TiO_2纤维的制备、表征及其光催化活性

采用常压乙二醇法制备出在可见光下具有较高催化活性的TiO2纤维。扫描电子显微镜表征结果表明,TiO2纤维直径为0.8～2.0μm、长度为5～25μm;BET比表面积和X射线衍射表征结果表明,随焙烧温度的升高,比表面积减小,TiO2纤维晶型逐渐由锐钛矿型向金红石型转变;紫外-可见漫反射光谱分析结果表明,TiO2纤维在可见光区有明显的吸收。在可见光下对甲基橙和苯酚的降解实验表明,焙烧温度为400℃时TiO2纤维的催化活性最好,对甲基橙和苯酚的降解率分别达到90.3%和84.0%;所制备的TiO2纤维比溶胶-凝胶法制备的锐钛矿型TiO2在可见光下具有更好的催化活性,原因是其能带间隙减小和吸收波长扩展到可见光区所致。     

Photostability of polyetherurethaneureas

Polyetherurethaneureas (PEUUs) were synthesised from polyethylene-glycols (PEGs) of molecular weight 400, 600 and 1000, 4,4′-diphenylmethanediisocyanate (MDI) and aliphatic diamine chain extenders, 1,3-propanediamine (PDA) and 1,6-hexanediamine (HDA). Polymer films were irradiated with 365 nm light at 293 K and the effects of polyether soft segment length and urea hard segment on photo-oxidative stability were studied by following the variation in weight-average molecular weight (M _w), gel formation and stress-strain properties. Changes in ultraviolet and infrared spectroscopy were monitored on photo-oxidation and hydroperoxide content determined. The soft segment length was increased by increasing the molecular weight of PEG from 400 to 1000 and hard segment structure was changed by variation of diamine. It was noted that the structure of urea and polyether soft segment length plays an important role in photostability of PEUUs. PDA chain extended PEUUs were more stable than HDA chain extended PEUUs.     

环氧乙烷合成乙二醇的研究进展

介绍了环氧乙烷合成乙二醇的主要生产方法，包括以壳牌、联碳化学公司以及Halcon—SD公司为代表的环氧乙烷直接水合法，环氧乙烷催化水合法和碳酸乙烯酯法，后两种乙二醇生产方法是目前国内外研究开发的热点。催化剂体系是催化水合法工艺的关键，重点介绍了国内外各主要公司对催化剂体系的研究进展及使用效果；碳酸乙烯酯法分为乙二醇和碳酸二甲酯联产法以及碳酸乙烯酯水解法，详细介绍了国内外各主要公司对该技术的研究进展，包括工艺流程、催化剂体系等方面。将3种乙二醇生产方法进行技术经济比较，结果表明，催化水合法和碳酸乙烯酯法在原料消耗和能耗方面占优势。并对我国乙二醇生产工艺技术提出建议。     

新型聚氨酯固-固相变储能材料的组成与热性能的关系

利用差示扫描量热仪、傅里叶红外光谱仪、广角X射线衍射仪研究了一种新型的以聚乙二醇为软段的聚氨酯相变储能材料。结果表明，当软段含量低于90％（质量分数，下同）时，即使温度高于聚乙二醇的熔点，此类材料仍不会熔化成液体，而表现出一种固-固相变行为。该聚氨酯储能材料相变焓较大，相变温度适中，且随着软段含量的减少，材料相变焓和相变温度呈递减趋势。其相变过程实质是聚氨酯软段聚乙二醇由结晶固态转变为无定形固态的过程。     

Biomimetic synthesis of spherical nano-hydroxyapatite in the presence of polyethylene glycol

Spherical nano-hydroxyapatite (nano-HA) was synthesized successfully by a biomimetic method using Ca(NO₃)₂·4H₂O and (NH₄)₃PO₄·3H₂O as reagents in the presence of polyethylene glycol (PEG). The crystalline phase, microstructure, chemical composition, and morphology of the obtained samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). The results show that spherical nano-HA with diameter of 30–50 nm can be synthesized in the presence of a certain concentration (2–6%) of PEG. The crystallinity of HA powder synthesized in the presence of PEG was higher than that synthesized in the absence of PEG, but the crystallinity of HA reduced with increasing the concentration of PEG. The electrical conductivity (EC) of the solution revealed that PEG reduced the transfer rate of Ca²⁺ in the process of HA crystallization, indicating the interaction between PEG and HA. The possible mechanism of formation spherical nano-HA was discussed.     

Synthesis and applications of heterobifunctional poly(ethylene oxide) oligomers

Poly(ethylene oxide) (PEO) oligomers are employed extensively in pharmaceutical and biomedical arenas mainly due to their excellent physical and biological properties, including solubility in water and organic solvents, lack of toxicity, and absence of immunogenicity. PEO can be chemically modified and reacted with, or adsorbed onto, other molecules and surfaces. Sophisticated applications for PEO have increased the demand for PEO oligomers with tailored functionalities, and heterobifunctional PEOs are often needed. This review discusses the synthesis and applications of heterobifunctional PEO oligomers possessing amine, carboxylate, thiol, and maleimide functional groups.     

正庚烷-甲苯-三甘醇三元体系液-液相平衡数据的测定与关联

利用气相色谱法测定了常压下２５℃、４０℃和５０℃时正庚烷－甲苯－三甘醇体系的液－液相平衡数据，采用峰面积归一化法定量，所得数据准确、可靠。用ＮＲＴＬ模型对所测数据进行了热力学关联，求出了相应的模型参数。用该模型对本三元体系进行了预测，结果令人满意。     

溶胶-凝胶法制备磷钨酸-硅胶催化合成苹果酯

采用溶胶-凝胶法制备了一系列磷钨酸-硅胶催化剂(PW/SG),考察了该催化剂催化乙酰乙酸乙酯与乙二醇液相缩合制备苹果酯的反应性能。实验结果表明,PW质量分数为40%时的PW/SG催化剂表现出最佳的催化活性;40%PW/SG催化剂制备苹果酯的最佳工艺条件为:n(乙酰乙酸乙酯)∶n(乙二醇)=1∶1.2,催化剂用量占反应物质量的0.36%,带水剂环己烷用量占反应物体积的30%,反应温度383K,反应时间90min;在此条件下,乙酰乙酸乙酯的转化率可达95.5%,苹果酯的选择性大于97%;催化剂稳定性实验表明,经5次重复使用,40%PW/SG催化剂的活性基本保持不变,乙酰乙酸乙酯转化率稳定在95.0%左右。     

草酸二甲酯加氢合成乙二醇反应的研究

在微型管式反应器中,采用Cu/SiO2催化剂,在温度190～210℃、压力1～3MPa、草酸二甲酯(DMO)与氢气的摩尔比(氢酯比)40～120、DMO空速6.0～25.0mmol/(g.h)的条件下,对DMO加氢制乙二醇的反应进行了研究。实验结果表明,高温、高压、高氢酯比和低DMO空速都能提高DMO的转化率和乙二醇的收率,但同时也增加了副产物的选择性。较适合的反应条件为:压力2MPa,温度205～210℃,氢酯比80～100,DMO空速10.0mmol/(g.h)。动力学研究表明,DMO加氢反应符合Langmuir-Hinshelwood吸附反应动力学模型,表面反应为速率控制步骤,氢气不解离吸附,由此得到了相应的动力学方程及参数。统计检验结果表明,该模型对DMO加氢反应高度适定。     

聚乙二醇-硫酸钠-硫氰酸钾体系中Co(Ⅱ)、 Ni(Ⅱ)、 Mo(Ⅵ)的萃取分离研究

用硫氰酸钾作萃取剂，探讨了在聚乙二醇（ＰＥＧ）２０００硫酸钠硫氰酸钾双水相体系中Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｍｏ（Ⅵ）等金属离子的萃取行为。控制一定条件，实现了Ｃｏ（Ⅱ）与Ｎｉ（Ⅱ）、Ｃｏ（Ⅱ）与Ｍｏ（Ⅵ）及Ｃｏ（Ⅱ）与Ｎｉ（Ⅱ）、Ｍｏ（Ⅵ）混合离子的定量分离，并研究了不同类型的表面活性剂对ＰＥＧ相萃取行为的影响。