O-(4-喹唑啉)羟肟酸硫代酯(酰胺)类化合物的合成及生物活性

用差示扫描量热分析研究了间规聚苯乙烯（ｓＰＳ）的非等温结晶及其动力学，并分别用Ｏｚａｗａ和Ｊｅｚｉｏｒｎｙ两种方法来处理ｓＰＳ的非等温结晶数据．结果表明，在２５～４０℃／ｍｉｎ的冷却速率范围内，ｓＰＳ的半结晶时间随冷却速率增大而呈指数式下降，ｓＰＳ非等温结晶过程遵循Ｏｚａｗａ动力学方程，但不符合Ｊｅｚｉｏｒｎｙ方法中的Ａｖｒａｍｉ动力学方程．所得到的ｓＰＳ非等温结晶Ａｖｒａｍｉ指数ｎ在３６～４１之间，高于等温结晶时的ｎ值     

苯乙烯—丙烯等规立构嵌段共聚物（iPS—b—iPP）的非等温结…

用ＤＳＣ法研究了苯乙烯－丙烯等规立构嵌段共聚物的非等温结晶动力学。结果表明，冷却速度在５－２０℃／ｍｉｎ范围内，共聚的非等温结晶动力学参数能很好地符合Ａｖｒａｍｉ动力学学方程，非等温结晶速率常数与冷却速率有关，动力学结晶能力则同时受到冷却速率和共聚物组成比的影响，文中还讨论了在非等温结晶条件下共聚物的结晶成核和生长方式与共聚物组成和结构的关系，联合Ａｖｒａｍｉ方程和Ｏｚａｗａ方程推导的非等温结晶动     

聚丙烯接枝马来酸酐及其离聚物的等温结晶行为

采用ＤＳＣ对马来酸酐接枝聚丙烯（ＰＰ ｇ ＭＡＨ）及其３种５个离聚物的等温结晶行为进行了研究,发现在相对结晶度２％～９０％的范围内符合Ａｖｒａｍｉ方程．马来酸酐的引入及离子化并不改变ＰＰ的结晶行为,但样品的结晶速率增大,同时结晶速率亦随中和度的提高而增大．从Ｈｏｆｍａｎ理论得到７个样品的垂直于晶核的界面自由能σｅ,其变化与Ａｖｒａｍｉ方程的结果是一致的．     

聚氧化乙烯梳状聚合物共混物的非等温结晶动力学

用ＤＳＣ方法对乙烯基甲醚／马来酸酐交替共聚物多缩乙二醇酯（ＣＢＰ） 聚氧化乙烯（ＰＥＯ）共混体系的非等温结晶动力学进行了研究，用Ｍａｎｄｅｌｋｅｒｎ、Ｚ Ｊ（Ｚｉａｂｉｋｉ Ｊｅｚｉｏｒｎｙ）、Ｏｚａｗａ和对Ｏｚａｗａ方法的一种修正方法对该体系进行了处理．结果表明：得到了一种既没有结晶又有较多ＥＯ单元含量的共混物，ＣＢＰ对ＰＥＯ的结晶有抑制作用．Ａｖｒａｍｉ指数随冷却速率的加快在３８～５７之间波动．Ｍａｎｄｅｌｋｅｒｎ方法求得的结晶动力学参数Ｚｃ随冷却速率的增加而增加，共混物的Ｇｃ值不随冷却速率的变化而变化，随ＰＥＯ含量增加而减少，处理结果表明而Ｚ Ｊ理论能较好地解释本体系的非等温结晶过程和机理．     

梳状共聚物／聚氧化乙烯共混体系的结晶行为

用ＤＳＣ研究了烯基甲醚／马来酸酐交替共聚物多缩乙二醇酯／聚氧化乙烯共混体系的结晶行为，结果表明：提高冷却速率试样结晶减少，乙烯基甲醚／马来酸酐交替共聚物多缩乙二醇酯／聚氧化乙烯≥４０：６０时没有结晶产生，结晶前期符合Ａｖｒａｍｉ方程，Ａｖｒａｍｉ指数，ｎ随冷却速率的增加在３．８～５．７之间波动，对表征非等温结晶的动力学参数Ｚｃ的关系式做了修正，使之更符合实际的结晶过程，同时△Ｈ也随冷却速率的增加而     

环氧乙烷和环氧丙烷共聚体系的等温结晶和熔融

环氧乙烷（ＥＯ）和环氧丙烷（ＰＯ）共聚体系的等温结晶前期符合Ａｖｒａｍｉ方程。ＰＯ组分含量增加，Ａｖｒａｍｉ指数ｎ值由１．８到２．４，体系的结晶生长速率与共聚体系的组成和结晶度有关，ＥＯ／ＰＯ共聚体系的平衡熔点随ＰＯ含量的增加而降低。随Ｔｃ增大，△Ｈｍ与△Ｓｍ呈线性降低。     

氧化钕填充聚丙烯的等温结晶动力学研究

用ＤＳＣ法研究了氧化钕微粉填充聚丙烯的等温结晶动力学．结果表明，加入少量氧化钕可明显提高聚丙烯的基体结晶速率和结晶度，降低球晶径向生长的单位面积表面自由能；从Ａｖｒａｍｉ和Ｈｏｆｆｍａｎ理论出发都可得出稀土氧化物Ｎｄ２Ｏ３填充聚丙烯后可明显改变聚丙烯的结晶行为．     

苯乙烯—丙烯嵌段共聚物等温结晶动力不宾研究

用ＤＳＣ法研究苯乙烯－丙烯嵌段共聚物（ｉＰＳ－ｂ－ｉＰＰ）的等温结晶动力学，结果表明，在所选择的结晶温度（１２７－１３２℃）范围内，共聚物很好地符合Ａｖｒａｍｉ动力学方程；共聚物结晶温度，结晶速率，结晶成和生长方式都与共聚物结构和组成比在关，随着嵌段共的中ｉＰＳ段含量的增加，结晶速率和Ａｖｒａｍｉ指数（ｎ）明显降低。     

聚丙烯-g-聚氨酯共聚物的非等温结晶动力学研究

用DSC法研究了聚丙烯 (PP)和聚丙烯接枝聚氨酯的共聚物 (PP g PU)在不同冷却速率下的非等温结晶动力学 .用Avrami方程和莫志深改进法对DSC测定结果进行了处理 ,结果表明 ,PP g PU的动力学参数能很好的符合Avrami方程和莫志深改进方程 .PP接枝了聚氨酯支链后 ,结晶速率增大 ,球晶的生长和成核机制也相应发生改变 ,而其变化规律与接枝物的组成和结构密切相关     

联苯聚醚醚酮酮的结晶动力学的研究

通过ｄｓｃ 方法对新型聚芳醚酮联苯聚醚醚酮酮（ＰＥＥＫＤＫ） 的等温及非等温熔融结晶动力学进行了研究,运用Ａｖｒａｍｉ 方程分析了其等温结晶行为,求得了等温结晶活化能,平衡熔点,成核参数,并与其它聚芳醚酮类聚合物进行了比较。同时,对ＰＥＥＫＤＫ的非等温结晶动力学也进行了研究。     

Thermodynamics of micelle formation in water, hydrophobic processes and surfactant self-assemblies

The critical micelle concentration (c.m.c.) for four cationic surfactants, alkyl-trimethyl-ammonium bromides, was determined as a function of temperature by conductivity measurements. The values of the standard free energy of micellisation DeltaG degrees(mic) at different temperatures were calculated by using a pseudo-phase transition model. Then, from the diagram (-DeltaG degrees(mic)/T)=f(1/T), the thermodynamic functions DeltaH(app) and DeltaS(app) were calculated. From the plots DeltaH(app)=f(T) and DeltaS(app) = f(ln T) the slopes DeltaC(p) = n(w(H))C(p,w) and DeltaC(p)=n(w(S))C(p,w) were calculated, with the numbers n(w(H)) and n(w(S)) negative and equal and therefore defined simply as n(w). The number n(w)<0, indicating condensed water molecules, depends on the reduction of cavity that takes place as a consequence of the coalescence of the cavities previously surrounding the separate aliphatic or aromatic moieties. The analysis, based on a molecular model consisting of three forms of water, namely W(I), W(II), and W(III), respectively, was extended to several other types of surfactants for which c.m.c. data had been published by other authors. The results of this analysis form a coherent scheme consistent with the proposed molecular model. The enthalpy for all the types of surfactant is described by DeltaH(app)= -3.6 + 23.1xi(w)-xi(w)C(p,w)T and the entropy by DeltaS(app)= +10.2+428xi(w)-xi(w)C(p,w) ln T where xi(w)= |n(w)| represents the number of molecules W(III) involved in the reaction. The term Deltah(w)= +23.1 kJ mol(-1) xi(w)(-1) indicates an unfavourable endothermic contribution to enthalpy for reduction of the cavity whereas the term Deltas(w)= +428 J K(-1) mol(-1) xi(w)(-1) represents a positive entropy contribution for reduction of the cavity, what is the driving force of hydrophobic association. The processes of non polar gas dissolution in water and of micelle formation were found to be strictly related: they are, however, exactly the opposite of one another. In micelle formation no intermolecular electronic short bond is formed. We propose, therefore, to substitute the term "hydrophobic bond" with that of "hydrophobic association".     

Synthesis, structure, and magnetic properties of two new ferromagnetic/antiferromagnetic one-dimensional nickel(II) complexes. Magnetostructural correlations

Two new one-dimensional nickel(II) complexes were synthesized and characterized: [Ni(N,N-dimethylethylenediamine)(N3)2] (1) and [Ni(2-aminoethylpyridine)(N3)2] (2). The crystal structures of 1 and 2 were solved. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n with a = 10.569(2) A, b = 7.331(4) A, c = 12.9072(8) A, beta = 111.324(10) degrees, and Z = 4. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c with a = 12.299(5) A, b = 14.307(2) A, c = 12.604(3), beta = 106.72(2) degrees, and Z = 4. The two complexes are similar and may be described as one-dimensional systems with double-azido-bridged ligands in end-to-end and end-on coordination alternatively. The end-on moiety is almost identical for 1 and 2, but the end-to-end moiety is different in each structure: for 1 this part is almost planar but for 2 is nonplanar. In both cases the Ni atoms are situated in similar distorted octahedral environments. The magnetic properties of the two compounds were studied by susceptibility measurements vs temperature. The chi M vs T plots for 1 and 2 show a global antiferromagnetic behavior with a maximum near room temperature for 1 and at very low temperature for 2. J values for 1 and 2 were deduced from the spin Hamiltonian -sigma(J1SiSi+1 + J2Si+1Si+2). The computational method was based on the numerical solution for finite systems of increasing size. J values for 1 were J1 = -187 cm-1 and J2 = +77 cm-1 and for 2 J1 = -28 cm-1 and J2 = +73 cm-1. The positive values correspond to end-on azido ligands and the negative values to end-to-end azido ligands. Since the geometries of the [Ni(N3)]2 moieties involving the end-on azido ligands are almost the same in the two structures, the ferromagnetic coupling is nearly identical in the two compounds, while the significantly different antiferromagnetic couplings reflect the near planarity of the end-to-end Ni2(N3)2 fragment in 1 and its twisted geometry in 2.     

Theoretical Investigation on Mechanism,Thermochemistry, and Kinetics of the Gas-phase Reaction of 2-Propargyl Radical with Formaldehyde

Gas-phase mechanism and kinetics of the reactions of the 2-propargyl radical(H2CCCH), an important intermediate in combustion processes, with formaldehyde were investigated using ab initio molecular orbital theory at the coupled-cluster CCSD(T)//B3LYP/6-311++G(3df,2p) method in conjunction with transition state theory(TST), variational transition state theory(VTST) and Rice-Ramsperger-Kassel-Marcus(RRKM) calculations for rate constants. The potential energy surface(PES) constructed shows that the H2CCCH+HCHO reaction has six main entrances, including two H-abstraction and four additional channels, in which the former is energetically more favorable. The H-abstraction channels slide down to two quite weak pre-complexes COM-01(-9.3 kJ/mol) and COM-02(-kJ/mol) before going via energy barriers of 71.3(T0/P1) and 63.9 kJ/mol(T0/P2), respectively. Two post-complexes, COM-1(-17.8 kJ/mol) and COM-2(-23.4 kJ/mol) created just after coming out from T0/P1 and T0/P2, respectively, can easily be decomposed via barrier-less processes yielding H2CCCH2+CHO(P1,-12.4 kJ/mol) and HCCCH3+CHO(P2,-16.5 kJ/mol), respectively. The additional channels occur initially by formation of four intermediate states, H2CCCHCH2O(I1, 1.1 kJ/mol), HCCCH2CH2O(I3, 4.5 kJ/mol), H2CCCHOCH2(I4, 10.2 kJ/mol), and HCCCH2OCH2(I6, 19.1 kJ/mol) via energy barriers of 66.3, 59.2, 112.2, and 98.6 kJ/mol at T0/1, T0/3, TOM, and TO/6, respectively. Of which two channels producing 14 and 16 can be ignored due to coming over tlie high barriers TOM and TO/6, respectively. The rate constants and product branching ratios for the low-energy channels calculated show that the H2CCCH+HCHO reaction is almost pressure-independent. Altliough the H2CCCH+HCHO→Ⅰ1 and H2CCCH+HCHO→Ⅰ3 channels become dominant at low temperature, however, they are less competitive channels at high temperature.     

Na促进的CuCoMn催化剂催化生物质合成气合成高醇

研究钠促进的CuCoMn催化剂的特性及其在生物质气化合成气合成高醇中的应用. 研究了催化剂中Na含量及合成条件(温度、压力和空速)对生物质基合成气合成高醇性能的影响. 发现CuCoMnNa_0.1催化剂较适合高醇合成, 在300 °C以下, 随着温度的上升, 碳转化率增大, 而醇选择性降低. 压力的增加有利于醇的合成, 增大空速会明显降低碳转化率, 但醇时空产率则因转换频率的增加而增大. 在所考察的范围内, 醇产率最高达到304.6 g·kg^-1·h^-1, 其中C₂₊高醇(C₂-C₆醇)占64.4% (w, 质量分数). 醇产物和烃产物均符合ASF (Anderson- Schulz-Flory)分布关系. 根据催化剂性能与表征分析, Na的加入有利于提高生物质气化合成气合成高醇的选择性和活性元素Cu、Co的分散性. X射线光电子谱(XPS)测试结果显示反应后的催化剂表面上, Cu以Cu⁺和Cu⁰的混合形式存在, 而Co则是Co²⁺/Co³⁺和Co⁰的混合物. 增加Na的含量, Cu⁰/Cu⁺比率和Co⁰的强度均随之减小.     

1,6-己二醇二丙烯酸酯和苯乙烯多单体熔融接枝制备长支链聚丙烯研究

采用哈克转矩流变仪制备了1,6-己二醇二丙烯酸酯(HDDA)和苯乙烯(St)多单体熔融接枝聚丙烯(PP)体系.红外测试结果表明St的加入能够促进HDDA接枝到PP主链,提高接枝率.动态流变行为研究结果也表明采用多单体熔融接枝PP更有利于体系在熔融接枝中生成长支链(LCB).随着St单体添加量的增加,HDDA的接枝率增大...     

Cp*TiCl2N[Si(CH3)3]2/MAO催化剂合成无规聚丙烯弹性体

合成了Cp TiCl2 N[Si(CH3) 3]2 甲基铝氧烷 (MAO)催化体系 ,以该体系进行丙烯聚合得到无规聚丙烯 ,具有高的分子量及良好的弹性 ,玻璃化温度为 - 8 8℃ .产物经DSC、1 3C NMR、DMA等方法表征 .结果表明 ,催化活性随着丙烯压力的增加 ,有明显的增大 .催化活性在 4 0℃下有最高的催化活性 ,而产物分子量随着温度的下降有明显增大 ,在 0℃～ 5 0℃范围内分子量MW =(2 0～ 6 0 )× 10 4 .     

Low-energy paths for the unimolecular decomposition of CH3OH: a G2M/statistical theory study

The potential energy surface (PES) of the CH3OH system has been characterized by ab initio molecular orbital theory calculations at the G2M level of theory. The mechanisms for the decomposition of CH3OH and the related bimolecular reactions, CH3 + OH and 1CH2 + H2O, have been elucidated. The rate constants for these processes have been calculated using variational RRKM theory and compared with available experimental data. The total decomposition rate constants of CH3OH at the high- and low-pressure limits can be represented by k infinity = 1.56 x 10(16) exp(-44,310/T) s-1 and kAr0 = 1.60 x 10(36) T-12.2 exp(-48,140/T) cm3 molecule-1 s-1, respectively, covering the temperature range 1000-3000 K, in reasonable agreement with the experimental values. Our results indicate that the product branching ratios are strongly pressure dependent, with the production of CH3 + OH and 1CH2 + H2O dominant under high (P > 10(3) Torr) and low (P < 1 atm) pressures, respectively. For the bimolecular reaction of CH3 and OH, the total rate constant and the yields of 1CH2 + H2O and H2 + HCOH at lower pressures (P < 5 Torr) could be reasonably accounted for by the theory. For the reaction of 1CH2 with H2O, both the yield of CH3 + OH and the total rate constant could also be satisfactorily predicted theoretically. The production of 3CH2 + H2O by the singlet to triplet surface crossing, predicted to occur at 4.3 kcal mol-1 above the H2C...OH2 van der Waals complex (which lies 82.7 kcal mol-1 above CH3OH), was neglected in our calculations.     

梳状聚合物电解质的力学松弛时间

以苯乙烯 /马来酸酐共聚物为骨架 ,聚乙二醇单甲醚为侧链合成了 3种不同侧链长度的梳状高分子聚合物 ,制成了锂盐络合物薄膜 .动态力学性能研究结果表明 ,本体系是主链刚性、侧链较柔软的梳状接枝聚合物 .应用时间温度等效原理 ,选择Tα 作为参考温度 ,建立了主曲线 ,得到了移动因子图和等自由体积图 .Williams、Landel和Ferry(WLF)经验方程的两个参数C1、C2 随着盐浓度增加而增大 .若T0 =50℃作为参考温度 ,平均松弛时间lgτc 与锂盐浓度C呈线性关系 .随着侧链分子量增加 ,主曲线向高频率移动 ;平均松弛时间lgτn 与侧链分子量的关系也是线性的 ;另外随着盐的不同 ,主曲线也会产生移动 ,表明盐种类对松弛时间产生影响 .     

聚α-氯甲基-α-甲基-β-丙内酯的非等温结晶动力学

我们曾报道［１］以二羟甲基丙酸为原料，通过氯化、水解和内酯化反应合成α 氯甲基 α 甲基 β 丙内酯（ＣＭＭＰＬ），并用多种引发剂如吡啶、三乙胺、三氟乙酸以及金属有机化合物如三乙基铝、异丙醇铝、钛酸四丁酯和辛酸亚锡等引发聚合，得到白色固体聚合物Ｐ（Ｃ...