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。     

In-chain functionalization by alternating anionic copolymerization of styrene and 1-(4-dimethylaminophenyl)-1-phenylethylene

Anionic copolymerizations of styrene (M₁) with excess 1-(4-dimethyl-aminophenyl)-1-phenylethylene (M₂) were conducted in benzene at 25°C for 24h, using sec-butyllithium as initiator. Narrow molecular weight distribution copolymers with M?;_n = 16.1 × 10³ g/mol (M?_w/M?_n = 1.04) and 38.2 × 10³g/mol (M?_w/M?_n = 1.05), and 24 and 38 moles of M₂ per macromolecule, respectively, were characterized by size exclusion chromatography, ¹H NMR spectroscopy and DSC. The monomer reactivity ratio, r₁ = 5.6, was obtained from the copolymer composition at complete consumption of M₁, assuming that the rate constant k₂₂ =0,i.e. r₂ =0. The polymers exhibited T_g values of 128 and 119°C, respectively, which correspond to an estimated T_g = 217°C for the hypothetical homopolymer of M₂.     

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.     

复合聚合物微粒乳液的制备与应用

对种子乳液聚合中加料方式、单体亲水性、引发剂等因素对复合微粒聚合物形成的影响作了介绍 ,总结了聚合物微粒形态预测的热力学和动力学方法。同时 ,讨论了复合聚合物微粒设计的原理并评述了其应用情况     

LLDPE及其催化剂技术进展

综述了线性密度聚乙烯（LLDPE）研究的最进展情况，特别对乙烯原位聚合工艺和后过渡金属镍、钯催化剂进行了详细的叙述，对我国LLDPE的生产提出了自己的看法。     

Halogen-induced charge transfer polymerization of pyrrole in aqueous media

Simultaneous polymerization and doping of pyrrole have been carried out in the presence of a halogenic electron acceptor, bromine (Br₂) or iodine (I₂), in aqueous dispersion or in a two-phase solvent system. The morphology of the polypyrrole (PPY) so produced is granular and porous. The electrical conductivity of the PPY-I₂ charge transfer (CT) complex is of the order of 10¹ ohm⁻¹ cm⁻¹ while that of the PPY-Br₂ complex is about one order of magnitude less. Both complexes are stable in the atmosphere. The physicochemical properties of the PPY-I₂ and PPY-Br₂ CT complexes prepared under various experimental conditions are examined in detail.