Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

用复合烷基锂引发丁二烯聚合

对以环己烷为溶剂、四氢呋喃为微观结构调节剂、复合烷基锂为引发剂的丁二烯聚合反应过程进行了研究，考察了不同引发温度、不同配比的复合烷基锂对聚合反应的影响，并与以正丁基锂为引发剂的丁二烯聚合反应过程进行了比较。     

自韧Si3N4陶瓷的显微结构及其性能研究

利用热压的方法制得室温断裂韧性和抗弯强度分别为１１．２ＭＰａ·ｍ￣（１／２）、８２３ＭＰａ，高温（１３５０℃）断裂韧性和抗弯强度分别为２３．９ＭＰａ·ｍ￣（１／２）、６３０ＭＰａ的自韧Ｓｉ＿３Ｎ＿４陶瓷。研究了显微结构和力学性能之间的关系。结果表明：玻璃相的含量、β－Ｓｉ＿３Ｎ＿４的长径比等对性能有重要影响。分析了自韧Ｓｉ＿３Ｎ＿４陶瓷的增韧机理，通过ＳＥＭ明显观察到Ｓｉ＿３Ｎ＿４中存在裂纹偏转、分支和β－Ｓｉ＿３Ｎ＿４拔出现象。     

Influence of two-step process and of different stoichiometric ratios on morphologies generated in castor oil epoxy resins

Phase separation during polymerization was studied in a model system consisting of a diepoxide based on diglycidyl ether of bisphenol A (DGEBA), variable amounts of ethylenediamine (EDA) and the mass of castor oil (CO) necessary to obtain a mass fraction equal to 0-15 in a final system where the stoichiometric ratio of amine to epoxy equivalents, r, was equal to 1. A two-step polymerization process was performed by curing first a system with r = 0-5, during variable times before phase separation, and then carrying the system to r = 1. Thermodynamic analysis of samples with different r values led to a linear relationship between the Flory-Huggins interaction parameter and r. The concentration (P) and average size (D?) of dispersed-phase particles followed opposite trends, i.e. P increased while D? decreased, when either r was increased or the time of curing in the first step of a two-step process was decreased. This was explained by assuming that the competition between nucleation and growth was determined by the viscosity at the cloud point, η_cp. Low values of η_cp favoured growth over nucleation and led to fewer but larger particles.     

环氧油一步合成的反应机理和动力学研究

研究了环氧油一步合成的反应机理和动力学；结合实验结果和理论分析动力学模型，首次提出：在适当的反应条件下，油脂的一步环氧化反应动力学模型可以表示为过氧酸生成反应动力学模型；其实验动力学模型方程为：ｒ０＝ｋ［Ｈ２Ｏ２］（０．９９）［ＨＯＡｃ］（０．９７），其中ｋ与催化剂用量有关。     

分子结构对增塑聚氯乙烯性能的影响

研究了聚合度、分子量分布和支化结构对增塑聚氯乙烯加工流变性能和物理力学性能的影响。结果表明，增塑ＰＶＣ的加工流变性能随聚合度的增加而恶化；拓宽分子量分布和引入支化结构均有利于加工流变性能的提高；增塑ＰＶＣ的拉伸强度随聚合度的增加而提高，而压缩永久变形却随之减小；分子量分布对物理力学性能的影响不大；支化ＰＶＣ的拉伸强度略有下降。     

乙烯基三甲基硅烷等离子体聚合反应历程

应用色谱—质谱(GC-MS)及裂解色谱-质谱(PGC-MS)测定了乙烯基三甲基硅烷等离子体聚合反应中的气体冷凝物及聚合物,研究推导了等离子体聚合反应历程。单体在气相中被电子撞击,然后扩散到基底,在基底发生链增长和链终止反应。     

HPVC／PP共混改性研究：Ⅲ低分子量反应性化合物作相容剂

采用低分子量反应性化合物作相容剂，即化学交联体系来改善ＨＰＶＣ／ＰＰ共混物的相容性。考察了在不同共混比下，不同化学交联体系对共混物力学性能的影响，并观察了共混物的微观形态。结果表明，采用低分子量反应性化合物作相容剂，共混物的拉伸强度提高，但冲击强度无改善。分散相尺寸减小，相间粘接得到改善。并比较了３种增容方法的效果，发现ＣＰＥ是ＨＰＶＣ／ＰＰ共混物的最佳相容剂。     

Control of the quality of polymer products in continuous reactors: comparison of performance of state estimators with and without updating of parameters

In the paper the control of the product quality in polymerization reactors is analysed in the presence of persistent perturbations (unmodeled disturbances, modeling errors), as met in industrial reactors. The free radical polymerization of methyl-methacrylate in a continuous stirred tank reactor is studied. It is shown that state estimators (Extended Kalman Filters) with constant parameters cannot give offset free performance. Criteria for the selection of a set of parameters to be updated as additional states in the filter and to evaluate their effectiveness in opposing the action of realistic perturbations are given by an analysis of the linearized model of the system. Performance of different types of estimators, including one and two-time scale filters, with and without updating of parameters, is analysed by simulation on the full order process and the predictions made by previous analysis are confirmed. In the most common case of presence of perturbations affecting the energy balance and the concentration of initiator in the reactor, offset free control of the molecular weight of the product can be achieved by means of a filter which is based only on measurements of temperature and conversion and makes an update of two parameters. In the case that also the kinetic model of the polymerization reaction is affected by errors, a two-time scale filter, which makes use also of Molecular Weight values and updates three parameters, becomes necessary to obtain offset free performance.