Influence of dispersion conditions and nature of the emulsifier on the dispersity and stability of artificial polymer suspensions based on polyetherimide

New methods for producing artificial polyetherimide suspensions in the presence of domestic cationic surfactants, their mixtures, and mixtures of cationic and organosilicon surfactants were proposed. The effect of the polymer concentration in the initial solution and conditions of emulsion dispersion on the stability and particle size of the final polymer suspensions is shown. The colloidal chemical properties of the obtained polymer suspensions are considered. Conclusions about the influence of the nature and concentration of surfactants on the stability of the obtained suspensions are drawn. When using a mixture of cationic and organosilicon surfactants, polymer suspensions stable during production and storage are formed, which is explained by the formation of structural mechanical and electrostatic stability barriers in the surface layers of the particles.

     

Polymerization of styrene in the presence of organosilicon surfactants of various natures

The properties of polymer suspensions obtained with the use of organosilicon surfactants of various structures are compared. The polymer suspensions are characterized by a narrow particle size distribution and contain functional groups on their surface.     

Surface activity and emulsification properties of hydrophobically modified dextrans

Neutral polymeric surfactants were synthesized by covalent attachment of hydrophobic groups (aromatic rings) onto a polysaccharide backbone (dextran). By changing the conditions of the modification reaction, the number of grafted hydrophobic groups per 100 glucopyranose units (substitution ratio) was varied between 7 and 22. In aqueous solution, these polymers behaved like classical associative polymers as demonstrated by viscometric measurements. The associative behavior was more pronounced when the substitution ratio increased. The surface-active properties of the modified dextrans were evidenced by surface tension (air/water) and interfacial tension (dodecane/water) measurements. In each case the surface or interfacial tension leveled down above a critical polymer concentration, which was attributed to the formation of a dense polymer layer at the liquid-air or liquid-liquid interface. Dodecane-in-water emulsions were prepared using the polymeric surfactants as stabilizers, with oil volume fractions ranging between 5 and 20%. The oil droplet size (measured by dynamic light scattering) was correlated to the amount of polymer in the aqueous phase and to the volume of emulsified oil. The thickness of the adsorbed polymer layer was estimated thanks to zeta potential measurements coupled with size measurements. This thickness increased with the amount of polymer available for adsorption at the interface. The dextran-based surfactants were also applied to emulsion polymerization of styrene and stable polystyrene particles were obtained with a permanent adsorbed dextran layer at their surface. The comparison with the use of an unmodified dextran indicated that the polymeric surfactants were densely packed at the surface of the particles. The colloidal stability of the suspensions of polystyrene particles as well as their protection against protein adsorption (bovine serum albumin, BSA, used as a test protein) were also examined.     

Polymerization of styrene in the presence of monoesters of aromatic dicarboxylic acids as surfactants

The colloidal properties of monoesters of aromatic dicarboxylic acids and the heterophase polymerization of styrene in their presence have been studied. It has been shown that particles are formed from micro-droplets of the monomer. A high stability of polymer suspensions during the synthesis has been found to be provided by a strong interfacial adsorption layer formed on the surface of particles from the polymer being synthesized and a surfactant.     

Thermal decomposition of polypyrroles

The thermal stability of polypyrrole (PPy) samples has been studied by thermogravimetry/mass spectrometry and pyrolysis-gas chromatography/mass spectrometry in inert atmospheres. PPy has been prepared by chemical oxidative polymerization using ferric sulfate as an oxidant and anionic surfactants, such as dodecylbenzenesulfonic acid and sodium dodecylbenzenesulfonate as co-dopants. For comparison we have studied polypyrrole (PPy-SO₄) prepared without any additive. It was found that the presence of anionic surfactants improved the thermal stability of PPy. The decomposition of PPy doped with ferric sulfate and anionic surfactants occurs at relatively high temperature indicating that chemical interactions exist between the polymer and the surfactants.     

Stability of manganese dioxide by guar gum in the absence or presence of surfactants

Stability of the manganese dioxide (MnO₂) suspensions by non-ionic guar gum (GG) in the absence or presence of the surfactants: anionic sodium dodecyl sulphate (SDS), cationic hexadecyltrimethylammonium bromide (CTAB) and non-ionic Triton X-100 (t-octylphenoxypolyethoxyethanol) and their equimolar mixtures (SDS/TX-100; CTAB/TX-100) was measured using turbidity. The obtained results of the manganese dioxide suspensions stability were discussed together with the adsorption data and with the data concerning the thicknesses of the adsorption layers. In order to gain more information about the structure of the electric double layer surface charge density and the zeta potential measurements were performed. The obtained results show that the addition of guar gum to the MnO₂ suspensions increases MnO₂ stability. The larger this increase is, the higher is the concentration of the polymer (concentration range 10–200 ppm). Moreover, the addition of single surfactants also causes the increase in the effectiveness of stabilizing the manganese dioxide suspensions. The reason for that is formation of multilayer complexes between the polymer and the surfactants. In such a system both the adsorption of polymer and the thickness of polymer adsorption layer increase. The greatest increase in the stability of MnO₂/GG suspensions was provided by the mixture of anionic and non-ionic surfactants due to a strong synergistic effect. Also, mixing the polymer and two surfactants reduces the stability of the suspension.     

Chemical composition and porous structure of polymer-derived silicoboron carbonitride ceramics prepared via a monomer route

Polymer-derived silicoboron carbonitride (SiBCN) ceramics were facilely prepared using organosilicon monomers tris(dichloromethylsilylethyl)borane and bis(trimethylsilyl)carbodiimide as the starting materials. The polymer precursors were obtained either without adding styrene or by adding an appropriate amount of styrene into the mixture of the organosilicon monomers, followed by heat treatment and purifying. The chemical composition and pore structure of the polymer-derived SiBCN ceramics were studied. It was found that styrene diluted the monomers and hindered their chemical reaction from forming the polymeric network. The polymer precursor prepared with styrene was composed of boron-modified polysilylcarbodiimide as the matrix and dispersed polystyrene mainly of sizes 20–50 μm. Accordingly, a polymer-derived SiBCN ceramic with a three-dimensional continuous macroporous structure containing pores mainly of 20.9–58.1 μm with a total porosity of 74% was achieved. The B/N atomic ratio reached 0.58 with low oxygen content of 2.81 wt%, which satisfied the requirement for high-temperature application.     

The influence of ionic and nonionic surfactants on aggregative stability and electrical surface properties of aqueous suspensions of titanium dioxide

The influence of concentration of nonionic TRITON X-100 and anionic ATLAS G-3300 surfactants, and pH of medium on the size and zeta-potential of TiO2 particles in the water suspensions has been studied. Suspensions have been prepared by mixing of the titanium dioxide in the suitable mediums at 10 min and 6 h correspondingly. It was established, that the duration of mixing of the suspensions has an essential influence on the dependence of zeta-potential and size of particles versus concentration of surfactant. However, the duration of mixing does not influence the dependence of electrical conductivity and pH of the suspensions on concentration of surfactant. It is shown that anionic ATLAS G-3300 surfactant is more effective stabilizator of aqueous suspensions of titanium dioxide, than nonionic surfactants of TRITON X-100. It is found that hydrophobic interaction has important role in the processes of stabilization of suspensions for nonionic surfactant, and for anionic surfactant--moving of psi(delta)-planes into solution's depth.     

Synthesis of azide‐functionalized nanoparticles by microemulsion polymerization and surface modification by click chemistry in aqueous medium

Stable translucent aqueous suspensions of azide‐functionalized cross‐linked nanoparticles (NPs), with diameters in the 15–20 nm range, were prepared using two synthetic approaches. Copolymerization of azidomethylstyrene (VBN₃), styrene, and divinylbenzene in various oil‐in‐water microemulsions led to NPs with modulable azide contents (0.53–0.78 mmol/g) and surface over volume distributions. Surface modifications of reactive NPs bearing chlorobenzyl groups, produced by microemulsion copolymerization of vinylbenzylchloride, with sodium azide led to azido‐coated NPs with high densities of peripheral groups (0.13–0.45 mmol/g). It is shown that the nature of the surfactant used for the preparation of the microemulsion has an impact on the incorporation of VBN₃ in the polymer particles as well as on the surface reaction yield. The azide‐functionalized NPs were used as clickable polymeric scaffolds for the grafting of sparingly water‐soluble dansyl and fluorescein derivatives through copper(I)‐catalyzed azide‐alkyne cycloaddition in water in the presence of surfactants as solubilizing agents to produce fluorescent NPs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A versatile preparation of azobenzene‐dye functionalized colored polymer nanoparticles by surface modification

A series of stable and translucent colored nanolatex, that is, colloidal aqueous suspensions of dye‐tagged polymer nanoparticles (NPs) in the 15‐ to 20‐nm diameter range, have been prepared by covalent attachment of azobenzene chromophores to the surface of reactive NPs. Primary crosslinked NPs bearing chlorobenzyl groups were produced by microemulsion copolymerization of styrene and vinylbenzylchloride. Amine‐functionalized NPs were obtained after a second functionalization step with polyamines (cyclam and polypropyleneimine dendrimers of first and third generations). Dye‐doped particles were obtained by reacting pyridylazo‐dimethylaminobenzene (PADA) with chlorobenzyl‐NPs and by reacting amine‐reactive dimethylaminoazobenzene dyes (DABsyl, DAB‐ITC) as well as Disperse Red 1 acrylate with polyamine‐coated NPs. Regardless the dye solubility, the grafting readily proceeded in aqueous suspensions at room temperature in the presence of a cationic surfactant without added solvent. Purple, red, and orange suspensions (maximum absorption around 550, 500, 430 nm), with dye loads ranging from 0.3 to 1.2 mmol/g, corresponding to 400–1800 azobenzene residues per NP, are obtained. The reported results indicate that functional polymer NPs, with remarkably accessible multiple anchoring sites, are useful building blocks. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3375–3386, 2008     

Surfactant‐free synthesis of amphiphilic diblock copolymer in aqueous phase by a self‐stability process

Amphiphilic polymeric particles with hydrophobic cores and hydrophilic shells were prepared via living radical emulsion polymerization of styrene using a water‐soluble poly(acrylamide)‐based macro‐RAFT agent in aqueous solution in the absence of any surfactants. Firstly, the homopolymerization of acrylamide (AM) was carried out in aqueous phase by reversible addition‐fragmentation chain transfer radical polymerization (RAFT) using a trithiocarbonate as a chain transfer agent. Then the PAM‐based macro‐RAFT agent has been used as a water‐soluble macromolecular chain transfer agent in the batch emulsion polymerization of Styrene (St) free of surfactants. The RAFT controlled growth of hydrophobic block led to the formation of well‐defined poly(acrylamide)‐copolystyrene amphiphilic copolymer, which was able to work as a polymeric stabilizer (self‐stability). Finally, very stable latex was prepared, having no visible phase separation for several months. FTIR and ¹H‐NMR measurements showed that the product was the block copolymer PAM‐co‐PS in the form of stable latex. Atomic force microscope (AFM), transmission electron microscope (TEM), and dynamic light scattering (DLS) studies indicated that the nanoparticles have a narrow particle size distribution and the average particle hydrodynamic radius was kept in the diameter of 58 nm. Core‐shell structure of the copolymer was also recorded by TEM. The mechanism of the self‐stability of polymer particles during the polymerization in the absence of surfactants was studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3098–3107, 2008     

Effects of surfactants and pH of medium on zeta potential and aggregation stability of titanium dioxide suspensions

The effects of benzethonium chloride, sodium dodecylbenzenesulfonate, and 4-(1,1,3,3-(tetramethylbutyl)phenyl poly(ethylene glycol) on the zeta potential and aggregation stability of aqueous rutile-form titanium dioxide suspensions are studied in the pH range of 2–12. It is shown that the nonionic surfactant does not affect significantly the zeta potential and aggregation stability of the suspensions. The influence of ionic surfactants on the aggregation stability of the suspensions considerably depends on the pH of a medium. At pH values above the isoelectric point of titanium dioxide suspensions (pH₀ = 6.2), the suspensions demonstrate a high aggregation stability in the presence of the anionic surfactant, sodium dodecylbenzene-sulfonate (irrespective of its content), while, at pH < pH₀, the aggregation stability of the suspensions markedly increases with the surfactant concentration. In the presence of the cationic surfactant, benzethonium chloride, the aggregation stability of the suspensions is independent of the surfactant concentration at pH < pH₀, whereas, at pH > pH₀, it increases with the surfactant concentration.     

Amphiphilic polysaccharides: useful tools for the preparation of nanoparticles with controlled surface characteristics

Polymeric surfactants obtained by hydrophobic modification of dextran are used as stabilizers for oil-in-water emulsions. The kinetics of interfacial tension decrease is studied as a function of polymer structural characteristics (degree of hydrophobic substitution) and at various polymer concentrations. Several hydrocarbon oils, either aliphatic (octane, decane, dodecane, and hexadecane) or aromatic (styrene), are tested. Kinetics exhibits the same general trends no matter which oil or polymer is considered. The emulsifying properties of the polymeric surfactants are illustrated by the preparation of oil-in-water emulsions. The droplet size at the preparation is correlated to the amount of oil and to the polymer concentration in the aqueous phase. For low polymer/oil ratios, it is shown that the droplet size is limited by the initial amount of polymer. On the contrary, for high polymer/oil ratios, the droplet size seems to level down, indicating that other parameters become predominant. Emulsion aging occurs by Ostwald ripening, and it is demonstrated that the theoretical equation of Lifshitz, Slyozov, and Wagner (LSW) correctly describes the experimental results. The nature of the oil has important effects on emulsion aging, as described by the LSW equation. The aging of emulsions containing oil mixtures is quantitatively described on the basis of the results with pure oils. The influence of polymer chemical structure can be conveniently correlated to interfacial tension results through the LSW equation. On the contrary, the influence of oil volume fraction seems to be overestimated by the usual correction factor, k(phi). The effect of temperature on emulsion aging is finally examined. Miniemulsions stabilized with dextran derivatives are used for the radical polymerization of styrene. Following this procedure, polysaccharide-covered polystyrene nanoparticles are prepared and characterized (size and surface coverage). The size of the particles is directly correlated to that of the initial droplets for styrene volume fractions around 10%. On the contrary, for initial styrene volume fractions around 20%, particles exhibit a larger size than the initial droplets, indicating that coalescence processes take place during polymerization. The amount of dextran at the surface of the particles is determined and compared to the adsorbed amounts resulting from emulsion preparation.     

Polymer Inclusion Compounds by Polymerization of Monomers in β-Cyclodextrin Matrix in DMF Solution

The investigations of the synthesis of polyrotaxanes by the radical polymerization of monomers (vinylidene chloride, methyl acrylate, styrene, and methacrylonitrile) in DMF in the presence of β-cyclodextrin have been carried out. The possibility of formation β-cyclodextrin inclusion compounds with some vinyl monomers or some other organic substances in DMF solution has been established. We assume that the inclusion in presence of the solvent is related to the unusual phenomenon of β-cyclodextrin crystallization in hot DMF solutions. The polymerization of vinyl monomers in DMF solution at increased temperatures in the presence of β-cyclodextrin leads to compounds containing a great amount of cyclic compounds (up to 80%). Similar results have been obtained for monomers introduced as previously prepared adducts with β-cyclodextrin. Stable compounds of polymer and β-cyclodextrin have been obtained in the case of vinylidene chloride. The lack of carbohydrate moieties in the product obtained by polymerization of vinylidene chloride in the presence of linear dextrin suggest the inclusion character of the linkage between polymer and β-cyclodextrin molecules. The structure of a topological compound of polyrotaxane type is most feasible after dehydrochlorination.     

ER suspensions of composite core‐shell microspheres with improved sedimentation stability

Electrorheological (ER) fluids are usually suspensions of solid polarizable particles in nonpolar carrier liquids. Such systems are particularly sensitive to the presence of electric fields, which transform them reversibly into solid‐like bodies. Fast (within milliseconds) and fully reversible reaction of ER fluids to electric field is a subject of great interest because of many possible applications in tunable vibration dampers, clutches, valves, or brakes. A novel type of ER fluids with composite microspheres composed of polymer electrolyte shell with defined shell thickness and inorganic hollow cores has been synthesized and tested in the presence of an electric field. It has been found that suspensions with composite grains possessed more stable ER response with temperature and lower power consumption in comparison to their polymer‐based counterparts. ER effect of the prepared fluids was measured and related to the applied electric field and solid phase properties. It has been also shown that suspensions of composite materials exhibited improved long‐term sedimentation stability in comparison to polymer‐based suspensions due to the formation of weak microstructure which suppressed the sedimentation of solid phase in off‐field state. Copyright © 2011 John Wiley & Sons, Ltd.     

Properties of emulsions and free emulsion (Aqueous) films stabilized with hexylamine-modified silica

The type and stability of emulsions, as well as the stability and thickness of free aqueous emulsion films stabilized with Aerosil-hexylamine mixtures, have been studied. The rheological characteristics (dynamic yield stress, elasticity modulae, and viscosity) have been measured for suspensions from which emulsions and films have been prepared. It has been shown that the properties of the films depend on the rheological properties of the suspensions.     

Stability of Polyaniline Aqueous Dispersions Prepared in the Presence of Surfactant Mixtures

Aqueous dispersions of doped polyaniline were synthesized in the presence of mixtures of a carboxylcontaining polymeric surfactant with low- and high-molecular-mass stabilizers. Polyaniline aqueous dispersions obtained using a mixture of carboxyl-containing polymeric and low-molecular-mass surfactants are characterized by high dispersity and narrow particle-size distribution but low sedimentation stability. The doping agent influences the stability of the dispersions prepared in the presence of polymeric and low-molecular-mass surfactants. The dispersions obtained using a mixture of macromolecular surfactants are characterized by larger particle size but higher sedimentation stability due to increased viscosity of the system.     

The polymerization of acrylic acid in the presence of copolymers containing interacting and non-interacting groups

There has been a kinetic examination of the polymerization of acrylic acid in dilute aqueous solution in the presence of copolymers of vinyl pyrrolidone with acrylamide or styrene. In general, the characteristics of the polymerizations are very similar to those found in the presence of polyvinyl pyrrolidone homopolymer, but the definite differences, taken in conjunction with gravimetric data on the polymer complexes, can be explained by the fact that acrylamide is hydrophilic while styrene is hydrophobic. The use of the copolymers has permitted an assessment of the effect of dilution of monomer adsorbed on the interacting polymer.     

Organosilicon hydrides in macromolecular design: Reactions of chain-transfer and hydrosilylation

The chain-transfer constants through silicon hydrides in bulk polymerization of styrene and methyl methacrylate (MMA) were measured with using 15 organosilicon compounds belonging to four classes: oligoorganohydrosilanes, oligoorganohydrosiloxanes, disilalkanes and alkylhydrosilanes. The linear dependences of the logarithm of chain-transfer constant on the sum of the Taft inductive constants of substituents at silicon atoms of a Si-H group were found. The negative values of reaction constants ρ indicate that an electrophilic attack of macroradical onto a hydrogen atom occurs at the limiting stage of the process. Oligoorganohydrosilanes proved to be the most effective chain-transfer agents that can be explained by high electron-donating properties of R₃Si substituents. The increase of the chain-transfer constant values takes place on the accumulation of both trimethylsilyl and silicon hydride groups in a molecule of hydrosilane. The high electrophilicity of PMMA macroradical as compared with a macroradical of polystyrene (PS) is responsible for a greater sensitivity of the polymerization reaction of MMA to the change of the electron density on a hydrogen atom of the organosilicon chain-transfer agent. In the radical polymerization of MMA and styrene in the presence of the chain-transfer agents till high conversion the polymers with a narrower molecular weight distribution (MWD) in comparison with those synthesized by usual polymerization in bulk are formed. The polymers prepared in the presence of multifunctional silanes can be functionalized by the reaction of hydrosilylation and further used in the synthesis of block copolymers.     

Preparation of pinewood/polymer/composites using gamma irradiation

Wood/polymer composites (WPC) have been prepared from pinewood with different compounds using gamma irradiation: butyl acrylate, butyl methacrylate, styrene, acrylamide, acrylonitrile, and unsaturated polyester styrene resin. The polymer loading was determined with respect to the compound concentration and the irradiation dose. The polymer loading increases generally with increase in the monomer or polymer concentration. Tensile and compression strength have been improved in the four cases, but no improvement was observed using unsaturated polyester styrene resin or acrylamide.