Rheology, morphology and tensile properties of reactive compatibilized polyethylene/polystyrene blends via Friedel–Crafts alkylation reaction

Attempts were made to study the effect of reactive compatibilization via Friedel?CCrafts alkylation reaction, using AlCl₃ as a catalyst, on rheology, morphology, and mechanical properties of polyethylene/polystyrene (PE/PS) blends. The results of linear viscoelastic measurements in conjunction with the results of the mixing torque variation indicated that PS showed much more degradation than that of PE in the presence of AlCl₃. It was also found that while for PE-rich blends, the viscosity, and storage modulus increased by reactive compatibilization, they decreased for PS-rich blends. The variation of viscosity and storage modulus for 50/50 blend was found to be dependent on frequency ranges showing the competitive effects of PE?Cg?CPS copolymer formation and PS degradation. The results of morphological studies showed that reactive compatibilization decreased the particle size and particle-size distribution broadness because of in situ graft copolymer formation. Reactive compatibilization enhanced the tensile strength and elongation at break for PE-rich blends. It was demonstrated that there is a close interrelationship between rheology, morphology, and mechanical properties of reactive compatiblized PE/PS blends. It was also demonstrated that rheological behaviors have a reliable sensitivity to follow the structural and morphological changes during compatibilization process, so that, those information can be used to predict the morphology as well as mechanical properties of the blends.     

Influence of pseudo-boehmite binder modified dealuminated mordenite on Friedel–Crafts alkylation

The influence of pseudo-boehmite binder on the catalytic properties of dealuminated mordenite (MOR) catalyst for Friedel–Crafts alkylation was investigated. Solid-state ²⁷Al MAS NMR spectroscopy, temperature-programmed desorption of ammonia (NH₃-TPD), BET surface area measurement and catalyst particle mechanical strength were used to characterize the catalysts. It was observed that the addition of pseudo-boehmite binder results in improvement in terms of pore size distribution and its mechanical strength. Furthermore, the dredged pore path of MOR was not destroyed although the acid amount and acid type were adjusted properly when the modified MOR was calcinated. Among these catalysts studied, the catalyst bound with 10 wt% pseudo-boehmite binder showed the best catalytic performance in terms of yield and stability, which can be attributed to its maximum medium strong acid amount and its structural properties which is favorable for fast diffusion of products.     

Structure and Catalytic Mechanism of a Bacterial Friedel–Crafts Acylase

C−C bond-forming reactions are key transformations for setting up the carbon frameworks of organic compounds. In this context, Friedel–Crafts acylation is commonly used for the synthesis of aryl ketones, which are common motifs in many fine chemicals and natural products. A bacterial multicomponent acyltransferase from Pseudomonas protegens (PpATase) catalyzes such Friedel–Crafts C-acylation of phenolic substrates in aqueous solution, reaching up to >99 % conversion without the need for CoA-activated reagents. We determined X-ray crystal structures of the native and ligand-bound complexes. This multimeric enzyme consists of three subunits: PhlA, PhlB, and PhlC, arranged in a Phl(A₂C₂)₂B₄ composition. The structure of a reaction intermediate obtained from crystals soaked with the natural substrate 1-(2,4,6-trihydroxyphenyl)ethanone together with site-directed mutagenesis studies revealed that only residues from the PhlC subunits are involved in the acyl transfer reaction, with Cys88 very likely playing a significant role during catalysis. These structural and mechanistic insights form the basis of further enzyme engineering efforts directed towards enhancing the substrate scope of this enzyme.     

Construction of inter-chain polymers and the investigation into Friedel–Crafts alkylation of styrene–acrylonitrile copolymers with chloroprene rubber and characterization

In this study, the Friedel–Crafts alkylation was realized in a solvent free processing of styrene–acrylonitrile copolymers/chloroprene rubber (SAN/CR) molten blending which contributes the formation of SAN-co-CR co-polymers and improved compatibility between SAN and CR. The properties of several Lewis acid compounds were tested as catalysts among which AlCl₃ was the most efficient. The effects of blending temperature and time on the co-polymer formation in situ were also investigated. The methodology of weighing and Fourier transform infrared analyses indicated that the reaction degree increases with increasing blending temperature and time in the ranges of this study. The micro-structures and reaction mechanisms of the resulted SAN-co-CR polymers and morphological structures of SAN/CR/AlCl₃ blends were characterized as well by differential scanning calorimetry, FT-IR spectra, GPC and scanning electron microscopy. The results showed that the inter-facial reactions between SAN and CR have been effectively improved. Moreover, the inter-chain structure of SAN-co-CR co-polymers was proposed which is different from general grafting or blocking co-polymers.     

Synthesis of chiral benzene-based tetraoxazolines and their application in asymmetric Friedel–Crafts alkylation of indole derivatives with nitroalkenes

A series of new chiral benzene-based tetraoxazoline ligands were prepared in good yields through the reaction of 1,2,4,5-benzenetetracarboxylic acid and chiral β-amino alcohols by continuous removal of water, and the asymmetric Friedel–Crafts alkylation of indole derivatives with nitroalkenes was tested using the chiral catalysts, which were generated in situ by refluxing the above ligands and anhydrous zinc chloride in solvent. In most case, good yields (up to 99%) and excellent enantioselectivities (up to 98% ee) were obtained.     

Friedel–Crafts green alkylation of xylenes with tert-butanol over mesoporous superacid UDCaT-5

Friedel–Crafts green alkylation of xylenes with tert-butanol was investigated in the presence of mesoporous superacidic catalysts named as UDCaT-4, UDCaT-5 and UDCaT-6. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability. The catalytic activity is in the order: UDCaT-5 (most active) > UDCaT-6 > UDCaT-4 > sulfated zirconia (least active). Synergistic effect of very high sulfur content present (9% (w/w) S) and preservation of tetragonal phase in UDCaT-5, in comparison with sulfated zirconia (4% (w/w) S), were responsible for higher catalytic activity. The performance of UDCaT-5 in alkylation of xylenes was studied with tert-butanol with reference to selectivity and stability. Alkylation of m-xylene over UDCaT-5 gives 96% conversion of tert-butanol with 82% selectivity towards 5-tert-butyl-m-xylene (5-TBMX) under optimum reaction conditions. The formation of products is correlated with the acidity of the catalyst. The reactions were conducted in liquid phase at relatively low reaction temperatures (130–160 °C). A systematic investigation of the effects of various operating parameters was done to describe the reaction pathway. The reaction was carried out without any solvent in order to make the process cleaner and greener. An overall second order kinetic equation was used to fit the experimental data, under the assumption that both xylene and tert-butanol are weakly adsorbed. An independent study of dehydration of tert-butanol (TBA) was also done. Alkylation of o-xylene and p-xylene with tert-butanol was also studied. The overall process is green and clean.     

Preparation and characterization of wood-fiber-reinforced polyamide 6–polypropylene blend composites

In this study, we used lithium chloride (LiCl) as a modifier to decrease the melting temperature (T _m) of polyamide 6 (PA6), and then, we fabricated wood-fiber-reinforced PA6–polypropylene (PP) blend composites via hot pressing. From crystallization analysis, the composites exhibited a lower T _m and a lower processing temperature compared to PA6. Color and Fourier transform infrared analyses showed that severe thermal degradation and discoloration of the composites could be prevented by the incorporation of LiCl. LiCl had positive effects on the mechanical properties of the final product and the interfacial compatibility among PA6, PP, and wood fiber. The flexural strength increased by 8.5%. In addition, both maleic anhydride grafted PP and wood fiber improved the mechanical properties. The flexural strengths increased by 7.9 and 40%, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47413.     

Friedel–Crafts type alkylation of benzene and other aromatic compounds using MgGa2O4 (spinel)–MgO based catalysts

The MgGa₂O₄ (spinel)–MgO catalyst (with Mg/Ga=2.0) requires a long induction period for exhibiting high catalytic activity in the benzylation of benzene, naphthalene, substituted benzenes and naphthalenes, depending upon the aromatic substrate. However, after its first use or pretreatment with gaseous HCl, the catalyst shows almost no induction period and also has very high benzylation activity, even in the presence of moisture in the reaction mixture. But its physico-chemical properties are changed drastically with a partial collapse of the spinel structure. The catalytically active species in this catalyst are expected to be mainly Ga₂O₃ and GaCl₃ dispersed on MgO.     

Fe2O3/TUD-1: an efficient catalysts for Friedel–Crafts alkylation of aromatics

Three-dimensional mesoporous (Fe-TUD-1) catalysts with different Si/Fe ratios (100, 50, 20 and 10) are prepared using triethanolamine as template. Physicochemical and textural measurements by XRD, elemental analysis, N₂ adsorption, UV–Vis spectroscopy and HR-TEM imaging indicate the formation of pure solid mesoporous materials and the presence of Fe₂O₃ nanoparticles in the prepared Fe-TUD-1 samples. The catalytic performance of Fe-TUD-1 catalysts is tested in Friedel–Crafts alkylations of single-ring aromatic compounds [e.g. toluene (T), ethyl benzene (EB) and cumene (C)] by benzyl alcohol (BnOH). Dispersion of Fe(III) in the mesoporous matrix of TUD-1 enhanced the catalytic activity of Fe-TUD-1 in the alkylation of aromatic compounds compared to pure Fe₂O₃ and TUD-1 catalysts. The catalytic activity further increases by the decreasing of Si/Fe ratio. Sample loaded with Si/Fe ratio = 10 (Fe-10) showed almost complete conversion of BnOH in a relatively very short reaction time (<30 min) with 95 % selectivity. The catalytic performance of Fe-TUD-1 was superior to other metal-containing TUD-1 (e.g. Ga, Sn, and Ti) catalysts, or other Fe-containing catalysts (e.g. Fe-MCM-41, ZSM-5 and Fe-HMS). Alkylation of C is the fastest among the three aromatic substrates investigated (at temperatures very close to their boiling points) due to the largest inductive effect by the isopropyl group compared to the methyl group of T and the ethyl group in EB. Dibenzyl ether is formed as a byproduct only in the early times of the reaction and proved to act as alkylating agent after being hydrolyzed backwards to reform BnOH. Leaching experiments show the Fe-TUD-1 materials are very stable and can be reused as alkylation catalyst.     

Synthesis of 1-phenyl-1-xylyl ethane by Friedel–Crafts alkylation of xylene with α-methylbenzyl alcohol over mordenite

In the Friedel–Crafts alkylation of xylene to prepare 1-phenyl-1-xylyl ethane (PXE), α-methylbenzyl alcohol was used as an alkylating agent over a mordenite catalyst. The catalyst was characterized by MAS-NMR, N₂ adsorption/desorption, NH₃-TPD, and various other techniques and was found to possess strong Brønsted acid sites. When temperature was low, the main product was bis-(α-methylbenzyl) ether. However, as the temperature went up, PXE and heavies, styrene trimers and heavier oligomers, became main products. The formation of PXE, occurring on strong acid sites, is favored by raising temperature, space velocity, pressure, and xylene/MBA ratio within the experimental ranges. As the catalyst deactivates, the selectivities to PXE and heavies decrease and those to linear dimer and styrene increase. A reaction mechanism is proposed.     

Characterisation of thermally treated and untreated polyethylene–polypropylene blends using DSC,TGA and IR techniques

Abstract

The thermal characteristics of thermally treated and untreated very low density polyethylene, isotactic polypropylene and their blends were investigated. Injection moulded blends containing five different weight percentages of VLDPE/iPP were prepared and thermally treated at 100°C for 2, 4, 7 and 14 days. Differential scanning calorimetry, thermogravimetry and infrared spectral analysis techniques were used to study the effect of thermal treatment and blending ratio on the thermal and chemical stability. The addition of PE had caused the T _m, heat of fusion and percentage crystallinity of PP main melting peak to decrease, indicating that both polymers are partially miscible. T _m has been found to increase with aging time, however, the heat of fusion is not significantly affected. The initial and final decomposition temperatures, maximum decomposition rate temperature, order of decomposition reaction, activation energy and activation enthalpy were calculated, in a dynamic nitrogen atmosphere, and discussed in terms of blending ratios and aging times. The IR spectra of all blends at different aging times do not show any degradation products.     

Effect of nanoclay on mechanical and thermal properties of triblock SBS (styrene–butadiene–styrene) and its binary blend nanocomposites: comparison between polyethylene and polystyrene

ABSTRACT

In this study, the effect of organo-modified nanoclay (OMMT) on the mechanical and thermal properties of SBS and its blend with low-density polyethylene (LDPE) and polystyrene was investigated. The effect of nanoclay content in the presence of LDPE or PS on the final properties of SBS was studied by tensile tester, dynamic mechanical thermal analysis (DMTA), thermal gravimetric analysis (TGA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Addition of nanoclay affected the mechanical and rheological properties. From X-ray and DMTA results, it was found that due to more affinity between the nanoparticles and the SBS/PE blend, the 2 theta characteristic peak of nanoclay shifted to lower angles. SEM studies showed better dispersion and lower inter-particle distance of nanoparticles in SBS/PE composites in comparison with SBS/PS and SBS composites, confirming the XRD and DMTA results. It can be concluded that nanoclay acts as a compatibilizer in the SBS/LLDPE blend. TGA studies showed higher stability of SBS/PS composites compared to SBS and SBS/PE ones.     

Isothermal crystallization and spherulite structure of partially miscible polypropylene–linear low-density polyethylene blends

Polypropylene (PP) was blended with a linear low-density polyethylene (LLDPE, containing 5% hexene comonomer) over a composition range of 10–90% of PP. The crystallization and morphology of the PP–LLDPE blends were studied by differential scanning calorimetry (DSC), polarized optical microscopy with a hot stage (HSOM), and scanning electron microscopy (SEM). In particular, the isothermal crystallization of PP in molten LLDPE was investigated. It was observed that the crystallization and melting behavior of PP and LLDPE changed in the blends, indicating that there was some degree of miscibility between the PP and the LLDPE. A depression of the equilibrium melting temperature (T) of PP in the blends with no more than 15% of PP confirmed that PP was miscible with LLDPE at and below 15% of PP. In addition, a drastic decrease in T from the 25% PP blend to the 20% blend led us to conclude that the miscible behavior between PP and LLDPE became favorable at a PP concentration of 20%. The optical microscopic images showed that, in the blends with 10 and 15% of PP, the PP crystallized as open-armed diffuse spherulites, similar to those in the miscible blends. In contrast, the PP crystallized in a phase-separated matrix or droplets with more than 25% of PP, when obvious phase separation occurred. The SEM image revealed that the PP lamella was able to penetrate the PP and LLDPE phase boundary and grow in the LLDPE phase. The above results displayed that the PP dissolved in the LLDPE, and, particularly, when the PP concentration was below 20%, the dissolution was substantial. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 628–639, 2001     

Influence of quinone grafting via Friedel–Crafts reaction on carbon porous structure and supercapacitor performance

High specific surface area carbon has been modified with para-benzoquinone (p-BQ) via Friedel–Crafts reaction catalyzed by Iron(III) chloride followed by oxidation, in order to explore alternative strategies for obtaining high energy density supercapacitor materials by the combination of the double layer capacitance of carbons with the redox pseudocapacitance of the organic redox couple added on the carbon surface.Suitable structural and physicochemical characterization proved the formation of covalent bonds between carbon and p-BQ, and the electrochemical characterization showed a significant increase in gravimetric capacitance values after the addition of p-BQ which is maintained even after many cycles.This gravimetric capacitance increase was not only due to the redox reactions of p-BQ, but also to an increased double layer capacitance after p-BQ modification even when the BET surface area decreases after modification. A correlation with the pore structure of carbons showed that the increased double layer capacitance can be attributed to a better matching of carbon pore size with the size of electrolyte ions after p-BQ addition. Thus, this new addition strategy opens the way for the development of carbon-based materials for supercapacitors with higher energy densities coming from both increased pseudocapacitive reactions and increased double layer capacitance.     

In situ synthesis,physical and mechanical properties of ZrB2–ZrC–WB composites

In this study, two composition ZrB₂–ZrC–WB composites were synthesized by reactive hot-pressing of Zr + B₄C + WC powder mixtures at 1900 °C. The microstructure of the resulting composites was characterized by a combination of scanning electron microscopy and X-ray diffraction. It is seen that highly-dense ZrB₂–ZrC–WB composites with a homogenous fine-microstructure were obtained after the sintering. The mechanical behavior of the composites was evaluated using by testing under four-point bend testing at room and high temperatures. The results show that the high-temperature strength of the ZrB₂–ZrC–WB composites was substantially improved, compared to ZrB₂–ZrC-based composites without WB. In addition, the elastic properties, electrical conductivity, hardness and fracture toughness of the composites were measured at room temperature. The results reveal that these properties were comparable to those of ZrB₂–ZrC-based composites without WB.     

Effect of blend ratio on the dynamic mechanical and thermal degradation behavior of polymer–polymer composites from low density polyethylene and polyethylene terephthalate

Microfibrillar polymer–polymer composites (MFCs) based on low-density polyethylene (LDPE) and polyethylene terephthalate (PET) were prepared by cold drawing-isotropization technique. The weight percentage of PET was varied from 5 to 45 %. Microfibrils with uniform diameter distribution were obtained at 15 to 25 wt% of PET as evident from the scanning electron microscopy (SEM) results. Dynamic mechanical properties such as storage modulus (E′), loss modulus (E″) damping behavior (tan δ) were examined as a function of blend composition. The E′ values were found to be increasing up to 25 wt% of PET. An effort was made to model the storage modulus and damping characteristics of the MFCs using the classical equations used for short-fiber reinforced composites. The presence of PET microfibrils influenced the damping characteristics of the composite. The peak height at the β-transitions of loss modulus was lower for MFCs with 25 % PET, showing that they had superior damping characteristics. This phenomenon could be correlated with the PET microfibrils morphology. The thermal degradation characteristics of LDPE, neat blends and microfibrillar blends (MFBs) were compared. The determination of activation energy for thermal degradation was carried out using the Horowitz and Metzger method. The activation energy for thermal degradation of microfibrillar blends was found to be higher than that for the corresponding neat blends and MFCs. The long PET microfibrils present in MFBs could prevent the degradation and enhance the activation energy.     

Melt spinning of silane–water cross-linked polyethylene–octene through a reactive extrusion process

The aim of this study is to produce silane–water cross-linked polyethylene–octene (PEO) fibers through a reactive extrusion process. First, PEO is silane-grafted during an extrusion process followed by a spinning step. Then, grafted PEO monofilaments are introduced in water-based solution to perform cross-linking. The influence of process parameters on bulk PEO cross-linking degree was first investigated through a mixture design methodology which revealed that the most influent parameters are extrusion temperature and time. Using these results and the response surface methodology, silane–water cross-linked PEO monofilaments could be produced with desired gel contents after proceeding to some adjustments of processing parameters. The influence of cross-linking degree and draw ratio on macroscopic properties of PEO monofilaments was investigated. In particular, the cross-linked PEO fibers thermomechanical stability increases with cross-linking degree up to 170 °C for cross-linking degrees higher than 55%. Moreover, cross-linked PEO fibers exhibit higher elastic properties than neat PEO fibers.     

Synthesis of a Re-usable Cellobiase Enzyme Catalyst through In situ Encapsulation in Nonsurfactant Templated Sol–Gel Mesoporous Silica

We present a re-usable enzyme catalyst system via direct encapsulation of cellobiase in nonsurfactant templated sol?Cgel mesoporous silica host material with d-fructose as the template. The pore diameter and porosity of the silica host material, controlled by the fructose content, controlled the diffusion of substrate to the enzyme. This in situ immobilized cellobiase showed little or no leakage while could be repeatedly used as biocatalyst with little or no loss of activity after at least 9 cycles.     

Assessment of compatibilization role of nanoclay in immiscible polystyrene/ethylene–octene copolymer blends via wide-angle X-ray scattering,microstructure, rheological analyses,and mechanical properties

Polystyrene (PS)/ethylene–octene copolymer (EOC) blends with 80/20 wt % composition containing different amounts (0, 1.0, 2.5, 5.0 and 7.5 wt %) of an organically modified nanoclay were prepared by one-step melt-mixing method. Also, the EOC-rich blends with 80 wt % EOC content loaded with 0 and 5.0 wt % of the nanoclay were prepared under the similar processing conditions. Presence of both PS and EOC chains in between clay layers localized at the interface of the blends could be deduced by X-ray diffraction analysis, which suggested formation possibility of PS-EOC physical structures at the blend interface. Transmission electron microscopy results confirmed that clay nanoparticles were mainly localized at the interface of the blends and also partly in the PS and EOC components of the systems. The localization of the nanoclay was also described by the linear viscoelastic melt rheological studies. It is also revealed that nanoclay had stronger interactions with PS than EOC. This is reflected in the higher tensile properties in the PS-rich system. The analysis of morphology of the developed systems by emulsification curve revealed that the optimum amount of nanoclay to modify PS-rich blend is 2.5 wt %. At this clay loading, the blend exhibited the highest impact resistance. According to the overall results, suitability of nanoclay was confirmed for compatibilization of the PS/EOC blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48748.