Fabrication of polymeric-Laponite composite hollow microspheres via LBL assembly

Hollow structure microspheres with composite polymeric-Laponite shells were prepared by electrostatic self-assembly of Laponite on the polymeric hollow microspheres in this work.The multilayer hydrophilic core/hydrophobic shell polymer latex particles containing carboxyl groups inside were first synthesized via seeded emulsion polymerization,followed by alkali treatment,generating polymeric hollow microspheres.Then,polyethyleneimine（PEI） and Laponite were alternately electrostatic adsorbed on the prepared polymeric hollow microspheres to form polymeric-Laponite composite hollow microspheres.It was indicated that the morphology of alkali-treated microspheres could be tuned through simply altering the dosage of alkali used in the post-treatment process.Along with the increasing of the coating layers,the zeta potential of microspheres absorbed PEI or Laponite approximately tended to be constant respectively,and the thickness of Laponite layer around the hollow microspheres increased clearly,getting more uniform and homogenous.Furthermore,the corresponding polymeric-Laponite hollow microspheres showed high pressure resistance ability compared to the polymeric hollow microspheres.

Effects of Shell Composition, Dosage and Alkali Type on the Morphology of Polymer Hollow Microspheres

Polymer hollow microspheres were prepared by performing alkali treatment on the multilayer core/shell polymer latex particles containing carboxyl groups. Effects of the shell composition and dosage as well as alkali type on the morphology of the microspheres were investigated. Results showed that in comparison with acrylonitrile（AN） and methacrylic acid（MAA）, using butyl acrylate（BA） as the shell co-monomer decreased the glass transition temperature（T_g） of shell effectively and was beneficial to the formation of uniform and big hollow structure. Along with the increase of the shell dosage, the alkali-treated microspheres sequentially presented porous and hollow morphology, and the size of microspheres increased, while the hollow diameter increased first and then decreased, and the maximum hollow ratio reached 39.5%. Furthermore, the multilayer core/shell microspheres had better tolerance to NH_3·H_2O than to NaOH. When the molar ratio of alkali to methacrylic acid（MR_（alkali/acid）） for Na OH ranged from 1.15 to 1.30 or MRalkali/acid for NH_3·H_2O ranged from 1.30 to 2.00, the regular polymer hollow microspheres could be obtained.