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(1)Journal of the Korean Chemical Society 2005, Vol. 49, No. 1 Printed in the Republic of Korea. PPVê %Ú 9 # 7ß9 . *^ÁBfK*ÁöËî ÁB'^ †. >ö&v ¶"& z" >ö&v "& *¶Òò" (2004. 10. 29 7>). †. †. Synthesis of PPV-Based Copolymers Hyun Ho Lee, Eun Ok Kim*, Jang Hoon Won†, and Young Ho Kim† Department of Chemistry, The University of Suwon, Kyunggi 445-742, Korea Department of Electronic Materials, The University of Suwon, Kyunggi 445-742, Korea (Received October 29, 2004). †. º £. Wittig >wö ~ Triphenylamine(TPA) group " phenylene unit(p-, o-, bi-), *¶ "² Î"& ®º ~~Ú¢ 7~ ¸f ÎN~ ïöB Óï'ræ~ B7j {~& . 7Ú(TPA-PPV, TPAPOPV, TPA-ROPPV, TPA-PBPV)~ UV-Vis., PL W> bº '' 378 nm~440 nm, 447 nm~503 nmöB ¾æÒ , Egº 2.53 eV~2.81 eV 'ªj {~& . *Ú: PPV, TPA-PPV, TPA-POPV, TPA-ROPPV, TPA-PBPV, PL, Band gap 1. ABSTRACT. The PPV related copolymers, TPA-PPV, TPA-POPV, TPA-ROPPV, and TPA-PBPV were synthesized by the Wittig polycondensation reaction to tune the emission wavelength from green to blue region. They showed UVVis. absorbance and PL in the ranges of 378 nm~440 nm and 447 nm~503 nm, respectively. The band gap energy of these copolymers were in the ranges of 2.53 eV~2.81 eV. Keywords: PPV, TPA-PPV, TPA-POPV, TPA-ROPPV, TPA-PBPV, PL, Band gap. * V FV zbf ¢>'b .Úö ³~æò, " ÒÒ(main chain)ö 7 FÖ" ¢ FÖ v& Ö>Ú ®º ¢ r *V*êW ¢ <º . ª¶º 7 Ö(multiple bond)ö ~ ÒÒ^ Ã& ' π-2ÿ>& 7Ï(overlap)> Ú ö.æ Z(energy band)& ;W> *¶º ÞÒz>æ p Ö ÒÒj V¢ jv' ¶F² æç¢ > ®º π-*¶¢ &æ ® . $ *¶f ; z' êw¾, 7 V(photo excitation) _ f *~ "« ª¶ ÒÒö &î r, * ~ "*ö π-*¶~ jÞÒz& ¢ÚÂ . Ò 2. ª¶º "ÒÒ~ z ¾ ~~V «~¢ : Þ¾, _f ÚÊ j ¦ªj "ÒÒ Úö ê« ~æ ÒÒ~ ^¢ ² ~¾ $º Ò Ò ~ ïW(coplanarity)j .b Z Sj . > ® . ª¶öB~ *êB7(electroluminescence: EL) poly(p-phenylenevinylene) PPVöB ¾r {B ¾ *Òræ · & ê¯>îº, · ïç ~ j áj > ®º O»bº PPV "ÒÒö ~ ~V¢ ê«~¾, rÒV¢ ã«~ ^¢ .~º O» ÒÏ>Ú z . ~ "º &6f ;"« bî(HTL) " * êB7 bî ¾ rJ^ ®b ¸f PL ·¶ÎN j <º Triphenylamine(TPA) group" phenylene unit 3-6. 7,8. 9,10. 11. V72V.

(2) ê %Ú 9 # 7ß9 . 73. PPV. Fig. 1. Synthetic methods of monomer.. (para-, ortho-, bi-), *¶ "² Î"& ®º ~~Ú¢ 7Ú W~ ïöB Óï'ræ B7ß W 5 'n;Wj {~º © . öB B7bî ÒÏ 7Ú f ² v ê¢ ö W>î . Ñ ® êº FVÏ. ö &ÏW ·ÏV¢ ~~~ Fig. 1öBf ?f ïÚ¢ W~º ©, v ® êº Ñ ® êöB WB ïÚf ylide¢ Wittig >wb 7 ~ Fig. 2" ?f &ÏW 7Ú¢ W~º " ; .. þ £ # 88 f TCI~ GR/ £j ;B~æ p ÒÏ ~& Ï º {Ö £~ B®j ;B~ ÒÏ~ & . Thin layer chromatographyº Silica Gel 60 F (Merck), Column chromatographyº Silica Gel(230~400 mesh) (Aldrich)j ÒÏ~& . >wb 5 Wb { j * FT-IR ª7V(Bomen B-100), H-NMR ª7 V(Bruker 500 MHz)¢ Ï~& . ò~ W> Ê¿ Aldrich. 254. 1. 2005, Vol. 49, No. 1. Þ"f UV-vis. ª7V(Hewlett-Packard 8453), B7(PL) Ê¿Þ"f Luminescence spectrofluorometer(PerkinElmer LB-50B)¢ ÒÏ~& . ; n;Wj {~ V * 7ï ªC(TGA) (NETZSCH STA 409C)j Ï~&, ª¶ ;ï z+f Spin coater(Laurell MS-200-4NPP)¢ ÒÏ~& . Monomer. 9. 9. 0 CöB POCl 38.8 g(0.2 mol)j DMF 14.87 g(0.2 mol)ö I 1 * v>~& . Nb RJ 1* v>Î ê, 1,2dichloroethaneö triphenylamine 10 g(40 mmol) j Î&~ 90 CöB 15* ~~ V . >wb ~ Nê¢ Nb ÚJ dichloromethaneb ºÂ ê, 6{~ Ï ¢ B~ Òºö WO B & îÆ¾b(n-Hexane: Ethylacetate=4:1) ªÒ~& . o. 4,4'-diformyltriphenylamine. 3. o. Dihexoxyxylylenebis(triphenylphosphoniumbromide). 9. Hydroquinone 11 g(0.1 mol)j DMF 200 mlö ê, K CO 27.6 g(0.2 mol)¢ Î&~, 1-bromohexane 36.3 g(0.22 mol)j Î& ê 85 CöB 24* ~~ 2. 3. o.

(3) *^ÁBfKÁöËîÁB'^. 74. Fig. 2. Structures of various triphenylamine unit contained PPVs.. V . >wb~ Nê¢ Nb ÚJ methylene chloride(M.C.) ºÂ ê n-hexaneb ÒÖ;~ ï Úªöj áî . Úªö 6.6 gj tolueneö ê triphenylphosphine 9.19 gj Î&~ 8* ;ê ~~ Î ê Nb ÚJ EtOH ÒÖ;~ Wï ªöj áî . 4,4'-Xylylenebis(triphenylphosphonium Chloride) 9. 4,4'-bis(chloromethyl)-1,1'-biphenyl 6.78 g(0.027 mol)j tolueneö ê, triphenylphosphine 21.25 g(0.081 mol)j Î&~, 8* ~~ V . Nb ÚÖ ê, n-hexaneb ÒÖ;~ ï Ú¢ áî .. 9 9. 4,4'-diformyltriphenylamine 0.5 g (1.66 mmol)" 1,4-Xylylenebis(triphenylphosphonium bromide) 1.31 g(1.66 mmol)¢ EtOH 30 mlf CH Cl 10 ml b Ï ö ê, t-BuOK 0.935 g(8.33 mmol)j Â Â® &~, N &Ê ~öB 5* v>V . ³» HCl 5 ml¢ ~º MeOH 200 ml¢ Î&~ > wj jÖ~, *B ª¶¢ jV ê, M.C. ºÂ~ 6{~ Ï ¢ B~ tolueneö ê, iodine¢ ²ï Î&~ 4* ~~ V . 6{~ Ï ¢ B ê, EtOH ÒÖ;~ 3¢ * Soxhlet extracter MeOH ~öB ;B~ ¦ ï ªöj áî . TPA-POPV 9. 4,4'-diformyltriphenylamine 0.5 g Polymer. TPA-PPV. 3. 2. " o-Xylylenebis(triphenylphosphonium bromide) 1.31 g(1.66 mmol)¢ EtOH 26 mlf CH Cl 15 ml b Ï ö ê, t-BuOK 0.935 g(8.33 mmol)j Â Â® &~, N &Ê ~öB 5* v>V . ³» HCl 5 ml¢ ~º MeOH 200 ml¢ Î&~ > wj jÖB *B ª¶¢ jV ê, M.C. ºÂ~ 6{~ Ï ¢ B~, tolueneö ê, iodine¢ ²ï Î&~ 4* ~~ V . 6{~ Ï ¢ B ê, EtOH ÒÖ;~ 3¢ * Soxhlet extracter MeOH ~öB ;B~ ¦ ï ªöj áî . TPA-ROPP 9. 4,4'-diformyltriphenylamine 0.25 g (0.83 mmol)" 2,5-dihexyloxy-1,4-Xylylenebis(triphenylphosphonium bromide) 0.821 g(0.83 mmol)¢ EtOH 25 mlf CHCl 8 mlö ê, t-BuOK 0.5 g(4.15 mmol) j ÂÂ® &~, N &Ê ~öB 5* v>V . ³» HCl 5 ml¢ ~º MeOH 200 ml¢ Î&~ >wj jÖV . *B ª¶¢ jV ê, M.C. ºÂ~ 6{~ Ï ¢ B~, toluene ö ê, iodine¢ ²ï Î&~ 4* ~~ V. . 6{~ Ï ¢ B ê, EtOH ÒÖ; ~ 3¢* Soxhlet extracter MeOH ~öB ;B~ ¦ï ªöj áî . TPA-PBPV 9. 4,4'-diformyltriphenylamine 0.5 g (1.66 mmol)" 4,4'-Xylylenebis(triphenylphosphonium chloride) 1.288 g(1.66 mmol)¢ EtOH 45 mlf CH Cl (1.66 mmol). 3. 2. 3. 2. 3. Journal of the Korean Chemical Society.

(4) ê %Ú 9 # 7ß9 . 75. PPV. bÏ ö ê, t-BuOK 0.935 g(8.33 mmol) j ÂÂ® &~, N &Ê ~öB 5* v>V . ³» HCl 5 ml¢ ~º MeOH 200 ml¢ Î&~ >wj jÖÊ, *B ª¶¢ jV ê, M.C. ºÂ~ 6{~ Ï ¢ B~, toluene ö ê, iodine¢ ²ï Î&~ 4* ~~ V. . 6{~ Ï ¢ B ê, EtOH ÒÖ; ~ 3¢ ÿn Soxhlet extracter MeOH ~öB ; B~ ¦ï ªöj áî . 15 ml. 2. Ö # 8 W dialdehyde monomerf copolymer j {~& . Fig. 3öB dialdehyde monomerº aldehyde ö ®º C=O stretchö ~ >bº 1694 cm , C-H stretchö ~ > bº 2732 cm öB '' ¾æÒ . Wittig reactionö ~ ª¶ 7>w >B aldehydeV b ^V& ² 6²~&b, 950 cm ~960 cm öB îÚ transvinylene & ¾æÒ . æ zböB jö2 7Ö ~ ;Wb 7Ú Wj {~& . W dialdehyde monomerf TPA-PPV~ H-NMR ¢ Fig. 4ö ¾æÚî . zbf 9.90 ppmöB 2B ~ aldehydeV, 7.81 ppmöB 7.19 ppmÒö phenyl Vö Ò~º proton peak 13B& {>î . ª ¶~ Î bº ïÚf jv~ Â]~² ¾æ ¾æ p~ . 9.90 ppmö Ò~º dialdehyde monomer ~ peakº ~ Ò¢rb, î² ;WB vinylic proton peakº £ 6.50 ppmöB ¾æÒbæ z FT-IR. −1. −1. −1. −1. 1. Fig. 4. (a) 1H-NMR spectra of Dialdehyde monomer (b) 1HNMR spectra of TPA-PPV.. Fig. 5. TGA thermograms of TPA-PPV.. böBº Wittig >w ¢ÚÒrj r > ®î . Fig. 5ö TPA-PPV~ TGA G;Ö"¢ ¾æÚî . TPA-PPVº 376 CöB Z² 6²& ·>Ú 430 C öB 5%~~ 6²¢ & . TPA-POPVº 391 C öB Z² 6²& ¢ÚÂ ê, 427 CöB 5%~~ o. o o. Fig. 3. FT-IR spectra of polymer and monomer. 2005, Vol. 49, No. 1. o.

(5) *^ÁBfKÁöËîÁB'^. 76. Z² 6²& ¾æÒ, TPA-ROPPVº 374 CöB Z ² 6²& ·~&b 415 CöB 5%~~ 6² ¢ & . TPA-PBPVº 273 CöB Z² 6²& ·>îb 416 CöB 5%~~ 6²& ¾æÒ . æ WB ª¶~ 5% Z² 6²(T )º Î v 400 C çöB ¾æÎj {~& . Chloroformö C Ïb UV-Vis." PL G; Ö" TPAf 7Ú>º ïÚö V¢ 2Ë æ z¢ & . Fig. 6" Fig. 7ö B7ª¶ ~ UV-Vis. & >2Ë(λ )" PL & OÂ2Ë(λ )j ¾æÚî . Fig. 6öB dialdehyde monomer~ UV-Vis. & > 2Ë(λ )f 383 nmf 334 nm(Sh)öB ¾æÒ . TPAPPV~ & >2Ë(λ )f 407 nm, & OÂ2Ë (λ )f 483 nmöB ¾æÒbæ dialdehyde monomer >Ê¿Þ" Ë2Ë ÿ(red-shifted)~& . o. o. o. o. d5%. o. max. max. max. max. max. º ª¶z>B îÚ transvinylene WN b Z S ·j^ π-π* *¶* { rV r^ . TPA-PPV Z Sf 2.65 eV(λ ) . TPAPOPVº & >2Ë(λ ) 378 nm, & OÂ2 Ë(λ )f 447 nmöB ¾æÒbæ TPA-PPVf j v~ OÂ2Ë(λ ) 2Ë ÿ(blue-shifted)~ & . º ^& z× jæ² > ÒÒ Ú *¶ ~ >BK ^ Z S æ² >Ú 2Ëb ÿ © . TPA-POPV Z Sf 2.81 eV(λ ) . TPA-ROPPV & >2Ë(λ )f 440 nm, & OÂ2Ë(λ )f 503 nm . "ÒÒ~ ¾ ö2ö *¶ "² Î"(electron-donating effect)& ® º r{ ~~Nb ª¶ ÒÒÚ π-*¶ ~ jÞÒz& {Ë>Ú TPA-PPVf jv~ Ë2 Ë ÿj & . TPA-PPVf TPA-ROPPV ''~ Z S 2.65 eV, 2.53 eV(λ )ª {>î . TPA-PBPVº & >2Ë(λ ) 394 nm, & O Â2Ë(λ )f 466 nmöB ¾æÒ . TPA-PPV. & OÂ2Ë(λ ) 2Ëb ÿ ©f ÒÒ Ú ïW(coplanarity)j NÒ ÒÒ~ Êæâ ¢Ú¾ ^& jæº Î" r^ . ¯, ÒÒ Ú ¾ö2 Ò Êæâb *¶~ ÞÒz(localization) & {&>Ú π-π* S ^B 2Ë ãb ÿ~ & . TPA-PBPV ZSf 2.78 eV(λ )î . onset. max. max. max. onset. max. max. onset. max. max. max. onset. Ö V " (para-, ortho-, bi-)phenylene *¶ "² Î"¢ <º ~~Ú¢ 7Ú~ ª7', ' 5 B7 ßWj {~ r" ? f Öj áî . TPA-PPV, TPA-POPV & >2Ë(λ )f '' 407 nm, 378 nm, & OÂ2Ë(λ )f 483 nm, 447 nm öB ¾æÒb. 429 C~430 C(T )ræ ' n; Wj & . TPA-POPVº TPA-PPVf jv~ 2Ë ÿ(blue-shifted)~&º, º ^& z × jæ² > ÒÒ Ú *¶ ~ >BK. ^ Z S æV r^ . TPA-ROPPV & >2Ë(λ )f 440 nm, & OÂ2Ë(λ )f 503 nm öB ¾æÒ . "ÒÒ~ phenyleneö *¶ "² Î" ¢ <º r{ ~~Nb ª¶ ÒÒÚ π-*¶~ jÞÒz& {Ë >îbæ TPA-PPVf j Triphenylamine(TPA). Fig. 6. UV-Vis. spectra of polymers.. unit,. max. max. o. max. Fig. 7. PL spectra of polymers.. o. d5%. max. Journal of the Korean Chemical Society.

(6) ê %Ú 9 # 7ß9 . PPV. v~ Ë2Ë ÿ ~& . TPA-PPVf TPA-ROPPV ''~ ZS 2.65 eV, 2.53 eV(λ )îb, 415 C (T )ræ ' n;Wj & . TPA-PBPV & >2Ë(λ )f 394 nm, & OÂ2Ë(λ )f 466 nm öB ¾æÒ,, 416 C(T )ræ ; n;Wj ¾æ Úî . TPA-PPVf jv~ 2Ë ÿ ©f Ò ÒÚ~ ïW(coplanarity) æB ÒÒ~ Êæâ ¢Ú¾ ^& jæº Î" r^î . * ~ Ö" TPAf 7ÚB PPVê B7ª¶~ ï, Óï' LEDÒò~ wÏWj {~& . o. onset. d5%. max. max. o. d5%. Ï^ò 1. Vanslkyke, S. A.; Chen, C. H.; and Tang, C. W. Appl. Phys. Lett. 1996, 69, 2160.. 2005, Vol. 49, No. 1. 77. 2. Parker, I.D. J. Appl. Phys. 1994, 75, 1657. 3. Kim, H. G.; Jung, T. H. Chemworld, 1997, 37(8), 33-47 4. Kim, H. G.; Seok, S. B.; Hwang, S. H. J. Kor. Chem. Soc. 1997, 41(3), 144-149. 5. Yang, Z.; Sokolik, I.; Karasz, F. E. Macromolecules, 1993, 26, 1188. 6. Virgili, T.; Lidzey, D. G.; Bradley, D. D, C. Adv. Mater., 2000, 12, 58. 7. Braun, D.; Heeger, A. J. Appl. Phys. Let. 1991, 58, 1982. 8. Zhang, C.; Hoger, S.; Pakbaz, K.; Wudl, F.; Heeger, A. J. J. Electron. Mater. 1993, 22, 413. 9. Zyung, T.; Hwang, D. H.; Kang, I.N.; Shim, H.K.; Hwang, W.-Y.; Kim, J.-J.; Chem. Mater. 1995, 7(8), 1499. 10. Yang, Z.; Sokolik, I.; Karasz, F. E. Macromolecules. 1993, 26, 1188. 11. Greenham N. C., Moratti S. C., Bradley D. D. C., Friend R. H., Holmes A. B., Nature. 1993, 365, 628-30..

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