六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

Charge compensation dynamics in a soluble copolymer of poly(aniline) and poly(phenylene sulfide)

Poly(phenylene sulfide phenyleneamine), PPSA, is a copolymer of poly(aniline) and poly(phenylene sulfide), soluble in conventional organic solvents as tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and cyclohexanone. In this research, its electrochemical behavior has been studied in acetonitrile in the presence of different electrolytes, where the loss of electroactivity was observed after few cycles. In this paper, the charge compensation dynamics of PPSA is analyzed through electrochemical quartz crystal microbalance experiments and electroacoustic impedance measurements. Raman spectroscopy data have shown that once the oxidation of the sulfur atom occurs, a loss of electroactivity is observed, being not possible to recover the pristine state of the polymer. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data obtained for the fully oxidized polymer are consistent with the formation of a networked polymer due to the electrophilic attack of the positive sulfur atom on the activated aromatic rings. Electrochemical quartz crystal microbalance results clearly show that the degree of irreversibility fully depends on the chemical nature of the anions with a negligible participation of the cations of the electrolytic solution. This work is in memoriam of Prof. Dr. Francisco C. Nart, dearest friend and colleague, whose scientific skills and enthusiasm will always be remembered.     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合过程热互补效应的研究

六甲氧基甲基三聚氰胺（HMMM）－多元醇－丙烯酸酯－酸催化剂的混合体系在较高温度下同时进行缩聚和自由基聚合并表现出协同效应，DSC研究结果表明，丙烯酸酯在HMMM和酸的催化作用下可在较低温度下发生自由基聚合反应，并把反应释放出来的大量的热量有效地传递给缩聚发反应，满足缩聚反应吸热的要求，从而节省固化所需要的能量，为了提高储存稳定性。本文以潜酸催化剂作为酸的来源，对该混杂聚合体系进行了研究，仍有明显的热互补效应。     

The dielectric properties of water in its different states of interaction

A tutorial on dielectric (relaxation) spectrometry of liquids is given in this article. Some methods of measuring complex (electric) permittivity spectra are briefly described. Results for water are presented and related to characteristic properties of the liquid structure and to models of the molecular dynamics, particularly as resulting from computer simulation studies. Dielectric spectra for aqueous solutions of low weight electrolytes, polyelectrolytes, small molecules, and polymers are discussed to illustrate effects of kinetic depolarization, structure saturation, as well as positive, negative, and hydrophobic hydration. Reference is also made to fluctuations in the hydrogen bond network of mixtures of water with liquids that are completely miscible with this unique solvent.     

Excess heat capacities and orientational order in systems containing hexadecane isomers of different molecular structure

Using the Picker flow microcalorimeter, excess heat capacities have been obtained at 25°C throughout the concentration range for 2,2-dimethylbutane,n-hexane, and cyclohexane each mixed with a series of hexadecane isomers of increasing degrees of orientational order, as determined by depolarized Rayleigh scattering. The isomers are 2,2,4,4,6,8,8-heptamethylnonane, 6-, 4-, and 2-methylpentadecane, andn-hexadecane. Thec _p ^E values are negative, increasing rapidly in magnitude with increase of orientational order, and are not predicted by the Prigogine—Flory theory which neglects order. Values ofc _p ^E are obtained at 10, 25, and 55°C for cyclohexane +6-, 4-, and 2-methylpentadecane which with other literature data lead to the temperature dependence of the thermodynamic excess functions for cyclohexane solutions of the five C₁₆ isomers. The excess enthalpy and entropy vary with the C₁₆ isomer and with temperature, but the corresponding variation of the excess free energy is small, indicating a high degree of enthalpy-entropy compensation. This is consistent with a rapid decrease with temperature of orientational order in the C₁₆ isomers.     

Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C1 and C18 ligands of different densities

Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C₁ and C₁₈ alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D_s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C₁ and C₁₈ ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D_s values under various RPLC conditions. The D_s values can be estimated with a mean square deviation of about 25–30%. The agreement between the D_s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C₁ and C₁₈ ligands and that the contribution of each ligand is proportional to the ligand density.     

Thermally stimulated depolarization currents of tactic polymethyl methacrylates and their mixtures

Summary Thermally stimulated depolarization currents (TSDC) of atactic (a), syndiotactic (s) and isotactic (i) PMMA and mixtures ofs- andi-PMMA were measured. In pure tactic PMMA, TSDC peak was obtained at a temperature corresponding to the glass transition temperature of each PMMA. TSDC of mixtures isolated as precipitates from 1/1 and 1/2 (i/sweight ratio) mixed solutions showed a peak which can be attributed to the glass transition temperature of the stereocomplex. TSDC of original l/1 mixture showed two peaks which are ascribed to the glass transition temperature of residual i-PMMA and the stereocomplex. The results suggests that stereocomplex formation occurs ini/s weight ratio of 1/2 independent of the way of preparation.With 9 figures and 1 table     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.     

基于BAS-BP-Bagging模型的光纤陀螺温度补偿

为提高光纤陀螺的输出精度,以天牛须搜索算法(BAS)优化后的BP神经网络模型为基学习器,采用Bagging并行集成学习算法建立了BAS-BP-Bagging温度补偿模型,并对某型号光纤陀螺进行了温度补偿实验。实验结果表明,在-40～+60℃温度变化环境下,该方法补偿后的光纤陀螺温度漂移相较于补偿前减小了近80%,相较于多项式补偿算法减小了55%,相较于BP神经网络补偿算法减小了30%左右。同时该模型在对新鲜样本的补偿过程中表现出了较为优越的泛化性能。     

位置敏感探测器光斑脱靶误差补偿方法研究

为了提高位置敏感探测器(PSD)的位置检测范围,解决光斑在探测器光敏面脱靶时无法准确定位光斑的问题,提出一种光斑脱靶误差补偿方法,分析了脱靶前后PSD检测光斑能量重心变化规律,建立了PSD光强信号与位置检测误差间的函数关系。实验结果表明:当PSD光敏面尺寸为12mm×12mm时,对于半径为5mm的高斯光斑,通过所提出的光斑补偿方案补偿后PSD的X轴检测范围提高了66.7%,位置检测平均相对误差不超过5%,该方法对提高PSD位置检测性能具有重要的意义。