Original fluorinated copolymers achieved by both azide/alkyne 'Click' reaction and hay coupling from tetrafluoroethylene telomers

Article abstract of DOI:10.1021/ma100634q

The synthesis and characterization of an original class of linear poly(alkyl aryl) ethers containing 1,2,3-triazolyl and fluorinated moieties based on oligo(tetrafluoroethylene) telomer are presented. These polymers were prepared, from α,ω-dipropargyl eth

Full text of DOI:10.1021/ma100634q

Macromolecules 2010, 43, 4489–4499 4489
DOI: 10.1021/ma100634q
Original Fluorinated Copolymers Achieved by Both Azide/Alkyne “Click”
Reaction and Hay Coupling from Tetrafluoroethylene Telomers
ꢀ
Aurelien Soules, Bruno Ameduri,* Bernard Boutevin, and Gerard Calleja
ꢀ
ꢀ
Ingenierie et Architectures Macromoleculaires, Institut Charles Gerhardt, UMR 5253 CNRS ENSCM UMI
ꢀ
ꢀ
UMII, Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de lEcole Normale,
34296 Montpellier Cedex 05, France
Received March 23, 2010; Revised Manuscript Received April 8, 2010
ABSTRACT: The synthesis and characterization of an original class of linear poly(alkyl aryl) ethers containing
1,2,3-triazolyl and fluorinated moieties based on oligo(tetrafluoroethylene) telomer are presented. These
polymers were prepared, from R,ω-dipropargyl ether bisphenol AF and 1,10-diazido-1H,1H,2H,2H,9H,9H,
10H,10H-perfluorodecane, in 62% overall yields via the azide/alkyne “click” reaction and/or oxidative coupling
of acetylenes (Hay reaction). The latter reactant was produced from the ethylene end-capping of oligo-
(tetrafluoroethylene) followed by a nucleophilic substitution with sodium azide. A simple tuning of the reaction
conditions allowed us to direct the originally favored “click” reaction toward a competitive homocoupling of the
terminal alkynes, thus leading to copolymers with drastically different structures, as evidenced by size exclusion
chromatography, DSC, Raman, and UV-vis spectroscopy. Hence, original poly(alkyl aryl) ether copolymers
with a high thermal stability (higher than 300 °C) that exhibit alternating statistic or block microstructures were
obtained.
Introduction
dipolar cycloaddition reaction between terminal acetylenes and
azides catalyzed by an organometallic complex. Different mechani-
Over the past decades, fluoropolymers have been attractive in
the development of advanced materials endowed with high
thermal and oxidative stabilities, chemical inertness, and superior
electrical insulating ability for high-tech applications such as thin
film coatings, cladding for optical fibers, membranes for fuel
cells, and separators for lithium ion batteries.1-3 Meanwhile,
efforts have been made to develop thermally curable materials
based on propargyl methacrylate4 and linear polymers of
propargyl derivatives of bisphenol.5-7 Dipropargyl ether of bis-
phenol A and its B-staged materials have been attractive substi-
tutes for epoxy resins involved in advanced composites, adhe-
sives, coatings, and for electronics applications.8-10 In fact, the
obtained resins exhibit thermoset characteristics, excellent ther-
mal stability (around 350 °C), low dielectric constants (ca. 2.77),
and are highly hydrophobic matrices.
Furthermore, it is known that terminal acetylenes that have
propargyl groups are able to undergo an oxidative homocou-
pling.11 One of the main methods to obtain oligo- or polyacetylene
consists in achieving such homocoupling via Hay’s protocole12a,b
(Scheme 1).
This coupling is based on dimerization through oxidation of
copper(I) acetylides species by copper(II). The use of aminated
bidendate ligands such as N,N,N,N0-tetramethylethylenediamine11b
(TMEDA) or 2,20-bipyridine13 (bpy) enables the formation of
copper(I) acetylide species. On the other hand, the ligand creates
a bridge between copper(I) and copper(II) that favors electron
transfer and thus increases the kinetics of the coupling. Indeed,
acetylenic coupling is currently a powerful tool in molecular14 and
macromolecular designs.15
sms of this reaction have been proposed. A recent one was
suggested by Bock et al.,17 who reported that “click” reaction is
a multistep 1,4 regiospecific reaction involving the formation of
complexes of copper(I) acetylide. The kinetics of this reaction18-20
have shown that it was of second order with respect to the copper
concentration when the metal is used in catalytic amounts. Usual
catalytic systems are aromatic and aliphatic aminated ligands.21-25
This methodology has been successfully applied in organic
chemistry,26,27 supramolecular chemistry,28-30 and materials
science,31,32 leading to interesting materials: dendronized poly-
mers,31-34 conjugated polymers,35 or incorporation of 1,2,3-tri-
azole ring into polymers by grafting.36-42 Only a few groups have
studied the incorporation of 1,2,3-triazole ring into the backbone
of linear polymers by polycondensation.43-51
When the respective mechanisms of Hay coupling and “click”
reaction are compared, it appears that in a system where both end-
groups are present, the course of the reaction depends on various
experimental conditions: (i) the presence or lack of oxygen, (ii) the
copper(II) salt concentration, and (iii) the nature of the copper
ligand. Under regular “click” reaction conditions (traces of
oxygen, addition of an appropriate reducing agent, and aliphatic
aminated ligand, such as N,N,N0,N00,N00-pentamethyldiethylene-
triamine), the “click” reaction is much faster than Hay coupling,
and the latter is generally not observed.
Recently, Cummins et al.52a have reported that in the course of
the grafting of polystyrene chains bearing alkyne functions by
“click” reaction onto a surface bearing azide groups the coupling
of these chains via the formation of diacetylenic segments
occurred. Since then, homocoupling (according to Hay’s proto-
col) of the alkyne extremities of a macromolecular polystyrene
synthesized by ATRP has been further confirmed by the same
group.52b
Acetylenic groups have also been involved in various reactions,
and recently Sharpless’ group16 has popularized the azide/alkyne
“click” reaction. This reaction is a variation of the Huisgen 1,3-
This work intends to bring some new insights in the still scarce
examples of competitive Hay coupling and “click” reaction
*Corresponding author: tel 33 467 144 368; fax 33 467 147 220; e-mail
Bruno.ameduri@enscm.fr.
r 2010 American Chemical Society
Published on Web 04/28/2010
pubs.acs.org/Macromolecules

4490 Macromolecules, Vol. 43, No. 10, 2010
Scheme 1. Hay Homocoupling of ω-Acetylenic Derivativesa
Soules et al.
a TMEDA = N,N,N,N0-tetramethylethylenediamine.
provided by the literature. The synthesis and characterization of
an original class of linear poly(alkyl aryl) ethers containing 1,2,3-
triazolyl and fluorinated moieties [based on oligo(tetrafluoro-
ethylene) telomers] is reported. By subtle changes in the reaction
conditions, the copolymerization between a fluorinated telechelic
telomer bearing azido functions and a propargylic oligomer
containing terminal alkynes could be controlled from classic
azide/alkyne “click” addition toward the promotion of a compe-
titive homocoupling of the alkyne end groups, thus leading to
either alternated or blockcopolymers bearing differentfunctional
groups.
n-hexane. The sample was heated from -150 to 220 °C, followed
by a cooling step and then a heating step again. The second runs
led to the Tg values assessed from the inflection point in the heat
capacity jump.
Thermogravimetric analyses were performed under air and
nitrogen on a TGA Q50 apparatus from TA Instruments at a
heating rate of 20 °C/min.
Synthesis of R,ω-Dipropargyl Ether Bisphenol AF (A). To a
flame-dried 250 mL three-neck round-bottom flask were added
propargyl bromide (10.05 g, 53.7 mmol), bisphenol AF (compound
2) (12.80 g, 107.4 mmol), and anhydrous potassium hydroxide
(20.70 g, 150 mmol). The flask was flushed with nitrogen, and then
dried acetone (20 mL) was added via a syringe. The mixture was
stirred at room temperature for 12 h. The resulting solution was
poured into diethyl ether (20 mL). The crude product was recrys-
tallized twice from methanol to give a light yellow powder (11.13 g)
(yield = 50%). FT IR (KBr, cm-1): 2280 (νCtC-H), 1000-
1200 (νC-F). Raman shift (cm-1): 904 (νC-F), 1000-1200
(νaromatic C-H in-plane bend), 1480 (νC-O), 1600 (νring stretch), 2133
cm-1 (νCtC). 1H NMR (400 MHz; d6-acetone): δ (ppm) 3.1
(2 H, t, 4JHH=2.4 Hz), 4.8 (4 H, d, 4J HH=2.3 Hz), 6.8 (4 H, d,
3JHH=8.55 Hz), 7.4 (4 H, d, 3JHH=8.55 Hz). 19F NMR (400 MHz;
d6-acetone): δ (ppm) -63.2 (6 F, m). 13C NMR (400 MHz; d6-
acetone): δ (ppm) 158.8, 132.2, 126.7, 115.4, 100.4, 78.6, 75.4, 56.7.
Synthesis of 1,10-Diiodo-1H,1H,2H,2H,9H,9H,10H,10H-
perfluorodecane (I-C2H4-C6F12-C2H4-I). The batch bis-mono-
addition of R,ω-diiodoperfluorohexane onto ethylene was per-
formed in a 160 mL Hastelloy autoclave Parr system equipped
with a manometer, a rupture disk, inlet and outlet valves, and a
mechanical anchor. An electronic device regulated and con-
trolled both the stirring and the heating of the autoclave. The
autoclave was left closed for 20 min and purged with 30 bar of
nitrogen pressure to prevent any leakage and degassed after-
ward. Then, a 2 mmHg vacuum was operated for 15 min. The
initiator, di-4-tert-butylcyclohexyl peroxydicarbonate (4.22 g,
10 mmol) and 30.13 g (54.2 mmol) of I-C6F12-I in dry tert-
butanol (40 mL) were introduced via a funnel tightly connected
to the introduction valve. Next, ethylene (3.0 g, 0.1 mol) was
introduced by double weighing. The autoclave was heated up to
50 °C for 7 h, and an increase of pressure from 5 to 13 bar was
noted followed by a drop of pressure to 4 bar. Then, the
autoclave was cooled to room temperature and put into an ice
bath. After releasing the unreacted monomer, the autoclave was
opened and tert-butanol was evaporated. The total product
mixture was solubilized in THF and then precipitated from cold
pentane. The fluorinated diiodo product was filtered, washed,
and dried at room temperature under a 20 mmHg vacuum for 24
h, leading to a white powder in 80% yield. FT IR (KBr, cm-1):
1138 (νC-F). 1H NMR (400 MHz, CDCl3): δ (ppm) 3.2 (4 H, t,
3JHH=7.01 Hz), 2.6 (4 H, m). 19F NMR (400 MHz; CDCl3): δ
(ppm) -115.2 (4 F, m), -121.8 (4 F, m), -123.8 (4 F, m).
Synthesis of 1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,10H-per-
fluorodecane (N3-C2H4-C6F12-C2H4-N3) (B). A mixture composed
of 7.80 g (12.8 mmol) of 1,10-diiodo-1H,1H,2H,2H,9H,9H,10H,
10H-perfluorodecane and 2.21 g (30.8 mmol) of sodium azide
dissolved in DMSO (25 mL) and water (1 mL) was stirred at
50 °C for 48 h. Then, the reaction mixture was poured into water
(1 L) and was extracted with diethyl ether. This procedure was
repeated twice. The organic layer was washed with water twice, 10%
sodium sulfite solution twice, water (3 times), brine, then dried over
MgSO4, and filtered. The solvent was evaporated under reduced
pressure to give 3.4 g of a pale green oil. The yield of the fluorinated
diazide was 60%. FT IR (KBr, cm-1): 2100 (νN3), 1000-1200 (νC-F).
1H NMR (400 MHz, CDCl3):δ(ppm) 3.5(4H,t,3JHH =7.07 Hz,),
Experimental Section
Reactants. Di(4-tert-butylcyclohexyl)peroxydicarbonate used
as the initiator was kindly supplied from Akzo Nobel. Dimethyl
sulfoxide (DMSO), tetrahydrofuran (THF), diethyl ether (from
Aldrich), and tert-butanol (Acros Organics, 98%) were distilled
prior to use. 1,6-Diiodoperfluorohexane was purchased from
Daikin. Copper(I) bromide (Acros Organics, 95%) was washed
with glacial acetic acid to remove any soluble oxidized species and
then filtered, washed with ethanol, and dried. Hexafluorobis-
phenol AF, propargyl bromide, sodium azide, Na2SO4, and
2,20-bipyridine (bpy) were purchased from Aldrich.
Analyses and Characterizations. 1H, 13C, and 19F NMR
€
spectra were recorded on a Bruker 400 MHz FT NMR spectro-
meter with either deuterated chloroform or acetone as solvents.
Chemical shifts are reported in ppm relative to tetramethylsilane
(TMS) for 1H and 13C spectra and to CFCl3 for 19F NMR spectra.
Letters s, d, t, and q stand for singlet, doublet, triplet, and quintet,
and the coupling constants are in hertz. Fourier transformed IR
spectra were performed on a Nicolet 510P Fourier spectrometer
with an accuracy of (2 cm-1 using OMNIC software.
The relative viscosity measurements were achieved in a thermo-
stated bath at 35 °C, using a Ubbelohde viscosimeter ref. no. 501
10 equipped with a capillary with an inner diameter of 0.53 mm.
Determination of intrinsic viscosity was based on four reduced
viscosity measurements at concentrations ranging from 0.1 to 0.5
g per 100 mL of acetone.
Size exclusion chromatography was carried out in DMF with
a flow rate of 0.8 mL min-1 and a PL gel Mix column at 30 °C.
Detection was performed using a RI Spectra-Physics detector
SP8430. Analyses were achieved by injection of 20 μL of the
polymer solution (5 mg mL-1) in DMF (polymer dissolved
readily in DMF leading to a clear solution). The molecular
weights and polydispersity indices were assessed using the
Waters Breeze software package. The system was calibrated
by using commercially available monodispersed poly(styrene)
standards from Polymer Laboratories.
The Raman spectra were recorded on a Labram Aramis
HORIBA Jobin Yvon with IR2 option (excitation wavelength
633.5 nm). The microscope lens was a LWD Olympus (X50).
The spectral resolution was 1.6 cm-1
.
The study of the thermal cross-linking of polymer 4 was
performed by means of a Perkin-Elmer UV20 spectrometer with
a scan speed of 480 nm/min. Polymer 4 was dissolved in THF
(2 mg/mL), and the solution was spread on a quartz substrate and
then spin-coated on a Karl Suss Technique SA apparatus (CT60
model) (acceleration of 1000 rpm, a spinning speed of 1500 rpm
for 30 s) to produce thin films (∼1 μm thick) for UV analysis.
Differential scanning calorimetry (DSC) analyses were car-
ried out with a Perkin-Elmer Pyris 1 DSC apparatus under a
nitrogen atmosphere at a heating rate of 20 °C/min. The DSC
system was first calibrated in temperature using indium and

Article
Macromolecules, Vol. 43, No. 10, 2010 4491
2.3 (4 H, m). 19F NMR (400 MHz, CDCl3): δ (ppm) -113.5 (4 F,
m), -121.8 (4 F, m), -123.8 (4 F, m).
Table 1. Experimental Conditions (Variation of Temperature (T),
Reaction Time (t), and [NaN3]0/[IC2H4C6F12C2H4I]0 Initial
Molar Ratio, and Yields of Telechelic N3-C2H4-C6F12-C2H4-N3
Diazido (B))
Synthesis of Poly(1,10-triazolofluorodecane-co-methylene ether
hexafluorobisphenol AF) Copolymer (1). To a 100 mL three-neck
round-bottom flask equipped with a magnetic stirrer were added
copper bromide (57.1 mg, 0.4 mmol) and 2,20-bipyridine (bpy)
(141.7 mg, 0.8 mmol). The flask was sealed with three septa, and
the suspension was purged with dry nitrogen for 60 min. In
experiment 1 (Table 2) 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,
10H-perfluorodecane (2.24 g, 5.10 mmol) and the aromatic
dialkyne (2.03 g, 4.94 mmol) in 20 mL of THF were syringed
through a septum.
The resulting mixture was stirred at room temperature for
48 h. The final mixture was passed through a short silica column
to remove the copper catalyst. The mixture was precipitated
from cold diethyl ether (500 mL). After filtration, the preci-
pitate was dried under vacuum to give 1.5 g of a colorless
gum (yield = 60%). Raman shift (cm-1) (Figure 2a): 904
(νC-F) 1000-1200 (νaromatic C-H in-plane bend), 971, 1253, 1384,
and 1487 (νtriazole ring stretch) 1480 (νC-O), 1600 (νaromatic ring stretch).
1H NMR (400 MHz, d6-acetone): δ (ppm) 3.0 (4 H, m), 4.9 (4 H, t,
3JHH=7.07 Hz), 5.3 (4 H, s), 7.4 (4 H, d, 3JHH =6.90 Hz), 7.2 (4 H,
d, 3J HH = 7.01 Hz), 8.4 (2 H, s). 19F NMR (400 MHz, d6-acetone):
δ (ppm) -63.2 (6 F, s), -113.5 (4 F, m), -121.8 (4 F, m), -124.3
(4 F, m). 13C NMR (400 MHz, d6-acetone): δ (ppm) 159.8, 144.1,
132.2, 126.1, 125.3, 115.3, 62.4, 42.9.
entry
T (°C)
t (h)
[NaN3]0/[IC2H4C6F12C2H4I]0
yield (%)
1
2
3
RT
RT
50
96
96
48
3
6
3
30
40
>95
from propargyl bromide and hexafluorobisphenol AF as
reported by Dirlikov et al.8e and Hay.53 Characteristic features
of monomer (A) were evidenced by Raman and NMR spectro-
scopies. Characteristic band of C-F vibration appeared at
904 cm-1 in the Raman spectrum (Figure S1 in the Supporting
Information). The peaks observed in the 1100-1300 cm-1
range and at 1600 cm-1 were attributed to aromatic C-H in-
plane bend and aromatic ring stretch,54 respectively. An
intense band at 2133 cm-1 characteristic of the triple-bond
vibration of acetylene moieties54 was also noted. Moreover,
the two characteristic signals of the acetylenic carbon atoms
were found in the 13C NMR spectrum at 75.4 and 78.6 ppm
while the aliphatic carbon in the R-position (CH2O) appeared
at 56.7 ppm. The 1H NMR spectrum exhibited the protons in
the ethynyl and CH2O groups as a triplet at 3.1 ppm and a
doublet at 4.8 ppm, respectively.
Synthesis of Poly(bis(ether bisphenol AF) diacetylene) by Hay
Coupling (3). The same mixture of copper bromide (57.1 mg, 0.4
mmol) and 2,20-bipyridine (bpy) (141.7 mg, 0.8 mmol) was
prepared as above and purged with dry nitrogen for 40 min. A
solution of the aromatic dialkyne (A) (0.50 g, 1.21 mmol) in THF
(10 mL) was syringed in the flask. The resulting mixture was stirred
at room temperature for 48 h. The polymer was then precipitated
in 400 mL of methanol. The white powder was filtered, precipitated
from methanol twice, and dried at room temperature under a
1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluoro-
decane (B) was obtained from commercially available R,ω-
diiodoperfluorohexane in two steps: (i) batch bis-monoaddi-
tion of ethylene onto R,ω-diiodoperfluorohexane and (ii)
nucleophilic substitution of iodine atoms of the resulting
1,10-diiodo-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane
in the presence of sodium azide. Step 1 was adapted from the
reaction of Manseri et al.,55 but carrying out the reaction at
50 °C for 8 h with di-4-tert-butylcyclohexyl peroxydicarbonate
as the initiator. This led to 1,10-diiodo-1H,1H,2H,2H,9H,9H,
10H,10H-perfluorodecane (I-C2H4-C6F12-C2H4-I) in 80%
yield. Step 2 was based on Malik et al.56 pioneering synthesis
of fluorinated diazides (yield = 40%). Indeed, the reaction
conditions were optimized to improve the yield. Particularly,
temperature, reaction time, and initial [NaN3]0/[IC2H4C6F12-
C2H4I]0 molar ratio were monitored (Table 1). When the
reaction was carried out with an excess of NaN3 (3 or 6 mol
equiv, entries 1 and 2, Table 1) at room temperature, it
proceeded smoothly and was not complete (30% and 40%
yields, respectively, even after 96 h), suggesting that the
amount of excess NaN3 was not a decisive parameter at room
temperature. Instead, when the reaction was carried out at
50 °C with a 3-fold molar excess of NaN3 with respect to
I-C2H4-C6F12-C2H4-I, it reached completion after 48 h (entry
3, Table 1), yielding, after purification, 60% of 1,10-diazido-
1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (N3-C2H4-
C6F12-C2H4-N3) (B).
20 mmHg vacuum for 24 h (yield=65%). Raman shift (cm-1
)
(Figure 2c): 904 (νC-F), 1000-1200 (νaromatic C-Hin-planebend), 1480
(νC-O), 1600 (νaromatic ring stretch), 2264 (νCtC). 1H NMR (400
MHz, d6-acetone): δ ppm 6.8 (4 H, d, 3JHH=8.55 Hz), 7.4 (4 H,
d, 3JHH=8.55 Hz), 4.8 (4 H, d, 4JHH=2.30 Hz). 19F NMR (400
MHz, d6-acetone): δ (ppm) -63.2 (6 F, m). 13C NMR (400 MHz,
d6-acetone): δ ppm 158.8, 132.2, 126.7, 79.2, 76.0, 71.1, 56.7.
Synthesis of Poly(1,10-triazolofluorodecane-co-methylene ether
hexafluorobisphenol AF) Copolymer Combining “Click” Reaction
and Hay Coupling (4). A 100 mL three-neck round-bottom flask
equipped with a magnetic stirrer was filled with a mixture of
copper(I) bromide (57.1 mg, 0.4 mmol), copper(II) bromide (25.2
mg, 0.2 mmol), and 2,20-bipyridine (bpy) (141.7 mg, 0.8 mmol).
The flask was then sealed with three septa. 1,10-Diazido-
1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (0.53 g, 1.20
mmol) and the aromatic dialkyne (A) (0.50 g, 4.9 mmol) in
20 mL of THF were syringed through a septum. The resulting
mixture was stirred at room temperature for 48 h and then passed
through silica powder to remove the copper catalyst. The mixture
was concentrated and precipitated from cold diethyl ether (500 mL).
After filtration, the precipitate was dried under vacuum to give
The 19F NMR spectrum of telechelic fluorinated diazido
compound (Figure S2 in Supporting Information) revealed
the low-field shift of the multiplet assigned to the difluoro-
methylene adjacent to methylene group from -114.8 to
-113.6 ppm, while the other fluoromethylene signals did
0.5 g of a colorless gum (yield = 50%). Raman shift (cm-1
)
(Figure 2d): 904 (νC-F) 1000-1200 (νaromatic C-H in-plane
bend), 971, 1253, 1384, and 1487 (νtriazole ring stretch) 1480 (νC-O),
1
1600 (νaromaticringstretch), 2264 (νCtC). H NMR (400 MHz, d6-
1
acetone): δ (ppm) 3.0 (4 H, m), 4.9 (4 H, t, 3JHH=7.07 Hz), 5.3 (4
H, s), 7.4 (4 H, d, 3JHH = 6.90 Hz), 7.2 (4 H, d, 3JHH = 7.01 Hz),
8.4 (2 H, s). 19F NMR (400 MHz, d6-acetone): δ (ppm) -63.2(6 F,
s), -113.5 (4 F, m), -121.8 (4 F, m), -124.3 (4 F, m). 13C NMR
(400 MHz, d6-acetone): δ (ppm) 159.8, 144.1, 132.2, 126.1, 125.3,
115.3, 62.4, 42.9.
not shift, as expected. The H NMR spectrum (Figure S3)
showed the low-field shift of the -CH2-X terminal group
from 3.2 ppm (X=I) to 3.4 ppm (X=N3) because of the
higher electron-withdrawing effect of azido group with
respect to that of iodine. Finally, the FT IR spectrum
(Figure S4) showed a strong sharp frequency at 2100 cm-1
,
characteristic of the azide function.56 The other expected
frequencies, corresponding to the C-F vibrations of the
perfluorohexane central group, were observed in the range
Results and Discussion
Monomer Synthesis. Telechelic R,ω-dipropargyl ether hexa-
fluorobisphenol AF (A) was prepared in satisfactory yield
1100-1200 cm-1
.

4492 Macromolecules, Vol. 43, No. 10, 2010
Soules et al.
Table 2. Experimental Conditions, Yields, Molecular Weights, Polydispersity Indices (PDIs), and Intrinsic Viscosities of the Polymers Synthesized
from the Condensation of 1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (B) with r,ω-Dipropargyl Ether Bisphenol AF (A)
expt
A/B/CuBr/bpy (mmol)a
r
atmosphere
yield (%)
Mnb (g/mol)
PDI
[η35 °C ]c (dL g-1
)
1
2
3
4
4.94/5.10/0.40/0.80
1.21/1.20/0.40/0.80
1.20/0.00/0.40/0.80
1.21/1.20/0.40/0.80
0.97d
0.99e
N2/O2 traces
N2/O2 traces
N2/O2 traces
O2
60
65
43
60
37 000
1.8
5.3
1.8
1.8
0.4
0.6
50 000 to >200 000
5000 to 40 000
60 000
0.99e
0.4
a A: nR,ω-dipropargyl ether bisphenol AF; B: n1,10-diazido1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane
.
b Mn assessed by SEC (polystyrene standards). c Intrinsic
viscosity assessed in acetone at 35 °C. d r = A/B. e r = B/A.
Scheme 2. Polycondensation Reaction of Telechelic 1,10-Diazido-
1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (B) with R,ω-Dipro-
pargyl Ether Hexafluorobisphenol AF (A) by the Azide/Alkyne “Click”
Reaction (bpy Stands for 2,20-Bipyridine)
Polycondensation of r,ω-Dipropargyl Ether Hexafluorobi-
sphenol AF (A) with 1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,
10H-perfluorodecane (B). Cummins et al.52a reported that
during the grafting of polystyrene derivative (in a confined
medium) onto a surface by “click” reaction a homocoupling
(Hay coupling) of the terminal alkynes was also observed.
Starting from this statement, we have decided to determine the
required experimental conditions to promote further the homo-
coupling of alkyne moieties in A with the objective to produce a
block copolymer. Hence, it was of interest to investigate a series
of reactions in which the experimental conditions were carefully
selected to favor one reaction with regards to the others
(Table 2).
Figure 1. Size exclusion chromatograms of copolymer 1 (Exp. 1,
Table 2, A/B=0.97) (upper figure) and copolymer 2 (Exp. 2, Table 2,
B/A= 0.99) (lower figure) calibrated with polystyrene standards.
coordination of azide by copper(I) acetylide.25 Here, 2,20-bipyr-
idine was used with the objective to slow down the rate of the
“click” reaction.
Experiments 1 and 2 were focused on the influence of
concentrations of the reactants onto the behavior of the
polycondensation, under quasi-inert atmosphere, by simply
varying the [dipropargyl]0/[diazido]0 A/B molar ratio. Once
the reactions completed, the total product mixtures were
characterized by size exclusion chromatography (SEC). The
SEC chromatograms corresponding to experiments 1 and 2
in Table 2 are presented in Figure 1.
Interestingly, the obtained SEC chromatograms evi-
denced a dependence of the molecular weight distributions
versus A/B molar ratio values. In experiment 1, an excess of B
with respect to A (nR,ω-dipropargyl ether bisphenol AF/n1,10-diazido-
1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane = 0.97) resulted in a
monomodal distribution centered at Mn = 37 000 g/mol
with a polydispersity index=1.8 (in polystyrene standards,
Figure 1-1). The theoretical value of the average degree
of polymerization (DPn) could be assessed by the Flory
equation:
Scheme 2 displays the predicted structure of the product
resulting from the stoichiometric polycondensation by the
azide/alkyne “click” reaction.51 Similar reaction conditions
as those reported by Lutz et al.57a,b were used.
The polycondensation was performed in THF at room
temperature, using 0.4 mmol of CuBr and 0.8 mmol. of 2,20-
bipyridine (bpy). The choice of the bpy ligand was driven by
a recent extensive study from Matyjaszewski’s group,22 who
reported that the nature of aminated ligands induced a neat
effect onto kinetics in the following increasing order of
magnitude: N,N,N0,N00,N00-pentamethyldiethylenetriamine
(PMEDTA) (ꢀ230) > N,N,N0,N00,N000,N000-hexamethyltri-
ethylenetetraamine (HMTETA) (ꢀ55) > tris[(dimethyl-
amino)ethyl]amine (Me6-TREN) (ꢀ20)>2,20:20,600-terpyridine
(tpy) (ꢀ8.6) > tris[(2-pyridyl)methyl]amine (TPMA) (ꢀ1.7)>
no ligand (ꢀ1) > 2,20-bipyridine (bpy) (ꢀ0.43). The increase of
the reaction rate by aminated aliphatic ligands is partially
explained by their strong basic behavior, which is higher than
that of aromatic amines. Indeed, various authors22,23 have noted
an increase of the “click” reaction rate in the presence of a base,
which is assumed to favor the formation of copper(I) acetyl-
ide complexes. Moreover, aliphatic amines are more labile
than ligands derived from pyridine, thus making easier the
1 þ r
DPn
¼
1 þ r - 2pr

Article
Macromolecules, Vol. 43, No. 10, 2010 4493
Scheme 3. Polycondensation Reaction between r,ω-Dipropargyl Ether Hexafluorobisphenol AF (A) and a Slight Excess of Telechelic Fluorinated
Diazido (B) Following the Azide/Alkyne “Click” Reaction Mechanism
where p is the extent of the reaction and r the initial molar
ratio between the reactive functions (with r e 1).
When r = 0.97 and p = 1 (excess of telechelic diazido
compound), i.e. experiment 1 (Table 2), the corresponding
theoretical DPn value is 65. As the average molecular weight
of monomeric unit is 426 g/mol, the resulting theoretical Mn
value for r = 0.97 is 28 000 g/mol,51 which is in close
agreement with the experimental value of 37 000 g/mol. To
confirm the high molecular weight of copolymer 1, the
intrinsic viscosity was assessed in acetone at room tempera-
ture, giving 0.40 dL g-1. This value confirms that “click”
reaction was very efficient, in spite of the excess of B with
respect to A (r=0.97).
However, the correlation of intrinsic viscosity with mole-
cular weight for this original linear polymer could not be
achieved by the Mark and Houwink equation since K and R
parameters have not been reported. In this case, the poly-
condensation seems to proceed via azide/alkyne “click”
reaction as displayed in Scheme 3, and copolymer 1 is
expected to exhibit a microstructure based on alternating
aromatic and fluorinated units, bearing azido end groups.
The 1H and 13C NMR spectra of copolymer 1 were consis-
tent with the proposed structure (Figures S5 and S6 in Support-
ing Information). The triazole ring formation was evidenced by
the presence of characteristic signals at 8.5 ppm (1H NMR) and
Figure 2. Raman spectra of (a) copolymer 1, (b) copolymer 2, (c)
homopolymer 3, and (d) copolymer 4 in the 880-2300 cm-1 range.
at 144.1 and 125.3 ppm (13C NMR).58 Furthermore, strong
low-field shifts of the aliphatic protons were noted for both
precursors in the 1H NMR spectrum. For example, the methy-
lene groups of the fluorinated diazido reactant shifted from
3.6 to 4.9 ppm and from 2.3 to 3.0 ppm in polymer 1. Similarly,
the singlet attributed to the methylene group in CH2O of
reactant A underwent a low-field shift from 4.9 to 5.3 ppm
after copolymerization. Raman spectroscopy provided addi-
tional structural evidences (Figure 2a) with bands at 971, 1253,
1384, and 1487 cm-1 that are characteristic of the triazole ring
stretch.59 No signal assigned to the triple bond vibration of
polymodal distribution covering a wide range of molecular
weights (from 50 000 to more than 200 000 g/mol). The high
molecular weight of copolymer 2 was further confirmed by a
higher intrinsic viscosity value of 0.60 dL g-1 (experiment 2,
Table 2). Here, a strong discrepancy between theoretical and
experimental Mn values is observed. To explain this result, the
reaction pathway depicted in Scheme 4 is proposed. The excess
of A allows some Hay acetylenic homocoupling between the
terminal alkyne groups of the copolymers generated by “click”
reaction. As a result, a high molecular weight copolymer
exhibiting an original microstructure with bridging bisacetylene
segments randomly distributed along the copolymer chain may
be obtained.
acetylene moieties54 was observed at 2133 cm-1
.
In experiment 2, a small excess of R,ω-dipropargyl ether
bisphenol AF (A) was added with respect to 1,10-diazido-
1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (nR,ω-dipro-
pargyl ether bisphenol AF/n1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluoro-
decane=1.01 and r=0.99). The theoretical value of the average
degree of polymerization assessed by the Flory equation
was 199, leading to a theoretical Mn value of 85 000 g/mol.
The SEC chromatogram (Figure 1-2) showed the presence of a
13C NMR spectroscopy analysis (Figure S6 in Supporting
Information) did not allow corroborating this mechanism as
the characteristic peaks of the two diacetylenic carbons at
76.0 and 71.2 ppm were not detected, probably due to the
expected low content of such isolated bridging units with

4494 Macromolecules, Vol. 43, No. 10, 2010
Soules et al.
Scheme 4. Polycondensation Reaction Combining “Click” Reaction (First Step, Major) and Hay Coupling (Second Step, Minor) Starting from r,ω-
Dipropargyl Ether Hexafluorobisphenol AF (A) and 1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (B)
Scheme 5. Synthesis of Poly(bis(ether bisphenol AF) diacetylene) by Hay Coupling of r,ω-Dipropargyl Ether Hexafluorobisphenol AF (A) (bpy =
2,20-Bipyridine)
regards to the high molecular weight of the copolymeric
chains. Also, to evidence the presence of diacetylenic units,
copolymer 2 was characterized by Raman spectroscopy. Besi-
des the signals observed in the 971-1500 cm-1 range and at
1600 cm-1 attributed to triazole ring stretch59 and aromatic
ring stretch,54 respectively, the Raman spectrum (Figure 2b)
showed a signal at 2264 cm-1, which may be assigned to the
triple-bond vibration of diacetylene moieties.60,61 No signal at
2133 cm-1, characteristic of the triple bond of terminal
acetylene,54 was noted.
used for the azide/alkyne “click” reaction in experiments 1
and 2 (Scheme 5).
Homopolymer 3 was isolated as a white fibrous material
and showed excellent solubility in THF. The weight-average
molecular weights as determined by size exclusion chromato-
graphy relative to polystyrene standards ranged from 42 000
to 200 000 g/mol (Figure S7 in Supporting Information).
1
The H and 13C NMR spectra of homopolymer 3 were
consistent with the assigned structure. No residual ethynyl
protons due to unreacted acetylene groups were observed for
the polymer by 1H NMR (Figure S8 in Supporting In-
formation). The 13C NMR spectra also showed that the
terminal ethynyl carbons were converted into diacetylenic
carbons after polymerization. For example, two diacetylenic
To further demonstrate that Hay coupling may indeed
occur in such an oxygen-poor atmosphere, a third reaction
was carried out in the absence of bisazido compound
(experiment 3, Table 2), under conditions similar to those

Article
Macromolecules, Vol. 43, No. 10, 2010 4495
Consumption of the alkyne groups by Hay coupling compe-
titive to the azide-alkyne reaction would result in an evolu-
tion of the original r ratio (excess of alkynes) toward an
excess of azide groups (Scheme 6). As in experiment 1, a
monomodal distribution was observed.
The 13C NMR spectrum (Figure S10 in Supporting In-
formation) of the obtained polycondensate did not provide
evidence for the characteristic signals of diacetylenic car-
bons, suggesting that the size of the diacetylenic segments
were still rather small (m , n).
A strong sharp frequency at 2100 cm-1 was observed in the
FTIR spectrum (Figure S11 in Supporting Information). This
result is consistent with the presence of terminal azide func-
tions, as depicted in Scheme 6. As in the case of copolymer 2,
the Raman spectrum of copolymer 4 (Figure 2d) exhibited the
signal at 2264 cm-1 corresponding to the triple-bond vibration
of diacetylene moieties.
Thermal Properties. In an attempt to provide further
evidence of the formation of blocks in polymer 4 in contrast
to polymers 1 or 2, the thermal behaviors of the four
polymers were investigated by differential scanning calorim-
etry (DSC). The corresponding DSC thermograms are dis-
played in Figure 4.
All polymers were amorphous. Copolymers 1 and 2 clearly
showed only one glass transition temperature centered at 60
and 90 °C, respectively. The 30 °C difference may be ex-
plained by the higher molecular weight distribution of poly-
mer 2. The diacetylene-containing polymer synthesized from
experiment 3 exhibited an exothermic peak close to 183 °C,
which was attributed to thermally activated cross-linking of
diacetylenes, as reported by several authors.62-66
Interestingly, the DSC thermogram of copolymer ob-
tained from experiment 4 exhibited two distinct thermal
transitions centered at 90 and 152 °C. The first transition
(90 °C) was assigned to a glass transition, as in copolymer 2.
The second transition at 152 °C may be attributed to block
that would be composed of diacetylene moieties. To define
the nature of this second block, we performed the thermal
curing at 175 °C of copolymer 4. After 15 min, the polymer
film became insoluble in all organic solvents. Interestingly,
the DSC analysis of cured polymer 4 (Figure 4) evidenced the
presence of one glass transition at 90 °C. The second transi-
tion was not observed. Consequently, this transition could be
attributed to the exothermic cross-linking of diacetylenes
moieties in a poly(aryl) block.
To confirm the thermal cross-linking of diacetylenic moi-
eties in copolymer 4, ultraviolet absorption spectra were
recorded before and after thermal curing. In the UV spec-
trum of the uncured film, the presence of diacetylenes units
was evidenced by an absorption band at 254 nm.66 The
signals observed at 260 and 279 nm were assigned to triazole
ring,67 while no absorption bands in the visible region were
noted.
After heating to 170 °C for 15 min, a new absorption band
appeared in the spectrum as a broad signal centered at
470 nm, while the band at 254 nm vanished. This was
concomitant with a drastic color change from colorless to
dark red, which is known to result from π-delocalization
along the cross-linked diacetylenes network.68
These additional thermal properties are consistent with
the block structure of copolymer 4, as depicted in Scheme 6.
Thermooxidative Stability. Thermal stabilities of copoly-
mer 1 and homopolymer 3 were investigated by thermo-
gravimetric analysis (TGA). The thermal behavior of poly-
(1,10-triazolofluorodecane-co-methylene ether hexafluoro-
bisphenol AF) copolymer 1 was established both under air
(Figure 6a) and under nitrogen atmosphere (Figure 6b).
Figure 3. Size exclusion chromatogram of copolymer 4 (experiment 4,
Table 2).
carbons at 76.0 and 71.1 ppm in the spectrum of homo-
polymer 3 (Figure S9) replaced the two ethynyl carbons at
78.6 and 75.4 ppm which were observed in the spectrum of
monomer A. In the Raman spectrum (Figure 2c), the intense
band corresponding to the triple-bond vibration of diacetyl-
ene moieties was observed at 2264 cm-1 60,61 These results
.
evidence that the Hay coupling reaction could be initiated in
the presence of oxygen traces.
The presence of a band at 2264 cm-1 in the Raman spectra
of both copolymer 2 and homopolymer 3, which is assigned
to diacetylenic moieties, brings evidence that some acetylene
homocoupling occurred during the synthesis of copolymer 2.
The difference of intensity of this characteristic signal
observed between both spectra is representative of the low
content of such isolated bridging units in copolymer 2 with
regards to the high molecular weight of the copolymeric
chains. Hence, it is worth considering that Hay coupling
occurred as a side reaction (Scheme 4, second step) when the
“click” reaction was carried out with an excess of alkyne as in
the case of experiment 2, in agreement with the work of
Cummins et al.52a
Consequently, these first three experiments (Table 2) ena-
bled us to target the experimental conditions (absence of
copper(II) reductive agent, ligand based on pyridine deriva-
tive, and alkyne functions in excess) in which Hay homo-
coupling of terminal alkynes may occur when performing
azide-alkyne “click” reaction.
This led us to implement the synthesis of an original
fluorine-containing poly(alkyl aryl) ether bearing a block
structure by promoting competition between “click” reac-
tion and Hay homocoupling.
Copper(II) salts are known to induce initiation of Hay
coupling by oxidation of copper(I) acetylide species.14 Hence,
experiment 2 was repeated in the presence of oxygen and a
copper(II) salt to favor Hay homocoupling (experiment 4,
Table 2). A small excess of R,ω-dipropargyl ether bisphenol
AF (A) was added with respect to 1,10-diazido-1H,1H,2H,
2H,9H,9H,10H,10H-perfluorodecane (B) (nR,ω-dipropargyl ether
bisphenol AF/n1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane
=
1.01 and r=0.99). The suspension was purged with dry nitrogen
for 10 min (experiment 4, Table 2). Interestingly, the SEC
chromatogram (Figure 3) exhibited a quasi-monomodal distri-
bution centered at Mn = 60 000 g/mol with a polydispersity
index of 1.8 (polystyrene standards), as opposed to the multi-
modal distribution observed in experiment 2. The correspond-
ing value of intrinsic viscosity obtained was 0.43 dL g-1
.
The differences in molecular weight distributions observed
by SEC between polymers 2 and 4 may be considered as an
evidence that the new conditions favored Hay coupling
enough to consume R,ω-dipropargyl ether bisphenol AF
(A) species faster than in the course of the “click” reaction.

4496 Macromolecules, Vol. 43, No. 10, 2010
Soules et al.
Scheme 6. Polycondensation Mechanism Proposed for the Competition between Hay Coupling and “Click” Reactions Starting from r,ω-Dipropargyl
Ether Hexafluorobisphenol AF (A) and 1,10-Diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane (B)
Thermal gravimetric analysis of copolymer 1 obtained under
air (Figure 6a) indicated that these original copolymers had a
good thermooxidative stability with a weight loss starting at
around 270 °C. Two stages were observed in the thermal
decomposition. The first step from 300 to 473 °C corresponded
to a 40 wt % loss and could be attributed to the loss of aliphatic
segments due to the cleavage of the CH2-N bonds, which has
been previously reported to occur at 360 °C, by Hans et al.69

Article
Macromolecules, Vol. 43, No. 10, 2010 4497
Figure 7. TGA thermogram of homopolymer 3 (exp. 3, Table 2) at
20 °C min-1 under air.
much slower and even reached a plateau above 650 °C up to
800 °C, showing a high residue weight (higher than 40%) at
800 °C. Such a difference of degradation rates above 550 °C
between air and nitrogen atmosphere has already been
reported in the case of polytriazole resins by Xue et al.,72
who suggested that the second stage corresponds to a
thermooxidative degradation. Under air, oxygen partici-
pates in the formation of chars at temperatures below
550 °C, which quickly decompose with increasing tempera-
ture. No residue remained at 800 °C (Figure 6a).
Figure 4. DSC thermograms of copolymer 1 (a), copolymer 2 (b),
homopolymer 3 (c), copolymer 4 (d) before thermal curing, and
copolymer 4 (e) after thermal curing (15 min at 170 °C).
The TGA thermogram for homopolymer (experiment 3,
Table 2) under oxygen atmosphere is presented in Figure 7.
As expected, the thermal stability of the homopolymer was
higher than that of copolymer 1, as justified by its aromatic
backbone. A single weight loss was observed (10 wt % loss
reached at about 550 °C) and corresponded to the thermal
full degradation of the polymeric chain.
The results of thermal analysis demonstrated that these
original polymers exhibit high thermooxidative stabilities
under air.
Conclusions
Original fluorinated copolymers containing triazoles and based
on oligo(tetrafluoroethylene) were synthesized by condensation
via azide/alkyne “click” reaction between a telechelic aryl
diyne and a fluorinated telechelic diazido compound. The latter
was synthesized in two steps from the bis(ethylenation) of the
R,ω-diiodo fluorinated telomers followed by a nucleophilic sub-
stitution of iodine atoms by sodium azide. This polycondensation
was simple, clean, occurred in mild conditions, and led to high
yields.
Figure 5. UV spectra of copolymer 4 (exp. 4, Table 2) prior to thermal
curing (dotted line) and after 15 min of thermal curing at 170 °C(solidline).
However, under low oxygen amount and in the absence of
copper(II) reductive agent, the homocoupling of terminal alkynes
in polycondensates obtained by “click” reaction occurred when the
alkyne concentration was higher than that of azide. The presence of
isolated diacetylenic units was demonstrated by the presence of
a signal at 2264 cm-1 in the Raman spectra of the obtained
copolymers. This side reaction enabled us to produce high mole-
cular weight copolymers (>200 000 g/mol) via bridging central
diacetylene units.
Furthermore, in the presence of oxygen, 2,20-bipyridine as
the ligand, and Cu(II) salt, the side reaction was turned into a
competitive reaction leading to the synthesis of block copoly-
mers. Such an original structure was confirmed by both DSC
and UV-vis analyses. The corresponding DSC thermogram
evidenced the presence of an exothermic peak close to 183 °C,
which was attributed to thermally activated cross-linking of
diacetylenes. The polymerization of diacetylenes moieties was
further confirmed by the presence of a broad absorption band
at 470 nm in the UV-vis spectrum of the thermally cured
copolymer.
Figure 6. TGA thermograms of copolymer 1 (Expt 1, Table 2) at 20 °C
min-1 under air (a) and under nitrogen atmosphere (b).
and by Gaur et al.70 Above 473 °C, the degradations of both
aryl moieties71 and of the triazole ring72 were observed, with a
complete decomposition reached at 520 °C.
The thermal degradation trace for copolymer 1 under
nitrogen atmosphere was unchanged between 270 and
410 °C (Figure 6b), confirming that the first stage of the
degradation of the copolymers is only temperature related.
However, from 550 up to 600 °C, the decomposition was

4498 Macromolecules, Vol. 43, No. 10, 2010
Soules et al.
Hence, thanks to the ability of the monomers to undergo either
Hay coupling or “click” reaction, a simple tune of the reaction
conditions allowed us to obtain three drastically different copo-
lymers from a same set of precursors. These new fluorinated
polymers exhibit interesting thermal and thermooxidative stabi-
lities by the presence of the triazole ring, which can withstand
high thermal temperatures (up to 550 °C) under air.
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Supporting Information Available: Raman spectrum of
hexafluorobisphenol AF dipropargyl ether, 1H NMR, 19F
NMR, and infrared spectra of N3C2H4C6F12C2H4N3, H and
13C NMR spectra and SEC chromatogram of homopolymer 3,
and 13C NMR and infrared spectra of copolymer 4. This
material is available free of charge via Internet at http://pubs.
acs.org.
1
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