Dynamic modeling of the morphology of latex particles with in situ formation of graft copolymer

Modification of the polymer–polymer interfacial tension is a way to tailor‐make particle morphology of waterborne polymer–polymer hybrids. This allows achieving a broader spectrum of application properties and maximizing the synergy of the positive properties of both polymers, avoiding their drawbacks. In situ formation of graft copolymer during polymerization is an efficient way to modify the polymer–polymer interfacial tension. Currently, no dynamic model is available for polymer–polymer hybrids in which a graft copolymer is generated during polymerization. In this article, a novel model based on stochastic dynamics is developed for predicting the dynamics of the development of particle morphology for composite waterborne systems in which a graft copolymer is produced in situ during the process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co‐continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low‐density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X‐ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co‐continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co‐continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 600–609, 2010     

Dynamic modeling of the morphology of multiphase waterborne polymer particles

Multiphase waterborne polymer particles provide advantages in more demanding applications, and their performance depends on particle morphology. Currently, no dynamic model for the prediction of the development of the morphology of multiphase latex particles is available. In this work, a model was developed for the prediction of the dynamic development of the morphology of multiphase waterborne systems, such as polymer–polymer and polymer–polymer–inorganic hybrids.     

Anisotropic janus magnetic polymeric nanoparticles prepared via miniemulsion polymerization

Anisotropic Janus magnetic polymeric nanoparticles are prepared via the miniemulsion polymerization of styrene and acrylic acid monomers in the presence of oleic acid‐coated magnetic nanoparticles (MNPs). The controllable phase separation between the polymer matrix and the encapsulated MNPs is a key success factor to produce Janus morphology. The effects of MNPs, 2,2′‐azobis(2‐isobutyronitrile) and sodium dodecyl sulfate contents, on the morphology, chemical composition and colloidal stability of the prepared Janus hybrid particles are investigated. Besides the determination of polymerization conversion, zeta potential, size analysis, TGA, and TEM are applied for characterization of the anisotropic particles. The results show the stable spherical Janus particles containing MNPs (15 wt % magnetic content) located on one side of each polymer particle. The anisotropic submicron Janus magnetic polymeric particles (250 nm) can be easily separated by an external magnet. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4779–4785     

Synthesis of the raspberry‐like PS/PAN particles with anisotropic properties via seeded emulsion polymerization initiated by γ‐ray radiation

We herein report a facile method to prepare the submicron‐sized raspberry‐like polystyrene/polyacrylonitrile particles with anisotropic properties and controllable structure via γ‐radiation‐induced seeded emulsion polymerization under ambient pressure and at room temperature, in which the monodisperse crosslinked styrene‐divinylbenzene‐acrylic acid terpolymer (P(S‐DVB‐AA)) particles were used as seed particles and acrylonitrile (AN) as the second monomer. The influence of the weight ratio of polymer/monomer, the absorbed dose rate, the absorbed dose, and the dispersion medium on the morphology of the as‐prepared particles was investigated. The final products were thoroughly characterized by Fourier transform infrared spectroscopy (FTIR), field‐emission scanning electron microscopy, and transmission electron microscopy. The results showed that the raspberry‐like particles could be fabricated in high yield. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Morphology of micron‐sized,monomer‐adsorbed,crosslinked polymer particles having snowmanlike shapes prepared by the dynamic swelling method

A series of monomer‐adsorbed, crosslinked polystyrene/polydivinylbenzene composite particles having snowmanlike shapes were prepared by the dynamic swelling method that the authors had proposed in 1991. The morphology of the snowman‐shaped particles was estimated with the contact angle of the monomer phase on the polymer particle. Influences of the kind of monomers and polyvinyl alcohol colloidal stabilizer on the morphology were obviously observed and discussed from the viewpoint of thermodynamic stability. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3106–3111, 2001     

The effect of different stabilizers on the formation of self‐assembled porous film via the breath‐figure technique

The Breath‐Figure technique was employed to imprint honeycomb structures in the polymer films via the condensation of water vapor on the surface of an evaporating polymer solution. Generally, the condensed water droplets can be stabilized by an end‐functional polymer or by particles added to the polymer solution. In this study, we carried out a systematic experiment on the effect of different stabilizers on the porous honeycomb structure under identical physical conditions. The end‐functional polymer produced a large area of regular spherical bubbles, whereas adding particles to the polymer solution leads to smaller arrays of the flattened bottom bubbles. The separation length between pores was larger for polymer/particle sample than that of the end‐functional polymer films. In the regular area of polymer/particle film many bubbles were not decorated by particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1430–1436, 2011     

Chromatographic performance of molecularly imprinted polymers: Core‐shell microspheres by precipitation polymerization and grafted MIP films via iniferter‐modified silica beads

In this work, two different surface imprinting formats have been evaluated using thiabendazole (TBZ) as model template. The first format is a thin film of molecularly imprinted polymer (MIP) grafted from preformed silica particles using an immobilized iniferter‐type initiator (inif‐MIP). The second format is molecularly imprinted polymer microspheres with narrow particle size distribution and core‐shell morphology prepared by precipitation polymerization in a two‐step procedure. For the latter format, polymer microspheres (the core particles) were obtained by precipitation polymerization of divinylbenzene‐80 (DVB‐80) in acetonitrile. Thereafter, the core particles were used as seed particles in the synthesis of MIP shells by copolymerization of DVB‐80 and methacrylic acid in the presence of TBZ in a mixed solvent porogen (acetonitrile/toluene). The materials were characterized by elemental microanalysis, nitrogen sorption porosimetry and scanning (and transmission) electron microscopy. Thereafter, the imprinted materials were assessed as stationary phases in liquid chromatography. From this study it can be concluded that grafted MIP beads can be obtained in a simple and direct manner, consuming only a fraction of the reagents used typically to prepare imprinted particles from a monolithic imprinted polymer. Such materials can be used in the development of in‐line molecularly imprinted solid‐phase extraction methods. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1058–1066, 2010     

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     

Flow‐induced particle orientation and rheological properties of suspensions of organoclays in thermoplastic resins

The influence of nano‐scale particles on the viscoelastic properties of polymer suspensions is investigated. We have developed a simulation technique for the particle orientation and polymer conformation tensors to study various features of the suspensions. The nano‐particles are modeled as thin rigid oblate spheroid particles and the polymers as FENE‐P type viscoelastic and Newtonian fluid. Both interparticle and polymer‐particle interactions have been taken into account in our numerical computations. The nonlinear viscoelastic properties of nanocomposites of layered silicate particles in non‐Newtonian fluids are examined at the start‐up of shear flow and are interpreted using the model to examine the effects of model parameters as well as flow conditions on particle orientation, viscosity, and first normal stress difference of the suspensions. We have studied the microstructure of polymer‐clay nanocomposites using X‐ray diffraction (XRD) scattering and transmission electron microscopy (TEM). The rheology of these nanocomposites in step‐shear is shown to be fairly well predicted by the model. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2003–2011, 2010     

Physical characteristics and properties of waterborne polyurethane materials reinforced with silk fibroin powder

Degummed silk filament was pulverized with a home‐made machine to obtain silk fibroin (SF) powder, and the structure, morphology, and particle size of the SF powder were investigated. The individual spherical particles and aggregates with different morphology of silk fibroin coexisted in water. A waterborne polyurethane (WPU) aqueous dispersion was blended with the SF powder to prepare novel blended materials with improved physical properties. The average particle size and zeta potential of the WPU/SF aqueous dispersions were characterized. The result showed that the WPU/SF dispersion with higher SF content exhibited a less negative zeta potential and a larger average particle size. Furthermore, the effect of SF content on the morphology, miscibility, and mechanical properties of the resulting blended films was studied by scanning electron microscopy, wide‐angle X‐ray diffraction, dynamic mechanical thermal analysis, and tensile testing. The films showed an improved Young's modulus and tensile strength from 0.3 to 33.8 MPa, and 0.6 to 5.2 MPa, respectively, with the increasing of SF up to a content of 26 wt %. The negative charges in the periphery and the small particle size made a good effort on dispersing SF powder into the WPU matrix as small aggregates, and the SF powder led to the efficient strengthening of WPU materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 940–950, 2010     

Morphology of epoxy/acrylic polymer‐dispersed liquid‐crystal film in DICY thermal cure

A polymer‐dispersed liquid‐crystal (PDLC) film was prepared from UV‐curable acrylic, thermally curable epoxy, and a liquid‐crystal (LC) mixture with a fixed LC content of 40 wt %. The UV irradiation and heat treatments were in sequential steps. At first, a phase diagram of a binary mixture of LC (E63) and epoxy [diglycidyl ether of polypropylene glycol (DER736)] was established to understand their miscibility. Then, the phase‐separation temperatures and morphologies of pre‐UV‐cured films with different equivalent DER736/dicyandiamide (DICY) molar ratios were observed. Finally, the polymerization‐induced phase‐separation behavior and morphology of the PDLC film were studied by real‐time observation while the film was maintained at 130 °C under the microscope. The results showed that the acrylic network would not affect the phase‐separation behavior of the E63/DER736 mixture. In both thermally induced and polymerization‐induced phase separations, the undissolved DICY particles acted as nucleation agents and were capable of inducing E63 to separate out early. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2033–2042, 2000     

Two‐phase crystallization kinetics of syndiotactic polystyrene

In this work, a two phase crystallization model based on the extension of the Kolmogoroff approach was proposed and verified by comparison with experimental isothermal and nonisothermal crystallization data of Syndiotactic Polystyrene (sPS) in a very wide range of cooling rates, up to 600 °C/s. To investigate the effects of high cooling rate on the sPS crystalline structure, a homemade apparatus was adopted. The morphology in solid samples was analyzed by densitometry, IR spectroscopy, and X‐rays diffraction. The coupling of these techniques allows the determination of the fractions of different crystalline phases. In agreement with melt‐crystallization studies of sPS proposed by different authors, either α and β forms could be produced depending on the thermal history of the sample. Results show that the stable β form is favored for specimens solidified at higher temperature or under low cooling rates, whereas α and mesomorphic forms are favoured at low temperature or high cooling rates. The proposed multiphase crystallization kinetics model successfully described all the range of experimental data. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1757–1766, 2010     

pH responsive surfaces with nanoscale topography

We report the preparation of nanostructured adaptive polymer surfaces by diffusion of an amphihilic block copolymer toward the interface. The surface segregation of a diblock copolymer, polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA), occurred when blended with high molecular weight polystyrene employed as a matrix. On annealing, the polymer surfaces changed both the chemical composition and the hydrophilicity depending on the environment and pH, respectively. By exposure to either water vapor or air, the surface wettability varied between hydrophilic and hydrophobic. In addition, surface enrichment on diblock copolymer by water vapor annealing led to self‐assembly occurring at the interface. Hence, nanostructured domains can be observed by AFM in liquid media. Moreover, the PAA segments placed at the interface respond to pH and can switch from an extended hydrophilic state at basic pH values to a collapsed hydrophobic state in acidic media. Accordingly, the surface morphology changed from swelled micelles to nanometer size holes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2982–2990, 2010     

Investigation of the effects of silicate modification on polymer‐layered silicate nanocomposite morphology

The morphological behavior of a series of polymer‐layered silicate nanocomposites (PLSNs) has been investigated. The goal was to probe the effect of “textured” silicate surfaces on PLSN morphology. The nanocomposites were fabricated by mixing montmorillonite clay that was carefully modified with tailor‐made polystyrene (PS) surfactants into a PS homopolymer matrix, where the chemical similarity of the matrix polymer and surfactants assures complete miscibility of surfactant and homopolymer. To examine the effect of silicate surface “texture,” clay was modified with combinations of long and short surfactants. The samples were then direct melt annealed to allow the equilibrium morphology to develop, and characterized by small‐angle X‐ray scattering. Based on the implications of the Balazs model and other work on the wetting behavior of polymer melts with longer surfactants and textured surfaces we expected that the intercalation of the homopolymer matrix material into the modified clay would be promoted. Extensive characterization of both the modified clays as well as the resultant nanocomposites clearly show that the modified clays exhibit a high degree of order, but also that only phase‐separated morphologies are formed in the corresponding nanocomposites. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4075–4083, 2004     

Multivariable structural characterization of semicrystalline polymer blends by small‐angle light scattering

A new multi‐variable‐measurement approach for characterizing and correlating the nanoscale and microscale morphology of crystal‐amorphous polymer blends with melt‐phase behavior is described. A vertical small‐angle light scattering (SALS) instrument optimized for examining the scattering and light transmitted from structures ranging from 0.5 to 50 μm, thereby spanning the size range characteristic of the initial‐to‐late stages of thermal‐phase transitions (e.g., melt‐phase separation and crystallization) in crystal‐amorphous polymer blends, was constructed. The SALS instrument was interfaced with differential scanning calorimetry (DSC), and simultaneous SALS/DSC/transmission measurements were performed. We show that the measurement of transmitted light and SALS under H_V (cross‐polarized) optical alignments during melting can be used to reliably measure the thermodynamic (e.g., crystal melting and melt‐phase separation temperatures) and structural variables (e.g., crystalline fraction within the superstructures and volume fraction of superstructures) necessary for describing the multiphase behavior of crystal‐amorphous blends in one combined measurement. We also evaluate the orientation correlations of crystalline volume elements within the superstructures. Our results indicate that simultaneous measurement of transmitted light can provide a reliable estimate of the total scattering from density and orientation fluctuations and the melt‐phase separation temperature of polymer blends. For solution‐cast poly(?‐caprolactone)/poly(D,L‐lactic acid) blends, our multivariable measurements during melting provide the parameters necessary to generate a crystal–liquid and liquid–liquid phase diagram and characterize the solid‐state morphology. This opens up the challenge to explore use of our vertical SALS instrument as a rapid and convenient method for developing structure–property relationships for crystal‐amorphous polymer blends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2714–2727, 2002     

Preparation of macroporous functionalized polymer beads by a multistep polymerization and their application in zirconocene catalysts for ethylene polymerization

Macroporous functionalized polymer beads of poly(4‐vinylpyridine‐co‐1,4‐divinylbenzene) [P(VPy‐co‐DVB)] were prepared by a multistep polymerization, including a polystyrene (PS) shape template by emulsifier‐free emulsion polymerization, linear PS seeds by staged template suspension polymerization, and macroporous functionalized polymer beads of P(VPy‐co‐DVB) by multistep seeded polymerization. The polymer beads, having a cellular texture, were made of many small, spherical particles. The bead size was 10–50 μm, and the pore size was 0.1–1.5 μm. The polymer beads were used as supports for zirconocene catalysts in ethylene polymerization. They were very different from traditional polymer supports. The polymer beads could be exfoliated to yield many spherical particles dispersed in the resulting polyethylene particles during ethylene polymerization. The influence of the polymer beads on the catalytic behavior of the supported catalyst and morphology of the resulting polyethylene was investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 873–880, 2003     

Temperature dependence of the phase separation in ethyl cyanoethyl cellulose/poly(acrylic acid)/4′‐n‐pentyl‐4‐cyano‐biphenyl composite films

A novel polymer‐dispersed liquid‐crystal film consisting of micrometer‐scale liquid‐crystal droplets in ultraviolet‐cured polymer composite matrices with cholesteric order was prepared and the influence of cure temperature on the phase separation was studied. The existence and pitch of the ethyl cyanoethyl cellulose cholesteric liquid‐crystalline phase were influenced by the existence of low molecular weight liquid crystals. The macromolecular cholesteric phase disappeared when the 4′‐n‐pentyl‐4‐cyano‐biphenyl concentration was over 40 wt %, and 4′‐n‐pentyl‐4‐cyano‐biphenyl domains were dispersed in the isotropic matrix of the polymer composite. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1334–1341, 2002     

Preparation and characterization of monodisperse CdS quantum dot‐polymer microspheres

A novel and effective method for the preparation of monodisperse CdS quantum dot‐polymer microspheres was proposed. The monodisperse hollow polymer microspheres were firstly swelled in chloroform. Then, the reaction precursor composed of CdO and sulfur, was impregnated into the hollow polymer microspheres. Subsequently, the CdS quantum dots were synthesized directly within the polymer microspheres by thermal decomposition. The morphology, structure, and fluorescence properties of CdS quantum dot‐polymer microspheres were studied by scanning electron microscope, transmission electron microscope, fluorescence microscope, and flow cytometry. The results indicate that the fluorescent CdS quantum dots are successfully synthesized in the monodisperse hollow polymer microspeheres, which provide very strong fluorescence intensity, and offer excellent photostability due to the compact structure of the polymer matrix. These CdS quantum dot‐polymer microspheres have potential applications in biotechnology and biomedicine. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 751–755, 2010     

An ambient self‐curable latex based on colloidal dispersions in water of two functionalized polymers and the thermally reversible crosslinked films generated

An ambient self‐curable latex (ASCL) was prepared by mixing colloidal dispersions in water of a chloromethylstyrene (CMS)‐functionalized polymer and a tertiary‐amine‐functionalized polymer. The two dispersions were obtained via the conventional emulsion copolymerization of CMS and 2‐(dimethylamino)ethylacrylate (DMAEA), respectively, with styrene (St), butyl acrylate (BA), or both. No visible coagulation was observed either in the blends after 6 months of storage or after the latexes were introduced into aqueous media with pHs in the range of 3–11. Continuous, transparent, crosslinked elastic films with smooth surfaces were obtained via casting and drying the ASCL at room temperature, when one or both of the two functional polymer particles contained BA monomeric units. Thermocompression cycles; swelling experiments; solubility tests; and ¹H NMR, IR, DSC, and transmission electron microscopy tests were carried out to investigate the crosslinking and morphology of the films. The following observations were made: (1) the crosslinks in the films were generated via the Menschutkin reaction (quaternization) between the  CH₂‐Cl groups of the CMS containing particles and the amine groups of the DMAEA containing particles; (2) the crosslinked films were thermally remoldable due to reversible decrosslinking (dequaternization) on heating and recrosslinking (requaternization) on cooling; and (3) phase separation in the films was observed when one of the functional polymers (for instance, the nonpolar CMS‐St copolymer) was incompatible with the other one (for instance, the polar BA‐DMAEA copolymer). The present ASCL might be useful in producing water‐borne coatings and adhesives, elastic films, and functional membranes. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 389–397, 2001