Conductive Polymer Brushes of Regioregular Head-to-Tail Poly(3-alkylthiophene) via Catalyst-Transfer Surface-Initiated Polycondensation

Transcription

1 Coutve Polymer uses o Reoreulr e-to-tl Poly(3-lkyltopee) v Ctlyst-Trser ure-itte Polyoesto Voloymyr ekovskyy*, Ntly Kuyev, rtmut Komer, Ulr Oertel, Mre tmm, Drk Kukl, Ato Kry* kry@p.e; sekovskyy@p.e C NMR rterzto o te P-, - -e roups P C C C ) l ssmet (solvet: CDCl 3 ) P δ( 13 C) δ( 1 ) δ( 13 C) δ( 1 ) δ( 13 C) δ( 1 ) ) 13 C NMR spetrum (solvet: CDCl 3 ) K I T C 5 11 B F C E G C 5 11 A D 1

2 ) 1 spetrum - serts: elre e roup sls reos ) tr-noey spetrum (reo) Te rles mrk te postve ross-peks etwee 3 6 proto sls v te sptl eouroo o ot protos, tus, te eml o etwee peyl roup topee. e) MQC spetrum (reo) 2

3 ) MBC spetrum (reos) Crles mrk 2 J C 3 J C orreltos llow te ssmet o qurterry ros very te peyl-topee strt roup. 3

4 2. Ket stuy. 2-omo-3-exyl-5-ootopee (8, 559 m, 1.5 mmol) ptlee (11m, 0.08 mmol) s terl str were ple rou-ottome lsk equppe wt met strrer r, te tmospere ws reple wt ro. Dry TF (20 ml) ws e v syre, te mxture ws oole to 0 C. Aterwrs, sopropylmesum lore (0.825 M soluto TF, 1.0 ml, 1.65 mmol) ws e v syre, te mxture ws strre t 0 C or 1. Aterwrs te rst porto o te reto mxture (1 ml) ws smple, quee wt 5 M Cl, extrte wt CCl 3, re over yrous MO 4, oetrte uer reue pressure. Alyss o ts rto y 1 NMR ve te ormto out te overso o 8 to te moomer 1, w ws er omplete our expermet. Te soluto o s(trpeylpospe)orto-tolylromokel(ii) prepre rom N(TPP) 4 o-romotoluee toluee (12.5 m 4 ml, mmol, 1.11 mol %) ws e v syre t 0 C te mxture ws strre t 0 C. To ollow te reto ourse we smple tolly 7 portos o te reto mxture (1 ml) o 1st, 10t, 30t, 60t, 95t, 125t, 155t mutes o te reto. E smple ws mmetely quee wt 5 M Cl, extrte wt CCl 3, re over yrous MO 4, oetrte uer reue pressure. Alyss o tese rtos y 1 NMR llowe presely mesure moomer overso y tert ompr te sls t 7.18 ppm sse to yrolze moomer te sls rou orrespo to P3T. Aterwrs, te sme seve rtos were repetely wse wt MeO solule P3T ws ollete y ltrto uer vuum. Alyss o te 1 NMR spetr o te pure rtos llowe estmto o te moleulr wet y terto omprso o te peks t ppm, orrespo to te romt lpt protos o te lst moomer ut o te polymer wt te peks t ppm orrespo to ll oter (terl) repet uts o te polymer. A vlule ormto ve lso lyss o te peks orrespo to te strt romt roup o te polymer (espelly t 2.49 ppm, s, 3 orrespo to metyl o te strt o-tolyl moety). Te est overso eve ts expermet (reto tme s 155 mutes) ws oly out 43%. At ts overso te polymer preptte polymerzto ws termte. owever, oter polymerzto expermets te oversos up to 100% t DP=30 were eve eve t 0 C wtout preptto o te prouts, us lower ee rto (see Low temperture polyoesto o te m text o ts rtle). 4

5 Frto 2 (polymerzto tme 10 m). petrum o te rue reto mxture. Te oserve overso 10-12%. R 5

6 6 petrum o te sme rto 2, ter rs wt metol. Te oserve polymerzto eree DP~10. Te sme spetrum, lpt prt: 1 1

7 Frto 7 (polymerzto tme 155 m). petrum o te rue reto mxture. Te oserve overso= 19/(24+19)=44%. R 7

8 8 petrum o te sme rto 7, ter rs wt metol. Te oserve polymerzto eree DP~38, ut tk to out tt ot ll P3T re termte y o-tl-roup, te rel DP o o-tol-p3t-() s out

9 Gel permeto romtorpy tre or te polyoesto o 1 ([1] 0 = 0.06 mol/l) perorme t 0 C ur 6 mete y 3.56 mol % o 4. ov=95%; M=5500, PDI= Volume, ml 9