Complexation of poly(dimethylsiloxane)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) latex with poly(dimethylsiloxane)/poly(vinyl acetate‐co‐butyl acrylate) latex

Two latices—the poly(dimethylsiloxane) (PDMS)/poly(methyl methacrylate‐co‐butyl acrylate‐co‐methacrylic acid) system (PA latex) and the PDMS/poly(vinyl acetate‐co‐butyl acrylate) system (PB latex)—were prepared by seeded emulsion polymerization, and PA/PB complex latices were obtained through the interparticle complexation of the PA latex with the PB latex. In addition, for the further study of the interparticle complexation of the PA latex with the PB latex, copolymer latices [PDMS/methyl methacrylate‐co‐butyl acrylate‐co‐vinyl acetate‐co‐methacrylic acid) (PC)] were prepared according to the monomer recipe of the complex latices and the polymerization process of the component latices. The properties of the obtained polymer latices and complex latices were investigated with surface‐tension, contact‐angle, and viscosity measurements. The mechanical properties of the coatings obtained from the latices were investigated with tensile‐strength measurements. The results showed that, in comparison with the two component latices (PA latex and PB latex) and the corresponding copolymer latices (PC latices), the PA/PB complex latices had lower surface tension, lower viscosities, and better wettability to different substrates. The tensile strengths of the coatings obtained from the complex latices were higher than the tensile strengths of the coatings from the two component latices and copolymer latices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2522–2527, 2004     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Preparation and characterization of the complex latex formed through complexation of two polymer latexes with chemically complementary structure

In this study, the intermacromolecular complexation of two polymers with chemically complementary structures in the latex state and the interparticle interactions were probed. Two latexes—a polydimethylsiloxane (PDMS)/poly(vinyl acetate‐co‐butyl acrylate) system, named PA latex, and a PDMS/poly(methacrylic acid) system, named PB latex—were prepared by seeded emulsion polymerization and the complex latexes were obtained through complexation of the PA latex with the PB latex. The properties of the obtained complex latexes were investigated using surface tension and viscosity measurements. The surface structure and composition of coatings obtained from the latexes were analyzed by X‐ray photoelectron spectroscopy and scanning probe microscopy. The results confirmed that there are interactions between the (or groups in PA and the groups in PB. The interactions result in unique properties of the polymer latex and lead to a formation of a new structure of the coatings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1405–1411, 2003     

Hydrolyzable‐emulsifier‐containing polymer latices as dispersants and binders for waterborne carbon black paint

Poly(styrene‐co‐butyl methacrylate) and poly(styrene‐co‐butyl acrylate) latices were prepared by emulsion polymerization with alkali‐hydrolyzable and nonhydrolyzable cationic emulsifiers and were used as a dispersant and binder for waterborne carbon black (CB) paint. CB was dispersed in the latex solutions and then coated on filter paper pretreated with dilute aqueous Na₂CO₃ under mild conditions. The styrene (St)‐rich rigid copolymer latices easily dispersed the CB but fixed a little amount of the pigment on the paper surface. In contrast, the methacrylate‐ and acrylate‐rich soft latices tended to increase the adhesibility on it. We also demonstrated that the hydrolyzable‐emulsifier‐containing latices always had a higher adhesibility than the nonhydrolyzable‐emulsifier‐containing ones. Thus, the hydrolyzable‐emulsifier‐containing latices with an appropriate St content had the highest paintability, rapid adhesion, quick drying, reduced fading, superior fastness, and so on. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3869–3873, 2013     

Effect of the monomer ratio on the properties of poly(methyl methacrylate butyl acrylate) latex‐modified mortars

This article deals with the effect of the monomer ratio on the typical properties of polymer‐modified mortars with poly(methyl methacrylate butyl acrylate) latices. Polymer‐modified mortars, with methyl methacrylate/butyl acrylate copolymer latices of various methyl methacrylate/butyl acrylate ratios, were prepared with different polymer/cement ratios and were tested for their workability, air content, compressive strength, flexural strength, and water absorption. On the basis of the test results, the effects of the monomer ratio and polymer/cement ratio on the typical properties were examined. The properties of the latex‐modified mortars were affected to a great extent by both the monomer ratio and polymer/cement ratio. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2403–2409, 2004     

Morphologies of polybutylacrylate/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization Part I. Thermodynamics equilibrium morphology

Heterogeneous latexes were prepared by a semicontinuous seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amounts of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. Phase separation towards the thermodynamic equilibrium morphology was accelerated either by ageing the composite latex at 80 °C or by adding a chain‐transfer agent during polymerization. The morphologies of the latex particles were examined by transmission electron microscopy (TEM). The morphology distributions of latex particles were described by a statistical method. It was found that the latex particles displayed different equilibrium morphologies depending on the composition of the second‐stage copolymers. This series of equilibrium morphologies of [poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate)] (PBA/P(St‐co‐MMA)) system provides experimental verification for quantitative simulation. Under limiting conditions, the equilibrium morphologies of PBA/P(St‐co‐MMA) were predicted according to the minimum surface free energy change principle. The particle morphology observed by TEM was in good agreement with the predictions of the thermodynamic model. Therefore, the morphology theory for homopolymer/homopolymer composite systems was extended to homopolymer/copolymer systems. © 2002 Society of Chemical Industry     

Synthesis and characterization of crosslinkable latex with interpenetrating network structure based on polystyrene and polyacrylate

Functional poly[styrene‐co‐(2‐ethylhexyl acrylate)‐co‐(1,6‐hexanediol diacrylate)]/poly[(methyl methacrylate)‐co‐(butyl acrylate)‐co‐(methacrylic acid)‐co‐(diacetone acrylamide)] (PS/PA) semi‐interpenetrating polymer networks (semi‐LIPNs) containing ketone carboxyl groups were synthesized by two‐stage emulsion polymerization, and characterized by Fourier transform infrared, transmission electron microscopy, dynamic light scattering and DSC. A unique feature of the PS/PA semi‐LIPNs is their ability to crosslink and form thermosetting full‐IPN polymers through the reaction of ketone carboxyl and hydrazide in the course of film formation at ambient temperatures. Series of latex particles with various levels of crosslinking density in the PS and PA domain and varied composition of PS/PA LIPNs were obtained. The effects of the LIPN PS/PA composition and the level of crosslinking density in the PS and PA domain on film density, swell ratio, mechanical properties and contact angle with water were investigated. Maximum synergy effects obtained at around 50/50 (PS/PA) in terms of mechanical properties, density and contact angle with water indicate that the maximum degree of interpenetration is obtained at this composition. Copyright © 2006 Society of Chemical Industry     

Effect of surfactant systems on the water sensitivity of latex films

The effects of three different types of surfactant systems (ionic, polymeric, and electrosteric stabilizers) on the water sensitivity of poly(butyl acrylate‐co‐methyl methacrylate) latex films was examined. The water sensitivity was found to be strongly dependent on the surfactant system used in their preparation. A number of factors, such as the surfactant mobility and crystallinity and surfactant/polymer polarity appeared to affect the water uptake of the films. Highly mobile and crystallizable surfactants yielded high water sensitivity for films containing ionic surfactants, whereas the surfactant polarity had a greater effect on latices stabilized by polymeric surfactants, with the more hydrophilic systems providing greater water uptake. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1813–1823, 2004     

Synthesis and characterization of functionalized polymer latex particles through a designed semicontinuous emulsion polymerization process

Monodispersed noncarboxylated and carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latices were synthesized with a well‐defined semicontinuous emulsion polymerization process. A modified theory to correlate the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture was developed. The resulting equation was used to determine the maximum polymerization rate only below or equal to which the polymerization could be operated in the highly monomer‐starved regime, which corresponded to an instantaneous conversion of 90% or greater. Experimental data from reaction calorimetry supported that the polymerization was under highly monomer‐starved conditions when the model latices were synthesized with the modified model. The estimation of the average number of free radicals per latex particle(n?) during the feeding stage revealed that n? was as high as 1.4 in the actual polymerization, which showed that the original selection of 0.5 as the n? value was not accurate in the developed model. From the conductimetric titration experiments, we found that most of the carboxyl groups from the methacrylic acid (MAA) were buried inside the latex particles, and the surface carboxyl group coverage increased as the MAA concentration in the comonomer feed increased. The glass‐transition temperatures of the synthesized polymers were close to the designed value from the Pochan equation, and only one glass transition was observed in the polymer samples in the differential scanning calorimetry measurements, indicating a homogeneous copolymer composition in the functionalized shell. Particle size characterization and transmission electron microscopy confirmed the uniformity in the latex particle size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 248–256, 2005     

Nanosize polymer latices made by microemulsion copolymerization: Preparation and characterization

Polymer nanoparticles were prepared by a methyl methacrylate/butyl methacrylate/2‐hydroxyethyl methacrylate/acrylate or methyl acrylate microemulsion copolymerization process. A microemulsion copolymerization method was used. With this process high polymer : surfactant weight ratios (≥15 : 1), relatively concentrated (～ 30 wt %) lattices, and small (～ 60 nm) particle diameters were obtained. Properties of the latices were characterized in detail by TEM, DSC, dynamic light scattering, spectrophotometry, and tensile strength testing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3625–3630, 2003     

PBT blends with rigid polymer and elastomer inclusions: the effect of component type and reactivity on mechanical behaviour

The present study shows the potential of the poly(butylene terephthalate) (PBT) matrix to form ternary blends with well‐balanced properties, analogous to Polyamide 6 (PA6) systems with a very fine (<100 nm) separately dispersed rigid polymer (poly(styrene‐co‐maleic anhydride)) and elastomer (maleated ethylene‐propylene elastomer). The use in PBT blends of maleated components analogous to those in the PA6 systems was much less effective, due to the presence of larger particles. Enhancement of all properties, including toughness, was found in the case of a blend containing at least one component with epoxide groups, such as rigid styrene‐glycidyl methacrylate copolymer or elastomeric poly[(ethylene)‐co‐(methyl acrylate)‐co‐(glycidyl methacrylate)]. In this case, the reactive compatibilization of the epoxy‐group‐containing component caused refinement of particle size of the other component due to enhanced viscosity. As a result, more advantageous micromechanical behaviour of this ternary in comparison with the binary system occurs. The PBT matrix offers a similar potential to PA6 in synergistic influencing of both well‐dispersed phases. This work supports the universality of rigid polymer‐elastomer combination for the enhancement of the properties of pseudoductile polymers. Copyright © 2004 Society of Chemical Industry     

Dynamic‐mechanical behavior of hydrophobic–hydrophilic interpenetrating copolymer networks

Sequential interpenetrating polymer networks (IPNs) were prepared by free‐radical polymerization. One of the components of the IPN was a poly(butyl acrylate) (PBA) network, and the other one was a poly(methyl methacrylate‐co‐hydroxyethyl methacrylate) copolymer network. Dynamic‐mechanical experiments show that the IPNs are phase separated: two main α relaxations occur in all samples, the low temperature one corresponding to the PBA network and that appearing at higher temperature due to the copolymer network. The latter shows a shape analogous to a pure poly(hydroxyethyl methacrylate) (PHEMA) network independently of the copolymer composition. The influence of water absorption on the dynamic‐mechanical spectrum shows that only a small amount of water reaches the butyl acrylate segments. The dependence of the mechanical behavior of the poly(methyl methacrylate‐co‐hydroxyethyl methacrylate) copolymer networks with the copolymer composition has been also analyzed. POLYM. ENG. SCI., 46:930–937, 2006. © 2006 Society of Plastics Engineers     

Narrow‐disperse or monodisperse crosslinked and functional core–shell polymer particles prepared by two‐stage precipitation polymerization

Narrow‐disperse and monodisperse cross‐linked core–shell polymer particles containing different functional groups, such as esters, hydroxyls, chloromethyls, carboxylic acids, amides, cyanos, and glycidyls, in the shell layers in the micrometer size range were prepared by a two‐stage precipitation polymerization in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80% DVB, was precipitation polymerized in acetonitrile without any stabilizer as the first‐stage polymerization and was used as the core. Several functional monomers, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2‐hydroxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t‐butyl acrylate, i‐octyl acrylate, acrylic acid, acrylamide, acrylonitrile, styrene, and p‐chloromethyl styrene, were incorporated into the shells during the second‐stage polymerization. The resulting core–shell polymer particles were characterized with scanning electron microscopy and Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1776–1784, 2006     

Morphology of poly(butyl acrylate)/poly(styrene‐co‐methyl methacrylate) latex prepared by starved emulsion polymerization: II. Development of particle morphology

Heterogeneous latexes were prepared by a two‐stage seeded emulsion polymerization process under monomer starved conditions at 80 °C using potassium persulfate as the initiator and sodium dodecyl sulfate as the emulsifier. Poly(butyl acrylate) latexes were used as seeds. The second‐stage polymer was poly(styrene‐co‐methyl methacrylate). By varying the amount of methyl methacrylate (MMA) in the second‐stage copolymer, the polarity of the copolymer phase could be controlled. It was found that the latex particles displayed different morphologies depending on the monomer ratio. The amount of MMA had a significant effect on the evolution of morphology. The morphologies were observed by transmission electron microscopy. In addition, the evolution of the particle morphology was predicted by the mathmatical model for cluster migration. The model gave the same trends as the experimental results. © 2002 Society of Chemical Industry     

Preparation of phosphor coated with a polymer by emulsion polymerization and its application in low‐density polyethylene

The long‐afterglow phosphor SrAl₂O₄ : Eu²⁺, Dy³⁺ is liable to hydrolyze in water with deterioration of its luminescent properties. In this study, in situ emulsion polymerization was first used to prepare phosphor coated with poly(methyl methacrylate‐co‐butyl acrylate) [P(MMA‐co‐BA)] to improve water resistance. Fourier transform infrared spectra suggested that the polymer attached to the phosphor by chemical bonding. Observation by scanning electron microscopy (SEM) showed that a polymer layer formed on the surface of the phosphor. The resistance to water of the phosphor coated with the polymer layer was much better than that of the uncoated phosphor because the transparent polymer layer could suppress its hydrolysis process. Low‐density polyethylene (LDPE) plastics, doped with long‐afterglow phosphors, were manufactured with an extrusion technique. Through coating with P(MMA‐co‐BA), the compatibility of phosphor with the LDPE matrix was improved, as determined by SEM. The luminous LDPE plastics blended with the phosphor coated with polymer showed long and strong phosphorescence with little loss of persistence phosphorescence compared to the uncoated phosphor. The LDPE plastics still retained their mechanical properties through doping with 3% (mass fraction) of the phosphors. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

BA‐MMA‐POMA copolymer latexes prepared by using HMPS polymerizable emulsifier

BA‐MMA‐POMA copolymer latex was successfully prepared by soap‐free emulsion polymerization of 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate(POMA) with butyl acrylate(BA), methyl methacrylate (MMA) initiated by K₂S₂O₈ in the water. POMA was synthesized from the intermediate perfluoro nonene and 2‐hydroxyethyl methacrylate as the staring reactants. The structure of BA‐MMA‐POMA copolymer latex was investigated by Fourier transform infrared (FTIR). The characteristics of the film such as hydrophobicity and glass transition temperature were characterized with the contact angle and differential scanning calorimetry respectively. The influences of the amount of the fluorinated monomer and the initiator on the soap‐free emulsion polymerization and performance of the latex were studied. In addition, comparison with the latex prepared by the conventional emulsifier SDBS is investigated. Results show that the hydrophobicity and glass transition temperature (T_g) of the latex are increased when the fluorinated monomer is introduced to copolymerize with other monomers. The hydrophobicity can be improved further with heating. Compared with the latices prepared by using SDBS emulsifier, the latices prepared by using HMPS emulsifier have larger particle size, higher surface tension. However, the difference of their T_g is extremely minute. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the MMA content on the emulsion polymerization process and adhesive properties of poly(BA‐co‐MMA‐co‐AA) latexes

In the past work, the shear resistance of pure poly(n‐butyl acrylate) was low, even incorporation of inorganic filler, silica in the composition. It is well‐known that the copolymerization of n‐butyl acrylate (BA) with methyl methacrylate (MMA) will increase the glass transition temperature, and enhance the shear resistance of acrylic polymers. In the current work, the preparation of a series of acrylic water‐borne pressure‐sensitive adhesives (PSAs) with the controlled composition and structure for the copolymerization of BA and acrylic acid (AA) with different MMA contents, poly(BA‐co‐MMA‐co‐AA) was reported and its effects on adhesive properties of the latices were investigated. The latices of poly(BA‐co‐MMA‐co‐AA) were prepared at a solid content of 50% by two‐stage sequential emulsion polymerization, and this process consisted of a batch seed stage giving a particle diameter of 111 nm, which was then grown by the semicontinuous addition of monomers to final diameter of 303 nm. Dynamic light scattering (DLS) was used to monitor the particle diameters and proved that no new nucleation occurred during the growth stage. Copolymerization of BA with MMA raised the glass transition temperature (T_g) of the soft acrylic polymers, and had the effect of improving shear resistance, while the loop tack and peel adhesion kept relatively high. The relationship between pressure‐sensitive properties and molecular parameters, such as gel content and molecular weight, was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymeric coatings based on acrylic resin latexes from miniemulsion polymerization using hydrocarbon resins as osmotic agents

Waterborne acrylic resins with a solid content higher than 40 wt % were obtained by miniemulsion polymerization of methyl methacrylate, butyl acrylate, and acrylic acid using a hydrocarbon coumarone–indene resin (HCR) as osmotic agent. HCR is a cheap polymer widely used for coatings and pressure‐sensitive adhesives. The resin leads to a higher hydrophobicity for the acrylic latex film and acts as osmotic agent in miniemulsion polymerization preventing Ostwald ripening, leading to latexes with particle sizes, size distributions, and stability comparable to those obtained using n‐hexadecane as osmotic agent. However, the monomer conversion and molecular weight were lower, indicating the occurrence of a chain‐transfer reaction. Atomic force microscopy analysis demonstrated that a smooth film surface with phase‐separated morphology was formed when using HCR. Faster film hardness development was achieved with HCR comparing with hexadecane. Compared with market standard in a paint formulation, a similar performance was achieved. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40569.     

Preparation of fluorescent pigment latex and its application on binder‐free printing of cotton fabrics

The recognized disadvantages of pigment printing are the stiff hand feel owing to the large particle size of the binder and pigments and the crosslinked binder introducing rigidity. In the current study, fluorescent pigment latex (FPL) was prepared via mini‐emulsion polymerization and further applied on cotton fabric printing in the absence of binder. The mini‐emulsions were prepared by dispersing the fluorescein in the monomers methyl methacrylate (MMA) and butyl acrylate (BA) with DNS‐86 as emulsifier, hexadecane as co‐emulsifier, and ammonium persulfate as initiator. The Fourier‐transform infrared‐attenuated total refraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis showed that the fluorescein was successfully encapsulated into P(MMA‐co‐BA) and the polymer content was 91.22%. The surface morphology study revealed that compact and smooth film was formed onto the surface of FPL printings, which resulted in better hand feel and rubbing fastness as compared to the conventional printings with a large amount of binder. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45826.     

Synthesis of well‐defined,functionalized polymer latex particles through semicontinuous emulsion polymerization processes

The design of a semicontinuous emulsion polymerization process, primarily based on theoretical calculations, has been carried out with the objective of achieving overall independent control over the latex particle size, the monodispersity in the particle size distribution, the homogeneous copolymer composition, the concentration of functional groups (e.g., carboxyl groups), and the glass‐transition temperature with n‐butyl methacrylate/n‐butyl acrylate/methacrylic acid as a model system. The surfactant coverage on the latex particles is very important for maintaining a constant particle number throughout the feed process, and this results in the formation of monodisperse latex particles. A model has been set up to calculate the surfactant coverage from the monomer feed rate, surfactant feed rate, desired solid content, and particle size. This model also leads to an equation correlating the polymerization rate to the instantaneous conversion of the monomer or comonomer mixture. This equation can be used to determine the maximum polymerization rate, only below or at which monomer‐starved conditions can be achieved. The maximum polymerization rate provides guidance for selecting the monomer feed rate in the semicontinuous emulsion polymerization process. The glass‐transition temperature of the resulting carboxylated poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) copolymer can be adjusted through variations in the compositions of the copolymers with the linear Pochan equation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 30–41, 2003