Halogenoaryl acrylates: Preparation, polymerization and optical properties

Article abstract of DOI:10.1016/S0022-1139(99)00048-2

Perhalogenoaryl and pyridyl acrylates were prepared and their bulk polymerization was studied. Thermal and optical properties of the homo and some copolymers are described. The lightlosses of poly(pentafluorophenyl) acrylate at 1300 and 1500 nm were found

Full text of DOI:10.1016/S0022-1139(99)00048-2

Journal of Fluorine Chemistry 97 (1999) 191±199
Halogenoaryl acrylates: preparation, polymerization
and optical properties
Jean-Claude Blazejewskia, Johannes W. Hofstraatb, Christelle Lequesnea,
Claude Wakselmana,*, Ulfert E. Wiersumb
CNRS-SIRCOB, Universite de Versailles, 45 avenue des Etats-Unis, 78035 Versailles, France
bAKZO NOBEL, Central Research b.v., Velperweg 76, PO Box 9300, 6800 SB Arnhem, The Netherlands
a
Â
Received 17 October 1998; received in revised form 24 November 1998; accepted 25 November 1998
This paper is warmly dedicated to Prof. Yoshiro Kobayashi on the occasion of his 75th birthday
Abstract
Perhalogenoaryl and pyridyl acrylates were prepared and their bulk polymerization was studied. Thermal and optical properties of the
homo and some copolymers are described. The lightlosses of poly(penta¯uorophenyl) acrylate at 1300 and 1500 nm were found to be <0.1
and <0.2 dB/cm, respectively. # 1999 Elsevier Science S.A. All rights reserved.
Keywords: Halogenoaryl acrylates; Fluorine; Acrylates; Esteri®cation; Photonics
1. Introduction
¯uoroalkyl acrylates, methacrylates, and a-¯uoroacrylates
have been studied widely during the last 20 years [3,4].
Although several alternatives to acrylic polymers were
described leading to highly transparent materials: ¯uori-
nated polyimides [5,6] and per¯uorinated polyethers like
CYTOPTM [7,8] and TEFLONTM AF [7,9], these polymers
are usually prepared by solution polymerization and are thus
not suitable for POPCORN technology which require in situ
bulk polymerization.
Recently, we have studied a variety of ¯uorinated mono-
mers which could be used as core raw materials (preliminary
communication [10]). Acrylate derivatives were preferred to
methacrylates and a-¯uoroacrylates; on one hand metha-
crylate derivatives should exhibit lower transparency than
acrylate ones, owing to their higher hydrogen content, and
on the other hand, ¯uoroacryloyl chloride is not commer-
cially available.
However, one major drawback of polyacrylates is their
relatively low glass transition temperature. Therefore, acry-
lates bearing perhalogenoaryl or perhalogenophenyl-hexa-
¯uoroisopropyl residues were prepared. Halogen atoms
were either ¯uorine or chlorine. Using an aryl group as
the residue, instead of commonly used alkyl chains, was
aimed at increasing both the Tg and the refractive index of
the resulting polymers. Actually, the refractive index of the
core material in a light-guiding structure must be slightly
higher than that of the cladding (or substrate), and poly-
The recent large demand for the construction of optical
telecommunication networks has been stimulating intense
development in the ®eld of integrated optics. Organic
polymeric materials offer a versatile medium for the
creation of low-cost optical guided structures [1]. For that
purpose, polyacrylates, especially poly(methylmethacry-
late) (PMMA), have been widely studied because of their
optical clarity, and the availability of a wide range of
monomers. However, the major disadvantage of polymers
is their lack of transparency in the near-infrared region
1.2±1.6 mm, which has been used increasingly for tele-
communication.
When no O±H or N±H bonds are present in the material,
intrinsic lightloss is mainly due to absorption by C±H bonds.
This loss may be reduced to a more acceptable level by
resorting to ¯uorinated compounds.
Within the framework of the European Commission
Program RACE (Project R2010 POPCORN), a low-cost
mass fabrication technique for polymeric passive waveguide
devices has been developed [2]; the formation of the wave-
guide structure involves in situ photopolymerization of the
core monomer. Optical polymeric materials derived from
*Corresponding author. Tel.: +33-01-39-25-44-11; fax: +33-01-39-25-
44-52.
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 0 4 8 - 2

192
J.-C. Blazejewski et al. / Journal of Fluorine Chemistry 97 (1999) 191±199
Scheme 1.
¯uorinated compounds are known to show very low indices
[11]: in the polymers we designed, the index may be tuned
by modulating the relative amounts of ¯uorine and chlorine
atoms borne by the aryl moiety.
situ polymerization of the monomers [10]. The monomers
2a, 3a, 5a, 6a, bearing one or two chlorine atom(s) on the
aryl moiety, consist of mixtures of regioisomers (see Sec-
tion 3 for more details).
Variously substituted poly(perhalogenoaryl acrylates)
were prepared and their optical and thermal properties
investigated.
2.2. Polymerization of the acrylates
Polymerization of the acrylates 1a±7a was performed in
bulk, in conditions as close as possible from the ones used in
the POPCORN technology, in the presence of the photo-
initiator 2-hydroxy-2-methyl-1-phenylpropan-1-one and of
a thermal initiator (AIBN). Table 1 reports the thermal and
optical properties of the homopolymers formed, referred to
as 1b±7b. None of these polyacrylates was found to be
soluble in the following solvents: THF, 1,2,4-trichloroben-
zene, N,N-dimethylacetamide, hexa¯uoroisopropanol, and
2. Results and discussion
2.1. Preparation of the acrylates
Seven substituted acrylates (Scheme 1) were prepared by
acylation of the corresponding phenols with acryloyl chlor-
ide. An hindered pyridine (2,6-lutidine) was used as proton
acceptor in place of pyridine itself in order to prevent the in
Table 1
Physical properties of homopolymers 1b±7b
Acrylate
residue
Monomer
Homopolymer Tg (8C)
derived
TGA results
Refractive indices
First mass loss %
(temperature)
Td (8C)
T80%
(8C)
633 nm
840 nm
1300 nm
1550 nm
1a
2a
3a
4a
5a
6a
7a
1b
2b
3b
4b
5b
6b
7b
64
66
1.4 (1048C)
5.1 (1008C)
9.4 (1118C)
ꢀ1.9a (1028C)
7.2 (1058C)
17.4 (1548C)
9.3 (1818C)
370
370
420
405
400
505
460
n.d.
n.d.
1.48
1.51
1.54
1.49
1.53
n.d.
1.47
1.50
1.53
1.48
1.51
n.d.
1.47
1.49
1.51
1.48
1.51
n.d.
1.47
1.49
1.51
1.47
1.51
n.d.
72
370
80
310
72
300
94
350
118
>380
1.44
1.43
1.43
1.43
a Because of static charges, the actual mass of this sample could not be measured accurately. The mass loss given is approximate. n.d.: not determined.

J.-C. Blazejewski et al. / Journal of Fluorine Chemistry 97 (1999) 191±199
193
cresol. Therefore, they could not be submitted to size
2.4. Refractive indices
exclusion chromatography analysis and we were not able
to determine the molecular weight distribution. This inso-
lubility was ascribed to crosslinking occurring during the
bulk polymerization and may be an advantage for the
application considered.
The refractive indices of the various polyacrylates at 633,
840, 1300 and 1550 nm are listed in Table 1. These wave-
lengths are commonly used in telecommunications. As one
can see, substitution by chlorine atoms causes the index to
increase; a tendency consistent with that predicted by theory
[12]. Indeed, chlorine is more polarizable than ¯uorine, and
the refractive index of a polymer is highly dependent on the
polarizability of each of its constituents [13]. For the same
reason, the indices of our polyacrylates 1b±7b are greater
than those of poly(poly¯uoroalkylacrylates), which are
generally below 1.4 [14]. Once more, this is to be attributed
to the higher polarizability of the aryl group, compared to
alkyl chains.
Currently, the polymeric substrate in use in POPCORN
industrial process consists of PMMA; the index of this
polymer is approximately 1.48. In order to achieve proper
single mode light-guiding inside the core material, the index
of the latter must be chosen to be a little greater than that of
the cladding, and the difference between the two be approxi-
mately 0.005. For this reason, we prepared copolymers of 1a
and 2a of various compositions. The indices of these two
monomers looked particularly attractive. The variation of
the index along with the composition of the copolymer for
the four telecommunication wavelengths is shown in Fig. 1.
As we can see, the index of the copolymer may be precisely
tuned, and a value of 1.485 is readily attainable.
2.3. Thermal properties of the polyacrylates
The results from TGA and DSC analyses of homopoly-
mers 1b±7b are gathered in Table 1. In order to characterize
the materials in the very state as they would be formed in the
waveguide (in situ polymerization), the analyses were per-
formed on the crude polymers, with no preliminary drying
treatment. The TGA thermograms of all polyacrylates
showed the same sigmoidal shape. A ®rst small weight loss
at low temperature is registered which was ascribed to the
evaporation of volatile compounds present in the material;
predominantly residual monomer. At higher temperatures,
the actual decomposition occurs. Temperatures at the max-
imum of decomposition (Td) and temperatures of 80%
decomposition (T80%) are reported. One can point out that
the polyacrylates studied show good thermal stability, as
degradation takes place only at high temperatures, and in a
dramatic way. At 6008C, there still remains a residue of
about 15%.
The glass transition temperatures of the various poly-
acrylates were measured at the maximum of the transition
on the second DSC heating runs. No other thermal transition
is to be seen on those thermograms. We checked that Tg
measured is the actual one by submitting 6b to further
heating/cooling cycles, thus Tg's of 968C, 1008C and
1008C were obtained respectively for the second, the third
and the fourth DSC heating runs. It is worth noting that
thermogravimetric analyses show that there is no degrada-
tion of the materials below 2008C. Therefore, submitting
them to several DSC heating/cooling runs up to 2008C is
actually consistent.
From the various experimental thermal data, a few obser-
vations may be highlighted. Replacing the phenyl moiety of
the polyacrylates by a pyridyl group results in an enhance-
ment of the glass transition temperature. On the other hand,
this substitution leads to a general decrease of the thermal
stability (Td), although the degradation is slower, as shown
by the value of T80%. The in¯uence of the aryl moiety on Tg
may be ascribed to the increase of the polarity, and therefore
of dipole±dipole interactions, which the introduction of
nitrogen atoms leads to. The substitution by chlorine atoms
in general induces Tg (5b is the exception) and the amount of
volatile residue to increase. Not surprisingly, the highest Tg
registered is that of 7b, which can be attributed to the steric
hindrance both CF3 groups give rise to, which lowers the
¯exibility of the polymer. As expected, the glass transition
temperatures registered are much higher than those of more
known poly(poly¯uoroalkylacrylates), which are generally
below 08C.
2.5. Transparency
Fig. 2 shows the general shape of the attenuation spectra
in the near-infrared region (1200±1600 nm) of the poly-
acrylates 1b±7b, recorded by near-IR spectrometry. The
experimental conditions brought about a baseline shift
towards higher lightlosses: the walls of the quartz cuvette
partly re¯ected the incident light, and shrinkage of the
material occurred during the polymerization, causing air
to enter the cuvette. These effects were not compensated for.
The vertical scale was arbitrarily set to zero in the region of
minimal attenuation. As one can see, the wavelengths
important for telecommunications (i.e., 1300 and
1550 nm) are located in the valleys of the spectrum.
Fig. 1. Variation of the refractive index of copolymers of 1a and 2a versus
compositions at various wavelengths.

194
J.-C. Blazejewski et al. / Journal of Fluorine Chemistry 97 (1999) 191±199
Fig. 2. IR absorption spectrum of polymer 2b in the 1200±1600 nm region.
The lightloss of a block of 1b was determined more
zene (85/15), dichlorotri¯uorophenol was obtained as a
mixture of 2,4 (80%), 3,4 (11%), 2,6 (6%) and 2,3 (3%)
isomers.
Chlorotri¯uoropyridinol was obtained, from a commer-
cially available (Aldrich) mixture (90/10) of 3-chloro and 4-
chlorotetra¯uoropyridine, as a mixture of the 3-chloro-4-
hydroxy (74%), the 5-chloro-2-hydroxy (13%), the 4-
chloro-2-hydroxy (10%) and the 3-chloro-2-hydroxy (3%)
isomers.
accurately by the cutback method. The values at 1300 and
1550 nm are respectively <0.1 and <0.2 dB/cm. These
results may be compared to the lightlosses of PMMA
measured under the same conditions: respectively 0.3 and
0.8 dB/cm, at the same wavelengths.
3. Experimental
3.1. General
Dichlorodi¯uoropyridinol was obtained from 3,5-
dichlorotri¯uoropyridine as a 65/35 mixture of the 3,5-
dichloro-4-hydroxy and the 3,5-dichloro-2-hydroxy iso-
mers.
Penta¯uorophenyl-hexa¯uoroisopropanol was prepared
by a slight modi®cation of the original procedure [18]
starting from chloropenta¯uorobenzene [19].
1H NMR, 13C NMR and 19F NMR spectra were deter-
mined on a Bruker AC 300 spectrometer, at 300.1, 75.5, and
282.4 MHz, respectively, using CDCl3 as solvent. Chemical
shifts are reported in ꢀ (ppm) from internal TMS (1H and
13C) or from internal CFCl3 19F). Mass spectra were mea-
sured at the mass spectrometry service of the University of
Paris VI.
3.2.2. Preparation of acrylates
IR spectra were obtained on a Perkin-Elmer 1420 spectro-
meter as solutions in CCl4 contained in a sodium chloride
cell. UV spectra were recorded on a Shimadzu UV-160
spectrometer with n-hexane as solvent. Gas chromato-
graphic analyses were performed on a Shimadzu GC-14A
apparatus with SE30 (30%) 25 m fused silica capillary
column. Microanalyses were performed by the analytical
service of the University of Paris VI. Melting points were
measured on a Mettler-FP61 apparatus.
All acrylates studied were synthesized following a pro-
cedure described for 1a in a preceding paper [10]. When the
starting phenol or pyridinol was a mixture of isomers, its
isomeric composition was re¯ected in the product acrylates
Table 2. GLC analysis showed a purity greater than 99.5%.
These monomers may be preserved at low temperature for
several years, when stabilized by 0.1% hydroquinone mono-
benzylether. That antioxidant may be removed prior to
polymerization by a simple short-path distillation at
0.02 mm Hg.
3.2. Synthesis of monomers
3.2.3. NMR spectra
3.2.1. Preparation of phenols and pyridinols
Penta¯uorophenol was purchased from Fluorochem. Phe-
nols [16] and pyridinols [17] not available commercially
were prepared by standard methods: Chlorotetra¯uorophe-
nol was obtained from chloropenta¯uorobenzene as a mix-
ture of 4-chloro (72%), 2-chloro (21%) and 3-chloro (7%)
isomers.
The proton NMR spectra for the acrylic moiety of
monomers 1a±7a were fairly constant with ꢀHa 6.15±
6.25, ꢀHb 6.63±6.78 and ꢀHc 6.28±6.40 ppm, Jab 0.8±
In the same way starting from a commercially available
(Aldrich) mixture of 1,3-and 1,2-dichlorotetra¯uoroben-

Table 2
Isomeric compositions, yields, IR absorptions, analyses, formulas and CIMS of monomers 1a±7a
1
Compound Isomeric composition (%)
Yield (%) IR CCl4 (cm
C=O
)
Found/required (%)
Formula
CIMS (M, %) isobutane
C
H
N
1a
2a
3a
±
86
86
1775
1771
1771
45.45/45.40
42.56/42.46
39.95/39.89
1.41/1.27
1.27/1.19
1.10/1.12
±
±
±
C9H3O2F5
239 (M‡1, 100), 155 (26), 117 (60), 93 (22)
255 (M‡1, 100), 200 (10)
4-Cl (72), 2-Cl (21), 3-Cl (7)
C9H3O2F4Cl
C9H3O2F3Cl2
2,4-Cl (80), 3,4-Cl (11), 2,6-Cl (6), 2,3-Cl (3) 69
271 (M‡1, 100), 270 (100), 216 (15), 187 (20), 152
(10), 133 (10), 117 (30), 69 (10)
4a
5a
±
82
95
1775
1772
44.23/43.46
40.65/40.45
1.33/1.37 6.22/6.33 C8H3O2NF4
222 (M‡1, 2), 221 (M, 0.25), 55 (100) HRMS found
221.009923 (221.0099858)
3-Cl-4-yl (60), 5-Cl-2-yl (23), 4-Cl-2-yl
(14), 3-Cl-2-yl (3)
1.29/1.27 5.95/5.90 C8H3O2NClF3 238 (M‡1, 100)
6a
7a
3,5-Cl-4-yl (63), 3,5-Cl-2-yl (37)
±
83
66
1780
1770
37.95/37.83
37.01/37.13
1.22/1.19 5.44/5.51 C8H3O2NCl2F2 253 (M, 100), 225 (31)
0.79/0.78
±
C12H3O2F11
389 (M‡1, 100), 317 (22)

196
J.-C. Blazejewski et al. / Journal of Fluorine Chemistry 97 (1999) 191±199
1.1, Jac 10.5 and Jbc 17.0±17.2 Hz. 19F NMR parameters
for 1a±6a are given in Table 3; the special case of 7a is
treated below. 13C NMR spectra of the acrylic moiety
were also fairly constant for all monomers, showing
three singlets with ꢀC1 in the range 134.8±136.4, ꢀC2
124.9±125.7, and ꢀC3 160.2±162.1 ppm. Other para-
meters are given in Table 4 for 1a±6a, and below for 7a.
7 spectrophotometer in the transmission mode. The samples
consisted of a 10 mm thick layer between two KBr pellets.
The wave number region 600±2000/cm was used for mon-
itoring the reaction. The absorption peak at about 795/cm,
characteristic of acrylates, was used for monitoring the
reaction [20].
Near-IR analyses were recorded on a Varian Cary 05
spectrophotometer between 600 and 2500 nm. The mono-
meric mixture was allowed to react in a 1 mm thick quartz
cuvette. The evaluation of the conversion was carried out by
following the sharp 1617 nm band [21].
3.2.4. (Pentafluorophenyl)hexafluoroprop-2-yl acrylate, 7a
3.5. Attenuation measurements
The transparency of the polyacrylates was evaluated by
near-IR spectrometry, using the preceding sample, once the
polymerization had ®nished.
This compound was obtained as a solid m.p. 388C;
19F NMR: 71.8 (6F, br. s, F1), 133.2 and 140.1 (2F,
two br. s, F2), 148.7 (1F, tt, JFFˆ21.5 and 5.9, F4), and
160.0 (2F, td, JFFˆ21.5 and 6.5, F3) ppm; 13C NMR:
145.9 (2C, br. d, 1JCFˆ254, C7), 142.8 (1C, dtt, JCFˆ255, 13
and 5, C9), 138.4 (2C, dddd, JCFˆ253, 12, 5 and 2, C8),
121.2 (2C, q, 1JCFˆ289, C5), 103.5 (1C, td, JCFˆ12 and 5,
A more precise measurement was allowed by the cutback
method: a polymer block was prepared, and light was
guided through it. The transmitted power was measured.
Part of the block was cut off and the transmitted power was
measured again. The input and output losses are the same for
both measurements, so their effects may be eliminated by a
simple substraction.
2
C6), and 81.0 (1C, heptet, JCFˆ33, C4) ppm.
3.6. Thermal analyses
3.3. Preparation of polyacrylates
TGA analyses were performed on a Hi-Res TGA 2950
Thermogravimetric Analyser, TA Instruments. The sample
consisted of crude polyacrylates prepared as 40 mm thick
layers on glass wafers, scratched from the substrates, and
put in unsealed sample cups. The temperature scanning was
carried out at 208C/min between 208C and 6008C under an
atmosphere of nitrogen. DSC measurements were done
using an RDC 220 Seiko Instruments, between 308C and
2008C, with a heating/cooling rate of 208C/min under an
atmosphere of nitrogen.
Except for the near-IR analyses, the polyacrylates were
prepared as thin ®lms on various substrates (KBr or glass).
The polymerization initiators used were: 2-hydroxy-2-
methyl-1-phenylpropanone (Darocur 1173TM, Ciba-Geigy),
a photoinitiator, and AIBN (Akzo Nobel), a thermal initia-
tor. The procedure was as follows: a mixture of monomeric
acrylate(s), of 2-hydroxy-2-methyl-1-phenylpropan-1-one
(1%) and of AIBN (0.1%) was spread out by means of a
coating knife under a slight stream of nitrogen. The mono-
mers, whose melting point is over room temperature, were
warmed slightly before being spread in a similar fashion.
The layer was covered with a 12.5 mm thick FEP foil
(DuPont), and then illuminated (UV) for 1 h under a nitro-
gen stream. The UV-lamp was an Hg arc lamp (100 W) set
8 cm away from the sample. A WG360 Schott ®lter was
used in order to remove the energetic wavelengths below
360 nm. After illuminating, the samples were wrapped in
aluminium foil and heated for 2 h in an oven at 858C. In
order to follow up the polymerization reaction, IR samples
were freed from the FEP-foil after UV-irradiation and
covered by a second KBr pellet for analyzing and for the
following heat treatment.
3.7. Measurement of the refractive indices
The refractive indices of the polyacrylates were measured
by preparing 10 mm thick ®lms on the hypotenuse of SF10
glass prisms. The indices were deduced from the critical
angle of re¯ection of a laser beam, determined with a
goniometric set-up. For the homopolymers, that angle
was evaluated by eye, and only three ®gures of the indices
are signi®cant. For the copolymers of 1a and 2a, the angle
was determined by a photodiode and the precision is better:
0.001.
4. Conclusion
3.4. Follow-up of the polymerization reaction
In conclusion, the thermal and optical qualities of the
poly(perhalogenoarylacrylates) we have studied make them
promising candidate materials for the construction of wave-
guiding devices [15].
A qualitative follow-up of the polymerization process
may be carried out just as well by IR as by near-IR spectro-
metries. IR-analyses were performed using a Bio-Rad FTS-

Table 3
19F NMR spectral parameters (282.4 MHz, CDCl3) for monomers 1a±6a
Compound
Isomer
X1
19F NMR ꢀ (ppm), multiplicity, J (Hz)
F1 F2
153.1 d 17.8 162.8 dd 21.6, 17.8
X2
F
X3
F
X4
F
X5
F
F3
158.4 t 21.6
F4
F5
1a
2a
F
=F2
=F1
F
F
Cl
F
F
F
F
F
F
F
152.2 m
141.4 m
±
=F2
=F1
F
Cl
F
131.5 d 7.5
±
136.9 d 21.3
157.6 t 21.4
161.9 td 21.3, 7.5
147.0 d 21.3
Cl
F
±
139.9 dd 7.3, 21.4
156.8 t 21.4
150.8 dd 21.4, 7.3
3a
Cl
Cl
F
F
Cl
F
F
F
F
F
F
±
±
118.2 d 9.0
±
±
135.6 d 20.6
150.5 dd 20.6, 9.0
F
Cl
F
134.2 d 21.7
157.2 t 21.7
=F2
±
Cl
Cl
Cl
F
127.5 d 8.5
152.4 m
±
±
137.1 dd 22.2, 8.5
156.4 t 20.5
146.8 d 22.2
Cl
F
±
132.7 dd 20.5, 5.5
145.4 dd 20.5, 5.0
4a
5a
F
F
=N±
F
F
88.6 m
±
=F2
=F1
Cl
F
F
F
F
=N±
Cl
F
F
F
±
±
±
±
72.7 dd 25.4, 15.2
71.2 dd 24.3, 11.2
87.7 dd 27.2, 21.6
84.2 dd 22.3, 18.2
±
±
87.0 dd 20.4, 15.2
115.4 dd 19.2, 11.2
153.1 dd 25.4, 20.4
=N±
=N±
=N±
F
F
153.8 dd 24.3,19.2
139.6 d 21.6
Cl
F
F
133.0 d 27.2
±
F
Cl
161.2 dd 22.3, 18.2
114.8 t 18.2
±
6a
Cl
=N±
F
F
=N±
Cl
F
F
Cl
Cl
±
70.5 s
69.3 d 14.1
±
±
=F2
94.5 d 14.1
±
±

Table 4
13C NMR spectral parameters (75.5 MHz, CDCl3) of the aromatic carbons for monomers 1a±6a
Compound Isomer
13C NMR ꢀ (ppm), multiplicity, J (Hz)
C2
141.4 dddd 250, 12, 9, 4 137.4 dm 250
X1 X2 X3 X4 X5 C1
C3
C4
C5
C6
1a
2a
F
F
F
F
F
125.0 m
139.6 dtt 253, 13, 4
=C3
=C2
F
F
Cl
F
F
F
F
F
F
F
127.9 tt 14, 3
n.d.
132.7 ddd 14, 4, 2
141.1 dm 235
144.4 dm 239
109.9 tt 19, 2
=C3
=C2
F
Cl
Cl
F
148.0 dq 254, 4
113.2 ddt 18, 5, 2
107.5 ddd 21, 19, 6
146.2 ddt 252, 13,4
138.1 dddd 253, 16, 14, 5 143.8 ddt 254, 13, 5
F
144.6 dddd 250, 13, 5, 3 140.0a dddd 253, 16, 12, 4 139.4a dddd 254, 16, 12, 3 141.7 dddd 253, 12, 5, 3
3a
Cl
Cl
F
F
Cl
F
F
F
F
F
F
135.7 dt 14, 3
140.8 dt 4, 2
113.1 ddd 20, 5, 1
113.9 m
151.2 ddd 249, 4, 3
146.9 ddd 253, 14, 4
117.3 dd 19, 5
109.9 ddd 23, 19, 1
139.1 dt 255, 16
119.8 dt 18, 1
146.6 ddd 253, 14, 4
=C3
141.6 ddd 254, 15, 5
=C2
F
Cl
F
Cl
Cl
Cl
F
127.6 ddd 17, 14, 3 148.3 ddd 251, 4, 3
144.7 ddd 250, 14, 5
139.5 ddd 255, 16, 14
143.2 ddd 256, 15, 4
143.7 ddd 255, 12, 4
Cl
F
133.4 ddd 13, 5, 2
123.5 dd 4, 2
117.7 ddd 18, 5, 1
146.3 ddd 252, 12, 3
4a
5a
F
F
=N±
F
F
139.3, m
136.3 dm 256
143.5 dm 246
±
=C3
=C2
Cl
F
F
F
F
=N±
Cl
F
F
F
147.8 dt 12, 5
141.9 ddd 16, 14, 5
137.5 ddd 16, 13, 4
n.d.
109.0 ddd 36, 8, 2
151.0 ddd 243, 14, 3
152.0 ddd 240, 6, 3
144.7 ddd 243, 15, 3
148.5 ddd 243, 13, 6
147.3 dt 246, 15
136.9 ddd 263, 23, 8
155.9 ddd 266, 13, 6
c.a. 124.5
=N±
=N±
=N±
F
F
±
±
±
105.0 ddd 39, 19, 3
140.9 ddd 265, 31, 2
c.a. 134 ddd n.d., 31, 14
138.1 ddd 262, 13, 7
144.8 ddd 262, 6, 3
Cl
F
F
Cl
F
155.4 ddd 266, 11,
7c.a. 111 m
6a
Cl
F
F
=N±
Cl
F
F
Cl
Cl
156.8 t 4
109.6 m
±
155.0 dd 246, 16
155.7 dd 240, 6
±
=C3
=C2
=N±
150.6 dd 16, 5
104.9 dd 38, 20
136.4 dd 265, 5
110.6 dd 13, 8
a Assignment may be reversed. n.d.: not determined.

J.-C. Blazejewski et al. / Journal of Fluorine Chemistry 97 (1999) 191±199
199
[9] P.R. Resnick, W.H. Buck, Modern Fluoropolymers, J. Scheirs, Wiley,
New York, 1997, p. 397.
Acknowledgements
[10] J.-C. Blazejewski, J.W. Hofstraat, C. Lequesne, C. Wakselman, U.E.
Wiersum, J. Fluorine Chem. 91 (1998) 175.
Â
[11] B. Boutevin, Y. Pietrasanta, Les acrylates et polyacrylates fluores,
This work enters partly in the frame of the European
TMR programme ERB FMRX-CT97.0120, entitled:
``Fluorine As a Unique Tool for Engineering Molecular
Properties''.
 Â
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[12] B. Boutevin, Y. Pietrasanta, G. Rigal, A. Rousseau, Ann. Chim. Fr. 9
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[13] N.J. Mills, Polymer Science, A.D. Jenkins, North Holland, 1972, p.
495.
Â
[14] B. Boutevin, Y. Pietrasanta, Les acrylates et polyacrylates fluores,
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