Differently from bulk, solution, suspension, emulsion, and miniemulsion polymerizations, the controlled radical dispersion polymerization (CRDP) demonstrates self-assembly of the block copolymers formed in the homogeneous system, forming various kinds of micelles or vesicles. Thus, this technology can prepare both the block copolymers and the polymeric aggregates directly. Among CRDP, the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization has been studied in relative detail and has been successfully developed to prepare a diverse range of assemblies. Several typical systems for RAFT dispersion polymerization are presented in detail and the factors influencing the polymerization and the in situ self-assembly are also highlighted in this minireview.

The development of controlled/“living” polymerization greatly stimulated the prosperity of the fabrication and application of block copolymer nano-objects.

The self-assembly of block copolymers attracts wide interest due to many potential applications of the polymeric aggregates. Great effort has been made to realize the convenient fabrication of abundant polymeric materials with well-defined nanostructures. This review introduces the development of the in situ preparation of block copolymer aggregates by heterogeneous polymerization. Great emphasis is put on discussing the formation mechanism of aggregates with different morphologies. Some important factors that influence the morphologies are illustrated when different polymerization methods are employed. By demonstrating some recent advances and existing problems in this area, more attention and effort should be paid to this field to facilitate its further progress.

A facile and versatile method to prepare mesoporous core-shell nanostructures with a reversibly switchable nanoshell is reported. Reversible addition-fragmentation chain transfer (RAFT) functionalities were anchored to the exterior surface of mesoporous silica nanoparticles (MSNs), forming RAFT agent coated MSNs. RAFT polymerization was then conducted to graft a poly(acrylic acid) (PAA) shell onto the exterior surface of MSNs, producing novel smart nanocontainers with a MSN as the container and a pH-responsive PAA nanoshell as a smart nanovalve. The PAA nanovalve can control the access of guest molecules to and from the MSN nanocontainer. This core-shell nanostructure should have potential applications in drug and gene delivery.