Supported zirconocene catalyst for preventing reactor fouling in ethylene polymerization

The commercial interest of metallocene complexes for olefin polymerization has led to additional efforts to prepare suitable metallocene complexes efficiently and economically. Ethylene polymerization was carried out with a series of heterogeneous catalysts which were prepared in various Zr/silica ratios by immobilization of Ind₂ZrCl₂ preactivated with methylaluminoxane (MAO) on silica. This method to form the catalyst system resulted in a polymerization catalyst with reduced fouling tendencies and improved reactor operability. Polymerization of ethylene was conducted in Buchi reactors in a slurry phase under mild pressure. Some of the physical properties of the obtained polymers were also determined. Copyright © 2005 Society of Chemical Industry     

Preparation of polymer‐supported zirconocene catalysts and olefin polymerization

A novel polymer‐supported metallocene catalyst with crosslinked poly(styrene‐co‐acrylamide) (PSAm) as the support has been prepared and characterized. The probability of long sequences of acrylamide (Am) in PSAm is still low even at an Am amount of 32.8 mol %, implying the relatively homogeneous distribution of Am. The infrared spectra of PSAm and the supported catalyst substantiate that an amide group in PSAm coordinates with methylaluminoxane through both oxygen and nitrogen atoms. Ethylene/α‐octene copolymerization showed that the catalytic activity is not markedly affected by adding α‐octene. ¹³C NMR analysis of the ethylene/α‐octene copolymer indicated that the composition distribution of the copolymer is uniform. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2253–2258, 1999     

Preparation and characterization of polypropylene–montmorillonite nanocomposites generated by in situ metallocene catalyst polymerization

An ion‐exchange method was applied to replace sodium cations inside the interlamellar space of montmorillonite with positively charged stearyl trimethyl ammonium chloride. The d₀₀₁‐spacing of montmorillonite is larger in toluene than in other solvents. The overexchanged stearyl methyl ammonium chloride in the montmorillonite layers can be completely washed out by ethanol. Polypropylene–montmorillonite nanocomposites were prepared by using the supported rac‐Et(Ind)₂ZrCl₂ catalyst on the montmorillonite. The nanocomposites that were polymerized by the supported catalyst were characterized by infrared spectroscopy, nuclear magnetic resonance, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy. Transmission electron microcopy shows that each silicate sheet of montmorillonite is randomly dispersed into the polypropylene matrix following polymerization by using a supported catalyst. The polypropylene nanocomposites had higher crystallinity, hardness, and thermal properties than pure polypropylene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1228–1236, 2005     

Graphene‐reinforced biodegradable poly(ethylene succinate) nanocomposites prepared by in situ polymerization

In this study, poly(ethylene succinate)(PES)/graphene nanocomposites were facilely prepared by in situ melt polycondensation of succinic acid and ethylene glycol in which contained well dispersed graphene oxide (GO). Fourier transform infrared (FTIR), GPC, TGA, and XRD were used to characterize the composites. The FTIR spectra and TGA measurement confirmed that PES chains had been successfully grafted onto GO sheets along with the thermal reduction of GO to graphene during the polymerization. GPC results indicated that increasing amounts of graphene caused a slight decrease in number average molecular weight of PES matrix when polymerization time was kept constant. The content of grafted PES chains on graphene sheets was also determined by TGA and was to be about 60%, which made the graphene sheets homogeneously dispersed in the PES matrix, as demonstrated by SEM and XRD investigations. Furthermore, the incorporation of thermally reduced graphene improved the thermal stability and mechanical properties of the composites significantly. With the addition of 0.5 wt % graphene, onset decomposition temperature of the composite was increased by 12°C, and a 45% improvement in tensile strength and 60% in elongation at break were also achieved. The enhanced performance of the composites is mainly attributed to the uniform dispersion of graphene in the polymer matrix and the improved interfacial interactions between both components. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3212–3220, 2013     

Gas phase polymerization of 1,3‐butadiene with supported neodymium‐based catalyst: Investigation of molecular weight

The gas phase polymerization of 1,3‐butadiene (Bd), with supported catalyst Nd(naph)₃/Al₂Et₃Cl₃/Al(i‐Bu)₃ or/and Al(i‐Bu)₂H, was investigated. The polymerization of Bd with neodymium‐based catalysts yielded cis‐1,4 (97.2–98.9%) polybutadiene with controllable molecular weight (MW varying from 40 to 80 × 10⁴ g mol^?1). The effects of reaction temperature, reaction time, Nd(naph)₃/Al(i‐Bu)₃ molar ratio, and cocatalyst component on the catalytic activity and molecular weight of polymers were examined. It was found that there are two kinds of active sites in the catalyst system, which mainly influenced the MW and molecular weight distribution of polybutadiene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1945–1949, 2004     

Comparison of gas‐ and liquid‐phase polymerization of propylene with heterogeneous metallocene catalyst

Sorption measurements are executed to study the sorption behavior of propylene in a semicrystalline polymer. Decreasing values for the Flory–Huggins interaction parameter with increasing temperature are obtained. Large deviations are found, especially at higher temperatures, compared to data from the literature. Propylene is polymerized in liquid and gaseous propylenes with Me₂Si[Ind]₂ZrCl₂/MAO/SiO₂ as the metallocene catalyst. Lower relative reaction rates are found in the gas phase compared to the experiments in the liquid phase. The activation energies from the experiments in both phases are on the same order of magnitude. However, the literature versus experimental sorption data has a large effect on the determined kinetic parameters. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1193–1206, 2001     

Gas‐phase olefin polymerization over supported metallocene/MAO catalysts: influence of support on activity and polydispersity

Three catalysts obtained by supporting bis(n‐butylcyclopentadienyl)zirconium dichloride/methylaluminoxane on: (1) porous crosslinked poly(2‐hydroxyethylmethacrylate‐co‐styrene‐co‐divinylbenzene) particles (CAT1); (2) swellable crosslinked poly(styrene‐co‐divinylbenzene) particles (CAT2); and (3) by evaporating the catalyst precursors solution to dry powder, CAT3 were used in gas‐phase polymerization of ethylene, and ethylene/1‐hexene in a 2 L semi‐batch reactor at 80 °C and 1.4 MPa. The average polymerization activities of the three catalysts were 12.3–15.5, 4.2–10.1, and 14.3–62.9 ton PE (mol Zr h)^?1 respectively. CAT1 and CAT3 produced polyethylenes with a polydispersity range of 2.3–2.7, while that of CAT2 was 3.5–6.4. The supported catalysts produced polyolefin particles with bulk density of 0.36–0.43 g ml^?1, and essentially no fines. Ethylene/1‐hexene co‐polymerization (7 mol m^?3 initial 1‐hexene concentration in the reactor) increased polymerization activities and produced lower‐molar‐mass co‐polymers. At 21 mol m^?3 1‐hexene the polymerization activities decreased, but the relative amount of the low‐molar‐mass co‐polymer for CAT2 increased, leading to higher polydispersity. Copyright © 2006 Society of Chemical Industry     

Crystallization behavior and UV‐protection property of PET‐ZnO nanocomposites prepared by in situ polymerization

The aim of this study was to investigate the crystallization behavior and UV‐protection property of polyethylene terephthalate (PET)‐ZnO nanocomposits. PET‐ZnO nanocomposites containing 0.5–3.0 wt % of ZnO were successfully synthesized by in situ polymerization. The Fourier transformed infrared (FTIR) spectroscopy indicated the silane coupling agent was anchored onto the surface of ZnO. Scanning electron microscope (SEM) images showed ZnO particles were dispersed homogeneously in PET matrix with amount of 0.5–1.0 wt %. Differential scanning calorimetry (DSC) results exhibited that the incorporation of ZnO into PET resulted in increase of the melting transition temperature (T_m) and crystallization temperature (T_c) of PET‐ZnO nanocomposites. The crystallization behavior of PET and PET‐ZnO nanocomposites was strongly affected by cooling rate. ZnO nanoparticles can act as an efficient nucleating agent to facilitate PET crystallization. UV–vis spectrophotometry showed that UV‐ray transmittance of PET‐ZnO nanocomposites decreased remarkably and reached the minimum value of 14.3% with 1.5 wt % of ZnO, compared with pure PET whose UV‐ray transmittance was 84.5%. PET‐ZnO nanocomposites exhibited better UV‐protection property than pure PET, especially in the range of UVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and crystallization of poly(ethylene terephthalate)/SiO2 nanocomposites by in‐situ polymerization

Poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were prepared by in situ polymerization. The dispersion and crystallization behaviors of PET/SiO₂ nanocomposites were characterized by means of transmission electron microscope (TEM), differential scanning calorimeter (DSC), and polarizing light microscope (PLM). TEM measurements show that SiO₂ nanoparticles were well dispersed in the PET matrix at a size of 10–20 nm. The results of DSC and PLM, such as melt‐crystalline temperature, half‐time of crystallization and crystallization kinetic constant, suggest that SiO₂ nanoparticles exhibited strong nucleating effects. It was found that SiO₂ nanoparticles could effectively promote the nucleation and crystallization of PET, which may be due to reducing the specific surface free energy for nuclei formation during crystallization and consequently increase the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 655–662, 2006     

Investigation on the melt spinning fibers of PP/organoclay nanocomposites prepared by in‐situ polymerization

Fibers prepared by melt spinning process from the PP (polypropylene)/organoclay nanocomposite were characterized in details with the aid of SEM, FTIR, XRD, DSC, and mechanical measurements. The results suggested that the lower content of organoclay (0.1%) added to the PP matrix increased the crystallinity and mechanical property (tensile strength) of the PP/organoclay nanocomposite fiber. With increasing the content of organoclay (≥ 0.3%), the crystallinity and the tensile strength both a little decreased, and the fiber containing organoclay exhibited multi‐peaks at the same draw ratio during the heating process. Furthermore, the degree of orientation of the fiber increased a little with lower content of organoclay (0.1%) introduction to PP during the infrared dichroism measurement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multizone circulating reactor modeling for gas‐phase polymerization. I. Reactor modeling

A new gas‐phase technology for polyolefin production is being developed to be commercially available for large‐scale production between 2004 and 2005. This new technology uses a multilane circulating reactor, which consists of two interrelated zones where two distinct and different fluodynamic regimes are realized, between which the polymer particles are kept in continuous circulation. This article presents a mathematical model for the multilane circulating reactor presenting the typical behavior of the reactor operation and a parameter sensibility analysis. Simulations were conducted for polyethylene production. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1042–1052, 2004     

Preparation of silica/polyurethane nanocomposites by UV‐induced polymerization from surfaces of silica

UV‐curable nanocomposites were prepared by the in situ photopolymerizaton with nanosilica obtained from sol–gel process. The photoinitiator 2‐hydroxy‐2‐methyl‐1‐phenylpropane‐1‐one (1173) was anchored onto the surface of the nanosilica with or without methacryloxypropyltrimethoxysilane (MAPS) modification. The photopolymerization kinetics was studied by real‐time Fourier transform IR (RTIR), and the microstructure and properties of the nanocomposite were investigated using transmission electron microscopy and UV–visible (UV–vis) transmistance spectra. RTIR analysis indicated that the nanocomposites without MAPS had higher curing rates and final conversion than those with MAPS. The nanocomposites with an uniformal dispersion of nanosilica had high UV–vis transmittance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The influence of the preparing conditions of SiO2 supported Cp2ZrCl2 catalyst on ethylene polymerization

In this work, ethylene was polymerized by using Cp₂ZrCl₂ supported on silica pretreated with methylaluminoxane (MAO) as the catalyst system. The influence of the conditions for the preparation of the heterogeneous catalyst, such as temperature, washing method of the catalytic solid, MAO and metallocene concentration in the support treatment, time of MAO, and metallocene immobilization on the support, type of alkylaluminum used in the support pretreatment, and calcination temperature of the support were investigated. Aluminum and zirconium content fixed on the silica surface were determined by inductively coupled plasma emission spectroscopy. Polymer characteristics were determined by gel permeation chromatography and differential scanning calorimetry. According to the results, the activity of some supported catalysts were far higher than with the homogeneous system. Moreover, polyethylene with very high molecular weights were also obtained and with molecular weight distribution larger than those produced with the homogeneous precursor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2054–2061, 2002     

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate)/silica nanocomposites prepared by emulsion polymerization

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate) (PSBM)/silica nanocomposite was prepared by emulsion polymerization in the presence of oleic acid surface modified nanosilica. The structure, morphology, size, and size distribution were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM), and dynamics laser scattering. The chemical bond was formed between PSBM and nanosilica revealed by FTIR and TEM studies. The composite particles with an averaged diameter ranging from 30 to 80 nm have the core‐shell structure. The effect of silica content on the glass transition temperature T_g, pyrolyze temperature, and rheological behavior of PSBM composites was systematically investigated. The results indicated that the addition of nanosilica could effectively inhibit chain movement, and improved the pyrolyze temperature of PSBM. The steady viscosity and dynamic modulus were strongly dependent on the content and distribution of nanosilica in PSBM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ethylene polymerization with iron‐based diimine catalyst supported on MCM‐41

A mesoporous molecular sieve MCM‐41 supported iron‐based diimine catalyst ( MC ) was prepared for the first time. The kinetic behavior of ethylene polymerization with MC was studied. The effects of Al/Fe molar ratio and various cocatalysts on the catalytic activity and properties of the polyethylene obtained were investigated. The results showed that good catalytic activities can be reached with cocatalyst methylaluminoxane (MAO) and triethylaluminium (TEA). Ethylene polymerization with MC gave polymers with higher molecular weight, melting temperature and onset temperatures of decomposition (T_onset) and better morphology than those obtained with the corresponding homogeneous catalyst. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of chlorine‐containing flame‐retardant polyurethane nanocomposites via in situ polymerization

We have developed flame‐retardant polyurethanes (FRPUs) and polyurethane (PU) nanocomposites via in situ polymerization. Three series of thermoplastic elastomeric PUs were synthesized to investigate the effect of incorporating 3‐chloro‐1,2‐propanediol (CPD) and nanoclay on mechanical, thermal properties, and also resistance to burning. PU soft segments were based on poly(propylene glycol). Hard segments were based on either CPD or 1,4‐buthane diol (BDO) in combination with methyl phenyl di‐isocyanate named PU or FRPU, respectively. In the third series, CPD was used as chain extender also nanoclay (1% wt) and incorporated and named as flame‐retardant polyurethane nanocomposites (FRPUN). Mechanical properties and LOI of PUs and nanocomposites have been evaluated. Results showed that increasing the hard segment (chlorine content) leads to the increase in flame retardancy and burning time. Addition of nanoclay to CPD‐containing PUs leads to obtain self‐extinguish PUs using lower CPD contents, higher Young's modulus, and strength without any noticeable decrease in elongation at break. Investigation of the TGA results showed that copresence of nanoclay and chlorine structure in the PU backbone can change thermal degradation pattern and improve nanocomposite thermal stability. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation and intercalation have been well done. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of aluminum alkyls on ethylene/1‐hexene polymerization with supported metallocene/MAO catalysts in the gas phase

The effects of aluminum alkyls on the gas‐phase ethylene homopolymerization and ethylene/1‐hexene copolymerization over polymer‐supported metallocene/methylaluminoxane [(n‐BuCp)₂ZrCl₂/MAO] catalysts were investigated. Results with triisobutyl aluminum (TIBA), triethyl aluminum (TEA), and tri‐n‐octyl aluminum (TNOA) showed that both the type and the amount of aluminum alkyl influenced the polymerization activity profiles and to a lesser extent the polymer molar masses. The response to aluminum alkyls depended on the morphology and the Al : Zr ratio of the catalyst. Addition of TIBA and TEA to supported catalysts with Al : Zr >200 reduced the initial activity but at times resulted in higher average activities due to broadening of the kinetic profiles, i.e., alkyls can be used to control the shape of the activity profiles. A catalyst with Al : Zr = 110 exhibited relatively low activity when the amount of TIBA added was <0.4 mmol, but the activity increased fivefold by increasing the TIBA amount to 0.6 mmol. The effectiveness of the aluminum alkyls in inhibiting the initial polymerization activity is in the following order: TEA > TIBA >> TNOA. A 2‐L semibatch reactor, typically run at 80°C and 1.4 MPa ethylene pressure for 1 to 5 h was used for the gas‐phase polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3549–3560, 2004     

Experimental proof of the existence of mass‐transfer resistance during early stages of ethylene polymerization with silica supported metallocene/MAO catalysts

The size of a silica supported metallocene/MAO (methylaluminoxane) catalyst plays an important role in determining its productivity during ethylene polymerization. From a chemical engineering point of view, this size dependency of catalytic activity of supported metallocenes is mathematically connected with the different levels of mass‐transfer resistance in big and small catalyst particles but no experimental evidence has been provided to date. The results of this systematic experimental study clearly demonstrate that the intraparticle monomer diffusion resistance is high in bigger catalyst particles during initial instants of ethylene polymerization and diminishes with the polymer particle growth. Two different silica supported metallocene/MAO catalysts provided the same results while highlighting the fact that catalyst chemistry should be carefully considered while studying complex chemical engineering problems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4476–4490, 2017     

Preparation of silica‐supported late transition metal catalyst and ethylene polymerization

A Correction has been published for this article in Polymer International 51(6) 2002, 561 The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. © 2002 Society of Chemical Industry     

In situ polymerization of ethylene with functionalized multiwalled carbon nanotubes using a zirconocene aluminohydride system in solution

This study reports nanocomposite synthesis based on high-density polyethylene with carbon nanotubes through in situ polymerization by coordination, and the use of an aluminohydride zirconocene/MAO system as a catalyst. Nanocomposites of linear polyethylene exhibit higher molar masses than pure high-density polyethylene synthesized under similar conditions; where multiwalled carbon nanotubes (MWCNTs) acted as nucleating agents, shifting the crystallization temperature to higher values than neat high-density polyethylene. Well-dispersed MWCNTs in the HDPE matrices of the obtained nanocomposites are observed by SEM, where most of the nanocomposites showed an improvement in their thermal stability and electric conductivity, besides it is possible to obtain nanocomposites containing up to 41 wt% of nanofiller in the polymeric matrix. The aluminohydride complex n-BuCp₂ZrH₃AlH₂, activated with MAO at Al/Zr ratios of 2000, produced homogeneous HDPE/MWCNT composites under in situ polymerization conditions, at 70°C and 2.9 bar of ethylene pressure, with minimal residual alumina in the HDPE matrix.