STUDIES ON ORGANO-MOLYBDENUM AND TUNGSTEN COMPOUNDS(Ⅲ)——CATALYTIC POLYMERIZATION OF ACETYLENE BY M-O-C BOND-CONTAINING COMPLEXES OF Mo AND W

Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.

Stabilizing the Extrinsic Porosity in Metal-Organic Cages-Based Supramolecular Framework by In Situ Catalytic Polymerization

Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of guest molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.

Apparent Kinetics of 1-Decene Polymerization Catalyzed Using the Ionic Liquid[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]

Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.

Effect of Clay Minerals on the Chemical Characteristics of Soil Humus

Chemical characteristics of humic substances in soils with different mineralogical characteristics and under different utilization patterns in Zhangpu, Fujian Province,together with two pairs of cultiwted soils in North China Plain were studied by chemical analysis,visible and IR spectroscopy and 13C NMR spectrometry.For soils in Zhangpu the HA/FA ratio and both the aromaticity and the degree of hundfication of HA were higher in soils with montmorillonite as the predominant clay mineral than in thO6e with kaolinite as the predominant clay mineral, provided these soils were under the same utilisstion pattern. While for eaCh pair of soils with similar mineralogical characteristics the HA/FA ratio was higher and the C/H ratio and the content of carboxyl group of HA were lower in paddy soil than in upland soil.Among the upland soils(or paddy soils) studied the HA/FA ratio of soil in Zhangpu with kaollnite as the predominant clay mineral was the lowest,and that of soil in Zhangpu with montmorillonite aa the predominant clay mineral was the highest.It was concluded that the presence of moatmorillonite favored the formation and maturation of humic acid.

Polymer nanoparticles with dendrimer-Ag shell and its application in catalysis

Polymer nanoparticles with dendrimer-Ag shell were prepared and their application in catalytic reduction of 4-nitrophenol （4-NP） was investigated. Cross-linked polystyrene （PS） microspheres were prepared through dispersion copolymerization of styrene, acrylic acid and crosslinking monomer 1, 2- divinylbenzene. PS microspheres with average size of 450 nm and narrow size distribution were used as support for the immobilization of dendrimer-Ag shell, The polyamidoamine （PAMAM） dendrimer shell was successively grafted onto the surface ofPS microspheres through repetitive Michael addition reaction of methyl acrylate （MA） and amidation of the obtained esters with large excess of ethylenediamine （EDA）. Silver nanoparticles were formed directly inside the PAMAM shell through reduction with NaBH4. The resulting PS@PAMAM-Ag nanopartides were packed in a stainless steel column and used successfully for catalytic reduction of 4-NP. This technique for packing catalytic polymer particles in a column could imnrove the efficiency of using the metal catalyst and the tedious seuaration in catalytic reaction.