Multilayered polymer particles. I. Synthesis of hydrophilic poly(dimethyl aminoethyl methacrylate) core particles (original) (raw)
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Journal of Applied Polymer Science, 2006
The evolution of the main colloidal parameters in the seeded starved-feed semi-continuous emulsion polymerization of butyl methacrylate (BMA) was investigated, with the main purpose of assessing the effectiveness of the semi-empirical relationship S ¼ K Á S S Á DA/A S as a tool to define the surfactant/monomer feed ratio (! K) best suited to achieve a target particle size. In particular, the effect of the type and amount of surfactant [i.e., anionic, sodium dodecyl sulfate (SDS), or nonionic, Brij 58P] added during the semi-continuous stage was considered. Coagulum formation was never observed under the adopted experimental conditions. To detect the occurrence of secondary nucleation or particle aggregation, or both, the particle size and number of particles, the surface tension and the particle surface cov-erage ratio were correlated. The best results were obtained with SDS and 0.8 K 3. In fact, under the selected experimental conditions, only with SDS did the number of particles remain nearly constant throughout the polymerization at the value defined by the seed latex; the particle size distribution was highly monodisperse, and the final particle diameter closely matched the calculated one ($ 120 nm). The above semi-empirical relationship based on the adjustable parameter K was validated by running test polymerizations aimed at lattices with well-defined particle size.
Journal of Applied Polymer Science, 2009
Monodisperse styrene/methyl methacrylate/acrylic acid (St/MMA/AA) copolymer microspheres have been prepared with surfactant-free emulsion polymerization in air. The presence of oxygen in the system not only caused an induction period but also decreased the average particle size (D p ). However increasing AA concentration ([AA]) gave a reduction in the induction period. The FTIR and NMR analysis of the latex copolymer confirmed that the correlation of the copolymer compositions with the feed compositions was much better at the lower [AA] than at the higher levels. The AA contents of the copolymers obtained in air were much lower than those of the copolymers obtained under N 2 protection.
Langmuir, 2007
Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). The surfmers were found to be miscible with the MMA-EA copolymer at room temperature, with 46-85 mol % of the reacted surfmer detected at the particle surfaces, and the remaining part buried in the particle bulk. In contrast, the NP100 surfactant formed a separate interphase between the copolymer particles with no mixing detected at room temperature or at 90 degrees C. For a 4.0% dry weight concentration, NP100 phase separated and further crystallized at room temperature over a period of several months. Composition fluctuations related to a limited blockiness on a length scale above approximately 2 nm were detected for PMMAEA particles, whereas the surfmer particles were found to be homogeneous also below this limit. On a particle-particle level, the dispersions tended to form colloidal crystals unless hindered by a broadened particle size distribution or, in the case of PMMAEA, by the action of NP100. Finally, a surface roughness (Rq) master plot was constructed for data above the glass transition temperature (Tg) from Tg + 11 degrees C to Tg + 57 degrees C and compared with the complex shear modulus over 11 frequency decades. Shift factors from the 2 methods obeyed the same Williams-Landel-Ferry (WLF) temperature dependence, thus connecting the long-time surface flattening process to the rheological behavior of the copolymer.
Journal of colloid and …, 2002
Following a previous work (J. L. Luna-Xavier et al., Colloid Polym. Sci. 279, 947 (2001)), silica-poly (methyl methacrylate) (PMMA) nanocomposite latex particles have been synthesized in emulsion polymerization using a cationic initiator, 2,2-azobis (isobutyramidine) dihydrochloride (AIBA), and a nonionic polyoxyethylenic surfactant (NP 30). Silica beads with diameters of 68, 230, and 340 nm, respectively, were used as the seed. Coating of the silica particles with PMMA was taking place in situ during polymerization, resulting in the formation of colloidal nanocomposites with a raspberry-like or a core-shell morphology, depending on the size and nature of the silica beads. The amount of surface polymer was quantified by means of ultracentrifugation and thermogravimetric analysis as extensively described in the first article of the series (see above reference). The influence of some determinant parameters such as the pH of the suspension, the initiator, silica, monomer, or surfactant concentration on the amount of coating polymer and on the efficiency of the coating reaction was investigated in details and discussed in light of the physicochemical properties of the seed mineral. Electrostatic attraction between the positive end groups of the macromolecules and the inorganic surface proved to be the driving force of the polymer assembly on the seed surface at high pH, while polymerization in adsorbed surfactant bilayers (so-called admicellar polymerization) appeared to be the predominant mechanism of coating at lower pH. Optimal conditions have been found to reach high encapsulation efficiencies and to obtain a regular polymer layer around silica.
Polymer, 2010
Three random and three block copolymers of methyl methacrylate (MMA) and octadecyl acrylate (ODA) were synthesized by atom transfer radical polymerization. These copolymers were assessed for their application as stabilizers in the one-step non-aqueous dispersion (NAD) polymerization of MMA and of acrylonitrile (AN) in a non-polar solvent mixture of hexane and dodecane. In all cases stable spherical micro-particle colloidal dispersions were formed with particle diameters in the range of 62e2725 nm for PMMA. Uniform monodisperse PMMA particles with standard deviations in size distributions of less than 5% were obtained in two cases demonstrating the utility of ODA:MMA copolymers as replacement preformed stabilizers in the one-step synthesis of MMA micro-spheres. Overall the block copolymer PMMA 64 -block-PODA 36 gave greater control over size when varying the solvent:monomer ration than a related gradient PMMAePODA copolymer. These copolymers were further used as stabilizers in the one-step NAD polymerization of MMA with ethylene glycol dimethacrylate (EGDMA) under similar conditions allowing for the preparation of monodisperse cross-linked PMMA particles with diameters ranging from 110 to 1700 nm. The general utility of the copolymers as stabilizers was demonstrated by the NAD polymerization of acrylonitrile (AN) in non-polar solvent mixture of hexane and dodecane giving 'crumpled' latex dispersions with particle diameters in the range 85e483 nm.
Polymer Bulletin, 2009
In the present work the synthesis and the chemical and thermal characterization of poly(methyl methacrylate-co-butyl methacrylate) copolymer, in three different macromolecular compositions, are reported. The aim of the present work was the identification of a standard method to obtain copolymers with controlled macromolecular composition, molecular weights and particle size distribution, together with the identification of the effect of the macromolecular composition on the material properties. A monomer-starved seeded semi-batch emulsion reaction was carried out and optimized, monitoring the kinetic of the copolymerization through the evaluation of residual monomer amounts. Then, an evaluation of the macromolecular composition was performed by Fourier transform infrared spectroscopy analysis. Molecular weight, molecular weight distribution, latex characteristics and thermal behaviour were also investigated.
Synthesis of ethylene and butyl methacrylate‐based copolymer by emulsion polymerization
Journal of Applied Polymer Science, 2019
The emulsion copolymerization of ethylene with butyl methacrylate (BMA) was carried out in an aqueous medium at 60 C under moderate reaction conditions. The polymer system is well controlled with a linear increase in the molecular weight (M n) versus ethylene feed pressure and narrow molecular weight distributions (>1.36) were observed throughout the copolymerization reaction. The spectroscopic analyses confirm the presence of acrylate functional as well as methylene group in the synthesized poly(ethylene-co-BMA) copolymer. Morphological behavior of poly(ethylene-co-BMA) has been studied using SEM and TEM analyses. Thermal stability of the copolymers was investigated by thermogravimetric analysis and it was observed that the copolymer is stable up to 380 C. X-ray diffraction analysis confirmed the amorphous behavior of poly(ethylene-co-BMA). Dynamic light scattering measurement confirms the formation of poly(ethylene-co-BMA) nanoparticles. The particle size of copolymer nanoparticles were in the range of 85-108 nm with low polydispersity indexes (>0.2). The viscous and the elastic property of the copolymer were investigated and established that at high temperature elastic behavior predominant over viscous effect.