Thiol‐ene emulsion polymerization using a semi‐continuous approach

• Published in: Canadian journal of chemical engineering Vol. 101; no. 9; pp. 5270 - 5280
• Main Authors: Wenzel, Fabian, Larrañaga, Urko, Aguirre, Miren, Leiza, Jose R.
• Format: Journal Article
• Language: English
• Published: Hoboken, USA John Wiley & Sons, Inc 01.09.2023
• Subjects: adhesives; batch versus semibatch; emulsion polymerization; nucleation mechanism; thiol‐ene polymerization
• ISSN: 0008-4034; 1939-019X
• DOI: 10.1002/cjce.24925

The thermally initiated thiol‐ene emulsion polymerization of diallyl phthalate (DAP) diene and ethylenedioxy diethanthiol (EDDT) dithiol monomers in batch and semibatch emulsion polymerization is investigated. The batch process leads to larger and broader particle sizes than when the polymerization is carried out in semibatch. The evolution of the particle size and the final particle size distribution indicate that the stability of the latexes is limited and, hence, aggregation phenomena occurred in both processes. In particular, the evolution of the particle size distribution (PSD) in the semibatch process indicates nucleation, growth, and aggregation occurring simultaneously that produced a bimodal particle size. When the diene monomer was changed to diallyl terephthalate (DATP), the semibatch polymerization yielded smaller particles and narrow distribution without any indication of aggregation. The partial substitution of the dithiol by a trithiol monomer that is substantially more water insoluble affected nucleation of the particles, yielding for both systems smaller particles. The polythioether polymers synthesized present low glass transition temperatures (~ −30/−40°C) and those containing the therephthalate yield crystalline films. The potential application of the polymers as pressure sensitive adhesives (PSAs) was preliminarily assessed. Batch and semibatch thiol‐ene emulsion polymerization of diallyl phthalate (DAP) diene and ethylenedioxy diethanthiol (EDDT) dithiol monomers was evaluated. The batch process leads to larger and broader particle sizes than when the polymerization is carried out in semibatch.