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Dario Pasini Department of Organic Chemistry University of Pavia, Italy

Cyclopolymerization as a Tool for the Synthesis of Functional Macromolecular Materials. Dario Pasini Department of Organic Chemistry University of Pavia, Italy 13 th International IUPAC Conference on Polymers and Organic Chemistry 8 th July 200 9. Outline. Previous work and introduction.

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Dario Pasini Department of Organic Chemistry University of Pavia, Italy

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  1. Cyclopolymerization as a Tool for the Synthesis of Functional Macromolecular Materials Dario Pasini Department of Organic Chemistry University of Pavia, Italy 13th International IUPAC Conference on Polymers and Organic Chemistry 8th July 2009

  2. Outline Previous work and introduction Cyclopolymers obtained from difunctional acrylic monomers Cyclopolymers obtained from difunctional styrenic monomers

  3. Difunctional monomers (usually for crosslinking) Efficient Cyclization and Propagation Linear, Soluble Polymers Mathias, L. J. Trends Polym. Sci.1996, 10, 330-336. Acar, A. E. et al. Macromolecules2008, 41, 9019-9024 Difunctional monomers (with differing reactivity) Cyclization, Alternation and Propagation Fréchet J. M. J, et al. Chem. Mater.2001, 13, 4136-4146 Stereochemical control, Steric positioning, Material properties (Tg, etc.)

  4. Recent Examples 2.7 Å 4.6 Å Prata, J. V. et al. React. Funct. Polym.2006, 66, 465-470 Holmes, A. B. et al. Chem. Commun.2000, 2419-2420 22-membered rings formed Control achieved using RAFT Endo, T. et al. J. Am. Chem. Soc.2008, 130, 10832-10833

  5. Previous work and introduction Cyclopolymers obtained from difunctional acrylic monomers Cyclopolymers obtained from difunctionalstyrenic monomers

  6. Inserting Recognition Elements 61% Quaternary centers holding crown ethers orthogonally to the growing chain 80%

  7. Gel Permeation 2% AIBN in THF Mn= 10600 Mw = 17800 DP = 21 1% AIBN in THF Mn= 5900 Mw = 15800 DP = 14 2% AIBN in Toluene Mn= 20900 Mw = 25900 DP = 50 2% AIBN in THF Mn= 4800 Mw = 13400 DP = 12

  8. Transport through a Liquid Membrane Distilled H2O (Receiving Phase) Acqueous Solution of Picrate Salt (10-2 M) Organic Solution (CHCl3) with carrier (10-3 M) Absorbance of receiving Phase (380 nm) measured by UV/Vis vs time With no carrier, no transport occurring

  9. Polymer Transport Rate (mmol/h) Monomer Na K Cs Selectivity- Monomer vs Polymer Cagnoni, E.; Pasini, D.; Galbiati, A.; Ricci, M.; Righetti, P. P.Macromolecules2003, 36, 8894-8897 Blazquez, E. ; Mustarelli, P.; Pasini,D.;Righetti, P. P.;Tomasi, C. J. Mater Chem.2004, 14, 2524-2529

  10. O M e O O M e O O M e O O M e O N N Novel D-p-A Chromophores Lewis Acid D-p-A. LA 1 1. LA D-p-A A 2.4 1.2 + Eu(OTf)3 In MeCN 300 450 600 l (nm) LA = Lewis acid cation (e.g. Ln3+) D. Pasini, P. P. Righetti, V. Rossi Org. Lett.2002, 4, 23-26. G. Garlaschelli I. Messina, D. Pasini, P. P. Righetti Eur. J. Org. Chem.2002, 3385-3392. D. Pasini, P. P. Righetti, M. Zema Org. Biomol. Chem.2004, 2, 1764-1769

  11. 3.5 2.8 2.1 1.4 n=1 n=2 n=3 0.7 0.0 A O O R O O O R n m O O O A r O O n D-p-A D-p-A Supramolecular Chromophore-Supporting Polymers A Double Chromophores 300 400 500 600 l(nm) Lanthanide ion Complexation A B D-p-A Eu3+ C

  12. 1H NMR Characterization p m o t r n a b AIBN (3%) c DP=13 n,a a’,b,b’ PhCH3 (0.025 M) f b t r o g d m e a AIBN (3%) d DP=58 c PhCH3 (0.25 M) d AIBN (3%) PhCH3 (0.025 M) e DP=17-35 e Differences between feed and observed ratios (70/30 to 65/35 and 50/50 to 30/70) 7 5 3 1 d (ppm)

  13. 40 e (x10-3) 24 8 300 500 700 l (nm) Eu3+ Binding 37.5 e (x10-3) 22.5 7.5 300 500 700 l (nm) Log Ka [Eu(OTf)3, MeCN]= 3.0 lmax complex = 480 nm emax complex = 7200 Copolymers have intermediate values Log Ka [Eu(OTf)3, MeCN]= 2.1 lmax complex = 480 nm emax complex = 3400 C. Coluccini, P. Metrangolo, M. Parachini, D. Pasini, G. Resnati, P. Righetti, J. Polym. Sci. A2008, 46, 5202-5213.

  14. Previous work and introduction Cyclopolymersobtained from difunctional acrylic monomers Cyclopolymers obtained from difunctional styrenic monomers

  15. Styrenic Systems Crosslinking 53-65% More flexible Efficient Cyclopolymerization 40-50% 70-80% a) R = Me R’ = Me b) R = Ph R’ = H

  16. Styrenic systems Polar groups (amphiphilic character) Deprotected polymer crosslinks thermally by the loss of H2O at 100°C protected deprotected Cyclopolymerization works efficiently in diluted conditions S. Edizer, B. Veronesi, O. Karahan, V. Aviyente, I. Değirmenci, A. Galbiati, D. Pasini, Macromolecules2009, 42, 1860-1866

  17. Inefficient cyclization Large extent of crosslinking Mn= 8800 Mw = 25800 PD = 2.9 Yield (prec.) =24% All soluble material Mn= 6300 Mw = 12600 PD = 1.9 Yield (prec.) =64% Introduce steric hindrance

  18. Controlled Polymerization RAFT RAFT = Mn Gives worse results Conversion (%)

  19. = = Towards Alternating Systems Ester cleavage

  20. Acknowledgments Claudio Cornaggia Dr. Arvind SharmaBarbara VeronesiEnrique Blazquez Federica Spiaggia Emanuela Cagnoni Seda Edizer Marco Parachini Luigi Garlaschelli- Pierpaolo Righetti Alessandro Galbiati (NPT) University of Pavia MIUR PRIN 2004 Fondazione CARIPLO 2007 Regione Lombardia Group website: www.unipv.it/labt

  21. Conclusions and Outlook Why Cyclopolymers? Previous work and applications Cyclopolymers obtained from difunctional acrylic monomers Cyclopolymers obtained from difunctional styrenic monomers

  22. Access to a Variety of Intermediates Easy Organic Functionalization Double Alkylation Knoevenagel Reaction Bingel reaction

  23. Fitting the Values. A 1:1 Model + Eu(OTf)3 in MeCN All spectroscopic titrations are fitted with a 1:1 model. R2 = 0,99 Log Ka = 3.8±0.1

  24. Imaging of a symmetrical cyclopolymer Carbon-rich functionality for Etch Resistance Polar Functionality for Development Wettability 70% yield Mn=5,800 PDI=2.0 A = 0.23 /m Initiator Acid-Labile Protecting Group Good resolution (down to 170 nm) PAG: 8% wt Etch: 1.22 vs APEX-E (50 Cl2 / 150 HBr) Pasini, D.; Low, E.; Fréchet, J. M. J. Adv. Mater.2000, 12, 347-351

  25. Transport in the Solid State (Li+) No Tg observed (up to 100°C) Mn= 6300 Mw = 12600 DP = 15 With Li+ Blends of Polymer and PEO (1:1) doped with LiTFSI does not show the expected orders of magnitude increase in conductivity in the solid state At 100°C Blazquez, E. ; Mustarelli, P.; Pasini,D.;Righetti, P. P.;Tomasi, C. J. Mater Chem.2004, 14, 2524-2529

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