INVESTIGATION OF VISCOSITY OF SOL-GEL SYSTEMS BASED ON 3-METHACRYLOXYPROPYLTRIMETHOXYSILANE AND TETRAETHOXYSILANE

2018;
58-66
1
L. M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry
2
L. M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry
3
L. M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry
4
L. M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry

One of the promising directions for production of advanced materials is creation of hybrid organic-inorganic nanocomposites that demonstrate not only the improved properties of organic matrix, but also the emergence of the new specific properties due to the presence of inorganic component. Hybrid organic-inorganic materials can be synthesized by sol-gel method as a result of sol-gel process involving organic-inorganic precursors. Nowadays sol-gel technique is considered as a simple and an ecologically friendly method of nanocomposite syntheses.

         The article is devoted to research of the rheological behavior of sol-gel systems on the basis of two organic-inorganic precursors – tetraethoxysilane (TEOS) and 3-methacryloxypropyltrimethoxysilane (MAPTMS). Dynamics of structure formation in these sol-gel systems was studied by viscometric method using RHEOTEST 2.1. The study of the viscosity of sol-gel systems with different ratio of MAPTMS / TEOS allowed to determine the effect of temperature, system composition, concentration of sol-gel process catalyst on the time of reaching the percolation threshold when gelation takes place.

          By the temperature dependence of the time of reaching the percolation point in the studied systems, the activation energy of gelation process was determined.

          Since it is known that MAPTMS hydrolysis and condensation reactions during sol-gel process occurs with a low rate, which may be explained by steric effect due to the presence of acrylate fragment in MAPTMS structure, this precursor was combined with the widespread precursor TEOS having a higher rate of sol-gel transformation. It was established that the replacement of the part of TEOS by MAPTMS slows down the gelation process under the given conditions.

          Studying of the gradient dependence of the viscosity of sol-gel systems allowed to determine the frictional ηo and elastic ηs components of the viscosity of sol-gel systems, depending on temperature and the initial system composition.

          The obtained results are of practical importance for the synthesis of organic-inorganic composites using sol-gel process, since they allow to find the appropriate ratio of precursors and the conditions for sol-gel transformation.

1. Терещенко Г. Ф., Орехова Н. В., Єрмилова М. М. Мембраны // Критические технологии. –
2007. – №1(33). – С. 4–20. 2. Волков В. В., Мчедлішвілі Б. В., Ролдугін В. І., Іванчев С. С., Ярославцев А. Б.
Мембрани і нанотехнології // Наноматеріали функційного призначення. – 2008. – Т. 3, № 11–12. –
С. 47–99. 3. Yoshimoto Abe, Yuki Honda, Takahiro Gunji. Preparation and properties of siliconcontaining
polymer hybrids from 3-methacryloxypropyltrimethoxysilane // Appl. Organometal. Chem. –
1998. – 12. – Р. 749–753. 4. Рубан О. В., Кисельова-Логінова К. В., Попов Є. В. Отримання
кополімеру акрилової кислоти і 3-метакрилоксипропілтриметоксисилану методом емульсійної
кополімеризації // Технологический аудит и резервы производства. – 2015. – № 3–4. – C. 17–23.
5. Amir A. El hadad, Diogenes Carbonell Violeta Barranco, Antonia Jimenez-Morales, Bianka Casal, Juan
Carlos Galvan. Preparation of sol-gel hybrid materials from γ-methacryloxypropyl trimethoxysilane and
tetramethyl orthosilicate: study of the hydrolysid and condensation reactions // Colloid Polym. Sci. –
2011. – 289. – Р. 1875–1883. 6. Evelisy Cristina de Oliveira Nassor, Lilian Rodrigues Avila, Paula
Fabiana dos Santos Pereira, Katia Jorge Ciuffi, Paulo Sergio Calefi, Eduardo Jose Nassar. Influence of
the hydrolysis and condensation time on the preparation of hybrid materials // Materials Research. –
2011. – 14(1). – Р. 1–6. 7. M.J. van Bommel, P.M.C. ten Wolde, T.N.M. Bernards. The influence of
methacryloxypropyltrimethoxysilane on the sol-gel process of TEOS // Journal of Sol-Gel Science and
Technology. – 1994. – Vol. 2, Iss. 1–3. – Р. 167–170. 8. Sacks M. D., Sheu R. S. Rheological Properties of
Silica Sol-Gel Materials // J. Non-Cryst. Solids. – 1987. – 92, 2. – Р. 383–396. 9. Klein L. C., Garvey G. J.
Soluble silicates, ACS Symp.Series No. 194, ed. Falcone J. S., Am. Chem. Soc., Washington, D.C. – 1982. –
Р. 293. 10. Christelle Alie, Rene Pirard, Jean-Paul Pirard. Preparation of low-density xerogels from
mixtures of TEOS with substituted alkoxysilanes. II. Viscosity study of the sol-gel transition // J. Non-Cryst.
Solids. – 2003. – 320. – Р. 31–39. 11. Xenopoulos C., Mascia L. and Shaw S. J. Polyimide-silica hybrids
derived from an isoimide oligomer precursor // J. Mater. Chem. – 2002. – 12. – Р. 213–218. 12. Colby M. W.,
Osaka A. and Mackenzie J. D. Temperature dependence of the gelation of silicon alkoxides // Journal of
Non-Crystalline Solids. – 1988. – 99. – Р. 129–139. 13. Brinker C. J., Scherer G. W. Sol-Gel Science. The
Physics and Chemistry of Sol-Gel Processing. San Diego: Academic Press. – 1990. – 908 p.
14. Medvedevskikh Yu. G., Voronov S. A., Zaikov G. E. Conformation of Macromolecules. Thermodynamic
and Kinetic demonstrations. Nova Science Publishers, Inc. – N. Y., 2007. – 249 p.