Using dispersion/flocculation phase diagrams to visualize interactions of associative polymers, latexes, and surfactants

The colloidal interactions of associative polymers and latexes in the presence of surfactant are complex. This is because, in addition to good particle dispersion, both brid-ging and depletion flocculation can occur. Therefore, we have developed phase diagrams to help visualize these interactions. The various phases have a significant effect on coatings and applications properties. Examples of phase diagrams are presented for a model HEUR nonionic associative polymer and latexes in the presence of sodium dodecylsulfate. The major variables affecting phase behavior were found to be associative polymer concentration, latex particle size, latex surface hydrophobicity, and electrolyte, cosolvent, and surfactant concentrations. Presented at the PMSE Waterborne Coatings Symposium at the ACS Meeting, August 26–30, 2001, in Chicago IL. P.O. Box 904, Spring House, PA 19477-0904, E-mail: ekostansek@rohmhaas.com.     

Associative polymer/particle dispersion phase diagrams III: Pigments

The colloidal interactions of both HEUR and HASE associative polymers with pigments in the presence of dispersant are complicated and subject to a number of variables. The objective of this work was to clarify the conditions needed to achieve good pigment dispersion in associative thickener systems by characterizing particle dispersion behavior. This had previously been done for latex particles, but not for pigments such as TiO₂. Good dispersion leads to optical properties, such as gloss and hiding, that are superior to nonassociative thicknener systems. Pigment dispersion phase diagrams represent a good way to visualize the complex interactions among pigments, dispersant, and thickener. The two most important variables were found to be pigment type (i.e., surface composition) and dispersant composition. Associative thickners can yield good pigment dispersion or flocculation, depending on the correct matching of dispersants and pigment type. Because of the hydrophobic functional groups governing associative thickner behavior, dispersants having some hydrophobic character yielded the best pigment dipersions and optical properties because they could couple the pigment particles with the associative thickener network. Interior-grade TiO₂ tended to yield better dispersions and optical properties than exterior-grade TiO₂. Optimized associative thickner systems generally had improved optical properties over comparable nonassociative systems. Optical properties correlated well with particle dispersion behavior as displayed by the dispersion phase diagrams. Presented at the Tess Symposium of the 230th American Chemical Society National Meeting, Aug. 28–Sept. 1, 2005, in Washington, D.C.     

Surfactant behavior and its influence on the viscosity of associative thickeners solutions, thickened latex dispersions, and waterborne latex coatings

Surfactants, varying in their chemical composition and hydrophobic behavior, are used in the formulation of a waterborne coating. These differences influence their aggregation in micellar structures, their interaction with associative thickeners, and in particular, the synergies present in their competitive adsorptions on the disperse phases in a waterborne coating. Adsorption of HEUR thickeners on latexes and the ability of surfactants to displace them from those surfaces is an important variable in the dispersion’s viscosity. With large particle latexes, viscosity increases arise primarily from the network built through the interaction of HEURs with surfactants in the aqueous phase. Fluorescence is used to verify the mechanism by which surfactants enhance associative thickener viscosities. That is best achieved with nonionic surfactants, because of their synergies with large hydrophobe HEURs at low concentration. With decreasing latex particle size the adsorbed species is an important contributor to the dispersion’s viscosity through its contribution to the latex’s effective volume fraction increase and when the size of the adsorbed HEUR is matched to the separation distances of the latex at 0.25 volume fraction. Achieving controlled shear-thinning behavior in small particle size latex paints with the economic constraints on the amount of HEUR required to obtain 90 KU viscosities are discussed. Presented at the 80th Annual Meeting of the Federation of Societies for Coatings Technology, October 30–November 1, 2002, in New Orleans, LA. Polymer and Coatings Dept., Fargo, ND 58103.     

Waterborne latex coatings of color: II. Surfactant influences on color development and viscosity

A matrix of coating variables, nonassociative versus associative thickeners, different latex median particle sizes, individual surfactants and colorants [carbon black (CB), red, and yellow pigments], was examined for their influence on variances in coatings rheology and color development. Within the different coating groups, the variable of interest in this study was the surfactant added to the colorant formulation. In all three colorant formulations, sodium dodecyl sulfate (an anionic surfactant) provided poorer color development (CD) than in applied formulations containing an equivalent nonylphenol oxyethylene (EO) surfactant. In CB formulations, nonionic surfactants with higher EO content provide improved color development at low (2 mM) concentrations, but near equality in CD is achieved with low EO surfactants at higher concentrations. In contrast to CB formulations, red and yellow colorants exhibit good color development with high EO content nonionic surfactants only at low nonionic surfactants concentrations. This variance appears to be related to the interactions of surfactants with inorganic pigments (talc and laponite) in the colorant formulation. The coating’s rheology is related to latex, thickeners, and surfactant components of the paint, as has been noted in previous studies, but not to the nature of the color pigment. The viscosity of the hydroxyethyl cellulose (nonassociative type) and HEUR (associative type) thickened paint decreased with colorant addition due to dilution effects. There were no unusual deviations with the NP(EO)_x surfactants, except when a large hydrophobe nonionic surfactant [e.g., C₁₈H₃₇(EO)₁₀₀] is added. In HEC thickened coatings, the viscosity decreases when C₁₈H₃₇-(EO)₁₀₀ is in the colorant due to that surfactant inhibiting depletion flocculation. In the C₁₈H₃₇(EO)₁₀₀ coatings containing the HEUR thickener, significant increases in viscosity were observed, above the dilution values observed with the colorant addition. This is related to the viscosity maximum in the low concentration of HEUR with the C₁₈H₃₇(EO)₁₀₀ surfactant. Color development is independent of the viscosity profile of the coating. Presented in part at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2003 in Philadelphia, PA.     

Control of rheology of water-borne paints using associative thickeners

Water-borne decorative topcoats generally show inferior leveling and open time compared to solvent-based paints. Basically, this behavior is caused by the divergent viscosity–solid content relationship for dispersions and emulsions and by the relatively high evaporation rate of water. Employment of associative thickeners may improve leveling and open time of latex paints only if they introduce a substantial amount of ‘network viscosity,' characterized by a short relaxation time and little dependence on solid content. This network viscosity enables one to formulate a paint with sufficient high-shear viscosity at a particle-packing density far below the value where low-shear viscosity starts to diverge. Addition of an associative thickener not only affects rheology, but also the interaction between latex particles: Associative HEUR thickeners may induce undesired phase separation by strong bridging between the latex particles. The influence of HEUR thickeners on latex particle interaction has been studied by turbidity measurements. The experimental results could qualitatively be interpreted very well by two-particle interaction potentials computed using the Self-Consistent-Field theory of Scheutjens and Fleer. It is demonstrated how viscosity, created by the addition of an associative thickener to a highly concentrated latex, can be split up into a polymer network viscosity and a contribution to (relative) dispersion viscosity. According to these analyses, reduction of the molecular weight of tri-block HEUR thickeners yields an increase of the favorable network viscosity and a reduction of the unfavorable dispersion viscosity. However, reduction of the molecular weight of the HEUR thickener is limited by the introduction of undesired phase separation (bridging flocculation) below a certain molecular weight.     

Syneresis and rheology mechanisms of a latex-HEUR associative thickener system

This study focuses on the phase behavior, rheology, and interactions of polymer latex particles and a hydrophobically modified ethoxylated urethane (HEUR) associative thickener in water. At constant 0.25 latex particle volume fraction, increasing HEUR caused stable, followed by phase separated (syneresis), and stable mixtures as HEUR concentration increased from 0% to 2.0% (by weight) in the latex-thickener aqueous mixture. The mixtures that underwent syneresis were flocculated. The relationship between the flocculation behavior and the composition of the latex-HEUR mixtures is consistent with previous work reported by other investigators. However, detailed rheological data on systems like these that have undergone syneresis have not been reported. This paper presents detailed viscosity vs shear rate data and correlates viscosity trends with the both flocculation and syneresis behavior. The stable latex-HEUR mixtures at low HEUR levels show Newtonian or shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased to levels at which syneresis is observed, erratic rheological profiles with shear thinning as well as thickening are observed. This type of shear thickening has been attributed to bridging flocculation by other investigators. When HEUR level is further increased to levels at which no syneresis is observed, low-shear Newtonian plateaus re-appeared, albeit at higher viscosities. Detailed analysis of syneresis and shear-thickening behavior of a latex-HEUR mixture containing 0.5% (by weight) HEUR showed two shear-thickening regions, one between 0.1 and 0.5 s^?1 shear rate range and another between 30 and 100 s^?1 shear rate range. Molecular weight distribution (MWD) of the HEUR thickener indicates that the two shear-thickening regions are related to the bi-modal nature of the thickener’s MWD.     

Waterborne latex coatings of color: I. Component influences on viscosity decreases

For almost two decades, it has been known that the addition of colorants to a waterborne latex coating thicknened with an associative thickener will result in a viscosity loss. The influence of surfactants on viscosity variations in waterborne latex coatings, as discussed in our most recent JCTCoatingsTech article,¹ is the source of the viscosity decreases. To evaluate this problem, aqueous solutions containing large quantities of five different surfactants, and the smallest particle size of the colorants, carbon black (CB), were prepared. Large quantities of surfactant were used to allow for adsorption on, and stabilization of, CB. When traditional associative polymers (HMHEC, HASE, and a telechelic HEUR) were used to thicken carbon black dispersions, viscosity decreases were not observed, for most of the surfactnat is adsorbed on the CB’s surface. There is enough surfactant, however, to promote viscosity decreases in comb-HEUR thickened CB dispersions. Moving beyond the colorant dispersions, the CB, yellow, or red colorants were then added to a commercial latex paint that contains many surfactants, glycol ether, and coalescing aids, and significant viscosity decreases were observed. The decreases were very dramatic as the colorant concentration was increased to obtain deeper color tones, due to the additional excess surfactant added to the coating. Reduction in total surfactant levels in the colorant was an obvious solution, but this led to rub-up incompatibility. The conflict between viscosity retention and rub-up incompatibility was resolved when the surfactant concentration was reduced by adding to the colorant formulation compositionally different hydrophobically-modified poly(oxyethylenes) and hydrophobe-modified maleic acid co-oligomers. Presented in part at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 13–14, 2003 in Philadelphia, PA     

Acrylic latices stabilized by polymerizable non-ionic surfactant

The final latex particle size is controlled by the concentration of polymerizable non-ionic surfactant NE-40 in the emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The particle size decreases with increasing NE-40 concentration and increases with increasing persulphate initiator concentration. The dependence of particle size on the initiator concentration does not follow conventional Smith–Ewart theory, which is attributed to the bridging flocculation process during the particle nucleation period. The differences in the particle nucleation and growth stages and colloidal stability observed in the NE-40 and nonyl phenol-40 mol ethylene oxide adduct (NP-40) stabilized systems can be attributed to the different distribution patterns of surfactant molecules in the particles. Experimental data also indicate that the particle size decreases with increasing electrolyte concentration, or agitation speed. The total scrap, presumably caused by the bridging flocculation process, increases rapidly with increase in the NaCl concentration The amount of large flocs formed during polymerization is generally greater for the run operated at higher agitation speed. As expected, the latex products stabilized by non-ionic surfactants show excellent stability toward added sodium salt.     

Influence of added surfactant on particle flocculation in waterborne polymer–particle systems

Polymer–particle interactions can cause particle flocculation and phase separation problems in waterborne coatings. The problems can be the result of interactions that are either too weak or too strong. It is known by empirical work that addition of surfactants can minimize these problems. In this study, the authors have investigated how different types of surfactants influence the polymer–particle interactions. Both hydrophobic and hydrophilic particles were included in the study, and nonionic, anionic, and cationic surfactants were used. A simple model is suggested that can be used to predict the surfactant concentration needed to stabilize the system. The model considers the cmc (critical micelle concentration) of the surfactant, the adsorption to the polymer, and the adsorption to the particles.     

Influence of ingredients in water-based polyurethane–acrylic hybrid latexes on latex properties

Polyurethane–acrylic (PU–AC) hybrid latexes were prepared. Main monomers for PU preparation were isophorone diisocyanate, DMPA (dimethylol propanic acid) and polypropylene oxides (PPO) of different molecular weights. Acrylic monomers included butyl acrylate, methyl methacrylate and a crosslinker, trihydroxymethyl propane triacrylates (TMPTA). Several important ingredients in PU–AC latex preparation, such as surfactants, initiator, DMPA and PU/AC ratio, etc., were varied, and their effects on latex properties studied. Compared with surfactant free latexes, a sharp increase in particle size was observed in latexes done with 0.1% of surfactant regardless of the nature of the surfactants used (anionic, nonionic and anionic with long chain of amphiphilic alkylphenyl polyethoxylate). Further increase in surfactant content, however, led to latexes with smaller particle size and narrower particle size distribution when compared between latexes prepared using a same surfactant. When amount of the oil soluble initiator, azobisisobutyronitrile, was increased, AC monomers conversion was increased. It is interesting to observe that PPO with long propylene oxides brought about larger particle size combined with broader size distribution and less charge on particle surface; whereas lower DMPA levels led to latexes also of larger size combined with broader size distribution but more charges on particle surface. AC monomer crosslinker, TMPTA, contributed to reduce particle size, narrower size distribution and lower particle surface charges. By increasing AC amount in PU–AC latex, latex particle size significantly increased accompanied by a remarkable increase in particle surface charges. Mechanisms of particle formation and of DMPA stabilization were discussed in order to understand the experimental results.     

Effects of nonionic surfactants and external factors on stability of latex in cement paste

To clarify why different surfactants affect stability of latex in cement paste and why many latexes qualified in standard stability test still coagulate when mixed with cement, several kinds of nonionic surfactants with different structures were selected to improve stability of latex and the interactions among cement, latex, and surfactant were discussed. Results show that a higher affinity of surfactant to polymer contributes to a higher stability of latex in cement paste. When surfactants have similar hydrophilic group with each other, surfactants with phenyl in hydrophobic group can more effectively improve stability of styrene–acrylate (SA) latex in cement paste than that with n‐alkyl. With the same hydrophobic group (octyl phenyl) in molecules, surfactants with shorter hydrophilic group show better stabilization effect on SA latex. The combined action of high Ca²⁺ concentration, high solid concentration, and mechanical shear during agitation process of cement paste is the decisive factor causing coagulation of latex. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45946.     

Characterization of polystyrene latexes

Polystyrene latexes were prepared by emulsion polymerization. Styrene was used as monomer, potassium persulfate was the reaction initiator and sodium hydrogen carbonate was used as buffer. Surfactant may or may not be used. Three types of surfactant, ie sodium dodecylbenzene sulfonate (anionic), Triton X‐100 and Vulcastab LW (nonionic), and hexadecyltrimethyl ammonium bromide (cationic), were used. The prepared latexes were characterized according to concentration, density, pH, ionic strength, particle size, particle size distribution and surface charge. For prepared latexes with anionic surfactant, the effects of temperature, initiator concentration, surfactant concentration and amount of monomer on the latex size were investigated. Scanning electron microscopy was used as a tool for latex characterization. The results show that by increasing temperature, initiator and emulsifier concentration, the latex diameter decreases. However, size increases by increasing the amount of monomer. A potentiometric titration technique was employed for determination of surface charge. It was found that for all latexes, surface charge densities are in the same range. © 2000 Society of Chemical Industry     

Synergistic effect of polymer-surfactant mixtures on the stability of aqueous silica suspensions

The aim of the present work was to investigate the effect of cationic/nonionic surfactant mixtures on the dispersion and flocculation behavior of aqueous silica suspensions. In the study dodecylamine (DDA) was used as the cationic surfactant and polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO–PPO–PEO) triblock copolymers were employed as the nonionic surfactant. The dispersion and flocculation behavior of aqueous silica suspensions were studied mainly by turbidity measurements at low solids loading (0.05 vol.%) to observe the stability of the system for a given time period. Rheological measurements were performed at higher solids loadings to determine the viscosity as a function of shear rate. Adsorption behavior of single and mixed surfactants onto silica surface was studied using a total organic carbon analyzer.Results of the study showed that dispersion and flocculation behavior of aqueous silica suspensions depends on the type and concentration of surfactant, cationic/nonionic surfactant ratio and surfactant addition sequence to the system.     

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.     

Interaction between styrene/butylacrylate latex and water soluble associative thickener for coalescent free wall paints

The effect of water soluble hydrophobically modified ethylene oxide urethane (HEUR) thickener on coalescent free wall paints was studied. Three systems were looked at: latex/thickener blends, model paints (containing no fillers that could have an effect on paint rheology) and satin paints (PVC 30%). The latexes used were a styrene/butylacrylate copolymer, designed for coalescent free wall paints. A full factorial statistical experimental design was employed to study the effect of latex and formulation variables on the viscosity response for the full range of shear rates encountered in paint application. The factors considered in the design were total latex surface area, polymerization surfactant level, thickener type and thickener concentration. The surfactant level was varied between 0.85 and 1.71 parts. The two HEUR thickeners were selected based on the manufacturer's claim that they exhibited good performance at different shear rates. The thickener levels were the extremes recommended by the manufacturer. Measurements were done on Haake, Rheometrics, Brookfield and ICI Cone & Plate rheometers. Total latex surface area and the thickener level are the two significant parameters for latex thickener blends and for model paints at the same significance level, this indicates good correlation between the two systems. The introduction of clay as a filler decreases the effect of all parameters studied.     

The application research of environment-friendly reactive surfactants in acrylate emulsion pressure sensitive adhesives

In this article acrylate pressure sensitive adhesive (PSA) latexes were synthesized via a pre-emulsion seeded semi-batch emulsion polymerization process with a conventional nonreactive surfactant (CO-436) and two polymerizable surfactants (traditional surfmer SE-10N and environment-friendly surfmer SR-10). The effects of surfactant contents on the particle size, zeta potential, electrolyte stability of the latexes and gel content, sol molecular weight (M_w, M_n), water absorption of the PSA copolymers were investigated. In addition, X-ray photoelectron spectroscopy (XPS) and contact angle measurements were used to characterize the latex films. The results showed that the particle sizes of latexes prepared with surfmers were smaller than their CO-436 containing counterparts. And the latexes prepared with surfmers had a lower storage stability than the one prepared with CO-436. However, surfmers can improve the electrolyte stability of the latex. Furthermore, the water resistances of the latexes prepared with surfmers were better than that of the latex with CO-436, which can be confirmed by water absorption, contact angle and XPS analysis. The results also indicated that the PSA prepared with SR-10 exhibited the highest gel content among the three surfactants. Finally, the effects of surfactants on the adhesive properties of the PSAs were also evaluated.     

Emulsion polymerization of styrene using mixtures of hydrophobically modified inulin (polyfructose) polymeric surfactant and nonionic surfactants

Polystyrene latex dispersions were prepared by emulsion polymerization, using a mixture of hydrophobically modified Inulin (INUTEC® SP1) and various nonionic surfactants (cosurfactants). Two series of nonionic surfactants were used, namely Synperonic A (C_13–15 alkyl chain with 7, 11, and 20 moles of ethylene oxide, EO) and Synperonic NP (nonylphenol with 10 and 15 moles of EO). For 5 wt % latex, the INUTEC SP1 concentration was kept constant at 0.0165 wt % and the initiator concentration was also kept constant at 0.0125 wt %, whereas the cosurfactant concentration was varied between 0.1 and 0.5 wt %. With the exception of Synperonic A20, all other cosurfactants showed an initial increase in particle diameter followed by a decreased reaching a value comparable with that obtained using INUTEC SP1 alone. However, A20 produced a continuous reduction in particle diameter with increase of surfactant concentration, reaching a value of 100 nm at 0.5 wt % which is lower than the value obtained using INUTEC SP1 alone (188 nm). In all cases, addition of a cosurfactant enhanced the stability of latexes by co‐adsorption at the solid–liquid interface. The enhanced stability produced by the addition of cosurfactants to INUTEC SP1 could be illustrated by using the mixture of INUTEC SP1 and Synperonic A7 at 40 wt % of styrene latex concentration. In this case, the mixture produced lower particle size, much lower polydispersity index and much higher stability. These results are of significant value for industrial applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of nonionic surfactant on the rheological property of associative polymers in complex formulations

The rheological properties of hydrophobically modified ethoxylated urethane (HEUR) were investigated in the presence of a nonionic surfactant, polyoxyethylene stearyl ether (C₁₈(EO)₂₀). The presence of nonionic surfactants played an important role in tuning the rheological properties of HEUR aqueous solutions. Observing both plateau modulus and viscoelastic relaxation time of HEUR aqueous solutions with varying the concentration of C₁₈(EO)₂₀ allowed us to demonstrate that C₁₈(EO)₂₀ readily interacts with the hydrophobic segments of HEUR polymers, which eventually formed a strong micellar network. Moreover, the micellar network formed at a critical concentration of C₁₈(EO)₂₀, ∼0.6% w/v, was indeed stable against both ionic strength and pH in the aqueous medium and complex formulations, such as a colloid suspension and an oil-in-water emulsion, thus providing more practical applications as thickeners for a wide variety of complex formulations.     

农药微乳剂复配表面活性剂的筛选与优化

以高效氯氰菊酯为例,通过相图考察了非离子与阴离子表面活性剂及其不同复配比例对农药微乳剂相行为的影响。研究结果表明,同等使用剂量下,非离子与阴离子表面活性剂复配比单用非离子或阴离子表面活性剂得到更大的微乳区域,并且存在最佳复配比例。以此确定了非离子与阴离子表面活性剂最佳复配比例,对配方进行了优化。