Synthesis And Properties Of Calix [4] Arene-β-cyclodextrin Polymers

β-Cyclodextrin polymers, which possess supramolecular properties inherited from their parents and maintain the polymer effect, are widely used in the aspects of drug delivery, solid adsorbent, molecular recognition, building chromatography stationary phase and inducing molecular self-assembly. In this paper, researches on synthesis of calix[4]arene-β-cyclodextrin derivatives and their cross-linking polymers and adsorption properties of the polymers for dyes(basic fuchsin, crystal violet) were shown as follow:1.A new calix[4]arene derivative containing coumarin fragment has been synthesized and its structure was confirmed by 1HNMR,13CNMR, MS and IR. The ring-opened and closed reaction of L in the condition of acid and base were studied by ultraviolet spectrophotometry, and the results showed that ring-opened reaction of compound L in alkaline solution took place easily but the ring-opened product transfered into trans isomer with a difficulty.2.Two new calix[4]arene-β-CD derivatives, compound 7 containing oneβ-CD unit and compound 8 containing twoβ-CD units, were synthesized by the reaction of epoxypropyl calix[4]arene derivatives and N-(2-aminoethyl) amino dexoxy-β-CD 4. The structure of 7 was confirmed by 1HNMR,13CNMR, MS and IR, and 8 by 1HNMR, IR and UV.3.Polymer P1 with the yield of 71% was obtained by two steps reaction of compound 8 firstly with epichlorohydrin and then 1,6-diisocyanate (HMDI), and its structure was confirmed by solid 13C NMR and IR. Polymer P2 with the yield of 75% was synthesized by crosslinking polymerization of 8 with HMDI, and its structure was confirmed by solid 13C NMR and IR; its thermal stability and aggregation state by TG and XRD.4.Polymer P3 with the yield of 80% was synthesized by crosslinking polymerization of single amide calix[4]arene-β-CD 10 with HMDI, and its structure was confirmed by solid 13C NMR and IR; its thermal stability and aggregation state by TG and XRD.5.The influences of adsorption conditions (temperature, initial concentration and solid-liquid ratio) on the adsorption capacity (Q) of P3 adsorbing basic fuchsin and crystal violet were studied. Results showed that under the condition of solid-liquid ratio 4.0 g·L-1, Q increased with the increasing of initial concentration of basic fuchsin and crystal violet, and appeared a maximum at 35℃in the range of 10℃-45℃. Q increased when solid-liquid ratio dropped. At the solid-liquid ratio 0.5g·L-1,Q of P3 adsorbing basic fuchsin and crystal violet were 19.7mg·g-1 and 21.9 mg·g-1 respectively under the condition of intial concentration 25 mg·L-1 and shaking time 2h.6.The adsorption models of P3 adsorbing basic fuchsin and crystal violet were studied. The results indicated that adsorption equations of P3 on basic fuchsin and crystal violet could be described by Freundlich isotherm equation with good linear relationship. Freundlich isotherm equations for basic fuchsin were Q=2.5639CW1/1.4075 (10℃) and Q=3.8824 Cw1/2.0178 (25℃); for crystal violet were Q=0.1852Cw1/1.0548 (15℃) and Q=0.1625Cw1/0.9809 (25℃). According to 2>n>0.5 shown in Freundlich isotherm equation, the adsorptions of P3 for basic fuchsin and crystal violet were preferential adsorption. Figure:51;table:9;formula:4;reference:42...