Surface-enhanced Raman scattering from bilayers of polystyrene,diglycidyl ether of bisphenol-A,poly(4-vinyl pyridine), and poly(4-styrene sulfonate)

Surface-enhanced Raman scattering (SERS) has been observed from thin films of polystyrene (PS), diglycidyl ether of bisphenol-A (DGEBA), and poly(4-vinyl pyridine) (PVP) deposited on silver island films Degradation of the polymers occurred rapidly during laser irradiation and was accompanied by the appearance of strong bands near 1375 and 1575 cm-1. These bands were attributed to the formation of graphite-like species by the silver-catalyzed thermal oxidation of the polymers induced by localized laser heating of the substrate. When the thin films of PS, DGEBA, or PVP were overcoated with much thicker films of a second polymer such as polystyrene sulfonate (PSS), the degradation was greatly reduced, and excellent SERS spectra of the PS, DGEBA, and PVP films were obtained. Overlayers reduced degradation within the first films deposited on silver island films by restricting the availability of oxygen at the interface to its solubility in the overlayer polymer or by altering the adsorption of oxygen onto the substrate. SERS was observed for the PS, DGEBA, and PVP films and the PSS overlayers when the films were deposited from relatively dilute solutions. When the PS, DGEBA, and PVP films were deposited from more concentrated solutions, SERS was not observed from the PSS overlayers. It was suggested that most of the SERS was due to a short-range, charge-transfer mechanism associated with sites of atomic scale roughness and that SERS was observed from the overlayer when the first film failed to occupy all of the sites.     

Formation of parallel strips in thin films of polystyrene/poly(vinyl pyrrolidone) blends via spin coating on unpatterned substrates

Patterns of parallel strips, consisting of alternating polystyrene (PS) and poly(vinyl pyrrolidone) (PVP) regions, were observed in thin films spin cast from a PS/PVP/chloroform solution on unpatterned substrates. The formation of anisotropic patterns, manifested not only in thickness variation but also in composition variation, was found to be driven by Marangoni instability, with the PS and PVP streams flowing toward the preferred regions as the phase separation induced by solvent evaporation proceeded. The initial viscosity of the polymer solution and the thickness of the spin-cast films were lumped into one single parameter to study the phase morphology development at various initial polymer solution concentrations. Interestingly, the ratio of the square of the film thickness to the viscosity, a parameter loosely related to the Marangoni number, was found to reach a maximum value at the concentration where the strip patterns were most well-developed.     

Impact modification of thermoplastics by methyl methacrylate and styrene-grafted natural rubber latexes

The preparation and characterization of polymer blends with structured natural rubber (NR)-based latex particles are presented. By a semicontinuous emulsion polymerization process, a natural rubber latex (prevulcanized or not) was coated with a shell of crosslinked polymethylmethacrylate (PMMA) or polystyrene (PS). Furthermore, core–shell latexes based on a natural rubber/crosslinked PS latex semi-interpenetrating network were synthesized in a batch process. These structured particles were incorporated as impact modifiers into a brittle polymer matrix using a Werner & Pfleiderer twin screw extruder. The mechanical properties of PS and PMMA blends with a series of the prepared latexes were investigated. In the case of PMMA blends, relatively simple core (NR)–shell (crosslinked PMMA) particles improved the mechanical properties of PMMA most effectively. An intermediate PS layer between the core and the shell or a natural rubber core with PS subinclusions allowed the E-modulus to be adjusted. The situation was different with the PS blends. Only core–shell particles based on NR-crosslinked PS latex semi-interpenetrating networks could effectively toughen PS. It appears that microdomains in the rubber phase allowed a modification of the crazing behavior. These inclusions were observed inside the NR particles by transmission electron microscopy. Transmission electron photomicrographs of PS and PMMA blends also revealed intact and well-dispersed particles. Scanning electron microscopy of fracture surfaces allowed us to distinguish PS blends reinforced with latex semi-interpenetrating network-based particles from blends with all other types of particles.     

Latex and hollow particles of reactive polypyrrole: preparation, properties, and decoration by gold nanospheres

Polypyrrole-coated polystyrene latex particles bearing reactive N-amino functional groups (PS-PPyNH2) were prepared by the in-situ copolymerization of pyrrole (Py) and the active amino-functionalized pyrrole (PyNH2) in the presence of 1.33 microm-diameter polystyrene (PS) latex particles. These particles were prepared by dispersion polymerization of styrene using poly(N-vinylpyrrolidone), PNVP, as a steric stabilizer. The functionalized polypyrrole-coated PS particles (PS-PPyNH2) were characterized in terms of their particle size and surface morphology using transmission electron microscopy (TEM). Infrared and X-ray photoelectron spectroscopy (XPS) detected pyrrole-NH2 repeat units at the surface of the latex particles, indicating that this monomer had indeed copolymerized with pyrrole. The core-shell structure of the PS-PPyNH2 particles was confirmed by etching the polystyrene core in THF, leading to the formation of hollow conducting polymer capsules. The PS-PPyNH2 particles were then decorated with citrate-stabilized gold nanoparticles via electrostatic interactions. Furthermore, etching of the polystyrene core resulted in the formation of gold-decorated PPyNH2 hollow capsules.     

Cagelike polymer microspheres with hollow core/porous shell structures

Submicron‐scaled cagelike polymer microspheres with hollow core/porous shell were synthesized by self‐assembling of sulfonated polystyrene (PS) latex particles at monomer droplets interface. The swelling of the PS latex particles by the oil phase provided a driving force to develop the hollow core. The latex particles also served as porogen that would disengage automatically during polymerization. Influential factors that control the morphology of the microspheres, including the reserving time of emulsions, polymerization rate, and the Hildebrand solubility parameter and polarity of the oil phase, were studied. A variety of monomers were polymerized into microspheres with hollow core/porous shell structure and microspheres with different diameters and pore sizes were obtained. The polymer microspheres were characterized by scanning electron microscopy, transmission electron microscopy, optical microscopy, and Fourier transform infrared spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 933–941, 2007     

聚苯乙烯/聚丙烯酸丁酯乳胶互穿聚合物网络的动态力学性能研究

<正> 互穿聚合物网络(IPN)是一种新型聚合物共混物.自Sperling在1969年合成聚丙烯酸乙酯/聚苯乙烯异步IPN(Sequential IPN)后,该领域进展很快.乳胶IPN(latex IPN)是用改进的乳液聚合法合成的一种微观互穿IPN.在前文中,我们报道了聚苯乙烯/聚丙烯酸丁酯(PS/PBA)乳胶IPN的合成,本文研究一些因素对PS/PBA乳胶IPN动态力学性能的影响.     

A study of three-layered latex interpenetrating polymer networks used as processing modifiers and impact modifiers of thermo-plastic resins

In this paper, the latex interpenetrating polymer network poly(n-butyl acrylate) polystyrene/poly(methyl methacrylate) (PBA/PS/PMMA, or PBSM) was synthesized by microagglomeration and three-stage emulsion polymerization. The initial poly(n-butyl acrylate) latex particle was agglomerated by methacrylic acid residue containing the polymer latex and then encapsulated by PS and PMMA. The polyblend of poly(vinyl chloride) (PVC) and PBSM (PVC/PBSM) was prepared by blending PVC and PBSM. The morphology and properties of the polyblend have been studied. Experimental results have shown that the processability and impact-resistance of PVC can be enhanced considerably by means of blending 6–20 per hundred resin (phr) PBSM. The three-layered latex interpenetrating polymer network is a promising modifier for rigid PVC (RPVC) manufactures.     

Poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks with well-defined phase-separated structure

A series of poly(2-acetoxyethyl methacrylate)/polystyrene(PAEMA/PS) latex interpenetrating polymer networks(LIPNs) were prepared by seeded soap-free emulsion polymerization of styrene on the crosslinked PAEMA seed particles using an oil-soluble initiator.These PAEMA/PS LIPNs showed a well-defined phase-separated structure with PS phase dispersing in continuous PAEMA phase.The domain size of PS phase was found to depend on the crosslinking degree of PAEMA seed particles and the amount of second-stage styrene monomer.     

Modification of aqueous polyurethanes by forming latex interpenetrating polymer networks with polystyrene

A series of latex particles with interpenetrating polymer network structure have been synthesized from waterborne polyurethane (PU) and polystyrene (PS). The effect of PU/PS composition, cross-linking density in the PS domain as well as in PU have been studied in terms of dispersion size, transmission electron microscopy morphology, mechanical and dynamic mechanical properties in addition to swellability in water and toluene of the dispersion cast film. It was found that inverted core (PS)–shell (PU) morphology was well defined and that the domain size as well as the film properties were well controlled by the latex composition and cross-linking density of both phases. Received: 15 March 2000 Accepted: 21 February 2001     

Synthesis and Characterization of Polystyrene/Nanosilica Organic-Inorganic Hybrid

IntroductionIn the past two decades, because of its potentialindustrial applications, organic-inorganic compositeshave attracted the attention of both researchers andacademicians. Organic-inorganic hybrids offer the pos-sibility to combine both the advant…     

Ballooning Behavior of Droplet Sizes in Pickering Emulsions Prepared by Flocculated PS Latexes

Pickering emulsions were prepared by mixing silicone oil whose methyl groups had been partly substituted by amine groups and water containing polystyrene (PS) latex particles in the presence of NaCl. The oil droplets rapidly enlarged after approximately 2 days of their preparation, and thereafter reached a steady-state size. After the ballooning behavior of the droplet growth, the droplet surfaces covered with PS latex particles were observed by a confocal laser scanning microscope. At NaCl concentrations above and below the critical flocculation concentration of the PS latex particles, the PS latex particles were flocculated into loosely packed and close-packed structures on droplet surfaces, respectively.     

Fabrication of zinc oxide/poly(styrene) grafted nanocomposite latex and its dispersion

Zinc oxide nanoparticles, with an average size of about 40 nm, were encapsulated by polystyrene using in situ emulsion polymerization in the presence of 3-methacryloxypropyltrimethoxysilane (MPTMS) as a coupling agent and polyoxyethylene nonylphenyl ether (OP-10) as a surfactant. Polymerization mechanism of nanocomposite latex was discussed. Transmission electron microscopy (TEM) proved the presence of ZnO nanoparticle appeared to be monodisperse in nanosize in polymer composite particles. ZnO/PS nanocomposites were characterized by Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results of FT-IR and XPS revealed that the surface of ZnO particle was successfully grafted by PS through the link of the coupling agent between ZnO and polymer. TGA and DSC results indicated an enhancement of thermal stability of composite materials compared with the pure polymer. SEM (scanning electron microscope) images showed a perfect dispersion of the ZnO particles in latex film. In addition, UV-visible absorption measurements demonstrated that the ZnO/PS composite coatings display a perfect performance of absorbing UV light.     

Control of nanoparticle location in block copolymers

A simple procedure is described to incorporate gold nanoparticles and control their location within symmetric poly(styrene-b-2 vinyl pyridine) (PS-PVP) diblock copolymers. Gold nanoparticles coated with thiol-terminated PS and/or PVP homopolymer chains (Mn approximately 1300 and 1500 g/mol, respectively) are incorporated into alternating lamellar layers of PS and PVP (total Mn approximately 196 500 g/mol). The location of the particles is controlled by varying the composition of ligands on the particle surfaces. In particular, gold particles coated with 100% PS or PVP reside near the center of the respective polymer domains, while particles coated with a mixture of both homopolymers reside at the interfaces between the two blocks.     

毛细微模塑法制作聚合物微球的有序结构

用毛细微模塑法在玻璃基片上组装了聚苯乙烯微球紧密的有序阵列.扫描电镜观察了组装后的微球排列.结果表明,在毛细通道的出口端,聚苯乙烯的微球堆积得紧密有序.毛细通道的尺寸,环境温度和聚合物微球乳液的浓度是毛细微模塑法的主要影响因素.     

Effect of supercritical CO2 in modified polystyrene 3D latex arrays

The effect of supercritical CO(2) (scCO(2)) in 3D latex arrays formed by monodispersed particles of polystyrene (PS), PS cross-linked with divinylbenzene (PS-DVB), and PS block copolymers with 2-hydroxyethyl methacrylate (PS-HEMA), methacrylic acid (PS-MA), acrylic acid (PS-AA), itaconic acid (PS-IA), and a mixture of methacrylic and itaconic acid (PS-IA-MA) has been studied. Sorption of CO(2) into the polymer particles leads to a decrease in the glass transition temperature of the polymer and the swelling of the particles and induces their coalescence. 3D-latex arrays of the former compositions were treated in scCO(2) at temperatures and pressures ranging from 40 to 80 degrees C and from 85 to 197 bar, respectively. The effect of CO(2) on the polymeric template was assessed by scanning electron microscopy and N(2) adsorption analysis. Bare PS and PS-HEMA particles sintered readily in scCO(2) at 40 degrees C and 85 bar. On the other hand, particles containing carboxylic acid groups on their surface (PS-MA, PS-AA, PS-IA, and PS-IA-MA) were, at the same temperature and pressure, more resistant to the CO(2) treatment. For a given polymer composition, the sorption of CO(2) inside the polymer particles, the swelling, and the degree of coalescence depend on the pressure, temperature, and time of the CO(2) treatment. Analysis of the pore size distributions from the N(2) adsorption data has allowed us to quantify the degree of coalescence of the particles in the matrix. By careful control of the experimental variables, the coalescence of the 3D latex array could be finely tuned using CO(2).     

Ion-Free latex films as dual-phase electrolytes: Styrene–butadiene rubber and nitrile–butadiene rubber synthesized by emulsion polymerization with poly-(vinyl pyrrolidone) stabilizer

Ion-free latices of styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR) were synthesized by emulsion polymerization with use of poly (vinyl pyrrolidone) (PVP) stabilizer. The goal was to prepare ion-free latex films, possessing dual-phase latex particle morphology, and swell the films with liquid electrolyte to yield dual-phase polymer electrolytes (DPE). SBR/PVP latex was prepared readily, but NBR/PVP latex was sensitive to coagulation. Differential scanning calorimetric (DSC) and scanning electron microscopic (SEM) analyses of latex films provided morphological evidence concerning particle structure and phase separation. Blends of NBR/PVP and PB/PVP latices (PB = polybutadiene) were also investigated, but particle structure was not present in the blended latex film, even though particle structure was present in the individual NBR/PVP and PB/PVP latex films. After extensive swelling of SBR/PVP latex films, PVP was extracted from the films, and ionic conductivities greater than 10^?3 S/cm were achieved. © 1994-John Wiley & Sons, Inc.     

Honeycomb pattern formation via polystyrene/poly(2-vinylpyridine) phase separation

The surface morphologies and properties of polystyrene (PS)/poly(2-vinylpyridine) (PVP) blend films cast on the mica substrate from ethylbenzene solution were investigated upon controlling different weight ratios and solvent evaporation rates. A near-honeycomblike surface morphology of the PS/PVP blend film formed under controlling the solvent evaporation rate due to the effect of Marangoni-Benard convection. The results of static water contact angles, X-ray photoelectron spectroscopy, solvent selective etching, and treatment by water illustrated that the near-honeycomblike structures on the surface of PS/PVP blend films were different for different weight ratios of PS and PVP. After treatment with water for several minutes, PVP islands-like structure emerged in the holes of the film for a PS/PVP weight ratio of 4/1, and a quasihexagonal arrangement of alternate big and small PVP droplets emerged on the top layer of the film for a PS/PVP weight ratio of 7/1. The formation mechanisms of different surface structures and their response behaviors to water were discussed.     

Microscopic observation of ordered colloids in sedimentation equilibrium and the important role of Debye screening length. 3. Heavy and monodisperse polystyrene type spheres in aqueous solution of neutral polymers

The ordered structures are observed directly by the metallurgical microscope for the heavy (specific gravity=1.50) and monodisperse polystyrene type spheres in sedimentation equilibrium and in the presence of neutral polymers, polyvinylalcohol (PVA), polyethyleneglycol (PEG), polyvinyl-pyrrolidone (PVP), hydroxypropylcellulose (HPC), and polyacrylamide (PAA_m). The intersphere distances in the ordered lattices decrease by the addition of neutral polymer in the order, PVA < PEG < PVP < HPC < PAA_m. These effects of neutral polymers are reasonably well-explained by the intersphere repulsion from the electrical double layer interaction, which is influenced by the polymer adsorption on the latex surface by the hydrophobic and/or dipole-dipole interactions.     

A Facile Method for Preparation of Polymer Particles Having a “Cylindrical” Shape

A facile and novel approach to prepare monodisperse polystyrene (PS) particles having a “cylindrical” shape was discovered. Spherical PS particles prepared by dispersion polymerization were stirred in a polyvinylpyrrolidone (PVP) aqueous solution for several hours using a magnetic stirrer at room temperature. In the presence of PVP, the spherical PS particles deformed into cylindrical shapes following stirring; however, the particles did not deform in the absence of PVP. The deformation rate of the particles was affected by the molecular weight of the dissolved PVP. This stirring method is not only highly efficient and high yielding, but also applicable to other materials such as polymethyl methacrylate. Moreover, the cylindrical particles were successfully applied as particulate surfactants in a Pickering emulsion system, which exhibited excellent stability in comparison to a system using spherical particles as a surfactant. In the first case, the emulsion was left standing for more than 4 months.     

Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part I. Synthesis and colloidal characterization

Polystyrene (PS) (1)/Poly(n-butyl acrylate (BA)-methacrylic acid (MAA)) (2) structured particle latexes were prepared by emulsion polymerization using monodisperse polystyrene latex seed (118 nm) and different BA/MAA ratios. Three main aspects have been investigated: i) the polymerization kinetics; ii) the particle morphology as a function of reaction time; iii) the distribution of MAA units between the water phase and the polymer particles.The amount of MAA in the shell copolymer was found to be the main factor controlling the particle shape and morphology. The shape of the structured particles was, generally, non-spherical, and the shape irregularities increased as a particles was, generally, non-spherical, and the shape irregularities increased as a function of reaction time. At the beginning of the second stage reaction, new small particles were observed, which coalesced onto the PS seed as the polymerization proceeded. The distribution of the MAA groups in the latex particles and the serum was analyzed by alkali/back-acid titration, using ionic exchanged latexes. No MAA groups were detected in the latex serum. Due to the lowTg of the BA-MAA copolymers, alkali conductimetric titrations accounted for all the MAA groups on and within the polymer particles. Therefore, for these systems, this method is not only limited to a thin surface layer, as it is often assumed.