PVA-Zr(Ⅳ)膜催化乙酸和丁醇酯化反应的性能

考察了PVA-Zr(Ⅳ)膜催化乙酸和丁醇酯化反应的宏观反应动力学,认为膜催化酯化反应为扩散-反应联合控制,膜溶胀实验表明反应液各组分浓度不同于膜中各组分平均浓度.假设膜催化反应分为：膜溶胀前及溶胀后两个阶段,分别求出了此两个阶段反应动力学常数.比较了PVA-Zr(Ⅳ)催化膜和无催化活性层的PVA膜渗透性能.     

交联聚乙烯醇渗透蒸发膜用于酯化反应过程

研究了交联聚乙烯渗透蒸发膜在酯化反应过程中的应用，以乙酸与正丁醇酯化反应为实验对象，通过渗透蒸发膜选择性地移走产物水，使最终反尖转化率超越平衡转化率，实验考察了温度，进料初始摩尔比，催化剂浓度对过程的影响。     

聚乙烯醇膜的研制及乙醇水溶液的渗透蒸发（PV）分离

选择以聚乙烯醇(PVA)作膜材料,制成具有一定通量及分离效果的聚乙烯醇均质膜及聚乙烯醇/聚砜复合膜。讨论了膜的抗水性及抗化学腐蚀性。用透射电镜及扫描电镜进行了结构测定,并研究了这两种膜在分离95%(重量浓度)乙醇水溶液时的性能以及温度、交联度对膜性能的影响。实验发现聚乙烯醇均质膜具有较高的分离系数;聚乙烯醇/聚砜复合膜在基本维持均质膜分离性能的前提下,通量有较大提高。还发现经Cr~(3 )的饱和溶液处理后再进一步交联的膜,交联度及稳定性都有提高,分离系数略有下降。     

渗透蒸发膜及其在酯化反应过程中的应用

根据３０余篇文献及有关的技术资料，从膜的结构，膜制备的材料，制备方法及表征等方面总结了近１０年来渗透蒸发膜国内外的研究情况，以及将渗透蒸发膜应用酯化反应体系的研究成果和动态。     

PVA/PEG/TEOS杂化膜制备及性能研究

以聚乙烯醇(PVA)与聚乙二醇(PEG)共混,并与正硅酸乙酯(TEOS)进行交联反应制备杂化膜。FTIR证实杂化溶胶液发生交联反应形成共价键Si—O—C,WXRD观察表明加入TEOS改变了膜结晶度,加入PEG提高了PVA膜对乙醇/水溶液的渗透通量,但分离因子下降,随着TEOS的加入,膜的分离因子提高。在TEOS质量分数为10%时,杂化膜的分离因子达到最大。提高退火温度可以提高膜的分离因子,但通量下降。在100℃下退火12 h的杂化膜对乙醇质量分数为85%的乙醇/水溶液的分离性能最佳。     

TiO2/PVA杂化膜的渗透蒸发性能及结构表征

通过纳米TiO2粒子填充改性制备了新型TiO2/PVA杂化膜。红外光谱表明纳米TiO2表面的羟基与聚乙烯醇(PVA)链上的羟基存在较强的氢键作用。扫描电镜显示当TiO2的质量分数低于1.5%时,在PVA中分散均匀。X射线衍射显示纳米TiO2的加入降低了膜的结晶度。通过对含水质量分数低于20%的水/乙醇体系的脱水研究了该杂化膜的渗透性能,考察了TiO2粒子填充量、料液质量分数和温度与膜分离性能之间的关系。渗透通量J随着TiO2、水质量分数和温度的升高而增加,分离因子随着温度和水质量分数的升高而下降,在TiO2质量分数为1.5%时分离因子达到最佳值。40℃下分离质量分数85%的乙醇水溶液,分离因子可达1 590,渗透通量为0.049kg/(m2.h)。     

乙酸与丁醇酯化反应和渗透蒸发耦合过程研究

以硫酸锆催化乙酸和丁醇的酯化反应为例对渗透蒸发和酯化反应耦合过程进行研究 ,考察了温度、反应物初始摩尔比、膜面积与反应液体积比和催化剂浓度对耦合过程的影响。     

聚乙烯醇/二氧化硅杂化膜的制备及渗透蒸发分离环己醇（酮）/环己烷

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,经溶胶-凝胶（sol-gel）法制备了不同二氧化硅（SiO2）含量的 PVA/SiO2杂化膜。傅里叶变换红外光谱（FT-IR）表明,随着SiO2含量增大,1060cm?1和970cm?1处Si—O—Si特征吸收峰的相对强度逐渐加强,说明TEOS与PVA发生了交联反应;同时膜的分解温度从248℃升高到342℃。杂化膜的SiO2含量从10 %增大到40 %,其玻璃态温度从115℃升高到124℃。以水为溶剂,测定了杂化膜的耐溶剂性能,与PVA膜相比,杂化膜的耐溶剂性能显著提高。以质量比为0.950/0.025/0.025的环己烷/环己醇/环己酮为原料,测定杂化膜的分离性能,结果表明SiO2含量从10 %增大到40 %,通量从15.94 g/(m2?h)升高到75.69 g/(m2?h),环己醇的分离因子从1.8升高到2.65。     

新型渗透蒸发膜及其透醇性能研究

采用溶液聚合法合成聚丙烯酸,并利用聚丙烯酸和环氧树脂的交联作用制备出交联聚丙烯酸（ＰＡＡ）,在聚砜酰胺（ＰＳＡ）膜上涂膜形成ＰＡＡ－ＰＳＡ复合膜。发现用交联聚丙烯酸－聚砜酰胺制成的复合膜在渗透蒸发领域内具有应用价值。通过对低浓度乙醇－水的渗透蒸发的试验研究,表明该膜是一种性能较好的新型优先透醇膜。     

PVA/SO42——AAO催化-渗透汽化双功能复合膜合成乙酸乙酯

采用浸渍-涂覆法制备了聚乙烯醇/阳极氧化铝固体酸（PVA/SO₄^2--AAO）催化-渗透汽化双功能膜,并用于乙酸与乙醇的催化酯化反应。用SEM、XRD、NH₃-TPD分析了双功能膜的结构及性能。考察了双功能膜用量、乙酸/乙醇摩尔比及反应温度对酯化反应转化率的影响。结果表明：乙酸/双功能膜质量比为30∶1,乙酸/乙醇摩尔比为4∶1,料液温度为80℃时乙醇的500 min转化率可以达到87%。反应活化能为41.84 kJ/mol,比浓硫酸作催化剂的经典反应活化能降低6.74 kJ/mol。     

Preparation and characterization of PSSA/PVA catalytic membrane for biodiesel production

Poly(styrene sulfonic acid) (PSSA)/Poly(vinyl alcohol) (PVA) blend membranes prepared by the solution casting were employed as heterogeneous acid catalysts for biodiesel production from acidic oil obtained from waste cooking oil (WCO). The membranes were annealed at different temperature in order to enhance their stability. The structure and properties of the membranes were investigated by means of Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), X-ray diffraction (XRD). It is found that the crosslinking structure among PVA and PSSA chains formed when the thermal treatment temperature was higher than 80 °C. The retention of PSSA in the blend membranes in the methanol/water solvent was markedly increased from 50% to 85% with the increase of the annealing temperature from room temperature (for the untreated membrane) to 150 °C due to the formation of the crosslinking structure. The results of esterification of acidic oil show that the conversion was slightly improve with the PVA content in the membrane at a fixed PSSA content. The thickness of the catalytic membrane had no significant effect on the conversion in the end. The membrane annealed at 120 °C exhibited the best catalytic performance among the membranes, with a stable conversion of 80% with the runs.     

Poly(vinyl alcohol)/Carboxyl Graphene Membranes for Ethanol Dehydration by Pervaporation

Carboxyl graphene (CG) with two functions of hybridization and crosslinking was incorporated into poly(vinyl alcohol) (PVA) matrix to form PVA/CG mixed-matrix membranes (MMMs). The membranes demonstrated excellent mechanical properties and thermal stability. The improved hydrophilicity and formed crosslinking structure led to moderate swelling. The membrane crystallinity decreased and the free volume was promoted with increasing CG loading amount. The pervaporation (PV) separation performance for ethanol dehydration indicated that both permeation flux and separation factor were enhanced simultaneously at the optimum CG loading. Subsequently, the permeation flux continued to increase while the separation factor declined at higher CG loadings.     

Mixed matrix membranes prepared from natural rubber/poly(vinyl alcohol) semi-interpenetrating polymer network (NR/PVA semi-IPN) incorporating with zeolite 4A for the pervaporation dehydration of water-ethanol mixtures

The pervaporation dehydration of water-ethanol mixtures was investigated using the mixed matrix (MM) membranes prepared from natural rubber (NR) and crosslinked poly(vinyl alcohol) (PVA) semi-IPN embedded with the zeolite 4A. With the presence of NR as well as zeolite, the swelling of MM membranes in water was effectively suppressed. Examined by DSC, the non-freezing bound water in the MM membranes was found decreasing with more zeolite loading because the water-polymer interaction is diminishing. The sorption study of MM membranes revealed a preferential sorption to water with improved water sorption selectivity as increasing the zeolite loading. For pervaporation at 5 vol% water in feed, the reversed trade-off with respect to the zeolite loading was encountered such that the total permeation flux increased along with an enhancement of the water separation factor. For higher feed water concentration, despite the greater total permeation flux, the separation factor was reduced owing to the extensive swelling of the polymer matrix. The temperature dependency of the partial water and ethanol fluxes followed the Arrhenius relationship and the estimated activation energies for water flux were lower than those of the ethanol flux, suggesting that the developed MM membranes are highly water selective.     

Novel PVA-silica nanocomposite membrane for pervaporative dehydration of ethylene glycol aqueous solution

To effectively suppress the swelling of poly(vinyl alcohol) (PVA) membrane, polymer-inorganic nanocomposite membranes composed of PVA and γ-mercaptopropyltrimethoxysilane (MPTMS) were prepared by in situ sol-gel technique for pervaporative separation of water-ethylene glycol (EG) mixtures. Effects of the types of catalyst for sol-gel process and MPTMS content on the physical and chemical structure of PVA-silica nanocomposite membranes (designated as PVA-MPTMS hereafter) were investigated by ²⁹Si NMR, FTIR, SEM, XRD and TGA-DTA. Due to the formation of more compact crosslinked structure, nanocomposite membranes exhibited enhanced thermal stability. It was found that when 50 wt% of MPTMS was incorporated into PVA, the nanocomposite membranes possessed optimum pervaporation performance for 80 wt% EG aqueous solution at 70 °C. Unexpectedly, there was no improvement in the pervaporation performance of PVA-MPTMS nanocomposite membranes after mercapto group was oxidized into sulfonic group.     

The Preparation and Characterization of Esterified Banana Trunk Fibers/Poly(vinyl alcohol) Blend Film

Polymer composite using natural fiber as reinforcement material is getting attention due to easy availability and its low cost. In this work, poly(vinyl alcohol) (PVA)/fatty acid esterified banana trunk fibers (FAGBTF) of various compositions were produced by a solution casting method. The characteristic properties of PVA/ FAGBTF composite films were examined by Fourier Transform Infra-Red (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. On the whole, the increase in the amount of BTF in the composite systems improved the thermal properties and decreased percentage degree of swelling as compared to pure PVA.     

Pervaporation of ethanol-water mixtures through poly(vinyl alcohol-g-acrylic acid) membranes prepared by use of Fenton's reagent in grafting

Ionic crosslinking of the ferric ions and the carboxylic groups in the poly(vinyl alcohol-g-acrylic acid) (poly(VA-g-AA)) membranes improves the size screening effect in the pervaporation of ethanol-water separation. In the grafting polymerization of acrylic acid monomer onto poly(vinyl alcohol) (PVA), ferric ions are remained in the polymer membranes as the Fenton's reagent(Fe²⁺-H₂O₂) is used to initiate the reaction. Completely reversed trends in terms of the degree of swelling, the pervaporation selectivity, and the flux of permeates are obtained depending on that the ferric ions are present or absent in the membranes. The degree of swelling decreases, the pervaporation selectivity increases, and the flux decreases as the grafting percentage increases for the membranes containing ferric ions. The degree of swelling and the flux of permeates increase but the pervaporation selectivity is reduced as the grafting percentage increases for the membranes which were washed with acid to remove ferric ions.     

Characterization of Poly(Vinyl Alcohol) and Poly(Vinyl Pyrrolidone) Co-polymer Blend Hydrogel Prepared by Application of Gamma Radiation

Hydrogel is prepared from a poly(vinyl pyrrolidone) (PVP) and poly(vinyl alcohol) (PVA) blend solution by gamma radiation with a ₆₀Co λ source at room temperature. Properties of the prepared hydrogel, such as gel fraction, gel strength swelling ratio, equilibrium water content, and water absorption in room temperature, were investigated. Blending hydrogel with PVP and PVA obviously increased the gel strength and decreased the swelling ratio of hydrogel. It was observed that the gel fraction increased while the swelling ratio and water content decreased with increased radiation dose, but gel strength increased up to a certain radiation dose and then decreased. The percentage of water absorption at room temperature increased with time but after a certain time it became steady and decreased with radiation dose.     

Preparation and characterization of α-chitin whisker-reinforced poly(vinyl alcohol) nanocomposite films with or without heat treatment

α-Chitin whisker-reinforced poly(vinyl alcohol) (PVA) nanocomposite films were prepared by solution-casting technique. The α-chitin whiskers were prepared by acid hydrolysis of α-chitin from shrimp shells. The as-prepared whiskers exhibited the length in the range of 150-800 nm and the width in the range of 5-70 nm, with the average length and width being about 417 and 33 nm, respectively. Thermal stability of the as-cast nanocomposite films was improved from those of the pure PVA film with increasing whisker content. The presence of the whiskers did not have any effect on the crystallinity of the PVA matrix. The tensile strength of α-chitin whisker-reinforced PVA films increased, at the expense of the percentage of elongation at break, from that of the pure PVA film with initial increase in the whisker content and leveled off when the whisker content was greater than or equal to 2.96 wt%. Both the addition of α-chitin whiskers and heat treatment helped improve water resistance, leading to decreased percentage degree of swelling, of the nanocomposite films.     

Fabrication of poly(vinyl alcohol)s (PVAs) nanotubes through the fusion of nanocapsules composed of PVAs multilayer films

Poly(vinyl alcohol) (PVA) nanocapsules were fabricated by the deposition of PVA multilayer films onto the surface of silica particles followed by the removal of the silica cores. When a water dispersion of PVA nanocapsules was dried on a substrate, PVA nanotubes were formed through the one-dimensional fusion of the nanocapsules. This fusion behavior of the PVA nanocapsules was strongly affected by the molecular weights and acetylation degrees of PVA, the capsule film thickness of the PVA nanocapsules and the temperature to dry a water dispersion of the nanocapsules. When nanocapsules composed of 20 layered films of acetylated PVA with a 14% acetylation degree were used, nanotube formation via the fusion of these nanocapsules occurred effectively upon drying the water dispersion at 20 °C.     

Miscibility and interactions in poly(methylthiomethyl methacrylate)/poly(vinyl alcohol) blends

Poly(methylthiomethyl methacrylate) (PMTMA) is miscible with poly(vinyl alcohol) (PVA) over the whole composition range as shown by the existence of a single glass transition temperature in each blend. The interaction between PMTMA and PVA was examined by Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the thioether sulfur atoms of PMTMA, and the involvement of the carbonyl groups of PMTMA in interactions is not significant. The measurements of proton spin-lattice relaxation time reveal that PMTMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. In comparison, we have previously found that PMTMA is miscible with poly(p-vinylphenol) and the two polymers mix intimately on a scale of 1-3 nm.