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T. Une-solution-de, 51 g, 1.81 mmol), de Thy-OH (1.18 g, 3.98 mmol) et de PPh 3 (1.04 g, 3.97 mmol)) est préparée dans 200 mL de THF anhydre et placée dans un bain de glace à 0 °C sous atmosphère inerte (argon) Une

. Ml-d-'eau-distillée, La phase organique est ensuite séchée avec du sulfate de magnésium anhydre (MgSO 4 ) et reconcentrée sous pression réduite. Le produit brut est finalement purifié par chromatographie sur colonne de silice (dichlorométhane:éthanol, 30:1), l'agent de transfert TTC-Thy se présente sous la forme d'une pâte jaune-orange

. Reconcentrée-sous-vide, Un dérivé bromé de la diaminopyridine DAP2 est ainsi obtenu après purification par chromatographie sur colonne de silice (acétate d'éthyle:cyclohexane 1:1), sous forme d'un solide cristallin blanc

H. Nmr, (d, -S-CH(CH 3 )-, 3H), 1.75 (m, CH 3, 2H), 2.34 (t, -(O=C)-CH 2 -, 2H), 4.92 (q, -S-CH(CH 3 )-, 1H), pp.0-99735, 2003.

. Une-solution-de-dap-br, 6 g, 1.91 mmol) et de xanthogénate de potassium (0.92 g, 5.73 mmol) est préparée dans 100 mL d'acétone séché sur tamis moléculaire

. De-dicyclohexylcarbodiimide, 76 mmol) et de 4- diméthylaminopyridine (DMAP, 0.07 g, 0.59 mmol) est préparée dans 200 mL de dichlorométhane anhydre Après une nuit d'agitation à température ambiante, la solution est filtrée et le solvant évaporé sous vide. Le produit brut est ensuite purifié par chromatographie sur colonne de silice (cyclohexane :acétate d'éthyle, ). L'agent RAFT TTC-Ada se présente sous la forme huile orange (1.14 g, 81%)

. Le-protocole-de-synthèse-de-ce-monomère-est-adapté-de-celui-de-ladmiral, Une solution d'alcool 3-(triméthylsilyl)propargylique (11.6 mL, p.78

H. Nmr, CDCl 3 , ?, ppm): 0.17 (s, -Si-(CH 3 ) 3 , 9H), pp.95-99

. La-polymérisation-de-l, acrylate de n-butyle (nBuA) a été effectuée en masse, en employant les agents RAFT TTC-Thy, DTB-DAP ou TTCnf, p.71

R. La-polymérisation-du-styrène-a-Été-effectuée-en-masse, D. Ttc-thy, A. Ou, and A. , Par exemple, l'agent RAFT TTC-Thy (40 mg, 4.8 x 10 -5 mol), l'ACPA-Thy (1.03 mg, 1.2 x 10 -6 mol), étalon interne) ont été dissous le styrène (2.2 mL, pp.5-10

. Mol, La solution a été dégazée par une série de 5 cycles de congélation-décongélation sous vide. Le tube Schlenk a été placé dans un bain d'huile à 80 °C. La réaction a été stoppée en plongeant le tube dans l'azote liquide

. La-polymérisation-de-l, isoprène a été effectuée en solution dans le toluène, en employant l'agent RAFT TTC-Thy et l'amorceur DCP (peroxyde de dicumyle) Par exemple, l'agent RAFT TTC-Thy (34.5 mg, 4.1 x 10 -5 mol), et l'isoprène

. La-polymérisation-de-l, acétate de vinyle (VAc) a été effectuée en masse, en employant l'agent RAFT X-DAP, et l'amorceur AIBN. Par exemple, l'agent RAFT X-DAP (42 mg

L. Polymères-fonctionnalisés-thymine-ou-diaminopyridine, Chapitre III) ont été analysés par spectrométrie de masse MALDI-TOF (« Matrix Assisted Laser Desorption Ionization Time of Flight ») au moyen d'un spectromètre Voyager-DE PRO (Applied Biosystems, Framingham, MA) equipé d'un laser N2 émettant à 337 nm avec une durée de pulse de 3 ns, en mode linéaire et réflectron. Les ions ont été accélérés par un potentiel de 20 kV, avec une détection des ions positifs. Le dithranol a été utilisé comme matrice

L. Polymères-fonctionnalisés-thymine and . Diaminopyridine, Chapitre III) ont été analysé avec un appareillage SEC dans le THF à 25 °C (débit : 1 mL.min -1 ), constitué d'une pompe

V. Viscotek, ) et d'un détecteur d'indice de réfraction (RI) Viscotek VE3580. Les masses molaires moyennes des polymères PnBuA, PS, PVAc et PI ont été évaluées sur la base d'une courbe de calibration basée sur des PS, 2005.

L. Polymères-ptbua-fonctionnalisés-adamantane, ainsi que les polymères à fonctions alcynes protégées PTMSPMA (Chapitre V) ont été analysés avec un appareillage SEC fonctionnant dans le DMF

V. Viscotek, de trois colonnes Waters HR4 et d'un détecteur d'indice de réfraction (RI)

V. Viscotek, Les masses molaires moyennes des polymères été évaluées sur la base d'une courbe de calibration basée sur des PS standards de masses molaires comprises entre 500 et 50000 g, p.1

Y. Mitsukami, M. S. Donovan, A. B. Lowe, and C. L. Mccormick, Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT, Macromolecules, vol.34, issue.7, pp.2248-2256, 2001.
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. Thy, = 3 x 10 -3 mol.L -1 , concentrations croissantes en motifs DAP

. Au-cours-de-la-dernière-décennie, quelques (rares) exemples de copolymères à blocs présentant des liens supramoléculaires entre les blocs constitutifs ont été décrits. En raison du caractère réversible de l'association des blocs macromoléculaires, de tels polymères sont d'un grand intérêt pour le développement de matériaux nanostructurés