Synthesis of uniform PMMA microspheres employing modified SPG (shirasu porous glass) emulsification technique

Application of the particulate microporous glass membrane (SPG) was extended to the synthesis of fairly monodisperse poly(methyl methacrylate) (PMMA) microspheres. Hydrophilic monomers have been believed to yield polymer particles of a broad size distribution when the SPG technique was employed. This difficulty was overcome by adopting the droplet swelling technique. The primary uniform emulsion composed of a mixture of hydrophobic diluent (and/or monomer), cosurfactant, and initiator was prepared with an SPG membrane and was allowed to absorb MMA (and diluent) under the principle of the degradative diffusion process from droplets in the secondary emulsion. The coefficient of variation of PMMA spheres was around 10%. Porous PMMA spheres possessing up to 185 m²/g of specific surface area were obtained as well as one-eyed spheres and smooth and solid spheres. © 1995 John Wiley & Sons, Inc.     

Dependence of morphological changes of polymer particles on hydrophobic/hydrophilic additives

Fairly uniform microspheres of poly(styrene‐co‐methyl methacrylate) were prepared by employing a microporous glass membrane [Shirasu porous glass (SPG)]. The single‐step SPG emulsification, the emulsion composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor, was then transferred to a reactor, and subsequent suspension polymerization followed. The droplets obtained were polymerized at 75°C under a nitrogen atmosphere for 24 h. The uniform poly(styrene‐co‐methyl methacrylate) microspheres with diameters ranging from 7 to 14 μm and a narrow particle‐size distribution with a coefficient of variation close to 10% were prepared by using SPG membrane with a pore size of 1.42 μm. The effects of the crosslinking agent and hydrophobic additives on the particle size, particle‐size distribution, and morphologies were investigated. It was found that the particle size decreased with a narrower size distribution when the additives were changed from long‐chain alkanes to long‐chain alcohols and long‐chain esters, respectively. Various microspheres with different morphologies were obtained, depending on the composition of the oil phase. The spherical poly(styrene‐co‐methyl methacrylate) particles without phase separation were obtained when using an adequate amount of the crosslinking agent and methyl palmitate as an additive. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1013–1028, 2000     

High-flux and solvent-selective membranes with aromatic functionalities and dual-layer structures

Efficient separation of aromatic-aliphatic hydrocarbon mixtures has long been an important topic in chemical industries. Organic nanofiltration (OSN) has been revealing great promise in separating solvent mixtures that has not been effectively resolved by the state-of-the-art technologies. Herein, novel OSN membranes are designed for the separation of toluene and n-heptane. Polyamide active layer with diaminonaphthalene as the aqueous phase monomer is prepared by interfacial polymerization for the first time. The addition of polydimethylsiloxane gutter layer, as well as the combination of spin coating technique and macroporous substrate, renders the membranes with loose and defect-free architectures. The as-designed membranes achieve a rather high selectivity of toluene over n-heptane (>4) together with ultra-high toluene permeance (>180 L m^?2 h^?1 bar^?1). These membranes also present excellent stability in the long-term operation.     

Two‐stage stabilizer addition protocol as a means to reduce the size and improve the uniformity of polymer beads in suspension polymerization

A two‐stage stabilizer addition protocol is suggested for reducing the size and improving the uniformity of polymer beads resulting from conventional suspension polymerization. The stabilizer load was divided into an initial charge and a secondary addition. The use of a low concentration of stabilizer in the initial charge served to assist drop rupture while avoiding significant reduction in drop size and production of too many satellite droplets. The secondary addition time of stabilizer occurred just before the onset of the growth stage when drops were vulnerable to coalescence but robust against break up due to their high viscosity. The secondary addition of stabilizer served to provide stability to monomer drops during the growth stage and as a result the drops underwent limited coalescence. This resulted in the formation of smaller and more uniform polymer beads in comparison to beads obtained by conventional suspension polymerization at the same overall concentration of stabilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45671.     

Seeded emulsion polymerization of n-butyl acrylate utilizing miniemulsions

Nucleation of polymer particles in the seeded emulsion polymerization of n-butyl acrylate (BuA) was studied through experiments designed to control the amount of new particles formed. The results show that for the batch and semicontinuous seeded polymerization of BuA, a small amount of new particles was formed in the system in which the monomer was added neat, whereas a singificant amount of new particles was formed when the monomer was added as a miniemulsion. This suggests that new particles formed in the miniemulsion process were from nucleation of the monomer droplets. These experiments also showed that monomer-droplet nucleation decreased with increasing seed concentration in the reactor. For the seeded semicontinuous polymerizations, monomer-droplet nucleation decreases with decreasing BuA miniemulsion feed rate. The results also show that monomerdroplet nucleation takes place whenever miniemulsion droplets exist in the reactor. This study suggests that miniemulsions can be used to control the particle size distribution of a polymer latex system.     

Preparation and characterization of silica/polypyrrole core‐shell colloidal particles in the presence of ethanol as the cosolvent

The silica/polypyrrole core‐shell composites were fabricated by in situ chemical polymerization of pyrrole monomer on the surface of the silica spheres. Silica sol particles with narrow size distributions were prepared by hydrolysis of tetraethoxysilane with sol–gel method. Polypyrrole shell was obtained by chemical polymerization of pyrrole monomer on the surface of the silica spheres in the water–ethanol mixture. It can be seen from the experiment, with the adding of small amount of ethanol cosolvent to the aqueous reaction solution, a uniform coating of polypyrrole appeared on the surface of silica. The core‐shell morphology of composite particles prepared with variation ethanol adding amount was analyzed by TEM. Meanwhile, the conductivity of the core‐shell composite is found to be enhanced apparently compared with those prepared from pure aqueous system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Semibatch emulsion polymerization of butyl acrylate. I. Effect of monomer distribution

The effects of initial monomer charge on the particle formation and on the rate of polymerization were investigated for semibatch emulsion polymerization of butyl acrylate using sodium lauryl sulfate (SLS) as a surfactant and potassium persulfate (KPS) as an initiator. For the semibatch process with monomer (M) feed, it was found that by varying the monomer distribution ratio between the initial reactor charge and the feed it is possible to alter the contribution of monomer‐flooded and monomer‐starved nucleation mechanisms to the whole nucleation process. The number of particles increases as the initial monomer charge decreases, if the monomer concentration is below a critical value for any fixed system. The increase in number of particles is associated with a broad particle‐size distribution which might depict an emerging second peak on the particle‐size distribution curve. For low emulsifier concentration systems, a larger number of particles was obtained for a lower amount of monomer charge. Particle coagulation and emulsifier adsorption on the monomer droplets were counted as the main reasons for such behavior. For a semibatch process with monomer emulsion (ME) feed, the larger number of particles was formed at a lower initial monomer charge, similar to an M‐add semibatch process. However, the application of monomer charge to an ME‐add process was found to increase the possibility of secondary nucleation and led to the occurrence of a bimodal particle‐size distribution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3094–3110, 1999     

Polymerizations of ethylene and propylene initiated by milled metallic oxides. II. Characterizations of the mechanochemically produced polymers

Polyethylene was mechanochemically produced by milling of alumina powder at room temperature in the presence of ethylene monomer. Nearly 50% of the produced polyethylene was chemically bonded with the matrix of the alumina. The other 50% of the polymer was extracted by the organic solvents. The polyethylene extracted by the hot n-heptane was characterized as having a structure similar to that of the branched polyethylene of low density, and the toluene extracted polyethylene had a structure similar to that of the high density polyethylene. The molecular weights of the mechanochemically produced polyethylene were found to distribute from 10² to 10⁶ by gel permeation chromatography. The weight average molecular weight was estimated as 260,000 after the 3 days milling. Mechanochemical polymerization of ethylene was also demonstrated by milling of silica in the presence of ethylene monomer. Polymerization of propylene by milling of alumina under propylene atmosphere was performed. The obtained polymer was found to be an atactic by IR measurement and the molecular weight of the extracted product was determined as ? 400 by the vapor pressure osmometer.     

Synthesis of 100 μm uniform porous spheres by SPG emulsification with subsequent swelling of the droplets

100 μm porous p(styrene-co-divinylbenzene) (PS-DVB) microspheres were synthesized by employing a particular membrane emulsification technique, and subsequent swelling of the seed droplets. DVB dissolving a water-insoluble substance, hexadecane (HD), and an initiator was permeated through a SPG (Shirasu porous glass) membrane, and the uniform (seed) droplets were released to a stabilizer solution acting as the continuous phase. The average droplet size was around 30 μm, and this emulsion was mixed with a secondary emulsion of much smaller size consisting of more hydrophilic components, a mixture of styrene, middle chain alcohol (C6 to C8), dichlorobenzene, and isoamyl acetate, which promotes the degradative diffusion process of the components. After all the droplets in the secondary emulsion virtually disappeared, the seed droplets were swollen to a maximum 110 μm. Polymerization was carried out at 348 K under a nitrogen atmosphere. Uniform porous spheres of 100 μm with the coefficient of variation less than 10% were obtained. Specific surface area was 350 m²/g. Careful controlling of the specific gravity of swollen droplets and the choice of solvents balancing between the good solvency for the polymer and polarity (solubility in water) proved vital in order that the polymerization may proceed without an extensive phase separation in the early stage, which eventually induces breakup of the droplets. The three component system, isoamyl acetate-hexanol-o-dichlorobenzene, provided an adequate cosolvent for these purposes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 931–942, 1997     

Kinetics and latex particles analysis on styrene emulsion polymerization induced by <Superscript>60</Superscript>Co γ rays in presence of anionic polymerizable emulsifier

⁶⁰Co γ rays induced styrene emulsion polymerizations were carried out with sodium undec-10-enoate (UDNa) as emulsifier at room temperature and the different kinetics was discussed. The influence of absorbed dose rate, monomer concentration and emulsifier concentration on kinetics and latex particles was studied. The polymerization kinetics relation was found as R _P ∝ D ^0.37 · M ^0.75 · E ^0.70 (R _P , maximum polymerization rate; D, absorbed dose rate; M, monomer concentration; E, emulsifier concentration). The particles’ diameter increases and particle size distribution (PSD) becomes narrower with the decrease of absorbed dose rate and increase of monomer content. The effect of UDNa content on particles’ diameter and particle size distribution is the same as that of emulsifier in conventional emulsion system. This type of emulsion polymerization can easily form monodisperse particles.     

Ultrasound‐assisted emulsion polymerization of poly(methyl methacrylate‐co‐butyl acrylate): Effect of initiator content and temperature

In this study, we propose an efficient method for preparation of large scale, monodisperse poly(methyl methacrylate‐co‐butyl acrylate) latexes by application of the low power ultrasound irradiation. The effect of polymerization temperature and initiator concentration on the polymerization nature, particle size, and particle size distribution were investigated. Results indicated that the ultrasound pulses in the first minutes of polymerization increase instant free radical to monomer ratio as well mixing efficiency which led to higher monomer conversion, improved polymerization rate (especially at first 15 min of the reaction), and remarkable decrease in molecular weight distribution. Transmittance electron microscopy (TEM) and dynamic light scattering (DLS) revealed that the particle size and particle size distribution were significantly affected, particle size decreased, and more uniform particles were obtained. Dynamic mechanical thermal analysis also showed that the initiator concentration affected glass transition temperature (T_g) of the final copolymers and in the case of ultrasound‐assisted emulsion polymerization T_g was in a very good agreement with theoretical predictions for copolymerization. POLYM. ENG. SCI., 56:214–221, 2016. © 2015 Society of Plastics Engineers     

A Comprehensive Framework for the Numerical Simulation of Evaporating Electrosprays

A framework for simulating the coupled physical phenomena that occur in evaporating electrosprays has been developed. This framework comprises a 3D Lagrangian model for droplets dynamics, evaporation, and Coulomb explosions, as well as steady-state 2D Eulerian models for gas flow induced by the droplets motions, the transports of vapor and heat in the gas phase, and the transport of the charged residues left behind by the fully evaporated droplets (residual-charge). To couple these different physics, the Lagrangian code and the four Eulerian ones are solved sequentially in order to attain a fully coupled solution of the global steady-state. This methodology has been applied to three electrospray systems made from solvents of different volatility (acetone, methanol, and n-heptane), with identical droplet size distribution at injection (a lognormal with mean diameter of 8 μm and CV = 10%). All fields converged after just a few (five) sequences of simulation. In the two systems in which the droplets travel fastest (acetone and methanol), conical fringes develop in the contour maps of volumetric rate of generation of residual-charge, which correspond to the first few Coulomb explosions. In the system in which the droplets moved slowest (n-heptane), such contour maps show an unstructured region, instead.

Copyright 2015 American Association for Aerosol Research     

Mass transfer effects in emulsion polymerization systems. I. Diffusional behavior of chain transfer agents in the emulsion polymerization of styrene

On the basis of the so-called two-films theory for mass transfer, a mathematical model for transfer of chain transfer agents from monomer droplets to polymer particles, where chain transfer agent molecules are consumed by the chain transfer reaction, is developed for an emulsion polymerization system. It is shown by the model that the concentration of chain transfer agent in the polymer particles during the polymerization is decreased to a value much less than that which would be attained if thermodynamic equilibrium for chain transfer agent were reached between the polymer particles and the monomer droplets, due mainly to the resistance to transfer of chain transfer agent molecules across the diffusion films at the interface between the monomer droplets and the water phase. The validity and utility of the model developed for predicting the diffusion and consumption rates for chain transfer agent are demonstrated experimentally using five normal aliphatic mercaptans from n-C₇ to n-C₁₂ as chain transfer agents in the seeded emulsion polymerization of styrene. © 1994 John Wiley & Sons, Inc.     

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate

Ultrasonically initiated emulsion polymerization of n‐butyl acrylate (BA) without added initiator has been studied. The experimental results show that high conversion of BA can be reached in a short time by employing an ultrasonic irradiation technique with a high purge rate of N₂. The viscosity average molecular weight of poly(n‐butyl acrylate) (PBA) obtained reaches 5.24 × 10⁶ g mol^?1. The ultrasonically initiated emulsion polymerization is dynamic and complicated, with polymerization of monomer and degradation of polymer occurring simultaneously. An increase in ultrasound intensity leads to an increase in polymerization rate in the range of cavitation threshold and cavitation peak values. Lower monomer concentration favours enhancement of the polymerization rate. ¹H NMR, ¹³C NMR and FTIR spectroscopies reveal that there are some branches and slight crosslinking, and also carboxyl groups in PBA. Ultrasonically initiated emulsion polymerization offers a new route for the preparation of nanosized latex particles; the particle size of PBA prepared is around 50–200 nm as measured by transmission electron microscopy. © 2001 Society of Chemical Industry     

Kinetics of vinyl chloride and vinyl acetate emulsion polymerization

The kinetics of vinyl chloride and vinyl acetate emulsion polymerization are reexamined. The validity of Ugelstad's model for systems with high desorption rate is confirmed by simulating conversion histories for both systems at different initiator concentrations and particle numbers. On the basis of the model, it is shown that at ordinary initiation rates, termination reactions are unimportant with respect to molecular weight development in both systems, and as a consequence, molecular weight development is independent of number and size distribution of polymer particles and of initiator and emulsifier level. Based on this conclusion, it is shown that in accordance with experimental facts, the molecular weight distribution obtained in vinyl chloride emulsion polymerization is the most probable distribution, and it is concluded that the number of long-chain branch points per repetition unit is less than 2 × 10^?4 at high conversions. In vinyl acetate emulsion polymerization, an almost logarithmic normal distribution is obtained. The distribution is strongly broadened by branching reactions with the number of long-chain branch points increasing rapidly with monomer conversion. The increase of M_n with increasing conversion is due to terminal double-bond polymerization, while the increase in M_w is due mainly to transfer to polymer.     

Facile preparation of cationic P (St-BA-METAC) copolymer nanoparticles and the investigation of their interaction with bovine serum albumin

Cationic copolymer nanoparticles were prepared by emulsifier-free emulsion polymerization of styrene and n-butyl acrylate, using [2-(methacryoyloxy ethyl] trimethylammonium chloride as the cationic functional comonomer and 2,2′-azobis (2-methypropionamidine) as the cationic initiator. FTIR spectroscopy, ¹H-NMR spectroscopy, and GPC were applied to characterize the chemical structure and molecular weight of the obtained copolymer. The size and size distribution of the nanoparticles were characterized through photon correlation spectroscopy. The interaction of nanoparticles with bovine serum albumin (BSA) was investigated by the means of transmission electron microscopy and fluorescence spectroscopy. It was found that the copolymer nanoparticles were monodisperse spheres with the diameter less than 90 nm and can complex well with BSA through electrostatic interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003     

On the effects of emulsion polymerization of furfuryl alcohol on the formation of carbon spheres and other structures derived by pyrolysis of polyfurfuryl alcohol

Carbon spheres were synthesized by emulsion polymerization and pyrolysis of polyfurfuryl alcohol. Pluronic F-127 was used as the structure-directing agent to synthesize polymer spheres that after pyrolysis led to carbon spheres with average sizes from 50 nm to few micrometers in diameter depending upon the conditions of polymerization. As-synthesized carbon spheres possess high surface areas of around 480 m²/g with an average mean pore size of 0.5 nm. These spheres can be activated using carbon dioxide to create much higher surface areas (>1500 m²/g). Different compositional regions of the pseudo-ternary phase diagram of surfactant/monomer/solvent were explored in order to determine the effects of changes in the emulsion polymerization variables on the kinds of carbon morphologies that could be derived from polyfurfuryl alcohol after pyrolysis. The diameter of the carbon spheres was found to be sensitive to monomer and surfactant concentrations, acid molarity and solvent composition. In general, the diameter of the spheres grew with increasing furfuryl alcohol concentration and decreasing surfactant concentration, respectively. By varying the acid concentration and solvent composition, a minimum diameter for spheres was found. The formation and size of the spheres are strongly influenced both by micelle growth and the polymerization mechanism.     

Influence of monomer preemulsification on formation of particles from monomer drops in emulsion polymerization

Evidence was obtained supporting the theory that monomer droplets can become a locus of initiation and propagation in emulsion polymerization. This was done by reducing the size of the monomer droplets prior to initiation of polymerization using different preemulsification techniques for a typical latex recipe containing a common anionic surfactant. Monomer droplet size reduction caused an increase in the total surface area of the monomer droplets and thereby increased the competitiveness of these droplets for capturing active free radicals which are generated in the aqueous phase. As the total surface area of the monomer droplets was increased by preemulsification, a corresponding increase in the number of large particles formed by polymerization of these monomer droplets was experimentally measured. This work shows that monomer droplets are a locus of emulsion polymerization. However, the importance of monomer droplet polymerization is limited by their total surface area because of the competition for free radicals with other surfaces and/or particle nucleation processes. The results offer a basis for explaining why broad, and sometimes bimodal, particle size distributions are obtained in some commercial processes where the reactants are preemulsified prior to being charged into a reaction vessel.     

Creating monodisperse polymer microspheres using membrane emulsification

This study used membrane emulsification (ME) as a pre‐treatment step to suspension polymerization to produce polystyrene microspheres with diameters from 200 to 300 µm and coefficient of variation (CV) as low 20%. Limited scientific information is available on utilizing suspension polymerization to prepare monodisperse polystyrene microspheres with diameters greater than 100 µm. Microspheres were produced by pumping monomer solution through uniform pores of nickel membranes to form dispersed phase droplets that were transferred to a reactor for suspension polymerization. Systematic studies were done to understand the roles of continuous phase composition, ME unit process parameters, and polymerization reactor stir speed on microsphere size and CV. For a specific microsphere size, there were particular stir speeds in each unit that minimized CV. The methodology developed in this study is being used to prepare monodisperse polymer resin beads to improve detection efficiency and accuracy in flow‐cell sensors for quantifying waterborne radioactivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44593.