Polymerization Kinetics of Fischer‐Tropsch Reaction on Iron Based Catalysts and Product Grade Optimization

The polymerization kinetics of Fischer‐Tropsch reactions on a K‐promoted Fe catalyst was studied. To represent the product distribution, a kinetic model was developed based on alkyl and alkenyl mechanisms for hydrocarbon chain propagation, which were assumed to occur simultaneously in the Fischer‐Tropsch synthesis. The conclusion was drawn that superimposed Anderson‐Schulz‐Flory (ASF) distributions with different chain growth probabilities, on iron catalysts, can be the result of different chain growth mechanisms. The polymerization mechanism was used to obtain the product distribution for several conditions, and the optimum conditions for the production of transportation fuels were found.     

Electrostatic destabilization of water-in-crude oil emulsions: Application to a real case and evaluation of the Aibel VIEC technology

In the current study, the Aibel Vessel Internal Electrostatic Coalescer (VIEC) technology was tested for a real case scenario encountered in the production train of a UK oil field. Depressurized samples were collected both upstream and downstream of the first stage separator. The separation performance was discussed with respect to water cut and droplet size distribution of the emulsions, and the effect of chemical treatment. Issues with respect to representative sampling and testing have been discussed. The application of an external AC electrical field has been shown to significantly enhance the separation of the aqueous phase from tight emulsions, both when it was used alone and in combination with a commercial demulsifier. By using the VIEC technology, the time for separation could be reduced from 8 min to 2 min and the overall BS&W in the emulsions was improved from 45% or 60% to a residual water content of 5-20%. Destabilization of a 45% water-in-oil emulsion by electrical and chemical treatment (20/40 ppm) produced oil in the 2-7% BS&W range whereas the corresponding tests without applying an electrostatic field led to a BS&W greater than 25%. The achieved results strongly suggest that the VIEC technology can resolve the stable emulsion bands encountered in the Schiehallion train and add flexibility or increased production rate to the process. The results also suggest the importance of further studies on the destabilization performances achieved by electrostatic means.     

Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.     

CR／MMA乳液接枝共聚物的研制

用乳液接枝共聚法制备ＣＲ／ＭＭＡ共聚物，讨论ＣＲ乳液、引发剂、接枝温度、ＭＭＡ用量对接枝共聚转化率，接枝ＭＭＡ含量、ＭＭＡ接枝效率和粘接性能的影响，用红外光谱对接枝共聚物进行表征，该共聚物具有较好的粘接性能。     

Comparison of RAFT polymerization of methyl methacrylate in conventional emulsion and miniemulsion systems

In this study, we have conducted the reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in two heterogeneous systems, i.e. conventional emulsion and miniemulsion, with identical reaction conditions. The main objective is to compare the living character in both systems according to the nucleation mechanism, the latex stability, the particle sizes and particle size distributions of latexes, the molecular weights and molecular weight distributions (or polydispersity index, PDI) of PMMA, and the kinetics of the RAFT polymerization. The RAFT agent used in both systems was 2-cyanoprop-2-yl dithiobenzoate (CPDB). The effects of an oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN) and a water-soluble initiator kalium persulfate (KPS) on the RAFT/emulsion and RAFT/miniemulsion polymerizations were investigated. Methyl-β-cyclodextrin (Me-β-CD) was used as a solubilizer. The average molecular weights and molecular weight distributions (PDIs) of dried PMMA samples were characterized by gel permeation chromatography (GPC). The experimental results showed that the RAFT/miniemulsion polymerization of MMA exhibited better living character than that of RAFT/emulsion polymerization under the conditions of our experiment. The PDI of PMMA in RAFT/miniemulsion polymerization was decreased with the addition of Me-β-CD. However, Me-β-CD did not have influence on the PDI of PMMA prepared in RAFT/emulsion polymerization.     

New catalyst systems for the polymerization of acetylene

The catalytic activities of WCI₆Ph₄Sn, MoCl₅Ph₄Sn and tetrabenzyltitanium were examined in the polymerization of acetylene. The structure, morphology and electrical conductivity of the doped and non doped polyacetylene were also studied.     

Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.     

三聚氰胺甲醛树脂合成与性能的研究

本文针对三聚氰胺甲醛树脂合成与性能上存在的几个问题，从理论和实践上进行了讨论。     

Polypyrrole composite membrane with high permeability prepared by interfacial polymerization

Novel polypyrrole (PPy)/polydimethylsiloxane (PDMS) composite membrane was prepared by interfacial polymerization to make a very effective gas separation membrane. We found that Polymerized PPy films as thin as ～200 nm could be chemically synthesized as freestanding membranes by using the interfacial polymerization technique. Additionally, we show that difference morphology of PPys films was obtained by controlling polymerization rate and more dense films were formed at low polymerization rate. Wide X-ray diffraction study showed the d spacing value of the PPy film decreased from 4.89 å to 3.67 å by the rate of polymerization decreases. According to d spacing value decrease, selectivity of a PPy composite membrane was increased dramatically and permeability was reduced gradually. This high selectivity was derived from d spacing closed to the kinetic diameter of nitrogen. These results indicated that the permeability is controlled by the diffusion coefficient, reflecting the packed structure of the PPy film. The highest selectivity value of composite membrane that was prepared by interfacial polymerization was O₂/N₂=17.2 and permeability for O₂ was 40.2 barrer.