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  • This article was downloaded by: [Universitat Politcnica de Valncia]On: 29 October 2014, At: 02:27Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

    Designed Monomers and PolymersPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/tdmp20

    Synthesis of an InorganicOrganicHybrid Material Based onPolyhedral OligomericSilsesquioxane and Polystyrenevia Nitroxide-MediatedPolymerization and ClickReactionsDeniz Sinirlioglu a & Ali Ekrem Muftuoglu ba Department of Chemistry, Fatih University,Buyukcekmece, Istanbul 34500, Turkeyb Department of Chemistry, Fatih University,Buyukcekmece, Istanbul 34500, Turkey;, Email:amuftuoglu@fatih.edu.trPublished online: 02 Apr 2012.

    To cite this article: Deniz Sinirlioglu & Ali Ekrem Muftuoglu (2011) Synthesis of anInorganicOrganic Hybrid Material Based on Polyhedral Oligomeric Silsesquioxane andPolystyrene via Nitroxide-Mediated Polymerization and Click Reactions, DesignedMonomers and Polymers, 14:3, 273-286

    To link to this article: http://dx.doi.org/10.1163/138577211X557558

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    http://www.tandfonline.com/page/terms-and-conditionshttp://www.tandfonline.com/page/terms-and-conditions

  • Designed Monomers and Polymers 14 (2011) 273286brill.nl/dmp

    Synthesis of an InorganicOrganic Hybrid Material Basedon Polyhedral Oligomeric Silsesquioxane and Polystyrene via

    Nitroxide-Mediated Polymerization and Click Reactions

    Deniz Sinirlioglu and Ali Ekrem Muftuoglu

    Department of Chemistry, Fatih University, Buyukcekmece, Istanbul 34500, Turkey

    AbstractSynthesis of an inorganicorganic hybrid polymeric material composed of polystyrene and polyhedraloligomeric silsesquioxane (POSS) was carried out via nitroxide-mediated polymerization (NMP) andClick reaction. First, 4-chloromethyl styrene was polymerized in bulk at 125C using AIBN and 4-hydroxy-TEMPO as the initiator and stable free radical, respectively. Reaction of poly(4-chloromethylstyrene) (PCMS) with NaN3 in DMF yielded azide side-functional polystyrene. In the other step, acety-lene functional POSS was obtained by Steglich esterification of 3-hydroxypropylheptaisobutyl-POSS,C31H70O13Si8 (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 andazide functionalities afforded POSS side-chain functional polystyrene. The obtained hybrid polymer wascharacterized using 1H-NMR, 29Si-NMR, FT-IR, GPC and DSC. The DSC analysis showed that the Tg ofazide side-chain functional polystyrene (PS-N3) was enhanced by 14C upon POSS attachment. Koninklijke Brill NV, Leiden, 2011

    KeywordsInorganicorganic hybrid polymeric material, POSS, NMP, Click reaction

    1. Introduction

    Inorganicorganic hybrid materials are a promising class of polymeric compos-ites, since hybrid properties can well be adopted by the careful adjustment of theinorganicorganic composition. The key parameter in tuning the macroscopic prop-erties is undoubtedly the extent of dispersion of the inorganic content in a givenpolymer matrix, i.e., how well the corresponding phases are mixed in the nanome-ter scale. Mechanical blending is a simple and inexpensive technique. However, thematerials thus obtained exhibit phase separation and aggregation of the inorganicmaterial, which limits the physical properties and, hence, the utility of the compos-ite [1].

    * To whom correspondence should be addressed. Fax: (90-212) 866-3402; e-mail: amuftuoglu@fatih.edu.tr

    Koninklijke Brill NV, Leiden, 2011 DOI:10.1163/138577211X557558

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  • 274 D. Sinirlioglu, A. E. Muftuoglu / Designed Monomers and Polymers 14 (2011) 273286

    One way to obtain nanocomposites is to blend polyhedral oligomeric silsesquiox-ane (POSS) groups with a polymer, since these nanocages with dimensions of about12 nm are supposed to be the smallest cage-like molecules [28]. However, a bet-ter approach is considerably the covalent linking of these POSS entities to polymerchains, since this will restrict POSS aggregation. In this manner, chain interac-tions and chain mobility are altered, possibly enhancing physical properties, suchas strength, modulus and thermal stability.

    A current technique to achieve a POSS-incorporated polymer is the co-polymeri-zation of POSS carrying monomers with other appropriate monomers or the homo-polymerization of the sole POSS monomer provided that steric hindrance effect ofthe POSS constituent is avoided via the insertion of a spacer chain. Among the poly-mers obtained by this approach are polystyrene, polymethacrylate, polyurethanes,polysiloxane and epoxies [921].

    Haddad et al. studied the mechanical properties of several POSS containingpolystyrenes and found that at temperatures above the glass transition the mod-uli were significantly higher depending on the type of corner alkyl groups ofPOSS [10]. Song et al. as well explored the thermal and mechanical properties ofPOSS-polystyrene nanocomposites. They found a 10C increase in the Tg value for3 wt% POSS content. They also observed simultaneous increase in tensile strength,elongation-at-break, elastic modulus and impact strength values when comparedwith pure polystyrene [13].

    Recently, Click chemistry, coined by Sharpless and co-workers [22], has gainedincreasing interest in synthetic polymer chemistry due to its high selectivity andquantitative reaction yields besides its mild reaction conditions including toleranceto solvent, and a wide variety of functional groups. Among the Click reactions,Huisgen 1,3-dipolar cycloaddition occurring between alkyne and organic azide toafford 1,2,3-triazole has attracted a great deal of research activity [2333]. Whencombined with controlled polymerization methods, quite a number of architectures,such as graft co-polymers, stars, H-shape, hyperbranched and dendritic polymers,have been obtained [3443].

    We herein report the synthesis of inorganic/organic hybrid material composed ofpolystyrene and heptaisobutyl-POSS via nitroxide-mediated polymerization (NMP)and Click reactions. By this approach, we present a model study on achieving poly-meric nanocomposites in a post-polymerization process based on highly selectiveHuisgen 1,3-dipolar cycloaddition reactions.

    2. Experimental

    2.1. Materials

    3-Hydroxypropylheptaisobutyl-POSS (C31H70O13Si8, 95%), 2,2-Azobis(2-methylpropionitrile) (AIBN, 98%), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO, 97%), N ,N ,N ,N ,N -pentamethyldiethylenetriamine(PMDETA, 99%), N ,N -dicyclohexylcarbodimide (DCC, 99%), 4-dimethylamino

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  • D. Sinirlioglu, A. E. Muftuoglu / Designed Monomers and Polymers 14 (2011) 273286 275

    pyridine (DMAP, 99%), copper(I) bromide and sodium azide were all purchasedfrom Aldrich and used as received. 4-Chloromethylstyrene (CMS) was purchasedfrom Aldrich and distilled over CaH2 under decreased pressure prior to use.Propiolic acid was purchased from Merck and used as received. Toluene anddichloromethane were purified by distillation over CaH2 under decreased pres-sure. Tetrahydrofuran (THF), methyl alcohol and N ,N -dimethylformamide werepurchased from Fluka and used without further purification.

    2.2. Characterization

    FT-IR spectra were obtained using a Bruker Alpha-P in ATR in the range of 4004000 cm1. 1H-NMR and 29Si-NMR spectra were recorded on a Bruker AM 400instrument in CDCl3. Chemical shifts are reported in ppm relative to TMS asinternal standard. Multiplicities are described using the following abbreviations:s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet and br = broad.Perkin Elmer JADE differential scanning calorimetry (DSC) was used to investi-g

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