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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.

[email protected]

Photopolymerization 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