Research Article Synthesis of Polyethers Containing Triazole Units in the Backbone by Click Chemistry in a Tricomponent Reaction

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1 Polymers Volume 2013, Artile ID , 8 pges Reserh Artile Synthesis of Polyethers Contining Trizole Units in the Bkone y Clik Chemistry in Triomponent Retion Moslem Mnsour Lkourj, Vhid sntr, nd znin Bgheri Deprtment of Polymer Chemistry, Fulty of Chemistry, University of Mzndrn, Bolsr 47416, Irn Correspondene should e ddressed to Moslem Mnsour Lkourj; lkourj@umz..ir Reeived 25 Mrh 2013; Revised 23 July 2013; Aepted 13 August 2013 Ademi Editor: Cyrille Boyer Copyright 2013 Moslem Mnsour Lkourj et l. This is n open ess rtile distriuted under the Cretive Commons Attriution Liense, whih permits unrestrited use, distriution, nd reprodution in ny medium, provided the originl work is properly ited. A series of liner romti polyethers ontining trizole units were synthesized vi the diret lik retion of diromide nd isethynyl ompounds in the presene of sodium zide s one pot retion. The strutures of polymers were pproved y using IR nd 1 MR tehniques. The soluility experiments showed tht polymers hve good soluility in polr proti solvents suh s DMS, DMF, nd MP t higher tempertures. Therml stility of the polymers ws mesured using thermogrvimetri nlysis (TGA) nd differentil snning lorimetry (DSC) whih indited tht they possessed good therml stility (T 50 up to 558 C) nd high T g ( C) under 2 tmosphere. All the polymers were morphous ording to the DSC nd X-ry diffrtion. These polymers exhiited strong UV-vis sorption mxim ner to 400 nm nd up to 500 nm in DMS solution. 1. Introdution Poly(ryleneether)s(PAEs)reknownsnimportntlss of the high-performne polymeri mterils whih onsist of romti rings nd ether linkges [1]. So fr, one of the most ommon nd effetive methods for the formtion of romti ether linkges in polyether synthesis ws nuleophili romti sustitution (S Ar) retion. Different poly(ryl ether)s inluding poly(ether sulfone)s, poly(ether ketone)s, nd poly(ether imide)s hve een prepred using the S Ar retion nd ommerilized [2]. owever, this method suffers from some serious limittions suh s high temperture nd hrsh onditions. In ddition, only pproprite monomers hving eletron-withdrwing groups t the ortho position to the leving group ould e polymerized. Reent innovtions in syntheti methodology hve improved polymer synthesis, enling the ustom design of lrge vriety of mromoleulr rhitetures under inorportion of desired funtionl units [3, 4]. To find n outstnding polymeriztion retion, polymer hemists nd iotehnologists hve inresingly turned towrds dvned syntheti orgni onepts. In this respet, the most interesting one is lik hemistry well doumented in the pst dede. The pplitions of lik retions re wide in sope. The lik retions give exellent yields nd generte inoffensive y-produts tht n e removed y onvenient methods. The required proess hrteristis inlude simple retion onditions, redily ville retnts, solvent free retions or using solvent tht is enign or esily removed, nd simple produt isoltion [5]. Todte,themostpopulrretionthtstisfiedthese fetures is the 1,3-dipolr yloddition, lso known s uisgen yloddition, etween n zide nd terminl lkyne whih ffords the trizole moiety [6]. The ppliility of this retion is very high, sine lkyne nd zide omponents n e inorported into wide rnge of sustituents [7]. Unfortuntely, this retion suffers from lk of seletivity yielding mixture of the 1,4- nd the 1,5-regioisomers. Furthermore, this trnsformtion requires heting nd long retion times to go to ompletion, nd the mixtures of regioisomers re t times lorious to seprte using lssil hromtogrphi proedures [7]. Reently, it hs een reported tht opper(i) slts elerte the retion rte enormously. Surprisingly, the opper tlyst produes only the 1,4-regioisomer t room tempertureinmoderteheting[8, 9].

2 2 Polymers R Aetone, K 2 C 3 Proprgyl romide R R= 1= C(Me) 2 1= S2 1= C 1d= C( ) 2 Sheme 1: Synthesis of is proprgyl ethers. Although, the pplitions of lik retion in mterils siene re espeilly interesting, most of them were foused on the preprtion of dendronized polymers [10, 11] nd onjugted polymers [12] orlimited to inorportionof 1,2,3- trizole rings into polymers y grft polymeriztion [13 15]. Aording to our literture survey, it is found tht the 1,2,3- trizole ring ws rrely inorported into the kone of liner poly(rylene ether)s [16 19]. In this pper, we wish to desrie the synthesis nd hrteriztion of novel lss of liner romti nd liphti polyethers suh s poly(ether ketone)s, poly(ether sulfone)s, nd fluorinted poly ether ontining trizole units inthekonevitheinsitulikretionofisethynylnd diromide ompounds in the presene of sodium zide s triomponents retion. 2. Mterils nd Methods Aetone ws dried over C 2 nd distillted efore use. ther regents or mterils were used s reeived. The hemils used in this experiment were purhsed from Merk (Germny) Chrteriztion. Melting points were mesured y n Eletrotherml 9100 pprtus. 1 MRspetrwere reorded on Bruker DRX-400. IR spetr were reorded on Perkin Elmer FT-IR spetrophotometer. Thermogrvimetri nlysis (TGA) nd differentil snning lorimetry (DSC) were reorded on therml siene PLSTA 1500 system under nitrogen tmosphere t heting rte of 10 Cmin 1. Inherent visosity t onentrtion of 0.5 g/dl ws mesured with n Uelohde suspended-level visometer t 25 C in DMS solution. X-ry diffrtion (XRD) ptterns were otined t room temperture on Rigku D/Mx-2550 powder diffrtometer with snning speed of 5 min 1,ndtheptternswerereordedinthe2θ rnge of 5 50.Reltivemoleulrweightsnddistriutions were mesured y gel permetion hromtogrphy (GPC) system equipped with Wters 1515 Isorti PLC pump, Wters 2414 refrtive index (RI) detetor, Wters 2487 dul wvelength λ sorne detetor, nd set of Wters Styrgel olumns (R3, R4, nd R5, 7.8 mm 300 mm). GPC mesurements were rried out t 35 CusingDMF s eluent t flow rte of 1.0 ml/min. Ultrviolet-visile spetr were reorded on Ceil 5503 (Ceil Instruments, Cmridge, UK) spetrophotometers using dilute polymer solution (0.20 g/dl) in DMS Synthesis of Bis Proprgyl Ether of Bisphenol. Bisphenol (0.05 mol), potssium ronte (0.15 mol), dry etone (50 ml), nd proprgyl romide (0.125 mol) were mixed in round ottom flsk equipped with ondenser nd heter stirrer. Then the mixture ws kept t 80 Covernight.n ompletion of the retion, the solvent ws evported nd the produt ws wshed with 5% K 2 C 3 q. nd deionized wter severl times. The rude produt ws purified y olumn hromtogrphy on sili gel using n-hexne/ethyl ette (4 : 1) s eluent to give 1 d.then,itwsrerystllized from ethnol twie to otin rystlline monomers. Synthesis of is proprgyl ethers of isphenols is shown in Sheme 1. 1: Yield: 90%. m.p C[20]. 1: Yield: 85%. m.p C[20]. 1: Yield:88%.m.p C[20]. 1d: Yield: 89%. il; IR (KBr, m 1 ): 3299 ( C), 2127 (C C); 1247 (Ar ); 1189 ( C 2 ); 827 ( ); 1 MR (400 Mz, CDCl 3 ) δ: 2.59(tr,J = 2.4z, 2, C), 4.79 (d, J=2.4z, 4, C 2 ), 7.06 (d, J=9.2z, 4, Ar ), 7.82 (d, J = 9.2 z, 4, C Ar ); 13 C MR (100 Mz, CDCl 3 ) δ: 55.8, 66.3, 76.1, 77.8, 114.3, 131.3, 132.1, 160.7, MS m/z (reltive intensity) SynthesisofPolymer1 d nd 2 d from Bis Proprgyl Aryl Ethers nd Diromides. In25mLflsk,tosolution of isethynyl ompounds (0.50 mmol), diromide (146 mg, 0.50 mmol) nd sodium zide (71.5 mg, 1.1 mmol) in DMF (10 ml), ws dded suspension of CuCl (9.85 mg, 20 mol %) in 2 (2 ml) in dropwise. Then Et 3 ws dded grdully until olor of mixture hnges from rown to light green. The retion mixture ws stirred t room temperture for 24 h. The retion mixture ws diluted y wter (20 ml) nd then onentrted mmoni (5 ml) ws dded nd stirred for nother1h.themixturewsfilteredndtheresultingsolid mteril ws wshed with 2, methnol, nd TF. Finlly, the otined polymer ws further purified using ontinuous extrtion y soxhlet in TF. P1: 90% yield. IR (KBr, m 1 ): 3180, 3085, 2929, 1650, 1604, 1508, 1430, 1307, 1226, 1180, 1018, 829, MR (DMS-d6, 400 Mz, ppm) δ: 8.11 (s, 2, C of trizole ring), 7.63 (r, 4, phenyl), 7.11 (r, 4, phenyl), 6.91 (r, 4, phenyl), 4.71 (r, 4, C 2 ), 4.25 (r, 4, C 2 ), 1.68 (s,

3 Polymers 3 Ar Br Br or Br Br + Ar 3 CuCl, Et 3 r.t Ar P1 d nd n P2 d n C 3 C 3, S Ar =, d Sheme 2: Synthesis of poly(trizole ether)s. 6, C 3 ). Anl. Cl. for (C ) n : C 70.73, 5.69, Found:C71.25,5.56,17.81%. P1: 93% yield. IR (KBr, m 1 ): 3140, 3058, 2920, 1592, 1494, 1459, 1294, 1253, 1177, 1149, 1106, 1050, MR (DMS-d6, 400 Mz, ppm) δ: 8.19 (s, 2, C of trizole ring), 7.83 (r, 4, phenyl), 7.51 (r, 4, phenyl), 6.95 (r, 4, phenyl), 4.83 (r, 4, C 2 ), 4.05 (r, 4, C 2 ). Anl. Cl. for (C S) n :C60.7,4.28,16.34.Found:C 61.23, 5.1, 16.93%. P1: 89% yield. IR (KBr, m 1 ): 3255, 3056, 2948, 1644, 1598, 1508, 1455, 1423, 1311, 1247, 1166, 998, MR (DMS-d6, 400 Mz, ppm) δ: 8.01 (s, 2, C of trizole ring), 7.52 (r, 4, phenyl), 7.21 (r, 4, phenyl), 7.01 (r, 4, phenyl), 4.64 (r, 4, C 2 ), 4.44 (r, 4, C 2 ). Anl. Cl. for (C ) n C 67.78, 4.6, Found: C 68.34, 4.86, 18.01%. P1d: 83% yield. IR (KBr, m 1 ): 3139, 3045, 2958, 2875, 1614, 1515, 1461, 1427, 1249, 1170, 1051, 962, MR (DMS-d6, 400 Mz, ppm) δ: 8.16 (s, 2, C of trizole ring), 7.43 (r, 4, phenyl), 7.25 (r, 4, phenyl), 7.08 (r, 4, phenyl), 4.75 (r, 4, C 2 ), 4.25 (r, 4, C 2 ). Anl. Cl. for (C F 6 ) n C 56.49, 3.57, Found: C55.63,4.03,14.05%. P2: 91% yield. IR (KBr, m 1 ): 3180, 3042, 2962, 1606, 1508, 1459, 1363, 1297, 1242, 1182, 1011, MR (DMSd6, 400 Mz, ppm) δ: 8.31 (s, 2, C of trizole ring), 7.78 (r, 4, phenyl), 7.08 (r, 4, phenyl), 5.15 (r, 4, C 2 ), Trnsmittne (%) C C C C Wvenumer (m 1 ) Figure 1:IR of 1d (up)nd P2d (down) using the KBr tlets (r, 4, C 2 ), 1.72 (s, 6, C 3 ), 1.54 (r, 4, C 2 C 2 ). Anl. Cl. for (C ) n C 67.56, 6.3, Found: C 68.22, 6.43, 19.01%. P2: 90% yield. IR (KBr, m 1 ): 3125, 3051, 2960, 1602, 1494, 1457, 1295, 1248, 1180, 1138, 1106, 1050, MR (DMS-d6, 400 Mz, ppm) δ: 8.21 (s, 2, C of trizole ring), 7.82 (r, 4, phenyl), 7.18 (r, 4, phenyl), 5.20 (r, 4, C 2 ), 4.36 (r, 4, C 2 ), 1.74 (r, 4, C 2 C 2 ). Anl. Cl. for (C S) n C56.65,4.72, Found: C 57.71, 4.85, 18.51%.

4 4 Polymers (ppm) CF e n 3 n d 2 DMS d e (ppm) Figure 2: 400 Mz 1 MRof1d in CDCl 3 nd P2d in DMS-d6. P2: 89% yield. IR (KBr, m 1 ): 3155, 3051, 2958, 1644, 1588, 1501, 1453, 1423, 1289, 1242, 1156, MR (DMSd6, 400 Mz, ppm) δ: 8.08 (s, 2, C of trizole ring), 7.63 (r, 4, phenyl), 7.01 (r, 4, phenyl), 5.31 (r, 4, C 2 ), 4.19 (r, 4, C 2 ), 1.65 (r, 4, C 2 C 2 ). Anl. Cl. for (C ) n C 64.18, 5.11, Found: C 65.11, 5.61, 19.27%. P2d: 85% yield. IR (KBr, m 1 ): 3129, 3055, 2978, 1624, 1505, 1451, 1407, 1239, 1159, 1045, 980, MR (DMSd6, 400 Mz, ppm) δ: 8.23 (s, 2, C of trizole ring), 7.12

5 Polymers 5 (r, 4, phenyl), 6.87 (r, 4, phenyl), 5.15 (r, 4, C 2 ),4.39(r,4,C 2 ), 1.78 (r, 4, C 2 C 2 ). Anl. Cl. for (C F 6 ) n C 54.34, 3.98, Found: C 55.69, 4.09, 15.61%. 3. Results nd Disussion 3.1. Synthesis nd Chrteriztion of Polymers. Sine trizole ring is hemilly inert towrd oxidtion, redution, nd hydrolysis onditions nd hs n intermedite polrity [21], inorportion of suh stle struturl unit in polyethers n enhne their thermophysil properties. Trditionlly, 1,2,3- trizoles were prepred from lik retion of zides nd lkynes under Cu(I) tlysis whih hs een omprehensively reviewed [22]. owever, low moleulr weight orgni zides my e unstle nd should e hndled with ution. Azides with C/ rtio greter thn one nd no more thn 3 n e synthesized nd isolted ut should e stored elow room temperture t no more thn 1 M onentrtion. rgni zides with C/ <1shouldnevereisoltednd prtilly they were used without further purifition [19]. Therefore, to void the use of zides, the polymers ontining trizole unites, poly(trizole ether)s (P1 d nd P2 d), were otined from diret lik retion of orresponding diromideswith isethynyl ompounds 1 d in the presene of sodium zide (Sheme 2). The retions were rried out in 10 : 2 solvent rtio of DMF : 2 ndusing20mol% CuCl with Et 3 s se nd stilizing gent [23, 24]troom temperture. It is found tht the retion in dry DMF nd/or in the sene of Et 3 gives polymers in low yield. It n e seen from the infrred spetr of P1 d nd P2 d the strong sorption peks out 3,300 nd 2,100 m 1 ssigned to strething virtions of C C nd C C, respetively, disppered, while new strong sorption peks t m 1 orresponding to strething virtion of C=C of the 1,2,3-trizole moiety ppered (Figure 1). Representtive 1 MR spetrum of monomer 1d nd its liphti polymer P2d is shown in Figure 2. It is ler tht the 1,2,3- trizole rings of the polymer were hrterized y signls ner 8.2 ppm orresponding to trizole protons. As seen in 1 MRspetrumofthepolymerP2d, itonfirmedtht theresultingpolymersontintrizoleunitsorresponding to IR nlysis. These dt indite tht diret polymeriztion etween diromide with isethynyl ompounds 1 d in the presene of sodium zide vi the lik retion ws suessful. In omprison with previous works for synthesis of these types of polymers [25], our method is novel, onvenient, nd in est greement with lik hemistry requirements (enign solvents, room temperture, simple isoltion,...) nd the most importnt feture of this method is the one pot synthesis tht prevents from further purifition nd use of dngerous dizide ompounds Considertion of Moleulr Weights nd Distriutions of Polymers. The orresponding dt of GPC nlysis in DMF for polymers were showed in Tle 1.Theresultsshowthtthe polymeriztion vi lik hemistry produed polymers with dequtely high moleulr weights nd nrrow distriutions. Weight loss (%) P2d P1 P2 P1d Temperture ( C) P2 P1 P2 P1 Figure 3: Thermogrvimetri nlysis under 2 tmosphere nd heting rte of 10 C/min. et flow Temperture ( C) P1 P1 P1 P1d P2 P2 P2 P2d Figure 4: Differentil snning lorimetri under 2 gs with heting rte of 10 C/min. The numer verge moleulr weights of them re etween 17,300nd24,800ndthedistriutionsrngeisfrom1.09to All polydispersities of polymers re less thn 1.68 whih is stndrd for polymeriztion retion [26]. Aording to the high moleulr weight nd nrrow distriution, it is found tht the lik hemistry is n effetive route for polymeriztion Soluility Behvior of Polymers. The soluility of polymers ws quntittively determined in ommon orgni solvents y dissolving 5.0 mg of solid polymers in 1.0 ml of solvents. In the soluility experiments, it ws found tht these polymers were ompletely insolule in Me, TF, EtA,

6 6 Polymers Asorne Asorne Wvelength (nm) P1 P1 P1 P1d Wvelength (nm) P2 P2 P2 P2d Figure 5: UV-vis sorption spetr of P1 d nd P2 d were reorded using dilute polymer solution (0.20 g/dl) in DMS. Tle 1: Moleulr weights nd distriutions of polymers. Polymers M n M w (M w /M n ) η inh (dl/g) P1 23,100 29, P1 21,000 32, P1 21,300 32, P1d 24,800 27, P2 19,100 30, P2 17,300 29, P2 20,500 27, P2d 22,400 27, GPC in DMF versus polystyrene in flow rte of 1.0 ml/min t 35 C. Tle 2: Therml properties of polymers. Polymers T 5 ( C) T 10 ( C) T 50 ( C) Chr yield (%) T g ( C) P P P P1d P P P P2d nd toluene t room nd high tempertures. But polymers showed low soluility in DMS, DMF, nd MP t room temperture nd good soluility t higher tempertures Therml Properties of Polymers. Therml stilities of P1 d nd P2 d were evluted y mens of thermogrvimetri nlysis (TGA) nd differentil snning lorimetri (DSC). The resulting dt re summrized in Tle 2.The resulting polymers exhiited high resistne to therml deomposition up to 558 C under nitrogen gs nd deompose grdully ove tht temperture whih is proly ttriuted to hin sission of ether linkge. It ws seen from Figure 3 thtrtesofweightlossofliphtipolymerswere greter thn romti polymers due to the deomposition of methylene groups. The glss trnsition temperture (T g ) of polymers, determined y DSC, rnged etween nd 260 C nd inresed with the inrese of onformtionl rigidity (Tle 2). As ws expeted, sine P1 hs rigid sulfone groups in the polymer, kone whih restrits moleulr rottion T g of P1 is the highest. P2 ws the lowest owing to higher flexiility of the methyl groups. The dt revel tht T g dereses with the nture of the liphti hin sper. Asene of rystlliztion temperture in DSC urves (Figure 4) lso shows the morphous nture of the polymers, whih ws onfirmed y X-ry diffrtion studies. Inherent visosity ((η) inh = ln η rel /) t onentrtion of 0.5 g/dl ws mesured with n Uelohde suspended-level visometer t 25 C in DMS solution. Visometry studies exhiited tht polymers hve moderte moleulr weight (Tle 1) UV-Vis Properties of the Polymers. The photophysil properties of the P1-d nd P2-d were investigted y UVvisile spetrosopy in DMS solution. There re similr pirurvessneseeninuv-visdigrms(figure 5) whih exhiited strong sorption t 283 nm nd 465 nm orresponding to phenyl nd trizole rings of the polymer kones, respetively. The presene of extr onjugtion of S 2 nd Cgroupsinthekoneofthepolymerused some lue shift. This effet hs not e seen for the polymers ering (C 3 ) 2 nd ( ) 2 sper due to onjugtion loss. Indeed, owing to the existene of different romti rings with different linkge etween them, three hrteristi sorption piks ould e seen in P2 nd P2. Thepiks

7 Polymers 7 Referenes Reltive intensity P2d P2 P2 P2 P1d P1 P1 P θ ( ) Figure 6: X-ry diffrtion (XRD) ptterns t room temperture on powder diffrtometer. out 280 nd 354 nd out 480 nm re orresponding to rylenes nd trizole rings, respetively [27, 28] X-Ry Diffrtion Studies of Polymer P1 d nd P2 d. In order to further onsider the rystllinity of these series of polymers, ll polyether trizoles were hrterized y X-ry diffrtogrms. The X-ry diffrtogrm urves of polymers were shown in Figure 6. XRD of ll polymers demonstrtes rod hlo t out 2θ t in the wide ngle region exhiiting tht the polymers P1 d nd P2 d re morphous in nture whih is in greement with the DSC nlysis. This result ould e explined tht the etheri linkgeusedtheflexiilityofthepolymerhinwhih restrited the ordered rrngement of polymer hins. 4. Conlusion In this work, onvenient triomponent lik polymeriztions of dilkynes ontining ether linkges nd diromides were hieved in the presene of sodium zide to synthesize vrious polyethers (P1 d nd P2 d). This polymeriztion ompnied the formtion of trizoles in the polyether min hin y Cu(I) tlyst in exellent yields. It is found tht trizole ring formtion in the polyether min hin leds to improved therml properties. This work is report of onvenient synthesis of polymers tht the trizoles rings inserted into kone of the polymers under mild onditions. These fundmentl results provide new guideline to synthesize frontier polyether-sed mterils. Aknowledgment The finnil supports y Reserh Counil of Mzndrn University re grtefully knowledged. [1] R. J. Cotter, Engineering Plstis: A ndook of Polyryl Ethers, Gordon nd Breh, Amsterdm, The etherlnds, [2] I.S.ChungndS.Y.Kim, Poly(ryleneether)svinitrodisplement retion: synthesis of poly(iphenylene oxide)s ontining trifluoromethyl groups from AB type monomers, Mromoleules,vol.33,no.26,pp ,2000. [3] C. J. wker nd K. L. Wooley, The onvergene of syntheti orgni nd polymer hemistries, Siene, vol. 309, no. 5738, pp , [4] S. eht, Constrution with mromoleules, Mterils Tody,vol.8,no.3,pp.48 55,2005. [5]. C. Kol, M. G. Finn, nd K. B. Shrpless, Clik hemistry: diverse hemil funtion from few good retions, Angewndte Chemie Interntionl Edition,vol.40,no.11,pp , [6] R. uisgen, S. Guenter, nd M. Lender, 1.3-Dipolre ylodditionen, XXXII. Kinetik der dditionen orgnisher zide n CC-mehrfhindungen, Chemishe Berihte, vol. 100, no. 8, pp , [7] R. uisgen, 1, 3-Dipolr Cyloddition Chemistry,JohnWiley& Sons, ew York, Y, USA, [8] V.V.Rostovtsev,L.G.Green,V.V.Fokin,ndK.B.Shrpless, A stepwise huisgen yloddition proess: opper(i)-tlyzed regioseletive ligtion of zides nd terminl lkynes, Angewndte Chemie Interntionl Edition, vol.41,no.14,pp , [9] C. W. Tornøe, C. Christensen, nd M. Meldl, Peptidotrizoles on solid phse: [1,2,3]-trizoles y regiospeifi opper(i)-tlyzed 1,3-dipolr ylodditions of terminl lkynes to zides, The rgni Chemistry,vol.67,no.9,pp , [10] A.J.Sheel,.Komer,ndB.I.Viot, ovelhyperrnhed poly([1,2,3]-trizole)s derived from AB 2 monomers y 1,3- dipolr yloddition, Mromoleulr Rpid Communitions,vol.25,no.12,pp ,2004. [11] P. Wu, A. K. Feldmn, A. K. ugent et l., Effiieny nd fidelity in lik-hemistry route to trizole dendrimers y the opper(i)-tlyzed ligtion of zides nd lkynes, Angewndte Chemie Interntionl Edition,vol.43,no.30,pp , [12] D.J.V.C.vnSteenis,.R.P.Dvid,G.P.F.vnStrijdonk,J.. VnMrseveen,ndJ...Reek, Clik-hemistrysn effiient syntheti tool for the preprtion of novel onjugted polymers, Chemil Communitions, no. 34, pp , [13] B.elms,J.L.Mynr,C.J.wker,ndJ.M.J.Fréhet, Dendronized liner polymers vi lik hemistry, the Amerin Chemil Soiety,vol.126,no.46,pp , [14] B.Prrish,R.B.Breitenkmp,ndT.Emrik, PEG-ndpeptide-grfted liphti polyesters y lik hemistry, the Amerin Chemil Soiety, vol. 127, no. 20, pp , [15] J.B.Crroll,B.J.Jordn,.Xuetl., Modelsystemsforflvoenzyme tivity: site-isolted redox ehvior in flvin-funtionlized rndom polystyrene opolymers, rgni Letters,vol.7, no.13,pp ,2005. [16] J. A. psteen nd J. C. M. vn est, Modulr synthesis of lok opolymers vi yloddition of terminl zide nd lkyne

8 8 Polymers funtionlized polymers, Chemil Communitions,no.1,pp , [17] D. D. Díz, S. Punn, P. olzer et l., Clik hemistry in mterils synthesis. 1. Adhesive polymers from opper-tlyzed zide-lkyne yloddition, Polymer Siene A, vol. 42,no.17,pp ,2004. [18] D. A. ssipov nd J. ilorn, Poly(vinyl lohol)-sed hydrogels formed y lik hemistry, Mromoleules, vol. 39, no. 5, pp , [19] Y. go nd A. Tksu, Clik polyester: synthesis of polyesters ontining trizole units in the min hin y lik hemistry nd improved therml property, Mromoleulr Rpid Communitions,vol.30,no.3,pp ,2009. [20] R. X. Yo, L. Kong, Z. S. Yin, nd F. L. Qing, Synthesis of novel romti ether polymers ontining perfluoroyloutyl nd trizole units vi lik hemistry, Fluorine Chemistry, vol. 129, no. 10, pp , [21] P. Wu nd V. V. Fokin, Ctlyti dipolr yloddition of zides nd lkynes: retivity nd pplitions, Aldrihimi At, vol. 40,no.1,pp.7 17,2007. [22] M. Meldl nd C. W. Tornøe, Cu-tlyzed zide-lkyne yloddition, Chemil Reviews, vol. 108, no. 8, pp , [23] G. C. Tron, T. Pirli, R. A. Billington, P. L. Cnonio, G. Sor, nd A. A. Genzzni, Clik hemistry retions in mediinl hemistry: pplitions of the 1,3-dipolr yloddition etween zides nd lkynes, Mediinl Reserh Reviews, vol. 28, no. 2, pp , [24] V.D.Bok,.iemstr,ndJ.V.Mrseveen, Cu I -tlyzed lkyne zide lik ylodditions from mehnisti nd syntheti perspetive, Europen rgni Chemistry, vol.2006,no.1,pp.51 68,2006. [25] L.Wng,J.Li,ndL.Wng, Studyonsynthesisofpeksontining trizole units through lik retion nd their properties, Bulletin of the Koren Chemil Soiety, vol.32,no.9,pp , [26] I. B. Mnsour, K. Alouni, E. Chuveu, V. Mrtin, F. Shiets, nd R. Merier, Synthesis nd hrteristion of poly(estermide)s from romti isoxzoline preursors, Europen Polymer Journl, vol. 46, no. 4, pp , [27] C. Srvnn, S. Senthil, nd P. Knnn, Clik hemistry-ssisted trizole-sustituted zoenzene nd fulgimide units in the pendnt-sed opoly(deyloxymethrylte)s for dul-mode optil swithes, Polymer Siene A, vol. 46, no. 23, pp , [28] B. pp, C. Friee, A. Winter, M. D. ger, nd U. S. Shuert, Clik hemistry meets polymeriztion: ontrolled inorportion of n esily essile ruthenium(ii) omplex into PMMA kone vi RAFT opolymeriztion, Europen Polymer Journl, vol. 45, no. 12, pp , 2009.

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