Phase Behavior of Cationic Hydroxyethyl Cellulose−Sodium Dodecyl Sulfate Mixtures: Effects of Molecular Weight and Ethylene Oxide Side Chain Length of Polymers
Department of Chemistry, College of Staten Island, The City University of New York, 2800 Victory Boulevard, 10314, USA.Langmuir (Impact Factor: 4.46). 10/2004; 20(20):8482-9. DOI: 10.1021/la049142n
Novel cationic hydroxyethyl cellulose (HEC) polymers with different molecular weights (1.1 x 10(5) to 1.7 x 10(6) g/mol) and ethylene oxide (EO) side chain lengths (1.5-2.9 EO units) were mixed with sodium dodecyl sulfate (SDS) in aqueous solutions. The phase diagrams of cationic HEC-SDS complexes were determined in the dilute polymer concentration regime (< 0.5 wt %) with gradual addition of SDS molecules. The viscosity and structures of the complexes during the phase evolution were studied using rheometry and dynamic light scattering. The gradual addition of SDS first induced interchain associations with the bound SDS aggregates serving as cross-linkers to form an open network structure, producing a very broad size distribution and high viscosities of the complex solutions, and then condensed the network and induced a structure reorganization, resulting in globular aggregates with narrow size distributions. The growth of these globular aggregates in size eventually led to macroscopic sedimentation near charge neutralization. Further addition of SDS randomly broke the sedimentary aggregates into small particles and SDS micelles with low solution viscosities. The effects of molecular weight and EO side chain length of polymers on the phase boundary, viscosity, and structure of cationic HEC-SDS complexes were discussed.
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ABSTRACT: Complexation behaviour of cellulose derivative/surfactant mixtures in aqueous solution was investigated by nonlinear enhanced Rayleigh scattering (NERS). The NERS spectra of polymer solutions, including second-order scattering, third-order scattering, frequency doubling scattering and triplet frequency scattering were created using by spectrofluorometer. The results indicated that NERS intensity of cellulose derivative/surfactant systems changes differently with continuing addition of surfactant due to the complexation between cellulose derivative and surfactant. The critical micelle concentration of cellulose derivatives/surfactants system is easy to obtain. The change of NERS intensity reveals the complexation behaviour of cellulose derivative/surfactant and the aggregation state of polymer chains in evidence. Therefore, NERS had been successfully developed to study complexation behaviour of cellulose derivative/surfactant mixtures in solution. KeywordsCellulose derivative–Nonlinear enhanced Rayleigh scattering–Complexation behaviour–Surfactant–Micelle–Aggregation
Conference Paper: Geometry And Temperature Extensions To The Gummel-poon Model
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ABSTRACT: Microcalorimetric techniques, combined with turbidity measurements, were used to study the thermodynamics of self-assembling of hydrophobically modified cationic polysaccharides and their mixtures with oppositely charged surfactants in aqueous solution. The studied polyelectrolytes were a series of polymers based on dextran having pendant N-(2-hydroxypropyl)-N,N-dimethyl-N-alkylammonium chloride groups randomly distributed along the polymer backbone. The parameters for their micellization process are evaluated from the results of the observed dilution enthalpy curves and compared with those of the related cationic surfactants (DTAC and CTAC). The microcalorimetric results for the mixed systems (polyelectrolytes with oppositely charged surfactants) are used along with turbidity measurements to characterize systematically the thermodynamics of their interaction. The phase behavior is described and the interaction enthalpies are derived from the differences between the observed enthalpy curves with and without polyelectrolyte. Therefore, we discuss in detail the effect of changing the alkyl chain length of polyelectrolyte pendant groups, the molecular weight of the dextran backbone, and the temperature of the measurements on the interactions between polyelectrolyte and surfactant.
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