Chitosan-immobilized Palladium Complex: a Green and Highly Active Heterogeneous Catalyst for Heck Reaction

A green heterogeneous catalyst for Heck reaction-chitosan-immobilized palladium complex was prepared. The catalyst exhibits high activity and stereoselectivity under the moderate reaction conditions. The catalyst can be separated easily from the reaction mixture and reused after washing. Under the suitable reaction conditions, the cross-coupling of iodobenzene (ArI) with acrylic acid (AA) or acrylate can be achieved 93.3% or 99% yield of trans-cinnamic acid or trans-cinnamic ester.

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.

Study on Polymerization of 4-Vinylpyridine by Neodymium Complex Catalyst

Polymerization of 4-vinylpyridine by complex catalyst of neodymium chloride was studied. The influence of Al/Nd (molar ratio), concentration of catalyst, reaction time and temperature on polymerization of 4-vinylpyridine was investigated. The results show that different kinds of ligand in the rare earth complex have an effect on the catalytic activity of the complex. The catalytic activity of the rare earth complex is higher than that of simple rare earth chloride. The catalytic activity of polymer-supported catalyst is higher than those of the similar small molecular system.

A Sterically Hindered Zirconocene Complex (1,2-Ph_2C_5H_3)_2ZrCl_2:Synthesis,Structure and Properties as Olefin Polymerization Catalyst

An unbridged zirconocene complex bis(1,2-diphenylcyclopentadienyl)zirconium dichloride [(1,2-Ph2-C5H3)2ZrCl2] 1 has been synthesized and structurally characterized. When activated by MAO, 1 produces ultra-high molecular weight polyethylene with high melting transition temperature, as well as atactic oligopropylene with average molecular weight of ~1150 g mol-1.

Polymerization of Styrene and 1,3-Butadiene by Catalyst Systems Based on Calix[4]arene Neodymium Complexes

Polymerization of styrene and 1,3-butadiene were performed by calix[4]arene-neodymium complexes using di-n-butylmagnesium and tri-iso-butylaluminum as cocatalyst respectively. The effect of the substituent groups in calix[4]arene on the catalytic activity was first investigated.

Friedel-Crafts Acylation Reactions Using Catalytic SbCl_5-TEBA Complex as an Efficient Catalyst

SbCl_5-TEBA (PhCH_2NEt_3Cl) complex catalyzes the Friedel-Crafts acylation reactionsefficiently.

1, 1'—BIS (BENZYLSELENO) FERROCENE PLATINUM COMPLEX AS HYDROSlLYLATION CATALYST FOR OLEFINS

1, 1'--Bis(benzylseleno)ferrocene and its platinum complex were synthesized. It was found that the platinum complex was efficient catalyst for the hydrosilylation of olefins with triethoxysilane.

SILICA-BOUND CROWN ETHERS PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.

STUDY ON POLYMER—Ru-Co—BIMETALLIC COMPLEXES CATALYSTS Ⅰ. SYNTHESIS OF CATALYSTS AND THEIR USE FOR THE HYDROFORMYLATION

Six kinds of polymer ligands, supported on SiO_2, containing coordinating atoms P, S and N respectively, have been synthesized. The Ru(Ⅲ)-Co(Ⅱ) bimetallic complexes of these polymer ligands have been obtained and examined as catalysts for the hydroformylation of cyclohexene. The effects of reaction temperature, pressure and Co/Ru ratio etc. on the activities of catalysts were investigated in detail. The catalysts are all polymer-noncarbonyl-metal complexes, easily to be prepared, active and stable. From the experimental results it can be suggested that under reaction conditions such polymer-noncarbonyl-metal complexes convert 'in situ' to polymer-carbonyl-metal complexes, thus become active catalysts. The course of this conversion is supposed as a preliminary approach.

CROWN FUNCTIONALIZED LINEAR POLYSILOXANE PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently.

Synthesis and Catalytic Activity of a Two-core Ruthenium Carbene Complex: a Unique Catalyst for Ring Closing Metathesis Reaction

The reaction of a ruthenium carbide complex RuCl2（C：）（PCy3）2 with [H（Et2O）x]＋[BF4]- at a molar ratio of 1：2 produced a two-core ruthenium carbene complex, {[RuCl（=CHPCy3）（PCy3）]2（μ-Cl）3}＋·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature（137 °C）, indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.

4-Selena-7-thiaoctyl Polystyrene-supported Platinum Complex as Hydrosilylation Catalyst

ＩｎｔｒｏｄｕｃｔｉｏｎＳｅｌｅｎｏｅｔｈｅｒｐｌａｔｉｎｕｍｃｏｍｐｌｅｘｅｓａｓａｎｅｗｋｉｎｄｏｆｈｙｄｒｏｓｉｌｙｌａｔｉｏｎｃａｔａｌｙｓｔｈａｖｅｂｅｅｎｄｒａｗｎｍｕｃｈａｔｅｎｔｉｏｎｒｅｃｅｎｔｌｙ．Ａｓｅｒｉｅｓｏｆｓｅｌｅｎｏｅ...

A Study of Heteropoly Complexes of Rare Earths as Catalyst Promoter in the Synthesis of Ethyl Acetate

The capability of the synthesized heteropoly complexes of rare earths {K10 [(O39W11Si) Ln(Gly)3Ln(SiW11O39)]?H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy)} as the catalyst promoter in the synthesis of the ethyl acetate was studied. The results showed that the quantity of H2SO4 used for synthesizing the ethyl acetate can be reduced by 75% and the yield reached 98% at the optional condition.

Trinuclear Metal Complexes Based on 1,10-Phenanthroline Derivates as Catalysts for Cleavage of a RNA-Model Substrate

Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.

CARBONACEOUS PRODUCTS OF POLYMER-PALLADIUM COMPLEXES AS CATALYSTS FOR THE HYDROGENATION OF METHYL ACRYLATE

Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.

Simple Preparation of Halogen-Substituted <i>α</i>-Diimine Nickel Complexes Immobilized into Clay Interlayer as Catalysts for Ethylene Oligo-/Polymerization

In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene&bull;g-cat–1&bull;h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.

新型Ti-Co复合负载化催化剂制备支化聚乙烯

以反应法制备了TiCl4、乙酰丙酮改性的TiCl4和Co(acac) 2 为主催化剂 ,SiO2 MgCl2 为载体的复合负载型催化剂 (TiCl4 CH3COCH2 COCH3 Co(acac) 2 SiO2 MgCl2 ) ,以烷基铝作为助催化剂 ,以单一乙烯单体制备了支化聚乙烯 .研究了复合催化剂的组成、烷基铝种类和聚合反应温度等对聚合反应和产物结构性能的影响 .探讨了聚合反应机理 .聚合产物经IR、1 3 C NMR谱分析 ,结果表明Ti Co复合催化剂具有低聚原位共聚功能 ,可制得含有丁基、戊基、己基等各类支链结构的支化聚乙烯 .

复合催化剂合成可降解共聚酯PBAT及性能表征

通过钛酸四丁酯、正硅酸乙酯以及磷酸三乙酯的反应制备了一种复合催化剂,然后以1,4-丁二醇、己二酸和对苯二甲酸为原料,使用该复合催化剂通过直接酯化法合成了聚对苯二甲酸丁二醇-co-聚己二酸丁二酯(PBAT)。研究了酯化率、缩聚时间对合成的PBAT特性黏度的影响,重点对比了制备的复合催化剂与传统聚酯催化剂的活性。采用核磁共振、傅里叶变换红外光谱对聚合物的结构进行了表征。结果表明,当酯化率由80%增加至95%时,PBAT的特性黏度从0.95 dL/g增加到1.25 dL/g;随着缩聚反应时间的增加,PBAT的特性黏度先增加后减小,当缩聚时间为65 min时,PBAT的特性黏度达到最大,为1.25 dL/g。当制备的复合催化剂质量分数为0.025%时,PBAT的特性黏度可以达到1.1 dL/g以上,并且缩聚温度只需要240℃左右(传统的催化剂需要270℃以上),这大大降低了反应能耗。从熔融温度、结晶温度、拉伸断裂强度以及断裂伸长率等性能测试结果来看,采用自制复合催化剂合成的PBAT的结晶温度为84.75℃,拉伸断裂强度为26.2 MPa,断裂伸长率为870%,性能得到了更好的提升。

金属配合物催化双氧水对棉织物的低温漂白

分别采用自制的Mn_(1)、Mn_(2)、Cu配合物作为棉拉架布低温漂白催化剂,探究碱剂、双氧水和金属配合物催化剂质量浓度,以及练漂时间和温度对织物漂白后性能的影响,并与传统练漂棉布的染色性能进行对比。结果表明:三种配合物均能催化双氧水有效分解,可以实现75℃低温漂白,双氧水用量和氢氧化钠用量可以分别降低20%、30%,且其漂白效果均能达到后续染整加工要求,不影响织物的染色性能,符合当前行业节能减排的需求。

硝基氰胺乙烯基咪唑过渡金属配合物的合成及结构与性能分析

为探索固体推进剂含能燃烧催化剂,以硝基氰胺根(NCA)为阴离子、1-乙烯基咪唑(VIM)为配体,过渡金属Mn、Co、Ni、Cu为中心离子,制备出4种新型含能配合物,结构式分别为[Mn(VIM)_(4)](NCA)_(2)(配合物1)、[Co(VIM)_(4)](NCA)_(2)(配合物2)、[Ni(VIM)_(4)](NCA)_(2)(配合物3)、[Cu(VIM)_(4)](NCA)_(2)(配合物4);通过元素分析、红外光谱(FT-IR)、X射线晶体衍射(XRD)、感度测试和氧弹量热法对其结构和物理化学性质进行了表征;用差示扫描量热法(DSC)和热重分析(TGA)研究了配合物1~配合物4的热分解过程,并利用DSC研究了配合物1~配合物4对高氯酸铵(AP)热分解的催化作用。结果表明,配合物1~配合物4均具有较高的能量密度,其中配合物2质量能量密度(E_(g))为19.00 kJ/g,体积能量密度(E_(v))为27.18 kJ/cm^(3);4种配合物的摩擦感度值均不小于288 N,撞击感度值均大于40 J。加入质量分数5%催化剂的AP样品高温分解温度均得到提前,放热量均显著提高;其中配合物2表现出最好的催化性能,加入配合物2的AP放热量升高至1564 J/g,分解温度提前了62.0℃,活化能降至142.9 kJ/mol,表明配合物2具有作为固体推进剂含能燃烧催化剂的潜力。