甲苯溶液中惰性卤代芳烃格氏试剂的制备

惰性卤代芳烃在格氏试剂反应中,由于反应引发困难,特别在甲苯溶液中制备尤为困难,影响了这类格氏试剂的应用.以镁粉为原料,以无水甲苯为溶剂,在一定条件下,制备了卤代芳烃的格氏试剂,拓展了其工业化应用,并对影响该格氏试剂反应的各种因素进行了探讨.     

Effects of the o‐aromatic ring in the molecular chain on the properties of polyester polyols

A series of liquid polyester polyols from adipic acid (AA), phthalic anhydride (PA), ethylene glycol, propanediol‐1,2, and trihydroxymethylpropane, varying in the molar ratio of PA to AA, were prepared. The effects of the o‐aromatic ring in the molecular chain, which came from PA, on the viscosity, glass‐transition temperature, and thermal degradation temperature of the polyester polyols were studied with viscometry, differential scanning calorimetry, and thermogravimetry. The intrinsic viscosity and glass‐transition temperature increased with the concentration of the o‐aromatic ring increasing. The temperature of the maximum thermal degradation rate for aliphatic polyester polyols was 434.20°C. Two steps of thermal degradation were found when there were o‐aromatic rings in the molecular chain. One thermal degradation temperature was 358.36–360.48°C, and the other was 412.85–427.18°C. Polyester polyols with o‐aromatic rings had higher stability at lower temperatures (<240.00°C). However, aliphatic polyester polyols had higher stability at higher temperatures (300.00–480.00°C). The activation energy and order of degradation were calculated from thermogravimetric curves. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1617–1624, 2002     

Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

Relationships between hydrogen donor abilities and chemical structure of aromatic compounds in terms of coal liquefaction

To obtain fundamental information about hydrogen transfer, the relationships between hydrogen donor ability and chemical structure of model compounds representing donor solvents is studied using gas chromatography,¹H n.m.r. and computing calculation methods. The order of the model compounds in terms of the ability as donor solvent to release hydrogen is: decalin < tetralin < 1,2-dihydronaphthalene < < 1,4-dihydronaphthalene. This trend closely correlates with the difference in binding energies of the hydroaromatic compounds and their radicals, determined by intermediate neglect of differential overlap (INDO) calculation. Electron spin resonance spectroscopy (e.s.r.) confirms that radical species are created after heat-treatment of the donor compounds. The ability of model compounds representing coal to accept hydrogen is assessed from a comparison of the¹H n.m.r. spectra. It is established that donor and acceptor efficacies are dependent upon chemical structure.     

异养菌与自养菌对好氧颗粒污泥稳定性的影响

研究了异养菌和自养菌颗粒污泥的特性：与异养菌相比,自养菌颗粒污泥粒径小、密度大、胞外多聚物（EPS）含量高但强度小。通过对粒径、EPS等特性与密度的变化规律分析,研究发现,自养菌颗粒污泥的粒径与密实度呈现出一致性,颗粒趋于稳定;而异养菌颗粒污泥粒径成长同时伴随着密度减小,粒径与密实度呈现不一致性,颗粒容易解体。颗粒强度的分析结果表明：在自养菌系统中EPS与孔隙率能够达到动态平衡是其长期维持稳定的主要原因,而异养菌中粒径与孔隙率无法达到平衡,操作条件无法控制高强度丝状菌的繁殖是其不稳定的主要因素。     

近海海洋生物体中多环芳烃的GC-MS分析

建立了气相色谱–质谱–定性离子扫描法测定近海海洋生物体中10种多环芳烃的方法.探讨了扫描方式对方法检出限的影响,以及定性离子强度比的匹配度对定性结果的影响.10种多环芳烃测定方法的检出限为0.10～0.61μg/kg,方法线性关系良好,加标回收率为63.1%～98.1%,相对标准偏差为3.9%～15.2%.此方法适用于海洋生物体中多环芳烃的分析.     

Synthesis and characterization of soluble aromatic azopolyamides containing sulfone and ether units

A series of new polyamides 3a–d containing aryl-azo, ether and sulfone groups in the main chain were synthesized from bis[4-(4-aminophenoxy)phenyl sulfone] 1 and several azo aromatic diacyl chlorides 2a–d by the low temperature solution polycondensation technique. FTIR spectroscopy, nuclear magnetic resonance (NMR) and elemental analyses confirmed the structure of these polymers. Owing to the aryl and amide groups in the main chain, these polymers exhibit photochromic properties as well as excellent thermal stabilities. The transition temperatures (T _g) are between 242 and 265 °C, and the char yields at 800 °C in nitrogen atmosphere were above 39%. Based on incorporation of flexible ether linkages and polar sulfone groups, the polyamides show desirable solubility in organic solvents such as DMAc, N,N-dimethylformamide (DMF), N-methyl-2-pyrroidinone (NMP) and dimethylsulfoxide (DMSO). And it is exemplified that polyamide containing 2 and 2′ substitutes performed better solubility. Funded by the National Natural Science Foundation of China (No. 50572081)     

Synthesis and characterization of polyamides based on dimer acid

A series of dimer acid-based polyamides were synthesized by melt-polycondensation of dimer acid and various aromatic diamines, and were characterized by Fourier transform infrared spectrum (FT-IR) and nuclear magnetic resonance (¹H NMR). The physical properties of the polyamides, such as glass transition temperature, melting temperature, decomposition temperature and mechanical properties were also investigated. The polyamides’ intrinsic viscosity ranges from 1.8 dL·g⁻¹ to 2.2 dL·g⁻¹, and the melting temperature ranges from 140 °C to 181 °C. The glass transition temperatures, observed from dynamic mechanical analysis, fall in the range of 34.8–48.2 °C. The physical and mechanical properties of the resultant polyamides are similar to those of the PA1212. The heat resistance and mechanical properties of poly (4, 4′-diphenylsulfone dimeramide) (PSD) and poly(4, 4′-diphenyl dimeramide) (PPDI) are comparable to those of PA1212.     

纳米二氧化钛胶体对脱墨浆中DCS絮聚去除的GC-MS研究

采用GC-MS表征絮聚前后DCS组分变化的方法研究了纳米TiO2胶体对脱墨浆中DCS絮聚去除的机理.结果表明,该脱墨浆中DCS可硅烷化主要组分为树脂酸、脂肪酸、苯二甲酸酯类物质、2,2-双（4-羟苯基）丙烷和甾醇类等物质;纳米Ti O2胶体对上述多数组分有较强的絮聚去除能力,去除机理主要为“桥连絮聚”作用,且去除效果随组分分子极性增大而增强,随分子结构的位阻屏蔽作用增强而减弱.     

应用Markov理论定量描述土壤剖面中菲的垂向运移分布特征

马尔可夫(Markov)链理论是用来描述随时间(空间)变化的一个离散状态序列的状态转移特性的,本文将其引入来研究土壤剖面多环芳烃有机污染物的垂向变化规律,建立了基于空间离散化的马尔可夫(Markov)链理论数学模型及垂向归趋极限.研究结果表明,基于空间离散化的马尔可夫(Markov)链理论数学模型及垂向归趋极限能够很好地模拟区域土壤剖面多环芳烃(菲)的垂向变化特征,并有迁移规律的识别功能.