Hybrid Emulsion Research Articles

Enhanced water repellence and thermal insulation of masonry by zinc oxide treatment

In this study a novel zinc oxide nano-particulate water repellent emulsion was applied to brick and mortar samples. The treatment used was an aqueous silane/siloxane hybrid emulsion designed to penetrate deep into a substrate. Possible water repellence and thermal insulation for household energy saving was investigated. Tests on brick and mortar assessed; porosity, treatment depth, surface energy, water contact angle, thermal conductivity and visual aesthetics. In addition, two model houses were built with one treated with the emulsion. A heating and monitoring regime was developed to quantitatively evaluate heating energy consumption in different conditions. It was found that the treatment imparted significant water repellence and enhanced thermal insulation to treated samples. The results from contact angle and surface energy measurements showed that the substrates became highly hydrophobic. Experimental results from the model houses showed approximately 5% heating energy reduction in dry conditions and approximately 20% in wet conditions. In addition, the internal humidity was reduced across various temperature scenarios. Negligible aesthetical alteration of substrates and ease of application additionally prove that significant contribution can be made by similar treatments in future nationwide retrofit projects.

Study on Polyurethane-Acrylic Hybrid Emulsion Applying to Water-Based Ink

Polyurethane-acrylic composite emulsion was synthesized by swelling polymerization with aqueous polyurethane dispersion as seed, and acrylic as monomers. The obtained polyurethane-acrylic (PUA) composite emulsion were characterized by means of IR spectra, and the results showed that the obtained emulsion was hybrid emulsion of polyurethane and acrylic, which had smaller particle size and higher viscosity and was more suitable for the preparation of ink. The obtained water-based PUA emulsion and alkyd resins were used as ink binder. The obtained water-based ink had good water resistance, color density, gloss and friction fastness.

Synthesis, Stability and Properties of Polyurethane/Acrylic Hybrids Using m-TMXDI-based Anionic Poly(urethane-urea) Dispersion

Waterborne polyurethane (WPU) dispersion was synthesized with isocyanic acid, m-TMXDI-based anionic poly(urethane-urea). WPU/AC hybrid emulsions were prepared by the emulsion polymerization of a mixture of AC monomers (styrene, methyl methacrylate and butyl acrylate) in the presence of WPU dispersion. The structures of WPU/AC hybrids were characterized by FTIR. Average particle size, distribution, and morphology of the latex particles were investigated by DLS and TEM, respectively. The stability of the emulsions was studied by the dispersion analyser LUMiSizer® with STEPTM-Technology. The thermal and mechanical properties of these films were studied from the TGA and strain–stress curves.

Study on Formulation for Epoxy Acrylic Hybrid Emulsion

The epoxy acrylate emulsion was made by hybrid emulsion polymerization. This method has simple technology, none solvent and friend to the environment. The epoxy acrylate hybrid emulsion was prepared by using core-shell emulsion polymerization technology. The factors, such as epoxy resin, emulsifier ,initiator and functional monomer, were investigated by the orthogonal experiment. The relation of interactional factors was confirmed, and one kind of steady emulsion was made. The best formulation condition of modified emulsion could be obtained when N-MA was 1%, MAA was 2%, emulsifier was 3%, epoxy resin was 6%, initiator was 0.6%. The structure of modified styrene acrylic hybrid emulsion was characterized by FT-IR, the peaks at 915cm-1 and 1251cm-1 correspond respectively to the motion of epoxy group and phenylate, so the graft polymer was confirmed.

Study on Properties of Modified Nano-ZnO/WPU Hybrid Material

Modified nanoZnO/WPU hybrid material was synthesized by three different ways in this paper, the effect of the addition method and content of modified nanoZnO on the hybrid material were discussed. The results showed that modified nanoZnO was added in polymerization process, the hybrid emulsion stability and the coating films mechanical strength all with excellent performance. The appropriate addition of nanoZnO modified by titanate coupling agent can improve the ultraviolet weatherproof, tensile strength, elongation at break even the abrasion resistance of the hybrid material. When modified nanoZnO content was 0.3%, the comprehensive performance of hybrid material was the best.

Structural, thermal and morphological properties of aqueous hybrid emulsion of silylated poly (urethane)/organic modified montmorillonite nanocomposites based on a new silicone and imide ring containing vinylic macromonomer

A new silicone and imide ring containing vinylic macromonomer, N-trimethylsiloxyethyltrimellitilimidomethacrylate (TMSETMIM), has been synthesized for the formulation of waterborne polyurethane (PU). A vinyl group containing silicone, the (3-methacryloyloxypropyl) trimethoxysilane (MPTMS) was used for comparison of the effects of silicone type with TMSETMIM on the PU. Then, a series of new siliconized PU hybrid nanocomposites, were successfully synthesized by the emulsion polymerization in the presence of organic modified montmorillonite (OMMT) and an aqueous PU dispersion using ammonium peroxodisulfate (APS) as an initiator. The PU dispersion was synthesized by a polyaddition reaction of hexamethylene diisocyanate (HMDI), on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as a chain extender. The obtained NCO chain ends reacted with water (which acts as a further chain extender producing some urea bonds). The structural elucidation of monomer was carried out by FTIR, 1H-NMR, and 13C-NMR spectroscopic techniques. The copolymers were also characterized by using FTIR. Thermal properties of the copolymers were studied by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The morphologies of the copolymers were characterized with scanning electron microscopy (SEM) and transition electron microscopy (TEM) and then the effects of silicone concentrations on the water absorption ratio was examined. The formed film from the hybrid emulsion containing TMSETMIM could provide obviously higher water-resistance property in comparison with MPTMS. Also, the heat stability increases while the Tg decreased.

Synthesis of core–shell acrylic–polyurethane hybrid latex as binder of aqueous pigment inks for digital inkjet printing

Acrylic–polyurethane (PUA) hybrid aqueous emulsion with core–shell structure was prepared via semibatch emulsion copolymerization of the acrylate monomers (AC) in the presence of a commercial polyurethane dispersion as seeds. The core–shell structure of the emulsion was observed by TEM. The particle size and distribution of the emulsion was found to vary drastically with the core–shell ratio. The thermal response properties of emulsion films were measured by DSC, and the results indicated the good compatibility between PA and PU moieties in PUA hybrids. The chemical structures of emulsion films were studied by FTIR, and the surface properties were tested by contact angle measurement. The results supported the idea that the surface of the cast films was rich in polyurethane component. The water resistance of the cast films became better by increasing the AC fraction. The rheological properties of the latex and its utilization as a binder for aqueous pigment inks of digital inkjet printing were thoroughly investigated, indicating that the prepared hybrid emulsion could be used safely for aqueous pigment inks of digital ink jet printing.

Waterborne polyurethane/poly(n-butyl acrylate-styrene) hybrid emulsions: Particle formation, film properties, and application

In this work, a hybrid synthesis technology has been used to fabricate waterborne polyurethane (WPU)/poly(n-butyl acrylate-styrene) (PBS) emulsions with dimethylol-propionic acid (DMPA) as chain extender. The influences of the PBS, styrene, and DMPA contents on the physical properties of the resultant emulsions and cast films have been investigated in detail using various characterization methods. The experimental results show that with an increase in the PBS or styrene content, the particle size in emulsions increases but the viscosity of the emulsions decreases and that the opposite applies for the DMPA content. For cast films, with an increase in the styrene or DMPA content, the tensile strength increases whereas the elongation decreases. The water absorption capacity of the film decreases with an increase in the styrene content or a decrease in the DMPA content. Furthermore, the emulsions synthesized have been used for paper sizing applications. The treated papers exhibit greatly improved water resistance, and the Cobb values at 30 and 60s are only 10.23 and 11.89%, respectively, of those of unsized papers. The other paper properties, such as gloss, smoothness, folding resistance, and burst strength, are also considerably improved.

Preparation of poly(styrene‐co‐butyl acrylate)/montmorillonite nanocomposite by emulsion polymerization: Characterization and nanoscratch behavior

AbstractOrganic–inorganic hybrid poly(styrene‐co‐butyl acrylate)/organically modified montmorillonite (PSBA/organo‐MMT) latex particles have been prepared by in situ emulsion polymerization. The effects of modifier variety and the level of organo‐MMT have been investigated on the basis of the characteristics and mechanical properties of the resulting hybrid emulsion polymers. Although the more hydrophilic intercalated organic modifiers increased the latex particle size, the hydrophobic ones decreased the particle size. A more heterogeneous copolymer chain intercalation was seen by widespread XRD reflection as the organo‐MMT (organoclay) level increases. The tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to determine the dispersion state of organoclay particles inside the nanocomposite copolymer films. Dynamic mechanical thermal analysis (DMTA) showed that adding the organoclay to the copolymer decreased the maximum loss tangent (tanδ) value and caused the shift to a lower temperature. Interestingly, the incorporation of organoclay decreased the glass storage modulus of the copolymer, while increased the rubbery storage modulus to some extent. In addition, a standard indenter for the nanoscratching of copolymer nanocomposite films was used under low applied loads of 150 and 250 μN. The nanoscratch results showed that incorporation of a 3 wt % hydrophobic organoclay, e.g., Closite15A, in the copolymer matrix enhanced considerably the near‐surface hardness and grooving resistance of the nanocomposite film at room temperature. In fact, copolymer nanocomposite films with higher near‐surface hardness and tanδ curve broadening exhibited more nanoscratch resistance through a specific variety of viscoelastic deformation, which did not create a bigger groove. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Synthesis of CaCO3–P(MMA–BA) nanocomposite and its application in water based alkyd emulsion coating

As part of broader effort to synthesize a new class of water-based composite, hybrid emulsion polymerization was carried out with acrylic monomers [methyl methacrylate (MMA), n-butyl acrylate (BA)]. Nanocomposite of P(MMA–BA)/nano CaCO3 was synthesized by in situ emulsion polymerization. Water-based alkyd coating with various proportions nano CaCO3, P(MMA–BA) and its nanocomposite was formulated. Extent of polymerization with and without nano CaCO3 was measured using gravimetric method. Thermal properties of neat polymer, nanocomposite and coating films were evaluated by TGA and DSC, DTA analysis. Uniform dispersion of nano CaCO3 in polymer matrix was ensured from SEM/TEM images. Incorporation of nanoparticles to hybrid polymer and nanocomposite to alkyd emulsion showed significant enhancement in mechanical and thermal properties. Dual role of nanocomposite in coating; as a partial binder and a filler to improve property profile of neat coating has been reported.

Organic–inorganic hybrid superhydrophobic surfaces using methyltriethoxysilane and tetraethoxysilane sol–gel derived materials in emulsion

By applying alkaline-catalyzed co-hydrolysis and copolycondensation reactions of tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) in organic siloxane modified polyacrylate emulsion (OSPA emulsion), we are able to demonstrate the potential for developing a sol–gel derived organic–inorganic hybrid emulsion for a superhydrophobic surface research. TEOS and MTES derived sol–gel moieties can be designed for a physical roughness and hydrophobic characteristic (Si–CH3) of the hybrid superhydrophobic surface, while OSPA emulsion can be endowed for good film-forming property. The effect of formulation parameters on superhydrophobicity and film-forming property was analyzed. The water contact angle (WCA) on the sol–gel derived hybrid film is determined to be 156°, and the contact angle hysteresis is 5° by keeping the mole ratio of TEOS:MTES:C2H5OH:NH3·H2O:AMP-95 at 1:4:30:10:0.63 and the mass percentage of OSPA emulsion at 25%. The nanoparticle-based silica rough surface is observed as the mole ratio of MTES/TEOS at 4:1. The sol–gel derived organic–inorganic hybrid emulsion shows remarkable film-forming property when the mole ratio of MTES/TEOS reaches or exceeds 4:1. With the primer coating, the performance of superhydrophobic film achieve actual use standard. It reveals that this new procedure is an effective shortcut to obtain a superhydrophobic surface with potential applications.

Preparation and properties of self-crosslinkable polyurethane/silane hybrid emulsion

Self-crosslinkable polyurethane emulsion containing active carbonyl group was obtained using dihydroxyketon N-[(1,1-dimethyl-2-acetyl)ethyl]-β-dihydroxyethylamino propanamide(DDP) and 1,4-butanediol as chain extenders, isophorone diisocyanate (IPDI), polyether polyol (PTMG1000), dimethylol propionic acid (DMPA) and trimethylol propane (TMP) as main materials, γ-aminopropyltriethoxysilane (APTES) as end capping agent. Then adipic dihydrazide was added into the emulsion. The structure and composition of DDP and the films were confirmed by means of FTIR and 1H nuclear magnetic resonance (1H-NMR) spectrometer, the test results indicated that the reaction between ketone carbonyl and hydrazine has happened during the film curing. The effects of n(NH2NH-)/n(C=O) and DDP content on the properties of the films were studied. The results show that water absorption of the films decreases from 39.3% to 18.9%, crosslinking degree increases from 51.5% to 90.2%, tensile strength increases from 20.1 MPa to 28.3 MPa and pencil hardness is 2H when the DDP content increases from 0% to 6.13%. TGA analysis indicates that the Ketone-Hydrazide crosslinking structure can improve thermal stability of the films.

Synthesis and Properties of Waterborne Polyurethane-Acrylate Hybrid Emulsion Modified by Organic Silicane

Waterborne polyurethane emulsions were synthesized with isophorone diisocyanate(IPDI), dihydromethyl propionic acid(DMPA) and poly-ε-caprolactone glycol(PCL), and then reacted with hydroxy-ethyl acrylate(HEA) and 3-aminopropyltriethoxylsilane(APTES) to cap the terminal -NCO groups. The polyurethane emulsions were used to copolymerize with acrylates to synthesize the modified waterborne polyurethane-acrylate hybrid emulsions. The structure, thermal stability and crystallinity of modified polyurethane were studied by FTIR, TG, XRD and the mechanical properties of modified polyurethane films was also investigated. The results show that crystallization of the modified waterborne polyurethane decreases and thermal stability is improved. When the mass fraction of acrylate is 20% and APTES content is 15%, tensile strength of the modified polyurethane films can reach 23.9MPa and elongation at break is 247%.

Preparation and Characterization of MWCNTs/FSiPUA Hybrid Film

CNTs/polymer hybrid films have been studied for hydrophobic surface in recent years. In this paper MWCNTs/FSiPUA hybrid films based on the excellent hydrophobicity have been prepared for the long term objective to prevent the marine fouling. MWCNTs/FSiPUA hybrid emulsion was prepared respectively by the methods of solution mixing with ultrasonic excitation and in-situ emulsion polymerization. Chemical and physical properties of the films were investigated by FTIR, contact angle meter and water absorption. The results showed that lauryl sodium sulfate（SDS）was a better dispersant than BYK-154 prepared via solution mixing with ultrasonic excitation. The performance of hybrid films approached by solution mixing with ultrasonic excitation was better than that by in-situ emulsion polymerization when same amount of MWCNTs was filled. The study indicated that the film surface properties reached best by both technologies when the content of MWCNTs was equal to 0.15wt%.

Novel urethane/acrylic hybrid emulsions for VOC compliant coatings

PurposeThe purpose of this paper is to develop a volatile organic component‐free water‐based binder with improved coating properties from urethane‐alkyd acrylate by emulsion polymerisation.Design/methodology/approachAlkyd resin based on interesterification of sardine fish and linseed oil (50:50 w/w) was synthesised and reacted with isophorone diisocyanate to form urethane alkyd. The resultant urethane alkyd and acrylic monomers in different ratios were polymerised by emulsion polymerisation to form air‐drying water‐based binders and studied for physicochemical and other coating properties.FindingsUrethane alkyd, co‐polymerised with acrylates by emulsion polymerisation process, can be used to prepare water‐based air‐drying binders with excellent coating and application performance. The increase in acrylate component in the system resulted in improvement of performance properties.Research limitations/implicationsIn the present study, refined fish oil (FO) was obtained from sardine fish. Different FOs can be used to produce alkyd resin. Urethane alkyd and acrylic monomers in different ratios can be polymerised by emulsion polymerisation techniques.Practical implicationsThe emulsion polymerisation is the most effective technique used to produce water‐based binders with excellent coating properties.Originality/valueWater‐based binders can be widely used in exterior coatings and waterproofing of cement and roofs.

The Research of Soy-Protein – Acrylate Hybrid Emulsion

This study researched the preparation of soy-protein and acrylic hybrid emulsion based on the emulsion formula preparation. The particle structure and shape was analyzed by DSC, ascertained by measuring adhesion properties of different emulsion on the same substrate by strength capability. The result show that the bonding strength of hybrid emulsion was better than the blending emulsion, and the glass temperature of hybrid emulsion was same with the blending emulsion.

Thermoset Alkyd-Acrylic Hybrid Emulsions for Coatings

Alkyd acrylic hybrid emulsions can offer cost/performance advantages over common 1K coatings such as polyurethane dispersions (PUDs), acrylic emulsions and blends. Hybrid emulsions with different ratios of alkyd resin to acrylic monomers were synthesized. Emulsion with resin-to monomer ratio of 1:1 (wt/wt) with total solids as high as 50% had a shelf stability of more than 8 months. Morphology of hybrid emulsions was studied by scanning electron microscopy. Hybrid emulsions were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Films obtained from the hybrid emulsions were found to be homogeneous and exhibited excellent thermal and coating properties.

Preparation and Performance of Waterborne Polyurethane/Nanosilica Hybrid Materials

The polyurethane prepolymer was synthesized, and hydrophilic nano-sized silica (A200) was added to the prepolymer with KH550 as a coupling agent, then a waterborne polyurethane/nanosilica hybrid material (WPUNS) was obtained by a sol-gel process. The structure and performance of the WPUNS films were studied by FTIR, TG, DSC and physical mechanical testing. The particle size and distribution of WPUNS hybrid emulsion was analyzed by a dynamic light scatter (DLS). The morphology of emulsion and films were observed by Transmission Electron Microscope (TEM) and Atomic Force Microscope (AFM), respectively. FTIR analysis indicates the formation of chemical bond between WPU and A200. TEM images display that A200 particles were encapsulated by PU macromolecules and formed a composite particles structure. As the mass fraction of A200 increased from 0 to 2%, the particle size increased from 79.9 nm to 139.9 nm, the tensile strength of the films increased from 6.32 MPa to 20.46 MPa, water absorption decreased from 28.3% to 6.3%, and the hardness was also improved. The TG result indicates that A200 can improve thermal stability of WPUNS. DSC shows that there is no clear effect of nanosilica on the glass transition of soft segments. AFM displays that the smoothness of the films increases with A200 addition.

Magnetic‐targeted pH‐responsive drug delivery system via layer‐by‐layer self‐assembly of polyelectrolytes onto drug‐containing emulsion droplets and its controlled release

AbstractNovel magnetic‐targeted pH‐responsive drug delivery system have been designed by the layer‐by‐layer self‐ assembly of the polyelectrolytes (oligochitosan as the polycation and sodium alginate as the polyanion) via the electrostatic interaction with the oil‐in‐water type hybrid emulsion droplets containing the superparamagnetic ferroferric oxide nanoparticles and drug molecules [dipyridamole (DIP)] as cores. Here the drug molecules were directly encapsulated into the interior of droplets without etching the templates and refilling with the desired guest molecules. The drug‐delivery system showed high encapsulation efficiency of drugs and drug‐loading capacity. The cumulative release ratio of dipyridamole from the oligochitosan/sodium alginate multilayer‐encapsulated magnetic hybrid emulsion droplets (DIP/Fe3O4‐OA/OA)@(OCS/SAL)4 was up to almost 100% after 31 h at pH 1.8. However, the cumulative release ratio was only 3.3% at pH 7.4 even after 48 h. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Performances of Polyvinyl Acetate Hybrid Emulsions with Nanoparticles SiO<sub>2</sub>

Polyvinyl acetate（PVAc）hybrid emulsions with nanoparticles SiO2 were prepared by the semi-continuous seeding emulsion polymerization. The micro-morphologies of the hybrid emulsions, the diameters and distributions of the latex particles were characterized with the aid of scanning electron microscope (SEM) and diameter analyzer. Adhesive properties of hybrid emulsions and the properties of the emulsion films were determined by mechanical properties tester and dynamic mechanics analyzer (DMA). And the rheological behaviors of hybrid emulsions were measured via rheometer. SEM and diameter analysis showed that the process of the nanoparticles SiO2 by ultrasonic made a good dispersibility of latex particles in emulsions, diameters of the latex particles were 0.68~0.89μm with the content of SiO2 from 0 to 1.0% (% in relation to the total mass VAc), and indexes of distributions of particle size were increased with the increasing of the content of SiO2 from 0 to 1.0%. Adhesion strengths of PVAc emulsions modified with nanoparticles SiO2 were improved. DMA results indicated that the films of PVAc/SiO2 hybrid emulsions had the higher storage modulus than the film of PVAc, the temperatures of glass transition of the films of PVAc/SiO2 hybrid emulsions were not changed obviously, and the water absorptions of films were decreased. Rheological results revealed that flow consistency indexes were increased then decreased with the increasing of the content of SiO2 from 0 to 1.0%, and PVAc/SiO2 hybrid emulsions were typical pseudoplastic fluid.