• Title/Summary/Keyword: Huggins constant

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Relation between Huggins Constant and Compatibility of Binary Polymer Mixtures in the Aqueous Ternary Systems

  • Isamu Inamura;Makoto Kittaka;Tatsuya Aikou;Kazuhiko Akiyama;Tomoyuki Matsuyama;Masatsugu Hiroto;Hirade, Ken-ichi;Yuji Jinbo
    • Macromolecular Research
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    • v.12 no.2
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    • pp.246-250
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    • 2004
  • We have classified a number of aqueous ternary systems containing two different polymers into three types by focusing on the deviation of the Huggins constant k'from the additivity line. Systems of type I have negative deviations of k'; the repulsive interaction between the two different polymers dominates. In systems of type II, k' almost follows the additivity relation; the repulsive and attractive interactions between the two different polymers are balancing. Type III systems have positive deviations of k'; the attractive interactions are relatively dominant. This classification of systems is supported by the fact that the positive and negative deviations of k' from the additivity line also correspond to the sign of interaction parameter between polymer 2 and 3, Δb$\_$23/. Furthermore, we have verified the relatively high compatibility between dextran and poly(vinyl alcohol) by determining the binodal concentration of a liquid-liquid phase separation for a water/dextran/poly(vinyl alcohol) system, which is classified as type III. Thus, we found that the compositional dependence of k' closely relates to the compatibility of binary polymer mixtures in aqueous ternary systems.

Copolymerization of N-Vinylurea and Vinyl Acetate (Ⅰ). Synthesis of N-Vinylurea-Vinylalcohol Copolymer (N-비닐尿素와 醋酸비닐의 混成重合 (第1報). N-비닐尿素-비닐알코올混成重合體의 合成)

  • Woo Sik Kim;Hak-ki Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.73-79
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    • 1980
  • N-Vinylurea(VU) was radically copolymerized with vinyl acetate (VAc). VU-vinyl alcohol (VA) copolymer, which is a water-soluble polymer with pendent urea and hydroxyl groups, was synthesized by the methanolysis of the VU-VAc copolymer.VU shows vinyl polymerization, and this result is in agreement with that of Nozakura, et al. Huggins constant for the aqueous solution of the VU-VA copolymer containing more than about 30 mole percent of VU was observed to be a high value.

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The rheological properties of poly(vinylidene fluoride-co-hexafluoropropylene) solutions in dimethyl acetamide

  • Lee, Ki-Hyun;Song, In-Kyu;Kim, Byoung-Chul
    • Korea-Australia Rheology Journal
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    • v.20 no.4
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    • pp.213-220
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    • 2008
  • The effects of temperature on the rheological properties of the solutions of poly(vinylidene fluoride-co-hexafluopropylene) (PVDF-HFP) in dimethyl acetamide (DMAc) were investigated in terms of frequency and concentration. The effects of temperature on the intrinsic viscosity of the solutions were discussed. In dynamic rheological measurement, the concentrated solutions showed a little unexpected rheological response; as temperature was increased dynamic viscosity was increased and the solutions exhibited more noticeable Bingham body character over the temperature range, 30 to $70^{\circ}C$. In addition, the solution gave longer relaxation time, lower value of loss tangent and higher value of yield stress at higher temperature and at higher concentration. On the other hand, the dilute solutions revealed that intrinsic viscosity was decreased and its Huggins constant was increased with increasing temperature. These physical parameters suggested that the increase of viscosity with increasing temperature resulted from the localized gelation of PVDF-HFP due to reduced solubility to the solvent.

Acid-Base Equilibria and Related Properites of Chitosan

  • Joon-Woo Park;Kyung-Hee Choi;Kwang-hee Koh Park
    • Bulletin of the Korean Chemical Society
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    • v.4 no.2
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    • pp.68-72
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    • 1983
  • The $pK_{a}$ of $-NH_{3}^{+}$ group of chitosan in water was 6.2, while that of D-glucosamine-HCl, monomer of chitosan, was found to be 7.8. The difference of $pK_{a}$ values between chitosan and D-glucosamine was attributed to the strong electrostatic interaction between $-NH_{3}^{+}$ groups in chitosan. The apparent binding constant of $Cu^{2+}$ to D-glucosamine was estimated to be $1{\times}10^{4}$. For chitosan, no significant binding of $Cu^{2+}$ to the polymer was observed when pH < 5, but strong cooperative binding was observed near pH 5.1. The mechanism of such cooperativity was proposcd. Chitosan in solution exhibited typical polyelectrolytic behaviors: viscosity increases with increased amount of charged group, and decreases with addition of salt. The concentration dependence of viscosity was measured, and the Huggins parameters and intrinsic viscosity were calculated at various ionic strength. The results were interpreted in terms of molecular properties of the chitosan molecule.

The Prediction of Solvent Mutual Diffusion Coefficient Using Vrentas-Duda's Self Diffusion Theory (Vrentas-Duda의 자기확산이론을 이용한 용매의 상호확산계수 예측)

  • 김종수;이광래;김기창
    • Membrane Journal
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    • v.10 no.1
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    • pp.19-29
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    • 2000
  • To estimatc mutual diffusion coefficient for the analysis of mass transfer phenomena in polymer/solvent system, two models are proposed and the equations are derived. The estimates of mutual diffusion coefficients are obtained by two models suggested in this work and compared with and experimental data and Vrentas-Duda's. Vrentas-Duda's self diffusion coefficient was used for the mutual diffusion coefficient. Derivative of chemical potential on solvent was derived and used using original UNIFAC-FV and modified UNIFAC-FV. However, Vrentas-Duda's equation for mutual diffusion coefficient contains Flory-Huggins parameter x. For the derivative of chemical potential term, Vrentas-Duda assumed that parameter x was constant and independent of temperatures and concentrations The assumption is one of shortcoming in vrentas-Duda's mutual diffusion coefficient. New methods proposed in this work do not have such assumptions and simplifications. For the solvent of cyclohexane, n-pentane, and n-hexane in PIB(polyisolbutylene) and PMS-BR (poly(p-methylstyrene-co-isobutylene), new methods well correlate the experimental data at various temperatures and concentrations, and predicted the experimental data much better than Vrentas-Duda's for the PIB/toluene system. It is shown that new methods are excellent tools for correlating mutual diffusion coefficient data in polymer/solvent system over wide ranges of temperature and concentration without any assumptions or simplifications.

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Rheological Measurement of Fiber Spinnability of PVA Solution Dopes in DMSO

  • Chae, Dong-Wook
    • Textile Coloration and Finishing
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    • v.22 no.3
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    • pp.187-193
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    • 2010
  • The effects of molecular weight (MW) and concentration on the rheological properties of poly(vinyl alcohol) (PVA) solutions in dimethyl sulfoxide (DMSO) were investigated at $30^{\circ}C$. Ubbelohde viscometer and rotational rheometer were employed for dilute and concentrated regime, respectively. In the dilute regime, the Mark-Houwink exponent ($\alpha$) of the solutions determined from three different MWs proved 0.73. The critical concentration (C*), in which the entanglement and overlap of polymer molecules began to take place, decreased with increasing the MW of PVA. Huggins constant ($K_H$) values ranged from 0.33 to 0.45 over the MW examined. In the log-log plot of $\eta_{sp}$ versus [$\eta$]C, the PVA with higher degree of polymerization (DP) gave a greater slope exhibiting the inflection point in the vicinity of C*. In the dynamic viscosity ($\eta'$) curve, the PVA solutions of DP 1700 presented Newtonian fluid behavior over most of the frequency range examined. However, the lower Newtonian flow region reduced with increasing the DP. As the PVA concentration increased, $\eta'$ was increased and the onset shear rate for pseudoplasticity was decreased. In the Cole-Cole plot, PVA solutions showed almost a single master curve in a slope of ca. 1.65 regardless of the DP. However, the increase of the concentration from 8 to 12 wt% for PVA solutions of DP 5000 decreased the slope from 1.73 to 1.57. In the tan $\delta$ curve, the onset frequency for sol-gel transition was shifted from 154 to 92 rad/s with increasing the DP from 3300 to 5000 and from 192 to 46 rad/s with increasing the concentration from 8 to 12 wt%. In addition, longer relaxation time ($\lambda$) was observed with increasing the DP and concentration.