大口径厚液膜二乙二醇丁二酸聚酯交联玻璃毛细管柱的研制和应用

用过氧化异丙苯为引发剂,制备了大口径厚液膜二乙二醇丁二酸聚酯交联毛细管柱,并用于植物油脂肪酸的分析。     

Studies on the Interaction of 12-Tungstophosphoric Acid and Diethylene Glycol

The homogeneous system of 12-tungstophosphoric acid and diethylene glycol was studied using IR and NMR spectra. It was found that the protons in 12-tungstophosphoric acid formed proton oxonium ions with the hydroxyl oxygen in diethylene glycol by hydrogen-bonds, and the formed proton oxonium ions could react with the terminal oxygens of heteropoly anions. The dehydration-cyclization mechanism of diethylene glycol in the presence of heteropoly acid was also proposed.     

一缩二乙二醇二甲基丙烯酸酯接枝真丝的结构

通过电子扫描电镜 (SEM)、红外光谱 (IR)、双折射、X 射线衍射及氨基酸分析等手段 ,研究了真丝用一缩二乙二醇二甲基丙烯酸酯 (P 2 )接枝后其结构与接枝率之间的关系 .氨基酸分析结果表明P 2接枝主要在真丝大分子中酪氨酸、丝氨酸、组氨酸和精氨酸的NH2 、OH和—NH—活性基团上 .通过X 射线衍射分析 ,P 2接枝并不直接影响结晶区 ,但引起分子取向的下降 ,接枝后真丝双折射下降说明接枝后因大分子取向度下降 ,接枝真丝的红外光谱显示出真丝具有 β折迭结构和P 2高聚物的结构特征峰 ,从而说明P 2接枝在纤维的无定型区内部进行 .当接枝率大于 35 %时 ,纤维的表面覆盖了一层高聚物 (P 2 ) ,并且纤维的横截面表现出明显的分纤现象 ,接枝真丝的红外光谱表明了纤维与P 2重叠吸收峰 ,说明了P 2在丝纤维内部接枝聚合 .     

Apparent Molar Volume and Apparent Molar Refraction of Mono-, Di-, Tri-, and Tetra(oxyethylene) Glycol in Aqueous, 1,4-Dioxane,and Benzene Solutions at 298.15 K

Summary. The density and refractive index of aqueous, 1,4-dioxane, and benzene solutions of poly (oxyethylene) glycols of the type HO–(CH₂CH₂O) _n –H (n varying from 1 to 4) were measured at 298.15K. From these experimental data the apparent molar volume and the apparent molar refraction at infinite dilution were calculated. The limiting apparent molar volume of the investigated compounds in a definite solvent depends linearly on the number of oxyethylene groups. From these data, the volume of the monomeric unit was evaluated and found to be greater in non-aqueous solvents than in water. The limiting apparent molar refraction of the solute for the investigated systems, within the experimental uncertainties, is equal to the molar refraction of the pure solute. The electronic polarizability of the solute molecule depends linearly on the number of monomeric units and the ratio of the electronic polarizability to the molecular van der Waals volume is constant and independent of the number of oxyethylene groups.Received February 24, 2003; accepted (revised) April 10, 2003 Published online August 18, 2003     

二乙烯三胺接枝壳聚糖的合成与表征

以壳聚糖为基体,与环氧氯丙烷反应,然后与二乙烯三胺反应,制得二乙烯三胺接枝壳聚糖(CTSN)。经红外光谱FTIR分析和X-射线衍射分析表征了结构,在活化及接枝过程中未破坏壳聚糖中的吡喃苷六元环结构,其结构与预期结构吻合。初步研究了它对Pd2 、Ag 、Ni2 、Cu2 、Co2 、Cd2 金属离子的静态吸附性能,试验结果表明,CTSN对金属离子有较大的吸附容量,对Pd2 、Ag 离子的吸附容量分别为1.29mmol/g和1.15mmol/g。     

Intelligent Fibrous Substrates with Thermal and Dimensional Memories

Binding of polyethylene glycols to any fibrous substrate (such as a natural cellulosic or wool, or synthetic fibers polyester, polyamide or polyolefin) is achieved by in situ network polymerization with polyfunctional resins and acid catalysts. The modified substrates contain crosslinked polyethylene glycols that impart several improved functional properties. Two of these properties (thermal adaptability and reversible shrinkage in the wet and dry states) make it appropriate to categorize the modified fibrous substrates as “intelligent materials”. The thermal and dimensional/shape memories of the substrates are influenced and, hence, controlled by the molecular weight of the polyol, crosslink density, curing conditions to affix the polyol and construction of the fibrous substrate. Verification of these effects has been noted by thermal analysis and infrared thermography (for thermal memories) and by measurement of power generated and work performed during wet shrinkage of appropriate substrates (for shape memories). Numerous potential commercial applications are described and some are being actively pursued. © 1997 John Wiley & Sons, Ltd.     

Modeling Binary and Multicomponent Systems Containing Supercritical CO2 with Polyethylene Glycols and Compounds Relevant to the Biodiesel Production

The CPA equation of state is applied to model binary, ternary, and multicomponent mixtures that contain CO₂ with polyethylene glycols or compounds relevant to biodiesel production, such as glycerol and various triglycerides. Effort has been made to evaluate the model performance on correlating both the liquid and the vapor phase compositions, which is a demanding task, revealing the model’s and parameters’ limitations, due to the rather low concentrations of heavy compounds in the vapor phase. Initially the model’s binary parameters, which in all cases were temperature independent, were estimated using experimental data for binary systems. Those parameters were used to predict the phase behavior of supercritical CO₂ containing ternary and multicomponent mixtures. Since no parameter was adjusted to ternary or multicomponent systems’ data, the reported CPA results for such mixtures are considered as pure predictions. This is the final part of a series of studies [Tsivintzelis et al. Fluid Phase Equilibria 430 (2016) 75–92 and 504 (2020) 112337] that complete the parameterization of the CPA equation of state for systems relevant to the biodiesel production, which allows the application of the model to multicomponent mixtures of the relevant processes.     

杂多酸对二甘醇脱水环化反应的催化作用

研究了杂多酸对二甘醇脱水环化的催化作用。结果表明,磷钨酸,硅钨酸,硅钼酸具有较高的催化活性,而磷钼酸的催化活性较低。采用ＴＧ,ＩＲ,ＧＣ－ＭＳ,电导等测试技术,对正丁胺酸性,杂多阴离子碱度,还原特性的测定及对产物结构的分析。     

纤维素丙酸酯-g-二乙二醇正十六烷基醚固-固相变材料的制备及性能

以二月桂酸二丁基锡(DBTDL)为催化剂,微晶纤维素为骨架材料,二乙二醇正十六烷基醚(E2C16)为相变材料,采用化学接枝法制备了系列纤维素丙酸酯-g-二乙二醇正十六烷基醚(CP-g-E2C16)固-固相变材料.利用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H NMR)、差示扫描量热仪(DSC)、热重分析(TG)和X射线衍射(XRD)对CP-g-E2C16相变材料的结构和热性能进行了表征.结果表明,得到了E2C16的取代度和接枝含量分别为0.12~0.37和17.1%~33.4%的CP-g-E2C16固-固相变材料.CP-g-E2C16接枝共聚物的相变温度和相变焓分别为25~34℃和40~62 J/g,符合人的体感舒适温度范围.CP-g-E2C16固-固相变材料的耐热温度高于237℃,与E2C16相比提高21~40℃,有望应用于熔融纺丝法制备纤维素基储热调温纤维领域.     

焙烧温度对Ni/La(Ⅲ)催化剂氢解山梨醇制备低碳二元醇性能的影响

采用水热法合成了纳米棒状La(OH)₃载体,通过湿式浸渍方法制备了10%Ni/La(Ⅲ)负载型催化剂,考察了500~800℃不同焙烧温度对于催化剂氢解山梨醇制备低碳二元醇的影响,结合XRD、SEM/EDS、BET、H₂-TPR-MS、CO/CO₂-TPD-MS、TG和ICP-AES等表征手段对Ni/La(Ⅲ)催化剂的构效关系进行了分析。结果表明,Ni/La(Ⅲ)催化剂表现出高的氢解反应活性,在较低的焙烧温度下(500℃)催化剂主要以NiO/La₂O₂CO₃结构形式存在。随着焙烧温度的升高,NiO/La₂O₂CO₃逐渐向La₂NiO₄-La₂O₃进行转变。碱性是影响不同催化剂活性的决定因素,高的焙烧温度促进了催化剂中强碱性位的生成,显著提高了氢解反应活性,但对液体产物的选择性无明显影响,在220℃、4MPa H₂、1.5h的条件下,山梨醇完全转化,低碳二元醇的产率可达到53%。低的焙烧温度则增加了催化剂的水热稳定性。催化剂的失活主要归结于活性金属粒子在水相反应中从载体表面脱落而发生团聚,降低氢解反应活性。