前驱体分子结构对聚糠醇基碳膜微结构及气体分离性能的影响

分别以草酸(OA)和碘(I)两种催化剂合成聚糠醇(PFA)前驱体制备气体分离碳膜. 采用TG, FTIR和XRD对其微结构进行研究, 并通过纯组分气体的渗透实验对碳膜的分离性能进行了探讨. 研究结果表明, 在热解过程中, 两种结构的聚糠醇都是通过脱氧、重排、环化、芳构化等热分解和热缩聚反应逐渐转化为无定形的乱层碳结构, 但热分解反应过程明显不同, 所形成碳膜微结构的差异也很大. 草酸催化剂制备的聚糠醇碳膜的微晶Lc值比碘催化剂制备碳膜的大, 而d(002)和La值则比后者的小, 表明草酸催化剂制备的聚糠醇碳膜碳微晶片层数多、排列规则、结构缺陷和孔隙均小于碘催化剂制备的聚糠醇碳膜, 而且其气体分离选择性较高、渗透通量较小, 表明聚糠醇的分子结构对所制备碳膜的微结构及气体分离性能有很大影响.     

聚糠醇炭分子筛膜的制备及O_2/N_2分离性能研究

以草酸为催化剂将糠醇单体直接聚合成所需黏度的聚糠醇液体作为涂膜液,仅需一步涂覆便可在价格低廉的煤基炭管支撑体上制备出高性能的聚糠醇炭分子筛膜.聚糠醇炭分子筛膜的热解过程、微观形貌和分离性能分别采用热重分析、扫描电镜以及O2、N2渗透实验进行表征.实验结果表明制备出的聚糠醇炭分子筛膜表面均匀且无缺陷.聚糠醇在热解过程中最终转化成具有超微孔的乱层石墨微晶结构.热解温度升高导致了起分离作用的有效超微孔尺寸的减小,进而表现出O2、N2的渗透速率逐渐降低,O2/N2的选择性逐渐增大的趋势.不同热解温度下制备的炭分子筛膜的O2渗透性和O2/N2选择性之间关系均超出了传统聚合物膜的Robeson上限.     

铝合金表面电合成聚甲基丙烯酸甲酯膜及其性能研究

为了改善6063铝合金的防腐蚀性能,以甲基丙烯酸甲酯(MMA)为功能单体,四丁基高氯酸铵为支持电解质,在6063铝合金表面上电聚合了一种甲基丙烯酸甲酯(PMMA)防腐蚀聚合膜。采用红外光谱、扫描电镜对合成的防腐膜层的结构及形貌分别进行了表征,结果表明制备了聚甲基丙烯酸甲酯;采用极化曲线、交流阻抗法(EIS)在3. 5 wt.%NaCl的溶液中对这种聚甲基丙烯酸甲酯防腐膜层的电化学性能进行了研究,结果显示6063铝合金的防腐蚀性能得到了显著改善。     

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.     

对甲苯磺酸掺杂聚吡咯的合成、表征及其对金属镁的防腐蚀性能研究

以对甲苯磺酸为掺杂剂, 三氯化铁为氧化剂, 化学氧化吡咯制备了对甲苯磺酸掺杂聚吡咯. 考察了掺杂剂与氧化剂的用量对掺杂聚吡咯电导率的影响, 得到了高电导率聚吡咯的优化条件, 用UV, IR和SEM对其结构和形貌进行了表征. 结果表明, n(对甲苯磺酸)∶n(吡咯)∶n(三氯化铁)＝0.75∶1∶0.5时, 合成的聚吡咯的形貌规则, 电导率达42.7 S•cm^－1. 以聚吡咯为功能成分, 环氧树脂为成膜物质, 得到一种功能膜, 旋涂于金属镁表面, 采用极化曲线和开路电位考察了含有聚吡咯的膜层对金属镁的防腐蚀性能. 结果表明, 含有聚吡咯的膜层对金属镁有很好的防腐蚀性能, 腐蚀电流为0.0981 A, 腐蚀电位为－0.88 V, 在膜层与金属镁之间形成了一层钝化膜.     

不同状态下聚吡咯膜的电化学阻抗

用恒电流法分别聚合了掺杂对甲苯磺酸根(pTS-)和十二烷基磺酸根(DS-)的聚吡咯膜(PPy/pTS和PPy/DS),通过循环伏安法(CV)和电化学阻抗法(EIS)测试了聚吡咯膜在NaCl溶液中‘过电位’电化学过程前后及不同电位下聚吡咯膜的电化学性能.同时,通过嵌入和脱出Na+和Cl-离子的聚吡咯膜在特定溶液中电化学阻抗图谱,研究了离子的嵌入对聚吡咯膜电化学性能的影响.结果表明‘过电位’现象可以提高聚吡咯膜的离子电导率和膜电容,Cl-离子的嵌入能提高PPy/pTS的电导率,而Na+离子的嵌入对聚吡咯膜的电导率影响不大.另外,嵌入离子对聚吡咯膜形貌的改变会对聚吡咯膜的离子传导率有一定影响,从而导致膜的电化学阻抗的变化.     

聚电解质PDDA/PSS层层自组装膜的渗透汽化性能

采用聚电解质层层自组装(LbL)技术, 在不同盐浓度下制备了聚(二烯丙基二甲基氯化铵)/聚苯乙烯磺酸钠(PDDA/PSS) 多层自组装膜, 并用于渗透汽化性能的研究. 重点考察了组装溶液中NaCl的浓度、组装层数及操作温度对自组装膜的异丙醇脱水性能的影响. 同时, 用扫描电镜观测了不同条件下制备膜的表面形貌. 结果表明, 在高NaCl含量的聚电解质溶液中只需组装几个双层的LbL膜, 即能获得较高的分离因子和较大的通量, 并解释了该LbL膜呈现反“trade-off”现象的原因.     

部分水解聚丙烯酰胺浓度对结构形貌的影响

本文用原子力显微镜(AFM)研究了不同浓度的部分水解聚丙烯酰胺(HPAM)溶液在云母片上成膜后的结构形貌。浓度不同,AFM下观察到的结构形貌差别很大。50ppm和1000ppm的HPAM在云母片上成膜后不能形成规则的排列,而100ppm的HPAM在云母片上成膜后形成规则的排列,但不同位置处的排列不同,500ppm的HPAM在云母片上成膜后可形成树枝生长的分形结构。     

液相法合成MOF-808催化糠醛转移加氢研究

采用简单易行的常压液相合成法,通过调节氧氯化锆和均苯三甲酸的比例,制备得到MOF-808-x,利用X-射线衍射(XRD)、傅里叶红外光谱(FT-IR)、场发射透射电子显微镜(TEM)等对其结构、形貌进行一系列表征。以糠醛加氢为探针反应,考察了MOF-808-x在异丙醇为氢供体体系中催化糠醛转移加氢制糠醇反应性能,并优化了反应条件。结果表明:合成催化剂适宜的原料配比可以提高反应活性。以MOF-808-1为催化剂时,在100℃反应2 h,糠醛转化率为100%,糠醇选择性>99%。     

两亲性嵌段共聚物PGMA-b-PMAPEG的制备及其胶束的布洛芬药物控制释放性能

利用自由基可逆加成-断链链转移(RAFT)活性/可控聚合法成功合成了两亲性嵌段共聚物聚(甲基丙烯酸缩水甘油酯)-b聚(甲基丙烯酸聚乙二醇酯)(PGMA-b-PMAPEG).利用傅立叶变换红外光谱、核磁共振谱仪、凝胶渗透色谱仪及透射电镜等分析了所合成聚合物的结构、胶束粒径及形貌.以布洛芬作为模型药物负载于聚合物胶束内,考...     

Alcohol elastomer based on superabsorbents

A microporous superabsorbent of poly(acrylic acid‐g‐cetyltrimethylammonium bromide) (PAA‐g‐CTAB) is synthesized by aqueous polymerization method. With the use of the superabsorbent as a host backbone, a large amount of alcohol is absorbed inside the micropores of PAA‐g‐CTAB to form an alcohol elastomer with an alcohol absorbency of 32 g/g. As a new kind of quasi‐solid‐state fuel, the alcohol elastomer is safe, low cost, and easy to use. The alcohol absorbency of the superabsorbent and the combustion properties of the alcohol elastomer can be adjusted by tuning the polymerization reaction conditions. The flame reactions in the alcohol elastomer arouse more interest for the alcohol elastomer. Copyright © 2011 John Wiley & Sons, Ltd.     

一步聚合法制备壳核型、可控阶层结构的羰基铁/聚苯乙烯复合微球

采用改进的悬浮聚合法合成了一系列粒径和结构可调的羰基铁粉/聚苯乙烯磁性高分子微球.利用傅立叶变换红外光谱仪、热重分析仪、X射线衍射仪、扫描电镜等分析了微球的结构、化学成分及形貌.结果表明,通过改变苯乙烯单体和聚乙烯醇(PVA)的加入量,可以制备三类不同形貌和结构的复合微球,即多孔复合微球,无孔复合微球和含"带状"突起的...     

Studies in the phase behavior of the microemulsions formed by mixed cationic and nonionic surfactants

The middle-phase behavior for the systems of cetyltrimethylammonium bromide (CTAB)/poly-ethyleneglycol-9-monododecyl ether (AEO₉)/alcohol/oil/brine and CTAB/octylphenolpolyoxyethylene-10-ether (Triton X-100)/alcohol/oil/brine have been studied with ɛ-β fishlike phase diagram method. The interfacial layer composition was determined, and some significant physicochemical parameters are derived from the hydrophilic-lipophilic balance plane equation. The effects of different alcohols, oils, temperature and inorganic salt (NaCl) on the middle-phase behavior of microemulsion formed by composite CTAB/AEO₉ systems were also investigated systematically. The effects of different factors on the phase behavior of microemulsions formed by CTAB/AEO₉ and CTAB/TX-100 systems were compared. The results suggest that the solubilization of CTAB/AEO₉ microemulsion is higher than that of CTAB/TX-100 system under the same conditions.     

Molecular sieving platinum nanoparticle catalysts kinetically frozen in nanoporous carbon

Highly active shape selective catalysts with excellent thermal stability are synthesized by entrapping well dispersed platinum nanoparticles in a polyfurfuryl alcohol derived nanoporous carbon matrix; these nanocomposites are excellent candidates for new catalytic applications including fuel cells, pharmaceutical synthesis and biomass conversion.     

硫酸氢钠催化合成丙烯酸异丁酯

利用一水硫酸氢钠为催化剂使丙烯酸和异丁醇酯化合成了丙烯酸异丁酯;研究了一水硫酸氢钠用量、异丁醇用量、反应时间、温度及阻聚剂用量对丙烯酸异丁酯收率的影响.结果表明,当异丁醇与丙烯酸物质的量之比为3∶1,硫酸氢钠催化剂用量为丙烯酸量的2%,阻聚剂(对苯二酚)用量为丙烯酸质量的0.05%,反应时间为3h,反应温度为115℃时,酯化产率可达88.51%.     

Synthesis of Poly(3,4-ethylenedioxythiophene) Hollow Spheres in CTAB/DBS — Mixed Surfactant Solutions

Summary: Hollow microspheres of PEDOT (poly(3,4-ethylenedioxythiophene) ranging from 0.5 to 10 µm have been synthesized by chemically oxidative polymerization of EDOT(3,4-ethylenedioxythiophene) using ammonium persulfate in a catanionic surfactant solution obtained by mixing cetyltrimethylammonium bromide (CTAB) and sodium dodecylbenzenesulfonate (SDBS). The effect of the molar ratio of CTAB to SDBS on the morphology of the PEDOT oxidation products has been investigated using SEM and TEM and by an analysis of the structural properties using UV-visible, FTIR and Raman spectroscopies, elemental analysis and conductivity measurements. The electro-catalytic activity of PEDOT hollow microspheres for the oxidation of ascorbic acid was investigated by cyclic voltammetry in a pH 6 citrate/phosphate buffer solution and compared to the activity of granular PEDOT particles formed in the absence of the catanionic surfactant.     

The intrinsic nanofibrillar morphology of polyaniline

Polyaniline nanofibers are shown to form spontaneously during the chemical oxidative polymerization of aniline. The nanofibrillar morphology does not require any template or surfactant, and appears to be intrinsic to polyaniline synthesized in water. Two approaches--interfacial polymerization and rapidly-mixed reactions--have been developed to prepare pure nanofibers. The key is suppressing the secondary growth that leads to agglomerated particles. The effects of different dopant acids and solvents are discussed. Changing the dopant acid can be used to tune the diameters of the nanofibers between about 30 and 120 nm. Changing the organic solvent in interfacial polymerization reactions has little effect on the product. A brief discussion of the processibility of the nanofibers is presented. The possibility of creating nanofibrillar structures for selected polyaniline derivatives is also demonstrated.     

Thermal properties of polyfurfuryl alcohol absorbed/adsorbed on arylated soy protein films

In this study, polyfurfuryl alcohol was absorbed/adsorbed on soy protein isolate films by immersing the SPI films in acid-catalysed furfuryl alcohol solution for 60 h followed by complete curing at 145–150 °C for 2 h. PFA absorbed/adsorbed soy protein films designated as SPI-PFA were then arylated in the presence of 0.5% (w/v) 2,2-diphenyl-2-hydroxyethanoic acid for 4 h to fabricate arylated soy protein films designated as SPI-PFA-Ar. The incorporation of PFA and introduction of aromatic backbone through arylation is revealed from Fourier transform infrared study. Thermal studies of SPI, SPI-PFA and SPI-PFA-Ar were carried out by thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical thermal analysis. In addition, mechanical properties, surface morphology and water uptake of all the three different types of the films were evaluated. Results indicated that PFA absorbed/adsorbed arylated soy protein films showed higher thermal stability than native SPI films.     

Structural effects of dopants and polymerization methodologies on the solid‐state ordering and morphology of polyaniline

The solid‐state three‐dimensional ordering of polyaniline–dopant complexes was investigated with four structurally different sulfonic acid dopants. The doped materials were produced in three different ways: polyaniline emeraldine base doped with sulfonic acid (aqueous route), in situ polymerization at the organic–water solvent interface (interfacial route), and in situ polymerization in organic and aqueous solvent mixtures (bilayer route). p‐Toluenesulfonic acid (PTSA), 5‐sulfosalicilic acid (SSA), camphorsulfonic acid (CSA), and dodecylbenzene sulfonic acid (DBSA) were employed as dopants. The conductivity of the aqueous‐route samples showed 10 and 100 times higher conductivity than the interfacial and bilayer routes, respectively. WXRD studies suggested that the crystallinity of the doped samples was dependent on both the structure of the dopants and the polymerization techniques. DBSA increases the polyaniline interplanar distance and produced highly crystalline materials via the aqueous and bilayer routes but failed with the interfacial route because of poor solubility in water. CSA, PTSA, and SSA produced highly crystalline samples by the interfacial route but failed with the aqueous (except for CSA) and bilayer routes. SEM analysis revealed that the doped materials of the interfacial route had excellent continuous morphology and uniform submicrometer‐size particle distributions in comparison with those of the aqueous and bilayer routes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1321–1331, 2005     

Effects of monomer concentration on the structure and properties of polybenzidine micro rods

Polybenzidine was synthesized by interfacial polymerization under various monomer concentrations. Effects of monomer concentration on morphology, structure, and properties of polybenzidine were studied by techniques of Fourier Transform Infrared Spectroscopy, Ultraviolet Visible Absorption Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscopy, X-ray Diffraction, and Cyclic Voltammetry. The results showed that the synthesized polybenzidine with monomer concentration less than 0.15 mol/L were micro rod-like and the surface of the micro rods was smooth and uniform, However, the micro rod-like polybenzidine cannot be obtained under high monomer concentration because of the explosive polymerization. The results of structural analysis indicated that the monomer concentration should not be very high to obtain the polybenzidine with the optimal degree of conjugation and order arrangement of molecular chain. The polybenzidine synthesized in different monomer concentrations showed different electrochemical activities and the sample with the best electrochemical activity was obtained at monomer concentration of 0.02 mol/L.