聚苯乙烯蜂窝状多孔膜的制备及应用

以线性聚苯乙烯(PS)为膜材料,采用Breath Figures法制备了高度规整的蜂窝状结构多孔膜.研究了溶液浓度、环境湿度、气体吹扫速度及不同溶剂对多孔膜结构的影响.结果表明,相比于苯和二氯甲烷,氯仿作为溶剂因其挥发度适宜,PS浓度在20～80mg/mL的铸膜溶液可形成规整的蜂窝状结构多孔膜,且膜孔分布均匀、大小均一;制膜的湿度需高于环境湿度,但随着湿度的增加孔径增大;气体吹扫速度可在400～1000mL/min范围,但吹扫速度较大时孔径略有降低.该膜可作为固定诸如辣根过氧化酶等活性酶的载体,用于酶催化反应.     

聚醚砜蜂窝状多孔膜的研究

以聚醚砜(PES)为材料通过水蒸汽辅助法制备蜂窝状多孔膜,利用扫描电镜(SEM)观察膜表面形貌特征.研究溶剂、铸膜液浓度和湿度等因素对形成多孔膜结构的影响,通过控制铸膜液浓度、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.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,形成蜂窝状多孔膜的最佳条件为溶剂CH_2Cl_2,相对湿度93.5%,铸膜液中PES质量分数为2%,注射量为60μL.     

PSf-CA中空纤维血液透析共混膜的制备及性能

以聚砜(PSf)和醋酸纤维素(CA)为膜材料,一缩二乙二醇(DEG)为添加剂,聚乙烯吡咯烷酮(PVP-K30)为改性剂,N,N-二甲基乙酰胺(DMAc)为溶剂,采用非溶剂致相分离法(NIPS)制备PSf-CA中空纤维血液透析膜,表征膜的微观结构、亲水性、渗透性能、溶质清除率以及机械性能,讨论不同共混比和不同品牌聚砜对PSf-CA中空纤维膜性能的影响,以及不同模拟液流速和不同透析液流速对溶质清除的影响.结果表明:当PSf(质量分数19%)与CA(质量分数2%)总量(质量分数)21%、PVP-K30(质量分数)10%和DMAc/DEG质量比5/1为铸膜液体系时,PSf-3所制备的膜具有最佳的透析性能,其超滤系数为1 695mL/(m~2·h·kPa),对肌酐、磷酸氢二钠、维生素B_(12)的清除速率分别为116 mL/min、115 mL/min和105mL/min,断裂强度为5.65 MPa.     

水辅助法制备左旋聚乳酸/聚乙烯醇复合多孔膜及其力学性能

以左旋聚乳酸(PLLA)/聚乙烯醇(PVA)为成膜材料,利用水辅助法制备了PLLA/PVA复合多孔膜。研究了溶剂及其组成、环境湿度和聚合物浓度对形成多孔膜的形貌影响。筛选出可完全溶解PLLA/PVA体系的二甲亚砜(DMSO)/二氯甲烷(DCM)混合溶剂。V(DMSO)/V(DCM)=1/9为溶剂得到孔径大小为(2.45±0.31)μm的规整蜂窝孔,且随着DMSO含量增多,孔径变小,孔分布变得无序。环境湿度从43%增加到91%,孔径大小由(1.43±0.63)μm增加到(4.30±0.63)μm,孔径与环境湿度基本上呈现一阶线性关系。与纯PLLA多孔膜相比,PLLA/PVA复合多孔膜的拉伸强度和断裂伸长率分别从33.32MPa和12.46%增加到40.66MPa和32.57%。PLLA/PVA复合多孔膜有利于细胞的粘附与生长,因而有望作为组织工程支架材料。     

Breath Figure法制备聚碳酸酯(PC)蜂窝状多孔膜

以单组分聚碳酸酯(PC)为膜材质,在一定的湿度环境下,利用Breath Figure法在玻璃基板上成功制备了蜂窝状孔结构的聚碳酸酯多孔膜。研究了溶剂、溶液浓度和湿度对所成多孔膜结构和形貌的影响。实验结果表明,采用二氯甲烷为溶剂所制得的孔结构规整,排列均匀紧密,孔径大小为(3.30±0.19)μm,而以三氯甲烷为溶剂只能得到孔径大小不均且无紧密排列的孔。环境湿度从43%增加到91%,孔径大小由(2.28±0.63)μm增加到(9.07±1.42)μm,且湿度与孔大小基本上呈现一阶线性关系,通过理论推导得出直线斜率为0.15μm/%,即在此体系中湿度每增加1%,所形成的孔大小增加0.15μm。     

水蒸汽诱导相分离法制备聚苯并咪唑多孔膜

以3,3′-二氨基联苯胺和4,4′-二羧基二苯醚为原料,通过亲核缩聚合成了分子主链上带有醚键结构且具备较好溶解性的聚苯并咪唑,通过核磁共振和红外光谱确定其化学结构.接着利用水蒸汽诱导相分离法制备了系列具有海绵状孔结构的多孔膜,用扫描电子显微镜观察其形貌结构.详细考察了溶剂种类、成膜时间、温度、湿度以及聚合物溶液浓度等因素对膜结构的影响.结果表明,在温度80℃、相对湿度60%时,以甲磺酸为溶剂可使聚苯并咪唑膜出现腔包状孔结构;以N,N-二甲基甲酰胺和N,N-二甲基乙酰胺为溶剂可使聚苯并咪唑膜出现海绵状孔结构;而二甲基亚砜、N-甲基吡咯烷酮这两种溶剂不能使其出现多孔结构.以N,N-二甲基乙酰胺为溶剂时,聚苯并咪唑膜出现海绵状孔结构的成膜时间应不小于10min,成膜湿度应不小于50%,膜表面和断面孔径随着聚合物溶液浓度的增加而减小,底面也越来越致密.温度一定时,膜表面和断面孔径随着湿度的增加而减小;湿度一定时,膜表面和断面孔径随着温度的增加而减小.     

蝌蚪型POSS丙烯酸酯嵌段共聚物及其蜂窝状多孔膜的制备和性能

采用一锅逐步加料的原子转移自由基聚合方法(ATRP)制备了一种蝌蚪型多面体低聚倍半硅氧烷(POSS)丙烯酸酯嵌段共聚物, 并用静态呼吸图法制备该共聚物蜂窝状结构的多孔膜, 研究成膜条件如溶剂种类、聚合物浓度、相对湿度等对聚合物多孔膜形貌的影响, 以及空气/硅片、空气/水和空气/冰3种成膜界面对膜形貌的影响。结果表明, 在空气/硅片界面上, 以三氯甲烷为溶剂, 环境相对湿度为80%, 浓度为20 mg·mL^-1时, 可形成圆形孔的多孔膜, 孔排列成六方形; 在相同的条件下在空气/水和空气/冰界面上均可制备出类似规整形貌的多孔结构, 但多孔膜的孔径、孔间距有很大的不同, 在空气/冰界面上的孔径更小、孔间距更窄。这种多孔膜具有良好的疏水性, 且其接触角随着孔径的减小而增大; 该多孔膜还具有良好的耐强酸强碱性和耐热性能。     

呼吸图法制备三醋酸纤维素蜂窝状多孔膜

选用三醋酸纤维素(CTA)为膜材质,采用呼吸图法制备有序的蜂窝状多孔膜.考察了溶剂、浓度、温度、湿度等条件对蜂窝状微孔膜微观结构和孔径大小及孔径均匀性的影响.实验表明,湿度(RH)在70%~90%,以载玻片为基板可以制得孔径3μm左右的蜂窝状膜.     

PVDF/PMMA/TiO_2型聚合物隔膜的制备

为提高锂离子电池聚偏氟乙烯(PVDF)基聚合物隔膜的导电性和降低PVDF基聚合物隔膜的结晶度,引入聚甲基丙烯酸甲酯(PMMA)与聚偏氟乙烯(PVDF)进行共混,掺杂无机纳米材料TiO_2,采用相转化方法制备PVDF/PMMA/TiO_2型聚合物隔膜。通过对制备的PVDF/PMMA/TiO2型多孔膜吸液率、微观形貌和电化学性能的分析研究,确定制膜的最佳工艺条件为聚合物浓度为5%,PVDF∶PMMA为72∶28,纳米TiO_2添加量为5%,非溶剂添加量为3%,水浴温度为55℃。该方案下制备的多孔膜结晶度较纯PVDF薄膜结晶度降低,吸液率达到109.76%,离子电导率为2.64mS/cm,电化学稳定窗口为4.86V,高于4.5V,能够满足锂离子电池正常工作需要。     

呼吸图案法制备聚苯乙烯有序多孔膜

有序多孔膜是一种可以应用于众多领域的功能性材料,建立简单、低廉和安全的制备方法能够强有力地推进多孔膜材料的广泛利用.本文用水作为模板剂,以溶解于甲苯的工业通用级聚苯乙烯(PS,PG-22)溶液为成膜材料,利用呼吸图案法成功地制备出多孔膜,并采用扫描电镜(SEM)对所制的多孔膜形貌进行了观察,分别研究了动态和静态气氛、制膜液用量、质量浓度、环境湿度等条件对孔径大小和分布的影响.结果表明,制备有序多孔膜的适宜条件为:在环境温度25℃和用甲苯为溶剂时,聚合物质量浓度为25 mg/m L,用量0.8 m L,环境湿度85%(相对湿度),并保持静态气氛.采用聚苯乙烯溶液多次涂覆方法可以增加多孔膜厚度,有利于提高其机械强度,也为有序多孔碳材料的制备奠定了基础.     

Preparation and properties of porous polyimide films with TiO2/polymer double shell hollow spheres

Without the template removal process, double shell hollow spheres were prepared by encapsulating the polymeric hollow spheres with TiO₂ shells. TiO₂ encapsulated hollow spheres were incorporated with the polyamic acid solutions and imidized to prepare the porous polyimide films. The final porous texture of the film depends on the as-doped arrangement and the properties of the hollow spheres. The TiO₂ shell exhibits good thermal stability and chemical resistance to prevent the collapse of hollow spheres during the polyamic acid solution/hollow particle mixing and the imidization procedures. The effects of preparation conditions on the morphology of the encapsulated hollow spheres were investigated. The dielectric constant of the porous polyimide films (pore diameter around 0.6 µm) decreased to 2.8. The influences of hollow particles on the porous textures, the dielectric and dynamic mechanical properties of the porous films were studied.     

Design,preparation, and application of ordered porous polymer materials

Ordered porous polymer (OPP) materials have extensively application prospects in the field of separation and purification, biomembrane, solid supports for sensors catalysts, scaffolds for tissue engineering, photonic band gap materials owing to ordered pore arrays, uniform and tunable pore size, high specific surface area, great adsorption capacity, and light weight. The present paper reviewed the preparation techniques of OPP materials like breath figures, hard template, and soft template. Finally, the applications of OPP materials in the field of separation, sensors, and biomedicine are introduced, respectively.     

《二氧化硅孔材料的模板合成》化学综合实验的建设

化学综合实验"二氧化硅孔材料的模板合成"是为大学化学专业本科生开设的一个实验教学课程。其实验的主要内容是,首先合成制备单分散的聚苯乙烯乳胶粒子,然后以此单分散的聚苯乙烯乳胶粒子为初始材料,利用胶体晶模板法制备二氧化硅三维有序孔材料。利用透射电子显微镜和扫描电子显微镜对所制备的各级样品进行表征。教学实践发现,当作为初始材料的聚苯乙烯乳胶粒子尺寸较大时,三维有序孔材料的制备成功率高。文中介绍了此实验的建立以及对其进行改进的过程。     

Highly conductive and porous activated reduced graphene oxide films for high-power supercapacitors

We present a novel method to prepare highly conductive, free-standing, and flexible porous carbon thin films by chemical activation of reduced graphene oxide paper. These flexible carbon thin films possess a very high specific surface area of 2400 m(2) g(-1) with a high in-plane electrical conductivity of 5880 S m(-1). This is the highest specific surface area for a free-standing carbon film reported to date. A two-electrode supercapacitor using these carbon films as electrodes demonstrated an excellent high-frequency response, an extremely low equivalent series resistance on the order of 0.1 ohm, and a high-power delivery of about 500 kW kg(-1). While higher frequency and power values for graphene materials have been reported, these are the highest values achieved while simultaneously maintaining excellent specific capacitances and energy densities of 120 F g(-1) and 26 W h kg(-1), respectively. In addition, these free-standing thin films provide a route to simplify the electrode-manufacturing process by eliminating conducting additives and binders. The synthetic process is also compatible with existing industrial level KOH activation processes and roll-to-roll thin-film fabrication technologies.     

Carbon nanotubes as liquid crystals

Carbon nanotubes are the best of known materials with a combination of excellent mechanical, electronic, and thermal properties. To fully exploit individual nanotube properties for various applications, the grand challenge is to fabricate macroscopic ordered nanotube assemblies. Liquid-crystalline behavior of the nanotubes provides a unique opportunity toward reaching this challenge. In this Review, the recent developments in this area are critically reviewed by discussing the strategies for fabricating liquid-crystalline phases, addressing the solution properties of liquid-crystalline suspensions, and exploiting the practical techniques of liquid-crystal routes to prepare macroscopic nanotube fibers and films.     

Liquid crystalline texture and hydrogen bond on the thermal conductivities of intrinsic thermal conductive polymer films

Polymer-dispersed liquid crystal(PDLC)films comprising polyvinyl alcohol(PVA)and liquid crystal monomer(LCM)were successfully obtained by the method of solution casting&thermal compress-ing.LCM was distributed orderly in PVA matrix by hydrogen bond interaction,to form PVA-LCM interpenetrating-layered networks.When the mass fraction of LCM was up to 35 wt％,the corresponding in-plane thermal conductivity coefficient(λ∥)of PDLC film was significantly increased to 1.41 W m-1 K-1,about 10.8 times that of neat PVA(0.13 W m-1 K-1).High intrinsic λ//values of PDLC films were mainly attributed to the formed microscopic-ordered structures from ordered stacking of LCM,ordered arrangement of PVA chains,and their hydrogen bond interaction.This work would offer a new way to design and prepare novel intrinsic high thermal conductive polymers.     

Fluorinated polyimide–silica films with low permittivity and low dielectric loss

A sol–gel process was used to prepare polyimide–silica hybrid films from the fluorinated polyimide precursors (6FDA-ODA) and tetraethylorthosilicate (TEOS) in N,N-dimethyl acetamide. The hybrid film was then treated with hydrofluoric acid to remove the dispersed silica particles, leaving inside the film pores with diameters ranged from 80 nm to 1 μm, which depended on the size of the silica particles. The chemical structures and morphology of the hybrid and porous films were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The synthesized porous fluorinated polyimide films show low relative dielectric permittivity of 1.9, rendering them promising for microelectronic packaging materials.     

The effect of the capillary forces on the desorption of hydrogels in contact with a porous cementitious material

This paper examines the desorption of hydrogels in contact with porous cementitious materials to aid in understanding the mechanisms of water release from superabsorbent polymers (SAP) into cementitious materials. The dependence of hydrogel desorption on the microstructure of cementitious materials and relative humidity was studied. It was shown that the capillary adhesion developed at the interface between the hydrogel and cementitious materials increased the desorption of the hydrogels. The size of hydrogels was shown to influence desorption, beyond the known size dependence of bulk diffusion, through debonding from the cementitious matrix, thereby decreasing the effect of the Laplace pressure on desorption. Microscopic examination highlighted a stark contrast in the desorption morphology of hydrogels with different chemical compositions.