Synthesis of an Inorganic-Organic Hybrid Material Based on Polyhedral Oligomeric Silsesquioxane and Polystyrene via Nitroxide-Mediated Polymerization and Click Reactions

Sinirlioglu D., Muftuoglu A. E.

DESIGNED MONOMERS AND POLYMERS, vol.14, no.3, pp.273-286, 2011 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 14 Issue: 3
  • Publication Date: 2011
  • Doi Number: 10.1163/138577211x557558
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.273-286
  • Yıldız Technical University Affiliated: No


Synthesis of an inorganic-organic hybrid polymeric material composed of polystyrene and polyhedral oligomeric silsesquioxane (POSS) was carried out via nitroxide-mediated polymerization (NMP) and Click reaction. First, 4-chloromethyl styrene was polymerized in bulk at 125 degrees C using AIBN and 4-hydroxy-TEMPO as the initiator and stable free radical, respectively. Reaction of poly(4-chloromethyl styrene) (PCMS) with NaN(3) in DMF yielded azide side-functional polystyrene. In the other step, acetylene functional POSS was obtained by Steglich esterification of 3-hydroxypropylheptaisobutyl-POSS, C(31)H(70)O(13)Si(8) (POSS-OH) and propiolic acid in the presence of N,N'-dicyclohexylcarbodiimide (DCC) and 4-dimethylamino pyridine (DMAP). Finally, Huisgen 1,3-dipolar cycloaddition between alkyne and azide functionalities afforded POSS side-chain functional polystyrene. The obtained hybrid polymer was characterized using (1)H-NMR, (29)Si-NMR, FT-IR, GPC and DSC. The DSC analysis showed that the T(g) of azide side-chain functional polystyrene (PS-N(3)) was enhanced by 14 degrees C upon POSS attachment. (C) Koninklijke Brill NV, Leiden, 2011