Kinetics of sunflower oil methanolysis catalyzed by calcium oxide

The methanolysis of sunflower oil was studied in the presence of CaO previously calcined at various temperatures and the optimal temperature for CaO calcination was determined. The sigmoidal process kinetics was explained by the initial triglyceride (TG) mass transfer controlled region, followed by the chemical reaction controlled region in the latter reaction period. The TG mass transfer limitation was due to the small available active specific catalyst surface, which was mainly covered by adsorbed molecules of methanol. In the later phase, the adsorbed methanol concentration decreased, causing the increase of both the available active specific catalyst surface and the TG mass transfer rate, and the chemical reaction rate become smaller than the TG mass transfer rate.     

Short poly(phenylene vinylene) chains grafted poly(organophosphazene)

Brominated poly(bis(4-methylphenoxyphosphazene) was allowed to react with 1,4-bischloromethylbenzene or 1,4-bischloromethyl-2,5-dimethoxybenzene in solution using phase transfer catalyst or potassium t-butoxide. Poly(p-phenylene vinylene) or poly(2,5-methoxy-1,4-phenylene vinylene) grafted organophosphazene copolymers were obtained. The UV-Vis absorption, photoluminescent, and thermal properties of the copolymers were measured. The copolymers are complete soluble in common organic solvents and fluoresce in the blue color range. The copolymers were used to build a series of organic light emitting diode (OLED). Only weak to nominated intensities with emission color from blue to red were obtained. The photoluminescent and electroluminescent (EL) spectra indicated there is a distribution in the PPV conjugated length. The compositions of the copolymers before and after the graft reaction were analyzed using NMR.     

松香酰甘氨酸表面活性剂的新合成法

研究以松香为原料,经松香酰氯和甘氨酸反应合成松香酰甘氨酸表面活性剂。发现在使用最廉价和最环保的混合溶剂水和丙酮时,甘氨酸与松香酰氯的反应是一个两相反应,使用相转移催化剂以及有机碱能明显提高反应产率。探讨了相转移催化剂、碱反应物的量及温度对合成反应的影响,找到了最佳的反应时间,反应温度及原料配比。     

Novel Hyperbranched predominantly Alternating Copolymers Made From A Charge Transfer Complex monomer pair of p-(chloromethyl)styrene and Acrylonitrile via Controlled Living Radical Copolymerization

Summary Novel hyperbranched copolymers were successfully synthesized by the controlled charge transfer complex inimer and living radical copolymerization of p-(chloromethyl)styrene (PCMS) and acrylonitrile (AN). The resulting copolymers were characterized by SEC, NMR, FTIR, DSC and elemental analysis etc.. The influences of reaction conditions, such as the polymerization temperature, the catalyst (CuBr) concentration and the monomer ratio, on the resulting copolymers were investigated in detail. The monomer reactivity ratios were evaluated to be r_PCMS=0.937 and r_AN=0.088 respectively by the Fineman-Ross method. The higher are the polymerization temperature and the ratio of catalyst to monomer, the higher is the branching degree of the resulting copolymer. When the amount of monomer AN was used in excess than that of the monomer PCMS in the raw feed, the hyperbranched predominantly alternating copolymers HP[PCMS-co-AN] could be obtained. These hyperbranched copolymers were successfully used as functional macroinitiators to synthesize the star-shaped poly(PCMS-co-AN)/poly(MMA) block copolymers.     

Considerations on film reactivity in the aqueous biphasic hydroformylation

In experiments and kinetic models it was shown that the reaction rate of the biphasic aqueous hydroformylation of 1‐octene is linear dependent on the created interfacial area. This phenomenon is directly linked to the question whether the reaction takes place in the bulk phase and is mass transfer limitation or at the surface which would mean an increase of reaction space. To evaluate the place of reaction a mass transfer analysis has been carried out. No mass transfer limitation for the gaseous components carbon monoxide and hydrogen as well as the olefin 1‐octene was determined for the aqueous catalyst phase by calculating the Hatta numbers. With this observation it is possible to exclude the mass transfer as a potential influence and hence the aqueous bulk as the place of reaction. Thus the reaction is most probably surface active. This can be either explained the increase in film volume fraction where non‐polar substrate as well as polar catalyst complex is present or through an increased catalyst concentration at the surface through dipole moment fluctuations. © 2017 American Institute of Chemical Engineers AIChE J, 63: 161–171, 2018     

Postcrosslinking of macroporous styrene–divinylbenzene copolymers via pendant vinyl groups: Effect of the starting copolymers on the pore structure of the postcrosslinked products

In the presence of anhydrous ferric chloride as a Friedel–Crafts catalyst, the postcrosslinking reaction of macroporous styrene–divinylbenzene (St–DVB) copolymers synthesized under different conditions was carried out with 1,2‐dichloroethane as a solvent. Without an externally added crosslinking agent, the specific surface area and pore volume, for copolymers with different DVB isomers or different DVB contents after reaction, in most cases increased significantly, and the increase was found to be heavily dependent upon the amount of the pendant vinyl groups in the starting copolymers. These results further confirm the role of the pendant vinyl groups in creating new crosslinking bonds in addition to those created by a free‐radical crosslinking reaction in the starting copolymers, and an alkylation reaction of the vinyl groups with neighboring aromatic rings is believed to dominate the course of the postcrosslinking at a relatively high level of the vinyl group contents. The synthesis conditions, including the n‐heptane content in a mixed diluent and the amount of the diluent, under which the starting copolymers were synthesized, play an important role in the increase of the surface area and pore volume of the copolymers after postcrosslinking. The effect of these conditions is attributed mainly to the swelling ability of the starting copolymers thus obtained in the solvent used for reaction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1668–1677, 2002     

Morphological study on the reactivity of styrene‐divinylbenzene copolymers in a chloromethylation reaction

Styrene‐divinylbenzene (S‐DVB) copolymers with different kinds of porous structures were synthesized by aqueous suspension polymerization using n‐heptane as the pore forming agent. The amount of this solvent (monomer dilution degree) and the DVB content in the organic phase were varied. The combination of three different dilution degree values and three DVB contents yielded three series of copolymers with a variety of porous structures. The three series were composed by copolymers with pore diameters (D) in the following ranges: D < 500 Å, 500 < D < 1000 Å, and D > 1000 Å, respectively. The effect of synthesis conditions on the pore size distribution and on the copolymer matrix rigidity was evaluated. These copolymers were submitted to a chloromethylation reaction with a paraformaldehyde/gaseous HCl mixture in the presence of zinc chloride as a Lewis acid catalyst and 1,2‐dichloroethane as solvent. The effect of the copolymer porosity on the chloromethylation reaction extension was evaluated. It was possible to observe that a gel copolymer with a high swelling capacity in the reaction medium achieved the same chloromethylation yield observed for a high porous copolymer. This result thus indicates that, in the case of the chloromethylation reaction studied here, the high swelling capacity of the gel copolymer can counterbalance its limited surface area, turning this type of polymer structure as reactive as a macroporous one. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The unsteady-state solution for a finite dispersion-type catalytic packed-bed tubular reactor

The unsteady-state solution is obtained by an operator theory in functional analysis setting for a general finite catalytic packed-bed tubular reactor model with axial dispersion in the bed, mass transfer between the catalyst particles and the flowing phase, and intraparticle diffusion and surface reaction in the catalyst particles.     

微波与碳基催化剂协同促进果糖制5-羟甲基糠醛

生物质转化为高附加值的化学品是替代石化产品的有效途径,微波与催化剂的协同作用有助于提升糖类的转化效率。碳材料具有良好的化学稳定性和介电性,是微波反应过程中理想的催化剂载体和吸波剂。为了探究碳基催化剂对微波场的响应能力,本文以4种碳材料为载体应用于果糖转化过程,包括碳纳米管（CNT）、碳纳米纤维（CNF）、炭黑（CB）和活性炭（AC）。以果糖转化率和5-羟甲基糠醛（5-HMF）收率为评价指标,对比不同催化剂在常规和微波加热条件下的催化性能,探究微波与不同载体的耦合作用对反应的强化效果。在微波场中测量不同碳材料悬浮液的温度曲线,评价碳基催化剂在微波场中的加热能力。通过表征样品结构和介电参数,解释载体与微波间耦合作用差异的原因。结果表明,碳基催化剂的微波诱导热效应可以有效提升反应转化率和收率,拥有高损耗角正切值和电导率的催化剂把微波能转化为热量的能力较强,更有助于将微波能量传递至反应表面。高比表面积、高长径比、低密度和高石墨化度的碳基催化剂也有利于产生微波热效应。另外,由于显著的微波热效应,碳纳米管基催化剂CNT-SA在4类催化剂中催化性能最优,以110℃微波辐射10min,5-HMF收率可达96.30%,且催化剂具有良好的循环使用性能。     

An approximate model for mass transfer with reaction inporous gas diffusion electrodes

An approximate model for reactant mass transfer in fuel cell electrodes has been formulated which considers gaseous diffusion in the hydrophobic Teflon phase, diffusion across a thin electrolyte film at the surface of the catalyst phase, and internal diffusion with first order reaction in the electrolyte-filled catalyst phase. An analytical solution is presented which indicates the fraction of the “activation only” current density that is obtained from the electrode. Application of this model for low reactant concentrations should allow a more quantitative evaluation of important mass transfer processes in fuel cell electrodes.     

Phase transfer catalyzed heterogeneous N-deacetylation of chitin in alkaline solution

Chitin was extracted from shrimp shell waste and its heterogeneous alkaline deacetylation under phase transfer catalysis (PTC) condition was performed. The reaction followed the first-order kinetics during an initial period. The influences of type and concentration of phase transfer catalyst, type of organic solvent, alkaline concentration, temperature, time and volume of organic phase to the volume of aqueous phase ratio on the N-deacetylation were investigated. The degree of deacetylation (DD) increased mainly with increasing temperature, catalyst concentration and time. In the temperature range of 30–100 °C, the apparent rate constant and the activation energy of the reaction were evaluated in presence and in absence of PTC condition.     

二维ZIF-L衍生的叶片状Fe-NC材料的制备及其氧还原催化性能研究

将柠檬酸铁铵作为Fe源掺入叶片状ZIF-L前驱体中,经过分段式高温热解成功制备出形貌维持良好的二维片状的Fe-NC催化剂。通过探究Fe载量对催化性质的影响发现,Fe-NC-1%催化剂在碱性电解质中呈现出最为优异的氧还原反应（ORR）活性,半波电位E_1/2达到了0.897 V,动力学电流密度J_{0.85 V}为26.70 mA/cm²,5 000次循环过后E_1/2衰减5 mV,均超过了商业Pt/C催化剂。结合Raman光谱、XPS、BET法比表面积测定等分析表明,Fe-NC-1%的大比表面积、高石墨化程度、丰富的含氮活性物种等优势赋予了较高的传质效率及催化活性位点利用率,是促进其ORR反应动力学的重要因素。     

Synthesis and characterization of poly(1,5-naphthylene vinylene) and its copolymers with poly(2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene)

Poly(1,5-naphthylene vinylene) (PNV) and its copolymers with poly(2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) were synthesized via a liquid-solid two-phase reaction. The liquid phase was a tetrahydrofuran (THF) solution of the monomers, 1,4-bis(bromomethyl)-2-methoxy-5-(2-ethylhexyloxy)benzene (MOEHODCX) and 1,5-bis(bromomethyl) naphthalene (DBMN), and contained a certain amount of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The solid phase was potassium hydroxide particles with diameters smaller than 2 mm. The structures of the polymers were studied by infrared and Raman spectroscopies. The solutions of the copolymers emitted green light. The UV-vis and photoluminescence spectral bands of the copolymers showed blue shifts with the increase in their PNV contents. A polymer light-emitting diode was fabricated with the copolymer prepared by copolymerization MOEHODCX and DBMN with feeding molar ratio of 1:1, and its luminescence efficiency was measured to be 0.069.     

Methanol synthesis in a three‐phase catalytic bed under nonwetted condition

To overcome the heat removal problem encountered in methanol synthesis at high syngas concentrations in the gas phase, a three‐phase nonwetted catalytic system was established by introducing an inert liquid medium into a fixed‐bed reactor. To form a repellent interface between the liquid and the catalyst, the catalyst was modified into hydrophobic, while the liquid medium was chosen as a room temperature ionic liquid with hydroxyl groups. The liquid‐solid contact angle was measured to be 115°, and only 20% of the catalyst external surface was wetted by the liquid. Under three‐phase condition, the reaction rate was measured to be 60%–70% of gas‐phase reaction, while it was merely 10%–20% for the fully wetted catalyst. From the resistance analysis on the mass transfer and reaction steps, the overall reaction rate is expected to increase further if the surface could be more wet proofed. © 2016 American Institute of Chemical Engineers AIChE J, 63: 226–237, 2017     

原子转移自由基聚合最新研究进展

概述了原子转移自由基聚合（ATRP）在引发体系、反应温度、反应介质、实施方法等方面的进展；介绍了3种不同催化剂脱除技术；结合最新的研究成果，着重论述了ATRP在进行聚合物分子设计，制备窄分子量分布聚合物、无规、梯度和交替共聚物，嵌段共聚物，末端官能团聚合物，接枝和梳状聚合物，星型及高支化聚合物等方面的应用。     

聚偏氟乙烯-b-聚乙烯基吡咯烷酮嵌段共聚物的制备和结构

以C₆F₁₃I为链转移剂,通过碘转移乳液聚合制得碘封端的聚偏氟乙烯（PVDF-I）,再以PVDF-I为大分子链转移剂进行N-乙烯基吡咯烷酮碘转移溶液聚合,得到聚偏氟乙烯-b-聚乙烯基吡咯烷酮（PVDF-b-PVP）两亲性嵌段共聚物;采用NMR、IR、XRD、DSC和AFM等对PVDF-b-PVP嵌段共聚物的分子和相态结构进行了表征。发现PVP能有效嵌入PVDF与末端碘之间,PVDF嵌段PVP后,PVDF分子链的有序度明显降低,产生γ晶型PVDF,同时结晶温度和结晶度降低。PVDF-b-PVP嵌段共聚物表现微相分离结构,相分离尺寸约20 nm,其亲水性也优于PVDF均聚物。     

THE STRING OF CATALYST SPHERES AS A TOOL FOR HEAT AND MASS TRANSFER STUDY IN A THREE-PHASE SYSTEM

A single vertical string of catalyst spheres with liquid film flowing over their surfaces was employed to model a three phase system. Simultaneous heat and mass transfer characteristics within a porous catalyst pellet and across the laminar liquid film was analyzed in terms of different values of reaction and transport parameters. It is shown that the liquid film thickness after the first three pellets reduces less than 10% even though a highly exothermic reaction is taking place within the pellets. It was also found that the mixing in pendular rings plays an important role in heat transfer from the pellets surface.     

Using conjugated system from natural sources for the synthesis of sulfur copolymers by bi-function catalysts at mild temperatures

Sulfur-rich polymers are promising materials to cover several applications including mercury capture adsorbents. Tung oil, a natural conjugated triene triglyceride oil, were selected to prepare sulfur-rich copolymers. The unique second monomer made reaching the gel point possible at a mild temperature of 130°C in 2.5 h. The reaction accomplishment was confirmed by the depletion of double bonds in tung-oil-sulfur copolymers measured by ¹H NMR, FTIR, XRD, and DSC. A bi-function catalyst calcium hydroxide accelerates the reactions between triglyceride and sulfur before it is removed to increase the surface area and achieve the aims of preparing adsorbents, which has zero free sulfur, high crosslinking degree, and efficient mercury capture. Newly developed tung-oil-sulfur copolymers catalyzed by calcium hydroxide offer the possibility to synthesize sulfur-rich copolymers that combine the advantages of the high performance and the utility of greener and more environmental friendly raw materials.     

Synthesis,morphology and properties of poly(dimethylsiloxane)/poly(n-butyl acrylate) mixed soft block-based copolymers: A new class of thermoplastic elastomer

Design, synthesis, morphology, mechanical properties and in vitro oxidative stability of new class of surface modified thermoplastic elastomers containing mixed soft rubbery poly(n-butyl acrylate-b-dimethylsiloxane-b-n-butyl acrylate) (PnBA-b-PDMS-b-PnBA) block and glassy poly methyl methacrylate (PMMA) end blocks have been reported. Thus well-defined pentablock copolymers such as PMMA-b-PnBA-b-PDMS-b-PnBA-b-PMMA were synthesized by Atom Transfer Radical Polymerization (ATRP). Moderate amount of PDMS (8–15 wt%) in the copolymers significantly enhances the oxidative stability of the surface and contact angle of water in compare to neat PMMA-b-PnBA-b-PMMA copolymer. The phase morphology of such type of copolymers was studied in detailed which suggests that the mixed soft PnBA-b-PDMS-b-PnBA part forms single phase and the degree of phase separation between PnBA-b-PDMS-b-PnBA and PMMA in PMMA-b-PnBA-b-PDMS-b-PnBA-b-PMMA copolymer is higher than the degree of phase separation between PnBA and PMMA in PnBA-b-PDMS-b-PnBA copolymer. This approach of surface modification was extended to synthesize PMMA-b-PLMA-b-PDMS-b-PLMA-b-PMMA (PLMA = polylauryl methacrylate) block copolymers with improved surface properties.     

Triazine-based polymers, 1. Synthesis of poly[(2,4-dichloro-6-ethoxy-s-triazine)-alt-(bisphenol a)]

Poly[(2,4-dichloro-6-ethoxy-s-triazine)-alt-(bisphenol A)] (T-BPA), a polymer with interesting mechanical and thermal properties, was synthesized by phase transfer catalysed interfacial polycondensation. The reaction conditions for the synthesis of T-BPA were investigated and optimized. The influence of several reaction parameters, such as temperature, reaction time, type and concentration of phase transfer catalyst, concentration of monomers, type of solvent, type of base, salt addition, and molecular weight terminator concentration on the reduced specific viscosity and yield of T-BPA was investigated. As a result, it is possible to synthesize T-BPA at reaction conditions being favourable with regard to the costs of energy and equipment.