嵌段离聚物的制备及其络合和缔合性质

报道了一种氢化ＳＢＳ（ＳＥＢＳ）的化学改性方法,由此得到了一种基于ＳＥＢＳ的离聚物,其中ＰＳ嵌段接有少量羧酸盐基．用动态光散射和粘度法表征了基于ＳＥＢＳ的不同配对离子的磺酸离聚物在非极性溶剂中的缔合行为,给出了缔合物存在的证据和缔合物尺寸的定量数据．ＳＥＢＳ磺酸盐离聚物与含吡啶基的无规共聚物在稀溶液和本体中能形成分子间的络合物,这从共混物溶液粘度的反常增大和本体Ｔｇ的显著增加得到了证明．用粘度法、透射电子显微镜表征和证实了ＳＥＢＳ羧酸钠离聚物在水中可以形成稳定的胶体分散．疏水粒子为表面的离子基团所稳定．     

离聚物共混研究进展

综述了十 多年来。人们旨在提高相容性及其它一些性能，将离聚物引人共混体系所展开的系列研究。总结出，离聚物共混体系中，离聚物起增容作用的根本原因是在共混休整 系中引入了一些特殊的离子相互作用：离子－离子作用，离子－偶极作用，过渡金属离子的配位作用，介绍了目前研究离聚物共混的主要方法。     

磺酸型聚氨酯离聚物的离子导电性能

本文以多种聚醚为软段，二异氰酸酯（ＭＤＩ和ＴＤＩ）为硬段，合成了多嵌段聚醚聚氨酯，以此聚氨酯为基材，与ＮａＨ及１，３－丙碳酸内酯反应，进一步合成了一系列不同离子化程度的阴离子型碳化聚氨酯离聚物，用交流阻抗谱仪测定了样品的阻抗谱，由此计算出样品的离子电导率。研究结果表明其他条件相同时，以聚乙二醇（ＰＥＧ）为软段的样品具有较高的离子电导率；以聚环氧丙烷（ＰＰＯ）为软段的样品次之，以聚四氢呋喃（ＰＴＭＯ）为软段的样品最低，对于离子化程度不同的聚氨酯离聚物以金属离子和烷氧单元之比为０．０５时导电性能最好。阳离子为Ｌｉ＋和Ｎａ＋的样品具有相近的离子电导率。     

液晶离聚物

液晶离聚物是一种兼具液晶高分子和离聚物结构特征的新型聚合物。本文根据有关文献就其分类、合成、表征作了简要的综述,并对其研究发展前景进行了必要的讨论。     

嵌段离聚物的缔合和络合行为(Ⅲ)──基于SEBS的嵌段离聚物和含吡啶基聚合物间的相互作用

制备了一系列基于氢化SEBS的嵌段离聚物(BCI),研究了具有不同金属对应离子的BCI分别和含聚乙烯吡啶基的无规共聚物MVP和SVP的共混物的溶液粘度和本体的热行为.结果表明,MVP和SVP可与BCI的PS离子化嵌段形成络合物,导致T_g增加且远高于FOX方程预示值,同时比浓粘度远高于加合性预示值.在所研究的金属离子中,Ni和Cu显示最佳的络合能力.     

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。     

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．     

离聚物及其共混体系的研究3.基于配位络合的增容作用

通过将苯乙烯(S)与少量的甲基丙烯酸(MAA)或马来酸酐(MA)共聚及甲基丙烯酸正丁酯(nBMA)与4-乙烯基吡啶(4-VP)共聚,从而在聚苯乙烯(PS)及聚甲基丙烯酸丁酯(PBMA)链上分别引入了功能基团羧酸基(-CO-OH)、酸酐基(-CO-O-CO-)和吡啶基(-N)。通过与锌盐作用获得相应的离聚物(Ionomer)。用红外光谱(IR)表征了共聚物和离聚物的形成;差热分析(DSC)测定共聚物、离聚物和共混物的玻璃化转变温度(Tg)。研究结果表明,随着共聚物中功能基团含量的增加或者共聚物形成离聚物后,其玻璃化转变温度(Tg)提高了;而共聚物的共混物因羧酸基与吡啶基间的质子转移作用而提高了相容性。特别是在引入Zn~(2+)的共混物中,增容作用十分明显,这可归结于BMAVP中的吡啶基和SMAA-Zn~(2+)(或SMA-Zn~(2+))中的Zn~(2+)间的配位络合作用的贡献。     

双亲性无规离聚物溶液的自组装

由可离子化单体甲基丙烯酸二甲胺乙酯(DMAM)、甲基丙烯酸羟丙酯(HPMA)、疏水性单体丙烯酸异辛酯(EHA)、苯乙烯(St)为共聚单体进行自由基溶液共聚,合成了一系列四元双亲性无规共聚物P(DMAM-co-HPMA-co-EHA-co-St),简称PDHES.以红外光谱、核磁共振、凝胶渗透色谱和差示扫描量热等对共聚物进行了表征;PDHES经乳酸离子化得到荷正电的离聚物PIDHES,以该离聚物在选择性溶剂(N,N-二甲基甲酰胺/水)中进行自组装,得到球形胶束.用紫外光谱仪、动态激光光散射仪、透射电镜和扫描电镜等对其组装过程和结果进行表征,考察了DMAM含量、PDHES离子化程度、离聚物溶液的初浓度等因素对胶束的形成、胶束临界聚集水含量(CWC)和胶束流体动力学半径(Rh)的影响.研究了该离聚物胶束粒子在电场诱导作用下的2次组装行为,考察了不同胶束浓度与电诱导时间对其2次组装行为的影响.     

Viscosimetric behaviour of hydrolyzed polyacrylamide-poly(4-vinylpyridine) [AD37-P4VP] mixture in aqueous solution

The interactions between 27% hydrolyzed polyacrylamide [AD37] and poly(4-vinylpyridine) [P4VP], in aqueous solutions and at neutralization degree α = 1, were studied by using viscosimetry technique.The reduced viscosities of these copolymer mixture solutions, at 25 °C, reach several orders of magnitude higher than the reduced viscosity of each polymer taken separately, and according to the ratio R of the chain numbers.Intermolecular electrostatic associations are favoured by increasing the P4VP concentration corresponding to high R values. Thus, mixtures rich in P4VP are characterized by a high decrease in the viscosity due to interpolymer complete complexation AD37-P4VP, leading to the totally contraction or collapse of the polymer chains. Strongest reduced viscosities, due to the inter-chain AD37 associations, are observed for the mixtures poor in P4VP (so the weakest ratios R of the chain numbers).In order to understand the relative effects of these two polymers on the reduced viscosity, two mixtures containing the same total quantity are compared. Reduced viscosities of each copolymer alone strongly increase by dilution of the aqueous solution. In the case of the mixture, an opposite behaviour is observed with a reduction in the reduced viscosity by dilution. So, the increase of the reduced viscosity according to AD37 concentration, at α constant, shows an intra and an inter-chain associative phenomenon.     

含离子聚合物体系的动力学

离子作用的可逆性赋予了含离子聚合物丰富的力学和电学性能,使其广泛应用在高抗冲材料、记忆材料、自修复材料和智能响应材料等新兴领域.本专论结合作者近年的研究工作,介绍了含离子聚合物体系的构效关系和分子流变学,从3个方面展开:第1部分介绍了对于含离子聚合物的离子聚集状态的调控,和离聚物与聚电解质的相互转化;第2部分介绍了离子高度聚集的无规离聚物丰富的线性黏弹性,重点介绍了非缠结体系在链均一个离子浓度附近区域的溶胶凝胶转变以及缠结体系在平均每个缠结链段一个离子浓度附近区域的单平台到双平台模量的转变;第3部分介绍了如何进行分子设计,使得含离子聚合物成为有效的离子传输介质.最后总结了该研究领域的科学问题和面临的挑战.     

Synthesis of Novel β-cyclodextrin Derivatives Bearing a 1-naphthyloxamino-oligo(ethyleneamino) Moiety and their Inclusion Complexation with some Fluorescent Dyes

Two novel g -cyclodextrin derivatives bearing a (1-naphthyloxamino)-ethyleneamino ( 4 ) or (1-naphthyloxamino)-diethylenediamino ( 5 ) moiety have been synthesized by a convenient method in 34% and 30% yields, respectively. Examinations of the circular dichroism (CD) spectra and fluorescence lifetime revealed that the naphthyloxamino-oligo (ethyleneamino) moiety tethered to g -cyclodextrin is not deeply embedded in the hydrophobic cavity of g -cyclodextrin itself even in the absence of a guest. The inclusion complexation behavior of 4 and 5 with some fluorescent dyes, i.e. ammonium 8-anilino-1-naphthalenesulfonate (ANS), sodium 2-( p -toluidinyl)naphthalenesulfonate (TNS), Acridine Red (AR) and Rhodamine B (RhB), was assessed in aqueous phosphate buffer solution (pH 7.2) at 25C by fluorometric titration to give the complex stability constants ( K S ) and Gibbs free energy changes ( j G 0 ) for the stoichiometric 1:1 inclusion complexation with the fluorescent dyes. The results obtained indicate that the naphthyloxamino-oligo(ethyleneamino) moiety attached to the g -cyclodextrin ( 1 ) can alter not only the original molecular binding-ability of the parent g -cyclodextrin, but also the molecular selectivity through the micro-environment changes of cyclodextrin cavity, which are discussed from the viewpoints of the size/shape-fit concept and the stereochemical complementary relationship between host cyclodextrin and model substrate.     

两性高分子与小分子及大分子的相互作用(下)

2 两性高分子与染料及表面活性剂的相互作用文献中对阳离子聚电解质、阴离子聚电解质及非离子性高分子与染料、去污剂、表面活性剂等小分子物质的相互作用有较多报道,而有关两性高分子与这些小分子物质相互作用的报道极少。本节就合成两性高分子与染料等小分     

Synthesis, structure and anion binding properties of lower rim α-hydroxyamide calix[4]arene derivatives

A new family of p-tert-butylcalix[4]arenes functionalized at the lower rim with α-ketoamide or α-hydroxyamide functions has been prepared. The ¹H and ¹³C NMR spectra indicate that the macrocycles preferably adopt a cone conformation. X-ray crystal study of the α-ketoamide derivative 4a shows the flattened cone conformation in the solid state. Reduction of α-ketoamide 4ab has produced the α-hydroxyamide derivatives 6ab. The introduction of chiral moieties on the lower rim position of the calix[4]arene allowed the synthesis of the chiral derivatives 7 and 8. Host-guest complexation properties towards various anions of the chiral α-hydroxyamide 8 have been examined by ¹H NMR spectroscopy. This new receptor has shown promising selectivity for and N-tosyl-(L)-alaninate.     

表面印迹交替层状组装薄膜

在简要概述非常规交替层状组装这一进展后,重点总结了如何利用非常规交替层状组装以实现表面印迹膜的制备.模板分子与聚电解质在溶液中组装形成超分子复合物,然后以此超分子复合物为构筑基元,与感光性高分子,如重氮树脂,通过常规交替层状组装形成聚合物多层膜.利用聚合物多层膜之间的光化学反应形成稳定的多层膜,然后去除模板分子得到分子印迹交替组装薄膜.该研究表明不同的分子间相互作用均可用于分子印迹交替组装薄膜的制备,并且通过引入多点相互作用可以提高其选择性.以此为基础,交替层状组装分子印迹薄膜分别与微接触印刷和膜分离技术相结合,制备了具有正电荷选择性的印章材料和电荷选择性的膜分离材料,从而提供一种新的制备表面分子印迹材料的方法.     

Local modes of molecular mobility in comb-shaped liquid crystalline ionomers containing alkaline metal ions

Molecular mobility of the comb-shaped copolymer poly(4-[6-(acryloyloxy)hexyloxy]benzoic acid-co-butyl acrylate) and Li- and Rb-containing LC ionomers based on this polymer was studied at low temperatures by the methods of dielectric spectroscopy and thermally stimulated depolarization current. The above copolymers are shown to experience the γ₂, γ₁, and β-processes, which are related by the reorientation of the end СООН groups, by the mobility of a spacer, and by the reorientation of mesogenic fragments (dimers of oxybenzoic acids) with respect to a long axis, respectively. The formation of multiplet structures in ionomers leads to a suppression of the intensity of the β-process that relates with a partial breakdown of hydrogen-bonded dimmers and with a decrease of their molecular mobility.