Abstract
The polymerization of several alkyl methacrylates in nanoemulsions made by the phase inversion temperature method is presented here. The temperature versus surfactant concentration fish-like phase diagrams for a fixed mixture of alkyl methacrylate/squalane (SQ) of 95/5 w/w, Brij 56 and water were elaborated. Reaction rates were extremely fast (ca. 100% conversion in less than 3 min), and only two reaction rate intervals were observed, which is typical of nanoemulsion polymerization. It suggests that chain transfer to monomer is the main termination mechanism. The addition of squalane inhibits monomer diffusion from small droplets to larger ones and prevents the diffusion of monomer from non-reacting droplets to reacting ones, which guarantees that each monomer droplet acted as a nanoreactor. Polymer particles have similar size than the original nanoemulsion droplets indicating that the nanodroplets act as templates for the formation of the polymer nanoparticles. Reaction rates, as well as kinetics and nanoparticle characterizations by quasielastic light scattering (QLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC), are reported. Spheroidal nanoparticles with similar sizes and narrow distribution were observed by TEM for poly(ethyl methacrylate), poly(butyl methacrylate), and poly(hexyl methacrylate). The large molar masses and the narrow molar mass distributions were obtained by gel permeation chromatography.
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References
Mailänder V, Landfester K (2009) Interaction of nanoparticles with cells. Biomacromolecules 10:2379–2400. https://doi.org/10.1021/bm900266r
Pankhurst QA, Connolly J, Jones SK, Dobson J (2003) Applications of magnetic nanoparticles in biomedicine. J Phys D Appl Phys 36:R167–R181. https://doi.org/10.1088/0022-3727/36/13/201
Hawker CJ, Wooley KL (2005) The convergence of synthetic organic and polymer chemistries. Science 309:1200–1205. https://doi.org/10.1126/science.1109778
Jang J, Bae J, Ko S (2005) Synthesis and curing of poly(glycidyl methacrylate) nanoparticles. J Polym Sci A Polym Chem 43:2258–2265. https://doi.org/10.1002/pola.20706
Carrillo A, Yanjarappa MJ, Gujraty KV, Kane RS (2006) Biofunctionalized block copolymer nanoparticles based on ring-opening metathesis polymerization. J Polym Sci Part A: Polym Chem 44:928–939. https://doi.org/10.1002/pola.21219
Tagne JB, Kakumanu S, Ortiz D, Shea T, Nicolosi R (2008) A nanoemulsion formulation of tamoxifen increases its efficacy in a breast cancer cell line. Mol Pharm 5:280–286. https://doi.org/10.1021/mp700091j
Striegler S (2009) Emulsion and miniemulsion polymers in catalysis. Mini-Rev Org Chem 6:234–240. https://doi.org/10.2174/157019309788922757
Wang X, Summers CJ, Wang ZL (2004) Large-scale hexagonal-patterned growth of aligned ZnO nanorods for nano-optoelectronics and nanosensor arrays. Nano Lett 4:423–426. https://doi.org/10.1021/nl035102c
Jang J (2006) Conducting polymer nanomaterials and their applications. In: Klemm D (ed) Emissive materials nanomaterials. Springer Verlag Berlin Heidelberg, Germany, pp. 189–260
Jang J, Oh JH (2005) Fabrication of a highly transparent conductive thin film from polypyrrole/poly(methyl methacrylate) core/shell nanospheres. Adv Funct Mater 15:494–502. https://doi.org/10.1002/adfm.200400095
Zhao J, Yang F, Chen Z, Diao H, Chu F, Yu S, Lu J (2008)) Microemulsion polymerization of cationic pyrroles bearing an imidazolum-ionic liquid moiety. J Polym Sci Part A Chem Ed 47:746–753. https://doi.org/10.1002/pola.23190
Chern CS (2008) Principles and applications of emulsion polymerization. Wiley, Hoboken,
Puig JE, Mendizábal E, López-Serrano F, López RG (2012) In: Somasundaram P (ed) Encyclopedia of surface and colloid science. Taylor and Francis, New York,
Crespy D, Landfester K (2010) Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers. Beilstein J Org Chem 6:1132–1148. https://doi.org/10.3762/bjoc.6.130
Rao JP, Geckeler KE (2011) Polymer nanoparticles: preparation techniques and size-control parameters. Prog Polym Sci 36:887–913. https://doi.org/10.1016/j.progpolymsci.2011.01.001
Galindo-Alvarez J, Boyd D, Marchal P, Tibet C, Perrin P, Marie-Bégué E, Durand A, Sadlter V (2011) Miniemulsion polymerization templates: a systematic comparison between low energy emulsification (near-PIT) and ultrasound emulsification methods. Colloids Surf A Physicochem Eng Asp 374:134–141. https://doi.org/10.1016/j.colsurfa.2010.11.019
Alvarado-Mendoza AG, Nolla J, Rabelero M, Pérez-Carrillo LA, Arellano M, Mendizábal E, Solans C, Puig JE (2013) Poly(hexyl methacrylate) nanoparticles templating in nanoemulsions-made by phase inversion temperature. J Macromol Sci Part A: Pure Appl Chem 50:385–391. https://doi.org/10.1080/10601325.2013.768119
Schork FJ, Luo Y, Smulder W, Russum JP, Butté A, Fontenot K (2005) Miniemulsion polymerization. In: Okubo M (ed) Polymer particles. Springer-Verlag Berlin Heidelberg, Heidelberg, pp. 129–255
Zhang J, Han B, Zhang C, Li W, Feng X (2008) Nanoemulsions induced by compressed gases. Angew Chem Int Ed 47:3012–3015. https://doi.org/10.1002/anie.200705362
Zhao Y, Zhang J, Li W, Zhang C, Han B (2009) Synthesis of uniform hollow silica spheres with ordered mesoporous shells in a CO2 induced nanoemulsion. Chem Comm 17:2365–2367. https://doi.org/10.1039/B822375K
Morales D, Gutierrez JM, García-Celma MJ, Solans YC (2003) A study of the relation between bicontinuous microemulsions and oil/water nano-emulsion formation. Langmuir 19:7196–7200. https://doi.org/10.1021/la0300737
Salager JL (1988) In: Betcher P (ed) Encyclopedia of emulsion technology, vol 3. Marcel Dekker, New York, pp. 79–134
Sole I, Maestro A, González C, Solans C, Gutiérrez JM (2006) Optimization of nano-emulsion preparation by low-energy methods in an ionic surfactant system. Langmuir 22:8326–8332. https://doi.org/10.1021/la0613676
Wang L, Mutch KJ, Esstoe J, Heenan RK, Dong J (2008) Nanoemulsions prepared by a two-step low-energy process. Langmuir 24:6092–6099. https://doi.org/10.1021/la800624z
Lamaallam S, Bataller H, Dicharry C, Lachaise J (2005) Formation and stability of miniemulsions produced by dispersion of water/oil/surfactants concentrates in a large amount of water. Coll Surf A 270-271:44–51. https://doi.org/10.1016/j.colsurfa.2005.05.035
Nishimi T, Miller CA (2000) Spontaneous emulsification of oil in aerosol-OT/water/hydrocarbon systems. Langmuir 16:9233–9241. https://doi.org/10.1021/la0006521
Chen S, Guo Y, Zetterlund PB (2010) Miniemulsion polymerization based on low energy emulsification with preservation of initial droplet identity. Macromolecules 43:7905–7907. https://doi.org/10.1021/ma101574x
Spernath L, Magdassi S (2007) A new method for preparation of poly-lauryl acrylate nanoparticles from nanoemulsions obtained by the phase inversion temperature process. Polym Adv Tech 18:705–711. https://doi.org/10.1002/pat.947
Alvarado AG, Pérez-Carrillo LA, Arellano M, Rabelero M, Ceja I, Mendizábal E, Solans C, Esquena J, Puig JE (2013) Polymerization of hexyl methacrylate in nanoemulsions made by low and high energy methods. J Macromol Sci Part A: Pure Appl Chem 50:812–820. https://doi.org/10.1080/10601325.2013.802147
Hutchinson RA, Beuermann S, Paquet Jr DA, McMinn JH (1997) Determination of free-radical propagation rate coefficients for alkyl Methacrylates by pulsed-laser polymerization. Macromolecules 30:3490–3493. https://doi.org/10.1021/ma970176u
Kunieda H, Shinoda KJ (1985) Evaluation of the hydrophile-lipophile balance (HLB) of nonionic surfactants. I. Multisurfactant systems. Colloid Interface Sci 107:107–121. https://doi.org/10.1016/0021-9797(85)90154-7
Kahlweit M, Strey R, Firman P, Hasse D, Jen J, Schomaker R (1998) General patterns of the phase behavior of mixtures of water, nonpolar solvents, amphiphiles, and electrolytes 1. Langmuir 4:499–511. https://doi.org/10.1021/la00081a002
Andrews RJ, Grulke EA (1999) In: Brandrup J, Immergut EH, Grulke EA (eds) Polymer handbook, vol I. 4th edn. Wiley, Hoboken, pp. VI/193–VI/277
Capek I, Juraničová V (1998) On the free-radical microemulsion polymerization of alkyl methacrylates. Eur Polym J 34:783–788. https://doi.org/10.1016/S0014-3057(97)00196-1
Ovando-Medina VM, Corona-Rivera MA, Márquez-Herrera A, Lara-Cisneros TE, Manríquez-González R, Peralta RD (2014) Heterophase polymerization of different methacrylates: effect of alkyl ester group on kinetics and colloidal behavior. J Appl Polym Sci 131:1–8. https://doi.org/10.1002/app.40191
Morgan JD, Lusvardi KM, Kaler EW (1997) Kinetics and mechanics of microemulsion polymerization of hexyl methacrylate. Macromolecules 30:1897–1905. https://doi.org/10.1021/ma9613704
Katime I, Arellano J, Mendizábal E, Puig J (2001) Synthesis and characterization of poly(n-hexyl methacrylate) in three-component microemulsions. Eur Polym J 37:2273–2279. https://doi.org/10.1016/S0014-3057(01)00122-7
Jansen TGT, Meuldijk J, Lovell PA, Van Herk AM (2016) On the polymerization of very hydrophobic monomers initiated by a completely water-insoluble initiator: thermodynamics, kinetics and mechanism. J Polym Sci Part A: Polym Chem 54:2731–2745. https://doi.org/10.1002/pola.28155
Jašo V, Radičević R, Stoiljković D (2010) Analysis of DSC curve of dodecyl methacrylate polymerization by two-peak deconvolution method. J Therm Anal Calorim 101:1059–1063. https://doi.org/10.1007/s10973-009-0594-2
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This study was funded by Universidad de Guadalajara (grant # UDG-P3E-235161).
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Alvarado, A.G., Hernández-Montelongo, R., Rabelero, M. et al. Polymerization of alkyl methacrylate nanoemulsions made by the phase inversion temperature method. Colloid Polym Sci 295, 2243–2249 (2017). https://doi.org/10.1007/s00396-017-4194-6
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DOI: https://doi.org/10.1007/s00396-017-4194-6