Synthesis Of Supramolecular Polymers Containing Calixarene And Cyclodextrin And Their Application In Water Pollution Treatment

At present,the problem of heavy metal pollution in China is very serious,and it threatens people’s lives and health.In view of heavy metal pollution,two kinds of supramolecular polymers were prepared by introducing urea-pyrimidinone into calix[4]arene andβ-cyclodextrin host molecules,which can be used for heavy metal ion adsorption.The supramolecular polymer assembled by quadruple hydrogen bond is composed of calixarene andβ-cyclodextrin,so it has the inclusion effect.It has a good adsorption effect on heavy metal ions.Supramolecular polymers have the characteristics of self-healing and solvent response,which make it easy to solvate the preparation of supramolecular polymers.The supramolecular polymers assembled by quadruple hydrogen bonds can adjust the host molecules according to different heavy metal ions to achieve the effective adsorption of different heavy metal ions.Finally,some effective methods can be taken to free heavy metal ions from supramolecular polymers,which can be reused.Therefore,the application of supramolecular polymers assembled by quadruple hydrogen bonds to the treatment of heavy metal contamination will be of great significance.The specific research contents are as follows:1.Synthesis of 5,11,17,23-tetra-butyl-25,26,27,28-tetrahydroxy-calix[4]arene starting from p-tert-butylphenol and formaldehyde;The imide-modified alkyl linear chain reaction can be used to introduce different lengths of alkyl carbon chains on the p-tert-butylcalix[4]arene;after hydrolysis by hydrazine,the amine group is introduced into the p-tert-butylcalix[4]arene;the calixarene derivative with an amine group is reacted with ureidopyrimidone to obtain a supramolecular polymer monomer.They are BC4PUPy and BC4HUPy.Starting from the 25,26,27,28-tetrahydroxy-calix[4]-arene,a similar method was used to obtain the supramolecular polymer monomers containing the calixarene main structure.It is a ureido pyrimidinone polymer monomer（C4PUPy）linked by a three-carbon chain on a calix[4]arene and a ureidopyrimidone polymer monomer（C4HUPy）linked by a six-carbon chain on a calix[4]arene.¹H NMR,¹³C NMR and MS were used to characterize and identify the polymer monomers.The results showed that the obtained polymer had the expected structure.2.Using the aqueous phase synthesis method,p-toluenesulfonyl chloride was inserted at the C-6 position of theβ-cyclodextrin to obtain 6-OTs-β-CD.Using6-OTs-β-CD as the raw material,and reacting with the alkyl straight chain with two amine groups at the end,respectively,anβ-cyclodextrin derivative containing an amine group can be prepared.Finally,it reacts with UPy.Three kinds of supramolecular polymer monomers containing theβ-cyclodextrin host structure assembled from four hydrogen bonds of ureidopyrimidone were prepared.They areβ-CDPUPy,β-CDBUPy andβ-CDHUPy.¹H NMR,¹³C NMR and MS were used to characterize and identify the polymer monomers.The results showed that the obtained polymer had the expected structure.3.By using the static adsorption method,four supramolecular polymers synthesized by self-assembly of four supramolecular monomers with calixarene as the main structure and three supramolecular monomers withβ-cyclodextrin as main monomers As the adsorption material,the heavy metal ions(Pb²⁺,Cd²⁺,Zn²⁺,Ni²⁺,Cu²⁺)were respectively adsorbed and detected with the pH value of heavy metal solution and adsorption time as the investigation factors.The results showed that the adsorption rate of Pb²⁺by BC4PUPy,BC4HUPy,C4PUPy and C4HUPy was 99%at pH=6.The adsorption rate of Cd²⁺byβ-CDPUPy,β-CDBUPy andβ-CDHUPy was99%.The adsorption rate of Pb²⁺byβ-CDHUPy was 99%.