离聚体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）共混体系的磺化聚苯醚离聚体／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较粘度，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     

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．     

以离子-离子相互作用增强共混相容性Ⅰ.聚苯醚离聚体/聚(苯乙烯-乙烯吡啶)共混体系

本文从溶液行为和固体热行为对聚（2，6-二甲基1，4-苯醚）（PPO）离聚体（磺化聚苯醚或接化聚苯醚）／聚（苯乙烯-4-乙烯吡啶）（PS－VP）共混物进行了研究。DSC研究表明磺化度为7．7％mol的SPPO／PS－VP和羧化度为15％molCPPO炉S－VP在整个组成范围都是相容的。溶液行为研究表明，与对应的PPO／PS－VP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，两组分间强烈的离子-离子相互作用导致分子间的络合，从而使比浓粘度的提高，也正是这种离子-离子相互作用使得这两对共混物完全相容。     

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     

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。     

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．     

磺化丁基橡胶离聚体在混合溶剂中的聚集行为

用顺磁共振（ESR）谱和粘度法考察了磺化丁基橡胶离聚体在二甲苯／正己醇混合溶剂中的聚集行为．ESR谱表明离聚体的离子基团发生聚集，其聚集程度受极性共溶剂（正己醇）的影响．粘度考察表明，在不同的浓度时离子基团有不同的聚集形式，低浓度时以分子内聚集为主，高浓度时以分子间聚集为主．离聚体的聚集度（DA）与浓度（c）的关系可用经验式DA＝Aexp（kc2）表示，其中A、k为常数．k值反映聚集度受浓度影响的程度，醇含量增大时k值减小，这是因为醇对离子的溶剂化作用导致离子聚集的倾向减小．     

FTIR法研究M-SIIR与PSVP之间的络合作用

制德了由金属离子中和磺化丁基橡胶（M－SⅡR）与苯乙烯－4－乙烯基吡啶共聚物（PSVP0组成的共混物，用FTIR考察该共混物组分间的相互作用。发现当使用含锌离子或铜（Ⅱ）离子的离聚体时，吡啶环的伸缩震动吸收峰从1600cm^-1移动1618cm^-1，表明形成了金属离子与吡啶环的络合物。对于Zn-SⅡR/PSVP共混物，与Zn-N络合物浓度相关的1618cm^-1吸收峰强度随共混的组成的改变而改变，当Zn-SⅡR与PSVP的摩尔比为1：1时达到最大，此时相当于Zn与Nr的比值为1：2。在该共混的中，锌的配位数为2。     

聚苯醚离聚体水基微乳液粒径及稳定性的研究

以乙酰磺酸为磺为磺化剂制备了磺化度为３～１７ｍｏｌ％的磺化聚苯醚（ＳＰＰＯ）,并中和成盐,在一定的温度和搅拌速度下,加水将ＳＰＰＯ离聚体溶液乳化成水包同的稳定水基微乳液。用光散射法及航向电镜法（ＴＥＭ）测定了ＳＰＰＯ离聚体水基微乳液的粒径及粒径分布,研究了磺化度、溶剂的极性、因含量等因素对微乳液粒径及稳定性的影响。     

Miscibility of blends of poly(2,6-dimethyl 1,4-phenylene oxide) with polystyrene-based ionomers and copolymers

Blends of poly(2,6-dimethyl 1,4-phenylene oxide) (PPhO) with the copolymer poly(styrene-co-methacrylic acid) (PS-MAA) and the ionomer poly(styrene-co-sodium methacrylate) (PS-MAA-Na), up to 10 mol% co-unit content, were investigated by dynamic mechanical thermal measurements. The PPhO/PS-MAA-Na blends are compared with PS/PS-MAA-Na blends. The blends of PPhO with PS-MAA are no longer miscible at 10 mol% acid content; this is attributed to a copolymer effect induced by the reduction of PS-PPhO interactions due to the presence of the MAA group which does not interact favorably with PPhO. The blends of PPhO with the ionomer are already immiscible at the lowest ion content studied (2.4 mol%), but become increasingly so as ion content is increased. Despite favorable PS-PPhO interactions, these blends are only a little more miscible than the PS/PS-MAA-Na blends. This is attributed to a combination of the increasing importance of the ionomer cluster phase (from which the homopolymer chains presumably are excluded) as ion content is increased, and of a copolymer effect between the homopolymers and the unclustered phase of the ionomer. These results are compared with published data indicating that blends of PPhO with another biphasic ionomer, zinc sulfonated polystyrene, are miscible. The contrasting behavior is rationalized in part by the suggestion that the copolymer effect between PPhO and the unclustered phase of the latter ionomer, but not of the former, is absent; this is related to multiplet structure and sizes. The analysis made of the above systems is extended to predict what might be the miscibility behavior between PPhO and other PS-based ionomer and related copolymer systems. © 1993 John Wiley & Sons, Inc.     

Poly(ethylene oxide)/poly(2vinylpyridne)/lithium perchlorate blends as solid polymer electrolytes: Composition/property/structure interrelationship

Poly(ethylene oxide) (MW 600,000)/poly(2vinylpyridine) (MW 200,000)/LiClO₄ blends have been prepared by the solution blending process. The ionic conductivities of the blends containing lower weight fractions (15, 17.5, 20 and 22.5%) of poly (2vinylpyridine) initially increases as the salt content is increased, reaches a maximum at an ethylene oxide/Li⁺ mole ratio of 10 and decreases as the salt content is further increased. Blends, which have higher weight fractions of poly(2vinylpyridine) (25 and 35%) display different electric behavior, i.e., the ionic conductivity continously increased as the salt content is increased to an ethylene oxide/Li⁺ mole ratio of 2. Thermal, ⁷Li solidstate NMR and semiempirical MNDO molecular orbital studies indicate that this contrasting behavior may be explained by the structure and ratios of the solvates (mixed solvate or homosolvate) of LiClO₄ present in the blends. © 1995 John Wiley & Sons, Inc.     

Structure and properties of dynamically cured EPDM and ionomer blends

The structure and properties of dynamically cured ethylene-propylene-diene terpolymer (EPDM) and ionomer blends have been studied. The blends were prepared in a laboratory internal mixer, where EPDM was cured under shear in the presence of ionomer with dicumyl peroxide (DCP) under different shear conditions. The effects of EPDM/ionomer compositions, DCP concentration and the intensity of shear mixing were investigated using capillary rheometer, differential scanning calorimeter (DSC) and scanning electron microscopy (SEM) techniques. Two kinds of poly(ethylene-co-methacrylic acid) ionomers containing different metal ions(Na⁺ and Zn⁺⁺) were compared and the effect of the metal ion type for neutralization was considered. The Zn-neutralized ionomer showed better miscibility with EPDM than the Na-neutralized ionomer. It is concluded from the rheological properties, crystallization behavior and morphology that the dynamically cured EPDM and Zn-ion ionomer blends show the behavior of a thermoplastic interpenetrating polymer network (IPN).     

Sulfonated poly(phenylene oxide) membranes as promising materials for new proton exchange membranes

Poly(phenylene oxide) (PPO) was sulfonated to different ion exchange capacities (IECs) using chlorosulfonic acid as the sulfonating agent. Tough, ductile films were successfully cast from sulfonated PPO (SPPO) solutions in N‐methyl‐2‐pyrrolidone or N,N‐dimethylformamide. The obtained membranes had good thermal stability revealed by thermogravimetric analysis (TGA). Compared with an unsulfonated PPO membrane, the hydrophilicity and water uptake of the SPPO membranes were enhanced, as shown by reduced contact angles with water. The tensile test indicated that the SPPO membranes with IEC ranging from 0.77 to 2.63 meq/g were tough and strong at ambient conditions and still maintained adequate mechanical strength after immersion in water at room temperature for 24 hr. The results of wide‐angle X‐ray diffraction (WAXD) showed amorphous structures for PPO and SPPO while the peak intensity decreased after sulfonation. The proton conductivity of these SPPO membranes was measured as 1.16 × 10^?2 S/cm at ambient temperature, which is comparable to that of Nafion 112 at similar conditions and in the range needed for high‐performance fuel cell proton exchange membranes. Copyright © 2006 John Wiley & Sons, Ltd.     

Block copolymer containing poly(3‐hexylthiophene) and poly(4‐vinylpyridine): Synthesis and its interaction with CdSe quantum dots for hybrid organic applications

Poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer was synthesized by RAFT polymerization of 4‐vinyl pyridine using a trithiocarbonate‐terminated poly(3‐hexylthiophene) macro‐RAFT agent. The optoelectronic properties and the morphology of the block copolymer blends with CdSe quantum dots were investigated. UV‐vis and fluorescence experiments were performed to prove the charge transfer between CdSe and poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

FTIR Investigation of ion-dipole interaction in styrene ionomer/poly(ethylene oxide) blends

Fourier-transform infrared (FTIR) spectroscopy was used to examine specific interactions contributing to the partial miscibility in blends of styrene-sodium methacrylate copolymer (S-NaMA) and poly(ethylene oxide) (PEO). From the shifts of carboxylatelon and ether group stretching bands, an important specific interaction was found involving ion-dipole bonding between the ionic group in styrene ionomer and the ether group in PEO. The asymmetric stretching vibration frequency of the carboxylate ion group increases as the fractional amount of PEO in the blend is increased, while the symmetric stretching frequency is decreased. The transition value of the fraction of PEO, above which both vibration frequencies of the carboxylate ion mentioned above remained almost unchanged, increases as the concentration of ionic groups in ionomer is increased. The ether group stretching band shifts to higher frequencies as the PEO content in the ionomer/PEO blend is increased. From the differential scanning calorimetry (DSC) and FTIR studies, we find that the iondipole interaction is the important mechanism that determines the miscibility of S-NaMA/PEO blends. © 1994 John Wiley & Sons, Inc.