超高分子量PE凝胶膜的超拉伸性与旁式构象关系研究

通过ＩＲ方法，观测并讨论了在不同条件下制备的超高分子量ＰＥ（ＷＨＭＰＥ）凝胶膜中旁式（Ｇ构象）构象与超拉伸性的关系，提出了Ｇ构象浓度及分布对ＵＨＭＰＥ凝胶膜超拉伸性影响的新概念，同时也讨论了它与链缠结之间的联系，发现：反映Ｇ构象的相对浓度的比值σ＝Ｉ１３０３Ｉ１３５２随制膜浓度的增大而增加，在临界浓度Ｃ０（０．４～０．５ｇ＠１００ｍｌ）附近所形成的膜，具有超高拉伸性（λ＝２００），其Ｇ构象的变化与Ｍａｔｓｕｏ由比浓粘度提出的缠结链改变相对应；热处理温度比热处理时间对σ值的影响更显著，在一定温度下约４分钟后σ值基本不变；在σ值最低的温度范围拉伸，凝胶膜具有良好的超高拉伸性．     

Polymerization of vinyl acetate in fatty acids and properties of poly (vinyl alcohols) derived from the poly (vinyl acetates)

Polymerization of vinyl acetate (VAc) in various fatty acids (carbon numbers 4–18) was carried out. Chain transfer constants to the acids were determined to be 20–35×10^–4, from which the constant to a methylene group was obtained to be 0.73×10^–4. Viscometry in aqueous solution of derived poly (vinyl alcohol) (PVA) showed the usual behavior in terms of Huggins constant obtained by the Schulz–Blaschkes equation for PVAs derived from fatty acid systems lower than hexadecanoic acid. PVA derived from octadecanoic acid system showed abnormality, indicating association of alkyl groups. Contact angles on surfaces of PVAs cast from aqueous solutions were measured. While those of PVA derived from lower acid systems were 62°, those of PVAs derived from higher aids were higher and increased to 92° with increase in carbon number to octadecanoic acid. Alkyl groups in the PVAs were estimated to appear on the surfaces. Surface tension of aqueous solution of the PVA derived from octadecanoic acid showed high surface activity, and depended on pH of the solution, indicating the presence and cleavage of lactone ring at the combined portion between PVA and the acid.     

聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯（ＰＥＴ）、聚对苯二甲酸丁二醇酯（ＰＢＴ）化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应、羧基加成型扩链反应和羟基加成型扩链反应、羧羟基同时加成型扩链反应。讨论了扩链反应、反应特性和扩链产物的性能，并简要介绍了国内研究概况。参考文献２０篇。     

大分子引发－转移－终止剂

大分子引发－转移－终止剂杨文君，李俊柏，沈家骢（青岛化工学院橡塑工程研究所，青岛，２６６０４２）（吉林大学化学系，长春，１３００２３）关键词聚苯乙烯，聚丙烯酰胺，嵌段共聚，扩链反应，引发－转移－终止剂含有二乙基二硫代氨基甲酸基的有机硫化物或大分子，在...     

MOLECULAR WEIGHT DISTRIBUTION OF AB, A, TYPE CONDENSATION POLYMERS OBTAINED BY ADDING AB MONOMERS IN BATCHES

The molecular weight distribution (MWD) and arm length distribution of AB, Ar type condensation polymers obtained by adding AB monomers in batches have been derived by statistical and kinetic methods. Calculations show the MWD of condensation polymers obtained by this process is much narrower than that of one batch reaction and agrees with the Monte Carlo results very well.     

Dynamic percolation transition induced by phase separation: A Monte Carlo analysis

The percolation transition of geometric clusters in the three-dimensional, simple cubic, nearest neighbor Ising lattice gas model is investigated in the temperature and concentration region inside the coexistence curve. We consider quenching experiments, where the system starts from an initially completely random configuration (corresponding to equilibrium at infinite temperature), letting the system evolve at the considered temperature according to the Kawasaki spinexchange dynamics. Analyzing the distributionn _l(t) of clusters of sizel at timet, we find that after a time of the order of about 100 Monte Carlo steps per site a percolation transition occurs at a concentration distinctly lower than the percolation concentration of the initial random state. This dynamic percolation transition is analyzed with finite-size scaling methods. While at zero temperature, where the system settles down at a frozen-in cluster distribution and further phase separation stops, the critical exponents associated with this percolation transition are consistent with the universality class of random percolation, the critical behavior of the transient time-dependent percolation occurring at nonzero temperature possibly belongs to a different, new universality class.     

Note on the fractal dimension of hard sphere trajectories

Using Monte Carlo molecular dynamics, a new, careful study is made of the approach of the trajectory of a typical particle in a hard sphere fluid to that of a Brownian particle, discussed before by Powles and Quirke and Rapaport. The apparent fractal dimension of the trajectory, as a function of reduced length scale,(), characterizes the transition from mechanical to Brownian motion and differs markedly from 2 in all present computer simulations.     

Extremality and the global Markov property II: The global markov property for non-FKG maximal Gibbs measures

We give a condition on a Gibbs measure for an attractive Markov specification, which assures extremality and the global Markov property. As an example of application we consider the class of attractive Markov specifications defined on a compact configuration space over a two-dimensional lattice by the interaction Hamiltonians (assumed to have a finite set of periodic ground configurations) satisfying Peierl's condition. We prove that each extremal Gibbs measure for such a specification, at sufficiently low temperature, has the global Markov property.On leave of absence from the Institute of Theoretical Physics, University of Wrocaw, Poland.     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

计算机Monte Carlo法模拟自由基交联共聚网络结构的增长

本文成功地用MonteCarlo方法模拟了以画面方式表示的苯乙烯-二乙烯苯交联共聚反应中大分子链增长、支化及交联的进化情况，并给出了相应的转化率，以定量模型的方式描述了该类反应。