Improved synthesis of functionalized 5,6-dihydro-pyrimido[4,5-b][1,4]oxazepines

Novel synthetic approaches toward 5,6-dihydro-pyrimido[4,5-b][1,4]oxazepines were reported that led to successful introduction of poorly reactive anilines and various 2-hydroxybenzaldehydes to this therapeutically relevant scaffold. More extensive SAR studies on this scaffold hence became possible.     

A model for thermal degradation of hybrid nanocomposites

A model is developed for thermal degradation of polymer nanocomposites. A composite is thought of as an equivalent network of linear chains with attached side-groups. Thermal degradation is treated as combination of (i) binary scission (fragmentation) of backbone chains, and (ii) detachment of side-groups and their subsequent annihilation (diffusion to the surface of a sample and desorption). An explicit solution is derived for the kinetic equation. This solution involves three adjustable parameters that are found by fitting observations on isotactic polypropylene reinforced with carbon nanofibres. Good agreement is demonstrated between the experimental data and the results of numerical simulation.     

Colour formation in poly(ethylene terephthalate) during melt processing

The discolouration, that occurs in virgin poly(ethylene terephthalate) - PET during melt processing, was studied using various bulk and surface analytical techniques. Proton nuclear magnetic resonance (¹H NMR) was used to study the bulk chemical changes occurring in the polymer during thermo-oxidative degradation. Chemical derivatisation with trifluoroacetic anhydride (TFAA) was used to label the hydroxyl groups introduced on the polymer surface by thermal oxidation.From the surface analysis studies using photoacoustic Fourier transform infrared spectroscopy (PA/FT-IR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and X-ray photoelectron spectroscopy (XPS) it was evident that colour formation starts initially with the hydroxylation of the terephthalic ring. Further, the formation of additional carbonyl functionalities and conjugated chromophoric systems complete the colour formation process.     

Atom transfer radical polymerization of 1-phenoxycarbonyl ethyl methacrylate monomer

Atom transfer radical polymerization conditions with copper(I) bromide/2,2^′-bipyridine (Cu/2,2^′-bpy) as the catalyst system were employed for the homopolymerization and random copolymerization of 1-phenoxycarbonyl ethyl methacrylate (PCMA) with methyl methacrylate (MMA). Temperature studies indicated that the polymerizations occurred smoothly in bulk at 110 °C. Poly(PCMA)(polydispersity index=1.27) homopolymer was characterized and then used as macroinitiator for increasing its molecular weight. The homopolymerization of PCMA was also carried out under free radical conditions using 2,2^′-azobisisobutyronitrile as an initiator.The monomer and polymers were characterized by FT-IR and ¹H and ¹³C-NMR techniques. The glass transition temperatures, the solubility parameters and average-molecular weights of the polymers were determined. Thermal stabilities of the polymers were given as compared with each other by using TGA curves. Thermal degradation products of poly(PCMA)s obtained by ATRP and free radical polymerization were compared with each other by using ¹H-NMR technique.     

Wavelength effect on the photoinduced reaction of polymethylmethacrylate

Polymethylmethacrylate (PMMA) containing benzophenone (BP) was photo-irradiated with monochromatic radiation of wavelength 260–360 nm using the Okazaki Large Spec-trograph (OLS). On irradiation of PMMA films containing BP in air, the sensitized main-chain scission and photocrosslinking of PMMA took place simultaneously. These reactions are dependent on irradiation wavelength. The threshold wavelength for both reactions is found to be ca. 380 nm. The number of main-chain scission and amount of gel increased with the increase of BP concentration in PMMA. Photosensitized main-chain scission favors the irradiation of radiation at ca. 280 nm and photocrosslinking takes place efficiently with the exposure of 340 nm radiation. A possible mechanism for photosensitized reaction is proposed. © 1995 John Wiley & Sons, Inc.     

A study on the influence of anionic surfactants on electrochemical degradation of polyaniline

The influence of anionic surfactants on the electrochemical degradation of polyaniline (PANI), deposited by electro-polymerization onto platinum electrodes, was investigated in an aqueous medium by means of cyclic voltammetry. The degradation rate was found to be greatly dependent on the pH of the solution. The electrochemical degradation of PANI/dodecylsulfate and PANI/dodecylbenzenesulfonate films was compared with that of a PANI/hydrochloride film. The degradation rate in the two former cases decreased by some 50% compared to the PANI/hydrochloride film in aqueous solution at pH = 2. The results were confirmed with theoretical calculations performed on the evaluation of head group charge of surfactants, the distance of anions from PANI positive sites and the shielding of anions on PANI positive sites.     

Exhaustive degradation of the ring D of 3,20-epoxy ent-kaurane-type diterpene maoecrystal A

This study described a new approach for exhaustive degradation of the ring D of maoecrystal A (1), an ent-kaurane-type diterpene from Isodon eriocalyx, in seven steps mainly involving retro-aldol reaction, epoxylation, NaIO₄ oxidation, and Baeyer-Villiger process in a 19% overall yield.     

活性炭纤维电极电解法处理墨绿B染料废水

将铁丝缠绕在活性炭纤维(简称ACF)上制成电极,并在阴极鼓入空气,用电解生成的Fenton试剂处理墨绿B染料模拟废水.研究了电压、pH值、温度、空气流量、支持电解质的浓度等因素对染料脱色率的影响.结果表明,pH值越低,温度越高,处理效果越好,气流量的改变对于处理效果影响不大.室温时处理浓度为50mg·L-1的活性染料墨绿B,在实验电压为11V,中性条件下,无水硫酸钠的浓度为20g·L-1,通入空气流量为60L·min-1时,处理60min,色度去除率达到95%左右.55℃时,电解30min色度去除率就达到96%,60min时达到100%.     

Thermal Degradation of Polychloroprene Rubber Under Isothermal and Non-Isothermal Conditions

The results of a kinetic investigation of the non-isothermal degradation and the isothermal degradation of the residual deformation under constant deflection for polychloroprene rubber are presented. A relationship was derived between the degree of non-isothermal conversion and the value of the investigated mechanical property. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚苯基不对称三嗪的热分解

用高分辨裂解气相色谱－质谱（ＨＲＰｙＧＣ－ＭＳ）考察了由对苯二眯腙和四种不同芳香族四酮合成的聚苯基不对称三嗪的热分解行为，鉴定了相应裂解产物的组成、分布及其与高分子结构的关系，并用热重法（ＴＧ）测定了它们的热分解反应动力学参数，提出了其热分解反应机理．