蝌蚪型POSS接枝含氟丙烯酸酯类杂化聚合物多孔膜的制备研究

以本实验室合成的3种结构的蝌蚪型POSS杂化聚甲基丙烯酸三氟乙酯(POSS-PTFEMA)、POSS杂化聚甲基丙烯酸三氟乙酯嵌段共聚聚甲基丙烯酸甲酯(POSS-PMMA-PTFEMA)及POSS杂化聚甲基丙烯酸甲酯嵌段共聚聚甲基丙烯酸三氟乙酯为成膜材质,利用呼吸图案法制备规整结构的蜂窝状聚合物多孔薄膜.利用扫描电镜(SEM)对薄膜表观形貌进行观察,分析了孔形貌的影响因素,并研究了多孔膜的疏水疏油性和耐温性.研究表明,以氯仿为成膜溶剂,3种不同结构的杂化聚合物均可以在较大的浓度范围下(5~30 mg/mL)制备规整的杂化聚合物多孔膜,膜的孔径随聚合物浓度的增大而增大;聚合物POSS-PTFEMA由于化学结构中含有最多的TFEMA结构单元,其规整性最好;相对疏水的硅片也有利于这类疏水的聚合物多孔膜的制备.所形成的多孔膜具有良好的耐温性能和疏水拒油性,其对水接触角介于98°~116°之间,对正十二烷的接触角则介于43°~66°之间.     

聚乳酸蜂窝状多孔膜的形成与控制

以单一组分聚L-乳酸(PLLA)为成膜材料,利用水辅助法制备了聚乳酸(PLLA)蜂窝状多孔膜.利用扫描电镜(SEM)和原子力显微镜(AFM)观察多孔膜形貌.研究溶剂、溶液浓度、环境温度和湿度等因素对所成多孔膜结构的影响.实验结果表明,高湿度环境和具有一定浓度的聚合物溶液是制备蜂窝状多孔膜的必要条件.溶剂的挥发性是形成规整蜂窝状孔结构的关键因素.环境相对湿度由43%增加到91%,PLLA多孔膜的孔径由(1.75±0.24)μm增加到(11.50±1.43)μm,且孔呈现六边形的蜂窝状结构.扫描电镜断面和AFM表明:膜表面形成了深度约为1.8μm的单层孔结构.通过控制溶液浓度、环境温度和湿度等因素来控制膜的表面形貌及其所成蜂窝状孔的大小.最佳的成膜条件为溶剂CH2Cl2,湿度75%RH,温度34℃,浓度3 wt%.讨论了蜂窝状多孔膜的形成机理.     

端硅烷基液体氟弹性体的合成与固化及性能

用两步法合成了端硅烷基液体氟弹性体:(1)以端羧基液体氟弹性体和五氟苯酚为原料,通过Steglich反应制备了端五氟苯酚酯液体氟弹性体;(2)端五氟苯酚酯液体氟弹性体与γ-氨丙基三乙氧基硅烷发生取代反应,制备端硅烷基液体氟弹性体.用FTIR,1H-NMR,19F-NMR和GPC对端羧基液体氟弹性体、端五氟苯酚酯液体氟弹性体和端硅烷基液体氟弹性体的化学结构进行了表征.端硅烷基液体氟弹性体可在室温下进行湿度固化,固化膜的T g随着固化前硅烷封端液体氟弹性体相对分子质量的增加而降低.固化膜具有很好的耐酸,航空煤油,非极性溶剂等化学药品性,且高分子量的固化膜的耐航空煤油,环己烷,盐酸性能优于低分子量的固化膜.固化膜具有较好的疏水疏油性,与水的接触角为91°~114°,与丙三醇的接触角为89°~111°.固化膜具有较好的耐热性能,5%热失重温度T5在215~280℃,800℃的残炭率为23.44%~38.69%.     

利用Breath Figures法制备具有蜂窝状结构的 PMMA/TBT复合膜

以聚甲基丙烯酸甲酯(PMMA)和钛酸四丁酯(TBT)的氯仿溶液为铸膜溶液,采用Breath Figures法制备了蜂窝状结构的PMMA/TBT多孔阵列薄膜,采用SEM、JR、XRD对制备的多孔膜进行了表征,探讨了聚合物浓度、PMMA/TBT配比以及水解抑制剂对膜蜂窝状结构的影响.实验结果表明,起始溶液浓度为20～30m...     

带有羧基的含氟丙烯酸酯共聚物的制备及超疏水性能研究

以甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸全氟烷基乙基酯为单体,以可逆加成-断裂链转移方法合成含氟嵌段共聚物,同时以常规自由基溶液聚合制备相似组成的无规共聚物.采用溶剂挥发成膜方法成膜,研究共聚物组成与结构对膜表面形貌和疏水性能的影响.结果表明,羧基单体的引入改变了含氟丙烯酸酯聚合物的溶解性能和成膜性能,使用常用溶剂就可...     

含氟丙烯酸酯共聚物制备超疏水表面及其形成机理的研究

以丙烯酸全氟烷基乙基酯和甲基丙烯酸甲酯为共聚单体, 分别以用微乳液聚合法和溶液聚合法制备的无规共聚物和用可逆加成-断裂链转移制备的嵌段共聚物作为成膜共聚物, 并以1,1,2-三氟三氯乙烷作为溶剂, 采用溶剂挥发成膜法可以直接制备出超疏水膜, 聚合物膜对水的接触角可达160°. 改变聚合物结构和成膜条件, 探讨了该类超疏水膜的形成机理和影响因素. 发现膜的表面形貌和疏水性与共聚物的组成、结构、分子量以及成膜条件密切相关, 随着共聚物中氟含量的增大, 膜的表面形貌都趋于平滑; 而且, 无规共聚物比嵌段共聚物更易形成粗糙度好的膜; 同时, 较大的聚合物分子量和适宜的高的成膜温度都对形成粗糙结构有利.     

基于D,L-丙交酯开环聚合制备具有自分散能力的毛发状聚合物微球

通过无皂乳液聚合法制备了单分散苯乙烯与甲基丙烯酸羟乙酯共聚的交联微球[poly(St-co-HEMA)], 利用其活性羟基, 引发D,L-丙交酯单体的开环聚合, 制备出一种新型的疏水性毛发状微球, 并用扫描电子显微镜、红外光谱及热失重分析等技术表征微球结构. 结果表明, 采用此方法不但能够成功地制备出一系列具有不同壳层厚度的疏水性毛发状聚合物微球, 而且随着D,L-丙交酯单体用量的增加, 微球在有机溶剂中的分散能力显著提高. 实验结果证明, 该方法是一种在聚合物微球表面生成高效、可控接枝疏水性大分子链的新方法.     

喷砂-阳极氧化-氟化处理构筑铝合金超疏水表面

为研究复合法制备超疏水表面过程中主要工艺参数对表面形貌及超疏水性能的影响, 开发了一种喷砂-阳极氧化复合方法, 在铝合金表面构筑了微米-纳米二级结构, 经氟化处理后获得了超疏水特性. 结果表明, 喷砂处理在铝合金表面通过冲蚀的凹坑构筑出微米结构, 阳极氧化则在铝合金表面通过蜂窝状氧化膜构筑纳米结构. 但单纯构筑粗糙结构或单纯改变表面化学组成均不能在铝合金表面获得超疏水特性. 单纯的微米结构或纳米结构, 即使有低表面能聚合物修饰也不能获得超疏水特性. 只有微米-纳米二级结构和低表面能聚合物的协同作用, 才能有效构筑铝合金超疏水表面. 这种铝合金与水滴接触时, 形成的气阱可减小固体表面与水滴的接触面积, 降低表面与水滴间的热量交换, 从而减缓水分子的凝结, 提高铝合金的抗霜冻性. 同时, 气阱还可有效减缓海水的腐蚀, 提高铝合金的耐海水腐蚀性.     

热处理对超疏水性含氟丙烯酸酯共聚物膜表面性能的影响

以微乳液聚合法和溶液聚合法制备丙烯酸全氟烷基乙基酯和甲基丙烯酸甲酯的共聚物, 以1,1,2-三氟三氯乙烷为溶剂, 采用溶剂挥发成膜法直接制备出超疏水膜, 并研究120 ℃热处理对超疏水膜表面性能的影响. 对于用乳液聚合方法制备的超疏水膜, 随着热处理时间的延长, 滚动角表现出先逐渐增大直至完全不能滚动, 然后重新回复到极小滚动角的特殊变化过程, 而静态接触角只是略微减小, 完全不同于热处理对平滑的含氟聚合物表面接触角的影响. 扫描电镜结果显示, 聚合物膜表面形貌对应出现从微/纳复合粗糙结构到微孔粗化并重新形成微/纳复合多层粗糙结构的变化.     

智能响应与自修复的层层组装聚合物膜

具有刺激响应性和自修复功能的复合膜是重要的仿生功能膜材料.层层组装是一种基于物质交替沉积而制备复合膜的方法,可以实现膜的结构和组成的精确调控.通过结构与组成的精确调控,基于层层组装制备的微米厚度的聚电解质厚膜可以对外界刺激产生快速有效的响应,因而在制备智能仿生膜材料方面具有重要的价值.本文以作者的研究结果为基础,阐明了基于层层组装的聚电解质膜可以成功用于制备湿度和温度响应的双结构自支持膜和高效的促动器及行走机器,以及自修复超疏水和划痕修复聚电解质膜.     

甲醇气氛静态呼吸图法制备蜂窝状有序多孔膜

以原子转移自由基聚合方法合成的聚二甲基硅氧烷-b-聚苯乙烯(PDMS-b-PS)为铸膜材料,在静态呼吸图的基础上,首次在甲醇氛围下利用PDMS-b-PS的二硫化碳溶液铸膜得到了高度规整的蜂窝状有序多孔结构.研究了聚合物溶液浓度对孔径的影响,并与水蒸汽氛围制备的孔结构进行了比较.结果表明,甲醇气氛下制备的多孔膜的孔径比水蒸汽氛围下的大,且孔的断面形貌呈“U”形;孔径随着溶液浓度的增大而减小.该研究有利于呼吸图法制备有序结构材料技术的进一步发展,有助于人们更加准确与全面地认识呼吸图机理.     

掺杂态聚苯胺蜂窝状有序多孔薄膜的制备及形成机制的探讨

近年来,由于微米、亚微米及纳米级有序多孔结构薄膜可以用于催化、生物培养基材、分离或吸附介质、光子晶体等诸多方面从而引起了科学家们极大的研究兴趣^[1～6].微制作是使材料表面具有新性能的重要手段,激光刻蚀及其相关技术已经被应用于不同表面的微图案化和微器件的制作^[7],另外,还可通过自组装技术进行多孔薄膜的制备^[8,9].Francois等^[10]于1994年首次提出了水辅助方法(Water-A ssisted Fab-rication),即在高湿度的环境下,以冷凝水滴为模板,在固体基片上制备了孔径分布均一,排列紧密的蜂窝状有序多孔薄膜.继而人们对此方法做了进一步的研究,不仅突破了最初的聚苯乙烯及其共聚物体系^[10～13],而且使用双亲共聚物^[14]、聚离子复合物^[15]和TiO₂前驱体的混合物^[16]等成功地获得了蜂窝状有序多孔薄膜,同时系统地研究了成膜体系及成膜条件对形成蜂窝状有序多孔薄膜的影响,并对形成机制进行了探讨.聚苯胺是典型的导电高分子,有关聚苯胺有序多孔结构薄膜的研究已有报道^[17～19].本文采用水辅助方法,在高湿度环境下,使用4-十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)为成膜材料,制备了双层蜂窝状有序多孔薄膜,并通过原子力显微镜(A FM)对薄膜的形貌和电学性质进行了表征.同时在已有成膜机制的基础上,提出了该双层蜂窝状有序多孔薄膜的形成机制.     

利用呼吸图案法制备聚(苯乙烯-b-丙烯腈)有序多孔薄膜

以自制的聚(苯乙烯-b-丙烯腈)(PS-b-PAN)嵌段共聚物为成膜材料, 采用呼吸图案法制备了有序多孔薄膜, 采用扫描电子显微镜(SEM)对薄膜形貌进行了分析, 研究了聚合物浓度、溶剂种类及共聚物结构对薄膜结构的影响. 结果表明, 薄膜表层为多孔结构, 且孔为圆形、以六方阵列形式排列; 薄膜表层下面是蜂窝状结构.以三氯甲烷(CHCl₃)为溶剂时, 在较高浓度下制备的薄膜表层孔间距较大, 蜂窝结构尺寸较小, 且形成了多层结构. 与CHCl₃为溶剂时相比, 挥发速度较快的二硫化碳(CS₂)作溶剂时制备的多孔薄膜有序性较好, 薄膜表层孔径和孔间距均较大, 蜂窝结构尺寸较小. 以没有PAN链段的聚苯乙烯大分子引发剂(PS-Cl)为成膜材料时, 制备的薄膜表层没有形成多孔结构, 而是形成了窝状结构. 同时, 通过对薄膜表层晕的研究证明了多孔薄膜表层缺陷是由水滴处于液膜下较深的位置造成的.     

Fabrication of Ordered Arrays of Biodegradable Polymer Pincushions Using Self-Organized Honeycomb-Patterned Films

Nano- and micropatterned structures of tissue engineering scaffolds made of biodegradable and biocompatible polymers profoundly influence cell behavior. The present study describes a technically simple and inexpensive method to rapidly fabricate hexagonal arrays of biodegradable polymer pillars (pincushions). As precursors to these polymer pincushion arrays, highly regular porous biodegradable polymer films (self-organized honeycomb-patterned films, called honeycomb films) were prepared on a glass substrate using a simple casting technique. Scanning electron microscope observations revealed that the honeycomb film was composed of a top and bottom layer. This double-layered structure is attributable to the self-organization of hexagonally packed arrays of water droplets that form the template. When we peeled off the top layer of the honeycomb film under ambient conditions using adhesive tape, we obtained arrays of polymer pincushions on both side of the glass substrate and on the adhesive tape. Each air hole is surrounded by six pincushions, each with a diameter of 0.1-1 µm. We also studied factors that determine the morphology of the pincushions, such as the thermal and mechanical properties of the polymers used. It was shown that the heights, widths, and distances of separation between the pincushions could be controlled by the choice of polymer and the pore structure of the original honeycomb film. Such well-ordered, biologically inspired pincushion structures could find application in biomedical, photonic, and electronic materials.     

Stabilization of self‐assembled microdroplets using short chain alcohols

The condensation of water vapor on a volatile polymeric solution leads to a porous surface after evaporation of both solvent and water. However, the stabilization of the water microdroplet is of great importance, which can be achieved using specific polymer or adding a third substance to the polymer solution. Short chain alcohols (methanol, ethanol, and n‐propanol) are utilized to fabricate a self‐assembled porous honeycomb film of linear, low molecular weight polystyrene using the breath figure technique. A combination of breath figure processing and the effect of alcohol on a water droplet can stabilize the pattern and make pores on the surface of the polymer film. The quality of the porous honeycomb film is strongly dependent on the type of alcohols and the concentration of polymer. In a specific range of polymer and alcohol concentration, pores cover all the surface of the polymer film. This method offers the possibility of producing a honeycomb structure with no trace of additive residual after the fabrication process and avoiding polymer modification. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 709–718     

聚丁二烯有序多孔膜在热缩型聚乙烯膜上的收缩

采用溶剂散逸自组装制备了聚丁二烯(PB)有序多孔膜。水珠能在冷的高分子溶液表面凝结形成有序的阵列,溶剂蒸发后,高分子材料按照水珠排列的形貌形成了有序多孔膜。两性共聚物的加入能够起到稳定水滴的作用,从而确保多孔膜成为有序的结构。利用聚乙烯可收缩膜将聚丁二烯多孔膜收缩2次,得到长方形、梭形、条形和哑铃形的孔。孔的尺寸从微米级收缩至亚微米级,并对产生各种形状的机理进行了研究。     

微孔型聚丙烯腈固体电解质的结构与导电性能研究

用蒸汽相沉析法和液相沉析法分别制备了两类高孔隙率的聚丙烯腈 (PAN)微孔膜 .用扫描电子显微镜对微孔膜的形态进行了观察 ,发现前者为均匀的蜂窝状结构 ,而后者则具有不对称的三层次结构 .又用这两类微孔膜分别制备了两个系列的微孔型PAN电解质 .电性能测试表明前者的室温电导率较高 ,可以达到 4×10 - 3 S cm ,后者的电导率则相对较低 .微孔膜本身诸因素对微孔型PAN电解质电导率的影响顺序为微孔膜结构—孔隙率—微孔孔径     

The effect of different stabilizers on the formation of self‐assembled porous film via the breath‐figure technique

The Breath‐Figure technique was employed to imprint honeycomb structures in the polymer films via the condensation of water vapor on the surface of an evaporating polymer solution. Generally, the condensed water droplets can be stabilized by an end‐functional polymer or by particles added to the polymer solution. In this study, we carried out a systematic experiment on the effect of different stabilizers on the porous honeycomb structure under identical physical conditions. The end‐functional polymer produced a large area of regular spherical bubbles, whereas adding particles to the polymer solution leads to smaller arrays of the flattened bottom bubbles. The separation length between pores was larger for polymer/particle sample than that of the end‐functional polymer films. In the regular area of polymer/particle film many bubbles were not decorated by particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1430–1436, 2011     

Self-organization-induced three-dimensional honeycomb pattern in structure-controlled bulky methacrylate polymers: Synthesis, morphology, and mechanism of pore formation

Here we report, for the first time, a novel molecular design for three-dimensional honeycomb structures through a self-organization of hydrogen-bonded bulky anchoring group in a methacrylic polymer backbone. The polymerizable monomer design includes a methacrylic double bond linked to various hydrophobic anchoring units such as ethane, n-decane, tricyclodecane (TCD), and adamantane via a hydrogen-bonded cycloaliphatic urethane linkage. The structures of the polymers were confirmed by nuclear magnetic resonance (NMR) and the molecular weights of the polymer were determined by gel permeation chromatography (GPC). The methacrylate polymers having tricyclodecane and adamantane bulky anchoring groups self-organized to produce three-dimensional honeycomb patterns in tetrahydrofuran-water solvent mixture at ambient conditions, whereas its linear analogues (ethane, n-decane) failed to produce any micropattern. The scanning electron microscopy (SEM) analysis of the above-prepared polymer films revealed that the structure of the polymer played a major role in the formation of the honeycomb patterns. The solution Fourier transform infrared (FTIR) measurements confirmed that the bulky tricyclodecane and adamantane polymers have strong hydrogen-bonding interaction compared to that of their linear analogues, which is the driving force for the micropatterns. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) analysis of the bulky polymers revealed that the polymers exist as vesicles or micelles in the solution, which leads to the formation of the honeycomb pattern. The honeycomb pattern formation in the bulky polymer systems suggests that two cooperative factors such as hydrogen-bonding interaction and hydrophobicity of bulky anchoring units are necessary to induce three-dimensional honeycomb structures. To investigate the effect of molecular weights and its distribution on the self-organization process, both benzoyl peroxide (BPO) initiated free radical and atom transfer radical polymerization (ATRP) techniques were employed for the polymerization. Micropores formed irrespective of differences in molecular weight and polydispersity index (PDI); however, the pore size distribution was influenced by both molecular weights and PDI. Low molecular weight samples afforded polydisperse pores with the ATRP samples with more narrow PDI producing pores with large dimensions. The approach has also been investigated for polystyrene-bulky methacrylic copolymer, and the results revealed that uniform honeycomb patterns were produced for copolymers having more than 50 mol % incorporation of bulky units.     

聚苯乙烯-嵌段-聚丁二烯有序多孔膜在可收缩膜上的形变研究和光学性质

利用溶剂散逸自组装法在潮湿的条件下,制备了聚苯乙烯-聚丁二烯嵌段聚合物（PS-b-PB）有序多孔膜。 利用聚乙烯可收缩膜将PS-b-PB多孔膜进行两次收缩,形成小孔径的有序多孔膜。 通过收缩,膜上的孔由圆形变为长方形或者梭形,孔的尺寸从微米级收缩至亚微米级。 利用扫描电子显微镜对膜收缩过程中2种形状产生的机理进行了研究。 结果表明,PS-b-PB结合了聚苯乙烯（PS）和聚丁二烯（PB）两个均聚物的优点,收缩后仍然保持膜结构的平整性,从而将不可见的热场变化转变为可见的光学变化。