Search

In this contribution, we describe the kinetics associated with the rac-Me2Si[2-Me-4-Ph-Ind]2ZrCl2 (Cat-1)/borate/TIBA catalyzed copolymerization of E/dienes (isoprene (IP), butadiene (BD), 5-ethylidene-2-norbornene (ENB), 4-vinylcyclohexene (VCH) and vinyl norbornene (VNB)), and E/diene/1-hexene (1H) terpolymerization by using thiophenecarbonyl chloride (TPCC) that was used in Ziegler-Natta (Z-N) and metallocene-catalyzed polyethylene (PE) and polypropylene (PP) and E/P polymerizations. In both types of polymerizations, a higher amount of dienes was incorporated when VNB (2.70 mole %) and VCH (1.56 mole %) were added as comonomer, but IP and BD were incorporated with the moderated rate (0.6-1.1 mole %) with higher activities (3.45x106gm/mmolMt·h). The active center [Zr]/[C*] fraction is higher (61%) than previously reported PE polymerizations, especially in the case of E/IP, E/BD and E/IP/1H but lower than E/P (87%) copolymerization. Significantly, IP and BD activated the inactive catalytic sites that were dormant in the PE. The propagation rate constant (kpE) with IP was higher (kp564 Lmol-1s-1), while kpE with VNB (kp379 Lmol-1s-1) and VCH (kp304 Lmol-1s-1), which were lower than PE. This difference is built because of the diffusion barrier in the system. Compared to E/diene copolymers, kpE values in E/diene/1H terpolymerizations for IP, VCH, and VNB are higher and stable except ENB and determine that 1H prevents the insertion of dienes and reduces the crystalline properties resultant moderate kpE. Even though the E/BD copolymers decreased butadiene content of over 2 mol% resulted in better crystalline characteristics, lower diffusion barriers, and a higher kpE value. In concept, IP and BD are linear and readily available for coordination. While VCH, ENB and VNB are cyclic and bulky, metallocene in contact ion pairs cannot accept ENB, VNB, and VCH for coordination and subsequently act as dormant in the polymerization. [ABSTRACT FROM AUTHOR]

To understand how the silyl-bridged metallocene catalysts rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 behave against dienes under the same reaction condition because of its importance as a commercial polymerization catalyst and ethylene propylene diene monomers (EPDM). Adding diene depressed the catalytic activity, especially 5-ethylidene-2-norbornene (ENB) exerted the most substantial deactivation effect. Firstly, we examine the (ENB, vinyl norbornene (VNB) and 4-vinylcyclohexene (VCH)) non-conjugated and conjugated (isoprene (IP), butadiene (BD)) diene and address how polymerization catalysts behave against these dienes. For example, the catalytic activity was enhanced with IP and BD (3–3.3106 gm/mmolMt·h) compared to ENB, VNB and VCH. The VNB incorporation rate was prolonged (5.4 mol%), but with IP and BD, it was relatively moderate. E/P/IP and E/P/BD with higher incorporation of E produced a higher MW, which means that the chain transfer reaction with ethylene is slower than P. Secondly, we address how the dienes exocyclic and exocyclicπ bonds of non-conjugated and conjugated properties of IP and BD affect the kinetic measurements such as active centers [Zr]/[C*] fraction, EPDM chain propagation, termination, and isomerization. Finally, we compare [Zr]/[C*] and kpPE, kpP and kpDienes for different EPDM. After collecting these kinetic parameters, we can describe the mechanism's intricacy and the existence of considerable catalyst dormancy with dienes under identical reaction conditions. [ABSTRACT FROM AUTHOR]

The objectives of this work were to address the fundamental characteristics of ansa-zirconocene catalyzed E/diene copolymerization and E/diene/1-hexene and E/diene/propylene terpolymerizations, and the quantitative relationship between diene structure and polymer chain propagation rate constant in term of quantifiable catalytic active sites. One of the most important but unknown factors in olefins ansa-zirconocene complexes is the distribution of the catalyst between sites actively participating in polymer chain formation and dormant sites. A set of ethylene/dienes copolymerizations, and ethylene/dienes/1-hexene and ethylene/dienes/1-hexene terpolymerizations catalyzed with ansa-zirconocenes/borate/triisobutylaluminium (rac-Et(Ind)2ZrCl2/[Ph3C][B(C6F5)4]/triisobutylaluminium (TIBA) were performed in toluene at 50 °C To determine the active center [C*]/[Zr] ratio variation in the copolymerization of E with different dienes and their terpolymerization with 1-hexene and propylene, each polymer propagation chain ends were quenched with 2-thiophenecarbonyl, which selectively quenches the metal–polymer bonds through acyl chloride. The ethylene, propylene, 1-hexene, and diene composition-based propagation rate constants (kpE, kpP, kp1-H, and kpdiene), thermal (melting and crystalline) properties, composition (mol% of ethylene, propylene, 1-hexene, and diene), molecular weight, and polydispersity were also studied in this work. Systematic comparisons of the proportion of catalytically [Zr]/[C*] active sites and polymerization rate constant (kp) for ansa-zirconocenes catalyzed E/diene, E/diene/1-hexene, and E/diene/propylene polymerization have not been reported before. We evaluated the addition of 1-hexene and propylene as termonomers in the copolymerization with E/diene. To make a comparison for each diene under identical conditions, we started the polymerization by introducing an 80/20 mole ratio of E/P and 0.12 mol/L of 1-hexene in the system. The catalyst behavior against different dienes, 1-hexene, and propylene is very interesting, including changes in thermal properties, cyclization of 1-hexene, and decreased incorporation of isoprene and butadiene, changes in the diffusion barriers in the system, and its effect on kp. [ABSTRACT FROM AUTHOR]

For enhancing the moisture resistance properties of the commercial CaO, the surface of the CaO has been modified using various aliphatic and aromatic groups as modifiers. The binding of the modifiers onto the surface of the CaO is confirmed through the FTIR and XPS techniques. For the first time, these modified CaO catalysts have been employed to carry out the transesterification reaction of glycerol and dimethyl carbonate forming glycerol carbonate. Under the optimized reaction conditions, benzyl modified CaO catalyst showed better catalytic activity yielding 82 % glycerol carbonate with 100 % selectivity. The 0.5‐Ben/CaO catalyst is found to resist the presence of 5 wt% H2O content in the reaction due to the formation of hydrophobic layer by the benzyl functionalization over the CaO surface. The humidity test also reveals that the modified CaO showed better resistance to moisture adsorption than its native counterpart. [ABSTRACT FROM AUTHOR]

The copolymerization of ethylene (E) with isoprene (Ip) was performed catalyzed by a symmetrical catalyst exhibiting a silicon bridge [rac-Me 2 Si(2-Me-4-Ph-Ind) 2 ZrCl 2 with the combination of borate/TIBA activator. The effect of cocatalyst, Ip concentration, and polymerization temperature on the activity, molecular weight (Mw), distribution (MWD), comonomer composition, chain structure (regio- and stereoselectivity), and resulting side reactions were logically addressed. Gel-permeation chromatography (GPC) was used to characterize the Mw and polydispersity, while nuclear magnetic resonance (NMR) was employed for the chain structure of the polymers. The catalytic activity was significantly lower by increasing the Ip concentration in the feed, and the isoprene content in resulting polymers was lower under the reaction condition, leading to higher activity. Insertion of isoprene units in polymer structure demonstrates the higher regioselectivity for the 3,4 connections than the 1,4 connections and is expected to be a high-resistance polymer against acids. The MWD presented monomodal even with a higher concentration (1.44 mol/L) and did not appear as low Mw peaks of Ip. The Mw was higher with a broader MWD when purely TIBA was used as a cocatalyst, and it significantly reduced and presented a narrowed MWD with TEA in the cocatalyst. The higher efficiency of the catalyst for the higher insertion of Ip (C=C double bond) effectively modifies the polymer backbone. It is expected to be a promising candidate for easily degradable and favorable solutions for solving environmental problems caused by PE. wastes. [Display omitted] • Environmentally benign methodology reaction conditions (low temperature and pressure) are hallmarks of this approach. • Ethylene α-olefin (linear conjugated diene) copolymerization catalyzed with a symmetrical Single-site homogeneous catalyst. • Ethylene α-olefin (linear conjugated diene) copolymerization catalyzed with a symmetrical Single-site homogeneous catalyst. • The MWD demonstrated monomodal even with a higher concentration of isoprene (1.44 mol/L). • Increased insertion of isoprene may lead to easily degradable and beneficial solutions for PE waste environmental issues. [ABSTRACT FROM AUTHOR]

Copolymerization of ethylene (E) and propylene (P) and their terpolymerizations with three kinds of diene (5-ethylidene-2-norbornene (ENB), 4-vinylcyclohexene (VCH) and 1,4-hexadiene (HD)) under 4 bar monomer pressure in n-heptane solution were studied. Two ansa-zirconocenes (rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (Mt-I) and rac-Et(Ind)2ZrCl2 (Mt-II)) activated by (Ph3C)B(C6F5)4/triisobutylaluminum were used as the catalyst, respectively. In general, addition of diene depressed the polymerization activity. ENB exerted the strongest deactivation effect on Mt-I, and HD caused the strongest deactivation on Mt-II. Among the two metallocenes, activity of Mt-I was more sensitive to the diene. Increasing diene concentration in the monomer feed caused lower propylene incorporation rate and shorter average length of polypropylene sequences, and the average length of polyethylene sequences was increased by adding more HD in E/P/HD terpolymerization with Mt-II. The Mt-II/borate catalyst showed high activity and diene incorporation rate for E/P/ENB terpolymerization. In contrast, Mt-I/borate catalyst showed high activity and propylene incorporation rate for E/P copolymerization, but was nearly inactive for E/P/ENB terpolymerization. [ABSTRACT FROM AUTHOR]

Abstract 5-Na/ZnO loaded SBA-15 has been prepared by one-pot method in atmospheric conditions (without employing hydrothermal treatment) and following wet impregnation method. The prepared catalyst was characterised by using several techniques viz., BET method for determination of surface area, FE-SEM for morphology of catalyst, XPS study to determine the oxidation state of constituent elements. The catalyst was utilised for transesterification from virgin cotton seed oil and the catalyst activity was dependant on its basic strength. Under optimal reaction conditions of catalyst amount 12 wt%, methanol to oil molar ratio of 24:1 at reaction temperature of 65 °C, the prepared catalyst yielded > 98% fatty acid methyl ester in 4 h of reaction duration. The catalyst was able to yield conversion level as good as ∼74% even in 5th cycle after regeneration. Leaching of < 5 ppm metal content was observed, in 4th and 5th cycle, which was within the ASTM specified limitations. The thermodynamic parameters for the reaction, viz. , activation energy E a , ΔH‡, ΔS‡, ΔG‡ were calculated as 77.3 kJ mol−1, 74.2 kJ mol−1, -0.064 kJ mol−1 and, + 93.2 kJ mol−1 respectively. Graphical abstract Image 1 Highlights • Synthesis of SBA-15 and impregnation of 5-Na/ZnO was performed in single step. • In situ method of synthesis saved lot of time and energy consumption compared to 2-step synthesis. • Prepared catalyst was employed for biodiesel production and reused for 5 consecutive runs. • The catalyst activity was found to be a function of its basic strength. [ABSTRACT FROM AUTHOR]

The development of low-cost earth-abundant electrocatalysts to produce ammonia (NH3) with high efficiency for the nitrogen (N2) reduction reaction (NRR) remains challenging. Herein, we propose the development of highly efficient ultrathin nitrogen-vacancy-rich molybdenum nitride nanosheets (MoN-NV) for NRR using basic electrolytes under ambient conditions. In 0.1 M KOH, this catalyst attained a high faradaic efficiency (FE) of ∼14% with an NH3 yield of 22.5 μg h−1 mg−1cat at −0.3 V vs. a reversible hydrogen electrode under ambient conditions. The characterization results and electrochemical studies disclosed that nitrogen vacancies in the MoN-NV nanosheets played a critical role in the enhanced electrocatalytic activity for NRR. Furthermore, the recycling tests confirmed the stability of the catalyst during NRR electrolysis. [ABSTRACT FROM AUTHOR]

Abstract: Lithium impregnated calcium oxide has been prepared by wet impregnation method in nano particle form as supported by powder X-ray diffraction and transmission electron microscopy. Basic strength of the same was measured by Hammett indicators. Calcium oxide impregnated with 1.75 wt% of lithium was used as solid catalyst for the transesterification karanja and jatropha oil, containing 3.4 and 8.3 wt% of free fatty acids, respectively. The reaction parameters, viz., reaction temperature, alcohol to oil molar ratio, free fatty acid contents, amount of catalyst and amount of impregnated lithium ion in calcium oxide support, have been studied to establish the most suitable condition for the transesterification reaction. The complete transesterification of karanja and jatropha oils was achieved in 1 and 2h, respectively, at 65°C, utilizing 12:1 molar ratio of methanol to oil and 5 wt% (catalyst/oil, w/w) of catalyst. Few physicochemical properties of the prepared biodiesel samples have been studied and compared with standard values. [Copyright &y& Elsevier]

Present work demonstrates an easy route by sol-gel method, without using any template, for the synthesis of flower shaped tungsten (W) supported TiO 2 /SiO 2 catalyst for the triglyceride transesterification. The structure of the catalyst was established by powder X-ray diffraction and surface morphology and particle size by field emission scanning and high resolution transmission electron microscopy studies, respectively. The oxidation state of tungsten by X-ray photoelectron spectroscopy was found to be +6. Under the optimized reaction conditions of 5 wt% of 20-W/TiO 2 /SiO 2 -700 catalyst, 30:1 methanol to oil molar ratio and 65 °C reaction temperature, more than 98% fatty acid ethyl ester yield was obtained in 4 h. The kinetic and thermodynamic parameter of the reaction was also evaluated following the pseudo-first order equation. The catalyst was recycled in four consecutive runs and total metal contents in biodiesel was observed <5 ppm to maintain the stability of the catalyst. [ABSTRACT FROM AUTHOR]

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 (kpE) in the soluble fraction was much smaller than that of the insoluble fraction. Rate constant of 1-hexene insertion (kpH) 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. [ABSTRACT FROM AUTHOR]

In this study, first biocatalytic synthesis of clinically important imidazo[1,2- a]pyridine based compounds has been achieved. The Candida antarctica lipase B (CALB) enzyme was found suitable to catalyze the Groebke-Blackburn-Bienaymé (GBB) multicomponent reaction of substituted 2-aminopyridine, benzaldehyde and isocyanides to synthesize imidazo[1,2-a]pyridine derivatives in very good yields. Further, CALB enzyme was immobilized on mesoporous silica and characterized using FT-IR, XRD, SEM-EDS and HR-TEM to use as a reusable catalyst in this transformation. The immobilized catalyst CALB@SiO 2 displayed high catalytic efficiency up-to many cycles. In addition, preliminary mechanistic studies such as molecular docking and molecular dynamics (MD) simulation were performed which suggested that Thr40 and Ser105 residues are playing an important role in catalyzing the GBB-reaction. Image 1 • First biocatalytic synthesis of clinically important imidazo[1,2-a]pyridine. • CALB catalyzed Groebke-Blackburn-Bienaymé multicomponent reaction. • Immobilization of CALB@SiO 2 as reusable catalyst. • Computational investigations suggested Thr40 and Ser105 residues play an important role in catalysis. [ABSTRACT FROM AUTHOR]

Kinetics of propylene polymerization with two TiCl4/MgCl2 model catalysts of different Ti load (Cat‐1: Ti 0.1 wt%; Cat‐2: Ti 1.0 wt%) was investigated in this work. Time‐dependent variations of active centers fraction ([C*]/[Ti]) and active center distribution of the two catalysts were compared. In propylene polymerization with Cat‐1, [C*]/[Ti] was only 7.8 % in the initial stage, but increased for more than three times in reaction period of 600 s. Propylene polymerization with Cat‐2 had much lower [C*]/[Ti]. Active center distributions of the two catalysts were markedly different. Cat‐1 has evidently higher proportion of aspecific active centers and less isospecific ones than that of Cat‐2. These catalysts also showed different time‐dependent variations of active center distribution. The chain propagation rate constant of isospecific centers in Cat‐2 was evidently higher than that in Cat‐1, but propagation rate constants of either aspecific and medium‐isospecific centers were only slightly changed by enhancing Ti content of the catalyst. The results suggest that isospecific centers are mainly originated from clustered Ti species, but non‐clustered Ti species are the main source of active centers with lower stereoselectivity. By considering factors like dispersion states of Ti species and release of shielded active species through disintegration of catalyst particles, active center models have been proposed to explain the different kinetic behaviors of the two model catalysts. [ABSTRACT FROM AUTHOR]