Binding of Phenols with Amphipathic Cationic Polyelectrolytes

The association of phenols, such as p-cresol, tribromophenol, and trichlorophenol, with several amphipathic poly (n-alkylmethyldiallylammonium) chlorides in aqueous solution was studied by ultrafiltration. The n-alkyl residues were octyl, decyl, and dodecyl and the binding degrees were significantly higher than those found with the hydrophilic poly (diallyldimethylammonium) chloride. The results agreed well with the Satake and Yang's treatment and Hill's empirical equation for the association process, thereby revealing, in both cases, an increasing cooperative effect as the polyelectrolyte side chain increased in length for the same phenol, and when the hydrophobic nature of the phenol increased for the same kind of polyelectrolyte. From the phenomenological association constants, the estimated molar standard free energies of association ranged from ?19 kJmol^?1, for the more hydrophilic phenoxide–polyelectrolyte pair, to ?28 kJmol^?1 for the more hydrophobic pairs. The main result is that the amphipathic nature of these polyelectrolytes makes them efficient systems to trap anionic contaminants, better than hydrophilic flocculants.     

Study on the Dynamic Rheological Behavior of Four Different Bimodal Polyethylenes

The dynamic rheological properties of four bimodal polyethylene samples with different molecular parameters were studied. The Cole-Cole plots, Han curves, Van Gurp’ plots, and master curves of elastic modulus, tan delta, and complex viscosity suggested that these four samples showed different micro-phase compatibility and the chain correlations affected strongly the chain dimensions of the polymer blends. A reduction of chain dimension would lead to a decrease of the possibility for a molecule in the melt to form a tie molecule and thus could affect the application performance of bimodal polyethylenes.     

Dynamic Rheological Behavior of HDPE/UHMWPE Blends

The rheological behaviors of high-density polyethylene (HDPE)/ultra-high molecular weight polyethylene (UHMWPE) blends prepared by melt blending and solution blending were studied. The results showed that the rheological parameters (G′, G ^″, and η*) of both types of blends increased gradually with increasing fraction of UHMWPE, while the tanδ decreased correspondingly. Comparing blends with the same UHMWPE content, all G′, G ^″, and η* values of solution blends were higher, and the tanδ of the solution blends were remarkably lower than those of the melt blends. Combined with the scanning electron microscopy (SEM) observations, it was proved that, because of its very high melt viscosity, the UHMWPE chain is difficult to diffuse and be distributed well in the HDPE matrix by melt blending, resulting in a two-phase-like morphology. On the other hand, the blends prepared by the solution blending showed a homogeneous distribution of UHMWPE in the HDPE matrix. In addition, the state of aggregation of the UHMWPE in the HDPE matrix can be distinguished well by time–temperature superposition (TTS) curves; i.e., the two-phase-like morphology in the melt blends can be detected by the failure of TTS in the high-frequency range, which cannot be reflected by Cole–Cole plots and Han curves.     

Flocculation Properties of Some Cationic Polysaccharides

Flocculation of a clay suspension model using some cationic polysaccharides has been studied by turbidity measurements. The investigated polyelectrolytes contain quaternary ammonium salt groups, N-ethyl-N, N-dimethyl-2-hydroxypropylene ammonium chloride, attached to a dextran backbone. The flocculation efficiency was studied as a function of the polycation charge density and some flocculation parameters (polycation dose, settling time, concentration of both clay suspension and parent solution of polymer). All investigated cationic polysaccharides showed high flocculating efficiency at optimum flocculant doses, which correlated well with the charge density of the polycations: the higher charge density, the lower the amount of dextran derivative was required for reaching the maximum clarity degree (of about 100%). This finding is consistent with the neutralization mechanism for a flocculation process. The residual turbidity values also varied with the settling time and the concentrations of clay suspension and parent solution of polymer. Possible reasons for these dependences are discussed.     

Solution Behavior of Hydrophobic Cationic Hydroxyethyl Cellulose

The hydrophobic cationic hydroxyethyl cellulose (HEC-g-DA) was prepared by grafting HEC with various alkyl ammonium chlorides (DA) in order to improve the thickening properties of cationic hydroxyethyl cellulose. The solution behavior of HEC-g-DA was studied, and showed that the apparent viscosity of HEC-g-DA increased with polymer concentration, and there existed a critical association concentration (Cp*). The alkyl chain length of DA had a great influence on Cp*, which decreased with increasing alkyl chain length; however, too long an alkyl chain of DA reduced the water solubility of the polymer, resulting in a slight increase of Cp*. The effect of temperature and electrolyte concentration on the thickening properties of HEC-g-DA was investigated; the value of viscous flow activation energy (E_a) was minimum for the sample of HEC-g-DA16 (glycidyl-N-hexadecyl–N,N-dimethyl-ammonium chloride), indicating the weakest sensitivity of the viscosity to temperature. In the whole range of shear rate investigated, the solutions of HEC-g-DA displayed the shear thinning behavior of a pseudoplastic fluid. The values of viscous index (n) from the Ostwald model simulation decreased with polymer concentration, indicating an improvement of the shear thinning property of the solution, whereas the increase of the consistency coefficient (k) indicated the enhancement of the thickening behavior of the polymer. With increasing polymer concentration, the molecular association of HEC-g-DA16 became strong, and high-shear stress was required to remove the association, while the difference between G′ and G″ became small, indicating that the elasticity of the system was enhanced at high polymer concentration. The amphiphilic structure of the HEC-g-DA16 molecules contributed to the low surface tension of the polymer.     

Effect of Stereodefects Distribution on Rheological Behavior of Isotactic Polypropylene

A series of five isotactic polypropylenes (iPP) used commercially for producing biaxial oriented polypropylene film (BOPP), which had similar average degrees of isotacticity but different stereodefects distribution, was studied. Xylene solubles (XS) at different temperatures and high temperature solution ¹³C NMR were used to characterize the stereodefects distribution of the five samples. These samples gradually became more random following the order of sample A to E. The plateau modulus (G ⁰ _N ≈ 0.2 MPa at 190°C) of these samples was lower than those of metallocene-catalyzed polypropylenes with very narrow molecular weight distributions (MWD) (G ⁰ _N ≈ 0.4 MPa at 190°C), indicating that the influence of MWD on G ⁰ _N cannot be neglected. The storage modulus and complex viscosity of the five samples decreased gradually with the widened stereodefects distribution, due to the formation of a less constrained network that finally caused the reduction of G ⁰ _N and the increase of the flow activation energy. The rheological behavior of the BOPP resin samples could be well related to the results of XS and ¹³C NMR, implying that the rheological measurement can be adopted as a simple and efficient method to characterize the stereodefects distribution of isotactic polypropylene.     

Rheological Behavior and Interaction of Polycarbonate/Barium Sulfate Composites

The effect of microsized barium sulfate (BaSO ₄ ) on the rheological properties of Polycarbonate (PC) was investigated. The composite exhibits a reduced viscosity as compared to pure PC, indicating that use of barium sulfate is a new method to enhance the mobility of PC melts. Model calculation of this behavior was carried out according to a viscosity rheological equation. Values of model parameters were obtained and discussed. Other rheological properties were also determined, including frequency dependence of storage modulus and loss modulus. Analysis by Fourier Transform Infrared (FTIR) spectroscopy and X-ray Photoelectron Spectroscopy (XPS) shows that the barium sulfate fillers strongly interact with PC chains, with the type of interaction being determined.     

Tearing and Rheological Properties of Fully Biodegradable Poly(Lactic Acid)/Poly(Ethylene Glutaric-Co-Terephthalate) Copolyester Blends

The tearing and rheological properties of poly(lactic acid) (PLA)/poly(ethylene glutaric-co-terephthalate) copolyester (FP) blends were investigated using a wide range of blending ratios. The tearing strength values of PLA/FP were always significantly higher than that of the PLA specimen. The melt flow indexer and capillary rheometer analyses indicated that the viscous flow became difficult and the melt strength of PLA was improved after the addition of FP. The interactions between the molecular chains of PLA and FP adds FP branching and lengthens the macromolecular chains and the degree of macromolecular entanglement increases. The blends with 5 wt% FP reached the maximum melt strength and minimum flow index n, while the tearing strength approached the maximum level. At higher FP contents, the melt flow properties PLA/FP blends increased and the melt strength decreased, the tearing strength of PLA/FP blends also decreased.     

Preparation,Characterization, and Rheological Properties of Dibutyrylchitin

Dibutyrylchitin was prepared by an acylating reaction in a heterogeneous system with butyric anhydride as an acylating agent and perchloric acid as a catalyst. The effects of the preparation conditions, including chitin grain size, reaction temperature, and reaction time, on conversion ratio of chitin to dibutyrylchitin are discussed in detail. By adjusting reaction time and reaction temperature, dibutyrylchitin with an adequate intrinsic viscosity could be obtained. Steady-state rheological measurement was also performed and the results revealed that concentration, temperature, and shear rate had a great influence on the rheological properties of dibutyrylchitin/dimethylformamide solutions. Thus, a suitable spinning condition could be determined from the rheological analyses.     

高压对食品胶溶液流变特性的影响

 经高压处理后,卡拉胶、琼胶、高甲氧基果胶、海藻酸钠、黄原胶和瓜尔豆胶等六种食品胶溶液的粘度变化不同。卡拉胶和琼胶溶液的粘度显著增加,高甲氧基果胶、海藻酸钠和瓜尔豆胶溶液的粘度变化较小,而黄原胶溶液的粘度明显降低。动态粘弹性测量表明,卡拉胶和琼胶溶液的贮藏模量（G′）在高压处理后明显减小,而且G′变得小于G″,这表明卡拉胶和琼胶溶液的弹性变小。高甲氧基果胶、海藻酸钠和瓜尔豆胶溶液的损耗正切值（tan δ=G″/G′）在处理后几乎没有变化,黄原胶溶液的tan δ略微减小。高压处理后食品胶溶液流变特性的不同变化表明,高压处理对食品胶的影响因其种类、胶分子的结构和胶在水溶液中的构象而异。文中对造成这些变化差异的可能原因进行了探讨。     

在相反电荷表面活性剂存在下阳离子瓜尔胶水溶液流变行为

合成了阳离子瓜尔胶(CG),研究了其水溶液在十二烷基硫酸钠(SDS)存在下的流变行为．测定结果表明,随SDS浓度的增加,溶液零切黏度增加了3个数量级以上．小幅振荡剪切实验结果表明模量几乎和SDS浓度无关,但是驰豫时间则随着SDS浓度增加而迅速增加．因此,SDS的加入将会使交联点的强度增加,但是不会改变交联点密度．SDS对CG流变行为的影响可以用两阶段模型加以描述．在SDS存在下CG水溶液流变行为主要受到由SDS胶束形成的交联点的控制．根据Arrhenius公式得到的瓜儿胶水溶液的流动活化能在将SDS分子疏水尾端从胶束移到水相之中所需能量是一致的.     

Preparation and Rheological Properties of Functionalized Multiwalled Carbon Nanotube/Waterborne Polyurethane Nanocomposites

Waterborne polyurethane (WBPU) was synthesized by a polyaddition reaction with toluene diisocyanate (TDI), polytetramethylene ether glycol (PTMEG), dimethylol propionic acid (DMPA), and triethylamine (TEA). Aqueous polyurethane dispersions with three different weight fractions, 30, 40, and 50 wt%, were prepared. All the dispersions made with these concentrations showed Newtonian viscosity behavior. Multiwalled carbon nanotubes (CNTs) were functionalized using a mixture of sulfuric and nitric acid at a ratio of 3:1 and added to these dispersions in two different loads of 0.1 and 0.5 wt%. Ultraviolet visible spectrometry (UV/Vis) spectroscopy proved the formation of stable suspensions following ultrasonic agitation. The rheology of these suspensions was characterized using dynamic and steady-state measurements. The higher amount of CNT in the suspension imparted non-Newtonian and complex viscoelastic behavior. This was attributed to a physical network formed due to the presence of the functionalized CNTs. The Cox-Merz rule was not observed for these suspensions.     

聚苯乙烯/纳米铝复合材料的流变特性及纺丝研究

为有效制得Z箍缩氘代聚苯乙烯/纳米铝(DPS/AlNPs)导电丝阵材料,采用PS中掺入AlNPs制备PS/AlNPs复合材料纤维进行模拟研究。研究了温度及剪切速率等因素对PS/AlNPs复合材料流变性能的影响、复合材料熔体的结构变化及流动状态与可纺性能的关系,以及PS/AlNPs纤维的形貌、热稳定性能和力学性能。结果表明：PS/AlNPs熔体属于典型剪切变稀型非牛顿流体,熔体的表观粘度与温度呈现负相关,240~260 ℃时复合材料的非牛顿指数介于0.462~0.546,结构黏度系数介于1.8~2.1,黏流活化能介于77.2~104.6 kJ·mol^-1,具有良好的可纺性。PS/AlNPs纤维表面光滑,对AlNPs粒子包覆良好且对其抗氧化非常有利,其中当AlNPs质量分数为1%时纤维的断裂伸长率突出、掺量为5%时其断裂强度较高。     

Dynamic Rheological Behavior of Copolymerized Linear Low-Density Polyethylenes: Effect of Molecular Weight and Its Distribution

The change of storage moduli (G′), loss moduli (G″), zero shear viscosity, and complex viscosity were studied for a series of butene and hexene copolymerized linear low-density polyethylenes (LLDPEs) with various characteristics by investigating the dynamic rheological behaviors. It was found that: (1) the dependence of the complex viscosity on the weight average molecular weight did not follow the Raju equation; (2) the slopes of the G′～ω and G″～ω curves in the low-frequency regions not only were smaller than those of the polymers with monodisperse molecular weight, but also decreased with the relative molecular weight increasing or its distribution broadening; (3) the dynamic storage moduli G′ were more sensitive to the shear rate than the dynamic loss moduli G″; (4) the change of the dynamic moduli was directly correlated with the orientation and disorientation of the chain segments, which is influenced by the frequency or shear rate, the temperature, the molecular weight, and the molecular weight distribution; and (5) the comonomer types showed little effect on the frequency dependence of the dynamic moduli at different temperatures.     

新型含咔唑聚芴类共轭聚电解质及其前驱体的合成与光电性能

采用Suzuki偶合反应成功地合成了一系列在主链上具有不同含量苯并噻二唑单元的聚咔唑和含胺基芴的衍生物:聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并噻二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BTDZ);通过对所得聚合物的季铵盐化后处理得到了其相应的聚电解质衍生物:聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并噻二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BTDZ)。通过对它们的电致发光性能的研究,发现所有的聚合物用高功函数铝作阴极的器件具有和用钡/铝作阴极的器件相近的发光性能,说明这类聚合物具有良好的电子注入性能。不同比例的2,1,3-苯并噻二唑(BTDZ)的引入使聚合物中发生有效的能量转移,调节了聚合物的发光颜色;同时也提高了聚合物的器件性能。其中聚合物PCzN-BTDZ1在器件结构为ITO/PEDOT/PVK/Polymer/BaAl时的效率达0.99%,高于PCzN在相同器件结构时的效率(0.14%)。     

Rheological Properties of Template Polymerization Polyacrylamide Aqueous Solutions

In this work, the aqueous solution rheology properties of both partially hydrolyzed polyacrylamide (HPAM) and the template copolymer (TPAM) synthesized from acrylic acid (AA) and acrylamide (AM) were investigated using an advanced rheometer and viscometer. The results were correlated with the corresponding molecular structures of HPAM and TPAM, which were characterized by high-resolution nuclear magnetic resonance. It was found that the thickening ability of TPAM is much stronger than that of HPAM due to its unique microblocky structure, while the viscosity of TPAM was more sensitive to shear rate. Furthermore, the effect of polymer concentration was also tested in an oscillation shear mode. It showed that the characteristic relaxation time of TPAM was much higher than that of HPAM at the high concentrations. The research on salt-resistance properties showed that the viscosity retention of TPAM was similar to HPAM at the same NaCl concentration. But, unexpectedly, at the same CaCl₂ concentration the viscosity retention of TPAM was much lower than that of HPAM, indicating a poor divalent salt-resistance property.     

Viscosity of Some Cationic Polyelectrolyte and its Potential Use as Flocculant in Solid/Liquid Separation Processes

Intrinsic viscosities of a cationic polyelectrolyte were determined in salt-free aqueous solution and aqueous/organic solvent mixtures. The investigated polyelectrolyte contains quaternary ammonium salt groups (N, N-dimethyl-2-hydroxypropylenammonium chloride), located along the main chain. In order to obtain the intrinsic viscosities, the experimental data were plotted based on the Wolf method. The results showed that the experimental data fit well with the Wolf model. From the estimated values of the intrinsic viscosities, the dependences of the polyion conformation on the polyelectrolyte concentration as well as on solvent composition were revealed. The flocculating efficiency of this polycation on a model clay suspension was studied by turbidity and zeta potential measurements as well. Moreover, flocs size measurement at the optimum polycation dose was carried out using laser diffraction technology. The results point to simultaneous contributions from both neutralization and patch mechanisms for flocculation process and a unimodal distribution in floc size.     

Rheological Behaviors of Polypropylene/Poly(1-butene) Blends

The rheological behaviors of polypropylene (PP)/poly(1-butene) (PB) blends with homo-polypropylene (PP₁) or impact polypropylene (PP₂), a poly(propylene-co-ethylene) as the PP component were studied. With increasing of PB resin content for both PP/PB blends, the blends showed higher G'(ω), G''(ω) and η*(ω) at low frequencies but lower values at high frequencies which implied that the processability was improved. A two-phase morphology was observed through the various rheological responses, including G'(ω)-ω terminal region curves, Cole-Cole plots and the weighted relaxation spectra with the PB contents up to 40?wt%. With the same PB content, the rheological parameters of the PP₂/PB blends were quite different from those of the PP₁/PB, which can be attributed to the stronger interaction between PB chains and the ethylene-co-propylene copolymer in PP₂. The impact strength of the PP₂/PB blends was improved dramatically over that of the PP₁/PB. The more significant toughening effect for the PP₂/PB blends can be attributed to the special responses of its rheological behaviors.     

Rheological Behavior of Some Aqueous Gels of Carbopol with Pharmaceutical Applications

The concentration and temperature dependence of the viscosity is observed for some aqueous dispersions of Carbopol. The experimental data are analyzed with the power model, and reveal non-Newtonian behavior （shear thinning） of the samples.     

The Thermal Stability and Rheological Properties of Alkylated Carboxymethyl Starch

Several alkylated carboxymethyl starches (CMS) with different alkyl chain lengths were prepared. The influence of the number of alkyls on the thermal stability and rheological properties, such as thickening properties, salt-tolerance, temperature sensitivity and time-dependent rheological behavior, are discussed. The initial decomposition temperature (IDT) of alkylated CMS reached 263°C ～293°C which, as compared to the IDT for CMS itself (230°C), indicated that the thermal stability of CMS was improved after being alkylated. The solution viscosities of the alkylated carboxymethyl starch increased with the increasing of alkyl length. With the alkyl chain length increasing from C₂ to C₈, the viscosity increased from 400 mPa·s to 38000 mPa·s. The weak hydrophobic aggregation of the alkyl groups did not improve the shear-resistance and relative hysteresis area. But the temperature sensitivity of alkylated CMS was improved as the chain length of the alkyl groups increased, as the activation energy (E_a) value decreased from 2.082 kJ·mol^?1 to 0.077 kJ·mol^?1; Improving the rigidity of the molecular chains and reducing the network structure of the hydrophobic contribution to the viscosity of the solution are benefits for improving the salt-tolerance and shear-resistance of the aqueous solution.