Hydroresin dispersions: new emulsifier free binders for aqueous coatings

Hydroresin dispersions are a new class of emulsifier free polyacrylate secondary dispersions. One advantage over conventional secondary dispersions is the fact that they are not only water dilutable but free of organic solvents. Another advantage is the extremely low content of hydrophilic salt groups in the polymer molecules, which leads to very hydrophobic films. The application properties of these aqueous systems are more similar to those of organic polymer solutions than to conventional emulsion polymers. Applications of these surfactant free binders are in areas such as road marking paints without solvents and corrosion protection coatings without active pigments. Hydroresin dispersions also show very interesting perspectives for applications in the field of solar energy conversion.     

Polymeric particles prepared with fluorinated surfmer

Fluoro-containing particles have been obtained by miniemulsion polymerization of styrene and n-butyl methacrylate in presence of fluorinated monomer mono-fluoroalkyl maleate (MFM) which acts as a surfmer providing efficient stability to obtained dispersion and functionalization of particle surface with fluoro-groups. Increase of the MFM concentration in reaction mixture reduces the particle size and dispersions with narrower particle size distribution can be obtained. Blends of fluorinated latexes with styrene-butadiene copolymer latex were examined with regard to formation of low free energy surfaces. It has been shown that blends containing MFM-functionalized polymeric particles possess more hydrophobic surfaces then similar latex films, where particles prepared by polymerization of expensive fluorinated monomer have been applied.     

The effects of latex coalescence and interfacial crosslinking on the mechanical properties of latex films

The effects of latex coalescence and interfacial crosslinking on the mechanical properties of latex films were extensively investigated by means of several series of model latexes with varying backbone polymer crosslinking density and interfacial crosslinking functional groups. It was found that the tensile strength of crosslinked model latex films increased with increasing gel content (i.e. crosslinking density) of latex backbone polymers up to about 75% and then decreased with further increase in gel, while their elongation at break steadily decreased with increasing gel content. These findings showed that latex particle coalescence was retarded above a gel content of about 75% so that the limited coalescence of latex particles containing gel contents higher than 75% prevented the tensile strength of crosslinked latex films from increasing by further crosslinking the latex backbone polymers. This was contrary to the theory of rubber elasticity that the tensile strength increases with increasing molecular weight and crosslinking density. This limitation was found to be overcome by the interfacial crosslinking among latex particles during film formation and curing. This paper will discuss the effects of both latex backbone polymer and interfacial crosslinking on latex film properties. It will also discuss the development of self-curable latex blends and structured latexes containing co-reactive groups: oxazoline and carboxylic groups.     

Contribution of hydrogen and/or covalent bonds on reinforcement of natural rubber latex films with surface modified silica

A macromolecular coupling agent containing hydrophilic and hydrophobic groups is made to react with precipitated silica. Interfacial interactions between  OH groups of silica and  COOH groups of macromolecule are found to be created through either hydrogen bonds alone or through hydrogen bonds and covalent bonds. Aqueous dispersions of unmodified and modified silica are prepared and the colloidal stability and particle size distribution of the dispersions are observed. The dispersions at neutral pH are incorporated into vulcanized/unvulcanized natural rubber latex. The formation of hydrogen bonds and/or covalent bonds is studied via FTIR spectroscopy and their contribution in encouraging filler‐rubber interactions is emphasized through mechanical and swelling properties. Uniform distribution and dispersion of modified filler particles throughout the rubber matrix is confirmed by the microstructures of the latex films cast from filler added natural rubber latex. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40380.     

Development of morphology in latex particles: The interplay between thermodynamic and kinetic parameters

A thermodynamic analysis and a mathematical model were developed to describe the free energy changes corresponding to various possible morphologies in composite latex particles. Two experimental composite latex systems were used to verify and establish limitations of the model. The two latex systems were based on polystyrene/poly(methyl methacrylate), one prepared by conventional seeded emulsion polymerization and the second system by direct emulsification of a solution of a blend of the two polymers. The influence of several experimental parameters on latex particle morphology was investigated. These included monomer/polymer ratio, surfactant type, and initiator type in the seeded emulsion polymerization system. The influence of local viscosity, shear effects, and molecular weights of polymers were investigated in the artificial latex system.     

Alkali-soluble resins (ASR) and acrylic blends: influence of ASR distribution on latex film and paint properties

Alkali-soluble resins (ASRs) are a special type of polymeric surfactant containing both hydrophobic moieties and carboxylic acid functional groups. Upon ionization, ASRs provide electrosteric stabilization to the latex particles, thus allowing reduction or even elimination of conventional surfactants while maintaining or improving latex stability. The distribution of ASR in the dried film depends on its miscibility with the latex polymer. Its presence in the blend system is expected to alter the film formation process and consequently performance properties of paint products based on the latex blends containing ASR. In this study, the effects of a high Tg, alkali-soluble resin (ASR), poly(styrene/alpha-methylstyrene/acrylic acid) terpolymer on the properties of latex and paint films were examined. The film formation of a soft acrylic latex in the absence and presence of the ASR was evaluated using a variety of analytical techniques. As expected, paint properties such as scrub resistance, wet adhesion, and block resistance were also affected by the inclusion of ASR. The results provide new insights into the structure and surface morphology of latex and paint films containing ASRs, as well as their impact on mechanical and the performance properties.     

Crosslinking of latex polymers

The physicomechanical properties and processes of thermal crosslinking of latex acrylic polymer films containing functional groups of different chemical nature were studied. Improvement of properties characteristic of latex copolymers containing methylolamide groups is explained by orientated location of hydrophilic groups on the surface of latex particles during emulsion copolymerisation, that, in its turn, leads to a more ordered arrangement of macrochains. An optimum content of methylolamide groups as regards crosslinking processes was established and explained by steric location of these groups on the surfaces of latex particles. A similar optimum is not observed for crosslinking by watersoluble resin of latex copolymers containing groups of hydrophobic glycidylmethacrylate.     

Stability and compatibility in blends of silicone and vinylacrylic polymer emulsions

Special, unexpected properties may arise from blending of polymer emulsions, depending on the miscibility and stability of the resulting dispersions on the one hand, and the morphology of the films obtained upon drying on the other hand. In the field of water-repellent paints, blends of silicone and vinylacrylic copolymer emulsions have been previously shown to be a tricky means to associate binding ability and water permeability properties in the same material. It is currently assumed that the resulting morphology and physical properties of films obtained from these blends upon drying is partially controlled by the compatibility of the two kinds of polymers. In the present paper, the crucial problem of stability and compatibility in blends of silicone and vinylacrylic copolymer emulsions is investigated; more particularly, the effect of pH of the vinylacrylic copolymer latex, as well as the influence of the stabilizing system of both emulsions, on the stability of emulsion blends is qualitatively described. As regards the morphology of the films, the strong incompatibility of the two polymers is shown, which results in large macroscopic heterogeneities in the dried composite films. Furthermore, semi-quantitative angle-resolved ESCA measurements have evidenced a pronounced diffusion of the silicone species towards the surface of the samples. Investigations into different ways to increase compatibility of the two phases is presented. It is shown that phase separation at the macroscopic scale can be controlled either by lowering the interfacial tension between the two phases by grafting silane compatibilizers on to the latex particles, or by decreasing the molecular mobility of the silicone phase by cross-linking. Diffusion of the silicone chains towards the surface of the composite films can only be significantly restricted by cross-linking of this species.     

Film formation from pigmented latex systems: Drying kinetics and bulk morphologies of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) blend films

The drying kinetics and bulk morphology of pigmented latex films obtained from poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex particles functionalized with carboxyl groups and ground calcium carbonate blends were studied. Latex/pigment blends with higher carboxyl group coverage on the latex particle surfaces dried faster than films with few or no carboxyl groups present. The latex/pigment dispersions also dried faster when there was more stabilizer present in the blend system because of the hydrophilic nature of the stabilizer. The net effect of increasing the pigment volume concentration in the blend system was to shorten the drying time. The bulk morphologies of the freeze‐fractured surfaces of the pigmented latex films were studied with scanning electron microscopy. Scanning electron microscopy analysis showed that increased surface coverage of carboxyl groups on the latex particles in the latex/pigment blends resulted in the formation of smaller pigment aggregates with a more uniform size distribution in the blend films. In addition, the use of smaller latex particles in the blends reduced the ground calcium carbonate pigment aggregate size in the resulting films. Scanning electron microscopy analysis also showed that when the initial stabilizer coverage on the latex particles was equal to 18%, smaller aggregates of ground calcium carbonate were distributed within the copolymer matrix of the blend films in comparison with the cases for which the initial stabilizer coverage on the latex particles was 8 or 36%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2267–2277, 2006     

有机无机杂化物作乳化剂的苯丙乳液制备及其性能表征

A poly (St-co-BA) latex was successfully synthesized by using an organic-inorganic hybrid compound (OIHC), an aliphatic carboxylate sodium/nano-silica composite, as the emulsifier, and investigated by particle size analyzer, transmission electron microscope (TEM), optical contact angle measurement (OCA) and dynamic mechanical analyzer (DMA). It was found that the protective agent, sodium polyacrylate (PA),could obviously improve the polymerization stability and the functional monomer, glycidyl methacrylate (GMA), could enhance the store stability of the latex. The particle size of poly(St-co-BA) latex decreased and then leveled off as OIHC content increased. TEM shows that the prepared polymers were a~:tually organic-inorganic nanocomposites, and these films have better waterproof property than those prepared by traditional poly(St-co-BA) latex or organic silicone modified poly(St-co-BA) latex. The nanocomposite polymer has much higher glass transition temperature than organic silicone modified poly(St-co-BA) polymer containing the same organic silicone content.     

The colloidal properties of alkaline‐soluble waterborne polymers

Waterborne polymer dispersions are widely used in coatings and graphic arts markets as environmentally friendly and more sustainable alternatives to solvent borne binders. Traditionally, waterborne (meth)acrylic dispersions are prepared by emulsion polymerization using low molar mass surfactants as a key ingredient to control particle size. However, these surfactants can have a negative influence on the performance of coatings such as reduced water resistance and adhesion. To mitigate the negative effects of surfactants, polymer latexes have been developed that employ alkaline‐soluble polymers as the sole stabilizer for a subsequent emulsion polymerization step. In this way surfactant‐free polymer dispersions are obtained. Despite the high commercial impact and relevance of this technology, fundamental studies regarding the physicochemical properties of the alkaline‐soluble polymers are lacking. In this article, the synthesis and colloidal properties of alkaline‐soluble waterborne methacrylic copolymers are reported. The dissolution behavior and colloidal properties of these alkaline‐soluble polymers were studied as function of molar mass, acid content, and pH. The dissolving polymer particles were characterized using static and dynamic light scattering, static and dynamic surface tension measurements, and cryogenic‐transmission electron microscopy analysis. It is concluded that the dissolution mechanism of alkaline‐soluble polymers follows a gradual process. As the pH increases deprotonation of the carboxylic acid groups swells the particle enhancing the further swelling with water. At a certain amount of base, the particles disintegrate into small polymer aggregates while the most water‐soluble polymer chains are dissolved in the water phase. An important learning is that part of the alkaline‐soluble polymer resides in very small particles (<5 nm). The formation of these polymer particles below 5 nm was not reported previously and offers a new insight into the dissolution mechanism of alkaline soluble polymers. The most important parameter steering this process is the acid value of the polymer, while the molar mass plays a modest role. The understanding gained in this study can be used to further advance alkaline‐soluble polymers as stabilizer in surfactant‐free emulsion polymerization technology, improving the performance of a wide range of industrially relevant coatings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46168.     

Structure and properties of multiphase particles and their impact on the performance of architectural coatings

Aqueous dispersions used as binders in low-pigmented solvent-free paint formulations have to cope with the challenge to simultaneously guarantee an excellent film formation and appearance as well as good block resistance and hardness. One strategy to fulfill these contradictory requirements is the employment of multiphase particles.

In this work it is proved that the structure of latex particles, synthesized by a two-stage emulsion polymerization process, can be correlated to the morphology and properties of the dispersion films as well as to the application properties of the corresponding paint films.

Two sets of model dispersions were made. In the first set, the hard/soft ratio was varied, in the second set the amount of the AA. The structure of the particles was determined by TEM, and a morphology map was derived. AFM demonstrated a clear correlation between the particle structure and the morphology of the latex film. Dynamic mechanical analyses verified the presence of two distinct polymers with the hard phase acting as a transparent filler. For the hard/soft series, the properties of the dispersion films such as block resistance, gloss and hardness could be attributed to their structure. A closer look on the block behavior revealed that it can be related to the tack and surface roughness of the dispersion film, but not to its internal strength. Solvent free emulsion gloss paints were formulated, and application tests performed. The properties of the paint films correlated very well with those of the dispersion films. The test results clearly show that dispersions of multiphase particles enable the formulation of solvent free paints with excellent film-forming ability in combination with high block resistance, hardness and gloss.     

Effect of microstructure of fluorinated acrylic coatings on UV degradation testing

This paper presents research results on the relationships between the microstructure and the performance/weatherability of fluoropolymer/acrylic coatings. We studied fluoropolymer/acrylic blends of identical composition, prepared as films using three different methods: 2-stage emulsion polymerization followed by latex film formation; cold-blending (physically mixing) acrylic and fluoropolymer latex dispersions followed by latex film formation; and solution casting using an organic solvent. We investigated the effects of the mixing method, and the level of acrylic in the blend on the microstructure/morphology and on the durability-related physical properties of the fluoropolymer/acrylic films. Small angle neutron scattering was performed to determine the microstructure/morphology of fluoropolymer-rich micro-domains in the coatings prepared using these three methods. The physical properties tested included the glass transition temperature, the crystallinity fraction, and the tensile strength. The mass loss rates observed during UV exposure testing correlate with the final microstructures of the films.     

Verstärkung von Polysiloxanen mit Thermoplasten

Radical polymerization of organic monomers in room-temperature curable polydimethylsiloxanes (PDMS) yields liquid dispersions of thermoplastic polymers in PDMS. Graft copolymers of organic polymers and PDMS generated in the polymerization stabilize these dispersions like nonionic surfactants and act as a link between organic polymer particles and PDMS-matrix after vulcanization. This linkage and the special, rod-like shape of the polymer particles cause reinforcing effects, leading to vulcanizates that show unusual toughness in comparison to ordinary silicone rubber.     

Phase behaviors and film properties of dispersions and coatings containing associative and conventional thickeners

Phase-separation behaviors of latex dispersions, using commercial latices of three different median sizes, and pigmented coatings are examined. Both the dispersions and pigmented coatings at a 0.32 volume fraction of total dispersed phase were thickened with water-soluble polymers, with and without surfactant hydrophobes. Latex dispersions thickened with water-soluble polymers without hydrophobe modification follow the phase-separation behavior described by the volume restriction flocculation (VRF) concept (i.e., molecular weight of the thickener or particle size of the latex). This is surprising since commercial latices contain a variety of surface-stabilizing moieties, in addition to surfactant. Latex dispersions thickened with commercial and model hydrophobically modified ethoxylated urethane (HEUR) polymers do not follow the phase-separation behavior predicted by the VRF concept. The lack of correlation of phase behavior with latex median size in HEUR-thickened formulations led to an examination of four secondary thickeners, noted for providing high viscosities at low shear rates. With an all-acrylic, large median-size latex, the combinations of commercial HEURs with secondary thickeners are effective in eliminating phase separation; only partial reduction in phase separation is observed with a vinyl acetateacrylic large-particle latex. The influence of HEUR/secondary thickener blends on the film properties also is discussed. © 1993 John Wiley & Sons, Inc.     

Polymer blend latex films: Miscibility and polymer diffusion studied by energy transfer

Fluorescence non-radiative energy transfer experiments were used to study latex blend films composed of high molar mass poly(butyl acrylate-co-methyl methacrylate) (PBA-co-MMA) and much lower molar mass PBA-co-MMA latex of the same chemical composition (50:50 BA:MMA by weight). These blends take advantage of the strong chain length dependence of T_g so that the particles consisting of oligomeric polymer (“low-M”) have a much lower T_g than the corresponding high-M latex. This type of blend represents a useful strategy for obtaining latex coatings with a reduced VOC content. Here we report on experiments which follow the rate at which the low-M polymer mixes via diffusion with the high-M polymer in the latex films. The high-M latex are doubly labeled, containing both donor and acceptor dyes covalently bound to the PBA-co-MMA backbone. Diffusion of the unlabeled low-M polymer into this phase dilutes the dyes, increasing their separation and lowering the quantum efficiency for energy transfer.     

有机硅改性丙烯酸酯聚合物研究进展

从物理共混和化学改性两个方面综述了有机硅改性丙烯酸酯的方法，重点介绍了缩（聚）合、硅氢加成、自由基共聚，讨论了无皂乳液聚合、壳／核乳液聚合和乳液互穿网络聚合等新型乳液聚合技术，其中性能优异、环保、多功能硅丙聚合物将是未来研究的重点。     

Characteristics of water-absorbent polymer emulsions

Water-in-Oil (W/O) and Oil-in-Water (O/W) type water absorbent polymer emulsions were studied using two different polymerization methods. W/O type water absorbent polymer emulsions were prepared by the inverse emulsion polymerization of ammonium acrylate (AA), the quaternized salt of dimethyl-aminoethyl methacrylate (DMQ) and acrylamide (AM) with N,N-methylene-bisacrylamide (MBA) as a crosslinker. A pH sensitive water absorbent polymer emulsion was prepared by the conventional emulsion polymerization of diethyl-aminoethyl methacrylate (DEAEMA) with ethylene glycol dimethacrylate (EGDMA) as a crosslinker. It was confirmed that the water absorption capacity of crosslinked polymers in inverse emulsion was controlled by crosslink density and dissociative charge density, and the crosslinked polyDEAEMA particles had a phase transition property of swelling and shrinking with pH. The dispersions of these water swollen crosslinked polymer particles exhibited an increase in viscosity and thixotropic fluidity.     

UV‐curable methacrylic epoxy dispersions for cationic electrodeposition coating

UV‐curable epoxy dispersions were prepared for cationic electrodeposition coating. Sequential reactions were used to introduce methacrylate groups to the epoxy‐amine polymer as coupling agents to the multifunctional acrylates. The molecular weight values of the prepared epoxy‐amine polymer were M_n = 2800 and M_w = 4300. The neutralized epoxy‐amine polymer containing photoinitiator with or without multifunctional acrylate (pentaerythritol triacrylate, PETA) could be dispersed into a stable dispersion without any phase separation. The size of the particles in these epoxy dispersions was approximately 77.7 nm, and increased with the incorporation of PETA. The electrodeposition process was introduced to the prepared epoxy dispersions, and the electrodeposited films were cured by UV irradiation after a 10‐min flash off at 80°C. Studies of the kinetics using photo‐DSC revealed that the crosslinked films containing PETA gave a higher conversion rate than those without PETA, resulting in better resistance to methyl ethyl ketone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5566–5570, 2006     

Film formation from pigmented latex systems: Mechanical and surface properties of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex blend films

The mechanical and surface properties of films prepared from model latex/pigment blends were studied using tensile tests, surface gloss measurements, and atomic force microscopy. Functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA)] and ground calcium carbonate (GCC) were used as latex and extender pigment particles, respectively. The critical pigment volume concentration of this pigment/latex blend system was found to be between 50 and 60 vol % as determined by surface gloss measurement and tensile testing of the blend films. As the pigment volume concentration increased in the blends, the Young's modulus of the films increased. Nielsen's equations were found to fit the experimental data very well. When the surface coverage of carboxyl groups on the latex particles was increased, the yield strength and Young's modulus of the films both increased, indicating better adhesion at the interfaces between the GCC and latex particles. When the carboxyl groups were neutralized during the film formation process, regions with reduced chain mobility were formed. These regions acted as a filler to improve the modulus of the copolymer matrix and the modulus of the resulting films. The carboxyl groups on the latex particle surfaces increased the surface smoothness of the films as determined by surface gloss measurement. When the initial stabilizer coverage of the latex particles was increased, the mechanical strength of the resulting films increased. At the same time, rougher film surfaces also were observed because of the migration of the stabilizer to the surface during film formation. With smaller‐sized latex particles, the pigment/latex blends had higher yield strength and Young's modulus. Higher film formation temperatures strengthen the resulting films and also influence their surface morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4550–4560, 2006