Triethylaluminum Research Articles

Kinetic and thermal study of ethylene-propylene copolymerization catalyzed by ansa-zirconocene activated with Alkylaluminium/borate: Effects of linear and branched alkylaluminium compounds as cocatalyst

Ethylene-propylene (EP) copolymerizations was carried out with two ansa-metallocene: rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (Mt-I) and rac-Et(Ind)2ZrCl2 (Mt-II) combined with borates activators like ([Me2NPh][B(C6F5)4] (Borate-I), [Ph3C][B(C6F5)4] (Borate-II). Different structures of alkylaluminum( triethylaluminium (TEA), triisobutylaluminium (TIBA) and TEA/TIBA mixture of 25/75, 50/50, 75/25 mol ratios were used as cocatalysts. The choice of ligand structure and, more importantly, the nature of the cocatalyst significantly impact these systems' activity and the polymeric materials' properties. Borate-II has been shown as giving higher activities than Borate-I with both ansa-metallocene, attending 5.6 × 106 g/mol Zr*h. Mt-I gives higher activities and molecular weight but produced copolymers with low ethylene content, melting points, and crystallinity than Mt-II. The activities were very close to each other with 100% TIBA. Still, Mt-I became more active than Mt-II when TEA was more than 25% in the cocatalyst system. The effects of alkylaluminiums catalysts cocatalyst on EP copolymer molecular weight (Mw) and molecular weight distribution (MWD) were much more complicated. The MWD curve changed from broad to narrow with Mt-I when TIBA was replaced by a different mole ratio of TEA/TIBA ratio. The technique used for the assessment of active centers [C*]/[Zr] fraction in the ansa-metallocene catalyst was quenched label by using 2-thiophenecarbonyl chloride (TPCC) to determine the effects of alkylaluminiums catalysts structure on the propagation rate constants (kP) of EP copolymers. The [C*]/[Zr] value of Mt-I/Borate-I/TIBA is lower than those of the Mt-I/Borate-I/TEA and Mt-I/Borate-I/TEA/TIBA system. The main differences appear between catalysts containing pure TIBA and those containing TEA, possibly due to the faster rate of chain transfer with Al—Et than with bulky Al—iBu. Adding TEA in metallocene/borate/alkylaluminiums catalysts catalysts can be applied as an effective method to regulate the molecular weight of EP copolymer with a high degree of activity

Effect of alkylaluminum cocatalyst on ethylene/1-hexene copolymerization and active center distribution of MgCl2-supported Ziegler-Natta catalyst

Ethylene-1-hexene copolymerization was catalyzed by TiCl4/diester/MgCl2 type Z-N catalyst activated by triethylaluminium (TEA), triisobutylaluminium (TIBA) or TEA/TIBA mixtures. Copolymerization activity decreased with increase of TIBA content in the cocatalyst. Each copolymer sample was fractionated into boiling n-heptane soluble and insoluble fractions. 1-Hexene content of the soluble fraction was 2 ∼ 6 times larger than that of the insoluble fraction. With introduction of TIBA in the cocatalyst, chemical composition distribution of the copolymer was broadened, attributable to increase of 1-hexene in the soluble fraction. Total number of active centers markedly decreased with increasing TIBA in cocatalyst, and active center number in the soluble fraction decreased more than that in the insoluble fraction. Rate constant of ethylene insertion (k pE) in the soluble fraction was much smaller than that of the insoluble fraction. Rate constant of 1-hexene insertion (k pH) of the soluble fraction became far larger than that of the insoluble fraction when TEA/TIBA ratio was lower than 80/20. In the presence of TIBA, only a part of active center precursors with stronger ability of incorporating 1-hexene were effectively activated in the soluble fraction. For the active centers in insoluble fraction, cocatalyst structure exerted more complicated effects on their activation. Active center models were proposed to explain the observed cocatalyst effects.

Experimental study of the auto-catalytic effect of triethylaluminum and TiCl4 residuals at the onset of non-additive polypropylene degradation and their impact on thermo-oxidative degradation and pyrolysis

In this article, the pyrolysis and thermo-oxidative degradation of five industrial waste products was carried out in a discontinuous quartz reactor at 550 °C under the auto-catalytic effect of residues of titanium tetrachloride (TiCl4), triethylaluminium (TEAL), and iron (Fe). We using the coupled on-site analysis of an GCMS/FID/PDHID with 7 valves and 8 columns in series. The study also discusses the effect of the concentration of the catalyst residuals with the Eac (activation energy) and the evolution of the profile of permanent oxygenated gases, hydrocarbons and sulfurs, as well as the functional waste groups from decomposition during pyrolysis and thermo-oxidative degradation. The origin of the degradation and the beginnings of PP pyrolysis and thermo-oxidative degradation are explained by hydrolysis mechanisms and thermal reactions that imply successive reactions with these (TEAL), TiO2, and chloride residues, giving rise to ethyl radicals and explaining the formation of alcohols, ketones, carboxylic acids, alkynes and alkenes. The study also found that the gaseous profiles are very consistent with the DTG curves and the Eac, in terms of the appearance of peaks and relevant stages throughout the total temperature range. The effect of Cl, Fe and TEAL on the PP degradation is very high upon passing from an inert to an oxidative atmosphere. This reduces the content of hydrocarbons and oxygenates to CO2 between 49 and 66% because of the attack of the oxygen atom. In the pyrolysis the propylene content oscillates between 42 and 56%. Finally, the initial reaction mechanisms, and the secondary reaction routes, are proposed and demonstrated experimentally in function of the primary volatile compounds quantified. The thermo-oxidative properties of the five PP waste products improve significantly with the addition of 0.1% of a secondary antioxidant.

Kinetic and Thermal Study of Ethylene and Propylene Homo Polymerization Catalyzed by ansa-Zirconocene Activated with Alkylaluminum/Borate: Effects of Alkylaluminum on Polymerization Kinetics and Polymer Structure.

The kinetics of ethylene and propylene polymerization catalyzed by homogeneous metallocene were investigated using 2-thiophenecarbonyl chloride followed by quenched-flow methods. The studied metallocene catalysts are: rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (Mt-I), rac-Et(Ind)2ZrCl2 (Mt-II) activated with ([Me2NPh][B(C6F5)4] (Borate-I), [Ph3C][B(C6F5)4] (Borate-II), and were co-catalyzed with different molar ratios of alkylaluminum such as triethylaluminium (TEA) and triisobutylaluminium (TIBA). The change in molecular weight, molecular weight distribution, microstructure and thermal properties of the synthesized polymer are discussed in detail. Interestingly, both Mt-I and Mt-II showed high activity in polyethylene with productivities between 3.17 × 106 g/molMt·h to 5.06 × 106 g/molMt·h, activities were very close to each other with 100% TIBA, but Mt-II/borate-II became more active when TEA was more than 50% in cocatalyst. Similarly, Polypropylene showed the highest activity of 11.07 106 g /molMt·h with Mt-I/Borate-I/TIBA. The effects of alkylaluminum on PE molecular weight were much more complicated; MWD curve changed from mono-modal in Mt-I/borate-I/TIBA to bimodal type when TIBA was replaced by different amounts of TEA. In PE, the active center fractions [C*]/[Zr] of Mt-I/borate were higher than that of Mt-II/borate and average chain propagation rate constant (kp) value slightly decreased with the increase of TEA/TIBA ratio, but the Mt-II/borate systems showed higher kp 1007 kp (L/mol·s). In PP, the Mt-I/borate presented much higher [C*]/[Zr] and kp value than the Mt-II. This work also extend to investigate the mechanistic features of zirconocenes catalyzed olefin polymerizations that addressed the largely unknown issues in zirconocenes in the distribution of the catalyst, between species involved in polymer chain growth and dormant state. In both metallocene systems, chain transfer with alkylaluminum is the dominant way of chain termination. To understand the mechanism of cocatalyst effects on PE Mw and (MWD), the unsaturated chain ends formed via β-H transfer have been investigated by 1H NMR analysis.

Catalytic reactions on magnesium dichloride clusters saturated by titanium tetrachloride

Magnesium dichloride, titanium tetrachloride, and triethyl aluminum are essential components in the Ziegler-Natta catalysts for olefin polymerization. We report a systematic computational investigation (M06-2X/def-TZVP level of theory, thus accounting for dispersion) of the thermodynamics of a sequence of catalytic reactions leading to ethylene polymerization in the absence of electron donors. The reactions are explored for a series of TiCl4-adsorbed magnesium dichloride clusters as a function of the adsorption site, involving (104)- and (110)-type ideal edge sites alongside with corners representing defect sites. The reactions comprise alkylation of TiCl4, reduction from Ti(IV) to Ti(III) and Ti(II), ethylene π-complexation to Ti(III), and chain growth. The polymerization process as a whole is shown to be strongly exergonic for all adsorption sites, with coordination numbers of the site mainly contributing to the reduction and π-complexation energies.

Application of Artificial Neural Networks for Producing an Estimation of High-Density Polyethylene.

Polyethylene as a thermoplastic has received the uppermost popularity in a vast variety of applied contexts. Polyethylene is produced by several commercially obtainable technologies. Since Ziegler–Natta catalysts generate polyolefin with broad molecular weight and copolymer composition distributions, this type of model was utilized to simulate the polymerization procedure. The EIX (ethylene index) is the critical controlling variable that indicates product characteristics. Since it is difficult to measure the EIX, estimation is a problem causing the greatest challenges in the applicability of production. To resolve such problems, ANNs (artificial neural networks) are utilized in the present paper to predict the EIX from some simply computed variables of the system. In fact, the EIX is calculated as a function of pressure, ethylene flow, hydrogen flow, 1-butane flow, catalyst flow, and TEA (triethylaluminium) flow. The estimation was accomplished via the Multi-Layer Perceptron, Radial Basis, Cascade Feed-forward, and Generalized Regression Neural Networks. According to the results, the superior performance of the Multi-Layer Perceptron model than other ANN models was clearly demonstrated. Based on our findings, this model can predict production levels with R2 (regression coefficient), MSE (mean square error), AARD% (average absolute relative deviation percent), and RMSE (root mean square error) of, respectively, 0.89413, 0.02217, 0.4213, and 0.1489.

The influences of alkylaluminium as cocatalyst on butene-1 polymerization with MgCl2-supported TiCl4 Ziegler-Natta catalysts

The influences of alkylaluminium compounds including triethylaluminium (TEA), triisobutylaluminium (TIBA) and diethylaluminium chloride (DEAC) on the catalyst activity, isotacticity and weight-average molecular weight (Mw) of the products in butene-1 (Bt-1) polymerizations with MgCl2-supported TiCl4 Ziegler-Natta catalysts were investigated. The catalytic activity of polybutene-1 (PB) increased in the order of TEA > TIBA > DEAC, while the Mw of PB synthesized with TEA was the lowest when compared with that with other alkylaluminium compounds. Solvent extracted fractionation combining with differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and carbon-13 nuclear magnetic resonance spectrometry (13C-NMR) were used to conduct composition analysis of PB. Fractions including atactic polybutene-1 (aPB), high isotactic polybutene-1 with high Mw (HiPB) and medium high isotactic polybutene-1 with medium high Mw (MHiPB) were isolated for the first time from the PB. Using TIBA resulted more HiPB fractions with higher Mw. A minor incorporation of TIBA or DEAC in TEA increased the HiPB fractions of PB. The contribution mechanism of alkylaluminium compound in TiCl4/MgCl2 Ziegler-Natta catalyst was proposed to explain the influence of alkylaluminium compound with different structures on the active species and polymer components in PB.

Tuning the Redox Chemistry of a Cr/SiO2 Phillips Catalyst for Controlling Activity, Induction Period and Polymer Properties.

The Cr/SiO2 Phillips catalyst has taken a central role in ethylene polymerization ever since its discovery in 1953. This catalyst is unique compared to other ethylene polymerization catalysts, since it is active without the addition of a metal‐alkyl co‐catalyst. However, metal‐alkyls can be added for scavenging poisons, enhancing the catalyst activity, reducing the induction period and altering polymer characteristics. Despite extensive research into the working state of the catalyst, still no consensus has been reached. Here, we show that by varying the type of metal‐alkyl co‐catalyst and its amount, the Cr redox chemistry can be tailored, resulting in distinct catalyst activities, induction periods, and polymer characteristics. We have used in‐situ UV‐Vis‐NIR diffuse reflectance spectroscopy (DRS) for studying the Cr oxidation state during the reduction by tri‐ethyl borane (TEB) or tri‐ethyl aluminum (TEAl) and during subsequent ethylene polymerization. The results show that TEB primarily acts as a reductant and reduces Cr6+ with subsequent ethylene polymerization resulting in rapid polyethylene formation. TEAl generated two types of Cr2+ sites, inaccessible Cr3+ sites and active Cr4+ sites. Subsequent addition of ethylene also revealed an increased reducibility of residual Cr6+ sites and resulted in rapid polyethylene formation. Our results demonstrate the possibility of controlling the reduction chemistry by adding the proper amount and type of metal‐alkyl for obtaining desired catalyst activities and tailored polyethylene characteristics.

Facile Investigation of Ti3+ State in Ti-based Ziegler-Natta Catalyst with A Combination of Cocatalysts Using Electron Spin Resonance (ESR)

This study aims to investigate the influences of a combination of cocatalysts including triethylaluminum (TEA) and tri-n-octylaluminum (TnOA) for activation of a commercial Ti-based Ziegler-Natta catalyst during ethylene polymerization and ethylene/1-hexene copolymerization on the change in Ti3+ during polymerization. Thus, electron spin resonance (ESR) technique was performed to monitor the change in Ti3+ depending on the catalyst activation by a single and combination of cocatalyst. It revealed that the amount of Ti3+ played a crucial role on both ethylene polymerization and ethylene/1-hexene copolymerization. For ethylene polymerization, the activation with TEA apparently resulted in the highest catalytic activity. The activation with TEA+TnOA combination exhibited a moderate activity, whereas TnOA activation gave the lowest activity. In case of ethylene/1-hexene copolymerization, it revealed that the presence of 1-hexene decreased activity. The effect of different cocatalysts tended to be similar to the one in the absence of 1-hexene. The decrease of temperature from 80 to 70 °C in ethylene/1-hexene copolymerization tended to lower catalytic activity for TnOA and TEA+TnOA, whereas only slight effect was observed for TEA system. The effect of different cocatalyst activation on the change of Ti3+ state of catalyst was elucidated by ESR measurement. It appeared that the activation of catalyst with TEA+TnOA combination essentially inhibited the reduction of Ti3+ to Ti2+ leading to lower activity. Furthermore, the polymer properties such as morphology and crystallinity can be altered by different cocatalysts. Copyright © 2020 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Temperature effect on propylene polymerization behavior over Ziegler-Natta catalyst with different cocatalyst systems

This study focused on the effect of temperature in propylene polymerization behaviors up on different cocatalysts employed. It revealed that triethylaluminum (TEA) exhibited higher activity than tri-n-octylaluminum (TnOA) with the optimal temperature of 60 °C, whereas the over reduction of catalyst occurred at 70 °C. However, at low temperature (ca. 50 °C), the mixed cocatalysts (TEA + TnOA) gave the highest activity among the sole cocatalyst. This can be attributed to the occurrence and stabilization of proper Ti oxidation state (Ti3+) form as proven by the electron spin resonance (ESR) with the combination of cocatalysts. In addition, temperatures and types of cocatalyst did not have significant effects on morphology and crystallinity of polymer.

Polymerization of heterophasic propylene copolymer with Me2Si(2-Me-4-PhInd)2ZrCl2 supported on SiO2 and SiO2-MgCl2 carriers

Me2Si(2-Me-4-pbind)2ZrCl2 supported on SiO2/MgCl2 binary support was prepared for the preparation of heterophasic copolymer of polypropylene. The bi-support underwent surface treatment with various alkyl aluminum compounds such as trimethylaluminum (TMA), triethylaluminum (TEAL), and triisobutylaluminum (TIBA) before supporting the metallocene catalyst for 3 or 24 hours and were used for homopolymerization. It was notable that the generated SiO2/MgCl2 bi-support had lower surface area, pore volume and size as compared to the conventional SiO2. Impact polypropylene copolymers (IPCs) were obtained using two-step polymerization in one reactor with the presence of metallocene catalyst supported on SiO2. Propylene was polymerized in the reactor to produce the iPP matrix followed by polymerization of ethylene resulting to heterophasic material. It is apparent that the molecular weight of the polymer increased with longer PE polymerization time and as the polymerization time was more than 40 min, PP peak appeared near 147.9–149.2 °C, and a new peak emerged at 116.9–119.9 °C which could be attributed to the melting temperature of iPP crystallites and a less intense peak to either chains of ethylene-propylene copolymers. SEM images also confirmed that spherical PE particles were deeply embedded in the crystalline PP matrix and a large amount was produced as the polymerization time of the second stage ethylene polymerization was increased.

Aluminum Alkyls as Highly Active Catalytic Chain Transfer Agents

AbstractDuring the production of free radical initiated low‐density polyethylene (LDPE), it was discovered that the addition of low levels of alkyl aluminum compounds caused the molecular weight of the LDPE to drop precipitously. Further investigation demonstrated that aluminum‐alkyl compounds are among the most effective chain transfer agents ever utilized. It was also shown that polymer chains, which transfer to Al alkyl species, contain almost exclusively vinyl terminated end groups. A catalytic chain transfer mechanism is proposed in which chain transfer occurs from a growing polymer chain to an aluminum center followed by beta hydride elimination to produce a vinyl terminated polymer chain and a new aluminum hydride bond. This new aluminum hydride bond can then undergo further chain transfer reactions. This is the first time such a catalytic chain transfer mechanism has been reported. As little as 10–20 mol ppm aluminum alkyl species decreased the degree of polymerization by a factor of 2 resulting in chain transfer constant (Cs) values as high as 1000–2000. Density functional theory (DFT) study elucidated the catalytic cycle of triethylaluminum (TEA). It is discovered that, depending on the reaction conditions, TEA can serve as a conventional as well as catalytic chain transfer agent.

A Li–Al–O Solid‐State Electrolyte with High Ionic Conductivity and Good Capability to Protect Li Anode

AbstractUsing a solid‐state electrolyte (SSE) to stabilize the Li metal anode is widely considered a promising route to develop next‐generation high energy density lithium batteries. Here, a new polycrystalline aluminate‐based SSE (named Li–Al–O SSE) with good capability is introduced to protect Li metal. The SSE is formed on the Li metal surface via a chemical reaction between LiOH and triethylaluminum (TEAL) with the existence of LiTFSI‐based electrolyte. It is a continuous film that consists of polycrystalline LiAlO2, Li3AlO3, Al2O3, Li2CO3, LiF, and some organic compounds. Such Li–Al–O SSE possesses a room‐temperature ionic conductivity as high as 1.42 × 10−4 S cm−1. Meanwhile, it effectively protects the Li anode from the corrosion of H2O, O2, and organic solvent, and suppresses the growth of Li dendrite. With the protection of the Li–Al–O SSE, the cycle life of Li|Li symmetric cell and Li|O2 cell is substantially elongated, indicating that the SSE exhibits an excellent protective effect under both inert and oxidizing circumstances.

Aluminium complexes as catalysts for ring-opening polymerization of ε-caprolactone bearing Schiff base ligands derived from 4,4′-Methylenebis (2,6-diisopropylaniline)

The mono and binuclear compounds, [4,4’ methylene bis (2,6-diisopropylaniline) (3,5-di-tert-butylsalicylaldehyde) AlEt2] (1), (2,6-diisopropylaniline) bis- (3,5-tBu2C6H2-O-2) AlEt2], obtained by reacting between triethyl-aluminium and Schiff base derived from reaction of 4,4’ methylene bis (2,6-diisopropylaniline with one and two equivalent of 3,5-Di-tert-butylsalicylaldehyde to form L1H and L2H2 respectively. The reaction of L1H with triethyl aluminium lead to form monometallic complex, while L2H reacted with two equivalent of triethyl aluminium formed bimetallic complex (2). Both ligands and catalysts have been prepared and characterized by IR, 1HNMR and CHN analysis. The compounds 1 and 2 are investigated as catalysts for the polymerization of ε-caprolactone in the presence of benzyl alcohol. Both complexes showed moderate activity as pre-catalysts for ε-caprolactone polymerisation.

Effect of alkylaluminium on the regio- and stereoselectivity in copolymerization of isoprene and butadiene using TiCl4/MgCl2 type Ziegler-Natta catalyst

Alkylaluminums as one of the most important components of the heterogeneous MgCl2-supported (TiCl4/MgCl2) type Ziegler-Natta catalysts, play significant roles in yielding active species with varied regio- and stereoselectivity. Studying the contribution of alkylaluminums on the conjugated diene isoprene (Ip) and butadiene (Bd) copolymerizations with TiCl4/MgCl2 - alkylaluminum catalysts system is little reported. In this work, effects of various alkylaluminums including triethylaluminium (TEA), triisobutylaluminium (TiBA), diisobutylaluminium hydride (DiBAH) and diethylaluminum chloride (DEAC) on the copolymerization behaviors of Ip and Bd using the TiCl4/MgCl2 - alkylaluminum catalysts system, such as catalytic activity, active center numbers, butadiene incorporation, trans-1,4 stereoselectivity, molecular weight Mw as well as molecular weight distribution Mw/Mn of copolymers were first investigated. TEA with smaller size ethyl groups showed higher copolymerization activity, higher reducing ability and then yielding more active center numbers ([C*]/[Ti]) when compared with TiBA, DiBAH and DEAC. Microstructure of copolymers gradually transformed from the cis-1,4/trans-1,4 mixed structure in the initial polymerization period to the finally high trans-1,4 structure, indicating a transformation of the active center nature during the early polymerization stage, which can be accelerated effectively through the addition of DEAC into the TiCl4/MgCl2-TEA catalyst system. TEA with smaller size ethyl group showed higher transformation rate from the mixed structures of trans-1,4 and cis-1,4 to highly trans-1,4 structure. The active center numbers of the copolymerization systems increased gradually with increasing time until reaching a stable level. The Mw/Mn of copolymers showed interesting evolution with increasing polymerization time from broad distribution with low to medium molecular weight fractions in the initial polymerization stage to relatively narrow distribution with high molecular weight fractions. The contribution of alkylaluminium compounds on the structure of active species which determining the regio- and stereoselectivity of Ip and Bd copolymerization using heterogeneous TiCl4/MgCl2 type catalysts were discussed in details

Preparation of Butadiene-Isoprene Copolymer with High Vinyl Contents by Al(OPhCH₃)(i-Bu)₂/MoO₂Cl₂∙TNPP.

In this study, a butadiene-isoprene coordination polymerization was initiated by a binary molybdenum (Mo)-based catalytic system consisting of modified MoO2Cl2 as the primary catalyst, triethyl aluminum substituted by m-cresol as the co-catalyst and tris(nonyl phenyl) phosphate (TNPP) as the ligand. The effects of the amount of catalyst and type of co-catalyst were investigated in detail. Experimental results indicated that when the butadiene-isoprene coordination polymerization was initiated by the binary Mo-based catalytic system, the monomer conversion could reach 90%. The resulting butadiene units were primarily based on 1,2-structures, and the reactivity ratios of butadiene and isoprene were 1.13 and 0.31, respectively. The reaction in the catalytic system was attributed to the non-ideal and non-constant ratio copolymerization. When the addition of isoprene monomers was relatively low, the isoprene units on the butadiene-isoprene copolymers were primarily based on the 1,2- and 3,4-structures. Moreover, the orientation of active centers to 1,2- and 3,4-structures gradually decreased with an increase in the addition of isoprene monomers, which resulted in the generation of high vinyl butadiene-isoprene copolymers.

Effect of electronegativity and steric hindrance of the cocatalyst on the activity and selectivity of butadiene polymerization catalyzed by molybdenum

ABSTRACTMolybdenum‐based random 1,2‐polybutadiene (1,2‐PB) rubber, with its excellent wet skid resistance, low rolling resistance, and low heat buildup, can be used for green tread rubber, and it has significant benefits for the enhancement of the mechanical strength of 1,2‐PB. In this study, we investigated in detail the effects of the electronegativity and steric hindrance of the cocatalyst on the stereoselectivity of the resulting polymers. In the case of cocatalysts with moderate electronegativities, the active centers were more stable; this resulted in a larger molecular weight and a higher conversion, whereas a cocatalyst with excessive electronegativity tended to initiate cationic polymerization. The high sterically hindered substituent restricted the coordination configuration of the monomer; this ultimately resulted in the increase in the 1,2 structure to 90%. Fourier transform infrared analysis showed that the content of trans‐1,4 structure increased from 7 to 66%, and its crystallinity reached 59.2%, as calculated with differential scanning calorimetry when triethyl aluminum was used as the cocatalyst. Consequently, trans‐1,4‐polybutadiene crystals were introduced into the 1,2‐PB elastomer in one step; this could be a promising facile route for strengthening 1,2‐PB. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46906.

M-Cresol-substituted triethyl aluminum/MoCl5/TBP catalytic system for coordination polymerization of butadiene

Coordination polymerization of butadiene was initiated by a catalyst system consisting of tributyl phosphate (TBP) as ligand, molybdenum pentachloride as primary catalyst and triethyl aluminum substituted by m-cresol as co-catalyst. The effects of the substitution of m-cresol on the activity of the catalyst system, molecular weight and molecular weight distribution, intrinsic viscosity and microstructures of the resulting polymers were investigated in details. The molecular weight and molecular weight distribution of the polymerization products were determined by GPC. The microstructure of the polymerization products was characterized by FTIR, 13C NMR and DSC techniques. The experimental results indicated that the polymerization activity of the reaction system and the molecular weight of the polymerization products gradually increased with the increase of the substitution content of m-cresol, namely, Al(OPhCH3)2Et > Al(OPhCH3)Et2 > Al(OPhCH3)0.5Et2.5>AlEt3. The 1,2-structure contents of the polymerization products could be adjusted between 89 and 91% through the control of the substitution of m-cresol, and there was minute quantities of crystalline structures in the resulting polymers due to the increasing content of the syndiotactic 1,2-polybutadiene. In a word, the existence and increase of steric hindrance of m-cresol made it easier for polymerization products to form interdisciplinary 1,2-structure.

Mechanism of internal and external electron donor effects on propylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: New evidences based on active center counting

ABSTRACTTwo TiCl4/Di/MgCl2 type supported Ziegler–Natta catalysts were prepared by loading dibutylphthalate or dicyclopentyldimethoxysilane (DCPDMS) (internal donor, Di) and TiCl4 on activated δ‐MgCl2 in sequence, and a blank catalyst was prepared by loading TiCl4 on the same δ‐MgCl2 without adding Di. These catalysts have similar specific surface area and pore size distribution, thus form a suitable base for comparative studies. Propylene polymerization with the catalysts was conducted in n‐heptane slurry using triethylaluminum (TEA) as cocatalyst, and the effects of Di as well as De (external donor, in this work it was DCPDMS) on the number of active centers, the distribution of active centers among three polypropylene (PP) fractions (isotactic, medium isotactic, and atactic PP chains), and chain propagation rate constants of the PP fractions were studied by counting the number of active centers in the PP fractions using a method based on selective quench‐labeling of the propagation chains by 2‐thiophenecarbonyl chloride. When De was not added in the polymerization, introducing a phthalate type Di in the catalyst evidently changed the active center distribution by enhancing the proportion of active centers producing isotactic PP (iPP) ( ), but scarcely changed reactivities of the three groups of active centers forming the three fractions. When the De was added in the polymerization system with TiCl4/phthalate/MgCl2 catalyst, further shifting of active center distribution in favor of took place, meanwhile reactivities of the three groups of active centers also remarkably changed in favor of . Mutual effects of these changes led to overwhelming dominance of iPP production in the TiCl4/Di/MgCl2–TEA/De system (Di = phthalate, De = alkoxysilane). In contrast, though using alkoxysilane as Di also caused shifting of active center distribution in favor of when De was not added, addition of alkoxysilane De caused reverse shifting of active center distribution in favor of those producing PP of lower stereoregularity. This unfavorable change largely counteracted the reactivity changes in favor of caused by the De, rendering the catalytic system rather poor isospecificity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46605.

Optimizing particle characteristics of nanocrystalline aluminum nitride

Aluminum nitride (AlN) nanopowders are synthesized in a chemical vapor synthesis (CVS) process using triethylaluminum (TEAl) and ammonia as precursors. A simple reaction-coagulation-sintering model is used to investigate the influence of process parameters, such as hot-wall reactor temperature and system pressure, on particle characteristics: size and agglomeration for example. The results of these simulations show good agreement with the experimental data and enable a better understanding of these effects of temperature and pressure on particle size and microstructure. Pure wurtzite phase AlN nanocrystals are obtained for all tested process parameters. The primary particle (crystallite) size ranges from 2.7nm to 11.5nm with (secondary) particle size in the range of 4.3nm to 12.4nm. As predicted by the simulations, the experiments show a low degree of (hard) agglomeration that even reaches the value of 1 for syntheses above 1400°C and 100mbar, implying the complete absence of hard agglomerates at those conditions.