马来酸及其酐和衣康酸与PP熔体接枝反应机理的研究

以马来酸酐作对照，用热分析、流变、化学分析等方法，研究了马来酸和衣康酸在非隔氧条件下与ＰＰ熔体催化接枝反应的特点和规律，阐述了单体结构－单元反应相对速率－－接枝产物结构之间的关系，提出了３种接枝物的结构模型。     

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.     

Ziegler-Natta烯烃聚合催化剂进展

综述了Ziegler-Natta催化剂在乙烯聚合和丙烯聚合方面的研究开发现状，重点介绍了采用新型二醚化合物作为内给电子体的丙烯聚合催化剂的进展。随着合成树脂向功能化方向发展，开发综合性能优越的新型催化剂及给电子体将是今后的研究方向。     

Phase separation studies in RIM polyurethanes catalyst and hard segment crystallinity effects

Polyurethanes were prepared from pure 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butane diol (BDO) or 1,2-ethane diol (EDO) and α,ω-hydroxyl poly(propylene oxide) (PPO) by reaction injection moulding (RIM). Hard segment (MDI + BDO or EDO) level was 45–50 wt%. The PPO had about 20% ethylene oxide copolymerized in at the chain ends to provide 80% primary OH end groups. M_n was varied from 2000 to 4000. Dibutyl tin dilaurate catalyst and mould temperature were varied. Dynamic mechanical, wide-angle X-ray, differential scanning calorimeter, molecular weight and tensile elongation measurements were made on the RIM polyurethanes. At low reaction rates (low catalyst or temperature) highly crystalline, well phase separated but low molecular weight polymers were produced. At high catalyst or temperature levels more poorly phase separated but high molecular weight, tough polymers resulted. Higher M_n PPO gave better phase separation and EDO gave higher melting temperatures. Preventing hard segment crystallinity by substituting asymmetric MDI or glycols resulted in phase compatibility.     

已二醇二丙烯酸酯对真丝的接枝改性研究

研究了用二醇二丙烯酸酯为接枝单体、过硫酸铵（APS）为引发剂对真丝的接枝共聚反应，分析了接枝率的影响素，并测试了改性真丝的主要应用性能。结果表明：乳液和乙醇/水为溶剂的2种体系都能在真丝上获得较高接枝率。对于乙醇/水体系v(乙醇）：v(H2O）=1:1，接枝单体20～30g/L,2%甲酸4ml，引发剂APS 0.5g/L,65～70℃接枝60min的接枝率高。改性后真丝的断裂强度、延伸度、吸湿性能都可获得改善，对酸、碱的溶解性提高，但染色性能提高不明显，对泛黄性改善一般。     

丙烯酸酯与甲基丙烯酸酯的共聚及性能研究

采用悬浮聚合法，以丙烯酸－２－乙基－己酯与甲基丙烯酸十二酯为单体，合成了共聚型高吸油性树脂。研究了共聚单体的配比、交联剂用量、引发剂用量诸因素对高吸油性树脂的性能影响。制得的树脂可以吸其自身质量的１１．８倍的煤油、１４．７倍的苯、６．５倍的泵油。     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.