Recoverable Mn~Ⅲ (salen) supported on diamine modified zirconium poly(styrene-isopropenyl phosphonate)-phosphate as an efficient catalyst for epoxidation of unfunctionalized olefins

Chiral Mn Ⅲ (salen) (Jacobsen’s catalyst) was axially immobilized onto a new type of organic polymer-inorganic hybrid materialzirconium poly(styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA) with different linkage lengths and evaluated as catalysts for the epoxidation of unfunctionalized olefins. The results demonstrated that the prepared catalysts exhibited moderate to good activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the immobilized catalysts were relatively stable and could be conveniently separated from the reaction system by simple precipitation in hexane. Moreover, higher enantioselectivity was obtained with catalyst 2c than that of homogeneous counterpart catalyzed even after eight times. The excellent recycling of the catalyst was attributed to its structure feature of ZPS-IPPA which is different from either pure polystyrene or pure zirconium phosphates.     

Preparation of polystyrene/silica nanocomposites by radical copolymerization of styrene with silica macromonomer

A two-stage process has been developed to generate the silica-based macromonomer through surface-modification of silica with polymerizable vinyl groups. The silica surfaces were treated with excess 2,4-toluene diisocynate (TDI), after which the residual isocyanate groups were converted into polymerizable vinyl groups by reaction with hydroxypropylacrylate (HPA). Thus, polystyrene/silica nanocomposites were prepared by conventional radical copolymerization of styrene with silica macromonomer. The main effecting factors, such as ratios of styrene to the macromonomer, together with polymerization time on the copolymerization were studied in detail. FTIR, DSC and TGA were utilized to characterize the nanocomposites. Experimental results revealed that the silica nanoparticles act as cross-linking points in the polystytene/silica nanocomposites, and the glass transition temperatures of the nanocomposites are higher than that of the corresponding pure polystyrene. The glass transition temperatures of nanocomposites increased with the increasing of silica contents, which were further ascertained by DSC.     

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn（ Ⅱ ） IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.     

POLYMER-SUPPORTED RARE EARTH CATALYSTS FOR STYRENE POLYMERIZATION

The neodymium complex supported on styrene-maleic anhydride copolymer (SMA·Nd) has been prepared for the first time and found to be a highly effective catalyst for the polymerization of styrene. The SMA·Nd polymeric complex is characterized by IR and its catalytic activity, and the polymerization features have been investigated in comparison with that of the conventional Ziegler-Natta catalysts. When [Nd]=1×10~(-3) mol/L, [M]=5mol/L, Al/Nd=170(mol ratio) and CCl_4/Nd=50(mol ratio), the polymerization conversion of styrene gets to 51.6% in six hours, and the catalytic activity reaches 1852 gPS/gNd, which is much higher than that of conventional rare earth catalysts. The polymerization reaction has an induction period and shows some characteristics of chain polymerization. The polymerization rate is the first order with respect to the concentration of styrene monomer. Addition of FeCl_3 does not suppress the polymerization.     

Tungsten Promoted Ni／Al2O3 Catalysts for Carbon Dioxide Reforming of Methane to Synthesis Gas

A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon diox-ide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM,and Laser Raman spectroscopy. It is shown that the addition of tungsten to the nickel catalyst can stabilize the catalyst and increase the resistance to carbon deposition. Adding a suitable amount of tungsten can also increase the catalyst activity to be close to that of supported noble metal catalysts. The carburisation of the tungsten modified nickel catalyst decreases the catalyst activity at lower reaction temperatures (＜1123K),but has no effect on the catalyst performance at higher reaction temperatures. The alumina supported nickel catalyst modified by 0. 67% (mass fraction) WO3 has the equivalent equilibrium constant of the dry reforming reaction to that of alumina supported 5% (mass fraction) Ru at 873 K, and also has a lower activation energy for dry reforming than the latter.     

Synthesis and Application of Novel Chiral Poly-nuclear-Mn(III) Catalysts on Asymmetric Epoxidation of Alkenes.

The interest of the coordination chemistry of manganese has been driver by the important roles of metalloenzymes and highly valuable catalysts in olefin expoxidation.1 Jacobsen Salen-Mn complexes with a simple structure have been commercially utilized to catalyze asymmetric epoxidation of unfunctionalized cis-alkenes2, but the catalytic enantioselectivity for trans-alkenes, unfortunately, are lower and this kinds of complexes are unstable and difficult to be recovered for reuse.3 In order to i…     

Preparation and Catalytic Properties of Polymer-Bound Schiff Base Ternary Complexes

The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L (L = Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phenanthroline (phen), 2,2‘-bipyridyl (bipy) and 8-quinolinol (8HQ). The polymer-bound Schiff base ternary manganese complexes were characterized by means of infrared spectrometry and ICPAES. The catalytic activities of the complexes have been studied in the aerobic epoxidation of long-chain linear aliphatic olefins. It is shown that 1-octene or 1-decene can be directly oxidized by molecular oxygen when catalyzed by PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ), and 1,2-epoxy alkane can be afforded in these reactions.     

SOME PRELIMINARY INFORMATION ON SYNDIOTACTIC POLYSTYRENE CATALYSTS

Syndiotactic specific polymerization of styrene has been investigated by ~(13)C NMR analysis and isotopic laelling methods. The value of the activation energy involved in the steric control has been determined. Some information of the number of the active sites and on the life of the catalysts is reported.     

SYNTHESES, PROPERTIES AND CRYSTAL AND MOLECULAR STRUCTURES OF THE COMPLEXES OF LANTHANIDE THIOCYANATES WITH 1,8-NAPHTHO-16-CROWN-5

Complexes formed from lanthanide thiocyanates (except Pm, Tm and Lu) and 1,8-naphtho-16-crown-5 have been synthesized and characterized by elemental analyses, IR spectra, TG-DTA and electrical conductivity measurements. A single crystal structural analysis for the complex of Er(NCS)_3 with 1,8-naphtho-16-crown-5 has been performed. The result shows that Er(Ⅲ) ion is coordinated simultaneously by five oxygen atoms of the crown ether and three nitrogen atoms of thiocyanates. The coordination number of Er(Ⅲ) ion is eight.     

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.     

Steroid-bismetalloporphyrin as enzyme model of cytochrome P-450 monooxygenase

The model compounds of androgenic steroid-bismetallopor-phyrins 3a-3d and androgenic monometalloporphyrins 2a-2d have been synthesized. Catalytic study in two-phase condition on epoxidation of styrene under the catalysis of model catalysts shows (hat the catalytic performances of steriod-bismet-alloporphyrin is superior to steroid- metalloporphyrin and the corresponding simple metalloporphyrin. The excellent catalytic property of steriod-bismetallopotphyrin can be rationalized as the hydrophobic action of steroid framework and the cooperative action of two metalloporphyrins in catalysis.     

Cobalt supported on CNTs-covered γ-and nano-structured alumina catalysts utilized for wax selective Fischer-Tropsch synthesis

Cobalt supported on carbon nanotubes(CNTs)-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis(FTS).Problems associated with shaping of Co/CNTs into extrudates or pellets as well as catalyst attrition rendered these materials unfavorable for industrial applications.In this investigation regularγ-and nano-structured(N-S)alumina as well as CNTs-covered regularγ-and N-S-alumina supports were impregnated by cobalt nitrate solution to make new cobalt-based catalysts which were also promoted by Ru.The catalysts were characterized and tested in a micro reactor to evaluate their applicability in FTS.γ-Al2O3 was prepared by calcination of bohemite and N-S-Al2O3 was prepared by sol-gel method using aluminum chloride as starting material.Catalyst evaluations indicated that N-S-Al2O3 was superior to regularγ-Al2O3 and that CNTs-covered alumina supports were favored over non-covered ones in terms of activity and heavy hydrocarbon selectivity.These were justified by porosimetric characteristics of the catalysts and existence of CNTs points of view. CNTs-covered catalysts also showed higher wax selectivity and better resistance to deactivation.Furthermore,TPR analysis indicated that the cobalt aluminate phase,which is responsible for the permanent deactivation of alumina supported Co-based catalysts,did not form on alumina supported Co-based catalysts covered with CNTs due to weaker interactions between cobalt and alumina.     

IndTiCl2(OR)/MAO体系催化苯乙烯间规聚合

Since Ishihara et al［1］ reported that a new macromolecule syndiotact ic polystyrene (s-PS) could be produced with high stereoregularity by using ( η5-Cp)TiCl3 activated with methylaluminoxane (MAO), more efforts were de voted to syntheses of new kinds of half-sandwich titanocenes and to elucidation of the relationship of precursor structure to its catalytic behavior［2～4］. The effect of the substituents attached to π-ligand on the styrene polym erization has been discussed［2～4］, but the effect of σ-bonded ligands has not been reported properly.     

Syndiospecific Polymerization of Styrene Catalyzed by IndTiCl2(OR)/Methylaluminoxane System

Since Ishihara et al［1］ reported that a new macromolecule syndiotact ic polystyrene (s-PS) could be produced with high stereoregularity by using ( η5-Cp)TiCl3 activated with methylaluminoxane (MAO), more efforts were de voted to syntheses of new kinds of half-sandwich titanocenes and to elucidation of the relationship of precursor structure to its catalytic behavior［2～4］. The effect of the substituents attached to π-ligand on the styrene polym erization has been discussed［2～4］, but the effect of σ-bonded ligands has not been reported properly.     

HYDROXYLATION OF n-HEXANE CATALYZED BY SUPPORTED Mn (Ⅲ)—PORPHYRIN COMPLEXES

Water-soluble Mn (Ⅲ)-porphyrins supported on various carriers as monooxygenase—like catalysts were used for n—Hexane hydroxylation by PhIO. The hydroxylation yields and XPS measurement of the catalysts indicate that the carriers containing—OH groups have favorable steric and electronic effect on Mn—porphyrins. Some influencing factors and the role of carriers are discussed.     

SYNTHESIS OF POLYMERS CONTAINING N-N LINKAGES

The N-N linkage in hydrazine is thermally stable when it is tetrasubstituted and there are electron-withdrawinggroups attached to the nitrogen atoms. Our research on the synthesis of polymers contaning N--N linkages is reviewed. TheN,N-bisimide structure has been introduced in the backbone of polymers as well as a pendant group in poly(aryl ether)s togive very thermoxidatively stable polymers with very high glass transition temperatures. Most of the polymers form tough,flexible films. N-Aminotriazoles also form stable imides by reaction with anhydrides and these N-imidotriazole groups havebeen introduced as pendent groups on poly(aryl ether)s. The polymers are highly fluorescent materials. Three methods for thesynthesis of polymers containing the tetrasubstituted-azine structure will be discussed: (1) oxidative coupling of bisimines;(2) condensation of bishydrazones with diketones; (3) poly(aryl ether azines) from the azine formed from 4-fluorobenzo-phenone by reaction with salts of bisphenols.     

METATHESIS OF 1-HEXENE OVER MOLYBDENUM AND TUNGSTEN CATALYSTS IMMOBILIZED ON POLYMERS

Molybdenum and tungsten components in catalysts Bu_4N〔Mo(CO)_5Cl〕-EtAlCl_2andWCl_6-Bu_4Sn were immobilized respectively on polymers.The influence of immobilization ofthe soluble catalysts on their catalytic behavior in the metathesis of 1—hexene was investi-gated.It has been found that polystyrene is a good supporting material among all thepolymers tested.The immobilized catalysts have higher stability and better selectivity incomparison with their homogeneous equivalents.The metathesis yield of 1-hexene is in-creased by fourfold with WCl_6immobilized on polystyrene.The reason for the increase ofstability of the immobilized catalyst is discussed.     

Oxidation of Styrene with Molecular Oxygen in Supercritical CO2

The oxidation of styrene with molecular oxygen catalyzed by PdCl2 CuCl2 has been investigated in supercritical CO2 with a batch reactor. The oxidative system of styrene contains four components at the beginning and seven components during the reaction. The critical temperature, critical pressure, and critical density at different conversions are determined by using a high-pressure view cell. The effect of phase behavior on the conversion and selectivity were studied. Experimental results showed that the critical parameters of the reaction mixture at fixed initial molar ratio changed with the conversion of reactant. The conversion of styrene reached maximum near the critical density of the reaction mixture. Product selectivity also varied with density of reaction mixture and could be tuned to some degree.