The effect of macromolecular architecture of ethylene copolymers with multi-alkenylsilsesquioxane on morphological, rheological and dynamic mechanical behavior

Abstract The influence of the degree and the way of incorporation of multi-alkenylsilsesquioxane into the polymer chain on morphological, rheological and dynamic mechanical parameters were determined. It was found that POSS incorporated into the polymer chain was located outside the crystalline structure of lamella in amorphous phase. The incorporation of POSS-6-2 as a pendant group resulted in significant increase of separation of macromolecules. The key factor in rheological and dynamic mechanical behavior of copolymers turned out to be the way of POSS incorporation into the polymer chain. The incorporation of POSS into the polymer chain as a pendant group resulted in decreased relaxation…

Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

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

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…

A supported titanium postmetallocene catalyst: Effect of selected conditions on ethylene polymerization

Ethylene polymerization with a titanium complex [N,N-ethylenebis(3-methoxysalicylideneiminato)titanium dichloride] immobilized on the magnesium support with the formula MgCl2(THF)0.32(Et2AlCl)0.36 was studied. In particular, the effects of polymerization temperature, monomer pressure, and polymerization time on the activity of the catalyst and on the polyethylene properties (molecular weight and its distribution, melting point, crystallinity, and bulk density) were evaluated. The findings of investigations prove that the studied supported titanium catalyst is highly active in ethylene polymerization, and its activity increases with increasing temperature and monomer pressure. Moreover, stab…

Synthesis and catalytic performance in ethylene and 1-octene polymerization of chlorotitanium(IV) silsesquioxane complexes. Effect of increasing ligand denticity and type of nonreactive organic substituents

Abstract The series of titanasilsesquioxanes that differ in a way of binding to the transition metal ( via one, two or three oxygen atoms) and type of nonreactive substituents bonded to inorganic oxygen-silicon cage ( i -Bu, Ph, c -C 6 H 11 ) were prepared by reacting of TiCl 4 with 1 eqv. of the silsesquioxane ligand. Upon treatment with an appropriate cocatalyst, all titanium precatalysts are active in ethylene and 1-octene polymerization and produce from low to high molecular weight polyethylenes and moderately ([ mmmm ] = 44–74%) isotactic poly(1-octene)s. The influence of polymerization parameters, type of cocatalyst and the silsesquioxane structure on the catalytic behavior of the tit…

Triclinic conformational polymorph of N,N,N′,N′-tetrakis(2-cyanoethyl)-1,2-ethylenediamine (TCED)

Abstract The crystal and molecular structures of two polymorphs of N,N,N′,N′-tetrakis(2-cyanoethyl)-1,2-ethylenediamine have been characterized by X-ray diffraction along with density functional theory (DFT) studies. The molecules differ from each other by conformation. N,N,N′,N′-tetrakis(2-cyanoethyl)-1,2-ethylenediamine has been synthesized by cyanoethylation of ethylenediamine. Cyanoethylation of vicinal diamines is important for the synthesis of hyperbranched polymeric materials applied as catalysts, surfactants and encapsulating agents in drug delivery systems. The molecular geometry of N,N,N′,N′-tetracyanoethyl-1,2-ethylenediamine is similar to that of homologous compounds. DFT calcul…

Studies on the microstructure of ethylene/1-hexene copolymers prepared over heterogeneous Ziegler - Natta catalysts

Three MgCl 2(THF) 2-supported, AlEt 2Cl-activated VOCl 3, VCl 4 and TiCl 4 Ziegler - Natta catalysts were used to copolymerize ethylene with 1-hexene in the presence of hydrogen to prepare low-M well-soluble copolymers that could be analyzed by 13C-NMR. The spectra (Fig. 1) showed resonance signals due to ethylene and 1-hexene units in positions unaffected by catalyst type and with intensities related to the degree of comonomer incorporation into the copolymer. The triad sequence distribution and comonomer reactivity ratios (r) were calculated by the Randall method [11] and Bernoulli statistics based on the known copolymer composition. The latter appeared to be the more valid in predicting …

Study and evaluation of dispersion of polyhedral oligomeric silsesquioxane and silica filler in polypropylene composites

Various methods were used for evaluation of homogeneity of polypropylene (PP) matrix composites with octakis([n‐octyl]dimethylsiloxy)octasilsesquioxane, octakis([n‐octadecyl]dimethylsiloxy)octasilsesquioxane, and silica (SiO2) fillers. The filler dispersion was determined on the basis of the results from the wide‐angle X‐ray scattering (WAXS) analysis, from the tests of selected mechanical properties, from scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy and from the decomposable entropic descriptor method. The use of different methods allowed to evaluate homogeneity of PP composites on various levels and with different precisions. The dispersion degree was found…

Effect of a new amido‐imidazolium compound as a clay modifier on properties of polypropylene composites

Halloysite nanotubes (HNT) and montmorillonite (Mt) were modified by a novel, dicarboxylic fatty acid substituted amido-imidazolium chloride. It was found that the modification process of the clays by the imidazolium compound improved their dispersion in the polymer matrix, while HNT were a more beneficial filler of PP than Mt. PP/imidazolium modified HNT composites (PP/HNT-M) showed significant increase in thermo-oxidative stability, flexibility, and toughness, combined with a slight reduction in stiffness, as well as a lack of changes in crystallinity and strength, compared with neat PP. These effects were not observed for PP/Mt composites. The formation of strong interactions between the…

Polymerization of ethylene in the presence of organometallic complexes formed by chloroisopropoxytitanium compounds and sesquiethylchloroaluminium

The catalytic activity of organometallic complexes obtained from chloroisopropoxytitanium compounds and sesquiethylchloroaluminium has been studied. The complexes are active as catalysts for polymerization of ethylene, living high molecular weight product with high output. It is found that the molar ratio of catalyst components affects the output and molecular weight of polyethylene. The optimum molar ratiofor three catalytic systems is given.

Physico-chemical characterization of polyethylenes obtained in the presence of different catalysts containing alkoxyligands

The effect of the kind and number of alkoxy ligands (OR) in organometallic Ti-Al catalyst on the properties of polyethylenes obtained i.e. molecular weight, mechanical and rheological properties, density, crystallinity, melting point, heat of fusion and number of chain branches was studied. Polyethylene obtained over Ti-Al catalyst with OR ligands has particularly high molecular weight, high den­sity, better mechanical properties, higher resistance to heat, different rheological characteristics and lower number ot chain branches in comparison with standard HDPE. It is possible to control the polyethylene synthesis process and to obtain the polymer of required properties by selecting the OR …

Synthesis of oxide-supported vanadium catalysts and their activity in ethylene polymerization

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 (Cp 2 ZrCl 2 )/methylaluminoxane (MAO), anchored on a MgCl 2 (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, trimethylaluminum (AlMe 3 ), or diethylaluminum chloride (Et 2 AlCl)] on the behavior of the MgCl 2 (THF) 2 /Cp 2 ZrCl/MAO catalyst in the copolymerization process and on the properties of the copolymers was explored. Immobilization of the Cp 2 ZrC…

The Formation of Glycerol Oligomers with Two New Types of End Groups in the Presence of a Homogeneous Alkaline Catalyst

The purpose of this work was to synthesize and characterize oligoglycerols with the chains of more than four repeating units. Those oligoglycerols may have some interesting applications, among others, as polyoxyalkylation starters. The glycerol oligomerization process was carried out during 12 h, at 230 &deg

Tri-alkenyl polyhedral oligomeric silsesquioxanes as comonomers and active center modifiers in ethylene copolymerization catalyzed by bis(phenoxy-imine) Ti, Zr, V and V salen-type complexes

Abstract In copolymerization of ethylene (E) with tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) were used bis(phenoxy-imine) titanium, zirconium and vanadium catalysts, as well as salen-type vanadium catalysts. There were obtained copolymers with POSS-R-3 units as side branches of polymer chains. The type of employed bis(phenoxy-imine) titanium, zirconium and vanadium catalysts and salen-type catalyst of vanadium determined the copolymer chain termination reactions, as well as the mechanism of modification of the active species by the POSS-R-3 comonomer. POSS-R-3 comonomers caused selective poisoning of bis(phenoxy-imine) zirconium catalyst and they provided protection against tight …

Thermal stability of ethylene copolymers with multi-alkenylsilsesquioxane comonomers synthesized by organometallic catalyst - Effect of copolymer structure

Abstract This study was focused on thermal properties of ethylene copolymers with di-, tri- and tetra-alkenylsilsesquioxanes (POSS) synthesized by ansa-metallocene complex. Ethylene copolymers with multi-alkenyl POSS were characterized by different thermal behavior depending on the kind of POSS comonomer and its content, as well as the copolymer structure. The copolymers differed in the incorporation way of POSS into the polymer chain (linear and crosslinked structure), content of specific unsaturation groups, molecular weight, as well as heterogeneity of polymer chain compositions. It was found that the kind and content of unsaturation groups in E/POSS copolymers played a significant role …

Ethylene/POSS copolymerization behavior of postmetallocene catalysts and copolymer characteristics

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…

High crystallinity polyethylene obtained in biphasic polymerization using pyridinium chloroaluminate ionic liquid

A series of N-n-alkylpyridinium chloroaluminate ionic liquids [C n -py][AlCl4] (where n-alkyl = n-butyl, n-hexyl, and n-octyl) was applied as a medium of the Cp2TiCl2 catalyst, activated by AlEtCl2 or AlEt2Cl, to evaluate the influence of the studied ionic liquids on the performance of the biphasic ionic liquid/hexane ethylene polymerization and the properties of the produced polyethylene (PE). The best results were obtained using N-n-butylpyridinium chloroaluminate. The polyethylene obtained in the biphasic polymerization have the high crystallinity, which was confirmed by DSC, WAXS and PALS methods, as well as the bulk density comparable to commercial HDPE. These unique properties results…

Conifer Needles as Thermoplastic Composite Fillers: Structure and Properties

This study describes the properties of thermoplastic polymer composites based on polyethylene (of low and high density) and ethylene-propylene copolymers using various types of conifer needles (pine, spruce, fir, and cedar) as fillers. For the needles, thermogravimetric analysis (TGA) and TGA/Fourier transform infrared spectroscopy (TGA/FTIR) were performed to investigate their structures and thermal resistance, as required for the composite processing methods. Moreover, structural differences were studied for the analyzed fillers and composite materials (FTIR). The results were compared with the values obtained for composites with conifer wood flour. Composites with conifer needles (pine) …

Transition metal complexes of tetradentate and bidentate Schiff bases as catalysts for ethylene polymerization: Effect of transition metal and cocatalyst

This article compares catalytic performance of ethylene polymerization in similar polymerization conditions of transition metal complexes having two ligands [O,N] (phenoxy-imine) and having one tetradentate ligand [O,N,N,O] (salphen or salen). It is shown that the activity of both complex types as well as the product properties depend in the same way on the type of central metal in the complex and on the cocatalyst used. Although the type of ligand has some effect on the catalyst activity, yet it does not control the properties of the obtained products. The vanadium and zirconium complexes, irrespective of the cocatalyst used, yield linear polyethylene with high molecular weight (a few hund…

Nature of activating effect of two-step polymerization of propylene

The prepolymerization effect on propylene polymerization in the presence of a TiCl 3 -based catalyst, modified by di-n-buthyl ether, was studied. The influence of prepolymerization on the electron spin resonance spectra and morphology of the catalyst, as well as the properties and the morphology of both prepolymer and regular polymerization products, was investigated. The polymer morphology was evaluated through scanning electron microscopy, polymer bulk density, and particle size distribution. Some evidence of the enhancement effect of prepolymerization on the catalyst activity and stereospecificity was obtained. No influence from prepolymerization was observed on molecular weight and its …

Synthesis and activity of zirconocene catalysts supported on silica-type sol-gel carrier for ethylene polymerization

Synthesis and activity of bis(cyclopentadienyl)zirconium dichloride catalyst supported on unconventional silica-type material obtained in sol-gel process and activated by organoaluminium co-catalyst were studied. The effect of support modification conditions (thermal dehydration and/or modification by organoaluminium compound) and a type of co-catalyst on an activity of the catalytic system in ethylene polymerization and properties of resulting polymers were investigated and compared with results obtained earlier for vanadium catalysts supported on mentioned sol-gel carrier. The most appropriate method of the sol-gel silica-type support preparation is thermal pre-treating (200°C) followed b…

On thermal behaviour of DMC catalysts for ring opening polymerization of epoxides

Abstract The thermoanalytical studies of two types of the double metal cyanide catalysts were carried out. The identity of the catalysts was characterized by an elemental analysis and FTIR. The thermoanalytical examinations performed with the use of TG-DSC, EGA-FTIR, EGA-MS shed new light on views of the bonding of the ligands in the DMC. The chemical justification of the processes responsible for the TG/DSC steps was proposed. Several organic ligand complexing states were found in both types of catalysts. The ligand-DMC bondings were decomposing stepwise in relatively low temperature ranges, which could suggest their negligible role at catalytic reaction being performed usually at higher t…

Sol–gel material as a support of organometallic catalyst for ethylene polymerization

Abstract The sol–gel procedure was applied to obtain powdery materials with different structures and morphology. It was possible to produce almost non-porous silica powder, with an extremely low surface area (ca. 4 m 2 /g) and very high uniformity of spherical particles as well as materials with various uniformity of particles and different porosity, most likely associated with increasing pore volume. Dependent on the properties of the carrier, the resulting supported vanadium catalysts (VOCl 3 /AlEt 2 Cl) showed significant differences concerning activity and stability. It was confirmed that improved hydrophobicity of the carrier’s surface may be useful and improve the activity of the syst…

Investigation of thermal stability of ethylene copolymers with POSS - Study under static and dynamic conditions

Abstract In the paper there was studied thermal stability of a series of ethylene copolymers with monoalkenylsiloxy- or monoalkenylsilsesquioxanes (POSS) under dynamic and static conditions. The copolymers proved to be more thermally stable than neat polyethylene and neat silsesquioxane comonomers. The kind and the content of the POSS units significantly affected degradation of the copolymers. Thermal oxidation process resulted in structural changes of the (co)polymers as it was evidenced by the variations in the kind and content of carbonyl, as well as by unsaturated end groups. Depending on the structure of the POSS comonomer incorporated into the polymer chain, the silsesquioxane units o…

Accelerated laboratory weathering of polypropylene composites filled with synthetic silicon-based compounds

Abstract Non-functionalized and n-alkyl functionalized polyhedral oligomeric silsesquioxanes (POSS), siloxane-silsesquioxane resins and the sol-gel silicas were for the first time examined as possible UV-stabilizers and/or antioxidants in polypropylene (PP). The obtained composites were subjected to the accelerated laboratory weathering tests. The influence of the weathering conditions on the structure and properties of the PP materials was evaluated on the basis of the results from Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) studies. It was found that weathering resistance of the PP materials was strongly de…

Thermal stability and flammability of polyolefin/halloysite nanotubes composites

Najnowsze badania w zakresie uniepalniania poliolefin są ukierunkowane na zastosowanie dodatku nanorurek haloizytowych (HNT) jako bezhalogenowego środka zmniejszającego palność, a jednocześnie zachowującego właściwości mechaniczne osnowy. Powstająca na powierzchni płonącego nanokompozytu, zawierającego HNT, warstwa tzw. zgorzeliny ogranicza przenikanie gazów oraz ciepła i zabezpiecza materiał przed dalszym paleniem. Unikatowa struktura HNT umożliwia dodatkowo pochłanianie produktów termicznego rozkładu poliolefinowej osnowy. Na podstawie dostępnej literatury dokonano oceny wpływu różnych czynników, m.in. modyfikacji nanorurek haloizytowych i/lub dodatku kompatybilizatora i/lub doboru odpowi…

Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties

1-(2-Phenylethyl)-3-methylimidazolium and 1-benzyl-3-methylimidazolium chloroaluminates, [Ph-C2mim][AlCl4] and [Bzlmim][AlCl4], were applied as media of the Cp2TiCl2 catalyst for biphasic ethylene polymerization. The studied aralkyl ionic liquids ensure greater stability of the catalyst at higher temperatures and more regular morphology of the produced polyethylene than analogous 1-n-alkyl-3-methylimidazolium chloroaluminates. The alkylaluminium compound participates in the termination reaction of the polymer chain. The catalyst is stable and enables recycling of the ionic liquid phase in the consecutive polymerization reactions. The [Ph-C2mim][AlCl4] ionic liquid and AlEt2Cl alkylaluminium…

The complementary structural studies of the double metal cyanide type catalysts for the ring opening polymerization of the oxiranes

Thermal Stability and Flame Retardancy of Polypropylene Composites Containing Siloxane-Silsesquioxane Resins

A novel group of silsesquioxane derivatives, which are siloxane-silsesquioxane resins (S4SQ), was for the first time examined as possible flame retardants in polypropylene (PP) materials. Thermal stability of the PP/S4SQ composites compared to the S4SQ resins and neat PP was estimated using thermogravimetric (TG) analysis under nitrogen and in air atmosphere. The effects of the non-functionalized and n-alkyl-functionalized siloxane-silsesquioxane resins on thermostability and flame retardancy of PP materials were also evaluated by thermogravimetry-Fourier transform infrared spectrometry (TG-FTIR) and by cone calorimeter tests. The results revealed that the functionalized S4SQ resins may for…

Polymerization of ethylene by oxide-supported titanium halide catalyst: kinetic model with a deactivation of active species

Abstract The effect of the calcination temperature of alumina, which was then used as a support for a titanium halide catalyst [TiCl4/Et2AlCl], on the catalyst activity in ethylene polymerization was investigated. α-Al2O3 was found to make a more advantageous catalyst support as compared to γ-Al2O3 despite the fact that the former offered a clearly lower specific surface area and its content of surface OH groups was inferior. The ethylene polymerization in the presence of the catalytic system on different alumina supports was investigated on the basis of a proposed kinetic model, taking into consideration the deactivation of active sites in the process. The improved activity was found to re…

Vanadium-based Ziegler-Natta catalyst supported on MgCl2(THF)2 for ethylene polymerization

A supported magnesium‐vanadium‐aluminium catalyst was prepared by depositing –with the use of a milling technique–VOCl3 on the MgCl2(THF)2 support and subsequent activation with diethylaluminium chloride. Catalytic activity of the obtained system for ethylene polymerization was evaluated as a function of Mg/V and Al/V ratios as well as catalyst ageing time and polymerization temperature. High concentrations of THF in the catalytic system and considerable excess of an organoaluminium co‐catalyst were found to have no deactivating action on vanadium active sites. The catalyst obtained is stable and its activity for ethylene polymerization is high. It yields polyethylene with higher molecular …

Study of thermal properties of polyethylene and polypropylene nanocomposites with long alkyl chain-substituted POSS fillers

The effect of incorporation of octakis({alkyl}dimethylsiloxy)octasilsesquioxanes molecules with n-octyl, n-octadecyl and 4-methyl-hexyl substituents on thermal properties of polypropylene (PP), low-density polyethylene (LDPE) and high-density polyethylene (HDPE) was investigated. Thermal properties of those composite materials were evaluated by means of the differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) methods. The type and mass% content of POSS nanofillers influenced the crystallization and melting properties as well as thermal stability of the obtained polyolefin nanocomposites. The incorporated POSS particles—acting as nucleating agents—improved the crystall…

Poliolefiny i woski polietylenowe Cz. I. Właściwości reologiczne

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 li…

Ethylene/1-olefin copolymerization behaviour of vanadium and titanium complexes bearing salen-type ligand

Ethylene/1-olefin copolymerization using vanadium and titanium complexes bearing tetradentate [O,N,N,O]-type ligand and EtAlCl2 or MAO as a cocatalyst is carried out. In the presence of the vanadium complex activated with EtAlCl2 is observed (a) negative “comonomer effect”, (b) high comonomer incorporation and narrow chemical composition distribution (CCD), (c) unexpected copolymer microstructure, and (d) increased molecular weight of copolymers when compared with the homopolymer. In contrast, titanium catalyst gives copolymers with lower 1-olefin content and broad CCD. Supported complexes show higher activity, lower 1-olefins incorporation and give copolymers with ultra high molecular weig…

Studies of structural composition distribution heterogeneity in ethylene/1-hexene copolymers using thermal fractionation technique (SSA)

Abstract Investigations into the compositional heterogeneity of ethylene/1-hexene copolymers obtained with various zirconocene/MAO catalysts, either homogeneous or supported on inorganic carriers such as a complex of magnesium chloride with tetrahydrofuran or methyl alcohol, were conducted. The dependence between metallocene structure, as well as catalyst immobilization, and the compositional heterogeneity of the related products was investigated. It was found that the heterogeneity of copolymers is determined by the metallocene catalyst structure. The amount of peaks on the DSC thermograms of copolymers and their division increase with the increase of bulkiness of the ligand in the catalyt…

Two-step polymerization of propylene over MgCl2-supported titanium catalyst

The prepolymerization effect on propylene polymerization in the presence of a MgCl 2 -supported titanium catalyst was studied. The catalyst was pre-activated by polymerizing a small amount of propylene in the presence of Et 3 Al and cyclohexylmethyldimethoxysilane under mild conditions, and then it was used in a second step of propylene polymerization. Comparative studies of the polymerization process involving the investigated catalyst and its unmodified counterpart showed the rate-enhancement effect of prepolymerization and the same molecular weights, MWD's and isotacticities of the polymers obtained. Concentrations of active sites and propagation rate as well as transfer rate constants w…

Studies of alumina as a support of titanium catalyst for low-pressure ethylene polymerization

The effect of alumina treatment with aqueous solutions of hydrochloric acid and ammonium fluoride as well as temperature of its calcination on the activity of Al-Ti/Al2O3 supported organometallic catalyst for ethylene polymerization has been studied. The dependence between the spe­cific surface area of the support and both the kind and concentration of the modifying agent, concentration of OH-groups on Its surface and concentration of active centres with various activities is discussed with reference to the activity of the supported Al-Ti/Al2O3 catalyst. It was demonstrated that there is no simple relationship between the concentration of OH-groups on the support and the activity of the Ti-…

Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: Effect of metal type and complex immobilization

A series of bis(phenoxy-imine) vanadium and zirconium complexes with different types of R3 substituents at the nitrogen atom, where R3 = phenyl, naphthyl, or anthryl, was synthesized and investigated in ethylene polymerization. Moreover, the catalytic performance was verified for three supported catalysts, which had been obtained by immobilization of bis[N-(salicylidene)-1-naphthylaminato]M(IV) dichloride complexes (M = V, Zr, or Ti) on the magnesium carrier MgCl2(THF)2/Et2AlCl. Catalytic performance of both supported and homogeneous catalysts was verified in conjunction with methylaluminoxane (MAO) or with alkylaluminium compounds (EtnAlCl3−n, n = 1–3). The activity of FI vanadium and zirc…

Effect of Superbasic Ionic Liquids on the Synthesis of Dendritic PolyaminesviaAza-Michael Addition Reaction

Catalytic effect of selected superbasic ionic liquids on the yield and selectivity of aza-Michael addition of ethylenediamine and ammonia to acrylonitrile was investigated. The reactions were performed in calorimetric reactor equipped with RT-IR probe (real-time IR), where all energy changes associated with chemical reactions and physical transformations were monitored. Catalytic activity of selected superbasic ionic liquids in aza-Michael addition ethylenediamine and ammonia to acrylonitrile were determined and obtained polynitriles were then hydrogenatated to final three- and four-directional dendritic polyamines. The products were characterized by instrumental analytical methods, includi…

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

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…

A library of monoalkenylsilsesquioxanes as potential comonomers for synthesis of hybrid materials

In this paper we demonstrate a facile and efficient synthesis of monoalkenylsubstituted POSS compounds, i.e., R7(Si8O12)-alkenyl and R7(Si8O12)(OSiMe2)-alkenyl with a functional alkenyl group of chain length (from vinyl to dec-9-enyl, with or without additional –OSiMe2– spacer between the silsesquioxane core and alkenyl moiety) and with five types of inert groups (Et, iBu, iOc, Cy, Ph) at the POSS core. These compounds constitute a library of monosubstituted POSS systems, including thorough spectroscopic and thermal characteristics. These findings could be especially useful for material chemists applying the compounds as modifiers or comonomers for copolymerization reaction, e.g., with olef…

Influence of accelerated ageing conditions on the process of polyolefines degradation

The process of polymers weathering and the methods of polymers weathering and accelerated ageing investigations were characterized. Accelerated ageing tests of polyethylene and polypropylene samples have been done in laboratory conditions. The ageing time (up to 400 h) influence, at various levels of ageing factors: UV radiation intensity (80—190 W/m2), temperature (35—55 °C) and humidity (30—90%), on the changes of the structures of polymers investigated (shares of carbonyl and olefinic groups from FT-IR spectra — Fig. 1, 2, 4 and 5), on the changes of polymers molecular weights (Fig. 3 and 6, Table 1) and on the changes of mechanical properties during tension (Table 1) has been investigat…

Titanium-aluminium catalysts with alkoxy ligands supported on aluminium oxide for ethylene polymerization

Activity of a model titanium-aluminium catalyst system with n-BuO-ligands has been investigated in the polymerization of ethylene. The effect of the concentration of titanium compound on the support, the Al/Ti molar ratio, and catalyst concentration in the polymerization process on polyethylene yield has been determined. A mathematical optimation method has been used for the interpretation of results. The intervals of the optimum parameters of catalyst synthesis have been established, to obtain catalyst with a high activity in low-pressure ethylene polymerization. These specified optimum parameters have been applied in the subsequent synthesis of similar catalytic systems, differing in the …

Synthesis and characterization of ethylene-1-hexene copolymers prepared by using MgCl2(THF)2-supported Ziegler-Natta catalysts

Ethylene was copolymerized with 1-hexene over vanadium (VOCl3 and VCl4) and titanium (TiCl4) catalysts supported on MgCl2(THF)2 and activated with Et2AlCl. So far these catalyst systems have not been known as initiators of ethylene-1-hexene copolymerization. The vanadium catalysts were more active than the titanium catalyst and, at identical comonomer concentrations in the feed, gave rise to a greater incorporation of 1-hexene into the copolymer. Even at relatively low fractions of 1-hexene, the MgCl2(THF)2-supported catalysts affected much the copolymer properties like density, melting point and crystallinity.

Effect of silica-type sol–gel carrier’s structure and morphology on a supported Ziegler–Natta catalyst for ethylene polymerization

Abstract Silica xerogels with different structures and morphology, synthesized using a sol–gel procedure, were used as a carrier of vanadium catalysts (VOCl 3 /AlEt 2 Cl) for ethylene polymerization. Two techniques of catalyst synthesis were applied: slurry impregnation and gas-phase adsorption and the relevant polymerization methods were then employed. The effect of the carrier structure and morphology on the vanadium loading in the catalysts, the catalyst’s activity and kinetic stability were investigated.

(Co)polymerisation Behaviour of Supported Metallocene Catalysts: Carrier Effect

The polymerisation and copolymerisation of ethylene with 1-hexene over metallocene catalysts L 2 ZrCl 2 / MAO (L = Cp, n-BuCp, t-BuCp, i-PrCp, Me 5 Cp) supported on different types of carriers (MgCl 2 (MeOH) 6 or silica with CH 3 surface groups obtained in the sol-gel process) were studied. It was demonstrated that both the metallocene structure and the type of inorganic support affected catalyst activity and polymer properties such as melting point, molecular weight and molecular weight distribution. The metallocene structure also determined comonomer incorporation, both for homogeneous and supported catalytic systems. When a catalyst is anchored on a support, it becomes less effective at …

Synthesis of Ultra-High-Molecular-Weight Polyethylene

The catalytic activity of organometallic Ti-Al complexes with donor ligands in the low-pressure polymerization of ethylene was studied. These complexes were obtained by the reaction of ethylaluminium compounds like AlEt2Cl or Al2Et3Cl3 and titanium compound of the type Ti(OR)nCl4-n (where: R = C2—C10 alkyl, C6H5, C6H4X; X — m-CH3, p-CH3, m-OCH3, p-OCH3, m-Cl, p-Cl, p-Br; n = 1—4). The optimum conditions for the synthesis of these compounds, as well as their physico-chemical properties were studied by means of EPR and polarographic methods. The effect of the type and number of OR ligands in a catalytic system on the yield of polyethylene and on its properties was examined. Ti-Al catalysts wi…

Weathering of low-density polyethylene grafted with itaconic acid in laboratory tests

Polyethylene grafted with itaconic acid was subjected to weathering under laboratory accelerated conditions. The course of the photo-oxidative degradation process of that material was studied by FTIR spectroscopy both through quantitative measurements of changes in absorbance values at selected wave numbers and through measurements of surface area values for absorption bands which were separated by means of deconvolution. The use of both those procedures of quantitative determinations resulted in a general conclusion that the oxidation process was initiated from the very first moment of irradiation, and it produced ketones, acids, esters (intramolecular and of acetate type), peracids, peres…

Fast-growing willow (Salix viminalis) as a filler in polyethylene composites

Abstract The study investigated the possibility of using wood flour obtained from fast-growing willow chips (Salix viminalis) as an alternative for standard hard- and softwood flours used in the production of wood polymer composites (WPCs). The composites contained willow flour and polyethylene matrix (OPCs) were prepared, characterized and compared with other WPCs which had been filled with hard- or softwood flours. Moreover, the structural and functional properties were investigated and discussed. Greater hemicellulose contents and lower lignin contents in OPCs resulted in better impact strength values of those materials. Which is interesting, the chemical composition of OPCs was found si…

Effect of hydrogen on the ethylene polymerization process over Ziegler-Natta catalysts supported on MgCl2(THF)2. I. Studies of the chain-transfer reaction

The effect of hydrogen on the molecular weight of polyethylene obtained over vanadium catalysts (based on VCl4 and VOCl3) supported on MgCl2(THF)2 was studied and the results were compared to those obtained for similar titanium catalysts. It was confirmed that the dependencies of the transfer reaction on the hydrogen concentration are a half-order in all investigated systems. However, the transition metal of the catalytic site affects the ratio of the transfer rate with hydrogen to the propagation rate (ktr,H/kp) and the results showed that hydrogen is a more effective agent of polyethylene molecular weight control in vanadium-based systems as compared to the titanium catalyst. © 2000 John …

Optimization of synthesis of a titaniumcatalyst supported on alumina for synthesis of ultra-high molecular-weightpolyethylene (UHMWPE)

Ethylene polymerized under low pressure over a catalytic system (modified Аl2Оз/ТlСl4 + AlEt2Cl) yields UHMWPE. Alumina gel chlorinated and calcined (above 773 K) was used as a catalyst carrier. The effect of the main variables of carrier chlorination (concentration of HCl, chlorination time and temperature) and of the calcination temperature on activity of the catalytic system was investigated. A mathematical method of planning experiments and evaluating experimental results was used in order to improve both the analysis of the conditions of the preliminary modification of the support and their optimization. Relationships between the surface properties of the alumina carrier and the activi…

Polyolefin-matrix composites with modified halloysite nanotubes

Przeprowadzono badania wybranych mechanicznych oraz przetwórczych właściwości kompozytów na osnowie wybranych poliolefin (polietylenu małej i dużej gęstości oraz polipropylenu) napełnionych nanorurkami haloizytowymi modyfikowanymi mleczanem dialkilodiamidoaminy wytworzonym na bazie surowców pochodzenia naturalnego. Zawartość haloizytu w kompozytach wynosiła 5% mas. Kompozyty wykazywały korzystniejsze właściwości wytrzymałościowe (wytrzymałość na zerwanie, wydłużenie względne przy zerwaniu, udarność) i przetwórcze (wskaźnik szybkości płynięcia) w porównaniu z kompozytami z niemodyfikowanymi nanorurkami haloizytowymi oraz nienapełnionymi poliolefinami.

Synthesis and structural characterization of ethylene copolymers containing double-decker silsesquioxane as pendant groups and cross-linkage sites by coordinative copolymerization

Abstract The copolymers of ethylene with the double-decker silsesquioxane (DDSQ) were synthesized by copolymerization with the use of metallocene and bis(phenoxy-imine) catalysts. The influence of the kind of the catalyst and polyreaction conditions on the performance of copolymerization as well as on the properties of the copolymers was studied. Depending on polyreaction parameters, the DDSQ contents in the copolymer varied in the range of 0.93–11.53 wt% which determined the compositions and the structural properties of copolymers. DDSQ incorporated into the polymer chain could constitute pendant groups in the main chain or it could act as a cross-linking agent. The ethylene/DDSQ copolymer…

The effect of the comonomer on the copolymerization of ethylene with long chain α-olefins using Ziegler–Natta catalysts supported on MgCl2(THF)2

Abstract The effect of the type of the comonomer (1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene) on the copolymerization of ethylene with α-olefin over vanadium (VOCl3 and VCl4) and titanium (TiCl4) catalysts supported on MgCl2(THF)2 and activated by Et2AlCl was studied. The results show that the introduction of a longer α-olefin in the ethylene polymerization feed depresses the catalytic activity of all investigated catalysts. The catalyst activity does not depend on the type of the comonomer applied but changes with the comonomer concentration in the feed. The incorporation of α-olefin in the polymer chain was found to be dependent on the type and concentration of the comonomer i…

Microstructure of ethylene-1-hexene and ethylene-1-octene copolymers obtained over Ziegler–Natta catalysts supported on MgCl 2 (THF) 2

Abstract The ethylene copolymerizations with 1-hexene or 1-octene in the presence of hydrogen using three catalysts, MgCl 2 (THF) 2 /VOCl 3 /Et 2 AlCl, MgCl 2 (THF) 2 /VCl 4 /Et 2 AlCl, MgCl 2 (THF) 2 /TiCl 4 /Et 2 AlCl, were investigated. It was found that the addition of hydrogen into the copolymerization feed reduces the molecular weight of the copolymers produced and decreases the activity of all the studied catalysts. The microstructure of the copolymers obtained was determined on the basis of 13 C NMR investigations and the reactivity ratios of the comonomers were calculated. The lack of tendency of the olefin comonomers to the creation of the polymer block was confirmed. It was found…

Organometallic vanadium‐based heterogeneous catalysts for ethylene polymerization. Study of the deactivation process

Slurry polymerizations of ethylene over vanadium catalysts (based on VCl4 and VOCl3) and their MgCl2(THF)2-supported equivalents were studied. Unsupported vanadium catalysts were found to be unstable while the vanadium active sites deposited on the MgCl2(THF)2 complex are stable. A sharply outlined correlation was found between the concentration of vanadium(III) and catalyst productivity. The high activity and stability of the vanadium catalyst when supported on the magnesium complex is attributed to the increase of resistance to reduction of active vanadium(III) to inactive vanadium(II) by an organoaluminium co-catalyst.

Halloysite nanotubes as polyolefin fillers

Artykuł stanowi przegląd najnowszej literatury dotyczącej nanokompozytów poliolefinowych napełnianych nanorurkami haloizytowymi (HNT). Omówiono wpływ dodatku HNT na osnowę poliolefinową, ze szczególnym uwzględnieniem morfologii oraz właściwości mechanicznych nanokompozytów poliolefina/HNT. Modyfikowane HNT wykazywały wysoki stopień rozproszenia w osnowie poliolefinowej, dzięki czemu powodowały poprawę właściwości mechanicznych poliolefinowych nanokompozytów napełnianych nanorurkami haloizytowymi. Połączenie korzystnych właściwości poliolefin, ekonomicznych metod ich przetwórstwa oraz unikatowych w³aoeciwooeci HNT pozwoli na szersze rozpowszechnienie nanokompozytów wytworzonych z ich udziałe…

Effect of hydrogen on the ethylene polymerization process over Ziegler-Natta catalysts supported on MgCl2(THF)2. II. Kinetic studies

This article reports on a study of the effects of hydrogen on the activity of vanadium and titanium catalysts supported on MgCl 2 (THF) 2 in ethylene polymerization. It was found that hydrogen did not change the stable nature of the active sites and the polydispersity index of the polyethylene obtained. The propagation rate, expressed as k p , was found to be independent of the presence and concentration of hydrogen, indicating that this reacting agent does not modify the reactivity of the active sites. However, the presence of hydrogen in the polymerization medium is responsible for partial deactivation of the active sites just before polymerization is initiated.

Kinetic studies of two-step polymerization of propylene over a titanium-aluminum catalyst

The influence was studied of the modification of an unsupported titanium-aluminum catalytic system with an internal Lewis base incorporated, via prepolymerization, on the activity of this system in propylene polymerization. In order to clarify the reasons for the activating effect of prepolymerization, comparative studies were carried out on the kinetics of polymerization catalyzed by a titanium system and its prepolymerized counter part. Based on the kinetic model suggested for the polymerization mechanism, the concentration of active sites and rate constants were determined for chain propagation, chain transfer and termination reactions. The following conclusions were deduced: (i) the ini…

Evaluation of wood-polyethylene composites biodegradability caused by filamentous fungi

Abstract This study describes the impact of filamentous fungi on wood-polymer composites (WPCs) containing various types of fillers (coniferous, deciduous, cellulose) in the amount of 30 wt.% to 50 wt.%. The selection of fungal strain of filamentous fungi was performed prior to the study on the impact of the wood type on the progress of WPCs biodegradability. The changes associated with various water absorption of the examined WPCs, were observed using scanning electron microscopy (SEM). The impact of fungal mycelium, which had affected the changes in WPCs material, was examined using thermogravimetric analysis (TG). The results showed, that the growth of mycelium on WPCs, influenced mainly…

Polyethylene composites filled with n‐alkyl‐functionalized siloxane‐silsesquioxane resins and sol‐gel silicas

High‐density polyethylene (HDPE) composites filled with silicon‐based fillers were prepared by melt blending. The use of non‐functionalized and n‐octyl‐functionalized siloxane‐silsesquioxane resins and the sol‐gel silicas as fillers allowed us to evaluate the influence of functionalization of the fillers on the properties of the composites. The melting and crystallization temperatures of the composites were found to be only slightly affected by the addition of the silicon‐based fillers. In turn, the crystallization degree values were increased, in particular for the materials containing non‐functionalized fillers. The free‐volume properties of the composites did not change significantly in …

Polypropylene/polyhedral oligomeric silsesquioxane nanocomposites – study of free volumes, crystallinity degree and mass flow rate

Nanokompozyty polipropylen/poliedryczne oligomeryczne silseskwioksany (PP/POSS) przygotowano metodą mieszania w stanie stopionym polimeru. Wpływ struktury oraz ilości zastosowanych nanonapełniaczy POSS na objętości swobodne w polipropylenie określono z zastosowaniem spektroskopii czasów życia pozytonów (PALS). Ustalono zależności pomiędzy parametrami PALS: czasem życia o-Ps (τ3) i natężeniem (I3) składowej o-Ps oraz wartościami stopnia krystaliczności (Xc ) i masowego wskaźnika szybkości płynięcia (MFR) badanych materiałów. Obecność nanonapełniaczy POSS wpłynęła na liczbę i rozmiary objętości swobodnych w polimerze, co spowodowało zmianę mikrostruktury osnowy polipropylenowej. Wraz ze zwięk…

Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene.

The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization par…

Synthesis and activity of zirconocene catalysts supported on silica-type sol-gel carrier for ethylene polymerization

Synthesis and activity of bis(cyclopentadienyl)zirconium dichloride catalyst supported on unconventional silica-type material obtained in sol-gel process and activated by organoaluminium co-catalyst were studied. The effect of support modification conditions (thermal dehydration and/or modification by organoaluminium compound) and a type of co-catalyst on an activity of the catalytic system in ethylene polymerization and properties of resulting polymers were investigated and compared with results obtained earlier for vanadium catalysts supported on mentioned sol-gel carrier. The most appropriate method of the sol-gel silica-type support preparation is thermal pre-treating (200°C) followed b…

Characterization of a Double Metal Cyanide (DMC)-Type Catalyst in the Polyoxypropylation Process: Effects of Catalyst Concentration

The alkaline catalysts commonly applied to alkoxylation are characterized by a limited spectrum of activity caused by an irreversible termination of the polyether chains. The presented results show that double metal cyanide (DMC) catalysts reduce or eliminate the aforementioned adverse rearrangement of hydroxyl groups. Moreover, DMC catalysts indicate high activity at low concentrations (ppm range), as expressed by high polymerization rates. It was demonstrated that decreased concentrations of DMC catalyst irreversibly influence its reactivity and the dispersity of the obtained products, as exemplified by the production and determination of selected polyoxypropylenediols at different concen…

Resistance of Conifer Needle Polyolefin Composites (CNPCs) Against Biodecomposition Caused by Fungi

This study describes the resistance of composites filled with conifer needles to biodecomposition processes caused by a single strain of Aspergillus niger as well as by a consortium of microorganisms present in the compost substrates (forest or spent mushroom composts). The impact of various types of conifer needles on the growth of A. niger was studied to determine whether the filler can show the fungistatic effect. The changes in chemical composition of the composites surfaces were examined using attenuated total reflectance Fourier transform infrared spectroscopy (FTIR/ATR). The results showed that the fungistatic effects of conifer needles polyolefin composites (CNPCs) were associated w…

Functionalized siloxane‐silsesquioxane resins and polypropylene‐based composites: Morphological, structural, thermal, and mechanical properties

Non‐functionalized and n‐alkyl‐functionalized siloxane‐silsesquioxane resins (S4SQ) were synthesized and characterized to confirm their structure and properties. Polypropylene (PP) composites with S4SQ resins as fillers were prepared by the melt blending. The influence of the kinds and amounts of fillers on the structural, morphological and thermal properties as well as mechanical characteristics and processability was determined. High compatibility of composites with functionalized resins resulted in more homogenous dispersion of filler particles in comparison with the composites which contained a non‐functionalized resin. Moreover, the introduction of S4SQ resins into PP strongly affected…

The effect of prepolymerization of a titanium catalyst on its deactivation in propylene polymerization

Propylene polymerization rate was investigated in the presence of anunsupported titanium catalyst (TiCl3) that had been modified with a Lewis base (di-n-butyl ether) and activated (precat), or not activated (cat), by being used in a suspension prepolymerization (70°C, 0.6 MPa) of an identical monomer. The initial polymerization rate was higher with the precat than with the cat catalyst. Prepolymerization was also found to enhance the kinetic stability of catalyst's active sites, presumably by reason of the prepolymerization-induced modification of catalyst's morphology. Deactivation rate constants were evaluated for the active sites of either catalyst examined.

Study of polyethylene nanocomposites with polyhedral oligomeric silsesquioxane nanofillers—from structural characteristics to mechanical properties and processability

High-density polyethylene (HDPE) and low-density polyethylene (LDPE) nanocomposites filled with octakis({alkyl}dimethylsiloxy)octasilsesquioxanes (POSS) were prepared by the melt blending method. The effects of the structure and the content of POSS nanofillers on free-volume properties and structural characteristics of nanocomposites were investigated by the positron annihilation lifetime spectroscopy (PALS) and X-ray diffraction methods: wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Incorporation of POSS nanofillers into polyethylene matrices modified the arrangement of the polymer chains and affected the size and number of free-volume holes in nanocomposites.…

(Co)polymerization behavior of supported metallocene catalysts. I. Ligand and substituent effect

Ethylene polymerization and its copolymerization with 1-hexene with a set of supported metallocene catalysts were studied. As a carrier, the complex of mag- nesium chloride with tetrahydrofuran, which was previously pretreated with a triiso- butylaluminium (TIBA), was used. The investigated metallocene compound differs in the metal type (Zr or Ti), the nature of the alkyl substituent in the cyclopentadienyl ring, and the type of ligand (Cp or Ind). The effect of catalyst composition on the anchored metal content, catalyst activity, comonomer reactivity, and polymer proper- ties was investigated. The results obtained with supported catalysts were compared with those obtained with their homog…

Studies on electron-beam irradiation and plastic deformation of medical-grade ultra-high molecular weight polyethylene

Abstract Separated and combined electron-beam irradiation and plastic deformation effects on the structures of ultra-high molecular weight polyethylene (UHMWPE) were studied. It was found that the concentration of carbonyl (ketones, esters and peresters), hydroxyl and vinyl groups increases with the growing dose of adsorbed electrons. It also tends to exhibit a slight increase in the melting point and crystallinity of the samples. A mechanical stress in the polymer was found to accelerate radiation-induced degradation. It was concluded that each of the factors studied (i.e. electron beam sterilization and plastic deformation) had a different impact on the polymer structure. The change in th…

CCDC 1528272: Experimental Crystal Structure Determination

Related Article: Bartłomiej Bereska, Krystyna Czaja, Krzysztof Ejsmont, Błażej Dziuk, Bartosz Zarychta, Jolanta Iłowska, Michał Szmatoła, Agnieszka Bereska|2018|Z.Naturforsch.,B:Chem.Sci.|73|305|doi:10.1515/znb-2018-0015

CCDC 1528273: Experimental Crystal Structure Determination

Related Article: Bartłomiej Bereska, Krystyna Czaja, Krzysztof Ejsmont, Błażej Dziuk, Bartosz Zarychta, Jolanta Iłowska, Michał Szmatoła, Agnieszka Bereska|2018|Z.Naturforsch.,B:Chem.Sci.|73|305|doi:10.1515/znb-2018-0015