SYNTHESIS OF FUNCTIONAL UNSATURATED POLYESTER BY USING RARE EARTH CATALYSTS 2.TERPOLYMERIZATION OF EPICHLOROHYDRINMALEIC ANHYDRIDE-CARBON DIOXIDE WITH Y(P_(204))_3-Al(i-Bu)_3

Teroolymerization of enichlorohydrin（ECH）-maleic anhydride（MAn）-carbon dioxide（CO;） was carried out by using Y(P;);-Al（i-Bu）;as catalyst for the first time.The terpolymersobtained were characterized by IR and;H-NMR.It was foundthat the composition of the teroolymer was influenced by theaddition mode,initial monomer charge ratio,etc.

POLYMERIZATION MECHANISM OF DIENES WITH HOMOGENEOUS RARE EARTH CATALYSTS

The reaction mechanisms of diene polymerization with homogeneous rare earth catalyst are studied by means of the spectra of ~1H-NMR, one-and two-dimensions ^(13)C-NMR. Based on the data of above NMR spectra, it is proposed that the polymerization reaction proceeds according to the following mechanism: η~4-diene (cis-trans-)and η~3-allyl (syn-anti-).

Research advances of rare earth catalysts for catalytic purification of vehicle exhausts-Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Nowadays,air pollution has become a prominent environmental problem and has attracted much attention.With the increase of vehicle retention quantity,the exhaust emissions have become the main sources of air pollution.To reduce pollution and hazards,vehicle exhaust emission regulations are becoming stricter and stricter,which puts forward higher requirements for purification of vehicle exhausts.At present,rare earths have been widely applied in vehicle exhaust purification because of their good catalytic performance,which is attributed to their unique 4 f electron layer structure occupied without full electrons,excellent oxygen storage/release capacity and redox ability.In this paper,the current status of rare earth catalysts and application of rare earth in different fuel vehicle exhaust catalysts,including three-way catalysts(TWCs)for gasoline vehicles,diesel exhaust catalysts for different pollutants(particulate matter(PM),NOx,CO and HC)and catalysts for new energy vehicles with different fuels,are summarized in detail.Meanwhile,the corresponding mechanisms and the role of rare earth in vehicle exhaust catalysts are also simultaneously described.Furthermore,the challenges and development directions of rare earth catalysts for the purification of vehicle exhausts are also proposed.

Studies on Ring-Opening Polymerization of Chloromethyl Thiirane with Rare Earth Catalysts and Functional Resins Synthesized therewith

Studies on ring-opening polymerization of chloromethyl thiirane with rareearth catalysts and functional resins synthesized therewith were reviewed.

Oxidative Dehydrogenation of Isobutane to Isobutylene over F￣－ Modified Rare Earth Metal Oxide Catalysts

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Copolymerization of Styrene with N-phenylmaleimide by Rare Earth Coordination Catalysts

Copolymerization of styrene (St) with N-phenylmaleimide (NPMI) was studied with rare earth coordination catalyst Nd(naph)3-AlEt3 in toluene. Characterization of the copolymers showed that the copolymers possess an alternating structure.

Rare earth metals modified Ni-S2O8^2-/ZrO2-Al2O3 catalysts for n-pentane isomerization

The effects of adding rare earth(RE) metals,such as Ce,Yb and Pr to Ni-S_2O_8^(2-)/ZrO_2-Al_2O_3(Ni-SZA) on the structure of catalysts as well as their isomerization performance were studied.The prepared catalysts were characterized by XRD,BET,FT-IR,Py-IR,and H_2-TPR,The results showed that the addition of RE metals can increase the strength and amounts of the acid sites,improve the redox properties of catalysts.The Yb-Ni-SZA catalyst showed the best redox properties,which could provide enough metallic sites.In addition,it provided the largest amounts of weak and moderately strong acid sites.Among RE metals modified Ni-SZA catalyst,Yb-Ni-SZA exhibited the highest isopentane yield of 61.7%at 160 °C.The optimum isomerization catalytic performance of the catalysts decreased in the order of Yb-Ni-SZA > Pr-Ni-SZA > Ni-SZA > Ce-Ni-SZA.

COPOLYMERIZATION OF 1-OCTENE WITH STYRENE BY RARE EARTH COORDINATION CATALYSTS

The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10^(-3) L^2/mol^2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR.

POLYMERIZATION OF γ-STEARYL-α,l-GLUTAMATE N-CARBOXYANHYDRIDE USING RARE EARTH COORDINATION CATALYSTS

A rare earth coordination system was first investigated as a new type of catalyst for the ring-openingpolymerization of α-amino acid N-carboxyanhydrides (NCAs). The results for the polymerization of γ-stearyl-α,L-glutamate(SLG) NCA using neodymium acetylacetonate (Nd(acac)_3)- or neodymium tris(2-ethylhexylphosphonate) (Nd(P_(204))_3)-triethylaluminum-water as catalysts were compared with those using conventional catalysts. It was found that the helicalpoly(γ-stearyl-L-glutamate) with high molecular weight as well as narrow molecular weight distribution can be obtained inthe presence of Nd(acac)_3/AlEt_3-1/2H_2O. The polymer obtained was characterized by IR and NMR spectroscopy.

Synthesis of 1-Octene Oligomer by Rare Earth Coordination Catalyst

The polymerization of 1-octene with Nd(P_(204))_3-AlEt_3 catalyst has been successfully carried out for the first time.Some features of polymerization of 1-octene are described.The 1-octene oligomer prepared has an average molecular weight of about 10~3 with molecular weight distribution of about 2.It has a terminal double bond,which can be transferred into terminal carboxy group by direct oxidation with KMnO_4 in acidic solution, and then can be esterified with polyglycol.

Kinetics and Mechanism of Bulk Polymerization of Styrene Catalyzed by Rare Earth Catalyst

The bulk polymerization of styrene catalyzed by Nd(P204)3/MgBu2/HMPA (hexamethyl phospho-ramide) was carried out in capped glass tubes. The effects of reaction conditions on polymerization conversion and molecular weight in the range of high conversion were investigated. The molecular weight of the resultant polymers is dramatically high and its distribution is relatively narrow. The polymerization process demonstrates the feature of living polymerization and auto-acceleration phenomenon. The auto-acceleration phenomenon is attributed to the non-instantaneous formation of the active species. The experimental data suggest that chain transfer to MgBu2 is one of the factors governing the molecular weight development. A mechanism of polymerization is presented with the chain transfer process incorporated.

Synthesis of Polyketone STCO Promoted by Rare Earth Catalyst

To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copolymerization of carbon monoxide （CO） and styrene （ST） to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2＇-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1 ,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectroscopy respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copolymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copolymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/（mol·h）.

Synthesis and Characterization of Poly(isoprene-b-butyl methacrylate) Block Copolymer in the Presence of Rare Earth Catalyst

Poly(isoprene-b-butyl methacrylate) block copolymer with a high molecular weight was synthesized in the presence of rare earth coordination catalyst [RE(P 204 ) 3-Al( i Bu) 3 DBE]. The block copolymer was characterized by means of GPC,IR,DSC,NMR and elemental analysis. The block copolymer prepared has two glass transition temperatures: -75 6 ℃ and 32 2 ℃. The microstructure of the diblock copolymer possessed 96 8% cis 1,4 addition for the isoprene segment and a 70% syndiotacticity for the butyl methacrylate segment.

THE RING-OPENING POLYMERIZATION OF D,L-LACTIDE WITH ONE COMPONENT RARE EARTH CATALYST

(D, L)-Lactide (LA) was first polymerized with one component of rare earth catalysts [Nd(naph)(3), Nd(oct)(3), Nd(O-iPr)(3), Nd(AcAc)(3), Y(AcAc)(3), Sm(AcAc)(3), Er(AcAc)(3))] respectively in solution and in melt state. The effects of [Cat]/[La] molar ratio, solvents, polymerization time, temperature, various rare earth Elements and ligands were investigated in detail. The results showed that both the conversion of polymerization and the molecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higher than that in solution polymerization, but the polymerization rate in melt was lower than in solution. The molecular weight distribution (MWD) of PLA is broader with increasing temperature. X-ray study indicated that PLA obtained by Nd(AcAc)(3) in melt polymerization is an amorphous polymer.

Recovery of rare earths from spent FCC catalysts by solvent extraction using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(EHEHPA)

A process to recover rare earth（RE） metals from spent fluid catalytic cracking（FCC） catalysts by solvent extraction was studied, using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester（EHEHPA or P507）. The recovery process involved three steps：（1） leaching REs（mainly lanthanum and cerium）;（2） solvent extraction by applying saponified P507-kerosene system;（3） stripping. Experiments to assure optimal operating conditions were conducted. Results indicated that RE metals could be recovered effectively from spent catalyst with saponified P507-kerosene-HCl system. At room temperature of 25 oC, 10 g spent catalyst with 110 m L of HCl（1 mol/L） could achieve a leaching efficiency of 85%. For extraction, initial pH value of 3.17, organic/aqueous ratio（O/A ratio） of 2：1 with an extractants＇ saponification rate of 20% could obtain 100% efficiency. In the stripping process, 1 mol/L HCl with O/A ratio of 1：1 led to a stripping efficiency of 96%. In the present study, RE metals from spent FCC catalysts were effectively recovered, which avoided wasting a large amount of RE resources. It provides a theoretical support for commercial recycling of RE resources.

Cu-Mn catalysts modified by rare earth lantnaum for low temperature water-gas shift reaction

The Cu-Mn catalysts doped with different amounts of lanthanum（La） for water-gas shift reaction（WGSR） were prepared, and characterized by X-ray diffraction（XRD）, temperature-programmed reduction（TPR）, temperature-programmed reduction of oxidized surfaces（s-TPR）, temperature-programmed desorption of CO_2（CO_2-TPD）, infrared spectrum（FT-IR） and X-ray photoelectron spectroscopy（XPS）. Catalytic activities were tested for a water-gas shift reaction. The results showed that the introduction of 0.5 mol.% La could significantly improve the catalyst activity for low-temperature shift reaction compared with the undoped catalyst, which might be from the introduction of La making the Cu and Mn components distribute uniformly and the synergistic effect between Cu and Mn increasing the dispersion of Cu on the surface of the catalyst. The apparent CuO phases besides Cu_（1.5）Mn_（1.5）O_4 were found in the samples with at least 3.0 mol.% La content, and the basic sites increased with the increasing of La contents at a decreased rate. With excessive La doping, La particles would aggregate and cover some active sites, resulting in that Mn could not effectively inhibit the gathering together and growing up of Cu crystalline grain, and decreased the dispersion of Cu on the surface, which resulted in the poor activity of the catalyst for WGSR.

Rare Earth Opted as Catalysts for Chinese Vehicles

China plans to implement the automobile exhaust emission regulation formulated with ref-erence to ECE R15.04 by the year of 1998, then the regulation formulated with reference to ECE R83.01 by 2002. To meet the require-ments of the regulations, automobiles should be equipped with three-way catalytic converters. At present, most of the catalysts used on foreign ye-

Effect of doping elements on catalytic performance of CeO_2-ZrO_2 solid solutions

CeZr, CeYZr, LaCeZr, LaCePrZr, LaCePrYZr, and LaCePr solid solutions were prepared via the coprecipitation method, and characterized by means of X-Ray Diffraction （XRD） and Brunauer-Emmett-Teller （BET） techniques. The oxygen storage capacity （OSC） of the solid solutions was evaluated by the pulse technique and the catalytic activity was assessed using a 4-channel catalysis device. It was seen that the solid solutions presented cubic structure. The specific surface area and thermal stability could be enhanced by doping Y into the solid solutions. Doping a small amount of La had a positive effect on the thermal durability while doping a large amount of La decreased the specific surface area and the thermal stability. LaCePrZr and LaCePrYZr solid solutions synthesized using Baotou rare earth mineral residue enriched with LaCePr after Nd extraction presented a certain higher value in specific surface area and thermal stability, thereby enabling to be used as economic catalysts for automobile exhaust purification. Coating Al2O3 or SiO2 layer on the surface of ceria-zirconia solid solutions increased the specific surface area and thermal resistance.

Research on poly(styrene-acrylic acid)-supported neodymium complex in catalytic copolymerization of styrene and 4-vinylpyridine

The catalytic activity of poly（styrene-acrylic acid） （PSAA） supported neodymium chloride （NdCl3） complex for the copolymerization of styrene and 4-Vinylpyridine was studied. The influence of various factors, such as Al/Nd molar ratio, reaction time, macromolecular carder （PSAA）, and ratio of styrene to 4-vinypyridine （g/g）, on the copolymerization yield of styrene and 4-Vinylpyridine was investigated. The results showed that the copolymerization of polar monomers with olefins occurred efficiently and the catalytic activity of polymer-supported catalyst was higher than that of the similar small molecular catalysts. The activity of PSAA.Nd complex increased with in- creasing Al/Nd molar ratios and decreased with increasing polymerization time. The highest activity of PSAA＇Nd was observed at 120 min, and the highest yield was found at the ratio of styrene to 4-vinylpyridine of 4：2. DSC analysis presented that the resulted polymer had only one glass transition temperature, and showed very good thermal stability.