镉（Ⅱ）－1－苯基－3－甲基－4－苯甲酰基－吡唑啉酮－5配合物吸附波的研究

在ｐＨ４．８的ＨＡｃ－ＮＨ＿（４）Ａｃ介质中，Ｃｄ（Ⅱ）与１－苯基－３－甲基－４－苯甲酰基－吡唑啉酮－５（ＰＭＢＰ）生成配合物，于－０．６７Ｖ（ｖｓ．ＳＣＥ）出现一尖锐、灵敏的极谱波。镉含量在０．００１～１．μｇ／ｍＬ范围内与峰高成线性关系。用多种电化学方法研究了极谱波的性质及电极反应机理，证明－０．６７Ｖ处的极谱波为配合物吸附波，峰电流由中心离子Ｃｄ（Ⅱ）还原产生。配合物组成为Ｃｄ（Ⅱ）：ＰＭＢＰ＝１：１。试验了３０多种离子对峰电流的影响，用ＳｒＳＯ＿４共沉淀分离Ｐｂ（Ⅱ），再经巯基棉分离其它干扰离子。用于矿样中镉的测定，结果满意。     

新显色剂5－NO_2－PADAP与镍的显色反应研究

本文研究了新显色剂２－（５－ＮＯ２－２－吡啶偶氨）－５－二乙氨基酚（５－ＮＯ２－ＰＡＤＡＰ）与镍的显色反应及分光光度测定镍，在ＰＨ３．５乙醇水溶液中，镍与５－ＮＯ２－ＰＡＤＡＰ形成稳定的深色配合物，最大吸收在５６５ｕｍ处，摩尔吸光系数为．１．５７×１０５Ｌ·ｍｏｌ（－１）·ｃｍ（－１），镍在０～１２μｇ／２５ｍＬ范围内服从比尔定律，用此法测定钢铁及茶叶中的微量镍，结果令人满意。     

碱金属离子改性聚乙烯醇渗透汽化膜

研究了含碱金属氯化物的聚乙烯醇。马来酸酐（ＰＶＡ－ＭＡ）交联膜对乙醇－水混合物的分高性能，盐含量低于６％质量时，膜的透量明显增加，原料液乙醇浓度较高时，分离系数也增大，含盐膜从５０％乙醇水溶液中吸附了５％～８％的自由水。     

吡啶－2，6－二甲酸镧钇异核配合物的合成及晶体结构

合成了吡啶－２，６－二甲酸镧钇异核配合物晶体。元素分析结果表明，化学式为ＬａＹ（ＨＤＰＡ）＿２·（ＤＰＡ）＿２．１２Ｈ＿２Ｏ，ＤＰＡ为吡啶－２，６－二甲酸根。用Ｘ射线衍射法测定了配合物的单晶结构，其结构式为［ＬａＹ（ＨＤＰＡ）＿２（ＤＰＡ）＿２（Ｈ＿２Ｏ）＿４」·８Ｈ＿２Ｏ，属单斜晶系，Ｐ２＿１／ａ空间群。晶胞参数：ａ＝１．２９７５（４）ｎｍ，ｂ＝１．１２６６（３）ｎｍ，ｃ＝１．４０７９（３）ｎｍ；β＝１０２；１５（２）°，Ｖ＝２．０１１９０（１）ｎｍ￣３，Ｚ＝４，Ｄｃ＝１．８３ｇ／ｃｍ￣３，稀土离子的配位数为９，其配位多面体为扭曲的三冠三角棱柱体。     

吡啶－2，6－二甲酸钪配合物［Sc（HDPA）（DPA）（H_2O）_2］·5

在水溶液中合成了吡啶－２，６－二甲酸抗配合物的晶体，元素分析结果表明，可用Ｓｃ（ＨＤＰＡ）（ＤＰＡ）·７Ｈ＿２Ｏ表示，用Ｘ射线衍射方法测定了配合物的单晶结构，其结构式为［Ｓｃ（ＨＤＰＡ）（ＤＰＡ）（Ｈ２Ｏ）２］·５Ｈ２Ｏ。晶体属正交晶系，空间群为Ｐｎ２１ａ。晶胞参数如下：ａ＝１．０１６９（２）ｎｍ，ｂ＝１．０１７２（２）ｎｍ，ｃ＝２．０２５４（４）ｎｍ；Ｖ＝２．０９５（１）ｎｍ３，Ｚ＝４，Ｄ＝１．５９ｇ／ｃｍ３。抗离子的配位数为８，其配位多面体为三角十二面体。     

填充Silicalite－Ⅰ沸石的PDMS橡胶醇－水分离膜

Ｓｉｌｉｃａｌｉｔｅ－Ⅰ沸石经过酸处理或水热处理可完善其晶体结构，提高对乙醇的吸附选择性，由此提高对乙醇－水混合物的分离系数。特别是先经过酸处理再经过水热处理的Ｓｉｌｉｃａｌｉｔｅ－Ⅰ沸石填充聚二甲基硅氧烷橡胶膜（ＰＤＭＳ橡胶膜），乙醇－水的分离系数可达３０左右。     

铜（Ⅱ）－聚丙烯酰胺和铜（Ⅱ）－聚乙烯醇配位聚合物的配位数

配位聚合物ＰＡＡｍ－ＣｕＣｌ＿２和ｃｕＣｌ＿２·２Ｈ＿２Ｏ的Ｃｕ￣（２＋）２ｐＸＰＳ谱上都有Ｓｈａｋｅ－ｕｐ峰，其与各自的Ｃｕ￣（２＋）２ｐ３／２肩峰或主峰距离ΔＥｓ２或ΔＥｓ分别为８．７和８．６ｅＶ；但配位聚合物Ｃｕ（Ⅱ）－ＰＶＡ却无此峰．由此推定，前者的Ｃｕ￣（２＋）是以ｓｐ￣３杂化轨道接受ＰＡＡｍ４个链节单元Ｃ－Ｎ上Ｎ的孤对电子部分转移形成配位键；而Ｃｕ（Ⅱ）－ＰＶＡ配位聚合物中的Ｃｕ￣（２＋）却以ｄｓｐ￣２杂化轨道接受ＰＶＡ４个链节单元侧基Ｏ的孤对电子部分转移，产生配位键，即Ｃｕ￣（２＋）与ＰＡＡｍ或ＰＶＡ的链节单元配位比均是１：４，此结果与电导率法测定ＰＡＡｍ－ＣｕＣｌ＿２的配位比相同．     

SYNTHESIS OF A NOVEL LADDERLIKE POLThITRILE KITH PHOTO－ELECTRIC FUNCTIONAL PROPERTIES

ＳＹＮＴＨＥＳＩＳ　ＯＦ　Ａ　ＮＯＶＥＬ　ＬＡＤＤＥＲＬＩＫＥ　ＰＯＬＴｈＩＴＲＩＬＥ　ＫＩＴＨ　ＰＨＯＴＯ－ＥＬＥＣＴＲＩＣ　ＦＵＮＣＴＩＯＮＡＬ　ＰＲＯＰＥＲＴＩＥＳ￥ＨｕｉＹｉｎｇＣＨＥＮ；ＹｕａｎＫａｎｇＨＥ；ＦｅｎｇＧＥＮＧ（Ｐｏｌｙｅｍｅ...     

高选择性透过二氧化硫气体分离膜的研究 （Ⅳ）不同烃基乙烯基亚砜接枝聚乙烯醇膜的透过性能

研究了不同烃基乙烯基亚砜接技聚乙烯醇（ＰＶＡ－ＲＶＳＯ，Ｒ＝Ｍｅ，Ｅｔ，ｔ－Ｂｕ，Ｐｈ）膜对纯ＳＯ２、Ｎ２的透过性能以及ＳＯ２／Ｎ２混合气体的分离性能，结果表明上述膜对ＳＯ２具有高的选择性，对不同烃基乙烯基亚砜接枝膜进行了比较。     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

Preferential sorption of modified PVA membrane in pervaporation

The swelling processes of an annealed poly(vinyl alcohol) membrane, a NaOH-crosslinked poly(vinyl alcohol) membrane, a poly(vinyl alcohol)-N,N′-methylene bisacrylamide irradiation-crosslinked membrane and a poly(vinyl alcohol)/poly (AMcoAANa) blend membrane were investigated. Water was preferentially sorbed by all four membranes. The selective sorption factor ^s and the selective diffusion factor ^d were defined, and were used to characterize the effects of sorption and diffusion on selectivity. The results have shown that preferential sorption has a marked effect on selectivity. The mean diffusion coefficients and pervaporation properties of the four membranes are also discussed.     

Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend composition and of the feed mixture composition. The results showed that a polymer blending method could be very useful to develop new membranes with improved permselectivity. The pervaporation properties could be optimized by adjusting the blend composition. All the blend membranes tested showed a decrease in flux with increasing poly(vinyl alcohol) content for both methanol—toluene and ethanol—toluene liquid mixtures. The alcohols permeated preferentially through all tested blend membranes, and the selectivity values increased with increasing poly(vinyl alcohol) content. The pervaporation characteristics of the blend membranes were also strongly influenced by the feed mixture composition. The fluxes increased exponentially with increasing alcohol concentration in the feed mixtures, whereas the selectivities decreased for both liquid mixtures.     

Modification and characterization of semi-crystalline poly(vinyl alcohol) with interpenetrating poly(acrylic acid) by UV radiation method for alkaline solid polymer electrolytes membrane

Semi-crystalline poly(vinyl alcohol) was modified by UV radiation with acrylic acid monomer to get interpenetrating poly(acrylic acid) modified poly(vinyl alcohol), PVAAA, membrane. The stability of various PVAAA membranes in water, 2 M CH₃OH, 2 M H₂SO₄, and 40 wt% KOH aqueous media were evaluated. It was found that the stability of PVAAA membrane is stable in 40 wt% KOH solution. The PVAAA membranes were characterized by differential scanning calorimetry, X-ray diffraction, and thermogravimetry analysis. These results show that (1) the crystallinity in PVAAA decreased with increasing the content of poly(acrylic acid) in the PVAAA membranes. (2) The melting point of the PVAAA membrane is reduced with increasing the content of poly(acrylic acid) in the membrane. (3) Three stages of thermal degradation were found for pure PVA. Compared to pure PVA, the temperature of thermal degradation increased for the PVAAA membrane. The various PVAAA membranes were immersed in KOH solution to form polymer electrolyte membranes, PVAAA-KOH, and their performances for alkaline solid polymer electrolyte were conducted. At room temperature, the ionic conductivity increased from 0.044 to 0.312 S/cm. The result was due to the formation of interpenetrating polymer chain of poly(acrylic acid) in the PVAAA membrane and resulting in the increase of charge carriers in the PVA polymer matrix. Compared to the data reported for different membranes by other studies, our PVAAA membrane are highly ionic conducting alkaline solid polymer electrolytes membranes.     

Preparation and Characterization of Interpenetrating Polymer Hydrogels Based on Poly(acrylic acid) and Poly(vinyl alcohol)

Interpenetrating polymer hydrogels (IPHs) of Poly (vinyl alcohol) (PVA) and Poly (acrylic acid) (PAAc) have been prepared by a sequential method: crosslinked PAAc chains were formed in aqueous solution by crosslinking copolymerization of acrylic acid and N, N′-methylenebisacrylamide in the presence of PVA. The application of freezing-thawing cycles (F-T cycles) leads to the formation of a PVA hydrogel within the synthesized PAAc hydrogel. The swelling and the viscoelastic properties of the prepared IPHs were evaluated on the basis of the structural features obtained from solid state ¹³C-NMR spectroscopy.     

Tribological and Mechanical Properties of Poly[(R)-3-hydroxybutyric acid] Grafted with Vinyl Compounds: Insight into Possible Application

Biodegradable graft copolymers were prepared by gamma radiation-induced graft polymerization of two vinyl monomers, vinyl acetate and vinyl alcohol, onto poly[(R)-3-hydroxybutyric acid]. Success of the grafting reaction was verified by Fourier-transform infrared and nuclear magnetic resonance spectroscopy. Thermal remolding was used to create membranes from the copolymers. We determined tribological and mechanical properties of the membranes obtained. The lowest elongation at break in tensile testing is seen for P(3HB) and the highest for P(3HB-g-VA). Up to 5 N or so, the highest scratch resistance is exhibited by P(3HB-g-VA). Piezoelectric behavior is seen for P(3HB-g-VA) while P(3HB-g-VAc) and plain P(3HB) showed no electric response. Explanation of the piezoelectric behavior in terms of molecular structures is provided.     

Grafting reactions of vinyl acetate onto poly[(vinyl alcohol)-co-(vinyl acetate)]

The grafting preference of vinyl acetate onto the methine carbon of poly(vinyl alcohol) (PVOH) versus the acetate group of poly(vinyl acetate) (PVAc) was determined as part of an attempt to prepare novel branched PVOH from partially hydrolyzed PVAc. The results showed long chain grafting on the acetate groups of the PVAc units rather than the methine carbons of the PVOH or PVAc units. Decreasing the monomer or initiator concentration decreased the molecular weight of the graft copolymer formed. Of the initiators studied, ammonium persulfate gave the largest increase in copolymer molecular weight. Both hydrolysis and reacetylation combined with gel permeation chromatography (GPC) and ¹³C-NMR of the fully hydrolyzed material were used to estimate the number and location of grafts. © 1996 John Wiley & Sons, Inc.     

Composite membranes prepared from glutaraldehyde cross-linked sulfonated cardo polyetherketone and its blends for the dehydration of acetic acid by pervaporation

Cardo polyetherketone (PEK-C) composite membranes were prepared by casting glutaraldehyde (GA) cross-linked sulfonated cardo polyetherketone (SPEK-C) or silicotungstic acid (STA) filled SPEK-C and poly(vinyl alcohol) (PVA) blending onto a PEK-C substrate. The compatibility between the active layer and PEK-C substrate is improved by immersing the PEK-C substrate in a GA cross-linked sodium alginate (NaAlg) solution and using water–dimethyl sulfoxide (DMSO) as a co-solvent for preparing the STA-PVA-SPEK-C/GA active layer. The pervaporation (PV) dehydration of acetic acid shows that permeation flux decreased and separation factor increased with increasing GA content in the homogeneous membranes. The permeation flux achieved a minimum and the separation factor a maximum when the GA content increased to a certain amount. Thereafter the permeation flux increased and the separation factor decreased with further increasing the GA content. The PV performance of the composite membranes is superior to that of the homogeneous membranes when the feed water content is below 25 wt%. The permeation activation energy of the composite membranes is lower than that of the homogeneous membranes in the PV dehydration of 10 wt% water in acetic acid. The STA-PVA-SPEK-C-GA/PEK-C composite membrane using water–DMSO as co-solvent has an excellent separation performance with a flux of 592 g m⁻² h⁻¹ and a separation factor of 91.2 at a feed water content of 10 wt% at 50 °C.     

聚乙烯醇/纳米纤维素复合膜的渗透汽化性能及结构表征

将聚乙烯醇/纳米纤维素(PVA/NCC)复合膜应用于乙醇-水混合溶液的渗透汽化脱水过程,探讨了纳米纤维素对膜的溶胀性能、机械性能和渗透汽化性能的影响; 利用原子力显微镜(AFM)探测了纳米纤维素的形貌特征; 采用傅里叶变换红外光谱仪(FTIR)、扫描电镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TGA)对膜结构...     

以交联聚乙烯醇为载体的阴离子交换剂的合成与性能研究

大孔乙酸乙烯酯－异氰尿酸三烯丙酯共聚物树脂经醇解生成亲水性的交联聚乙烯醇，然后相继与环氧氯丙烷和二乙胺反应，合成出含二乙基氨基羟丙基的阴离子交换剂，研究了交联聚乙烯醇环氧基化的最佳条件，发现以二甲基亚砜作溶剂能够显著地提高活化程度，反应时间以３ｈ为最佳，并研究了该阴离子交换剂的交换量、亲水性、热稳定性、溶胀稳定性，发现它具备常压分离蛋白质所需的基本性能，是较为理想的生化用的离子交换剂。     

Pervaporation separation of water-acetic acid mixtures through poly(vinyl alcohol) membranes crosslinked with glutaraldehyde

Poly(vinyl alcohol) (PVA) membranes crosslinked with glutaraldehyde (GA) were prepared by a solution method for the pervaporation separation of acetic acid-water mixtures. In the solution method, dry PVA films were crosslinked by immersion for 2 days at 40°C in reaction solutions which contained different contents of GA, acetone and a catalyst, HCl. In order to fabricate the crosslinked PVA membranes which were stable in aqueous solutions, acetone was used as reaction medium in stead of aqueous inorganic salt solutions which have been commonly used in reaction solution for PVA crosslinking reaction. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of GA was characterized by IR spectroscopy. Swelling measurements were carried out in both water and acetic acid to investigate the swelling behavior of the membranes. The swelling behaviour of a membrane fabricated at different GA content in a reaction solution was dependent on crosslinking density and chemical functional groups created as a result of the reaction between PVA and GA, such as the acetal group, ether linkage and unreacted pendent aldehydes in PVA. The pervaporation separation of acetic acid-water mixtures was performed over a range of 70–90 wt% acetic acid in the feed at temperatures varying from 35 to 50°C to examine the separation performances of the PVA membranes. Permeation behaviour through the membranes was analyzed by using pervaporation activation energies which had been calculated from the Arrhenius plots of permeation rates.