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.     

Frontolimbic Response to Negative Feedback in Clinical Depression.

Functional neuroimaging suggests that limbic regions of the medial frontal cortex may be abnormally active in individuals with depression. These regions, including the anterior cingulate cortex, are engaged in both action regulation, such as monitoring errors and conflict, and affect regulation, such as responding to pain. The authors examined whether clinically depressed subjects would show abnormal sensitivity of frontolimbic networks as they evaluated negative feedback. Depressed subjects and matched control subjects performed a video game in the laboratory as a 256-channel EEG was recorded. Speed of performance on each trial was graded with a feedback signal of A, C, or F. By 350 ms after the feedback signal, depressed subjects showed a larger medial frontal negativity for all feedback compared with control subjects with a particularly striking response to the F grade. This response was strongest for moderately depressed subjects and was attenuated for subjects who were more severely depressed. Localization analyses suggested that negative feedback engaged sources in the anterior cingulate and insular cortices. These results suggest that moderate depression may sensitize limbic networks to respond strongly to aversive events. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

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.     

新型阳离子聚丙烯酰胺微粒的研究--含PEO支链阳离子聚丙烯酰胺微粒的合成、助留性能及作用机理

本文采用反相微乳液聚合的方法合成了丙烯酰胺(AM)/丙烯酰氧基乙基三甲基氯化铵(AD-AMQUAT)/聚氧乙烯大单体(PEO-A)/N,N'-亚甲基双丙烯酰胺(Bis)的四元共聚物微粒.研究了该微粒助留剂的结构与性能.这种微粒和纸纤维能够通过离子键和氢键作用显著地增强助留效果.     

Control of structure and tack properties of acrylic pressure‐sensitive adhesives designed by a polymerization process

Free radical emulsion polymerization of methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) results in the synthesis of pressure‐sensitive adhesives (PSAs) with good tack properties. Management of both the copolymer composition and the polymerization process allows one to control the behavior of the PSA. Semicontinuous (SC) processes create polymer particles whose instantaneous composition is close to that of the feed particle The SC Mixture process (continuous feeding with comonomer blends) affords nearly homogeneous latex particles and PSA films. The SC Gradient process (separate feedings at inversely varying rates) affords heterogeneous particles and films. The Batch process leads to somewhat heterogeneous films, but the hard (MMA‐rich) microdomains are made compatible with their soft (EHA‐rich) matrix because of the assumed formation of tapered‐type copolymers. Tack measurements indicate the importance of the particle and film structures. Too much hardness or softness leads to unacceptable lacks of adhesion and cohesion, respectively. Homogeneous structures prove adequate, but their tack properties collapse with rising temperature. Heterogeneous structures, with extensive phase segregation, prove unsatisfactory because they lack adhesion and cohesion. Finally, the association of well‐balanced composition and compatible heterogeneity is the criterion for suitable PSA behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2749–2756, 2003     

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。