Polymerization of propylene by mixed Ziegler–Natta and metallocene catalysts

The polymerization of propylene using a mixture of racemic metallocenes and Ziegler–Natta catalysts was investigated. The polypropylene was obtained as a mixture of a fine powder and beads, with the powder being absorbed partially on the beads. The relative amount of the powder can be controlled by the concentration of the metallocene. The compatibility between the components of the mixed catalytic systems and the effect of the components on the rate of polymerization and on the properties of the new polymers were studied. The metallocene system dramatically affects the melt viscosity, isotacticity and molecular weight of the polymers. The two catalytic systems are able to act jointly, producing different polymers, for which separate melting and crystallization temperatures are obtained. © 1998 John Wiley & Sons, Ltd.     

Polymerization of propylene by metallocene and Ziegler–Natta mixed catalytic systems. Study of polypropylene properties

Propylene was polymerized with metallocene and Ziegler–Natta mixed-catalytic systems to obtain reactor blends of metallocene and Ziegler–Natta-derived propylene homopolymers. The two catalytic systems are able to act jointly, providing individual polymers with different melting and crystallization temperatures. Compatibility between the components of the mixed-catalytic systems and the influence of the components on the polymerization process and on the properties of the reactor blends were studied. Thermal, mechanical, viscoelastic, rheological, and optical properties of the blends were tested and compared with those of conventional polypropylene grades. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3063–3072, 1998     

Thermoplastic Polymer Shrinkage in Emerging Molding Processes

In this paper, in situ experiments have been designed using the full-field deformation technique of Digital Image Correlation (DIC) to characterize non-uniform shrinkage in thermoplastic polymers commonly used in traditional and emerging molding processes. These experiments are capable of characterizing the differences in strains that develop due to thermal gradients and stiction as the polymer shrinks from the molten to the solid state during molding processes. The experimental set-up consists of simulated open molds, a heating stage, thermocouples for temperature measurements, and a video imaging system for DIC. From these experiments, it has been shown that there is a large increase in shrinkage strain associated with the transition of the polymer from the molten to the solid state in a mold with reduced side rigidity, and as it is cooled below the Vicat softening point. Changing the cooling rate from air-cooled to quasi-steady state can eliminate the transition at the Vicat softening point. Furthermore, substantial decreases in shrinkage strain are observed when the polymer is melted in an open mold without mold release, while using mold release produces results similar to that observed with reduced side rigidity. A simple 1D model reasonably explains and predicts the observed trends in the shrinkage behavior due to temperature differences through the thickness of the polymer melt when using high conductivity molds as well as constraint in the polymer melt near the mold resulting from stiction.     

New Ionic Liquid Compounds Based on Tantalum Pentachloride TaCl5: Synthesis,Structural, and Spectroscopic Elucidation of the (μ‐Oxido)‐Chloridotantalates(V) [BMPy][TaCl6], [BMPy]4[(TaCl6)2(Ta2OCl10)], and [EMIm]2[Ta2OCl10]

1‐Butyl‐4‐methylpyridinium hexachloridotantalate(V), [BMPy][TaCl₆] ( 1 ), tetrakis(1‐butyl‐4‐methylpyridinium) bis(hexachloridotantalate(V) (μ‐oxido)‐decachloridotantalate(V), [BMPy]₄[(TaCl₆)₂(Ta₂OCl₁₀)] ( 2 ), and bis(1‐ethyl‐3‐methylimidazolium)‐(μ‐oxido)‐decachloridoditantalate(V), [EMIm]₂[Ta₂OCl₁₀] ( 3 ) were synthesized and characterized by single‐crystal X‐ray diffraction and vibrational spectroscopy. Compounds 1 and 3 crystallize in the monoclinic space group P2₁/c (no. 14), whereas compound 2 crystallizes in the triclinic space group P (no. 2). All compounds are built up by the mentioned bulky organic cations and octahedral [TaCl₆]^– respective linear [Ta₂OCl₁₀]^2– anions. Coulomb interactions are dominant between the ionic species. FT‐IR and FT‐Raman spectra were recorded and interpreted, especially with respect to the inorganic species [TaCl₆]^– (O_h) and [Ta₂OCl₁₀]^2– (C_i symmetry, approximately D_4h). The melting temperatures of compounds 1 – 3 are given.     

Study of J/psi-->pp[over],LambdaLambda[over] and observation of eta(c)-->LambdaLambda[over] at Belle

We study the baryonic charmonium decays of B mesons B+-->etacK+ and B+-->J/psiK+, where the etac and J/psi subsequently decay into a pp[over] or LambdaLambda[over] pair. We measure the J/psi-->pp[over] and LambdaLambda[over] anisotropy parameters alphaB=-0.60+/-0.13+/-0.14 (pp[over]), -0.44+/-0.51+/-0.31 (LambdaLambda[over ]) and compare to results from e;{+}e;{-}-->J/psi formation experiments. We also report the first observation of etac-->LambdaLambda[over]. The measured branching fraction is B(etac-->LambdaLambda[over ])=(0.87(+0.24)/(-0.21)(stat)(+0.09/-0.14) (syst)+/-0.27(PDG))x10-3. This study is based on a 357 fb-1 data sample recorded on the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e+ e- collider.     

Measurement of the quark mixing parameter cos2phi1 using time-dependent Dalitz analysis of B0 -->D[KS(0)pi + pi-]h0

We present a measurement of the angle phi1 of the Cabibbo-Kobayashi-Maskawa unitarity triangle using a time-dependent Dalitz analysis of D-->KS(0)pi + pi- decays produced in neutral B meson decay to a neutral D meson and a light meson (B0-->D*h0). The method allows a direct extraction of 2phi1 and, therefore, helps to resolve the ambiguity between 2phi1 and pi-2phi1 in the measurement of sin2phi1. We obtain sin2phi1= 0.78 +/- 0.44 +/- 0.22 and cos2varphi1 = 1.87(-0.53-0.32)(+0.40 + 0.22). The sign of cos2phi1 is determined to be positive at 98.3% C.L.     

Oligosilane‐ and Oligosiloxane‐bridged Phosphines – Synthesis,Structures, and Metalation

The range of molecular silicon phosphorus compounds has been extended by some new species containing oligosilane ((R₂Si)_n; n ≥ 2) or oligosiloxane ((R₂SiO)_mSiR₂; m ≥ 1) fragments bound to phosphorus atoms. Primary and secondary compounds of these types allow for the synthesis of metal derivatives. Such metalated species usually form oligomers and exhibit a versatile structural chemistry with cyclic, polycyclic, and cage‐like patterns. The main results obtained in the field of oligosilane‐ and oligosiloxane‐bridged phosphines will be presented below and the structures of the metal derivatives will be discussed. Moreover, the synthesis of an inorganic ligand on the basis of siloxane‐bridged phosphines will be presented. This compound opens up a new chapter in host‐guest chemistry.     

Search for invisible decay of the Upsilon(1S)

We report results of a search for the invisible decay of the Upsilon(1S) via the Upsilon(3S)-->pi+ pi- Upsilon(1S) transition using a data sample of 2.9 fb-1 at the Upsilon(3S) resonance. The data were collected with the Belle detector at the KEKB asymmetric-energy e+ e- collider. No signal is found, and an upper limit for the branching fraction at the 90% confidence level is determined to be B(Upsilon(1S)-->invisible)<2.5 x 10(-3).     

The Combination of 4‐Hydroxythiazoles with Azaheterocycles: Efficient Bidentate Ligands for Novel Ruthenium Complexes

Herein the syntheses of three novel ligands, in which an azaheterocycle is connected with a thiazole subunit: 4‐methoxy‐5‐methyl‐2‐pyridine‐2‐yl‐1,3‐thiazole ( 1 ), 4‐methoxy‐5‐methyl‐2‐pyrimidine‐2‐yl‐1,3‐thiazole ( 2 ) and 4‐methoxy‐5‐phenyl‐2‐pyridine‐2‐yl‐1,3‐thiazole ( 3 ) are reported. Because these ligands are cyclic versions of 1,4‐diazadienes, they offer good prerequisites for the synthesis of metal complexes and were employed as chelating ligands. Three novel heteroleptic cationic complexes of the type Ru(bpy)₂( L ), with bpy = 2,2′‐bipyridine were successfully synthesised. The Ru^II complexes as well as the ligands were characterised by means of mass spectrometry, NMR, UV/Vis and IR spectroscopy and elemental analysis. Furthermore, an X‐ray structure of Ru(bpy)₂ 2 (PF₆), as far as we know the first example where a thiazole is directly connected to a Ru^II core, is presented in this paper.