甲基丙烯酸三氟乙酰氧乙酯的聚合

对甲基丙烯酸三氟乙酰氧乙酯(TFAOEMA)的阴离子聚合及原予转移自由基聚合进行了研究。常用的阴离于引发剂如丁基锂、1，1-二苯基已基锂等很难引发TFAOEMA的阴离子聚合，而碱性较弱的引发剂如三乙基铝却容易引发，且产率较高。以氯化亚铜、五甲基二乙基三胺、溴代丙酸乙酯为引发体系的TFAOEMA的本体原子转移自由基聚合符合活性聚合特征。但在四氢呋喃为溶剂的原子转移自由基聚合中却存在活性中心失活现象。以末端含卤素的聚甲基丙烯酸甲酯为大分子引发剂，引发TFAOEMA的原子转移自由基聚合，得到了含氟双嵌段聚合物。     

Copolymerization of bromophenylmaleimide with ethyl or butyl methacrylate

N‐p‐Bromophenylmaleimide (BrPMI) does not polymerize in solution by conventional free radical mechanism. However, it readily polymerized in bulk when mixed with a free radical initiator and heated in a microwave oven for 7–8 min. Copolymerization of ethyl methacrylate or butyl methacrylate with BrPMI was conducted in dioxane. The copolymers were characterized by IR and ¹H NMR spectroscopy and gel permeation chromatography. The monomer reactivity ratios were calculated by a non‐linear least‐square analysis. Thermal analysis indicated a great improvement in thermal stability of the copolymers compared with the methacrylate homopolymers. BrPMI was also polymerized in bulk in the DSC pan, which allowed the calculation of the activation energy of its polymerization. Copyright © 2003 Society of Chemical Industry     

乙炔黑吸附聚合制导电聚苯胺

用乙炔黑吸附化学聚合新工艺制备导电聚苯胺，可保持电导率不变，但转化率和堆密度提高，并明显改善了聚苯胺的颗粒形态和制膜加工性，使由其制备的聚苯胺复合正极膜和固体聚苯胺锂蓄电池的电化学性能得以改进。     

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.     

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。     

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.