Properties of poly(styrene/alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol) microspheres suspended in water. Effect of sodium chloride and temperature on particle diameters and electrophoretic mobility.
Hydrodynamic and electrophoretic properties of core-shell poly(styrene/alpha- tert-butoxy-omega-vinylbenzyl-polyglycidol) (P(S/PGL)) microspheres suspended in water are described. The microspheres were obtained by surfactant-free emulsion copolymerization of styrene and alpha- tert-butoxy-omega-vinylbenzyl-polyglycidol macromonomer ( M n = 2800, M w/ M n = 1.05). The process yielded microspheres with number average diameter D n = 270 nm and with low diameter dispersity index D w/ D n = 1.01. Shells of P(S/PGL) microspheres were enriched in polyglycidol. Molar fraction of polyglycidol monomeric units in the shells (determined by X-ray photoelectron spectroscopy) was equal to 0.34, which is much higher than the average molar fraction of polyglycidol monomeric units in whole particles of 0.048. Influences of NaCl concentration and temperature on P(S/PGL) microsphere diameters and on their electrophoretic mobility were investigated. It was found that hydrodynamic diameter of P(S/PGL) microspheres, determined by photon correlation spectroscopy, decreased significantly when temperature did exceed a certain value (transition temperature, T t). It has been found that the decrease is more pronounced for higher concentrations of NaCl in the medium. For microspheres suspended in 10 (-1) M NaCl, the hydrodynamic diameter decreased by 8% whereas for the same particles in pure water the diameter decreased by 5.2%. The process of shrinkage was fully reversible. Values of T t for P(S/PGL) microspheres were lower for higher concentrations of NaCl. Adjustment of salt concentration allowed controlling T t in a range from 44.4 to 49.9 degrees C. 13C NMR relaxation time measurements (T 1) for carbon atoms in polyglycidol macromonomer revealed that T 1 did increase with increasing temperature (in temperature range from 25 to 75 degrees C) indicating higher motion of chains at higher temperature. Addition of NaCl did not induce a substantial change of T 1 in the mentioned temperature range. The swelling-deswelling properties of P(S/PGL) microspheres' interfacial layer affected adsorption of P(S/PGL) particles on modified with (3-aminopropyl)triethoxysilane mica. It was shown that the deposition of P(S/PGL) microspheres at 25 degrees C on mica led to formation of two-dimensional crystal-shape assemblies, whereas at 60 degrees C (far above T t = 49.8 degrees C in H2O) the microspheres were randomly adsorbed without formation of colloidal crystal assemblies.
Basinska
Teresa
T
Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, ul. Sienkiewicza 112, Lodz, Poland. basinska@bilbo.cbmm.lodz.pl
Slomkowski
Stanislaw
S
Kazmierski
Slawomir
S
Chehimi
Mohamed M
MM
D004586:Electrophoresis; D009682:Magnetic Resonance Spectroscopy; D008855:Microscopy, Electron, Scanning; D008863:Microspheres; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry / Q000648:ultrastructure; D010316:Particle Size; D011137:Polystyrenes / Q000737:chemistry*; D011409:Propylene Glycols / Q000737:chemistry*; D012965:Sodium Chloride / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry*
D011137:Polystyrenes; D011409:Propylene Glycols; C531371:poly(styrene-alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol); D014867:Water; D012965:Sodium Chloride