Competing Interfacial and Hydrotrope-like Behavior of Co-Surfactants in Miniemulsion Copolymerization
Zoriana Demchuk1,2, Tetiana Shevtsova1, Bohdan Domnich1
1Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, North Dakota58102, United States.
Langmuir : the ACS Journal of Surfaces and Colloids
|August 11, 2026
Summary
Cosurfactants linalool (LO) and benzyl acetate (BAc) influence miniemulsion polymerization differently. Benzyl acetate promotes successful latex formation, while linalool leads to polymerization issues.
Area of Science:
- Polymer Chemistry
- Colloid Science
- Materials Science
Background:
- Miniemulsion polymerization relies on stabilized droplets as nucleation sites.
- Understanding cosurfactant behavior is crucial for controlling polymerization outcomes.
Purpose of the Study:
- To investigate the distinct molecular redistribution pathways of linalool (LO) and benzyl acetate (BAc) in miniemulsion polymerization.
- To determine how these pathways affect nucleation and particle formation during copolymerization.
Main Methods:
- Studied miniemulsion copolymerization of styrene (St) and a soybean oil-based acrylic monomer (HOSBM) using sodium dodecyl sulfate (SDS) with varying LO and BAc fractions.
- Assessed interfacial activity of LO and BAc in model systems under different mixing regimes.
- Analyzed latex formation, monomer conversion, particle size distribution, and coagulum formation.
Main Results:
- Replacing up to 70 wt % SDS with BAc yielded successful latex, high conversion, and monomodal distribution.
- Increased LO fractions resulted in reduced conversion, coagulum, and bimodal distribution.
- LO exhibited hydrotrope-like behavior, creating competing nucleation sites, while BAc partitioned into the styrene phase, supporting droplet templating.
Conclusions:
- Cosurfactant redistribution pathways significantly impact miniemulsion polymerization.
- BAc supports droplet-templated polymerization, leading to desirable outcomes.
- LO's hydrotrope-like behavior can disrupt polymerization, necessitating careful selection of cosurfactants.
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