• Carbon letters
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• 제11권1호
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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.

• 한국염색가공학회지
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• 제28권3호
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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.

• 대한화학회지
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• 제31권6호
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• pp.509-519
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• 1987

네자리 Schiff base 리간드인 3,4-bis(salicylidene diimine) toluene [o-BSDT $H_2$]를 salicylaldehyde에 3,4-diaminotoluene를 Duff 반응시킴으로써 합성하였으며 이들 리간드와 Ni(II), Co(II) 및 Cu(II)이온들과의 새로운 착물 [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)_2$] 및 [Cu(o-BSDT)]를 합성하였다. 이들 착물에 대한 원소분석, 전자흡수스펙트럼, 적외선 스펙트럼 및 T.G.A. 측정결과에 의하여 Ni(II)와 Co(II) 착물은 리간드대 금속이 1 : 1 몰비의 4배위 착물임을 알았다. 0.1M TEAP-DMSO 용액에서의 폴라로그래피와 순환전압-전류법을 조사한 결과 [Ni(o-BSDT)${\cdot}(H_2O)_2$]는 비가역적인 electron transfer 다음에 빠른 화학적 반응을 하는 EC반응기구를 보이며 [Co(o-BSDT)${\cdot}(H_2O)_2$]는 Co(II) - Co(I)로의 환원과 Co(II) - Co(III)로의 산화가 일어나며, [Cu(o-BSDT)]착물은 Cu(II) - Cu(I)로의 환원이 일어남이 밝혀졌다.

• 대한화학회지
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• 제31권3호
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• pp.250-257
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• 1987

DMSO와 $H_2O$용매 중에서 결합구조가 밝혀진 동공의 크기를 달리한 토륨(IV) 착물들의 전기전도도를 측정하여 해리현상과 전해질의 행동을 알아 보고 DMSO용매중에서 polarography와 cyclic voltammography적 거동을 조사하여 합성착물의 산화환원반응 메카니즘, 가역성을 알아 보고 환원과정에 관여하는 전자수 및 착물의 확산계수를 계산하였다. 그 결과 반양성자성 용매에서 모든 착물들은 1:1전해질로, 물에서는 1:4전해질로 각각 행동하고, DMSO용매중에서 각 착물의 환원반응은 1전자 1단계의 환원반응으로 가역적이며 확산계수는 착물종에 따라 $5.831{\times}10^{-6}{\sim}6.900{\times}10^{-6}$이었다. 그리고 모든 착물의 물분자는 -1.8V(대조전극, SCE)이상에서 분해를 일으켜 수소기체를 발생한다.

• 대한화학회지
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• 제31권6호
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• pp.542-554
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• 1987

네자리 schiff base cobalt(II) 착물로서 Co(SED), Co(SND) and Co(SOPD)들을 합성하여 이들 착물들의 DMSO 용액에서 산소를 가하여 산소첨가 생성착물로 $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ 및 $[Co(SOPD)(DMSO)]_2O_2$들을 합성하였다. 이들의 원소분석과 Cobalt정량, IR-Spectra, T.G.A. 및 자화율을 측정하여 산소:cobalt(II) 착물의 결합비가 1:2이고 네자리 schiff base cobalt(II)와 DMSO 및 산소가 6배위 결합으로 주어짐을 알았으며 Co(SED), Co(SND) 및 Co(SOPD) 착물들의 0.1M TEAP-DMSO용액에서 순환전압-전류법에 의한 산화 환원 과정이 Co(SED) 및 Co(SOPD)는 Co(II) / Co(III)와 Co(II) / Co(I) 과정이 가역적으로 일어나고 Co(SND)는 Co(II) / Co(III)과정은 가역적이지만 Co(II) / Co(I) 과정은 비가역적이다. 또한 산소 첨가 생성물의 착물들은 0.1M TEAP-DMSO 용액에서 산소결합의 환원과정이 $E_{pc}$ = -0.80~-0.89V에서 일어나고 이에 Couple인 산화과정은 $E_{pa}$ = -0.70~-0.76V에서 준가역적으로 일어남을 알았다.

• 분석과학
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• 제11권5호
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• pp.332-340
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• 1998

Salicylaldehyde와 2-hydroxy-1-naphthaldehyde를 2-aminophenol과 2-amino-p-cresol에 반응시켜 세자리 Schiff base 리간드($SIPH_2$, $SIPCH_2$, $HNIPH_2$, $HNIPCH_2$)들을 합성하였다. 이들 리간드를 Ni(II) 이온과 반응시켜 세자리 Schiff base Ni(II) 착물들을 합성 하였다. 이들 리간드와 그 착물들의 가상적인 구조와 특성을 원소분석, $^1H$-NMR, IR, UV-vis 분광법과 열 무게 분석법으로 알아보았다. Schiff base 리간드와 Ni(II) 착물의 몰비는 1:1로 결합하며, Ni(II)착물들은 3분자의 수화물이 배위된 6배위의 8면체 구조임을 알았다. 지지 전해질로서 0.1 M TBAP를 포함한 DMSO 용액에서 순환 전압전류법과 미분 펄스 전압전류법으로 세자리 Schiff base 리간드와 이들의 Ni(II) 착물들의 전기 화학적인 산화 환원 과정을 알아보았다. 세자리 Schiff base 리간드들의 전기 화학적 환원은 확산 지배적이고 비가역적으로 진행되었다. Ni(II) 착물의 전기화학적 환원과정은 1단계 1전자 반응으로 확산 지배적이고 준가역적으로 진행되었다. Ni(II) 착물들의 환원전위는 [$Ni(II)(HNIP)(H_2O)_3$]>[$Ni(II)(SIP)(H_2O)_3$]>[$Ni(II)(SIPC)(H_2O)_3$]>[$Ni(II)(HNIPC)(H_2O)_3$]순으로 양전위 방향으로 이동하였으며, 리간드의 영향은 크게 받지 않았다. 이들 결과로 부터 본 연구에서 합성한 Ni(II)착물은 [$Ni(II)(HNIPC)(H_2O)_3$] 착물이 DMSO용매에서 가장 안정함을 알 수 있다.

• Bulletin of the Korean Chemical Society
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• 제30권1호
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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.

• 한국펄프종이공학회:학술대회논문집
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• 한국펄프종이공학회 2000년도 추계학술발표논문집
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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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• 제29권3호
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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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• 제13권3호
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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.