Large-scale and narrow dispersed latex formation in batch emulsion polymerization of styrene in methanol–water solution

This work is an extension of previous research results reported by our team (Colloid Polym Sci 291:2385–2389, 2013), where monodisperse, large-scale, and high-solid-content latexes of poly(n-butyl acrylate) were obtained with the particle coagulation method induced by the electrolyte. However, large-scale polystyrene latex particle is difficult to synthesize with this approach; moreover, demulsification phenomena easily take place especially in high solid content. In this article, a new approach to prepare large-scale polystyrene latex particle was proposed. Methanol was added to aqueous phases to decrease the interfacial tension between the polymer particle surface and continual phases, further decreasing interfacial free energy. Consequently, the surfactant molecules would loosely pack on the polymer particle surface, which is favored by particle coagulation. Experimental investigations showed that the final polystyrene particle scale only reaches to 93.5 nm when the methanol/water ratio is equal to 0:100, but the particle size attains 270 nm when the methanol/water ratio is equal to 30:70. These results indicated that polystyrene particle coagulation can be induced by methanol by varying the surfactant molecule adsorption on the particle surface. This investigation also provided a new simple approach to prepare large-scale, stable latex particles.     

Synthesis of Sub-100 nm and Narrow Particle Size Distribution Cationic Latex by One-Step Emulsion Polymerization

A novel approach to synthesize narrow particle size distribution cationic latex particles based on styrene and butyl acrylate was proposed. The effect of monomer/water ratios, surfactant (cetyltrimethylammonium chloride) concentrations, and monomer compositions on the evolution of particle size, distribution, number, and morphology as a function of monomer conversion was concerned in order to confirm the optimum polymerization condition. As expected, the particle size of the ultima latex increased with monomer/water ratios and styrene contents decreased with increasing surfactant concentrations. Continuous nucleation phenomena occurred when monomer/water ratio was lesser than 30/70, resulting in a gradual increase in the number of particles in the whole polymerization process. Combined with the previous work (Colloid and Polymer Science, 2014, 292: 519–525), it was concluded that particle coagulation easily took place in cationic emulsion polymerization of styrene. Thus, the narrow particle size distribution cationic latexes with particle scale between 50 nm and 80 nm, 30 wt% solid content could be prepared in a short reaction time.     

International interlaboratory study for sizing and quantification of Ag nanoparticles in food simulants by single-particle ICPMS

This publication describes the first international intercomparison of particle-size determination by single-particle inductively coupled plasma mass spectrometry (sp-ICPMS). Concentrated monodisperse silver nanoparticle suspensions with particle diameters of 20, 40 and 100 nm and a blank solution were sent to 23 laboratories in Europe, the USA and Canada. Laboratories prepared eight nanoparticle preparations in two food simulants (distilled water; 10 % ethanol) and reported median particle size, Ag particle mass concentration and Ag particle number concentrations. Average repeatability and reproducibility standard deviation (s _r and s _R) for the median particle diameter were 1 and 14 nm, respectively. Relative precision was worse for Ag particle number concentrations (RSD _r?=?11 %; RSD _R?=?78 %). While further improvements of the method, especially with respect to software tools for evaluation, hardware options for shorter dwell times, calibration standards for determining nebuliser efficiency and further experience by laboratories are certainly desirable, the results of this study demonstrate the suitability of sp-ICPMS for the detection and quantification of certain kinds of nanoparticles.     

Preparation of monodisperse latexes and study of their rheological properties

The synthesis of (monodisperse) poly(styrene) latexes was reexamined using sodiumdodecyl sulfate as emulsifier and potassium persulfate as initiator. It has been shown, that at fixed emulsifier concentration c_E the variation of persulfate amount produces similar particle size variations as changes of electrolyte (potassium sulfate) concentration at a given low initiator level. For c_E << cmc a maximum of particle size versus initiator or electrolyte concentrations has been found. Concentrated monodisperse poly(styrene) dispersions and carboxylated latexes up to 50% have been prepared by a carefully controlled seeding process using monomer feed. Particle size influence on steady shear viscosity has been studied for different kinds of polymer dispersions: for electrostatic stabilized poly(styrene) latexes at high ionic strengths, for electrostatic and sterically stabilized carboxylated latexes at different pH values and for steric stabilized dispersions of poly(vinyl chloride) in plasticizer (dioctyl phthalate). All three kinds of dispersions give pronounced particle size effects on viscosity, which is different from hard-sphere-behaviour. Simple model equations have been formulated to describe the concentration and shear rate dependence on viscosity. Particle size influence may be discussed on the basis of the effective hydrodynamic particle diameter. Causes for the increase of the hydrodynamic particle size are given either by surface swelling or by the formation of particle clusters which are formed and destroyed within the shear field.     

Acetal‐functionalized polymer particles useful for immunoassays. II. Surface and colloidal characterization

Monodisperse polymer colloids with dimethyl and diethyl acetal functionalities were synthesized by a two‐step emulsion polymerization process. The first step consisted of a batch emulsion homopolymerization of styrene (St). The dimethyl and diethyl acetal functionalities were obtained by batch emulsion terpolymerization of St, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA) or methacrylamidoacetaldehyde diethyl acetal (MAADA) in the second step, onto the previously formed polystyrene latex particles. The latexes were characterized by TEM and conductimetric titration, in order to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. The chemical stability of the functionalized surface groups during the storage time was analyzed. The hydrophilic character of the surface of the polymer particles was determined by means of nonionic emulsifier titration. The colloidal stability of the synthesized latexes was studied by measuring the critical coagulation concentration (CCC) against KBr electrolyte, and the existence of a hairy layer on the surface of the latex particles was analyzed by measuring the hydrodynamic particle diameter at several electrolyte concentrations. The surface functionalized groups remained stable for 2 years. The relative hydrophilic character and the colloidal stability were affected by the pH of the medium. On the other hand, the higher the surface charge, the larger the thickness of the hairy layer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 501–511, 1999     

Acetal-functionalized polymer particles useful for immunoassays

The synthesis of core-shell type polystyrene monodisperse particles with surface acetal groups was carried out by a two-step emulsion polymerization process. In a first step, the core was synthesized by batch emulsion polymerization of styrene (St), and in the second step, the shell was polymerized by batch emulsion terpolymerization of styrene, methacrylic acid (MAA), and methacrylamidoacetaldehyde dimethyl acetal (MAAMA), using the seed obtained previously. With the aim of analyzing the effect of the thickness of the shell, the pH of the reaction medium and the weight ratio of the termonomers to prepare the shell, on the amount of the functionalized groups, several core-shell type latex particles were synthesized by two-step emulsion polymerization in a batch reactor. The latexes were characterized by TEM and conductimetric titration to obtain the particle size distribution and the amount of carboxyl and acetal groups on the surface, respectively. Looking for the applicability of the synthesized latexes in immunoassays, IgG a-CRP rabbit antibody was covalently bonded to the surface of the particles synthesized in neutral medium. The complex latex-protein was immunologically active against the CRP antigen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1605–1610, 1997     

Preparation and characterization of carboxylic-containing poly(methyl methacrylate) nanolatexes

Poly(methyl methacrylate) (PMMA)-based latex particles bearing carboxylic groups at the surface were prepared via emulsion polymerization. The polymerization recipe and process were optimized in order to target monodisperse particles with diameters around 100 nm. The polymerizations were performed using 4,4-azobis(4-cyanopentanoic) acid (ACPA) as initiator and sodium dodecyl sulphate (SDS) as surfactant. The polymerization conversion was determined by both gas chromatography and gravimetry. The final latexes were characterized with respect to particle size, size distribution, surface charge density, electrokinetic properties (i.e. electrophoretic mobility vs pH and ionic strength) and colloidal stability (i.e. coagulation rate constants vs pH and stability factor vs ionic strength).     

Effect of cosolvent NMP on properties of cationic fluorocarbon emulsifier-free emulsion

Cationic fluorocarbon emulsifier-free emulsion was prepared via a novel method of adding organic cosolvent N-methylpyrrolidone (NMP), which was characteristic of the reaction transferring from solution to emulsion polymerization system. The emulsion stability was analyzed by the coagulation and precipitation ratio. The properties of particles were characterized by dynamic laser light scattering, surface potential particle size analyzer, and transmission electron microscopy, respectively. The latex film surface properties and immersion behaviors were investigated by contact angles. The results showed that, with NMP increasing from 5 to 30 %, the emulsion stability became better. Also, particle sizes decreased from 264.0 to 95.5 nm, and their distribution transformed from multidispersion to monodispersion. Zeta potentials increased gently. Meanwhile, the latex film surface performance was slightly improved, and the more the content of NMP, the less the influence of the cure temperature on surface property. There was less mobility of fluorinated groups in the films with more NMP used.

SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH) ACRYLATES WITH HIGH-SOLID CONTENT: EFFECT OF THE OPERATION CONDITIONS

The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA),2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate(HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solidcontent. The effects of monomer emulsion feed rates (R_a) and (R/E)_E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E),on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,T_g and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.     

Particle Nucleation and Growth in the Emulsion Polymerization of Styrene: Effect of Monomer/Water Ratio and Electrolyte Concentration

This work is an extension of previous research results reported by our team (Colloid and Polymer Science 2013, 291: 2385-2398), where large scale and high solid content latexes of poly(n-butyl acrylate) were obtained with the particle coagulation method induced by the electrolyte. However, how to prepare controlled particle size distribution polymer latex has not been studied. Thus, in this study, the effect of the monomer/water ratios and electrolyte concentrations on particle formation and growth methods were studied by following the tracks of the evolutions of particle size, number and distribution as a function of reaction time or conversion. Experimental results showed that the length of time that particle nucleation occurred increased with increasing monomer charged for the systems without electrolyte. A point worthy of attention here is that homogeneous nucleation may occur at high monomer concentrations (30/70, 40/60). However, electrolyte added could be made the nucleation mechanism shift from micellar/homogeneous nucleation to micelle /coagulation nucleation. As a result, the final particle size distribution can be controlled by adding an appropriate electrolyte to regulate the nucleation mechanism. Spherical and uniformly sized particles could be obtained when electrolyte concentration is between 0.2 wt% and 0.4 wt% for water at the high monomer/water ratio (40/60). The effects of electrolyte concentration on nucleation mechanism mainly were expressed by decreasing the solubility of the monomer and interparticle potential, and then preventing homogeneous nucleation and enhancing particle coagulation.     

Preparation and Characterization of Nano-TiO2/poly (methyl methacrylate) Hybrid Latex by Reverse Microemulsion Method and In-Situ Polymerization

The organic nano-TiO₂ was synthesized in reverse (W/O) microemulsion, using tetrabutyl titanate (TBOT) as precursor and γ-methacryloxypropyl trimethoxy silane (KH-570) as modifier. After phase inversion from W/O microemulsion to oil-in-water (O/W) emulsion, nano-TiO₂/poly(methyl methacrylate) hybrid latex was prepared via in-situ polymerization based on the O/W emulsion containing organic nano-TiO₂. Fourier transform infrared spectroscopy (FTIR) indicated that KH-570 was successfully grafted onto the surface of TiO₂ particles. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) demonstrated that the average diameter of nano-TiO₂ was about 10 nm and the hybrid latex had obvious core-shell structure with particle size of 155 nm. The TBOT content and the mass ratio of KH-570 to TOBT have important effect on the polymerization stability and storage stability of the hybrid latex. When the TBOT content was 5% and the mass ratio of KH-570 to TOBT was 0.6, the coagulation rate (C_r) was 3.0% and the zeta potential reached 36.1 mV. The possible formation mechanism of the hybrid latex was also proposed.     

Monodisperse superparamagnetic pH‐sensitive single‐layer chitosan hollow microspheres with controllable structure

Facile strategy was developed for the fabrication of the monodisperse superparamagnetic pH‐sensitive single‐layer chitosan (CS) hollow microspheres with controllable structure. The carboxyl group‐functionalized polystyrene microspheres prepared by soap‐free emulsion polymerization were used as the templates. After the Fe₃O₄ nanoparticles were in situ formed onto the surface of the templates, the single‐layer CS was self‐assembled and cross‐linked with glutaraldehyde subsequently. Then, the magnetic single‐layer CS hollow microspheres were obtained after the templates were removed. It was found that the feeding ratio of the monomer acrylic acid in the soap‐free emulsion polymerization had played an important role on the particle size and surface carboxyl group content of the templates, which determined the particle size and shell thickness of the magnetic single‐layer CS hollow microspheres in the proposed strategy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

“Nanosized latexes for textile printing applications obtained by miniemulsion polymerization”

We report the synthesis and design of aqueous monodisperse copolymer latexes by miniemulsion polymerization and their application as binders in pigment printing and ink-jet printing of cotton fabrics. For that purpose, miniemulsion radical polymerization was carried out with a high content of the soft butyl acrylate (BA) and a low content of the hard methyl methacrylate (MMA) in the presence of hexadecane as osmotic costabilizer. The addition of small amounts of functional monomers such as methacrylic acid MAA and N-methylol acrylamide NMA to some miniemulsion recipes allowed to impart cross-linking sites and functionality to the copolymer chains. Dynamic light scattering (DLS), small angle neutron scattering (SANS), and transmission electron microscopy (TEM) showed that the particle size diameter and size distributions could be controlled in the range of 50 to 400 nm by the amount of SDS surfactant, while the presence of a costabilizer such as hexadecane determines the particle size and, to a lesser extent, the polydispersity of the obtained miniemulsion latex dispersions. The glass transition temperature of the different miniemulsion latexes ranged between ?14 and ?33 °C, depending on the monomer composition. Selected samples of these nanolatexes were then employed in textile printing. The miniemulsion binders with their uniform shape and smaller size have technological advantages over conventional processes for the pigment and ink-jet printing and yielded better printing properties in terms of softness, fastness, and color strength of the printed fabric. Accordingly, by optimized use of the miniemulsion method, one is not only able to control the particle size but also to improve the properties of these latexes for textile applications.     

Synthesis of latex particles with surface amino groups

Monodisperse latex particles with surface amino groups were prepared by a two‐step emulsion polymerization. In the first step, the seeds were synthesized by batch emulsion polymerization of styrene; and in the second step, two different amino‐functionalized monomers [aminoethylmethacrylate hydrochloride (AEMH) and vinylbenzylamine hydrochloride (VBAH)], two different initiator systems (K₂S₂O₈ and K₂S₂O₈/Na₂S₂O₅) and mixtures of emulsifiers sodium dodecylsulfate (SDS) and Tween 21 were used to synthesize the final latexes. To characterize the final latexes, conversions were obtained gravimetrically and particle size distributions and average particle diameters were determined by transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). The amount of amino groups was determined by the SPDP (N‐succinimidyl 3‐(2‐pyridyldithio)propionate) method. The influence of the different conditions used to synthesize the latexes on the colloidal stability of the particles was evaluated by measuring the diameters of the final latexes dispersed in solutions at different pHs and ionic strengths. The most stable latexes were obtained using the smallest seed, VBAH monomer, and the K₂S₂O₈/Na₂S₂O₅ initiator system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4230–4237, 2000     

Preparation and electrochemical characterization of a new NiMoO4 catalyst for electrochemical O2 evolution

The NiMoO₄ catalyst has been obtained by a precipitation method under a controlled pH condition and characterized ex situ by infrared, X-ray diffraction, Brunauer–Emmett–Teller (BET), and particle size, and in situ by cyclic voltammetry, impedance and steady-state anodic Tafel polarization techniques. Results show that NiMoO₄ has pure crystalline monoclinic phase with the crystallite size ~50 nm and the lattice constants, a?=?9.597 Å, b?=?8.765 Å, c?=?7.667 Å, and β?=?114.22°. Values of the average particle size and BET surface area of the oxide powders are found to be 730 nm and 11.75 m²/g, respectively. The oxygen evolution reaction follows the first-order kinetics with respect to OH^? concentration, the Tafel slope being ~70 mV.     

Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part I. Synthesis and colloidal characterization

Polystyrene (PS) (1)/Poly(n-butyl acrylate (BA)-methacrylic acid (MAA)) (2) structured particle latexes were prepared by emulsion polymerization using monodisperse polystyrene latex seed (118 nm) and different BA/MAA ratios. Three main aspects have been investigated: i) the polymerization kinetics; ii) the particle morphology as a function of reaction time; iii) the distribution of MAA units between the water phase and the polymer particles.The amount of MAA in the shell copolymer was found to be the main factor controlling the particle shape and morphology. The shape of the structured particles was, generally, non-spherical, and the shape irregularities increased as a particles was, generally, non-spherical, and the shape irregularities increased as a function of reaction time. At the beginning of the second stage reaction, new small particles were observed, which coalesced onto the PS seed as the polymerization proceeded. The distribution of the MAA groups in the latex particles and the serum was analyzed by alkali/back-acid titration, using ionic exchanged latexes. No MAA groups were detected in the latex serum. Due to the lowTg of the BA-MAA copolymers, alkali conductimetric titrations accounted for all the MAA groups on and within the polymer particles. Therefore, for these systems, this method is not only limited to a thin surface layer, as it is often assumed.     

Control of surfactant level in starve-fed emulsion polymerization. I. Sulfate-containing oligomers: Preparation and application as surfactant in emulsion polymerization

It is well known that the amount of surfactant must be carefully controlled during starve-fed emulsion polymerization processes. Too little surfactant leads to emulsion instability and coagulation, while too much surfactant leads to secondary particle formation. Although these relationships are qualitatively understood in the art, there is little quantitative basis to guide the synthetic chemist, especially in multistep starve-fed emulsion polymerization processes to make larger supermicron particles. We have developed a method, which will be described in a companion article, to control the surfactant level by monitoring the surface tension during polymerization. In order to quantitatively predict how much surfactant to add at any given time, one needs to know in advance the adsorption characteristics of the soap. Further complicating the matter is the formation of “in situ” or oligomeric surfactant during polymerization with aqueous initiators such as ammonium persulfate. This work demonstrates how to prepare surface-active oligomers and how to make latex particles using them as surfactant. First, we established the mass balance for the initiator-derived sulfate groups in seed latexes by conductometric, potentiometric, and iodometric titrations. Based on the characterization of seed latexes, a method for determining the effective sulfate concentration has been developed. When surface-active oligomers were used as the only surfactant, we obtained a series of monodisperse, supermicron copolymer latex particles with diameters up to 3.22 μm. This is a similar result to that obtained with a commercially made anionic surfactant. © 1995 John Wiley & Sons, Inc.     

Kinetics of successive seeding of monodisperse polystyrene latexes. II. Azo initiators with and without inhibitors

Oil soluble azo initiators in combination with water soluble inhibitors were used to extend the particle size limit in studies of the kinetics of successive seeding of monodisperse polystyrene latexes. Monodisperse latexes were prepared up to 2.5 μm in diam using 4.0 mM AMBN and 14.5 mM hydroquinone with a constant 15% emulsifier (Aerosol–MA) surface coverage throughout the seven step sequence. The polymerization kinetics were measured in a piston/cylinder dilatometer designed for microgravity experiments. The Interval III kinetics were dominated by the gel effect although these were affected by the nature of the inhibitor. In general, the overall polymerization rate decreased with increasing particle size (decreasing N_p) up to a size of about 1 μm. Thereafter, the kinetics were independent of these variables, exhibiting Smith-Ewart Case 3 (bulk) kinetics. The initiator efficiencies were found to be of the order of 10%, considerably lower than reported for bulk polymerizations.     

Kinetics of successive seeding of monodisperse polystyrene latexes. I. Initiation via potassium persulfate

The polymerization kinetics of monodisperse polystyrene latexes prepared via successive seeding were studied in the region between Smith-Ewart Case 2 (n? = 1/2) and Case 3 (n? ? 1). Potassium persulfate was used as the initiator. The kinetics were measured in a piston/cylinder dilatometer designed for microgravity experiments. A recipe formulation method was developed by which a constant emulsifier (Aerosol-MA) surface coverage was maintained throughout a sequence, beginning with a 0.19 μm polystyrene seed. Monodisperse latexes up to 1 μm in size were prepared using 0.5 mM K₂S₂O₈ with a 4% emulsifier surface coverage. The polymerizations were commenced in Interval III, the particles being swollen with twice their weight in monomer. The kinetics were characterized by the autoacceleration of the gel effect with the overall polymerization rate decreasing with increasing particle size (decreasing N_p). The Case 2 to Case 3 kinetic transition was experienced in the first seeding step, however, independence of the rate on the number of particles was not evident even at high values of n? (n? > 10). This was attributed to a dependency of the free radical capture efficiency on the particle size (constant solids). Corroborating indirect evidence was supplied through surface charge analysis and detailed examination of the polymerization kinetics.     

Effects of surface charge density on emulsion kinetics and secondary particle formation in emulsifier-free seeded emulsion polymerization of methyl methacrylate

 Experiments were carried out to investigate the effects of surface charge density on emulsion kinetics and secondary particle formation in emulsifier-free seeded emulsion polymerization. Three monodisperse seed latices with different surface charge densities were prepared from styrene/NaSS comonomers using the two-stage shot-growth process. After purification of the seed latices, they were used in seeded emulsion polymerization of methyl methacrylate. The initial rate of poly-merization and the average number of radicals per particle for the high-charged seed latex system were lower than that of the low-charged case. The low rate of polymerization resulted from the low rate of radical adsorption in the beginning of the reaction due to the electrical repulsion between seeds and oligomeric radicals. In this case, because of the secondary particles, particle size distribution became bimodal. The low rate of radical adsorption and the formation of secondary particles reduced the average number of radicals per particle. The rate of polymerization (R _p) increased, but the rate of polymerization per particle (R _p/N _p) decreased. Received: 9 December 1996 Accepted: 7 March 1997