聚苯醚离子聚体／聚（苯乙烯—co—4—乙烯吡啶）共混体系的溶液行为

聚（２，６－二甲基－１，４－苯醚）高聚体／聚（苯乙烯－ｃｏ－４－乙烯吡啶）共混物的溶液行为研究表明，与对应的ＰＰＯ／ＰＳＶＰ共混物相比，这两个系列的共混的都表现出较高的比浓粘度。     

离聚物及其共混体系的研究──2．配位络合和质子转移对共混体系的增容作用

通过将苯乙烯（Ｓ）及甲基丙烯酸正丁酯（ｎＢｍａ）分别与少量的４－乙烯基吡啶（４－Ｖｐ）自由基共聚，在聚苯乙烯（ＰＳ）及聚甲基丙烯酸丁酯（ＰＢｍａ）链上分别引入了功能基团吡啶基制得共聚物ＳＶｐ和ＢｍａＶｐ．然后将共聚物络合上过渡金属离子或结合上来自羧酸的质子，以制得离聚物及其共混物．这里共混物的两组分均具有正电荷．红外光谱（ＩＲ）、差示扫描量热法（ＤＳＣ）及透射电镜（ＴＥＭ）的研究结果表明，通过配位络合和质子转移而引入两聚合物的同种离子对共混体系有显著的增容作用．     

聚环氧乙烷与聚2—乙烯基吡啶共混物的导电率及高氯酸锂的…

研究了聚环氧乙烷（ＰＥＯ）／聚２－乙烯基吡啶（Ｐ２ＶＰ）的共混物分别经ＬｉＣＬＯ４、四氰基代苯醌二甲烷（ＴＣＮＱ）及两者共同掺杂后其共混物的离子、电子及混合导电率，当ＰＥＯ与Ｐ２ＶＰ的重量比分别为６／４、５／５及４／６时，共混物的混合导电率大于相应的离子及电子导电率的总和，呈现协同效应，从共混物外观的研究发现ＬｉＣＬＯ４能作为ＰＥＯ／Ｐ２ＶＰ共混体系的增容剂。     

聚苯醚离聚体/聚(苯乙烯-co-4-乙烯吡啶)共混体系的溶液行为

聚（２，６ 二甲基 １，４ 苯醚）（ＰＰＯ）离聚体（磺化或羧化聚苯醚）／聚（苯乙烯 ｃｏ ４ 乙烯吡啶（ＰＳＶＰ）共混物的溶液行为研究表明，与对应的ＰＰＯ／ＰＳＶＰ共混物相比，这两个系列的共混物都表现出较高的比浓粘度．这是由于聚苯醚离聚体上的酸基发生质子转移，产生了酸根阴离子和吡啶基阳离子，两组分间的酸 碱相互作用导致了分子间的缔合，从而使比浓粘度提高．     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的特殊相互作用表征（Ⅱ）

通过测定醋酸纤维素（ＣＤＡ）和聚乙烯基吡咯烷酮（ＰＶＰ）共混物溶液的绝对粘度和特性粘数，发现ＣＤＡ和ＰＶＰ分子链段间有缔合现象，用富里哀变换红光谱（ＦＴＩＲ）研究了共混物的吸收光谱，发现共混物中ＣＤＡ的羟基吸收峰和ＰＶＰ的羰基吸收峰均向低频方向迁移，证明了ＣＤＡ的羟基和ＰＶＰ的羧基之间有氢键形成，研究结果表明ＣＤＡ和ＰＶＰ的相容性及其特殊相互作用来源于不同分子链段间的氢键相互作用。     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的特殊相互作用表征（Ⅱ）

通过测定醋酸纤维素（ＣＤＡ）和聚乙烯基吡咯烷酮（ＰＶＰ）共混物溶液的绝对粘度和特性粘数，发现ＣＤＡ和ＰＶＰ分子链段间有缔合现象．用富里哀变换红外光谱（ＦＴＩＲ）研究了共混物的吸收光谱，发现共混物中ＣＤＡ的羟基吸收峰和ＰＶＰ的羰基吸收峰均向低频方向迁移，证明了ＣＤＡ的羟基和ＰＶＰ的羰基之间有氢键形成．研究结果表明ＣＤＡ和ＰＶＰ的相容性及其特殊相互作用来源于不同分子链段间的氢键相互作用．     

4-乙烯吡啶型聚皂与表面活性剂相互作用的研究

１实验部分１１试剂Ｎ－乙基聚４－乙烯吡啶溴化盐（ＱＰＶＰＥ）和Ｎ－十二烷基聚４－乙烯吡啶溴化盐（ＱＰＶＰＤ）是根据文献方法合成〔７〕,其中ＱＰＶＰＤ－２０、ＱＰＶＰＤ－３０分别表示溴十二烷与４－乙烯吡啶投料的物质的量比为２０％和３０％．ＳＤＳ（北京化工厂,分析纯）,ＢＤＤＡＣ（北京化工厂,分析纯）使用前未做进一步提纯．１２待测溶液的配制向５×１０－５ｍｏｌ／Ｌ的表面活性剂溶液（ＳＤＳ、ＢＤＤＡＣ）中,在缓慢搅拌下加入质量浓度为２５ｇ／Ｌ的ＱＰＶＰＥ和ＱＰＶＰＤ溶液,最后加入蒸馏水定容．温度保持在３０℃,溶液静置２４ｈ后进行测定．１３实验方法相对粘度采用乌氏粘度计在（３０±１）℃水浴中测定．ＱＰＶＰＥ、ＱＰＶＰＤ与ＳＤＳ混合溶液的可见光透射率采用７２１分光光度计在室温下测定．以质量浓度为５ｇ／Ｌ的聚合物溶液为参比,波长为４２０ｎｍ,比色皿厚度为１ｍｍ．采用ＤＤＳ－１２Ａ数字式电导率仪（电极为ＤＪＳ－１光亮电极）．温度补偿为２５℃．２结果与讨论ＱＰＶＰＤ分子链上的长链疏水烷基在水溶液中可聚集成胶束,形成紧缩构象,这种聚集体又称为疏水微区（Ｈｙｄｒｏｐｈｏｂｉｃｍｉｃｒｏｄｏｍａｉｎ）．同聚电解质类似,聚皂     

POM／EVA共混物的研究

用力学测试、扫描电镜（ＳＥＭ）、热分析（ＤＳＣ）等手段研究了聚甲醛（ＰＯＭ）与乙烯－醋酸乙烯酯共聚物（ＥＶＡ）共混物（ＰＯＭ／ＥＶＡ）的力学性能及其微同形态；用聚甲醛与马来酸二丁酯（ＤＢＭ）的接枝物（ＰＯＭ－ｇ－ＤＢＭ）作相溶剂，能改变共的两相间的粘结力，从而提出了共混物的力学性能，ＳＥＭ观察表明接枝物的加入改变了ＰＯＭ／ＥＶＡ共混物的断裂方式，微观形态及结晶性能，对其热性能影响不大；通过改变ＰＯ     

羧化聚苯醚／聚（苯乙烯—乙烯吡啶）共混相容性

用ＤＳＣ、ＤＭＡ研究了羧化聚苯醚（ＣＰＰＯ）／聚（苯乙烯－乙烯吡啶）（ＰＳＶＰ）共混体系的相容性，结果表明，与ＣＰＰＯ／ＰＳ体系相比，乙烯吡啶基的引入大大提高了共混相容性．这主要是由于ＣＰＰＯ中的羧基与ＰＳＶＰ中的吡啶基之间通过质子转移形成的正负离子间的相互作用，推动了两组分分子的均匀混合．     

聚β－羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性与结晶行为

研究了制样过程对聚β－羟基丁酸酯（ＰＨＢ）／聚醋酸乙烯酯（ＰＶＡｃ）共混体系的相容性和结晶行为的影响，ＤＳＣ、ＳＡＸＳ、ＰＯＭ等实验结果表明，ＰＨＢ／ＰＶＡｃ共混物经溶液成膜后处于分相的状态，ＰＶＡｃ对ＰＨＢ的结晶能力影响不大，而经熔融处理后，ＰＨＢ／ＰＶＡｃ共混物则处于相容的均相状态，随ＰＶＡｃ在共混物中含量的增加，ＰＨＢ的冷结晶温度升高，球晶增长速率下降，织态结构变得不规整。当ＰＶＡｃ的含量高于８０％时，ＰＨＢ失去结晶能力。     

离聚物共混体系在溶液中分子间缔合的粘度研究

研究了磺化聚苯乙烯离聚体／聚（苯乙烯 ４ 乙烯吡啶）共混体系、磺化聚苯醚离聚体／聚（苯乙烯 ４ 乙烯吡啶）共混体系和磺化聚苯醚离聚体／胺化聚苯醚共混体系在氯仿／甲醇混合溶剂中的粘度行为，结果表明，和它们分别对应的不含离子基的共混物相比，这三个共混体系都表现出较高的比浓粘度．这是由于体系中的酸基及其盐和含氮碱基的引入，在共混组分间产生了强烈的离子相互作用，从而导致分子间的缔合，使比浓粘度提高．并讨论了溶剂体系、功能基种类及共混组分的主链结构等因素对这种分子间缔合作用的影响．     

磺化聚芳醚砜/磺化聚酰亚胺复合质子交换膜的制备与性能研究

利用溶液浇铸法制备了一系列双磺化型磺化聚芳醚砜/磺化聚酰亚胺(SPAES/SPI)复合质子交换膜.扫描电子显微镜(SEM)结果显示复合膜不存在明显的相分离,表明二者具有很好的相容性.由于SPI的引入,复合膜在甲醇中稳定性较纯SPAES具有大幅的提高,比Nafion112低得多的甲醇吸收率表明了这些复合膜具有比后者更低的甲醇透过率.复合膜显示了与单组分膜相类似的高温分解稳定性,磺酸基团的分解温度达到了290℃以上.复合膜显示出远高于纯SPAES膜的尺寸稳定性能,在130℃高温中200h处理后,所有的复合膜均保持了高的机械性能,而此时纯SPAES膜已经溶解于水中.而且由于两种磺化聚合物间的复合,复合膜维持了较高的IEC水平,显示了较高的质子导电率,在80%相对湿度时的质子导电率与Nafion112相近,而在水中的质子导电率均高于Nafion112.     

Formation of molecular ladder elements with macrocyclic platforms via linear bifunctional ligands

Reaction between 4-aminopyridine and a dinuclear zinc(II) component of a Robson macrocyclic ligand has resulted in the formation of a molecular ladder element motif. X-ray single crystal structural analysis indicates that two pyridine rings are assembled at the same direction of the macrocycle, which are placed in a nearly parallel way via pi-pi interactions, forming a concavity structure with a macrocyclic base. It is significantly noted that one hydrogen-bond cycle generated from hydrogen atoms of two amino groups with two perchlorate anions has sustained such an assembly of two 4-aminopyridine species to stand in a face to face pattern through a weak molecular interaction on the macrocyclic platform by one-end coordination bonding. The self-assembly of 4-carboxylic pyridine acid and the same macrocyclic component in the presence of sodium hydroxide has yielded an interesting wheel-like complex. Two macrocyclic dinuclear zinc(II) components have been linked through coordination bonding with two pyridine derivatives situated on the same direction of a macrocycle. X-ray structural results suggest that the compound has a unique sandwich-like structure consisting of two macrocyclic covers with two inversely positioned bridging pyridine carboxylic groups in the middle.     

侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能

制备了一类侧链型含氟磺化聚醚砜(s SPFES)与磺化聚酰亚胺(SPI)共混质子交换膜(s SPFES/SPI),研究了其吸水率、尺寸变化、质子电导率及稳定性等性能.结果表明,2种磺化聚合物以三乙胺盐型溶液共混及铸膜时相容性良好,制备的s SPFES/SPI共混质子交换膜结构均一,透明结实,离子交换容量为1.76~1.88 mmol/g.s SPFES/SPI共混质子交换膜表现出横向低于纵向的各向异性尺寸变化特性,在60℃水中横向尺寸变化率低于10%,经140℃加压水处理24 h后仍能保持较好的机械强度,质量损失低于6.1%.当温度高于50℃时,完全水合状态下的s SPFES/SPI共混质子交换膜的质子电导率均达到0.1 S/cm.     

Structural investigations of a lead(IV) tetraacetate-pyridine complex

A 1 : 1 crystalline complex of lead(IV) tetraacetate and pyridine (LTA-py) has been prepared. The single-crystal X-ray structure, at 296 and 150 K, establishes the presence of a relatively short Pb-N bond (2.307 A) within an intriguing seven-coordinate lead inner sphere consisting of the pyridine ligand and two bidentate and two monodentate acetate ligands. The pyridine occupies a surprising amount of the available coordination space and has induced a dramatic change in coordination compared to the four chelating acetate ligands found in lead tetraacetate (LTA). Thermal measurements (TGA/DSC) indicate the de-coordination of pyridine and its loss from the solid between 360 and 380 K. (207)Pb CP/MAS NMR spectroscopy also demonstrates the existence of the Pb-N bond through observation of (1)J((207)Pb,(14)N)= 63 Hz and a (207)Pb-(14)N dipolar coupling constant, of 149 Hz. The solid-state (207)Pb NMR parameters are used to give insight into the coordination environment of Pb(iv) in LTA-py. In solution, ligand exchange is rapid on chemical shift and J-coupling time scales. A (207)Pb NMR study of the titration of an LTA solution by pyridine yields a stability constant for LTA-py of K = 1.5 M(-1) and predicts it to have a (207)Pb NMR chemical shift essentially identical to that observed by CP/MAS NMR in the solid state. This correlation between the solid state and solution indicates that the seven-coordinate LTA-py structure found in the crystalline state does persist in solution, and this could further explain why the addition of pyridine has such profound effects on lead(IV) carboxylate-mediated organic reactions. Simulations of exchange-broadened line shapes of (13)C CP/MAS NMR spectra in the temperature regime above 280 K indicate local motion of the pyridine rings in the form of 180 degrees jumps (activation energy 72.5 kJ mol(-1)); these are first such ring flips reported for a coordinated pyridine ligand.     

Synthesis,Characterization and Properties of Novel Amphiphilic Phosphated Ionomers by Ring‐Opening Reaction of Epoxidized Styrene‐Butadiene‐Styrene Triblock Polymer

A method for synthesis of novel phosphated ionomer of (styrene‐butadiene‐styrene) triblock polymer (SBS) from epoxidized SBS was developed. The optimum conditions for the ring‐opening reaction of the epoxidized SBS with aqueous solution of disodium hydrogen phosphate were studied. It was found that during the ring‐opening reaction phase transfer catalyst, ring‐opening catalyst and pH regulator were necessary to enhance the conversion of epoxy groups to ionic groups. The products were characterized with Fourier Transform Infrared Spectrophotometry (FTIR) and transmission electron microscopy (TEM). Some properties of the phosphated ionomer were studied. With increasing ionic groups or the ionic potential of the cation of the ionomer, the water absorbency emulsifying volume and the intrinsic viscosity of the ionomer increase, whereas the oil absorbency decreases. The ionomer possesses excellent emulsifying property, as compared with the sulfonated ionomer. The disodium phosphated ionomers in the presence of 10% zinc stearate showed better mechanical properties than the original epoxy SBS. Optimum mechanical properties occurred at the ionic group content of 0.95 mmol/g ionomer. When the ionomer was blended with crystalline polypropylene, a synergistic effect occurs with respect to the tensile strength. The ionomer behaves as a compatibilizer for blending equal amount of SBS and oil‐resistant chlorohydrin rubber (CHR) to form an oil resistant thermoplastic elastomer. SEM microphotographs indicated enhanced compatibility between the two components of the blend in the presence of the ionomer.     

Solution viscosity behavior of complexes of poly(γ-benzyl-L-glutamate) with lightly sulfonated polystyrene or its zinc salt

The rheological behavior of solutions containing blends of poly(γ-benzyl-L -glutamate) (PBLG) and either the free acid or the zinc salt of lightly sulfonated polystyrene (SPS) was studied as a function of blend composition, polymer concentration, degree of sulfonation of the SPS, and the polypeptide molecular weight. The zinc salt of SPS formed a transition metal complex with the amine-end groups of the PBLG, and this resulted in an enhancement of the solution viscosity relative to a weighted average of the viscosities of the individual polymer solutions. The ZnSPS/PBLG solutions showed no anomalous time or shear dependencies. In contrast, solutions containing PBLG and the sulfonic acid derivative of SPS also had enhanced viscosities, but in addition, they exhibited time-dependent viscosities (thixotropic behavior) and shear thickening (dilatant behavior). This was attributed to a nonequilibrium structure of the interpolymer complex due to a competition between acid-amine and acid-ester interactions. Although the acid-amine interaction is enthalpically favored, when sufficient sulfonic acid groups were available, interactions between the sulfonic acid and the glutamate ester side groups of PBLG developed and this interaction promotes a helix-to-coil transition of the PBLG. ©1995 John Wiley & Sons, Inc.     

Crystallographic report: Crystal structure of a one‐dimensional zinc(II) coordination polymer containing 4,4′‐biphenyldicarboxylate hemihydrate

A one‐dimensional zinc(II) coordination polymer has been constructed from zinc(II), 4,4′‐biphenyldicarboxylate and pyridine in which each zinc(II) atom is coordinated by two pyridine ligands and two monodentate 4,4′‐biphenyldicarboxylate ligands that define a distorted tetrahedral geometry. Copyright © 2003 John Wiley & Sons, Ltd.