Chemorheology of linear polymers. II

The chemical stress relaxation of crosslinked polymers had long been studied. The chemorheology of linear polymers is difficult to study because molecular flow by diffusion is generally much more rapid than relaxation or flow caused by chemical reaction. Our previous paper dealt with the chemorheology of linear polymers on taking such physical flow into consideration. By using another modified expression suggested by Tobolsky, good consistency between the theoretical chemical stress relaxation curve and an experimental one was obtained for polydisperse polystyrene and the commercial polystyrene used.     

Flow birefringence and polydispersity

Flow birefringence data for dilute solutions of various linear and branched polymers of different degrees of polydispersity are discussed. The polymers considered are polystyrene, polypropylene, and polyethylene. By making use of a well-known stress-optical relation, reduced elastic normal stresses, which can also be interpreted as coil expansions, are plotted against reduced shear stresses. As elastic normal stresses are rather sensitive to the shape of the molecular weight distribution at high molecular weight, a characteristic, p, related to the skewness of the distribution, is obtained. Experimental values of p are compared with theoretical ones based on special types of distribution functions. Attention is paid to the method of extrapolating experimental results to zero shear stress and concentration.     

Effect of temperature and pressure on surface tension of polystyrene in supercritical carbon dioxide

The surface tension of polymers in a supercritical fluid is one of the most important physicochemical parameters in many engineering processes, such as microcellular foaming where the surface tension between a polymer melt and a fluid is a principal factor in determining cell nucleation and growth. This paper presents experimental results of the surface tension of polystyrene in supercritical carbon dioxide, together with theoretical calculations for a corresponding system. The surface tension is determined by Axisymmetric Drop Shape Analysis-Profile (ADSA-P), where a high pressure and temperature cell is designed and constructed to facilitate the formation of a pendent drop of polystyrene melt. Self-consistent field theory (SCFT) calculations are applied to simulate the surface tension of a corresponding system, and good qualitative agreement with experiment is obtained. The physical mechanisms for three main experimental trends are explained by using SCFT, and none of the explanations quantitatively depend on the configurational entropy of the polymer constituents. These calculations therefore rationalize the use of simple liquid models for the quantitative prediction of surface tensions of polymers. As pressure and temperature increase, the surface tension of polystyrene decreases. A linear relationship is found between surface tension and temperature, and between surface tension and pressure; the slope of surface tension change with temperature is dependent on pressure.     

Effects of molecular weight distribution in drag reduction and shear degradation

A reduction of frictional drag in turbulent flow was obtained in benzene by using three monodisperse polystyrene samples having weight-average molecular weights of 1.8, 4.1 and 7.1 × 10⁶. By testing these polymers individually and in mixtures, data were obtained for samples with known molecular weight distributions. The drag reduction of these samples was studied as a function of polymer concentration and flow rate so that a generalized picture of the effects of polydispersity could be obtained. These results are used to help explain much of the behavior that was observed for polystyrene and other polymers. This includes the fact that the polystyrene samples exhibit a remarkably high resistance to the loss of drag reduction via degradation in turbulent flow. Such experiments indicate that drag reduction and degradation depend strongly on molecular weight distribution. Thus a molecular level interpretation of experimental results cannot be made unless the effects of the distribution are considered.     

Highly entangled polymer primitive chain network simulations based on dynamic tube dilation

The concept of dynamic tube dilation (DTD) is here used to formulate a new simulation scheme to obtain the linear viscoelastic response of long chains with a large number of entanglements. The new scheme is based on the primitive chain network model previously proposed by some of the authors, and successfully employed to simulate linear and nonlinear behavior of moderately entangled polymers. Scaling laws are generated by the DTD concept, and allow for prediction of the linear response of very long chains on the basis of suitable simulations performed on shorter ones, without introducing adjustable parameters. Tests of the method against existing data for linear monodisperse polyisoprene and polystyrene show good quantitative agreement.     

A theoretical study of the interfaces between aluminium and poly(ethylene terephthalate), polycaprolactone,and polystyrene: Illustration of the reactivity of aluminium towards ester groups and phenyl rings

The interfaces between aluminium and poly(ethylene terephthalate), poly(ε-caprolactone), and polystyrene are investigated theoretically in order to assess the reactivity of aluminium towards the functional groups (i.e., ester functions and phenyl rings) present at the surface of the polymers. The theoretical approach consists in performing quantum-chemical calculations on small molecular model systems interacting with a few Al atoms. The geometric structures of the organometallic complexes are optimized and their stabilities and changes in charge densities due to Al bonding are evaluated. The results are compared to experimental X-ray photoelectron spectroscopy data collected during the early stages of interface formation following aluminium deposition on the polymer surfaces. In agreement with experimental data, it emerges from this study that aluminium interacts strongly wirth both polyesters by forming covalent bonds with the carbon and oxygen atoms of the ester functions. The attack of the poly(ethylene terephthalate) phenyl rings occurs only for high metal coverage and does not hamper the interaction with the ester sites. Furthermore, our theoretical investigation has confirmed, on one hand, that the aluminium/polystyrene interactions are weak, and on the other hand, the absence of strong reactions at the interfaces between aluminium and saturated hydrocarbon polymers.     

Synthesis of difunctional polystyrenes and their incorporation in block copolymers with bisphenol a polycarbonate

Block polymers of polystyrene and bisphenol A polycarbonate have been prepared and their bulk viscosities studied as functions of both shear stress and polystyrene block length. The polystyrene blocks were α,ω-diacid chlorides prepared from the reaction of “living” polystyrenes with diacid chlorides. These reactions were studied in order to discover the most effective way of preparing the polystyrene diacid chlorides. The polystyrene diacid chlorides are best prepared by reaction of disodiopolystyrene with phosgene. The flow properties of the block copolymers depend on the composition of the polymers but do not depend on the length of the polystyrene blocks.     

Simulation of size-exclusion chromatography distribution coefficients of comb-shaped molecules in spherical pores comparison of simulation and experiment

Simulations of the distribution coefficients of linear polymers and regular combs with various spacings between the arms have been performed. The distribution coefficients were plotted as a function of the number of segments in order to compare the size exclusion chromatography (SEC)-elution behavior of combs relative to linear molecules. By comparing the simulated SEC-calibration curves it is possible to predict the elution behavior of comb-shaped polymers relative to linear ones. In order to compare the results obtained by computer simulations with experimental data, a variety of comb-shaped polymers varying in side chain length, spacing between the side chains and molecular weights of the backbone were analyzed by SEC with light-scattering detection. It was found that the computer simulations could predict the molecular weights of linear molecules having the same retention volume with an accuracy of about 10%, i.e. the error in the molecular weight obtained by calculating the molecular weight of the comb-polymer based on a calibration curve constructed using linear standards and the results of the computer simulations are of the same magnitude as the experimental error of absolute molecular weight determination.     

Statistical mechanical estimation of the entropy of fusion of linear vinyl polymers

The entropy of fusion of linear vinyl polymers [polypropylene, polystyrene, and poly(vinyl chloride)] having asymmetric carbon atoms was calculated on the basis of the rotational isomeric state model. The results are found to be in good agreement with the experimental entropies of fusion per bond for these polymers.     

铜电极阳极溶解过程恒电位电流振荡的动力学模型

研究了铜电极在酸性氯化钠溶液中的恒电位电流振荡行为,分析了电极过程中的非线性步骤及电化学耦合因素,提出了一个可能的电极过程动力学模型,并借助线性稳定性分析及分支分析得到了参数坐标空间中的动力学行为区域图。在此基础上,将极化曲线视为稳定非平衡定态区态函（电流）与外控参数（电位）的关系,同时将恒电位电流振荡模拟为稳定极限环振荡,分别计算出了极化曲线与时间－电流振荡曲线,其结果与实验数据相符,表明该类电     

Thermal degradation and microstructure of vinyl copolymers. A mathematical model

A mathematical model is presented for the thermal degradation of monosubstituted vinyl copolymers. The model is based on a relatively simple radical mechanism, proved valid for several polymers including polypropylene, poly(methyl acrylate) and polystyrene. The aim of the modelling is to obtain information about the sequence distribution of the copolymers and about the reactions during decomposition. The theoretical and experimental product distributions can be compared using the method of least squares.     

Effect of polymer as cosolvent on chemical reactions in solution—II. Effects of polyoxyethylene and polystyrene on the reaction of dansyl chloride with primary amino-ended polyoxyethylene in chloroform

The second-order rate constants for the reaction of 5-dimethylamino-1-naphthalenesulphonyl chloride (dansyl chloride) with primary amino-ended polyoxyethylene in chloroform were measured in the presence of polymers such as polyoxyethylene and polystyrene and compared with those in the presence of low molecular weight models, diethoxyethane and toluene respectively. Both polymers exhibit the polymer effect which is characterized by acceleration of the reaction depending on the degree of polymerization of the polymer cosolvent and on the fraction of the cosolvent. The effect by polymer cosolvents on chemical reactions between a low molecular weight species and a polymer is explained generally in terms of the thermodynamics of polymer solutions.     

Spontaneous formation of an exfoliated polystyrene-clay nanocomposite using a star-shaped polymer

Mixtures of five-arm star polystyrene with an organoclay spontaneously formed exfoliated nanocomposites when annealed, validating a recent theoretical prediction by Singh and Balazs (Polym. Int. 2000, 49, 469.). An analogous linear polystyrene sample produced only an intercalated morphology under the same conditions. The nanocomposite morphologies were characterized by X-ray diffraction and transmission electron microscopy. These results suggest a general strategy for forming exfoliated nanocomposites in commodity polymers via melt compounding.     

Rheology of polymers that are initially in the disentangled state

An attempt was made to measure the effects of molecular entanglements on the rheological properties of polymer melts. Two classes of polymers were studied; glassy atactic polystyrene polymers covering a 60-fold range in molecular weight, and semicrystalline high-density polyethylene from two sources covering about a twofold range in molecular weight. The entanglements initially present were removed or greatly reduced in number by freeze drying the polystyrene polymers from dilute solutions below and above C*, the critical overlap concentration, and by slowly crystallizing the polyethylene from very dilute solutions. Since only minor rheological changes were observed with polystyrene, it would appear that the initially isolated coils interpenetrate more rapidly than is indicated by the results of Liu and Morawetz, or that the rheological behavior is rather insensitive to whether the flow obstacles are intermolecular or intramolecular. The enhancement of the viscosity and elasticity observed with polyethylene polymers indicate the importance of the crystallization step on the local melt topology of the polymer chains.     

Chemical reactions and reactivity of primary,secondary, and tertiary diamines with acid functionalized polymers

Reactive melt processing of different types of diamines with polyethylene containing carboxylic acid groups and polystyrene containing anhydride groups was carried out. The reactivity of primary, secondary, and tertiary diamines with these acid polymers was determined using various techniques. Molecular weight increases due to crosslinking were observed through (1) changes in the torque during the reactive processing, (2) decrease in melt flow indices, and (3) decrease in solubility of the reaction products. The chemical compositions of the reaction products were examined by Fourier transform infrared (FTIR) spectroscopy. Thermal analysis using differential scanning calorimetry (DSC) was carried out to determine the crystallization behavior, glass transition temperatures, and thermal stabilities of the reaction products. Results show that the primary amine is the most reactive towards carboxylic acid or anhydride groups followed by the secondary and then the tertiary amine. Anhydride groups on polymers are of higher activity towards secondary or primary amino groups than carboxylic acid groups in the nucleophilic acyl substitution reactions. Reaction products crosslinked with the primary diamine are less stable than their parent acidic polymers. On the other hand, crosslinking with the secondary or tertiary diamine gives products with higher thermal stability than the parent acidic polymers. The formation of reversible and irreversible crosslinks with different types of diamines is also reported. © 1992 John Wiley & Sons, Inc.     

HyperMacs - long chain hyperbranched polymers: A dramatically improved synthesis and qualitative rheological analysis

We have previously reported a novel (albeit modestly successful) strategy for the synthesis of polystyrene HyperMacs - long chain branched analogues of hyperbranched polymers. The building blocks for HyperMacs, AB₂ macromonomers are synthesized by living anionic polymerization and as such are well-defined in terms of molecular weight and polydispersity but the nature of the coupling reaction used to generate the highly branched HyperMacs results in branched polymers with a distribution of molecular weights and architectures. In our previously reported studies the extent of the coupling reaction was significantly hampered by side reactions, however, we report here dramatic improvements to the coupling chemistry which overcome the previously experienced limitations resulting in a fourfold increase in the extent of the coupling reactions. Furthermore we report the effect of the addition of varying amounts of a B₃ core molecule to the coupling reaction and the resultant ‘control’ of the final molecular weight of the HyperMac. Melt rheology showed polystyrene HyperMacs to be thermorheologically simple, obeying William-Landel-Ferry (WLF) behaviour. HyperMacs showed little evidence for relaxation by reptation and when the molecular weight of the macromonomer was ?M_e for polystyrene, HyperMacs resemble unentangled polymers below the gel point, despite being well above the entanglement molecular weight for linear polystyrene. Increasing the molecular weight of the macromonomer to substantially above M_e seems to introduce some entangled nature to the HyperMac as evidenced by the emergence of a near horizontal plateau in G″ - the loss modulus.     

Dynamical and rheological properties of soft colloid suspensions

Soft colloids comprise a wide class of materials, ranging from linear polymers over polymeric assemblies, such as star polymers and dendrimers, to vesicles, capsules, and even cells. Suspensions of such colloids exhibit remarkable responses to imposed flow fields. This is related to their ability to undergo conformational changes and elastic deformations, and the adaptation of their dynamical behavior. The rational design of soft particles for targeted applications or the unraveling of their biological function requires an understanding of the relation between their microscopic properties and their macroscopic response. Here, mesoscale computer simulations provide an invaluable tool to tackle the broad range of length and time scales. In this article, we discuss recent theoretical and simulation results on the rheological behavior of ultrasoft polymeric colloids, vesicles, capsules, and cells. The properties of both, individual particles and semi-dilute suspensions, are addressed.     

Simulating chromatographic separation of topologically different polymers

Chromatography which is sensitive to the sizes of macromolecules and to their adsorption serves as an appropriate method to separate complex polymers. Unfortunately, the molar mass also influences the chromatographic retention, thus making quite difficult the problem of separation of polydisperse polymers by their topology.By using a theory of chromatographic behavior of macromolecules, we simulate chromatograms of polydisperse polymers that differ solely in their topology, and discuss possibilities to separate complex polymers (such as eight-, tadpole-, theta-, manacle-shaped polymers, etc.) from their linear, branched, or macrocyclic precursors or topo-isomeric products.As follows from the simulations, two approaches towards the separation of polydisperse polymers by topology are especially promising. The first one is the chromatography at optimized (critical or near-critical) interaction conditions, where molar-mass effects are minimized; The second one consists in combing different chromatographic modes, which allows obtaining a separation by both molar mass and topology in a 2D chromatogram.Some of the simulated chromatographic separations are qualitatively very similar to the real ones, the others are the theoretical prediction.     

Glass transition temperature of low molecular weight styrene–isoprene block copolymers

Different series of poly(styrene–isoprene) diblock and poly(styrene–isoprene–styrene) triblock copolymers were prepared. In each series, the low molecular weight polystyrene block was kept constant, and the molecular weight of the polyisoprene block varied. The glass transition behavior of these polymers was studied and their glass transition temperatures compared with those of the random copolymers of styrene and isoprene. It is concluded that some low molecular weight styrene-isoprene block copolymers form a single phase. Krause's thermodynamic treatment of phase separation in block copolymers was applied to the data. One arrives at a polystyrene–polyisoprene interaction parameter χ1,2 ≈ 0.1. The experimental and theoretical limitations of this result are discussed.