The influence of anhydrous ferric chloride on the catalytic properties of chloroaluminate ionic liquids catalyst for Friedel-Crafts alkylation was investigated. The catalysts were characterized by Fourier-transform infrared (FT-IR) (acetonitrile molecule as probe), specific gravity, and 27 Al NMR. Besides, the effect of the mass ratio of FeCl 3 to AlCl 3 , catalysts dosage, toluene/olefin molar ratio, reaction temperature, and reaction time on long-chain alkenes alkylation were investigated thoroughly. And bromine value and high-performance liquid chromatography (HPLC) were employed as the evaluation method for alkylation products. It was observed that the addition of anhydrous ferric chloride results in improvement in terms of Lewis acid and its catalytic recyclability. Among these catalysts studied, the catalyst modified with 1.0 wt.% anhydrous FeCl 3 showed the best catalytic performance in terms of yield and stability, which can be attributed to the formation of new stronger acidic ions [Al 2 FeCl l0 ] − when the added ferric chloride reacts with acidic ions [Al 2 Cl 7 ] − .

In this work, using divinylbenzene (D), 1-vinylimidazole (V) and 1-vinyl-3butylimidazolium bromide ([VBIM][Br]) as monomers, the binary-monomer poly (ionic liquids) (PILs) and ternary-monomer PILs were successfully synthesized, via hydrothermal polymerization and anion exchange, sequentially. Compared with each other, the ternary polymeric acidic IL catalyst has a clear spongy porous structure, while having a more stable macroporous structure, a larger specific surface area, more acidic groups and more active sites. Catalytic performance of catalyst was investigated through the alkylation of o-xylene and styrene. The effect of the amount of IL added and the length of the cation chain on the ternary polymerization of acidic IL was systematically investigated.Under optimal reaction conditions (molar ratio of monomers was D:V: [VBIM][Br] = 2:1:1, the most suitable cation chain length was C 4 ), the synthesized MPD-[C 4 V]-[VBIM][SO 3 CF 3 ] has a larger specific surface area (89.47 m 2 /g), large pore volume (0.29 cm 3 /g), and abundant mesopores and macropores, which help to improve the contact between the active site and reactants. Moreover, the catalyst could maintain a relatively high conversion of styrene (99.0%), 1,2-diphenylethane yield (98.7%) and high thermostability under reaction and be easily be divided from the solution, which is critical for heterogeneous solid catalysts.

Catalysts based on different halo‐alkanes structures with durable catalytic performance were synthesized and applied to the Friedel–Crafts alkylation of long‐chain alkenes (mixed C16–24 olefins) with toluene. Surprisingly, compared with the usual industrial catalysts (~10 runs), the cyclic times of the ionic liquid (IL) catalysts reached up to 24 runs, which greatly promotes the industrialization process. Then, Lewis acids of catalysts with different precursor/AlCl3 molar ratios were investigated and a close relation was discovered between the Lewis acid and catalytic activity. In addition, a comparison of the different halo‐alkanes structures about those catalysts was made. The results showed that the [C6Et3N]Cl–AlCl3 had the strongest Lewis acid, corresponding to the highest catalytic performance. Also, the structures of precursors and the specific gravity and active site species of catalysts were investigated by Fourier transform infrared and Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Meanwhile, the various parameters (catalyst dosage, toluene/olefin molar ratio, reaction temperature and reaction time) of long‐chain alkenes alkylation with toluene were studied. Finally, under the optimized reaction conditions, the conversion and selectivity of long‐chain alkenes alkylation reached 99.92 and 32.99%, respectively.

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.

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-SO 3 H-[C 3 V][SO 3 CF 3 ] has the most uniform with a specific surface area of 97.30 m 2 /g and a pore volume of 0.35 cm 3 /g. Benefiting from the unique structure features, MPM-SO 3 H-[C 3 V][SO 3 CF 3 ] 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.