Synthesis and physicochemical properties of poly(perfluoro-2-trichloromethylisopropyl acrylate)

Article abstract of DOI:10.1134/S0012500816030125

A new acrylic monomer derived from perfluoro-2-trichloromethylisopropanol was synthesized. Poly(perfluoro-2-trichloromethylisopropyl acrylate) was prepared by radical bulk polymerization, and its physicochemical properties were studied. It was found that the prepared polyacrylate can be used to manufacture optical waveguides.

Full text of DOI:10.1134/S0012500816030125

ISSN 0012ꢀ5008, Doklady Chemistry, 2016, Vol. 467, Part 1, pp. 88–90. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.A. Tyutyunov, A.V. Sin’ko, S.M. Igumnov, O.A. Mel’nik, Ya.S. Vygodskii, E.V. Khaidukov, V.I. Sokolov, 2016, published in Doklady Akademii Nauk,
2016, Vol. 467, No. 3, pp. 305–307.
CHEMISTRY
Synthesis and Physicochemical Properties
of Poly(perfluoroꢀ2ꢀtrichloromethylisopropyl acrylate)
A. A. Tyutyunova, b, A. V. Sin’koa, b, S. M. Igumnova, b, O. A. Mel’nika,
Ya. S. Vygodskiia, E. V. Khaidukovc, and V. I. Sokolovc
Presented by Academician A.M. Muzafarov September 14, 2015
Received September 14, 2015
Abstract—A new acrylic monomer derived from perfluoroꢀ2ꢀtrichloromethylisopropanol was synthesized.
Poly(perfluoroꢀ2ꢀtrichloromethylisopropyl acrylate) was prepared by radical bulk polymerization, and its
physicochemical properties were studied. It was found that the prepared polyacrylate can be used to manuꢀ
facture optical waveguides.
DOI: 10.1134/S0012500816030125
Fluoroaliphatic acrylate polyesters, as a rule, have analysis [8–12], we supposed that poly(perfluoroꢀ2ꢀ
homopolymer glass transition temperature Tg
<
trichloromethylisopropyl acrylate) (PA6) should also
satisfy these requirements.
100°C, and therefore these polyacrylates are not conꢀ
sidered as polymeric materials for manufacture of
optical waveguides [1–6]. It was shown recently that
poly(perfluoroꢀ2ꢀphenylisopropyl acrylate) can be
Perfluoroꢀ2ꢀtrichloromethylisopropyl acrylate (
was prepared by the reaction of perfluoroꢀ2ꢀtrichloꢀ
romethylisopropanol ( ) with acryloyl chloride
(Scheme 1). This method provides a preparation of
high optical transparency in the telecommunication acrylic monomer
of 99.7% purity (according to gasꢀ
2)
1
used for the above purposes since it has Tg = 118°C and
2
wavelength range [7]. On the basis of literature data liquid chromatography).
CH2=CHC(O)Cl
CF3
O
CF3
CF3
O
N(C2H5)3
CCl3CO2Na
DMF
CF3
HO CCl3
CH3CN
O
CF3
CF3
CCl3
1 (50%)
2 (80%)
Scheme 1.
The radical bulk polymerization of acrylic monoꢀ is a transparent solid polymer with the following therꢀ
mal characteristics: g = 130°C, d = 270°C.
T
T
mer
2 was carried out in evacuated sealed glass
ampules in the presence of 0.2 wt % of azobis(isobutyꢀ
ronitrile) as initiator at 60°C. The structure of
obtained polymer PA6 was confirmed by elemental
analysis and IR spectroscopy. Molecular weight was
The refractive indices nD for acrylate
homopolymer PA6 measured at 20°C and wavelength
589.3 nm equal to 1.4132 and 1.4443, respectively.
2 and its
The figure shows the absorption spectra of acrylic
found to be 270
103. The prepared polyacrylate PA6
×
monomer
2 and polyacrylate PA6 in the telecommuꢀ
nication wavelength range. One can see that attenuaꢀ
tion coefficient for polymer PA6 is 0.05, 0.08, and
0.15 dB/cm in proximity to 840, 1310, and 1550 nm,
respectively.
a Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, ul. Vavilova 28,
Moscow, 119991 Russia
To reveal variation in the thermal and optical propꢀ
erties of acrylic polymers, close analogs of polymer
b P&MꢀInvest Research and Production Association,
Leninskii pr. 47, Moscow, 119334 Russia
PA6, we prepared fluoroaliphatic esters of acrylic
alphaꢀchloroacrylic , and alphaꢀfluoroacrylic
acids and their polymers containing perfluoroꢀ2ꢀ
trichloromethylisopropyl (PCA6), perfluoroꢀtert
4,
5–6
c Institute of Laser and Information Technologies, Russian
Academy of Sciences, Svyatoozerskaya ul. 1, Shatura,
Moscow oblast, 140700 Russia
3
ꢀ
eꢀmail: tuytuynov@rambler.ru
88

SYNTHESIS AND PHYSICOCHEMICAL PROPERTIES
89
butyl (PA9, PFA10), and perfluoroꢀtertꢀpentyl (PFA12)
Attenuation, dB/cm
groups. The table exhibits their properties revealed in
the study.
8
РА6
The analysis of obtained data shows that polyacryꢀ
late PA9 and poly(alphaꢀfluoroacrylates) PFA10 and
PFA12 have insufficiently high glass transition temꢀ
peratures and low refractive indices. The substitution
of a hydrogen atom in the acrylic monomer molecule
by a chlorine or fluorine atom has no considerable
effect on the optical transparency of the polymer.
6
4
2
Thus, one can draw a conclusion that poly(perfluꢀ
oroꢀ2ꢀtrichloromethylisopropyl acrylate) PA6 is supeꢀ
rior to its closest analogues PCA6, PA9, PFA10, and
PFA12, as well as poly(perfluoroꢀ2ꢀphenylisopropyl
acrylate) [7] and poly(perfluoroꢀtertꢀbutyl methacryꢀ
late) [10], in terms of a combination of thermal and
optical properties. The synthetic availability of PA6
makes it promising polymeric material for the manuꢀ
facture of optical waveguides and other devices of inteꢀ
grated optical circuits.
2
0
800
1000
1200
1400
1600
Wavelength, nm
1800
Absorption spectrum of acrylic monomer
late PA6.
2 and polyacryꢀ
spectra are presented using the residual solvent signal
= 7.26) as a reference and given in ppm relative to
tetramethylsilane. Chemical shifts in 19F NMR specꢀ
(
δ
EXPERIMENTAL
1H and 19F NMR spectra were recorded on a
Bruker AVANCEꢀ300 spectrometer (Bruker Corp.,
tra are given in ppm relative to CFCl3. Downfield
USA) at 300 and 282 MHz, respectively, using CDCl3 shifts have positive values. Purity of the monomers was
as an external reference. Chemical shifts in 1H NMR determined by gasꢀliquid chromatography (GLC) on
Properties of fluorinated polyacrylates
Polyacrylate
code
α
(1550 nm),
dB/cm
Shore
hardness D scale
*
nD
Monomer structure
Tg,
°
C
Td
,
°
C
CF3
O
O
CCl3
CF3
PA6
130
164
62
270
270
275
360
355
1.4443
1.4677
1.3534
1.3475
1.3470
<0.15
<0.15
<0.15
<0.1
83
70
79
83
80
2
2
2
2
2
2
O
O
Cl
CF3
CCl3
CF3
PCA6
PA9
3
CF3
CF3
CF3
O
4
O
F
F
CF3
CF3
CF3
O
O
PFA10
PFA12
88
5
O
O
CF3
CF2CF3
CF3
82
<0.13
6
* n is refractive index at wavelength 589.3 nm and 20°C.
D
DOKLADY CHEMISTRY Vol. 467
Part 1
2016

90
TYUTYUNOV et al.
a Shimadzu 2010+ chromatograph (Japan) using acryloyl chloride (47.5 g, 0.525 mol) is added dropꢀ
Restek RTXꢀ1701 column (VWR, USA), 14% of wise. The mixture is stirred for 3 h at 20–25°C, poured
cyanopropylphenyl, 86% polysiloxane, the column is into ice water, the lower layer is separated, washed
30 m long, 0.32 mm internal diameter, 1 m df, flame twice with water, and distilled over P2O5 in vacuum
µ
ionization detector, nitrogen carrier gas. Elemental
analysis was performed in the Laboratory of
Microanalysis, Nesmeyanov Institute of Organoeleꢀ
ment Compounds, Russian Academy of Sciences.
(0.5–1 mmHg) collecting a fraction with bp 40–60°C.
The resultant product was purified by fractional vacꢀ
uum distillation (0.5–1 mmHg) with addition of copꢀ
per powder and an inhibitor.
Molecular weights of the polymers were deterꢀ
mined by dynamic light scattering in tetrahydrofuran
on a Malvern Zetasizer Nano ZS (Malvern, GB) at
25°C. IR spectra were recorded on a Nicolet Magnaꢀ
750 spectrometer (Nicolet, USA) as KBr pellets. Glass
transition temperature Tg of polyacrylates was deterꢀ
mined by thermomechanical analysis (probe 2.54 mm
in diameter, load weight 100 g) on a TA Instruments
TMA Q400 device at heating rate 5 K/min in temperꢀ
ature range 20–300°C. Onset degradation temperaꢀ
ture Тd or 5% weight loss temperature of polymer were
determined by dynamic thermogravimetric analysis
on a MOM Qꢀ1500 derivatograph (Hungary) in air at
heating rate 10 K/min.
Yield 135 g (80%), purity according to GLC
1
99.7%, bp 68°C (10 mmHg). H NMR (
6.1–6.3 (m, 2H), 6.6–6.7 (m, 1H). F NMR (
ppm): –64.6 (s, CF3).
δ
, ppm):
19
δ
,
ACKNOWLEDGMENTS
We are grateful to A.S. Dubovik for the determinaꢀ
tion of molecular weights of polyacrylates and to
M.I. Buzin (Nesmeyanov Institute of Organoelement
Compounds, Russian Academy of Sciences) for therꢀ
mogravimetric analysis of the polymers.
This work was supported by the Russian Science
Foundation (project no. 14–19–01659) and the Rusꢀ
sian Foundation for Basic Research (project no. 13–
03–12265 ofi_m).
Refractive indices were measured on an IRFꢀ454ꢀ
B2M refractometer, absorption spectra in the teleꢀ
communication wavelength range were obtained on a
Shimadzu UV3600 spectrophotometer. Polymer hardꢀ
ness was determined by the Shore method (type D scale)
using TVRꢀD durometer manufactured by Vostokꢀ7
company (Russia)
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19
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in acetonitrile (600 mL) on stirring at 5–10°C, and
Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 467
Part 1
2016