Wide-angle X-ray scattering observations of alpha-cyclodextrin (CD)-poly(ethylene glycol) (PEG) inclusion complexes (ICs) have shown for the first time that two crystalline columnar modifications (forms I and II) are produced in the process of their formation. This was made possible by precise azimuthal X-ray diffraction scanning of oriented IC samples. Form I is characterized by CDs threaded onto PEG chains and arranged along channels in the order head-to-head/tail-to-tail, while form II is formed by unbound CDs also arranged into columns in a head-to-tail and also possibly a head-to-head/tail-to-tail manner, probably as a result of template crystallization on the form I IC crystals. It was shown that similar structural peculiarities are inherent for channel structures based on ICs obtained with PEG with a wide range of molecular weights (MWs). The characteristic feature of ICs based on PEG, especially with MW > 8000, is the presence of unbound polymer in the composition of the complex. The amount of unbound PEG was shown to rise with increasing MW of PEG, resulting in greater imperfections in the IC crystalline structure. The polyblock structure of ICs based on alpha-CD and PEG was therefore proposed.
The layer-by-layer (LbL) deposition of poly(sodium 4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) over cotton fibres is reported. Cotton fibres offer unique challenges to the deposition of nanolayers because of their unique cross section as well as the chemical heterogeneity of their surface. Cationic cotton substrates were produced by using 2,3-epoxypropyltrimethylammonium chloride. Attenuated total reflectance FTIR, x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to validate the presence of the nanolayers as well as to corroborate their self-organized structure. TEM images indicated conformal and uniform coating of the cotton fibres. XPS spectral data were found to be in quantitative agreement with previous published work that studied the LbL deposition of PSS and PAH over synthetic substrates.
In this study, we successfully report an intimate ternary blend system of polycarbonate (PC)/poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) obtained by the simultaneous coalescence of the three guest polymers from their common γ‐cyclodextrin (γ‐CD) inclusion compound (IC). The thermal transitions and the homogeneity of the coalesced ternary blend were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The observation of a single, common glass transition strongly suggests the presence of a homogeneous amorphous phase in the coalesced ternary polymer blend. This was further substantiated by solid‐state 13C NMR observation of the T1ρ(1H)s for each of the blend components. For comparison, ternary blends of PC/PMMA/PVAc were also prepared by traditional coprecipitation and solution casting methods. TGA data showed a thermal stability for the coalesced ternary blend that was improved over the coprecipitated blend, which was phase‐segregated. The presence of possible interactions between the three polymer components was investigated by infrared spectroscopy (FTIR). The analysis indicates that the ternary blend of these polymers achieved by coalescence from their common γ‐CD–IC results in a homogeneous polymer blend, possibly with improved properties, whereas coprecipitation and solution cast methods produced phase separated polymer blends. It was also found that control of the component polymer molar ratios plays a key role in the miscibility of their coalesced ternary blends. Coalescence of two or more normally immiscible polymers from their common CD–ICs appears to be a general method for obtaining well‐mixed, intimate blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4182–4194, 2004
We report on the preparation and characterization of poly(vinyl alcohol) (PVA) hydrogels formed during freeze-thaw (F-T) cycles of their aqueous solutions containing γ-cyclodextrin (γ-CD). Crystalline inclusion compound (IC) formation was observed between PVA and γ-CD in these gels at low concentrations of γ-CD (γ-CD:PVA molar ratios < 1:25). Confirmation of the existence of the channel structure for γ-CD was achieved by characterizing the dried PVA/γ-CD hydrogels with solid-state DSC, TGA, WAXD, and 13 C NMR. Some aspects regarding the mechanism and structure of PVA gels obtained via F-T cycles in the presence/absence of γ-CD are presented based on UV-vis, swelling, solution 1 H NMR, and rheological observations. It was observed that the swelling and rheological responses of the aqueous PVA gels formed during F-T cycles in the presence of γ-CD can be controlled by adjustment of the PVA:γ-CD molar ratio employed during their gelation.
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