-transfer radical polymerization
(ATRP),27–29 (iii) iodine-transfer polymerization (ITP),30–40
(iv) reversed addition-fragmentation chain transfer,41,42 (v)
macromolecular design by interchange of xanthate,43 and
(vi) organometallic radical polymerization,44,45 including
organocobalt-mediated radical polymerization, based on
(Co(acac)2),46 and CRP controlled by boron derivatives.47–53
The literature reports a few studies on the CRP of fluori-
nated monomers23,31–40,45 compared to those of hydrogen-
ated styrenic and methacrylic monomers. This article aims at
synthesizing a new poly(fluoroalkyl styrene) by controlled
free radical polymerization. To the best of our knowledge,
scarce fluorinated styrene monomers, for example 2,3,4,5,6-
pentafluorostyrene, have been polymerized by radical con-
trolled conditions, either by ATRP17,54,55 or by NMP,19–21
only. However, to the best of our knowledge, no fluorinated
styrene has been polymerized under degenerative transfer.
Hence, this article deals with the synthesis of 40-nonafluoro-
butyl styrene, its radical polymerization under conventional
or controlled conditions (by ITP), and the comparison of the
surface and thermal properties on both the resulting
polymers.
Size exclusion analyses were performed using a Spectra-
Physics apparatus equipped with a set of two PLgel 5 mm
MIXED-C columns from Polymer Laboratories. The eluent
was pure THF at a flow rate of 0.8 mL min21. The calibra-
tion curve was established using monodispersed PS stand-
ards from Polymer Laboratories (now Agilent).
Thermogravimetric analyses (TGAs) were carried out with a
TGA 51 apparatus from TA instruments, under air, at the
21
ꢁ
heating rate of 10 C min from room temperature up to a
ꢁ
maximum of 500 C. The sample size was 15 mg.
GC/MS spectra were measured on a Carlo Erba Instrument
MFC 500/QMD1000 using a silica-fused capillary PS264 col-
umn (30 m 3 0.25 mm) on a Finnigan Mat TSQ7000 (capil-
lary column, 30 m 3 0.32 mm). Typical conditions were as
ꢁ
follows: temperature program is 60 C for 2 min, heating at
21
ꢁ
ꢁ
10 C min up to 280 C. Helium was used as the gas car-
rier (1 mL min21).
Differential scanning calorimetry (DSC) measurements were
conducted using a Pyris 1 apparatus from Perkin-Elmer
Scans were recorded at a heating rate of 20 ꢁC min21 from
2100 to 1150 ꢁC and values of Tg and Tm were assessed
from the second cycle. The sample weight was 10 mg.
The static, advancing, and receding contact angles were
€
assessed using a KRUSS GmbH EasyDrop, Drop Shape Analy-
sis System, with a measuring range of 1–180ꢁ, volume of one
drop of water: 5 mL, volume of one drop of diiodomethane: 2
mL, with a monochrome interline CCD, 25/30 fps camera
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TABLE 1 Methods of Radical Polymerization, Molecular Weights, and Thermal Properties of Several Fluorinated and Fluoroalkyl
styrene-based Polymersa
Monomer
Polymerization
Mn
Mw/Mn
Tg (ꢁC)
Td (ꢁC)
Ref.
CONV.
ATRP
NMP
470,000
11,400
3,500
1.83
1.21
1.03
107
95
–
420
436
–
Lou et al.15
Jankova and Hvilsted17
Remzi et al.19
CONV.
CONV.
CONV.
390,000
59,700
88,800
2.20
3.23
3.00
112
165
160
–
Lou et al.15
Teng et al.16
Teng et al.16
382
366
a
CONV., ATRP, and NMP stand for conventional, atom-transfer radical
polymerization, and nitroxide-mediated polymerization, respectively.
with halogen lamp. The contact angles were determined
using KRUSS DSA1 v1.91 program. The values mentioned in
this article were obtained from the average of 10
measurements.
polymer surface by a syringe until a drop volume of 5 mL
is reached. Then, the test liquid was withdrawn from the
surface until the liquid was completely removed. During
this process, the instrument automatically recorded the
contact angles with a preset speed of 25 frames per sec-
ond. Each frame was then acquired at a specific time which
corresponds to a specific drop volume. This event recorded
by the instrument, which is called “run number,” is associ-
ated to a specific contact angle measurement. Alternatively
to run number, the x-axis could be converted in time and
expressed in seconds.
€
The polymer film obtained for the contact angle assessments
was formed using the spin coater (Karl Suss Technique SA
apparatus, CT60 model). A solution of 20 mg of 40-nonafluor-
obutyl styrene in 2 mL of THF was placed on a 20 mm 3 20
mm 3 1 mm of quartz substrate. The substrate surface was
covered using a pipette and followed by spinning at 1000
rpm for 3 min to spread and form a uniform thin film over
the substrate.
Synthesis of 40-Nonafluorobutyl styrene Monomer (3)
The synthesis of 40-nonafluorobutyl styrene monomer was
achieved in two steps: the reduction of 40-nonafluorobutyl
acetophenone (1) followed by the dehydration of the result-
ing 40-nonafluorobutyl phenylethanol (2) into 40-nonafluoro-
butyl styrene (3) as shown in Scheme 1.
During the static contact angle determination, the size of
the drop did not alter during the measurement. For the
assessments of the advancing angle, the syringe needle
remained in the drop. Advancing and receding contact
angles were determined by the sessile drop method, also
carried out on the same polymer samples using a stainless
steel needle connected with an automatically microliter sy-
ringe (diameter of the needle, 0.5 mm). Further, the differ-
ence between advancing and receding contact angles
represents the hysteresis which is the result of the surface
reorganization and mobility of the outer most atom groups.
The water introduction and its withdrawal were monitored
by a video camera that recorded the profile during the pro-
cess. All calculation methods were based on the sessile
drop method, whereas the surface energies calculation were
assessed by the Owens–Wendt method.57 Further experi-
ments were carried out with the same apparatus as fol-
Synthesis of 40-Nonafluorobutyl phenylethanol (2)
40-Nonafluorobutyl acetophenone (1) (15.5 g, 45.8 mmol),
sodium borohydride (1.802 g, 47.7 mmol), and THF (50 mL)
as the solvent were stirred into a 100-mL round-bottom
flask in an ice bath. Methanol (50 mL) was slowly added
drop-wise into the flask and the mixture was refluxed for 2
h under heating after being stirred for 30 min at room tem-
perature. Then, methanol was removed by distillation. Water
was added to the ether solution and the ether layer was sep-
arated from the aqueous one. The ether was removed by
rotavapor and 14.4 g of colorless oil was distilled (b.p., 60–
ꢁ
65 C/0.2 mmHg; yield, 90%).
lows:
a drop of testing liquid was deposited on the
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SCHEME 1 Synthetic route for the preparation of 40-nonafluorobutyl styrene (3).
1H NMR of 40-nonafluorobutyl phenylethanol (2) (Supporting
Information Fig. S1), d (in CDCl3): 1.48 (d, 3JHH 5 6.0 Hz,
CH3, 3H); 2.29 (s, AOH, 1H); 4.93 (m, CH, 1H); 7.50 (dd,
mol ꢀ L21) of 40-nonafluorobutyl styrene, and 4 mL of aceto-
nitrile. The flask was evacuated and backfilled with argon
for 20 min and five thaw–freeze cycles were applied prior to
the polymerization. The reaction mixture was then placed in
4
3JHH 5 16 Hz, JHH 5 8 Hz, protons form phenyl ring, 4H). 19F
NMR spectrum of 40-nonafluorobutyl phenylethanol (Sup-
porting Information Fig. S2) d: 281.1 (CF3ACF2ACF2
ACF2APh); 2125.7 (CF3ACF2ACF2ACF2APh); 2122.8 (CF3
ACF2ACF2ACF2APh); 2110.8 (CF3ACF2ACF2ACF2APh).
GC–MS (rel. ab. %): 340 ([M]1, 5%); 325 ([M-CH3]1, 70%);
121 ([M-C4F9]1, 15%).
a preheated oil bath at 80 C for 270 min. Then, the solvent
ꢁ
was removed by rotavapor, the residue was solubilized in
minimum of THF, and precipitated from a large excess of
cold methanol. After filtration, the precipitated product was
dried in a vacuum oven at 60 ꢁC for 15 h and 1.00 g (50%
yield) of a white powder was obtained.
ITP of 40-nonafluorobutyl styrene was carried out by using
the same conditions mentioned above. The mixture was com-
posed of 10.1 mg (1.02 3 ꢀ 1022 mol ꢀ L21) of AIBN, 2.002 g
(1.03 mol ꢀ L21) of 40-nonafluorobutyl styrene, 138.0 mg
(5.15 3 ꢀ 1022 mol ꢀ L21) of 1-iodoperfluorohexane, 153.7 mg
(0.26 mol ꢀ L21) of 1,2-dichloroethane, and 4 mL of acetoni-
trile. After bubbling argon for 20 min, five thaw–freeze
cycles were applied andꢁthen the mixture was placed in a
preheated oil bath at 80 C. The same purification procedure
was adopted as mentioned above. For the kinetics, samples
were periodically withdrawn from the medium during the
polymerization to monitor the monomer conversion by 1H
and 19F NMR spectroscopy. The precipitated product was
dried in vacuum oven at 60 ꢁC for 15 h, leading to 1.01 g
Synthesis of 40-Nonafluorobutyl styrene (3)
A mixture composed of 40-nonafluorobutyl phenylethanol (2)
(14.41 g, 42.3 mmol), toluene (50 mL), and potassium
hydrogen sulfate (4.02 g, 29.5 mmol) was heated under stir-
ring at 100 ꢁC for 48 h in a 100-mL round flask connected
to a reflux condenser. The reaction was monitored by GC. Af-
ter reaction, the mixture was distilled under vacuum to led
to 9.35 g of a colorless liquid (b.p., 66–69 ꢁC/0.39 mmHg;
yield, 77%).
1H NMR of 40-nonafluorobutyl styrene (3), d (in CDCl3, Sup-
porting Information Fig. S3): 5.39 (d, cis @CH2, 3JHH 5 10.0
Hz, 1H); 5.87 (trans @CH2, 3JHH 5 17.5 Hz, 1H), 6.71–6.82
3
(dd, JHH 517.5 Hz, 3JHH 5 10 Hz, @CH, 1H); 7.52 (d,
ꢁ
3JHH 5 10.0 Hz, m-protons about C4F9, 2H), 7.56 (2H, d,
3JHH 5 10.0 Hz, o-protons about C4F9). 19F NMR, d (in CDCl3,
Supporting Information Fig. S4): 281.1 (CF3ACF2ACF2A
CF2APh); 2125.7 (CF3ACF2ACF2ACF2APh); 2122.9 (CF3A
CF2ACF2ACF2APh); 2111.0 (CF3ACF2ACF2ACF2APh) (Sup-
porting Information Fig. S4). GC–MS measurement m/z (rel.
ab. %): 322 ([M]1, 20%); 253 ([M-CF3]1, 5%); 153
([M-C3F7]1, 100%).
(yield 50%) of a white powder (Tm 5 47 C, the DSC thermo-
gram is shown in Supporting Information Fig. S9).
RESULTS AND DISCUSSION
Synthesis of 40-Nonafluorobutyl styrene
The preparation of 40-nonafluorobutyl styrene was achieved
into two steps (Scheme 1): (i) first, a reduction of 40-nona-
fluorobutyl acetophenone (1 that was optimized in the previ-
ous study56) in the presence of NaBH4 as the reducing agent,
leading to the formation of alcohol (2); (ii) the dehydration
of the latter, in the presence of KHSO4, enabled us to synthe-
size monomer (3) in good yields (77%).58
Radical Polymerizations of 40-Nonafluorobutyl
styrene (3)
The conventional radical polymerization of 40-nonafluorobu-
tyl styrene was carried out in a 50-mL two-necked round
flask equipped with a magnet bar, a rubber septum, and a
condenser connected to argon source, and containing 10.1
1H (Supporting Information Fig. S3) and 19F (Supporting In-
formation Fig. S4) NMR spectra of 40-nonafluorobutyl styrene
are reported in the Supporting Information material and
mg (1.02 3 ꢀ 1022 mol ꢀ L21
) of AIBN, 1.210 g (1.03
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exclusion chromatography (SEC) (Supporting Information
-
Fig. S8) from which the polydispersity value (D) of 1.3 was
obtained.
Second, the ITP of monomer (3) required both the initiator
and the iodine chain-transfer agent (in the present case, 1-
iodoperfluorohexane was chosen) (Scheme 2).
CRP was carried out in similar experimental conditions as
mentioned above, but with the presence of 1-iodoperfluoro-
hexane as the chain-transfer agent, with [3]0/[C6F13I]0/
[AIBN]0 initial molar ratio of 10:5:1. This reaction was sim-
ply carried out at atmospheric pressure and, after purifica-
tion, the resulting poly(40-nonafluorobutyl styrene) was
characterized by NMR spectroscopy (Supporting Information
Fig. S7) and SEC (Supporting Information Fig. S9).
SCHEME 2 ITP of 40-nonafluorobutyl styrene (3) in the pres-
ence of 1-iodoperfluorohexane as the chain-transfer agent, ini-
tiated by AIBN.
show the characteristic signals assigned to ethylenic (range,
5.39–6.82 ppm) and aromatic protons (7.50–7.58 ppm), and
to CF3 (281.1 ppm) and to C3F7 (from 2126.5 to 2111.1
ppm) groups, respectively.
The average number of monomer units present in the final
polymer was calculated by 19F NMR. In the case of ITP, the
19F NMR spectrum (Fig. 1) of the produced polymer exhibits
an overlapping between the signals assigned to CF2 of the
perfluorobutyl chain, resulting from the monomer units and
the signals of perfluorohexyl group which belongs to the
chain-transfer moiety. However, the CF3 end groups were the
only ones to be distinguished by two different signals: one
peak is centered at 282.14 ppm (signal a) assigned to the
perfluorobutyl chain arising from the pendant styrene,
whereas that the other located at 282.44 ppm (signal m)
attributed to CF3 group results from the perfluorohexyl
group of the chain-transfer agent. Hence, the integrals of
these signals obtained from the 19F NMR spectrum enabled
Radical Polymerization of 40-Nonafluorobutyl styrene (3)
Both the conventional and the controlled free radical poly-
merizations of 40-perfluorobutyl styrene (3) have been inves-
tigated in this article in quasi-similar conditions; except for
the second method that involves C6F13I as the chain-transfer
agent.
First, the conventional radical polymerization was initiated
by AIBN with an initial [3]0/[AIBN]0 molar ratio of 100,
using acetonitrile as the solvent. The resulting poly(40-nona-
fluorobutyl styrene) was characterized by NMR spectroscopy
(Supporting Information Figs. S6 and S7), which shows the
absence of the ethylenic signals of monomer (3), and by size
FIGURE
1
19F NMR spectrum of poly(40-nonafluorobutyl styrene) (4) synthesized by ITP (recorded in d-THF, from
[3]0:[C6F13I]0:[AIBN]0 5 100:5:1).
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and 1.15 (Supporting Information Fig. S8) for the ITP. The
thermal stability of the polymers, assessed by TGA (Fig. 2),
was satisfactory (the 10% weight loss under air was noted
at 305 ꢁC, Table 2) and the melting point (Tm) was 47 ꢁC
(from DSC (Supporting Information Fig. S9)).
Kinetics of ITP of 40-Nonafluorobutyl styrene
The kinetics of radical homopolymerization of monomer (3)
1
by ITP was monitored by H NMR spectroscopy (Fig. 3) from
the calculation of the integrals of the characteristic signals of
40-nonafluorobutyl styrene. 19F NMR spectra are also sup-
plied (Supporting Information Fig. S10) but are not convinc-
ing for that kinetics. Thus, 1H NMR spectroscopy enabled
one to assess the conversion (v) of monomer (3) using 1,2-
dichloroethane as the internal standard (which exhibits a
singlet centered at 3.66 ppm assigned to four equivalent pro-
tons). When the polymerization reaction was carried out in
the presence of acetonitrile as the solvent, the NMR spec-
trum did not exhibit any signals attributed to the polymer
but only those of the monomer, because the polymer precipi-
tated when it was formed. However, these NMR spectra
(Fig. 4) permitted to monitor fluorinated styrene (3) conver-
sion (v) versus time during ITP of 40-nonafluorobutyl
styrene.
FIGURE 2 TGA thermograms of the poly(40-nonafluorobutyl
styrene) (under air) obtained by conventional radical polymer-
ization and ITP of 40-nonafluorobutyl styrene (3).
us to assess the average monomer units in the polymer, as
DPn (eq 1).
DP n
ꢀ
ꢁ
ꢀ
ꢁ
Ð
Ð
Ð
Ð
P
(1)
Styrene CF32
CF3
1
Styrene CF22
CF2
C6F13
C6F13
5
Number of fluorine atoms for each monomer unit ð9Þ
Ð
where CFt stands for the integral of the NMR signal
assigned to CFt in x-unit (monomer or CTA).
40-Nonafluorobutyl styrene conversion (v) is calculated from
eq 2.
x
Subtracting the values of the integrals of signals assigned to
½Mꢂ02½Mꢂ
ꢂÐ
ꢃ
v5
3100
(2)
the fluorinated moiety in the pendant chains Styrene CF3
½Mꢂ0
from the integral of the peaks corresponding to the chain-
ꢂÐ
ꢃ
where [M]0 and [M] represent the initial concentration of
monomer (3) and the monomer concentration at time t,
respectively. Values of v were assessed from the integrals of
the signals of 40-nonafluorobutyl styrene deduced from the
1H NMR spectra (eq 3).
transfer agent
CF3 enabled us to obtain an average
C6F13
DPn value of 8 monomeric units.
-
The values of polydispersity indices (Ds) are 1.30 (Support-
ing Information Fig. S7) for the conventional polymerization
ꢄ
ꢅ
ꢄ
ꢅ
ð
ð
ð
ð
ð
ð
7:4ppmC6H41 6:7ppmCH1 5:8ppmCH2
2
7:4ppmC6H41 6:7ppmCH1 5:8ppmCH2
7:3ppm
6:6ppm
5:3ppm
7:3ppm
6:6ppm
5:3ppm
t50
t
ꢄ
ꢅ
v51003
(3)
ð
ð
ð
7:4ppmC6H41 6:7ppmCH1 5:8ppmCH2
7:3ppm
6:6ppm
5:3ppm
t50
Values of 40-nonafluorobutyl styrene conversion (v) are listed
in Table 3. The maximum of v value was reached at 84% af-
ter 270 min.
TABLE 2 Values of the Average Molecular Weight (Mn), Poly-
-
dispersity Index (D) Assessed by SEC, and Temperature of the
Thermal Stability After 10% Weight Loss (Under Air) of the
Polymer Obtained by Conventional Radical Polymerization and
ITP of 40-Nonafluorobutyl Styrene (3) With
Values of ln([M]0/[M]) versus time are plotted in Figure 4
and show a linear tendency.
[3]0:[C6F13I]0:[AIBN]0 5 100:5:1 Initial Molar Ratio
The mechanism of free radical polymerization59,60 requires
that the polymerization rate to be of first order with respect
to the monomer and of half-order with respect to the initia-
-
Method of radical Polymerization
Mn
D
Td (10%)
Conventional
7,400
7,500
1.30
1.15
305
305
tor concentration. Using the Tobolsky’s equation61
:
Controlled (ITP)
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1
FIGURE 3 H NMR spectra of samples from the CRP of 40-nonafluorobutyl styrene in the presence of C6F13I after 40 (bottom), 60,
120, 180, and 270 min (top) of reaction (recorded in CDCl3).
sffiffiffiffiffiffiffiffiffi
compare kp2/kt values assessed from different surveys
because the results can be influenced by temperature, the
nature of the solvent, and the initiator (as evidenced by the
first three values reported from the polymerization of sty-
rene, Table 4). Monomer (3) was found to exhibit the highest
kp2/kt value with respect to those of the other styrenic
monomers.
ꢄ
ꢅ
t
2kd
½Mꢂ0
½Mꢂ
f ½Iꢂ0
2
ln
52kp
ð12e
Þ
(4)
kdkt
and plotting the experimental values of ln([M]0/[M]) versus
ꢀ
ꢁ
k
2
t
d
12e2
enabled to assess the square of the propagation
rate to the termination rate, kp2/kt, (Fig. 5) from the slope of
the straight line,62 considering the rate of decomposition
of the initiator,63 kd (AIBN in acetonitrile at 80 ꢁC) as
1.25 3 ꢀ 1024 s21, whereas the efficiency of the initiator61 (f)
was 0.6.
Contact Angle Assessment
The surface morphology of the polymers affects their surface
property.68–71 Besides the chemical inertness and the ther-
mal stability, one of the most relevant properties of fluoro-
polymers is the hydro- and oleophobicity1,2,72 which can be
assessed by contact angle measurements between solid and
liquid interfaces. Spontaneous spreading of a solvent (water
and diiodomethane as polar and apolar solvents, respec-
tively) onto the surface of a polymer film has been studied
with the sessile drop method. Three different types of con-
tact angles can be measured: (i) the static contact angle, hs
2
The kp /kt value of 40-nonafluorobutyl styrene obtained is
3.62 3 1022 at 80 C. Table 4 lists the different kp2/kt values
ꢁ
of several styrenic monomers. However, it is difficult to
TABLE 3 Evolution of the 40-Nonafluorobutyl Styrene
Conversion (v) Monitored by 1H NMR Spectroscopy
([3]0:[AIBN]0:[C6F13I] 5 100:1:5 at 80 ꢁC).
Time (min) [M]/[M]0 ln([M]0/[M]) 1 2 exp(2kd 3 t/2) v (%)
0
1.000
0
0
0.0
40
0.9929
0.9200
0.5071
0.2100
0.1514
0.0072
0.0834
0.6790
1.5606
1.8876
0.1393
0.2015
0.3624
0.4908
0.6367
0.7
60
8.0
FIGURE 4 Ln([M]0/[M]) versus time for the CRP of 40-nonafluor-
obutyl styrene (3) in the presence of 1-iodoperfluorohexane
as the chain-transfer agent ([monomer 3]0:[C6F13I]0:[AIBN]0 5
100:5:1) at 80 ꢁC.
120
180
270
49.3
79.0
84.9
3208
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reported by Takahara’s team for a coating made of poly(2-
perfluorooctyl-ethyl acrylate).75 Yet, this latter polymer has
four CF2 units more than poly(40-nonafluorobutyl) styrene.
The total surface energy of poly(40-nonafluorobutyl styrene)
calculated by the Owens and Wendt equation57 synthesized
by conventional radical polymerization is about 18 6 2 mN
m21. Interestingly, the surface energy value of the polymer
obtained by ITP is 15 6 2 mN m21
.
These results underline that ITP process improves not only
-
the D-value but also the hydro- and oleophobicity of the
polymer. Yamaguchi et al.75 compared the surface properties
of
poly(2-perfluorooctyl-ethyl acrylate)
with
broad
-
-
(D 5 1.86) and narrow (D 5 1.05) polydispersity indices syn-
thesized by surface-initiated ATRP on a flat silicon substrate.
These authors found that the contact angle hysteresis
FIGURE 5 Ln([M]0/[M]) versus 1 2 exp(2kd 3 t/2) for the CRP of
40-nonafluorobutyl styrene initiated by AIBN at 80 ꢁC in the
presence of C6F13I (slope 5 2.664).
-
strongly depended on the D-values of such fluoropolymers.
Conversely, no significant difference was noted between
static contact angles assessed on poly(2-perfluorooctyl-ethyl
-
acrylate) with broad and narrow D-values. The difference on
(a drop is produced before the measurements and has a con-
stant volume during the experiment), (ii) the advancing con-
tact angle, ha (the mean of the contact angle measurements
during the advancing of the liquid boundary over a dry clean
surface), and (iii) the receding contact angle, hr (the mean of
the contact angle values determined during the retreating of
the liquid boundary over a previously wetted surface). The
contact angle hysteresis is defined as the difference between
the advancing and the receding angles (Dh 5 ha 2 hr).73,74
-
contact angle hysteresis recorded for low and high D poly-
mers can be probably explained by the different surface ori-
entations of fluorinated chains on the polymer surfaces.
Takahara75 performed GI-WAXD experiments on poly(2-per-
fluorooctyl)ethyl acrylates having low and high D-values.
This study nicely revealed that, in the polymers with high D-
values, the Rf groups formed hexagonal packing states with
a direction normal to the air/polymer interface and thus
reducing the surface free energy. In contrast, the Rf density
-
-
The values of static contact angles were calculated for water
and diiodomethane drops on the surface of a glass spin-coated
with poly(40-nonafluorobutyl styrene) (Fig. 6), to assess the
surface tension of the solid. Measurements were achieved
onto polymeric coatings produced from both conventional
radical polymerization and CRP of 40-nonafluorobutyl styrene
and are listed in Table 5. Poly(40-nonafluorobyutyl styrene)
achieved by CRP displayed a water and diiodomethane static
contact angles of 110 6 1 and 85 6 1ꢁ, respectively, higher
than that obtained by the conventional method that led to
static contact angles of 103 6 1 and 84 6 1ꢁ, respectively.
-
at the outermost surface of the brush with low D would be
high enough to stretch the polymer backbone in the perpen-
dicular direction. As a consequence, Rf groups lay parallel to
the surface and thus decreasing their contribution to the sur-
face energy reduction. Though we did not deeply character-
ize the polymeric layer by SAXS or GI-WAXD techniques, the
-
relationship between D-values and surface-free energy for
poly(40-nonafluorobutyl styrene) is in agreement with that
obtained by Takahara’s team for poly(2-perfluorooctylethyl
acrylate) (Table 6).
Values of advancing and receding water contact angles are
shown in Figure 7 which represents the advancing and
receding contact angle values versus the progressive number
Static contact angles of a surface spin-coated with poly
(40-nonafluorobutyl styrene) are comparable to those
TABLE 4 Values of kp2/kt for Different Styrenic and Fluorinated Styrenic Monomers
Monomer
kp2/kt (L mol21 s21
)
T (ꢁC)
Initiator
Ref.
Styrene
8.37 3 1023
3.84 3 1023
1.11 3 1023
2.96 3 1023
36.20 3 1023
3.40 3 1023
0.29 3 1023
0.17 3 1023
100
80
60
60
80
80
30
30
AIBN
DTBPa
DTBPa
AIBN
AIBN
AIBN
AIBN
AIBN
Tobolsky61
Pryor et al.64
Pryor et al.64
Pryor and Huang65
Styrene
Styrene
Pentafluorostyrene
40-Nonafluorobutyl styrene (3)
Vinylbenzyl chloride
p-Chlorostyrene
p-Methylstyrene
This study
Couture and Ameduri66
Boyer et al.67
Boyer et al.67
a
DTBP stands for di t-butyl peroxide.
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FIGURE 6 Drops of water (left, h 5 110 6 1ꢁ) and diiodomethane (right, h 5 85 6 1ꢁ) deposited on a surface treated with a poly(40-
nonafluorobutyl styrene) polymerized by ITP.
of measurements acquired by the instr0ument (run number).
rene), the mean advancing contact angle (ha) was 102 6 1ꢁ,
whereas the average receding contact angle (hr) was 84 6 1ꢁ
with a hysteresis of 18 6 2ꢁ. Instead, in the case of narrow
with poly(40-nonafluorobutyl styrene) achieved from both
strategies. Values of contact angles evidenced the satisfactory
hydro- and oleophobicity of the synthesized polymers, and
no significant difference was noted for the static contact
angles between the polymer synthesized by both techniques
-
In the case of broad D-value of poly(4 -nonafluorobutyl sty-
D, the mean advancing contact angle (ha) of poly(4 -nona-
fluorobutyl styrene) reached 113 6 1ꢁ, whereas mean reced-
ing contact angle (ha) was 66 6 1ꢁ with an hysteresis of
47 6 2ꢁ. This observation features that water repellency of
poly(40-nonafluorobutyl styrene) is strongly influenced by
with a surface tension of 15 6 2 and 18 6 2 mN ꢀ m21
,
0
-
respectively. Conversely, an increase of the hysteresis in poly-
mer with lower polydispersity (47 6 2ꢁ) compared to those
ꢁ
-
with higher D (18 6 2 ) was observed. These obtained
-
results suggest a strong correlation between D-values and
surface properties of poly(40-nonafluorobutyl styrene). These
preliminary results deserve to be extended to higher-molecu-
lar-weight polymers and to further polymerizations (also in
-
the D-value. Similar to the study reported by other
authors,75,76 the relationship between the aggregation state
of the fluorinated chains and the D-values should deserve to
-
be further investigated.
TABLE 6 Comparison Between the Dynamic Water Contact
Angle Measurements of Poly(40-nonafluorobutylstyrene) and
Poly(2-perfluorooctylethyl acrylate) with Narrow and Broad Pol-
CONCLUSIONS
For the first time, ITP of 40-nonafluorobutyl styrene con-
trolled by 1-iodoperfluorohexane has been reported and
compared to the conventional radical polymerization. As
expected, polymers obtained by ITP displayed more narrow
-
ydispersity (D)
Hysteresisc
(ꢁ)
a
ha (ꢁ)
hrb (ꢁ)
-
D
-
polydispersity index (D 5 1.15) than those synthesized by
-
conventional radical polymerization (D 5 1.30). The thermal
Poly(40-nonafluorobutyl 1.30 102 6 1 84 6 1 18 6 2
stability of the polymers was satisfactory with a 10% weight
loss under air noted at 305 ꢁC. Though the molar masses–
conversion linear relationship was not investigated, the
kinetics of radical homopolymerization enabled to assess the
kp2/kt value (3.62 3 1022 L mol21 s21 at 80 ꢁC). Static
water and diiodomethane contact angles and dynamic water
contact angles were determined from surfaces spin-coated
styrene)
1.15 113 6 1 66 6 1 47 6 2
Poly(2-perfluorooctyl-
ethyl acrylate)74
1.86 128
1.05 115
105
80
23
35
a
ha, advancing contact angle.
hr, receding contact angle.
Hysteresis 5 ha 2 hr.
b
c
TABLE 5 Comparison Between the Static Contact Angle Measurements and Surface Tension of Poly(40-nonafluorobutyl styrene)
and Poly(2-perfluorooctylethyl acrylate)75 with Broad And Narrow D, achieved by Conventional Radical Polymerization and CRP,
-
respectively
Water Contact
Angle (ꢁ)
CH2I2 Contact
Angle (ꢁ)
Polar Part
Dispersive Part
Surface Tension
(mN m21
)
(mN m21
)
(mN m21
)
-
D
Poly(40-nonafluorobutyl styrene)
1.30
1.15
1.86
1.05
103 6 1
110 6 1
122
84 6 1
85 6 1
99
3 6 1
1 6 1
–
15 6 1
18 6 2
15 6 2
7.7
14 6 1
Poly(2-perfluorooctyl-ethyl acrylate)75
–
–
115
103
–
9.4
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FIGURE 7 Advancing and receding water contact angles assessed with water drop on surface spin-coated with poly(40-nonafluoro-
butyl styrene) polymer synthesized by conventional radical polymerization (left) and ITP (right).
11 O. Ziemann, J. Krauser, P. E. Zamgow, W. Daum, Plastic Op-
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13 M. N. Wadekar, F. J. Jager, E. J. R. Sudholter, S. J. Picken,
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14 G. B. Bachman, L. L. Lewis, J. Am. Chem. Soc. 1947, 69,
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