• Title/Summary/Keyword: Diamines

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High Proton Conductivity Crosslinked Sulfonated Polyimide Membranes (높은 수소이온전도성을 가진 가교술폰화폴리이미드막)

  • Lee, Chang-Hyun;Park, Chi-Hoon;Park, Ho-Bum;Lee, Young-Moo
    • Proceedings of the Membrane Society of Korea Conference
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    • 2003.11a
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    • pp.61-63
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    • 2003
  • A major research objective related to proton exchange membrane(PEM) for DMFC is to achieve high proton conductivity over 10$^{-2}$ S/cm, high hydrolytic stability and low methanol permeability with low cost base materials. for the purpose, a lot of thermoplastic polymers such as polysulfones, polyethersulfone, polyetherketones, polyimides, polyoxadiazole, polyphosphazene and polybenzimidazol have been investigated. Amongst those polymers, polyimides have been suggested as a potential PEM due to their excellent thermal, chemical stability and good mechanical properties. Generally, polyimides are synthesized by polycondensation with numerious diamines and dianhydriedes. In our study, polyimide was prepared using non-sulfonated diamine, sulfonated diamine directly synthesized by fuming sulfuric acid, and naphthalenic dianhydride to improve the hydrolysis stability under acidic condition. Through monomer sulfonation-subsequent polymerization method, the high proton conducting capability and the desired sulfonation level were effectively controlled at the same time. To reduce severe methanol transport through the membrane, the chemical crosslinking among polymer chains was introduced using various crosslinking agents with different chain lengths. The crosslinked sulfonated polyimide membranes showed high proton conductivity up to 8.09$\times$10$^{-2}$ S/cm and from crosslinking effect methanol transport through the membranes was considerably reduced as compared with unmodified membranes. For increase of chain length of crosslinker, methanol permeability was adversely reduced to 10$^{-8}$ $\textrm{cm}^2$/s due to decrease of IEC and increase of crosslinking desity.

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A COMPARATIVE STUDY OF FREE AMINO ACIDS IN HEALTHY AND VIRUS DISEASED CHINESE DATE TREE (Virus에 감염된 대추나무의 병엽과 건전엽에 있어서의 유이 amino산의 정성적 비교)

  • Hong, Soon-Woo;Hah, Yung-Chil
    • Journal of Plant Biology
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    • v.4 no.1
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    • pp.9-11
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    • 1961
  • A comparative investigation of free amino acids content in healthy check and virus diseased leaves of Chinese date tree, Zyzyphus jujuqa Mill var. inermis Rhed, was carried out by authors throughout the growing season of 1959 and 1960 from June to October. The methods of qualitative analysis of free amino acids aplied in this experiment is followed by Moore and Stein. Free amino acids determined in this experiment are shown in Fig. 1 and Table 1. As the figure and the table are shown, three more amino acids such as glutamine, asparagine and histidine are detected in the diseased material. The additional amino acids which are known as diamines in diseased leaves are conspicuous. It is presumed that the diamine might be incresed by the self-reproduction of the virus in cooporation with certain enzymes which are carrying out the protein metabolism in the host protoplast in contrast with the healthy checks which is carrying out normal protein metabolism. From the histological poing of view, the facts of phloem degeneration or necrosis in diseased leaves, it seems to interrupt to move free amino acids from roots to leaves and it possibly takes place an excessive production of NH3 which is diaminated by the metabolism of nitrogen compounds in such conditioned leaves. Therefore, it is also presumed that additional diamino acids are accumulated in diseased leaves. There are no change of amino acids are accumulated in diseased leaves. There are no change of amino acids in both materials of this plant throughout the growing season qualitatively, and this result agress with the paper of Knight.

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Depolymerization of Waste Polyurethane from Automotive Seats (자동차 시트용 폐폴리우레탄의 해중합)

  • Min, Sung-Jin;Kong, Seung-Dae;Yoon, Cheol-Hun;Kang, An-Soo;Eom, Jae-Yeol;Shin, Pan-Woo;Lee, Seok-Woo
    • Journal of the Korean Applied Science and Technology
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    • v.18 no.2
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    • pp.103-110
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    • 2001
  • Resource recovery and recycling of materials and products, including polyurethanes is viewed as a necessity in today's society. Most urethane polymers are made from a polyol and a diisocyanate. these and be chemicals such as water, diamines or diols that react with isocyanate groups and add to the polymer backbone. The problems of recycling polyurethane wastes has major technological, economic and ecological significance because polyurethane itself is relatively expensive and its disposal whether by burning is also costly. In general, the recycling methods for polyurethane could be classified as mechanical, chemical and feedstock. In the chemical recycling method, there are hydrolysis, glycolysis, pyrolysis and aminolysis. This study, the work was carried out glycolysis using sonication ant catalyzed reaction. Different kinds of recycled polyols were produced by current method(glycolysis), catalyzed reaction and sonication as decomposers and the chemical properties were analyzed. The reaction results in the formation of polyester urethane diols, the OH value which is determined by the quantity of diol used for the glycolysis conditions. The glycolysis rates by sonication for the various glycols, increased as fallows: PPG

A Study on the Reactions of Diamines with 2,5-Dimethoxytetrahydrofuran and 1,3-Acetonedicarboxylic Acid (1,3-Acetonedicarboxylic acid와 2,5-dimethoxytetrahydrofuran에 의한 diamine들의 반응에 관한 연구)

  • Jung Dai-Il;Song Ju-Hyun;Lee Do-Hun;Lee Yong-Gyun;Choi Soon-Kyu;Park Yu-Mi;Hahn Jung-Tai
    • Journal of Life Science
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    • v.16 no.2 s.75
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    • pp.206-212
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    • 2006
  • In order to synthesize novel anticonvulsants, we researched that the reactions of diamines with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid. The reaction of ethylenediamine with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid afforded 8-(2-pyrrol-1-yl-ethyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 5.0%) and 1,2-di-(8-aza-bicyclo[3,2,1]octan3-onyl)ethane (yield; 17.0%). In case of 1,3-diaminopropane, 8-(3-pyrrol-1-yl-propyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 6.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)propane (yield; 21.0%) were obtained. In case of 1,8-diaminooctane, 8-(8-pyrrol-1-yl-octyl)-8-aza-bicyclo-[3,2,1]octan-3-one (yield; 2.6 %) and 1,8-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)octane (yield; 24.9%) were obtained. In diaminobenzene reactions, synthetic yields of 8-aza-bicyclo-[3,2,1]octan-3-one derivatives were higher than those of pyrrole derivatives because re actions were done under room temperature. The longer the carbon chain of diaminoalkane is, the more reactive N atom is due to more electron donating effect, and the less steric hindrance around the carbon gave the higher chemical yields. The reaction of p-phenylenediamine as a diaminobenzene with 2,5-dimethoxyte-trahydrofuran and 1,3-acetonedicarboxylic acid produced p-dipyrrolylbenzene (yield; 4.0%), 8-(4-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 12.0%), and 1,4-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield; 59.0%). In case of m-phenylenediamine, 8-(3-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 2.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield ; 28.0%) were obtained. But, synthesis of 1,2-di-(8-aza-bicyclo[3,2,l]octan-3-onyl)benzene by treatment of o-phenylenediamine was not successful, presumably due to the steric hindrance of 8-aza-bicyclo-[3,2,1]octan-3-one rings.

Gas Transport Properties of Crosslinked Polyimide Membranes Induced by Aliphatic Diamines with Different Chain Length (사슬 길이가 다른 지방족 디아민으로 가교된 폴리이미드 분리막의 기체 투과 특성)

  • Lee, Hye Rim;Lee, Jung Moo;Nam, Sang Yong
    • Membrane Journal
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    • v.23 no.6
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    • pp.450-459
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    • 2013
  • 2,3,5,6-Tetramethyl-1,4-phenylenediamine (TMPD) based polyimide (PI) were crosslinked with 1,2-Diaminoethane (DAE) and 1,6-Diaminohexane (DAH) to enhance gas transport properties. Fourier transform infrared (FT-IR) studies show that imide groups were converted into amide groups during crosslinking process. Thermogravimetric analysis (TGA) results indicate that the degradation temperature of crosslinked PI membranes decreased after crosslinking. This is due to degradation of alkyl group in crosslinking agent. The d-space of crosslinked PI membranes decreased with increasing crosslinking time. The ideal permeability for $CH_4$, $N_2$, $O_2$, and $CO_2$ decreased after crosslinking and the ideal permeability of crosslinked PI membranes induced by DAH is larger than that by DAE. In contrast, the permselectivity of $CO_2/CH_4$, $CO_2/N_2$ and $O_2/N_2$ increased during crosslinking. For the gas pair of $CO_2/CH_4$, the maximum increment is about 39.5% after 6 minutes of DAE crosslinking. Also, that of $O_2/N_2$ gas pair is about 20.5% after 6 minutes of DAE crosslinking. According to these result, DAE is more suitable for enhanced permselectivity than DAH. On the contrary, DAE is not useful for $CO_2/N_2$ separation due to reduction in $CO_2/N_2$ permselectivity after 3 minutes DAE crosslinking.

The Effect of DMPA Contents on the Water Dispersability and Mechanical Properties of Urea Resin (DMPA의 함량이 우레아 수지의 수분산 안정성과 기계적 성질에 미치는 영향)

  • Park, Jae Cheol;Kim, Dong Soo;Lee, Soo
    • Journal of the Korean Applied Science and Technology
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    • v.36 no.4
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    • pp.1128-1135
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    • 2019
  • In this study, different types of polyether amines and H12MDI were used to synthesize water dispersed urea resins, which can be applied to coating material on the concrete slabs for bicycle road using the ordinary application equipments. The concentrations of several polyether amines with different molecular weights and the number of amine functionality were varied to set up the optimal condition for water dispersed urea resin preparation with both an excellent tensile strength and an elongation. In addition, the effect of DMPA[2,2-Bis(hydroxymethyl)propanoic acid] concentration on the storage stability of the water dispersed urea resin was also investigated. The formation of urea bonds from isocyanate and polyether amines was confirmed through FT-IR ATR spectroscopy. From the mechanical properties of urea resins, PU-4 and PU-6, which were prepared with both diamines and triamine of different molecular weights and number of functionality, showed the tensile strength of 10.5 N/㎟ and 12.7 N/㎟, respectively and the elongation of 1165 % and 969%, respectively. Among the water dispersed urea resin synthesized with different contents of DMPA, PU-6 showed the highest mechanical properties, a tensile strength of 14.2 N/㎟ and an elongation of 993%. In addition, the water dispersion state of this PU-6 was the most stable even after 8 weeks.

Optimum Chain Extension and Change of the Average Particle Size of Aqueous Polyurethane Dispersion (수분산 폴리우레탄 제조시 최적 사슬연장 조건과 입도 변화에 관한 연구)

  • Kong, H.C.;Jhon, Y.K.;Cheong, I.W.;Kim, J.H.
    • Journal of Adhesion and Interface
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    • v.3 no.2
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    • pp.9-16
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    • 2002
  • In the synthesis of water-based polyurethane using self-emulsification process, after being neutralized, polyurethane pre-polymers containing ionic pendant groups are dispersed by simple convective mixing. Preparation of dispersion is followed by chain extension reaction, which is considered as important step for growth of the molecular weight of polyurethane. In this work, pH variations in the aqueous phase were monitored during the chain extension process in the presence of water-soluble diamines. The optimum degree of chain extension and the average particle size in the polyurethane dispersions were examined with varying ionic pendent group contents, type of chain extenders, and feed rate of chain extenders, The initial pH value in the aqueous phase linearly increased and the optimum chain extension point could be obtained from the intersection of two linear lines having different slopes, All average particle sizes before chain extension reaction were almost same, however, the final average particle size increased as feed rates of chain extenders increased, In addition, as the ionic pendant group contents increased, the particle size decreased since the hydrophilicity and hydrodynamic volume increased. As carbon numbers of the chain extenders increased, the final particle size increased significantly. From the results, it was concluded that the chain extension reaction took place among the particles not only in a particle.

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The Alignment of Liquid Crystals on the Film Surfaces of Soluble Aromatic Polyimides Bearing t-Butylphenyl and Trimethylsilylphenyl Side Groups

  • Hahm, Suk-Gyu;Jin, Kyeong-Sik;Park, Sam-Dae;Ree, Moon-Hor;Kim, Hyung-Sun;Kwon, Soon-Ki;Kim, Yun-Hi
    • Macromolecular Research
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    • v.17 no.12
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    • pp.976-986
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    • 2009
  • With the study goal of firstly elucidating the anisotropic interactions between oriented polymer chain segments and liquid crystal (LC) molecules, and secondly of determining the contributions of the chemical components of the polymer segments to the film surface topography, LC alignment, pretilt, and anchoring energy, we synthesized three dianhydrides, 1,4-bis(4'-t-butylphenyl)pyromellitic dianhydride (BBPD), 1,4-bis(4'-trimethylsilylphenyl)pyromellitic dianhydride(BTPD), and 2,2'-bis(4"-tert-butylphenyl)-4,4',5,5'-biphenyltetracarboxylic dianhydride (BBBPAn), and a series of their organosoluble polyirnides, BBPD-ODA, BBPD-MDA, BBPD-FDA, BTPD-FDA, and BBBPAn-FDA, which contain the diamines 4,4'-oxydianiline (ODA), 4,4'-methylenediamine (MDA), and 4,4'-(hexafluoroisopropylidene)dianiline (FDA). All the polyimides were determined to be positive birefringent polymers, regardless of the chemical components. Although all the rubbed polyimide films exhibited microgrooves which were created by rubbing process, the film surface topography varied depending on the polyimides. In all the rubbed films, the polymer chains were unidirectionally oriented along the rubbing direction. However, the degree of in-plane birefringence in the rubbed film varied depending on the polyimides. The rubbing-aligned polymer chains in the polyimide films effectively induced the alignment of nematic LCs along their orientation directors by anisotropic interactions between the preferentially oriented polymer chain segments and the LCs. The azimuthal and polar anchoring energies of the LCs ranged from $0.45{\times}10^{-4}\;-\;1.37{\times}10^{-4}\;J/m^2$ and from $0.86{\times}10^{-5}\;-\;4.26{\times}10^{-5}\;J/m^2$, respectively, depending on the polyimides. The pretilt angles of the LCs were in the range $0.10-0.62^{\circ}$. In summary, the soluble aromatic polyimides reported here are promising LC alignment layer candidates for the production of advanced LC display devices.

Metal Complexes of Ambidentate Ligand(Ⅳ). Nickel(Ⅱ) and Palladium(Ⅱ) Complexes of bis(isonitrosoacetylacetone)diimine Derivatives (Ambidentate 리간드의 금속착물 (제 4 보). Bis(isonitrosoacetylacetone)diimine 유도체를 리간드로 하는 니켈(Ⅱ) 및 팔라듐(Ⅱ) 착물)

  • Man-Ho Lee;Seon-Ho Lee
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.428-435
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    • 1988
  • Some nickel(Ⅱ) and palladium(Ⅱ) complexes of the ambidentate ligands derived from condensation of the isonitrosoacetylacetone and various diamines, $Ni(IAA)_2-en$, $Ni(IAA)_2-pn$, $Ni(IAA)_2-tn$, $Pd(IAA)_2-en$, PdCl(IAA)-pn, and $Pd(IAA)_2$-tn, where (IAA)$_2$-en, $(IAA)_2$-tn, and (IAA)-pn represent N,N'-enthylenbis(isonitrosoacetylacetone imine), N,N'-propylenebis(isonitrosoacetylacetone imine), N,N'-trimethylenebis(isonitrosoacetylacetone imine) and N-(2-aminopropyl)isonitrosoacetylacetone imine, respectively, have been prepared. The nickel(Ⅱ) and palladium(Ⅱ) complexes were characterized on the bases of the elemental analysis, IR, NMR, and electronic spectra. It is suggested that a isonitroso group of (IAA)$_2$-en or (IAA)$_2$-tn coordinates to the metal ion through the nitrogen atom to form five-membered ring, while the other isonitroso group of (IAA)$_2$-en or (IAA)$_2$-tn coordinates to the metal ion through the oxygen atom to form six membered ring in square-planar complexes of Ni(IAA)$_2$-tn and Pd(IAA)$_2$-en. And two isonitroso groups of (IAA)$_2$-en, (IAA)$_2$-pn, or (IAA)$_2$-tn coordinate to the metal ion through the nitrogen atom to form five-membered rings in square-planar complexes of Ni(IAA)$_2$-en, Ni(IAA)$_2$-pn, and Pd(IAA)$_2$-tn. On the other hand, square-planar PdCl(IAA)-pn is formed by the reaction of propylenediamine with a isonitrosoacetylacetone in the presence of palladium(Ⅱ)ion.

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Macrotri-and Macrotera-cyclic Ni (II) and Cu (II) Complexes. Synthesis of the Complexes and the Square Planar-Octahedral Equilibrium of the Ni (II) Complexes (거대세고리와 거대네고리 리간드의 니켈 (II) 및 구리 (II) 착물의 합성과 니켈 (II) 착물의 평면사각형-팔면체 평형)

  • Shin-Geol Kang;Jung Soo-Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.527-533
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    • 1991
  • Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(II) or Cu(II) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands $[M(L)]^{2+}$(M = Ni(II) or Cu(II); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,$1^{8,11}$]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,$1^{12,15},0^{4,9}]$docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,$1^{8,12}$]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,$1^{12,16},0^{4,9}]$tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(II) and Cu(II) complexes are presented. The effects of the ligand structure on the equilibrium $[Ni(L)]^{2+}2H_2O{\rightleftharpoons}[Ni(L)(H_2O)_2]^{2+}$ in aqueous solutions are described.

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