SYNTHESIS OF MONODISPERSE HOLLOW POLYMER MICROSPHERES WITH FUNCTIONAL GROUPS BY DISTILLATION PRECIPITATION POLYMERIZATION

Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.

A review of recent progress in preparation of hollow polymer microspheres

The preparation methods of hollow polymer microspheres both at home and abroad are summarized, and their preparation mechanisms and developmental states are presented. These methods include the liquid droplet method, dried-gel droplet method, self-assembly method, microencapsulation method, emulsion polymerization method and the template method. Hollow polystyrene microspheres are the most extensively studied in the research of hollow polymer microspheres. Through comparison of the advantages and disadvantages of different preparation methods, it is concluded that microencapsulation method is most suitable for preparing polystyrene hollow microspheres.

PREPARATION OF SILICA/POLY(METHACRYLIC ACID)/POLY(DIVINYLBENZENE-CO-METHACRYLIC ACID) TRI-LAYER MICROSPHERES AND THE CORRESPONDING HOLLOW POLYMER MICROSPHERES WITH MOVABLE SILICA CORE

Hollow poly（divinylbenzene-co-methacrylic acid） （P（DVB-co-MAA）） microspheres were prepared by the selective dissolution of the non-crosslinked poly（methacrylic acid） （PMAA） mid-layer in ethanol from the corresponding silica/PMAA/P（DVB-co-MAA） tri-layer hybrid microspheres, which were afforded by a three-stage reaction. Silica/PMAA core-shell hybrid microspheres were prepared by the second-stage distillation polymerization of methacrylic acid （MAA） via the capture of the oligomers and monomers with the aid of the vinyl groups on the surface of 3-（methacryloxy）propyl trimethoxysilane （MPS）-modified silica core, which was prepared by the Stober hydrolysis as the first stage reaction. The tri-layer hybrid microspheres were synthesized by the third-stage distillation precipitation copolymerization of functional MAA monomer and divinylbenzene （DVB） crosslinker in presence of silica/PMAA particles as seeds, in which the efficient hydrogen-bonding interaction between the carboxylic acid groups played as a driving force for the construction of monodisperse hybrid microspheres with tri-layer structure. The morphology and the structure of silica core, silica/PMAA core-shell particles, the tri-layer hybrid microspheres and the corresponding hollow polymer microspheres with movable silica cores were characterized by transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy （XPS）.

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.