Polymerization of high‐solids‐content acrylic latexes using a nonionic polymerizable surfactant

Stable high‐solids‐content methyl methacrylate/butylacrylate latexes with small particle sizes (in the range of 150–180 nm) were obtained with a nonionic polymerizable surfactant (surfmer). Three percent of surfmer with respect to monomer was proven to be enough for the stabilization of the latexes. The influence of different operational variables on the stabilization of the final latex was analyzed, and the conditions needed to obtain coagulum‐free latex were assessed. The inorganic potassium persulfate/sodium metabisulfite initiator system provided better stability than the organic tert‐butyl hydroperoxide/ascorbic acid as a result of the end groups. In addition, the feeding of acrylic acid during the second half of the polymerization improved the stability of the final latex. The reduction of the feeding time was effective in the stabilization. Proof of the surfmer incorporation into the particles is presented. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1552–1559, 2002     

Synthesis,characterization, and utilization of itaconate‐based polymerizable surfactants for the preparation of surface‐carboxylated polystyrene latexes

Two polymerizable surfactants (surfmers), namely, monododecyl itaconate (MDDI) and monocetyl itaconate (MCI), were synthesized by reacting itaconic anhydride with 1‐dodecanol and cetyl alcohol, respectively. A series of uncrosslinked and crosslinked surface‐carboxylated latexes were prepared from styrene and styrene–divinylbenzene, respectively, using varying amounts of these two surfmers. The latexes were characterized by gravimetry, dynamic light scattering, and conductometric titration in order to obtain the conversion, particle size distribution, and concentration of surface carboxyl groups, respectively. The size of latex varied between 41–72 nm and was seen to depend inversely on the surfmer concentration. In the case of the soluble polystyrene latexes, solution ¹H NMR spectra provided conclusive evidence for surfmer incorporation into the polymer chain. Comparison of the incorporation levels determined by NMR with the surface carboxylic acid concentrations in the latexes, determined by conductometric titrations, revealed that the majority of the surfmers, as ancticipated, were present on the latex surface. The study of the stability of the latexes to varying salt concentrations clearly demonstrated that the smaller‐size latexes having higher surface carboxyl group density exhibited far improved stability when compared with the larger‐size ones having lower surface carboxyl group density. Similarly, enhanced freeze‐thaw stability was also observed for the smaller‐size latexes. MCI‐based latexes exhibited marginally improved stability compared with those prepared using MDDI, which again seems to be because of the higher surface functional group density in the former. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3257–3267, 2005     

Reactive Surfactant in the Emulsion Copolymerization of Methyl Methacrylate and Octyl Acrylate

The emulsion copolymerization of methyl methacrylate and octyl acrylate was studied using a reactive surfactant ammonium sulfate allyloxy nonylphenoxy poly(ethyleneoxy) (10) ether (DNS‐86), and a conventional surfactant sodium dodecylbenzene sulfonate (DBS) with a similar structure as a comparison sample. A series of latex samples have been prepared with two kinds of surfactants, and their properties have been characterized and compared. ¹H‐NMR proves that the reactive surfactant has been incorporated into the resulting copolymers. The atomic force microscopy (AFM) proves that the reactive surfactant DNS‐86 migrate to the surface of the latex film to a much less degree than the conventional surfactant DBS. Transmission electron microscopy (TEM) demonstrates that there are some differences in the particle morphologies. The stability and water‐resistance of the latex films prepared by reactive surfactant DNS‐86 are better than those prepared by the conventional surfactant DBS.     

Effect of different surfactants on colloidal and polymer properties of fluorinated acrylate latex

Fluorinated acrylate latex was successfully prepared by semi-continuous seeded emulsion polymerization of dodecafluoroheptyl methacrylate (DFMA) with butyl acrylate (BA), methyl methacrylate (MMA) initiated by potassium persulfate in the water. The resultant latexes and their films are characterized with Fourier transform infrared (FTIR) spectrometry, contact angle determinator, dynamic light scattering detector and surface tension determinator. Effect of different surfactants on colloidal and polymer properties of fluorinated acrylate latex was studied. Results show that the latex prepared with sodium dodecyl benzene sulfonate surfactant has the smallest particle size and contact angle but the moderate surface tension. The latex prepared with perfluorooctanesulfonic acid potassium surfactant has the smallest surface tension, moderate particle size but the biggest contact angle. The latex prepared with sodium 2-hydroxy-3-(methacryloyloxy) prop- ane-1-sulfonate surfactant has the biggest particle size and surface tension but moderate contact angle. In addition, the latex prepared with sodium 2-hydroxy-3-(methacryloyloxy) prop- ane-1-sulfonate has higher electrolyte stability.     

Electrical,Film and Surface Properties of Water-Based Latexes Prepared by Semicontinuous Emulsion Polymerization

Summary: In this study, the results obtained with latexes prepared by semicontinuous emulsion polymerization with conventional anionic and nonionic emulsifiers and their different mixtures were presented. For this study, vinyl acetate-butyl acrylate latexes with a conventional anionic emulsifier (sodium lauril ether sulfate) and a nonionic emulsifier (30 mole nonyl phenol ethoxylate), of which films can be easily cast, were used. The latex properties in terms of mechanical stability, film-water absorption, and film-emulsifier exudation, and surface and electrical properties were assessed and compared.     

Effect of sulfonated 3-pentadecyl phenyl acrylate as surfmer in the emulsion polymerization of styrene: synthesis and polymer properties

In this work, the evaluation of a newly developed anionic polymerizable surfactant (surfmer), viz., sulfonated 3-pentadecyl phenyl acrylate, in the emulsion polymerization of styrene and its effect on the polymer properties is reported. The results were compared with the commercially available non-reactive anionic surfactant sodium lauryl sulfate. The surfmer has a low critical micellar concentration value of 40.11 mg/L (8.7?×?10^?5?mol/L) in comparison to 2,400 mg/L (8.28?×?10^?3?mol/L) for sodium dodecyl sulfate. Nanosized polystyrene dispersions with varying concentration of this surfmer were prepared and characterized for conversion, particle size, and size distribution at a fixed monomer/water ratio of 0.1. The particle radii decreased from 560 nm for the surfactant-free dispersions to 45 nm for the dispersion with 2.3 mol% surfmer. Increasing surfmer content above this concentration did not further affect the particle size but increased the width of the particle size distribution. Transmission electron microscopy results along with particle size data show that with increasing surfmer content the particle size distribution broadens, and film formation is facilitated. The microstructure analysis of the copolymers using infrared and ¹H-NMR spectroscopy confirms that the surfmer is chemically attached to the polymer chains. The effect of the ionic sulfonate groups and the alkyl chains of the surfmer moieties on the polymer properties have been studied through measurement of dilute solution viscosity and thermal and viscoelastic properties. These results indicate that the behavior of surfmer-containing polymers resembles that of plasticized ionomers.     

Film‐formation property of vinylidene chloride‐methyl methacrylate copolymer latex. II. Effect of latex storage temperature

Changes in the minimum film‐formation temperature (MFFT) of 91:9 wt % vinylidene chloride (VDC)‐methyl methacrylate (MMA) latex prepared by the seeded batch process during storage at 5, 20, and 40 °C were investigated. MFFT of the latex rose the fastest at 20 °C. Infrared absorption of fresh and stored latexes and wide‐angle X‐ray diffraction of powder polymers obtained by lyophilization of fresh and stored latexes indicated a much greater increase in polymer crystallinity during latex storage at 20 °C than at 5 and 40 °C. Observed increases in MFFT during latex storage correlated with increases in polymer crystallinity. Infrared absorption of polymer stored at 5–60 °C in the dry state, such as lyophilized polymer and coating film, indicated that a polymer crystallinity increase was greater during storage at higher temperatures. These results showed that crystallization behavior of 91:9 wt% VDC‐MMA copolymer latex differed from that of VDC‐MMA copolymer in the dry state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 948–953, 2002     

A Facile One‐Step Method to Prepare Three‐Dimensional Ordered Latex Particles

Three‐dimensional ordered latex particles were prepared in presence of polymerizable anionic emulsifier—sodium undec‐10‐enoate (UDNa) in emulsion polymerization. Only under a certain monomer/emulsifier ratio can we get such a result. Three‐dimensional ordered latex particles cannot be acquired with the use of conventional emulsifiers such as sodium dodecyl sulfate (SDS), etc. The double bond of polymerizable emulsifier can copolymerize with the main monomer and become covalently bound to integrate with the main polymer chains which result in stable latexes. TEM and SEM images show that whether it is diluted or not the latexes can always keep in the three‐dimensional regularly order.     

Miniemulsion copolymerization of vinyl acetate and butyl acrylate. I. Differences between the miniemulsion copolymerization and the emulsion copolymerization processes

Differences between the emulsion copolymerization and miniemulsion copolymerization processes, in terms of emulsifier adsorption, emulsion stability, polymerization kinetics, copolymer composition and dynamic mechanical properties were studied for the comonomer mixture of 50:50 molar ratio vinyl acetate (VA+)—butyl acrylate (BuA), using sodium hexadecyl sulfate (SHS) as a surfactant and hexadecane (HD) as a co-surfactant. The use of hexadecane with the appropriate SHS initial concentration led to a higher adsorption of surfactant, smaller droplet size, higher stability of the emulsions, lower polymerization rates, and larger latex particle size. The copolymer composition during the initial 70% conversion was found to be less rich in Vac monomer units for the miniemulsion process. The dynamic mechanical properties of the copolymer films showed less mixing between the BuA-rich core and the VAc-rich shell in the miniemulsion latexes compared to the conventional latex films.     

Film‐formation property of vinylidene chloride‐methyl methacrylate copolymer latex. I. Effect of emulsion‐polymerization process

Changes in minimum film‐formation temperature (MFFT) during storage of latexes prepared from 91:9 wt % vinylidene chloride (VDC)‐methyl methacrylate (MMA) monomer mixture by seeded batch and seeded semicontinuous emulsion polymerization were investigated, with attention centered on polymer‐crystallization behavior during storage in the dispersed state. MFFT of latex prepared by the seeded batch process rose to 47 °C, whereas that of latex prepared by seeded semicontinuous process remained below 14 °C with storage at 20 °C for 12 weeks. Infrared absorption of latexes in the dispersed state and wide‐angle X‐ray diffraction of powder polymers obtained by lyophilization of fresh and stored latexes both indicated a much greater increase in polymer crystallinity during storage with latex prepared by the seeded batch process than with that prepared by the seeded semicontinuous process. Analysis of the copolymer composition drift calculated from reactivity ratios and ¹H NMR analysis indicated a wider sequence distribution and longer VDC sequences in polymer prepared by the seeded batch process than in polymer prepared by the seeded semicontinuous process. This explained the higher rate of crystallization during storage with latex prepared by the seeded batch process than with that prepared by the seeded semicontinuous process. Rising crystallinity during storage in the dispersed state is believed to have caused the MFFT rise. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 939–947, 2002     

EFFECT OF SURFACTANTS ON FILM FORMATION OF POLY (VINYL ACETATE) AND POLY (VINYL ACETATE-BUTYL ACRYLATE) LATEXES

Effect of ethoxylated nonyl phenol type non-ionic and alkyl sulfate type anionic surfactants on the film formation process of poly (vinyl acetate) and poly (vinyl acetate-acrylate) latexes are discussed. HLB value of non-ionic surfactant is shown to affect glass transition temperature, minimum film formation temperature and rate of film coalescence of vinyl acrylic latexes. Higher HLB non-ionic surfactant appears to be more compatible than the lower HLB ones with the fairly polar vinyl acrylic latex and form a well coalesced film. Presence of sodium lauryl sulfate in the latex is observed to result in incompatible regions on the latex film surface, typical of two phase morphology. Influences of surfactants on the film formation process in the polar vinyl acrylic latexes are compared and contrasted with the available data on the effects of surfactants in styrene butadiene latexes. The findings are discussed in terms of adsorption and interaction behavior of surfactants at polar vinyl acrylic latex surfaces and current theories of latex film formation mechanisms.     

Diene‐based polymer nanoparticles: Preparation and direct catalytic latex hydrogenation

The diene‐based polymer nanoparticles represented by poly(butadiene‐co‐acrylonitrile) were prepared in the semibatch emulsion polymerization system using Gemini surfactant (GS) trimethylene‐1,3‐bis(dodecyldimethylammonium bromide) as the emulsifier. The nanoparticles within the range of 17–54 nm were achieved with narrow molecular weight and particle size distributions. A spherical morphology was observed for the produced nanoparticles. The effects of GS concentration on the particle size, molecular weight, polymerization conversion and solid content, and composition of copolymer were investigated. The semibatch process using monomeric and conventional surfactant sodium dodecyl sulfate (SDS) was compared. At the second stage of this study, the prepared unsaturated nanoparticles were employed as the substrates for the latex hydrogenation in the presence of Wilkinson's catalyst, that is, RhCl(P(C₆H₅)₃)₃. The effects of the particle size and catalyst concentration on the latex hydrogenation rate were investigated. The particle size is found to have a significant effect on the reaction rate. When the 17‐nm nanoparticles were used as the substrates, a high conversion of 95 mol % was obtained within 18 h using only 0.1 wt % RhCl(P(C₆H₅)₃)₃. The latex hydrogenation process was completely free of organic solvents. The present synthesis and following “green” hydrogenation process can be extended to latices made from semibatch emulsion containing other diene‐based polymers. This study shows great promise for decreasing the demanded quantity of expensive catalyst and eliminating the organic solvent in the hydrogenation process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Mechanism of emulsion polymerization of styrene using a reactive surfactant

The emulsion polymerization of styrene using the reactive surfactant sodium dodecyl allyl sulfosuccinate (TREM LF‐40) was studied. The polymerization kinetics were found to be unusual in that R_p was not directly proportional to N_p (R_p ∝ N_p^0.67). Several reasons are stated to explain the unusual kinetics, including chain transfer to TREM LF‐40, copolymerization of styrene with TREM LF‐40, and the influence of the homopolymer of TREM LF‐40 [poly(TREM)] and/or the copolymer [poly(TREM‐co‐styrene)] on the entry and exit rates of free radicals. The possibility of both chain transfer and copolymerization exists primarily at the oil/water interface, whereas both can also occur in the aqueous and monomer phases. Bulk polymerizations of styrene in the presence of TREM LF‐40 and poly(TREM) were conducted, and the results show that the reaction rate decreased for the styrene/TREM LF‐40 system. Latex characterization by serum replacement and titration measurements provided evidence for the chemical bonding of TREM LF‐40 to the polymer particles. The fraction of chemically bound reactive surfactant decreased with increasing surfactant concentration and increased with increasing initiator concentration. Relatively high contact angles of water on films cast from the latexes showed that TREM LF‐40 did not migrate significantly to the surface of the film, which was consistent with the latex‐surface characterization results. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3093–3105, 2001     

Well-Characterized Monodisperse Latexes as Model Colloids

Monodisperse polystyrene latexes prepared with persulfate-ion initiator can be ion exchanged to remove the adsorbed emulsifier and solute electrolyte. Rigorous purification of the ion-exchange'resins is necessary to avoid contamination with leached polyelectrolytes. These ion-exchanged latexes are stabilized with the residual sulfate end-groups of the polymer molecules, the number of which is determined by conductoroetric titration. The result is a dispersion of monodisperse spheres with-a constant and known surface charge due to chemically-bound strong-acid groups. These latexes are ideal models for colloidal studies. Preliminary experiments of stability, adsorption, sedimentation, viscosity, interference colors, and conductance give consistent results, e.g., the particle double-layer interactions determined by viscosity are in accord -with the particle spacings estimated from interference colors, the double-layer parameters estimated from conductometric titration and conductance measurements account for the measured decrease in sedimentation rate due to double-layer interactions, and the molecular area of sodium dodecyl sulfate measured by adsorption in latex is in agreement with literature values.     

Comparative study of classical surfactants and polymerizable surfactants (surfmers) in the reversible addition–fragmentation chain transfer mediated miniemulsion polymerization of styrene and methyl methacrylate

Cationic and anionic amphiphilic monomers (surfmers) were synthesized and used to stabilize particles in miniemulsion polymerization. A comparative study of classical cationic and anionic surfactants and the two surfmers was conducted with respect to the reaction rates and molecular weight distributions of the formed polymers. The reversible addition–fragmentation chain transfer process was used in the miniemulsion polymerization reactions to control the molecular weight distribution. The reaction rates of the surfmer‐stabilized miniemulsion polymerization of styrene and methyl methacrylate were similar (in most cases) to those of the classical‐surfactant‐stabilized miniemulsion polymerizations. The final particle sizes were also similar for polystyrene latexes stabilized by the surfmers and classical surfactants. However, poly(methyl methacrylate) latexes stabilized by the surfmers had larger particle sizes than latexes stabilized by classical surfactants. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 427–442, 2006     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. II. Polymerization mechanism

The mechanism of growth of latex particles in the emulsion polymerization of vinyl acetate using a polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) was investigated. Both the aqueous phase and the particle/water interface were found to be loci for the copolymerization of TREM LF-40 with vinyl acetate. Competitive growth experiments using TREM LF-40 and its nonpolymerizable derivative were conducted to separate the effects of aqueous phase and particle surface. Particle size analysis of the seeded and unseeded polymerizations coupled with kinetic results suggested that the reactions at the particle/water interface are more important and that the particle size of the latexes is a key parameter controlling the polymerization rate through copolymerization and chain transfer to the polymerizable surfactant at the particle surface. A decrease in particle size lead to an increase in the amount of TREM LF-40 polymerized at the particle surface and to a decrease in polymerization rate. © 1992 John Wiley & Sons, Inc.     

Fabrication of high‐performance,gradient‐refractive‐index plastic rods with surfmer‐cluster‐stabilized nanoparticles

A novel method was developed with surfmer‐cluster‐stabilized silver nanoparticles to prepare high‐performance, gradient‐refractive‐index (GRIN) plastic rods based on methyl methacrylate. To fabricate the GRIN plastic rods, a novel polymerizable surfactant (surfmer) of 4‐(11‐acryloxyundecyloxy)benzoic acid (AUBA) was synthesized. Silver nanoparticles were prepared with a reverse micelle method in the presence of the novel surfmer. During the fabrication of the silver nanoparticles, the sodium salt of AUBA was formed. GRIN plastic rods were fabricated through centrifugal polymerization and then were heat‐treated at 100 °C under 0.1 Torr for 24 h to remove residual monomers and water. The distribution of the surfmer‐cluster‐stabilized nanoparticles inside the plastic rods was studied with transmission electron microscopy (TEM). The real‐image transmission through the fabricated rods was also confirmed. The results obtained in this investigation suggested that the control of the distribution of surfmer‐cluster‐stabilized nanoparticles could be used to fabricate GRIN rods. Furthermore, the existence of the crosslink‐like surfmers increased the thermal stability of the plastic rods. The GRIN distribution of the rods was established by the dispersion of nanoparticles inside the plastic rods through TEM analysis, refractive‐index analysis, and real‐image transmission. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5933–5942, 2006     

A Conventional Surfactant Becomes CO2‐Responsive in the Presence of Switchable Water Additives

We have developed a new benign means of reversibly breaking emulsions and latexes by using “switchable water”, an aqueous solution of switchable ionic strength. The conventional surfactant sodium dodecyl sulfate (SDS) is not normally stimuli‐responsive when CO₂ is used as the stimulus but becomes CO₂‐responsive or “switchable” in the presence of a switchable water additive. In particular, changes in the air/water surface tension and oil/water interfacial tension can be triggered by addition and removal of CO₂. A switchable water additive, N,N‐dimethylethanolamine (DMEA), was found to be an effective and efficient additive for the reversible reduction of interfacial tension and can lower the tension of the dodecane/water interface in the presence of SDS surfactant to ultra‐low values at very low additive concentrations. Switchable water was successfully used to reversibly break an emulsion containing SDS as surfactant, and dodecane as organic liquid. Also, the addition of CO₂ and switchable water can result in aggregation of polystyrene (PS) latexes; the later removal of CO₂ neutralizes the DMEA and decreases the ionic strength allowing for the aggregated PS latex to be redispersed and recovered in its original state.     

有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究

用一次投料法、单体乳液滴加法和引发剂滴加法有机硅改性丙烯酸酯共聚乳液，聚合过程、胶粒形态及乳液稳定性的观测结果表明：单体乳液滴加法是合成该类乳液的最佳方法，研究了单体乳液滴加法中有机硅含量与聚合反及胶膜性能的关系，结果表明：有机硅含量在１５％以下时，聚合反应可以顺利进行，胶膜性能不仅依赖于聚合时有机硅单体的总量，而且还依赖于有机硅单体中活性硅氧烷所占的比例。     

Emulsion polymerization of methyl methacrylate in the presence of novel addition–fragmentation chain‐transfer reactive surfactant (transurf)

Reactive surfactants allow the surfactant molecules to become covalently bound to the particles and thus provide added stability to the colloid particles, longer shelf life, better shear resistance, and polymer particles that can be redispersed. This article reports for the first time the use of a novel addition–fragmentation chain‐transfer reactive surfactant (transurf) in ab initio emulsion polymerizations of methyl methacrylate at 70 °C. It was found that the rate was lowered and average particle diameter nearly doubled when the transurf was used as compared with the SDS experiments (control). In addition the molecular weight distribution was very broad but had a lower Mn than observed in the sodium dodecyl sulfate experiment. Unfortunately because of the formation of many water‐soluble oligomers, the amount of transurf incorporated could not be obtained accurately. However, it was estimated theoretically that only a very small amount of transurf would be consumed, but for an alternative method to increase the incorporation of transurf into the particles, the ratio of monomer to transurf must be kept as low as possible. The best way to achieve this would be to carry the experiments out under starved‐feed conditions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2813–2820, 2001