Miniemulsion polymerization of methyl methacrylate with dodecyl mercaptan as cosurfactant

Miniemulsions of methyl methacrylate with sodium lauryl sulfate as the surfactant and dodecyl mercaptan (DDM) as the cosurfactant (or hydrophobe) were prepared and polymerized. The emulsions were of a droplet size range common to miniemulsions and exhibited long-term stability (greater than 3 months). Results indicate that DDM retards Ostwald ripening and allows the production of stable miniemulsions. When these emulsions were initiated, particle formation occurred predominantly by monomer droplet nucleation. The effects of the concentration of surfactant, cosurfactant and initiator were determined. Rates of polymerization, monomer droplet sizes, polymer particle sizes, molecular weights of the polymer, and the effect of initiator concentration on the number of particles vary systematically in ways that indicate predominant droplet nucleation in these systems. © 1996 John Wiley & Sons, Inc.     

Starved Semi-Batch Emulsion Polymerization for Polystyrene Nanolatexes Preparation With n-Pentanol as Cosurfactant

In the starved semi-batch emulsion polymerization, the n-pentanol was predissolved in the sodium dodecyl sulfate (SDS) solution as cosurfactant, for the purpose of polystyrene nanolatexes preparation. The effects of styrene (St) monomer feeding rate, n-pentanol dosage and SDS concentration on the monomer conversion (total and instantaneous conversions), the latex particles size (average volume diameter, d_v) and the latex particles number in a unit volume (N_p) were discussed. The function of n-pentanol not only debased the surface tension of the SDS solution, but also formed the smaller nanolatex particles size. With the 1.5 wt% n-pentanol dosage, 0.8 wt% SDS concentration and 6.0 mL/h St feeding rate for 6 h, the d_v and N_p of the final latex particles were 45.1 nm and 8.52×10¹⁵/ mL, respectively. The final latex solid content was 24.1%. All results were original and available compared to the state of the art.     

Cosurfactant effects on the microemulsion polymerization of styrene

The polymerization of styrene in o/w microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB) with or without cosurfactant (n-butanol, n-hexanol or n-octanol) is examined here. The addition of a cosurfactant enhances the one-phase region in the order: n-butanol > n-hexanol > n-octanol. The kinetics of polymerization slows down in the presence of the alcohol. With the alcohol, the molar masses increase, but no particular trend was noticed on particle size of the lattices. However, by changing the surfactant counter-ion to chloride, alcohol effects on the kinetics almost vanish. Possible explanations to these results are given here. To cite this article: J.E. Puig et al., C. R. Chimie 6 (2003).     

Studies of cyclohexane/TX 100 + ethylpropionate/water system: effect of ethylpropionate as cosurfactant

 Pseudoternary phase diagram of cyclohexane/TX 100-ethylpropionate/water system was determined at 30 ^°C. One phase microemulsion was obtained over a small area. The surfactant/cosurfactant ratio was both kept at 1:1 and 1:2 w/w. Viscosity, conductance, adiabatic compressibility values at various temperatures show the expected trend. The addition of NaCl changes one phase microemulsion to Winsor II system and no Winsor III system was obtained. Contact angle data, conductance, etc., show oil continuous system at a constant surfactant weight fraction. The microstructure of Winsor IV microemulsion seems to be W/O. Received: 14 May 1996 Accepted: 23 October 1996     

Kinetic model for reactivity in quaternary water-in-oil microemulsions

A study was carried out on the nitrosation of piperazine (PIP) and N-methylbenzylamine (MeBzAm) by N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in quaternary microemulsions of tetradecyltrimethylammonium bromide (TTABr)/isooctane/alcohol/water, varying the nature and the concentration of the following alcohols: 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol keeping the [1-alcohol]/[TTABr] = 4 relationship constant. In addition a study was carried out on the influence of the alcohol concentration, working with molar relationships [1-hexanol]/[TTABr]=3, 4 and 5. On the basis of the molar volumes of the alcohol and surfactant and the concentration of alcohol at the interface it was possible to calculate the change in its volume with as varying compositions of the microemulsion. In order to interpret the experimental results a kinetic model was devised which takes into account the distribution of the reactants between the different pseudophases and the change in the volume of the interface. The rate constants at the interface of the microemulsion are lower than in pure water and are independent of the nature of the alcohol used as a cosurfactant and the molar relationship [alcohol]/[TTABr]. This independence indicates that the main role of the cosurfactant is to increase the volume of the interface with the consequent dilution of the reactants.     

Kinetics of the microemulsion polymerization of styrene with short‐chain alcohols as the cosurfactant

The kinetics of styrene microemulsion polymerization stabilized by sodium dodecyl sulfate (SDS) and a series of short‐chain alcohols (n‐C_iH_2i+1OH, abbreviated as C_iOH, where i = 4, 5, or 6) at 60 °C was investigated. Sodium persulfate was used as the initiator. The microemulsion polymerization process can be divided into two intervals: the polymerization rate (R_p) first increases to a maximum at about a 20% conversion (interval I) and thereafter continues to decrease toward the end of the polymerization (interval II). For all the SDS/C_iOH‐stabilized polymerization systems, R_p increases when the initiator or monomer concentration increases. The average number of free radicals per particle is smaller than 0.5. The molecular weight of the polymer produced is primarily controlled by the chain‐transfer reaction. In general, the reaction kinetics for the polymerization system with C₄OH as the cosurfactant behaves quite differently from the kinetics of the C₅OH and C₆OH counterparts. This is closely related to the different water solubilities of these short‐chain alcohols and the different concentrations of the cosurfactants used in the preparation of the microemulsion. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 898–912, 2001     

A Visible Spectroscopic Study of Microstructure of O/W Microemulsions of Anionic Surfactants: Effect of Cosurfactant

The microstructure of o/w microemulsions, stabilized by sodium dodecyl benzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS) with different cosurfactants, has been studied by partitioning of a dye, phenol red, between the oil‐water interface and bulk water. The cosurfactants used are propan‐1‐ol, propan‐2‐ol, butan‐1‐ol, butan‐2‐ol, pentane‐1‐ol, pentane‐2‐ol, and pentan‐3‐ol. The effects of changing the oil volume fraction and surfactant‐cosurfactant w/w ratio on the oil‐water interface and droplet size have also been discussed. Larger droplet size was predicted for SDS than SDBS. The predicted droplet radius increased with increase in the oil fraction, decrease in the surfactant concentration, increase in the C‐number of the linear cosurfactant, and decrease in branching of the cosurfactant. Surfactant‐cosurfactant ratio and pH did not affect the droplet size significantly. The minimum concentrations of surfactants with which microemulsions were formed were found to be higher for larger oil fraction, smaller C‐number of the alcohol, more branching of the alcohol, and higher pH.     

Effect of Addition of Cosurfactant on the Phase Behaviour of Oil-in-water Aminosilicone Oil Microemulsion

Stable and transparent aminosilicone oil microemulsion of the average particle size below 0.05 micron was prepared. The interaction of the aminosilicone oil, water, complex surfactants and cosurfactant was studied by part pseudotemary phase diagram. The effect of cosurfactants (such as alcohol) and the mechanism of its effect on the phase behaviour of the pseudotemary system were investigated.     

醇的链长对微乳状液形成的影响

本文研究了醇对非离子型表面活性剂ＡＥＯ９［Ｃ１２Ｈ２５Ｏ（Ｃ２Ｈ４Ｏ）９ＯＨ］、正庚烷、水体系形成微乳液的影响。通过四组分的拟三元相图，得到各体系的微乳区。结果表明，当醇的链长不同时，体系的微乳区的类型及面积均不同。其中，丁醇体系的微乳区面积最大，它比Ｂａｎｓａｌ－Ｓｈａｈ－Ｏ＇ｃｏｎｎｅｌ相关方程的结果少一个碳原子。     

Synergistic Effect of Mixed Cosurfactants on Transdermal Delivery of Indomethacin from O/W Microemulsion

Since large amounts of oils, surfactants and penetration enhancers used in microemulsion systems might lead to seriously skin irritation, the percutaneous absorption and penetration of indomethacin(IMC, model drug) from O/W microemulsion were enhanced by simply changing the composition of cosurfactants. Pseudo-ternary phase diagrams were constructed with mixed cosurfactants at different ratios. Hairless rat skin was used as a barrier for permeation experiments. Four formulations were prepared with fixed oil, surfactant and different cosurfactant content(4%, 20% and 20%, mass fraction), and formulation F4 with menthol added was evaluated to compare the enhancement effect of it with those of mixed cosurfactants. The O/W microemulsion region was the largest when the mass ratio of ethanol/transcutol was 1:1. However, the region changed slightly for the system with incorporated mixed cosurfactants propylene glycol/transcutol. The flux and skin retention of IMC from O/W microemulsion with mixed cosurfactants were much higher than that with single cosurfactant(P<0.01), while incorporation of menthol would only enhance the drug flux through the skin. To conclude, mixed cosufactants could affect the phase behavior and improve the percutaneous absorption and penetration of IMC. Based on this, it provided a promising solution to enhance drug release from microemulsions without raising potential skin damage.