基于环糊精(CD)的单链与双链包结聚准轮烷(PPR)和聚轮烷(PR)的研究引起人们的极大兴趣.大量证据表明聚乙二醇(PEG)链段能够以折叠双链或双链并行的方式穿过γ-CD空腔.利用双2-溴异丁酰为端基的PEG与γ-CD进行自组装能形成双链包结聚准轮烷,并可作为大分子引发剂引发甲基丙烯酸正丁酯(BMA)发生本体原子转移自由基聚合(ATRP),聚合产物与其作为大分子引发剂的聚准轮烷都为PEG折叠双链包结结构的聚准轮烷.聚合产物能够在三氯甲烷中流延成膜.由于加入的γ-CD以管道结晶形式存在,与PBMA-PEG-PBMA三嵌段共聚物相比,该材料表现出较高的力学强度,但延伸性明显降低.与PBMA均聚物相比,其静态接触角有显著降低,却比PBMA-PEG-PBMA有少许增加.如将其溶于二氯甲烷中,可通过电纺丝加工成结构均匀的无纺布纤维,纤维形貌受到溶液浓度的影响.
Recently a variety of cyclodextrin(CD)-based polypseudorotaxanes(PPRs) and polyrotaxanes(PRs) have attracted trememdous attention as building blocks for hierarchical nanostructured materials.γ-CDs are known to include two chains of poly(ethylene glycol)(PEG) into their cavity,either bent double chains or two parallel chains to create PPRs or PRs.A distal 2-bromoisobutyryl end-capped PEG(Mn=4000) was found to self-assemble with γ-CDs to form PEG bent double chain stranded PPRs which are stable enough to further initiate the bulk atom transfer radical polymerization(ATRP) of n-butyl methacrylate(BMA) to give rise to the same conformational PPR-based block copolymers.As attached PBMA possesses good processing and mechanical properties,the resulting copolymers were soluble in chloroform to be cast into films.Due to added γ-CDs in the conformation of PEG bent double chain remaining the characteristic channel-type crystal structure,the higher mechanical strength was noted in the copolymers,while the elongation ratio was remarkedly got down.The static contact angle was substantially decreased as compared to the homopolymer PBMA,but was slightly enhanced with regard to the triblock copolymer PBMA-PEG-PBMA.Furthermore,they were electrospun into uniform non-woven fibers in a solution of dichloromethane,and morphology of fibers was affected by the polymer solution concentration.