催化脱氢法合成新型偶氮化合物

催化脱氢法合成新型偶氮化合物王彩兰王玉炉王晓阳李建平王红马东兰（河南师范大学化学系新乡４５３００２）偶氮化合物是一类重要的有机化合物，它被广泛用作染料和分析试剂，还能用于现代科技中的非线性光学材料、油溶性染料等［１］。近来许多研究表明，偶氮苯类衍生物...     

偶氮金属螯合物的合成及其光学和热学性质

偶氮金属螯合物的合成及其光学和热学性质;噻唑基偶氮金属螯合物;光学性质     

牛血清白蛋白与有机小分子偶氮磺Ⅲ,溴偶氮磺Ⅲ相互作用的研究

本文研究了在不同酸度下，偶氮磺、溴偶氮磺Ⅲ与牛血清白蛋白质的作用情况，用光度法求出不同条件下偶氮磺Ⅲ、溴偶氮磺Ⅲ与牛血清白蛋白的结合个数，并用三种不同的方法相互对照，证明偶氮磺Ⅲ、溴偶氮磺Ⅲ在牛血清白蛋白上有两类不同接合部位。     

偶氮苯高分子的光致可逆固液转变

偶氮苯化合物是一种极具吸引力以及较为常用的光响应材料,本文主要介绍偶氮苯的光响应性质以及一些偶氮苯高分子的合成方法,解析光化学反应导致偶氮苯高分子固液转变的机理,并介绍其在粘结性材料、光致动器、光致热导开关器件及非热纳米压印中的应用。     

大分子偶氮引发剂──聚偶氮酰胺的合成与表征

本文应用里特（Ｒｉｔｔｅｒ）反应机理将偶氮二异丁腈与三聚甲醛在浓硫酸催化作用下反应，制备出一类新型的大分子偶氮引发剂──聚偶氮酰胺，研究了催化剂用量，溶剂和反应时间对产物转化率的影响，选择出最佳反应条件；ＩＲ，１Ｈ—ＮＭＲ，ＵＶ和ＧＰＣ对其结构进行了表征，ＤＳＣ研究了热分解反应动力学，结果表明其热分解反应活化能和反应速度常数均与偶氮二异丁腈有所差异．     

显色剂2-[3-(5-硝基苯并异噻唑)偶氮]-α-萘酚与铋的显色反应

杂环偶氮类是一类发展十分迅速的有机显色剂,其中噻唑偶氮、吡啶偶氮、喹啉偶氮的应用研究较多,而异噻唑偶氮研究甚少。在合成2-[3-（5-硝基苯并异噻唑）偶氮]-6-异丙基苯酚的基础上,合成2-[3-（5-硝基苯并异噻唑）偶氮]-α-萘酚显色剂,并对其性质进行了研究。     

甲醛还原法制备2,2'-二氯氢化偶氮苯

二氯氧化偶氮苯;二氯联苯胺;还原过程;甲醛还原法制备2;2'-二氯氢化偶氮苯     

3-(4-氨基苯基偶氮)苯磺酸钠的合成

氨基甲基苯基偶氮苯磺酸钠;3-(4-氨基苯基偶氮)苯磺酸钠的合成     

牛血清白蛋白与有机小分子偶氮磺Ⅲ、溴偶氮磺Ⅲ相互作用的研究

本文研究了在不同酸度下．偶氮磺、溴偶氮磺Ⅲ与牛血清白蛋白的作用情况，用光度法求出了不同条件下偶氮磺Ⅲ、溴偶氮磺Ⅲ与牛血清白蛋白的结合个数，并用三种不同的方法相互对照．证明偶氮磺Ⅲ、溴偶氮磺Ⅲ在牛血清白蛋白上有两类不同接合部位。利用Forster非幅射转移理论确定了有机小分子在牛血清白蛋白上的结合位置并对反应机理作了初步讨论。     

两各氮苯冠醚的合成及其及其光致变色机理

报道了４－氮杂１５－－５－４＇－甲氮基偶氮苯和４－氮杂１５－冠－５－４＇－硝基偶氮苯的合成及其分子内扭曲电荷转移的光致变色机理。     

Synthesis and characterization of polyurethane anionomers with bisazoaromatic chromophores and carboxylate groups

A new diol with a bisazoaromatic pendant was prepared to obtain photosensible polymers suitable for dyed aqueous systems. A polyurethane bearing bisazoaromatic chromophores, based on a poly(tetramethylene oxide) diol (average molecular weight = 2000), 2,4‐tolylene diisocyanate, and the aforementioned azo diol, was synthesized and characterized. Bichromophoric polyurethane anionomers, prepared by a two‐step substitution of urethane hydrogen atoms with sodium carboxylate groups, were studied. The influence of the concentration of carboxylate groups (30–158 mequiv of ionic groups/100 g of polymer) on some polymer properties and photoisomerism in polymer solutions and thin films was examined. In particular, the polymer structure and its morphology dictated the proximity of anchored bisazo chromophores and the capability of intermolecular forces between dyes producing hydrogen aggregates in solutions and thin films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5463–5470, 2004     

含氟聚氨酯的研究进展

综述了溶剂性、水性含氟聚氨酯的合成及研究，并进行了讨论。     

Structure and properties of polyurethanes based on halogenated and nonhalogenated soy–polyols

Four polyols were prepared by a ring opening of epoxidized soybean oil with HCl, HBr, methanol, and by hydrogenation. Two series of polyurethanes were prepared by reacting the polyols with two commercial isocyanates: PAPI and Isonate 2143L. Generally, the properties of the two series were similar. The crosslinking density of the polyurethane networks was analyzed by swelling in toluene. Brominated polyols and their corresponding polyurethanes had the highest densities, followed by the chlorinated, methoxylated, and hydrogenated samples. The polyurethanes with brominated and chlorinated polyols had comparable glass transition and strength, somewhat higher than the polyurethane from methoxy containing polyol, while the polyurethane from the hydrogenated polyol had lower glass‐transition and mechanical properties. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4062–4069, 2000     

硬段侧链含有氟化双季铵盐的聚氨酯表面性能及抗菌性能分析

研究了硬段侧链含有氟化双季铵盐的系列聚氨酯(FQPUs)的表面性能和抗菌性能. 水接触角测试和表面自由能测试结果表明, 加入少量氟化双季铵盐扩链剂, 可以使聚氨酯表面富集氟碳链, 氟化双季铵盐聚氨酯表面自由能很低, 具有很好的抗黏附性能. 迁移到表面的两条氟碳链在常温下不会发生链反转, 使材料的抗黏附性能得以保持. 同时, 使材料表面形成一层疏水层, 减小材料的吸水率. XPS研究结果表明, 氟碳链的-CF₃位于材料的最外层, 材料的次表面是具有良好杀菌性能的双季铵盐, 这样形成了具有多重抗菌性能的表面. 另外, XPS研究结果表明, 材料表面化学结构与材料本体的微相分离结构相关. 抗菌性能测试结果表明, 氟化双季铵盐聚氨酯抗金黄色葡萄球菌的能力很强, 对于大肠杆菌的抗菌效果有所下降, 但相对于单季铵盐聚氨酯的抗菌效果有一定提高.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.     

可溶性聚酰亚胺类偶氮高分子的合成与表征

用聚合物的后重氮偶合方法合成了以可溶性聚酰亚胺为主链 ,偶氮生色团为侧基的新型偶氮高分子 ,并通过引入线性长链烷烃侧基来提高聚合物的溶解性 .采用红外光谱、氢核磁共振、紫外光谱和热分析等手段 ,对产物的结构、热性能及光学性能等进行了表征 .该聚合物膜在氩离子干涉激光的照射下形成正弦波形的表面起伏光栅 ,起伏深度可达 2 0 0nm .     

Oxidative and enzymatic degradations of l-tyrosine based polyurethanes

Oxidative and enzymatic degradations of l-tyrosine based polyurethanes were studied for biomaterial applications. Oxidative degradation was performed with 0.1 M cobalt chloride (CoCl₂) in hydrogen peroxide solutions at 37 °C and the degradation was assessed by ATR-FTIR. Results indicate that polyurethane with polyethylene glycol (PEG) shows soft segment degradation while polyurethane based on polycaprolactone (PCL) shows hard segment degradation. Enzymatic degradation of the polyurethanes was studied using proteolytic enzyme α-chymotrypsin in phosphate buffer solution (pH 7.4) at 37 °C. The enhanced degradability of l-tyrosine based polyurethanes is due to both the presence of amino acid based chain extender and the action of enzyme. The changes in the morphology of polyurethanes were analyzed by SEM. The results of the degradation study were correlated to the structure of the polyurethanes.     

Polyurethane foams as solid chromogenic reagents for diffuse reflectance spectroscopy

The chemical reactions of the functional groups in polyurethane foams (PUF) have been studied by use of diffuse reflectance spectroscopy and infrared spectroscopy. It was found that the functional groups are highly reactive towards diazotization by sodium nitrite, azo coupling with 4-nitrophenyldiazonium tetrafluoroborate, oxidation by active chlorine, and condensation with formaldehyde, resulting in the formation of intensely colored products. Heterogeneous chemical reactions of PUF with these compounds in aqueous solution proceed rapidly at room temperature and at low solute concentrations. PUF do not undergo degradation as a result of chemical interactions. The linear response of the Kubelka-Munk function to analyte concentration makes it possible to recommend PUF as solid chromogenic reagents for the determination of nitrite, nitrate, and 1- and 2-naphthols.     

环氧改性水性聚氨酯乳液的制备及其膜性能

以聚己内酯二元醇(CAPA)为软段,异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为硬段,环氧树脂E-44为大分子交联剂,经相转化法合成了一系列环氧树脂改性负离子水性聚氨酯(EPPU)自乳化乳液,并制备了改性水性聚氨酯的固化膜.通过FTIR、TGA及接触角、力学性能测试对聚合物结构及其膜性能进行了研究.通过原子力显微镜(AFM)观察膜表面形态和表面粗糙度.乳液粒径及粒径分布通过动态激光光散射法(DLLS)测定.FTIR分析表明环氧树脂的羟基和环氧基都参与了发应.TGA表明,环氧树脂的加入可以提高聚氨酯的热稳定性.随着w(E-44)增大,改性聚氨酯膜的拉伸强度得到改善,断裂伸长率减小.随着w(E-44)增大,乳液粒径增大,薄膜的接触角增大,改性后的PU膜表面光滑度下降,拒水性增强.     

SURFACE STRUCTURE AND BULK PROPERTIES OF FLUORINATED POLY(ETHER URETHANE)S AND POLY(ETHER URETHANE) BLENDS

INTRODUCTIONPolyurethanes (PU) have been widely used for manufacturing medical devices because of their excellentmechanical properties and moderate biocompatibility[1]. Although polyurethanes used in applications requiringall of the above properties have been successful for short-term use, the problems of long-term thromboresistanceand biostability in a biological environment still remain unsolved[2,3]. A legitimate approach to improving theproperties of polyurethanes is introduction of f…