Studies On Design, Syntheses And Properties Of Novel Calixarene Polymers

Calixarenes, as the third host molecule in the supramolecular chemistry, have attracted considerable attentions. Due to calixarenes contain a hydroxyl array, a three-dimensional cavity and several readable positions, they are broadly used as building blocks to construct well preorganized host molecules and they usually exhibit good recognization abilities for alkali metal, transition metal and heavy metal cations, etc, which make them have widely potential in the field of analytical chemistry, ion sensors, etc. Calixarene polymers are important part among all kinds of calixarene derivatives. In this thesis, the syntheses, complexation properties of calix[4]arene and calix[6]arene polymers containing N or S groups were described. Some meaningful results were obtained.In chapter one, the research progress of calixarenes were reviewed, including the syntheses, the structural characteristics, the chemical modifications, the molecular recognition as well as various applications of calixarene derivatives, especially the calixarene polymer, calixcrowns in details.In chapter two, reacting cellulose poly(ethyleneimine) derivatives with 1,3-bisepoxypropyl calix[4]arene, a series of cellulose resins grafted with calix[4]arene were obtained for the first time. These novel resins combined the adsorption advantages of cellulose derivatives and calixarene polymers, exhibited not only high adsorption capacities but also high adsorption selectivity towards Ni²⁺.In chapter three, a novel calixarene-chitosan polymer was synthesizedby reacting 1,3- bisepoxypropyl calix[4]arene with chitosan. The new polymer not only keeps high adsorption capabilities but also exhibits excellent adsorption selectivity to Hg2+ due to the synergetic effect of calix[4]arene and chitosan.In chapter four, another novel calixarene-chitosan polymer were synthesized by reacting terachloroacetylcalix[4]arene and hexochloroacetyl-calix[6]arene with chitosan. The new polymer not only kept high adsorption capabilities but also exhibited excellent adsorption selectivity.In chapter five, a series of calix[6]-l,4-crown-based polymers were synthesized by reacting calix[6]-l,4-crown tetraester with poly(ethyleneimine) and their adsorption capabilities were also studied. It was found that their adsorption selectivities were higher than that of calix[6]arene polymer with no stable conformation. All of them showed good selective adsorption capabilities towards Cu2+ among the tested cations.