Thermodynamic aspects of the heterogeneous structure of “golf-ball-like” polymer particles

Recently, we found that “golf-ball-like” polystyrene (PS)/poly(butyl acrytlate) composite particles could be produced by seeded emulsion polymerization of butyl acrylate with PS seed particles. In this article, the theoretical and experimental thermodynamic instabilities of the golf-ball-like structure are discussed and are compared with core-shell and hemispherical morphologies. Received: 2 February 1999 Accepted in revised form: 3 June 1999     

Production of polymer microparticles by “dissolution” of submicron-sized water-insoluble ionized carboxylated polymer particles in the presence of various nonionic emulsifiers

Styrene-butyl acrylate-methacrylic acid terpolymer (50.4/40.9/8.7, molar ratio) particles, 276 nm in diameter, were produced by emulsifier-free emulsion terpolymerization. The emulsifier-free carboxylated terpolymer particles did not dissolve in water even under alkaline condition. However, they dissolved in the presence of nonionic emulsifier under alkaline condition, resulting in polymer microparticles having diameter less than 40 nm. Such a dissolution behavior was examined using five kinds of different polyoxyethylene nonylphenylether nonionic emulsifiers having hydrophilic-lipophilic balance values between 12.2 and 17.5 at various initial pH values, temperatures and times, and its mechanism was discussed.Part CXLIV of the series Studies on Suspension and Emulsion.     

Core–shell particles with conductive polymer cores

Heterocoagulation of large cationic polypyrrole particles with small anionic polyacrylate beads followed by heat processing of the heterocoagulate units proved to be an efficient method in the preparation of core-shell particles with conductive cores and dielectric shells. Specific conditions required for producing monodispersed composite particles with uniform shells were examined in the stages of the synthesis of polypyrrole particles with controlled size, in "one-step" heterocoagulation of oppositely charged polypyrrole microbeads with small polyacrylic particles, and during shell formation by spreading of the acrylic polymer on the surface of polypyrrole cores.     

Preparation of titania hollow particles with independently controlled void size and shell thickness by catalytic templating core–shell polymer particles

Organic/inorganic hybrids were prepared by catalytic hydrolysis and subsequent polycondensation of tetra-n-butyl titanate (TnBT) in shell layers grafted on core particles. The core particles were synthesized by emulsifier-free emulsion polymerization of styrene, N-n-butyl-N-2-methacryloyloxyethyl-N,N-dimethylammonium bromide (C₄DMAEMA), and 2-chloropropionyloxyethyl methacrylate using 2,2′-azobis(2-amidinopropane) dihydrochloride as an initiator. The core diameters were controlled in the range of 70–550 nm by adjusting a C₄DMAEMA feed concentration. The core–shell particles were prepared by surface-initiated activator generated electron transfer–atom transfer radical polymerization of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA). The sizes of core–shell particles were found to increase monotonically with an increase in a DMAEMA concentration. The hybrid particles were fabricated by adding TnBT into a water/ethanol dispersion of core–shell particles. The amounts of titania deposited increased in proportion to the grafted amounts of poly[2-(N,N-dimethylamino)ethyl methacrylate] on the core particles. The X-ray diffraction measurement revealed that the hollow titania particles obtained by heat treatment of hybrids have an anatase crystallographic phase.     

Formation mechanism of anomalous “golf ball-like” composite polymer particles by seeded emulsion polymerization

Recently, the authors found that anomalous polystyrene/polybutyl acrylate composite particles, whose surfaces had many dents, were produced by emulsifier-free seeded emulsion polymerization of butyl acrylate with polystyrene seed particles. Such a particle was named a golf ball-like particle. In this article, the morphology and the formation mechanism of the golf ball-like composite polymer particles were studied.Part CLV of the series Studies on Suspension and Emulsion     

Preparation of core–shell composite polymer particles by a novel heterocoagulation based on hydrophobic interaction

Submicron-sized cationic polystyrene shell particles with active ester groups were effectively self-assembled on hydrophobic surfaces of cross-linked polystyrene (PST) particles, uncharged core particles with ca. 8.5-µm diameter in aqueous systems. The hydrophobic interactions between the shell particles and core particles play a key role in heterocoagulation. The resulting heterocoagulates were highly physically stable in water, and the morphology was controlled by several factors including the solid content of latex, self-assembling time, and electrolyte concentration. Composite polymer particles with a core–shell structure were successfully obtained from the heterocoagulates by heat treatment for 3 h at a temperature above the glass transition temperature (T_g) of the cationic polymer shell particles.     

A novel approach for preparation of “cage-like” multihollow polymer microspheres through sulfonated polystyrene particles

A new and effective process has been developed for fabrication of novel cage-like multihollow polymer particles by using sulfonated polystyrene (SP) particles as the templates, with heptane as the phase separation agent, in an ethanol/water medium. The ratio of water/ethanol and the heating temperature play important roles in the formation of these multihollow particles. It was found that the cage-like polymer particles could be obtained when the ratio of ethanol/water is 5:5 (w/w), with a temperature above 50?°C. After a detailed study, the formation mechanism was proposed based on an SP swollen (ethanol and heptane penetrating process) and phase separation process. This new method for fabricating the cage-like multihollow polymer particles has a great meaning not only on confirming the formation mechanism, but also on providing an effective way to prepare the special hollow core/porous shell polymer particles, which could have wide range of potential applications, such as catalysts, sensors, and drug release.     

Formation of polymer–colloid complexes of aluminoxane particles with poly(acrylic acid) and its copolymers with acrylamide

Formation of polymer–colloid complexes formed by positively charged aluminoxane particles with a size of ~4.6 nm, which constitute the main part of the dispersed phase in aluminum polyhydroxychloride sols with poly(acrylic acid) and acrylic acid copolymers with acrylamide, is studied. Conditions of preparing water-soluble polymer–colloid complexes are determined. It is shown that water-soluble polycomplexes are obtained through the interaction of aluminoxane particles with acrylic acid–acrylamide copolymers containing no more than 0.8 mol% acrylic acid units. In the polymer–colloid complex, aluminoxane particles are uniformly distributed over polyelectrolyte macromolecules and the optimum composition is attained at the molar ratio of components Z equal to 1:1. In semidilute solutions, the addition of aluminoxane particles to the copolymer brings about formation of the gel featuring viscoelastic properties. For all copolymers, the maximally elastic properties of the gels are attained at Z ≈ 1.     

Synthesis of 4″-benzyloxyimino-4″-deoxyavermectin Bla derivatives

Six new 4″-benzyloxyimino-4″-deoxyavermectin Bla derivatives were synthesized from avermectin Bla by the selective protection of C-5-hydroxy group,oxidation of C-4″-hydroxy group,and deprotection followed by reaction with O-substituted hydroxylamine hydrochlorides.Their structures were confirmed by IR,~1H NMR,~(13)C NMR and MS.Insecticidal activities of the derivatives against Phopalosiphum pseudobrassicae,Spodoptera exigua and Pluteua xylosteua were evaluated.     

Combinational simulations of free energy of polymer solution

It is conceptually proposed that the total entropy of polymer solution is contributed from two distinct parts: the positional and the oomformational. The former can be represented analytically, while the latter can be simulated with the random self-avoiding walk model on the simple cubic lattice for multichain systems. The obtained results indicated that both the conformational entropy and the mixing heat are consistent with the scaling laws wry well.     

Biomimetic synthesis of raspberry-like hybrid polymer–silica core–shell nanoparticles by templating colloidal particles with hairy polyamine shell

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core–shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core–shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 °C for 2.5 h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA–silica hybrid shell. The resulting hybrid silica core–shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core–shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA–silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core–shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules.     

Thermodynamic and kinetic considerations on the morphological stability of “hamburger-like” composite polymer particles prepared by seeded dispersion polymerization

Micrometer-sized, monodisperse, “hamburger-like” polystyrene (PS)/poly(2-ethylhexyl methacrylate)/decane composite particles were obtained by seeded dispersion polymerization of 2-ethylhexyl methacrylate with PS seed particles in the presence of decane. The morphological stability of the hamburger-like particles was investigated based on thermodynamic and kinetic aspects. The hamburger-like morphology was maintained at 60 °C (above glass transition temperature (T _g)) for at least 1 week in spite of less thermodynamic stability than hemispherical morphology. T _g of the particles gradually increased throughout the polymerization due to monomer consumption. Geometric calculation result indicates that the degree of reduction of the interfacial free energy at the early stage of the morphological development is significantly low. From these results, it is concluded the morphological stability of the hamburger-like particles is considerably high because the development from hamburger-like to hemispherical morphologies is retarded by the gradual increase in viscosity inside the particles and the significantly lower interfacial free energy reduction.     

Electrical currents resulting from reduction/oxidation processes of tested particles on “inner” and “outer” surfaces of electroactive polymer films

Heterogeneous reactions of tested particles proceeding on electroactive films with different kinds of thin pores are described formally in terms of diffusion equations complicated with an accompanying volume reaction inside the film interior. As it is shown, in polarization curves of such processes, there might appear limiting flows, which are essentially smaller than the limiting diffusion flow of tested particles in the bathing electrolyte. These flows should not depend on a film pores’ topology, but be determined by the ratio of the total surface of pores and the visible film one. The obtained results are compared with those followed for the case when tested particles actually inculcate into the film matrix and react with either oxor red-fragments of the film. Identification criteria of the compared mechanisms are discussed.     

Preparation and application of streptavidin magnetic particles

Two kinds of streptavidin magnetic particles,namely streptavidin GoldMag particles and streptavidin amino terminal particles were prepared by the methods of physical adsorption and covalent interaction respectively.The streptavidin coated on magnetic particle surface,crucial to many applications,was greatly influenced by the choice of the different buffer.Compared with DynalbeadsM-270 streptavidin, the binding capacity for biotin of different streptavidin magnetic particles was determined by enzyme inhibition method,and the coupling capacity and activity of biotinylated oligonucleotide on their sur- face were also analyzed.The results indicated that the streptavidin GoldMag particle prepared by physical adsorption was stable in STE(NaCl-Tris-EDTA)buffer that was frequently used in nucleic acid hybridization and detection.The streptavidin amino terminal particles prepared by covalent interaction could be used both in STE buffer and PBS(phosphate buffered saline)buffer.The biotin binding ca- pacity for 1 mg of streptavidin GoldMag particles and streptavidin amino terminal particles was 4950 and 5115 pmol respectively.The capacity of biotinylated oligonucleotide(24 bp)coupled on 1 mg of GoldMag and amino terminal magnetic particles was 2839 and 2978 pmol separately.These data were about 6-7 times higher than those of DynabeadsM-270 streptavidin.The hybridization results with FITC-labeled complementary probe on magnetic particle surface demonstrated that the oligonucleotide coupled on streptavidin magnetic particles had high biological activity.     

Synthesis of 5,4″-di-O-succinoylavermectin B1

A reaction of avermectin B₁ with succinic anhydride at ultrahigh pressure (10 kbar) gave previously unavailable 5,4″-di-O-succinoylavermectin B₁, which is of interest as potential antiparasitic agent.

     

Kinetic study for adsorption of α-naphtholphthalein onto silica gel surface-imprinted polymer and non-imprinted polymer

In this study, the molecular imprinting polymer (MIP) was prepared using α-naphtholphthalein as a template, 2-(diethylamino)ethyl acrylate as a functional monomer and ethylene glycol dimethacrylate as a crosslinking agent by aid of free radical polymerization onto surfaces of vinyltrimethoxysilane modified silica gel. The MIP was extracted with acetonitrile for overnight to remove the template molecule from the MIP. Non-imprinted polymer (NIMP) was synthesized using the same materials except α-naphtholphthalein as template molecule. α-Naphtholphthalein adsorption on surfaces of the both polymer was studied at three different temperatures (19°C, 25°C and 35°C). It was observed that the adsorption capacity increased with increasing temperature and with time. The time required to reach the equilibrium for two polymers and all temperature was accepted to be nearly 6 h. The saturated adsorption amounts at the equilibrium were found as 120 mg/g, 123 mg/g and 127 mg/g at 19°C, 25°C and 35°C, respectively, for MIP, and 78 mg/g, 98 mg/g and 120 mg/g at 19°C, 25°C and 35°C, respectively, for NIMP. The mechanism of adsorption of α-naphtholphthalein onto MIP and NIMP is nearly appropriate to pseudo-first-order kinetic model with an activation energy of 11.63 kJ/mol for MIP, and 23.69 kJ/mol for NIMP. Thermodynamic parameters of activated complex in the adsorption process showed that the adsorption was carried out with an endothermic activation enthalpy, large negative entropy changes and the positive values of ΔG* that the adsorption processes is not favorable.     

Intramolecular reaction of polymer coordinated cationic rhodium complex

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