POLYMERIZATION OF METHYL METHACRYLATE WITH ETHYLENE BRIDGED HETERODINUCLEAR METALLOCENE OF SAMARIUM AND TITANIUM-STUDY ON SYNERGISM AND KINETICS

ＩＮＴＲＯＤＵＣＴＩＯＮＨｅｔｅｒｏｄｉｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓａｒｅｏｆｇｒｅａｔｉｍ ｐｏｒｔａｎｃｅｆｏｒｔｈｅｓｔｕｄｙｏｆｔｈｅｓｙｎｅｒｇｉｓｔｉｃｅｆｆｅｃｔｓｆｏｕｎｄｉｎｂｉｍｅｔａｌｌｉｃｃａｔａｌｙｓｉｓ (Ａｄａｍｓ,1 988;Ｒｅｄｄｙｅｔａｌ.,1 989;Ｚｈｅｎｇｅｔａｌ.,1 989;Ｗｅｒｎｅｒｅｔａｌ.,1 992 ) ,ｗｈｉｃｈｉｎｄｉｃａｔｅｄｄｉｓｔｉｎｃ ｔｉｖｅｅｌｅｃｔｒｏｎｉｃ ,ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌａｎｄｍａｇｎｅｔｉｃｐｒｏｐｅｒｔｉｅｓａｒｉｓｉｎｇｆｒｏ…     

Polymerization of methyl methacrylate with iron-ytterbium dinuclear metallocene catalyst

A novel iron-ytterbium dinuclear catalyst, FcB(MeCp) Yb (MeCp) Cl (Fc: ferrocenyl, B: diethylene ether), was synthesized for the polymerization of methyl methacrylate (MMA). Synergistic effects between the ferrocenyl group and the lanthanocene part were investigated regarding their catalytic behaviors. UV, IR, GPC and NMR were used to characterize the structures of the catalyst and polymer. Kinetic study showed that polymerization is first order in monomer concentration and fractional order (0.78) in the catalyst. The bimetallic complex is a good catalyst for the polymerization of MMA, giving high molecular weight PMMA with 78% syndiotactivity. Project (29774021) supported by NSFC and Laboratory of Rare-Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences     

POLYMERIZATION OF METHYL METHACRYLATE WITH IRON-YTTERBIUM DINUCLEAR METALLOCENE CATALYST

ＩＮＴＲＯＤＵＣＴＩＯＮＨｅｔｅｒｏｄｉｎｕｃｌｅａｒｃｏｍｐｌｅｘｅｓａｒｅｏｆｇｒｅａｔｉｎｔｅｒ ｅｓｔｆｏｒｔｈｅｓｔｕｄｙｏｆｓｙｎｅｒｇｉｓｔｉｃｅｆｆｅｃｔｓｆｏｕｎｄｉｎｂｉｍｅｔａｌｌｉｃｃａｔａｌｙｓｉｓ(Ｄｏｍｂｅｋ ,1 985;ＪｎＬｉｎｇｅｔａｌ.,1 993 ;Ｍｃｃｏｌｌｕｍｅｔａｌ.,1 996) .Ｍｏｒｅａｎｄｍｏｒｅｓｙｎｔｈｅｔｉｃｒｏｕｔｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄｉｎｔｈｅｌａｓｔｄｅｃａｄｅ(Ｈａｒｔｅｒｅｔａｌ.,1 989;Ｓｃｏｔｔｅｔａｌ.,1 993 ;Ｄｉａｍｏｎｄｅｔａｌ.…     

The polymerization of methyl methacrylate with a new Tin-bridged yttrocene/Al(I-Bu)3

A new catalyst composed of Tin-bridged yttrocene Ph₂Sn(MeCp)₂YCI (MeCp=methylcyclopentadienyl) and Al (i-Bu)₃ was successfully developed for the polymerization of methyl methacrylate (MMA). Detailed study of factors (such as the molar ratio of Al/Cat., catalyst concentration, various solvents, temperature and time) influencing polymerization reaction indicated that the catalytic active species may be still somewhat stable at high temperature and still have a long catalytic lifetime.¹H NMR spectrum showed about 65% syndiotactic content in the polymethyl methacrylate (PMMA) prepared. From kinetic studies, the polymerization rate equation may be expressed as Rp=Kp[Cat.]^2.4. The overall activation energy of polymerization is 20.9±3.1 kJ/mol. Project(29774021) supported by the Natural Science Foundation of China and National Laboratory of Element-Organic Chemistry, Nakai, University.     

Ethylene polymerization with novel silicon bridged homo-dinuclear cyanoethyl cyclopentadienyl complexes of titanium and zirconium

Novel homo-dinuclear silicon bridged cyanoethyl cyclopentadienyl complexes of titanium and zirconium (CH₃)₂Si((η⁵ ? C₅H₃CH₂CH₂CN)(C₅H₅)MCl₂)₂(M = Ti(1), Zr(2)) were synthesized and developed for the polymerization of ethylene. Compared with their corresponding mononuclear complexes (η⁵ ? C₅H₄CH₂CH₂CN)(C₅H₅)MCl₂(M = Ti(3), Zr(4)), the dinuclear complexes had higher catalytic activity. And the polyethylene produced had a higher molecular weight than that obtained with mononuclear catalysts. Effects of conditions on the ethylene polymerization catalyzed by (2)/MAO (methylaluminoxane) were studied in detail. The catalyst showed a very high activity (> 10⁶ g PE/mol Zr·h) under low catalyst concentration and high molar ratio of Al/Zr.     

Preparation of poly (methyl methacrylate)/nanometer calcium carbonate composite by in-situ emulsion polymerization

Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate (nano-CaCO3) surface modified with (-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.     

DSC法研究MMA/纳米Si3N4体系的聚合过程

利用差示扫描量热仪(DSC)对MMA/纳米Si3N4体系的聚合过程进行研究,着重考察了聚合温度,纳米Si3N4粉体加入量及引发剂AIBN用量对体系聚合速率的影响.结果表明:升高聚合反应温度,增大引发剂用量,均可使体系的凝胶效应提前出现,聚合速率增大;而纳米Si3N4粉体的加入对体系的聚合起到延缓的作用,且随着加入量的增加,聚合速率逐渐降低.     

Copolymerization of Acrylonitrile/1-Vinyl-3-Ethylimidazolium Bromide and Rheological,Thermal Properties of the Copolymer

Acrylonitrile(AN)/1-vinyl-3-ethylimidazolium bromide(VIMB) copolymer was prepared via solution polymerization using dimethyl sulfoxide(DMSO) as a solvent and azodiisobutyronitrile as an initiator. The effects of comonomer VIMB on the polymerization, rheological properties of the polymer solution and thermal properties of the copolymer were investigated. The ionic liquid VIMB resulted in higher polymerization conversion ratio and higher average molecular weight when copolymerized with AN than itaconic acid(ITA). Rheological measurements indicated that the transition shear rate increased linearly with increasing temperature for P(AN/ITA)/DMSO solution, while an exponential growth with temperature was observed for P(AN/VIMB)/DMSO solution. The exothermic peaks of DSC curves in N_2 appeared at 276.67 and 257.34 °C for P(AN/VIMB) and P(AN/ITA), respectively. As a potential comonomer of AN for PAN carbon fibers, the VIMB resulted in about 7% higher char yield in N_2, and 23.7% less weight loss at 600 °C in air than ITA copolymer.     

Impact of diesel emission fluid soaking on the performance of Cu-zeolite catalysts for diesel NH<Subscript>3</Subscript>-SCR systems

Diesel emission fluid (DEF) soaking and urea deposits on selective catalytic reduction (SCR) catalysts are critical issues for real diesel engine NH₃-SCR systems. To investigate the impact of DEF soaking and urea deposits on SCR catalyst performance, fresh Cu-zeolite catalyst samples were drilled from a full-size SCR catalyst. Those samples were impregnated with DEF solutions and subsequently hydrothermally treated to simulate DEF soaking and urea deposits on real SCR catalysts during diesel engine operations. Their SCR performance was then evaluated in a flow reactor with a four-step test protocol. Test results show that the DEF soaking leached some Cu from the SCR catalysts and slightly reduced their Cu loadings. The loss of Cu and associated metal sites on the catalysts weakened their catalytic oxidation abilities and caused lower NO/NH₃ oxidation and lower high-temperature N₂O selectivity. Lower Cu loading also made the catalysts less active to the decomposition of surface ammonium nitrates and decreased low-temperature N₂O selectivity. Cu loss during DEF impregnation released more acid sites on the surface of the catalysts and increased their acidities, and more NH₃ was able to be adsorbed and involved in SCR reactions at medium and high temperatures. Due to lower NH₃ oxidation and higher NH₃ storage, the DEF-impregnated SCR catalyst samples showed higher NO _x conversion above 400 °C compared with the non-soaked one. The negative impact of urea deposits during DEF impregnation was not clearly observed, because the high-temperature hydrothermal treatment helped to remove the urea deposits.     

异丁烯酸甲酯/氰酸酯树脂半互穿聚合物的合成与表征

于加热熔融的氰酸酯树脂(BACDy)中加入异丁烯酸甲酯(MMA),在引发剂存在下,引发单体及预聚体MMA发生本体聚合,采用同步合成法和异步合成法分别制备互穿聚合物网络氰酸酯树脂/聚异丁烯酸甲酯(BACDy/MMA-SIPN)高分子材料,研究了几种不同配比的SIPN体系.结果表明,BACDy/MMA-SIPN网络形成的反应条件对体系的力学性能和耐热性能都有较大提高.给出了较合理的制备工艺条件.     

Green epoxidation of cyclooctene with molecular oxygen over an ecofriendly heterogeneous polyoxometalate-gold catalyst Au/BW<Subscript>11</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

An ecofriendly heterogeneous polyoxometalate (POM)-gold catalyst Au/BW₁₁/Al₂O₃ was synthesized and used for solvent-free epoxidation of cyclooctene under mild reaction conditions using molecular oxygen as an oxidant and t-butyl hydroperoxide (TBHP) as an initiator. The catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), induced coupled plasma optical emission spectrometry (ICP-OES), and Brunauer-Emmett-Teller (BET). The catalyst showed good conversion and high selectivity without use of solvents or environmentally harmful oxidants. Moreover, the catalyst is recyclable up to three cycles with no significant loss in selectivity towards epoxide.     

Effect of mineral admixtures and repeated loading on chloride migration through concrete

The effect of fly ash (FA) and ground granulated blast furnace slag (GGBFS) on chloride migration through concrete subjected to repeated loading was examined. Portland cement was replaced by three percentages (20%, 30%, and 40%) of mineral admixtures. Five repeated loadings were applied to concrete specimens using a WHY series fully automatic testing machine. The maximum loadings were 40% and 80% of the axial cylinder compressive strength (f′c). Chloride migration through concretes was evaluated using the rapid chloride migration test and the chloride concentration in the anode chamber was measured. The results showed that the replacement percentages of mineral admixtures, the curing time and repeated loading had a significant effect on chloride migration through concrete. The transport number of chloride through concrete cured for 28 d increased with increasing FA replacement and markedly decreased with extension of the curing time. 20% and 30% GGBFS replacement decreased the transport number of chloride through concrete, but 40% GGBFS replacement increased the transport number. Five repeated loadings at 40% or 80% f′c increased the transport number of chloride for all mixes.     

Ethylene polymerization with novel silicon bridged homo-dinuclear cyanoethyl cyclopentadienyl

Novel homo-dinuclear silicon bridged cyanoethyl cyclopentadienyl complexes of titanium and zirconium (CH3)2Si((η5-C5H3CH2CH2CN)(C5H5)MCl2)2 (M=Ti(1), Zr(2)) were synthesized and developed for the polymerization of ethylene. Compared with their corresponding mononuclear complexes (η5-C5H4CH2CH2CN)(C5H5)MCl2 (M=Ti(3), Zr(4)), the dinuclear complexes had higher catalytic activity. And the polyethylene produced had a higher molecular weight than that obtained with mononuclear catalysts. Effects of conditions on the ethylene polymerization catalyzed by (2)/MAO (methylaluminoxane) were studied in detail. The catalyst showed a very high activity ( >106g PE/mol Zr*h) under low catalyst concentration and high molar ratio of Al/Zr.     

Preparation and application of supported amorphous alloy catalyst CoP/TiO2

A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC Its application in decomposing PH3 to high purity phosphor and its catalytic activity were studied. The decomposition rate is over 95% at 450 ℃. For comparison, unsupported CoP amorphous catalyst was prepared by the same method. The result suggests that CoP/TiO2 exhibits higher thermal stability and catalytic activity than CoP, which is attributed to the high dispersion of CoP alloy particles on the support-TiO2.     

Novel Method for Preparing a Carbon Nanotube-Supported Cobalt Catalyst for Fischer–Tropsch Synthesis:Hydrogen Dielectric-Barrier Discharge Plasma

Hydrogen dielectric-barrier discharge (H₂-DBD) plasma was successfully used to prepare carbon nanotubes (CNTs)-supported cobalt (Co) catalyst. The H₂-DBD plasma treatment simultaneously decomposed and reduced the cobalt precursor at a lower temperature and in a shorter time than the conventional method (calcination and hydrogen reduction). It is considered that the H₂-DBD plasma method can remarkably decrease the amount of energy input compared to traditional methods used to prepare the Co-based catalyst in Fischer–Tropsch synthesis (FTS). Results showed that the Co catalyst prepared by H₂-DBD plasma had an equivalent catalytic performance for FTS as that prepared using the conventional method in calcination and hydrogen reduction, thereby determining that H₂-DBD plasma was an effective alternative treatment for preparing the Co/CNTs catalyst for FTS. This technology will provide a new strategy for preparing catalysts in other catalysis processes.     

Performance Evaluation of Modified Black Clay as a Heterogeneous Fenton Catalyst on Decolorization of Azure B Dye: Kinetic Study and Cost Evaluation

Black clay(BC) was used as a catalyst for the decolorization of Azure B dye by Fenton process. BC was modified by acid, alkali, distilled water, and calcination to check their changes in characterization and efficiency on decolorization of Azure B. Among three modified catalysts, maximum decolorization was obtained by acid-modified BC(AMBC) catalyst due to the highest removal of impurities, comparatively. The characterization of AMBC was done by Fourier-transform infrared spectroscopy and X-ray diffraction spectroscopy which show the presence of metal ion. The BET surface area, pore volume, pore size, and density of AMBC were calculated to be 79.402 m~2/g, 0.0608 m~3/g, 0.00306 nm, and 16 g/cm~3, respectively. The highest decolorization of 97.59% was achieved only in 10 min using AMBC at optimized calcination of 100 °C and 3 h of aging. AMBC was considered as the main catalyst for optimizing the different process parameters. Optimized conditions were obtained: pH 2, 0.2 mL of H_2O_2, catalyst dose 0.3 g, room temperature(30 °C), and stirring speed 400 r/min. The catalyst has showed excellent stability and reusability. It could remove more than 85% of color even after four cycles of run and less than negligible leaching of iron. AMBC has good recycling ability among other modified catalysts. To check the selectivity of catalyst, different dyes such as Congo red and mixed dye(mixture of Azure B and Congo red) decolorization were studied. In the present work, kinetic study was also carried out and a three-stage decolorization process was found.     

磁性导电聚苯乙炔薄膜的合成与表征

文章以苯乙烯为原料,通过溴化和脱溴化氢生成苯乙炔。利用无水AlCl3作催化剂合成聚苯乙炔(PPA),并通过物理共混法制得聚苯乙炔/磁流体复合物薄膜。对其磁性、成膜性进行了研究,结果表明:产物磁性、成膜性均良好并且受催化剂用量影响较大。     

Dual bed catalyst system for oxidative dehydrogenation of mixed-butenes: a synergistic mechanism

Oxidative dehydrogenation (ODH) of mono and mixed-butenes to 1,3-butadiene (BD) was conducted using individual and dual bed catalyst systems, consisting of ZnFe₂O₄, Co₉Fe₃Bi₁Mo₁₂O₅₁ or both. The dual bed catalyst system gave improved catalytic performance. A mechanism based on synergy between the catalysts is proposed to explain the improved overall butene conversion. The proportion of the reactants differed between the catalyst beds in the dual bed system, making better use of the catalytic activity of the second bed. The existence of all butene isomers inhibited isomerization, leading to a higher proportion of ODH reactions and thus improved the conversion of butene and the yield of BD. The packing sequences and the volume ratio of the catalysts in the bed were optimized. The results indicated that the sequence with ZnFe₂O₄ on top and a catalyst packing ratio of between 4:6 and 6:4 led to better activity.     

Metal Oxide/Nitrogen-Doped Carbon Catalysts Enables Highly Efficient CO2 Electroreduction

The metal oxide/nitrogen-doped carbon (NC) compounds zirconium oxide/NC (ZrO₂/NC) and cerium oxide/NC (CeO₂/NC) were synthesized via the pyrolysis of polyaniline on the metal oxide surface. The characterization of the ZrO₂/NC and CeO₂/NC catalysts showed more active CO₂ reduction reaction activity than that of NC catalyst without metal oxide. Gas chromatography analysis revealed that CO and H₂ were the primary products, and no liquid-phase products were detected via proton nuclear magnetic resonance spectroscopy or high-performance liquid chromatography. The maximum Faraday efficiency of ZrO₂/NC reached 90% at − 0.73 V (vs. RHE), with the current density of CO at 5.5 mA/cm²; this Faraday efficiency value was higher than that of NC (41%), with the current density of CO at 3.1 mA/cm². The interaction between the metal oxide and carbon allowed the efficient formation of defect sites, especially imine-type nitrogen, strengthening the adsorption of the key reaction intermediate CO₂^•− and thus promoting the CO₂ reduction reaction.

     

Strong influences of polymerization temperature on ethylene/1-hexene copolymerization catalyzed by (2-PhInd)2ZrCl2/methyl aluminoxane

Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)₂ZrCl₂/MAO (methyl aluminoxane) at 0°C and 50°C respectively. High copolymerization activity and 1-hexene incorporation were observed at 0°C, with the copolymer formed having random sequence distribution and narrow molecular weight distribution. Ethylene polymerization at 50°C showed high activity, but copolymerization at 50°C showed much lower activity, which decreased sharply with increasing 1-hexene concentration in the monomer feed. Copolymer formed at 50°C showed blocky sequence distribution and broad molecular weight distribution. A mechanism model based on ligand rotation hindered by the propagation chain has been proposed to qualitatively explain the observed phenomena. Project (Nos. 29734144 and 20274037) supported by the National Natural Science Foundation of China