| In recent years, 1-(1,3,3,3-tetrachloropropyl)benzene has attracted much attention because of its ability as intermediate for synthesis of cinnamon acid. Cinnamic acid is an important intermediate in organic synthesis, which can be widely used for production of fine chemicals, such as perfume, medication, pesticide, plastics, photosensitive resin and so on. There are many kinds of methods for synthesis of cinnamic acid, since the 50's industrialization, the process improves gradually, and has become the main method of production of cinnamic acid. However, the new process synthesis of cinnamic acid has attracted more and more attention because of the low yield and high energy consumption. In recent years, a new synthetic method using the styrene and carbon tetrachloride as the raw material has been coveraged at home and abroad, and it has advantageous of higher yield and lower production costs.Ionic liquids are more and more famous for their friendly physical and chemical properties to environment (almost negligible vapor pressure in room temperature, wide liquid temperature, good electrical conductivity, strong acidity, function). It has been widely applied to organic synthesis, catalysis, separation and electrochemistry. However, at present, ionic liquids have many defaults, such as expensive price, large dosage and difficulty in extracting products from catalyst. In addition, for non-tvolatile or non-volatile reactants and products, it is very difficult to separate ionic liquids from reaction mixtures. Immobilized ionic liquids can be formed from grafting ionic liquids by means of chemical bonds. This kind of ionic liquids, which successfully combines the advantages of homogeneous catalysis with heterogeneous process technology, exhibits excellent catalytic activity in many organic synthesis systems.Herein, in this paper, two kinds of heterogeneous catalysts immobilized functional ionic liquids containing Cu ion have been synthesized, and their catalytic abilities for Kharasch addition reaction between CC14 and styrene are investigated. The details are as follows:1. Two kinds of supporting functional pyridinium and imidazolium ionic liquids were prepared, and synthesis of 1-(3-Aminopropyl) pyridinium chloride and SBA-15 incorporating pyridium ionic liquids by one step which has never been reported in the previous works. And then we synthesized the immobilized liquids by covalent bonds between the ionic liquid's cation and MWCNTs carboxyl groups on the surface, but 3-trimethoxysilylpropyl-pyridinium chloride and1-(3-trimethoxysilyl-propyl)-3-methylimidazolium chloride supported on SBA-15 by one step, compared with traditional way, this method combined synthesizing SAB-15 with supporting by one step. Followed by addition of CuCl2, CuCl, CuBr? and Cu(NO3)2. These two methods have their own advantages. First, choose functionalization ionic liquids; then immobilise ionic liquid on support in the chemically bonded; at last, add metal salts.2. The supports, intermediates and catalysts were characterized by HRTEM, BET, TG, FT-IR and EA. The results show that ionic liquids and Cu ions have been immobilized on the supports successfully. After grafting and complexing reaction, the surface area and pore volume of the supports by MWCNTs increased, but the surface areas of SBA-15 as support markedly decreased. The results of XRD and HRTEM images indicated that the crystallinity of SBA-15 molecular sieve retains its structural integrity after immobilizing the ionic liquid groups and Cu ions.3. Under the reaction conditions of 100℃, styrene:carbon tetrachloride (n/n)=1:4, Cu:styrene (n/n)=1:100,24 h, under argon atmosphere, using MWCNTs-immobilized catalysts, the conversion of styrene and selectivity of 1-(1,3,3,3-tetrachloropropyl)benzene were 15.6% and 8.8%, respectively. Whereas using SBA-15-immobilized as catalysts, the conversion of styrene and selectivity of 1-(1,3,3,3-tetrachloropropyl)benzene were 16.0% and 77.3%, respectively.The later one exhibits higher catalytic activity. It is easier to separate in the biphasic reaction system, and decrease the corrosion of equipment obviously. |
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