表面分子印迹共轭聚合物传感薄膜对2,4-DNT的选择性响应

将侧链含氨基的强电子离域性共轭聚合物(PDD)化学键合到纤维素纳米微纤(TOCN)薄膜上,利用表面分子印迹技术,制备了以2,4-二硝基甲苯(2,4-DNT)为模板的表面印迹共轭聚合物传感薄膜(MI-PDD/TOCN薄膜);并深入研究了该MI-PDD/TOCN薄膜对2,4-DNT检测的应用。研究结果显示,TNT溶液(或蒸气)对MI-PDD/TOCN薄膜的荧光猝灭常数(或荧光猝灭效率)仅为1.6×104M-1(或暴露300 s,18.2%),而2,4-DNT溶液(或蒸气)对其的荧光猝灭常数(或荧光猝灭效率)高达2.78×104M-1(或暴露300 s,88.4%),表明了MI-PDD/TOCN薄膜对2,4-DNT分子具有优良的响应灵敏度与特异的选择性。     

侧链含有两种介晶基元的聚硅氧烷类液晶聚合物的制备与性能

合成了侧基带有两种介晶基元的聚硅氧烷类系列液晶聚合物（P1－P5），所用介晶单体M1为4－联苯二酚基－4’－（2－乙基已酰基）－4－烯丙氧基苯甲酸酯，M2为4－烯丙氧基苯甲酰氧基－4’－甲氧基苯，它们介晶区间分别为39℃和7．9℃。只含有单体M1的聚合物P1和只含有单体M2的聚合物P5的介晶区间分别为70．8℃和75．1℃；但是同时含有不同摩尔比的M1和M2的液晶聚合物P2－P4的介晶区间为240－250℃，比只含有一种介晶基元的P1或P5拓宽了约170℃，所有聚合物均低于室温就有液晶性能，且耐热性达310℃以上，属于非晶近晶织构。     

具有多层结构的聚合物复合薄膜的介电和磁性能

采用旋涂法制备了 Fe3 O4/聚偏氟乙烯(PVDF)复合薄膜(A)、多壁碳纳米管(MWCNT)/PVDF复合薄膜(B)以及纯PVDF薄膜(P)。利用热压法制备具有3层结构的AAA、ABA及APA 复合薄膜。为了探究层状结构对复合薄膜介电和磁性能的影响,制备了单层膜A作为对比(厚度与AAA复合薄膜相同)。分别研究了薄膜的介电和磁性能。结果表明：由于界面效应,同等厚度的AAA复合薄膜较A膜而言具有较高的介电常数;以B和P薄膜替代AAA结构中间层薄膜后,其中ABA复合薄膜的介电常数高于AAA及APA复合薄膜,同时保持较低的介电损耗。对于磁性能,层状结构对复合薄膜的饱和磁化强度及矫顽力均无明显的影响,而ABA复合薄膜的饱和磁化强度高于AAA及APA复合薄膜,且ABA和APA复合薄膜的矫顽力增加。层状结构设计不仅能够调节复合材料的介电性能和磁性能,而且有利于不同纳米填料的分散,为制备多功能聚合物复合材料提供了一定的借鉴作用。     

基于芘丁酸的SAMs薄膜制备及荧光氧猝灭特性

利用SAMs(self-assembled monolayers)技术将芘丁酸分子接枝于经过3-氨丙基三乙氧基硅烷分子(APTES)修饰的玻璃基片表面。通过XPS、荧光发射光谱的表征以及接触角测试等来考察薄膜的结构及性能,考察了薄膜在不同溶剂中的荧光氧猝灭特性。实验表明,芘丁酸分子以化学键合的方式固定于玻片表面,形成了SAMs薄膜,其在甲苯、三氯甲烷、二氯甲烷等极性较小的有机溶剂中的氧猝灭效率较高,并具有良好的重复性。     

模板法制备TiO_2纳米介孔薄膜

采用模板法在FTO玻璃上制备TiO2介孔薄膜,其中模板为PVC-g-POEM聚合物。通过控制PVC与POEM聚合物的质量比例来调节TiO2介孔薄膜孔径的大小及致密程度,分别得到高透过型的TiO2(对光波的透过率较高)介孔薄膜及高反射型的TiO2介孔薄膜(对光波的吸收率较低)。将高透过型、高反射型、高透过型/高反射型的TiO2介孔薄膜组装成染料敏化电池(DSSCs),结果表明:相同厚度下,基于高反射层/高吸收层的TiO2介孔薄膜的DSSCs的转化效率(4.7%)远远高于高吸收层的DSSCs(2.3%)、高反射层的DSSCs(1.5%)。     

六氯化钨/正丁基三苯基锡催化聚苯乙炔的制备及荧光性能研究

使用新型WCI6-n-BuPh3Sn催化体系聚合苯乙炔,获得了高产率和高分子量的聚苯乙炔。研究了不同聚合溶剂对聚合物结构及分子量影响,使用UV、IR、NMR、GPC等分别对聚合物结构进行表征。采用不同波长的激发光对聚合物荧光性能进行详细研究,结果表明：在低于290nm和高于400nm激发光皮长,聚合物几乎不呈现荧光性能。当聚合物在350nm被激发时呈现较强发光量子效率。对聚合物溶液荧光性能的研究表明：当溶液浓度低于0.1g／L时,聚苯乙炔发光强度与溶液浓度成正比,在溶液浓度高于0.1g／L,例如0.5g／L时呈现了浓度自猝灭效应。同时,从荧光性能研究显示这种催化剂获得的聚合物具有较差的规整性。     

2,4,6-三硝基甲苯磁性分子印迹聚合物的合成

以2,4,6-三硝基甲苯(TNT)为模板分子、氨丙基三乙氧基硅烷为功能单体、正硅酸乙酯为交联剂,采用溶胶凝胶法成功制备了对TNT具有特异选择识别功能的磁性分子印迹聚合物。合成制备的磁性分子印迹聚合物具有良好的磁响应性,在外加磁场下可实现快速分离。红外光谱(FT-IR)、X射线光电子能谱和扫描电镜结果证实聚合物为核壳结构,磁性粒子由硅烷偶联剂完全包覆,并在其表面形成了一层分子印记聚合物;静态吸附实验结果表明,制备的磁性分子印迹聚合物对模板分子TNT具有良好的吸附能力,其饱和吸附量为77mmol/kg;通过以3,4-二硝基甲苯(DNT),为结构相似物的吸附选择性实验,磁性印迹聚合物对模板分子表现出良好的特异选择性。     

含苯乙烯基噻吩生色团聚合物的制备及与纳米金的相互作用

合成了含苯乙烯基噻吩生色团,通过酰氯化反应制备出含苯乙烯基噻吩生色团单体,将单体与丙烯酸酯类单体进行自由基共聚反应制备出侧链上含生色团的高分子.利用1H-NMR、FTIR等对分子结构进行了表征.应用荧光发射光谱研究了纳米金对含生色团高分子的荧光猝灭作用.通过温度对猝灭常数Ksv的影响说明了猝灭是动态猝灭,同时考察了溶剂极性对猝灭常数Ksv的影响,发现了猝灭的原因是纳米金与聚合物发生了电子转移,并阐述了猝灭机理.     

共价连接的类石墨烯二维四苯并卟啉薄膜的合成与表征

利用热凝聚法合成四苯并卟啉锌的经典反应,将原料中的邻苯二甲酰亚胺钾替换为具有双齿结构的均苯四酸二酰亚胺钾,从而在合成四苯并卟啉锌单体的过程中构筑了共价桥连的聚卟啉原子级薄膜。该薄膜大小为几微米,厚度为几纳米,具有高定向度、扩展共轭、可独立存在的特点。该薄膜具有锌氮四配位的卟啉局域结构,且薄膜的中心离子可以被其他金属离子替换,形成不同电子性质的卟啉聚合物,给其电子结构的调控提供了广阔的空间。由于具有广泛的二维扩展共轭结构,该四苯并卟啉聚合物薄膜具有独特的电子与光电子性质,其在电子与光电子器件、传感器、催化剂等方面有潜在的应用前景。     

聚乙烯基三苯乙炔基硅烷的制备及热性能分析

为研究聚乙烯基三苯乙炔基硅烷树脂的热性能,以苯乙炔和乙烯基三氯硅烷为原料,运用格利雅反应合成了乙烯基三苯乙炔基硅烷单体,并通过红外(FT-IR)、核磁(1H-NMR,13C-NMR,29Si-NMR)证实了合成产物.以此单体为原料,通过热聚合法制备了聚乙烯基三苯乙炔基硅烷树脂,并采用TGA-DTG研究该聚合物的热分解动力学,计算了相应动力学参数.结果表明:该树脂的热分解温度(Td5%)在550℃左右,800℃时聚合物的残炭率约80%;用Kissinger法和Ozawa法求得的聚合物热分解活化能分别为266.55和236.89 k J/mol;用Crane法求得聚合物的热分解反应级数为0.93,近似为一级反应.     

A mesoporous silica modified conjugated polymer film: Preparation and detection nitroaromatics in aqueous phase

The linear conjugated polymer of polyfluorene/poly(p-phenylenevinylenes) (PFO/PPV) was synthesized and selected as the matrix film. The incorporation of a small fraction of inorganic mesoporous silicas into the polymer matrix resulted in a significant increase in overall detection efficiency of nitroaromatics. The structure of the obtained mixed films was characterized by ¹H-NMR, IR, and XRD. The optical and fluorescence properties of the mixed films were demonstrated by ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra in ethanol/water solution. Compared with the pure conjugated polymer film, the mixed films had high fluorescence quenching sensitivity toward nitroaromatic compounds, especially 2,4,6-trinitrophenol (TNP), in the aqueous phase. The fluorescent emission quenching is quantitative and can be analyzed on the basis of the Stern-Volmer model relation with the quenching process. The results revealed that such mixed matrix films of conjugated polymer/mesoporous silicas can be a promising strategy of designing chemosensory materials for detecting nitroaromatic compounds.     

A mesoporous silica modified conjugated polymer film: Preparation and detection nitroaromatics in aqueous phase

The linear conjugated polymer of polyfluorene/poly(p-phenylenevinylenes) (PFO/PPV) was synthesized and selected as the matrix film. The incorporation of a small fraction of inorganic mesoporous silicas into the polymer matrix resulted in a significant increase in overall detection efficiency of nitroaromatics. The structure of the obtained mixed films was characterized by ¹H-NMR, IR, and XRD. The optical and fluorescence properties of the mixed films were demonstrated by ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra in ethanol/water solution. Compared with the pure conjugated polymer film, the mixed films had high fluorescence quenching sensitivity toward nitroaromatic compounds, especially 2,4,6-trinitrophenol (TNP), in the aqueous phase. The fluorescent emission quenching is quantitative and can be analyzed on the basis of the Stern-Volmer model relation with the quenching process. The results revealed that such mixed matrix films of conjugated polymer/mesoporous silicas can be a promising strategy of designing chemosensory materials for detecting nitroaromatic compounds.     

氮掺杂改性TiO_2多孔薄膜光催化降解4-硝基苯酚

本文采用溶胶-凝胶法制备了N掺杂TiO_2光催化剂,并对N掺杂TiO_2进行了改性,分别以P25、N掺杂TiO_2、改性的N掺杂TiO_2为原料,通过逐步研磨、旋转涂膜以及高温煅烧制得三种多孔薄膜,并对其进行了表征。场发射扫描电子显微镜(FESEM)观察结果显示,煅烧后薄膜呈现显著的多孔结构。以4-硝基苯酚(4-NP)溶液为目标污染物,研究紫外光下TiO_2多孔薄膜的光催化性能,确定最佳降解条件,并研究了薄膜耐用性以及三种薄膜对4-NP的光催化性能的比较。结果表明,三种多孔薄膜中,改性N掺杂TiO_2多孔薄膜光催化性能最佳,10mg/L的4-NP溶液吸附30min,在pH=2条件下180min,降解率达到了90%以上,改性N掺杂TiO_2多孔薄膜单次降解180min,循环使用4次的降解率仍接近80%,显示了薄膜具有较好的可耐用性。     

多孔聚合物微球成孔技术的最新研究进展

综述了多孔聚合物微球的制备方法及成孔机理。种子溶胀法和微膜乳化法用于制备具有微孔、中孔结构的单分散聚合物微球;而大孔聚合物微球的制备通常采用传统的悬浮聚合,并通过后交联法改善其孔性能,提高其比表面积。     

Highly ordered poly(thiophene)s prepared in mesoporous silica nanoparticles

Nanostructured PEDOT was synthesized using mesoporous silica as a nano-template. The polymerization of thiophene monomers was performed with an oxidant and mesoporous silica nanoparticles. The silica particles took essential role in absorbing monomers and oxidant molecules, and growth of polymers inside their pores. As prepared polymer/silica composite was treated with HF solution to remove silica template to result in 1D wire structure and mesh type porous 3D structures from SBA-15 and KIT-6 template, respectively. The average size of the poly(thiophene) wires was 10 15 nm, which was matched well to the pores size of the silica templates, as determined from an electron microscopy. At optimized condition, the room temperature electrical conductivities of the PEDOT grown from SBA-15 and KIT-6 template were similar as 1.1 and 1.0 S/cm, respectively. However, the evolution of the PEDOT conductivity versus temperature was different depending on the templates. These results gave a unique chance to tailor made 3 dimensional structure as well as properties of conductive polymer.     

纤维素基多孔碳膜的制备及其电化学性能研究

以α-纤维素分散液为前驱体,采用简单的抽滤和热处理工艺制备多孔超薄碳膜。采用扫描电子显微镜、透射电子显微镜等方法对其结构进行了表征;采用循环伏安、恒流充放电、交流阻抗等方法研究了其电化学性能;并且研究了多级孔结构对所制备的碳膜电化学性能的影响。结果表明:制备的超薄多孔碳膜呈现多级孔结构,厚度约为1.5μm,在电流密度为0.5A·g-1时,容量达到169F·g-1;在2A·g-1的电流密度下,在循环5 000圈后,可以保持80%的容量,同时库伦效率几乎保持100%。     

Design of single-site Ti embedded highly hydrophilic silica thin films with macro-mesoporous structures

Single-site Ti-containing macroporous silica thin films with mesoporous frameworks were successfully prepared on quartz substrate with high transparency by using poly(methyl methacrylate) (PMMA) microspheres and organic surfactant as template of porous structures. The presence of mesoporous structure and the differences of macroporous structure of film surface were investigated by XRD and FE-SEM measurements. The local structure of Ti moieties embedded within silica matrixes were also confirmed by UV-vis investigations. It was found that the macroporous structure and the embedded single-site Ti moieties within mesoporous frameworks were quite effective for improvement of surface hydrophilicity, i.e., the water droplet was entirely spread on the film surface even before and after irradiation of UV light.     

乙腈对环己烷单体溶液中沉降聚合聚3,4-乙撑二氧噻吩涂层结构与光电性能的影响EI北大核心CSCD

为利用溶剂化效应来优化液相沉降聚合聚3,4-乙撑二氧噻吩(PEDOT)的结构和光电性能,将吸附Fe(OTs)3的聚对苯二甲酸乙二醇酯(PET)膜悬于含乙腈的EDOT环己烷溶液中,于60℃原位合成PEDOT涂层。以紫外-可见吸收光谱、X射线光电子能谱分析所合成PEDOT的共轭链结构和掺杂度,以四探针测量表面电阻,研究乙腈含量对合成PEDOT结构与性能的影响。当乙腈体积分数为0.05%时,添加的乙腈能抑制短共轭链的生成,提高掺杂度,在降低表面电阻的同时,改善透光率。乙腈体积分数在0.24%以内时,PEDOT的导电性随乙腈体积分数的上升而增加。当乙腈体积分数超过0.7%时,PEDOT中短共轭链数目增加,光电性能下降。当乙腈体积分数为8%时,由于吸附的Fe(OTs)_3溶解太快,无法在PET表面合成导电PEDOT膜。乙腈体积分数为0.24%时,获得的PEDOT膜的表面电阻可达174Ω,透光率80%,粘附力为5B级。     

介孔纳米羟基磷灰石/左旋聚乳酸复合材料的制备及性能

为考察介孔纳米羟基磷灰石(MHA)/左旋聚乳酸(PLLA)复合材料的性能,以十六烷基三甲基溴化铵(CTAB)为模板合成MHA,采用溶液相分离结合粒子沥滤法制备了不同纳米粒子含量的MHA/PLLA多孔支架复合材料,考察了其抗压缩性能和淬断面微观结构。采用溶液浇注法制备了MHA/PLLA复合膜,并对其拉伸性能和拉伸断面微观结构进行了研究。FTIR、XRD、TEM和氮气吸附测试等结果显示:合成的MHA具有典型的晶体结构、介孔结构和较高的比表面积。力学测试结果显示:在发生10%压缩形变时,填料含量为1%、5%和10%的MHA/PLLA多孔支架复合材料的抗压缩强度随填料含量增加而提高,与相应含量的纳米羟基磷灰石(HA)/PLLA多孔支架复合材料相比,分别提高了约37.0%、67.7%和144.7%。在填料含量为5%和10%时,MHA/PLLA复合膜的拉伸强度较HA/PLLA复合膜分别提高约38.7%和46.1%,拉伸模量分别提高约35.4%和14.5%。而且MHA/PLLA复合膜具有更高的断裂伸长率,填料含量为1%、5%和10%时断裂伸长率分别较HA/PLLA复合膜提高约91.3%、79.7%和96.1%。FESEM结果显示:尤其当填料含量较高时,MHA/PLLA多孔支架复合材料或复合膜中填料粒子分布较HA/PLLA中均匀。结果表明:与HA/PLLA复合材料相比,随着MHA含量增加,MHA/PLLA复合材料具有更好的力学性能,MHA在PLLA基体中分布相对更均匀。     

Flow of a Polymer Solution between Two Rotating Rolls

A new model of calendering the film of a viscoelastic polymer solution based on the principles of mechanics of saturated porous media is suggested. The point of exit of the film from the gap is not prescribed as is done in traditional approaches but is determined from the condition of adhesion strength of the contact of the polymer with the rolls. An analytical solution of the stationary problem is obtained. Disturbances of this solution caused by periodic changes in the thickness of an incoming flow or a pulling rate are investigated.