Waterborne oil‐modified polyurethane coatings via hybrid miniemulsion polymerization

As part of a wider effort to develop a new class of waterborne coatings, hybrid miniemulsion polymerization was carried out with acrylic monomers (methyl methacrylate, butyl acrylate, and acrylic acid) in the presence of oil‐modified polyurethane resin. Latexes with different ratios of resin to acrylic monomers were synthesized. The monomer emulsions prepared for hybrid miniemulsion polymerization showed excellent shelf‐life stability (>5 months) and the polymerization was run free of coagulation. Solvent extraction indicated that the grafting efficiency of polyacrylics was greater than 29% for all the samples produced. A ¹³C solution NMR spectrum showed that a substantial fraction of the original carbon double bonds (>61%) in oil‐modified polyurethane remained after polymerization for film curing. Films obtained from the latexes presented good adhesion properties and fair hardness properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 105–114, 2000     

Thermotropic systems with fixed domains exhibiting enhanced overheating protection performance

Within this study, a time saving photo‐initiated miniemulsion polymerization process (duration of polymerization was 15 min) was established in order to encapsulate a paraffin wax with an acrylate polymer shell. The obtained freeze‐dried latex was an off‐white powder exhibiting spherical particles with mean diameters around 400 nm and a concentration of paraffin wax around 56%. Mixing the reaction product with a UV‐curable resin matrix resulted in thermotropic overheating protection glazings with high light‐shielding efficiency. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40417.     

In‐situ formation of metal nanoparticle/acrylic polymer hybrid and its application to miniemulsion polymerization

We present in‐situ formation of metal nanoparticle/acrylic polymer hybrid and its application to prepare hybrid latex particles by miniemulsion polymerization. On the surface of a silver nanoparticle/silica nanoparticle/acrylic polymer hybrid layer formed in‐situ on a polyethylene terephthalate (PET) substrate, a copper film is deposited using electroless copper deposition. Silver nanoparticles, which are formed in‐situ via the reduction of silver ion by radical species and subsequent annealing, work as a catalyst for the electroless deposition. Miniemulsion polymerization via the in‐situ formation of nanoparticles affords nanoparticle/acrylic polymer hybrid latex particles and polymer particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42675.     

Emulsion and miniemulsion copolymerization of acrylic monomers in the presence of alkyd resin

Emulsion and miniemulsion copolymerizations were carried out with acrylic monomers (methyl methacrylate, butyl acrylate, and acrylic acid) in the presence of an alkyd resin. Poly(methyl methacrylate) was used as a hydrophobe or cosurfactant in the miniemulsion reactions. The results demonstrate that miniemulsion polymerization is the preferred process, probably because of mass transport limitations of the alkyd in the conventional emulsion polymerization reactions. The monomer emulsions prepared for the miniemulsion reactions were much more stable and the polymerizations were free of coagulum. Reaction rates, particle size characteristics, grafting efficiencies, and some film properties were measured. © 1996 John Wiley & Sons, Inc.     

Water‐based crosslinkable coatings via miniemulsion polymerization of acrylic monomers in the presence of unsaturated polyester resin

Hybrid miniemulsion polymerization was performed with a three‐component acrylic system of methyl methacrylate, butyl acrylate, and acrylic acid in the presence of a Bayer® Roskydal TPLS2190 unsaturated polyester resin. Latexes were obtained in which the polyester resin was grafted to the acrylic polymer, forming a water‐based crosslinkable coating. Grafting between the resinous component and the acrylic polymer is a feature different from the work of others who have attempted to combine the properties of both systems in water‐based blends. Both emulsions and latexes were shelf‐stable for over 6 months, shear‐stable, and resistant to at least one freeze/thaw cycle. Resin‐to‐monomer ratios were studied as high as 1 : 1 (wt : wt), and total emulsion solids, as high as 45%. Monomer droplet and latex particle sizes were similar, suggesting evidence of the preponderance of droplet nucleation. A high level of crosslinking (>70%) during polymerization was observed in this particular hybrid system in contrast to those involving alkyd or polyurethane resins (<5%). Films, both homogeneous and hard, were achieved with exceptional adhesion. Electron microscopy showed the hybrid particle morphology to have internal domains of polyester resin in an acrylic matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 916–927, 2000     

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 Hybrid Quaternized Chitosan/Acrylic Resin Emulsions and their Films

An acrylic resin emulsion containing a quaternary ammonium salt (hybrid q‐chitosan/acrylic resin emulsion) was prepared by emulsion polymerization using an acrylic monomer with and without DAAM. DAAM was used to incorporate a functional keto group into the acrylic resin emulsion. Furthermore, a hybrid chitosan/acrylic resin emulsion was prepared for comparison. The elution of q‐chitosan in water from the acrylic resin film with a keto group was less than that from the acrylic resin emulsion without a keto group. In addition, the mechanical properties of the hybrid q‐chitosan/acrylic resin film could be modified by q‐chitosan that was crosslinked between acrylic resin particles. Furthermore, hybrid q‐chitosan/acrylic resin films had adsorption ability for formaldehyde, and the antimicrobial properties of these films were superior to those of the hybrid chitosan/acrylic resin film.

     

Emulsifier‐free miniemulsion polymerization of styrene using a cationic initiator

Polystyrene latex particles were synthesized using a method based on emulsifier‐free miniemulsion polymerization under ultrasonic irradiation in the presence of 2,2′ azobis (2‐amidinopropane) dihydrochloride (V‐50) as a cationic ionizable water‐soluble initiator and cetyl alcohol as costabilizer. The optimized conditions were obtained by using various parameters, such as the amounts of monomer and initiator, and the time and power of ultrasonic irradiation. In optimal conditions, the latex particles appeared to be about 250 nm in diameter through scanning electron microscopy (SEM). The SEM and gel permeation chromatography (GPC) analyses and monomer conversions of emulsifier‐free miniemulsion polymerization were compared with those of conventional emulsifier‐free emulsion polymerization using V‐50 as initiator in both cases. The results showed that in the miniemulsion polymerization, the rate of polymerization (Rp) was significantly higher, and latex particles were significantly smaller than those in the conventional emulsion polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modeling for primary radical desorption in miniemulsion polymerization initiated by oil‐soluble initiator

Primary radical (PR) desorption in the miniemulsion polymerization initiated by oil‐soluble initiator was investigated. Both the aqueous phase inhibition experiments and the theoretical predictions, which combined the two film theory and aqueous phase mass balance, were performed to evaluate the PR desorption process quantitatively. The theoretical predictions agreed well with the experiment results. It was found that the organic phase diffusion, particle size, surfactant layer, aqueous phase resistance, and different initiator type affected the PR desorption. The desorption rate of PR was faster than its reaction rate at the early stage of polymerization, while the former decreased to a comparable level as the latter at the high conversion. PR was prone to desorb in the polymerization and the desorption of PR played a critical role in the miniemulsion polymerization initiated by oil‐soluble initiator. It is concluded that the PR desorption–reabsorption is a process to generate effective radicals in the miniemulsion polymerization initiated by oil‐soluble initiator. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3276–3285, 2014     

Miniemulsion polymerization of fluorinated siloxane‐acrylate latex and the application as waterborne textile finishing agent

Fluorinated siloxane–acrylate polymer latex was synthesized via miniemulsion polymerization, which was carried out by pseudo one‐step method. In the synthesis protocol, the monomers of octamethylclotetrasiloxane (D₄), tetravinyltetramethylcyclotetrasiloxane (D₄^v), methyl methylacrylate, butyl acrylate, N‐methylol acrylamide, and dodecafluoroheptyl methacrylate (DFMA) were first mixed and homogenized into a miniemulsion, which was stabilized by dedecybenzene sulfonic acid. The ring‐opening polymerization of cyclosiloxane was then steadily performed under miniemulsion conditions and followed by the postaddition of radical initiators to initiate the polymerization of acrylate and DFMA monomers. The influences on the emulsion properties by acrylic monomer with different addition protocol were investigated in this work. In addition, the synthesized latexes were characterized by using dynamic laser scattering, transmission electron microscope, differential scanning calorimetry, and Fourier transform infrared spectroscopy. These results indicated that the introduction of D₄^v in the latex can successfully suppress the phase separation between the thermodynamically incompatible components for the formation of uniform hybrid latex particles. The further application of the as‐synthesized latex was investigated as a new kind of waterborne textile finishing agent. Moreover, the influences of the content of D₄^v and DFMA on the finishing properties, especially for the softness, the water repellence, and the antimoisture properties, were systematically studied in this work. With a proper design on the content of the D₄^v and DFMA, stable textile finishing emulsion was prepared, which can endow the fabric both desirable softness and excellent water resistances. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40161.     

Incorporation of high oil content in polyvinyl acetate nanoparticles produced by batch miniemulsion polymerization stabilized with a polymeric stabilizer

Nanoparticles (NPs) have been widely applied in the biomedical area. In order to satisfy the requirements for biomedical applications, sodium lauril sulfate (SLS) and hexadecane, widely used as anionic surfactant and co‐stabilizer, were successfully replaced by biocompatible compounds, in order to obtain poly(vinyl acetate) (PVAc) NPs via miniemulsion polymerization. The incorporation of high oil content in PVAc NPs was investigated, using different poly(vinyl alcohol) (PVOH) concentrations as polymeric surfactant. Besides the polymeric surfactant, lecithin and Miglyol 812, a triacylglycerol of saturated fatty acids obtained from coconut oil, were used as surfactant and co‐stabilizer, respectively. A high Miglyol 812 content was incorporated in the PVAc NPs and the morphology was investigated by TEM. The influence of PVOH concentration on the droplet nucleation mechanism and final morphology of PVAc NPs was evaluated. High PVOH concentration favored micellar particle nucleation. According to the TEM images, hemispheres nanoparticles were obtained. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41365.     

Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.     

Synthesis of two PET waste derived bisacrylic and bisallylic monomers and their potential use as crosslinking agents and dental resin composites

Two novel bifunctional monomers obtained from PET waste glycolisis are reported. Bis(2‐(acryloyloxy)ethyl) terephthalate and bis(2‐(((allyloxy)carbonyl)oxy)ethyl) terephthalate (BACET) monomers were obtained from bis(hydroxyethyl) terephthalate derived from PET waste and acryloyl chloride and allyl chloroformate, respectively. The monomers were characterized by FTIR and ¹H‐NMR spectroscopies. They were evaluated as crossslinking agents for acrylic acid (AA) and methacrylic (MA) acids using thermally initiated polymerization. The obtained copolymers showed higher thermal stability than the acrylic homopolymers. They were also tested for dental formulations as Bis‐GMA substitutes in heat curing resin composites. In spite of its lower reactivity, only BACET was able to substitute Bis‐GMA, due to its high solubility in the TEGDMA comonomer. Resin formulations containing nanosized silica and the mixture Bis‐GMA/TEGDMA or BACET/TEGDMA were prepared in order to compare physical and chemical properties. Water sorption, solubility, and flexural strength were found statistically similar for both formulations. However, flexural modulus was lower and double bond conversion was higher for the BACET resin, which could make it appropriate for its potential use in dental resin composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41487.     

The tough microcapsules of acrylic acid–styrene–isoprene–styrene quadrablock copolymer shell via Pickering emulsion technique

Pickering emulsion technique has been demonstrated a simple method to fabricate the microcapsules. However, the resulted microcapsules are often fragile. This limits their applications. Here, we report that the microcapsules with the nanostructured shell of poly(acrylic acid‐b‐styrene‐b‐isoprene‐b‐styrene) (ASIS), which is of high toughness and elasticity, could be fabricated via Pickering emulsions using ASIS nanoparticles as stabilizing particles. The surfactant‐free ASIS latex (with theoretical molecular weight for each block: 1.5k–15k–55k–10k) was synthesized by reversible additional fragmentation transfer (RAFT) emulsion polymerization using amphiphilic macro‐RAFT agent [poly(acrylic acid)₂₀‐b‐polystyrene₅ trithiocarbonate] as both reactive surfactant and polymerization mediator. It was found that the ASIS nanoparticles were able to self‐assemble on oil/water interface to stabilize Pickering emulsion of hexadecane in the pH range from 8 to 12. The droplet diameter was finely tuned from 17 to 5 µm by increasing the ASIS particle levels from 0.13 to 12 wt % based on the mass of the ASIS aqueous dispersions. With toluene as a coalescing aid, the capsules with a coherent and nonporous shell were obtained with the dispersed phase volume percentage as high as 50%. The toluene treated capsules were so mechanically strong to survive the utrasonic treatment. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46700.     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A polyampholyte triblock copolymer synthesized for using as the surfactant of miniemulsion polymerization and production of highly uniform microspheres

Miniemulsions based on styrene/azobisisobutyronitrile (AIBN) in the presence of polyampholyte triblock copolymers as a surfactant and hexadecane (HD) as a cosurfactant were developed. The polyampholyte was prepared by using methyl methacrylate (MMA), methacrylic acid (MAA), and 2‐(dimethylamino) ethyl methacrylate (DMAEMA) as monomers. For the sake of comparison, a miniemulsion polymerization with sodium dodecyl sulfate (SDS) was carried out using the same procedure as the above series. The monomer droplet sizes and their shelf life tests revealed that the polyampholyte could stabilize miniemulsion and lead nucleation mechanisms to droplet nucleation. Miniemulsion polymerization using SDS as the surfactant possess a higher polymerization rate than that of polyampholyte, probably due to the smaller droplet size. Production of uniform microspheres was also carried out in this work. Highly uniform microspheres prepared using polyampholyte as the surfactant in the presence of acetone could be obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2230–2237, 2003     

Homogeneously distributed magnetite in the polystyrene spherical particles using the miniemulsion polymerization

The polystyrene spherical particles with homogeneously distributed magnetites were prepared using the conventional miniemulsion polymerization. In the first, the magnetite nanoparticles were coated with oleic acid in aqueous Fe³⁺/Fe²⁺ solution using excess ammonium hydroxide via co-precipitation method. In the second, the miniemulsion polymerization of styrene was carried out using various concentrations of potassium persulfate (KPS) as an initiator, H-08E as an emulsifier, hexadecane as a co-emulsifier and acrylic acid as a dispersing agent in the presence of oleic acid coated magnetite at 70 °C for 24 h. The particle size and its distribution of the homogeneously embedded magnetites were influenced by the concentration of the initiator (KPS) and acrylic acid (AAc). In addition, the emulsifier, H-08E, affects the size and the shape of the PS particles. The optimum conditions for the homogeneously distributed magnetite in the spherical PS particles with the narrow distribution were 5 wt.% styrene, 0.2 g KPS, 0.2 g AAc, and 0.12 g H-08E by inducing 364 nm in diameter, 12.04% in the coefficient of variation (C_v) and 22.1% of the maximum magnetite content.     

Magnetite‐coated polystyrene hybrid microspheres prepared by miniemulsion polymerization

Hybrid microspheres with a polystyrene core coated with magnetite nanoparticles were prepared by miniemulsion polymerization. Acrylic acid was used as a comonomer to promote the anchoring of the magnetite nanoparticles onto the polymeric surface. The addition of a hydrophobic agent prevents effectively the monomer from diffusing into the aqueous phase. Magnetite was treated with a silane coupling agent in order to introduce some interactions with the polymers. The morphology and the structure of the hybrid microspheres were characterized using X‐ray diffraction, infrared spectroscopy, transmission electron microscopy and thermogravimetric analysis. The results show that the morphology of the hybrid microspheres was influenced by the concentrations of acrylic acid, hydrophobic agent and surfactant, and that the degree of coating can be tuned by changing these parameters. The miniemulsion polymerization technique is adaptable to the synthesis of magnetite‐coated polymer particles, and the synthesis can be scaled up. Copyright © 2008 Society of Chemical Industry     

Comparison of rigid divinylbenzene with flexible 1,7‐octadiene crosslinks in acrylic acid resins—effects on kinetics of swelling and loading of heavy metal ions from water

Acrylic acid–1,7‐octadiene resin was synthesized in beaded form by a two‐step process: suspension polymerization of ethylacrylate and 1,7‐octadiene monomers, followed by hydrolysis using either 98% H₂SO₄ or 10 M NaOH. Acrylic acid–divinylbenzene resins were also synthesized by the same process for the purpose of comparing a rigid divinylbenzene with a flexible 1,7‐octadiene crosslinkage in the acrylic acid resins. Swelling of the resins in distilled water shows that replacing divinylbenzenes with 1,7‐octadiene makes the resin achieve greater swelling in a significantly shorter time. 1,7‐Octadiene also allowed for an increase in crosslinkage to 20% compared to 4% in the case of divinylbenzene, without compromising the loading rates of toxic heavy metal ions like Pb²⁺, Cu²⁺, and Cr³⁺ from water samples. The acrylic acid–1,7‐octadine resin was found useful for removal of the toxic heavy metal ions from wastewater samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41038.     

Miniemulsion and conventional emulsion copolymerization of styrene and butadiene: A comparative kinetic study

The kinetics of conventional and miniemulsion copolymerizations of styrene and butadiene were compared using the Mettler RC1 calorimeter. A two‐step homogenization procedure was applied to obtain miniemulsions of these monomers with hexadecane as the costabilizer. The results indicated that the miniemulsion polymerizations proceeded mainly by nucleation in the monomer droplets, while in the conventional emulsion polymerizations, particle formation occurred by a combination of micellar and homogeneous nucleation. The overall rate of miniemulsion polymerization was faster than the corresponding conventional emulsion system if the surfactant concentration was below the critical micelle concentration (cmc) and slower if the surfactant concentration was above the cmc. The homogenization process is important for making stable miniemulsion systems, but had no effect on the conventional emulsion system (without hexadecane), most likely because of the second stage addition of the butadiene monomer. The dependencies of the rate of polymerization (heat of reaction) and number of particles on the surfactant concentration differed for the two types of polymerization systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2304–2312, 2006