2016 (3) 8

https://doi.org/10.15407/polymerj.38.03.244

Graft copolymers PVA-g-PAA as effective matrix for formation and stabilization silver nanoparticles

Т.B. Zheltonozhskaya, S.V. Fedorchuk, D.O. Klymchuk, Yu.P. Gomza, S.D. Nesin

Kiev Taras Shevchenko National University

60, Vladimirskaya str., Kyiv, 01033, Ukraine

Institute of Botany NAS of Ukraine

2, Tereschenkivska str., Kyiv, 01601, Ukraine

Institute of Macromolecular Chemistry NAS of Ukraine

48, Kharkivske shose, Kyiv, 02160, Ukraine

Polym. J., 2016, 38, no. 3: 244-254.

Section: Synthesis polymers.

Language: Ukrainian.

Abstract:

A series of PVA-g-PAAm graft copolymers based on chemically complementary poly(vinyl alcohol) and polyacrylamide, which ones contained different quantity and length of grafted chains, have been synthesized in aqueous medium using the radical template “grafting from” polymerization technique. The constant concentration of the matrix (PVA macromolecules with Mw=90 kDa) and variable concentrations of the redox initiator and monomer, which determined the quantity and length of the grafts, were applied. The main molecular parameters of the graft copolymers were characterized and the changes in the grafted chain quantity N from 10 to 40 per one copolymer macromolecule were found. A high activity of PVA-g-PAA as templates in the processes of in situ synthesis and stabilization of silver nanoparticles (AgNPs) in water was revealed. The kinetic regularities of AgNP formation and the nanoparticle yield were established basing on the analysis of the position and integrated intensities of the nanoparticle surface plasmon resonance band (SPRB) in UV-Vis spectra. It was shown that the graft copolymers, which form in aqueous solutions the micelle-like structures, ensured both the high rate of formation and large yield of AgNPs as well as their long-term stabilization in time. An interesting effect of a sharp reduction in the maximum position of SPRB in 16-19 nm within narrow time interval (~ 3 min) that took place at the accumulation of a large enough quantity of AgNPs in the reaction mixture has been established too. By this phenomenon, the process of regularization (crystallization) of primary AgNPs could be fixed in time. The growth of the graft number in the copolymer macromolecules from 10 to 40 resulted in the increase in nanoparticle yield, especially at a low concentration of polymeric template. The obtained AgNPs/PVA-g-PAAm compositions were studied in solutions by transmission electron microscopy and in a bulk state by wide-angle and small-angle X-ray scattering. It was shown that AgNPs synthesized had a crystalline structure, spherical shape, small size (< 10 nm), and low polydispersity. The compositions AgNPs/PVA-g-PAAm in a bulk state demonstrated the two-level fractal organization of their structure. Silver nanoparticles with a small size and smooth surface constituted the 1-st lower level of the composition fractal structure but the mass-fractal clusters of the graft copolymer matrix formed the 2-nd higher level of that structure.

Key words: graft copolymer, micelle-like structure, silver nanoparticles, polymer/metal compositions.

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