210 CameOLa HuOubeL a nδ DumLtru PopovLcL AnotKer approacK Ls tKe Ln corporatLon of buONy anδ asymmetrLcaO Jroups OarJe penδent or poOar substLtuents. -10 TKe LntroδuctLon of aOLcycOLc structure usLnJ aOLcycOLc δLanKyδrLδe Ls aOso stuδLeδ . 11-15 It Ls e[pecteδ tKat tKe combLnatLon Ln tKe poOymer bacNbone of epLcOon moLetLes toJetKer wLtK aromatLc rLnJs anδ fOe[LbOe aOLpKatLc sequences wouOδ δeveOop new syntKetLc poOymers offerLnJ a favorabOe baOance structure-propertLes. From tKe tetracarbo[yOLc δLanKyδrLδes EpLcOon Ls a cycOoaOLpKatLc asymmetrLcaO anδ fOe[LbOe cKemLcaO structure. TKree poOymers semL-aOLpKatLc anδ aOLpKatLc poOyLmLδes were prepareδ by usLnJ cOassLcaO soOutLon poOyconδensatLon. ImLδL]atLon was LnLtLateδ at 0 ºC anδ Lt was performeδ at 1 5 ºC. TKe propertLes of tKese poOymers wLtK respect to tKeLr cKemLcaO stabLOLty anδ JOass transLtLon temperature soOubLOLty anδ fLOm formLnJ abLOLty Kave been evaOuateδ. A JeneraO reactLon scKeme for tKe syntKesLs of tKe poOyLmLδes PI1-PI3 HMD HOOC COOH COOH NMP EpLcOon PAA1-PAA3 PI1 - PI3 100 0 50 50 0 100 PI1 PoOymer DLamLne moOar ratLo DDM HMDA ScKeme 1 – SyntKesLs of tKe poOyLmLδes TKe poOymers were obtaLneδ by conventLonaO two-step poOyconδensatLon reactLon vLa poOyamLc acLδ precursor. TKe reactLons proceeδeδ KomoJeneousOy poOyLmLδes PI2 wLtKout JeOatLon or precLpLtatLon of tKe resuOtant poOymers. It was founδ tKat a consLδerabOe JeOatLon occurreδ δurLnJ tKe aδδLtLon of 16 Ke[ametKyOeneδLamLne HMDA to a soOutLon of EpLcOon poOyLmLδe . TKe soOutLon became cOear on stLrrLnJ. TKLs pKenomenon Ls probabOy δue to tKe formatLon of saOt compOe[ between KLJKOy basLc aOLpKatLc δLamLne anδ carbo[yOLc acLδ Jroups of tKe poOyamLc acLδ wKLcK preventeδ tKe cKaLn JrowtK of poOymer anδ tKus e[pOaLns tKe Oow moOecuOar weLJKt of tKe resuOtLnJ poOyLmLδe NoveO poOyLmLδes contaL nLnJ aOLcycOL c unLts 211 SpectraO cKaracterL]atLon. TKe structures of poOyLmLδes were cKaracterL]eδ by FT-IR anδ H-NMR spectroscopy. FLJure 1 sKows tKe FT-IR spectra of tKe poOyLmLδes In FT-IR spectra measureδ Ln transmLssLon moδe tKree cKaracterLstLc peaNs attrLbutabOe to tKe LmLδe structure can be observeδ at about 10 cm anδ 10 cm assLJneδ to tKe symmetrLcaO anδ asymmetrLcaO stretcKLnJ vLbratLons of tKe carbonyO Ln LmLδe rLnJs 130 -130 cm δue to C–N stretcKLnJ Ln LmLδe rLnJ anδ at 5–60 cm possLbOy assocLateδ to LmLδe rLnJ δeformatLon . PoOyLmLδes PI1 anδ presenteδ stronJ Lnfrareδ absorptLons at 1510 cm attrLbutabOe to tKe =CH Ln aromatLc rLnJs. AOO poOymers sKoweδ cKaracterLstLc peaNs at 2 30–2 20 cm assocLateδ wLtK tKe aOLpKatLc sequences Ln tKe monomers. TKe broaδ absorptLon banδ at 3350–3450 cm cKaracterLstLc of NH amLδLc anδ tKe narrow absorptLon peaN at 1650–1660 cm δue to C=O Jroup Ln amLδe OLnNaJe δLsappeareδ entLreOy LnδLcatLnJ tKe compOetLon of tKermaO LmLδL]atLon of tKe LntermeδLate poOyamLδLc acLδ Lnto fLnaO poOyLmLδe structure anδ confLrms tKe successfuO syntKesLs of poOymers by poOyconδensatLon Ln soOutLon H-NMR spectroscopy confLrms tKe poOymer structures. TKe H-NMR spectra contaLns tKe sLJnaOs cKaracterLstLc to tKe monomers TabOe 1 . TKe peacNs between 1.0 – 4.15 ppm were assocLateδ wLtK tKe resonance vaOues of tKe aOLpKatLc protons Ln tKe poOymer unLt structure metKyO metKyOene anδ metKLne protons Ln tKe cycOoaOLpKatLc anδ aOLpKatLc moLetLes. TKe aromatLc protons can be observeδ Ln tKe .10 - .6 ppm reJLon. FLJ. 1 – FT-IR spectra of tKe poOyLmLδes PI3 H-NMR δata of tKe poOymers PI1 PoOymer H-NMR spectraO δata δ ppm .10-.5 m H aromatLc 4.15 s 2H CH 3.35-3.4 m 3H CH CH succLnLmLδe LmLδe 2.55-3.01 m 5H CH CH cycOoaOLpKatLc succLnLmLδe LmLδe . .20 - .6 m H aromatLc 4.10 s 2H CH 3.20-3.65 m 10H CH succL nLmLδe LmLδe aOLpKatLc 2.45-2.0 m 10H CH CH cycOoaOLpKatLc succLnLmLδe 1.30-1.55 m H CH aOLpKatLc 212 CameOLa HuOubeL a nδ DumLtru PopovLcL TabOe 1 contLnueδ 3.10-3.5 m H CH CH succLnLmLδe LmLδe aOLpKatLc 2.35-2.5 m 5H CH CH cycOoaOLpKatLc succLnLmLδe LmLδe 1.30-1.6 m H CH aOLpKatLc. MuOtLpOLcLty s = sLnJOet δ = δoubOet t = trLpOet m = muOtLpOet. LnternaO reference TMS. SoOutLon propertLes. TKe soOubLOLtLes of tKe poOymers towarδ varLous NLnδs of orJanLc soOvents were testeδ. AOO tKe poOyLmLδes obtaLneδ Kave e[ceOOent soOubLOLty Ln poOar soOvents sucK as DMF NMP DMAc DMSO anδ -cresoO. In aδδLtLon poOyLmLδe PI3 δLssoOve easLOy Ln cKOoroform MoOecuOar weLJKt anδ SoOubLOLty δata SampOe moOar ratLo DDM HMDA Mn Mw NMP DMAc DMSO -cresoO CHCO 100 0 50000 2.3 - - 50 50 2000 1. - 0 100 1100 1. - InsoOubOe - sOLJKtOy soOubOe at r.t. soOubOe at r.t. Improvement Ln poOymer soOubLOLty Ls δue to cKaLn fOe[LbLOLty promoteδ by tKe aOLpKatLc anδ cycOoaOLpKatLc moLetLes wLtK Jreater rotatLonaO freeδom. TKe LntroδuctLon of tKe EpLcOon unLt wKLcK Ls aOso a buONy anδ asymmetrLc structure δecreases cOose pacNLnJ by δecreasLnJ of tKe entropy enerJy of LnternaO rotatLon. TKus Lt Ls facLOLtateδ an easLer δLffusLon of tKe soOvent amonJ macromoOecuOes LncreasLnJ tKe soOubLOLty. TKermaO beKavLour. TKe tKermaO stabLOLty of tKe poOymers TabOe 3 was evaOuateδ by δLfferentLaO scannLnJ caOorLmetry DSC anδ tKermoJravLmetrLc anaOysLs T*A . TKe JOass transLtLon temperature T as a seconδ orδer enδotKermLc transLtLon couOδ be consLδereδ as tKe temperature at wKLcK a poOymer unδerJoes e[tensLve cooperatLve seJmentaO motLon aOonJ tKe bacNbone. TKe fOe[LbOe OLnNaJes δecrease tKe enerJy of LnternaO rotatLon OowerLnJ tKe TJ. DLfferent Lntra- anδ LntermoOecuOar LnteractLons LncOuδLnJ KyδroJen bonδLnJ eOectrostatLc anδ LonLc forces cKaLn pacNLnJ effLcLency anδ cKaLn stLffness affect tKe T . TKe T s of tKe poOyLmLδes were observeδ Ln tKe ranJe of 122 – 255 °C δepenδLnJ on tKe structure of δLamLne component anδ δecreaseδ wLtK tKe δecreasLnJ of rLJLδLty of tKe poOymer bacNbone. TKermaO stabLOLty of tKe poOyLmLδes TKermaO stabLOLty PoOymer coδe % 255 440 465 50 - 24.4 1 0 30 440 4 5 55 1. 122 345 30 40 565 14.2 DetermLneδ by 2 KeatLnJ at rate of 20 °C / mLn Ln aLr f δeJraδatLon 1st 2 Ma[. δecomposLtLon temperature ResLδue at 00°C. TKe obtaLneδ poOyLmLδes beJLn to δecompose between 345 - 440 °C anδ sKow 10% wt Ooss Ln tKe ranJe of 30- 465 °C. TKe poOyLmLδes PI2 sKoweδ two-step weLJKt Ooss beKavLor δue to tKe NoveO poOyLmLδes contaL nLnJ aOLcycOL c unLts 213 tKermaOOy OabLOe metKyOene seJments Ln tKe aOLpKatLc δLamLne moLety . TKe prepareδ poOyLmLδes were tKermaOOy stabOe up to about 440 °C accorδLnJ to T anδ δrastLc δeJraδatLon T occurreδ Ln tKe ranJe of 40-4 5 °C wKLcK was foOOoweδ by tKe seconδ δeJraδatLon T above 560°C. TKe Oow cKar resLδue for tKese poOymers may be assocLateδ wLtK tKeLr Oow aromatLc rLnJ Surface propertLes. In orδer to e[amLne tKe surface morpKoOoJy of PI 3 fLOm atomLc force mLcroscopy measurements were maδe. FLJure 2 pOots tKe bL- anδ tKree-δLmensLonaO structure observLnJ tKat tKe fLOm surface Ls covereδ wLtK nanometers-scaOeδ JranuOes mean δLameter of tKe JraLns was 0 nm . FLJ. 2 – AFM cKaracterL]atLon of – fLOm a. 3D AFM LmaJe b 2D tappLnJ moδe AFM LmaJe c KeLJKt profLOe taNen aOonJ tKe OLne from 2D AFM LmaJe δ surface KeLJKt KLstoJram. Scan area 2 µm [ 2 µm. 214 CameOLa HuOubeL a nδ DumLtru PopovLcL TKe AFM anaOysLs sKoweδ a smootK topoJrapKy of tKe surface wLtK root-mean-square Sq rouJKness of tKe 1.1 nm orδer anδ averaJe rouJKness Sa of 0.4 nm orδer over an 2 µm [ 2 µm area. From KeLJKt profLOe fLJure 2c anδ KeLJKt KLstoJram anaOysLs fLJure 2δ Lt can be obtaLneδ tKe averaJe KeLJKt of 3.1 nm. TKe surface morpKoOoJy anδ rouJKness of tKe poOyLmLδe fLOm couOδ be maLnOy tKe resuOt of poOymer cKaLns cKaracterLstLcs tKat Jovern aJJreJatLon anδ moOecuOar orδerLnJ δurLnJ δryLnJ anδ tKermaO LmLδL]atLon processes. OptLcaO propertLes. PoOyLmLδes contaLnLnJ aOLcycOLc structures are e[pecteδ to Kave better transparency tKan aromatLc poOyLmLδe δue to tKe proKLbLtLon of eOectron conMuJatLon by tKe LntroδuctLon of aOLcycOLc moLety. TKe fLOms obtaLneδ from tKe resuOtLnJ poOyLmLδes were paOe- yeOOow. TKeLr optLcaO transparency was e[perLmen- taOOy measureδ by UV-vLsLbOe spectroscopy anδ tKe resuOts are sKown Ln TabOe 4. OptLcaO transparency of fLO ms δerLveδ from poOyLmLδes PI T % λ 0% cutoff semLaromatLc poOyLmLδe 43 636 400 partLaO aromatLc copoOyLmLδe 31 606 302 nonaromatLc poOyLmLδe 36 61 301 TransmLttance at 500 nm. :aveOenJtK of 0% transmLttance. :aveOenJtK of UV cutoff. From tKe transmLssLon sp ectra tKe transmLttance at 500 nm waveOenJtK δecreaseδ from 43% to 31% anδ e[KLbLteδ a sKLft Ln tKe cutoff waveOenJtK from 400 to 300 nm. TKese fLOms sKoweδ transparency KLJKer tKan 0% above 606 nm. EXPERIMENTA/ PART MaterLaOs 5- 25-δLo[otetraKyδro-3-furanyO -3-metKyO-3-cycOoKe[- ene-12-δLcarbo[yOLc anKyδrLδe EpLcOon B-4400 44 - metKyOeneδLanLOLne anδ 16-Ke[ametKyOeneδLamLne were provLδeδ by δLfferent commerc LaO sources anδ were useδ as receLveδ sLnce tKey were of a KLJKOy purLfLeδ Jraδe for poOymer syntKesLs. N-metKyO-2-pyrroOLδLnone NMP was δrLeδ before usLnJ b y stanδarδ metKoδs. Measurements Infrareδ spectra were recorδeδ wLtK a BruNer Verte[ spectrometer Ln transmLssLon moδe at 24 cm resoOutLon by usLnJ precLpLtateδ poOymers Jrounδ Ln potassLum bromLδe peOOets. UV-VLsLbOe spectra were recorδeδ on a SPECORD 200 AnaOytLN Jena UV-vLsL bOe spectropKotometer. TKe H-NMR spectra were recorδeδ on a BruNer Avance DRX 400 MH] spectrometer for poOymer soOutLon Ln δLmetKyOsuOfo[Lδe-δ DMSO-δ usLnJ tetrametKyOsLOane TMS as LnternaO stanδarδ. PoOymer soOubLOLtLes were δet ermLneδ at room temperature at a concentratLon of 1% w/v . TKe moOecuOar weLJKt were δetermLneδ by JeO permeatLon cKromatoJrapKy *PC usLnJ a P/-EMD 50 evaporatLve mass δetector Lnstrument. PoOystyrene stanδarδs of Nnown moOecuOar weLJKt were useδ for caOLbratLon anδ δLmetKyOformamLδe as mobLOe pKase. TKermoJravLmetrLc anaOyses T*A were performeδ on a MOM δerLvatoJrapK HunJary Ln aLr at a KeatLnJ rate of 10°C/mLn. TKe LnLtLaO δecomposLtLon temperature IDT Ls cKaracterL]eδ as tKe temperature at wKLcK tKe sampOe acKLeves a 5% weLJKt Ooss. TKe temperature of 10% weLJKt Ooss T was aOso recorδeδ. TKe JOass transLtLon temperatures T of tKe precLpLtateδ poOymers were δetermLneδ wLtK a MettOer δLfferentLaO scannLnJ caOorLmeter DSC 12E. TKe sampOe s were Keateδ from ambLent temperature to above 300°C at a KeatLnJ rate of 10°C/mLn unδer nLtroJen. Heat fOow versus temperature scans from tKe seconδ KeatLnJ run were pOotteδ anδ useδ for reportLnJ tKe JOass transLton temperature. TKe mLδ-poLnt of tKe LnfOectLon curve resuOtLnJ from tKe typLc aO seconδ KeatLnJ was assLJneδ as tKe JOass transLtLon temperat ure of tKe respectLve poOymers. TKe atomLc force mLcroscopy AFM measurements were maδe on a ScannLnJ Probe MLcro scope SoOver Pro-M pOatform NT-MDT RussLa Ln aLr at room temperature 23°C Ln tappLnJ moδe. A rectanJuOar "JoOδen" sLOLcon cantLOever NS*10 NT-MDT RussLa wLtK a typLcaO force constant . = 11. N m anδ 20 NH] oscLOOatLon frequency was useδ. TKe tLp curvature raδLus anδ KeLJKt was 10 nm anδ 14-16 µm respectLveOy. TKe scan area was 2 µm [ 2 µm 256 [ 256 scan poLnt sL]e LmaJes beLnJ tKus obt aLneδ. For LmaJe acquLsLtLon anδ LmaJe anaOysLs tKe Oast versLon of tKe NT-MDT NOVA software was useδ. SyntKesLs of poOyLmLδes PoOyLmLδes were syntKesL]eδ by reactLnJ EpLcOon EPI wLtK 44 -metKyOeneδLanLOLne DDM anδ /or 16 Ke[ametKyOene δLamLne HMDA . An equLmoOar ratLo of botK δLamLnes Kas been appOLeδ for preparatLon of tKe copoOyLmLδe. TKe combLnatLon of tKe cycOoaOLpKatLc Jroups wLtK botK fOe[LbOe NoveO poOyLmLδes contaL nLnJ aOLcycOL c unLts 215 aromatLc anδ / or aOLpKatLc δL amLnes proδuceδ a systematLc varLatLon Ln tKe propertLes of t Kese poOyLmLδes. TKe poOymers were prepareδ by poOyconδensa tLon of equLmoOar amounts of EpLcOon anδ δLamLne Ln NMP unδer anKyδrous conδLtLons Ln a nLtroJen atmospKere. As a JeneraO proceδure tKe reactor was purJeδ wLtK δry nLtroJen for 10 mLn. TKe δLamLne DDM anδ/or HMDA Ln δLfferent moOe ratLos was cKarJeδ Lnto tKe reactor tKrouJK an aδδLtLon funneO tKe TabOe 1 . NMP soOLδ content 30% was tKen cKarJeδ. UntLO compOete δLssoOutLon of δLamLnes epLcOon was aδδeδ to tKe reactor Ln two portLons wLtKLn one KaOf Kour. To δLOute tK reactLon mL[ture soOLδ content 15% after epLcOon was cKarJeδ resLδuaO NMP was aδδeδ Lnto tKe reactor. TKe reactLon mL[ture was stLrreδ 24 K at room temperature Ln atmospKere resuOtLnJ Ln a poOy amLc acLδ PAA after tKat by tKermaOOy LmLδL]atLon was transf ormeδ Ln tKe poOyLmLδe PI . PoOyLmLδe fLOms PoOyLmLδe fLOms were prepa reδ tKrouJK LmLδL]atLon of poOy amLc acLδ fLOms cast on a JOass substrate wKLcK was pOaceδ overnLJKt Ln an 0 °C oven to remove most of tKe soOvent. TKe semLδrLeδ poOy amLc acLδ fLOms were furtKer δrLeδ Ln an oven anδ transformeδ Lnto poOyLmLδes by tKe foOOowLnJ KeatLnJ proJram 120 °C 160 °C 10 °C 210 °C anδ 250 °C for 1K at eacK temperature. After strLppLnJ tKe fLOms Ln Kot water tKe resuOtLnJ sampOes were δrLeδ at 65 °C L a vacuum oven for 24 K. CONC/USION TKe LncorporatLon of cycOoaOLpKatLc EpLcOon unLts toJetKer wLtK metKyOene sequences Lnto tKe maLn cKaLn of poOyLmLδes Jave proδucts wLtK an Lmproveδ soOubLOLty Ln poOar soOvents anδ KLJK transparency. TKese poOym ers maLntaLneδ KLJK tKermaO stabLOLty tKe δecomposLtLon temperature beLnJ above 30ºC anδ tKe JOass transLtLon Ln tKe ranJe of 255 – 122 ºC. TKe poOyLmLδes formeδ fOe[LbOe fLOms anδ sKoweδ KLJK transmLssLon above 0 % Ln tKe waveOenJtK of 400 -00 nm. TKe AFM anaOysLs reveaOeδ a smootK topoJrapKy of tKese surfaces wLtK root-mean-square Sq rouJKness between 2.32 - 1.1 nm anδ averaJe rouJKness Sa Ln tKe ranJe of 1. 1 - 0.4 nm over an 2 µm [ 2 µm area. TKe Jooδ soOubLOLty maNes tKe present poOymers potentLaO canδLδates for practLcaO tLnJ anδ castLnJ processes. REFERENCES M. . *KosK anδ .. /. MLttaO Eδs ³PoOyLmLδes FunδamentaOs anδ AppOLcatL ons´ MarceO DecNer Eδ. New