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 and mechanical properties of the alkoxysilane-functionalized poly (styrene-co-butyl acrylate) latex prepared by miniemulsion copolymerization

Alkoxysilane-functionalized poly (styrene-co-butyl acrylate) latex was prepared via miniemulsion copolymerization of γ-methacryloxypropyltrimethoxysilane (MPS), styrene and butyl acrylate using AIBN at neutral condition. The effects of initiator types, pH values, and MPS contents on the premature cross-linking of the latex particles and the mechanical properties of the films were investigated by the swelling experiments and dynamic mechanical analysis. It was found that the storage modulus of the latex films and the glass transition temperature (T_g) increased with increasing MPS content. The acidification of latex prior to film formation and annealing the latex films could improve the mechanical properties of the films.     

Preparation and reticulation of styrene acrylic/epoxy complex latex

The styrene acrylic/epoxy (SA/EP) complex latex with high content of epoxy resin was successfully prepared through emulsion polymerization initiated by both water-soluble and oil-soluble initiators. The resulting complex latex demonstrated regular spherical morphology with a diameter ranging 150–300 nm and with a narrow size distribution. The compatibility between epoxy and styrene acrylic improved due to the styrene acrylic grafting epoxy formation during grafting copolymerization. The factors influencing the structure and storage time of the complex latex were investigated and the corresponding mechanism was revealed. The SA/EP complex latex can form crosslinking structure with epoxy curing agent at room temperature. The crosslinked complex latex film shows good mechanical properties and excellent chemical resistance. These SA/EP complex latexes show great potential in developing high-performance aqueous paints and adhesive.     

Impact of functionalised dispersing agents on the mechanical and viscoelastic properties of pigment coating

The effect of poly(acrylic acid) – poly(styrene sulphonic acid) (AA-SSA) and poly(acrylic acid) – poly(2-acrylamido-2-methylpropane sulphonic acid) (AA-AMPS) dispersing agents on the viscoelastic and mechanical properties of precipitated calcium carbonate-latex composites used was investigated. Four different formulations were prepared using carboxylated styrene butadiene (SBR) and styrene-acrylate (SA) latexes. Pore space was characterised using mercury porosimetry. The storage modulus and loss factor were evaluated through dynamic mechanical thermal analysis (DMTA) low frequency single cantilever bending mode. The ultimate tensile strength and the Young modulus were also measured. At low latex contents, storage modulus was found to be higher for SBR latex composites. At high latex content, the SA storage modulus was found to be higher. It is suggested that at lower latex content, the viscoelastic properties are function of physical microstructure, which at low latex is influenced by the latex glass transition temperature (Tg). Softer latex spreads more on the pigment surface providing higher stiffness, since pigments are held together by latex bridges. At higher latex content, the composite stiffness tends to be more dependent on the stiffness of the pure latex. The AA-SSA dispersant creates strong pigment–latex interfacial adhesion in dry composites, which is reflected in high elastic modulus and tensile strength. The AA-AMPS dispersant formulations had greater resistance to water. Due to the compatibility between the AMPS blocks and the SBR latex within the composite, higher storage modulus stability in water saturated composites is measured (at room temperature 56% of the storage modulus is preserved).     

Reaction and characterization of crosslinking hyperbranched poly (amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly (amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties.     

Latex Interpenetrating Polymer Networks

Abstract

Latex interpenetrating polymer networks are a unique type of polymer blend, synthesized by swelling crosslinked seed latex particles of polymer I with monomer II, plus cross-linking agents, and polymerizing monomer II in situ. In a manner similar to polymer blends generally, polymer 1 and II are incompatible to greater or lesser extents, and phase separate. In IPN materials, however, the phase separation is hindered by the presence of the double networks, giving rise to especially finely divided phase domains.

The synthesis of polybutadiene/polystyrene and poly(ethyl methacrylate)/poly(n-butyl acrylate) latex IPN's is considered, and the dynamic mechanical properties of the resulting films or molded materials is measured as a function of temperature. Two transitions were found for incompatible materials, while one broad transition arises with semicompatible polymer pairs. While regions of true interpenetration are indicated, the effect on the mechanical properties of inverting the order of polymerization suggests the presence of a shell-core phase separation. The origin of the shell-core separation effect is considered qualitatively, the underlying cause being ascribed to the statistics of mixing of polymer I with solvent (monomer II) and non-solvent, surrounding water.     

Dual crosslinking of carboxylated nitrile butadiene rubber latex employing the thiol‐ene photoreaction

At present, the most common used crosslinking process for carboxylated nitrile butadiene rubber (XNBR) latex is an accelerated sulfur curing system with zinc oxide. To avoid allergenic reactions related to residual accelerator levels in dipped XNBR latex articles such as medical gloves, a dual curing process has been developed combining thermal and photochemical crosslinking reactions. The two‐step procedure involves the formation of covalent and ionic bonds to ensure good mechanical properties of the final products. The photochemical thiol‐ene reaction is used to generate covalent crosslinks between the remaining C?C double bonds of the butadiene units whereas the carboxylic moieties are conventionally cured with divalent metal oxides (ZnO) under elevated temperature (formation of ionic crosslinks). The photochemical curing step is carried out both in the latex phase using a falling film photoreactor (prevulcanization) as well as in the solid phase by UV irradiation of dried XNBR films (postvulcanization). The mechanical properties and crosslink densities of the cured XNBR films are determined and the influence of selected curing parameters is assessed. The results give evidence that a combined approach of thermal prevulcanization and photochemical postvulcanization makes the production of latex articles (e.g., gloves) with tailored properties and good skin compatibility feasible. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reaction and characterization of crosslinking hyperbranched poly(amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly(amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties. __________ Translated from Journal of East University of Science and Technology (Natural Science Edition), 2006, 32(10): 1,164–1,168 [译自: 华东理工大学学报 (自然科学版)]     

Water vapour permeability,diffusion and solubility in latex films

Water vapour diffusion D, solubility S and permeability P coefficients have been determined for films obtained from carboxylated styrene-butadiene (SB) copolymer latexes. The experimental method is water vapour sorption performed in the range 30–60d?C. Using the small angle neutron scattering (SANS) method and a selective labelling with D₂O vapour, it has been shown that water molecules mainly diffuse in the films through the particle-particle interfaces, which consist of a polar carboxyl-rich copolymer. It has been shown that the degree of cross-linking of the particles does not significantly affect the values of D and S. Moreover, the effect of neutralization conditions, regarding both the pH value of the initial latex and the nature of the neutralizing agent, has also been investigated. It has been found that D does not depend on these parameters, whereas S appears to be very sensitive to them. The results have been interpreted on the basis of the structural modifications of the films induced by neutralization. Finally, the hydrophilicity (or hydrophobicity) of the neutralizing agent has been identified as one of the key features for controlling the affinity of the latex film for water vapour and hence its permeability properties.     

Acetoacetoxy functionalized natural rubber latex capable of forming cross-linkable film under ambient conditions

This work demonstrates that natural rubber (NR) latex particles containing acetoacetoxy (AcAc) groups are able to undergo cross-linking upon film formation at ambient temperature by reaction with glutaraldehyde (GTA). Natural rubber latex grafted with poly(acetoacetoxyethyl methacrylate) (NR-g-PAAEM) was synthesized by seeded emulsion polymerization, using benzoyl peroxide (BPO) as an initiator in free radical polymerization. The degree of grafting of PAAEM in the graft copolymers was evaluated by ¹H NMR technique. Transmission electron microscope (TEM) was used for investigation the particle morphology of the grafted NR latex. Since the AcAc groups are intentionally attached to the NR particles providing sites of cross-linking at ambient temperature, the cross-linking ability of these sites by reaction with GTA was then investigated. The results revealed that the latex film of NR-g-PAAEM with the addition of GTA had a much higher tensile strength in comparison with the film without GTA. The surface morphology of the NR-g-PAAEM latex film formed in the absence and presence of the GTA cross-linker was also investigated using atomic force microscopy (AFM). By GTA addition into the NR-g-PAAEM latex before film formation, an increase in the root-mean-square (RMS) roughness of the surface of the latex film was observed. Moreover, it was also observed that the NR-g-PAAEM films with the addition of GTA had higher activation energy for thermal degradation than that without the cross-linker. This confirms that the cross-linking reaction took place in the NR-g-PAAEM latex film as a result of its reaction with the GTA.     

Blend modification of feather keratin‐based films using sodium alginate

Feather keratin (FK), which can be extracted from waste feathers, is a kind of biodegradable and renewable protein resource and it has a great potential in the field of materials such as keratin sponges, films, and microcapsules. The aim of the current study was to investigate the blend modification of FK‐based films using sodium alginate (SA). A series of FK‐based films blended with different ratios of SA were prepared by the casting process. The cross‐section of blend films had a compact and homogeneous structure and no distinct phase separation was observed, indicating the favorable compatibility between FK and SA. The result of DSC analysis, in which there was a change in crystal structure, confirmed the interaction between FK and SA in the blend films. The FTIR spectra pointed out that the main interaction between the two components would be through the formation of hydrogen bonds. The incorporation of SA to FK significantly enhanced the strength and maintained the extensibility of the resultant films. The water vapor permeability reached its lowest level when the ratio of FK to SA was 7:3. Moreover, the blend films exhibited a relatively high level of transparency with SA content below 30%. These improvements by incorporation of SA provided the potential to expand the application of FK‐based films in packing and bio‐medical industries. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44680.     

Photo-vulcanization using thiol-ene chemistry: Film formation,morphology and network characteristics of UV crosslinked rubber latices

The photo-vulcanization with versatile thiol-ene chemistry represents an innovative approach to crosslink diene-rubber materials both in latex and in solid film state. In this work, the structure of elastomer-based thiol-ene networks and the morphology after film formation are studied in detail using electron microscopic techniques, atomic force microscopy and multiple-quantum solid-state NMR spectroscopy. Additionally, film formation properties and corresponding macroscopic properties of photo-vulcanized natural rubber (NR) latex and its synthetic counterpart, isoprene rubber (IR) latex, are determined in dependence on the curing procedure (pre- and post-vulcanization). The results reveal that thiol-ene cured elastomers comprise homogenously distributed crosslinks with a low amount of short chain defects. Whilst photochemically pre-cured NR latex particles provide coherent films, the film formation and mechanical properties of IR are strongly governed by the crosslink density of the latex particles. In film state, photo-vulcanization promotes narrow crosslink distributions and excellent tensile properties of both NR and IR.     

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     

Fabrication and characterization of polysiloxane/polyacrylate composite latexes with balanced water vapor permeability and mechanical properties: effect of silane coupling agent

In order to improve the water vapor permeability and mechanical properties of latex films, polysiloxane/polyacrylate (PSi/PA) composite latexes were fabricated via seeded emulsion polymerization of methyl methacrylate and butyl acrylate onto PSi latex particles, and the effects of the silane coupling agent 3-methacryloyloxypropyl trimethoxysilane (MATS) on the morphologies of the latex particles and films, as well as the microphase separation degree, the water vapor permeability and the mechanical properties of the latex films were investigated. Results indicated that MATS was essential for obtaining the PSi/PA composite latex particles with PSi as core and PA as shell and made a great contribution to restrict the phase separation. The PSi/PA core/shell latex films showed similar tensile strength and elongation with pure PA film, while exhibiting promising water vapor permeability. It was found that the influences of MATS content on the water vapor permeability and mechanical properties were opposite, and on the premise of the requirements for mechanical properties, lower MATS content could provide the PSi/PA core/shell latex films with better water vapor permeability.     

Liquid chromatographic separation of xylene isomers on α-cyclodextrin bonded phases

Mesoporous glass beads and silica were modified with α-cyclodextrin (CD) for the separation of xylene isomers by means of direct bonding, linking spacer group, and cross-linking agent. The separation efficiency of the (α-CD modified silica particles was tested by using simple column chromatography. A strong inclusion complex formation of p-xylene was observed from the column packed with α-CD bonded phases. Spacer group and crosslinking agent decreased the formation of the inclusion complex of p-xylene and increased selectivity between m-xylene and o-xylene. The inclusion complex formation of p-xylene was strongly diminished when the mobile phase was switched from methyl alcohol to toluene. The column packed with the cross-linked a-CD bonded silica showed the best performance in the separation of xylene isomers.     

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     

Starch–poly(ethylene-co-acrylic acid) composite films. Effect of processing conditions on morphology and properties

Formulations containing 4 parts cornstrach, 5 parts poly(ethylene-co-acrylic) (EAA), 1 part urea, and 1.6 parts of either water or aqueous ammonia were extruded at either 110–120°C or 150–160°C; and the resulting extrudates were then extrusion-blown into films. Complex formation between EAA and starch was measured by either X-ray diffraction or by solvent extraction of uncomplexed EAA. Although the processing temperature had only a minor effect on the amount of EAA complexed by starch, use of aqueous ammonia rather than water in these formulations increased the amount of complexed EAA by about a factor of 2. In films prepared with aqueous ammonia, the polysaccharide phase was present as submicron-sized domains. When ammonia was omitted from these formulations, the polysaccharide phase was less uniform in size and contained particles that were over an order of magnitude larger than those observed with ammonia.     

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.     

Film formation from polystyrene–poly(butyl acrylate‐co‐methyl methacrylate) latex blends

We have employed steady sate fluorescence (SSF) and UV‐visible (UVV) techniques to determine the film formation behavior of latex blends. Blend films were prepared from mixtures of a high‐T_g pyrene (P) labeled polystyrene (PS) latex and a low‐T_g copolymer of poly(butyl acrylate‐co‐methyl methacrylate) (BuA/MMA4). Eleven different blend films were prepared in various hard/soft latex compositions at room temperature and annealed at elevated temperatures above glass‐transition (T_g) temperature of polystyerene for 10 min. Fluorescence intensity (I_P) from P was measured after each annealing step to monitor the stages of film formation. The evolution of transparency of latex films was monitored using photon transmission intensity, I_tr. Film morphologies were examined by atomic force microscopy (AFM). A significant change occurs in both I_P and I_tr intensities at a certain critical weight fraction of hard latex (R_c = 0.3). Above R_c, two distinct film formation stages, which are named as void closure and interdiffusion processes, were seen in fluorescence data. Transparency of the films was decreased with decreasing PS content, indicating that a phase separation process occurs between PS and BuA/MMA4 phases by thermal treatment, which results in turbid films. However, below R_c, no change was observed in I_P and I_tr upon annealing, whereas transparency increased overall with increasing BuA/MMA4 ratio. We explained this result as the phase separation process between PS and BuA/MMA4 blends. These results were also confirmed by AFM pictures. Film formation stages above R_c were modeled and related activation energies were calculated. POLYM. COMPOS., 27:431–442, 2006. © 2006 Society of Plastics Engineers     

Miscibility behavior of poly(n‐butyl methacrylate) latex films containing alkali‐soluble resin

The dynamic mechanical properties of poly(n‐butyl methacrylate) (PBMA) latex films postadded with alkali‐soluble resin (ASR) have been studied and compared with those of latex films prepared by emulsion polymerization in the presence of ASR (ASR‐fortified latex). The miscibility between PBMA and ASR, poly(styrene/alpha‐methylstyrene/acrylic acid) (SAA), was found to influence the dynamic mechanical behavior of the films. The dynamic properties of PBMA latex films postadded with SAA show two distinct damping peaks, which correspond to those of PBMA and SAA, respectively, in the phase‐separated state. The SAA migrates onto film surface during film formation and, as a result SAA preserved their domains in the matrix phase, showing two distinct relaxations in the dynamic mechanical spectrum. On the other hand, the ASR‐fortified films exhibit single damping peak. SAA‐fortified latex particles would be core/shell structured, and the miscibility between PBMA and SAA is clearly improved by the grafting reaction between PBMA and SAA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 639–649, 2000