@article{MaticSchlaad2018,
  author    = {Matic, Aleksandar and Schlaad, Helmut},
  title     = {Thiol-ene photofunctionalization of 1,4-polymyrcene},
  series = {Polymer international},
  volume    = {67},
  journal   = {Polymer international},
  number    = {5},
  publisher = {Wiley},
  address   = {Hoboken},
  issn      = {0959-8103},
  doi       = {10.1002/pi.5534},
  pages     = {500 -- 505},
  year      = {2018},
  abstract  = {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},
  language  = {en}
}