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Projekt: Polypyrrol

Department of Chemistry FP TUL
Department of Chemistry FP TUL

Specialni anorganicke slouceniny pro pripravu a dopovani polypyrrolu

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Michal Martinek 3. ron鱈k NT Vedouc鱈 pr叩ce: Ing. Jan Gr辿gr
C鱈l bakal叩sk辿 pr叩ce p鱈prava polypyrrolu chemickou metodou za pou転it鱈 vybran箪ch p-toluensulfon叩t哲 pechodn箪ch kov哲 proven鱈 vlivu tchto sol鱈 na v箪sledn辿 vlastnosti polypyrrolu optimalizace postup哲 pro p鱈pravu tchto p-toluensulfon叩t哲 [Fe(III), Co(II), Cu(II), Ni(II), Cr(III)]
Re邸er邸e studovan辿 problematiky Elektricky vodiv辿 polymery Makromolekuly s konjugac鱈 -vazeb Delokalizace elektron哲 voln箪 pohyb po molekule Dopov叩n鱈 vn叩邸en鱈 nositele n叩boje do etzce zv箪邸en鱈 elektrick辿 vodivosti P typ odebr叩n鱈 elektronu (vznik vodiv辿 d鱈ry) N typ pid叩n鱈m elektronu obr. delokalizace elektron哲 u aromatick辿ho kruhu
Re邸er邸e studovan辿 problematiky P叩sov辿 modely vodi哲, polovodi哲 a nevodi哲
Re邸er邸e studovan辿 problematiky P叩sov箪 model dopov叩n鱈 polovodi哲
Re邸er邸e studovan辿 problematiky Dopov叩n鱈 elektrovodiv箪ch polymer哲 odebr叩n鱈 nebo pid叩n鱈 elektron哲 do etzce vznik lokalizovan箪ch stav哲 v zak叩zan辿m p叩su sn鱈転en鱈 peskokov辿 energie elektronu zv箪邸en鱈 elektrick辿 vodivosti Mno転st鱈 dopantu v polypyrrolu
Re邸er邸e studovan辿 problematiky Polypyrrol d哲le転it箪 z ady vodiv箪ch polymer哲 velk箪 rozsah vodivosti v z叩vislosti na pou転it辿m dopantu a postupu v箪roby dobr叩 stabilita v哲i vnj邸鱈m vliv哲m snadno pipraviteln箪 dosa転iteln叩 vodivost 叩dov a転 102 S/cm prakticky nejedovat箪
Re邸er邸e studovan辿 problematiky
Re邸er邸e studovan辿 problematiky Elektrolytick叩 p鱈prava polypyrrolu N叩ron辿 na technick辿 vybaven鱈 Oxidace pr哲chodem stejnosmrn辿ho proudu roztokem monomeru v rozpou邸tdle Shroma転ov叩n鱈 produktu u anody (platina) Nan叩邸en鱈 na substr叩t substr叩tem povrstvena anoda problematick辿. Lep邸鱈 ovlivov叩n鱈 tlou邸泥ky vrstvy pro邸l箪 proud Vy邸邸鱈 vodivost
Re邸er邸e studovan辿 problematiky Chemick叩 p鱈prava polypyrrolu Nen叩ron辿 na technick辿 vybaven鱈 Oxidace monomeru vhodn箪m oxidan鱈m inidlem Nejlep邸鱈 v箪sledky za pou転it鱈 sol鱈 Fe3+ (chlorid 転elezit箪) Nevhodn叩 siln叩 oxidovadla (nap. chromany) mnoho polymeran鱈ch center kr叩tk辿 etzce Velk叩 variabilita vodivosti v z叩vislosti na pou転it辿m okysliovadle a dopantu Jednoduch叩 aplikace na textiln鱈 substr叩ty
Re邸er邸e studovan辿 problematiky Odzkou邸en辿 chemick辿 reakce p鱈pravy polypyrrolu na TUL [1-3] n PyH2 + 2n FeCl3 [Py]n + 2n FeCl2 + 2n HCl (poskytuje nejlep邸鱈 v箪sledky) n PyH2 + n (NH4)2S2O8 [Py]n + 2n NH4HSO4 5n PyH2 + 2n KMnO4 + 3n H2SO4 5 [Py]n + 2n MnSO4 + n K2SO4 + 8n H2O 3n PyH2 + n K2Cr2O7 + 4n H2SO4 3 [Py]n + n Cr2(SO4)3 + n K2SO4 + 7n H2O n PyH2 + 2n AgNO3 [Py]n + 2n Ag + 2n HNO3
Re邸er邸e studovan辿 problematiky Dopov叩n鱈 polypyrrolu Po転adavky na velikost a strukturu dopantu Vhodn鱈 kandid叩ti: Aromatick辿 sulfonov辿 kyseliny a jejich soli Kationt (obvykle H+)* m哲転e vniknout do makromolekuly nositel n叩boje Aniont (ide叩l objemn箪) p哲sob鱈 z vnj邸ku na makromolekulu udr転uje elektrodynamickou rovnov叩hu mezi nabitou molekulou a nenabit箪m prosted鱈m makromolekula z哲stane stabiln鱈 *) otevenou ot叩zkou z哲st叩v叩, zda se dopov叩n鱈 nemohou 炭astnit i jin辿 kationty ne転 H+
Re邸er邸e studovan辿 problematiky Praktick辿 vyu転it鱈 polypyrrolu mikroelektronika polymern鱈 tranzistory baterie Li/PPy, PPy/grafit cyklick辿 rychl辿 nab鱈jen鱈 a vyb鱈jen鱈 (superkondenz叩tory) zdravotnictv鱈 sledov叩n鱈 hladiny Li v krvi na principu vzniku l叩nku Li/PPy (budoucnost) chemick辿 senzory na z叩klad zmn elektrick辿 vodivosti v p鱈tomnosti detekovan辿 chemik叩lie (detekce vysoce toxick箪ch plyn哲) inteligentn鱈 textilie elektrovodiv辿, ochrana ped elektromagnetick箪m smogem
Re邸er邸e studovan辿 problematiky Elektromagnetick辿 st鱈n鱈c鱈 aplikace pou転it鱈 PPy nanesen辿ho na textiln鱈 substr叩t pou転it鱈 v m鱈stech, kde nen鱈 prostor pro kovy Parametry: n鱈zk叩 hustota, dobr叩 tvarovatelnost, dostauj鱈c鱈 st鱈n鱈c鱈 炭innost Mo転n辿 aplikace: spotebn鱈 elektronika (mobil), ochrann辿 odvy
Stav problematiky na TUL v r叩mci dvou doktorsk箪ch dizertan鱈ch prac鱈 je na FT TUL druh箪m rokem e邸ena problematika vyu転it鱈 polypyrrolu pro p鱈pravu textili鱈 chr叩n鱈c鱈ch proti elektromagnetick辿mu smogu [1-5] v pr叩ci Ing. V. af叩ov辿 byly nalezeny z叩vislosti vlastnost鱈 produkt哲 na chemick箪ch postupech p鱈pravy polypyrrolu a tato bakal叩sk叩 pr叩ce by mohla sv箪mi experimenty a men鱈mi prospt k praktick辿mu objasnn鱈 problematiky [1-3]
Publikovan辿 odborn辿 l叩nky na TUL 1) GRGR J., af叩ov叩 V.: Bari辿rov辿 textilie chr叩n鱈c鱈 proti elektromagnetick辿mu smogu, Textilie vnov辿m tis鱈cilet鱈 IX 14.4.2011, str. 93-110, Liberec, ISBN 978-80-7372-723-9 2) AFOV, V. , J. Gr辿gr: Preparation and Characterization of Conducting PET Fabric/Polypyrrole Composite for EMI Shielding. In:/IDMS 2011: Book of Abstracts, p. 62/, ISBN 978-80-7395-419-2 3) AFOV Veronika, Jan Gr辿gr: Functional PET fabric/polypyrrole composites,18th International Conference STRUTEX, TU Liberec, December 2011, pp: 405-410, ISBN 978-80-7372-786-4 4) ABBASI M. Rehan, M. Marsalkova , J. Militky: Rheological and electrical properties of polypyrrole nanocomposites , 18th International Conference STRUTEX, TU Liberec, December 2011, pp: 401-404, ISBN 978-80-7372-786-4 5) ABBASI, M. Rehan, M. Marsalkova, V. K. Baheti , J. Militky, Optimization of milling conditions for the production of polypyrrole nanoparticles, 18th International Conference STRUTEX, TU Liberec, December 2011, pp: 237-242, ISBN 978-80-7372-786-4
Re邸er邸e studovan辿 problematiky Vzorek PET tkaniny ped a po aplikaci polypyrrolu povrchov箪 odpor: 4,89 . 1012立 povrchov箪 odpor: 5,26 . 106 立 [1]
Re邸er邸e studovan辿 problematiky SEM sn鱈mky n叩nos哲 polypyrrolu na PES tkanin [1]
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Pipraveny p-toluensulfon叩ty 転elezit箪, nikelnat箪, kobaltnat箪, mnat箪 a chromit箪 Provedena IR spektroskopie tchto slouenin Po鱈zeny makrofotografie produkt哲 Provedena ED rentgen-fluorescenn鱈 anal箪za pipraven箪ch produkt哲 Studov叩no chov叩n鱈 p-toluensulfon叩tu 転elezit辿ho na bodot叩vku pod optick箪m mikroskopem.
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Laboratorn鱈 za鱈zen鱈 pro p鱈pravu p-toluensulfon叩tu 転elezit辿ho z FeCl3 Dopanty
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t nikelnat箪 hexahydr叩t p-toluensulfon叩t 転elezit箪 bezv. p-toluensulfon叩t mnat箪 hexahydr叩t Fotografie vlastn鱈 - zvt邸eno 40x
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t chromit箪 p-toluensulfon叩t kobaltnat箪 hexahydr叩t
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky FTIR spektra pipraven箪ch produkt哲: p-toluensulfon叩t 転elezit箪 a chromit箪 0,16 0,14 Fe(OT s)3 oran転 Cr(OT s)3 0,12 0,10 absorbance 0,08 0,06 0,04 0,02 0,00 3600 3100 2600 2100 1600 1100 600 v lnoet (cm-1) Spektra zmena FTIR spektrometrem iN10 MX metodou reflexn鱈.
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky FTIR spektra pipraven箪ch produkt哲: p-toluensulfon叩t nikelnat箪, mnat箪 a kobaltnat箪 0,20 Ni(OTs)2 Vibrace C-H 0,18 Cu(OTs)2 1,4 substituce Co(OTs)2 Vibrace SO2 0,16 0,14 Voda (vibrace O-H) 0,12 Vibrace C=C absorbance 0,10 0,08 0,06 0,04 0,02 0,00 3600 3100 2600 2100 1600 1100 600 vlnoet (cm-1)
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t 転elezit箪 - Fe(OTs)3 Rentgenfluorescenn鱈 anal箪za metodou ED-XRF, p鱈stroj ElvaX2
Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Cr(OTs)3 Co(OTs)2 Ni(OTs)2 Cu(OTs)2 Rentgenfluorescenn鱈 anal箪za metodou ED-XRF, p鱈stroj ElvaX2
N叩vrh dal邸鱈ho postupu prac鱈 DSC pipraven箪ch p-toluensulfon叩t哲 polymerizace pyrrolu v roztoku na textiln鱈 substr叩t (PET) za pou転it鱈 pipraven箪ch slouenin z叩kladn鱈 charakterizace vzork哲 polypyrrolem povrstven辿 tkaniny (elektrick叩 vodivost, st鱈n鱈c鱈 elektromagnetick叩 炭innost) Dkuji Ing. Jan M端llerov辿, Ph.D. a Ing. Martinu Stuchl鱈kovi za pomoc pi sejmut鱈 a interpretaci spekter a Ing. Ev Ko邸泥叩kov辿 za pomoc pi charakterizaci p-toluensulfon叩tu 転elezit辿ho.
Literatura citovan叩 v re邸er邸i [2] PROKE, J. - STEJSKAL, J. - OMASTOV, M.: Polyanilin a polypyrrol - dva pedstavitel辿 vodiv箪ch polymer哲. Chemick辿 Listy 95, p. 484 - 492 (2001) [3] LI B. - SANTHANAM, S. - SCHULTZ, L. - JEFFRIES- EL, M. - IOVU, M. C. - SAUV, G. - COOPER, J. ZHANG, R. - REVELLI, J. C. - KUSNE, A. G. - SNYDER, J. L. - KOWALEWSKI, T. - WEISS, L. E. - MCCULLOUGH, R. D. - FEDDER, G. K. - LAMBETH, D. N: Inkjet printed chemical sensor array based on polythiophene conductive polymers. Sensors and Actuators B: Chemical 123, p 651-660, (2007) [4] SHIRAKAWA, H. - LOUIS, E. J., - MACDIARMID, A. G. - CHIANG, C. K. - HEEGER, A.: Synthesis of electrically conducting organic polymers: halogen derivates of polyacetylene. J. Chem. Soc., Chem. Commun. 16 , p. 578-580 (1977) [5] MCNEILL, R SIUDAK, R. - WARDLAW, H. - WEISS, D. E. Electronic conduction in polymers. I. The chemical structure of polypyrrole. Australian journal of chemistry 16, p. 1056-1075 (1963) [6] KANAZAWA, K. K. - DIAZ, A. F. - GLEISS, R. H. - GILL ,W. D. - KWAK, J. F. - LOGAN, J. A. RABOLT, J. F. - STREET, G. B.: "Organic metal": polypyrrole, a stable synthetic "metallic" polymer. J. Chem. Soc., Chem. Commun. 19, p. 854- 857 (1979) [7] HOLMES, S. M. - MCKINLEY, S. G. - GIROLAMI, G. S.: 13. transition metal p-toluensulfonates. Inorganic Syntheses 33, p. 91-103 (2002) [8] BALCI, N. - AKBULUT, U. - TOPPARE, L. - STANKE, D. - HALLENSLEBEN, M. L.: Electrically conductive polymer grafts prepared by electrochemical polymerization of pyrrole onto Poly[(methylmethacrylate)-co-(2-(N- pyrrolyl)ethylmethacrylate)] electrodes. Journal of Chemistry 22, p. 73-80 (1998) [10] YAVUZ, . - MANOJ, K. R. - ALDISSI, M. - PODDAR, P. - SRIKANTH, H.: Polypyrrole composites for shielding applications. Syntetic Metals 151, p. 211-217 (2005) 28
[11] TAKAKUBO, M.: Electrochemical polymerization of pyrrole in aqueous solutions. Synthetic Metals 16, p. 167-172 (1986) [12] WI店EVSKA, M.: Elektrovodiv辿 polymery - materi叩ly 21. stolet鱈. Diplomov叩 pr叩ce. stav chemie, Univerzita ve Vratislavi (PL), (2007) [13] SUBRAMANIAN, P. - NOEL, B. - SPICCIA, C. - DOUGLAS, L. -MACFARLANE, R.- WINTHER-JENSEN B .- FORSYTH, C.: Vapour phase polymerisation of pyrrole induced by iron(III) alkylbenzenesulfonate salt oxidising agents. Synthetic Metals 17-18, p. 704-711 (2008) [14] FERENETS, M. - HARLIN, A.: Chemical in situ polymerization of polypyrrole on poly(methylmetacrylate) substrate, Thin Solid Films 13, p. 5324-5328 (2007) [15] OMASTOV M.: Vplyv tenzidov na vlastnosti vodiv箪ch polym辿rov a kompozitov. Disertan鱈 pr叩ce. stav polymer哲, Slovensk叩 akademie vd (2008) [16] SAVILLE, P.: Polypyrrole formation and use. Technical Memorandum TM 2005-004, DRDC Atlantic, (2005). Voln dostupn辿 na webu: http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ada436284.pdf&Location=U2&doc=GetTRDoc.pdf [17] DRAGO-VIOREL B.:Polypyrrole films prepared by chemical oxidation of pyrrole in aqueous FeCl3 solution. Journal of Science and Arts 1 (12), p. 53-58 (2010) [18] WINTHER-JENSEN, B. - BREIBY, D. W. - WEST, K.: Base inhibited oxidative polymerization of 3,4-ethylenedioxythiophene with iron(III)tosylate, Synthetic Metals 152, p. 1-3 (2005) [19] GARNIER, F. - HAJLAOUI, R. - YASSAR, A. - SRIVASTAVA, P.: All polymer field effect transistor realized by printing techniques. Science 265 (5179) p. 1684-1686 (1994) [20] VOSS, D.: Cheap and cheerful circuits. Nature 407, p. 442-444 (2000) 29
[21] MOTT, N. F. - DAVIS, E. A.: Electron Processes in Non-Crystalline Materials, Clarendon Press, Oxford 1979 [22] REN, L WANG, L AN, H. - ZHANG, F.: Study of lithium/polypyrrole secondary batteries with Lithium as cathode and polypyrrole anode. Rare Metals 26, p. 591-600 (2007) [23] CHEMSPIDER chemick叩 datab叩ze [online] Dostupn辿 z www: http://www.chemspider.com/ [24] SULTANA, I, M.M. RAHMAN, SHA LI, JIAZHAO WANG, CAIYUN WANG, G.G. WALLACE, HUA-KUN L.: Electrodeposited polypyrrole (PPy)/para (toluene sulfonic acid) (pTS) free-standing film for lithium secondary battery application. Electrochimica Acta, Available online 16 November 2011, http://www.sciencedirect.com/science/article/pii/S0013468611017087 [25] HYUNG-SUK, O. - KWANGHYUN K. - HANSUNG K.: Polypyrrole-modified hydrophobic carbon nanotubes as promising electrocatalyst supports in polymer electrolyte membrane fuel cells, International Journal of Hydrogen Energy 36 (18), p. 11564-11571 (2011) ( http://www.sciencedirect.com/science/article/pii/S0360319911015515) [26] SMELA, E.: Conjugated polymer actuators for biomedical application. Advanced materials 15, p. 481-494 (2003). [online] Dostupn辿 online z webu: http://atmsp.whut.edu.cn/resource/pdf/4987.pdf [27] LIN, T. - WANG, L. - WANG, X.- KAYNAK, A.: Polymerising pyrrole on polyester textiles and controlling the conductivity through coating thickness. ScienceDirect: Thin Solid Films 479, p. 77-82 (2005) [28] JAMADADE, S. - JADHAV, S. V. - PURI, V.: Electromagnetic reflection, shielding and conductivity of polypyrrole thin film electropolymerized in P-Tulensulfonic acid, Journal of Non-Crystalline Solids 357, p. 1177-1181 (2011) [29] KIM, M.S. - KIM, H.K. - BYUN, S.W. - JEONG, S.H. - HONG, Y.K. - JOO, J.S. - SONG, K.T. - KIM, J.K. - LEE, C.J. - LEE, J.Y.: PET fabric/polypyrrole composite with high electrical conductivity for EMI shielding, Synthetic Metals 126, p. 233-239 (2002) 30
[30] WICKOWSKI, T. W. - JANUKIEWICZ, M. J.: Methods for Evaluating the Shielding Effectiveness of Textiles. (2009) [online], dostupn辿 z www: http://www.fibtex.lodz.pl/59_09_18.pdf [31] HKANSSON, E. - AMIET, A. - KAYNAK, A.: Electromagnetic shielding properties of polypyrrole/polyester composites in the 118 GHz frequency range. Synthetic Metals 156, p. 917-925 (2006) [32] BRIE, M.- TURCU, R. - NEAMTU, C. - PRUNEANU, S.: The effect of initial conductivity and doping anions on gas sensitivity of conducting polypyrrole films to NH3. Sensors and Actuators B: Chemical 37, p. 119-122 (1996) [33] JOSHI, A GANGAL, S.A. - GUPTA, S.K.: Ammonia sensing properties of polypyrrole thin films at room temperature. Sensors and Actuators B: Chemical 156, p. 938 942 (2011) [34] OMASTOV, M.: Synt辿za, vlastnosti a aplik叩cie polypyrolu a jeho kompoziotov. Chemick辿 listy 85, p. 794-816 (1991) [35] VOTOEK, E.: Anorganick叩 chemie, STNL Praha, (1954) [36] WIKIPEDIA: p-toluensulfonic acid. [online] dostupn辿 z webu: http://en.wikipedia.org/wiki/P-Toluenesulfonic_acid [37] ALI, M. A. - KIM, H. - LEE, CH. - NAM, H. - LEE, J.: Effects of iron(III) p-toluenesulfonate hexahydrate oxidant on the growth of conductive poly(3,4-ethylenedioxythiophene) (PEDOT) nanofilms by vapor phase polymerization. Synthetic Metals 161, p. 1347-1352 (2011) [38] SPAFFORD, M. J. - ANDERSON, E. D. - LACEY, J. R. - PALMA, A.C. - MOHAN, R. S.: Iron(III) p-toluenesulfonate catalyzed synthesis of homoallyl ethers from acetals and aldehydes, Tetrahedron Letters 48, p. 8665-8667 (2007) [39] BOTHWELL, J. M. - ANGELES, V. V. - CAROLAN, J. P. - OLSON, M. E. - MOHAN, R. S.: A mild and chemoselective method for the deprotection of tert-butyldimethylsilyl (TBDMS) ethers using iron(III) tosylate as a catalyst. Tetrahedron Letters 51 p. 1056-1058 (2010) 31
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Projekt: Polypyrrol

  • 1. Michal Martinek 3. ron鱈k NT Vedouc鱈 pr叩ce: Ing. Jan Gr辿gr
  • 2. C鱈l bakal叩sk辿 pr叩ce p鱈prava polypyrrolu chemickou metodou za pou転it鱈 vybran箪ch p-toluensulfon叩t哲 pechodn箪ch kov哲 proven鱈 vlivu tchto sol鱈 na v箪sledn辿 vlastnosti polypyrrolu optimalizace postup哲 pro p鱈pravu tchto p-toluensulfon叩t哲 [Fe(III), Co(II), Cu(II), Ni(II), Cr(III)]
  • 3. Re邸er邸e studovan辿 problematiky Elektricky vodiv辿 polymery Makromolekuly s konjugac鱈 -vazeb Delokalizace elektron哲 voln箪 pohyb po molekule Dopov叩n鱈 vn叩邸en鱈 nositele n叩boje do etzce zv箪邸en鱈 elektrick辿 vodivosti P typ odebr叩n鱈 elektronu (vznik vodiv辿 d鱈ry) N typ pid叩n鱈m elektronu obr. delokalizace elektron哲 u aromatick辿ho kruhu
  • 4. Re邸er邸e studovan辿 problematiky P叩sov辿 modely vodi哲, polovodi哲 a nevodi哲
  • 5. Re邸er邸e studovan辿 problematiky P叩sov箪 model dopov叩n鱈 polovodi哲
  • 6. Re邸er邸e studovan辿 problematiky Dopov叩n鱈 elektrovodiv箪ch polymer哲 odebr叩n鱈 nebo pid叩n鱈 elektron哲 do etzce vznik lokalizovan箪ch stav哲 v zak叩zan辿m p叩su sn鱈転en鱈 peskokov辿 energie elektronu zv箪邸en鱈 elektrick辿 vodivosti Mno転st鱈 dopantu v polypyrrolu
  • 7. Re邸er邸e studovan辿 problematiky Polypyrrol d哲le転it箪 z ady vodiv箪ch polymer哲 velk箪 rozsah vodivosti v z叩vislosti na pou転it辿m dopantu a postupu v箪roby dobr叩 stabilita v哲i vnj邸鱈m vliv哲m snadno pipraviteln箪 dosa転iteln叩 vodivost 叩dov a転 102 S/cm prakticky nejedovat箪
  • 9. Re邸er邸e studovan辿 problematiky Elektrolytick叩 p鱈prava polypyrrolu N叩ron辿 na technick辿 vybaven鱈 Oxidace pr哲chodem stejnosmrn辿ho proudu roztokem monomeru v rozpou邸tdle Shroma転ov叩n鱈 produktu u anody (platina) Nan叩邸en鱈 na substr叩t substr叩tem povrstvena anoda problematick辿. Lep邸鱈 ovlivov叩n鱈 tlou邸泥ky vrstvy pro邸l箪 proud Vy邸邸鱈 vodivost
  • 10. Re邸er邸e studovan辿 problematiky Chemick叩 p鱈prava polypyrrolu Nen叩ron辿 na technick辿 vybaven鱈 Oxidace monomeru vhodn箪m oxidan鱈m inidlem Nejlep邸鱈 v箪sledky za pou転it鱈 sol鱈 Fe3+ (chlorid 転elezit箪) Nevhodn叩 siln叩 oxidovadla (nap. chromany) mnoho polymeran鱈ch center kr叩tk辿 etzce Velk叩 variabilita vodivosti v z叩vislosti na pou転it辿m okysliovadle a dopantu Jednoduch叩 aplikace na textiln鱈 substr叩ty
  • 11. Re邸er邸e studovan辿 problematiky Odzkou邸en辿 chemick辿 reakce p鱈pravy polypyrrolu na TUL [1-3] n PyH2 + 2n FeCl3 [Py]n + 2n FeCl2 + 2n HCl (poskytuje nejlep邸鱈 v箪sledky) n PyH2 + n (NH4)2S2O8 [Py]n + 2n NH4HSO4 5n PyH2 + 2n KMnO4 + 3n H2SO4 5 [Py]n + 2n MnSO4 + n K2SO4 + 8n H2O 3n PyH2 + n K2Cr2O7 + 4n H2SO4 3 [Py]n + n Cr2(SO4)3 + n K2SO4 + 7n H2O n PyH2 + 2n AgNO3 [Py]n + 2n Ag + 2n HNO3
  • 12. Re邸er邸e studovan辿 problematiky Dopov叩n鱈 polypyrrolu Po転adavky na velikost a strukturu dopantu Vhodn鱈 kandid叩ti: Aromatick辿 sulfonov辿 kyseliny a jejich soli Kationt (obvykle H+)* m哲転e vniknout do makromolekuly nositel n叩boje Aniont (ide叩l objemn箪) p哲sob鱈 z vnj邸ku na makromolekulu udr転uje elektrodynamickou rovnov叩hu mezi nabitou molekulou a nenabit箪m prosted鱈m makromolekula z哲stane stabiln鱈 *) otevenou ot叩zkou z哲st叩v叩, zda se dopov叩n鱈 nemohou 炭astnit i jin辿 kationty ne転 H+
  • 13. Re邸er邸e studovan辿 problematiky Praktick辿 vyu転it鱈 polypyrrolu mikroelektronika polymern鱈 tranzistory baterie Li/PPy, PPy/grafit cyklick辿 rychl辿 nab鱈jen鱈 a vyb鱈jen鱈 (superkondenz叩tory) zdravotnictv鱈 sledov叩n鱈 hladiny Li v krvi na principu vzniku l叩nku Li/PPy (budoucnost) chemick辿 senzory na z叩klad zmn elektrick辿 vodivosti v p鱈tomnosti detekovan辿 chemik叩lie (detekce vysoce toxick箪ch plyn哲) inteligentn鱈 textilie elektrovodiv辿, ochrana ped elektromagnetick箪m smogem
  • 14. Re邸er邸e studovan辿 problematiky Elektromagnetick辿 st鱈n鱈c鱈 aplikace pou転it鱈 PPy nanesen辿ho na textiln鱈 substr叩t pou転it鱈 v m鱈stech, kde nen鱈 prostor pro kovy Parametry: n鱈zk叩 hustota, dobr叩 tvarovatelnost, dostauj鱈c鱈 st鱈n鱈c鱈 炭innost Mo転n辿 aplikace: spotebn鱈 elektronika (mobil), ochrann辿 odvy
  • 15. Stav problematiky na TUL v r叩mci dvou doktorsk箪ch dizertan鱈ch prac鱈 je na FT TUL druh箪m rokem e邸ena problematika vyu転it鱈 polypyrrolu pro p鱈pravu textili鱈 chr叩n鱈c鱈ch proti elektromagnetick辿mu smogu [1-5] v pr叩ci Ing. V. af叩ov辿 byly nalezeny z叩vislosti vlastnost鱈 produkt哲 na chemick箪ch postupech p鱈pravy polypyrrolu a tato bakal叩sk叩 pr叩ce by mohla sv箪mi experimenty a men鱈mi prospt k praktick辿mu objasnn鱈 problematiky [1-3]
  • 16. Publikovan辿 odborn辿 l叩nky na TUL 1) GRGR J., af叩ov叩 V.: Bari辿rov辿 textilie chr叩n鱈c鱈 proti elektromagnetick辿mu smogu, Textilie vnov辿m tis鱈cilet鱈 IX 14.4.2011, str. 93-110, Liberec, ISBN 978-80-7372-723-9 2) AFOV, V. , J. Gr辿gr: Preparation and Characterization of Conducting PET Fabric/Polypyrrole Composite for EMI Shielding. In:/IDMS 2011: Book of Abstracts, p. 62/, ISBN 978-80-7395-419-2 3) AFOV Veronika, Jan Gr辿gr: Functional PET fabric/polypyrrole composites,18th International Conference STRUTEX, TU Liberec, December 2011, pp: 405-410, ISBN 978-80-7372-786-4 4) ABBASI M. Rehan, M. Marsalkova , J. Militky: Rheological and electrical properties of polypyrrole nanocomposites , 18th International Conference STRUTEX, TU Liberec, December 2011, pp: 401-404, ISBN 978-80-7372-786-4 5) ABBASI, M. Rehan, M. Marsalkova, V. K. Baheti , J. Militky, Optimization of milling conditions for the production of polypyrrole nanoparticles, 18th International Conference STRUTEX, TU Liberec, December 2011, pp: 237-242, ISBN 978-80-7372-786-4
  • 17. Re邸er邸e studovan辿 problematiky Vzorek PET tkaniny ped a po aplikaci polypyrrolu povrchov箪 odpor: 4,89 . 1012立 povrchov箪 odpor: 5,26 . 106 立 [1]
  • 18. Re邸er邸e studovan辿 problematiky SEM sn鱈mky n叩nos哲 polypyrrolu na PES tkanin [1]
  • 19. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Pipraveny p-toluensulfon叩ty 転elezit箪, nikelnat箪, kobaltnat箪, mnat箪 a chromit箪 Provedena IR spektroskopie tchto slouenin Po鱈zeny makrofotografie produkt哲 Provedena ED rentgen-fluorescenn鱈 anal箪za pipraven箪ch produkt哲 Studov叩no chov叩n鱈 p-toluensulfon叩tu 転elezit辿ho na bodot叩vku pod optick箪m mikroskopem.
  • 20. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Laboratorn鱈 za鱈zen鱈 pro p鱈pravu p-toluensulfon叩tu 転elezit辿ho z FeCl3 Dopanty
  • 21. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t nikelnat箪 hexahydr叩t p-toluensulfon叩t 転elezit箪 bezv. p-toluensulfon叩t mnat箪 hexahydr叩t Fotografie vlastn鱈 - zvt邸eno 40x
  • 22. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t chromit箪 p-toluensulfon叩t kobaltnat箪 hexahydr叩t
  • 23. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky FTIR spektra pipraven箪ch produkt哲: p-toluensulfon叩t 転elezit箪 a chromit箪 0,16 0,14 Fe(OT s)3 oran転 Cr(OT s)3 0,12 0,10 absorbance 0,08 0,06 0,04 0,02 0,00 3600 3100 2600 2100 1600 1100 600 v lnoet (cm-1) Spektra zmena FTIR spektrometrem iN10 MX metodou reflexn鱈.
  • 24. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky FTIR spektra pipraven箪ch produkt哲: p-toluensulfon叩t nikelnat箪, mnat箪 a kobaltnat箪 0,20 Ni(OTs)2 Vibrace C-H 0,18 Cu(OTs)2 1,4 substituce Co(OTs)2 Vibrace SO2 0,16 0,14 Voda (vibrace O-H) 0,12 Vibrace C=C absorbance 0,10 0,08 0,06 0,04 0,02 0,00 3600 3100 2600 2100 1600 1100 600 vlnoet (cm-1)
  • 25. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky p-toluensulfon叩t 転elezit箪 - Fe(OTs)3 Rentgenfluorescenn鱈 anal箪za metodou ED-XRF, p鱈stroj ElvaX2
  • 26. Experiment叩ln鱈 pr叩ce na e邸en鱈 problematiky Cr(OTs)3 Co(OTs)2 Ni(OTs)2 Cu(OTs)2 Rentgenfluorescenn鱈 anal箪za metodou ED-XRF, p鱈stroj ElvaX2
  • 27. N叩vrh dal邸鱈ho postupu prac鱈 DSC pipraven箪ch p-toluensulfon叩t哲 polymerizace pyrrolu v roztoku na textiln鱈 substr叩t (PET) za pou転it鱈 pipraven箪ch slouenin z叩kladn鱈 charakterizace vzork哲 polypyrrolem povrstven辿 tkaniny (elektrick叩 vodivost, st鱈n鱈c鱈 elektromagnetick叩 炭innost) Dkuji Ing. Jan M端llerov辿, Ph.D. a Ing. Martinu Stuchl鱈kovi za pomoc pi sejmut鱈 a interpretaci spekter a Ing. Ev Ko邸泥叩kov辿 za pomoc pi charakterizaci p-toluensulfon叩tu 転elezit辿ho.
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