Preparation of sulphonate-containing core/shell latex particles via seeded emulsion copolymerization

<正>In this study,P(St-MAA) seed latex particles were first prepared via soap-free emulsion polymerization of styrene(St) and methacrylic acid(MAA),then the seed particles were allowed to swell with St at room temperature,and the P(St-MAA)/P(StNaSS) core/shell latex particles were then synthesized via seeded emulsion copolymerization of St and sodium styrene sulphonate (NaSS) using AIBN as initiator in the presence of N,N'-methylenebisacrylamide(BAA,water-soluble crosslinker).Results showed that the polymerization could be carried out smoothly when the ratio of BAA to total monomers was less than 3 mol%,the narrow dispersed P(St-MAA) seed particles with the diameter of 150 nm and the P(St-MAA)/P(St-NaSS) core/shell latexes with the particle size of about 200 nm were synthesized.When the 25/75 mole ratio of NaSS/(St + MAA) and 2 mol%of BAA were used in the seeded emulsion polymerization,the resulted P(St-MAA)/P(St-NaSS) latex product showed a low weight loss after water extraction,and the NaSS unit content in the whole particle and in the shell reached 11.7 mol%and 34.6 mol%,respectively.     

Fabrication and Characterization of Sulfonate‐containing Polystyrene/CaCO3 Core‐shell Nanoparticles

Polystyrene (PSt) seed latex was first prepared via soap‐free emulsion polymerization in the presence of a small amount of methacrylic acid using ammonium persulfate as initiator, and then seeded emulsion polymerization of sodium 4‐styrenesulfonate (NaSS) and St was carried out to synthesize P(St‐NaSS) core latex using 2,2′‐azobisisobutyronitrile as initiator. After that, P(St‐NaSS)/CaCO₃ core‐shell nanoparticles were fabricated by sequentially introducing Ca(OH)₂ aqueous solution and CO₂ gas into the core latex. The morphology of the core and core‐shell nanoparticles was characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and the state of CaCO₃ shell was confirmed with high‐resolution scanning transmission electron microscope (HR‐STEM) and selected area electron diffraction (SAED). Results showed that PNaSS chains were successfully grafted onto the PSt seed surface, and length of the PNaSS "hairs" could be modulated by adjusting NaSS amount. Sulfonic groups of the PNaSS hairs served as additives in the formation and stabilization of amorphous CaCO₃(ACC) and prevented ACC from sequent transformation into crystalline states. The amount of the anchored CaCO₃ increased with the growth of PNaSS hair length, and reached 51 wt% (by thermalgravimetric analysis) under the optimal encapsulating temperature of 45°C. Moreover, the forming mechanism of P(St‐NaSS)/CaCO₃ core‐shell nanoparticles was proposed.     

Preparation of sulphonate-containing polymer particles <Emphasis Type="Italic">via</Emphasis> semi-continuous emulsion copolymerizaion of styrene and sodium styrene sulphonate

Submicron-sized P(St-NaSS) latexes were prepared via a semi-continuous emulsion copolymerization of styrene (St) and sodium styrene sulphonate(NaSS) in the presence of anionic surfactant,in which NaSS aqueous solution and St were separately dropwise charged into the polymerization system at the same time.The hydrodynamic diameter of the latex particles was measured by dynamic light scattering(DSL) method,and the NaSS unit content of the purified copolymer by water extraction was calculated based on the elementary analysis.Results showed that the copolymerization could be performed smoothly with the monomer conversion more than 96%in the absence of crosslinker,and PNaSS homopolymer could be removed from the latex product by water extraction for 28 h.The weight loss in the water extraction tended to decrease and the NaSS unit content of the purified copolymer tended to increase with the increase of monomer feeding time, and both of them increased with the increase of NaSS/St mole ratio in the charge.The introduction of divinyl benzene (DVB) could decrease the weight loss in the water extraction and increase the NaSS unit content of the purified copolymer. When 25/75 mole ratio of NaSS/St and 11 mol%DVB of total NaSS and St were used in the recipe,and the monomer feeding time was 3 h in copolymerization,the NaSS unit content of the purified copolymer reached 7.31 mol%.     

Tailoring of carboxyl‐decorated magnetic latex particles using seeded emulsion polymerization

In this research, submicron and carboxyl‐functionalized magnetic latex particles were elaborated by using seeded emulsion polymerization technique in presence of oil‐in‐water (o/w) magnetic emulsion as seed. The polymerization conditions were optimized in order to get well‐defined latex particles with magnetic core and polymer shell bearing carboxylic (–COOH) functionality. Starting from (o/w) magnetic emulsion as seed, synthesis process was performed by copolymerization of styrene (St) monomer with the cross‐linker divinylbenzene (DVB) in presence of 4,4′‐azobis(4‐cyanopentanoic acid) (ACPA) as a carboxyl‐bearing initiator. The prepared magnetic latex particles were first characterized in terms of particle size, chemical composition, morphology, magnetic properties, magnetic content, and colloidal stability using various techniques, e.g. particle size analyzer using dynamic light scattering (DLS) technique, Fourier transform infrared, transmission electron microscopy, vibrating sample magnetometer, thermogravimetric analysis, and zeta potential measurements as a function of pH of the dispersion media, respectively. The prepared magnetic latex particles were then used as second seed for further functionalization with methacrylic acid (MAA) in order to enhance carboxylic groups on the magnetic particle's surface. The results showed that final magnetic latex particles possessed spherical morphology with core‐shell structure and enriched carboxylic acid functionality. More importantly, they exhibited superparamagnetism with high magnetic content (58.42 wt%) and high colloidal stability, which considered as the main requirements for their application in the biomedical diagnostic domains. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation and Characterization of Polymer Core Shell Latex Particles

Stable core‐shell latex was synthesized by semicontinuous seeded emulsion polymerization with core monomers consisting of styrene (St), butyl acrylate (BA), and shell monomers consisting of methyl methacrylate (MMA), eutyl acrylate (EA), and methacrylic acid (MAA). The effects of compound emulsifier amount, mass ratio of anionic/nonionic emulsifier, and initiator amount on latex performance were investigated. By particle size analysis and transmission electron microscopy (TEM) observation, results suggest that final latex particles have clearly core shell structures.     

Morphology control of magnetic latex particles prepared from oil in water ferrofluid emulsion

The use of magnetic latex particles as solid support in biomedical applications is favourable when homogeneous and well-defined core–shell polymer particles are used. Accordingly, this paper concerns with the synthesis of magnetic poly(styrene–divinylbenzene) latex particles using emulsion polymerization of styrene (St) and divinylbenzene (DVB) monomers in the presence of preformed oil in water organic ferrofluid emulsion droplets as seed. The key parameters which affect on formation and morphology of the prepared magnetic latexes were investigated, including type of magnetic emulsion, St/DVB monomers ratio, DVB amount, type of initiator and surfactant nature. In this study, two different magnetic emulsions were used, low and high octane content magnetic emulsions. The magnetic emulsions were stabilized using different types of surfactants including AP, Triton X 405 and SDS. In addition, four different initiators, including AIBN, V50, ACPA and KPS were examined. The morphology of the prepared magnetic latexes was investigated using transmission electron microscopy. In addition, particle size and size distribution, magnetic content and magnetic properties of the prepared magnetic latexes were also examined, using various techniques, e.g. dynamic light scattering, thermal gravimetric analysis and vibrating sample magnetometer, respectively. The results showed that the morphology type (Janus like, moon like and/or core–shell) of the prepared magnetic latex particles could be controlled depending mainly on the used formulation. In fact, the use of styrene monomer leads to anisotropic morphology. Whereas, the progressive use of DVB in presence of KPS intiator leads to a well-defined magnetic core and polymer shell structure.

Effect of Monomer Feeding Mode on thePreparation of Hollow Latexes with High MAA Content in the Core Latex Preparation简

In order to prepare hollow latex particles with optimum morphology based on osmotic swelling principle, three- layer core/shell latex particles with 40 wt% MAA in the core were first prepared via multistep seeded emulsion copolymerization, in which monomers were added by a semi-continuous process with monomer addition under two different forms： pure monomers＇ mixture （monomer addition）, and pre-emulsified monomers （pre-emulsion addition）. Then, the hollow latex particles with different morphologies were obtained after alkali post-treatment. Influences of the monomer feeding mode on the emulsion polymerization and the particle morphology were investigated. Results showed that the pre- emulsion addition could significantly improve the polymerization stability in each step, and greatly enhance the uniformity of shell encapsulation. The sizes of the core and core/shell latex particles obtained by the pre-emulsion addition were smaller and more uniform than those synthesized by the monomer addition, and the hollow latex particles with intact morphology were generated by alkali post-treating of the core/shell latexes prepared from the pre-emulsion addition. As the core size increased, the morphology of the post-treated particles underwent evolution from hollow to collapse. Moreover, the mechanism of the particle morphological evolution was proposed.     

Emulsifier-free emulsion polymerization of the comonomer system styrene/tetrahydrofurfuryl metacrylate

 The emulsifier-free emulsion copolymerization of styrene and tetrahydrofurfuryl methacrylate (TMA) in aqueous phase is described. Monodisperse latex particles with diameters from about 280 to 620 nm are obtained consisting of a hydro-phobic polystyrene core and a hydrophilic poly-TMA shell. The influence of a variation of TMA, styrene and initiator (potassium persulfate) concentration in the original emulsion on particle size, molecular weight and composition of the copolymer is described. The concentration of TMA and initiator affects the number of primary particles but not the size of the final particles, whereas the styrene concentration strongly influences the particle diameter, a large size being favored by a high styrene concentration. The molecular weights of the polymers are between 6.2×10⁴ and 7.0×10⁵ g/mole. Size exclusion chromatography of polymer solutions in tetra-hydrofuran shows that high molecular weights are especially found in large particles, which are preferentially formed in emulsions with a high concentration of styrene. ¹H-NMR spectroscopy of the polymer shows that only about 50% of the initial TMA concentration are polymerized in the particles. Thus the copolymers prepared at increasing styrene concentration and constant initiator concentration of the emulsion show an increasing polystyrene content and are formed in particles of increasing size. Received: 4 June 1997 Accepted: 19 August 1997     

Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007     

Miniaturization of anisotropic composite particles incorporating a silica particle smaller than 100 nm

Two-step aqueous polymerizations with a water-soluble initiator of potassium persulfate were conducted to prepare anisotropic composite particles incorporating a silica core smaller than 100 nm. The two-step polymerization consisted of the first polymerization to coat the silica cores with cross-linked polymethylmethacrylate (PMMA) shell and the second polymerization to protrude a polystyrene (PSt) bulge from the core–shell particles. The concentration of ionic comonomer of sodium p-styrenesulfonate (NaSS) in the first polymerization was an important factor to stabilize the core–shell particles during the second polymerization as well as the first one, and an appropriate concentration of NaSS could prepare the anisotropic composite particles incorporating a single core. Another important factor for small, anisotropic composite particles was duration time for swelling the core–shell particles with the second monomer of styrene. Extension of the duration time from 2 to 4 h facilitated protrusion of the PSt bulge from the particles incorporating a 44-nm silica core. The composite particles were also employed to fabricate anisotropic hollow particles. Chemical etching of silica component in the composite particles with hydrofluoric acid successfully created anisotropic hollow polymer particles with a cavity size corresponding to the silica cores.     

Synthesis of core-shell type polystyrene monodisperse particles with chloromethyl groups

The synthesis of core-shell type polystyrene monodisperse particles with surface chloromethyl groups was carried out by a two-step emulsion polymerization process at different reaction temperatures. In a first step, the core was synthesized at 90 °C by means of batch emulsion polymerization of styrene (St), and in the second step, the shell was polymerized by batch emulsion copolymerization of St and chloromethylstyrene (CMS) using the seed obtained previously. With the aim of optimizing the production of these core-shell type polystyrene monodisperse particles with surface chloromethyl groups, the reaction temperature in the second step, the purification or not of the functionalized monomer (CMS), the amount and type of the redox initiator system used, and the type of addition of the initiator system to the reactor were studied.     

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.     

Effect of the Shell Crosslinking Level andCore/Shell Ratio on the Morphology of LatexParticles in the Preparation of Hollow Latexes简

Three-layer core/shell latex particles with various shell crosslinking level and shell thickness were prepared by multistep emulsion polymerization, and the hollow latex particles with different morphologies were then obtained after alkali post-treatment. Influences of divinyl benzene(DVB) content and the core/shell mass ratio on emulsion polymerization and particle morphology were investigated. Results showed that with the increase of DVB content, the percentage of total amount of ―COOH on the particle surface and free in aqueous phase(PSFa) decreased, and the morphology of the post-treated particles underwent evolution from cracked, intact hollow to deficient swelling structure. Decreasing the core/shell mass ratio could not only make more carboxyl groups encapsulated by the shell, but also increase the shell resistance to the swelling of the core. The uniform hollow latex particles with intact morphology were obtained when the DVB content was 3.54 wt% and the core/shell mass ratio was 1/6.     

Effect of an anionic monomer on the pickering emulsion polymerization stabilized by titania hydrosol

Polystyrene (PS) nanocomposite particles with high titania content are prepared by Pickering emulsion polymerization. A self‐made titania hydrosol modified by an anionic monomer sodium styrene sulfonate (NaSS) is used as a stabilizer and photocatalyst. The stability of the emulsion system is greatly improved by the electrostatic interaction between negatively charged NaSS and positively charged titania nanoparticles. The nanocomposite spheres with the diameter of around 120 nm are highly charged, indicating titania‐rich surfaces of latex particles. It is also proven by the field‐emission transmission electron microscope and field‐emission scanning electron microscope images. The well‐defined core‐shell structure of the obtained PS/titania composite particles is confirmed by the formation of fragile hollow titania nanospheres after thermogravimetric analysis tests. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5728–5736, 2009     

Starved Semi-Batch Emulsion Polymerization for Polystyrene Nanolatexes Preparation With n-Pentanol as Cosurfactant

In the starved semi-batch emulsion polymerization, the n-pentanol was predissolved in the sodium dodecyl sulfate (SDS) solution as cosurfactant, for the purpose of polystyrene nanolatexes preparation. The effects of styrene (St) monomer feeding rate, n-pentanol dosage and SDS concentration on the monomer conversion (total and instantaneous conversions), the latex particles size (average volume diameter, d_v) and the latex particles number in a unit volume (N_p) were discussed. The function of n-pentanol not only debased the surface tension of the SDS solution, but also formed the smaller nanolatex particles size. With the 1.5 wt% n-pentanol dosage, 0.8 wt% SDS concentration and 6.0 mL/h St feeding rate for 6 h, the d_v and N_p of the final latex particles were 45.1 nm and 8.52×10¹⁵/ mL, respectively. The final latex solid content was 24.1%. All results were original and available compared to the state of the art.     

DESIGN AND CONTROL OF SOAP-FREE HYDROPHILIC-HYDROPHOBIC CORE-SHELL LATEX PARTICLES WITH HIGH CARBOXYL CONTENT IN THE CORE OF THE PARTICLES

Soap-free hydrophilic-hydrophobic core-shell latex particles with high carboxyl content in the core of the particles were synthesized via the seeded emulsion polymerization using methyl methacrylate(MMA),butyl acrylate(BA), methacrylic acid(MAA),styrene(St)and ethylene glycol dimethacrylate(EGDMA)as monomers,and the influences of MMA content used in the core preparation on polymerization,particle size and morphology were investigated by transmission electron microscopy,dynamic light scattering and conductometric titration.The results showed that the seeded emulsion polymerization could be carried out smoothly using "starved monomer feeding process" when MAA content in the core preparation was equal to or less than 24 wt%,and the encapsulating efficiency of the hydrophilic P(MMA-BA-MAAEGDMA) core with the hydrophobic PSt shell decreased with the increase in MAA content.When an interlayer of P(MMAMAA -St)with moderate polarity was inserted between the P(MMA-BA-MAA-EGDMA)core and the PSt shell,well designed soap-free hydrophilic-hydrophobic core-shell latex particles with 24 wt%MAA content in the core preparation were obtained.     

Submicron Sized Hollow Polymer Particles: Preparation and Properties

The considered method for obtaining hollow polymer particles is based on the following pathway: (1) preparation of a carboxylated core latex by emulsion copolymerization of acrylic monomers with methacrylic acid, (2) synthesis of a core-shell latex comprising a styrene (co)polymer shell, (3) neutralization of the core carboxylic groups with a base followed by the core ionization and hydration to a high degree, shell expansion and formation of water-filled hollows. A number of approaches to improve the hydrophilic core – hydrophobic shell compatibility and enlarge the hollow volume are considered. The synthesized hollow particles are of a submicron size with the relative hollow volume V_hol : V_part.= 0.43 – 0.64. Methods for cationic hollow particle latex preparation by anionic latex recharging with a cationic surfactant or acidic melamine resin are discussed. Recharging with a melamine resin is shown to afford hollow particles with an external polymer shell providing a high thermal stability of the particles.     

Highly magnetic latexes from submicrometer oil in water ferrofluid emulsions

The synthesis of functionalized submicrometer magnetic latex particles is described as obtained from a preformed magnetic emulsion composed of organic ferrofluid droplets dispersed in water. Composite (polystyrene/γ‐Fe₂O₃) particles were prepared according to a two‐step procedure including the swelling of ferrofluid droplets with styrene and a crosslinking agent (divinyl benzene) followed by seeded emulsion polymerization with either an oil‐soluble [2,2′‐azobis(2‐isobutyronitrile)] or water‐soluble (potassium persulfate) initiator. Depending on the polymerization conditions, various particle morphologies were obtained, ranging from asymmetric structures, for which the polymer phase was separated from the inorganic magnetic phase, to regular core–shell morphologies showing a homogeneous encapsulation of the magnetic pigment by a crosslinked polymeric shell. The magnetic latexes were extensively characterized to determine their colloidal and magnetic properties. The desired core–shell structure was efficiently achieved with a given styrene/divinyl benzene ratio, potassium persulfate as the initiator, and an amphiphilic functional copolymer as the ferrofluid droplet stabilizer. Under these conditions, ferrofluid droplets were successfully turned into superparamagnetic polystyrene latex particles, about 200 nm in size, containing a large amount of iron oxide (60 wt %) and bearing carboxylic surface charges. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2642–2656, 2006     

Emulsifier-free emulsion copolymerization of styrene and acrylamide using an amphoteric initiator

Emulsifier-free emulsion copolymerization of styrene (St) and acrylamide (AAm) has been investigated in the presence of an amphoteric water-soluble initiator, 2,2′-azobis[N-(2-carboxyethyl)-2-2-methylpropionamidine]hydrate (VA057). The kinetics of polymerization and the colloidal properties of the resulting latices were studied and compared with the cases using ionic initiators. When adopting the amphoteric initiator at pHs lower than 10, stable amphoteric poly (St/AAm) latices, evidenced by the electrophoretic mobility, were prepared directly. Meanwhile, almost the same conversion versus time curves appeared and there were no apparent differences in the final particle sizes for those polymerizations, whereas in the polymerization at pH 10, a much lower rate of copolymerization and a larger size of particles were observed. The surface charge density and the growth rate of latex particles produced with VA057 at pH<10 were comparable to those of the particles with a cationic initiator, 2,2′-azobis(2-amidinopropane)dihydrochloride, but were apparently lower than those with an anionic initiator, potassium persulfate, when the polymerizations were carried out under corresponding conditions. The number of initiator fragments incorporated onto the particle surfaces was independent of polymerization pH, except for pH 10. The abnormal performance of VA057 at pH 10 was attributed to its degradation due to hydrolysis. Received: 14 December 1999 Accepted: 22 February 2000     

Preparation of polymeric microspheres with high content of sulphonate groups

<正>Poly(styrene-co-sodium styrene sulphonate)(P(St-NaSS)) latex particles were prepared using the mixture of ethanol and water as continuous phase in the presence of surfactant by dispersion--emulsion combined polymerization.The influence of recipes on polymerization process as well as the content of sulphonate group in the purified products was investigated.Results showed that the copolymerization could be performed smoothly.When the mole ratio of NaSS/St/divinyl benzene(DVB) was 25/75/2 and the weight ratio of ethanol/water was 2/11,the product showed a low weight loss in methanol extraction purification,and the NaSS unit ratio in the purified product reached 20.6 mol%,which was close to its theoretical value of 24.9 mol%.