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.

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.

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.

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.

Morphology of Membranes Formed from Polysulfone/Polyethersulfone/N-methyl-2-pyrrolidone/Water System by Immersion Precipitation

Baik, Ki-Jun,Kim, Je-Young,Lee, Jae-Sung,Kim, Sung-Chul,Lee, Hwan-Kwang The Polymer Society of Korea 2001 Korea polymer journal Vol.9 No.5

The polysulfone(PSf)/polyethersulfone(PES) blend membranes were prepared by an immersion precipitation method. N-methyl-2-pyrrolidone(NMP) was used as a solvent and water as a nonsolvent. The composition of the coagulation bath and the dope polymer concentration as well as the blend ratio of two polymers were varied. The membrane morphologies were interpreted on the basis of the phase diagram of the PSf/PES/NMP/water system. As the solvent content in the coagulation bath increased in the single polymer system, the number of macrovoids decreased and the morphology was changed from finger-like to cellular structure. In the given bath condition phase separation occurs earlier for the solutions of PSf/PES blend than for those of single polymer. A horizontally layered structure and horizontal protuberances inside the macrovoid were observed for the membranes formed from PSf/PES blend solutions. This peculiar structure formation can be interpreted by a PSf-rich/PES-rich phase separation followed by a polymer-rich/polymer-lean phase separation during the exchange of solvent and nonsolvent.

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.

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.

Effect of Poly(butyl acrylate)-Poly(methyl methacrylate) Rubber Particle Texture on the Toughening Behavior of Poly(methyl methacrylate)

Chung, Jae-Sik,Park, Kyung-Ran,Wu, Jong-Pyo,Han, Chang-Sun,Lee, Chan-Hong The Polymer Society of Korea 2001 Korea polymer journal Vol.9 No.2

Monodisperse composite latex particles with size of ca. 300 nm, which consist ofn-butyl acrylate as a soft phase and methyl methacrylate as a hard phase with different morphology, were synthesized by seeded multi-stage emulsion polymerization. Three types of composite latex particles including random-, core/shell-, and gradient-type particles were obtained by using different monomer feeding methods during semi-batch emulsion polymerization. Effect of poly(butyl acrylate)-poly(methyl methacrylate) rubber particle morphology on the mechanical and rheological properties of rubber toughened poly(methyl methacrylate) was investigated. Among three different rubber particles, the gradient-type rubber particle showed better toughening effect than others. No significant variation of rheological property of poly(methyl methacrylate)/rubber blends was observed for the different rubber particle morphology.

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.

Effects of the Interaction between Intercalant and Matrix Polymer in Preparation of Clay-dispersed Nanocomposite

Ko, Moon-Bae,Kim, Jyunkyung,Choe, Chul-Rim The Polymer Society of Korea 2000 Korea polymer journal Vol.8 No.3

Clay-dispersed nanocomposites have been prepared by simple melt-mixing of two components, styrenic polymers with different content of functional groups and two different organophilic clays (Cloisite(R) 25A and Cloisite(R)30A) with a twin screw extruder. Dispersibility of 10-$\AA$-thick silicate layers of clay in the hybrid was investigated by using an X-ray diffraction method and a transmission electron microscope. It was found that if the interaction force between intercalant and matrix polymer is attractive, the matrix polymer intercalates more rapidly into the gallery of silicate layers. The faster intercalation of matrix polymer leads to the better dispersibility of silicate layers in the matrix polymer.