Search results for "Metallocene"

Micelle Formation from Amphiphilic“Cylindrical Brush”—Coil Block Copolymers Prepared by Metallocene Catalysis

2004

Thermal behavior of ethylene copolymers with di- and tri-alkenylsilsesquioxane comonomers synthesized by post-metallocene catalysts

2020

AbstractThis paper reported thermal properties of ethylene copolymers with di- and tri-alkenylsilsesquioxanes (POSS) synthesized by bis(phenoxy-imine) Ti, Zr, V, and V salen-type complexes. Ethylene copolymers with multi-alkenyl POSS obtained by such complexes contain multi-alkenyl POSS incorporated into the polymer chain as a side group. They were characterized by different thermal behavior depending on the kind of multi-alkenyl POSS comonomer, and type of the catalyst used, as well as polymerization conditions and thus the structure of the copolymer chain. Ethylene/POSS copolymers differed in incorporation of POSS into the polymer chain, content of specific unsaturation groups, and molecu…

Ethylene/POSS copolymerization behavior of postmetallocene catalysts and copolymer characteristics

2017

Copolymerization of ethylene with iso-butyl substituted monoalkenyl(siloxy)- or monoalkenylsilsesquioxane (POSS) comonomers over bis(phenoxy-imine) and salen-type titanium and zirconium catalysts was studied. It was found that the polyreaction performance was significantly depended by the kind of the catalyst and by the structure and concentration of POSS in the feed. The POSS comonomer was efficiently incorporated into the polymer chain at up to 0.2 mol %. The differences in the copolymer compositions as the functions of the catalyst kind and the POSS comonomer were observed, including the varied number-average sequence length of ethylene and unsaturated end groups, as determined by 1H NMR…

Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex

2006

Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl 2TiCpC5H4(CH2) (3,4ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl − anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substi…

Direct synthesis of fibrous high molecular weight polyethylene using vanadium catalysts supported on an SiO2ionic liquid system

2015

Polyethylene of fibrous morphology was obtained using Cp2VCl2 and VCl2(salenCl2) catalysts activated by AlEt2Cl and AlEtCl2 and heterogenized on a supported ionic liquid system prepared with SiO2 and 1-(3-triethoxysilyl)propyl-3-methylimidazolium chloroaluminate. The fibre length ranges from 15 to 60 µm, depending on the reaction conditions. The polyethylene is characterized by a high molecular weight ((1.1–2.4) × 106 g mol−1) and a narrow molecular weight distribution (1.4–2.5). It is a linear polymer, properly without branching. The DSC method reveals characteristic changes in melting temperature and crystallinity degree between the first and second scan heating cycles (141 °C and 136 °C,…

Copolymers of ethylene with monoalkenyl- and monoalkenyl(siloxy)silsesquioxane (POSS) comonomers – Synthesis and characterization

2017

Abstract The hybrid ethylene/POSS copolymers were obtained using the rac -Et(Ind) 2 ZrCl 2 catalyst activated by MAO. A series of monoalkenyl- and monoalkenyl(siloxy)silsesquioxanes derivatives with different structures of reactive alkenyl substituent and types of non-reactive groups attached to the T 8 POSS cage was used as comonomers. The kind and concentration of the POSS comonomer in the reaction feed as well as extended reaction time were found to strongly influence the catalyst efficiency and incorporation of POSS units into polymer chains. The comonomer reactivity was significantly dependent on the length of the alkenyl reactive substituent in the POSS molecule and it was highest for…

Uranocenium: Synthesis, Structure, and Chemical Bonding

2019

Abstraction of iodide from [(η5 -C5 i Pr5 )2 UI] (1) produced the cationic uranium(III) metallocene [(η5 -C5 i Pr5 )2 U]+ (2) as a salt of [B(C6 F5 )4 ]- . The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non-negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to domin…

Isolation of a perfectly linear uranium(II) metallocene

2020

Reduction of the uranium(III) metallocene [(eta(5)-(C5Pr5)-Pr-i)(2)UI] (1) with potassium graphite produces the "second-generation" uranocene [(eta(5)-(C5Pr5)-Pr-i)(2)U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f(3) 6d(1). Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbi…

Tuning the magnetic properties in the layered molecular based magnets A[FeIIRuxIIIM1−xIII(ox)3] (MIII=Cr or Fe; ox=oxalate; A=organic or organometall…

2001

Abstract The magnetic properties of the family of layered molecular magnets A[FeIIMIII(ox)3] (MIII=Cr, Fe, Ru; ox=oxalate; A+=[NBu4]+, [ CoCp 2 ∗ ] + ) are reported. In particular, a detailed magnetic study of the solid solutions FeII(RuIIICrIII) and FeII(RuIIIFeIII) has been undertaken. We show that in these magnets both, transition temperatures and coercive fields, can be easily tuned by changing the chemical composition of the material, i.e. the ratio RuIII/MIII (MIII=Cr, Fe) within the magnetic layers and the type of cation A+ inserted in between the layers. Coercive fields as high as 2.2 T have been reached in this way.

New concepts in multidentate ligand chemistry: effects of multidentarity on catalytic and spectroscopic properties of ferrocenyl polyphosphines.

2008

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing “through-space” N…