Preparation and Characterization of Silica/Polymer Hybrid Submicron Particles via a Semi-Continuous Soap-Free Emulsion Polymerization

Abstract:

Submicron hybrid particles were prepared by direct polymerization of three monomers of styrene, methyl methacrylate (MMA), and vinyl acetate (VAC) onto the hydrophilic surface of 230 nm silica submicron particles without any coupling agent in a semi-continuous emulsifier-free emulsion polymerization at a monomer starved condition. The polymerization was initiated by potassium persulfate with constant monomer feed at 0.01, 0.02, or 0.04 mL/min, after adding 230 nm silica seed particles. The particle growth was investigated with a laser particle size analyzer and SEM, and the particle surfaces by Fourier transform infrared spectroscopy (FT-IR). It was founded that the growth of the hybrid particles depended on the hydrophobic characteristics of the polymers. When monomer was the most hydrophobic styrene, polystyrene (PS) shells split off from the hydrophilic surface of the unmodified silica particle whenever the shells reached a limit of ~20 nm. However, both polymethyl methacrylate (PMMA) and polyvinyl acetate (PVAC) shells grew constantly on the hydrophilic surface of silica particles. In the process of the whole reaction, the SiO₂/PMMA and SiO₂/PVAC hybrid particles kept almost monodisperse.

• Periodical: Advanced Materials Research (Volumes 1120-1121)
• Pages: 225-232
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.1120-1121.225
• Online since: July 2015
• Authors: Joshua Qing Song Li*, Yan Qiu Wang, Hai Wang
• Keywords: Core-Shell, Emulsifier-Free, Emulsion Polymerization, Hybrid Submicron Particle

References

[1] H. Zou, S. Wu, J. Shen, Polymer/silica nanocomposites: preparation, characterization, properties, and applications, Chem. Rev. 108 (2008) 3893-3975.

DOI: 10.1021/cr068035q

[2] T. Wang, J.L. Keddie, Design and fabrication of colloidal polymer nanocomposites, Adv. Colloid Interface Sci. 147-148 (2009) 319-332.

DOI: 10.1016/j.cis.2008.06.002

[3] C.F. Lee, H.H. Tsai, L.Y. Wang, C.F. Chen, W.Y. Chiu, Synthesis and properties of silica/polystyrene/polyaniline conductive composite particles, J. Polym. Sci. Part A: Polym. Chem. 43 (2005) 342-354.

DOI: 10.1002/pola.20515

[4] A. L. Rogach, D. Nagesha, J. W. Ostrander, M. Giersig, N. A. Kotov,  Raisin bun, -type composite spheres of silica and semiconductor nanocrystals, Chem. Mater. 12 (2000) 2676-2685.

DOI: 10.1021/cm000244i

[5] C.P. Wong, R.S. Bollampally, Thermal conductivity, elastic modulus, and coefficient of thermal expansion of polymer composites filled with ceramic particles for electronic packaging, J. Appl. Polym. Sci. 74 (1999) 3396-3403.

DOI: 10.1002/(sici)1097-4628(19991227)74:14<3396::aid-app13>3.0.co;2-3

[6] C.L. Lu, C. Guan, Y. Liu, Y. Cheng, B. Yang, PbS/polymer nanocomposite optical materials with high refractive index, Chem. Mater. 17 (2005) 2448-2454.

DOI: 10.1021/cm050113n

[7] P. Barber, S. Balasubramanian, Y. Anguchamy, S. Gong, A. Wibowo, H. Gao, H.J. Ploehn, H. zur Loye, Polymer composite and nanocomposite dielectric materials for pulse power energy storage, Materials 2 (2009) 1697-1733.

DOI: 10.3390/ma2041697

[8] M.N. Tchoul, S.P. Fillery, H. Koerner, L.F. Drummy, F.T. Oyerokun, P.A. Mirau, M. F. Durstock, R.A. Vaia, Assemblies of titanium dioxide-polystyrene hybrid nanoparticles for dielectric applications, Chem. Mater. 22 (2010) 1749-1759.

DOI: 10.1021/cm903182n

[9] C. Barthet, A.J. Hickey, D.B. Cairns, S.P. Armes, Synthesis of novel polymer-silica colloidal nanocomposites via free-radical polymerization of vinyl monomers, Adv. Mater. 11 (1999) 408-410.

DOI: 10.1002/(sici)1521-4095(199903)11:5<408::aid-adma408>3.0.co;2-y

[10] G.H. Hsiue, J.K. Chen, Y.L. Liu, Synthesis and characterization of nanocomposite of polyimide-silica hybrid from nonaqueous sol-gel process, J. Appl. Polym. Sci. 76 (2000) 1609-1618.

DOI: 10.1002/(sici)1097-4628(20000613)76:11<1609::aid-app1>3.0.co;2-w

[11] H. Zou, S.P. Armes, Efficient synthesis of poly(2-hydroxypropyl methacrylate)-silica colloidal nanocomposite particles via aqueous dispersion polymerization, Polym. Chem. 3 (2012) 172-181.

DOI: 10.1039/c1py00406a

[12] J. Lee, C.K. Hong, S. Choe, S.E. Shim, Synthesis of polystyrene/silica composite particles by soap-free emulsion polymerization using positively charged colloidal silica, J. Colloid Interface Sci. 310 (2007) 112-120.

DOI: 10.1016/j.jcis.2006.11.008

[13] P.J. Colver, C.A.L. Colard, S.A.F. Bon, Multilayered nanocomposite polymer colloids using emulsion polymerization stabilized by solid particles, J. Am. Chem. Soc. 130 (2008) 16850-16851.

DOI: 10.1021/ja807242k

[14] Y. Xia, B. Gates, Y. Yin, Y. Lu, Monodispersed colloidal spheres: old materials with new applications, Adv. Mater. 12 (2000) 693-713.

DOI: 10.1002/(sici)1521-4095(200005)12:10<693::aid-adma693>3.0.co;2-j

[15] Y.C. Chen, C.C. Tsai, Y.D. Lee, Preparation and properties of silylated PTFE/SiO2 organic-inorganic hybrids via sol-gel process, J. Polym. Sci. Part A: Polym. Chem. 42 (2004) 1789-1807.

DOI: 10.1002/pola.20033

[16] S. Reculusa, C. Mingotaud, E. Bourgeat-Lami, E. Duguet, S. Ravaine, Synthesis of daisy-shaped and multipod-like silica/polystyrene nanocomposites, Nano. Lett. 4 (2004) 1677-1682.

DOI: 10.1021/nl049161h

[17] J. L. Luna-Xavier, A. Guyot, E. Bourgeat-Lami, Synthesis and characterization of silica/poly (methyl methacrylate) nanocomposite latex particles through emulsion polymerization using a cationic azo initiator, J. Colloid Interface Sci. 250 (2002).

DOI: 10.1006/jcis.2002.8310

[18] I. Sondi, T.H. Fdeynyshyn, R. Sinta, E. Matijevic, Encapsulation of nanosized silica by in situ polymerization of tert-butyl acrylate monomer, Langmuir 16 (2000) 9031-9034.

DOI: 10.1021/la000618m

[19] V. Monteil, J. Stumbaum, R. Thomann, S. Mecking, Silica/poly ethylene nanocomposite particles from catalytic emulsion polymerization, Macromolecules 39 (2006) 2056-(2062).

DOI: 10.1021/ma052737k

[20] L. Yang, Y. Luo, B. Li, Batch-semi-batch two-stage RAFT mini-emulsion polymerization of styrene, J. Chem. Ind. Eng. (China) 59 (2008) 2149-2155.

[21] M.J. Percy, C. Barthet, J.C. Lobb, M.A. Khan, S.F. Lascelles, M. Vamvakaki, S.P. Armes, Synthesis and characterization of vinyl polymer-silica colloidal nanocomposites, Langmuir 16 (2000) 6913-6920.

DOI: 10.1021/la0004294

[22] M. Chen, L. Wu, S. Zhou, B. You, Synthesis of raspberry-like PMMA/SiO2 nanocomposite particles via a surfactant-free method, Macromolecules 37 (2004) 9613-9619.

DOI: 10.1021/ma048431f

[23] S.W. Zhang, S.X. Zhou, Y.M. Weng, L.M. Wu, Synthesis of SiO2/polystyrene nanocomposite particles via miniemulsion polymerization, Langmuir 21 (2005) 2124-2128.

DOI: 10.1021/la047652b

[24] J. Li, R. Salovey, Continuous, emulsifier-free emulsion polymerization for the synthesis of monodisperse polymeric latex particles, J. Polym. Sci. Part A: Polym. Chem. 38 (2000) 3181-3187.

DOI: 10.1002/1099-0518(20000901)38:17<3181::aid-pola170>3.0.co;2-5