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．     

离聚体溶液粘度方程

离聚体（ionomer）是指合少量离子基团（低于15％mo）的聚合物．在低极性溶剂中，离子基团发生聚集，因而离聚体溶液的粘性行为明显不同于普通高分子溶液．很多实验表明［1］，用于描述普通高分子溶液粘性行为的哈金斯公式并不适用于描述离聚体溶液的粘性行为．因此，到目前为止，对离聚体溶液的离子聚集行为及粘性行为的考察或者是定性的，或者是通过图表曲线直接描述的．本文提出适用于高聚体溶液的半经验关系式，并用实验数据验证，以求更深入和更系统地研究离聚体溶液的粘性行为．1实验部分采用两种分子量的丁基胶（牌号286，加拿大产品…     

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。     

离聚体溶液

离聚体（ionomer）是指含离子基团低于15mol％的聚合物，这些离子基团能聚集成多重离子对[1]或离子簇[2-6]，使大分子链发生物理文联形成聚集体，导致性质起很大变化。例如常温下因物理交联而具有良好弹性，而高温时物理交联被破坏而具有流动性，所以离聚体能制成热塑性弹性体。由于物理交联存在，离聚体不能轻易溶于非极性溶剂中；由于离子含量低，又不易溶于水或其它强极性溶剂中．因此，尽管离聚体固体的研究和应用已有40多年的历史，但有关溶液研究的报导到70年代末才见发表[7-9]，近10年取得较大进展，其独特的粘度关系使人们考虑利用…     

离聚体的聚集态结构模型

由于离子对的聚集作用，离聚体形成了独特的微相结构。本文对有关离聚体的聚集态结构的理论和定性模型进行了综述。     

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．     

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（ＣＴＢＮ）合成了Ｌｉ＾＋、Ｎａ＾＋、Ｋ＾＋、Ｍｇ＾２＋、Ｚｎ＾２＋、Ａｌ＾３＋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。     

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     

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     

3,4-聚异戊二烯的磺化反应及其离聚体的结构研究

本工作合成了磺化的3,4-聚异戊二烯及其离子聚合体,IR和NMR谱图证明对3,4-聚异戊二烯的磺化反应是成功的,并且磺酸基团主要与3,4-链节的侧基双键发生反应。WAXD对磺化3,4-聚异戊二烯及其离聚体的研究表明,磺化度的增加使离聚体的结晶能力降低,SAXS结果表明,在离子含量为3.29mol％的离聚体中,未观察到离子簇聚集,只观察到多重离子对的散射。     

Influence of ionic association on the nonisothermal crystallization kinetics of sodium sulfonate poly(butylene succinate) ionomers

We evaluated the relationship between the ionic substituents and nonisothermal crystallization behavior in poly(butylene succinate) (PBS) ionomers, synthesized by the introduction of sulfonated dimethyl fumarate (SDMF) with sodium sulfonate. In addition, we investigated the effect of sodium ions on the molecular structure of the PBS backbone by solid‐state ²³Na NMR analysis. Sodium ion aggregates (multiplets) was predominately created with the ionic group concentration, and melt rheology and dynamic melt analysis results showed that multiplet formation induced not only remarkable heterogeneity, but also a high degree of clustering in the PBS chains. At low ionic group concentration, well dispersed multiplets behaved as effective nuclei during the crystallization of the PBS ionomer and accelerated the rate of crystallization. As ionic group concentration grew higher, crystallization rates decreased due to hindered chain mobility by clusters consisting of numerous multiplets. A combined Ozawa and Avrami equation proved to be more effective than the Ozawa equation in describing the nonisothermal crystallization kinetics of PBS and its ionomers. The observed nucleation activity indicates that the nonisothermal crystallization rate is not directly proportional to the ionic group concentration. Superior nucleation activity was observed in PBS ionomer containing 1 mol % SDMF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 925–937, 2008     

Effects of Na‐sulfopropyl groups on the mechanical properties and morphology of polystyrene‐co‐methacrylate ionomers

The dynamic mechanical properties and morphology of poly(styrene‐co?3‐sulfopropyl sodium‐methacrylate) SSPMANa ionomers were investigated. It was found the increasing rate of ionic moduli of the SSPMANa ionomer was very low, and the cluster T_g of the ionomers remained more or less constant with increasing ion content. A well‐developed SAXS peak was seen for low ion content SSPMANa ionomers and the peak position changed slightly with ion content. Thus, it was suggested that the presence of the alkyl ester side chains made the ion pairs form multiplets more easily at their prevalent distances, and the small‐agglomerated multiplets were dispersed in the polymer matrix relatively evenly. The interpretation of ionic moduli using a number of theories implied that the multiplets and clusters acted as effective crosslinks and filler particles, respectively, and the size and shape of the clusters were irregular. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1043–1053     

Deformation and fracture behavior of polystyrene ionomer and ionomer blends

The deformation and fracture behavior of sulphonated polystyrene ionomers, and of blends of these with polystyrene have been investigated. The microstructure of the ionomer, which varies with ion content, appears to have a significant effect on mechanical properties. Both tensile strength and toughness increase appreciably at ion contents near 5 mol%, where clusters become dominant over ion pairs and multiplets. In blends of the ionomers and polystyrene, phase separation occurs and the ionomer component appears in the form of fine particles dispersed in the polystyrene matrix. These particles possess a greater effective entanglement density than the matrix, as a result of ionic crosslinking, and they provide reinforcement against early craze breakdown and fracture. Tensile strength and fracture energy increase rapidly as the ionomer concentration in the blend is increased and they become essentially independent of blend ratio above about 10 wt% of the ionomer. Tests carried out on thin film specimens of the blends show that the dispersed ionomer particles adhere well to the matrix and contribute to the fracture energy both by inducing matrix crazing and by internal fibrillation within the particles.Dedicated to Professor Hans-Henning Kausch on the occasion of his 60th birthday.     

Dispersions of polymer ionomers: I

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.     

嵌段聚氨酯阴离子离聚物的小角X射线散射研究

用小角Ｘ射线散射研究了嵌段聚氨酯阴离子离聚物中不同离子化程度对离子聚集体形态结构的影响．结果表明：离子含量少时，主要以非聚集离子或多重离子对的形式存在；离子含量多时，主要以离子簇的形式存在．聚氨酯离子化后，有利于软、硬段的微相分离．     

SAXS study on ionic aggregates of styrene‐isoprene‐sulfonated isoprene terpolymer ionomer

The small‐angle X‐ray scattering profile of styrene‐isoprene‐sulfonated isoprene terpolymer ionomers was studied to clarify the structure of ionic aggregates at ambient temperature as a function of the degree of neutralization of Na or Mg cations. An ionic cluster peak was observed for ionomers with a degree of neutralization greater than 25%. The ionic cluster peak was analyzed by the modified hard sphere model proposed by Yarusso and Cooper [Macromolecules, 1983, 16, 1871], and the size of the ion cluster, the closest approach distance between the clusters, and the average system volume per ion cluster were evaluated by a curve‐fitting method. The size of the ion clusters of the ionomer with monovalent Na cation increased with the degree of neutralization, but for divalent Mg cation slightly changed. The number of ion clusters of the styrene‐isoprene‐sulfonated isoprene ionomer with Na and Mg cations characteristically increased with the neutralization. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1307–1311, 2000     

聚苯醚羧酸盐的聚集态结构

本文用热学、力学和散射方法研完了聚苯醚羧酸盐的链结构、羧化聚苯醚(C-PPO)在二氧六环溶液中用0.5 NaOH或CsOH的醇水溶液中和成钠型或铯型的C-PPO离聚体,用DSC测定一系列羧酸盐含量的C-PPO离聚体的玻璃化转变温度得到形成离子微区的临界阳离子浓度约为5mol％;动态力学谱中在高于玻璃化转变温度域出现的α松弛峰亦证明了微相结构的存在;SAXS结果表明其离子微区的尺寸约为30(?),其尺寸大小和离聚体中阳离子浓度无     

轻度磺化聚苯乙烯与聚苯乙烯共混物的流变性能表征

采用DSR-200动态应力流变仪研究了磺化度为0.98%(摩尔分数)的轻度磺化聚苯乙烯(SPS)离聚物及其锌盐(ZnSPS)与聚苯乙烯(PS)的共混物(PS/SPS,PS/ZnSPS)的流变性能.由于离聚物中离子聚集的物理交联作用,使其流变性能与PS相比有明显差别.动态频率实验结果表明,所有样品均可采用时温等效处理.另外,在与分子链运动相关的低频区,由于离子聚集的作用使得离聚物的模量远大于PS的模量.离聚物在稳态剪切作用下,由于离子聚集的破坏而表现出明显的屈服现象,并能用Utracki的屈服应力公式表征其屈服应力和零切粘度.此外,离聚物的屈服现象还与温度相关.由于动态和稳态实验分别测试离子聚集存在和破坏的不同材料状态,因此对离聚物无法应用Cox-Merz规则.动态和稳态实验结果均表明,PS/SPS和PS/ZnSPS的性能与组成的变化规律不同,意味着二者之间存在不同的离子聚集结构或相互作用.     

Halato-telechelic polymers. VII. Viscoelastic behavior of α,ω-divalent cation dicarboxylato polybutadiene

Ba, Ca, Mg, and Zn short-length carboxylato-telechelic polybutadienes (M?_n = 4,600) exhibit thermorheological simplicity. A secondary relaxation characteristic of ionic aggregates obeys an Arrhenius type of activation, the energy of which is in inverse proportion to the ionic radius of the cation, whereas the mean size of the ionic aggregates is proportional to it. The glass transition of the carboxy-telechelic polybutadiene is quite independent of the degree of neutralization and of the subsequent phase separation by the metal cations. The increase in cation size favors the growth of the multiplets into layered structures. Two sets of relaxation times are reported for the smallest alkaline-earth cation (Be). They suggest the existence of small multiplets unable to grow except into clusters.     

苯乙烯－丁二烯－苯乙烯工嵌段共聚物／聚（苯乙烯－甲基丙烯酸盐）热塑性IPN中离子聚集结构的研究

苯乙烯－丁二烯－苯乙烯工嵌段共聚物／聚（苯乙烯－甲基丙烯酸盐）热塑性ＩＰＮ中离子聚集结构的研究韦雨春，袁惠根，潘祖仁（浙江大学化工系杭州３１００２７）关键词互穿聚合物网络，离子聚集，远红外光谱，Ｘ－光散射以苯乙烯－丁二烯－苯乙烯三嵌段共聚物（ＳＢＳ）...