Mechanical and morphological properties of waterborne ABA hard-soft-hard block copolymers synthesized by means of RAFT miniemulsion polymerization

High molecular weight waterborne ABA block copolymers of styrene (St) and 2-ethylhexyl acrylate (2EHA) containing hard and soft domains were synthesized by means of RAFT (mini)emulsion polymerization using a bifunctional symmetric S,S-dibenzyl trithiocarbonate (DBTTC) RAFT agent. Miniemulsion polyme...

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Detalles Bibliográficos
Autores: Petreska, G. S., Arbe, Arantxa, Auschra, Clemens, Paulis, Maria
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2019
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/203967
Acceso en línea:http://hdl.handle.net/10261/203967
Access Level:acceso abierto
Palabra clave:RAFT
Miniemulsion polymerization
ABA hard-soft-hard block copolymers
Particle and film morphology
Films viscoelastic properties
Temperature responsiveness
Descripción
Sumario:High molecular weight waterborne ABA block copolymers of styrene (St) and 2-ethylhexyl acrylate (2EHA) containing hard and soft domains were synthesized by means of RAFT (mini)emulsion polymerization using a bifunctional symmetric S,S-dibenzyl trithiocarbonate (DBTTC) RAFT agent. Miniemulsion polymerization was initially used for the synthesis of the A-block, which forms hard domains, followed by 2EHA pre-emulsion feeding to build the B-block soft domains. Polymerization kinetics and the evolution of the MolecularWeight Distribution (MWD) were followed during the synthesis of different ABA block copolymers. The thermal properties of the final symmetric block copolymers were studied on dried films by means of DSC. It was found that the block copolymers have two glass transitions, which indicates the presence of a two-phase system. Phase separation was investigated by means of microscopic techniques (AFM and TEM) and SAXS, both of the particles in the latex form, as well as after film formation at room temperature and after different post-treatments. Films were annealed at temperatures well above the glass transition temperature (T) of the hard phase to study the bulk morphology of the films after complete particle coalescence. Moreover, for comparison purposes, the films were re-dissolved in THF, and films were again cast directly from the homogeneous THF solutions. As THF is a good solvent for both blocks, such films serve as a reference for the equilibrium morphology. Finally, DMTA studies of the films annealed at different temperatures were performed to correlate the morphology changes with the mechanical properties of the block copolymers.