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1,4-Polymyrcene was synthesized by anionic polymerization of -myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, ethyl 2-mercaptopropionate and 2-methyl-2-propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4-polymyrcene decreased in the order 1 degrees thiol (ca 95%) > 2 degrees thiol (ca 80%) > 3 degrees thiol (<5%), due to the reversibility of the thiol-ene reaction. Remarkably, thiol addition to the side-chain double bonds was 8 - 10 times (1 degrees thiol) or 24 times (2 degrees thiol) faster than to the main-chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10-fold excess of thiol with respect to myrcene units, the thiol-ene addition was accompanied by chain coupling reactions, which in the extreme case of 3 degrees thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl-thioglycolate-functionalized 1,4-polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. (c) 2018 Society of Chemical Industry