• Korea-Australia Rheology Journal
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• v.14 no.4
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• pp.189-201
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• 2002

The interaction between hydrophobically modified hydroxyethyl cellulose (hmHEC), containing approximately 1 wt% side-alkyl chains of $C_{16}$, and an anionic sodium dodecyl sulphate (SDS) surfactant was investigated. For a semi-dilute solution of 0.5 wt% hmHEC, the previously observed behaviour of a maximum in solution viscosity at intermediate SDS concentrations, followed by a drop at higher SDS concentrations, until above the cmc of surfactant when the solution resembles that of the unsubstituted polymer, was confirmed. Additionally, a two-phase region containing a hydrogel phase and a water-like supernatant was found at low SDS concentrations up to 0.2 wt%, a concentration which is akin to the critical association concentration, cac, of SDS in the presence of hmHEC. Above this concentration, SDS molecules bind strongly to form mixed micellar aggregates with the polymer alkyl side-chains, thus strengthening the network junctions, resulting in the observed increase in viscosity and elastic modulus of the solution. The shear behaviour of this polymer-surfactant complex during steady and step stress experiments was examined In great detail. Between SDS concentrations of 0.2 and 0.25 wt%, the shear viscosity of the hmHEC-polymer complex network undergoes shear-induced thickening, followed by a two-stage shear-induced fracture or break-up of the network. The thickening is thought to be due to structural rearrangement, causing the network of flexible polymers to expand, enabling some polymer hydrophobic groups to be converted from intra- to inter-chain associations. At higher applied stress, a partial local break-up of the network occurs, while at even higher stress, above the critical or network yield stress, a complete fracture of the network into small microgel-like units, Is believed to occur. This second network rupture is progressive with time of shear and no steady state in viscosity was observed even after 300 s. The structure which was reformed after the cessation of shear is found to be significantly different from the original state.

• Journal of the Korean Applied Science and Technology
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• v.27 no.4
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• pp.545-551
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• 2010

Hydrophobically monoendcapped poly(sodium acrylate)s formed hydrophobic microdomains in water. This was concluded on poly(sodium acrylate)s with a linear $C_{12}$-alkyl chain attached specifically at the end of the polymer. There was no well defined CMC (critical micelle concentration), but rather a gradual transition from a micelle free solution to a micelle solution. Steady state fluorescence spectroscopy indicates that the micro domains are rather hydrophobic. At pH 5 in the abscence of salt and at pH 9 in the prescence of 1 M sodium citrate the CAC (critical aggregation concentration) was in the range of 0.1 to 2.4 mM. However at pH 5 there was a linear increase in the transition concentration with a head-group size due to an increase in steric and electrostatic repulsions between polymer main chains. At pH 9 in the abscence of salt the transition concentration was in the range of 1 to 80 mM. For the larger polymers there was a effect which consisted of a concentration gradient of sodium counterion toward the hydrophobic domain. The effect was larger for the larger polymers because of the higher total sodium concentration and the less steep counterion concentration gradient.

• Korea-Australia Rheology Journal
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• v.12 no.2
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• pp.93-100
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• 2000

The interactions between methylated $\beta$-cyclodextrin (CD) and hydrophobically modified alkali-soluble associative polymers (HASE) were examined by a rheological technique. The effect of "capping" of hydrophobes by methylated $\beta$-cyclodextrin on the viscosity and modulus was evaluated. Model HASE polymers with $C_1$to $C_{20}$ alkyl hydrophobic groups ethoxylated with~10 moles of ethylene-oxide (EO 10) and at concentrations up to 3 wt% were examined. With the addition of methylated $\beta$-CD, the steady shear viscosity profiles shift from a Newtonian profile to one that display a shear-thinning characteristic. Significant "capping" of the hydrophobes occurs for HASE polymers with $C_{l2}$, $C_{16}$ and $C_{20}$ hydrophobes as reflected by the large reduction in the viscosity. However, the steady shear viscosity remains constant when the concentration of $\beta$-CD exceeds 1 wt%, suggesting that $\beta$-CD is not able to fully encapsulate the hydrophobes of the HASE polymer. The temperature variation plots indicate that the activation energy of the HASE-EO10-$C_{20}$ system and $\beta$-CD is dependent on the magnitude of the applied shear stress. These results further reinforce the hypothesis that $\beta$-CD is not able to completely remove all the hydrophobic associations.phobic associations.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.295-295
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• 2006

In present study, poly(acrylic acid) (PAA) and hydrophobically modified poly(ethylene oxide) (HM-PEO) multilayers based on the hydrogen bonding between the component polymer pair have been prepared by the LbL deposition method. Dip assembled HM-PEO/PAA multilayers yield unique film morphologies in comparison with PEO/PAA multilayers due to the micellar formation of HM-PEO owing to the hydrophobic attraction between alkyl chains end-capped with the PEO chains. Individual HM-PEO micelles were connected through the bridging PEO chains to form temporary networks on multilayer surface and induced peculiar surface morphology on HM-PEO/PAA multilayers above the critical number of bilayers.

• Macromolecular Research
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• v.12 no.5
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• pp.451-458
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• 2004

Water-soluble polyacrylamides hydrophobically modified with small amounts of N,N-dialkylacrylamides [N,N-dihexylacrylamide (DHAM) and N,N-dioctylacrylamide (DOAM)] have been prepared through free radical solution polymerizations using two hydrophobic initiators derived from 4,4' -azobis(4-cyanopentanoic acid) (ACVA) and long linear chains consisting of 12 and 16 carbon atoms (C12 and C16). This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. We compare the properties of this class of polymers, termed "combined associative polymers", with those of the multisticker (with hydrophobic groups along the polymer chain) and telechelic (with hydrophobic groups at the chain ends) associative polymers. These materials were prepared using DHAM or DOAM and a hydrophobic initiator (ACVA) modified with alkyl chains of two different lengths. Polymers having molecular weights (M$\_$w/) of ca. 175,000 and hydrophobic contents [H] of ca. 0.8 mol% were prepared using 0.07 mol% of initiator relative to the total monomer feed. We investigated the effects that the type, localization, and concentration of the hydrophobic groups have on the viscosities of the associative polymer solutions.

• Korea-Australia Rheology Journal
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• v.14 no.1
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• pp.1-9
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• 2002

Steady and dynamic shear properties of two hydrophobically modified alkali soluble emulsions (HASE), NPJI and NPJ2, were experimentally investigated. At the same polymer concentration, NPJ1 is appreciably more viscous and elastic than NPJ2. The high hydrophobicity of NPJ1 allows hydrophobic associations and more junction sites to be created, leading to the formation of a network structure. Under shear deformation, NPJ1 exhibits shear-thinning behaviour as compared with Newtonian characteristics of NPJ2. NPJ1 and NPJ2 exhibit a very high and a low level of elasticity respectively over the frequency range tested. For NPJ1, a crossover frequency appears, which is shifted to lower frequencies and hence, longer relaxation times, as concentration increases. Three different surfactants anionic SDS, cationic CTAB, and non-ionic TX-100 were employed to examine the effects of surfactants on the rheology of HASE. Due to the different ionic behaviour of the surfactant, each type of surfactant imposed different electrostatic interactions on the two HASE polymers. In general, at low surfactant concentration, a gradual increase in viscosity is observed until a maximum is reached, beyond which a continuous reduction of viscosity ensues. Viscosity development is a combined result of HASE-surfactant interactions, accompanied by constant rearrangement of the hydrophobic associative junctions, and electrostatic interactions.