Synthesis of Miktoarm Star-Shaped Polymers with POSS Core via a Combination of CuAAC Click Chemistry, ATRP, and ROP Techniques

DOĞANCI E., Tasdelen M. A., Yilmaz F.

MACROMOLECULAR CHEMISTRY AND PHYSICS, cilt.216, sa.17, ss.1823-1830, 2015 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 216 Sayı: 17
  • Basım Tarihi: 2015
  • Doi Numarası: 10.1002/macp.201500199
  • Dergi Adı: MACROMOLECULAR CHEMISTRY AND PHYSICS
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.1823-1830
  • Anahtar Kelimeler: arm-first, copper(I)-catalyzed 1, 3-dipolar cycloaddition click chemistry, core-first, miktoarm star-shaped polymers, polyhedral oligomeric silsesquioxanes, ring-opening polymerization, RING-OPENING POLYMERIZATION, POLYHEDRAL OLIGOMERIC SILSESQUIOXANE, TRANSFER RADICAL POLYMERIZATION, AZIDE-ALKYNE CYCLOADDITION, INCLUSION COMPLEXES, BETA-CYCLODEXTRIN, DIELS-ALDER, COPOLYMERS, 3-MIKTOARM, STYRENE
  • Kocaeli Üniversitesi Adresli: Evet

Özet

Well-defined AB-type miktoarm star-shaped polymers with a polyhedral oligomeric silsesquioxane (POSS) core are prepared by combination of the core-first and arm-first approaches using ring-opening polymerization (ROP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reactions. The clickable octakis-azido-hydroxyl-POSS as the core molecule and alkyne end-functionalized precursor polymers (methoxypoly(ethylene glycol), poly(methyl methacrylate) (PMMA), and polystyrene) are synthesized independently according to the well-known procedures including ring-opening reaction of octaglycidyldimethylsilyl POSS using sodium azide, etherification of poly(ethylene glycol) (PEG) monomethyl ether using propargyl bromide and sequential atom transfer radical polymerization of methyl methacrylate or styrene and following nucleophilic substitution reactions of the these polymers with sodium azide. In subsequent step, octa-armed poly(epsilon-caprolactone) star-shaped polymer ((PCL)(8)-POSS-(N-3)(8)) containing azido functionalities in the core is synthesized via core-first approach through ROP of epsilon-caprolactone (epsilon-CL). Finally, alkyne end-functionalized polymers are introduced to the (PCL)(8)-POSS-(N-3)(8) via arm-first approach using the CuAAC click reaction under ambient conditions, yielding AB-type miktoarm star-shaped polymers. Based on H-1 NMR spectroscopy calculations, the number of PEG, PMMA, and PSt arms in (PCL)(8)-POSS-(mPEG)(7), (PCL)(8)-POSS-(PMMA)(5), and (PCL)(8)-POSS-(PSt)(6) star-shaped polymers is found as 7.1, 4.9, and 5.9, respectively.