纳米金修饰分子印迹聚合膜电极检测双酚A

以纳米金修饰玻碳电极为基础电极,以双酚A为模板分子,以邻氨基苯硫酚为聚合单体,采用循环伏安法电聚合制备分子印迹聚合膜,利用循环伏安和交流阻抗法研究电极的电化学特性。结果表明,双酚A在修饰电极表面的反应是一个受吸附控制的等电子、质子转移的不可逆反应。采用差分脉冲伏安法检测双酚A,线性范围为5. 0×10~(-6)mol/L～4. 0×10~(-4)mol/L,检出限为2. 3×10~(-7)mol/L。将该电极用于自来水和牛奶样品的测定,结果均为未检出,加标回收率分别为93. 5%和95. 4%,3次测定结果的RSD分别为4. 0%和5. 7%。     

微乳液介质 - 4- (6- 甲氧基 - 8- 喹啉偶氮 )- 间苯三酚分光光度法测定微量铜

研究了溴代十六烷基吡啶、正丁醇、正庚烷和水自制微乳溶液介质中,4-（6-甲氧基-8-喹啉偶氮）-间苯三酚与铜的显色反应,建立了分光光度法测定微量铜的新方法。在显色液中铜的质量浓度在0.010 mg/L～0.700 mg/L范围内符合比尔定律,方法检出限为0.003 mg/L,铝合金和水样测定的RSD为0.3%～1.7%,加标回收率为96.3%～104%。     

微乳液法合成掺硫纳米TiO_2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚（Triton X-100）/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能。烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是提高,然后迅速降低;在600℃烧结2 h时催化剂的降解性能达到最佳。掺杂硫可提高TiO2的光催化活性,随着掺杂量的增加,催化剂对甲基橙的降解率先快速增加然后缓慢降低,当掺杂量为S/Ti（摩尔比）=0.01∶1时TiO2的光催化降解效果最好。催化剂在用量较小时迅速提高TiO2的光催化降解性能,而后随着用量的增大反而降低,当催化剂用量为1.5 g/L时,对甲基橙的降解效果最好。     

Fenton氧化/混凝沉淀协同处理腈纶聚合废水

采用Fenton法处理湿法腈纶聚合废水,考察了H2O2投加量、Fe2+投加量、p H和反应时间等因素对氧化和混凝作用去除废水污染物的影响,并分析了废水可生化性和特征污染物的变化。结果表明,Fenton法可以有效去除废水中有机污染物,在初始p H为3.0,Fe2+投加量为15.0 mmol/L,H2O2投加量为90.0 mmol/L的条件下,反应120 min后废水COD去除率可以达到56.8%,其中氧化和混凝作用对应的去除率分别为43.3%和13.5%;处理后废水的BOD5/COD由0.24升高至0.43;处理后废水中丙烯腈以及其他多数有机污染物能被有效去除。     

纳米腐植酸基复合树脂的制备及其对Ni~(2+)和Cd~(2+)的吸附

采用水溶液聚合法,以丙烯酸、丙烯酰胺及改性蒙脱土为原料,纳米腐植酸为基体,N,N’-亚甲基双丙烯酰胺为交联剂,过二硫酸钾为引发剂,制备了丙烯酸-蒙脱土-丙烯酰胺/纳米腐植酸复合树脂(简称复合树脂)。考察了溶液pH、吸附时间、吸附温度、初始离子浓度等因素对复合树脂分别吸附Ni~(2+)和Cd~(2+)的影响。实验结果表明:在吸附温度35℃、吸附时间90 min、溶液pH为7、初始Ni~(2+)和Cd~(2+)的浓度分别为0.02 mol/L、复合树脂加入量16.7 g/L的条件下,Ni~(2+)和Cd~(2+)的吸附量分别为383.02 mg/g和359.27 mg/g;复合树脂吸附Ni~(2+)和Cd~(2+)的吸附等温线均满足Langmuir等温吸附方程;吸附过程均符合准二级动力学方程;复合树脂重复使用6次,其对Ni~(2+)和Cd~(2+)的吸附量分别降低了17.1%和9.3%。     

Reaction mode between Si and Fe and evaluation of optimal species in poly-silicic-ferric coagulant

A kind of Fe-polysilicate polymer, poly-silicic-ferric （PSF） coagulant was prepared by co-polymerization （hydroxylation of mixture of Fe^3＋ and fresh polysilicic acid （PS））, in which PSF0.5, PSF1 or PSF3 denotes Si/Fe molar ratio of 0.5, 1 or 3, respectively. The effects of Si/Fe ratio and reaction time （co-polymerization time or aging time） on the reaction mode between Si and Fe were studies, and the optimal species of PSF was evaluated by pH change during the preparation of PSF and coagulation tests. The results showed that the characteristics of PSF are largely affected by both reaction time and Si/Fe ratio. PSF is found to be a essential complex of Si, Fe, and many other ions. The reaction mode between Si and Fe differs with various Si/Fe ratios. The pH of PSF0.5, PSF1 or PSF3 tended to be stable when reaction time is 10, 25 or 55 rain, respectively, which is almost consistent with the time reaching the relative stable morphology that is just the optimal species of higher coagulation efficiency. The optimal reaction time reaching optimal species can be evaluated by measuring the pH change during the polymerization process.     

一种船舶自修复防腐涂料的制备与表征

以脲醛树脂为囊壁、复合环氧树脂为囊芯,采用原位聚合法成功合成了脲醛树脂包覆环氧树脂体系微胶囊。采用扫描电子显微镜观察微胶囊的表面形貌,测量微胶囊的壁厚;利用红外光谱分析判定微胶囊壁材是否形成,芯材是否被完整包覆。结果表明,应用一步原位聚合法可以制备包覆完整、均匀分散、含有特殊芯材的微胶囊。合成的微胶囊形状基本呈球形,粒径分布均匀,平均粒径约为100μm;胶囊表面粗糙致密,粗糙表面主要是由纳米微胶囊沉积而成。微胶囊表面粗糙度的增加有利于增加微胶囊与基体的接触面积,改善微胶囊与基体的界面粘结力,从而提高自修复材料的修复效率。     

微乳液和混合表面活性剂对甲苯的增溶作用

以Tween系列非离子型表面活性剂及助表面活性剂组成的混合表面活性剂溶液作为增溶试剂,增溶吸收难溶有机物甲苯。结果表明,当表面活性剂浓度大于临界胶束浓度(CMC)时增溶效果显著,甲苯的表观溶解度与表面活性剂浓度呈线性关系,且随着表面活性剂浓度的增加而增大,增溶曲线在CMC处出现折点;微乳液较单一表面活性剂溶液对挥发性有机物甲苯的增溶能力更强,增溶比更大;添加助表面活性剂可以不同程度的提高表面活性剂溶液的增溶能力,其规律为:正丁胺正丁醇正丁酸;温度对微乳液及混合表面活性剂溶液的增溶作用有很大的影响,且低温条件更有利于增溶吸收挥发性有机物甲苯。非离子型微乳液是一种良好的增效试剂,在挥发性有机废气污染治理中具有较好的应用前景。     

Probe into effect of the initiator on the thermal runaway hazards of methyl methacrylate bulk polymerization

The bulk polymerization of methyl methacrylate (MMA) is of great importance in chemical industry, but the polymerization process is highly hazardous, and few reports have focused on the effect of initiators on its thermal hazards. In this work, to thoroughly explore the thermal hazard characteristics, the runaway behavior of MMA bulk polymerization is investigated by a combination of thermodynamics experimental and kinetics theoretical methods. The results indicate that the presence of initiator exhibits an undesirable thermal hazard to the MMA bulk polymerization, and its exothermic behavior is also greatly influenced by the type and concentration of initiator. For azobisisoheptanenitrile (ABVN), azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) initiators as examples, the AIBN-initiated reaction has the shortest adiabatic induction period (39.51 min), whereas the BPO-initiated polymerization exhibits the strongest maximum temperature-rising rate and maximum pressure-rising rate. Under adiabatic runaway, the temperature and pressure change significantly with increasing AIBN concentration, revealing a great potential risk of thermal runaway. Kinetic parameters are calculated to further understand the thermal runaway mechanisms, showing a strong agreement with the adiabatic experimental data. Finally, based on the cooling failure scenario, severity grading is determined by the evaluation criteria. The current work provides extensive data as a reference and guidance for the process design and optimization of MMA bulk polymerization from the perspective of safety.     

Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol^–1 min^–1, which is significantly higher than for related Y₅(-O)(O ⁱ Pr)_13– or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.