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Polymer Chemistry 2018
Polymer Sciences
ISSN: 2471-9935
Page 54
March 26-28, 2018
Vienna, Austria
3
rd
Edition of International Conference and Exhibition on
Polymer Chemistry
P
hotosensitive polymer materials are prospective for the
development of optical elements in integrated and diffractive
optics. For this purpose, photopolymer hybrid organic–inorganic
compositions are actively developed and studied. Acrylate groups,
which can undergo free-radical photopolymerization, are frequently
used as monomer groups in such materials. When multifunctional
acrylates are used, a cross-linked polymer is formed by the action
of UV light. It is accepted that the disadvantage of free-radical
photopolymerization in thin films is its inhibition by atmospheric
oxygen. This inhibition results from the formation of peroxide
radicals, which traps free radicals and prevent further polymerization.
It is known that the use of thiol compounds in acrylate photopolymer
compositions helps to eliminate the oxygen inhibition of radical
polymerization. The synthesis of hybrid oligomers for photopolymer
compositions was carried out based on the thiolene reaction
between the tetraacrylate dihydroxydiphenylsulfide derivative and
siloxane-thiol oligomer. Siloxane-thiol oligomer was synthesized
by condensation of diphenylsilanediol and 3-(mercaptopropyl)-
trimethoxysilane. The siloxane-thiol oligomer structure was
identified by 1H, 13C, 29Si NMR spectroscopy including COSY, HSQC,
and HMBC methods and by MALDI-TOF mass spectrometry. The
hybrid oligomers were obtained at different tetraacrylate: siloxane-
thiol oligomer ratios. The obtained compositions were resistant
to the oxygen inhibition of photopolymerization and give flexible,
thermostable, and rigid polymer films under UV light. The degree of
the film photopolymerization was monitored by IR spectroscopy. The
thermomechanicalpropertiesofphotopolymerfilmsweredetermined
using thermogravimetric, differential scanning calorimetric, and
dynamic mechanical analyses. The storage modulus (E
0
) at room
temperature (1.16–1.88 GPa) and the glass transition temperatures
(78–133°C) were determined for photopolymer films obtained at
different ratios of acrylate and thiolsiloxane units. The photocured
hybrid films exhibit high stability to thermal decomposition in the inert
(T10% over 321 °C) and oxidizing (T10% over 314°C) atmospheres.
The kinetics of thiol–enol photopolymerization of a hybrid
composition based on a tetraacrylate monomer and a thiol-siloxane
oligomer was studied with the use of a holographic recording of
elementary transmission phase gratings. The degrees of conversion
of doublebonds in the tetraacrylatemonomer after thepolymerization
in air and in an inert atmosphere of SF6 were measured via IR
spectroscopy. It is shown that the use of the thiol-siloxane oligomer
efficiently suppresses oxygen inhibition of the photopolymerization.
An increase in the thiol-siloxane oligomer concentration leads
to an extremal dependence of the photopolymerization rate on
the oligomer concentration; the maximum rate is reached at an
oligomer concentration of about 0.07 mol/L. The kinetic scheme of
photopolymerization in the hybrid photopolymer composition was
analyzed, and an analytical expression for the photopolymerization
rate was obtained. The correlation between the kinetic constants of
the thiol-enol photopolymerization was evaluated on the basis of the
obtained parameters of the kinetic model. The results of the laser
recorded structures in the hybrimers are represented.
Acknowledgement
. The authors are grateful to the RSF (grant N 16-
13-10156) for the financial support.
Recent Publications
1.
IYuKargapolova,NAOrlova,KDErinandVVShelkovnikov(2016)
Synthesis of unsymmetrical thioflavylium dyes from julolidine
derivatives and polyfluorinated triphenyldihydropyrazoles.
Russian Journal of Organic Chemistry 52(1)37–41.
2.
V V Shelkovnikov, D I Derevyanko, L V Ektova, N A Orlova, V A
Loskutov,
et al.
(2016) Photopolymerization kinetics of a thiol-
enol composition determined via recording/playback of a
transmission holographic diffraction grating. Polymer Science
Series B 58(5)519–528.
3.
N GMironnikov, V P Korolkov, D I Derevyanko, V V Shelkovnikov,
O B Vitrick,
et al.
(2016) Study of optical and thermo-optical
properties of a hybrid photopolymer material based on
thiol-siloxane and tetraacrylate oligomer. Optoelectronics,
Instrumentation and Data Processing 52(2):180–186.
4.
VVShelkovnikov, GALyubas andSVKorotaev (2016) Enhanced
reflective interference spectra of nanoporous anodic alumina
films by double electrochemical deposition of chemical metal
nanoparticles. Nanoscale and Nanostructured Materials and
Coatings, Protection of Metals and Physical Chemistry of
Surfaces 52(2)227–231.
5.
E F Pen, I A Zarubin, V V Shelkovnikov and E V Vasil’ev
(2016) Method for determining the shrinkage parameters
of holographic photopolymer materials. Optoelectronics,
Instrumentation and Data Processing 52(1)60–69
Biography
Vladimir Shelkovnikov is Head of Laboratory of the Light-Sensitive Materials in
the Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian
Academy of Sciences. Education: Tomsk Polytechnical Institute, Tomsk, USSR,
1978, Chemistry, Radiation Chemistry, Chemical Technology Engineer; Kemero-
vo State University, Kemerovo, USSR, 1984; PhD in Physical Chemistry; Institute
of Inorganic Chemistry, Novosibirsk, Russia, 2009, Degree Doctor of Science in
Physical Chemistry. His field of research interests are chemistry and photonics
of the organic chromophores and polymer compositions. He has more than 30
years of varied experience in chemistry and photonics of organic medium.
vice@nioch.nsc.ruPhotopolymerization of siloxane-thiol-acrylate oligomers
Vladimir Shelkovnikov
1, 2
, Dmitry Derevyanko
1
, Natalya Orlova
1
and
Viktor Korolkov
3
1
N.N. Vorozhtzov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy
of Sciences, Russia
2
Novosibirsk State Technical University, Russia
3
Institute of Automation and Electrometry, Siberian Branch of the Russian Academy of Sciences, Russia
Vladimir Shelkovnikov et al., Polym Sci, Volume 4
DOI: 10.4172/2471-9935-C1-008