Core-Shell Polymerization with Hydrophilic Polymer Cores

Park, Jong-Myung The Polymer Society of Korea 2001 Korea polymer journal Vol.9 No.1

Two-stage emulsion polymerizations of hydrophobic monomers on hydrophilic seed polymer particles were carried out to make core-shell composite particles. It was found that the loci of polymerization in the second stage were the surface layer of the hydrophilic seed latex particles, and that it has resulted in the formation of either eccentric core-shell particles with the core exposed to the aqueous phase or aggregated nonspherical composite particles with the shell attached on the seed surface as many small separated particles. The driving force of these phenomena is related to the gain in free energy of the system in going from the hydrophobic polymer-water interface to hydrophilic polymer-water interface. Thermodynamic analysis of the present polymerization system, which was based on spreading coefficients, supported the likely occurrence of such nonspherical particles due to the combined effects of interfacial free energies and phase separation between the two polymer phases. A hypothetical pathway was proposed to prepare hydrophilic core-hydrophobic shell composite latex particles, which is based on the concept of opposing driving and resistance forces for the phase migration. It was found that the viscosity of the monomer-swollen polymer phase played important role in the formation of particle morphology.

Polymers and Inorganics: A Happy Marriage?

Wegner Gerhard,Demir Mustafa M.,Faatz Michael,Gorna Katazyrna,Munoz-Espi Rafael,Guillemet Baptiste,Grohn Franziska The Polymer Society of Korea 2007 Macromolecular Research Vol.15 No.2

The most recent developments in two areas: (a) synthesis of inorganic particles with control over size and shape by polymer additives, and (b) synthesis of inorganic-polymer hybrid materials by bulk polymerization of blends of monomers with nanosized crystals are reviewed. The precipitations of inorganics, such as zinc oxide or calcium carbonate, in presence and under the control of bishydrophilic block or comb copolymers, are relevant to the field of Biomineralization. The application of surface modified latex particles, used as controlling agents, and the formation of hybrid crystals in which the latex is embedded in otherwise perfect crystals, are discussed. The formation of nano sized spheres of amorphous calcium carbonate, stabilized by surfactant-like polymers, is also discussed. Another method for the preparation of nanosized inorganic functional particles is the controlled pyrolysis of metal salt complexes of poly(acrylic acid), as demonstrated by the syntheses of lithium cobalt oxide and zinc/magnesium oxide. Bulk polymerization of methyl methacrylate blends, with for example, nanosized zinc oxide, revealed that the mechanisms of tree radical polymerization respond to the presence of these particles. The termination by radical-radical interaction and the gel effect are suppressed in favor of degenerative transfer, resulting in a polymer with enhanced thermal stability. The optical properties of the resulting polymer-particle blends are addressed based on the basic discussion of the miscibility of polymers and nanosized particles.

Fabrication of Pre-Exfoliated Clay Masterbatch via Exfoliation-Adsorption of Polystyrene Nanobeads

Khvan, Svetlana,Kim, Jun-Kyung,Lee, Sang-Soo The Polymer Society of Korea 2007 Macromolecular Research Vol.15 No.1

The approach studied in the present work produced an exfoliated state of clay layers via confinement of the charged nano-sized polystyrene (PS) beads within the gallery of swollen pristine clay. It was demonstrated that adsorption of the polymer nanobeads dramatically promotes expansion of the clay gallery. A comparative study of incorporation was conducted by employing organo-modified clay along with two different colloid polymer systems: electrostatically stabilized PS nanobeads and cationic monomer-grafted PS nanobeads. The mechanism of adsorption of the monomer-grafted polymer beads onto clay via cationic exchange between the alkyl ammonium group of the polymer nanobeads and the interlayer sodium cation of the layered silicate was verified by using several techniques. As distinct from the polymer nanobeads formed using conventional miniemulsion polymerization method, competitive adsorption of stabilizing surfactant molecules was be prevented by grafting the surface functional groups into the polymer chain, thereby supporting the observed effective adsorption of the polymer beads. The presence of surface functional groups that support the establishment of strong polymer-clay interactions was suggested to improve the compatibility of the clay with the polymer matrix and eventually play a crucial role in the performance of the final nanocomposites.

Multiwalled Carbon Nanotubes Functionalized with PS via Emulsion Polymerization

Park, In-Cheol,Park, Min,Kim, Jun-Kyung,Lee, Hyun-Jung,Lee, Moo-Sung The Polymer Society of Korea 2007 Macromolecular Research Vol.15 No.6

This study demonstrated the in-situ functionalization with polymers of multi-walled carbon nanotubes (MWNTs) via emulsion polymerization. Polystyrene-functionalized MWNTs were prepared in an aqueous solution containing styrene monomer, non-ionic surfactant and a cationic coupling agent ([2-(methacryloyloxy)ethyl]trime-thylammonium chloride (MATMAC)). This process produced an interesting morphology in which the MWNTs, consisting of bead-string shapes or MWNTs embedded in the beads, when polymer beads were sufficiently large, produced nanohybrid material. This morphology was attributed to the interaction between the cationic coupling agent and the nanotube surface which induced polymerization within the hemimicellar or hemicylindrical structures of surfactant micelles on the surface of the nanotubes. In a solution containing MATMAC alone without surfactant, carbon nanotubes (CNTs) were not well-dispersed, and in a solution containing only surfactant without MATMAC, polymeric beads were synthesized in isolation from CNTs and continued to exist separately. The incorporation of MATMAC and surfactant together enabled large amounts of CNTs (> 0.05 wt%) to be well-dispersed in water and very effectively encapsulated by polymer chains. This method could be applied to other well-dispersed CNT solutions containing amphiphilic molecules, regardless of the type (i.e., anionic, cationic or nonionic). In this way, the solubility and dispersion of nanotubes could be increased in a solvent or polymer matrix. By enhancing the interfacial adhesion, this method might also contribute to the improved dispersion of nanotubes in a polymer matrix and thus the creation of superior polymer nanocomposites.

Radiolytic Synthesis of Ag-Loaded Polystyrene(Ag-PS) Nanoparticles and Their Antimicrobial Efficiency Against Staphylococcus aureus and Klebsiella pneumoniase

Oh, Seong-Dae,Byun, Bok-Soo,Lee, Seung-Ho,Choi, Seong-Ho,Kim, Moon-Il,Park, Hyun-Gyu The Polymer Society of Korea 2007 Macromolecular Research Vol.15 No.4

Ag nanoparticles were distributed onto polystyrene nanoparticle (PS-Ag) beads using two synthetic methodologies. In the first methodology, polystyrene (PS) beads were prepared via emulsion polymerization, with Ag nanoparticles subsequently loaded onto the surface of the PS beads. The polymerization of styrene was radiolytically induced in an ethanol (EtOH)/water medium, generating PS beads. Subsequently, Ag nanoparticles were loaded onto the PS beads via the reduction of Ag ions. The results from the morphological studies, using field emission transmission electron microscopy (FE-TEM), reveal the PS particles were spherical and nanosized, and the average size of the PS spherical particles decreased with increasing volume % of water in the polymerization medium. The size of the PS spherical particles increases with increasing radiation dose for the polymerization. Also, the amount of Ag nanoparticle loading could be increased by increasing the irradiation dose for the reduction of the Ag ions. In the second methodology, the polymerization of styrene and reduction of Ag ions were simultaneously performed by irradiating a solution containing styrene and Ag ions in an EtOH/water medium. Interestingly, the Ag nanoparticles were preferentially homogeneously distributed within the PS particles (not on the surface of the PS particles). Thus, Ag nanoparticles were distributed onto the surface of the PS particles using the first approach, but into the PS clusters of the particles via the second. The antimicrobial efficiency of a cloth coated with the Ag-PS composite nanoparticles was tested against bacteria, such as Staphylococcus aureus and Klebsiella pneumoniase, for 100 water washing cycles.

Interaction between Poly(L-lysine) and Poly(N-isopropyl acrylamide-co-acrylic acid) in Aqueous Solution

Sung, Yong-Kiel,Yoo, Mi-Kyong,Cho, Chong-Su The Polymer Society of Korea 2000 Korea polymer journal Vol.8 No.1

A series of pH/temperature sensitive polymers were synthesized by copolymerizing N-isopro-pyl acrylamide(NIPAAm) and acrylic acid(AAc) . The influence of polyelectrolyte between poly(allyl amine) (PAA) and poly(L-lysine)(PLL) on the lower critical solution temperature(LCST) of pH/temperature sensitive polymer was compared in the range of pH 2∼12. The LCST of PNIPAAm/water in aqueous poly(NIPAAm-co-AAc) solution was determined by cloud point measurements. A polyelectrolyte complex was prepared by mixing poly(NIPAAm-co-AAc) with poly(allyl amine) (PAA) or poly(L-lysine) (PLL) solutions as anionic and cationic polyelectrolytes, respectively. The effect of polyelectrolyte complex formation on the conformation of PLL was studied as a function of temperature by means of circular dichroism(CD). The cloud points of PNIPAAm in the aqueous copolymers solutions were stongly affected by pH, the presence of polyelectrolyte solute, AAc content, and charge density. The polyelectrolyte complex was formed at neutral condition. The influence of more hydrophobic PLL as a polyelectrolyte on the cloud point of PNIPAAm in the aqueous copolymer solution was stronger than that of poly(allyl amine)(PAA). Although polymer-polymer complex was formed between poly(NIPAAm-co-AAc) and PLL, the conformational change of PLL did not occur due to steric hinderance of bulky N-isopropyl groups of PNIPAAm.

Liquid Crystal Alignment on the Films of Polymethacrylate and Polyurethane Bearing an Aminotroazobenzene Chromophore

Park, Dong-Hoon,Kim, Jae-Hyung,Cho, Kang-Jin The Polymer Society of Korea 2000 Korea polymer journal Vol.8 No.4

We synthesized polymethacrylate and polyurethane bearing a photosensitive azobenzene chromophore. Photo-induced birefringence of the thin film was observed under a linearly polarized light(λ = 532 nm). Dynamic behaviors of birefringence in two polymers were investigated in terms of the rate constants of growth and decay. An induced dichroism was observed from polarized UV-VIS absorption spectroscopy. Layers of two photosensitive polymers were used for aligning liquid crystal (LC) molecules instead of one of the rubbed polyimide layers in the conventional twisted nematic cell. For producing homogeneous alignment of a nematic LC molecule, a linearly polarized light was exposed to the films of two polymers. The stability of the LC alignment upon the linearly polarized light exposure was also studied.

Holographic Polymer-Dispersed Liquid Crystals and Polymeric Photonic Crystals Formed by Holographic Photolithography

Kyu Thein,Meng Scott,Duran Hatice,Nanjundiah Kumar,Yandek Gregory R. The Polymer Society of Korea 2006 Macromolecular Research Vol.14 No.2

The present article describes the experimental and theoretical observations on the formation of holographic, polymer-dispersed, liquid crystals and electrically switchable, photonic crystals. A phase diagram of the starting mixture of nematic liquid crystal and photo-reactive triacrylate monomer was established by means of differential scanning calorimetry (DSC) and cloud point measurement. Photolithographic patterns were imprinted on the starting mixture of LC/triacrylate via multi-beam interference. A similar study was extended to a dendrimer/photocurative mixture as well as to a single component system (tetra-acrylate). Theoretical modeling and numerical simulation were carried out based on the combination of Flory-Huggins free energy of mixing and Maier-Saupe free energy of nematic ordering. The combined free energy densities were incorporated into the time-dependent Ginzburg-Landau (Model C) equations coupled with the photopolymerization rate equation to elucidate the spatio-temporal structure growth. The 2-D photonic structures thus simulated were consistent with the experimental observations. Furthermore, 3-D simulation was performed to guide the fabrication of assorted photonic crystals under various beam-geometries. Electro-optical performance such as diffraction efficiency was evaluated during the pattern photopolymerization process and also as a function of driving voltage.

Polymerization of 3-Ethynylphenol Try Transition Metal Catalysts

Gal, Yeong-Soon,Lee, Won-Chul,Jin, Sung-Ho,Lee, Hyung-Jong The Polymer Society of Korea 2000 Korea polymer journal Vol.8 No.5

The polymerization of 3-ethynylphenol, phenylacetylene having hydroxy functionality, was carried out by tungsten and molybdenum-based transition metal catalysts. The polymerization proceeded to give a moderate yield of polymer. The effects on the mole ratio of monomer to catalyst (M/C), initial monomer concentration ((Mb), and the polymerization temperature for the polymerization of 3-ethynylphenol were investigated. The catalytic activity of W-based catalysts was found to be greater than that of Mo-based catalysts. The resulting polymers were brown or black powders and mostly insoluble in organic solvents. Structural analysis of the polymer by instrumental methods revealed the conjugated polymer backbone structure carrying hydroxyphenyl moieties. Thermal and morphological properties of the resulting poly(3-ethynylphenol) were also discussed.

Swelling Behavior of Biodegradable Crosslinked Gel based on Poly(aspartic acid) and PEG-diepoxide

Min, Suk-Kee,Kim, Ji-Heung,Chung, Dong-Jun The Polymer Society of Korea 2001 Korea polymer journal Vol.9 No.3

Poly(aspartic acid), PASP, is a biodegradable, water-soluble polymer and offers a biodegradable alternative to polycarboxylates and other non-degradable water-soluble polymers. PASP one of poly (amino acid)s, possesses carboxylic acid pendant group in its repeating unit, which can be used for various further modification purposes. In this study we prepared high molecular weight polysuccinimide, as the precursor polymer for PASP, by thermal polycondensation ofL-aspartic acid in the presence of phosphoric acid. The polysuccinimide was hydrolyzed with 0.1 N sodium hydroxide, and then acidified to give PASP. High water-absorbent gels were produced by thermal crosslinking of freeze-dried mixture of partially-neutralized PASP and different amount of low moi. wt. PEG-diepoxide compounds in aqueous medium. The swelling behavior of the prepared gels from different size and composition of crosslinking reagent in different media was investigated and the results were discussed. This PASP-based hydrogel materials possessing inherent biodegradability, potential non-toxicity and biocompatibility, is expected to be used as a substrate for various biomedical applications as well as a general purpose super-absorbent polymer.