Copolymerization of ethylene with 1‐hexene over metallocene catalyst supported on complex of magnesium chloride with tetrahydrofuran

The study of ethylene/1‐hexene copolymerization with the zirconocene catalyst, bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂)/methylaluminoxane (MAO), anchored on a MgCl₂(THF)₂ support was carried out. The influence of 1‐hexene concentration in the feed on catalyst productivity and comonomer reactivity as well as other properties was investigated. Additionally, the effect of support modification by the organoaluminum compounds [(MAO, trimethlaluminum (AlMe₃), or diethylaluminum chloride (Et₂AlCl)] on the behavior of the MgCl₂(THF)₂/Cp₂ZrCl₂/MAO catalyst in the copolymerization process and on the properties of the copolymers was explored. Immobilization of the Cp₂ZrCl₂ compound on the complex magnesium support MgCl₂(THF)₂ resulted in an effective system for the copolymerization of ethylene with 1‐hexene. The modification of the support as well as the kind of organoaluminum compound used as a modifier influenced the activity of the examined catalyst system. Additionally, the profitable influence of immobilization of the homogeneous catalyst as well as modification of the support applied on the molecular weight and molecular weight distribution of the copolymers was established. Finally, with the successive self‐nucleation/annealing procedure, the copolymers obtained over both homogeneous and heterogeneous metallocene catalysts were heterogeneous with respect to their chemical composition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2512–2519, 2004     

Effect of the Structure of Selected Metalloporphyrins on their Chromatographic Properties

JPC – Journal of Planar Chromatography – Modern TLC - We have determined the effect of the structure of selected metallo-porphyrins on their chromatographic properties. Separations of...     

Development of a High Performance Liquid Chromatography with Diode Array Detector (HPLC-DAD) Method for Determination of Biogenic Amines in Ripened Cheeses

Biogenic amines (BAs) are organic, basic nitrogenous compounds formed during the decarboxylation of amino acids. A method for the determination of eight biogenic amines (tryptamine, 2-phenyletylamine, putrescine, cadaverine, histamine, tyramine, spermidine, spermine) in ripened cheeses was developed and validated. Cheese samples with the addition of internal standards were extracted with 0.2 M perchloric acid and pre-column derivatized with dansyl chloride at 60 °C for 15 min, purified with toluene and dried under a stream of nitrogen. The samples were analyzed using high performance liquid chromatography with diode array detector (HPLC-DAD). The method was validated with the BAs at three concentration levels: 50, 100, and 200 mg/kg, respectively. The obtained values of correlation coefficient (R²) ranged at 0.9997–0.9998 for all of compounds. The limits of detection (LOD) and quantification (LOQ) were in ranges 1.53–1.88 and 5.13–6.28 mg/kg, respectively. The recovery for all of biogenic amines ranged from 70 to 120% and the precision (RSDr) value were <20%. The validated method was applied to analysis of 35 real ripened cheese samples purchased in Poland.     

Design of advanced multicomponent ferroelectric liquid crystalline mixtures with submicrometre helical pitch

New functional multicomponent ferroelectric liquid crystalline mixtures have been designed while searching smart self-assembling materials with submicrometre periodicity of the helical structure responding definite demands for application in electro-optic devices and photonics that exploit the deformed helix ferroelectric effect. The resulting designed mixtures possess the paraelectric smectic A* and the tilted ferroelectric smectic C* phases over a very broad temperature range down below the room temperature. The mesomorphic, electro-optic and dielectric properties have been studied and discussed. The presence of a very stable enantiotropic ferroelectric smectic phase exhibiting almost temperature independent helical pitch within 150–250 nm range and reasonably high values of the tilt angle might allow these mixtures to be applicable for practical purposes.     

Solvent-dependent resonance Raman spectra of high-valent oxomolybdenum(V) tris[3,5-bis(trifluoromethyl)phenyl]corrolate

UV-visible, infrared (IR), and resonance Raman (RR) spectra were measured and analyzed for a high-valent molybdenum(V)-oxo complex of 5,10,15-tris[3,5-bis(trifluoromethyl)phenyl]corrole (1) at room temperature. The strength of the metal-oxo bond in 1 was found to be strongly solvent-dependent. Solid-state IR and RR spectra of 1 exhibited the MoVO stretching vibration at nu(MoVO)=969 cm(-1). It shifted up by 6 cm(-1) to 975 cm(-1) in n-hexane and then gradually shifted to lower frequencies in more polar solvents, down to 960 cm(-1) in dimethyl sulfoxide. The results imply that stronger acceptor solvents weaken the MoVO bond. The 45-cm(-1) frequency downshifts displayed by 1 containing an 18O label in the molybdenum(V)-oxo unit confirmed the assignments for the observed IR and RR nu(MoVO) bands. The solvent-induced frequency shift for the nu(MoVO) RR band, measured in a series of 25 organic solvents ranging from n-hexane (AN=0.0) to N-methylformamide (AN=32.1), did not decrease in direct proportion to Gutmann's solvent acceptor numbers (ANs). However, a good linear correlation of the nu(MoVO) frequency was found against an empirical "solvent polarity" scale (A+B) of Swain et al. J. Am. Chem. Soc. 1983, 105, 502-513. A molecular association was observed between chloroform and oxomolybdenum(V) corrole 1 through MoO...H/CCl3 hydrogen-bonding interactions. This association manifested itself as a shift of the nu(MoVO) RR band of 1 in CDCl3 to a higher frequency compared to that in CHCl3.     

Azomacrocyclic derivatives of imidazole: synthesis, structure, and metal ion complexation properties

New azocrown ethers comprising imidazoles in the macrocycle have been synthesized. Imidazole, 2-methyl-, 4-methyl-, and 4-phenylimidazole were incorporated to form macrocyclic units by coupling with the appropriate bis-diazonium salts. The syntheses were performed under high dilution conditions. The X-ray structure of a water adduct of the 21-membered crown ether derivative of 4-methylimidazole 8 has been solved. Metal cation binding was investigated with the use of UV-vis spectroscopy in acetonitrile, methanol, and methanol-water mixtures. The obtained chromoionophores were tested as ion-carriers in ion-selective membrane electrodes.     

Spin‐orbit ZORA and four‐component Dirac–Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble gas dimers

Hartree–Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange‐correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin‐orbit zeroth‐order regular approximation Hamiltonian in combination with the large Slater‐type basis set QZ4P as well as with the four‐component Dirac–Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles with noniterative triple excitations [CCSD(T)] calculations using the very large polarization‐consistent basis sets aug‐pcSseg‐4 for He, Ne and Ar, aug‐pcSseg‐3 for Kr, and the AQZP basis set for Xe. For the dimers also, zero‐point vibrational (ZPV) corrections are obtained at the CCSD(T) level with the same basis sets were added. Best estimates of the dimer chemical shifts are generated from these nuclear magnetic shieldings and the relative importance of electron correlation, ZPV, and relativistic corrections for the shieldings and chemical shifts is analyzed. © 2015 Wiley Periodicals, Inc.     

Structure, Conformation, and Stereodynamics of N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes and N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones(1)

The variable temperature (1)H, (13)C, and (19)F NMR spectra were measured for the title N-nitrosamines. The observed unusually low N-N rotation barriers (12-15 kcal/mol) result from a significant deviation of the nitrosamino system from planarity. A pyramidal character of the amino nitrogen was confirmed by the X-ray crystal structures of two compounds and by bathochromic shifts of the n-pi absorption bands in the UV spectra. The nonplanarity of the nitrosamino moiety is due to the strong pseudoallylic A((1,3)) strain caused by the steric interaction of the NNO group with the neighboring aryl substituents fixed in the equatorial positions of the bicyclic skeleton. In addition, the barriers to the C-C rotation of aryl groups were examined at temperatures lower than required to "freeze" the N-N rotation and different DeltaG() values were observed for the aryls oriented syn and anti to the nitroso oxygen.     

Dichlorovanadium (IV) complexes with salen‐type ligands for ethylene polymerization

Vanadium complexes with tetradentate salen‐type ligands were first time explored in ethylene polymerizations. The effects of the vanadium complex structure, the alkyl aluminum cocatalysts type (EtAlCl₂, Et₂AlCl, Et₃Al, and MAO), and the polymerization conditions (Al/V molar ratio, temperature) on polyethylene yield were explored. It was found that EtAlCl₂ in conjunction with investigated vanadium complexes produced the most efficient catalytic systems. It was shown, moreover, that the structural changes of the tetradentate salen ligand (type of bridge which bond donor nitrogen atoms and type of substituent on aryl rings) affected activity of the catalytic system. The complexes containing ligands with cyclohexylene bridges were more active than those with ethylene bridges. Furthermore, the presence of electron‐withdrawing groups at the para position and electron‐donating substituents at the ortho position on the aryl rings of the ligands resulted in improved activity in relation to the systems with no substituents (with the exception of bulky t‐Bu group). The results presented also revealed that all vanadium complexes activated by common organoaluminum compounds gave linear polyethylenes with high melting points (134.8–137.6 °C), high molecular weights, and broad molecular weight distribution. The polymer produced in the presence of MAO possesses clearly lower melting point (131.4 °C) and some side groups (around 9/1000 C). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6940–6949, 2008