Terpene-based amphiphilic copolymers have been designed as biobased stabilizers for waterborne latex synthesized by miniemulsion or emulsion polymerization of 1,3-diene terpene monomers. The pH-responsive P(AA--My) amphiphilic copolymers were synthesized by nitroxide-mediated radical copolymerization of β-myrcene (My) and acrylic acid (AA) with reactivity ratios of = 0.24 ± 0.06 and = 0.05 ± 0.10. Polymerization was controlled for My-rich monomer feed ratios ( > 0.3). Though AA NMP exhibited reasonable control, a low fraction of My ( ≤ 0.3) produced branched structures with higher molar masses. P(AA--My) was the most efficient copolymer to stabilize monomodal PMy latexes ( ∼ 150-350 nm) synthesized by miniemulsion or emulsion polymerization. P(AA--My) copolymers with a higher hydrophobic PMy fraction (>35 mol %) were less efficient stabilizers. The more hydrophobic β-farnesene monomer was successfully polymerized by miniemulsion polymerization, whereas emulsion polymerization failed. The biobased waterborne latexes are pH-responsive with pH-triggered flocculation at low pH.
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