The Polymerization of Metal-Containing Vinylic Monomers of Iron and Tungsten with Metal–Carbon σ Bonds

A series of metal-containing vinylic monomers of the type and was homopolymerized using 2,2-azobisisobutyronitrile (AIBN) as the free-radical initiator. These monomers were also copolymerized with styrene in the presence of AIBN. These compounds represent a class of organometallic polymers in which the metal is bonded to the polymer backbone via a metal–carbon bond. The new compounds were characterized by IR and ¹H NMR spectroscopy as well as scanning electron microscopy, gel permeation chromatography, and thermoanalytical studies (DSC and TGA). The properties of the new organometallic polymers are discussed.     

流变仪旋转叶片法在自由基聚合反应中的应用研究Ⅲ:有机羧酸对丙烯酰胺自由基聚合的阻聚作用

使用装备自制的四叶片旋转叶片的应力控制流变仪研究过硫酸铵和四甲基乙二胺氧化还原体系作为引发体系引发丙烯酰胺自由基聚合过程的模量曲线,交联剂为N,N’-亚甲基双丙烯酰胺。测试了添加柠檬酸、聚丙烯酸和乙酸的丙烯酰胺聚合反应的空闲时间(idle time),研究了有机羧酸浓度、体系pH以及缓冲溶液对丙烯酰胺聚合体系的影响,发现在较低pH(小于4.5)的体系中有机羧酸对丙烯酰胺的自由基聚合反应存在阻聚或缓聚作用,并且发现可以调节体系的pH到较高值(10.5)可使被阻聚的自由基被重新激活,激活后的聚合反应的idle time不受有机羧酸浓度和阻聚时间的影响。     

连苯三酚法条件的优化及其在红薯梗活性评价中的应用

本实验中对连苯三酚法测定超氧阴离子自由基(O2)清除的条件进行了研究,确认了波长325nm,连苯三酚浓度1.875mmol/L,温度25℃为此体系最佳条件。应用于红薯梗实验结果表明,各有机溶剂梯度提取物对超氧阴离子自由基(O2)有一定的清除作用,其中以乙醚组分最强,约相当于同样浓度茶多酚活性的0.26。-•-•     

阳光引发下溴与麦克尔受体的加成

以阳光引发溴与麦克尔受体的加成，合成了一系列有机合成的中间体和工业上有应用价值的化合物，如二溴肉桂腈，二溴肉桂酸，二溴丙烯腈、苯丙炔酸等。     

Photoinitiation of polymerization of styrene by oxotris(dimethyl dithiocarbamato) vanadium(V)

Oxotris(dimethyl dithiocarbamato) vanadium(V) [VO(S₂CN(CH₃)₂)₃] sensitizes the polymerization of styrene when irradiated by light of λ = 365 nm at 25°C. Under the experimental conditions employed, no retardation occurs, and the rate of initiation is independent of monomer concentration. The mean values of the quantum yield of iniiation (?_i) and polymerization (?_o) are 2.85 × 10^?3 and 6.72 respectively. Spectroscopic analysis shows that initiation occurs predominatly through scission of the N,N-dimethyl dithiocarbamate ligand (—SC(S)N(CH₃)₂) with reduction of vanadium(V) to (IV), and VO (S₂CN(CH₃)₂)₂ is the final photolytic product. A reaction mechanism is proposed based on an intramolecular photoredox reaction which leads to the primary formation of SC(S)N(CH₃)₂ radicals and a vanadium(IV) chelate complex. The rellevant kinetic parameters are evaluated. The polystyrene produced shows a photoactivity when irradiated with UV-light.     

晶溶发光自由基的鉴别及探测系统

1895年Wiedemam首次发现晶溶发光现象以来,在国外已对各种糖类、氨基酸、蛋白质、核酸与尿素及其衍生物进行了研究,而且目前正在寻找它的应用。 当辐照过的物质溶解在一定溶剂中时,会产生光辐射,其光辐射与自由基的反应有密切关系。     

Spontaneous polymerization and chain microstructure evolution in high-temperature solution polymerization of n-butyl acrylate

This study concerns understanding of the underlying mechanistic pathways in high temperature solution polymerization of n-butyl acrylate (nBA) in the absence of added thermal initiators. The particular system of interest is the batch polymerization of nBA in xylene at temperatures between 140 and 180 °C with initial monomer content between 20 and 40 wt%. A mechanistic process model is developed to capture the dynamics of the polymerization system. Postulated reaction mechanisms include chain-initiation by monomer (self-initiation), chain-initiation by unknown impurities, chain-propagation by secondary and tertiary radicals, intra-molecular chain-transfer to polymer (back-biting), chain-fragmentation (β-scission), chain-transfer to monomer and solvent, and chain termination by disproportionation and combination. The extent of the reactions is quantified by estimating the reaction rate constants of the initiation and the secondary reactions, based on a set of process measurements. The set of measurements considered in the parameter estimation includes monomer conversion, number- and weight-average molecular weights, and average number of chain-branches per chain (CBC). Effect of temperature on chain microstructures was observed to be most evident when microstructures are expressed in terms of their quantities per chain. The evolution of other microstructural quantities such as average number of terminal double bonds per chain (TDBC) and average number of terminal solvent groups per chain (TSGC) was then also investigated. Microstructural quantities per polymer chain (TDBC, TSGC, CBC) are defined based on combinations of ¹³C, ¹H NMR and chromatographic measurements. This study presents (i) a mechanistic explanation for the competing nature of short-chain-branch and terminal double bond formation (i.e. as temperature increases, number of chain branches per chain decreases and number of terminal double bonds per chain increases), (ii) quantitative insights into dominant modes of chain-initiation and chain-termination reactions, and (iii) mechanistic explanations for the observed spontaneous polymerization. The study also reports estimated Arrhenius parameters for second-order self initiation, tertiary radical propagation, secondary radical backbiting and tertiary radical β-scission reaction rate constants. Validation of the mechanistic process model with the estimated Arrhenius parameters and comparison of estimated parameter values to recently reported estimates are also presented.     

Application of optimal temperature trajectory to batch PMMA polymerization reactor

A mathematical model is developed for the polymerization of methyl methacrylate (MMA) in a batch reactor. The model includes chain transfers to the monomer and solvent and termination by both combination and disproportionation and also takes into account the density change of the reactor contents and the gel effect. The usual pseudo-steady-state assumption is relaxed here. The validity of the proposed model is tested by an isothermal experiment of batch PMMA polymerization. Indeed, the experimental results show that the proposed model can describe the real polymerization system very well in view of both monomer conversion and average molecular weights. The optimal control theory is applied together with Pontryagin's minimum principle to calculate the optimal temperature trajectory for a batch polymerization reactor system which would lead to a polymer product having the desired properties set a priori. The performance index of the control system is composed of three factors—the desired monomer conversion and number- and weight-average molecular weights. The desired values of number- and weight-average molecular weights are obtained at a specified monomer conversion within acceptable error ranges. Control experiments are conducted to track the optimal temperature trajectory obtained from the model and the results are found to be in good agreement with the desired values. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 59–68, 1998     

羟丙基甲基纤维素的体外自由基降解研究

通过Fenton-AH-H2O2体系模拟体内的活性氧簇自由基(ROS)条件对美容填充辅料羟丙基甲基纤维素(HPMC)进行降解,研究了降解过程中HPMC分子量与动力粘度的变化。结果发现,在降解过程中,E3-HPMC与E50-HPMC的分子量均下降了90%,E4M-HPMC的动力粘度下降了75%,E10M-HPMC的动力粘度下降了40%。表明ROS对HPMC具有显著的降解作用。