0000000000053511
AUTHOR
Katarzyna Dziubek
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…
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…
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 …
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…
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…
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…
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…
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…
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…
Metallocenes and post-metallocenes immobilized on ionic liquid-modified silica as catalysts for polymerization of ethylene
Abstract The supported ionic liquid (SIL) strategy was used for the first time to metallocene and post-metallocene heterogeneous catalysts for olefin polymerization. The metal complexes: Cp2TiCl2, Cp2ZrCl2, FI–Ti, and Sal–Ti were immobilized in the 1-(3-triethoxysilyl)propyl-3-methylimidazolium alkylchloroaluminate ionic liquid, anchored on the surface of the mesoporous amorphous silica. The SIL systems were characterized by FTIR, 29Si NMR, N2 adsorption, EA, AAS, TG, and SEM techniques. The developed supported catalytic systems were found to be active in the ethylene polymerization and produce the polyethylene of various properties.
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…
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…
Improvement of biphasic polymerization by application of binary ionic liquid mixture
Abstract The mixture of two ionic liquids, 1- n -butyl-3-methylimidazolium and 1-(2-phenylethyl)-3-methylimidazolium chloroaluminates, [C 4 -mim][AlCl 4 ] and [PhC 2 -mim][AlCl 4 ], were applied as a medium to immobilize the Cp 2 TiCl 2 titanocene catalyst for biphasic ionic liquid/hexane ethylene polymerization. The system makes possible to perform the reaction at lower temperatures, below the melting temperature of the aralkyl ionic liquid. A better separation of the ionic liquid phase was observed and an easier mass transfer of the polymer product from the ionic liquid to the hexane phase was obtained. The polyethylene reveals bimodal distribution of molecular weight. It is characterized…
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…
Biphasic ethylene polymerisation using 1-n-alkyl-3-methylimidazolium tetrachloroaluminate ionic liquid as a medium of the Cp2TiCl2 titanocene catalyst
Abstract A systematic analysis was performed on a series of 1- n -alkyl-3-methylimidazolium tetrachloroaluminates (where alkyl = ethyl, butyl, hexyl, and octyl), applied as a medium of the Cp 2 TiCl 2 titanocene catalyst, to evaluate the influence of the physical properties of the ionic liquids on the polymerisation reaction carried out in the biphasic ionic liquid/hexane mode. Two alkylaluminium compounds, AlEtCl 2 and AlEt 2 Cl, were used as activators. The influence of the activator/catalyst molar ratio on the performance of the ethylene polymerisation was determined for each ionic liquid studied. The best results were obtained using 1- n -octyl-3-methylimidazolium tetrachloroaluminate. …
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…
Densities and viscosities of imidazolium and pyridinium chloroaluminate ionic liquids
Abstract The chloroaluminate ionic liquids are used in various types of reactions. However, due to their particular vulnerability on water, their physical properties have not been previously investigated very extensively. The densities and viscosities of series imidazolium and pyridinium chloroaluminate ionic liquids having alkyl (butyl, hexyl, octyl) or aralkyl (benzyl, ethylphenyl) chain at the cation, various effective molar fraction of AlCl 3 (χ AlCl3 = 0.5, 0.65, 0.7), as well as they mixture and mixture with common organic solvents (hexane, toluene) were measured at the temperature range 293.15–343.15 K (20–70 °C). Densities, and particularly viscosities decrease with the increase of…
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.…