Simultaneous continuous,nonchromatographic monitoring and discrete chromatographic monitoring of polymerization reactions

Automatic continuous nonchromatographic monitoring and discrete chromatographic monitoring were coupled together for the first time and used to monitor free radical and controlled‐radical polymerization reactions. This was achieved by adding a multidetector Size Exclusion Chromatography (SEC) system (alternatively termed Gel Permeation Chromatography, GPC) to the ACOMP platform (Automatic Continuous Online Monitoring of Polymerization reactions). The fact that the reactor solution is already preconditioned in the ACOMP front‐end to the concentration levels used in SEC makes direct coupling possible. Kinetics from two different types of reactions, Reversible Addition Fragmentation Transfer (RAFT) and free radical polymerization of butyl acrylate were studied, including the production of a bimodal population. Complementary and contrasting features from the continuous and SEC approaches are highlighted. The main advantage of the SEC detection is to follow the evolution of full molecular weight distributions (MWD), especially in ‘living’ type reactions, where polydispersity decreases with monomer conversion, whereas the continuous detection provides a much more detailed characterization of the reaction. Interestingly, in the case where a bimodal molecular weight distribution was produced, the continuous method automatically detected the onset of the second mode in a model independent fashion, whereas SEC could only discern the bimodality by applying preconceived models. The SEC approach will have valuable niche applications, however, such as when reactions are relatively slow, monitoring narrow polydispersity is of primary importance, and also in copolymerization and terpolymerization reactions where complex mixtures of reagents (e.g., RAFT agents, copper ions, etc.) make unfractionated spectroscopic resolution of comonomers difficult. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Methyl acrylate/1‐octene copolymers: Lewis acid‐mediated polymerization

Copolymerization of methyl acrylate (MA) with 1‐octene (1‐Oct) was conducted in the presence of free radical initiator, 2,2′‐azobis(2‐methylpropionitrile) (AIBN) using heterogeneous Lewis acid, acidic alumina. The polymers obtained were transparent and highly viscous liquids. The copolymer composition calculated from ¹H NMR showed alkene incorporation in the range of 10–61%. The monomodal nature of chromatographic curves corresponding to the molecular weight distribution in gel permeation chromatography (GPC) further confirmed that the polymers obtained are true copolymers. The number–average molecular weights (M_n) of the copolymers were in the range of 1.1 × 10⁴–1.6 × 10⁴ with polydispersity index of 1.75–2.29. The effects of varying the acidic alumina amount, time of polymerization, and monomer infeed on the incorporation of 1‐Oct in the polymer chain were studied. Increased 1‐Oct infeed led to its higher inclusion in the copolymer chain as elucidated by NMR. DEPT‐135 NMR spectral analysis was used to explicate the nature of arrangement of monomer sequences in the copolymer chain. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

循环模式DSG槽式太阳能集热器出口蒸汽温度控制策略研究

循环模式直接蒸汽发电(direct steam generation,DSG)强度变化的影响很大,并具有大滞后、大惯性、参数时变等特点。针对该控制对象,提出采用多模型切换受限增量广义预测控制策略,建立典型工况下的子模型并设计相应的控制器。按照跟踪实际工况的运行结果,根据模糊推理的隶属度概念评判子模型的匹配程度,选择适配的子模型和控制器整定参数,并采用输入增量加权控制律和等待周期法实现平滑切换和无扰切换。仿真分析表明,提出的控制策略与常规PI控制方法相比,具有响应速度快、无稳态偏差、系统输出波动小、降低了模型失配影响等优点。仿真结果验证了该控制模型和策略的可行性和有效性。     

凝胶渗透色谱净化-气相色谱-质谱法测定肉品中的甲氧滴滴涕

建立肉品中甲氧滴滴涕残留的气相色谱-质谱(GC-MS)分析方法。采用均质提取方法提取样品中的甲氧滴滴涕,经凝胶渗透色谱净化,浓缩定容后用GC-MS检测分析,外标法定量。样品添加水平为0.005、0.01、0.02mg/kg时,甲氧滴滴涕的回收率在82.8%～103.2%之间,方法检测限为0.001mg/kg。本方法操作简便、准确、灵敏度高,净化效果好,满足残留分析要求。     

Real-time comparison of a number of predictive controllers

Many model predictive control (MPC) algorithms have been proposed in the literature depending on the conditionality of the system matrix and the choice of its cost-function. This paper presents the newer MPC schemes such as extended predictive control (EPC) and shifted MPC as well as other well known forms. The control performance of these controllers are compared using two systems that are slow and fast reacting. The closed-loop responses are compared and the differences and similarities are explained on the basis of the structure of the control schemes. Disturbance rejection and the tracking of various setpoint trajectories are performed with good closed-loop results from all the controllers. It was found that the controllers that were specifically designed to reduce the system matrix ill-conditionality such as EPC and generalized predictive control provided better control performance when compared to other MPC methods.     

Simplified modeling and generalized predictive position control of an ultrasonic motor

Ultrasonic motors (USM's) possess heavy nonlinear and load dependent characteristics such as dead-zone and saturation reverse effects, which vary with driving conditions. In this paper, behavior of an ultrasonic motor is modeled using Hammerstein model structure and experimental measurements. Also, model predictive controllers are designed to obtain precise USM position control. Simulation results indicate improved performance of the motor for both set point tracking and disturbance rejection.     

液闪法研究~(14)C-尿素在小鼠体内的吸收及分布和排泄

本文报道应用液体闪烁测量方法研究14C-尿素在小鼠体内的吸收、分布和排泄。小鼠口服14C-尿素后,血药浓度时间曲线符合二房室开放模型。吸收速率常数Ka为3.64/h,分布相半衰期T1/2(α)为0.72h,消除相半衰期T1/2(β)为5.15h,清除速率常数CL为0.617L-1.Kg-1.h-1,表观分布容积Vd为5.59L/Kg,达峰时间Tmax为0.11h,峰浓度Cmax为1.57KBq/mL。在所测12种组织中均有14C-尿素存在,0.25h肾中放射性最高,心,肝,脾,肺,肠,胃较多,2h肺中放射性最高,脂肪最少。24h肝中放射性最高。24h粪尿排出给药量的65%,其中46%经尿排出,19%经粪排出。     

新型有机硅自洁耐沾污机理的研究

以有机硅树脂低聚物为主要成分制备的耐沾污剂，不仅具有优异的自洁耐沾污性能，而且固化迅速。用FTIR、GPC等分析仪器对有机硅低聚物的结构与性能进行了表征测试，并通过SEM、接触角测量仪等对影响有机硅防污剂的耐沾污因素及机理进行了研究。     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Reverse atom transfer radical polymerization of stearyl methacrylate using 2,2′‐azobisisobutyronitrile as the initiator

The living/controlled radical polymerization of stearyl methacrylate was carried out with a conventional radical initiator (2,2′‐azobisisobutyronitrile) in N,N‐dimethylformamide in the presence of a 2,2′‐bipyridine complex of hexakis(N,N‐dimethylformamide)iron(III) perchlorate. The polymerization mechanism was thought to proceed through a reverse atom transfer radical polymerization. The molecular weights of resulting poly(stearyl methacrylate) increased with conversion, and the resulting molecular weight distributions were quite narrow. The rates of polymerization exhibited first‐order kinetics with respect to the monomer. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1236–1245, 2002