| The dendritic polymer has the advantages of unique macromolecular configuration,perfect space structure,high density of peripheral functional groups and so on. It has important application prospects as anticancer drugs,information storage material,high efficiency catalyst.The preparation method is deeply concerned,two kinds of divergence and convergence are the most common,the complicated process of the preparation of dendritic polymers,the difficulty of product separation and purification,one pot method often can be synthesized defects exist in the structure of hyperbranched polymers.Today,the click reaction has received much attention in the preparation of dendritic polymer,which has the advantages of high efficiention,mild reaction conditions,less by-products and higher yield.Etherification reaction have the advantages of efficiention,mild conditions,simple postprocess.This paper through the iterative method(thiol-ene click reaction and etherification) for the preparation of the Hyperbranched Poly(ether-thioether).This paper through a series of hydroxyl protection,hydroxyl substitution,acid hydrolysis,were successfully prepared two high purity of thiol monomers:1-thioglycerol and 2- ethyl-2- mercaptomethyl-1,3- propylene glycol;at the same time,the polyol of hydroxyl etherification reaction synthesis four high purity polyol-polyether:trimethylolpropane triallyl ether,pentaerythritol four allyl propyl ether,BIS-TRIS five ene propyl ether and BIS-TRIS six vinyl propyl ether.The1 H NMR and GC-MS show the purity of the material.Under the action of the photo initiator,thiol-ene click reaction between polyol-polyether nucleus and thiol monomer was initiated by UV-light,washing and sedimentation to purify the product,the process is efficiention, expanding, high atomic utilization,mild reaction condition and high yield of over 95%;then allyl chloride happen etherification in strong alkaline conditions,purified by simple extraction and washing.The reaction conditions of etherification process is mild,simple operation,easy separation and purification products.The two step reaction are carried out in this iteration.The last,synthesis a higher algebra of hyperbranched poly(ether-thioether).In this paper,1H NMR,GPC,FT-IR,MALDI-TOF-MS showed that the hyperbranched poly(ether-thioether) has the advantages of large molecular structure,narrow molecular weight distribution and so on.Research show that thiol-ene click reaction cause the generally increasing of the multi dispersion index(PDI) of hydroxyl terminated hyperbranched poly(ether-thioether),GPC leaching curve of macromolecules exist acromial end,it is speculated that a small number of coupling termination occurs during the reaction of thiol-ene click reaction.In summary, thiol-ene click reaction and etherification iteration is effective method for the preparation of the Hyperbranched Poly(ether-thioether) with narrow molecular weight distribution and fewer defects. |
