邻硝基二苯胺合成新工艺研究

以苯胺、邻硝基氯苯为原料，采用直接缩合法引入相转移催化剂合成邻硝基二苯胺。对影响反应的各种因素进行了研究，通过正交实验确定了缩合反应最佳工艺条件：邻硝基氯苯：K2CO3：PEG＝1：0．55：0．015，反应温度为185℃，反应时间为2h。反应收率为99．1％。该方法是邻硝基二苯胺的最佳合成工艺。     

聚醚增韧酚醛树脂及其泡沫的研究

本文介绍了两类聚醚改性剂-PEG和活性聚醚增韧酚醛树脂及其泡沫的方法和工艺。对一系列不同分子量PEG和活性聚醚改性酚醛树脂的力学性能进行了比较，同时研究了各种改性酚醛泡沫的尺寸稳定性、压缩强度及表观密度等；并对几种改性酚醛泡沫和未改性酚醛泡沫进行了电子显微镜扫描泡孔结构的研究和红外分析；结果表明，树脂中导入活性聚醚的柔性链段，可使酚醛树脂及其泡沫的韧性及综合性能得到明显的改善，其中尤以分子量为1000活性聚醚改性树脂及其泡沫的各种性能为优。     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

纳米铝/氧化铜复合材料的制备及热性能

以聚乙二醇(PEG)为模板制备了纳米氧化铜。以一种高分子材料为包覆材料自组装制备了纳米铝/氧化铜(Al/CuO)复合材料。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能谱仪(EDS)、X射线衍射(XRD)等对材料的结构形貌进行了表征。利用热重分析法(TG)和差示扫描量热法(DSC)对比研究了自组装法(含包覆材料)与超声共混法(不含包覆材料)制得样品的热性能。研究了不同Al与CuO摩尔比下Al/CuO复合材料的放热量。结果表明,纳米铝与CuO发生铝热反应的放热峰约为576.4℃,放热量达1 093J/g。含有包覆材料的复合材料比不含包覆材料的复合材料具有更大的放热量。在纳米铝与CuO摩尔比为1.0∶1.2时铝热反应放热量最大,可达1 093J/g。     

Excess properties and spectroscopic studies for binary system polyethylene glycol 600 + dimethyl sulfoxide at T =(298.15, 303.15,308.15, 313.15, and 318.15) K

The work presents density (ρ) and viscosity (η) data of binary system polyethylene glycol 600 (PEG) + dimethyl sulfoxide (DMSO) over the entire concentration range at T =(298.15,303.15,308.15,313.15 and 318.15) K and atmospheric pressure.On the basis of density and viscosity values,the excess properties of PEG (1) + DMSO (2) mixtures,including excess molar volume (VEm),viscosity deviation (△η),excess free energies of activation (△G*E),and isobaric thermal expansion coefficient (αp),were calculated.At the same time,in order to conjecture the density viscosity under different conditions,the density and viscosity data were fitted with the corresponding formula.The calculated results of VEm,△η,and △G*E were fitted with the Redlich-Kister equation to derive coefficients and estimate the standard deviations (σ) between the experimental and calculated values.Moreover,the intermolecular interaction of PEG with DMSO was discussed on the basis of FTIR and UV-Vis spectral results of PEG (1) + DMSO (2) mixtures.The results indicated that there were the hydrogen bonding and interactions of hvdroxvl hydrogen atoms in PEG with oxygen atoms in DMSO.     

酸性离子液体(PEG1000-DAIL)催化合成6-烷氧基嘌呤化合物

以6-氯嘌呤衍生物为原料,使用PEG1000-DAIL为催化剂,在相应的醇溶剂中回流反应合成了一系列6-烷氧基嘌呤衍生物。聚乙二醇酸性双子离子液体(PEG1000-DAIL)作为催化剂具有优良的催化性能,反应条件温和,多次重复使用能保持很高的催化活性,损失量小,避免了资源的浪费。     

N-mPEG-O-季铵化壳聚糖微球的制备及其载药性能

将聚乙二醇单甲醚（mPEG）醛化改性后,通过西佛碱反应接枝到自制的O-季铵化壳聚糖的NH2上,硼氢化钠还原制得N-mPEG接枝O-季铵化壳聚糖（QACS-mPEG）,反相悬浮法制备二乙烯基砜交联QACS-mPEG微球。用FTIR、1 H NMR、EA和SEM对产物进行表征,并且以酮洛芬为模型药物研究微球的载药性能及释放行为。结果表明,mPEG和季铵盐基团的引入提高了N-mPEG-O-季铵化壳聚糖微球的载药量,为4.31mg/mg;载药N-mPEG-O-季铵化壳聚糖微球在模拟肠液的缓释效果优于胃液,微球释药具有pH响应性。     

Argon-plasma-assisted graft polymerization of thick hydrogels with controllable water swelling on Chronoflex

Chronoflex, a polyurethane, is a suitable material for use in polymeric tracheobronchial stents. A controlled release layer on the stent is required for effective localized delivery of cancer drugs to the tumor cells. This paper reports on the investigation of coating Chronoflex with acrylated oligomers by argon plasma assisted UV graft polymerization. Coatings of poly(ethylene glycol) diacrylate (PEGDA) with molecular weight 700 or a 50 : 50 mixture of PEGDA with poly(propylene glycol) diacrylate (PPGDA) with molecular weight 900 which were tens of micrometers thick were shown to have good adhesion to Chronoflex. No photoinitiator was added. Formulations containing photoinitiator or a trifunctional crosslinker which increases strength and decreases water swelling showed poor adhesion to Chronoflex. The degree of water swelling of grafted PEGDA coating reached about 709%, making it suitable for use as a hydrogel coating for controlled drug release on Chronoflex. Adding PPGDA to PEGDA was shown to decrease the degree of water swelling. Hence, removal of the photoinitiator, use of oligomeric diacrylate with high molecular weight per acrylate group and a clean Chronoflex surface are found to be important factors for ensuring adhesion between the thick hydrogel coating and Chronoflex.     

工艺条件对ZrO2粒度的影响

以工业ZrOCl2·8H2O和分析纯Nh3·H2O为主要原料,采用化学沉淀法制备了ZrO2纳米粒子,研究了不同阶段添加表面活性剂聚乙二醇(PEG)对ZrO2粉体颗粒尺寸的影响机理.通过测定ZrO2粉体比表面积计算出其粒度在10～40nm之间.     

Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film

Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. A two-step reaction was conducted. First, EAA film was activated with PCl₅ at room temperature. Second, the acid chloride was reacted with dansyl cadaverine or a PEG derivative to form a modified film. ATR-FTIR spectroscopy and fluorometry were employed to analyze the modified films after each step. It was found that dichloromethane yielded the highest grafting efficiency, with the dansyl cadaverine penetrating throughout the ATR-FTIR analysis region (∼400 nm) in a few minutes. As the grafting depth increased with time, so did the amount of fluorescence intensity of grafted dansyl cadaverine. ATR-FTIR spectra for PEG grafting indicated that the acid chloride peak decreased with time, while the ester peak increased. However, hydrolysis occurred at later times, consuming the acid chloride groups within the film. A marked decrease of static water contact angle was observed for EAA grafted with PEG99 (PEG that contains 99 ethylene glycol repeat units), almost 40° lower than that of neat EAA (∼99°). For other PEG-grafted films, the surface hydrophilicity was also improved.