高分子稀溶液中偏离Huggins方程式的五种情况

在对高分子溶液的粘度研究中发现,在稀溶液中会出现五种偏离Huggins方程式的情况。本文就这五种情况作了较为详细的介绍,尤其就高分子－高分子和高分子－溶剂分子间的相互作用对二元体系（溶剂－聚合物）和三元体系（溶剂－聚合物A－聚合物B）粘度的影响进行了深入的讨论。     

多分散高分子的稀溶液粘度-浓度依赖性

依据最近提出的关于单分散高分子的稀溶液粘度的团簇理论,对多分散高分子的稀溶液粘度的浓度依赖性进行了更新的理论分析。最后得到一个新的多分散高分子的稀溶液粘度与浓度的关系式。实验研究表明,该关系式是与实验数据相一致的。     

聚丙烯酸/聚氧化乙烯高分子复合溶液的结构与粘度

通过溶液折光指数和粘度测定,研究了聚丙烯酸（ＰＡＡ）与聚氧化乙烯（ＰＥＯ）高分子链间在复合溶液中的相互作用和ＰＡＡ／ＰＥＯ高分子氢键复合溶液的结构与粘度,研究了复合溶液粘度随溶液ｐＨ值的变化规律及不同浓度时剪切速率对复合溶液粘度和复合增粘效果的影响。结果表明：ＰＡＡ／ＰＥＯ复合溶液结构不同于ＰＡＡ和ＰＥＯ两组分聚合物溶液结构,ＰＡＡ与ＰＥＯ高分子链间的氢键相互作用形成构象更为伸展、流体力学体积列大     

壳聚糖浓溶液流变性质研究──分子量的依赖性

壳聚糖浓溶液流变性质研究──分子量的依赖性王伟，徐德时（中国科学院长春应用化学研究所高分子物理开放实验室长春１３００２２）关键词壳聚糖，浓溶液，粘度，零剪切粘度，分子量作者曾研究了一些外部条件对壳聚糖浓溶液流变学性质的影响，如浓度、温度、溶剂性质、外...     

高分子电解质溶胶－凝胶相转移与溶剂效应

以溶质、溶剂间的协同作用作为高分子电解质体系的凝胶化条件，以松软粒子结构（Ｂｌｏｂ）间的三维逾渗的凝胶化模型，将高分子电解质体系的凝胶化分为松软粒子的形成和逾渗过程。结合海藻酸溶液的Ｃｕ２＋、Ｃａ２＋、Ｍｎ２＋和Ｃｏ２＋离子添加体系的凝胶化，分析了高分子电解质溶胶－凝胶相转移的实质，得到了体系相对粘度的临界指数ｋ＝０．９０～１．１４，与逾渗模型的预测值相吻合，探讨了松软粒子的形成对相转移临界点ｆｃ的影响，明确了临界点附近相对粘度的幂次公式ηｒｅｌ∝（ｆｃ—ｆ）－ｋ）的适用范围。     

二丁基次膦酸锌高聚物溶液的平衡粘度

通过对二丁基次膦酸锌聚合物溶液平衡粘度与体系中水含量间关系的研究,证明:高分子溶液的相对粘度随体系中水含量的增加而减少。反之亦然。在室温下可很快地建立起平衡。高分子溶液的平衡粘度值取决于体系的水蒸汽分压。     

一个热致液晶高分子－高聚物复合体系的粘度函数

一个热致液晶高分子－高聚物复合体系的粘度函数益小苏，赵高明，王惠民（浙江大学高分子科学与工程学系杭州３１００２７）关键词热致液晶高分子，原位复合，流动模型，粘度函数国内外对热致液晶高分子材料（ＴＬＣＰ）的研究均发现，将少量ＴＬＣＰ加入到树脂基体中能有...     

聚丙烯酸水溶液及α-A12O3悬浮液的流变性研究

研究了pH、聚丙烯酸(PAA)浓度和分子量对PAA水溶液的粘度的影响,发现溶液的流变行为与溶液中PAA高分子链的离子化程度和构型密切相关,高分子链刚性程度的增加和链的伸展使溶液在pH为7～9时的粘度最大;研究了在PAA溶液中引入陶瓷粉体后悬浮液的粘度变化,发现当陶瓷粉体和PAA的量达到一定比值时悬浮液体系的粘度达到最小值,同时发现陶瓷粉体的粒径大小与这一粘度最小值和悬浮液流变特性也有关.     

高分子电解质溶胶—凝胶相转移与溶剂效应

以溶质、溶剂间的协同作用作为高分子电解质体系的凝胶化条件，以松软粒子结构（Ｂｏｌｂ）间的三维逾渗的凝胶化模型，将高分子电解质体系的凝胶化分为松软粒子的形成和逾渗过程。结合海藻酸溶液的Ｃｕ＾２＋、Ｃａ＾２＋、Ｍｎ＾２＋和Ｃｏ＾２＋离子添加体系的凝胶化，分析了高分子电解质溶胶－凝胶相转移的实质，得到了体系相对粘度的临界指数ｋ＝－０．９０￣１．１４，与逾渗模型的预测值相吻合，探讨了松粒子的形成对相转移介     

PABA疏水缔合水溶性共聚物溶液的合成与性能研究

本文根据高分子的分子设计原理，合成了带苯基的疏水单体N－苯基对正丁基丙烯酰胺（BBAM）。采用自由基胶束共聚的方法制备了水溶性丙烯胺／N－苯基对正丁基丙烯酰胺（BBAM）疏水缔合型共聚物（PABA）。研究了共聚物溶液的性能及影响因素。结果表明，随共聚物溶液浓度的增加，在临界缔合浓度以上，分子间缔合大量形成，水溶液表现粘度迅速增加，表现出明显的疏水缔合行为，与HPAM相比有优异的抗盐性。     

A new viscometric criterion for polymer-polymer interaction

Based on a simple cluster theory recently proposed for the viscosity of polymer dilute solution, a new viscometrical criterion was suggested to probe the interaction between unlike polymers. The new criterion was applied into some polymer mixture solutions to study the polymer-polymer interactions. It was found the new criterion is more reasonable.     

Thermodynamics of miscible polymer blends studied by inverse gas chromatography

Use of inverse gas chromatography for the investigation of polymer-polymer interactions is compromised by a dependence of the measured polymer-polymer interaction coefficient, B₂₃, on the chemical nature of the probe in contradiction to theory currently used. We have developed a procedure whereby the “true” B₂₃, may be extracted from the probe dependent data. Additionally a theory of mixing based on a multidimensional solubility parameter approach has been developed. The new theory has been used to predict the polymer-polymer interaction coefficients and these are compared with experimentally determined values on several miscible blends.     

Enhancement of poly(vinyl ester) solubility in supercritical CO2 by partial fluorination: the key role of polymer-polymer interactions

An enhancement of poly(vinyl ester) solubility in supercritical carbon dioxide (sc-CO(2)) can be achieved by decreasing the strength of the polymer-polymer interactions. To demonstrate this, a library of statistical copolymers of vinyl acetate and vinyl trifluoroacetate was synthesized by RAFT/MADIX polymerization with varying compositions at a given number-average molecular weight. These copolymers exhibited unprecedentedly low cloud-point pressures in sc-CO(2) at 40 °C compared with previously reported poly(vinyl esters). Surface tension measurements combined with a computational approach evidenced the prominent role played by polymer-polymer interactions.     

Polymer-colloid complexes in three-component system: poly(styrene-alt-maleic acid)-poly(ethylene oxide)-silica sol in aqueous medium

Complex formation in the model three-component system, including polymer-polymer complex of poly(styrene-alt-maleic acid) (PSMA) and poly(ethylene oxide) (PEO), and also silica sol (SiO₂) in aqueous solution as a function of molecular weight of PEO and the order of component mixing, were investigated. The degree of binding of PSMA links with PEO and SiO₂ as well as the Gibbs energy of formation of the polymer-polymer complex and polymer-colloid complexes were defined. It was shown that the main factor of stabilization of the structure is hydrogen bonds. The conditions of three-component polymer-colloid system are practically independent of the order of component mixing. The spontaneous formation of polymer-colloid complexes between chemically complementary polymers and small dispersed particles is considered as the main reason for the abnormally high binding ability of colloid particles to the polymer-polymer complex.     

Studies of poly(vinyl chloride)/solution chlorinated polyethylene blends by inverse gas chromatography

The interactions between two polymers, poly(vinyl chloride) and solution chlorinated polyethylene, with a series of solvents have been studied using inverse gas chromatography. Values of the interaction parameters show the importance of specific interactions in these systems. From these values and studies of polymer mixtures, values of the polymer-polymer interaction parameter have been calculated. The values were small in agreement with values of the heat of demixing of the two polymers reported previously.Measurements using PTFE and kaolin as the substrate for these polymers show the importance of the substrate. Results suggest that the pore structure of PTFE leads to problems in obtaining reliable results.By making measurements for the mixed polymer system over a range of temperatures, it has been found possible to detect the temperature of phase separation. The phase diagram obtained agrees well with results reported previously.     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

Changes in thermodynamic interactions at highly immiscible polymer/polymer interfaces due to deuterium labeling

Deuterium labeling has been shown previously to affect thermodynamic interactions at polymer surfaces, polymer/polymer heterogeneous interfaces, and in bulk (away from a surface or interface). However, the changes in polymer-polymer interactions due to deuterium labeling have not been thoroughly investigated for highly immiscible systems. It is shown here that deuterium labeling can influence polymer-polymer interactions at heterogeneous interfaces with highly immiscible systems, namely, polystyrene/poly(2-vinylpyridine) (PS/P2VP), polystyrene/poly(4-vinylpyridine) (PS/P4VP), and polystyrene/poly(methyl methacrylate) (PS/PMMA). Using secondary ion mass spectrometry, segregation of deuterium labeled polystyrene (dPS) in a dPS + unlabeled PS (dPS:hPS) blend layer was observed at the dPS:hPS/hP2VP, dPS:hPS/hP4VP, and dPS:hPS/hPMMA heterogeneous interfaces. However, a reference system involving PS on a PS brush shows no segregation of dPS to the interface.     

Effects of polymer-polymer interactions in multiphase blends or alloys

The interaction energy between two polymers determines whether they form a miscible blend or a phase separated one. In the latter, these interactions also determine the nature of the interface between phases which in turn influences stress transfer between the phases in the solid state and morphology generation during formulation. Estimates of polymer-polymer thermodynamic interactions are used to rationalize the behavior of polycarbonate/ABS materials and a series of polyamides toughened by reactive blending with a functionalized elastomer.     

粘度法研究氯化聚丙烯和涂料树脂间的相容性

用稀溶液粘度法研究了氯化聚丙烯与石油树脂、丙烯酸树脂和醇酸树脂间的相容性,并用α判据对相容性结果进行判别。结果显示,石油树脂/氯化聚丙烯的共混体系是相容的;丙烯酸树脂/氯化聚丙烯的共混体系是不相容的。而醇酸树脂与氯化聚丙烯的相容性情况复杂,由二者的组成决定。当m(醇酸树脂)∶m(氯化聚丙烯)1∶1时,体系是相容的;当m(醇酸树脂)∶m(氯化聚丙烯)1∶1时,体系是不相容的。通过共溶剂法和涂膜宏观特性对上述体系的相容性进行测定,所得结果与α判据的结果相符合,印证了稀溶液粘度法研究溶液中高分子间的相互作用来预测涂料树脂的相容性具有一定可行性。