Thermal storage nanocapsules by miniemulsion polymerization

Paraffin wax was nanoencapsulated by miniemulsion polymerization. Low solid content batch polymerizations were carried out and the influence of paraffin wax/methyl methacrylate ratio on polymeriztion kinetics, phase change properties, and thermal stability were investigated. Paraffin concentration controls the nucleation mechanism and nanocapsules particle size. The latent heat capacity increases as the content of encapsulated paraffin wax increases. The maximum amount of encapsulated paraffin wax achieved under the experimental conditions was 60 wt %, presenting a latent heat capacity of 140.3 J/g. Moreover, the encapsulated systems present in all cases better thermal stability than pure paraffin wax. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Controlled preparation of nanocolorants via a modified miniemulsion polymerization process

Nanocolorants were successfully prepared via a modified miniemulsion polymerization process into which styrene, a polar monomer, crosslinkers, a highly hydrophobic solvent, dyes, and so forth were introduced. The obtained nanocolorants were nanocomposite entities in which a fraction of dye molecules attached to the crosslinked macromolecular chains and more dye molecules formed clustering because of the phase separation between the dye and polymer during the polymerization process and were further embedded in the interior of the crosslinked polymer because of the high hydrophobicity of the dyes. The effects of the polar monomers, the amounts of the dyes dissolved in styrene, and the polymer crosslinking, as well as the effects of the water‐soluble and oil‐soluble initiator, the amount of the surfactant, and the ultrasonic homogenization time, on the preserving fastness of the dyes in the polymeric matrix and the morphology and particle size distribution of the nanocolorants were studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Particle morphology development in hybrid miniemulsion polymerization

Incompatibility between polymer phases resulting from hybrid minienulsion polymerization of acrylic monomers in the presence of alkyd resin leads to interesting particle morphologies. In this paper, morphology was deduced through crosscomparison of results from several forms of microscopy. For the combination of methyl methacrylate and alkyd, a derivative of core/shell morphology was observed through the combination of transmission electron microscopy, scanning electron microscopy, and spin diffusion NMR. A raspherry-like shell was found to form on the hybrid particle surface consisting of a full coverage of small (roughly 25 nm) polymethyl methacrylate spheres anchored to the particle surface through grafting with the alkyd core. Migration of the spheres to tha surface is thought to be induced by phase separation, and the size of the spheres precludes their origin from homoparticles from homogeneous nucleation. Homopolymethyl methacrylate particles were also detected in the particle distribution, resulting from the aqueous-phase initiator and hydrophilicity of methyl methacrylate monomer. For copolymer/alkyd systems (either methyl methacrylate/butyl acrylate/acrylic acid/alkyd or methyl methacrylate/butyl acrylate/alkyd), more traditional core/shell morphologies were observed with a lesser degree of homonucleated particles. A significantly different result was found in the combination of butyl acrylate and alkyd, resulting in a continuous particle-phase of polylbutyl acrylate and small internally dispersed island domains of alkyd. This is likely due to the lesser incompatibility between polybutyl acrylate and alkyd along with their similar hydrophobicity and glass transition temperatures. A higher degree of grafting between the alkyd and polybutyl acrylate also contributed to the compatibility between the two components, when compared to hybrid methyl methyl methacrylate/alkyd systems.     

Challenges for industrialization of miniemulsion polymerization

Miniemulsion polymerization facilitates the synthesis complex materials that cannot be produced otherwise. These materials have a broad range of potential applications including among others adhesives, coatings, anticounterfeiting, textile pigments, bio-based polymer dispersions, gene and drug delivery, anti-viral therapy, tissue engineering, catalyst supports, polymeric photoresists, energy storage and self-healing agents. However, 40 years after the pioneering work of Ugelstad, El-Aasser and Vanderhoff the promises have not been fulfilled and the presence of miniemulsion polymerization in commercial products is scarce. This article reviews the advances in the field, discusses the reasons for this delay and analyzes the challenges that have to be overcome in order to fully use this process in commercial practice.     

Synthesis of styrene based liquid-filled polymeric nanocapsules by the use of RAFT-mediated polymerization in miniemulsion

Nanocapsules (below 100 nm) with liquid cores and molar mass controlled polystyrene shells were synthesized by an in situ miniemulsion polymerization reaction in the presence of a RAFT (reversible addition fragmentation chain transfer) agent. The formation of structured particles with the targeted core/shell morphology, i.e. liquid cores and polymeric shells, is extremely dependent on the type of RAFT agent used in conjunction with the type of initiator used. Different RAFT agents lead to different polymerization rates, thus resulting in different chain lengths as a function of time. This will influence viscosity and consequently chain mobility and can therefore cause a deviation from the desired morphology. The type of initiator used influences the surface activity of entering oligomers and is therefore also an important factor in obtaining the correct structure. Results showed that a RAFT agent that causes no rate retardation (phenyl 2-propyl phenyl dithioacetate, PPPDTA), used in conjunction with a surface active initiating species (potassium persulfate, KPS), is able to lock the locus of polymerization at the droplet/water interface. This results in entering oligomers being anchored at the droplet/water interface with consequent core/shell (nanocapsule) formation only if the RAFT agent used leads to a sufficiently rapid increase in chain length with time and thus a restriction of chain mobility of the mediated species.     

含氟丙烯酸酯共聚物细乳液的制备及表征

采用细乳液聚合法,制备了稳定的含氟丙烯酸酯(FA)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)的三元共聚细乳液.用FT-IR表征了聚合物的结构组成;考查了细乳液的稳定性、乳胶膜的吸水性及耐溶剂性;用接触角法表征了乳胶膜的表面自由能.     

Preparation of polymer nanocapsules for use as carriers via one-step redox interfacially initiated miniemulsion polymerization

In this work, one-step redox interfacially initiated miniemulsion polymerization (IMEP) was employed to fabricate polystyrene (PS) nanocapsules 80 nm in diameter with a 2,2′-bipyridine core by the redox-initiated coupling of cumene hydroperoxide (CHPO) to iron(II) sulfate (FS) using waterborne polyurethane (WPU) as surfactant and hexadecane (HD) as costabilizer. The morphology of the nanocapsules was characterized by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). Dynamic light scattering (DLS) was used to determine the size and polydispersity of the nanocapsules. It was found that the latexes prepared by miniemulsion polymerization via the redox-initiated method had relatively small diameters (40–100 nm) and a relatively narrow particle size distribution index (PDI: 0.086–0.124), which indicated that polymeric nanoparticles with small diameters and a narrow PDI can easily be prepared via one-step IMEP. The release of 2,2′-bipyridine from the nanocapsules was monitored by UV-visible spectroscopy. These results indicate that polymeric nanocapsules with a functional liquid core can be successfully fabricated via IMEP.     

Synthesis of trimellitic anhydride microcapsule toner by liquid‐phase separation

A microcapsule toner containing trimellitic anhydride for use as a foam inhibitor in printing applications was synthesized by liquid‐phase separation in organic solvents. It is possible to determine materials appropriate for the microencapsulation of trimellitic anhydride from solubility parameters calculated on the basis of the molecular structures of raw material candidates. Considering solubility parameters of various polymers, the polyethylene/methacrylic acid copolymer was selected for the microcapsule wall material. In addition, two kinds of solvents, toluene [solvent (a)] and isoparaffin [solvent (b)], were employed. It was necessary for the microcapsule materials to meet the following conditions: (1) the wall material must completely dissolve in solvent (a); (2) the core material must disperse well, but not dissolve in solvent (a); and (3) the wall and core materials must not dissolve in solvent (b). By using mixtures of either lecithin and basic barium petronate or lecithin and basic calcium petronate as charge control agents, the trimellitic anhydride microcapsules could be charged either positively and negatively, respectively. The microcapsule toner fabricated in this method was successfully applied in commercial printing machines, where it inhibited foaming effectively enough to satisfy product requirements in the printing industry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3822–3826, 2003     

Molecular characterization of alkyd/acrylic latexes prepared by miniemulsion polymerization

The molecular characterization of alkyd/acrylic hybrid latexes produced by miniemulsion polymerization was characterized in terms of the resin degree of grafting, acrylic degree of grafting, reacted double bonds in the alkyd, gel content, and molecular weight distribution of the sol part. A simple method based on conventional size exclusion chromatography measurements was developed to estimate the fraction of alkyd resin grafted to the acrylic polymer. The method could be applied to completely soluble hybrids and to hybrids containing gel. Also, the limits of the extraction method used in the literature to estimate the fraction of acrylic polymer grafted to the alkyd was investigated; we found that this technique only provided accurate results at high values of the acrylic degree of grafting. The combination of this information with the reacted double bonds of the alkyd (determined by iodine titration) and the molecular weight distribution of the sol polymer provided a detailed characterization of the alkyd–acrylic hybrid polymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Wet‐phase‐separation membranes from the polysulfone/N,N‐dimethylacetamide/water ternary system: The formation and elements of their structure and properties

Asymmetric and porous polysulfone (PSf) membranes were prepared by wet phase separation. Binary (PSf)/N,N‐dimethylacetamide (DMA) solutions with polymer concentrations of 12.5–30 wt % were cast in thicknesses of 80–700 μm and immersed in a coagulation bath of pure water. The morphology of the formed membranes' cross sections consisted of a cellular structure and macrovoids; the cellular structure density was highest when the cast solution contained about 21 wt % PSf, regardless of the cast thickness. The membranes' pure water permeability decreased as the cast thickness increased. The instantaneous onset of the turbidity, regardless of the PSf content and cast thickness, its steep growth, and relatively high end value were the main characteristics of the turbidity phenomena taking place during the formation of the protomembranes. Again, the membrane‐forming system with a PSf/DMA solution with about 21 wt % polymer, regardless of the cast thickness, had the highest turbidity end value. The shrinkage of the cast solutions into the corresponding protomembrane was also examined quantitatively. Inverse experiments showed that the direction of the gravitation field had no influence on the shrinkage of the membrane‐forming ternary system or the membranes' morphology and its water permeability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1667–1674, 2005     

Preparation and characterization of poly(ethylene‐co‐vinyl alcohol) membranes via thermally induced liquid–liquid phase separation

Porous membranes were prepared through the thermally induced phase separation of poly(ethylene‐co‐vinyl alcohol) (EVOH)/glycerol mixtures. The binodal temperature and dynamic crystallization temperature were determined by optical microscopy and differential scanning calorimetry measurements, respectively. It was determined experimentally that the liquid–liquid phase boundaries were shifted to higher temperatures when the ethylene content in EVOH increased. For EVOHs with ethylene contents of 32–44 mol %, liquid–liquid phase separation occurred before crystallization. Cellular pores were formed in these membranes. However, only polymer crystallization (solid–liquid phase separation) occurred for EVOH with a 27 mol % ethylene content, and the membrane morphology was the particulate structure. Scanning electron microscopy showed that the sizes of the cellular pores and crystalline particles in the membranes depended on the ethylene content in EVOH, the polymer concentration, and the cooling rate. Furthermore, the tendency of the pore and particle sizes was examined in terms of the solution thermodynamics of the binary mixture and the crystallization kinetics. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 853–860, 2003     

Preparation of epoxy resin/acrylic composite latexes by miniemulsion polymerization method

Epoxy resin/acrylic composite latexes were prepared by miniemulsion polymerization. Epoxy resins have a functional epoxy group in them and excellent characteristics, such as heat resistance and good adhesion. Acrylic latexes have weather and water resistance. Combining the epoxy resin and the acrylic latex was an attempt to actualize these advantages. The miniemulsion polymerization method was effective in obtaining the composite latex. A less than 500‐nm droplet size for the monomer preemulsion was necessary to obtain the latex in a stable manner. Dimethylaminoethylmethacrylate and methacrylic acid as the reactive functional monomer with an epoxy group were introduced to the latexes. The effect of the polymerization method of these functional groups on the properties of latexes and their films was investigated. The latex prepared by the two‐stage polymerization method had good polymerization stability, storage stability, and solvent resistance. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 128–133, 2001     

Preparation and characterization of paraffin microcapsules for energy-saving applications

A series of microencapsulated phase-change materials (PCMs) with styrene–divinyl benzene shells composed of an n-octadecane (OD or C₁₈)–n-hexadecane (HD or C₁₆) mixture as the core were synthesized by an emulsion polymerization method. The effects of the core/shell ratio (C/S) and surfactant concentration (C_surf) on the thermal properties and encapsulation ratios of the PCMs were investigated. The chemical structures and morphological properties of the microcapsules were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy analysis, respectively. The characteristic peaks of the paraffin mixtures and shell material located in the FTIR spectrum of the microencapsulated PCMs proved that the encapsulation of the PCM mixture was performed successfully. The thermal properties of the paraffin microcapsules were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis. DSC analysis demonstrated that the microcapsules containing the maximum amount of paraffin mixture (C/S = 2:1) and the minimum C_surf (45 mmol/L) had the highest latent heat value of 88 kJ/kg and a latent heat of temperature of 21.06°C. Moreover, the maximum encapsulation ratio of the paraffin mixture was found to be 56.77%. With respect to the analysis results, the encapsulated binary mixture, which consisted of OD–HD with a poly(styrene-co-divinyl benzene) shell, is a promising material for thermal energy storage applications operating at low temperatures, such as in the thermal control of indoor temperatures and air-conditioning applications in buildings for desirable thermal comfort and energy conservation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47874.     

Grafting mechanisms in hybrid miniemulsion polymerization

The ultimate objective of hybrid miniemulsion polymerization is to produce a water‐based crosslinkable coating through in situ grafting of a free radical growing acrylic polymer with an unsaturated resin. Certain authors have reported low grafting while others have reported higher. This article explores the factors that influence the grafting tendencies of these systems. Methacrylates such as methyl methacrylate (MMA) have a sterically hindered radical center that lowers its reactivity toward unsaturated resin. This steric hindrance from the methyl group forces grafting of this type of monomer to occur by abstraction of a hydrogen allylic to a resinous double bond. This chain transfer produces a relatively inactive radical on the resin that reduces the grafting efficiency. The transfer process also inherently produces some degree of terminated PMMA polymer within the particle. Grafting occurs in this type of system through termination of living PMMA chains with that radical produced on the resin. For relatively water‐soluble monomers such as MMA, grafting efficiency is further lessened by homogeneous nucleation resulting from the monomer hydrophilicity. These newly created particles cannot contain alkyd due to its hydrophobicity and thus inability to transport across the aqueous phase, and hence cannot produce grafted polymer. Nonetheless, degree of grafting of nearly 50% was observed in these systems. For hybrid systems involving an acrylate monomer such as butyl acrylate (BA), virtually complete grafting with alkyd was observed. This is due to the uninhibited BA radical center allowing the molecule to add directly through a resin double bond. This process offers the possibility for complete grafting. Homogeneous nucleation is not involved in this system due to the insolubility of BA in the aqueous phase. Resin double bond content and degree of conjugation also play an integral role in the grafting process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1825–1836, 2003     

Preparation and characterization of novel polyamide paraffin MEPCM by interfacial polymerization technique

A novel polyamide‐paraffin microencapsulated phase change material (MEPCM) was prepared by interfacial polymerization technique using 1,3,5‐benzenetricarbonyl chloride (TMC) and ethylenediamine as monomers and 30# paraffin as core material. Morphology, chemical composition, thermal properties of the MEPCM were studied by scanning electron micrograph, FT‐IR spectrum, differential scanning calorimeter analysis and thermogravimetric analysis. The solvent resistances of the MEPCM were also studied by observing the morphology changes of the MEPCM under optical microscope. Results indicate that the MEPCMs prepared under optimal conditions have spherical shape with average diameter of 6.4 µm, and the polyamide shell has successfully packaged the paraffin core. The MEPCM has a high efficiency in storing and releasing heat. The latent heat is 121.7 J/g and the microencapsulation ratio is 87%, 5% weight loss temperature is 260°C. The MEPCM is stable in H₂SO₄ solution (ω = 0.98), NaOH solution (ω = 0.40), ethanol, acetone, ether, dimethylformamide while can be destroyed by ZnCl₂ solution (ω = 0.60). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Preparation and characterization of microcapsules containing capsaicin

With urea‐formaldehyde (UF) resin as walls and capsaicin as core substances, microcapsules were prepared based on in situ polymerization process. The morphology and size distribution of the microcapsules were analyzed by Fourier transform infrared spectroscopy, laser particle size analyzer, and scanning electron microscopy. The microcapsulated capsaicin (MC) agents had a mean diameter of about 30–50 μm. Moreover, the thermal properties of the MC agents were measured by differential scanning calorimetry and thermogravimetric analysis. It was demonstrated that the melting point and thermal stability of the MC agents were greatly improved compared with that of the uncovered capsaicin, which were caused by the encapsulating crosslinked UF resin over the surface. The shell formation mechanism and the effects of the process conditions such as U/F ratio, shearing force, and acidification time on the particle size of the MC agents were discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Magnetite core-shell nano-composites with chlorine functionality: preparation by miniemulsion polymerization and characterization

Magnetic composite particles with a magnetic core consisting of superparamagnetic iron oxide and a cover layer of hydrophobic polyvinylbenzylchloride are described. The magnetite was prepared by precipitation starting with mixed iron II and iron III salts and coating of the solid with oleic acid. The coating is conducted via the liquid–liquid phase transfer. Thereby oleic acid adsorbed on the magnetite surface. In a second step the oleic acid treated magnetite was coated with polyvinylbenzylchloride in a miniemulsion polymerization to get a protective layer. The obtained magnetite core-shell nano-composites with chlorine functionality were characterized by different methods: particle size measurement, acid treatment, iron content, morphology and elemental profiles across the composite particles diameter. The test result reveals the binding of the iron oxide inside the composites which can be also recognize in TEM pictures.     

Hybrid acrylic–polyurethane latexes: Emulsion versus miniemulsion polymerization

Two kinds of hybrid acrylic–polyurethane (PUA) latexes are compared according to their synthesis and properties. The acrylic part is a copolymer of styrene, methyl methacrylate, and butyl acrylate. The PUAs are based on the polycondensation of isophorone diisocyanate and poly(propylene glycol) using butanediol and ethylene diamine as chain extenders. The first class result from the polymerization of miniemulsions of solutions of PU in the mixture of monomers using benzoyl peroxide as an initiator at 80°C. In the second class PUs modified by neutralized dimethylolpropionic acid are used as seeds and emulsifiers for emulsion polymerization of the monomer mixtures initiated with azobisisobutyronitrile at 75°C. The polymerization kinetics are compared, as well as the morphology of the latex particles. Films are obtained upon coalescence of these latexes, and the surface composition of these films and their tensile properties are studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3927–3941, 2006     

Emulsion and miniemulsion polymerization of isobornyl acrylate

Isobornyl acrylate, a highly hydrophobic monomer, was batch‐polymerized in both emulsion and miniemulsion recipes. Surfactant levels above and below the critical micelle concentration were used, as were two different initiator types: ionic (potassium persulfate) and nonionic (t‐butyl hydroperoxide) Samples were analyzed for degree of conversion, molecular weight, and particle size. The effects of reaction type (emulsion versus miniemulsion), surfactant level, type of initiator (ionic versus nonionic) of the polymer properties are discussed. Issues of monomer transport across the aqueous phase, and mechanisms of nucleation, especially at very low surfactant concentrations are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 819–833, 2007     

RAFT miniemulsion polymerization of methyl methacrylate

It has been well documented that RAFT miniemulsion polymerization has broader molecular weight distribution, compared with its bulk polymerization counterpart. Interestingly, it was found that the PDI value of RAFT miniemulsion polymerization of methyl methacrylate (MMA) mediated by 2-cyranoprop-2-yl dithiobenzoate (CPDB) was still as low as its corresponding bulk polymerization did. PDI could be as low as 1.13 even with typical sodium dodecyl sulfate (SDS, 1 wt%, surfactant) and n-hexadecane (HD, 2 wt%, costablizer) concentrations. When the polymerization was carried out at 60 °C, a dramatic increase in PDI (>1.4) was observed after 80% monomer conversion since RAFT addition reaction became diffusion-controlled. Increasing the polymerization temperature to 80 °C could reduce the PDI to 1.2 even at 100% monomer conversion. The compartmentalization effect of radicals was surprisingly absence before 30% monomer conversion but became pronounced afterwards in the miniemulsion polymerization. Thus, it still took less time to finish the miniemulsion polymerization with the increase of the surfactant levels.