表面“原位”聚离子复合修饰的乙烯-乙烯醇共聚物膜的结构

聚离子复合物(Polyionic complexes,PICs)是由聚正离子和聚负离子所构成的高度亲水的合成材料,可以通过不同聚离子的组合使其带有"净"电荷.因此,它具有优良的血液相容性.PIC透析膜对小分子电解质和低分子物质有很高的透过性[1],然而,在高含水状态下PIC离子键的水合使其强度明显降低,并且由于其只溶于一定组成的三组份屏蔽溶剂(Shielding solvent),因此,给加工制膜带来诸多不便.乙烯-乙烯醇共聚物(Ethylene-vinyl alcohol copolymer,EVAL)表现出一定的亲水性,并且高分子链中含疏水性链段,有一定的机械强度,是一种性能很好的成膜材料,由EVAL制成的膜已应用于血液过滤等领域[2].     

聚乙烯醇衍生的聚离子复合物的研究 Ⅳ．乙烯－乙烯醇共聚物衍生的聚离子复合物的电荷性质与抗凝血性

分别将３－磺酸丙基、磷酸基和４—Ｎ一苯基三甲基碘化铵基引进乙烯－乙烯醇共聚物（ＥＶＡ）链中制得了聚阳离子和聚阴离子，然后得到相应的聚离子复合物．当ＥＶＡ分子链中的羟基的取代度在６０％以上时，所制得的中性聚离子复合物的血浆凝固时间和空白玻璃的血浆凝固时间之比可在８～１３之间，而负电性聚离子复合物可高达１１０左右．这些聚离子复合物膜对小分子电解质或小分子中性物质如氯化钠、尿素、葡萄糖等表观渗透系数皆在１０－７ｃｍ２＼ｓ以上．     

聚乙烯醇衍生的聚离子复合物的研究 Ⅳ.乙烯—乙烯醇共聚物衍生的聚离子...

分别将３－磺酸丙基、磷酸基和４－Ｎ－苯基三甲基碘化铵基引进乙烯－乙烯醇共聚物（ＥＶＡ）链中制得了聚阳离子和聚阴离子，然后得到相应的聚离子复合物，当ＥＶＡ分子链中的羟基的取代度在６０％以上时，所制得的中性聚离子复合物的血浆凝固时间和空白玻璃的血浆凝固时间之比可在８－１３之间，而负电性聚离子复合物可高达１１０左右，这些聚离子复合物膜对小分子电解质或小分子中性物质如氯化钠、尿素、葡萄糖等表观渗透系数皆在     

聚离子复合物单分子膜的聚集结构研究

LB膜在非线性光学材料、生物传感器等众多领域有着诱人的应用前景,受到了广泛的关注.为了充分发挥LB 膜的功能,必须制备高度取向、无缺陷的LB 膜,因此充分把握LB膜的构成单元单分子膜的聚集结构显得十分重要.由于气液界面离子复合结构的形成对单分子膜的聚集结构产生很大的影响,近年,有关这方面的工作越来越活跃.本文以探讨     

聚乙烯醇聚离子复合物膜对95%乙醇脱水的红外光谱研究

将聚乙烯醇(PVA)聚离子复合物(PIC)膜在95%乙醇中浸泡48 h,在20~120℃(间隔20℃)下测定吸水后PIC膜的红外光谱,分析了3000 cm-1以上羟基伸缩振动基频随温度的变化情况,探讨了水与PIC膜中羟基的氢键作用。由于羟基谱带在3000 cm-1以上重叠比较严重,结合1000~1700 cm-1水与PIC膜中离子键之间的静电作用,采用二维相关分析提高光谱分辨率,定性地描述了95%乙醇中水与PIC膜之间的结合方式。结果表明:>3000 cm-1羟基的重叠谱带得到了分辨,证明了水与膜内羟基缔合优先吸附渗透,随温度变化早于膜内羟基自缔合被解吸与乙醇分离;确认了水和PIC膜内聚电解质基的吸收,证明了水与聚电解质基团靠静电作用被吸附,随温度升高被解吸与乙醇分离。为PIC膜对95%乙醇脱水分离性能研究提供了一种新方法。     

聚电解质复合物

本文介绍了聚电解质复合物的研究及发展状况，包括聚电解质复合物的形成、结构以及影响形成聚电解质复合物的各种因素，还介绍了近年来以聚电解质复合物为材料 质的渗透汽化膜的应用和在生物医药方面的研究成果。     

重氮树脂型聚离子复合物

高分子化合物沿分子链(主链和侧链)排列多量可离解基团(每个链节可有1～2个)称聚电解质或聚离子^[1]。聚电解质在水中可离解成两部分,若离解后,聚合物链带负电荷,称聚阴离子电解质或聚负离子;若带正电荷,称聚阳离子电解质或聚正离子。     

QPVA/SMPVA自组装聚离子复合物膜对乙醇中水的渗透汽化性能研究

聚乙烯醇-N,N-二甲基-3-氨基-2-羟基丙基醚的季铵化产物(quaternized PVA-N,N-dimethyl-3-amido-2-hydroxy-propyl ether,简称QPVA)与硫酸单酯化聚乙烯醇(sulphate monoesterified polyvinyl alcohol,简称SMPVA)自组装聚离子复合物(self-assembled polyion complex,简称SAPIC),自组装溶液pH=7时,膜在水中的溶胀度最小.SAPIC均质膜在60vol%～90vol%(间隔10%)乙醇中浸泡48h,观察不同浓度乙醇中水在均质膜中的扩散行为.SAPIC均质膜在95%乙醇中浸泡48h,在20～120℃(间隔20℃)下,观察乙醇中水在膜中的汽化行为.应用FTIR技术跟踪两类吸水膜,确认了水和膜内聚离子基的吸收.改变浓度的一维(1D)和二维(2D)FTIR相关分析表明,渗透过程中形成两种状态的水,游离水和缔合水,随乙醇中水的增加游离水优先变化.游离水靠静电作用与膜内聚离子基优先缔合形成缔合水;改变温度的1D-和2D-FTIR显示,汽化过程中也存在两种状态的水,游离水和缔合水,随温度升高游离水优先变化.游离水较缔合水优先挥发,脱离膜与乙醇分离.同时测定了SAPIC复合膜对95%乙醇/水的渗透汽化性能,分离因子870,渗透通量1400g/(m2·h).为SAPIC膜用于乙醇脱水的渗透汽化过程研究提供了一种简便的方法.     

聚乙烯醇衍生的聚离子复合物的研究——聚离子复合物的制备及其溶解性能

从乙醛酸、醛基苯甲酸、醛基苯磺酸、醛基吡啶、二甲氨基苯甲醛等醛基化合物,通过缩醛化反应,在聚乙烯醇上引进了阳离子及阴离子基团,制备了相应的聚乙烯醇型聚离子复合物,研究了它们的溶解性,找到了较好的溶剂体系H_2O-DMF-NaSCN。     

聚合物复合物层层组装膜

层层组装是一种基于物质交替沉积而制备复合膜的方法,可以实现膜的结构和组成的精确调控.聚合物复合物是基于各种分子间弱相互作用力而形成的超分子聚集体,其种类包括聚阳离子-聚阴离子复合物、聚电解质-有机小分子复合物、中性聚合物-聚合物复合物以及聚合物-无机杂化复合物等.在本文中,以作者的研究结果为基础,阐明聚合物复合物的层层组装是一种方便、快捷的功能复合膜的构筑方法,具有如下优点:(1)聚合物复合物大的尺度可以实现聚合物复合物层层组装膜的快速构筑;(2)聚合物复合物的结构在组装溶液中和成膜后都容易调控,方便聚合物复合物层层组装膜结构的精细调控.(3)聚合物复合物层层组装膜可以构筑非复合的聚合物层层组装所不能获得的膜结构及功能.     

聚乙烯醇衍生的聚离子复合物的研究——Ⅳ.聚离子复合物膜的力学行为及透过性能

The mechanical behavior of polyionic complex (PIC)membranes derived from polyvinyl alcohol(PVA) or ethylene-vinyl alcohol copolymer (EVA) have been investigated. The presence of ethylene block segment in the backbone of polyions can endow PIC membranes with more toughness. Increasing the degree of substitution of the polyions, the formed PIC becomes harder and more brittle. Under the environment of relative humidity (R. H. ) of 40%, the tensile strength, relative elongation and modulus of PICs are at about 300kg/cm²,10% and 8×10³kg/cm²,respectively,whereas inthe environment of 90% R.H.M these of PICs derived from EVA are at about 90 kg/cm²,150% and 13kg/cm²,respectively,better than that of PVA derived polyionic membrane and ordinary PIC such as Ioplex 101. The permeabil-ity of PIC membranes derived from EVA have also been studied.     

POLYIONIC COMPLEXES DERIVED FROM POLYVINYL ALCOHOL Ⅱ. WATER ABSORBILITY AND ANTITHROMBOGENECITY OF PVA-TYPE POLYIONIC COMPLEXES*

Effect of both structure of substituents and degree of substitution of polyions derived from poly-vinyl alcohol on water-absorbility and antithrombogenecity of formed polyionic complexes (PIC)have been investigated. It was found that the water content of the PIC formed from p-formylben-zenesulfonic acid substituted PVA was higher than that of the PIC formed from p-formylbenzoicacid substituted PVA. When the substitution degree of polycation increased from 27% to 64%,the water content of the formed PIC increased from 170% to 1270%. Effect of water content andnet charge of PVA-type PIC on the antithrombogenecity was also investigated by plasma recalci-fication method.     

POLYIONIC COMPLEXES DERIVED FROM POLYVINYL ALCOHOL Ⅰ. PREPARATION AND THEIR SOLVATION BEHAVIOR*

Polycations and polyanions of polyvinyl alcohol (PVA) with various substitution degrees were pre-pared by acetalization of PVA with aldehyde derivatives such as p-formylbenzoic acid, glyoxalic acid, p-formyl-benzenesulfonic acid, p-formylpyridine, and p-dimethylaminobenzaldehyde and then neutral-ized or quaternarized with methyl iodide. The corresponding PVA type polyionic complexes wereobtained by mixing the aqueous solutions of these polycations and polyanions. The solvation behaviourof these polyionic complexes were investigated. It was found that the H_2O-DMF-NaSCN solventsystem is superior to the H_2O-DMF-NaBr system for these PVA type polyionic complexes.     

表面修饰乙烯－乙烯醇共聚物膜的“原地”聚离子复合化及其若干性能

表面修饰乙烯－乙烯醇共聚物膜的“原地”聚离子复合化及其若干性能张军，王大力，刘新三（天津市合成材料研究所，天津，３００２２０）李福绵（北京大学化学系，北京，１００８７１）关键词聚离子复合物，“原地”聚离子复合，磷酸酯化，乙烯－乙烯醇共聚物膜聚离子复合...     

聚乙烯醇纤维金属配合物的合成和表征

以聚乙烯醇纤维(PVA)为配体原料,分别与FeCl3、NiCl2、CuCl2和Pb(Ac)2反应,制备了宏观上仍保持原纤维形态的PVA Fe(Ⅲ)、PVA Ni(Ⅱ)、PVA Cu(Ⅱ)、PVA Pb(Ⅱ)纤维配合物(用PVA M表示).用红外光谱仪分别对PVA和4种配合物在4000～400cm-1范围进行傅立叶变换红外光谱测量,对各PVA M的FTIR主要吸收峰做了经验归属,并与PVA的相应吸收峰做对比分析,结果表明,与金属离子形成配合物后,PVA分子中O—H氢键缔合状态被破坏,向高波数位移了65～86cm-1,PVA中的羟基氧与金属离子发生配位作用.PVA Fe(Ⅲ)的XPS显示,PVA中O1s只出现532.5eV单峰,而PVA Fe(Ⅲ)中O1s分裂为531.4eV和532.3eV两个峰,且Fe2p只有一个峰710.9eV,比FeCl3的结合能值711.2eV下降,说明OH氧与Fe3+形成配位键.     

RESEARCH AND DEVELOPMENT OF FUEL ALCOHOL SYNTHESIS FROM SYNGAS

The research and development of catalyst preparation and catalytic technology for fuel alcohol synthesis from syngas have been conducted. The laboratory research work includes the investigation on the effects of preparation method, the composition and K2O content on the catalyst performance. The influences of reaction temperature, pressure, GHSV and feed composition on higher alcohols synthesis have also been investigated. On the basis of laboratory results, the catalysts have been further tesied in micro-pilot reactor under the industrial condition to investigate the effects of commercial preparation of catalyst, the reactor scaling up and (he use of industrial coal based syngas on the fuel alcohol ( mixture of methanol and higher alcohols ) synthesis. The catalyst stability has been tested by a 1000 h continuous operation. These provide the fundamental for further commercial plant design.     

聚乙烯醇—Cr^3＋树胶状物的形成

在12≤pH≤13的5%PVA中添加0.2g CrCl_3·6H_2O有灰蓝色树胶状物析出。XPS、ESR、IR和电泳等研究表明,PVA的部分羟基发生脱质子反应而提供配位基L~-该配位基能与Cr(Ⅲ)盐和NaOH生成的初生Cr(OH)_3·nH_2O的Cr~(3+)形成配位键,从而发生配位体与Cr~(3+)间的交联反应,生成Cr(Ⅲ)-PVA配位聚合物。该析出物具有顺磁性,溶于盐酸,从而可用以富集和回收Cr(Ⅲ)。     

VANADIUM(III) AND VANADIUM(IV) COMPLEXES WITH PYRAZINE IN ALCOHOL SOLUTION

Abstract

The V(III)-pyrazine system was examined spectroscopically in the isoamyl alcohol solution. An unstable, violet-red, binuclear vanadium(III) complex [V₂(pyraz)Cl₄]²⁺ was found to be formed. On exposure to air it was slowly converted into a sparingly soluble green vanadium(IV) compound, [VO(pyraz)OH]Cl.H₂O. This compound was examined by the analytical, spectroscopic (electronic and infra-red spectra) and magnetic methods.