Preparation And Modification Of Calixarene And Its Application In Hydrocarbon Fuel

Calixarenes are a class of macrocyclic oligomers, which can be modified with different functional groups, and were widely used in many fields. Hydrocarbon fuels are faced with many challenges in use, such as antioxidant, improvement of conversion rate and coke inhibitation. In order to meet the needs, a variety of fuel additives were developed. Because the molecular structure of calixarenes is similar with the commercial phenolic antioxidants, there is the possibility of becoming antioxidant. Calixarenes can be modified with some special functional groups and used as free radical initiator. In addition, the calixarene or its derivatives can be used for the preparation of lipophilic nano metal, which can serve as quasi-homogeneous catalyst for the cracking of hydrocarbon fuels. In this work, special calixarenes were prepared and used as additives for hydrocarbon fuels. It can significantly affect the antioxidation, radical initiation and quasi-homogeneous catalysis of hydrocarbon fuels。1. Tetra-methylcalix[4]resorcinarene and Tetra-undecylcalix[4]resorcinarene, referred to as C1-C[4]R and C11-C[4]R, were prepared with resorcinol and aldehyde. Then, calix[4]resorcinarene derivatives containing sulfur and nitrogen group, referred to as Cx-SCy or Cx-NCy, were prepared by the mannich reaction. In addition, p-tert-butylcalix[4]arene and its oxygenated derivative were prepared. All products were characterized by NMR and TGA.2. Static autoclave-gas chromatography method used in the antioxidant investigation of C11-C[4]R, with the commercial antioxidant BHT as comparison. Both C11-C[4]R and BHT are able to decrease the hydrogen peroxide concentration peaks, while this effect for C11-C[4]R is more remarkable. In the analysis of reaction residue, it can be found C11-C[4]R can inhibit the generation of oxides and the depth oxidation of model fuel.3. Using the dynamic method, the pyrolysis of model fuel with calixresorcinarene derivatives as additive was studied. Experimental results show that the use of calixarene derivatives C11-NC2N is beneficial for improving the pyrolysis conversion rate of fuel model, and can significantly improve the olefin selectivity and reduce coke rate.4. Nano nickel and nickel-boron amorphous alloy had been prepared by using C11-C[4]R as wrapped agent. The average size for these particles are in the range of20～40nm. The nanoparticles were used as quasi-homogeneous catalytic for model fuel cracking. Experimental results show that, compared with the conversion rate of pyrolysis, the conversion rate of quasi-homogeneous catalytic cracking is significantly increased. In this work, C11-SC3was also used as wrapped agent for preparing nano nickel and platinum particles. the average sizes of obtained products are all less than10nm, which exhibit good dispersion in hedrocarbon fuels.