Bis(3-aminophenyl)methyl phosphine oxide-based (methyl) nadicimide resins

Ten nadicimide/methyl nadicimide end-capped oligomeric resins were prepared by reacting endo-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic anhydride), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6F), and bis(3-aminophenyl) methyl phospine oxide (BAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, IR, and ¹H-NMR. Multistep decomposition was observed in the TG scan of uncured resins in a nitrogen atmosphere. Residual weight at 800°C depended on the structure and ranged between 25 and 51%. Isothermal curing of the resins was done at 300°C for 1 h in an air atmosphere. These cured resins were stable to 350 ± 30°C and decomposed in a single step above this temperature. The char yield of the resins increased on curing and was in the range 34–70%. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:861–869, 1997     

硫代磷酸三(4-氨基苯酯)的合成及应用进展

介绍了硫代磷酸三(4-氨基苯酯)的国内外研究现状、各种合成方法以及它在聚氨酯、涂料、照相乳剂等方面的应用进展。     

Aluminiumalkyle mit Heteroatomen. II [1]. Darstellung von Tris(3-trimethylsilyl-propyl)aluminium

Aluminium Alkyls with Heteroatoms. II. Preparation of Tris[(3-trimethylsilyl)-propyl]aluminium Tris[(3-trimethylsilyl)-propyl]aluminium is prepared by disproportionation and by an olefine displacement reaction in a circulation process. The reaction way is investigated with the aid of ¹H-n.m.r.- and i.r.-spectroscopy.     

Synthesis,characterization, and thermal properties of tris (3‐aminophenyl) phosphine oxide‐based nadimide resins

This article describes the synthesis, characterization, and thermal properties of nadimides obtained by reacting endo‐5‐norbornene‐2,3‐dicarboxylic acid anhydride (nadic anhydride) (NA), 4,4′‐oxodiphthalic anhydride (ODA), 1,4,5,8‐naphthalene tetra carboxylic dianhydride (NTDA) in glacial acetic acid/DMF. Structural characterization of the resins was done by elemental analysis, IR, ¹H‐NMR, and ¹³C‐NMR. The DSC scan showed the endothermic transition in the temperature range of 120–270°C. Multistep decomposition was observed in the TG scan of uncured resins in nitrogen atmosphere. Isothermal curing of the resins was done at 250 and 300°C for 1 h in an air atmosphere. These cured resins were stable to (350 ± 30)°C and decomposed in a single step above this temperature. This may be due to the retro Diels Alder (RDA) reaction. The char yield of the resins increased significantly on curing. The char yield was highest for P‐2N resin and this could be due to the presence of rigid skeleton i.e. naphthalene. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and Characterization of Poly[bis(3-aminophenyl) diselenide] and Poly[bis(3-aminophenyl) diselenide-co-aniline]

Summary Bis(m-aminophenyl)diselenide was synthesized by diazotation of m-nitroaniline followed by incorporation of potassium selenium cyanate, and the reduction of the nitro groups by addition of tin and concentrated HCl. This dihydrochloride monomer was polymerised using ammonium persulphate in 0.25 M HCl as oxidizing agent. Copolymers of aniline with bis(m-aminophenyl)diselenide were prepared by oxidation of diselenide and aniline mixtures, at several mole ratios of aniline in the feed (f₁), with the same oxidizing agent. In the all the range of polymers analysed there are more diselenide comonomer units than aniline units. The polymer and copolymers were characterized by FTIR, elemental analysis, thermal stability and electrical conductivity, showing a high thermal stability, with a weight loss of 10% at 400 °C and there is an important effect of groups diselenide on the electrical properties, because conductivities are highly modified when the substitution is in m-position in the aniline ring. Therefore, it is necessary to add a high mole ratio of aniline in the feed to obtain copolymers with conductivities within the semi-conduction range.     

Studies on thermosetting bisimide resins based on N,N-(4-aminophenyl)-p-quinone diimine

The paper describes two novel bisimide resins, i. e. MQA and NQA, prepared by reacting N,N'-(4-aminophenyl)-p-benzoquinone diimine (QA) with maleic anhydride or 5-norbornene-2,3-dicarboxylic (nadic) anhydride in glacial acetic acid. These resins were characterised by IR spectroscopy, DSC and thermogravimetric analysis. The char yield (at 800°C) in nitrogen atmosphere for MQA and NQA was found to be 56% and 61%, respectively. Chain extension of bismaleimides containing flexible ether linkages, i. e. 1,3-bis(4-maleimidophenoxy)benzene and 1,4-bis(4-maleimidophenoxy)benzene with QA was also carried out. The thermal stability of the chain-extended bismaleimide resins was lower than that of the neat bismaleimide resins.     

双(3-氨基苯基)苯基氧化膦的合成与表征

以三苯基氧化膦为原料,通过硝化和还原反应合成了标题化合物,并采用差示扫描量热法、红外光谱、核磁共振和质谱等方法对产品进行了表征.     

Laser Initiation of Tris(carbohydrazide)metal(II) Perchlorates and Bis(carbohydrazide)diperchlorato‐copper(II)

The literature‐known tris(carbohydrazide)metal(II) perchlorates [M(CHZ)₃](ClO₄)₂ (MMg²⁺ ( 1 ), Mn²⁺ ( 2 ), Co²⁺ ( 3 ), Ni²⁺ ( 4 ), and Zn²⁺ ( 5 )) and the bis(carbohydrazide)diperchloratocopper(II) ( 6 ) were prepared and characterized by elemental analysis, IR and Vis/NIR spectroscopy. The sensitivities toward mechanical, thermal, and electrical stimuli were determined for all complexes 1 – 6 . Following, confined samples of 1 – 6 were irradiated with a monopulsed laser beam at a wavelength of 940 nm. The function times between beginning irradiation and complete decomposition (“breakout” at the end of the device) were measured. Further, the influence of light‐absorbing additives was investigated to proof if the laser initiation mechanism might be photothermal or photochemical. Addition of 1 % active carbon to the samples decreased the function time and the correlated initiation threshold enormously. This was an indication that the initiation mechanism seems to be thermal.     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445     

Cure of polyester resins. II

The copolymerization reaction between unsaturated polyesters and styrene has been studied by a torsional pendulum. The accuracy of the dynamic-mechanical measurements obtained is discussed briefly, and the results are compared with those of previous work on the change of hardness during cure.     

1-(3-氨基苯基)-3-(4-氨基苯基)-2-丙烯-1-酮的合成

以对乙酰氨基苯甲醛、间乙酰氨基苯乙酮为原料经两步反应合成具有光敏性能的1 (3 氨基苯基) 3 (4 氨基苯基) 2 丙烯 1 酮。通过优化实验得到最佳的合成工艺条件为:对乙酰氨基苯甲醛、间乙酰氨基苯乙酮在温度为0℃下,以乙醇为溶剂、氢氧化钠为催化剂,进行羟醛缩合反应3h。分离提纯后,加入盐酸溶液在100℃下水解3h,产物经重结晶提纯。总收率达到61 9%,较1998年的文献[6]提高39 3%。并对产物的结构进行了表征。     

Tris(2,2′-bipyridyl) ruthenium(II)-bisoprolol-based electrochemiluminescence coupled with capillary zone electrophoresis

Capillary zone electrophoresis (CZE) coupled with tris(2,2′-bipyridyl) ruthenium(II)-based end-column electrogenerated chemiluminescence (ECL) has been utilized to detect bisoprolol in drugs and tablets after its separation from metoprolol. Tetrahydrofuran was used as an additive in the running buffer to obtain the absolute ECL peak of bisoprolol. Bisoprolol reacts as a co-reactant in tris(2,2′-bipyridyl) ruthenium(II) ECL system. Under the optimized experimental conditions, bisoprolol was separated successfully and efficiently from metoprolol and other co-existed materials in tablets and urine samples. The ECL intensity of tris(2,2′-bipyridyl) ruthenium(II)-bisoprolol-based system is linear with the concentration of bisoprolol from 1.5 μM to 0.3 mM with a detection limit of 0.3 μM. Relative standard derivations of the ECL intensity are 2.58% for the detection of 15 μM bisoprolol. This method is a simple, rapid, selective, and sensitive. It was applied successfully for the monitoring of bisoprolol in market available tablets and human urine samples.     

三（对—羟基苯基）—膦的合成研究

以对溴苯酚为原料,经过三步反应合成三（对－羟基苯基）－膦,。反应产物分离方便,产率达到６５％。     

Group II Tris(glycolato)silicates as Precursors to Silicate Glasses and Ceramics

Group II tris(glycolato)silicates, MSi(OCH₂CH₂O)₃ (where M = Ba, Ca, Mg), can be synthesized directly by reaction of silica with ethylene glycol and alkaline-earth (group II) oxides at 200°C. These hexa-alkoxy silicates serve as precursors to silicate glass and ceramic powders. They are readily modified by exchange with longer-chain diols into processable polymer precursors. These Theologically useful precursors may provide access to silicate or aluminosilicate powders, thin fllms, fibers, and coatings. Thus, we have examined the utility of hexacoordinate glycolatosilicates as model precursors. Pyrolysis of the compounds, MSi(OCH₂-CH₂O)₃, in air transforms them to their anticipated ceramic products, MO-SiO₂. The phase transformations and chemical changes that occur during pyrolysis were characterized using X-ray powder diffractometry (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The hexacoordinate glycolatosilicates oxidatively decompose at ∼300°C to form amorphous materials. Moderate to significant quantities of the group II carbonates, MCO₃ (15–50 wt%), form coincidentally as the amorphous intermediates trap CO₂ generated by ligand oxidation. At ∼900°C, the amorphous materials crystallize into the expected, phase-pure, MO-SiO₂.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Copper-selective chelating resins. II. Column extractions

Two chelating resins based on poly(glycidylmethacrylate-co-ethyleneglycol dimethacrylate) and two based on poly(styrene-co-divinylbenzene) have been used in small-scale column extractions of Cu(II) from sulphate solutions containing 1.0 mg l⁻¹ of metal ion at pH 5. Two of the resins bearing 2-aminomethylpyridine residues with saturation capacities up to ∼ 15 g Cu(II) l⁻¹ resin showed sharp breakthrough profiles and rapid exchange kinetics. The other two with higher ligand loading displayed shallow profiles and did not reach saturation capacity, indicating a significant proportion of the ligand groups to be inaccessible under the conditions employed. For a column of 10 ml bed volume, increasing the flow rate of the feed solution from 1 ml min⁻¹ progressively to 30 ml min⁻¹, using one of the more efficient resins, showed that above a rate of ∼ 5 ml min⁻¹ the bulk movement of ions through the column was too fast for all the resin-bound ligands to be accessed. As a result breakthrough moved to lower volumes and the working capacity dropped. No difference was found in the elution of all four resins with 1 M H₂SO₄ at a flow rate of 1 ml min⁻¹. In all cases Cu(II) was rapidly and efficiently eluted from the column.The selectivity properties of the two efficient resins in extracting Cu(II) ions from a solution containing a large excess of Zn(II) ions were also investigated. The effect of a 250-fold excess of Zn(II) proved negligible in both cases, and Cu(II) was rapidly and selectively extracted with a separation factor of ∼ 900: 1 in the case of the polystyrene-based resin, and ∼ 500: 1 in the case of the methacrylate-based species.In terms of kinetic performance and metal ion selectivity (in both loading and elution) the results of the batch extraction experiments were confirmed in these column tests, hence proving the predictive value of careful batch testing. On considering kinetic factors, capacity factors and metal ion selectivity factors, a resin carrying a 2-aminomethylpyridine group attached to a polymethacrylate backbone proved to be the optimum one.     

Synthesis of strong basic resins for uranium recovery (part II)

Summary Ion exchange resins were synthesized by a crosslinking reaction and a subsequent alkylation of the branched polyethylenimine. In general, all the resins have a good retention behaviour for uranium at the pH range tested, besides of an adequate selectivity for uranium compaired to copper.     

9,9-二(4-氨基苯基)芴的合成研究

9,9-二(4-氨基苯基)芴是一种高质量电子发光材料聚酰亚胺的重要中间体。以芴、四氯化碳及苯胺为原料,采用两步法合成了目标化合物,探讨了反应温度、时间等因素对反应的影响。在优化的反应条件下,产品收率达65%,纯度高达99.6%。该合成方法经济,适合工业化生产。     

三(二乙胺基)氯化硅烷的合成

随着半导体集成电路技术的发展,器件表面钝化保护膜的重要性日益显著。氮化硅薄膜是半导体集成电路中最具应用前景的表面钝化材料之一,发展低温的热化学气相沉积(CVD)工艺来沉积氮化硅表面钝化膜是集成电路发展的趋势,而开发新的硅源、氮源前驱体是实现低温淀积氮化硅薄膜的有效途径。设计了一种新的低温CVD氮化硅薄膜的有机硅源前驱体——三(二乙胺基)氯化硅烷,以四氯化硅和乙二胺为原料,在氮气气氛下,研究了原料预处理、二乙胺用量、反应温度和反应时间等工艺因素对合成收率的影响。最佳工艺条件下,收率达77.4%,并利用核磁共振、元素分析及红外光谱表征了产物的组成及结构。     

9,9-二(3-甲基-4-胺基苯基)芴的合成研究

用工业芴酮和邻甲基苯胺为原料,在158～160℃下合成了9,9-二(3-甲基-4-胺基苯基)芴.分析了芴酮和邻甲基苯胺的投料比、反应温度、反应时间、溶剂甲苯的加入量的不同对产品收率的影响.9,9-二(3-甲基-4-胺基苯基)芴采用元素分析、HPLC和荧光光谱等对产品纯度、杂质含量和结构进行分析验证.