离聚体水基微乳液化的研究——聚苯乙烯离聚体微乳化过程相反转的表征

以乙酰磺酸为磺化剂制备磺化度为３～１５ｍｏｌ％的磺化聚苯乙烯（ＳＰＳ）并中和成盐．在一定的温度和搅拌速率下，加水将ＳＰＳ乳化成水包油的稳定水基微乳液．用乳化过程中体系电导率和粘度的变化表征了乳化相反转过程．研究了溶剂的极性和离子含量对聚苯乙烯离聚体溶液可乳化性和乳化过程及乳液稳定性的影响．     

胺中和的磺化乙丙三元胶离聚物的研究

分别用氢氧化铵、乙胺、二乙胺和三乙胺中和磺化乙现三元胶（Ｓ－ＥＰＤＭ－Ｈ）溶液，制得含－ＳＯ３＾－Ｎ＾＋Ｈ４－ｘＥｔｘ离子对的４种离聚物。元素分析、应力－应变、介电性能和密度测试结果表明：随着中和试安中乙基数（ｘ）的增加，中和度、离聚物的机械强度和密度均下降，介电损耗β＇峰移向低温。ｘ＝０时，β＇峰分裂成β和α两个损耗峰。说明该离聚物子聚集成离子簇，成为两相体系；ｘ＞１，离子聚集成多重离子，离聚物     

碘化丁基橡胶离聚体在溶液中的聚集行为（I）：ESR谱研究

用ＥＳＲ谱考察了磺化丁基橡胶锰盐（Ｍｎ－ＳＩＩＲ）离聚体在二甲苯／醇（少量）混合溶剂中的离子聚集行为。结果表明，在所考察的范围内，浓度及磺化度增大时ＥＳＲ谱的形状变不大，这反映了离子聚集程度并没有发生明显变化，另外，极性共溶剂（醇）增多时，线分辨度增大，反映了离子聚庥程度下降；温度升高时谱线变模糊，反映了离子聚集程度增大，这些结果有力地支持了Ｌｕｎｄｂｅｒｇ等人提出的离聚体溶液粘度变化平衡式。     

离聚体分子链的络合作用对溶液性质的影响

考察了磺化丁基橡胶锌盐离聚体（Ｚｎ－ｓＩＩＲ）与苯乙烯－４－乙烯基吡啶共聚物（ＰＳＶＰ）的络合作用及其共混物溶液性质的影响，小分子含氮化合物（胺及吡啶）对Ｚｎ－ＳＩＩＲ的离子聚集体有强烈的破坏作用，表明大分子链上的锌离子能与碱性氮原了发生络合作用，Ｚｎ－ＳＩＩＲ／ＰＳＶＰ共混物粘度高于单组分溶液的粘度，这是两种分子链间存在络合作用而形成大分子交联网络的结果，根据粘度最大时所对应的组分含量，估计Ｚｎ     

端羧基聚丁二烯及端羧基聚（丁二烯－co－丙烯腈）离聚体的合成及表征

用溶液法由液体端羧基聚丁二烯（ＣＴＰＢ）及液体端羧基聚（丁二烯－ｃｏ－丙烯腈）（ＣＴＢＮ）合成了Ｌｉ＋、Ｎａ＋、Ｋ＋、Ｍｇ２＋、Ｚｎ２＋、Ａｌ３＋的遥爪型离聚体．考察了反应条件对离聚体形成的影响及离聚体稀溶液的性质。并用红外光谱，透射电子显微镜、动态粘弹谱仪研究和表征了部分ＣＴＰＢ、ＣＴＢＮ遥爪型离聚体．     

用罗丹明B和钼酸铵水相光度法测定痕量锇

本研究在聚乙烯醇存在下，锇与钼酸铵形成络阴离子，继而与罗丹明Ｂ（ＲＢ）形成离子缔合物，该缔合物的摩尔吸光系数ε值为２．６２×１０＾６Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，性范围０－１．２μｇ／２５ｍＬ，检测限为１．３ｎｇ／ｍＬ（ｎ＝８），ＲＳＤ为２．２％（ｎ＝７），缔合物稳定４周，考察了３０多种共存离子的影响，除贵金属和能形成杂多酸的元素外，大多数贱金属不干扰。方法已用于测定某些催化剂和岩矿中的锇，结果     

钌（Ⅲ）—钼酸盐—耐尔蓝—PVA124体系缔合显色反应的研究

在聚乙烯醇存在下，钌与钼酸盐和耐尔蓝（ＮＢ）形成离子缔合物，缔合物的λｍａｘ为５８５ｎｍ，ε为１．３２×１０＾６Ｌ．ｍｏｌ．ｃｍ＾－１，符合比耳定律范围０～１．２μｇ／２５ｍＬＲｕ，检测限为２．６ｎｇ／ｍＬ（ｎ＝１１），用平衡移动法测定缔合物的摩尔比为Ｒｕ：ＮＢ＝１：２。考察了４３种共存离子的影响，仅Ｏｓ（Ⅲ），ＳｉＯ＾２－３，Ａｓ（Ⅲ），Ｓｂ（Ⅲ），Ｇｅ（Ⅳ）有干扰，需用蒸馏分离。本法已用于某些     

金钨杂多酸-丁基罗丹明B光度法测定痕量金

研究了金钨杂多酸（ＡｕＷ）－丁基罗丹明Ｂ（ＢＲＢ）－聚乙烯醇（ＰＶＡ）体系的显色反应．离子缔合物的最大吸收位于５６５ｎｍ，表现摩尔吸光系数ε值为２．９６×１０７ｄｍ３·ｍｏｌ－１·ｃｍ－１，金量在０～２．８μｇ／Ｌ范围内服从比耳定律，检出限为０．１２μｇ／Ｌ（ｎ＝１２），对２．４μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差为１．９％（ｎ＝１１）．离子缔合物至少稳定２４０ｈ．研究了离子缔合物的红外光谱，考察了４０多种共存离子的影响，大多数常见离子不干扰，允许２００倍量Ｐｔ（ＩＶ）、４００倍量Ｐｄ（Ⅱ）存在．本法用于某些矿物和炭粉中金的测定，结果与ＡＡＳ法吻合     

丁基罗丹明B-钇钼杂多酸缔合显色反应的研究

本文报道在聚乙烯醇存在下，钇与钼酸铵和丁基罗丹明Ｂ形成离子缔合物．该缔合物的λｍａｘ为５８０ｎｍ，表观摩尔吸光系数ε为４．７４×１０５Ｌｍｏｌ－１ｃｍ－１，钇量在０～３．０μｇ／２５ｍＬ范围服从比耳定律．缔合物吸光度可稳定７２ｈ以上．缔合物中Ｙ与ＢＲＢ的摩尔比为ＹＢＲＢ＝１２．考察了４０多种共存离于的影响，大多数常见元素不干扰钇的测定．本法用于某些矿样中钇的测定，获得满意的结果．     

阴离子型离聚物的研究进展

参考近年来文献资料,总结了磺酸型、羧酸型、膦酸型等阴离子型离聚物的合成方法,对离聚物的几种重要聚集态结构模型进行了介绍,对于文献报道的各种模型在应用方面的不足之处也进行了总结。对于离聚物形态结构,介绍了有关微相分离方面的研究以及利用电镜技术得到的新突破。在离聚物的溶液性质方面,介绍了溶液粘度和溶剂作用的相关研究。对于离子对含量和类型等因素对离聚物力学性能和玻璃化转变温度的影响进行了总结,最后指出了离聚物尚需进一步研究的问题。     

Solution properties of ionomers. I. Counterion effect

The effect of counterions on the solution properties of two types of ionomers, one based on sulfonated polystyrene and the other based on styrene–methacrylic acid copolymer, was studied by viscosity and light scattering measurements. It was found that the order of counterion binding of ionomers in a polar solvent and the order of aggregation of ionomers in a low-polarity solvent were the same for the same ionomer system. However, the order for the sulfonated ionomer was Li < Na < K < Cs, whereas that for the carboxylated ionomer was the opposite. This can be explained by a difference in desolvation during anion–cation interaction and by considering site-binding in a polar solvent and the association of ion pairs in a low-polarity solvent. These findings for ionomer systems are parallel to the association behavior of small ions in water, cation affinity in crosslinked resins, and counterion binding of polyelectrolytes in water.     

PBMA-b-PSt磺化嵌段离聚体在DMF溶液中的聚集行为

采用激基缔合物荧光光谱法研究了轻度磺化聚甲基丙烯酸丁酯－b－聚苯乙烯（PBMA-b－PSt）嵌段离聚体在极性溶剂N，N－二甲基甲酰胺（DMF）溶液中的聚集行为；发现嵌段离聚体的磺化度和浓度强烈影响溶液中聚合物链的聚集态结构，不同的磺化度样品具有不同的临界聚集浓度；随磺化度增加，聚合物链缠绕密集，形成具有多苯环的聚集体，而且当磺化度为摩尔分数x＝3．59％时，荧光发射光谱最大发射峰波长出现最大红移，临界聚集浓度最低，说明最容易形成多苯环聚集体，该磺化点可以认为是磺化聚甲基丙烯酸丁酯－b－聚苯乙烯体现离聚体行为和聚电解质行为的临界磺化度。     

羧化聚苯醚离聚体/磺化聚苯乙烯离聚体共混体系中离子基团的增容作用

用ＤＳＣ方法研究了羧化聚苯醚（ＣＰＰＯ）／磺化聚苯乙烯（ＳＰＳ）、以及它们对应的碱金属离子（Ｌｉ＋、Ｎａ＋、Ｃｓ＋）中和的离聚物共混体系的相容性．结果表明，这一体系具有较宽的相容范围，金属离子的引入使共混体系的相容性有所变化，Ｌｉ＋和Ｃｓ＋能促进相容性，而Ｎａ＋则使相溶性略有减弱．     

Crystalline structure of polypropylene in blends with thermoplastic elastomers after electron beam irradiation

Isotactic polypropylene (PP) was blended in extruder with 0–50% addition of styrene–ethylene/butylene–styrene (SEBS) and styrene–butadiene–styrene (SBS) block copolymers. Granulated blends were irradiated with electron beam (60 kGy) and 1 week later processed with injection molding machine. Properties of samples molded from irradiated and non-irradiated granulates were investigated using DSC, WAXS, MFR, SEM and mechanical and solubility tests. It was found that the SEBS based systems are more resistant to irradiation in comparison to similar blends with SBS copolymer. Such behavior can be explained by the presence of double bonds in elastic SBS block. Irradiation of PP-SBS blends leads to considerable structure changes of crystalline and amorphous PP phases and elastic SBS phase. It indicates creation of new (inter)phase consisting of products of grafting and cross-linking reactions. Irradiated PP-SBS blends show significant improvement of impact strength at low temperatures.     

Viscoelastic properties of sulfonated styrene ionomers

The solid-state viscoelastic properties of polystyrene containing randomly distributed groups of styrene-p-sodium sulfonate are studied and compared with the corresponding properties of copolymers of styrene and sodium methacrylate (S-NaMA). The viscoelastic behavior in the primary transition region of these two ionomers is very similar. As for the S-NaMA copolymers, it is proposed that sulfonated polystyrene is composed of ion-rich regions (clusters) immersed in a matrix of low ion concentration. Two peaks are observed in the plot of mechanical loss tangent versus temperature for the sulfonated material. The lower peak is assigned to the glass transition of the ion-poor matrix and the upper to the glass transition of the clustered regions. As for some other ionomers, the presence of ions is found to slow down the stress relaxation rate, giving a broad distribution of relaxation times. Above a certain ion concentration, the sulfonated polystyrenes are thermorheologically complex owing to the onset of a secondary relaxation mechanism associated with the ion-rich regions.     

Synthesis of amphiphilic block–graft copolymers [poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)‐g‐poly(acrylic acid)] and their aggregation in water

Novel block–graft copolymers [poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene)‐g‐poly(tert‐butyl acrylate)] were synthesized by the atom transfer radical polymerization (ATRP) of tert‐butyl acrylate (tBA) with chloromethylated poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) as a macromolecular initiator. The copolymers were composed of triblock SEBS as the backbone and tBA as grafts attached to the polystyrene end blocks. The macromolecular initiator (chloromethylated SEBS) was prepared by successive hydrogenation and chloromethylation of SEBS. The degree of chloromethylation, ranging from 1.6 to 36.5 mol % according to the styrene units in SEBS, was attained with adjustments in the amount of SnCl₄ and the reaction time with a slight effect on the monodispersity of the starting material (SEBS). The ATRP mechanism of the copolymerization was supported by the kinetic data and the linear increase in the molecular weights of the products with conversion. The graft density was controlled with changes in the functionality of the chloromethylated SEBS. The average length of the graft chain, ranging from a few repeat units to about two hundred, was adjusted with changes in the reaction time and alterations in the initiator/catalyst/ligand molar ratio. Incomplete initiation was detected at a low conversion; moreover, for initiators with low functionality, sluggish initiation was overcome with suitable reaction conditions. The block–graft copolymers were hydrolyzed into amphiphilic ones containing poly(acrylic acid) grafts. The aggregation behavior of the amphiphilic copolymers was studied with dynamic light scattering and transmission electron microscopy, and the aggregates showed a variety of morphologies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1253–1266, 2002     

含氟嵌段共聚物离聚体的合成表征及其性能研究

嵌段共聚物离聚体具有独特的形态和固体及溶液性质 ,在热塑性弹性体、极性材料与非极性材料共混相溶剂和粘度调节剂等领域具有十分广阔的应用前景 ,引起了人们的普遍关注 .文献报道较多的是聚苯乙烯 乙烯 丙烯[1] 、聚苯乙烯 乙烯 丁烯 苯乙烯[2 ] 、聚苯乙烯 异丁烯 苯乙烯[3 ] 等共聚物中 ,聚苯乙烯链段部分磺化后所得离聚体的合成与性质研究 .众所周知 ,含氟聚合物具有低表面能和高表面活性等特性 ,因而将含氟基团引入到嵌段共聚物离聚体中有望开发出一种新型的特殊功能材料 .原子转移自由基聚合 (ATRP)自 1 995年问世以来 ,已成功…     

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．     

Fourier transform infrared/attenuated total reflectance analysis of water diffusion in poly[styrene‐b‐isobutylene‐ b‐styrene] block copolymer membranes

A Fourier transform infrared/attenuated total reflectance technique was used to study the diffusion of water through poly(styrene‐b‐isobutylene‐b‐styrene) block copolymers (BCPs), as well as sulfonated (H⁺) and Na⁺‐sulfonated ionomer versions. Diffusion data were collected and interpreted for these membranes versus polystyrene block composition, degree of sulfonation, Na⁺ ion content in the ionomers, and the effect of initially dry versus prehydrated conditions. An “early time” diffusion coefficient, D, decreased with increasing percent polystyrene for a series of unmodified BCPs. D decreased with increasing degree of sulfonation, and with increasing ion content for the Na⁺‐exchanged samples and this was interpreted in terms of diffusion limitations caused by a strong tendency for ion hydration. The method also yielded information relating to the time evolution of water structure from the standpoint of degree of intermolecular hydrogen bonding. Membrane prehydration causes profound increases in D for both the unmodified BCP and sulfonated samples, as in plasticization. The simultaneous acquisition of information relating to interactions between water molecules and interactions of water molecules with functional groups on the host polymer matrix offers more information than conventional diffusion measurement techniques that simply count transported molecules. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 764–776, 2005     

The synthesis of sulfonated polymers by free radical copolymerization. Poly(butadiene-co-sodium styrene sulfonate)

The copolymerization of butadiene with sodium styrene sulfonate was studied and the copolymer products characterized. In general these copolymers contain 0.5–4 mole% of sulfonated monomer. The effects of the following reaction variables are described: emulsifier type and concentration, monomers feed ratio, chain transfer agent concentration, and reaction conversion. The products were heterogeneous with regard to composition, molecular weight, and solubility behavior. Copolymers prepared under certain conditions exhibited strong intermolecular interactions derived from associations of the ionic species as observed in other ionomers.