Calcined Zn/Al hydrotalcites as solid base catalysts for glycolysis of poly(ethylene terephthalate)

In this research, glycolysis of poly(ethylene terephthalate) (PET) with ethylene glycol (EG) was carried out using Zn/Al mixed oxide catalyst. These mixed oxides were prepared by calcining crystalline Zn/Al hydrotalcites at different calcination temperatures. The samples and corresponding precursors were characterized by X‐ray diffraction, BET, Fourier‐transform infrared spectra, thermogravimetry/differential thermal analysis, and Hammett titration method. The experimental results showed that Zn/Al mixed oxides obtained from hydrotalcites were found to be more active than their individual oxides for glycolysis of PET. The relationship between catalytic performance and chemical–physical features of catalysts was established. In addition, a study for optimizing the glycolysis reaction conditions, such as the weight ratio of EG to PET, catalyst amount and reaction time, was performed. The conversion of PET and yield of bis(2‐hydroxyethyl terephthalate) (BHET) reached about 92% and 79%, respectively, under the optimal experimental conditions. Moreover, it should be noted that Zn/Al mixed oxide not only provided an effective heterogeneous catalyst for glycolysis of poly(ethylene terephthalate), but also presented a novel method for decolorization of discarded colored polyester fabric. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41053.     

The morphology and degradation behavior of electrospun poly(3‐hydroxybutyrate)/Magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/Magnetite composites

Electrospinning of biodegradable poly(3‐hydroxybutyrate) (PHB)/magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/magnetite composites in 2,2,2‐trifluoroethanol (TFE) and chloroform are investigated to develop nonwoven nanofibrous structure. Ultrafine PHB/magnetite fibers are obtained and the resulting fiber diameters are in the range of 690–710 nm and 8.0–8.4 µm for the polymer dissolved in TFE and chloroform. The surface of PHB composites fiber fabricated in chloroform contains porous structures, which are not observed for the sample of PHB composites fiber dissolved in TFE. The fiber diameters for PHBV5/magnetite composites are in the range of 500–540 nm and 2.3–2.5 µm, depending on the use of TFE and chloroform. The average diameters of PHBV5/magnetite composite fibers are smaller than those of PHB/magnetite composites fiber. All electrospun PHB/magnetite and composite fibers are superparamagnetic. The degradation behaviors of PHB/magnetite and PHBV5/magnetite composite fibers were investigated using Caldimonas manganoxidans. For the fabricated composite fibers, it is found that the degradation rate increased with the increasing loading of magnetite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41070.     

Preparation of oligochitosan via In situ enzymatic hydrolysis of chitosan by amylase in [Gly]BF4 ionic liquid/water homogeneous system

The preparation of oligochitosan with excellent performance via in situ enzymatic hydrolysis of chitosan by amylase in ionic liquid system is reported. It has been found that [Gly]BF₄ ionic liquid leads to the good solubility and assistant degradation for chitosan, as well as good biocompatibility for amylase. In the homogeneous system that contained 1.0 g chitosan (degree of deacetylation = 88.5%) and 99.0 g 2 wt % [Gly]BF₄ aqueous solution, oligochitosan with 2200 viscosity‐average molecular weight has been obtained after 0.12 g amylase being used for 3 h at 50°C and pH 5.0. This result is superior to that conducted in acetic acid system. Moreover, [Gly]BF₄ can be easily separated from the product and reused with only slight performance loss (oligochitosan product with 2700 viscosity‐average molecular weight has been obtained after [Gly]BF₄ being reused for five times). In addition, the mechanism for enzymatic hydrolysis of chitosan in [Gly]BF₄ ionic liquid has been described. The research on the moisture‐absorption, ‐retention, and antibacterial activity of oligochitosan product shows that the smaller molecular weight would bring the better moisture‐absorption and antibacterial properties. The oligochitosan product with 2200 viscosity‐average molecular weight exhibits preferable antibacterial properties to S. aureus and E. coli. At the same time, the moisture‐absorption and ‐retention capacity of the above product can reach 32% (relative humidity (RH) = 43%), 62% (RH = 81%), and 150% (RH = 43%), 35% (dry silica gel) respectively. The enzymatic preparation of oligochitosan through [Gly]BF₄ ionic liquid/water homogeneous system can be an efficient and environment‐friendly method for academics and industry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41152.     

反渗透复合膜研究(Ⅱ)初生态膜的原位改性

界面聚合是制备超薄复合膜是通过两种互不相溶的单体溶液在多孔支撑的表面进行聚合,再经热处理,洗涤等工艺后得到超薄复合膜。初生态膜(IniM)是指完成界面聚合反应而未经后处理（热处理,洗涤等）的膜。采用间苯二胺和均苯三甲酰氯通过在多孔聚砜膜上界面聚合得到初生态反渗透复合膜,再用四乙烯五胺对初生态膜进行表面原位改性,经后处理得到改性反渗透复合膜。对改性反渗透复合膜面XPS分析结果为：改性膜表面的O/N比明显低于未改性的,这说明四乙烯五胺通过反应接枝在膜表面;同时,改性膜面接触角大于未改性膜的,进一步证明了这一点。脱盐性能测试结果为：改性反渗透复合膜的水通量和NaCl脱除率随着进水pH值的增大而减小,这与未改性的反渗透复合膜变化趋势完全相反;这是因为改性反渗透复合膜面含有氨基（—NH₂）或亚胺基（=NH）,当pH值增大时,其与水的亲和力减小;而未改性的反渗透复合膜表面含有羧基（—COOH）, 当pH值增大时,其与水的亲和力增大。     

含磷阻燃共聚酯的热降解动力学及耐热性能研究

采用不同的升温速率,用Kissinger法研究了聚对苯二甲酸乙二酯(PET)和侧基含磷共聚酯(FR-PET)在氮气气氛中的热降解动力学;采用时-温等效原理对其耐热性能进行了深入研究,确定了动力学参数与材料寿命方程之间的关系,为直接估算材料的使用寿命提供了捷径。结果表明,阻燃剂的引入降低了PET整个热降解过程的平均活化能、指前因子及反应级数,并使PET的不同失重率所对应的时间延长,即FR-PET的耐热性能有所提高;在同一温度下,360℃以前FR-PET失重一半的时间要短于纯PET,在360℃以后则长于纯PET,说明在高温下相对于纯PET要难于点燃。利用Kissinger法确定的寿命与动力学关系式可较准确地预测材料的寿命。     

Molecular weight studies of the γ‐irradiation degradation of poly(methyl methacrylate) doped with poly(p‐sulfanilamide)

The protection of some poly(methyl methacrylate) (PMMA) samples against γ rays was investigated in the absence and presence of poly(p‐sulfanilamide). Pure PMMA (without additives) and PMMA–poly(p‐sulfanilamide) blend samples were irradiated with γ rays for different exposure doses (5, 15, 25, 35, 50, 75, and 100 kGy). The viscosity‐average molecular weights were determined and thin‐layer chromatography measurements were carried out after each irradiation dose. The maximum protection against γ rays was found when 1% poly(p‐sulfanilamide) was used. The radiation chemical yield for main scission (G_s) was calculated and had lower values in the case of 1% poly(p‐sulfanilamide). The energy absorption per scission was maximum for 1% poly(p‐sulfanilamide), and this confirmed the obtained G_s data. From thin‐layer chromatography studies, it was observed that both the retention factor (R_f) values and polydispersity of the PMMA samples increased with an increasing exposure dose. The effect of γ irradiation on PMMA films doped with 1% poly(p‐sulfanilamide) was investigated with UV spectroscopy after the extraction of the additives. A change in the intensity of the absorption bands with an increasing irradiation dose was recorded. It is suggested that PMMA films doped with this type of polymer can be used as dosimeters. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

空气气氛CR-g-BMA热降解机理研究

用热重分析法研究了氯丁橡胶/甲基丙烯酸丁酯接枝共聚物(CR-g-BMA)在空气气氛条件下的热降解过程。结果表明,CR-g-BMA 热降解分两步完成,其特征起始降解温度为571.66 K;特征终止降解温度为754.35 K。通过Achar 方程和 Coats-Redfern 方程对30种常见机理函数进行计算比较,得到 CR-g-BMA 第一步热降解反应和第二步热降解反应的微分和积分机理函数,并进一步计算出第一步和第二步热降解反应的活化能分别为176.03 kJ/mol 和171.09 kJ/mol。最后,提出相应的热降解动力学模型,确定 CR-g-BMA 热降解动力学参数。     

氨氮降解微生物菌株的分离筛选及去除效果初步研究

从活性污泥中分离筛选并驯化出4株具有氨氮降解能力的菌株,研究了氨氮废水的浓度、pH值、温度及反应时间对4株菌去除氨氮效果的影响。结果表明,在pH值7.5～8.0左右、温度30～32℃时,4株菌对氨氮浓度200mg/L的模拟废水去除效果较好,反应时间在7～8d为宜。     

UV／H2O2联用工艺对甲霜灵农药的降解

研究了高级氧化联用技术UV/H2O2光激发工艺去除水中甲霜灵的性能。试验结果表明,降解效果明显,其降解曲线呈现拟一级反应动力学的特征。研究了不同的影响因素,诸如不同H2O2的投加量、甲霜灵初始浓度、初始pH和水中常见阴离子等,对UV/H2O2光激发工艺对甲霜灵的降解的影响。在试验H2O2投加量范围内,随着H2O2投加量的增加,甲霜灵的降解速率增加;随着甲霜灵初始浓度的升高,光解反应的初始反应速率也随之增加,拟一级反应速率常数k下降;最佳pH为5;水中常见阴离子对UV/H2O2工艺降解甲霜灵影响的大小顺序为CO2-3＞NO-3＞SO2-4＞Cl-。     

降解含硫杂环芳烃中度嗜盐菌的筛选及降解特性研究

从胜利油田石油污染土壤中筛选分离出6株对二苯并噻吩具有降解能力的中度嗜盐菌,其中SL-4菌株的降解效果最好,在底物浓度为50 mg·L-1、培养基盐度为5％条件下对二苯并噻吩的降解率达到37.2％.通过单因素实验考察了底物初始浓度、pH值、温度、氮磷比对SL-4菌株降解效果的影响.正交实验结果表明：氮磷比是影响SL-4菌株降解效果的主要因素,其次是pH值和温度;SL-4菌株的最佳培养条件为：pH值7.5、温度25℃、氮磷比6∶1.