Gas-Phase Polymerization with Transition Metal Catalysts Supported on Montmorillonite – A Particle Morphological Study

This investigation focuses on the mechanism of particle fragmentation and growth when clay-supported metallocene catalysts are used to polymerize ethylene in gas-phase reactors. We supported bis(cyclopentadienyl)-zirconium dichloride (Cp₂ZrCl₂) on montmorillonite (MMT) pretreated with triisobutylaluminum and 10-undecence-1-ol to produce in-situ polyethylene-clay nanocomposites. During gas phase polymerization, the MMT layers were exfoliated by the growing polymer chains, starting from the openings of the clay galleries. After microtoming, the cross-section of the fragmented MMT particles showed bundles of distorted silicate layer stacks, proving that exfoliation took place during polymerization, producing an in-situ polyethylene-clay nanocomposite. Calculations of d-spacing by transmission electron microscopy (TEM) matched those measured by X-ray diffraction (XRD) analysis.     

Asymmetric Polymerization of Menthyl Methacrylate by Anionic Catalysts

In this paper,(-) menthyl methacrylate(-) MnMA) was polymerized at -78℃ in toluene with three types of anionic catalysts, which were complexes of fluorenyllithium with (-) sparteine-((-)-Sp),(S,S)-( )-2,3-dimethoxy-1,4-bis(dimethylamino) butane( )DDB) and N,N,N,N′-tetra-methylethylenediamine(TMEDA), and the chiral optical property of the obtained polymer was studied. The circular dichroism (CD) spectrum of the polymer showed negative Cotton effect.     

Catalytic Oxidation of Cyclohexene by Dendrimer-bond Metal Catalysts

Since Tomalia and Dovornic discussed the promising outlook of surface-functionalized dendrimer catalysts in 1994, [1] dendritic catalysts have been proposed to many kinds of catalysis. These well-defined macromolecular structures enable the construction of precisely controlled catalyst structures. The large number of the peripheral functionalities enhanced their activity in many processes. [2,3]We report herein a new method of using the dendritic catalysts in the oxidation of cyclohexene. The…     

High-molecular-weight Polyethylene Prepared with Early Transition Metal Catalysts

Early transition metal catalysts [N,N]MCln, in which [N,N] is N-（2,6-diisopropylphenyl） pyridine-2-carboxaldimine （C18H22N2, NN-1）, N-（2,6-diisopropylphenyl）-6-methylpyridine-2- carboxaldimine （C19H24N2, NN-2）, N-（2,4,6-trimethylphenyl）pyridine-2-carboxaldimine （CIsH16N2, NN-3）, M is Ti, Zr and V, and n is 3 or 4, e.g. [NN-1]TiCh 1a, [NN-1]ZrCh 1b, [NN-1]VC13 1c, [NN-2]TiCh 2a, [NN-2]ZrCh 2b, [NN-2]VC13 2e, [NN-3]TiCh 3a have been investigated to catalyze ethylene polymerization in the presence of methylaluminoxane （MAO）. It was noteworthy that polyethylene characteristic of high molecular weight and wide or bimodal molecular weight distribution was formed with moderate to high activities.     

Lanthanide and Transition Metal Complexes of Dialkyl α-Hydroxyiminophosphonates

Abstract

α-Hydroxyiminophosphonic acid derivatives are widely known not only as intermediates in the synthesis of the important aminophosphonic acids,^1,2 but also as phosphorylating agents,³ potential metalloenzyme inhibitors,⁴ and as compounds having fungicidal activity.⁵ In this work the scope of these compounds has been extended considerably by the synthesis of a number of novel dialkyl derivatives. Novel lanthanide (La^III, Pr^III, Nd^III, Gd^III and Dy^III) and transition metal (Co^II and Ni^III) complexes of dialkyl α-hydroxyiminophosphonates (RO)₂P(O)C(R')N(OH) where R = Et. Prⁱ and R′ = Me, Et have been prepared and the NMR shift properties of the Pr^III complex (R = Et; R′ = Et) indicate the potential of these compounds as NMR shift reagents for the analysis of geometric isomers.^6,7 X-ray crystal structure analysis of [Ni(L¹)₂C1₂] (L¹: R = Et; R′ = Et) shows a distorted cis octahedral coordination at the nickel atom giving two symmetry related diethyl-(E)-α-hydroxyiminopropanephosphonate ligands and two chlorine donors, and those of [Pr(L²)₃Cl₃] and [Nd(L²)₂(NO₃)₃(H₂O)] (L²: R = Prⁱ; R′ = Et) show nine-coordination geometries with asymmetric bidentate and monodentate L² bonding respectively. Thus the metal complexes show unusual coordination ambivalence, changing from symmetrically bidentate to asymmetrically bidentate and then to monodentate bonding modes, to accommodate the different steric requirements of the coordinating anions in facilitating neutral complex formation.     

Catalytic Hydrogenation of Diacetyl Monoxime to Tetramethylpyrazine with the Soluble Transition Metal Catalysts

Tetramethylpyrazine(TMP)isausefulcompoundinfoodindustry'.InrecentyearsithasbeenfoundasanactiveingredientinChuanxi0ng(ligusticumwallichiifranch),whichisatraditionalChineseherb.NowTMPhasbeenwidelyusedinthetreatmentofpatientswithcerebralischemicdiseasesinChina2.OneoftheimportantmethodsforthepreParationoftetramethylpNazineistheselfcondensati0noftwomoleculesof2-aminobutanoneto2,5-dihydrotetramethlipyrazineandsubsequentoxidati0ntoTMP3.2-Aminobutanoneispreparedusuallyinsituviathereductionofthec…     

Transformation of Structure and Properties of Vesicles Induced by Transition Metal Ions

This paper proved that octodecyl propylenediamine could form vesicles in pure water and aqueous solution of CuCl2 or Cu（NO3）2. The structure and morphology of vesicles were different when the copper （Ⅱ） salt was added to the solution. The results showed that both the counterions and the ligands had strong influence on the configuration of coordinated structures and packing model in bilayer membrane of vesicles.     

Ionic Polymerization of α-lsopropyl-a-methylstyrene

The polymerization of p-isopropyl-α-methylstyrene was carried out with anionic and cationic initiators. Polymers prepared in bulk through an anionic mechanism yielded narrowly dispersed products whereas those prepared with sodium-naphthalene complex in solution as well as with cationic initiators gave broad or bimodal distributions when analyzed with gel-permeation chromatography. The presence of microgels was also detected in these latter polymers and has been attributed to chain transfer reactions leading to branching and possibly crosslinking. The comparison of the proportions of different protons in these polymers, as computed from their nuclear magnetic resonance and infrared spectra, with those obtained for a polymer of regular structure suggests that reactions originating from the isopropyl group, along with substitutions on the benzene ring, are responsible for the anomalous structures.     

Anionic Polymerization Behavior of α-Methylene-N-methylpyrrolidone

Anionic polymerization of α-methylene-N-methylpyrrolidone ( MMP ) was carried out in THF at −78∼0 °C with diphenylmethylpotassium (Ph₂CHK) and with diphenylmethyllithium (Ph₂CHLi) in the presence of Lewis acidic diethylzinc (Et₂Zn). Poly( MMP )s possessing predicted molecular weights based on the molar ratios between monomer and initiators and narrow molecular weight distributions (M_w/M_n < 1.1) were obtained in quantitative yields. It was demonstrated that the propagating chain end of poly( MMP ) was stable at −30 °C to form the polymers with well-defined chain structures. From the polymerizations at the various temperatures ranging from −50 to −30 °C, the apparent rate constant and the activation energy of the polymerization were estimated as follows: ln k = −6.93 × 10³/T + 25.7 and 57 ± 5 kJ mol⁻¹, respectively.     

Improving the Catalytic Performance of the Hydrogen Evolution Reaction of α-MoB2 via Rational Doping by Transition Metal Elements

Abundant transition metal borides are emerging as promising electrochemical hydrogen evolution reaction (HER) catalysts which have a potential to substitute noble metals. Those containing graphene-like (flat) boron layers, such as α-MoB2, are particularly promising and their performance can be further enhanced via doping by the second metal. In order to understand intrinsic effect of doping and rationalize selection of dopants, we employ density functional theory (DFT) calculations to study substitutional doping of α-MoB₂ by transition metals as a route towards systematic improvement of intrinsic catalytic activity towards HER. We calculated thermodynamic stability of various transition metal elements to select metals which form a stable ternary phase with α-MoB₂. We inspected surface stability of dopants and assessed catalytic activity of doped surface through hydrogen binding free energy at various hydrogen coverages. We calculated the reaction barriers and pathways for the Tafel step of HER for the most promising dopants. The results highlight iron as the best dopant, simultaneously lowering the reaction barrier of the Tafel step while having suitable thermodynamic stability within MoB₂ lattice.     

Polymerization Mechanism of α-Linear Olefin

The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl₃/AlEt₂Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetryrestrictions for reactants, products, the possible transition states, and intermediates wascalculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes:(i) Coordination compounds were formed on the optimum configuration of TiCl₃/AlEt₂Cl.(ii) The transition states were formed. The energy di?erence between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showedthat the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.     

Synthesis of Titanium–Magnesium Catalysts for Propylene Polymerization: Substitution of Ketones by Dibutyl Phthalate

Kinetics and Catalysis - Titanium-magnesium catalysts (TMCs) of propylene polymerization have been synthesized in the presence of ketones as internal donors. The molar ratio of titanium chloride to...     

Polymerization of Butadiene Using Ziegler-Natta Catalysts—Recent Developments

The products of Ziegler-Natta catalyzed reactions, including high density polyethylene, polypropylene, and other thermoplastics and elastomers, have become familiar to all. While an enormous volume of experimental work was completed during the 1950s and 1960s, it has only been during the 1970s that the multiplicity of mechanistic schemes developed have been subjected to scrutiny. The majority of these have been concerned with polymerization of ethylene and α-olefins and because they have been adequately reviewed recently, are discussed only briefly here. A similarly large volume of empirical experimental work has enabled commercial production of polybutadiene using stereoregular catalysts. However, the mechanisms involved are of recent development, largely due to the additional configurational complexity of products, the multicompound nature of the catalyst complex, and the susceptibility of the system to contamination. Advances which have been made during the last decade are highlighted, with particular emphasis on those modifications to catalyst or to polymer structure which are of practical importance. In Australia, all production of stereoregular (high cis) polybutadiene is achieved using an aluminum alkyl halide-cobalt salt based catalyst. The fundamental technology of this process is discussed with emphasis upon process control. In particular, the control of molecular weight, processing behavior, and reduction in cross-linked material are included in more recent developments. In a broader context, technological changes which have been stimulated by such diverse influences as the increased awareness of industrial hygiene, fluctuations in feedstock availability and cost, and the general acceptance of radial ply tires are discussed. Experimental activities currently in progress in Australia, together with challenges still remaining, are examined.     

Methoxycyclization of 1,5-Enynes by Coinage Metal Catalysts: Is Gold Always Superior?

Au(I) catalysts promote the intramolecular cycloisomerization of 1,n-enynes, as well as facilitate reactions with alcohols, characteristics that have led to their wide-spread in the synthesis of complex natural products. Literature reports of Cu and Ag species catalyzing the same or similar reactions are much less common. Here, we utilize molecular volcano plots to assess the activity of 45 coinage metal phosphine/phosphite catalysts possessing a variety of stereoelectronic properties for the methoxycyclization reaction of a prototypical 1,5-enyne. Our analysis reveals that the intrinsic properties of gold allow it to be coupled with a wide range of ligands, all of which exhibit high catalytic activity. On the other hand, the coupling of silver and copper with more traditional phosphines, such as triphenylphosphine, leads to catalysts with diminished catalytic ability. The activity of Ag and Cu species, however, can be enhanced by appending ligands with strong π-accepting character, which shifts these species closer to the volcano peak.     

Kinetic Study of Cationic Polymerization of α-Methylstyrene Initiated by BuOTICl3 In Dlchloromethane Solution

The cationic polymerization of α-methylstyrene Initiated by n-BuOTiCl₃ has been studied at -70° C in dlchloromethane solution by using a calorlmetric technique. Polymerizations were performed under high vacuum either in dry conditions for which low monomer conversions were observed (4-12%), or In the presence of added cocatalyst (H₂O or HCl). In these last cases, yields were quantitative, and it was shown that polymerization rate was proportional to added water concentration and first order with respect to catalyst and to monomer. A kinetic scheme is proposed, based on a monomer-Independent initiation step and on a unimolecular termination process. At -70° C, the initiation rate is higher than termination rate during the whole course of the polymerization, and the concentration of active centers increases continuously. The following rate constants were found at -70°C: k_i. = 17 ± 6, k = 2.2 ± 1.1 ± 10⁴,k_trm = 30 ± 15 liter/mole-Sec, and k_t =0 54 ± 0 05 sec^?1. At -50 and -30° C, the concentration of active centers goes through a maximum during the polymerization and incomplete monomer conversions were observed, showing that all the catalyst is consumed. The different rate constants were tentatively estimated at these temperatures by using a simulation method, and this led to a negative value of ca. -7 kcal/mole for the apparent activation energy for propagation, and to a value of ～ 5 kcal/ mole for E_i. The observation of a negative (E_p)_app might be explained either by a shift of the dissociation equilibrium of the growing ends or by a solvation process of these growing ends by monomer prior to the propagation step.     

Efficient Addition Polymerization of Norbornene with Polar Norbornene Derivatives by Neutral Nickel(Ⅱ) Catalysts

A series of nickel complexes {4 a: [(2,6-iPr_2C_6H_3)N=CHC_(16)H_(12)O]Ni(Me)(Py), 4b: [(2,6-iPr_2C_6H_2OCH_3)N=CHC_(16)H_(12)O]-Ni(Me)(Py), 4 c: [(2,6-iPr_2C_6H_2Cl)N=CHC_(16)H_(12)O]Ni(Me)(Py), and 4d: [(2,6-iPr2C6H2CF3)N=CHC_(16)H_(12)O]Ni(Me)(Py)} based on β-ketiminato ligands bearing various electron-donating or electron-withdrawing substituents on the para-position of the aniline group were synthesized and unambiguously characterized. The X-ray crystallographic analysis showed that complexes 4 b and 4 d adopted a nearsquare-planar geometry, and the anilines bearing a para-OMe or ―CF_3 group were found to situate on the axial position of the metal center. All complexes exhibited high activities up to 1.25 × 10~7–1.35 × 10~7 g PNB·mol_(Ni)~(–1)·h~(–1) toward norbornene(NBE) addition polymerization(conversion 91.2% in 2 min) under low loading of B(C_6F_5)_3(B/Ni = 3) at 30 °C, affording polymers with high molecular weight up to 2.54 × 10~6–3.18 × 10~6. Different levels of decrease in catalytic activities could be observed for all catalysts as the reaction temperature increased; 4 d bearing a strong electron-withdrawing ―CF_3 group showed the highest activity at 70 °C, while others exhibited notable decrease in catalytic activity with the raise in reaction temperature. Complexes 4 a–4 d showed remarkable tolerance to polar groups and could efficiently promote the copolymerization of NBE with its polar derivatives, including NBE bearing small acetate and hydroxyl group, as well as bulky oligomers, yielding copolymers with high functional NBE incorporations. Novel NBE copolymers with high functional comonomer incorporations and improved solubility were obtained in high yields.     

Synthesis of α-Bromine- Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. Α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93.8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate(MMA) in the presence of copper(Ⅰ) halogen and 2,2-bipyridine(bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1.2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by 1H NMR spectra.     

Recyclable Transition Metal Catalysis using Bipyridine-Functionalized SBA-15 by Co-condensation of Methallylsilane with TEOS

Well-defined recyclable Pd- and Rh-bipyridyl group-impregnated SBA-15 catalysts were prepared for C−C bond coupling reaction and selective hydrogenation reactions, respectively. These SBA-15 derived ligands for the catalysts were prepared by direct and indirect co-condensation method using bipyridyl-linked methallylsilane. This indirect method, involving methoxysilane generated from methallylsilane shows higher loading efficiency of transition metal catalysts on SBA-15 than the direct use of methallylsilane.     

Preparation of Metal Particle Catalysts Wrapped in Organosilicon Compound via Metal Vapor Synthesis

Three kinds of metal catalysts Ni/D_4, Ni-Mn/D_4, Ni-Mn-La/D_4, wrapped in organosilicon compound were prepared by metal vapor synthesis. Their feature was characterized with XRD, TEM, XPS, FMR and static magnetic measurement. The metal particle size in catalysts was less than 3.5 am. The results of XPS showed that the metals in the catalysts existed in zero and other valent state. Inner metal, as an organosilicon compound folded around the metal particle, was protected from oxidation. FMR and static magnetic measuremeat revealed that metal particles were spheroidal and of superparamagnetism. Of all the caralysts the catalytic activity of Ni-Mn-La/D_4 was the highest in hydrogenating furfuraldehyde into furfuralcohol.