红色基RL的合成工艺改进

详细研究了红色基RL(对硝基邻甲苯胺,简称RL)的合成工艺,对传统的合成工艺进行了改进,通过用乙酐作氨基保护试剂,混酸硝化,酸性水解等分步操作合成了RL。与传统方法相比,采用乙酐作氨基保护试剂,高温酰化,减少了乙酐用量;用混酸硝化,增强了硝化能力,提高了收率。分别研究了乙酐用量、反应时间、反应温度以及混酸配比对RL收率及熔点的影响规律,得到了反应的较佳条件。采用乙酐酰化分步合成法,RL总收率为56·4%(以邻甲苯胺计),氨基值为91·26%。     

Synthesis and air separation of soluble terpolymers from Aniline,Toluidine, and Xylidine

A series of terpolymers were synthesized by oxidative polymerization of aniline, o-toluidine, and 2,3-xylidine with three monomer ratios using ammonium persulfate as an oxidant in two acidic media. The yield and intrinsic viscosity of the terpolymers were studied by changing the polymerization temperature and medium. The resulting terpolymers were characterized by ¹H–NMR, wide-angle X-ray diffraction, differential scanning calorimetry, thermogravimetry, and constant pressure-variable volume methods. The results showed that the terpolymers are amorphous and exhibit enhanced solubility, high thermostability, and high char yield, greater than 35 wt % at 900°C in nitrogen. A blend membrane of the terpolymer with ethyl cellulose shows good air-separation ability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 790–798, 2001     

Anti-corrosive properties of waterborne polyurethane/poly(o-toluidine)-ZnO coatings in NaCl solution

The aim of this research was to prepare waterborne polyurethane (WPU) coating blended with a series of poly(o-toluidine)-nano ZnO composites and study its anti-corrosion performance after its application over carbon steel. The synthesized composites were characterized by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The corrosion resistance of coatings with and without nano ZnO were studied in 3.5% NaCl solution at a temperature of 25?°C, by electro-chemical techniques such as potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS). It was observed that the composite coating containing 7% poly(o-toluidine)-nano ZnO composite had higher corrosion resistance than poly(o-toluidine) and 14% poly(o-toluidine)-nano ZnO composite. The presence of appropriate amount of ZnO significantly improved the corrosion resistance, due to the formation of passive layer on steel surface and the synergistic effects of poly(o-toluidine) along with a suitable amount of nano-ZnO reduced the porosity of the coating surface.     

对甲苯磺酸掺杂聚邻甲苯胺的合成及电流变性能

以对甲苯磺酸(TSA)作为掺杂剂和乳化剂,乳液聚合合成了对甲苯磺酸掺杂聚邻甲苯胺(TSA-POT)。采用红外光谱、热重分析和扫描电镜对聚合物的结构、热稳定性及形貌进行了表征。制备了TSA-POT/硅油(SO)无水型电流变流体(ER流体),测试了其电流变性能,考察了电场强度、反掺杂条件、粒子浓度等因素对TSA-POT/SO体系电流变性能的影响。结果表明,由于强极性的磺酸基团与聚邻甲苯胺的主链相连,极大地改善了聚合物粒子的极化性能,因此TSA-POT/SO体系的电流变性能显著改善。结果同时表明,低浓度的TSA-POT/SO体系的屈服应力与电场强度具有二次线性关系。     

Self-Assembly of Methyl Substituted Polyaniline Hollow Nanospheres in a Polyelectrolyte Solution

Hollow nanospheres of poly(m-toluidine), poly(o-toluidine), and poly(N-methylaniline) were successfully prepared in a solution of poly(methyl vinyl ether-alt-maleic acid) by using ammonium persulfate as the oxidant. The polymerization processes of methyl substituted aniline were monitored by recording pH and temperature changes of the reaction medium. The experimental results showed that the substitution position of methyl group affected the characteristics of formed hollow nanospheres. The formation mechanism of such hollow nanospheres was suggested. The produced hydrophobic oligomers self-assembled at the interface of water/droplet of monomers and acted as the soft template for the formation of hollow spheres.     

还原桃红R中间体2-羟基-4-甲基-6-氯苯并[1,2,3]二噻唑的合成研究

以邻甲苯胺为原料,与盐酸成盐制得邻甲苯胺盐酸盐,其再经硫化得2-氯-4-甲基-6-氯苯并[1,2,3]二噻唑,最后经水解合成还原桃红R中间体2-羟基-4-甲基-6-氯苯并[1,2,3]二噻唑。笔者对成盐反应物质的量及硫化反应的物物质的量比、反应温度、反应时间及溶剂用量等因素进行了探讨,得出优化反应条件为:n(邻甲苯胺)∶n(氯化氢)=1∶1.13,成盐收率可达99.8%;邻甲苯胺盐与一氯化硫硫化,n(邻甲苯胺盐)∶n(一氯化硫)=1∶3.75,硫化反应温度60±2℃,保温反应时间4 h,溶剂质量与邻甲苯胺盐物质的量的比为182.1 g/mol,此时目标产物的收率可达95.5%。产物结构经IR、LC/MS与1H NMR确证。     

"一锅法"合成2-氨基-4-甲基苯并噻唑的工艺研究

以邻甲苯胺为原料,采用“一锅法”直接合成2-氨基-4-甲基苯并噻唑,获得了最佳工艺条件。该方法避免了通过合成N-邻甲苯基硫脲后再合成产品的两个环节,具有工艺过程简单,操作方便的优势。放大实验结果表明,在最佳工艺条件下,产品的平均收率达到了88％。     

Adsorption of reaction species for hydrogenation of o-nitrotoluene on copper chromite under catalytic conditions

Adsorption of reaction species involved in vapour phase hydrogenation of o-nitrotoluene (viz. o-nitrotoluene, o-toluidine and water) on copper chromite in presence of an inert gas (He) or hydrogen (which is one of the reactants) at temperature (473-560 K) and partial pressures at which the catalytic reaction is carried out has been investigated using the gas chromatographic pulse technique. The presence of hydrogen was found to cause a very significant decrease in the adsorption of toluidine but a little effect on the adsorption of water. The adsorption data for all the reaction species could be fitted to the Freundlich adsorption equation. The isoteric heats of adsorption obtained from the adsorption isotherm indicated that o-toluidine and water are physically absorbed, whereas o-nitrotoluene is chemisorbed on the catalyst. The heat of adsorption of water and o-nitrotoluene was found to decrease with the increase in the surface coverage, indicating repulsive interactions between the adsorbed species. On the other hand the heat of adsorption of o-toluidine (in presence or absence of H₂) was found to increase with the increase in the surface coverage, suggesting attractive interactions between the absorbed species.     

Towards enhanced electrochemical capacitance with self‐assembled synthesis of poly(pyrrole‐co‐o‐toluidine) nanoparticles

Poly(pyrrole‐co‐o‐toluidine) (PPOT) nanoparticles for electrochemical capacitors are easily and productively synthesized by a chemical oxidative polymerization of pyrrole (PY) and o‐toluidine (OT) in 0.5M HCl without any external additive. The polymerization yield, electrical conductivity, and size of the copolymer nanoparticles can significantly be optimized by the oxidant/monomer molar ratio and polymerization temperature. The chemical structure of the obtained copolymer is characterized by UV–vis and FTIR. The copolymer nanoparticles synthesized at 10°C are found to generally have irregular granular morphology with a diameter of 60–100 nm and a small polydispersity index of 1.06 by laser particle‐size analyzer, FE‐SEM, and TEM, and good dispersibility in water. The formation mechanism of the nanoparticles is proposed based on the powerful amphipathicity from comonomer aggregate formed by PY and OT in the monomer solution. The PPOT nanoparticles possess a specific capacitance of 310 F g^?1 at 25 mV s^?1 as well as retain 81% of the initial specific capacitance value after 1000 cycles, while its energy density and power density are found to be 40.2 and 1196 W Kg^?1 at 2 A g^?1. The enhanced electrochemical properties can be attributed to the nanostructural advantage of the PPOT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42995.     

Peroxy Disulphate Initiated Graft Copolymerization of o-toluidine onto Wool and Nylon6 Fibres -A Kinetic Approach

Abstract

Graft copolymerization of o-toluidine (OT) onto wool and nylon6 fibres were carried out by using Peroxy disulphate (PDS) as a lone initiator in aqueous acidic medium under nitrogen atmosphere. Various graft parameters like % grafting, % grafting efficiency and rate of grafting were determined. Grafting occurs with simultaneous homopolymer formation. Rate of homopolymerization was also followed. The content of poly(o-toluidine) (POT) in the backbone fibres were found to vary while changing the [OT], [PDS], (amount of fibre). Chemical grafting was confirmed by FTIR spectroscopy, cyclicvoltammetry (CV) and conductivity measurements. Probable mechanism has been proposed to explain the experimental results obtained.