ABC型准聚轮烷的构建及其响应性薄膜  

Construction of ABC-Type Polypseudorotaxane and Its Responsive Membrane

作　　者：尹晓璇 李进杰[1] 禚可欣 牟蔚鑫 黄灵丽 陈健壮[1] 林绍梁[1] Yin Xiaoxuan;Li Jinjie;Zhuo Kexin;Mou Weixin;Huang Lingli;Chen Jianzhuang;Lin Shaoliang(Shanghai Key Laboratory of Advanced Polymeric Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]上海市先进聚合物材料重点实验室华东理工大学材料科学与工程学院,上海200237

出　　处：《化学学报》2024年第7期790-796,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.52325308,52073092);上海市自然科学基金(No.21ZR1415900)资助.

摘　　要：响应性薄膜的表面微观结构和浸润性会随着外界环境的改变发生自适应性变化,在高端制造和生物医药等领域研究意义重大.本研究利用1,4-二乙氧基柱[5]芳烃(DEP5A)对聚乙烯嵌段聚乙二醇嵌段聚己内酯(PE-b-PEG-b-PCL)中聚乙烯和聚己内酯链段的选择性识别作用,通过DEP5A和PE-b-PEG-b-PCL共组装,构建了ABC型准聚轮烷;再采用静电喷雾和呼吸图法相结合的制膜新技术,制备得到由多孔纳米片堆叠而成的准聚轮烷薄膜.研究发现该薄膜的微结构和浸润性可通过改变柱芳烃含量、聚合物浓度和制膜湿度等实验条件来调控.此外,通过乙醇或竞争客体分子1,4-二溴丁烷的引入,可方便且精准地调控准聚轮烷薄膜的微结构和浸润性.这种响应性薄膜在催化剂载体和智能涂层等方面应用潜力巨大.The surface microstructure and wettability of responsive membranes will change adaptively with changes in the external environment,which is significant in fields such as high-end manufacturing and biomedicine.However,it is still very challenging to precisely control the response of such films in an extensive range.Due to their incorporation of non-covalent bonds,polypseudorotaxanes exhibit distinctive reversibility and stimuli-responsiveness,rendering them a pivotal avenue in advancing smart materials,especially responsive membranes.Polypseudorotaxane membranes have the characteristics of easy control of structure and properties and multiple responses,which are of great significance in theoretical research and practical applications.This study capitalizes on the selective recognition property of 1,4-diethoxy pillar[5]arene(DEP5A)towards the polyethylene(PE)and polycaprolactone(PCL)segments within the polyethylene block polyethylene glycol block polycaprolactone(PE-b-PEG-b-PCL)copolymer,obtaining ABC-type polypseudorotaxane with competitive guest re-sponsiveness.The successful assembly and competitive guest responsiveness to 1,4-dibromobutane is validated through 1H NMR spectroscopy.Additionally,a polypseudorotaxane membrane consisting of porous nanosheets and featuring superhy-drophobicity is fabricated utilizing a novel technique combining electrospraying and the breath figure method.Notably,the polypseudorotaxane forms porous nanosheets during the membrane fabrication process,which then stack into a thin mem-brane.In addition,the polypseudorotaxane membrane's regular microstructure and superhydrophobicity can be achieved by controlling the molar ratio of DEP5A to polymer,polymer concentration,and relative humidity.Furthermore,the polypseu-dorotaxane membrane exhibits responsiveness to solvents and competing guest molecules,thus giving rise to different micro-structure and hydrophobicity.Such responsive membranes hold immense promise for diverse applications,including catalyst supports and smart coatings.

关 键 词：准聚轮烷 静电喷雾 呼吸图法 刺激响应性 浸润性调控 

分 类 号：O641.3[理学—物理化学] TB383.2[理学—化学]