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Showing papers on "Polymer published in 1997"


Book
01 Jan 1997
TL;DR: In this article, the properties of conjugated polymers and their properties were investigated at submicron scale with a scanning force microscope magnetic properties of conducting polymers Optically Detected Magnetic Resonance (ODMR).
Abstract: Vol 1: From electron acceptor molecules to photoinduced intramolecular electron transfer systems perylene based conductors tetrachalcogenafulvalenes, metal 1,2-dichalcogenolenes and their conductive salts conductive hetero-TCNQs molecular metals and superconductors based on transition metal complexes conductivity and superconductivity in doped fullerenes electrochemistry of fullerenes photophysics, charge separation and associated device applications of conjugated polymer/fullerene composites photoconductivity in fullerenes organic photoconductive materials for xenographic photoreceptors photoconductive polymers graphite intercalation compounds electrically conductive metallophthalocyanines electrically conductive Langmuir-Blogett films magnetism of stable organic radical crystals. Vol 2: Polyacetylene electrically conductive polyacetylene copolymers perconjugated organic polymer - early synthesis attempts and applications electrochemical synthesis of polyheterocycles and their applications (-conductive polymers prepared by organometallic polycondensation poly(p-phenylenes) - preparation techniques and general properties synthesis and properties of processable polythiophenes molecular conductive materials - from polythiophenes to oligothiophenes charge-state incorporation in bis-thienyl polyenes and thienylene polyenylene oligomers and polymers polypyrroles - from basic research to technological applications polythiophene and polypyrrole copolymers polyanilines electrically conductive polytoluidines silicon containing thiophene monomers, oligomers and polymers - synthesis, characterization and properties silicon and germanium containing conductive polymers polyazines - synthesis, structure, spectroscopy and conducting properties conductive metallophthalocyanine polymers conductive polymer blends and composites organometallic conductive polymers self-doped conductive polymers. Vol 3: Crystallography of conductive polymers the structure of polythiophenes photoelectron spectroscopy of conductive polymers spectroelectrochemistry and spectroscopy of conducting polymers structural investigation of soluble conjugated polymers and modification of their structure at submicron scale with a scanning force microscope magnetic properties of conducting polymers Optically Detected Magnetic Resonance (ODMR) Studies of conjugated polymer films, LEDs, and fullerenes microwave properties of conductives polymers electrochemistry of conjugated polymers electrocatalytic properties of conductive polymers due to dispersion physical and spectroscopic properties of polypyrrole films containing transition metal complexes as counteranions thin film properties of oligothiophenes electrochroism in polyanilines thermochromism and solvatochromism in polythiophenes degradation and stability of conductive polymers. Vol 4: Transport in conducting polymers electronic structure of (conjugated polymers). (Part contents)

2,272 citations


Journal ArticleDOI
28 Nov 1997-Science
TL;DR: 2-ureido-4-pyrimidone that dimerize strongly in a self-complementary array of four cooperative hydrogen bonds were used as the associating end group in reversible self-assembling polymer systems.
Abstract: Units of 2-ureido-4-pyrimidone that dimerize strongly in a self-complementary array of four cooperative hydrogen bonds were used as the associating end group in reversible self-assembling polymer systems. The unidirectional design of the binding sites prevents uncontrolled multidirectional association or gelation. Linear polymers and reversible networks were formed from monomers with two and three binding sites, respectively. The thermal and environmental control over lifetime and bond strength makes many properties, such as viscosity, chain length, and composition, tunable in a way not accessible to traditional polymers. Hence, polymer networks with thermodynamically controlled architectures can be formed, for use in, for example, coatings and hot melts, where a reversible, strongly temperature-dependent rheology is highly advantageous.

2,011 citations


Journal ArticleDOI
28 Aug 1997-Nature
TL;DR: The synthesis of a thermosensitive, biodegradable hydrogel consisting of blocks of poly(ethylene oxide) and poly(L-lactic acid) and aqueous solutions of these copolymers exhibit temperature-dependent reversible gel–sol transitions.
Abstract: Polymers that display a physicochemical response to stimuli are widely explored as potential drug-delivery systems. Stimuli studied to date include chemical substances and changes in temperature, pH and electric field. Homopolymers or copolymers of N-isopropylacrylamide and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (known as poloxamers) are typical examples of thermosensitive polymers, but their use in drug delivery is problematic because they are toxic and non-biodegradable. Biodegradable polymers used for drug delivery to date have mostly been in the form of injectable microspheres or implant systems, which require complicated fabrication processes using organic solvents. Such systems have the disadvantage that the use of organic solvents can cause denaturation when protein drugs are to be encapsulated. Furthermore, the solid form requires surgical insertion, which often results in tissue irritation and damage. Here we report the synthesis of a thermosensitive, biodegradable hydrogel consisting of blocks of poly(ethylene oxide) and poly(L-lactic acid). Aqueous solutions of these copolymers exhibit temperature-dependent reversible gel-sol transitions. The hydrogel can be loaded with bioactive molecules in an aqueous phase at an elevated temperature (around 45 degrees C), where they form a sol. In this form, the polymer is injectable. On subcutaneous injection and subsequent rapid cooling to body temperature, the loaded copolymer forms a gel that can act as a sustained-release matrix for drugs.

1,930 citations


Journal ArticleDOI
TL;DR: In this paper, the authors derived the stability requirements on electrode potentials of n-type doped conducting polymers and compared the predictions with experimental data on stability of polymers, and showed that an electrode potential of about 0 to + 0.5 V (SCE) is required for stable polymers.

1,349 citations


Journal ArticleDOI
07 Mar 1997-Science
TL;DR: In this article, a simple technique for precisely controlling the interfacial energies and wetting behavior of polymers in contact with solid surfaces is described, where end-functionalized statistical random copolymers of styrene and methylmethacrylate are synthesized, with the styrene fraction f varying from 0 to 1, and were end-grafted onto silicon substrates to create random polymers about 5 nanometers thick.
Abstract: A simple technique for precisely controlling the interfacial energies and wetting behavior of polymers in contact with solid surfaces is described. End-functionalized statistical random copolymers of styrene and methylmethacrylate were synthesized, with the styrene fraction f varying from 0 to 1, and were end-grafted onto silicon substrates to create random copolymer brushes about 5 nanometers thick. For f < 0.7, polystyrene (PS) films (20 nanometers thick) rapidly dewet from the brushes when heated well above the glass transition temperature. The contact angle of the resulting polymer droplets increased monotonically with decreasing f . Similar behavior was observed for poly(methylmethacrylate) (PMMA) films but with an opposite dependence on f . The interfacial energies of the random copolymer brushes with PS and PMMA were equal when f was about 0.6. Thus, precise control of the relative surface affinities of PS and PMMA was possible, demonstrating a way to manipulate polymer-surface interactions.

1,293 citations


Journal ArticleDOI
TL;DR: In this paper, the effect of silicate functionalization, anneal temperature, polymer molecular weight, and constituent interactions on polymer melt intercalation of a variety of styrene-derivative polymers in alkylammonium-functionalized silicates is examined.
Abstract: The effect of silicate functionalization, anneal temperature, polymer molecular weight, and constituent interactions on polymer melt intercalation of a variety of styrene-derivative polymers in alkylammonium-functionalized silicates is examined. Hybrid formation requires an optimal interlayer structure for the organically-modified layered silicate (OLS), with respect to the number per host area and size of the alkylammonium chains, as well as the presence of polar interactions between the OLS and polymer. From these observations and the qualitative predictions of the mean-field lattice-based model of polymer melt intercalation (preceding paper in this issue), general guidelines may be established for selecting potentially compatible polymer−OLS systems. The interlayer structure of the OLS should be optimized to maximize the configurational freedom of the functionalizing chains upon layer separation while maximizing potential interaction sites with the surface. The most successful polymers for intercalatio...

976 citations


Book
01 Jan 1997
TL;DR: Inverse emulsion and microemulsion polymerization (F. El-Aasser and E. Sudol) as mentioned in this paper, the formation and properties of Latex Films are discussed.
Abstract: Partial table of contents: BASIC SCIENCE. Free--Radical Polymerization (P. Lovell). Features of Emulsion Polymerization (M. El--Aasser & E. Sudol). Stabilization of Polymer Colloid Dispersions (R. Ottewill). THEORY. Harkins, Smith--Ewart and Related Theories (A. Dunn). Modelling Rates, Particle Size Distributions and Molar Mass Distributions (R. Gilbert). PRACTICE. Formulation Components (A. Klein & E. Daniels). Batch and Semi--batch Processes (P. Lovell). Control of Particle Morphology (V. Dimonie, et al.). Process Modelling and Control (F. Schork). Latex Polymer Characterization (A. German, et al.). The Formation and Properties of Latex Films (M. Winnik). MAJOR INDUSTRIAL USES. Diene--based Synthetic Rubbers (D. Blackley). Vinyl Acetate Polymerization (G. Vandezande, et al.). RELATED HETEROGENEOUS POLYMERIZATION. Miniemulsion Polymerization (E. Sudol & M. El--Aasser). Inverse Emulsion and Microemulsion Polymerization (F. Candau). Indexes.

878 citations


Journal ArticleDOI
TL;DR: Polydimethylsiloxane (PDMS) is a commercially available physically and chemically stable silicone rubber as mentioned in this paper, which has a unique flexibility with a shear elastic modulus due to one of the lowest glass transition temperatures of any polymer.
Abstract: Polydimethylsiloxane (PDMS) is a commercially available physically and chemically stable silicone rubber. It has a unique flexibility with a shear elastic modulus due to one of the lowest glass transition temperatures of any polymer . Further properties of PDMS are a low change in the shear elastic modulus versus temperature , virtually no change in G versus frequency and a high compressibility. Because of its clean room processability, its low curing temperature, its high flexibility, the possibility to change its functional groups and the very low drift of its properties with time and temperature, PDMS is very well suited for micromachined mechanical and chemical sensors, such as accelerometers (as the spring material) and ISFETs (as the ion selective membrane). It can also be used as an adhesive in wafer bonding, as a cover material in tactile sensors and as the mechanical decoupling zone in sensor packagings.

868 citations


Journal ArticleDOI
TL;DR: In this paper, the authors used FTIR spectroscopy measurements to confirm a high level of hydrogen bonding between polyaniline and the nonionic polymer in the multilayer films.
Abstract: The molecular-level layer-by-layer processing of polyaniline with a variety of different nonionic water soluble polymers has been demonstrated. This new type of layer-by-layer adsorption process is driven by hydrogen-bonding interactions and has been accomplished with poly(vinylpyrrolidone), poly(vinyl alcohol), poly(acrylamide), and poly(ethylene oxide). FTIR spectroscopy measurements confirm a high level of hydrogen bonding between polyaniline and the nonionic polymer in the multilayer films. The effects of solution pH and polymer molecular weight on the deposition process were investigated. Comparisons with polyaniline films assembled via an electrostatic mechanism with sulfonated polystyrene indicate that the nonionic polymers adsorb onto polyaniline with a greater density of loops and tails and form highly interpenetrated bilayers with a high polyaniline content. The conductivities of these self-assembled multilayer films were found to be on the order of 1−4 S/cm for films doped with methane sulfonic...

855 citations


Journal ArticleDOI
TL;DR: At the concentrations studied, these polymers interact electrostatically with DNA forming a unit structure with toroidal morphology; the extent of aggregation of the unit structures in solution depends upon the characteristics of the individual polymer.
Abstract: Four cationic polymers used to deliver DNA into cultured cells: polylysine, intact polyamidoamine dendrimer, fractured polyamidoamine dendrimer and polyethylenimine, are examined for their ability to interact with DNA. Complexes between the polymers and DNA were examined using electron microscopy. Similar toroidal structures with diameters of 55 +/- 12 nm were formed from all of the cationic polymers with DNA. The DNA complexes of the fractured dendrimer and polyethylenimine were observed as single, distinct units; their apparent diameters in solution as measured by dynamic light scattering ranged from 90 to 130 nm. The DNA complexes of polylysine and intact dendrimer generally appeared as clusters in electron micrographs; their diameters in solution were larger than 1000 nm, which suggests that their toroidal complexes aggregate in solution. The cationic polymers bind to DNA in a stoichiometry that is nearly 1:1 in primary amines to DNA phosphates. The apparent binding of all cationic polymers to DNA decreases linearly with increasing ionic strength, up to 0.8 M NaCl. Thus, at the concentrations studied, these polymers interact electrostatically with DNA forming a unit structure with toroidal morphology; the extent of aggregation of the unit structures in solution depends upon the characteristics of the individual polymer.

803 citations


Journal ArticleDOI
TL;DR: In this article, the synthesis and metal ion responsive properties of two 2,2‘-bipyridyl-phenylene-vinylene-based polymers are reported.
Abstract: The synthesis and metal ion responsive properties of two 2,2‘-bipyridyl-phenylene-vinylene-based polymers is reported. These polymers are designed to be partially conjugated in their metal-free state and fully conjugated when exposed to metal ions so that the ion-induced conjugation enhancement can be transduced into a measurable signal. It is found that these polymers exhibit highly ionochromic effects with a wide variety of transition and main group metal ions excluding metal ions of the alkali and alkaline earth groups. For instance, both absorption and fluorescence emission bands of the polymers upon exposure to metal ions can be red-shifted up to 120 nm, depending on the metal ions present and the polymers used.

Journal ArticleDOI
TL;DR: In this paper, a UV laser photoablation method for the production of miniaturized liquid-handling systems on polymer substrate chips was described. But the method was used for producing channels in polystyrene, polycarbonate, cellulose acetate, and poly(ethylene terephthalate).
Abstract: This report describes a UV laser photoablation method for the production of miniaturized liquid-handling systems on polymer substrate chips. The fabrication of fluid channel and reservoir networks is accomplished by firing 200 mJ pulses from an UV excimer laser at substrates moving in predefined computer-controlled patterns. This method was used for producing channels in polystyrene, polycarbonate, cellulose acetate, and poly(ethylene terephthalate). Efficient sealing of the resulting photoablated polymer channels was accomplished using a low-cost film lamination technique. After fabrication, the ablated structures were observed to be well defined, i.e., possessing high aspect ratios, as seen by light, scanning electron, and atomic force microscopy. Relative to the original polymer samples, photoablated surfaces showed an increase in their hydrophilicity and rugosity as a group, yet differences were noted between the polymers studied. These surface characteristics demonstrate the capability of generating electroosmotic flow in the cathodic direction, which is characterized here as a function of applied electric field, pH, and ionic strength of common electrophoretic buffer systems. These results show a correlation between the ablative changes in surface conditions and the resulting electroosmotic flow. The effect of protein coatings on ablated surfaces is also demonstrated to significantly dampen the electroosmotic flow for all polymers. All of these results are discussed in terms of developing liquid-handling capability, which is an essential part of many μ-TAS and chemical diagnostic systems.

Journal ArticleDOI
TL;DR: In this article, the preparation of lignocellulosic composites by reactive extrusion processing in which good interfacial adhesion is generated by a combination of fiber modification and matrix modification methods is discussed.
Abstract: Biofibers, natural lignocellulosics, have an outstanding potential as a reinforcement in thermoplastics. This study deals with the preparation of lignocellulosic composites by reactive extrusion processing in which good interfacial adhesion is generated by a combination of fiber modification and matrix modification methods. PP matrix was modified by reacting with maleic anhydride and subsequently bonded to the surface of the modified lignocellulosic component, in-situ. The fiber surface was modified by reacting it with a silane in a simple and quick aqueous reaction system, similar to that employed for glass fibers. The modified fibers are then extruded with the modified polymer matrix to form the compatibilized composite. The various reactions between the lignocellulosic fiber/filler and modified polymer chains, is expected to improve the interfacial adhesion significantly as opposed to simple mixing of the two components, since new covalent bonds between the fiber surface and matrix are created in the former case. These composite blends were then injection molded for mechanical characterization. Typical mechanical tests on strength, toughness and Izod impact energy were performed and the results are reported. These findings are discussed in view of the improved adhesion resulting from reactions and enhanced polar interactions at phase boundaries.

Journal ArticleDOI
TL;DR: Water soluble polymers with pendant hydrophobic substituents associate in water to form extended structures as mentioned in this paper, which have important applications in technologies ranging from paints and paper coatings (as rheology modifiers) to DNA sequencing (where the network structure serves as a sieving medium).
Abstract: Water soluble polymers with pendant hydrophobic substituents associate in water to form extended structures. Solutions of the polymers have important applications in technologies ranging from paints and paper coatings (as rheology modifiers) to DNA sequencing (where the network structure serves as a sieving medium). Recent experiments are beginning to reveal the nature of the structures formed and their response to shear. Many facets of the behavior of these polymers are under active investigation.

Journal ArticleDOI
TL;DR: In this article, the anodes were doped with a variety of polymer and monomer-based acids and cast from either water or organic solvents to determine the effect of the dopant and solvent on the hole-injection properties.
Abstract: We have studied polyaniline and polyethylenedioxythiophene transparent electrodes for use as hole-injecting anodes in polymer light emitting diodes. The anodes were doped with a variety of polymer and monomer-based acids and cast from either water or organic solvents to determine the effect of the dopant and solvent on the hole-injection properties. We find that the anodes with polymeric dopants have improved device quantum efficiency and brightness relative to those with small molecule dopants, independent of conductivity, solvent, or type of conducting polymer. For the most conducting polymer anodes [σ>2(Ωcm)−1], diodes could be made without an indium tin oxide underlayer. These diodes show substantially slower degradation.

Journal ArticleDOI
TL;DR: In this article, the thermal stability, mechanical strength, conductivity, electrochemical stability window, and Li/electrolyte interface stability of poly(vinylidene fluoride)−hexafluoropropene (PVdF−HFP) copolymer plasticized with a solution of LiSO3CF3, LiN(SO2CF3)2, or LiPF6 in oligomeric poly(ethylene glycol) dimethyl ethers (PEGDME, Mw = 250, 400, and 500).
Abstract: Polymer electrolyte membranes comprising poly(vinylidene fluoride)−hexafluoropropene (PVdF−HFP) copolymer plasticized with a solution of LiSO3CF3, LiN(SO2CF3)2, or LiPF6 in oligomeric poly(ethylene glycol) dimethyl ethers (PEGDME, Mw = 250, 400, and 500) were prepared by hot-melt-rolling or solvent-casting techniques. Since the electrolytes containing PEGDME400 and PEGDME500 are “dry” with essentially no volatile components up to 150 °C, we have dubbed them PEO-like. Their thermal stability, mechanical strength, conductivity, electrochemical stability window, and Li/electrolyte interface stability were characterized. Plasticizing PVdF−HFP with the PEGDME/LiX solutions disordered the polymer structure leading to polymer electrolytes having lower crystallinity than the polymer host itself. The mechanical strength of the electrolyte membranes varied depending on the PVdF content. Tensile strength (stress) as high as 420 psi at an elongation-at-break value (strain) of 75% was observed. The conductivities of t...

Patent
01 May 1997
TL;DR: In this article, a method for forming polymer/drug microparticles comprising the steps of (1) forming a polymer solution/drug mixture comprising a polymer dissolved in an organic solvent and a suspended labile drug; (2) removing the solvent from the polymer solution and drug mixture, and (3) fragmenting the polymer and drug matrix at a temperature below the glass transition temperature of the polymeric matrix.
Abstract: A method for forming polymer/drug microparticles comprising the steps of (1) forming a polymer solution/drug mixture comprising a polymer dissolved in an organic solvent and a suspended labile drug; (2) removing the solvent from the polymer solution/drug mixture, thereby forming a solid polymer/drug matrix; and (3) fragmenting the polymer/drug matrix at a temperature below the glass transition temperature of the polymer/drug matrix, thereby forming polymer/drug matrix microparticles. In one embodiment, the solvent is removed from a polymer solution/drug mixture by freezing the polymer solution/drug mixture and extracting the solvent from the resulting solid polymer solution/drug matrix. The polymer can be a biocompatible polymer, such as poly(lactic acid-co-glycolic acid). The drug can be a labile drug, such as a protein, or a polynucleotide. Another embodiment of the present invention includes the polymer/drug matrix microparticles which are formed by the method outlined above. A further embodiment of the present invention includes a method for producing an implantable polymer/drug matrix mass, comprising the steps of (1) forming a polymer solution/drug mixture comprising a polymer dissolved in an organic solvent and a suspended labile drug; (2) removing the solvent from the polymer solution/drug mixture, thereby forming a solid polymer/drug matrix; and (3) mechanically compressing the polymer/drug matrix, thereby forming an implantable polymer/drug matrix mass.

Journal ArticleDOI
Igal Szleifer1
TL;DR: In this article, a general theoretical framework for studying the adsorption of protein molecules on surfaces with grafted polymers is presented, where the potentials of mean force of the protein with the surface are calculated as a function of polymer surface coverage and amount of protein adsorbed.

Journal ArticleDOI
TL;DR: In this paper, a new approach for the fabrication of a multilayer film assembly is explored, which is based on the alternating assembling of poly(4-vinylpyridine) and poly(acrylic acid) via hydrogen bonding.
Abstract: A new approach for the fabrication of a multilayer film assembly is explored, which is based on the alternating assembling of poly(4-vinylpyridine) and poly(acrylic acid) via hydrogen bonding. The homogeneous multilayer films were characterized by UV-Vis, X-ray diffraction and atomic force microscopy (AFM) measurements. The nature of interaction between the two polymers is identified as hydrogen bonding by IR spectroscopy.

Book ChapterDOI
01 Jan 1997
TL;DR: In this article, the effect and influence of the ligands can more and more be predicted and understood by molecular modeling and other calculations, and it is possible to tailor the microstructure of polymers by changing the ligand structure of the metallocene.
Abstract: Metallocenes are very versatile catalysts for the production of polyolefins, polystyrene and copolymers. Some polymers such as syndiotactic polypropene, syndiotactic polystyrene, cycloolefin copolymers, optically active oligomers, and polymethylenecycloalkenes can be produced only by metallocene catalysts. It is possible to tailor the microstructure of polymers by changing the ligand structure of the metallocene. The effect and influence of the ligands can more and more be predicted and understood by molecular modeling and other calculations.

Journal ArticleDOI
TL;DR: In this article, the hydrogen bonding in hard and soft segments was examined for the extent of phase separation, and the microstructure was evidenced by differential scanning calorimetry (DSC).
Abstract: Three types of amine-containing polyurethanes and poly(urethane−ureas), N-methyldiethanolamine (MDEA) and/or tetraethylenepentamine (TEPA) as the chain extender and poly(ethylene glycol) of MW 400 as the soft-segment component, have been studied by FTIR. The hydrogen bonding in hard and soft segments was examined for the extent of phase separation, and the microstructure was evidenced by differential scanning calorimetry (DSC). The temperature effects on the hydrogen bonding were also investigated. They show a significant amount of hydrogen bonding between the hard and soft segments. It indicates that there exists a large amount of partial phase mixing of hard and soft segments compared to the conventional polyurethanes. The bulky CH3 groups of MDEA in hard segments restrict the hydrogen bonding within the hard segments, while the TEPA-containing urethane−urea polymers have more distinct phase separation. However, all of the polymers studied are amorphous materials such that the dissolved soft segments in...

Journal ArticleDOI
TL;DR: In this article, a β-cyclodextrin crosslinked with epichlorohydrin was used for the preparation of high molecular weight water soluble polymers, and the influence of preparation conditions on the molecular weight distribution has been investigated.

Journal ArticleDOI
TL;DR: In this paper, multilayer thin films comprised of sequentially adsorbed layers of partially doped polyaniline and a polyanion, sulfonated polystyrene, were fabricated via the use of a simple layer-by-layer molecular-level processing scheme.
Abstract: Multilayer thin films comprised of sequentially adsorbed layers of partially doped polyaniline and a polyanion, sulfonated polystyrene, were fabricated via the use of a simple layer-by-layer molecular-level processing scheme. Using this simple multilayer polymer adsorption process, uniform thin films of polyaniline in the 40−600 A thickness range were readily fabricated onto a variety of different substrates. Doping of these films with strong acids such as HCl and methane sulfonic acid results in electrically conductive thin films with conductivities comparable to those obtained with spin cast films (0.5−1.0 S/cm). The adsorption process used to fabricate the films was found to be driven primarily by the electrostatic attractions developed between the partially doped chains of polyaniline (polycation) and the negatively charged chains of the polyanion.

Journal ArticleDOI
TL;DR: In this article, the pyrolysis kinetics of polyethylene, polypropylene, polystyrene, and polyamide were investigated at temperatures below 450 C using isothermal thermogravimetric analysis (TGA) experiments.
Abstract: The pyrolysis kinetics of low-density polyethylene, high-density polyethylene, polypropylene, and polystyrene has been studied at temperatures below 450 C. In addition, a literature review on the low-temperature pyrolysis of these polymers has been conducted and has revealed that the scatter in the reported kinetic data is significant, which is most probably due to the use of simple first-order kinetic models to interpret the experimental data. This model type is only applicable in a small conversion range, but was used by many authors over a much wider conversion range. In this investigation the pyrolysis kinetics of the forementioned polymers and a mixture of polymers has been studied at temperatures below 450 C by performing isothermal thermogravimetric analysis (TGA) experiments. The TGA experimental data was used to determine the kinetic parameters on the basis of a simple first-order model for high conversions (70-90%) and a model developed in the present study, termed the random chain dissociation (RCD) model, for the entire conversion range. The influence of important parameters, such as molecular weight, extent of branching and -scission on the pyrolysis kinetics was studied with the RCD model. This model was also used to calculate the primary product spectrum of the pyrolysis process. The effect of the extent of branching and the initial molecular weight on the pyrolysis process was also studied experimentally. The effect of the extent of branching was found to be quite significant, but the effect of the initial molecular weight was minor. These results were found to agree quite well with the predictions obtained from the RCD model. Finally, the behavior of mixtures of the aforementioned polymers was studied and it was found that the pyrolysis kinetics of the polymers in the mixture remains unaltered in comparison with the pyrolysis kinetics of the pure polymers.

Journal ArticleDOI
TL;DR: In this paper, a new class of layered, microcrystalline polymers from a simple hydrolytic polycondensation of n-alkyltrichlorosilanes in water is demonstrated.
Abstract: Formation of a new class of layered, microcrystalline polymers from a simple hydrolytic polycondensation of n-alkyltrichlorosilanes in water is demonstrated. The structure of the polymeric condensate, determined from a combination of spectroscopic, diffraction, and thermal analysis techniques, consists of highly uniform, pillared microcrystallites in which the inorganic siloxy backbones are present in periodic layers, each containing a monomolecular layer of intercalated water, separated by crystalline assemblies of alkyl chains. The alkyl-chain organization shows a remarkable resemblance to that in highly organized, self-assembled monolayers formed from the precursor silane molecules on hydrophilic substrates and this parallel lends support to the critical importance of water in monolayer self-assembly of silanes.

Journal ArticleDOI
TL;DR: In this paper, the authors consider that even without specific, indications thereof, they are not to be considered unprotected by law and propose a solution to the problem of "right-to-information".
Abstract: Registered names. trademarks. etc. used in this journal. even without specific, indications thereof, are not to be considered unprotected by law. Printed in the Federal Republic of Germany

Book
01 Jan 1997
TL;DR: In this article, the authors present an approach for non-chain polymerization based on Chemical Structure Chain Polymerization and Non-Chain Polymer Hydrodynamics (CSH).
Abstract: Introduction CHEMISTRY Chemical Structure Chain Polymerizations Non-Chain Polymerizations PHYSICAL CHEMISTRY Molecule Size and Shape Solution Thermodynamics Polymer Hydrodynamics PHYSICS Polymer Assemblies Transitions and Relaxations Solid State Properties TECHNOLOGY Auxiliaries Elastomers Fibers Plastics Appendix

Patent
24 Jan 1997
TL;DR: In this paper, the metal oxides can be provided in the form of a fine dispersion of particles on the surface of a polymer that coats or forms the devices, which enhances the ability of the devices to bind to mucosal membranes.
Abstract: Methods and compositions are provided for enhancing the bioadhesive properties of polymers used in drug delivery devices. The bioadhesive properties of a polymer are enhanced by incorporating a metal compound into the polymer to enhance the ability of the polymer to adhere to a tissue surface such as a mucosal membrane. Metal compounds which enhance the bioadhesive properties of a polymer include water-insoluble metal compounds such as water-insoluble metal oxides, including oxides of calcium, iron, copper and zinc. The metal compounds can be incorporated within a wide range of polymers including proteins, polysaccharides and synthetic biocompatible polymers. In one embodiment, metal oxides can be incorporated within polymers used to form or coat drug delivery devices, such as microspheres, which contain a drug or diagnostic agent. The metal oxides can be provided in the form of a fine dispersion of particles on the surface of a polymer that coats or forms the devices, which enhances the ability of the devices to bind to mucosal membranes. The polymers, for example in the form of microspheres, have improved ability to adhere to mucosal membranes, and thus can be used to deliver a drug or diagnostic agent via any of a range of mucosal membrane surfaces including those of the gastrointestinal, respiratory, excretory and reproductive tracts.

Journal ArticleDOI
TL;DR: In this paper, the authors review previous work on adsorption of various ionic and non-ionic surfactants, polymers and their mixtures and mechanisms involved, in aqueous and nonaqueous media.

Journal ArticleDOI
TL;DR: Data demonstrate directly that the biological activity of PEG is not due solely to properties of simple polymers such as the excluded volume, but is also coupled to the competitive interactions between solvent and other materials such as proteins for the chain segments and to the ability of this material to adopt higher order intrachain structures.
Abstract: The surface force apparatus was used to measure directly the molecular forces between streptavidin and lipid bilayers displaying grafted Mr 2,000 poly(ethylene glycol) (PEG). These measurements provide direct evidence for the formation of relatively strong attractive forces between PEG and protein. At low compressive loads, the forces were repulsive, but they became attractive when the proteins were pressed into the polymer layer at higher loads. The adhesion was sufficiently robust that separation of the streptavidin and PEG uprooted anchored polymer from the supporting membrane. These interactions altered the properties of the grafted chains. After the onset of the attraction, the polymer continued to bind protein for several hours. The changes were not due to protein denaturation. These data demonstrate directly that the biological activity of PEG is not due solely to properties of simple polymers such as the excluded volume. It is also coupled to the competitive interactions between solvent and other materials such as proteins for the chain segments and to the ability of this material to adopt higher order intrachain structures.