Showing papers on "Polymer published in 1998"

Nanocomposite polymer electrolytes for lithium batteries

Abstract: Ionically conducting polymer membranes (polymer electrolytes) might enhance lithium-battery technology by replacing the liquid electrolyte currently in use and thereby enabling the fabrication of flexible, compact, laminated solid-state structures free from leaks and available in varied geometries1. Polymer electrolytes explored for these purposes are commonly complexes of a lithium salt (LiX) with a high-molecular-weight polymer such as polyethylene oxide (PEO). But PEO tends to crystallize below 60 °C, whereas fast ion transport is a characteristic of the amorphous phase. So the conductivity of PEO–LiX electrolytes reaches practically useful values (of about 10−4 S cm−1) only at temperatures of 60–80 °C. The most common approach for lowering the operational temperature has been to add liquid plasticizers, but this promotes deterioration of the electrolyte's mechanical properties and increases its reactivity towards the lithium metal anode. Here we show that nanometre-sized ceramic powders can perform as solid plasticizers for PEO, kinetically inhibiting crystallization on annealing from the amorphous state above 60 °C. We demonstrate conductivities of around 10−4 S cm−1 at 50 °C and 10−5 S cm−1 at 30 °C in a PEO–LiClO4 mixture containing powders of TiO2 and Al2O3 with particle sizes of 5.8–13 nm. Further optimization might lead to practical solid-state polymer electrolytes for lithium batteries.

Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects

Abstract: The synthesis, spectroscopy, and fluorescence quenching behavior of pentiptycene-derived phenyleneethynylene polymers, 1−3, are reported. The incorporation of rigid three-dimensional pentiptycene moieties into conjugated polymer backbones offers several design advantages for solid-state (thin film) fluorescent sensory materials. First, they prevent π-stacking of the polymer backbones and thereby maintain high fluorescence quantum yields and spectroscopic stability in thin films. Second, reduced interpolymer interactions dramatically enhance the solubility of polymers 1−3 relative to other poly(phenyleneethynylenes). Third, the cavities generated between adjacent polymers are sufficiently large to allow diffusion of small organic molecules into the films. These advantages are apparent from comparisons of the spectroscopic and fluorescence quenching behavior of 1−3 to a related planar electron-rich polymer 4. The fluorescence attenuation (quenching) of polymer films upon exposure to analytes depends on seve...

Why do phospholipid polymers reduce protein adsorption

Abstract: The amount of plasma protein adsorbed on a phospholipid polymer having a 2-methacryloyloxyethyl phosphorylcholine (MPC) moiety was reduced compared to the amount of protein adsorbed onto poly[2-hydroxyethyl methacrylate (HEMA)], poly[n-butyl methacrylate (BMA)], and BMA copolymers with acrylamide (AAm) or N-vinyl pyrrolidone (VPy) moieties having a hydrophilic fraction. To clarify the reason for the reduced protein adsorption on the MPC polymer, the water structure in the hydrated polymer was examined with attention to the free water fraction. Hydration of the polymers occurred when they were immersed in water. The differential scanning calorimetric analysis of these hydrated polymers revealed that the free water fractions in the poly(MPC-co-BMA) and poly(MPC-co-n-dodecyl methacrylate) with a 0.30 MPC mole fraction were above 0.70. On the other hand, the free water fractions in the poly(HEMA), poly(AAm-co-BMA), and poly(VPy-co-BMA) were below 0.42. The conformational change in proteins adsorbed on the MPC polymers and poly(HEMA) were determined using ultraviolet and circular dichroism spectroscopic measurements. Proteins adsorbed on poly(HEMA) changed considerably, but those adsorbed on poly(MPC-co-BMA) with a 0.30 MPC mole fraction differed little from the native state. We concluded from these results that fewer proteins are adsorbed and their original conformation is not changed on polymer surfaces that possess a high free water fraction.

Open pore biodegradable matrices formed with gas foaming

Abstract: Engineering tissues utilizing biodegradable polymer matrices is a promising approach to the treatment of a number of diseases. However, processing techniques utilized to fabricate these matrices typically involve organic solvents and/or high temperatures. Here we describe a process for fabricating matrices without the use of organic solvents and/or elevated temperatures. Disks comprised of polymer [e.g., poly (D,L-lactic-co-glycolic acid)] and NaCl particles were compression molded at room temperature and subsequently allowed to equilibrate with high pressure CO2 gas (800 psi). Creation of a thermodynamic instability led to the nucleation and growth of gas pores in the polymer particles, resulting in the expansion of the polymer particles. The polymer particles fused to form a continuous matrix with entrapped salt particles. The NaCl particles subsequently were leached to yield macropores within the polymer matrix. The overall porosity and level of pore connectivity were regulated by the ratio of polymer/salt particles and the size of salt particles. Both the compressive modulus (159+/-130 kPa versus 289+/-25 kPa) and the tensile modulus (334+/-52 kPa versus 1100+/-236 kPa) of the matrices formed with this approach were significantly greater than those formed with a standard solvent casting/particulate leaching process. The utility of these matrices was demonstrated by engineering smooth muscle tissue in vitro with them. This novel process, a combination of high pressure gas foaming and particulate leaching techniques, allows one to fabricate matrices with a well controlled porosity and pore structure. This process avoids the potential negatives associated with the use of high temperatures and/or organic solvents in biomaterials processing.

Controlling polymer shape through the self-assembly of dendritic side-groups

Abstract: The chain conformation of polymers plays an important role in controlling their phase behaviour and associated material properties In the case of flexible polymers, conformation is controlled by the degree of polymerization (DP), with low-DP polymers having extended polymer chains and high-DP polymers adopting random-coil conformations in solution and the bulk amorphous state1, and folded conformations in the crystalline phase2 Exceptions to this general rule are polymers that contain structurally rigid building blocks, or that are subjected to directional shear forces during solidification The backbones of semi-flexible and rigid rod-like polymers, for example, are always extended in liquid crystalline and crystalline phases3,4,5, and gel-spun flexible polymers form extended-chain crystals2 Here we report a general strategy for the rational control of polymer conformation through the self-assembly of quasi-equivalent monodendritic (branched) side-groups attached to flexible backbones At low DPs, the conical monodendrons assemble to produce a spherical polymer with random-coil backbone conformation On increasing the DP, the self-assembly pattern of the monodendritic units changes to give cylindrical polymers with extended backbones This correlation between polymer conformation and DP is opposite to that seen in most synthetic and natural macromolecules We anticipate that our strategy will provide new approaches for the rational design of organized supramolecular materials6,7,8,9 in areas such as nanotechnology, functional films and fibres, molecular devices, and membranes, expanding the synthetic and technological uses of dendritic building blocks7,10,11,12,13,14,15

Polymer-layered silicate nanocomposites: Synthesis, properties and applications

Abstract: Polymer nanocomposites, especially polymer-layered silicate (PLS) nanocomposites, represent a radical alternative to conventionally (macroscopically) filled polymers. Because of their nanometer-size dispersion, the nanocomposites exhibit markedly improved properties when compared with the pure polymers or conventional composites. These include increased modulus and strength, decreased gas permeability, increased solvent and heat resistance and decreased flammability. In addition to their potential applications, PLS nanocomposites are also unique model systems to study the structure and dynamics of polymers in confined environments. Using both delaminated and intercalated hybrids, the statics and dynamics of polymers confined over distances ranging from the radius of gyration of the polymer to the statistical segment length of the chains can be studied. © 1998 John Wiley & Sons, Ltd.

Synthesis of Poly(styrene) Monolayers Attached to High Surface Area Silica Gels through Self-Assembled Monolayers of Azo Initiators

Abstract: We report on the radical-chain polymerization of styrene using self-assembled monolayers of azo initiators covalently bound to high surface area silica gels. In this process monolayers of poly(styrene) molecules terminally attached to the surface of the inorganic substrate are obtained. As the initiator molecules are immobilized at the surfaces in a one-step reaction, well-reproducible layers can be prepared and the surface concentration of the initiator can be adjusted in a wide range between the limit of detection and full surface coverage. In the subsequent polymerization reactions polymer monolayers with high, controlled graft density can be obtained. The synthesis of the attached layers and the characterization by X-ray photoelectron spectroscopy, diffuse reflectance infrared spectroscopy (DRIFT), and elemental analysis are described. After cleavage of an ester group that connects the polymers to the surface, the molecular weights of the polymers were determined. The results of the study show that th...

A Composite from Poly(m‐phenylenevinylene‐co‐2,5‐dioctoxy‐p‐phenylenevinylene) and Carbon Nanotubes: A Novel Material for Molecular Optoelectronics

Abstract: As research progresses towards smaller and more efficient devices, the need to develop alternative molecular scale electronic materials becomes apparent. Integrated electronic component fabrication from organics has been recognized theoretically as the ultimate goal. In order to gain a comprehensive insight into these materials, extensive research has been carried out on conjugated carbon systems over the last few decades to optimize their optical and electrical properties. For example, doping polyacetylene with I2 has been shown to result in a large increase in conductivity compared to the pristine material. However, doping polymers tends to retard their optical properties as regards luminescence by reducing their bandgaps and introducing trapping sites such as solitons, polarons, or bipolarons. The simple lesson over the years is that if materials are to be considered for luminescence, doping should not be carried out despite the desire to improve charge transport properties. We report here the first physical adopingo, to use the traditional term, using small concentrations of multiwalled nanotubes in a conjugated luminescent polymer, poly(m-phenylenevinylene-co-2,5-dioctoxyp-phenylenevinylene) (PmPV), in a polymer/nanotube composite. This can increase electrical conductivity of the polymer by up to eight orders of magnitude. The nanotubes appear to act as nanometric heat sinks, preventing the buildup of large thermal effects, caused either optically (photobleaching) or electrically, which degrade these conjugated systems. We also report that electroluminescence was achieved from an organic light-emitting diode (LED) using the composite as the emissive layer in the device. Since initial work on conjugated systems, attempts have been made to find an area where polymers and/or fullerenes could be used as active semiconductor components. Although many new and interesting materials have been synthesized to this end, very few have found a practical application. One exception is polyphenylenevinylene (PPV), first reported by Burroughes et al. as being the light-emitting semiconductor in a Schottky diode. This encouraged scientists to study a wide variety of conjugated systems, including derivatives of this polymer, in order to optimize the efficiency of light emission from such devices. Polymers for use in LEDs must possess a number of important qualities. A high quantum yield of photoluminescence is necessary and the material must remain undoped, as dopants act as trapping sites, quenching the radiative decay of excitons. It is essential therefore to find a polymer that is reasonably conductive while maintaining its luminescent properties. Most undoped polymers possess a very low conductivity and so require high aturn-ono fields to generate sufficient carriers in order to produce the excitons, which decay radiatively. This is, in practical terms, very inefficient as fields generally induce large thermal effects, consequently causing device breakdown. There are other problems that must be addressed, but elimination of these very basic ones should substantially improve efficiencies and soon lead to applications for these polymers. The polymer used in our studies is PmPV, whose structure is a variation of the more common PPV. In this case the substitution pattern leads to dihedral angles in the chain and, according to molecular mechanics energy minimization calculations, the polymer chain tends to coil, forming a helical structure. The calculated diameter of this helix in vacuum is ca. 20 Š, whilst the pitch is ca. 6 Š. Multiwalled nanotubes were produced by the arc discharge method, resulting in multiwalled nanotubes of 20 nm average diameter and lengths between 500 nm and 1.5 mm. The nanotube powder and PPV were mixed together in toluene and sonicated briefly. It is probable that the coiled polymer conformation allows it to surround layers of nanotubes, permitting sufficiently close intermolecular proximity for p±p interaction to occur. The color change was dramatic in that the polymer has a bright yellow color while the composite, at high nanotube concentrations, possesses a deep green color. Photoluminescence studies were carried out using an Ar laser at the pump wavelength of 457 nm. Electrical conductivity was measured using a twopoint probe sandwich geometry and Pt electrodes. The LED was fabricated by casting the composite onto indium tin oxide (ITO) then sputtering an aluminum electrode on top. As the polymer structure possesses helicity, it is not surprising that it is able to wrap itself around the nanotubes and keep them suspended in solution indefinitely. The actual texture of the composite can be observed in Figure 1,

Surface-induced structure formation of polymer blends on patterned substrates

Abstract: Phase separation in bulk mixtures commonly leads to an isotropic, disordered morphology of the coexisting phases1. The presence of a surface can significantly alter the phase-separation process, however2,3. Here we show that the domains of a phase-separating mixture of polymers in a thin film can be guided into arbitrary structures by a surface with a prepatterned variation of surface energies. Such a pattern can be imposed on a surface by using printing methods for depositing microstructured molecular films4, thereby allowing for such patterns to be readily transferred to a two-component polymer film. This approach might provide a simple means for fabricating polymer-based microelectronic circuits5 or polymer resists for lithographic semiconductor processing.

Nanometer Gold Clusters Protected by Surface-Bound Monolayers of Thiolated Poly(ethylene glycol) Polymer Electrolyte

Abstract: W. Peter Wuelfing, Stephen M. Gross, Deon T. Miles, andRoyce W. Murray*Kenan Laboratories of ChemistryUniVersity of North CarolinaChapel Hill, North Carolina 27599-3290ReceiVed September 8, 1998Metal nanoparticles that are stabilized in solutions by polymersurfactants or are imbedded in polymer composites have been ofintense recent interest

Highly active metallocene catalysts for olefin polymerization

Abstract: The fascinating story of the discovery of the metallocene–methylaluminoxane catalysts for olefin polymerization is reviewed from its conception up until the first commercial production of polymers. A great number of different titanocenes and zirconocenes have been synthesized that give tailored polymers of totally different structures, and allows control of polymer tacticity, molecular weight and molecular weight distribution to be more efficient. New kinds of copolymers and elastomers can be synthesized.

Chain geometry, solution aggregation and enhanced dichroism in the liquidcrystalline conjugated polymer poly(9,9-dioctylfluorene)

Abstract: We report on the physical characterization of a dioctyl-substituted polyfluorene, both in solution and in the solid state. We focus on studies of chain geometry both by molecular modeling and by gel permeation chromatography coupled with light scattering. We determine experimentally a Kuhn segment length, lk = 17.1 ± 2.1 nm and a characteristic ratio C∞ = 21.5 %plusmn; 4.3 indicative of a stiff polymer chain. The effects on absorption and emission spectra of intermolecular interactions that lead to gelation or precipitation from solution are reported. We discuss these results in the context of the strong current interest in the nature of aggregation phenomena and their role in controlling the emissive properties of conjugated polymers. We further show that a markedly enhanced dichroism can be achieved through suitable control of the polymer microstructure.

Thermally Stable Blue-Light-Emitting Copolymers of Poly(alkylfluorene)

Abstract: We have prepared a variety of high molecular weight, thermally stable, blue-light-emitting random copolymers of 9,9-di-n-hexylfluorene by nickel(0)-mediated polymerization. The copolymers are readily soluble and easily processable from organic solvents. Both the polymer and electronic properties may be tuned by selection of comonomer structure. The electronic properties also vary with composition and film morphology. A blue-light-emitting device has been prepared using ionic salts for electrochemical doping.

The use of UV irradiation in polymerization

Abstract: Photoinitiation is one of the most efficient methods for achieving quasi-instantaneous polymerization, transforming a liquid molecule into a solid polymer material within less than 1s. The kinetics of such ultrafast reaction can be advantageously followed by real-time infrared spectroscopy, a technique which records directly conversion versus time curves and allows evaluation of the important kinetic parameters of cross-linking polymerization. Photoinitiation has proved to be well suited to inducing frontal polymerization and achieving a deep-through cure of thick specimens. UV technology is also capable of causing fast polymerization in solid media, despite severe mobility restrictions, because of the high initiation rate provided by intense illumination. This review presents some recent advances in the UV-curing technology, special emphasis being given to the kinetic aspect of ultrafast polymerization reactions induced by light. © 1998 SCI.

Bonding layers for medical device surface coatings

Abstract: A medical device is coated with a thin coherent bond coat of acrylics, epoxies, acetals, ethylene copolymers, vinyl polymers, polymers containing hydroxyl, amine, carboxyl, amide, or other reactive groups, and copolymers thereof. Outer layers may be applied and remain adherent to the substrate in water for an extended period. The bond coat may comprise cross linkers such as urea resins, melamines, isocyanates, and phenolics. Preferred polymers include vinylpyrrolidone-vinyl acetate, styrene acrylic polymer, ethylene acrylic acid copolymer, carboxyl function acrylic polymer, hydroxyl function acrylic polymer, and acrylic dispersion polymer. The coatings may be applied to inert metal or plastic surfaces of medical devices such as needles, guide wires, catheters, surgical instruments, equipment for endoscopy, wires, stents, angioplasty balloons, wound drains, arteriovenous shunts, gastroenteric tubes, urethral inserts, laparoscopic equipment, pellets, and implants. Methods of coating and coating liquids are provided.

Adherent, flexible hydrogel and medicated coatings

Abstract: The adherent coating of the invention comprises a stabilizing polymer together with an active agent (a hydrophilic polymer and/or a bioactive agent) in a layer bonded to the surface of a medical device. This invention encompasses the coating liquids used for coating medical devices, methods of coating the devices, and the coated devices. The stabilizing polymer is selected to entrap the active agent in a coating that has a high degree of flexibility and has improved bonding to a wide variety of substrates. Preferred stabilizing polymers are cross-linkable acrylic and methacrylic polymers, ethylene acrylic acid copolymers, styrene acrylic copolymers, vinyl acetate polymers and copolymers, vinyl acetal polymers and copolymers, epoxy, melamine, other amino resins, phenolic polymers, copolymers thereof, and combinations.

Solubility of homopolymers and copolymers in carbon dioxide

Abstract: The cloud points of various amorphous polyether, polyacrylate, and polysiloxane homopolymers, and a variety of commercially available block copolymers, were measured in CO2 at temperatures from 25 to 65 °C and pressures of ca. 1000−6000 psia. Almost without exception, the solubility of amorphous polymers increases with a decrease in the cohesive energy density, or likewise, the surface tension of the polymer. With this decrease in surface tension, the polymer cohesive energy density becomes closer to that of CO2. Consequently, solubility is governed primarily by polymer−polymer interactions, while polymer−CO2 interactions play a secondary role. The solubility is strongly dependent upon molecular weight for the less CO2-philic polymers. The solubilities of high-molecular-weight poly(fluoroalkoxyphosphazenes) in CO2 were comparable to those of poly(1,1-dihydroperfluorooctylacrylate), one of the most CO2-soluble polymers known.

Novel propylene polymers and products thereof

Abstract: The present invention concerns nucleated propylene polymers having a xylene soluble fraction at 23 °C of less than 2.5 %, a crystallization temperature of over 124 °C and a tensile modulus of greater than 2,000 MPa. These polymers can be prepared by nucleating a propylene polymer with a polymeric nucleating agent containing vinyl compound units, and by polymerizing propylene optionally with comonomers in the presence of a Ziegler-Natta catalyst system primarily transesterified with a phthalic acid ester - a lower alcohol pair to provide said propylene polymer. The catalyst contains a strongly coordinating external donor.

Dendrimer-like Star Polymers

Abstract: Dendrimer-like star polymers, a novel type of molecular architecture, have been synthesized. The architecture of the new polymers resembles that of three-dimensional spherical dendrimers as well as classical star polymers. The controlled structures, based on aliphatic polyesters, are synthesized by a divergent growth approach. A hexa hydroxy-functional 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) derivative was used as the “initiator” for the stannous-2-ethylhexanoate (Sn(Oct)2) catalyzed living ring opening polymerization of e-caprolactone. The polymerization generated a six-arm polymer with a molecular weight of 14 300 (Mn) and a Mw/Mn of 1.06. The new polymer was functionalized with a protected bis-MPA, deprotected, and used as the “macroinitiator” for the polymerization of a second generation 12 armed poly(e-caprolactone) (Mn = 42 300, Mw/Mn = 1.16). Another iteration of the same procedure generated a third generation 24 arm dendrimer-like star polymer with a Mn of 96 000 and Mw/Mn of 1.14. The comp...

Polymer Layers Through Self-Assembled Monolayers of Initiators

Abstract: A novel concept for the generation of molecularly thin polymer layers attached to a solid surface is described. In contrast to commonly used techniques, where functional groups of the polymers are reacted with appropriate sites on the surfaces of a substrate the polymer layers are formed in situ by using self-assembled monolayers of an initiator. As an example, the formation of polystyrene monolayers terminally attached to silicon oxide surfaces through radical chain polymerization which has been started by a self-assembled monolayer of an azo initiator is described. The thickness of the attached polymer films can be adjusted over a wide range up to values of several hundred nanometers by variation of polymerization parameters such as temperature and azo conversion. When suitable conditions are chosen, monolayers with thicknesses inaccessible by other techniques of preparation can be obtained.

Room-Temperature Molten Salt Polymers as a Matrix for Fast Ion Conduction.

Abstract: Vinyl polymers having either imidazolium group or sulfonamide group in the side chain were prepared as components to form a molten salt. After mixing, these polymers formed a molten-salt-like flexi...