• Carbon letters
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• v.11 no.1
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• pp.22-27
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• 2010

The precipitation polymerization of acrylonitrile (AN) was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at $50{\sim}65^{\circ}C$ using ${\alpha},{\alpha}'$-azobisisobutyronitrile (AIBN) as an initiator. The increased molecular weight polyacrylonitrile (PAN) was prepared with increasing the $H_2O$/DMSO ratio from 10/90 to 80/20. The viscosity average molecular weight of $H_2O$/DMSO solvent was 4.4 times larger than that of $H_2O$/DMF solvent, and precipitation polymerization was accelerlated due to the far decreased chain transfer effect of DMSO. Based on the experimental results, the increased PAN molecular weight was regarded as the summation of two mechanisms: i) particle-particle aggregation and ii) particle-radical attachment. The theoretical equation derived from the mechanisms was well coincided with the experimental results showing the linear relationship between the viscosity average molecular weight and the H2O/DMSO ratio.

• Textile Coloration and Finishing
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• v.28 no.3
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• pp.125-133
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• 2016

In this study, efforts were made to enhance the mechanical properties of the poly(vinyl alcohol) (PVA) fibers of medium molecular weight(number-average degree of polymerization=1735) varying the ratio in $DMSO/H_2O$ mixed solvent and spinning/drawing conditions. The gel fibers prepared from pure DMSO were opaquely frozen in the coagulating bath of $-20^{\circ}C$. However, transparent gel fibers were formed without freezing for the mixture to contain water less than 80wt%. As the amount of water in the mixture increased the residual solvent in the coagulated gel fibers decreased ranging from 85 to 42wt%. The complex viscosity increased with increasing PVA concentration in 80/20 $DMSO/H_2O$ exhibiting remarkable shear thinning at 18wt%. In the Cole-Cole plot, the 18wt% PVA solutions gave a deviated curve from 12 and 15wt% ones. Thus the optimum PVA concentration for the spinning processing of medium MW PVA solutions in 80/20 $DMSO/H_2O$ was determined to 18wt% with rheological concept. Low degree of drawing during hot drawing process in the dry state was available for high bath draft in the coagulation bath. The most improved mechanical properties were observed by applying the highest possible draw ratio attained by reducing bath draft over multi-step drawing process. In the given bath draft, linear relationship was observed between both tensile strength and modulus and draw ratio showing the inflection points at the draw ratio of 19.5 and 18.0 for tensile strength and modulus, respectively.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.542-554
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• 1987

Tetradentate schiff base cobalt(II) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(III) complexes; $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ and $[Co(SOPD)(DMSO)]_2O_2$. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (III), DMSO and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(II) / Co(III) and Co(II) / Co(I) for cobalt(SED) and cobalt(SOPD) complexes and Co(II) / Co(III) process for cobalt(SND) complex are reversible process but Co(II) / Co(I) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, $E_{pc}$ = -0.80~-0.89V and $E_{pa}$ = -0.70~-0.76V.

• Analytical Science and Technology
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• v.11 no.5
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• pp.332-340
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• 1998

Tridentate Schiff base ligands, $SIPH_2$, $SIPCH_2$, $HNIPH_2$, and $HNIPCH_2$ were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. Ni(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Ni(II) complexes were contemplated to be hexa-coordinated octahedral configuration containing three water molecules. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Ni(II) complexes were quasi-reversible and diffusion-controlled as one electron by one step process Ni(II)/Ni(I). The reduction potentials of the Ni(II) complexes shifted in the positive direction in the order [$Ni(II)(HNIP)(H_2O)_3$]>[$Ni(II)(SIP)(H_2O)_3$]>[$Ni(II)(SIPC)(H_2O)_3$]>[$Ni(II)(HNIPC)(H_2O)_3$] and their dependence on ligands were not so high. Consequently the [$Ni(II)(HNIPC)(H_2O)_3$] complex among the synthesized Ni(II) complexes was found to be most stable in the DMSO solution.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.214-218
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• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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• 2000.11a
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• pp.15-21
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• 2000

In chlorine dioxide delignification and bleaching the formation of chlorate is undesirable because it does not react with lignin and is harmful to the environment. Chlorate is mainly formed from the in-situ generated hypochlorus acid which is also the main reason for AOX formation. In previous literature scavengers of hypochlorous acid such as sulfamic aicd, DMSO, and hydrogen peroxide have been added to bleaching stages to reduce AOX formation but less attention has been paid to chlorate reduction. This paper thus focuses on the reduction of chlorate content caused by the following additives, sulfamic acid, DMSO, hydrogen peroxide, and oxalic acid. The results show that only sulfamic acid and DMSO reduce chlorate formation under our chlorine dioxide prebleaching conditions. Results by UV spectroscopy and pH adjustment show that scavengers react with hypochlorous acid much faster than with chlorine. Hydrogen peroxide and oxalic acid react with HClO/$Cl_2$much slower than DMSO and sulfamic acid do. The reason for the ineffectiveness of hydrogen peroxide and oxalic acid is ascribed to their slow reaction rates with HClO compared to that of chlorate formation. The fact that only 30-35% of the chlorate can be reduced by sulfamic acid and DMSO when charged in same mole ratio to chlorine dioxide, suggested that the reaction rate of DMSO and sulfamic acid with hypochlorous aicd are of the same magnitude as that of chlorate formation.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.585-589
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• 2008

Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

• Carbon letters
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• v.13 no.3
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• pp.133-138
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• 2012

According to kinetic mechanisms, liquid phase polymerization and solid phase polymerization are different in acrylonitrile (AN) polymerization, and so the relationship between the contribution ratio and molecular weight distribution (MWD) was obtained through theoretic analysis. The precipitation homopolymerization of AN was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at $50{\sim}65^{\circ}C$ using ${\alpha}$,${\alpha}^{\prime}$-azobisisobutyronitrile as an initiator. The contribution ratio decreased and approached 0; the MWD also decreased and approached 2 with the increase of the $H_2O$/DMSO ratio from 10/90 to 90/10. The experimental data were found to coincide well with the theoretical equation derived from the mechanisms.