Polymerizations with homogeneous chromium catalysts

Homogeneous catalysts derived from chromium complexes and organo-aluminum compounds have been discovered which effect the polymerization of ethylene and the oligomerization of simple olefins. The applicable chromium derivatives are halide complexes of the type CrX₂L₂, CrX₂L₂(NO)₂, CrX₃L₃, and [CrX₃L₂]₂, wherein the ligands L are pyridine, tri-n-butylphosphine, and the like. The nature of the systems with regard to polymerization or oligomerization has been demonstrated to be primarily a function of the organoaluminum halide cocatalyst and of the reaction conditions. In general, systems containing ethylaluminum dichloride cocatalyst afford simple oligomerization products at reaction temperatures above 50°C, while at lower temperatures those containing organoaluminums of the type R₃Al₂X₃ or R₂AlX effect the polymerization of ethylene as the principal reaction.     

Polymerization of butadiene by neodymium catalysts on oxide supports

The suspension polymerization of butadiene in hexane and toluene in the presence of catalysts composed of organoaluminum compounds and neodymium versatate applied on oxides (Al₂O₃, aluminum silicate A-14, Aerosil A-300, and white soot BS-200) has been studied. Triisobutylaluminum and its combination with ethylaluminum sesquichloride are used as organoaluminum compounds. The activity and stereospecificity of the catalysts has been found to depend strongly on the nature of supports. Catalysts based on Aerosil and white soot appear to be the most active. With the use of these catalysts, polybutadiene containing up to 97.5% 1,4-cis-units has been synthesized.     

Free radical polymerization of methyl methacrylate initiated by the diphosphine Mo(0) complexes

The polymerization of methyl methacrylate MMA catalyzed by [Mo(CO)₄L₂] [L₂ = diphenylphosphinomethane (dppm), diphenylphosphinoethane (dppe) or diphenylphosphinopropane (dppp)] has been studied. The activity of these single‐component catalysts depends on the length of the (CH₂)_n bridge of diphosphine ligand. Thus, the dppm derivative displays higher activity than dppe or dppp ligands. These complexes, as free radical initiators, afforded the methyl methacrylate polymerization in chlorinated solvents. The mechanism of the polymerization was discussed and a radical mechanism was proposed. Copyright © 2006 John Wiley & Sons, Ltd.     

Ethylenebis(5‐chlorosalicylideneiminato)vanadium dichloride immobilized on MgCl2‐based supports as a highly effective precursor for ethylene polymerization

Ethylenebis(5‐chlorosalicylideneiminato)vanadium dichloride supported on MgCl₂(THF)₂ or on the same carrier modified by Et_nAlCl_3?n, where n = 1–3, was used in ethylene polymerization in the presence of MAO or a common alkylaluminium compounds as a cocatalyst. The support type alter vanadium loading and also change the characteristic of the catalytic active sites. Et₂AlCl is the best activator for a catalyst which has been immobilized on a nonmodified support, whereas the systems which contain a carrier which has been modified by an organoaluminium compound reveal the highest activity in conjunction with MAO. That difference, together with different temperature effects on polymerization efficiency (i.e., decrease and increase of catalytic activity for increasing temperatures, respectively) suggest the formation of different types of active sites in the catalytic systems supported on modified and nonmodified magnesium carrier. However, all supported precatalysts possess a long lifetime, still being active towards ethylene polymerization after 2 h. All the systems yield wide MWD polyethylene, while bimodal MWD is found for some part of analyzed samples. Polyethylene with bimodal particle size distribution is formed with the system which contain modified carriers at higher temperatures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3480–3489, 2009     

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     

Synthesis and transformations of metallacycles. 31. Catalysts based on cobalt complexes in reactions of trialkyl- and alkylhaloalanes with olefins,allenes, and acetylenes

Cobalt-containing complexes capable of catalyzing reactions of trialkyl- and alkylhaloalanes (R _n AlCl_3–n ) with olefins, allenes, and acetylenes were synthesized. The reactions afford cyclic and acyclic organoaluminum compounds.     

1,4-<Emphasis Type="Italic">trans</Emphasis>-Polymerization of Dienes: 1. Synthesis of Polybutadiene in the Presence of Mixed Systems Based on VOCl<Subscript>3</Subscript> and Titanium Compounds

Polymerization of butadiene in toluene at 25°C in the presence of catalytic systems based on VOCl₃ and various titanium compounds in combination with Al(i-C₄H₉)₃ is studied. If the organoaluminum compound is added in portions to the VOCl₃-titanium component mixture and the primary suspension of the catalyst is heat-treated, two maxima are observed in the dependence of the activity of the catalytic system on the size of the first Al(i-C₄H₉)₃ portion. The kinetic parameters of the polymerization are determined. The difference in activity between the mixed catalytic systems is due to the difference in structure and reactivity between active sites containing atoms of both transition metals.__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 394–398.Original Russian Text Copyright © 2005 by Mullagaliev, Kharitonova, Monakov.     

Regioselective intermolecular cycloalumination of cyclic allenes and ethylene with R<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>AlCl<Subscript>3−<Emphasis Type="Italic">n</Emphasis></Subscript>, catalyzed by titanium and zirconium complexes

Intermolecular cycloalumiation of cyclic 1,2-dienes and ethylene with organoaluminum compounds R _n AlCl_3−n in the presence of zirconium- and titanium-based catalysts occurred regioselectively with formation of unsaturated bicyclic organoaluminum compounds in high yields.     

Soluble magnesium–titanium catalysts for ethylene polymerization. I

A study has been made of a catalyst system comprising the heptane-soluble magnesium and titanium compounds in combination with an organoaluminum compound for ethylene polymerization at a high temperature. The productivity for ethylene polymerization of the catalyst system, n-butylethyl magnesium (BEM)-2-ethyl hexanol (C₈H₁₇OH)-tetra-n-butoxytitanium[Ti(OBu)₄]/diethyl aluminum chloride (DEAC) is higher than for MgCl₂-Cl₂-C₈H₁₇ OHTi(OBu)₄/DEAC and much higher than MgCl₂-Ti(OBu)₄/DEAC. The nature of the three different catalyst systems have been discussed in comparison with experimental data on polymerization behavior and the data of the elemental and x-ray diffraction analysis of the solid products obtained from the reactions between the catalyst components.     

Salicylaldiminato-based cobalt(III)-, iron(III)-, and chromium(III)/methyl aluminoxane catalyst systems for polymerization of <Emphasis Type="Italic">t</Emphasis>-butyl acrylate

A new series of penta-coordinated Co(III)-, Fe(III)-, and Cr(III)- complexes (6–10) bearing N-salicylidineisopropylaniline and sodium N-(4-sulfonitsalicylidineisopropyl-aniline) ligands has been synthesized and utilized, after activation with methyl aluminoxane, as catalysts for the polymerization of tert-butylacrylate (t-BA). High molar mass P(t-BA) polymers with very low molecular weight distributions were produced (M _w/M _n = 1.06–1.09). Cobalt- and chromium-based precatalysts showed higher activity towards the polymerization reaction than those of the iron complexes. The presence of sulfonated groups on the para position of the aryl group in the backbone of the ligand decreases the catalytic activity of the complexes. The ortho alkyl substituents on the aryl groups of the ligand have a favorable influence on the polymerization activity compared to the alkyl-free analogue (11).     

Bulk propylene polymerization in the presence of ansa-metallocenes of C 2 and C 1 symmetries: From a rigid thermoplastic to elastomeric stereoblock polypropylene

Bulk propylene polymerization in the presence of ansa-metallocenes with C ₂ and C ₁ symmetries has been studied. The catalytic activity, polymerization kinetics, and the molecular weight of polypropylene (PP) depend strongly on catalyst formation conditions. Mixtures of rac and meso isomers of metallocenes make it possible to rapidly produce a high-molecular-weight isotactic PP with high stereoregularity and mechanical characteristics and thus skip the stage of the isolation of pure rac isomer in the catalyst synthesis. The ability of triisobutylaluminum to serve as a cocatalyst is studied for ansa-metallocenes of C ₁ symmetry. In this case, the molecular weight of PP is higher, indicating that organoaluminum compounds participate in chain termination reactions. An increase in the reaction temperature results in an increase in the stereoregularity and crystallinity of PP. Polypropylene synthesized using ansa-metallocenes of C ₁ symmetry has good elastomeric properties.     

High-temperature polymerization of ϵ-caprolactam by using as catalyst the Li,Na, or K salts derived from MAlEt4 or MOAlEt2·AlEt3 and monomer

High-temperature polymerization of ?-caprolactam by using the salts derived from MAlEt₄ (where M is Li, Na, and K) and monomer as catalyst was carried out. Polymerization occurs at 140–170°C, a temperature at which alkali metal caprolactamate has almost no catalytic activity for initiation. m-Cresol-insoluble polymer was obtained at temperatures lower than 231°C. Formation of a m-cresol-insoluble polymer depends on the polymerization temperature and time, and was observed under conditions where Al(Lac)₃ has no catalytic activity. All the polymers obtained by NaAl(Lac)_4–n(NHBu)_n (n = 1 or 2) at 202°C were soluble in m-cresol. These trends observed in the case of MAl(Lac)₄ are considered to be due to initiation by Al(Lac)₃, which is a component of the catalyst used.     

Mixed-ligand Copper(II) Complexes: Investigation of their Spectroscopic, Catalysis, Antimicrobial and Potentiometric Properties

Schiff base ligands HL¹–HL⁶ have been prepared from the reaction of 2,6-diformyl-4-t-butylphenol and 2,6-di-formyl-4-methylphenol with various aromatic amines in ethanolic solution. The Schiff base ligands 2,2′-dipyridine (dp) mixed-ligand Cu^II complexes have been obtained. Mixed-ligand Cu^II complexes containing the dp ligand have ionic nature and they conduct the electricity in solution media. The complexes have been obtained in two different forms: one of them is [Cu₂(Lⁿ)Cl₃] (n: 1, 2, 3, 4, 5 and 6) and other complexes have the general formula [Cu₂(Lⁿ)(dp)₂]3Cl. Ligands and their complexes have been characterized by elemental analyses, FT-IR, electronic spectra, molar conductance, ¹H(¹³C)-n.m.r. and mass spectral data. Their stoichiometric protonation constants have been determined potentiometrically in dioxan using a combined pH electrode at 25 °C, under a nitrogen atmosphere. For the calculation of the protonation constants, PKAS computer programme has been used. The effects of the substituents on the protonation constants and the additivities of these effects are discussed. The antimicrobial activity studies of the ligands and their complexes have been studied against the Bacillus megaterium, Micrococcus luteus, Corynebavterium xenosis, Enterococcuc faecalis, bacteria and Saccoramyces cerevisia, yeast. The catalytic properties of the complexes have been studied on the ascorbic acid, catechol and 2,6-di-t-butylphenol substrates. Thermal behaviour of the complexes has been studied by thermal techniques.     

Immobilization of transition metal ion complexes and their catalytic activity towards the activation of hydrogen peroxide

Transition metal ion-imidazole complexes have been immobilized on silica, silica–alumina (25%Al₂O₃), and alumina supports by adsorption and functionalization methods. The catalytic activity of these supported complexes in the decomposition of H₂O₂ has been studied. The reaction exhibits first-order kinetics with respect to [H₂O₂] and the quantity of catalyst. The rate of reaction decreases as [H₂O₂]₀ increases. The order of catalytic reactivity is strongly dependent on the type of metal ion, support, and the immobilization method. The complex anchored via adsorption exhibited a higher activity compared to the corresponding complex anchored via functionalization of the surface. The reaction proceed via formation of the peroxo-intermediate, which has an inhibiting effect on the reaction rate. The reaction is enthalpy-controlled as is concluded from the isokinetic relationship. A mechanism is proposed involving the generation of HO₂ radicals from the peroxo-intermediate in the rate-determining step.     

Organoaluminum‐mediated polymerization of diazoketones

Polymerization of diazoketones mediated by organoaluminum compounds was investigated. Trialkylaluminum R₃Al (R = iBu, Et, Me) and diisobutylaluminum hydride (DIBAL) polymerized (E)‐1‐diazo‐3‐nonen‐2‐one ( 1 ) to give polymers with M_n = 2000–3500, which contained nearly 33 mol % of azo group (? N?N? ) along with the dominant acylmethylene unit in the main chain. On the other hand, when (E)‐1‐diazo‐4‐phenyl‐3‐buten‐2‐one ( 2 ) was used as a monomer for the organoaluminum‐mediated polymerization, the resulting polymers had ethylidene (? CH[CH₃]? ) units in the main chain along with acylmethylene and azo group, as a result of reductive cleavage of the acyl group during the polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5209–5214, 2007     

Coupled hydrogenation of alkenes and arenes in the presence of catalytic systems based on cobalt Bis(acetylacetonate) and tributylphosphine

The effect of the composition of the catalytic systems based on Co(acac)₂ and tertiary phosphines on the activity and efficiency of cobalt catalysts in the coupled hydrogenation of alkenes and arenes is reported. The process occurs in the presence of cobalt catalysts formed under the action of both organoaluminum compounds and tert-butoxy derivatives of complex aluminum hydrides. NMR and IR spectroscopic methods show that the interaction of the components of the catalytic systems yields mono- and/or trihydrido cobalt phosphine complexes, whose composition depends on the nature of the reducing agent and gas atmosphere. The homogeneous character of the process is hypothesized. The most probable schemes are proposed for the reaction mechanism, according to which the kinetic coupling of alkene (alkadiene) and arene hydrogenations is due to the fact that the reaction proceeds through a σ-alkyl or σ-alkenyl cobalt complex with two phosphorus-containing ligands.     

Catalytic polymerization of ethylene by non-metallocene Zirconium(IV) calix[4] pyrrole complexes

Some zirconium compounds containing chelating diamido dipyrrole or tetra-amido tetra-pyrrole ligands were synthesized and used as polymerization catalyst with high polymerization activity of ethylene at 40 °C and 1 bar, in presence of MAO or B(C₆F₅)₃ as co-catalyst. The maximum catalytic activity reached 1100 Kg/mol bar h for ethylene polymerization by Zr₂(octa-phenyl calix[4]pyrrolidine)Cl₄. These results reveal that half-zirconocene like complexes including four terminal chlorine and one calix[4]pyrrolidine in middle with both π and σ-interaction have the highest ethylene polymerization turnover (compounds 13, 14).     

Effect of Rh(III) and Ru(II) complexes in the polymerization of vinyl monomers initiated by charge transfer mechanism

The initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and methyl acrylate (MA) by a charge transfer complex formed between n-butylamine(nBA) and carbon tetrachloride (CCl₄) in dimethylsulfoxide (DMSO) at 30°C is slow. The effect of the dimethylsulfoxide complexes of Rh(III) and Ru(II) on the polymerization of MMA and MA in the presence of nBA, and CCl₄ in DMSO has been studied. The rate of polymerization and percent conversion of the MMA and MA at 30°C are evaluated at the critical concentration of the metal complexes. At the critical range of the metal complex concentrations, both R_p, and percent conversion of MMA and MA were found to be highest. However, above and below the critical concentrations, R_p and percent conversion of the monomers were found to decrease. A suitable mechanism for the polymerization has been proposed.     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.     

Nitrogen-containing organozinc and organoaluminum as catalyst for stereospecific polymerization of propylene oxide

Catalytic activities of the reaction products of diethylzinc or triethylaluminum with primary amines in the polymerization of propylene oxide were studied. Generally, organozinc compounds give higher ratio of the crystalline to the amorphous polymer than the organoaluminums. In the reactions of organometallic compounds with primary amines, Et₂AlNPhAlEt₂, Et₂AlN-t-BuAlEt₂, EtZnNH-t-Bu, and EtZn-t-BuZnEt were isolated in crystalline state. EtZnN-t-BuZnEt proved to be an excellent catalyst for the stereospecific polymerization of propylene oxide and forms coordination complexes with some electron donors such as dioxane, pyridine, epichlorohydrin and propylene oxide. The propylene oxide complex is unstable in solution and decomposes at temperatures above room temperature to give poly(propylene oxide), while the pyridine complex has no catalytic activity. Therefore, it is concluded that the polymerization of propylene oxide with this catalyst proceeds through the coordination of propylene oxide to the zinc atom of the catalyst.