Polymerization of Myrcene in Both Conventional and Renewable Solvents: Postpolymerization Modification via Regioselective Photoinduced Thiol–Ene Chemistry for Use as Carbon Renewable Dispersants

[Image: see text] Polymeric dispersants are useful materials used in many different industries and often derived from oil-based chemicals, for example, in automotive fluids so as to prevent particulates from precipitation and causing potential damage. These are very often polyisobutene derivatives, and there is a growing need to replace these using chemicals using renewable resources such as the use of naturally occurring myrcene. Polymyrcene (PMy), with an ordered microstructure, has been successfully synthesized via both anionic and radical polymerization in different solvents and subsequently subjected to functionalization via photoinduced thiol–ene click reactions with a number of thiols, methyl thioglycolate, 3-mercaptopropionic acid, 3-mercapto-1-hexanol, 2-mercaptoethanol, and 1-thioglycerol, using 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator under UV irradiation (λ = 365 nm) at ambient temperature. The polarity of the solvent has an important impact on the microstructure of the produced polymyrcene and, in particular, 1,2-unit (∼4%), 3,4-unit (∼41%), and 1,4-unit (∼51%) PMy were obtained via anionic polymerization in a polar solvent (THF) at ambient temperature, while 3,4-unit (∼6%) and 1,4-unit (∼94%, including cis and trans) PMy were obtained with cyclohexane as the solvent. Subsequently, photochemical thiol–ene reactions were carried out on the resulting PMy with different isomers exhibiting different reactivities of the double bonds. This strategy allows for the introduction of functional/polar groups (−COOH, −OH) into hydrophobic PMy in a controlled process. Hydrogenation of PMy and derivatized PMy was carried out to investigate any effects on the stabilities of the products which are desirable for many applications.