人工神经网络阻抑动力学光度法同时测定对苯二胺和间苯二胺

在硫酸性介质中,Fe(Ⅲ)能够催化H2O2氧化甲基红褪色反应,对苯二胺和间苯二胺都能阻抑该催化氧化褪色反应的速度,两者对Fe(Ⅲ)催化H2O2氧化甲基红褪色反应阻抑作用不具有加和性,根据这一现象,用人工神经网络处理非线性体系的优势进行数据处理,从而建立了一种新的测定对苯二胺和间苯二胺混合物的人工神经网络阻抑动力学光度法。对6组混合样品进行测定,回收率均在95%～105%之间。该方法运用于实验室水样的分析。     

13-Nuclear Magnetic Resonance Studies of Polyetherurethaneureas

A series of linear polyurethaneureas was prepared by a two-step solution polymerization method. The prepolymer formed by the reaction of 4,4′-diphenyl methane diisocyanate with polyethylene glycol/polypropylene glycol was further chain extended with ethylene diamine/propane diamine/hexane diamine. The chemical shift values of various carbon species of the block copolymer were analyzed and assigned. The products formed due to the presence of water at different stages of polymerization were also characterized.     

脂二胺在颜料分散体中光化学反应活泼自由基的ESR研究

用自旋捕捉技术与ESR相结合的方法研究了脂二胺在ZnO、TiO₂的庚烷或苯的分散体系中光诱导的电子转移过程。观察到DMPO与氮中心自由基加合物的ESR信号,表明捕捉到的自由基是脂二胺与光生空穴作用而产生的胺的阳离子自由基。     

芳香-脂肪族共聚酰胺溶致液晶行为的研究

本文对脂肪族二元胺(ADA、NH_2(CH_2)_nNH_2、n=2、6、8、10、12),对苯二胺(PPD)和对苯二甲酰氯(TPC)三元芳香-脂肪族共聚酰胺硫酸溶液的溶致液晶性能进行了研究.利用偏光显微镜、小角和宽角X-光衍射确定了该类共聚酰胺溶致液晶中介相的类型随共聚物中脂肪族二胺链单元含量的变化规律.     

活性炭和H2O2存在下辉光放电等离子体降解邻苯二胺

活性炭和H2O2存在下辉光放电等离子体降解邻苯二胺;辉光放电等离子体;降解;邻苯二胺;废水处理     

Adsorption mechanism of mixed cationic/anionic collectors in feldspar-quartz flotation system

The adsorption mechanism of mixed cationic alkyl diamine and anionic sulfonate/oleate collectors at acidic pH values was investigated on microcline and quartz minerals through Hallimond flotation, electrokinetic and diffuse reflectance FTIR studies. In the presence of anionic collectors, neither of the minerals responded to flotation but the diamine flotation of the minerals was observed to be pH and concentration dependent. The presence of sulfonate enhanced the diamine flotation of the minerals by its co-adsorption. The difference in surface charge between the minerals at pH 2 was found to be the basis for preferential feldspar flotation from quartz in mixed diamine/sulfonate collectors. The infrared spectra revealed no adsorption of sulfonate collector when used alone but displayed its co-adsorption as diamine-sulfonate complex when used with diamine. The presence of sulfonate increased the diamine adsorption due to a decrease in the electrostatic head-head repulsion between the adjacent surface ammonium ions and thereby increasing the lateral tail-tail hydrophobic bonds. The mole ratio of diamine/sulfonate was found to be an important factor in the orientation of alkyl chains and thus the flotation response of minerals. The increase in sulfonate concentration beyond diamine concentration leads to the formation of soluble 1:2 diamine-sulfonate complex or precipitate and the adsorption of these species decreased the flotation since the alkyl chains are in chaotical orientation with a conceivable number of head groups directing towards the solution phase.     

Chiroptical nanofibers generated from achiral metallophthalocyanines induced by diamine homochirality

Optically active cofacial π-π phthalocyanine (Pc) stacked supramolecules were spontaneously and successfully generated from a mixture of four possible geometric isomers (C(4h), D(2h), C(2v), C(s)) of achiral 4(5),4'(5'),4'(5'),4'(5')-tetracarboxymetallophthalocyanine (tcPcM; M=Ni, Cu) induced by an equimolar amount of inexpensive chiral diamine molecular sources in DMSO/CHCl(3) mixed solvent under optimized conditions of the volume ratio of poor/good cosolvents, the molar ratio of chiral molecular diamine to tcPcM, the cavity metal of phthalocyanine, and the addition order of the amines. The sign and amplitude of circular dichroism spectra due to the supramolecular chirality and structure of the diamine molecules are impossible to remove by additions of the antipode diamine and trifluoroacetic acid. The chiral diamine was partly contained in nanofibers, and that retained in the solution can be recycled and reused to induce optically active tcPcM supramolecules.     

Regular copolyamides. II. Preparation and characterization of regular aliphatic copolyoxamides

Regular copolyoxamides were prepared from diamine-oxamides and aliphatic diacid chlorides by interfacial and solution polymerization. Interfacial polymerization is preferred with diamineoxamides where the diamine portion has two to six methylene groups and the diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides with more than six methylene groups in the diamine portion of the molecule are better prepared by solution polymerization in dimethyl acetamide. Regular aliphatic oxamides are soluble in trifluoroacetic acid and hexafluoroisopropanol and show a considerable alternation of the melting point behavior in the diamine portion of the polyamides with up to five methylene groups. Copolyoxamides with two and four methylene groups melt higher than the copolyoxamides with three and five methylene groups. Aliphatic copolyoxamides/adipamides melt at approximately 260°C and show a steady decrease in melting points to about 220°C for polyoxamides with twelve methylene groups.     

A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis

A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443     

Synthesis and characterization of water‐soluble hyperbranched poly(ester amine)s from diacrylates and diamines

Various water‐soluble hyperbranched poly(ester amine)s were synthesized by the direct polyaddition of diamines to diacrylates in the absence of a catalyst. Each diamine contained a secondary amino group and a primary amino group such as 1‐(2‐aminoethyl)piperazine, N‐methyl‐1,3‐propanediamine, or N‐ethylethylenediamine. When the ratio of diacrylate to diamine was 1/1, no gelation was observed throughout the polymerization. When the ratio of diacrylate to diamine was 3/2, no crosslinking occurred in the diluted solution, whereas an insoluble network formed in the concentrated solution. Fourier transform infrared and mass spectrometry were used to investigate the reaction procedure. The secondary amino group of diamine reacted faster with the vinyl group of diacrylate; this resulted in the formation of the intermediate with an acrylate group and two active hydrogen atoms attached to a nitrogen atom. Further self‐polyaddition of the intermediate, a kind of AB₂‐type monomer, gave the hyperbranched poly(ester amine). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2340–2349, 2002     

Synthesis of cross-linked epoxy microparticles: effect of the synthesis parameters

Epoxy crosslinked microparticles were synthesized from the reaction between diglycidyl ether of bisphenol A and a diamino hardener, through precipitation polymerization in a polypropylene glycol solvent. The influence of the monomer concentration, the amine/epoxy stoichiometric ratio, the reaction temperature and the structure of the diamine (aromatic or cycloaliphatic) were investigated, since these parameters may affect the structure and properties of the particles. Morphological analysis revealed that, in all cases, spherical particles were obtained with diameters ranging from 1 to 6 μm. The glass transition temperatures of the particles was found to vary between 130 and 160 °C using the aromatic diamine and between 116 and 141 °C using the cycloaliphatic diamine. It was also found that the effective stoichiometry of the particles was different from the initial stoichiometry in the feed solution.     

功能聚间苯二胺膜用于免疫传感器分析

以电化学聚合法在石墨电极上获得聚间苯二胺膜（ＰＭＰＤ），并建立了快速、灵敏的膜质量检验方法：辣根过氧化物酶（ＨＲＰ）标记ＰＭＰＤ膜－邻苯二胺（ＯＰＤ）反应法，对聚合、活化等条件作了研究；进一步制成了检测乙肝表面抗原（ＨＢｓＡｇ）和检测鼠免疫蛋白（ＭＩｇＧ）的免疫电极，对血清样品作了检测．结果表明：２．５Ｖ电池电压下，于含０．１２ｍｏｌ／ＬＭＰＤ的１．２ｍｏｌ／ＬＨ２ＳＯ４中聚合２０ｍｉｎ，再以３０ｇ／Ｌ浓度的戊二醛活化４ｈ，所得ＨＲＰ标记电极及免疫电极重现性好；检测ＨＢ－ｓＡｇ和ＭＩｇＧ的线性范围分别为０．１～３．２ｍｇ／Ｌ及０．１～１０ｍｇ／Ｌ     

A calorimetric study on the relative thermal stabilities of some cobalt(III)-tris(diamine) and -bis(triamine) complexes in the solid phase

The enthalpy changes for the reaction of [Co(AA)₃]X₃ and [Co(dien)₂]X₃ type complexes with an alkaline sodium sulfide solution were calorimetrically measured at 25°C, where AA is the diamine such as en, pn, tn, bpy or phen and X is Cl, Br, NO₃, I or ClO₄. The thermal stabilities were found to decrease in the following orders: chloride > bromide > nitrate > iodide > perchlorate; aliphatic diamine > aromatic diamine complexes; five-membered chelate > six-membered chelate compounds; and tris(diamine) > bis(triamine) complexes.     

Synthesis and characterization of novel aromatic polyamides from 3,4-bis(4-aminophenyl)-2,5-diphenylfuran and aromatic diacid chlorides

A new highly phenylated heterocyclic diamine, 3,4-bis(4-aminophenyl)-2,5-diphenylfuran, was synthesized in three steps from 4–-nitrodeoxybenzoin. The low temperature solution polycondensation of the diamine with various aromatic diacid chlorides afforded tetraphenylfuran-containing aromatic polyamides with inherent viscosities of 0.2–0.8 dL/g. Copolyterephthalamides were obtained from the diamine and 4,4′-oxydianiline. The polyamides were generally soluble in a wide range of solvents that included N,N-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, and m-cresol. Glass transition temperatures of the polyamides and copolyamides ranged from 302–342°C, and 10% weight loss was observed above 480°C in nitrogen.     

Preparation of silicon containing polymers. II.. Effect of structure on the thermal stability of organosilicon aramids

Two silicon-containing acid dichlorides, bis(4-chlorocarbonylphenyl)dimethylsilane and bis(4-chlorocarbonylphenyl)diphenylsilane, were synthesized and reacted with 1,3-phenylene diamine, 1,4-phenylene diamine, 4,4′-diaminodiphenyl, 4,4′-diaminodiphenyl methane 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl sulfone in the preparation of 12 structurally different high molecular weight aromatic polyamides. A low-temperature interfacial polycondensation technique was used. Most of the polyamides formed tough, transparent, flexible films and were characterized by solubility, solution viscosity, infrared spectroscopy (IR), and glass transition temperature (T_g). The thermal behavior of these aramids was studied by dynamic thermogravimetry. The effect of diamine and acid dichloride structure on the aramids properties is also discussed.     

Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations

The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane‐1,diamine, propane‐1,3‐diamine and nonane‐1,9‐diamine) and their N,N′‐dimethyl and N,N,N′,N′‐tetramethyl derivatives in chloroform solution has been investigated by ¹H and ¹³C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)_n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH₃) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane‐1,9‐diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane‐1,2‐diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.     

Optimization of catalyst enantioselectivity and activity using achiral and meso ligands

The optimization of asymmetric catalysts for enantioselective synthesis has conventionally revolved around the synthesis and screening of enantiopure ligands. In contrast, we have optimized an asymmetric reaction by modification of a series of achiral ligands. Thus, employing (S)-3,3'-diphenyl BINOL [(S)-Ph(2)-BINOL] and a series of achiral diimine and diamine activators in the asymmetric addition of alkyl groups to benzaldehyde, we have observed enantiomeric excesses between 96% (R) and 75% (S) of 1-phenyl-1-propanol. Some of the ligands examined have low-energy chiral conformations that can contribute to the chiral environment of the catalyst. These include achiral diimine ligands with meso backbones that adopt chiral conformations, achiral diimine ligands with backbones that become axially chiral on coordination to metal centers, achiral diamine ligands that form stereocenters on coordination to metal centers, and achiral diamine ligands with pendant groups that have axially chiral conformations. Additionally, we have structurally characterized (Ph(2)-BINOLate)Zn(diimine) and (Ph(2)-BINOLate)Zn(diamine) complexes and studied their solution behavior.     

Synthesis,characterization, and thermal properties of novel arylene sulfone ether polyimides and polyamides

A new aromatic sulfone ether diamine was synthesized by nucleophilic aromatic substitution reaction of 5‐amino‐1‐naphthol with bis(4‐chlorophenyl) sulfone in the presence of potassium carbonate in a polar aprotic solvent. Polycondensation reactions of the obtained diamine with pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), and hexafluoroisopropylidene diphthalic anhydride (6FDA) resulted in preparation of thermally stable poly(sulfone ether imide)s. Poly(sulfone ether amide)s also were prepared by reaction of the diamine with terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC). The prepared monomer and polymers were characterized by conventional methods. Physical and mechanical properties of polymers, including thermal stability, thermal behavior, solution viscosity, solubility behavior, and modulus, also were studied. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1487–1492, 2000     

Synthesis of Poly(galactaramides) from Alkylene- and Substituted Alkylenediammonium Galactarates

Polyhydroxypolyamides (PHPAs) represent a class of synthetic polyamides derived from aldaric acid and diamine monomer units. This paper describes the synthesis of some poly(galactaramides), a class of polyhydroxypolyamides, that employs alkylene and substituted alkylenediammonium galactarate salts, with 1:1 molar equivalency of the diacid and diamine monomer components, as precursors for the polyamides. The salts were treated with acid/alcohol and then base in order to initiate the polymerization in methanol. The polyamides, labeled as prepolyamides, precipitated from solution and were then subjected to a second polymerization (postpolymerization) in a different solvent to produce a generally larger polyamide, labeled as a postpolyamide.     

Condensation polymerization of pyromellitic dianhydride with aromatic diamine in aprotic solvent: A reaction mechanism

Based on nuclear magnetic resonance (NMR) studies, a probable reaction mechanism was proposed for the condensation polymerization of pyromellitic dianhydride with aromatic diamines in aprotic solvent, N,N-dimethylacetamide (DMAc), to yield aromatic polyimides. The mechanism shows the essential role played by the solvent during polymerization reaction and in imidization. It explains the formation of polyamic acid and that of its high molecular weight buildup under the conditions in which solid dianhydride was added to the solution of diamine in DMAc. A prepolymer complex formation was observed, along with the main polyamic acid, when solid diamine was added to the solution of dianhydride in DMAc. The structure of the prepolymer was derived on the basis of NMR and its formation explained in the mechanism. The nature of the prepolymer was such that on treatment with anhydride it goes to polyamic acid.