铟参与的4-溴-1,1,1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应:4,4,4-三氟-γ-羟基缬氨酸的合成

铟参与的4-溴-1,1,1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应以中等的产率和高非对映选择性生成了高烯丙基胺3.从甘油醛亚胺和4-溴-1,1,1-三氟-2-丁烯反应制备的高烯丙基胺3g出发,以7步反应24%的总产率合成了4,4,4-三氟-γ-羟基缬氨酸11.

由炔的金属烯丙化合成二烯烃和环烯烃

炔的金属烯丙化(allylmetallation)是炔的金属烃化反应(carbometallation)的一种,是立体专一地合成多取代烯烃的有效途径。铝烯丙化(allylalumination)和锌烯丙化(allyl-

钯催化下膦盐与烯丙基胺的偶联反应

报道了无酸性添加剂条件下,5 mol%Pd(PPh3)4催化的膦盐与烯丙基胺的直接偶联反应,以32%～74%收率高效地合成α,β-不饱和酮、酯和腈。对照试验表明:烯丙基胺在该反应中展现出其他烯丙化试剂无可替代的优势。

Evaluation of Catalysts and Optimization of Reaction Conditions for the Dehydration of Methyl Lactate to Acrylates

The production of acrylates from biomass-originated lactic acid is of extraordinary importance, to overcome the increasing worldwide shortage of petroleum. In this study, the catalytic dehydration of methyl lactate over a calcium sulfate catalyst, with various promoters, has been carried out to identify potential catalyst/promoter combinations for acrylate production. The best catalyst for methyl acrylate formation in this study has been calcium sulfate, with cupric sulfate and phosphates as promoters. The optimal mass ratio of m（CaSOa） ： m（CuSOa） ： m（Na2HPO4） ： m（KH2PO4） is 150.0 ： 13.8 ： 2.5 ： 1.2. Effects of carrier gas, reaction temperature, feed concentration as well as contact time on the dehydration of methyl lactate have been investigated. With nitrogen as a carrier gas, a combined yield of acrylic acid and methyl acrylate is 63.9% from 60% （by mass） methyl lactate at 400℃ with 7.7 seconds contact time.

A new solid acid SO_4^(2-)/TiO_2 catalyst modified with tin to synthesize 1,6-hexanediol diacrylate

A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.

Commercial Application of CPP for Producing Ethylene and Propylene from Heavy Oil Feed

A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional catalytic activities for both carbonium ion reaction andfree radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trialshowed that the yield of ethylene and propylene was 20.37% and 18.23% respectively inmaximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylenewas 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene andpropylene.

Study on the Performance and Commercial Application of New Generation DMMC-1 Type Catalyst for Deep Catalytic Cracking

Over the past decades SINOPEC has been uninterruptedly engaging in the development and upgrading of deep catalytic cracking （DCC） technology for manufacturing propylene from heavy oil. Recently SINOPEC after having made a lot of progress in the area of oil refining at the molecular level has developed a new generation DMMC-1 type catalyst designed for the DCC process. The laboratory evaluation tests have shown that compared to the existing MMC-2 type catalyst that features the best comprehensive performance, the DMMC-1 type catalyst has increased the propylene yield by 2.2% with the propylene selectivity increased by 10%. The said catalyst has improved its ability for heavy oil cracking and coke selectivity along with reduction of olefin content in gasoline to achieve a better product distribution and improve the product quality. The results of application of the said catalyst in a 650-kt/a commercial DCC unit at SINOPEC Anqing Branch Company have revealed that the DMMC- 1 catalyst demonstrated an enhanced capability for heavy oil cracking and could increase the total liquid yield to 84.56 m% from 83.92 m%, the LPG yield to 38.90 m % from 34.60 m %, the propylene yield to 17.80 m% from 15.37 m% and the propylene concentration to 45.91 m% from 44.91 m%, and reduce the coke yield from 7.61 m% to 7.05 m% and the olefin content in gasoline from 42.3 v% to 37.5 v%, resulting in an incremental profit amounting to 52.19 million RMB a year. This technology has further upgraded and developed the DCC technology which has been commanding a leading position among the industry peers.

Simulation and Off-line Optimization of an Acrylonitrile Fluidized-bed Reactor Based on Artificial Neural Network

A mathematical model is developed for an industrial acrylonitrile fluidized-bed reactor based on arti-ficial neural networks. A new algorithm, which combines the characteristics of both genetic algorithm (GA) andgeneralized delta-rule (GDR) is used to train artificial neural network (ANN) in order to avoid search terminatedat a local optimal solution. For searching the global optimum, a new algorithm called SM-GA, incorporating ad-vantages of both simplex method (SM)and GA, is proposed and applied to optimize the operating conditions of anacrylonitrile fluidized-bed reactor in industry.

Monte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst (Mo-Bi)

Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition over the commercial propylene ammoxidation catalyst(Mo-Bi). The simulation is quite in agreement with experimental results. Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

Gel time of calcium acrylate grouting material

Calcium acrylate is a polymerized grout, and can polymerize in an aqueous solution. The polymerization reaction utilizes ammonium persulfate as a catalyst and sodium thiosulfate as the activator. Based on the theory of reaction kinetics, this study on the relation between gel time and concentration of activator and catalyst showed that gel time of calcium acrylate is inversely proportional to activator and catalyst concentration. A formula of gel time is proposed, and an example is provided to verify the proposed formula.

DFT studies on the SCR reaction mechanism of nitrogen monoxide with propylene catalyzed by copper oxide

The SCR reaction mechanism of NO with C3H6catalyzed by CuO was studied by the method of Density Functional Theory(DFT)at the B3LYP/LanL2DZ levels.The optimized geometries of the stationary points on the potential surface were obtained and the transition state was confirmed by IRC and vibration analysis.The activation energy was calculated being 34.26 kJ/mol.It was shown that propylene reacted firstly with Cu forming intermediate,and then nitrogen monoxide immediately reacted with the intermediate to be reduced.It was proved to be a direct interaction mechanism.

Monte Carlo Simulation of Propylene Selective Oxidation and Ammoxidation overβ-Bi2Mo2O9 Catalyst under Anaerobic Condition

A random walk Monte Carlo （RWMC） simulation model of catalytic particle was established on the basis of the structures of bismuth molybdate catalysts and mechanisms of catalytic reactions with propylene selective oxidation and ammoxidation. The simulation results show that rationality of the RWMC model is proved on the basis of pulse experimental data. One of the most remarkable factors affecting catalytic behavior is the transfer of bulk lattice oxygen, which decides the rate of ammonia-consuming and propylene-consuming. The selectivity of main products reaches the maximum after the reduction of catalysts to a certain degree. It is inferred that catalytic performance improves greatly if the ratio of capacity for dehydrogenation from adsorbed propylene molecule on catalytically active site of molybdenum metal-imido group （Mo=NH） to that on catalytically active site of molybdenum metal-oxo group （Mo=O） becomes much higher.

FCC Catalysts to Meet Demand of New Era

The CGP series FCC catalysts for manufacture of clean gasoline and propylene and the catalyst RSC-2006 for processing inferior residuum with high yield of light distillates are novel catalysts jointly developed by Qilu Catalyst Branch Company of SINOPEC Corp. and the Research Institute of Petroleum Processing (RIPP). The results of commercial application of these catalysts have revealed that they can satisfactorily meet the requirements for environmental protection, good economic benefits and capability for processing inferior FCC feed under new circumstances.

Novel MgCl2-supported Catalysts Containing Succinate Donors for Propylene Polymerization

A novel MgCl2-supported Ziegler-Natta catalyst containing diethyl diisopropylsuccinate donor was prepared and propylene polymerizations with the combination of such catalyst and four external donors were investigated in detail. The catalyst was compared with a commercial one with phthalate as internal donor in terms of catalytic activity, hydrogen sensitivity and stereospecificity in propylene polymerization. The molecular weight,molecular weight distribution and microstructure of the produced polypropylenes were compared also. It was found that the novel catalyst containing succinate internal donor showed higher activity and higher stereospecificity than those with phthalate as internal donor. Consequently, polypropylenes obtained by the succinate-based catalyst showed high molecular weight, high melting temperature, high isotactic index and broad molecular weight distribution than those obtained with the commercial catalyst.

Catalytic Degradation of Mixed Polypropylene, Low and High Density Polyethylene into Environmental Friendly and Useful Products

Using novel catalyst the pyrolysis of mixed plastics has been considered as an effective way to convert waste plastics into environmental friendly and industrially useful hydrocarbon gas and liquid products. Catalytic cracking is a promising alternative for plastic wastes recycling. More than 99% of a polymer mixed converted into combustible hydrocarbon in a catalytic converting reaction. The products are mainly middle distillates. In this work equally weighted mixed HDPE （high density polyethylene）, LDPE （low density polyethylene） and Polypropylene were degraded. The reaction occurred in a semi batch reactor at several temperatures and catalyst/polymer ratios in search for an optimum operating condition. The products are liquid and gaseous hydrocarbons with minor of residue. The liquid and gas products were in the range of middle distillate cuts of gasoline, kerosene and gas oil. Finally, with a metallic base, yielded 99.5% of given mixed to valuable middle distillate products that include 86% liquid hydrocarbon and 13.5% gas, ranging between C1 and C5 with less percent of residue. The optimum condition for this yield reports at a temperature of 450 ℃ and 10% of catalyst w/w at atmosphere pressure.

Effect of polyoxypropylene chain length on the critical micelle concentration of propylene oxide-ethylene oxide block copolymers

In this work, the surface activity of block copolymer nonionic surfactants (RPE) has been determined, i.e., critical micelle concentration (CMC), surface excess concentration (Γ), surface area demand per molecule (A), surface tension at CMC (γCMC). A linear decrease of ln[CMC] vs number of oxypropylene units in copolymer molecule was observed. The change in the work of cohesion per oxypropylene group when passing from molecular into micellar state, calculated from the Shinoda equation, was 0.43kT for the studied compounds.

Effects of ion chemistry and mass on the electrical properties of ion implanted pyrolyzed polyacrylonitrile

This paper describes the conductivity modifications induced by heavy ion implantation in pyrolysis products obtained by thermal treatment of polyacrylonitrile （PAN） thin films at temperatures of 435℃ （PAN435） and 750℃ （PAN750） under vacuum. Ionic species having different chemical reactivities such as Kr, As, Cl. and F ions were utilized to allow interpretation of the conductivity＇ data either in terms of implantation induced molecular rearrangements or in terms of specific chemical doping effects. The temperature dependence of conductivity in the range between 25-3000C followed nearly a simple activation conduction relationship from which the temperature coefficients of resistivity （ct） were determined. In this temperature range, PAN750 provided the smallest α value compared with ion implanted PAN750 or with products obtained at the lower pyrolysis temperature. However. the corresponding lowest rate of conductivity change with temperatures （0.49%/℃） obtained in this study far exceeds the specification value required for thin film resistor applications （〈 0.1%/℃）.

Synthesis, characterization and catalytic application of H4SiW12O40/MCM-48 in the esterification of methacrylic acid with n-butyl alcohol

A novel environmental friendly catalyst, H4SiW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H4SiW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H4SiW12O40/MCM-48 was an excellent catalyst for the synthesis of n-butyl methacrylate and Keggin structure ofH4SiW12O40 kept unchanged after impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）： n（n-butyl alcohol）, catalyst dosage, cyclohexane （water-stripped reagent） and reaction time on the yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.5, mass ratio of catalyst used to the reactant is 1.5%, cyclohexane is 10 mL and reaction time is 1.5h. Under these conditions, the yield of n-butyl methacrylate can reach 73.2%.

C–H allylation of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with iodide catalysis

A dual catalytic system, combing visible light photoredox catalysis and iodide catalysis, has been developed for the functionalization of inert C–H bonds. By doing so, radical allylation reactions of N-aryl-tetrahydroisoquinolines(THIQs) were realized under extremely mild conditions, affording a wide variety of allyl-substituted THIQs in up to 78% yields.

Palladium-catalyzed oxidative cyclopropanation of enamides and norbornenes initiated by C–H activation

A novel palladium-catalyzed oxidative cyclopropanation of enamides and norbornenes has been developed. The reaction proceeded through palladium-catalyzed vinyl C–H bond activation of enamides followed by two migratory insertions, β-(N)H elimination and hydrolyzation cascade steps. The reaction tolerates a range of functional groups and provides an effective method for the synthesis of cyclopropane-fused norbornanes in good yields under mild conditions.