6196-95-8Relevant academic research and scientific papers
Green synthesis of 1-phenyl-1-ortho-xylene ethane in IL and reaction mechanism
Sun, Xuejun,Zhou, Xinming,Cao, Bobo,Cao, Ziping,Fu, Hui
, p. 14998 - 15004 (2017)
1-Phenyl-1-ortho-xylene ethane (PXE) in IL was synthesized, and the catalysts used were AlCl3 in 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) or 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), and H2SO4. When the concentrations of AlCl3 in IL, ortho-xylene and styrene were 0.35, 0.03 and 0.005?mol, respectively, it could be discovered that ([BMIM][Br]) was the best catalyst. When the mole fraction concentration of AlCl3/[BMIM][Br] was more than 0.40%, the reaction was able to achieve 100% conversion. When the reaction time was longer than 60 minutes, the percentage conversion of ortho-xylene attained was 100%. The mechanisms of the reaction were investigated by the DFT method at the B3LYP/6-311++G(d, p) level. The potential energy surface (PES) profile indicated that the energy of transition state was 22.59 kcal mol?1. This indicated that the activation energy of reaction was 28.24 kcal mol?1, which illustrated that the reaction occurred easily. Vibrational frequencies were observed in FT-IR spectra, the corresponding vibrational modes νs(H4-C3Al-H5) and νas(H4-C3Al-H5) indicated that an Al3+ ion was combined with a C3 atom. In addition, the repeated use of the catalysts was studied; the ionic liquids could still catalyze the reaction and the percentage yield of PXE was larger than 91% after 6 runs.
The catalytic performance study of polymerized ionic liquid synthesized in different conditions on alkylation of o-Xylene with styrene
Liu, Yonghui,Gao, Huaying,Sheng, Xiaoli,Zhou, Yuming,Wang, Beibei,Sha, Xiao,Jin, Maolu,Zhao, Jie,Liu, Wenqi
, (2019)
In this work, a series of novel acidic polymerized ionic liquids were used as heterogeneous catalyst for alkylation of o-Xylene with styrene. And the effect of the amount of initiator and the type of acid used for ion exchange on catalyst structure and the catalytic performance of catalysts for alkylation were studied thoroughly. The experiment results show: when the percentage of the amount of initiator in the total material is 3%, the polymerized ionic liquid catalyst MPM-SO3H-[C3V][SO3CF3] has the most uniform with a specific surface area of 97.30?m2/g and a pore volume of 0.35?cm3/g. Benefiting from the unique structure features, MPM-SO3H-[C3V][SO3CF3] manifested an excellent catalytic performance for alkylation of o-Xylene with styrene, along with the conversion of styrene was 96.8% and the yield of 1-Phenyl-1-ortho-xylene ethane was 94.7%. Therefore, this work provides a novel reference to the synthesis of polymerized ionic liquids and clearly explains the advantage of novel acidic polymerized ionic liquids on alkylation.
Alkylation of O-xylene and styrene catalyzed by cross-linked poly acidic ionic liquids catalyst with novel mesoporous-macroporous structure
Gao, Huaying,Zhou, Yuming,Sheng, Xiaoli,Zhao, Shuo,Zhang, Chao,Fang, Jiasheng,Wang, Beibei
, p. 138 - 146 (2018)
Cross-linked poly acidic ionic liquids (MPM-C6V-SO3CF3-IL) with mesoporous and macroporous network structure have been synthesized in different solvents. The novel solid acid catalyst with special network structure has a large surface area (103.83 m2/g), large pore volume (0.72 cm3/g) and abundant mesopores and macropores, which help to improve the contact between active site and reactants. Catalytic performance of catalyst was investigated through alkylation of o-xylene and styrene. Different reaction parameters specifically solvent on obtained catalyst and production of PXE were systematically investigated. Under optimal reaction conditions (reaction time was 3 h, reaction temperature was 120 °C, catalyst amount was 0.17 g (0.5 wt%), and o-xylene/styrene mass ratio was 7.5:1), a high conversion of styrene (100%) and 1,2-diphenylethane (PXE) yield of 99.67% was obtained, which is superior to commercial acid in liquid and even previous acids synthesized by our own group. Moreover, catalyst could keep relatively high thermostability under reaction and are easy to be separated and recycled from the solution, which are critical for heterogeneous solid catalysts. Thus, this novel catalyst can be potentially applied in other acidic reactions.
Synthesis of P123-Templated and DVB-Cross-linked Meso-macroporous Poly (ionic liquids) with High-Performance Alkylation
Liao, Qiang,Liu, Yonghui,Sha, Xiao,Sheng, Xiaoli,Wang, Beibei,Zhou, Yuming,Zhu, Zhiying
, (2020)
Meso-macroporous poly (ionic liquids) (MPILs) were successfully synthesized through a novel strategy with P123 (PEO20PPO70PEO20) as the pore-forming agent and divinylbenzene as crosslinker. Then effects of reaction temperature and the molar ratio of ionic liquid to divinylbenzene (IL to DVB) were systematically investigated together with the morphology and structure of MPILs. It was found the MPILs owned a meso-macroporous channel-like structure, large surface area (up to 732 m2/g), large pore volume (1.42 cm3/g) and high thermal stability. Meanwhile, the Brunauer–Emmett–Teller surface of MPILs could be fabricated by adjusting the reaction temperature and especially the IL to DVB molar ratio. In the probe reaction of alkylation of styrene and o-xylene, a 100% conversion of styrene and 96.4% PXE yield was acquired, and this is more expert than common commercial liquid acid catalyst. This work might develop a novel way for synthesizing porous heterogeneous polymer catalysts in the future and owning a promising future applied in other acidic catalytic reactions.
Highly active and green aminopropyl-immobilized phosphotungstic acid on mesoporous LaSBA-15 for alkylation of o-xylene with styrene
Sheng, Xiaoli,Zhou, Yuming,Zhang, Yiwei,Duan, Yongzheng,Xue, Mengwei
, p. 360 - 367 (2012)
The Keggin phosphotungstic acid, H3PW12O40 (HPW), was successfully immobilized on the surface of mesostructured LaSBA-15 by means of chemical bonding to aminosilane groups. The catalysts were characterized by elemental analysis, N2 adsoption, TEM, DRS-UV, and FTIR spectroscopy. Characterization results suggest that the surface area decreased after grafting amino groups to silica and the structures of heteropolyanions on amine-modified LaSBA-15 was maintained. Their catalytic behaviors were investigated in the alkylation of o-xylene with styrene. Among the functionalized catalysts, when the content of amino-groups was suitable, it had the best catalytic performances in terms of yield and stability. It is worth mentioning that the catalysts could be used repeatedly without loss of the activity and selectivity during several catalytic cycles. The good stability can be attributed to the strong interaction between the amino groups on the surface of LaSBA-15 and HPW anions.
H3PW12O40/mpg-C3N4 as an efficient and reusable catalyst in the alkylation of o-xylene and styrene
Zhu, Zhiying,Wang, Beibei,Yao, Qingzhao,Zhou, Yuming,Yang, Haiyong,Liu, Yonghui
, (2019)
A heterogeneous catalyst (HPW/mpg-C3N4) for the alkylation of o-xylene and styrene reaction was acquired by the immobilization of phosphotungstic acid (HPW) on mesoporous graphitic carbon nitride (mpg-C3N4) through electrostatic interaction. The results of Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) proved that HPW was successfully immobilized on the protonated mpg-C3N4 by electrostatic interaction. The textural properties and morphology of HPW/mpg-C3N4 were characterized by N2 adsorption–desorption, scanning electron microscopy (SEM). Among them, 40% HPW/mpg-C3N4 displays the best catalytic performance in the alkylation reaction with 91.8% yield and 96.5% selectivity to 1, 2-diphenylethylane. Moreover, protonated mpg-C3N4 not only displays as a support to facilitate great dispersion of HPW but also promotes the alkylation product diffusion effectively. Besides, the HPW/mpg-C3N4 catalyst could be recycled easily without significant loss of catalytic activity, which is demonstrate by the recyclability of HPW/mpg-C3N4 catalyst test.
One-step synthesis of hierarchical aluminosilicates using alkoxy-functionalized ionic liquid as a novel template
Fu, Xiaoqin,Sheng, Xiaoli,Zhou, Yuming,Fu, Zhiwei,Zhao, Shuo,Zhang, Zewu,Zhang, Yiwei
, p. 6036 - 6045 (2016)
Hierarchical zeolites have bridged the gap between conventional zeolite and mesoporous materials, which not only maintain the excellent advantages of microporous sieves, but also effectively resolve the diffusion limitations. Herein, a novel alkoxy-functionalized ionic liquid was employed as a mesoporous structure-directing agent to synthesize hierarchical aluminosilicates with dual micro-mesoporous channels. X-ray diffraction (XRD), N2 adsorption-desorption isotherms (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed desorption (TPD), thermogravimetric analysis (TGA) and 27Al magic-angle spinning nuclear magnetic resonance (27Al MAS NMR) were used to characterize the structural and textural features of the hierarchical aluminosilicates. The results showed that the ionic liquid (MTPI) employed played the role of a mesoporous structure-directing agent which was trapped within the pores of a faujasite structure through -Si-O-Al- and -Si-O-Si- linkages. The mesoporous diameters and structures of the final hierarchical materials could be uniformly tailored by tuning the added amount of template. Hierarchical aluminosilicates with the combined advantages of both mesoporous properties and the microporous crystalline structure of zeolites exhibited high catalytic activity and resistance to deactivation in the alkylation of o-xylene with styrene, as compared to the conventional zeolite with the sole presence of micropores. The distinct catalytic performance of hierarchical aluminosilicates could be attributed to the short diffusion routes and abundant exposed acidic sites on the external surface.
Design of micro-mesoporous zeolite catalysts for alkylation
Fu, Xiaoqin,Sheng, Xiaoli,Zhou, Yuming,Fu, Zhiwei,Zhao, Shuo,Bu, Xiaohai,Zhang, Chao
, p. 50630 - 50639 (2016)
Hierarchical zeolite Y was hydrothermally synthesized using ionic liquid 1-methyl-3-[3′-(trimethoxysilyl)propyl]imidazolium chloride, which was added into the conventional synthesis composition for crystalline microporous aluminosilicate as a mesopore-directing agent. An extremely short diffusion path length and abundant exposed acid sites in the hierarchical zeolite Y made it suitable for the catalytic transformation of bulky molecules. Then the catalytic performance of hierarchical zeolites Y was investigated using the alkylation of o-xylene with styrene. The ionic liquid directed hierarchical zeolite Y exhibited a remarkably high catalytic activity and long catalytic lifetime for the production of 1-phenyl-1-xylylethane via alkylation reaction, as compared with that of solely microporous zeolite Y. The distinct catalytic performances of the novel hierarchical zeolite Y could be attributed to the enhancement of medium strong acid amount and its micro-mesoporous structural properties which are favorable for the fast diffusion of products.
Deep compositional understanding of TBA: AlCl3 ionic liquid for its applications
Bhakthavatsalam, Vishnupriya,Chandra, Sudeshna,Choudhury, Rudra Prosad,Lande, Sharad V.,Pradhan, Jeevan,Sakhalkar, Mangesh
, (2020/07/31)
Chloroaluminate ionic liquids (ILs) have been immensely used as homogeneous catalyst in Friedel-Crafts reaction. We have recently synthesized chloroaluminate ILs by reacting aluminium chloride with a hydrophobic neutral ligand i.e. tributylamine (TBA:AlCl3). The current study elaborates on the investigations of the composition of the ionic liquids at various stages of their formation. The ionic liquids were synthesized using various mole ratios of tributyl amine and aluminium chloride in range of 1:1 to 1:2.3, in presence of an aromatic solvent in a one pot reaction. Various characterization techniques like Mass spectrometry, 27Al Nuclear Magnetic Resonance, 31P Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopy were used to elucidate the formation of various moieties of the TBA:AlCl3 Ionic Liquid. This study also elaborates on the investigations of the cationic and anionic moieties and their structure-property relationship for various applications. Various Friedel-Crafts reaction of industrial importance were performed using the ionic liquid having (Al2Cl7)?moiety to assess its performance and compared with conventional processes. The synthesized products were characterised by sophisticated analytical techniques like 1H NMR, 13C NMR, FTIR, GC–MS, GC-FID, to name a few. This class of ionic liquids also have importance in various electrochemical applications like aluminium deposition and aluminium batteries.
Room Temperature Catalyst System for the Hydroarylation of Olefins
Lee, Siu Yin,Villani-Gale, Alexander,Eichman, Chad C.
supporting information, p. 5034 - 5037 (2016/10/14)
A simple protocol for the hydroarylation of olefins to yield diarylmethine products is described. A Friedel-Crafts-type synthetic strategy allows direct access to biorelevant products in high atom efficiency. A combination of substoichiometric amounts of TMSCl and ZnBr2 promotes a rapid hydroarylation process at ambient temperature. The method is high yielding and is amenable to scale-up protocols.
