• 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.

• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.673-678
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• 1997

Associative acrylic thickeners were prepared by emulsion copolymerization using nonionic vinyl surfactant esters as an associative macromonomer and their rheological properties were investigated. The thickening efficiency was shown to depend on the chain length of therminal hydrophobe and degree of ethoxylation of VSE. increasing the content of VSE enhanced the efficiency of the resulting polymers as a thickener. It was attributed to the intermolecular association of terminal hydrophobes of associative thickener in aqueous solution. The chain transfer agent caused to reduce the molecular weight of associative thickener, resulted in decrease of thickening efficiency.

• 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.

• 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.