Development of novel chromium oxide/metallocene hybrid catalysts for bimodal polyethylene

The investigation of a multicomponent catalyst in polyolefin field came up as an alternative for synthesizing bimodal polymers in only one step process under constant reaction conditions.In the present work, new bifunctional catalysts were prepared by combining chromium and metallocene species on the same solid and tested in ethylene polymerization in order to evaluate the possibility of producing bimodal polyethylene. The catalytic system methylaluminoxane (MAO)/(nBuCp)₂ZrCl₂ was immobilized on activated chromium catalysts supported onto several inorganic carriers (silica, silica-alumina, aluminophosphate and mesostructured SBA-15-type materials). The reaction results showed a clear influence of the physicochemical properties of the support on the relative contribution of metallocene and chromium centers as well as on polymers molecular weight distribution. A bimodal polyethylene was obtained by supporting the MAO/metallocene system on a mesostructured chromium catalyst prepared by direct synthesis.     

Control of molecular weight distribution (MWD) for polyethylene catalyzed over Ziegler-Natta/Metallocene hybrid catalysts

Two types of inorganic supports, MgCl₂ and SiO₂, for the impregnation of catalysts were prepared by the recrystallization and sol-gel methods, respectively. The Ziegler-Natta/Metallocene hybrid catalysts were prepared in order to control the molecular weight (Mw) and the molecular weight distribution (MWD) during ethylene polymerization. The polyethylene produced by the hybrid catalysts can control the Mw and the MWD of polymer, showing two melting temperatures and a bimodal MWD, corresponding to products arising from each of the individual catalysts. This suggests that these hybrid catalysts acted as individual active species and produced a blend of polymers. This paper was presented at the 8th APCChE (Asia Pacific Confederation of Chemical Engineering) Congress held at Seoul between August 16 and 19, 1999.     

新型后过渡金属烯烃催化剂的研究进展

综述了近年来－系列新型α－二亚胺型后过渡金属（Ni、Pd、Fe、Co）催化剂在烯烃聚合、极性单体共聚、烯烃齐聚、环烯烃加成聚合、烯烃活性聚合和聚烯烃纳米复合物等方面的最新进展。系统地阐述了不同的中心过渡金属离子、α－二亚胺骨架、骨架上的取代基和不同的聚合条件（温度、压力）分别对催化剂的聚合活性、聚烯烃支化率、聚合物分子量和分子量分布以及聚合产物的性质等影响，并且简要说明了这一类催化剂的制备方法和新特点。     

后过渡金属烯烃聚合催化剂的研究进展

综述了以后过渡金属 (Ni,Pd ,Fe和Co)络合物为主催化剂的烯烃聚合催化剂的发现、沿革及研究进展 ,包括催化剂的合成、结构、性能、催化烯烃聚合机理等。     

负载复合后过渡金属烯烃聚合催化剂研究进展

综述了负载和复合型后过渡金属烯烃聚合催化剂的研究进展。把后过渡金属催化剂负载化,可以适合现有工业生产的工艺要求,改善聚合物产品的形态结构、抑制粘釜现象等。用后过渡金属催化剂与其他过渡金属催化剂(如Ziegler-Natta催化剂、茂金属催化剂等)进行复合的目的主要是制备具有某些特定性能聚烯烃产物及使单一乙烯单体聚合制备支化聚乙烯。后过渡金属催化剂进行负载和复合后在改善聚烯烃产物性能、降低生产成本等方面有突出的优势．具有十分广阔的工业应用前景。     

烯烃聚合后过渡金属催化剂负载化研究进展

综述了后过渡金属催化剂负载化方式和载体的种类及其催化特性,该催化剂载体包括无机载体、聚合物载体、自固载和介孔分子筛等。通过与均相催化剂性能的比较,进一步阐述了负载的目的和必要性。随着这一领域研究深入,将对后过渡金属催化剂工业化发展具有重要的意义。     

Direct synthesis of fibrous high molecular weight polyethylene using vanadium catalysts supported on an SiO2 ionic liquid system

Polyethylene of fibrous morphology was obtained using Cp₂VCl₂ and VCl₂(salenCl₂) catalysts activated by AlEt₂Cl and AlEtCl₂ and heterogenized on a supported ionic liquid system prepared with SiO₂ and 1‐(3‐triethoxysilyl)propyl‐3‐methylimidazolium chloroaluminate. The fibre length ranges from 15 to 60 µm, depending on the reaction conditions. The polyethylene is characterized by a high molecular weight ((1.1–2.4) × 10⁶ g mol^?1) and a narrow molecular weight distribution (1.4–2.5). It is a linear polymer, properly without branching. The DSC method reveals characteristic changes in melting temperature and crystallinity degree between the first and second scan heating cycles (141 °C and 136 °C, 71% and 46%, respectively). The wide angle X‐ray spectroscopy and Fourier transform infrared spectroscopy methods give crystallinity degree values of 40% and 41%–51%. The influence of type of catalyst precursor, alkylaluminium activator, catalyst/activator molar ratio, reaction time and temperature is discussed. © 2015 Society of Chemical Industry     

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino) pyridyl]‐cobalt(II) dichloride ( 1 ), known as an active catalyst for producing linear polyethylene, and [1,4‐bis(2,6‐diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide ( 2 ), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight‐average molecular weights , crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small angle X‐ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T_m), crystalline temperatures (T_c), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4188–4198, 2007     

Crosslinking of ultra-high molecular weight polyethylene in the oriented state with dicumylperoxide

Dicumylperoxide was used to crosslink ultra-high molecular weight polyethylene in the oriented state. Completely gelated fibre-networks with a tenacity up to 1.4 GPa were obtained. Storage at 195°C for 1 h left the tensile properties of the crosslinked filaments at room temperature practically unchanged, and vulcanization avoided fibre fibrillation upon failure. It was concluded that to combine high strength with high gel content, crosslinking should be peformed after the polyethylene chains have attained a high degree of orientation.     

Optimal process operation for the production of linear polyethylene resins with tailored molecular weight distribution

An optimization model is presented to determine optimal operating policies for tailoring high density polyethylene in a continuous polymerization process. Shaping the whole molecular weight distribution (MWD) by adopting an appropriate choice of operating conditions is of great interest when designing new polymers or when improving quality. The continuous tubular and stirred tank reactors are modeled in steady state by a set of differential‐algebraic equations with the spatial coordinate as independent variable. A novel formulation of the optimization problem is introduced. It comprises a multi‐stage optimization model with differential‐algebraic equality constraints along the process path and inequality end‐point constraints on product quality. The resulting optimal control problem is solved at high computational efficiency by means of a shooting method. The results show the efficiency of the proposed approach and the benefit of predicting and controlling the complete MWD as well as the interplay between operating conditions and polymer properties. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Performance and characterization of supported metal catalysts for complete oxidation of formaldehyde at low temperatures

Activities of a series of metals (Pt, Pd, Rh, Cu, Mn) supported on TiO₂ were investigated for the catalytic oxidation of formaldehyde. Among them, Pt/TiO₂ was found to be the most promising catalyst. Nitrogen adsorption, hydrogen chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and temperature programmed reduction (TPR) by H₂ were used to characterize the platinum catalysts. Using Ce_0.8Zr_0.2O₂, Ce_0.2Zr_0.8O₂, SiO₂ as supports instead of TiO₂, the activity sequence of 0.6 wt.% platinum with respect to the supports is TiO₂ > SiO₂ > Ce_0.8Zr_0.2O₂ > Ce_0.2Zr_0.8O₂, and this appears to be correlated with the dispersion of platinum on supports rather than the specific surface areas of the catalysts. Platinum loading on TiO₂ has a great effect on the catalytic activity, and 0.6 wt.% Pt/TiO₂ catalyst was observed to be the most active, which could be attributed to the well-dispersed platinum surface phase. The reduction temperature greatly affects the particle size and, consequently, the catalytic activity. The smaller particle size of platinum, due to its high dispersion on support, has a positive effect on catalytic performance. Increasing formaldehyde concentration and space velocity exhibits an inhibiting effect on the catalytic activity.     

Supported titanium–magnesium catalysts with different titanium content: Kinetic peculiarities at ethylene homopolymerization and copolymerization and molecular weight characteristics of polyethylene

The effect of Ti content on the activity of titanium–magnesium catalysts (TMC) and molecular weight distribution (MWD) of polyethylene (PE) produced has been studied. It was found that the activity enhances sharply as Ti content decreases from 0.6 to 0.07 wt %, and shows no significant changes in the Ti content range of 0.6–5.0 wt %. The maximum activity (36 kg PE/mmol Ti × h × bar C₂H₄) was observed for TMC with the lowest Ti content. The catalyst with low titanium content (～ 0.1 wt % of Ti) produced PE with narrower MWD (M_w/M_n = 3.1–3.5) as compared to catalysts with higher titanium content (3–5 wt % of Ti; M_w/M_n = 4.8–5.0). New data on the effect of hydrogen on MWD of PE have been found. Increasing hydrogen concentration results in broadening the MWD of PE, especially in the case of TMC with high titanium content. The data presented indicate the heterogeneity of active centers of TMC in the reaction of chain transfer with hydrogen. The data on the ethylene–hexene‐1 copolymerization over TMC with different titanium content are presented. Comonomer reactivity ratios were shown to be independent of the Ti content in TMC. Presumably the difference in activity of these catalysts is mainly caused by the difference in the number of active centers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5436–5442, 2006     

Supported gold and gold palladium catalysts for selective chemical synthesis

Catalysts based on gold are now well established as very active and selective for broad ranges of redox reactions. Although primarily known for selective and preferential oxidation reactions, gold catalysts are also highly effective for selective hydrogenation. Hydrogenation reactions provide the focus for this perspective paper that is based on a François Gault lecture given at the Sabatier Conference in 2007. In particular, two reactions will be discussed; namely, the use of supported gold catalysts for selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols, and the use of supported gold palladium alloys for the direct hydrogenation of molecular oxygen to form hydrogen peroxide in preference to water.     

Deactivation and regeneration of hybrid catalysts in the single-step synthesis of dimethyl ether from syngas and CO2

Synthesis of dimethyl ether (DME) has been studied in a single reaction step, from H₂ + CO and H₂ + CO₂, in a fixed bed reactor on CuO-ZnO-Al₂O₃/γ-Al₂O₃ and CuO-ZnO-Al₂O₃/NaHZSM-5 hybrid catalysts. It has been proven that water content in the reaction medium (which is higher when CO₂ is fed) contributes to efficiently decreasing deactivation by coke in both catalysts and, consequently, when water is in the feed deactivation is insignificant for 30 h reaction. Nevertheless, water also decreases the activity of γ-Al₂O₃ acid function, due to its high adsorption capacity on the acid sites. Due to its importance in the viability of the industrial process, a study has been carried on the regeneration of both catalysts by coke combustion under controlled conditions (in order to avoid CuO sintering). For this study, the catalysts have been used under severe deactivation conditions. It has been proven that γ-Al₂O₃ does not have a suitable hydrothermal stability and that CuO-ZnO-Al₂O₃/NaHZSM-5 catalyst has an excellent performance and is suitable for using it in uninterrupted reaction–regeneration cycles.     

双金属中心双峰聚乙烯催化剂研究进展

双峰聚乙烯因兼具优良的加工性能和优异的力学性能,被广泛应用于PE100、PE100RC等高等级管材的生产,其在聚乙烯市场中的地位越来越重要。目前工业上基本采用双釜串联工艺生产双峰聚乙烯,该工艺设备投资及能耗较高,且均被国外公司垄断。相比之下,单釜双峰工艺因采用双金属中心催化剂在单一反应器中生产双峰聚乙烯,其设备投资和操作费用更低,且更加绿色环保,因而成为近年来国内外研究的热点。综述了本课题组近期基于铬系催化剂开发的新型双金属中心双峰聚乙烯催化剂,同时对其他双金属中心聚乙烯催化剂进行了介绍,并对该领域的未来发展进行了展望。     

烯烃聚合后过渡金属催化剂的研究进展

综述了烯烃聚合后过渡金属催化剂的主要进展,提出了有待研究的问题,展望了后过渡金属催化剂在烯烃聚合中的应用。     

A colorimetric method for the molecular weight determination of polyethylene glycol using gold nanoparticles

A gold nanoparticle (AuNP)-based colorimetric method was developed for the molecular weight (MW) determination of polyethylene glycol (PEG), a commonly used hydrophilic polymer. Addition of a salt solution to PEG-coated AuNP solutions helps in screening the electrostatic repulsion between nanoparticles and generating a color change of the solutions from wine red to blue in 10 min in accordance with the MW of PEG, which illustrates the different stability degrees (SDs) of the AuNPs. The SDs are calculated by the absorbance ratios of the stable to the aggregated AuNPs in the solution. The root mean square end-to-end length (〈h²〉^1/2) of PEG molecules shows a linear fit to the SDs of the PEG-coated AuNPs in a range of 1.938 ± 0.156 to 10.151 ± 0.176 nm. According to the Derjaguin-Landau-Verwey-Overbeek theory, the reason for this linear relationship is that the thickness of the PEG adlayer is roughly equivalent to the 〈h²〉^1/2 of the PEG molecules in solution, which determines the SDs of the AuNPs. Subsequently, the MW of the PEG can be obtained from its 〈h²〉^1/2 using a mathematical relationship between 〈h²〉^1/2 and MW of PEG molecule. Applying this approach, we determined the 〈h²〉^1/2 and the MW of four PEG samples according to their absorbance values from the ordinary ultraviolet–visible spectrophotometric measurements. Therefore, the MW of PEG can be distinguished straightforwardly by visual inspection and determined by spectrophotometry. This novel approach is simple, rapid, and sensitive.     

Raman and IR studies of surface metal oxide species on oxide supports: Supported metal oxide catalysts

Raman and infrared spectroscopy provide complementary information about the nature of the surface metal oxide species present in supported metal oxide catalysts. This paper reviews the type of fundamental information that is typically obtained in Raman and IR characterization studies of supported metal oxide catalysts. The molecular structures of the surface metal oxide species are reflected in the terminal M=O and bridging M-O-M vibrations. The location of the surface metal oxide species on the oxide supports is determined by directly monitoring the specific surface hydroxyls of the support that are being titrated. The surface coverage of the surface metal oxide species on the oxide supports can be quantitatively obtained since at monolayer coverage all the reactive surface hydroxyls are titrated and additional metal oxide results in the formation of crystalline metal oxide particles. The nature of surface Lewis and Brønsted acid sites present in supported metal oxide catalysts are determined by adsorbing basic probe molecules like pyridine. Information about the behavior of the surface metal oxide species during catalytic reactions are provided by in situ characterization studies. Such fundamental information is critical for the development of molecular structure-reactivity relationships for supported metal oxide catalysts. This paper will be limited to supported metal oxide catalysts containing group V-VII transition metal oxides (e.g., V, Nb, Cr, Mo, W and Re) on several different oxide supports (alumina, titania, zirconia, niobia and silica).     

On the influence of molecular weight and crystallisation condition on the development of defect in highly drawn polyethylene

Longitudinal morphology of highly drawn high density polyethylenes has been investigated. Three grades of HDPEs with different molecular weights were used. Two different initial morphologies were obtained by quenching and slow cooling from the melt. The samples were drawn at 75 °C close to their breaking points and their longitudinal morphologies examined under SEM after etching. Two types of defects were observed. These are the structure containing a large number of parallel longitudinal etched pockets laid in the regions between almost parallel continuous transverse bands or ‘Pisa’ structure recently reported and transverse cracks. The appearance of these defects was found to correlate with molecular weight and thermal history of the samples. For all quenched samples, both Pisa structure and transverse cracks were observed. The number of transverse cracks was found to increase with increasing molecular weight. Apparently, the transverse cracks, which thought to limit the drawing to high draw ratios, can be retarded by drawing at higher temperature (100 °C). This suggests that the formation of transverse cracks relates to chain mobility and drawability of the materials. The Pisa structure was found to disappear from slowly cooled low molecular weight samples. For slowly cooled high molecular weight sample, the Pisa structure became less salient. It is suggested that the formation of Pisa structure is determined by molecular entanglement. Analysis of the band separation of the Pisa structure shows that there seems to be a characteristic value which depends on drawing temperature.     

Novel diphenyl thioether‐bridged binuclear metallocenes of Ti and Zr for synthesis of polyethylene with broad molecular weight distribution

Two diphenyl thioether‐bridged binuclear metallocenes of Ti and Zr, [(C₅H₅)Cl₂MC₅H₄CH₂(p‐C₆H₄)]₂S [M = Ti (1) and Zr (2)], have been synthesized by treating the dilithium salts of the corresponding ligand [(C₅H₅CH₂(p‐C₆H₄)]₂S with two equivalents of C₅H₅TiCl₃ and C₅H₅ZrCl₃(DME), respectively, in toluene at 0°C. Both new complexes have been characterized by ¹H‐NMR spectroscopy and elemental analysis. Homogeneous ethylene polymerization using both complexes was performed in the presence of methylaluminoxane (MAO). The influences of molar ratio of [MAO]/[Cat], concentration of the catalysts, time, and temperature have been studied systematically. The catalytic activity of 1 is higher than that of the corresponding oxygen‐bridged catalyst [(C₅H₅)Cl₂TiC₅H₄CH₂(p‐C₆H₄)]₂O. The catalytic activity of 2 is at least two times higher than that of 1 under any tested polymerization conditions. The melting points of polyethylene (PE) produced by 1 and 2 are higher than 130°C, indicating a highly linear and highly crystalline PE. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011