RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN WITH RARE EARTH-CONTAINED CATALYSTS

Rare earth trifluoroacetates, Ln(CF3CO2)(3) (Ln = thirteen rare earth elements), combined with R(n)AlH(3-n) (R = methyl, octyl, n = 3; R = ethyl, i-Butyl, n = 2, 3) were used as catalysts for the polymerization of tetrahydrofuran (THF). The activity increased by adding propylene oxide (PO), as a promoter, to the polymerization system, producing high molecular weight polytetrahydrofuran (PTHF). The effects of Ln, PO/Ln, and Al/Ln, and others on the polymerization of THF were also studied. (C) 1993 John Wiley & Sons, Inc.

RARE-EARTH ION-SELECTIVE ELECTRODES

In this article, we report the rare earth ion selective electrodes developed in our laboratory. Rare earth containing functional copolymers, rare earth oxides, and chelates have been used as active materials. Methods for preparing raw materials, behavior of electrodes, and application of rare earth ion selective electrodes in flow injection analysis have been discussed as well.

THE SYNTHESES CHARACTERIZATION AND CRYSTAL-STRUCTURE OF RARE-EARTH COMPLEXES WITH L-PROLIN

The complexes of Ln(L-Pro)s(H2O)2(ClO4)3(Ln = Pr, Nd and Er. L-Pro = L-Proline) were synthesized and characterized by elemental analysis, IR. spectra and thermal analysis. The singal crystal Pr2(L-Pro)6(H2O)4(ClO4)6 Was also obtained. The crystal belongs to monoclinic, P2(1), a = 0.9879 (3) nm, b = 2.1883 (4) nm, c = 1.3393 (2)nm, beta = 91.23(2)-degrees, V = 2.895(1) nm3, Z = 2. R = 0.035 for 5032 observed reflections. The coordination polyhedron of Pr(III) ion comprises six oxygen atoms from L-Pro molecules and two water molecules. Each L-Pro molecule coordinates to two Pr(III) ions through its carboxyl group which serves as a bridging bidentate ligand to form onedimensional chain structure.

CRYSTALLIZATION OF RARE-EARTH OXIDE-FILLED POLYPROPYLENE

A study has been made of the crystallization behavior of polypropylene (PP) filled with rare earth oxides under isothermal conditions. These rare earth oxides include lanthanum oxide (La2O3), yttrium oxide (Y2O3), and a mixture of rare earth oxides containing 70% Y2O3 (Y2O3-0.70). A differential scanning calorimeter was used to monitor the energetics of the crystallization process from the melt. During isothermal crystallization, dependence of the relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of any of the three rare earth oxides causes a considerable increase in the overall crystallization rate of PP but does not influence the mechanism of nucleation and growth of the PP crystals. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PP in the composites is due to the decrease in surface energy of the extremity surfaces. The relative contents of the beta-form in the composites are somewhat higher than that in the plain PP. However, the contents of the beta-form in the plain PP and the composites are all very low relative to those of the alpha-form and the influence of the formation of the beta-form on the crystallization kinetics can be neglected.

PHOTOELECTRON-SPECTRA OF VARIOUS CORE LEVELS IN SOME RARE-EARTH N-ACETYLVALINE BIOINORGANIC COMPLEXES

X-ray photoelectron spectra of some bioinorganic complexes of La, Pr, Nd, Sm, and Gd with N-acetylvaline have-been measured. The complex formation does not give any detectable influence on the binding energy of the N 1s peak in the amino group, but has some appreciable effect on the binding energy of the C 1s peak and the O 1s peak in the carboxyl and carbonyl group of the biological ligand. The spin-orbit splitting between the 3d5/2 and 3d3/2 core level of the rare earth ion in these bioinorganic complexes also becomes slightly larger than that of the free rare earth atom due to the effect of the crystal field from the biological ligands.

THERMAL-DECOMPOSITION PROCESS OF SOME RARE-EARTH NITRILOTRIACETIC ACID SERINE MIXED COMPLEXES

Thermal decomposition processes of the mixed complexes of nitrilotriacetates of Pr, Sm, Tb, Ho and Tm with 2-amino-3-hydroxypropionic acid have been investigated. The results indicate that serine may coordinate to the rare earth ion via its hydroxyl group, not by means of its carboxyl group. From the thermogravimetric and the derivative thermogravimetric curves it can be deduced that there may be six or seven steps in the thermal decomposition process of these mixed complexes, and that not all thermal decomposition processes in these mixed complexes are the same. Some possible thermal decomposition reactions have been proposed, and the differences between the thermal decomposition processes of these complexes are also discussed.

A NEW HYDROGEN SENSOR WITH RARE-EARTH COMPLEX FLUORIDE

A new type of solid-state galvanic cell for detecting a small amount of hydrogen in air at room temperature is proposed. The sensor cell is a potentiometric cell using Ce0.95Ca0.05F2.95 as solid-state electrolyte. The cell exhibits good sensing properties to hydrogen in air at room temperature.

STUDY ON COMPLEXES OF RARE-EARTH WITH L-PHENYLALANINE BY POTENTIOMETRY WITH CALORIMETRY

The stability constants and thermodynamic functions for complexes of rare earth with L-phenylalanine have been determined by potentiometry and calorimetry at 25-degrees-C and ionic strength of 0.15mol.dm-3(NaCl). Stability of the complexes shows the "Tetrad effect". The entropy change makes a predominant contribution to the stability of these complexes. The ligand is coordinated to rare earth ions through its -CO2- and -NH2 group, and dehydration of ions plays an important role in coordination reaction.

STUDY ON RARE EARTH-HEDTA-SERINE TERNARY SYSTEM BY POTENTIOMETRY AND FLUORESCENCE SPECTROSCOPY

In this pare earth-HEDTA-serine (Ser) ternary system has been studied by potentiometric titration at 25 degrees C with an ionic strength of 0.15 mol.L-1 (NaCl). The excitation and fluorescence spectra of TbCl3, Tb-Ser, Tb-HEDTA and Tb-HEDTA-Ser have hem determined at room temperature. The stability constants of these ternary complexes have been obtained, It lieu been found that Tb-HEDTA-Ser ternary system exhibit characteriatic fluorescence spectrum of Tb3+ sensitized by two ligands,The results mean that the chemical hood between the control ion and the ligand in this ternary system is predominantly ionic in character,and the energy transfer from ligand to Tb8+ is performed by a kind of abort-range electron exchange action.

XPS STUDY ON RARE-EARTH PHTHALOCYANINE COMPLEXES

The rare earth monophthalocyanine complexes, LnPcCl and LnPc(OAc)2 (Ln = Tb, Ho, Tm, Lu, Pc=Phthalocyanine, OAc = Acetate), were synthesized. The electronic structures of the complexes have been studied by means of XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L-->Ln charge transfer. This L-->Ln charge transfer process of phythalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O1s binding energies of coordinating oxygen atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination number, valence state and so on. Because coordination number of Ln in LnPc(OAc)2 is larger than that in LnPcCl and electronegativity of Clin LnPcCl is larger than that of O in LnPc(OAc)2, the Ln4d5/2 binding energies of LnPc (OAc)2 are less than those of LnPcCl.

DIELS-ALDER REACTION CATALYZED BY RARE-EARTH CHLORIDES

Rare earth chlorides were used to catalyze the synthesis of 2-butoxy-3, 4-dihydro-2H-pyran using equimolar acrolein and vinyl butyl either. The cycloadduct is unstable which undergoes catalytic ring opening oligomerization. The way to stabilize the cyclo adduct has been studied, thus high yields of 90-95% were obtained.