Particle Nucleation and Growth in the Emulsion Polymerization of Styrene: Effect of Monomer/Water Ratio and Electrolyte Concentration

This work is an extension of previous research results reported by our team (Colloid and Polymer Science 2013, 291: 2385-2398), where large scale and high solid content latexes of poly(n-butyl acrylate) were obtained with the particle coagulation method induced by the electrolyte. However, how to prepare controlled particle size distribution polymer latex has not been studied. Thus, in this study, the effect of the monomer/water ratios and electrolyte concentrations on particle formation and growth methods were studied by following the tracks of the evolutions of particle size, number and distribution as a function of reaction time or conversion. Experimental results showed that the length of time that particle nucleation occurred increased with increasing monomer charged for the systems without electrolyte. A point worthy of attention here is that homogeneous nucleation may occur at high monomer concentrations (30/70, 40/60). However, electrolyte added could be made the nucleation mechanism shift from micellar/homogeneous nucleation to micelle /coagulation nucleation. As a result, the final particle size distribution can be controlled by adding an appropriate electrolyte to regulate the nucleation mechanism. Spherical and uniformly sized particles could be obtained when electrolyte concentration is between 0.2 wt% and 0.4 wt% for water at the high monomer/water ratio (40/60). The effects of electrolyte concentration on nucleation mechanism mainly were expressed by decreasing the solubility of the monomer and interparticle potential, and then preventing homogeneous nucleation and enhancing particle coagulation.

[1]  Mingyao Zhang,et al.  Effect of aqueous phase composition on particle coagulation behavior in batch emulsion polymerization of styrene , 2014 .

[2]  Tetsuya Yamamoto Synthesis of nearly micron-sized particles by soap-free emulsion polymerization of methacrylic monomer using an oil-soluble initiator , 2013, Colloid and Polymer Science.

[3]  Mingyao Zhang,et al.  Synthesis of monodisperse, large scale and high solid content latexes of poly(n-butyl acrylate) by a one-step batch emulsion polymerization , 2013, Colloid and Polymer Science.

[4]  Zhiyong Li,et al.  Mechanism of Narrowly Dispersed Latex Formation in a Surfactant-Free Emulsion Polymerization of Styrene in Acetone–Water Mixture , 2012 .

[5]  K. Landfester,et al.  Influence of size and functionality of polymeric nanoparticles on the adsorption behavior of sodium dodecyl sulfate as detected by isothermal titration calorimetry , 2011 .

[6]  J. Herrera‐Ordonez,et al.  On the Evolution of the Rate of Polymerization, Number and Size Distribution of Particles in Styrene Emulsion Polymerization Above CMC , 2010 .

[7]  M. Jonker,et al.  Using solid phase micro extraction to determine salting-out (Setschenow) constants for hydrophobic organic chemicals. , 2010, Chemosphere.

[8]  Oğuz Balci,et al.  Size controlled synthesis of sub-100 nm monodisperse poly(methylmethacrylate) nanoparticles using surfactant-free emulsion polymerization. , 2010, Journal of colloid and interface science.

[9]  G. Mohr,et al.  Ratiometric pH-nanosensors based on rhodamine-doped silica nanoparticles functionalized with a naphthalimide derivative. , 2009, Journal of colloid and interface science.

[10]  T. McKenna,et al.  New routes to high solid content latexes: A process for in situ particle nucleation and growth , 2004 .

[11]  K. Kataoka,et al.  Surface plasmon resonance study on the interaction between lactose-installed poly(ethylene glycol)-poly(D, L-lactide) block copolymer micelles and lectins immobilized on a gold surface , 2002 .

[12]  A. Jakubowska,et al.  Effect of electrolytes on the physicochemical behaviour of sodium dodecyl sulphate micelles , 2002 .

[13]  L. Park,et al.  Synthesis and properties of agglomerating agent for high‐solids NBR latices , 2002 .

[14]  M. Nagai,et al.  Study of particle growth by seeded emulsion polymerization accompanied by electrostatic coagulation , 2002 .

[15]  Henmei Ni,et al.  Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine: Characteristics of Reaction in the Monomer Phase, Aqueous Phase, and Their Interface , 2001 .

[16]  B. Brooks,et al.  Unseeded semibatch emulsion polymerization of butyl acrylate: Bimodal particle size distribution , 2000 .

[17]  Andrew Klein,et al.  Emulsion polymerization of styrene using reaction calorimeter. II. Importance of maximum in rate of polymerization , 1999 .

[18]  Andrew Klein,et al.  Emulsion polymerization of styrene using reaction calorimeter. III. Effect of initial monomer/water ratio , 1999 .

[19]  C. Petcu,et al.  Notes: Polymer-Water Interaction in Emulsion Copolymerization of Vinyl Acetate , 1998 .

[20]  E. Sudoł,et al.  Role of the nonionic surfactant Triton X‐405 in emulsion polymerization. III. Copolymerization of styrene and n‐butyl acrylate , 1997 .

[21]  Shi-Yow Lin,et al.  Emulsion polymerization of styrene stabilized by mixed anionic and nonionic surfactants , 1997 .

[22]  I. Capek,et al.  Microemulsion polymerization of butyl acrylate. IV: Effect of emulsifier concentration , 1995 .

[23]  J. Meuldijk,et al.  Influence of disproportionated rosin acid soap on the emulsion polymerization kinetics of styrene , 1995 .

[24]  D. H. Napper,et al.  Coagulative nucleation and particle size distributions in emulsion polymerization , 1984 .

[25]  D. H. Napper,et al.  The mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate , 1983 .

[26]  F. K. Hansen,et al.  Particle nucleation in emulsion polymerization. IV. Nucleation in monomer droplets , 1979 .

[27]  John Ugelstad,et al.  Particle nucleation in emulsion polymerization. I. A theory for homogeneous nucleation , 1978 .

[28]  W. D. Harkins,et al.  A general theory of the mechanism of emulsion polymerization. , 1947, Journal of the American Chemical Society.