Uniform polymer in synthetic polymer chemistry

The preparation of uniform polymers and their use in fundamental polymer chemistry are reviewed. A typical method of preparation is a combination of living polymerization and supercritical fluid chromatography separation. Synthetic uniform polymers allow us to solve ambiguous problems in polymer chemistry due to molecular weight distribution and are of significant importance for studies on structure–property relationships. A close inspection of an isotactic uniform chloral oligomer with a symmetrical chemical structure reveals that oligomers are the first examples of stable atropisomers of aldehyde oligomers and that their chiroptical properties are due only to their helical geometries. A molecular-level understanding of the mechanism and stoichiometry of the association process of polymer molecules is possible only with uniform polymers, and stereocomplex formation between isotactic and syndiotactic poly(methyl methacrylate)s in acetone has vigorously been studied by size exclusion chromatography (SEC) and NMR. End-functionalized uniform polymers have enabled us to prepare uniform polymer architectures, such as block, graft, comb, and star polymers. A uniform stereoblock poly(methyl methacrylate) with an isotactic (methyl methacrylate)₄₆-syndiotactic (methyl methacrylate)₄₆ structure shows a single SEC peak in chloroform but three peaks in acetone, which are ascribable to intermolecularly and intramolecularly associated complexes and nonassociated molecules. A three-arm star polymer with one isotactic chain and two syndiotactic chains shows a peculiar SEC behavior in acetone due to a braid type of intramolecular stereocomplex formation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 416–431, 2004     

Compatibilizer-aided toughening in polymer blends consisting of brittle polymer particles dispersed in a ductile polymer matrix

Blending brittle polymer particles in a ductile polymer matrix is a new way to obtain toughened plastics. Although the nylon-6/poly(acrylonitrile-co-styrene) (SAN) system is a ductile/brittle combination, the blend does not result in a toughened plastic. We have investigated the effect of adding a small amount of a third component, poly(styrene-co-maleic anhydride) (SMA), to the nylon/SAN system. SMA significantly improves the tensile and impact strength of the blend. Morphological observations indicate a finer dispersion of the SAN particles when SMA is present in the blend. The improved dispersion is attributed to the formation of nylon-SMA graft copolymer, and infrared analysis supports this supposition. That is, a “compatibilizer” seems to be produced during melt mixing of the ternary system. The role that the compatibilizer plays in improving the stress transfer in the two-phase system and its potential to induce a brittle-ductile transition of the glassy SAN particles are considered to explain the toughening mechanism.     

Liquid-liquid phase equilibria in polymer solutions and polymer mixtures

The pressure dependence of liquid-liquid equilibria in weakly interacting binary macromolecular systems (homopolymer solutions and blends) will be discussed. The common origin of the separate high-temperature/low-temperature and high-pressure/low-pressure branches of demixing curves will be demonstrated by extending the study into the region of metastable liquid states including the undercooled, overheated and stretched states (i.e. states at negative pressures). The seemingly different response of the UCST-branch of solutions and blends when pressurized (pressure induced mixing for most polymer solutions, pressure induced demixing for most blends) will be explained in terms of the location of a hypercritical point found either at positive (most solutions) or negative pressure (most blends). Further, it is shown that the pressure dependence of demixing of homopolymer solutions and blends may be described using a ‘master-curve’ which, however, is sometimes partly masked by degradation or by vapour-liquid and/or solid-liquid phase transitions. Experimental results demonstrating the extension of liquid-liquid phase boundary curves into the metastable regions will be presented, and the existence of solubility islands in the vicinity of the hypercritical points discussed.     

Probing polymer/polymer interfaces

Infrared-visible sum frequency generation spectroscopy (SFG) has been used to study the interface between poly(vinyl-N-octadecylcarbamate-co-vinyl acetate) (Comb) and deuterated or hydrogenated polystyrene (dPS or hPS) films. Strong methyl symmetric and Fermi resonance bands associated with the alkyl side chains of the Comb polymer are observed in the SFG spectra. In addition, for Comb/hPS spectra, symmetric and asymmetric vibration modes of phenyl groups are observed. The presence of asymmetric modes indicates the phenyl rings are tilted with respect to the interface normal.     

Welding dynamics in an atomistic model of an amorphous polymer blend with polymer–polymer interface

We consider an atomistic model of thermal welding at the polymer-polymer interface of a polyetherimide/polycarbonate blend, motivated by applications to 3D manufacturing in space. We follow diffusion of semiflexible chains at the interface and analyze strengthening of the samples as a function of the welding time t_w by simulating the strain–stress and shear viscosity curves. The time scales for initial wetting, and for fast and slow diffusion, are revealed. It is shown that each component of the polymer blend has its own characteristic time of slow diffusion at the interface. Analysis of strain–stress demonstrates saturation of the Young's modulus at t_w = 240 ns, while the tensile strength continues to increase. The shear viscosity is found to have a very weak dependence on the welding time for t_w > 60 ns. It is shown that both strain–stress and shear viscosity curves agree with experimental data.     

聚合物纳米材料研究进展——Ⅰ.纳米聚合物

聚合物纳米材料包括纳米聚合物和聚合物／无机纳米复合材料。本文综述了纳米聚合物的研究进展，重点介绍了分子自组装，微乳液聚合，模板聚合，树枝状聚合物，超支化聚合物，机械粉碎，相反转技术的研究进展。     

Polymer-solvent interaction parameters in polymer solutions at high polymer concentrations

Ion chromatography (IC) is widely used for the compliance monitoring of common inorganic anions in drinking water. However, there has recently been considerable interest in the development of IC methods to meet regulatory requirements for analytes other than common inorganic anions, including disinfection byproduct anions, perchlorate, and haloacetic acids. Many of these new methods require the use of large injection volumes, high capacity columns and analyte specific detection schemes, such as inductively coupled plasma mass spectrometry or postcolumn reaction with UV-Vis detection, in order to meet current regulatory objectives. Electrospray ionization mass spectrometry (ESI-MS) is a detection technique that is particularly suitable for the analysis of permanently ionized or polar, ionizable compounds. The combination of IC with MS detection is emerging as an important tool for the analysis of ionic compounds in drinking water, as it provides increased specificity and sensitivity compared to conductivity detection. This paper reports on the application of IC-ESI-MS for the confirmation and quantitation of environmentally significant contaminants, i.e. compounds with adverse health effects which are either regulated or being considered for regulation, such as bromate, perchlorate, haloacetic acids, and selenium species, in various water samples.     

聚合物纳米材料研究进展——Ⅱ.聚合物/无机纳米复合材料

复合物纳米材料包括纳米聚合物和聚合物／无机纳米复合材料。本文综述了聚合物／无机纳米复合材料的研究进展，重点介绍了溶胶－凝胶法，原位生成法，模板法，插层复合，沉积法，机械粉碎，分子平壤 ，溶液或融混合法的研究进展。     

Analysis in polymer research

Summary The aims of analysis in polymer research are a) to obtain accurate data on the composition of a polymer sample with respect to non-polymer constituents and b) to obtain information on structure and composition of the polymer molecules themselves.Analytical methods directed towards the first aim are discussed only briefly. The emphasis is on the discussion of the more specialized techniques for the analysis of the polymer molecules themselves and a number of these methods are discussed more fully.These methods comprise methods for the determination of molecular weight (ebulliometry, osmometry, viscometry, light scattering, sedimentation) and molecular weight distribution (fractionation, turbidimetry). Information on structural details of polymer molecules can be obtained by spectroscopic techniques and from one of the newer techniques in this field: the analysis of products of pyrolytic decomposition.

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Zusammenfassung Analytische Methoden finden bei der Erforschung von Polymeren Anwendung, um die genaue Zusammensetzung einer Probe in bezug auf nichtpolymere Bestandteile zu erfahren und um die Struktur und Zusammensetzung des Polymerenmoleküls selbst aufzuklären. Die dem erstgenannten Zweck dienenden Verfahren werden nur kurz diskutiert, während die Methoden, die zur Untersuchung des Moleküls selbst benutzt werden, eingehender besprochen werden. Sie umfassen Methoden zur Molekulargewichtsbestimmung (ebullioskopisches Verfahren, Osmometrie, Viscosimetrie, Lichtstreuungsmethode, Sedimentationsmessung) sowie solche zur Bestimmung der Molekulargewichtsverteilung (Fraktionierung, Trübungsmessung). Einzelheiten der Molekülstruktur können durch spektralanalytische Verfahren aufgeklärt werden oder auch mit Hilfe der Analyse der Pyrolyse-Zersetzungsprodukte, einer auf diesem Gebiet noch neueren Methode.

     

Interfaces in polymer blends

We investigate the structure and thermodynamics of interfaces in dense polymer blends using Monte Carlo (MC) simulations and self‐consistent field (SCF) calculations. For structurally symmetric blends we find quantitative agreement between the MC simulations and the SCF calculations for excess quantities of the interface (e.g., interfacial tension or enrichment of copolymers at the interface). However, a quantitative comparison between profiles across the interface in the MC simulations and the SCF calculations has to take due account of capillary waves. While the profiles in the SCF calculations correspond to intrinsic profiles of a perfectly flat interface the local interfacial position fluctuates in the MC simulations. We test this concept by extensive Monte Carlo simulations and study the cross‐over between “intrinsic” fluctuations which build up the local profile and capillary waves on long (lateral) length scales. Properties of structurally asymmetric blends are exemplified by investigating polymers of different stiffness. At high incompatibilities the interfacial width is not much larger than the persistence length of the stiffer component. In this limit we find deviations from the predictions of the Gaussian chain model: while the Gaussian chain model yields an increase of the interfacial width upon increasing the persistence length, no such increase is found in the MC simulations. Using a partial enumeration technique, however, we can account for the details of the chain architecture on all length scales in the SCF calculations and achieve good agreement with the MC simulations. In blends containing diblock copolymers we investigate the enrichment of copolymers at the interface and the concomitant reduction of the interfacial tension. At weak segregation the addition of copolymers leads to compatibilization. At high incompatibilities, the homopolymer‐rich phase can accommodate only a small fraction of copolymer before the copolymer forms a lamellar phase. The analysis of interfacial fluctuations yields an estimate for the bending rigidity of the interface. The latter quantity is important for the formation of a polymeric microemulsion at intermediate segregation and the consequences for the phase diagram are discussed.     

Nanostructures in polymer systems

General concepts concerning the formation, structure, and some properties of nanosized structural elements in polymers and polymeric materials are summarized from the standpoint of feasibility of formation of nanoparticles and nanoreactors in such systems and practical use of advantages offered by these structures. The familiar concepts are complemented with the results obtained recently. Examples are given to illustrate the implementation of elements of nanotechnology based on the principles of creation of nanostructures in amorphous and crystalline polymers, copolymers, and molecular composites. Practicable methods for the preparation of polymeric nanostructures by controlled crystallization, microphase and nanophase separation of components, and their dispersion, as well as the formation of interfaces, are discussed.     

聚合物纳米材料研究进展

聚合物纳米材料包括纳米聚合物和聚合物/无机纳米复合材料.本文综述了纳米聚合物的研究进展,重点介绍了分子自组装,微乳液聚合,模板聚合,树枝状聚合物,超支化聚合物,机械粉碎,相反转技术的研究进展.     

Polarography in polymer science

A review of polarography in polymer science is presented.     

Imperfections in polymer crystals

Summary The crystal-defect model of polymer structure is briefly reviewed along with the evidence for the existence, mobility and generation of dislocations. Starting with the hypothesis that a completely crystallizable homopolymer crystallizes one molecule at a time, it is shown that crystallization at temperatures well below the melting point should result in folded-chain crystals. Such crystals represent metastable equilibrium states which can increase their stability by rejecting or excluding the low molecular weight species. The amount of molecular species segregation which occurs is determined by the kinetics of crystallization and thus kinetics controls which metastable state (i. e. fold-period) occurs under a given set of crystallization conditions. As the annealing temperature is increased both molecular species segregation and molecular fold-period increase. If these processes could go to completion the equilibrium crystal at the melting temperature would be the completely segregated, completely extended-chain molecular crystal. In any practical case molecular species segregation is in complete so that the partial melted or unpeeled model represents the crystal which exists in equilibrium with the melt.

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Zusammenfassung Das Kristalldefektmodell polymerer Struktur wird kurz hinsichtlich der Evidenz des Auftretens, der Beweglichkeit und Erzeugung der Dislokationen dargestellt. Ausgehend von der Hypothese, daß vollkommen kristallisierbare Homopolymere kristallisieren, jeweils Molekül für Molekül, wird gezeigt, daß Kristallisation bei Temperaturen weit genug unter dem Schmelzpunkt zu kettengefalteten Kristallen führen sollte. Solche Kristalle repräsentieren metastabile Gleichgewichtszustände, die ihre Stabilität durch Ausscheiden oder Ausschließen von Molekülen niedrigen Molekulargewichts erhöhen können. Der Betrag der Molekulargewichtstrennung, der stattfindet, wird durch die Kinetik der Kristallisation bestimmt, und so kontrolliert die Kinetik, welche metastabilen Zustände, z. B. welche Faltungslänge bei einer gegebenen Zahl von Kristallisationsbedingungen auftritt. Wenn die Temperungstemperatur erhöht wird, steigt beides, die Entmischung und die Faltungsperiode. Wenn die Prozesse vollkommen ablaufen könnten, würde der Gleichgewichtskristall bei der Schmelztemperatur vollkommen entmischt sein und den vollkommen gestreckten molaren Kettenkristall bilden. In praktischen Fällen ist Entmischung unvollständig, so daß das teilweise geschmolzene oder gestörte Modell den Kristall repräsentiert, der im Gleichgewicht mit der Schmelze existiert.

     

Universality in polymer viscoelasticity

This paper brings together seven aspects of universality in viscoelasticity of linear flexible polymers: (1) the stress relaxation modulus G(t) being a universal function of the normalized molecular weight (MW), M/M_e; (2) the MW dependence of the zero shear viscosity; (3) the MW dependence of the steady state compliance; (4) the MW dependence of the diffusion constant; (5) the damping functions; (6) slip-stick melt fracture being a universal phenomenon; and (7) the number of entanglement strands per cubed entanglement distance being a universal constant. As presented in the text, the consistency, agreement and relation among these different aspects of universality can be properly brought to light.     

Polymer-polymer interaction parameters in solvent/polymer/polymer ternary systems

Empirical equations defining the relationships between b₂₃ and χ₂₃ interaction parameters for the ternary systems toluene (1)/poly(dimethylsiloxane), PDMS, (2)/polystyrene, PS, (3) and benzene (1)/PDMS(2)/PS(3) have been determined. The dependences of both interaction parameters on the mean molecular weights of the macromolecular components have also been studied. A single dependence of b₂₃ (or χ₂₃) upon the mean molecular weight is found when both polymeric components have intermediate to high molecular weights. However, that single dependence is not found when the molecular size of polymer (2) is low.     

Switching of the helical polymer conformation in a solid polymer film

A chiral photochromic polyisocyanate was incorporated into a solid polymer matrix of poly(methyl methacrylate) (PMMA), yielding an isotropic polymer film. Isomerization of the chiral photochromic azo side groups (cis‐trans) triggers a reversible conformational change of the helical polyisocyanate backbone. Thus the chirooptical properties of the film can be switched photochemically. The isomerization of the helix is much slower than the isomerization of the azo side groups. Below T_g , the photochemically modified helix conformation is thus stable, despite thermal relaxation of the azo chromophores.     

Thermal transitions and polymer/polymer miscibility

Poly(vinyl chloride) was blended with ethylene-vinyl acetate copolymer containing 70 wt% of vinyl acetate. The system shows a single glass transition temperature for all compositions, indicating their miscibility. TheT _g vs. composition curves display an inflection, which changes with the chemical environment of the initial solution. The best fit to the shape of the curve was well reproduced by the Kovacs-Braun equation. The T _g values reveal local heterogeneity, which means no total miscibility at a molecular level. Negative values of the Flory-Huggins interaction parameter were obtained from the calorimetric data.Support for this research by CNP_q, FINEP and CAPES is appreciated.