非等活性加核自缩合乙烯基聚合体系回转半径的Monte Carlo模拟

利用Monte Carlo模拟方法研究了加核自缩合乙烯基聚合反应体系中超支化高分子的二次回转半径随双键转化率的变化情况. 在模拟中, 重点考察了两类活性基团的反应活性差异、 引发核的配比及基团数等因素对超支化高分子均方回转半径的影响. 结果表明, 上述因素对于超支化高分子的尺度有着显著影响, 从而可为调控体系中高分子的空间尺度提供有效途径.     

三元非等活性自缩合乙烯基聚合体系的Z均回转半径

利用Monte Carlo模拟方法研究了由单体、引发单体和引发核组成的三元自缩合乙烯基聚合反应体系. 重点考察了两类活性基团反应活性的差异、引发单体分数、引发核的配比及活性基团数等因素对体系中无核和有核两类超支化高分子Z均回转半径的影响. 结果表明, 这些因素对超支化高分子的结构和尺度影响显著, 因而通过调节有关参数可以实现对超支化高分子结构和尺度的调控.     

加核自缩合乙烯基聚合反应体系的热力学特征

从统计力学角度出发,对加核二元自缩合乙烯基聚合反应体系的热力学特征进行了研究.给出了引发核与引发单体间的配料比、反应物的体积分数及引发核的官能度等因素与反应体系热力学统计特征之间的定量关系,重点讨论了内能、比热、多分散性指数和均方回转半径等物理量随反应条件的变化规律.结果表明,通过调控反应温度、改变反应物的浓度(体积分数)和配料比以及选取合适的引发核等方法可制备出具有预期结构和性能的超支化高分子.     

典型超支化高分子体系的统计热力学及其应用

以典型的超支化聚合反应体系为例概述了体系的热力学和统计力学性质,重点集中在平均分子量、均方回转半径及支化点密度等特征与热力学量间的关联,以期阐明超支化高分子空间结构与物理性质的调控机制.从空间关联的角度赋予重均聚合度以相应的物理解释,建立其与等温压缩系数的直接关系.通过子链分布导出均方回转半径和流体力学半径的解析形式,并利用高分子的邻接矩阵进行具体计算.在此基础上,从相变与临界现象的角度出发,解释了体系中相关物理量的标度行为,给出相应的广义标度律.为了优化超支化高分子的工业生产流程,引入生成函数方法系统地探讨了分批投料过程中的相关参数对平均高分子量的影响.此外,提出了基于生长代数的Monte Carlo模拟方案,用以辅助研究高分子结构与特征的对应关系.作为应用,揭示了环化效应、溶剂效应及非等活性等因素对聚合反应的影响.     

Af+AB星型聚合体系的统计热力学

应用统计力学和热力学原理研究了 A_f+AB星型聚合体系的性质. 首先从两种不同的角度给出了与聚合反应相应的配分函数, 并据此得到反应体系的平衡自由能、质量作用定律及数量分布函数, 进而得到了体系的平衡状态方程和比热. 在此基础上, 以反应体系的回转半径为例研究了溶剂效应对星型高分子空间尺度的影响.     

AB_g型超支化聚合反应中的环化效应

研究了ABg型超支化聚合反应中的环化效应,给出高分子代数生长的微分动力学方程,并通过环化反应的内在特征确定了环化反应与分子间反应的速率常数.进而利用Monte Carlo模拟方法得到了树状高分子和含环高分子的数量、环的尺寸分布以及高分子数均和重均分子量等,讨论了环化效应对聚合体系平均特征的影响.结果表明,环化效应取决于单体体积分数、溶剂效应和官能度之间的协同作用,其中单体的体积分数在环化反应中起着主导作用,而溶剂效应和官能度之间则相互竞争.     

ABg型超支化反应体系的平衡统计特征

应用统计力学原理, 从两种不同角度对ABg型超支化反应体系中的平衡特征进行研究, 得到该体系平衡自由能以及反应程度与热力学量之间关系的解析表达式. 进一步指出获得超支化高分子数量分布函数的两种新方法, 并结合改进的高分子格子流体理论探讨了聚合反应对体系状态方程的影响.     

超支化聚合反应的多尺度模拟

超支化聚合物具有与树枝状大分子相似的物理和化学性质,其具有合成简单、分子量分布宽等突出特点,超支化聚合物分子的结构形成取决于聚合反应过程,本文介绍了超支化聚合反应模拟研究的最新进展.首先介绍了八位置键涨落粗粒化格子模型在超支化聚合反应模拟中的应用,该方法考虑了聚合物分子空间位阻效应、分子内成环和反应点活性等影响因素,从而可以模拟不同类型的超支化聚合反应;为了定量描述单体和聚合物分子结构,研究者进一步发展了杂化多尺度超支化聚合反应模拟方法,该方法通过玻尔兹曼反演迭代方法获取单体和聚合物特异性粗粒化力场,然后通过粗粒化分子动力学方法结合反应性Monte Carlo方法对特异性超支化聚合反应进行定量模拟.多尺度聚合反应模拟不仅可以精确计算超支化聚合物分子量、多分散性指数和支化度等一般性聚合物参数,还可以获取分子成环率、超支化大分子构象等重要分子结构信息,在超支化聚合反应基础研究与预测方面具有重要应用价值.     

自缩合乙烯基聚合体系中的环化效应

基于超支化高分子的生长代数模型,利用Monte Carlo模拟方法研究了不同溶剂条件下自缩合乙烯基聚合(SCVP)体系的环化效应.根据SCVP体系的反应机理给出含环反应的微分动力学方程,并通过环化反应的内在特征确定了分子间反应和内环化反应的速率常数.在此基础上,利用Monte Carlo模拟方法得到了高分子的数量分布函数、重均分子量、环数以及含环分子的链段分数等相关物理量,分析了环化效应对于体系平均物理量的影响.进一步根据模拟结果对单体浓度和溶剂效应等对内环化反应的影响予以分析.结果表明,环化效应取决于单体浓度和溶剂效应之间的协同作用,其中单体浓度在环化反应中起着主导作用.     

含引发机制的Ａf—Ａg型缩聚反应Z—均回转半径研究

讨论了含引发机制的Ａf-Ａg型缩聚反应体系Z－均回转半径,利用枝状高分子成键的统计分析,给出组合因子分解公式,并得到均方回转半径的表达式;进一步结合数量分布函数,定义k次高分子半径,并给出计算k次高分子回转半径的循环公式,最后得到凝胶点前Z－均回转半径的解析表达式。     

数据离群值的检验及处理方法讨论

由目前普遍使用的分析化学教材中与离群值相关的内容出发,对其进行对比和分析,说明数据离群值检验的意义和重要性。对几种常见的离群值判定方法进行了列举和比较,并对已确认为异常值的数据的处理方法也进行了对比和讨论。各种检验和处理方法各有其优势和劣势,根据实际情况选择不同方法或多种方法配合使用,能够更好地实现对离群值的检验和处理。     

Simple correction for perturbations of peak amplitudes in statistical models of overlap

Summary The application of statistical models of overlap (SMOs) to saturated separations is made possible by theory that addresses variable peak amplitudes. These amplitudes cause peak widths to vary, and this variation can be modeled by a random variable whose effect on the probability of overlap is expressed by a convolution integral. Modified probabilities of overlap are derived for both homogeneous and nonhomogeneous one-dimensional separations, and the new probabilities are compared to results determined from published computer simulations. The new theory can describe overlap at saturations that are 3 to 4 times larger than before. Previously reported experimental chromatograms are reinterpreted to show the capabilities of theory. The theoretical extension is an important step towards making SMOs into practical tools for screening analytical separations.     

聚丙烯β型球晶形态及成因的探讨

本文主要采用扫描电子显微镜,对主含夕球晶的iPP,或其与LDPE共混的试样的表面、切面、热处理样,紫外线及光、热老化样等大量试样中的β球晶形态进行了观察,结合前人工作,对iPPβ球晶的形态及成因,提出了一些新的看法。     

寡糖和多糖的合成

本文重点介绍了寡塘及多馆在化学合成方面的进展,述及了寡掂经典合成方法及近年来发展的一些新方法,如三氯乙酸亚胺基作为离去基团的方法,以缩水内醚糖为糖的给体的方法等。对多糖的合成主要介绍了1,6-、1,4-、1,3-、1,2-缩水内醚搪的阳离子聚合制备均聚多塘,及用糖原酸醋衍生物通过缩聚反应制备多塘。     

3GPa下高聚物固体的等温压缩行为

十种聚合物固体的等温压缩实验证明Tait方程和Murnaghan方程在0—3GPa范围内能够精确地描述非晶、半晶和结晶聚合物的P-V关系;Tait参数C_T=0.0894,Mumaghan参数C_M=0.1016为普适值。这两个方程的线性式用起来颇方便;当有压致松弛时可进行分段处理,能获得有关结构松弛的信息。对Bridgman多项式的适用性也进行了讨论。并计算了Gr(?)neisen参数。     

Relative energy of organic compounds III. Components of the heat of reactions

The relative enthalpies of organic compounds described in Parts I and II of this series made possible to show the contribution of the reactants and products to the heat of reactions. First, the meaning of the relative enthalpies is demonstrated. The components of the heats of reactions are exemplified by a series of reactions: formation of alkyl halides, esters, amides, acid halides, and anhydrides. Further examples are hydrogenation of alkenes, alkynes, benzene, ethylene oxide, aldehydes, and nitriles, and addition of chlorine, water, and hydrogen chloride to ethylene. Acetal and hemiacetal formations and cyclization reactions are also among the examples.     

What can we learn about the mechanisms of thermal decompositions of solids from kinetic measurements?

Aspects of the theories that are conventionally and widely used for the kinetic analyses of thermal decompositions of solids, crystolysis reactions, are discussed critically. Particular emphasis is placed on shortcomings which arise because reaction models, originally developed for simple homogeneous reactions, have been extended, without adequate justification, to represent heterogeneous breakdowns of crystalline reactants. A further difficulty in the mechanistic interpretation of kinetic data obtained for solid-state reactions is that these rate measurements are often influenced by secondary controls. These include: (i) variations of reactant properties (particle sizes, reactant imperfections, nucleation and growth steps, etc.), (ii) the effects of reaction reversibility, of self-cooling, etc. and (iii) complex reaction mechanisms (concurrent and/or consecutive reactions, melting, etc.). A consequence of the contributions from these secondary rate controls is that the magnitudes of many reported kinetic parameters are empirical and results of chemical significance are not necessarily obtained by the most frequently used methods of rate data interpretation. Insights into the chemistry, controls and mechanisms of solid-state decompositions, in general, require more detailed and more extensive kinetic observations than are usually made. The value of complementary investigations, including microscopy, diffraction, etc., in interpreting measured rate data is also emphasized. Three different approaches to the formulation of theory generally applicable to crystolysis reactions are distinguished in the literature. These are: (i) acceptance that the concepts of homogeneous reaction kinetics are (approximately) applicable (assumed by many researchers), (ii) detailed examination of all experimentally accessible aspects of reaction chemistry, but with reduced emphasis on reaction kinetics (Boldyrev) and (iii) identification of rate control with a reactant vaporization step (L’vov). From the literature it appears that, while the foundations of the widely used model (i) remain unsatisfactory, the alternatives, (ii) and (iii), have not yet found favour. Currently, there appears to be no interest in, or discernible effort being directed towards, resolving this unsustainable situation in which three alternative theories remain available to account for the same phenomena. Surely, this is an unacceptable and unsustainable situation in a scientific discipline and requires urgent resolution?     

Dynamical relaxations in mixtures of different polymers and nonsymmetrical copolymers in solution

Dynamical relaxation properties of nonsymmetrical mixtures of homopolymers and of copolymers in solution are examined. In particular, examples of bimodal mixtures in solution, ternary mixtures of two different homopolymers and a solvent, and nonsymmetrical diblock copolymers in solution are examined. The frequencies of the eigenmodes Γ and Γ′, those of the cooperative mode Γ_T and the interdiffuse mode Γ_I are calculated for these systems. It is found that the variations of T_T and T_I, with the scattering wave number q are practically identical to those of Γ_T and Γ_I, respectively. This identity is rigorous only for mixtures or copolymers where the two polymer components are identical except for their contrast factors (i.e., indices of refraction or scattering lengths). Here, it is argued that the identification of the eigenmodes with the cooperative and interdiffuse modes can be extended qualitatively to mixtures of different polymers and to nonsymmetrical copolymers in solution.     

The evaluation and use of properties of individual ions in slution

A critical examination is given of extra-thermodynamic methods for evaluation of properties of individual ions in solution. The ways in which such data may be applied, or are required in various problems concerning specific properties of electrolyte solutions and in the fields of kinetics, electrochemistry, colloid and interfacial chemistry, are outlined. Special attention is given to the problem of evaluation of individual ionic thermodynamic functions for the hydration of ions but, in some cases, corresponding data for nonaqueous solutions are available for discussion and are of interest in a comparative way. The reliability of the various methods is assessed and estimates of numerical values for various individual ionic functions are tabulated. The question of scales of individual ionic radii, on which some of the derived data depend, is also examined. The dependence of various properties for anions and for cations on ionic radius is discussed and data are plotted comparatively. It is shown that for most, but not all, properties, the values for anions are more sensitive to increasing ionic radius than are the values for cations. This behavior, as well as the exceptions, is of theoretical interest. The significance of ion-specific behavior at interfaces is considered and the importance of interactions between ions of like sign of charge is indicated.Presented at the Symposium on Electrolytes, University of Reading, September 13, 1977.     

Solvation of amides of formic and acetic acids in water-glycerol mixture. Additivity of thermochemical characteristics of solutions

Values of the solution enthalpy of are measured and values of solvation enthalpy are calculated for formamide and N,N-two-substituted methyl-and ethylamides of formic and acetic acids in the mixed solvent: water-glycerol. Enthalpy coefficients of pair interactions between amides and glycerol in aqueous solutions are calculated. The influence of mixture composition and also of a structure and properties of the dissolved compounds on enthalpy characteristics is considered. Within the frames of the offered additive scheme the contributions from the structural fragments of molecules of amides to enthalpy characteristics of solutions are established. It has allowed us to analyze quantitatively the role of nonspecific and specific solvation of amides in solution, to predict the enthalpy of evaporation, solution, solvation, the enthalpy coefficients of pair interactions of experimentally unstudied N-methylformamide, N-ethylformamide, N-methyl-N-ethylformamide, N-methylacetamide, N-ethylacetamide, and N-methyl-N-ethylacetamide in the mixtures of water-glycerol, and also to evaluate the donor numbers of these specified amides.