ORIGINAL CONTRIBUTION Influence of the third monomer on lauryl methacrylate–methyl methacrylate emulsion terpolymerization Rukhsana Shabnam & Abu M. I. Ali & Muhammad A. J. Miah & Klaus Tauer & Hasan Ahmad Received: 9 February 2013 / Revised: 23 March 2013 / Accepted: 27 March 2013 / Published online: 11 April 2013 # Springer-Verlag Berlin Heidelberg 2013 Abstract An experimental study shows how the emul- sion terpolymerization of lauryl methacrylate (LMA) and methyl methacrylate is influenced by the nature of the third monomer. The third monomer is either glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or styrene. We report the synthesis of terpolymer particles with an appreciably high content of the very hydrophobic LMA (between 0.2515 and 0.238 molar fraction in the monomer mixture) in 60:40 weight water/ethanol mixture as the continuous phase, poly(vinyl pyrrolidone) as a polymeric steric stabilizer, and potassium peroxodisulfate as the initiator. The emulsion terpolymerization proceeds smoothly with- out the formation of coagulum and leads to particles with an average diameter clearly below 1 μm. We discuss the overall polymerization behavior regarding conversion–time curves, particle morphology, and glass transition temperature of the terpolymers in dependence of the lyophilicity/lyophobicity of the monomer mixture. Keywords Emulsion copolymerization . Lauryl methacrylate . Rate of polymerization . Particle shape Introduction For several decades, emulsion polymerization is a matter of great attention and attraction in both the academia and the industry [1] because it is a convenient, effective, and simple method of preparing sub-micron-sized microspheres with var- iable surface characteristics evenly dispersed in the aqueous continuous phase. The simplest recipe for this kind of poly- merization includes water, monomers whose polymers are hydrophobic, initiators generating radicals with certain hydro- philicity, and, in many cases, surfactants. In ab initio batch polymerizations with lyophilic initiators, as considered here, moderately hydrophobic monomers such as styrene or methyl methacrylate are present as monomer drops which act as a monomer reservoir. After an initial period where polymeriza- tion is restricted to the continuous phase and particle forma- tion takes place, the main polymerization locus shifts to the interior of the latex particles. In the further course of polymer- ization, the monomer drops supply monomer to the monomer- swollen polymer particles by diffusion through the continuous phase. This brief description already illustrates the important role of both the solubility of the monomers in the continuous phase and the solubility of the polymers in the monomers. It is a matter of fact that emulsion polymerization cannot proceed smoothly if the solubility of the monomer(s) in the continuous phase is below a certain threshold [2, 3]. This prerequisite often limits the synthesis of extremely hydrophobic polymers via aqueous emulsion polymerization. However, for certain special applications such as resins for chromatographic sepa- ration, oil absorbency agents, viscosity modifiers, and oil- soluble drag reducers, it is highly desirable to increase the hydrophobicity of latex particles [4, 5]. But also for water- borne coatings, the hydrophobicity of the polymer particles is a crucial application property. Lauryl methacrylate (LMA) is one of the industrially important hydrophobic R. Shabnam : M. A. J. Miah : H. Ahmad (*) Department of Chemistry, University of Rajshahi, Rajshahi 6205, Bangladesh e-mail: samarhass@yahoo.com A. M. I. Ali Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, UK K. Tauer (*) Max Planck Institute of Colloid and Interfaces, 14424 Potsdam, Germany e-mail: klaus.tauer@mpikg.mpg.de Colloid Polym Sci (2013) 291:2111–2120 DOI 10.1007/s00396-013-2952-7