Triethylaluminum Research Articles

Experimental and first-principles investigation on how support morphology determines the performance of the Ziegler-Natta catalyst during ethylene polymerization

One class of the Ziegler–Natta catalysts (ZNC) – the TiCl4/MgCl2 having triethyl aluminum (AlEt3), has been widely utilized during ethylene polymerization. Although the Ti species plays the role of a major active site, an increase of Ti species does not always improve the activity of ZNC. Herein, investigations of experiments and density functional theory (DFT) elucidate this inverse effect of the increased amount of TiCl4 deposition in ZNC because of the pretreatment process. However, the activity of ZNC on pretreated MgCl2 dropped to 60% of the unpretreated one. The DFT demonstrates that the pretreatment strengthened the interaction between TiCl4 and ZNC, especially on the (104) surface, forming the TiCl4-TiCl4 cluster. The existence of this TiCl4-TiCl4 cluster found on the ZNC (104) surface weakens the adsorption of the first AlEt3 molecule and obstructs further alkylation process, making another Ti site of the alkylated TiCl4-TiCl4 cluster inactive. However, the difficult formation of the TiCl4-TiCl4 cluster found on the ZNC (110) is an important key point that enables the activation of all adsorbed TiCl4 on this surface by facilitating the alkylation process. Moreover, the existence of the MgCl2 (110) surface prevents the formation of the TiCl4-TiCl4 cluster significantly. Hence, it is suggested that the existence of the (110) plane on ZNC plays a key role in controlling the performance of the ZNC, especially the stability via the prevention of deactivation caused by the clustering of TiCl4.

Negative comonomer effect induced by TiCl3-like clusters in MgCl2-based Ziegler-Natta catalysts

The comonomer effect of ethylene/α-olefin copolymerization in the Ziegler-Natta (Z-N) catalytic system, remaining largely elusive and less understood at the molecular level, has been of huge industrial importance and absorbing research interest for decades. Herein, four catalysts with similar physical structures but different polymerization activities and comonomer effects were synthesized by using n-butanol in combination with different secondary electron donors. By tracking catalyst formation, it was found that altering the secondary donor changes the ν(O-H) stability and in turn the MgCl2 facet growth, to influence the polymerization activity. In situ diffuse reflectance Ultraviolet–visible spectra show that different types of active Ti centers are in function in the ethylene polymerization and the ethylene/1-butene copolymerization. Tracing further the microscopic structures of active species upon triethylaluminium (TEA) activation by using Extended X-ray Absorption Fine Structure, it is found that: (i) for the catalysts with negative comonomer effect, the enhanced donor migration promotes the aggregation of active species and leads to the formation of TiCl3-like clusters; (ii) by contrast, for the catalysts with positive comonomer effect, the less mobile donors hinder the aggregation of active species, thus inducing the formation of isolated Ti3+ sites. Our work reveals an evident correlation between the active center and the comonomer effect, which may be strongly modified by the aggregation of the former.

A Continuous-Wave EPR Investigation into the Photochemical Transformations of the Chromium(I) Carbonyl Complex [Cr(CO)4bis(diphenylphosphino)]+ and Reactivity with 1-hexene.

Chromium complexes containing a bis(diphenylphosphino) ligand have attracted significant interest over many years due to their potential as active catalysts for ethylene oligomerisation when combined with suitable co-catalysts such as triethylaluminium (TEA) or methylaluminoxane (MAO). While there has been considerable attention devoted to the possible reaction intermediates and the nature of the Cr oxidation states involved, the potential UV photoactivity of the Cr(I) complexes has so far been overlooked. Therefore, to explore the photoinduced transformations of bis(diphenylphosphino) stabilized Cr(I) complexes, we used continuous-wave (CW) EPR to study the effects of UV radiation on a cationic [Cr(CO)4(dppp)]+[Al(OC(CF3)3)4]- complex (1), where dppp represents the 1,3 bis-(diphenylphosphino)propane ligand, Ph2P(C3H6)PPh2. Our preliminary investigations into the photochemistry of this complex revealed that [Cr(CO)4(dppp)]+ (1) can be readily photo-converted into an intermediate mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ complex (2) and eventually into a trans-[Cr(CO)2(dppp)2]+ complex (3) in solution at room temperature under UV-A light. Here, we show that the intermediate species (2) involved in this transformation can be identified by EPR at much lower temperature (140 K) and at a specific wavelength (highlighting the wavelength dependency of the reaction). In addition, small amounts of a 'piano-stool'-type complex, namely [Cr(CO)2(dppp-η6-arene)]+ (4), can also be formed during the photoconversion of [Cr(CO)4(dppp)]+ using UV-A light. There was no evidence for the formation of the [Cr(L-bis-η6-arene)]+ complex (5) in these UV irradiation experiments. For the first time, we also evidence the formation of a 1-hexene coordinated [Cr(CO)3(dppp)(1-hexene)]+ complex (6) following UV irradiation of [Cr(CO)4(dppp)]+ in the presence of 1-hexene; this result demonstrates the unprecedented opportunity for exploiting light activation during Cr-driven olefin oligomerisation catalysis, instead of expensive, difficult-to-handle, and hazardous chemical activators.

Chemical dealcoholation of MgCl2·EtOH adduct by Al compounds and its effect on the performance of Ziegler–Natta catalysts

MgCl2·nEtOH adducts play a major role in the industrial production of polyethylenes. Their chemical dealcoholation, usually accomplished during the catalyst synthesis step, has had a pronounced impact on the microstructure of the final Ziegler–Natta pre‐catalysts and the properties of the resulting polymers. Due to the industrial and academic importance of this issue, different aluminum‐based compounds including triethylaluminum (TEAL), triisobutylaluminum (TIBA), and ethylaluminumdichloride (EADC) were used in this research in the chemical dealcoholation of a MgCl2·1.5EtOH adduct, to provide the target catalysts. According to the analytical results, the catalysts synthesized using aluminum compounds (especially TEAL and EADC) generally had a more fractured structure, a smaller particle size and a vast surface area. Aluminum precursors bind to the catalyst structure together with TiCl4, which is manifested from their higher adsorption energies obtained by DFT calculations, and the presence of Al atom in the elemental analysis. Varying the chemical structure and physical properties of the catalysts, established using Al compounds, caused significant variation in the ethylene polymerization kinetic curves, their related rate constants, and the flow characteristic of the final polymers. The overall results outstandingly affirm that by appropriate choice of the Lewis acid compound, during the chemical dealcoholation of the adduct, various Ziegler–Natta catalysts can be achieved for different polyethylene grades.

Area-Selective Deposition by Cyclic Adsorption and Removal of 1-Nitropropane.

The ever-greater complexity of modern electronic devices requires a larger chemical toolbox to support their fabrication. Here, we explore the use of 1-nitropropane as a small molecule inhibitor (SMI) for selective atomic layer deposition (ALD) on a combination of SiO2, Cu, CuOx, and Ru substrates. Results using water contact angle goniometry, Auger electron spectroscopy, and infrared spectroscopy show that 1-nitropropane selectively chemisorbs to form a high-quality inhibition layer on Cu and CuOx at an optimized temperature of 100 °C, but not on SiO2 and Ru. When tested against Al2O3 ALD, however, a single pulse of 1-nitropropane is insufficient to block deposition on the Cu surface. Thus, a new multistep process is developed for low-temperature Al2O3 ALD that cycles through exposures of 1-nitropropane, an aluminum metalorganic precursor, and coreactants H2O and O3, allowing the SMI to be sequentially reapplied and etched. Four different Al ALD precursors were investigated: trimethylaluminum (TMA), triethylaluminum (TEA), tris(dimethylamido)aluminum (TDMAA), and dimethylaluminum isopropoxide (DMAI). The resulting area-selective ALD process enables up to 50 cycles of Al2O3 ALD on Ru but not Cu, with 98.7% selectivity using TEA, and up to 70 cycles at 97.4% selectivity using DMAI. This work introduces a new class of SMI for selective ALD at lower temperatures, which could expand selective growth schemes to biological or organic substrates where temperature instability may be a concern.

Effect of Ligand Steric Hindrance on Catalytic Polymerization of Cycloolefin Polymer (COP)

AbstractThe traditional two‐component Ziegler‐Natta catalyst has low catalytic activity when initiating ring‐opening metathesis polymerization (ROMP) and is unstable and easy to generate polymerization gels. Therefore, it is necessary to add a third group of ligands with appropriate steric hindrance to improve the catalytic activity of the catalyst. The effects of ligands′ steric hindrance and other reaction conditions on the catalytic activity of tungsten hexachloride (WCl6) as catalyst and aluminum triethyl (AlEt3) as co‐catalyst were investigated. The results showed that the size of the ligands′ steric hindrance affected the catalytic activity of ROMP, and the small steric hindrance caused the polymerization rate to be too fast, which was easy to produce gels, and when the steric hindrance of the ligands was too large, its solubility was not good, which was not conducive to the normal polymerization. When stearyl alcohol was selected as the ligand, the highest catalytic activity was 3123 mol cycloolefin polymer (COP)/mol W, and the reaction speed of polymerization was also the fastest and the complete transformation only needed 30 min when the ligand/W was 25. It was found that the polymerization reaction was stable without gels and the obtained polymer molecular weight was appropriate, 17.8 kDa, under the conditions of Al/W=80, reaction temperature 60 °C, monomer concentration 10 w/v %, catalyst/monomer 5*10−4 : 1, chain transfer agent/monomer 0.005 : 1.

Indirect GC‐MS Method via Alcoholysis Reaction for Rapid Detection of Organoaluminum Compounds and its Impurities: A Case Study of Triethylaluminium

AbstractOrganoaluminum compounds have been employed as catalysts in many reactions. However, due to their high reactivity of the Al−C bond towards water or air, the accurate analysis and detection of organoaluminum compounds are still challenging. Here we demonstrate the possibility of rapidly and precisely detecting the purity and impurities of triethylaluminium (TEAL). An indirect GC‐MS method via alcoholysis reaction using a designed alcoholysis reactor was adopted to detect and separate the main components and impurities of the synthesized TEAL. Previously, the nuclear magnetic resonance (NMR) and the inductively coupled plasma‐mass spectrometer (ICP‐MS) methods were also selected to detect the main compounds in the synthesized TEAL. The impurities in TEAL was identified as n‐butyl aluminum, and the purity of synthesized TEAL is 97.47 % with high accuracy (ca. 99 %). This work suggests a new strategy to detect the purity and impurities of some kind of hazardous compounds.

Effect of multi-component gaseous fuel on the explosion behaviors and mechanism of aluminum dust

Hydrogen/ethylene/aluminum dust hybrid mixture may pose a potential explosion risk in the production process of triethyl aluminum. To investigate the effect of multi-component gaseous fuel on the hybrid explosion, the flame propagation behaviors and explosion characteristics of hydrogen/ethylene/aluminum dust hybrid mixtures were studied in a confined space. The explosion residues were analyzed, and the reaction mechanism was further established. The results show that the effect of hydrogen-rich fuel on increasing the maximum flame propagation velocity of two-phase fuel was more obvious than that of ethylene-rich fuel. Ethylene-rich fuel can promote the explosion intensity of aluminum dust only in an oxygen-rich environment, while hydrogen-rich fuel can promote aluminum dust explosion in both an oxygen-rich and oxygen-deficient environment. A modified formula for predicting the lower explosion limit of the hybrid mixtures is proposed, and the accuracy of the formula is significantly improved by introducing effective coefficients. The hydrogen-rich gaseous fuel mainly regulated H and OH production through R2 (H2 +O <=> H + OH) and R3 (H2 + OH <=> H + H2O) reactions to dominate the explosion reaction, while the ethylene-rich gaseous fuel affected the explosion reaction through R69 (O + CH3<=>H + CH2O) and R205 (C2H4 + M <=> H2 + C2H2 + M) reactions to regulate the degree of participation of C–C, C–H, and C–O. These results can provide corresponding reference for preventing and reducing the explosion hazard of multi-component gaseous and dust hybrid mixtures.

In-situ polymerization of silica/polyethylene using bisupported Ziegler-Natta catalyst of nanosilica/BOM/TiCl4/TEAL: Study of thermo-mechanical properties system

• Preparation of silica/PE nanocomposite using a bisupported Ziegler-Natta catalytic system. • The nanosilica/BOM/TiCl 4 /TEAL was characterized by TEM, FTIR, BET, and SEM analysis. • The thermal properties of the nanocomposites were studied by DSC and TG analysis (TGA). The physical and chemical properties of silica-supported Ziegler-Natta catalysts industrially important for polyethylene/silica production. Polyethylene (PE)/silica nanocomposites were prepared through in-situ polymerization using a bisupported Ziegler-Natta catalytic system. Since the silica and nanosilica-supported Ziegler-Natta catalysts have shown low efficiency in the ethylene polymerization. This problem was solved through the prepared bisupported catalyst in this study. This approach includes the preparation and utilization of a bisupported nanosilica/BOM/TiCl 4 /TEAL catalytic system in which nanosilica and BOM (butyl octyl magnesium) were used as conjugate supports and also TEAL (triethyl aluminum) was as an activator. It was found that the performance of the nanosilica-BOM bisupported catalyst was efficient in the ethylene polymerization towards the preparation of the PE/silica nanocomposites. Hydrogen was applied to control the molecular weight of the nanocomposites. An unusual polymerization behavior was observed in the presence of hydrogen. The nanocomposites were not soluble in any solvent. The nanostructure of the resulting PE/silica nanocomposites was characterized by transmission electron microscopy (TEM), FTIR, BET, and SEM. The thermal properties of the nanocomposites were studied by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA).

Sensitivity analysis and multi-objective optimization of gas-phase polymerization of propylene using Ziegler-Natta catalysts

Gas-phase polymerization of propylene via 4th generation Ziegler-Natta (ZN) catalysts was studied and optimized using intelligent data-based methods. The effect of co-catalyst (triethylaluminium (TEA)) and external donor (ED) compositions on the activity and PP-isotacticity for two commercial MgCl2/TiCl4/phthalate(ID)/TEA/silane(ED) catalyst systems with different Ti-contents were investigated using design-of-experiment (DOE) combined with response-surface-methodology (RSM). Sobol’s sensitivity analysis was employed to determine the quantitative impact of catalyst compositions on the target variables. Both catalysts performance was optimized via multi-objective genetic algorithm (GA) to maximize the activity and PP-isotacticity. Results revealed that the activity and PP-isotacticity for both catalysts will be enhanced at low co-catalyst and high ED amounts, respectively. Increasing the ED improved the activity of low-Ti catalyst, whereas it reduced the activity of high-Ti one. Sensitivity results for both catalysts depicted the comparable influence of co-catalyst and ED on the activity and the strong influence of ED on PP-isotacticity. GA optimization offered the activity of 3.7 – 4.65 gPP/mgCat and PP-isotacticity of 95.8 – 97.5 % for low-Ti catalyst at the optimal TEA/Catalyst = 7 – 7.2 and TEA/ED = 6.0 – 7.2 and the activity of 3.9 – 4.7 gPP/mgCat and PP-isotacticity of 93 % for the high-Ti one at the optimal TEA/Catalyst = 7 – 11.2 and TEA/ED = 12.

Exploring cocatalyst type effect on the Ziegler–Natta catalyzed ethylene polymerizations: experimental and DFT studies

Due to the important role of cocatalyst in the polymerization process employing industrially favored Ziegler–Natta catalysts, its effect on kinetic behavior, catalyst activity, and polymer properties is discussed. In this paper, triethyl aluminum (TEA) and triisobutyl aluminum (TIBA) have been used as the main cocatalyst ingredient with 10–20 mol percent of diethyl aluminum chloride (DEAC) and ethyl aluminum dichloride (EADC) cocatalysts, being neat TEA the cocatalysts with the highest activity. Moreover, TEA-DEAC and TEA-EADC cocatalysts revealed a built-up kinetic profile, while TIBA-DEAC and TIBA-EADC show a decay-type kinetic curve. According to melt flow index results, no considerable change in flowability was detected in the synthesized polyethylenes (PE). On the other hand, the ethylene insertion and chain termination mechanisms were investigated by means of density functional calculations using Ti active center located in (110) and (104) facets of the MgCl2 surface. To shed light on the bulkiness level of employed cocatalysts, buried volume (VBur) together with the two-dimensional map of cocatalyst systems were considered. Higher VBur of TIBA complex can explain its lower activity and decay type kinetic profile obtained by experimental studies.

Effect of different chain transfer agents in the coordinative chain transfer oligomerization of dec-1-ene

Our recently developed new procedure was recalled to synthesize saturated polyalphaolefin (PAO)-based lubricants, in situ in a single step manner, using different chain transfer agents (CTA)s. To this aim, coordinative chain transfer oligomerization (CCTO) of dec-1-ene monomer was conducted to achieve saturated PAOs employing [Ti{2,2ʹ-(OC6H2-4,6-tBu2)2NHMePhMeNH}Cl2] complex and MAO as pre-catalyst and cocatalyst, respectively. Along with catalyst, various mole fractions of diethylzinc (ZnEt2), triethylaluminium (TEAL), and n-butylethylmagnesium (nBuEtMg) were utilized as CTAs during oligomerization procedure. Results disclosed that ZnEt2 lead to a reversible chain transfer reaction but TEAL, and nBuEtMg caused an irreversible chain transfer manner. Molecular weight of the synthesized PAO samples decreased by utilizing CTAs. Kinetic and 13C-NMR results exhibited that the catalyst consumption diminished and PAO tacticity degraded in CCTO procedure in comparison to the traditional oligomerization process. Furthermore, 1HNMR results confirmed the preparation of fully saturated PAO chains in the presence of proper amounts of ZnEt2 and nBuEtMg, which reveals their high efficiency in performing the CCTO mechanism. Kinematic viscosity (KV) and viscosity index (VI) values of the fabricated samples were comparable with commercial PAOs which are traditionally produced by the dangerous BF3 catalyst in industry.

Disentangled UHMWPE@silica powders for potential use in power bed fusion based additive manufacturing

Disentangled ultrahigh molecular weight polyethylene dUHMWPE (Mw ∼ 2.106Da) particles in a reactor blend with HDPE are catalytically prepared from ethylene, mediated by a new catalyst from N,N'-(2,6-pyridinediyl diethylidyne) bis[2,6-di-3-propenyl-benzenamine] iron dichloride and triethyl aluminum. These particles could be laser sintered, but not automatically processed in an SLS machine. The same catalyst supported on microsilica particles gives access to composite dUHMWPE@silica particle powder with particle sizes below 200 µm. Testing bars prepared by heat pressing have an Emod of 150 MPa, an elongation at break at 450 % and an ultimate strength of 39 ± 11 MPa. A SEM image indicates a silica induced crystallization into pseudo spherulites of 500 µm size. The dUHMWPE@silica composite particles have an fcc flowability value of 3.4 in a ring shear tester, and a low density of 150 kg.m−3. Additivation with nanosilica powder (1 wt%) and carbon black (0.25 wt%) allowed to process the composite in an SLS machine. The printed parts showed severe caking, but also a complete welding of the powder, albeit with voids on account of the low particle density.

Al-alkyls as acceptor dopant precursors for atomic-scale devices

Atomically precise ultradoping of silicon is possible with atomic resists, area-selective surface chemistry, and a limited set of hydride and halide precursor molecules, in a process known as atomic precision advanced manufacturing (APAM). It is desirable to expand this set of precursors to include dopants with organic functional groups and here we consider aluminium alkyls, to expand the applicability of APAM. We explore the impurity content and selectivity that results from using trimethyl aluminium and triethyl aluminium precursors on Si(001) to ultradope with aluminium through a hydrogen mask. Comparison of the methylated and ethylated precursors helps us understand the impact of hydrocarbon ligand selection on incorporation surface chemistry. Combining scanning tunneling microscopy and density functional theory calculations, we assess the limitations of both classes of precursor and extract general principles relevant to each.

Influence of temperature on ethylene octene-1 copolymerization catalyzed by supported metallocene catalyst

A supported (nBuCp)2ZrCl2 metallocene catalyst was prepared and used in the slurry copolymerization of ethylene/octene-1 with triethylaluminium (TEAL) as co-catalyst. The effects of polymerization temperature on the properties of both the catalyst and resulted copolymers were investigated. The results show that the yield of supported metallocene catalyst reaches 4.3 kgPE/gcat and the bulk density of PE is higher than 0.4 g/cm3, the fines content of the polymer is less than 12.0 wt%, and the molecular weight distribution (MWD) of products ranges from 2.9 to 4.0 within the polymerization temperature range of 73~88 °C. These results are beneficial for large-scale industrialization of supported metallocene catalysts, and also provide a reference for academic research.

Electronic Properties of Ti Sites in Ziegler–Natta Catalysts

Although Ziegler–Natta (ZN) catalysts play a major role in the polyolefin market, a true understanding of their properties at the molecular level is still missing. In particular, there is a lack of knowledge on the electronic properties of Ti sites. Theoretical calculations predict that the electron density of the Ti sites in the precatalysts correlates with the activation energy for olefin insertion in the Ti-alkyl bond generated at these sites after activation by Al-alkyls. It is also well known that the effective charge on the Ti sites in the activated catalysts affects the olefin π-complexation. In this contribution, we exploit two electronic spectroscopies, UV–vis and Ti L2,3-edge near-edge X-ray absorption fine structure (NEXAFS), complemented with theoretical simulation to investigate three ZN precatalysts of increasing complexity (up to an industrial system) and the corresponding catalysts activated by triethylaluminum (TEAl). We provide compelling evidence for the presence of monomeric 6-fold-coordinated Ti4+ species in all of the precatalysts, which however differ in the effective charge on the Ti sites. We also unambiguously demonstrate that these sites are reduced by TEAl to two types of monomeric 5-coordinated Ti3+, either alkylated or not, and that the former are involved in ethylene polymerization. In addition, small TiCl3 clusters are formed in the industrial catalyst, likely due to the occurrence of severe reducing conditions within the catalyst pores. These data prove the potential of these two techniques, coupled with simulation, in providing an accurate description of the electronic properties of heterogeneous ZN catalysts.

Optimization of 1,3-butadiene monomer coordination polymerization using response surface methodology (RSM)

Laboratory runs can be minimized via experimental design which yields the optimum and best data regarding the independent parameters. In this research work, response surface methodology (RSM) based on a threelevel central composite design (CCD) was utilized to optimize and evaluate the interactive effects of processing conditions for polymerization of 1,3-butadiene (Bd) diene monomer using Ziegler-Natta catalyst. The polybutadiene rubber (PBR) having different cis content and molecular weight was obtained. The catalyst components included neodymium versatate (NdV3) as catalyst, triethyl aluminum (TEAL) as cocatalyst or activator, and ethylaluminum sesquichloride (EASC) as chloride donor. For the modeling, three independent variables, namely monomer concentration (8-28 wt%), reaction time (1.5-2.5 h), and reaction temperature (45-75oC) at three levels were selected to optimize the dependent variables or responses including monomer conversion, viscosity-average molecular weight and the cis isomer content of the obtained polymer. The interaction between three crucial parameters was studied and modeled. Quadratic models were obtained to relate process conditions to dependent variables. It was observed that the optimal conditions predicted by RSM were consistent with the experimental data. Statistical analysis demonstrated that concentration of the monomer and the time of reaction significantly affected cis content. Moreover, processing conditions to achieve the desired response variables were predicted and experimentally approved. The optimal reaction conditions derived from RSM are monomer concentration = 19 wt%, polymerization time = 2 hours, and polymerization temperature = 50oC. Polymerization was carried out at optimum conditions. The appropriate level of dependent variables including 94.2% monomer conversion, 151812 g/mol viscosity-average molecular weight and 98.8% cis content was acquired.

The Effect of Titanium Tetra-Butoxide Catalyst on the Olefin Polymerization.

The purpose of this study was to assess the ability of titanium Ti(IV) alkyloxy compounds supported by organic polymer polyvinyl chloride (PVC) to polymerize ethylene by feeding triethylaluminium (TEA) as a cocatalyst. Additionally, the impacts of the molar ratio of [Al]/[Ti] on the catalytic activities in ethylene’s polymerization and of the comonomer through utilization of diverse quantities of comonomers on a similar or identical activity were studied. The optimal molar ratio of [Al]/[Ti] was 773:1, and the prepared catalyst had an initial activity of up to 2.3 kg PE/mol Ti. h. when the copolymer was incorporated with 64 mmol of 1-octene. The average molecular weight (Mw) of the copolymer produced with the catalysts was between 97 kg/mol and 326 kg/mol. A significant decrease in the Mw was observed, and PDI broadened with increasing concentration of 1-hexene because of the comonomer’s stronger chain transfer capacity. The quick deactivation of titanium butoxide Ti(OBu)4 on the polymers was found to be associated with increasing oxidation when supported by the catalyst. The presence of Ti(III) after reduction with the aluminum alkyls cleaves the carbon-chlorine bonds of the polymer, producing an inactive polymeric Ti(IV) complex. The results show that synergistic effects play an important role in enhancing the observed rate of reaction, as illustrated by evidence from scanning electron microscopy (SEM). The diffusion of cocatalysts within catalytic precursor particles may also explain the progression of cobweb structures in the polymer particles.

Atomic layer deposition of tungsten and tungsten-based compounds using WCl5 and various reactants selected by density functional theory

Atomic layer deposition (ALD) of metals and metal nitrides consist a major portion of the advanced thin film deposition technology owing to their wide applications in the field of the semiconductor industry. In this regard, the ALD of tungsten (W) is one of the vital processes which is mostly studied using WF6 precursor. However, the presence of corrosive fluorine in WF6 restricts its applications due to severe disadvantages like F-contamination and etching of the deposited films and/or the underlying substrate. Therefore, developing F-free W (FFW) precursor to deposit W (and other W-based compounds like WNx) is of significant importance. The current article investigates several possible routes that can give rise to the successful growth of ALD-W or W-based thin films using WCl5 as an FFW precursor. Density functional theory (DFT) simulation was carried out to check the feasibility of the reactions between a reactant and tungsten chloride as well as to predict the composition of the deposited film. The exothermic reactions for ALD of W metal were realized with H, diethylamine borane (DEAB), and dimethylamine borane (DMAB), whereas it was endothermic for H2, triethylaluminum (TEA), trimethylaluminum (TMA), tert-butyl hydrazine (TBH), and NH3. The detailed reaction mechanisms for predicting the growth of tungsten or tungsten compounds were simulated and are helpful to explain the growth of WNxCy by TBH and WCx by TEA. On the other hand, the experimental findings also confirm the W film deposition with H2 plasma and DEAB, between 200 and 300 °C. However, the best quality as-grown W-films (polycrystalline with a resistivity of ~395 µΩ-cm) were obtained only with H2 plasma as a reactant, which shows the largest negative reaction energy (ΔE) in DFT calculation. Further, the Cl content of much below 1 atomic% in the as-grown films deposited with H2 plasma was evident. Additionally, the experimental findings also confirmed the deposition of crystalline-W2N when NH3 was used as a reactant.

Modification of the Acyl Chloride Quench-Labeling Method for Counting Active Sites in Catalytic Olefin Polymerization

The reliable and efficient counting of active sites in catalytic olefin polymerization has been realized by using acyl chloride as the quench-labeling agent. However, the molar ratio of acyl chloride to the alkylaluminum cocatalyst must be larger than 1 in order to completely depress side reactions between the quencher and Al-polymeryl that is formed via chain transfer reaction. In this work, a tetrahydrofuran/thiophene-2-carbonyl chloride (THF/TPCC) mixture was used as the quenching agent when counting the active sites of propylene polymerization catalyzed by MgCl2/Di/TiCl4 (Di = internal electron donor)-type Ziegler–Natta catalyst activated with triethylaluminum (TEA). When the THF/TEA molar ratio was 1 and the TPCC/TEA molar ratio was smaller than 1, the [S]/[Ti] ratio of the polymer quenched with the THF/TPCC mixture was the same as that quenched with only TPCC at TPCC/TEA &gt; 1, indicating quench-labeling of all active sites bearing a propagation chain. The replacement of a part of the TPCC with THF did not influence the precision of active site counting by the acyl chloride quench-labeling method, but it effectively reduced the amount of acyl chloride. This modification to the acyl chloride quench-labeling method significantly reduced the amount of precious acyl chloride quencher and brought the benefit of simplifying polymer purification procedures after the quenching step.