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Synthesis of an Inorganic–OrganicHybrid 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 anInorganic–Organic Hybrid Material Based on Polyhedral Oligomeric Silsesquioxane andPolystyrene via Nitroxide-Mediated Polymerization and Click Reactions, DesignedMonomers and Polymers, 14:3, 273-286

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Designed Monomers and Polymers 14 (2011) 273–286brill.nl/dmp

Synthesis of an Inorganic–Organic 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 inorganic–organic 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 125◦C 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 14◦C upon POSS attachment.© Koninklijke Brill NV, Leiden, 2011

KeywordsInorganic–organic hybrid polymeric material, POSS, NMP, Click reaction

1. Introduction

Inorganic–organic hybrid materials are a promising class of polymeric compos-ites, since hybrid properties can well be adopted by the careful adjustment of theinorganic–organic 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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One way to obtain nanocomposites is to blend polyhedral oligomeric silsesquiox-ane (POSS) groups with a polymer, since these nanocages with dimensions of about1–2 nm are supposed to be the smallest cage-like molecules [2–8]. 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 [9–21].

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 10◦C 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 [23–33]. 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 [34–43].

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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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 400–4000 cm−1. 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-gate the thermal transitions of the samples. The samples (approx. 10 mg) were filledinto aluminum pans and then heated to the desired temperature at a rate of 10◦C/minunder a nitrogen atmosphere. The glass transition temperatures were taken as themidpoint of the capacity change. In the measurements, Tg was taken from the sec-ond scans. Gel-permeation chromatography (GPC) measurements were performedon THF solutions of the polymers using an Agilent GPC 1100 instrument. Themeasurements were standardized against THF solutions of polystyrene standards.

2.3. Synthesis of Alkyne-Terminated Polyhedral Oligomeric Silsesquioxane(POSS-Alkyne)

POSS (0.1 g, 1.14 × 10−4 mol) was dissolved in CH2Cl2 (5 ml). Propiolic acid(11 µl, 1.71 × 10−4 mol), DCC (38 mg, 1.82 × 10−4 mol) and DMAP (2.3 mg,1.82 × 10−5 mol) were added to the solution, which was then allowed to stir atroom temperature for 2 days. After several extractions with water, dichloromethanewas removed in a rotary evaporator. The final product was obtained in reddishcolor. It was kept 48 h in a vacuum oven at 40◦C for further use (78% yield).FT-IR (cm−1): 3323 (–C≡CH, alkyne asymmetric C–H stretching), 2948 (aliphaticC–H stretching), 2864 (aliphatic C–H stretching), 2123 (–C≡CH, alkyne asymmet-ric C–H stretching), 1719 (ester C=O stretching), 1457, 1231 (asymmetric esterC–O bending), 1095 (Si–O–Si bending). 1H-NMR (CDCl3, ppm, δ): 4.08–4.02(t, 2H, SiCH2CH2CH2–OCOCCH), 2.56 (s, 1H, SiCH2CH2CH2–OCOC≡CH),1.82–1.75 (m, 2H, SiCH2CH2CH2–OCOCCH), 1.62 (m, 1H, –CH2CH(CH3)2)from R groups, 1.29 (d, 2H, CH2CH(CH3)2) from R groups, 0.91 (d, 6H,CH2CH(CH3)2) from R groups, 0.81–0.77 (t, 2H, Si–CH2CH2CH2–OCOCCH).29Si-NMR (CDCl3, ppm, δ): −108.3.

2.4. Synthesis of p-Chloromethylstyrene (PCMS)

p-Chloromethylstyrene (4-vinylbenzyl chloride) (6.8 ml, 0.0483 mol), 4-hydroxy-TEMPO (97 mg, 5.62 × 10−4 mol) and AIBN (46 mg, 2.81 × 10−4 mol) were

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placed into a Schlenk tube. After three freeze–pump–thaw cycles, the flask wasplaced in an oil bath at 125◦C, and kept there for 9 h. After the given time, themixture was diluted with THF, and the polymer was precipitated in a 10-fold ex-cess volume of methanol. The solid was then collected after filtration and dryingat 40◦C under reduced pressure overnight (conversion 58%). FT-IR T % (cm−1):3026 (aromatic C–H stretching), 2920 (aliphatic C–H stretching), 2849 (aliphaticC–H stretching), 1680, 1612 (aromatic C=C stretching), 1506, 1428, 822, 670.1H-NMR (CDCl3, ppm, δ): 6.99–6.41 (br, 4H, from aromatic rings), 4.46 (br, 2H,–CH2–Cl). GPC: Mn 15 400 g/mol, PDI: 1.33.

2.5. Preparation of Azide Side-Functional Polystyrene (PS-N3)

PCMS (3 g, 0.01967 mol) and NaN3 (1.66 g, 0.0256 mol) were dissolved in 90 mlDMF in a Schlenk tube. The solution was allowed to stir at 25◦C for 2 days. Af-ter this period, DMF was removed in a rotary evaporator and the remaining solidwas dissolved in CH2Cl2. The solution was extracted three times with distilledwater to remove excess NaN3. Finally, the polymer was precipitated in 10-fold ex-cess methanol, collected by vacuum filtration, and kept 24 h at 50◦C in a vacuumoven for drying before analysis (87% yield). FT-IR T % (cm−1): 3026 (aromaticC–H stretching), 2925 (aliphatic C–H stretching), 2864 (aliphatic C–H stretching),2090 (azide –N3 asymmetric stretching), 1680, 1607 (aromatic C=C stretching),1512, 1433, 820, 710. 1H-NMR (CDCl3, ppm, δ): 6.90–6.48 (br, 4H, from aromaticrings), 4.17 (br, 2H, –CH2–N3). GPC: 16 100 g/mol; PDI: 1.34.

2.6. Synthesis of Polystyrene Containing Pendent POSS Cages via Click Reaction

PS-N3 (0.0129 g, 8 × 10−7 mol), POSS-alkyne (0.080 g, 8 × 10−5 mol), CuBr(0.115 g, 8 × 10−4 mol), PMDETA (115 µl, 8 × 10−4 mol) and 30 ml CH2Cl2were placed in a reaction balloon with a magnetic bar. The mixture was bubbledwith nitrogen for 20 min and stirred for 2 days at room temperature. After thereaction, the mixture was further diluted with CH2Cl2 and passed through a basicalumina column to remove the catalyst. The product was precipitated in 10-foldexcess methanol 3 times, filtered and dried at 40◦C in a vacuum oven for 48 h (96%yield). FT-IR T % (cm−1): 3023 (aromatic C–H stretching), 2925 (aliphatic C–Hstretching), 2863 (aliphatic C–H stretching), 1715 (ester C=O stretching), 1680,1607 (aromatic C=C stretching), 1517, 1438, 1349, 1248 (asymmetric ester C–Obending), 1113 (Si–O–Si bending), 810, 726. 1H-NMR (CDCl3, ppm, δ): 7.57 (s,1H, from triazole ring), 6.90–6.48 (b, 4H, aromatic ring) 5.23 (s, 2H, –CH2–N3).29Si-NMR (CDCl3, ppm, δ): −108.3, GPC: Mn 27 200 g/mol, PDI: 1.39.

3. Results and Discussion

Alkyne-terminated POSS (POSS-alkyne) was prepared by the esterification be-tween 3-hydroxypropyl heptaisobutyl-POSS and propiolic acid in the presenceof DCC/DMAP. This reaction, so-called Steglich esterification, is depicted inScheme 1.

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Scheme 1. Synthesis of alkyne-terminated polyhedral oligomeric silsesquioxane (POSS-alkyne).

Figure 1. The 1H-NMR spectrum of alkyne-terminated POSS (POSS-alkyne).

The 1H-NMR spectrum of alkyne-POSS is shown in Fig. 1. The signals at4.08 (c), 2.55 (d), 1.82 (b) and 0.81 (a) ppm are assigned, respectively, to the res-onance of (–SiCH2CH2CH2O–, –SiCH2CH2CH2OCOCCH, –SiCH2CH2CH2–,–SiCH2CH2CH2–) methylene, methine and methylene protons from POSS. Thesignals at 1.62 (k), 1.29 (m) and 0.91 (n) ppm belong to the resonance of(–CH2CH(CH3)2, –CH2–CH(CH3)2, –CH2–CH(CH3)2) methine, methylene andmethyl protons originating in the R-groups from the POSS cage.

In addition, compared to the FT-IR spectrum of POSS, two new bands appearat 3323 and 2123 cm−1 in the spectrum of POSS-alkyne, which are assigned tothe stretching vibration of the alkyne group as depicted in Fig. 2. The band at1719 cm−1 is due to the formation of ester group. Also, the FT-IR spectrum hasa strong peak around 1095 cm−1 originating from Si–O–Si groups of POSS. Basedon the results of 1H-NMR and FT-IR, POSS-alkyne was prepared successfully.

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Figure 2. The FT-IR spectrum of alkyne-terminated POSS (POSS-alkyne).

PCMS was obtained with 58% conversion in 9 h via NMP of the monomerin bulk using AIBN and hydroxy-TEMPO [44–46]. The GPC analysis yieldedMn,GPC: 15 400 g/mol with a PDI of 1.33. This is in good agreement with themolecular weight determined from 1H-NMR, Mn,H-NMR (15 600 g/mol), and thetheoretical molecular weight, Mn,theo (15 300 g/mol), calculated using the follow-ing equation:

M̄n,theo = [M0][I0] (Mw)(conversion) + MI,

where M0 and I0 are the initial molar concentrations of monomer and initiator, andMw and MI are the molecular weights of the monomer and initiator, respectively.

Reaction of PCMS with NaN3 in DMF at room temperature yielded azide side-functional polystyrene (PS-N3; Scheme 2). The chloride atoms in each repeatingunit were quantitatively transformed into azide groups via nucleophilic substitution.

In the 1H-NMR spectrum of PS-N3, the signal at 4.46 ppm corresponding toCH2–Cl protons of the PCMS completely shifted to 4.17 ppm, which arose fromprotons of –CH2 linked to azide groups, as seen in Fig. 3. The FT-IR spectral analy-sis also supports this result. A sharp peak at 2090 cm−1 appears, due to the existenceof azide groups in the spectrum of PS-N3 (Fig. 4).

Finally, the Click coupling between the azide side-functional polystyrene andalkyne-POSS afforded POSS-containing inorganic–organic hybrid polystyrene asillustrated in Scheme 3. After the reaction, the mixture dissolved in CH2Cl2 waspassed through a basic alumina column to remove the catalyst, and the polymer was

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Scheme 2. Synthesis of azide side-functional polystyrene (PS-N3).

precipitated in excess methanol 3 times to assure complete removal of the unreactedPOSS. Since POSS-alkyne was quite soluble in methanol, pure hybrid polymer wasthe sole precipitate, and was obtained with a 96% yield. The 29Si-NMR spectrumof the product, therefore, gave a strong evidence of the existence of POSS moietiesin the resulting hybrid. In Fig. 5, the 29Si-NMR spectra of POSS, POSS-alkyne andthe hybrid polystyrene are compared. The signal appearing at −108.3 ppm in allPOSS-containing compounds clearly proves POSS attachment to PS.

The 1H-NMR spectrum of the Click product is shown in Fig. 6. The appearanceof the signals at 7.57 (h) and 5.23 (i) ppm, regarding the methine proton and themethylene protons adjacent to the triazole ring, respectively, indicates the triazoleformation. This proves that a Click reaction occurred between azide and alkynefunctionalities. However, the peak at 4.17 (e) ppm (br, 2H, –CH2–N3) remainingfrom the initial PS-N3 indicates that some azide functions were not involved in theclicking process. From the ratio of integrals of peaks at 5.23 (i) and 4.17 (e) ppmit can be concluded that approximately one in every 3 repeating units carries thePOSS functionality in the resulting nanohybrid. This is quite reasonable when thesteric hindrance effect of the POSS is considered [47, 48]. The efficiency of POSSfunctionalization can further be increased upon introducing longer spacer groups.

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Figure 3. The 1H-NMR spectra of (a) PCMS and (b) PS-N3.

Figure 4. The FT-IR spectra of (a) PCMS and (b) PS-N3.

Further evidence was provided by FT-IR analysis. The FT-IR spectra confirm theClick reaction, as the azide stretching band at around 2090 cm−1 is reduced and anew peak at 1113 cm−1 arising from the stretching vibration of Si–O–Si appears.

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Scheme 3. Synthesis of POSS-containing inorganic–organic hybrid polystyrene by Click reaction.

The triazole units show several medium or strong peaks in the 1438–1680 cm−1

range due to C=N linkage while C–N vibrations and the aliphatic C–H stretchingwere observed at 1349–1438 and 2800–3000 cm−1 regions, respectively (Fig. 7).

The molecular weights of the polymers were determined by GPC using monodis-perse polystyrene standards. All the traces are symmetrical and unimodal. As seenin Fig. 8, the GPC trace of PS-N3 shifted to lower retention time after Click reac-tion with POSS-alkyne signifying successful incorporation of the POSS moietiesto the PS backbone. Number average molecular weight, Mn, of POSS-alkyne andthe resulting inorganic–organic hybrid polymer were found to be 1200 (PDI 1.18)and 27 200 (PDI 1.39), respectively. A mass increase of 11 100 amu, which corre-sponds to nearly 9 POSS units, was determined from GPC analysis. However, asmentioned previously, 1H-NMR results imply an increase of approx. 33 000 amuwhen the actual molar mass of POSS (1000 g/mol) is taken, considering that onePOSS was linked in every 3 repeating units of PS and that the degree of polymer-ization is around 100. Since the molecular weight values of the polymers obtainedby GPC are relative and not absolute values, 1H-NMR results are more reliable.

The thermal properties of azide side-functional polystyrene and its POSS hybridwere studied using DSC. DSC curves showed a single glass transition for both sam-

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Figure 5. The 29Si-NMR spectra of (a) POSS, (b) POSS-alkyne and (c) polystyrene bearing pendentPOSS cages.

ples, as shown in Fig. 9. The Tg values were taken as the midpoint of the capacitychange. It was observed that the Tg of PS-N3 increased by 14◦C in the final PS–POSS hybrid. This observation is similar to those reported by Haddad [9], Mather[49] and Xu [50, 51]. The Tg improvement mechanism may be explained on the ba-sis of inter- and/or intra-chain POSS–POSS interaction, which physically governslocal polymer chain motion [50].

In conclusion, an inorganic–organic hybrid polymer composed of POSS andpolystyrene was synthesized by the successful attachment of alkyne-terminatedPOSS onto the azide side-functional polystyrene backbone via the Click reac-tion. POSS-alkyne has been obtained through a Steglich esterification of thehydroxy-POSS, whereby azide functions have been introduced to the polymer back-bone by the quantitative azidation of the chloromethyl groups in each repeatingunit of the skeletal chain. Poly(4-chloromethyl styrene), serving as a backbone forthe attachment of POSS cages, has been obtained by NMP. 1H-NMR analysis re-vealed that each PS chain carried, on average, about 33 pendent POSS groups. TheDSC analysis showed that the Tg of azide side-chain functional polystyrene (PS-N3)increased by 14◦C upon POSS attachment. Based on the results of 1H-NMR, 29Si-NMR, FT-IR and GPC, Click chemistry has been shown to be one of the versatileapproaches in accessing inorganic–organic hybrid polymers.

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Figure 6. The 1H-NMR spectra of (a) POSS-alkyne, (b) PS-N3 and (c) polystyrene bearing pendentPOSS cages.

Figure 7. The FT-IR spectra of (a) POSS-alkyne, (b) PS-N3 and (c) polystyrene bearing pendentPOSS cages.

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Figure 8. The GPC traces of (a) POSS-alkyne, (b) PS-N3 and (c) polystyrene bearing pendent POSScages.

Figure 9. The DSC curves of (a) PS-N3 and (b) polystyrene bearing pendent POSS cages.

Acknowledgement

This work is supported by the Scientific Research Fund of Fatih University underthe project number P50020901_2.

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References

1. J. Wu and P. T. Mather, J. Macromol. Sci. Part C: Polym. Rev. 49, 25 (2009).2. P. Iyer, G. Iyer and M. Coleman, J. Membr. Sci. 358, 26 (2010).3. S. Y. Li, G. P. Simon and J. G. Matisons, Polym. Eng. Sci. 50, 991 (2010).4. A. Fina, D. Tabuani and G. Camino, Eur. Polym. J. 46, 14 (2010).5. K. W. Huang, L. W. Tsai and S. W. Kuo, Polymer 50, 4876 (2009).6. Y. Feng, Y. Jia, S. Y. Guang and H. Y. Xu, J. Appl. Polym. Sci. 115, 2212 (2010).7. Y. Feng, Y. Jia and H. Y. Xu, J. Appl. Polym. Sci. 111, 2684 (2009).8. F. Baldi, F. Bignotti, A. Fina, D. Tabuani and T. Ricco, J. Appl. Polym. Sci. 105, 935 (2007).9. T. S. Haddad and J. D. Lichtenhan, Macromolecules 29, 7302 (1996).

10. T. S. Haddad, B. D. Viers and S. H. Phillips, J. Inorg. Organomet. Polym. 11, 155 (2001).11. L. Zheng, R. M. Kasi, R. J. Farris and E. B. Coughlin, J. Polym. Sci. Polym. Chem. 40, 885 (2001).12. G. Z. Li, L. Wang, H. Toghiani, T. L. Daulton and C. U. Pittman, Polymer 43, 4167 (2002).13. X. Y. Song, H. P. Geng and Q. F. Li, Polymer 47, 3049 (2006).14. A. Kotal, S. Si, T. K. Paira and T. K. Mandal, J. Polym. Sci. Polym. Chem. 46, 1111 (2008).15. E. T. Kopesky, T. S. Haddad, R. E. Cohen and G. H. McKinley, Macromolecules 37, 8992 (2004).16. G. Z. Li, H. Cho, L. C. Wang, H. Toghiani and C. U. Pittman, J. Polym. Sci. Polym. Chem. 43, 355

(2005).17. H. Y. Xu, B. H. Yang, J. F. Wang, S. Y. Guang and C. Li, J. Polym. Sci. Polym. Chem. 45, 5308

(2007).18. G. Z. Li, L. C. Wang, H. Toghiani, T. L. Daulton, K. Koyama and C. U. Pittman, Macromolecules

34, 8686 (2001).19. A. Strachota, I. Kroutilova, J. Kovarova and L. Matejka, Macromolecules 37, 9457 (2004).20. B. S. Hsiao, H. White, M. Rafailovich, P. T. Mather, H. G. Jeon, S. Phillips, J. Lichtenhan and

J. Schwab, Polym. Int. 49, 437 (2000).21. H. Y. Li, J. Y. Zhang, R. W. Xu and D. S. Yu, J. Appl. Polym. Sci. 102, 3848 (2006).22. H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem. Int. Edn 40, 2004 (2001).23. B. Helms, J. L. Mynar, C. J. Hawker and J. M. J. Frechet, J. Am. Chem. Soc. 126, 15020 (2004).24. B. Gacal, H. Akat, D. K. Balta, N. Arsu and Y. Yagci, Macromolecules 41, 2401 (2008).25. B. N. Gacal, B. Koz, B. Gacal, B. Kiskan, M. Erdogan and Y. Yagci, J. Polym. Sci. Part A: Polym.

Chem. 47, 1317 (2009).26. B. Karagoz, Y. Y. Durmaz, B. N. Gacal, N. Bicak and Y. Yagci, Designed Monomers Polymers 12,

511 (2009).27. M. A. Tasdelen, W. Van Camp, E. Goethals, P. Dubois, F. Du Prez and Y. Yagci, Macromolecules

41, 6035 (2008).28. M. Ak, B. Gacal, B. Kiskan, Y. Yagci and L. Toppare, Polymer 49, 2202 (2008).29. M. Ergin, B. Kiskan, B. Gacal and Y. Yagci, Macromolecules 40, 4724 (2007).30. B. Kiskan, G. Demiray and Y. Yagci, J. Polym. Sci. Part A: Polym. Chem. 46, 3512 (2008).31. M. Kukut, B. Kiskan and Y. Yagci, Designed Monomers Polymers 12, 167 (2009).32. M. Degirmenci and N. Genli, Polym. Int. 59, 859 (2010).33. M. Degirmenci and N. Genli, Macromol. Chem. Phys. 210, 1617 (2009).34. W. H. Binder and R. Sachsenhofer, Macromol. Rapid Commun. 29, 952 (2008).35. S. R. Gondi, A. P. Vogt and B. S. Sumerlin, Macromolecules 40, 474 (2007).36. R. Vestberg, M. Malkoch, M. Kade, P. Wu, V. V. Fokin, K. B. Sharpless, E. Drockenmuller and

C. J. Hawker, J. Polym. Sci. Part A: Polym. Chem. 45, 2835 (2007).37. K. Takizawa, H. Nulwala, R. J. Thibault, P. Lowenhielm, K. Yoshinaga, K. L. Woole and

C. J. Hawker, J. Polym. Sci. Part A: Polym. Chem. 46, 2897 (2008).

Dow

nloa

ded

by [

Uni

vers

itat P

olitè

cnic

a de

Val

ènci

a] a

t 02:

27 2

9 O

ctob

er 2

014

286 D. Sinirlioglu, A. E. Muftuoglu / Designed Monomers and Polymers 14 (2011) 273–286

38. A. Dag, H. Durmaz, E. Demir, G. Hizal and U. Tunca, J. Polym. Sci. Part A: Polym. Chem. 46,6969 (2008).

39. V. Ladmiral, G. Mantovani, G. J. Clarkson, S. Cauet, J. L. Irwin and D. M. Haddleton, J. Am.Chem. Soc. 128, 4823 (2006).

40. O. Altintas, B. Yankul, G. Hizal and U. Tunca, J. Polym. Sci. Part A: Polym. Chem. 44, 6458(2006).

41. O. Altintas, G. Hizal and U. Tunca, J. Polym. Sci. Part A: Polym. Chem. 44, 5699 (2006).42. E. Gungor, G. Cote, T. Erdogan, H. Durmaz, A. L. Demirel, G. Hizal and U. Tunca, J. Polym. Sci.

Part A: Polym. Chem. 45, 1055 (2007).43. C. N. Urbani, D. E. Lonsdale, C. A. Bell, M. R. Whittaker and M. J. Monteiro, J. Polym. Sci.

Part A: Polym. Chem. 46, 1533 (2008).44. M. Ergin, B. Kiskan, B. Gacal and Y. Yagci, Macromolecules 40, 4724 (2007).45. D. Gromadzki, A. Jigounov, P. Stepanek and R. Makuska, Eur. Polym. J. 46, 804 (2010).46. A. Dag, H. Durmaz, E. Demir, G. Hizal and U. Tunca, J. Polym. Sci. Part A: Polym. Chem. 46,

6969 (2008).47. J. Pyun, K. Matyjaszewski, J. Wu, G. M. Kim, S. B. Chun and P. T. Mather, Polymer 44, 2739

(2003).48. J. Wu and P. T. Mather, Polym. Rev. 49, 25 (2009).49. P. T. Mather, H. G. Jeon, A. Romo-Uribe, T. S. Haddad and J. D. Lichtenhan, Macromolecules 32,

1194 (1999).50. H. Xu, S. W. Kuo, J. S. Lee and F. C. Chang, Macromolecules 35, 8788 (2002).51. H. Xu, S. W. Kuo, J. S. Lee and F. C. Chang, Polymer 43, 5117 (2002).

Dow

nloa

ded

by [

Uni

vers

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a] a

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