Preparation and properties of poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)]/silica nanocomposite latex prepared using an acidic silica sol

BACKGROUND: Polyacrylate/silica nanocomposite latexes have been fabricated using blending methods with silica nanopowder, in situ polymerization with surface‐functionalized silica nanoparticles or sol–gel processes with silica precursors. But these approaches have the disadvantages of limited silica load, poor emulsion stability or poor film‐forming ability. RESULTS: In this work, poly[styrene‐co‐(butyl acrylate)‐co‐(acrylic acid)] [P(St‐BA‐AA)]/silica nanocomposite latexes and their dried films were prepared by adding an acidic silica sol to the emulsion polymerization stage. Morphological and rheological characterization shows that the silica nanoparticles are not encapsulated within polymer latex particles, but interact partially with polymer latex particles via hydrogen bonds between the silanol groups and the ? COOH groups at the surface of the polymer particles. The dried nanocomposite films have a better UV‐blocking ability than the pure polymer film, and retain their transparency even with a silica content up to 9.1 wt%. More interestingly, the hardness of the nanocomposite films increases markedly with increasing silica content, and the toughness of the films is not reduced at silica contents up to 33.3 wt%. An unexpected improvement of the solvent resistance of the nanocomposite films is also observed. CONCLUSION: Highly stable P(St‐BA‐AA)/silica nanocomposite latexes can be prepared with a wide range of silica content using an acidic silica sol. The dried nanocomposite films of these latexes exhibit simultaneous improvement of hardness and toughness even at high silica load, and enhanced solvent resistance, presumably resulting from hydrogen bond interactions between polymer chains and silica particles as well as silica aggregate/particle networks. Copyright © 2009 Society of Chemical Industry     

Emulsifier‐minor emulsion copolymerization of BA‐MMA‐St‐MAA (or AA)‐N‐MA

A novel emulsion polymerization technique referred to as emulsifier‐minor emulsion polymerization was achieved by the copolymerization of methyl methacrylate, butyl acrylate, and styrene (MMA‐BA‐St) with a combination of water‐soluble ionic monomers [methacrylic acid (MAA) or acrylic acid (AA)] and nonionic monomers (N‐methylol acrylamide). In the technique, water‐soluble monomers play a crucial role in the stabilization of the latex particles as they can be bound to the particle surface and form a hydrate protective layer, which exhibits steric and/or electrostatic effects to prevent particle coagulation. The minor but over its critical micelle concentration emulsifier sodium alkylated diphenyl ether disulfonate (DSB) results in the nucleation of particles mainly by the micelle nucleation mechanism and thus determines the polymerization rate, the particle size, and the number. The film water resistance of the latices can be improved, and the foaming capacity of can be lowered by using technique instead of conventional emulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2923–2929, 2004     

Synthesis and properties of 4‐(ω‐methoxyoligodimethylsiloxanyl)butyl maleate: A new surfmer

Anionic reactive maleate with hydrophobic oligosiloxane chain was synthesized to use as a stabilizer in the batch and seeded emulsion polymerization of traditional monomers (acrylates, methacrylates, styrene, etc.). Polymerizable surfactant is obtained in a three‐step synthesis, starting from the anionic polymerization of cyclic siloxanes, followed by the silylation of methanol with the obtained cyclic oligomer, and finishing with the acylation of the linear oligomer by maleic anhydride. The improved technique of the synthesis of 4‐chlorobutoxydimethylchlorosilane, one of the initial substances for obtaining siloxane monomer, was elaborated. The anionic polymerization of octamethylcyclotetrasiloxane using cyclic alkoxysilane was carried out to form siloxane cyclic oligomer for the first time. The chemical structure of the monomer synthesized was confirmed by IR spectroscopy and functional analysis. Critical micelle concentration of the obtained surfactant was measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 310–313, 2004     

Latex film performance of styrene–acrylic particles functionalized with acrylic acid

Latex polymers are frequently used as substitutes for solvent‐borne coatings in environmental friendly technologies. However, the relationship between the copolymer composition and the latex film performance must be established. The preparation of a series of styrene–n‐butyl acrylate latexes functionalized with different amounts of acrylic acid through semicontinuous emulsion polymerization is presented. In this work, latexes were employed to study the modification of the latex film properties by the addition of acrylic acid during the polymerization; mainly, the adhesion to the substrate, the water vapor permeability, and the electrical film resistance were examined. The most advantageous acrylic acid content was established by a balance of the tested properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

聚硅氧烷/聚丙烯酸酯共聚乳液的合成与表征

合成了含氢聚甲基硅氧烷／聚丙烯酸酯共聚乳液。研究了聚合工艺，配组成及操作方式对聚合稳定性，动力学，乳液的粒径分布和产物性能的影响。采用部分预乳化单体滴加法（工艺A）的部分纯单体滴加法（工艺B）两种工艺，聚硅氧烷采用高速预乳化滴加进料方式。用COULTER LS粒径仪和Nicolet傅立叶变换红外光谱仪分别测定共取乳液的粒径分布和产物的结构。研究结果表明，采用A，B两种工艺均能得到平均粒径为0.101-0.103μm的单峰窄分布共聚乳液，并能有效地将含氢聚硅氧烷引入了到共取物大分子中。含氢聚硅氧烷的引入量为3％（质量）时，共聚物涂膜具有柔软，滑爽和强度高等优点。     

In situ preparation and properties of high‐solid‐content and low‐viscosity poly(methyl methacrylate/n‐butyl acrylate/acrylic acid)/poly(styrene/acrylic acid) composite latexes

With monodispersed poly(methyl methacrylate/n‐butyl acrylate/acrylic acid) [P(MMA/BA/AA)] seeded latex with a particle size of 485 nm and a solid content of 50 wt % as a medium, a series of stable P(MMA/BA/AA)/poly(styrene/acrylic acid) composite latexes with a high solid content (70 wt %) and low viscosities (500–1000 mPa · s when the shear rate was 21 s^?1) was prepared in situ via simple two‐step semicontinuous monomer adding technology. The coagulum ratio of polymerization was about 0.05 wt %. The particle size distribution of such latexes was bimodal, in which the large particle was about 589 nm and the small one was about 80 nm. The latexes combined good mechanical properties with good film‐forming properties. Differential scanning calorimetry showed that the corresponding latex film had a two‐phase structure. The morphology of the latex film was characterized with atomic force microscopy and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1815–1825, 2007     

Characterization of Molecular Structure of Emulsion Acrylic Microgels: Exploring the Impact of Molar Mass on Coating Properties of Self-Cross-Linkable Latexes

Self-cross-linkable latexes of core–shell microgel particles were synthesized by the emulsion polymerization of acrylic monomers. The molar mass of copolymers forming the shell layer was gradually reduced by isooctyl 3-mercaptopropionate included in the synthesis of the shell layers. The molar mass distribution of latex particles was determined using size exclusion chromatography and asymmetric flow field-flow fractionation, respectively, both separation methods being coupled with a multiangle light scattering detector. The results confirmed theoretical predictions and described empirically the effects of molar mass of the shell layer copolymer on decreasing the minimum film-forming temperature and influencing the end-use properties of coatings.     

Study of the preparation of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of linear or cross-linked poly(dimethyl siloxane–methyl vinyl siloxane) latexes. The monomers were added in either continuous or swelled-continuous modes. Core–shell particles with poly(butyl methacrylate), or poly(methyl methacrylate), as the shell were obtained by using either addition mode. The core–shell structure was not observed for polysiloxane–polystyrene particles. The influence of monomer addition mode, the compatibilities of the monomers and their homopolymers with silicone rubber, and the reactivity ratios of the vinyl monomers with the vinyl group of linear polysiloxane particles, on the formation of the core-shell structure is discussed.     

Surface grafting of polyacrylamide from polyethylene‐based copolymer film

Atom transfer radical polymerization (ATRP) was used to grow polyacrylamide from the surface of ethylene–acrylic acid copolymer (EAA) film. The surface functionalization constituted initiator immobilization and surface graft polymerization. All reaction steps were conducted at 24 ± 3°C; polymerization was done in aqueous solution. For initiator immobilization, the carboxylic acid groups on EAA film were converted to acid chloride groups; further reaction with ethanolamines gave hydroxyl groups onto which 2‐bromoisobutyryl bromide initiator was attached. ATR‐FTIR data indicated that 1.64 ± 0.09 times higher initiator density was achieved by using diethanolamine, relative to ethanolamine. Acrylamide monomer was polymerized from the initiator by ATRP to yield nondistorted, transparent films with polymerization times of up to 1 h. For films prepared using diethanolamine, 1 h polymerization time reduced the static water contact angle by more than 50°, significantly increasing the hydrophilicity of the film surface. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1589–1595, 2004     

Self film‐forming and opaque hollow latexes fabricated via seeded emulsion polymerization followed by alkali post‐treatment

In order to obtain novel hollow latexes with both opaque and self film‐forming properties, the four‐layer core/shell latex particles—sequentially consisting of a high carboxyl‐containing soft core, a transition layer, a rigid supporting layer, and an outermost film‐forming layer—are first designed and prepared by emulsion polymerization, and then treated with alkali to fabricate self film‐forming hollow latexes. On the basis of the previous research on the three‐layer core/shell latex, influences of the composition and thickness of the film‐forming layer on the properties and morphologies of the four‐layer core/shell and the final hollow latexes are investigated. Results show that under optimized conditions with butyl acrylate/styrene (BA/St) mass ratio of 2/1, divinyl benzene (DVB) content of 1 wt %, and core/film‐forming layer mass ratio of 1/6 in the film‐forming layer preparation, the final hollow latex particles exhibit best morphology considering both light scattering efficiency and film‐forming capability at room temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42541.     

Preparation and properties of alkoxysilane/acrylate copolymer microemulsion

A novel alkoxysilane/acrylate copolymer microemulsion was prepared by copolymerization of vinylmethyldiethoxysilane and acrylic monomers using a composite emulsifier system composing of ordinary anionic sodium dodecyl sulphate (SDS), nonionic po1yoxyethylene octylphenol ether (OP-10), and n-butanol as co-surfactant, ammonium persulfate (APS) as initiator. The effects of polymerization processes, reaction conditions and the polymer content on the copolymer microemulsion were investigated, respectively. The structure of the copolymer was characterized by FT-IR spectroscopy. FT-IR spectrum analysis of the latex film indicated that copolymerization occurred. The morphology and size of the microlatex particles had been characterized by TEM and photon correlation spectroscopy (PCS), respectively. Results showed that seeded microemulsion polymerization with a high temperature emulsification process was superior for producing stable copolymer microlatexes. With high alkoxysilane content (30 wt.%), high copolymer content (37.5 wt.%) and low emulsifiers content (5 wt.%), the nanoparticles in the range from 20 nm to 60 nm were obtained.     

Surface immobilisation of fluorinated polystyrene‐acrylate latex nanoparticles with core–shell structure by crosslinking

Fluorinated polystyrene‐acrylate (PSA) latex nanoparticles with core–shell structure were synthesised by two‐stage seeded emulsion polymerisation method in the presence of reactive emulsifier DNS‐86. Diallyl phthalate (DAP) and Vinyltriethoxysilicone (VTES) were used as crosslinking agent to immobilise the fluorinated copolymer on the surface of the latex film. Fourier transform infrared spectroscopy (FTIR) spectra show that fluorine and siloxane monomers were effectively involved in the emulsion copolymerisation. Transmission electron microscope (TEM) observation shows that the prepared emulsion particles had a core–shell structure with fluorinated copolymer in the shell. X‐ray photoelectron spectroscopy (XPS) analysis reveals that fluorine atom has the tendency of migrating to the film–air interface and the incorporation of VTES helps the migration of fluorine atom towards the film–air interface. Water contact angle (WCA) test proved that DAP and VTES as crosslinking agent can immobilise the fluorinated copolymer on the surface of the latex films. © 2011 Canadian Society for Chemical Engineering     

A new route for the preparation of cyano‐containing poly(N‐isopropylacrylamide) microgel latex for specific immobilization of antibodies

A prepolymerization process was used to prepare functionalized poly(N‐isopropylacrylamide) latexes with surface cyano groups. The functionalized latexes prepared were characterized by FTIR, ¹H NMR, scanning electron microscopy and quasi‐elastic light scattering. In addition, the polymerization conversion and the water‐soluble polymer amounts were quantified. The polymerization conversions were found to be above 80% with 5–14 wt% of water soluble polymer formation. The immobilization of antibody (immunoglobulin) onto such cyano‐containing thermally sensitive particles, suggests the feasibility of specific dipole–dipole interactions between the cyano and hydroxyl functional groups from particle and antibody, respectively. Copyright © 2004 Society of Chemical Industry     

Modification research on the peel strength of the acrylate emulsion pressure‐sensitive adhesives

Pressure‐sensitive adhesives (PSAs) were produced with latexes synthesized via starved semibatch emulsion polymerization processes with butyl acrylate, three different kinds of hard monomers [styrene (St), methyl methacrylate, and 2‐phenoxy ethyl methacrylate (SR340)], acrylic acid, and 2‐hydroxy ethyl acrylate. The management of both the copolymer composition and the polymerization process allowed us to control the behavior of the PSAs. For the acrylate latexes, the types of hard monomers and their contents, the concentration of buffer [bicarbonate (NaHCO₃)], and three kinds of semibatch processes were manipulated to modify the polymer properties. The performance of the PSA films cast from these latexes was evaluated by the peel strength. The results show that the PSA prepared with St exhibited the highest peel strength among the three hard monomers, and the latex synthesized by SR340 showed the largest gel content compared with the other two hard monomers. With increasing buffer, the latex particle size increased, and the peel strength initially increased to a maximum and then decreased. Nevertheless, the stability of the latexes decreased with increasing buffer concentration. In addition, the effects of the three kinds of semibatch processes on the peel strength of the PSA were also evaluated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40095.     

Emulsifier‐free synthesis and self‐assembly of an amphiphilic poly(styrene‐co‐acrylic acid) copolymer

A poly(styrene‐co‐acrylic acid) copolymer was synthesized by surfactant‐free polymerization with the assistance of power ultrasound in water. Fourier transform infrared, NMR, and differential scanning calorimetry measurements revealed that the copolymer was random. Atomic force microscopy and laser light scattering were used to investigate the self‐assembly of the copolymer, and it was found that the copolymer chains formed micelles or other self‐assemble structures in solution. Atomic force microscopy also indicated that the self‐assembled structures developed into nanospheres with a poly(acrylic acid)‐rich or polystyrene‐rich surface in a film, depending on the solvent used for the preparation of the film. In particular, a wheel‐like structure could resulted in a film when the copolymer film was prepared in a moist environment; it resulted from heterogeneous aggregates of poly(acrylic acid) at the rim of water bubbles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:3718–3726, 2006     

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     

A novel alkoxysilane‐modified high solids hydroxyl acrylic polyurethane: Preparation and surface properties

Alkoxysilane‐modified high solids hydroxyl acrylic polyurethane was prepared by solution polymerization. Its structure, surface, and thermal properties were investigated by ¹H NMR, device of contact angle, thermo gravimetric analysis (TGA), atomic force microscopy (AFM), and X‐ray photoelectron spectroscopy (XPS). Research showed that alkoxysilane modified high solids hydroxyl acrylic polyurethane has superior properties that can be used for automotive paints. The contents of silicone in the alkoxysilane‐modified high solids hydroxyl acrylic polyurethane were 1.25, 1.5, 2, and 2.5 wt %. In this study, γ‐methacryloxypropyltrimethoxysilane (MPTS) was chosen as the modifier. Results showed that the contact angles of water and surface roughness on the film of MPTS modified high solids hydroxyl acrylic polyurethane increased, and thermal stability of the film at high temperatures improved with the increasing of the silicone content in the resins. MPTS modified high solids hydroxyl acrylic polyurethane with 2.5 wt % silicone content had better water resistance, better acid resistance, higher hardness, and excellent weatherability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1866–1871, 2006     

Silicone-polyacrylate composite latex particles. Particles formation and film properties

Composite latex particles with a polydimethylsiloxane PDMS core and a poly(methyl methacrylate-co-n-butyl acrylate) P(MMA-BA) copolymer shell were synthesized by seeded emulsion polymerization using the PDMS latex as the seed. The compatibility between the two polymer phases was changed by introducing vinyl groups in the latex core. Monomer conversions and particle size evolution were monitored to see the influence of the nature of the core functionality on the polymerization kinetics and on the extent of secondary nucleation. Particle morphology was characterized by cryo-transmission electron microscopy. The P(MMA-BA) copolymer formed a regular shell around the PDMS seed, whereas nonuniform coatings were formed when vinyl functionalities were introduced into the seed. Films were produced from the latexes, and their surface property was analyzed by X-ray photoelectron spectroscopy and contact angle measurements. It was shown that the PDMS component segregated to the polymer/air interface and that the extent of segregation depended on the original particles structure. Because PDMS has a very low glass transition temperature, it can easily diffuse throughout the film material. However, protected by an acrylic shell, polymer diffusion is significantly hindered and the film then displays all the characteristic properties of the acrylic copolymer. The surface composition of the films formed by the structured particles which PDMS core was not totally covered by the polyacrylate, was found to be intermediate between the composition of the films issued from the core-shell latexes and that of the films produced from blends of pure polyacrylate and PDMS latexes.     

Effect of the carboxylic acid monomer type on the emulsifier‐free emulsion copolymerization of styrene and butadiene

Carboxylated styrene–butadiene rubber latexes were prepared through the emulsifier‐free emulsion copolymerization of styrene and butadiene with various carboxylic acid monomers. The effects of various carboxylic acid monomers on the particle formation process were investigated. The type of carboxylic acid monomer strongly affected the particle nucleation. The number of particles and thus the polymerization rate increased with the increasing hydrophobicity of the carboxylic acid monomers. There was a significant difference in the polymerization rate per particle. The results showed that particle nucleation and growth were dependent on the hydrophilic nature of the carboxylic acid monomers. The average particle diameter of the carboxylated styrene–butadiene rubber latexes in the dry state was obtained through some calculations using direct measurements of the average particle diameter in the monomer‐swollen state by a dynamic light scattering technique. Several parameters, such as the polymerization rate, number of latex particles per unit of volume of the aqueous phase, and polymerization rate per particle, were calculated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007