Microgels graft copolymerization

Temperature- and pH-sensitive core-shell microgels consisting of a PNIPAAm core crosslinked with BIS and a polyvinylamine (PVAm) shell were synthesized by graft copolymerization in the absence of surfactant and stabilizer [106] The core-shell morphology of the microgels was confirmed by TEM and zeta-potential measurements. Other examples of core-shell microgel systems are PNIPAAm-g-P(NIPAM-co-styrene) colloids [107] or PS(core)-g-PNIPAAm (shell) particles [108],... 

Indicating that only physically adsorbed layers exist. An obvious consequence is that the dispersed oligomers or microgel particles in the matrix phase near the silane layers will modify the properties of the matrix, which forms the interphase. The modes of polymerization of the matrix resin are either a graft copolymerization at the surface of the particles, a random co-polymerizatlon with the silane, or interpenetrating network formation. Similar considerations can be extended to the more tightly bound silane layers. 

Yin et al. [73,74] prepared new microgel star amphiphiles and stndied the compression behavior at the air-water interface. Particles were prepared in a two-step process. First, the gel core was synthesized by copolymerization of styrene and divinylbenzene in diox-ane using benzoylperoxide as initiator. Microgel particles 20 run in diameter were obtained. Second, the gel core was grafted with acrylic or methacryUc acid by free radical polymerization, resulting in amphiphilic polymer particles. These particles were spread from a dimethylformamide/chloroform (1 4) solution at the air-water interface. tt-A cnrves indicated low compressibility above lOmNm and collapse pressnres larger than 40 mNm With increase of the hydrophilic component, the molecnlar area of the polymer and the collapse pressure increased. 

Different architectures, such as block copolymers, crosslinked microparticles, hyperbranched polymers and dendrimers, have emerged (Fig. 7.11). Crosslinked microparticles ( microgels ) can be described as polymer particles with sizes in the submicrometer range and with particular characteristics, such as permanent shape, surface area, and solubility. The use of dispersion/emulsion aqueous or nonaqueous copolymerizations of formulations containing adequate concentrations of multifunctional monomers is the most practical and controllable way of manufacturing micro-gel-based systems (Funke et al., 1998). The sizes of CMP prepared in this way vary between 50 and 300 nm. Functional groups are either distributed in the whole CMP or are grafted onto the surface (core-shell, CS particles). 

Reactive microgels are crosslinked polymer particles which have a diameter of some 100 A and contain pendant reactive groups like vinyl groups. Such microgels may be copolymerized with bifunctional monomers to obtain crosslinked polymers in which the microgel particles act as multifunctional cross-linking sites (J ). In some respects such crosslinked polymers are comparable with other multiphase polymer systems like block or graft polymers. 

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