BOOK OF ABSTRACTS 8TH INTERNATIONAL CONFERENCE ON ADVANCED POLYMERS VIA MACROMOLECULAR ENGINEERING

APME 2009

October 4th to 7th, 2009 Dresden, Germany

CONTENTS

Page N° Organization…………………………………………………………………………... 1

General Information………………………………………………………………….. 2

Social Events………………………………………………………………………..... 3

Scientific Program Overview………………………………………………..…….… 4

Scientific Program……………………………………………………………...…….. 6

List of Posters………………………………………………………………………. 12

Lectures……………………………………………………………………………… 21

Posters……………………………………………………………………………… 103

ORGANIZATION Local organizers Brigitte Voit (Leibniz-Institut für Polymerforschung Dresden e.V.) – Chair Hans-Juergen Adler (Technische Universität Dresden) - Chair Rainer Jordan (Technische Universität Dresden) - Chair Evelin Jaehne (Technische Universität Dresden) Kerstin Wustrack (Leibniz-Institut für Polymerforschung Dresden e.V.) - Technical Organization Ulrike Schulze (Leibniz-Institut für Polymerforschung Dresden e.V.) - Technical Organization

International advisory board Daniel M. A. Egbe (Linz, Austria) Tatsuki Kitayama (Osaka, Japan) Munmaya K. Mishra (Richmond, VA, USA) Yusuf Yagci (Istanbul, Turkey)

Contact address Leibniz-Institut für Polymerforschung Dresden e. V. Kerstin Wustrack Hohe Str. 6, 01069 Dresden Phone: +49 351 4658-282 Fax: +49 351 4658-214 E-Mail: [email protected] www.ipfdd.de/apme09

APME 2009 is sponsored by

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GENERAL INFORMATION Registration/Conference office Technische Universität Dresden, Andreas-Schubert-Bau Zellescher Weg 19, 01067 Dresden The conference office is located at the first floor (main entrance) Opening hours: Sunday, Oct. 4, 2009: 16:30 to 19:30 Monday, Oct. 5, 2009 – Wednesday, Oct. 7, 2009 from 8:00 throughout all sessions Posters Posters should be mounted by the end of the lunch break on Monday at the latest and will be up during the entire duration of the meeting. Posters are presented on the ground, first and second floor of the main entrance as well as on the ground and first floor of the northern entrance. Poster Award Poster awards, sponsored by Wiley-VCH, will be assigned to the five best poster presentations and will be handed over to the awardees in the closing session of the meeting on October 7, 2009.

Exhibition Postnova Analytics GmbH, Landsberg, Germany – first floor, main entrance

Coffee and lunch breaks Drinks and a lunch buffet are served on the ground and second floor of the main entrance, as well as on the ground floor of the northern entrance.

Internet WLAN access will be possible for participants during the meeting. Name of the wireless network: VPN/WEB Login: APME2009@gast Password: dresden.. In addition, you may use an internet terminal at the conference office. -2-

SOCIAL EVENTS ƒ

Welcome Mixer: Sunday, Oct. 4, 2009, 18:00 to 20:00 free of charge - registration required Andreas-Schubert-Bau, ground floor, main entrance

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Sightseeing and Conference Dinner Tuesday, Oct. 6, 2009 free of charge only for participants who registered for the event and have got the voucher ƒ Guided sightseeing walk Buses will leave at 16:00 in front of the conference venue Andreas-Schubert-Bau Start sightseeing walk: 16:15 Theaterplatz, at the equestrian statue in front of the Semperoper ƒ Visit to the Frauenkirche (incl. organ recital) Entrance E: 17:45, Start: 18:00 ƒ Dinner at ‘Pulverturm’: 19:30 An der Frauenkirche 12, 01067 Dresden

Start sightseeing

Frauenkirche, entrance E

Dinner

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SCHEDULE OVERVIEW P room 120

A room 120

B room 28

C room 328

Sunday, Oct. 4, 2009 16:30-19:30 18:00-20:00

Registration Welcome Mixer

It is possible to fix posters on Sunday. Monday, Oct. 5, 2009 P 9:00-9:15

9:15-9:50 9:50-10:25

P1 P2

10:25-11:00 11:00-11:20 11:20-12:40 12:40-12:00 12:00-12:20

Break A A1 A2 A3 A4

12:20-14:00 14:00-14:35 14:35-15:10 15:10-15:40

18:00-20:30

Y. Gnanou B. Voit A. Dworak J.-F. Lutz F. Böhme

B B1 B2 B3 B4

H. Frey S. Spange B. Ivan N. Ritter D. Pospiech

C C1 C2 C3 C4

A. Thünemann K. Saalwächter K. Dušek J. Weber M. Erber

S. Spange Y. Lu A. Wittemann A. Synytska S. K. Dolui J. Pfleger

C C5 C6 C7 C8 C9

K. Saalwächter A. F. Thünemann E. Ozkaraoglu E. Birckner J. W. Cho U. De

Lunch buffet and posters P P3 P4 P5

15:40-16:10 16:10-16:30 16:30-16:50 16:50-17:10 17:10-17:30 17:30-17:50

B. Voit Opening: B. Voit Message of greetings: Prof. Dr. M. Ruck, Dean of the Faculty of Science of the Technische Universität Dresden K. Matyaszewski D. N. Haddleton

R. Jordan L. Leibler T. Aida J. P. Kennedy Break

A A5 A6 A7 A8 A9

R. Jordan H. Frey R. Luxenhofer H. T. T. Duong L. H. Gan E. Berndt

B B5 B6 B7 B8 B9

Postersession

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Tuesday, Oct. 6, 2009

9:00-9:35 9:35-10:10 10:10-10:45

P P6 P7 P8

10:45-11:15

Y. Yagci K. Müllen Y. Gnanou O. Nuyken Break

11:15-11:35

A A 10

D. Kuckling A.H.E. Müller

B B 10

11:35-11:55 11:55-12:15 12:15-12:35

A 11 A 12 A 13

H. Ritter R. Buchmeiser W. H. Binder

B 11 B 12 B 13

12:35-14:00

R. Turcu P. Papadopoulos T. Uragami S. Seiffert L. Ionov

C C 10

A. Lederer M. Zhu

C 11 C 12 C 13

H. Palza J. Pionteck R. Muñoz-Espí

K. Dušek A. Lederer M. DuškovaSmrčkova H. Deligöz U. Yahşi M. Abdel Rehim

Lunch buffet and posters

14:00-14:20 14:20-14:40

A A 14 A 15

A. Müller D. Kuckling A. Pich

B B 14 B 15

U. Wiesner P. J. Lutz M. D. Soucek

C C 14 C 15

14:40-15:00 15:00-15:20 15:20-15:40

A 16 A 17 A 18

Y. Zhao A.P. Ramaswamy M. Li

B 16 B 17 B 18

M. Sangermano Z. Czech M. R. Whittaker

C 16 C 17 C 18

16:00 16:15 18:00 18:30

Departure for Sightseeing Sightseeing, Start: Theaterplatz Frauenkirche Dinner in the restaurant ‘Pulverturm’

Wednesday, Oct. 7, 2009

9:00-9:20

A A 19

9.20-9:40 9:40-10:00 10:00-10:20 10:20-10:40

A 20 A 21 A 22 A 23

10:40-11:10 11:10-11:45 11:45-12:20 12:20-12:55 12:55-13:05

H. Ritter E. Jähne, H.-J. P. Adler P. Vana A. Kiriy R. Jordan M. Steenackers

B B 19

M. Ballauff J. Koetz

C C 19

B. Voit R. M. Peetz

B 20 B 21 B 22 B 23

A. Fahmi R. Turcu J. Keilitz O. Weichold

C 20 C 21 C 22 C 23

D. A. M. Egbe G. Maier B. Tieke H.-W. Schmidt

Break P P9 P 10 P 11

H.-J. P. Adler U. Wiesner Y. Yagci M. Ballauff Closing

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PROGRAM Monday, Oct. 5, 2009 Page N° Mo R. 120 9:00-9:15

P

9:15-9:50

P1

9:50-10:25

P2

10:25-11:00 Mo R. 120 11:00-11:20

11:20-11:40

A A1

A2

A3

12:00-12:20

A4

11:20-11:40

B B1

B2

11:40-12:00

B3

12:00-12:20

B4

Mo R. 328 11:00-11:20

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Break

11:40-12:00

Mo R. 28 11:00-11:20

B. Voit Opening: B. Voit Message of greetings: Prof. Dr. M. Ruck, Dean of the Faculty of Science of the Technische Universität Dresden K. Matyaszewski: Advanced nanostructured materials by atom transfer radical polymerization D. N. Haddleton et al.: Glycopolymers via catalytic chain transfer polymerisation and double click reactions

C C1

11:20-11:40

C2

11:40-12:00

C3

Y. Gnanou B. Voit: Functional block copolymers prepared by combining controlled radical polymerization and highly efficient polymer analogous reactions A. Dworak et al.: Functional core-shell star-like polyacids and polyalcohols via controlled polymerizations J.-F. Lutz: New strategies for controlling polymer sequences F. Böhme et al.: Ionic polypseudorotaxanes bearing a chromophore in the side chain H. Frey S. Spange: Twin polymerisation - A new strategy for producing nanostructured materials B. Iván et al.: Nanophasic amphiphilic polymer conetworks as a new material platform for specialty nanohybrids N. Ritter: Intrinsically microporous high performance polymers D. Pospiech et al.: Nanostructured polymer/silica hybrids obtained by using block copolymer templates: preparation, characterization and properties A. Thünemann K. Saalwächter: Diffusion mechanisms and chain dynamics in swollen model networks as studied by NMR and FCS K. Dušek et al.: Gelation and swelling of biohybrid hydrogels J. Weber et al.: Mesoporous, cross-linked poly(styrene)s and poly(acrylates) Enlightning finer details of mesopore stability

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12:00-12:20

C4

12:20-14:00 Mo R. 120 14:00-14:35

P P3

P4

15:10-15:40

P5

15:40-16:10

16:30-16:50

16:50-17:10

17:10-17:30

17:30-17:50

Mo R. 28 16:10-16:30

16:30-16:50

16:50-17:10

R. Jordan L. Leibler et al.: Oleo-chemistry meets supramolecular chemistry: Design of selfrepairing materials T. Aida: Programmed self-assembly for tailoring electronic soft materials J. P. Kennedy et al.: A novel bioartificial pancreas

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Break A A5

A6

A7

A8

A9

B B5

B6

B7

17:10-17:30

B8

17:30-17:50

B9

Mo R. 328 16:10-16:30

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Lunch buffet and posters

14:35-15:10

Mo R. 120 16:10-16:30

M. Erber et al.: Characterization of the molecular dynamic in thin polymer films in dependence on their macromolecular structure

C C5

R. Jordan H. Frey et al.: Building polymer architectures with ethylene oxide: From a simple construction kit to novel biomaterials R. Luxenhofer et al.: Poly(2-oxazoline)s for biomedical applications: From synthesis to endocytosis H. T. T. Duong et al.: Core cross-linked and shell RGD containing peptide conjugated micelles via RAFT polymerization L. H. Gan et al.: A novel stimuli-responsive organic/inorganic hybrid vesicle based on diblock copolymer of 2-(dimethylamino)ethyl methacrylate and 3-(trimethoxysilyl)propyl methacrylate E. Berndt et al.: Synthesis and characterization of functional block and graft copolymers with defined architecture for switchable and biocidal anti-biofouling coatings S. Spange Y. Lu et al.: Well-defined crystalline TiO2 nanoparticles generated and immobilized on a colloidal nanoreactor A. Wittemann et al.: Fabrication of hybrid clusters by the combination of different spherical particles A. Synytska et al.: Stimuli-responsive anisotropic Janus particles: Design, switching behavior and orientational control S. K. Dolui et al.: Polythiophene based fluorescent sensor for acids and metal ions J. Pfleger et al.: Semiconducting polymer composites with plasmonic nanoparticles: Optical and electrical properties K. Saalwächter A. F. Thünemann et al.: In situ analysis of size distributions of polymer-stabilized nanoparticles

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84

16:30-16:50

16:50-17:10

17:10-17:30

17:30-17:50

C6

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C8

C9

18:00-20:30

E. Ozkaraoglu et al.: Gold nanoparticles in PMMA matrix: in-situ synthesis and gold nanoparticle-PMMA interactions E. Birckner et al.: Dilute solution photophysical properties of poly(dioctylfluorene)s incorporating different contents of DTT-S,S-dioxide J. W. Cho et al.: Impact of hyperbranched polymer on conductivity and mechanical properties of carbon nanotube-polymer nanocomposites U. De et al: Diverse damage due to gamma and ion irradiations in thermal properties of PEO-based ion conducting polymers and related characterizations

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Postersession

Tuesday, Oct. 6, 2009 Tue R. 120 9:00-9:35

P P6

9:35-10:10

P7

10:10-10:45

P8

10:45-11:15 Tue R. 120 11:15-11:35

11:35-11:55

11:55-12:15

12:15-12:35

Tue R. 28 11:15-11:35

11:35-11:55

Y. Yagci K. Müllen: Chemistry of core-shell particles Y. Gnanou et al.: The exceptional breadth of N-heterocyclic carbenes as catalysts of both chain and step-growth polymerizations O. Nuyken et al.: Spinning disk reactor for polymers and nanoparticles

28 29 30

Break A A 10

A 11

A 12

A 13

B B 10

B 11

11:55-12:15

B 12

12:15-12:35

B 13

D. Kuckling A.H.E. Müller et al.: Nanorods and nanowires: Soluble unimolecular hybrid materials from polymer templates H. Ritter: Cyclodextrin-click-cucurbit[6]uril: Combi-receptor for supramolecular polymer systems in water R. Buchmeiser et al.: Sequence-selective, alternating ring-opening metathesis copolymerizations W. H. Binder et al.: Structuring blockcopolymers under supramolecular and geometrical constraints R. Turcku P. Papadopoulos et al.: Hierarchies in the structural organization of spider silk - A quantitative model T. Uragami et al.: Effect of addition of ionic liquid to polymer membranes on removal performance of VOCs in water S. Seiffert et al.: Advanced fabrication of polymer microgels in microfluidic devices L. Ionov et al.: Controlling biomolecular transport by smart polymers

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43

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66

67 68 69

Tue R. 328 11:15-11:35

11:35-11:55

C C 10

C 11

11:55-12:15

C 12

12:15-12:35

C 13

12:35-14:00 A A 14

14:20-14:40

A 15

14:40-15:00

A 16

15:20-15:40

Tue R. 28 14:00-14:20

A 17

A 18

B B 14

14:20-14:40

B 15

14:40-15:00

B 16

15:00-15:20

15:20-15:40

89

90 91 92

Lunch buffet and posters

Tue R. 120 14:00-14:20

15:00-15:20

A. Lederer M. Zhu et al.: Controllable molecular architecture and fabrication of organic/inorganic hybrids through in-situ polyester synthesis H. Palza et al.: Effect of carbon nanotubes on the melt instabilities of polyethylenes J. Pionteck et al.: Reactive polymers for interfacial modification of polymer blends R. Muñoz-Espí et al. : Polymer-assisted strategies for crystallization of inorganic nanostructures

B 17

B 18

Tue R. 328 14:00-14:20

C C 14

14:20-14:40

C 15

A. Müller D. Kuckling: Synthesis of smart nano-materials A. Pich et al.: Ampholytic microgels Y. Zhao: Photocontrollable polymer micelles: Dissociation and reversible cross-linking Arun Prasath Ramaswamy et al. : Thiol-ene and thiol-yne ‘click’ chemistry for preparation of functional beads M. Li et al.: Preparation and application of N-succinyl chitosan immobilized with β-cyclodextrin U. Wiesner P. J. Lutz: New hybrid self-assembling macromolecular materials based on macromonomers and silsesquioxanes M. D. Soucek: A new class of acrylated alkyds M. Sangermano et al. Hybrid organic-inorganic coatings with excellent scratch resistance properties Z. Czech et al.: Synthesis and modification of biodegradable pressure-sensitive adhesives based on acrylic M. R. Whittaker et al.: ‘Smart’ thermo-sensitive, anti-fouling hybrid polymer/gold nanoparticles with stealth attributes K. Dušek A. Lederer et al.: Separation of (hyper)branched polymers M. Duškova-Smrčkova et al.: Swelling and elasticity of particulate composites with rubbery matrix

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47 48 49

50

51

70 71 72

73

74

93 94

14:40-15:00

15:00-15:20

15:20-15:40

C 16

C 17

C 18

16:00 16:15 18:00 19:30

H. Deligöz et al.: Highly conductive non-aqueous composite polymer electrolytes based on ionic liquid and polyamic acid U. Yahşi et al.: A study on the investigation of a relationship between Free Volume and Ionic Conductivity of Polymer-Salt Electrolytes M. Abdel Rehim et al.: Utilization of hyperbranched polymers in fabric finishing enhancing new properties

95

96

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Departure for Sightseeing Sightseeing, Start: Theaterplatz Frauenkirche Dinner at ‘Pulverturm’

Wednesday, Oct. 7, 2009 Wed R. 120 9:00-9:20

A A 19

9.20-9:40

A 20

9:40-10:00

A 21

10:00-10:20

A 22

10:20-10:40

A 23

Wed R. 28 9 :00-9 :20

B B 19

9.20-9 :40

B 20

9:40-10:00

10:00-10:20

10:20-10:40

Wed R. 328 9:00-9:20

B 21

B 22

B 23

C C 19

H. Ritter E. Jähne, H.-J. P. Adler et al.: Phosphorous-containing oligo(ethylene glycol) derivatives for protein resistant metal oxides surfaces P. Vana et al. Functional surfaces via RAFT unctionalised from solid surfaces A. Kiriy et al.: Controlled surface initiated polycondensation: a new tool in engineering of functional architectures of conjugated polymers R. Jordan: Engineered polymer brushes by surface-initiated polymerization M. Steenackers et al.: Micro- and nanostructured polymer brushes by carbon templating M. Ballauff J. Koetz et al. : Polyelectrolyte-gold nanoparticles A. Fahmi et al.: Nanofibres fabrication via self-assembled dendrimers templating in-situ metallic nanoparticles R. Turcu et al. Encapsulation of unctionalised magnetic nanoparticles in polymeric gels J. Keilitz et al.: Homogenization of heterogeneous catalysts: Stabilization of metal-nanoparticles by soluble dendritic architectures and applications thereof O. Weichold: Silver/poly(ethylene terephthalate) hybrid materials with anisotropic electrical conductivity by solvent crazing B. Voit R. M. Peetz: Homologous conjugated polymer chains and macrocycles containing group 4 heteroatoms

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75 76

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9.20-9:40

C 20

9:40-10:00

C 21

10:00-10:20

C 22

10:20-10:40

C 23

10:40-11:10 Wed R. 120 11:10-11:45

11:45-12:20

12:20-12:55

12:55-13:05

D. A. M. Egbe et al.: Anthracene-based PPE-PPVs for solar cell applications: Effect of side chains combination and density G. Maier et al.: ‘Design rules’ for fuel cell membranes B. Tieke et al.: Coordinative supramolecular assembly of electrochromic films based on metal ion complexes of polyiminoarylenes with terpyridine substituent groups H.-W. Schmidt et al.: Polymer blends with azobenzene-containing blockcopolymers and azobenzene-containing molecular glasses as stable rewritable volume holographic media

99 100

101

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Break P P9

P 10

P 11

H.-J. P. Adler U. Wiesner: Combining polymer science with inorganic chemistry into novel materials Y. Yagci: Inorganic/polymer hybrid nanocomposites by photochemical and controlled polymerization processes M. Ballauff: Hybrids of metallic nanoparticles and polymer colloids: Synthesis, characterization, and applications in catalysis Closing

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LIST OF POSTERS Poster N° 1

2

3

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6 7 8

9

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Page N °

Molecular weight controlled brittle-tosemiductile-to-ductile transition in S(S/B)-S triblock copolymers Influence of molecular architecture and morphology on the hysteresis behaviour of multigraft copolymers Viscoelastic phase separation in poly (acrylonitrile-butadiene-styrene) modified epoxy/DDS system The role of phase separation in the cure kinetics of poly (acrylonitrilebutadiene-styrene) modified epoxy amine systems Formation of porous hydrogels with controlled physical-mechanical properties Studies of copolymer chitosan-graftpolyvinylpyrrolidone for smart hydrogels Hydrophobic chitosan particles Polyelectrolyte complexes of chitosan soluble over a wide pH-range: formation and properties Characterization of dendronized oligosaccharide-modified polymers via A4F Preparation and characterization of hyperbranched aliphatic-aromatic polyester/TiO2 nanocomposites New hyperbranched polyester modified DGEBA thermosets with improved chemical reworkability Influence of the molecular weight of a poly(ester-amide) hyperbranched polymer on the characteristics of modified epoxy thermosets The use of XPS methods in studying polymeric composites with magnetic nanoparticles A XRD study of the organic modifier structures effect on the interlayer distance and dispersion of montmorillonite clays in polyamide-clay nanocomposites

Martin Ganß, Bhabani K. Satapathy, Mahendra Thunga, Roland Weidisch, 105 Konrad Knoll R. Schlegel, D. Wilkin, Roland Weidisch, Konrad Schneider, J. Mays, 106 D. Uhrig, N. Hadjichristidis Parameswaran Jyotishkumar, Ceren Ozdilek, Paula Moldenaers, Christophe 107 Sinturel, Joachim Koetz, Rüdiger Häßler, Sabu Thomas Parameswaran Jyotishkumar, Christophe Sinturel, Joachim Koetz, Brigitte Tiersch, Rüdiger Häßler, 108 Vincent Janssens, Ceren Özdilek, Paula Moldenaers, Sabu Thomas V.J. Samaryk, A.S. Voronov, S.M. Varvarenko, N.G. Nosova, I.T. 109 Tarnavchyk, A.M. Kohut, N. Puzko, S.A. Voronov N. Solomko, O. Budishevska, Viktoria Kochubey, A. Popadyuk, S. Voronov 110 Katharina Fink, Susanne Höhne, Stefan Spange, Frank Simon I.F.Volkova, Marina Yr. Gorshkova, V.A. Izumrudov

111 112

Susanne Boye, Viktor Boyko, Dietmar Appelhans, Stefan Zschoche, Albena 113 Lederer Hamed Elsayed, Brigitte Voit 114 David Foix, Michael Erber, X. Ramis, 115 Y. Yu, Ana Mantecón, Brigitte Voit, Angels Serra Mirea Morell, Michael Erber, Brigitte Voit, X. Ramis, J.M. Salla, F. Ferrando, 116 Angels Serra Ioan-Ovidiu Pana, J. Martin, M. L. Soran, Rodica Turcu, C. Leostean, C. 117 Mijangos Viviane N. Dougnac, R. Quijada, Doris Pospiech, Dieter Jehnichen 118

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Monitoring of the growth of poly(Nisopropyl-acrylamide) brushes synthesized by surface initiated room temperature ATRP Comparing MALDI/ESI mass spectroscopy in the characterization of telechelic oligo- and poly(3-hexyl) thiophenes Charge carrier transport in conjugated polymers Blend or copolymer? Spectroelectrochemical evidence of copolymerisation or blending two monomer: synthesis of a dipyrromethane copolymerisation monomer and optoelectrochromic properties of its homopolymer, copolymer and blend with EDOT Thermal degradation and pyrolysisGC/MS studies on polystyrene/PVC blends In-situ monitoring of reactive extrusion by using of nir-spectroscopy and ultrasonic measurements Particle size and particle size distribution of nanoparticles - A compare of centrifugal separation analysis and dynamic light scattering Formation, stability, and application of complex nanoparticles based on chitosan Characterization of polymers by fieldflow fractionation Sensoric properties of poly(3,4ethylenedioxythiophene)-poly(styrene sulfonate) to volatile compounds Humidity sensing properties of thin polymeric films based on core-shell particles and microgel composites Behaviour of nanoparticles under physiological conditions – dispersion, corona evolution and cellular uptake Styrene-butadiene block copolymers with high cis-1,4 configuration Click chemistry combined with nitroxide-mediated radical and cationic ring opening polymerisation: a versatile method for preparation of well –defined block copolymers

Michael Erber, Jan Stadermann, Klaus-Jochen Eichhorn, Brigitte Voit

119

Claudia Enders 120 Petr Toman, Stanislav Nešpůrek, Martin Weiter, Martin Vala, Wojciech Bartkowiak Mine Sulak Ak, Metin Ak, Halil Çetişli, Ramazan Donat

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122

Zahoor Ahmad, N.A. Al-Awadi, F. AlSagheer Sven Kummer, Jan Müller, Dieter Fischer, Bernd Kretzschmar, Karin Sahre Mandy Mende, Simona Schwarz, Stefan Zschoche, Gudrun Petzold, Karl-Friedrich Arndt Ecaterina Stela Dragan, Marcela Mihai, Simona Schwarz Evelin Moldenhauer, Thorsten Klein

123

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126 127

Sergii Pochekailov, Stanislav Nešpůrek, Aleš Hamáček, Jan Řeboun 128 David Rais, Stanislav Nešpůrek, Jessica Hain, Andrij Pich, Hans 129 Juergen P. Adler, Jan Řeboun and Aleš Hamáček Nadine Haentzschel, Anna BratekSkicki, Sonia Ramírez-García, 130 Francesca Baldelli, Anna Salvati,Iseult Lynch, Kenneth Dawson Han Zhu, Yixian Wu, Jiangwei Zhao, 131 Qinglei Guo, Guanying Wu Saber Ibrahim, Brigitte Voit

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In situ analysis of a bimodal size distribution of superparamagnetic nanoparticles Design and characterisation of combshaped copolymers New photoinitiating systems for living/controlled cationic polymerization and crosslinking of vinyl ethers New thioxanthone photoinitiators with extended absorption in the visible range Synthesis of block copolymers by the combination of ATRP, photoinduced coupling and iniferter processes Perfectly alternating amphiphilic polyphenylenes by combination of controlled polymerization and Suzuki coupling processes ROMP-NMP-ATRP combination for the preparation of 3-miktoarm star terpolymer via click chemistry Synthesis and characterization of telechelic polymers by combination of atrp and "click" chemistry Graft copolymers by the combination of ATRP and photochemical acylation process by using benzodioxinones One-pot double click reactions for the preparation of H-shaped ABCDE type quintopolymer Synthesis of block and star copolymers by photoinduced radical coupling process Synthesis and characterization of welldefined diblock copolymers of poly(Nisopropylacrylamide) and poly(vinylacetate) Synthesis and characterization of onecomponent polymeric photoinitiator by simultaneous double click reactions and its use in photoinduced free radical polymerization Three-arm star ring opening metathesis polymers via alkyne-azide click reaction Tuning the LCST of poly(2-oxazoline)s Synthesis of block copolymers with poly(para-phenylene) and stimulisensitive segments by combination of SPC and NMRP

A. F. Thünemann, P. Knappe, S. Rolf, 133 S. Weidner Lionel Petton, Filip Du Prez Muhammet U. Kahveci, M. Atilla Tasdelen, Mustafa Uygun, Wolfram Schnabel, Wayne D. Cook, Yusuf Yagci Ali Gorkem Yilmaz, Binnur Aydogan, Yusuf Yagci

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Halime Cengiz, Binnur Aydogan, 137 Gokhan Temel, Nergis Arsu, Yusuf Yagci Elif L. Sahkulubey, Yasemin Yuksel Durmaz, Demet G. Colak, Yusuf Yagci 138 Aziz Gozgen, Aydan Dag, Hakan Durmaz, Okan Sirkecioglu, Gurkan Hizal, Umit Tunca Suleyman Serdar Okcu, Yasemin Yuksel Durmaz, Yusuf Yagci

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Yasemin Yuksel Durmaz, Volkan Kumbaraci, A. Levent Demirel, Naciye 141 Talinli, Yusuf Yagci Eda Gungor, Gurkan Hizal, Umit 142 Tunca Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci

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Cimen Ozguc, Turgut Nugay 144 Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci 145

Aydan Dag, Hakan Durmaz, Okan Sirkecioglu, Gurkan Hizal, Umit Tunca 146 Stephan Huber, Rainer Jordan Simon Schmücker, A. Britze, Dirk Kuckling

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Combinatorial anionic synthesis of functional block copolymers with welltailored compositions Peroxide derivatives of alternate copolymers for reverse micelle formation Living radical polymerization of methyl methacrylate using cyclometalated complexe of ruthenium (II) Living radical polymerization of vinyl acetate controlled by cyclometalated complex of Ru (II) The role of solvent ligated metal complexes associated with weakly coordinating anions in isobutylene polymerization Kinetic investigation of polyisobutylene/polysyrene copolymerization bearing polar side chains Synthesis and characterization of poly(10-undecene-1-ol)

Robin Pettau, Klaus Kreger, Christian Erdelen, Hans-Werner Schmidt

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Olena Kudina, O. Budishewska, O. Khomenko, S. Voronov

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Nelson Vargas, R. Le Lagadec, L. Alexandrova

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Jessica Olvera-Mancilla, Ronan Le Lagadec, L. Alexandrova

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Hui Yee Yeong, Brigitte Voit, Yang Li, Bernd Diebl, Silvana Rach, Fritz E. 153 Kühn, Hannah König, Klaus Mühlbach Katharina Hackethal, Wolfgang H. Binder

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Matthias Johannsen, Ulrich Schulze, Dieter Jehnichen, Liane Häußler, 155 Hartmut Komber, Brigitte Voit Synthesis, rheology, and crystallization Elena Ostas, Wolfgang H. Binder, Kay behavior of cyclic poly(εSaalwächter, Kerstin Schäler, Thomas 156 caprolactone)s Thurn-Albrecht, Klaus Schröter Supramolecular materials via a Steffen Kurzhals, Wolfgang H. Binder 157 bimetallic ROMP-catalyst Ring-opening metathesis Gajanan Pawara, Bhasker Bantua, polymerization-derived, polymer-bound Jochen Weckesserb, Siegfried Cu-catalysts for click-chemistry and Blechertb, Klaus Wurstd, Michael R. 158 hydrosilylation reactions under micellar Buchmeisera conditions Regioselective cyclopolymerization of P. Santhosh Kumar, Klaus Wurst, various chemically different 1,6Michael R. Buchmeiser 159 heptadiynes by RuIV-based metathesis initiators Dendritic glycopolymer layers for the Dietmar Appelhans, Monika Warenda, interaction with Anne Richter, Stefan Zschoche, Klaus- 160 bio-active (macro-)molecules Jochen Eichhorn, Brigitte Voit Multifunctional macromolecules with Nikita Polikarpov, Jörg Kluge, Dietmar oligosaccharide shell for (A) Appelhans, Brigitte Voit encapsulation study and (B) 161 incorporation in hydrogel as potential container molecules Preparation and characterization of Martina Warenda, Dietmar Appelhans, (oligo-)saccharide modified Hartmut Komber, Klaus-Jochen hyperbranched poly(ethylene imine) Eichhorn, Brigitte Voit 162 layers and their protein resistant properties New amphiphilic multishell star-block- Florian Wolf, Daniel Wilms, Holger copolymers as biodegradable Frey 163 encapsulation devices for medical application

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Liposomes with polyglycerol anchor groups: synthesis and characterization of novel stealth architectures New synthetic strategies for branched polylactides Monomers and polymers based on chiral aromatic amino acids as recognition biological systems with cyclodextrin Synthesis of crosslinked cyclodextrin polymers and the creation of nano- and microgels Novel microgel carriers for enzyme encapsulation Mimic of enzyme behaviour by smart block copolymers Study on aggregation of diblock poly(2substituted-2-oxazoline)s in aqueous solutions Polymersomes from organic solvent based double emulsions in PDMS microfluidics PH sensitive polymeric nanoparticles of hyperbranched poly(arylene oxindoles) Mesoglobules of random poly(glycidolco-ethyl glycidyl carbamate) as the nucleus of nanoparticles Towards macromolecular nano-carriers from star polymers produced via RAFT polymerization Poly(2-oxazoline) micelles: size, toxicity and endocytosis α,ω--functionalized poly(2-oxazoline) lipopolymers Microgel-based stimuli-responsive capsules Synthesis of stimuli-responsive multiarm star polymers by atom transfer radical polymerisation Design of temperature-responsive polymers for motility control of microtubules Cationic polymerization of oxazolines using benzyl bromide as initiators for the preparation of star molecules with hyperbranched core Aliphatic-aromatic polyesters with different branching topology

Anna Maria Hofmann, Frederik Wurm, 164 Eva Hühn, Thomas Nawroth, Peter Langguth, Holger Frey Anna Fischer, Florian Wolf, Holger 165 Frey Ella Bezdushna, Sabrina Gingter, Helmut Ritter 166 Markus J. Kettel, Juergen Groll, Karola Schaefer, Martin Moeller 167 Susanne Schachschal, S. Wetzel, A. Pich, Hans-Jürgen P. Adler Artjom Döring, Dirk Kuckling Neli Koseva, Violeta Mitova, Barbara Trzebicka, Andrzej Marcinkowski, Andrzej Dworak Julian Thiele, Stephan Förster, Ho Cheung Shum, David Weitz Agnieszka Kowalczuk, Barbara Trzebicka, S. Rangelov, M. Smet, Andrzej Dworak, W. Dehaen Barbara Trzebicka, Alicja UtrataWesolek, Pawel Weda, Christo B. Tsvetanov, Andrzej Dworak Martin Mänz, Philipp Vana

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174 Anita Schulz, Robert Luxenhofer, 175 Alexander V. Kabanov, Rainer Jordan Michael Reif, Rainer Jordan 176 Sebastian Berger, Haiping Zhang, 177 Andrij Pich, Hans-Jürgen Adler Agnes Wycisk, R. Frind, Dirk Kuckling 178 Wolfgang Birnbaum, Dirk Kuckling, Till Korten, Stefan Diez, Manfred Stamm 179 Frank Däbritz, Dirk Schmaljohann, Brigitte Voit

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Anionic copolymerization of DGEBA/hydroxyl-terminated hyperbranched polymer mixtures initiated by 1-methylimidazole Stimuli-responsive degradable cryogels Preparation of hydrogels with stimuliresponsive pores Reversible switching of microtubule mobility using smart polymers Synthesis and characterisation of thermoresponsive hydrophobic hydrogel microcapsules Homogeneous polyacrylamide hydrogels made by large size, flexible dimethacrylate crosslinker Synthesis of polyacrylamide using inverse-emulsion polymerization and its application as sand dune stabilizer Synthesis of polyacrylamide cryogels using free radical photopolymerization Anticoagulant polyzwitterionic effect Removal and recovery of heavy metal ions from wastewater Functionalized block copolymers for the preparation of structured and functional surfaces Synthesis and application of TEMPO containing norbornene block copolymers Polymer nanotubes with complex wall architectures by melt infiltration of block-copolymers Films and dispersions of polyelectrolyte complexes of poly(amines) and poly(carboxylates) Specifics of interaction of sodium dodecyl sulfate with [2(methacryloyloxy)ethyl]thrimethylammo nium methyl sulfate and polymerization of resultant architectures with formation of polyelectrolyte – surfactant complex Physical and chemical properties of plasma polymerized acrylic acid thin films Inverse switching of micro-patterned polymer surfaces based on responsive polymers

Surface-initiated Suzuki

Xavier Fernández-Francos, Xavier Ramis, Xavier Sala, Josep Mª 182 Morancho, Ana Cadenato, Josep Mª Salla, Angels Serra, Ana Mantecón Tugba Dispinar, Wim Van Camp, Filip 183 Du Prez Tuba Tirisoglu Demir, Oguz Okay 184 Leonid Ionov, Manfred Stamm, Stefan 185 Diez Marta Horecha, Volodymyr 186 Senkovskyy, Anton Kiriy, Manfred Stamm Suzan Abdurrahmanoglu, Oguz Okay 187 Mahmood A. Mohsin 188 Muhammet U. Kahveci, Zeynep Beyazkilic, Yusuf Yagci Vasil Atanasov, V. Toncheva, G. Georgiev Ufuk Yildiz, Ö. Ferkan Kemik

189 190 191

Jan Stadermann, Sven Fleischmann, Hartmut Komber, Brigitte Voit

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Onur Kir, Dirk Enke, Nicola Hüsing, Wolfgang H. Binder

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Bhanuprathap Pulamagatta, Eric Yau, Martin Steinhart, Wolfgang H. Binder 194 Martin Müller, Wuye Ouyang, Vitali Starchenko, Sebastian Paulik, O. Adekunle, Bernd Keßler Yulia V. Shulevich, Michail V. Motyakin, Julia A. Zakharova, Alexander M. Wasserman, Alexander V. Navrotskii, Ivan A. Novakov

Amir Fahmy, Renate Mix, A. Schönhals and J. F. Friedrich

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Alla Synytska, Ekaterina Svetushkina, 198 Leonid Ionov, Manfred Stamm

Ksenia Boyko, Tetyana Beryozkina,

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polycondensation of polyfluorene

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Volodymyr Senkovskyy, Natalya Khanduyeva, Anton Kiriy, Manfred Stamm Evgeniy V. Bryuzgin, Alexander V. Navrotskiy, Ivan A. Novakov, Hiroyuki 200 Nishide Falk Tomicki, M. Ulbricht

Grafted polymers and blockcopolymers on aluminium surface for lyophilic properties control Stimuli-responsive polymer architectures in cylindrical pores via surface-initiated living radical polymerization Molecular brushes of poly(2oxazoline)s Polymer brushes on diamond

201 Ning Zhang, Rainer Jordan

Self-assembly of functional polymer multilayered composite membranes with enhanced proton conductivity and methanol barrier properties Preparation of crosslinked poly (2bromoethyl methacrylate) microspheres and decoration of their surfaces with functional polymer brushes by SIP A facile and general approach towards hydrophilic silicones Development of a new silicone formulation for very high speed coating machines Photophysical properties of PPP and PPV derivatives bearing polystyrene or polycaprolactone as side groups Conjugated microporous polymer networks Photoinduced decomposition of dibenzoyldiethylgermane: a photochemical route to polygermanes Tuning of the neutral state color of the π-conjugated donor-acceptor-donor type polymer from blue to green via changing the donor strength on the polymer New amperometric alcohol biosensors based on polypyrrole, poly(3,4ethylenedioxythiophene) and poly(3,4ethylenedioxypyrrole) Synthesis of π-conjugated heterocyclic fused polymer via donor-acceptor approach and its electrochromic application

Naima A. Hutter, Andreas Reitinger, José A. Garrido, Rainer Jordan Serpil Yılmaztürk, Hüseyin Deligöz, Mesut Yılmazoğlu, Hakan Damyan, Faruk Öksüzömer, S. Naci Koç, Ali Durmuş M. Ali Gürkaynak Bunyamin Karagoz, Deniz Gunes, Niyazi Bicak

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Paul Böhm, Tammo J. Menke, Holger 206 Frey T. Ireland, E. Pouget, L. Saint-Jalmes 207 Demet Goen Colak, Daniel Ayuk Mbi Egbe, Eckhard Birckner, Seda Yurteri, 208 Ioan Cianga, Emine Tekin, Ulrich S. Schubert, Yusuf Yagci Johannes Schmidt, Markus Antonietti, 209 Arne Thomas Yasemin Yuksel Durmaz, Manolya Kukut, Norbert Monszner, Yusuf Yagci 210 Simge Tarkuc, Yasemin Arslan Udum, Levent Toppare 211

Özlem Türkarslan, Levent Toppare 212 Yasemin Arslan Udum, Simge Tarkuc, Levent Toppare

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Fluorescence sensing of glucose using 110 glucose oxidase modified by PVApyrene prepared via ‘click chemistry’ Coordinative supramolecular assembly of luminescent films based on metallo111 polymers with terpyridyl- and benzimidazolylpyridyl-zinc moieties Synthesis of poly (sulfopropyl 112 methacrylate) based copolymers for proton exchange membrane fuel cell Preparation and properties of hyperbranched polymer-based 113 electrolyte membranes for fuel cells Synthesis and characterization of thermally curable benzoxazine 114 containing polyesters for improved adhesion property Calix[4]pyrrole containing cross-linked 115 polymers

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Dilek Odaci, Bahadir N. Gacal, Burcin 214 Gacal, Suna Timur, Yusuf Yagci Anna Maier, Irina Welterlich, A. Raman Rabindranath, Bernd Tieke

Tuba Erdogan Bedri, Elif Erdal Unveren, Begum Elmas

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Takahito Itoh, Takahiro Sakakibara, Yuki Takagi, Keita Hirai, Masashi 217 Tamura, Takahiro Uno, Masataka Kubo, Yuichi Aihara Alev Tuzun, Baris Kiskan, Yusuf Yagci 218

Abdullah Aydogan, Christopher W. Bielawski, Jonathan L. Sessler, Ahmet 219 Akar Synthesis and characterization of a Bahadir N. Gacal, Burcin Gacal, Yusuf novel linear polymer containing 1,2,3- Yagci triazole and benzoxazine groups in the 220 main chain by a step-growth clickcoupling reaction Substituted oligo (ethylene glycol) Mandy Gnauck, Evelin Jaehne, Hans221 derivatives for surface modification Jürgen P. Adler Selective adsorption of oligo(ethylene Rene Luther, Evelin Jaehne, Marcus 222 glycol) derivatives on oxide surfaces Textor, Hans-Juergen P. Adler Synthesis and characterization of a Kristian Kempe, Matthias Lobert, series of diverse poly(2-oxazoline)s Richard Hoogenboom, Ulrich S. 223 Schubert Biodegradable poly(ethylene Nai Xu, Demin Jia carbonate)/montmorillonite 224 nanocomposites prepared in supercritical carbon dioxide fluid The effect of organic modifiers on the Patricio Toro, R. Quijada, M. Yazdaniproperties of polypropylene/clay Pedram, Doris Pospiech, D. Fischer, 225 nanocomposites Bernd Kretzschmar Exfoliation targeted toughness Cüneyt Bağcıoğlu, Esra Altuntaş, enhancement in polypropyleneSinan Şen, M.Bora Đşlier, Osman G. 226 montmorillonite nanocomposites Ersoy, Nuri Ersoy, Turgut Nugay, Nihan Nugay In-situ intercalative polyamidation of Anastasia C. Boussia, S. N. 227 PA n,6 nanocomposites Vouyiouka, C. D. Papaspyrides Microwave-assisted synthesis and Alexander Türke, Andrij Pich, W.-J. characterisation of silver hybrid Fischer, Hans-Jürgen P. Adler 228 particles One-pot synthesis and characterization Stefan Bokern, Julia Getze, Seema of metal nanoparticles stabilized by Agarwal, Andreas Greiner 229 functionalized polymers

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Formation of gold nanoparticles in presence of mixed phosphatidylcholine-anionic surfactantvesicles using oligosaccharidemodified poly(ethyleneimine) Synthesis of rigid and flexible hyperbranched polyurethanes and their selective interactions with multi-walled carbon nanotubes Perylenediimide (PDI) encapsulated in silica core-shell nanoparticles Polymer-based nanosized silica dispersions - quantitative comparison of the stability in dependence on polymer architectures Ionic hybrids based on chitosan and clinoptilolite Silver/(2-hydroxyethyl methacrylate-coitaconic acid/poly(vinyl pyrrolidone)) semi-interpenetrating hydrogel networks In situ synthesis of acrylamide hydrogels containing silver nanoparticles by photoinduced processes and their antibacterial properties Organic-inorganic conducting polymer hybrid with green color in neutral state Gold nanoparticle effect on conducting poly( 4-(2,5-di(thiophen-2-yl)-1h-pyrrol1-yl)benzenamine) biosensor Synthesis and selective segregation of Fe3O4 nanoparticles inside of the polyvinylpyridine domain of poly(styrene-bvinylpyridine Patterned surfaces from hybrid “coreshell” particles: possibilities for design hydrophobic and superhydrophobic materials Superhydrophobic surfaces by polymer-stabilized oxide layers on aluminium

Anja Köth, Joachim Koetz, Dietmar Appelhans 230

Sravendra Rana, Sibdas Singha Mahapatra, Jae Whan Cho

Hailin Wang, Karola Schaefer, Martin Moeller Gudrun Petzold, Christine Goltzsche, Simona Schwarz

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Ecaterina Stela Dragan, Maria 234 Valentina Dinu, Daniel Timpu Simonida Lj. Tomić, Suzana I. Dimitrijević, Jovanka M. Filipović, Sava 235 N. Dobić Mustafa Uygun, Muhammet U. Kahveci, Dilek Odaci, Suna Timur, Yusuf Yagci

Metin Ak, Gulbanu Koyundereli Çilgi, Mehmet Karakus Sevinc Tuncagil, Caglar Ozdemir, Dilek Odaci, Suna Timur, Levent Toppare Andriy Horechyy, Nikolaos E. Zafeiropoulos, Peter Formanek, Constantinos Tsitsilianis, Manfred Stamm Alla Synytska, Leonid Ionov, Karina Grundke, Manfred Stamm

Ralf Frenzel, Susanne Höhne, Christa Blank, Axel Mensch, Michael Thieme, Hartmut Worch, Martin Müller, Frank Simon Coating and flexible materials for radar Udayan De, Kriti Ranjan Sahu, N. absorption and EMI shield Dutta Gupta Stretching of polyelectrolyte molecules Konstantin Demidenok, Anton Kiriy, on the hydrophobic surface Manfred Stamm Fabrication of nanoassemblies based Smrati Gupta, Marin Steenackers, on polymer brushes and metal Rainer Jordan nanoparticles Adaptive layers based on switchable Anja Rollberg, Petra Uhlmann, P. core shell silica particles Formanek, A. Janke, Manfred Stamm

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LECTURES

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P1

ADVANCED NANOSTRUCTURED MATERIALS BY ATOM TRANSFER RADICAL POLYMERIZATION Krzysztof Matyjaszewski Carnegie Mellon University, Pittsburgh [email protected] Copper-based ATRP (atom transfer radical polymerization) catalytic systems with polydentate nitrogen ligands such as bpy and aliphatic polyamines is among most efficient controlled/living radical polymerization systems. Recently, by applying new initiating/catalytic systems, Cu level in ATRP was reduced to a few ppm. ATRP of acrylates, methacrylates, styrenes, acrylamides, acrylonitrile and many other vinyl monomers provides polymers with molecular weights in a large range 200 7.0 the ion pairs dissociated gradually with the increase in pH. The system of on pairs was broken almost completely at pH 9.0 where the onset of CTS precipitation took place. Thus, the complexing extends the pH range of soluble CTS with ∆pH of 2.5 in alkaline media, i.e. from pH 6.5 to pH 9.0. The properties of soluble CTS/PSS complexes were studied and it was found that they obey the regularities inherent in water-soluble nonstoichiometric polyelectrolyte complexes (NPEC). The developed strategy could be of particular importance for preparing water-soluble biocompatible and biodegradable CTS-based complexes suitable for application at physiological pH and ionic strength. [1] I.F.Volkova, M.Yu.Gorshkova, V.A.Izumrudov, Polymer Science, Ser.A (2008) 50, N8, pp1-8.

112

Poster 9

CHARACTERIZATION OF DENDRONIZED OLIGOSACCHARIDE-MODIFIED POLYMERS VIA A4F Susanne Boye, Viktor Boyko, Dietmar Appelhans, Stefan Zschoche, Albena Lederer Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden [email protected] Dendritic polymers are of great industrial and scientific interest and their range of application is rapidly growing. The unique multifunctionality of these polymers allows applications especially in thin films, in catalysis, in sensors and diagnostics, in pharmacy and biomedicine. Due to the increasing number of functional groups with increasing molar masses at a nearly globular molecular shape, these molecules could strongly interact with surfaces (i.e. column packing material) and this is the reason for their challenging characterization by SEC. Therefore new characterization methods are required. A suitable alternative is the Asymmetric Flow Field-Flow Fractionation (A4F) with multi-angle laser light scattering detection. This is a recently established technique in the area of polymer separation and the main advantage of using A4F is the possibility to characterize macromolecules over a wide range of molar masses without shear degradation and the well known problem of interactions with SEC column packing. In respect to the specific type of application of dendritic polymers e.g. in blends or as bioactive polymers, they exhibit different chemical structures and different end group modifications. We carried out measurements on different generations of dendronized structures coupled on a maleimide copolymer backbone and subsequently modified with maltose end groups. Combination of SEC with A4F method development gave an inside into the molar mass and dimensions of these polymers as well as into their aggregation behavior depending on the sample concentration, pH value of the aqueous environment as well as on the dendron generation number.

113

Poster 10

PREPARATION AND CHARACTERIZATION OF HYPERBRANCHED ALIPHATIC-AROMATIC POLYESTER/TIO2 NANOCOMPOSITES. Hamed Elsayed (1), Brigitte Voit (2) (1) National Research Center Giza, Cairo, Egypt (2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany [email protected] Recently, organic–inorganic hybrids, as a kind of composite material prepared from organic polymers and inorganic nanoscale compounds, have attracted much attention because they can combine the properties of both polymers and inorganic compounds [1,2]. Hybrid materials are widely used in various fields, such as abrasion resistant coatings, optically active films, and contact lenses due to their good mechanical and optical properties [2,3]. They are usually prepared utilizing a sol-gel process by incorporating metal alkoxides in organic polymers or oligomers. In the sol-gel process the hydrolysis and condensation of metal alkoxides usually takes place, which results in the formation of inorganic networks the formation of well defined nanoparticles when the particle growth is controlled and stabilized by the organic components. The most frequently used precursors for TiO2 nanoparticles are titanates, such as titaniumisopropoxide. A series of organic–inorganic hybrids were prepared based upon modified and unmodified hyperbranched aliphatic polyesters which reacted with 1,6-diisocyanatohexane as crosslinker, and dibutyltin dilaurate as catalyst, forming the matrix resin in the presence of precondensed titaniumisopropoxide. The incorporation of titanium oxide nanoparticles in thin films and coatings is especially encouraging since by this surface hardness can be significantly improved and, on the other hand, self-cleaning and antimicrobial properties can be introduced based on the photocatalytic effect induced by some titanium oxide modification [4,5]. The TiO2 nanoparticles were synthesized via sol-gel process directly in a solution containing the HBP polyester as stabilizer, and then the polymer/TiO2 hybrid mixtures were thermally cured by means of a diisocyanate crosslinker to obtain a hard coating or a film [4]. In this work, a series of hybrid materials with different titania contents based upon modified and unmodified hyperbranched aliphatic polyester were prepared and characterized with NMR, GPC, Dynamic Light Scattering (DLS), Atomic Force Microscopy (AFM), Small Angle X-ray Scattering (SAXS), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). [1] [2] [3] [4] [5]

Ochi M, Takahashi R, Terauchi A. Polymer 2001;42:5151. J. Zou et al., Composites: Part A 36 (2005) 631–637. Frings S, Meinema HA, Van Nostrum CF, et al. Prog Org Coat 1998; 33:126. A. Di Gianni et al., Macromol. Chem. Phys. 2007, 208, 76–86. Y. Zhao et al., Microporous and Mesoporous Materials 92 (2006) 251–258.

114

Poster 11

NEW HYPERBRANCHED POLYESTER MODIFIED DGEBA THERMOSETS WITH IMPROVED CHEMICAL REWORKABILITY D. Foix (1), M. Erber (2), X. Ramis (3), Y. Yu (1,4), A. Mantecón (1), B. Voit (2), A. Serra (1) (1) Department of Analytical and Organic Chemistry, University Rovira i Virgili, C/ Marcel·lí Domingo s/n, 43007, Tarragona, Spain (2) Leibniz-Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany (3) Thermodynamics Laboratory, ETSEIB University Politècnica de Catalunya, C/ Av. Diagonal 647, 08028, Barcelona, Spain (4) The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China [email protected] Epoxy resins are among the most used materials in the coating of electronic devices. This is because they present good properties in terms of electrical insulation, adhesion to various components and thermal stability. However, they present a lack in reworkability: the encapsulated material can not be recovered in order to be repaired or recycled. They also exhibit poor toughness and considerable shrinkage on curing. Hyperbranched polymers (HBPs) have proved in recent years to allow overcoming some of these drawbacks [1,2)] New epoxy thermosets based on diglycidylether of bisphenol A (DGEBA) and a hyperbranched polyester [3], synthesized from 4,4-bis(4-hydroxyphenyl) valeric acid, cured by ytterbium triflate have been obtained. The chemical degradability was evaluated by treating the cured material with a 1M NaOH in EtOH solution under reflux and determining the Tg at different reaction times by means of differential scanning calorimetry (DSC). The addition of HBP allows the degradation of the thermoset to occur in a much shorter period of time. This is a remarkable result in terms of improving the reworkability. Moreover, the thermal stability, studied by thermogravimetry (TGA) was slightly improved with the addition of the HBP. The gelation of these systems was studied using thermomechanical analysis (TMA) and no remarkable differences were observed both in time and conversion at gelation with the addition of the HBP. Also by means of TMA, the evolution of the shrinkage during the curing process was followed. When the proportion of HBP in the reaction mixture is increased a large expansion takes place at the beginning of the curing and afterwards the materials contracts. The lowering of the global shrinkage on curing was confirmed by measuring the densities of the material before and after curing. The kinetics of the curing process was evaluated from the calorimetric curves and using integral non-isothermal kinetic analysis. Acknowledgements We would like to thank MICINN projects MAT2008-06284-C03-01, MAT2008-06284-C0302 and HA2007-0021 for financial support. D.F. acknowledges the grant FPU-2007 from the Spanish Government. [1] Mezzenga R and Manson J-AE. Polym. Mater. Sci. Eng. 2001; 84:947. [2] Varley RJ and Tian W. Polym. Int. 2004;53(1):69. [3] Schallausky F, Erber M, Komber H, and Lederer A. Macromol. Chem. Phys. 2008; 209:2331.

115

Poster 12

INFLUENCE OF THE MOLECULAR WEIGHT OF A POLY(ESTER-AMIDE) HYPERBRANCHED POLYMER ON THE CHARACTERISTICS OF MODIFIED EPOXY THERMOSETS M. Morell (1), M. Erber (2), B. Voit (2), X. Ramis (3), J.M. Salla (3), F. Ferrando (4), A. Serra (1) (1) Department of Analytical and Organic Chemistry, University Rovira i Virgili, C/ Marcel·lí Domingo s/n, 43007, Tarragona, Spain (2) Leibniz-Institute of Polymer Research Dresden, Hohe Str. 6, 01069, Dresden, Germany (3) Thermodynamics Laboratory, ETSEIB University Politècnica de Catalunya, C/ Av. Diagonal 647, 08028, Barcelona, Spain (4) Department of Mechanical Engineering, University Rovira i Virgili, C/ Països Catalans 26, 43007, Tarragona, Spain [email protected] Despite the combination of good properties, epoxy thermosets show volume contraction during the curing process, which leads to the origination of internal defects into the matrix, decreasing adhesion and protection capacity especially requiered in some applications such as coatings for electronic devices. Moreover, the poor toughness of these materials due to their high crosslinking character can easily result in fractures in the thermoset. Nowadays, the effect of hydroxyl terminated hyperbranched polymers (HBPs) on the curing behavior and toughening performance of a commercial epoxy resin has been broadly studied [1,2,3]. One important aspect that should be considered in order to control the curing shrinkage and optimize the final properties of the materials is the influence of the molecular weight of this kind of dendritic type modifiers. In the present work, two aliphatic poly(ester-amides) HBPs, SPEA (Mw=1.500 g/mol) and BPEA (Mw=30.000 g/mol), have been employed as chemical epoxy resin modifiers to study the influence of the molecular weight on the characteristics of diglycidylether of bisphenol A (DGEBA) thermosets cured with anhydride. SPEA is a commercial product, whereas BPEA was synthesized in melt by polycondensation of diisopropanolamine (DIPA) and cyclohexahydrophtalic anhydride (HHPA). The new modified materials were prepared as the conventional thermosets, using methyltetrahydrophthalic anhydride (MTHPA) as curing agent and benzyldimethylamine (BDMA) as the accelerator, but adding the corresponding proportion of hyperbranched polymer to the matrix from 5% to 10% (by weight). The curing process was followed by FTIR and DSC. The use of BPEA leads to the retardance of the curing process comparing with SPEA. By TMA we could conclude that the conversion at the gelation was not influenced by the molecular weight of the hyperbranched. For both systems, SPEA and BPEA, the shrinkage after gelation was reduced on increasing the amount of modifier in the thermoset. The Tgs of the materials were determined by DSC and DMTA observing that SPEA leads to higher values of Tg than BPEA. By TGA we proved that the incorporation of both HBPs increased the thermal reworkability of these materials compared with pure DGEBA, due to the introduction of secondary ester groups in the hyperbranched structure. Finally, mechanical properties such as impact strength and microhardness were also tested showing enhancements in both properties. Acknowledgments: We would like to thank MICINN for (MAT2008-06284-C03-01) (MAT2008-06284-C03-02) and (HA2007-0021) for financial support. DSM is acknowledged for Hybrane® H1500 and Hunstman Advanced Materials for the HY918® (MTHPA) supply. M.M. acknowledges the grant FI-2008 from the Catalonian Government. [1] Boogh, L., Petterson, B., Manson, J.A. Polymer. 40, 2249 (1999). [2] Ratna, D., Simon G.P. Polymer. 42, 8833 (2001). [3] Yang, J.P et al. Polymer. 49, 3168 (2008).

116

Poster 13

THE USE OF XPS METHODS IN STUDYING POLYMERIC COMPOSITES WITH MAGNETIC NANOPARTICLES O. Pana (1), J. Martin (2), M. L. Soran (1), R. Turcu (1), C. Leostean (1), C. Mijangos (2) (1) NatI. Inst. for R&D of Isotopic and Molec. Technol., P.O.B. 700, 400293 Cluj-Napoca 5, Romania (2) Instituto de Ciencia y Tecnología de Polimeros, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain [email protected] In this work we report different methods based on X-ray photoelectron spectroscopy technique (XPS) in studying magnetic heterocomposites with polymers. Two types of materials are involved, first, magnetic nanoparticles covered with polymers or functionalized polymers having a core-shell or globular structure and second,. Magnetic nanoparticles dispersed in polymeric matrices respectively. The preparation methods involve the inverse micelles method, sol gel, and different dispersion methods inside polymers and polymeric gels. Special care is focused in preparing magnetic nanoparticles caped with functionalized copolymers. The evolution of different chemical states inside the different materials under investigation is studied by performing the so called depth profile analysis. In order to obtain a coherent picture concerning the structure – properties relationship the XPS results are correlated to other investigation methods like AFM/STM, transmission electron spectroscopy, FTIR and magnetization measurement. The effects of the core-shell or globular structure formation on the magnetic properties of these hybrid materials are discussed. Various applications such as magnetic molecular separations, drugs delivery or magnetic uptake of toxic substances are discussed.

117

Poster 14

A XRD STUDY OF THE ORGANIC MODIFIER STRUCTURES EFFECT ON THE INTERLAYER DISTANCE AND DISPERSION OF MONTMORILLONITE CLAYS IN POLYAMIDE-CLAY NANOCOMPOSITES V.N. Dougnac (1), R. Quijada (1), D. Pospiech (2), D. Jehnichen (2) (1) Depto. de Ingeniería Química y Biotecnología y Centro para la Investigación Interdisciplinaria Avanzada en Ciencia de los Materiales (CIMAT), Universidad de Chile, Av. Blanco Encalada 2008, Santiago, Chile (2) Institute of Polymer Research Dresden, P.O. Box 120411, 01005, Dresden, Germany [email protected] Polymeric nanocomposites prepared through the addition of organically modified natural clays to polymeric matrices have attracted great attention in recent years because they possess enhanced mechanical, thermal, barrier and flame retardant properties compared to the pure polymers. A critical parameter in the production of these nanocomposites is the interaction between the matrix and the organically modified clay. If the interaction is adequate, the polymer chains enter between the clay layers and as a result the clay layers separate and disperse into the polymer matrix. If the interaction is not sufficient the clay does not disperse well into the polymer matrix. In this work the modification of two clays (montmorillonites) from different origins was studied; a commercial clay, Cloisite Na+ (d001:1.0 nm, CEC: 92.6 meq/100g) and a natural clay obtained from a site in Chile which was sieved and used without further treatment, Chilean clay (d001:1.3 nm, CEC: 80 meq/100g). The clays were modified with 11aminoundecanoic acid (A), dodecylbis(2-hydroxyethyl) methyl ammonium chloride (B), hexadecyl (2-hydroxyethyl)dimethyl ammonium dihydrogen phosphate (C) and octadecyl bis(2-hydroxyethyl) methyl ammonium chloride (D). PA-clay nanocomposites were prepared via direct melt compounding in a microcompounder. XRD was used to evaluate the effect of the organic modifier structure both on the clay interlayer separation and the dispersion of the clay in polyamide 6 (PA). XRD results show that the Cloisite Na+ modified with B, C and D present an increase in the interlayer space of around 8 Å while compound A did not produce any significant change in the interlayer distance. Chilean clay showed a greater interlayer distance than Cloisite Na+ when modified with compound C and D, 2.2 nm and 2.7 nm, respectively; even compared to a commercially modified clay, Cloisite 30 B, (1.8 nm). Indicating that there is likely more organic modifier between the layers or that the long alkyl chain is more vertical in the chilean clay than in the Cloisite clay. The PA-nanocomposites prepared with the clays modified with compounds B, C and D show a good dispersion into the PA matrix as indicated by the d001 diffraction peak. The dispersion of the Chilean clay modified with C was not as complete as the commercial clay presented an interlayer distance of 3.3 nm. This demonstrates that the interaction was not as good between the clay and PA.

118

Poster 15

MONITORING OF THE GROWTH OF POLY(N-ISOPROPYLACRYLAMIDE) BRUSHES SYNTHESIZED BY SURFACE INITIATED ROOM TEMPERATURE ATRP M. Erber, J. Stadermann, K.-J. Eichhorn, B. Voit Leibniz Institute of Polymer Research Dresden, Hohestr. 6, 01069 Dresden, Germany [email protected] The in situ formation of dense polymer brushes is possible through a “grafting from” approach in which covalently attached polymers are grown by surface-initiated polymerization from the substrate, yielding larger packing densities than those prepared in a “grafting to” approach that seeks to direct macromolecules to a surface and immobilize them there [1]. Polymer brushes with switchable phase transition behaviour, such as copolymers on the base of poly(N-isopropylacrylamide) (PNiPAAM), can be exploited in sensing and actuation devices with potential application for protein adsorption leading to controlled adsorption and desorption processes [2]. PNiPAAM undergoes a reversible phase transition in which solvated polymer chains collapse to a non solvated, hydrophobic globule in response to external stimuli such as changes in temperature [3]. This work is focused on the synthesis of PNiPAAM by means of surface-initiated atom transfer radical polymerization (ATRP). In particular, ATRP has been demonstrated to be a versatile technique to synthesize well-defined polymer chains with high grafting densities [3]. In our case the synthesized polymer is solely localized at the interface so that the need for extraction of loosely physisorbed polymer is eliminated. Different highly ordered and spatially confined self-assembled monolayers (SAMs) serving as initiator for the polymerization of polymer brushes are investigated. The SAM molecules forming are bifunctional where the surface binding group (silane or thiol) is chosen to match the substrate chemistry. Beside the preparation we report the extensive characterization of the grafting process by means of spectroscopic vis-ellipsometry (in-situ and ex-situ), AFM and contact-angle measurement to characterize the thickness, roughness, hydrophilicity, swelling behaviour of the polymer brushes. [1] Prucker, O.; Rühe, J. Langmuir 1998, 14, 6893-6898. [2] Wittemann, A.; Haupt, B.; Ballauff, M. Physical Chemistry Chemical Physics 2003, 5, 1671-1677. [3] Brittain, W. J.; Minko, S. Journal of Polymer Science Part A-Polymer Chemistry 2007, 45, 3505-3512.

119

Poster 16

COMPARING MALDI/ESI MASS SPECTROSCOPY IN THE CHARACTERIZATION OF TELECHELIC OLIGO- AND POLY(3-HEXYL) THIOPHENES Claudia Enders Martin-Luther Universität Halle-Witterberg [email protected] Electrospray ionization time-of-flight (ESI-TOF) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) have become important techniques in polymer science as softest and most sensitive ionization methods. In particular their simple coupling to separation techniques such as HPLC or SEC is an efficient method for characterization, analysis and structural elucidation of polymers. This report compares both ionization methods for characterizing endgroup functionalized oligothiophenes (OTPh) and poly(3-hexylthiophene)s (PTPh). The current project aims at the synthesis of functional layer materials consisting of immiscible OTPhs or PTPhs, which are microphaseseparated by other polymer layers of defined thickness. These oligomers as well as polymers are held together into a sheet-structure via attractive supramolecular interactions such as H-bonding. Over the past years, we have published about microphaseseparated oligomers and polymers, in particular the generation of supramolecular pseudo-blockcopolymers via endgroupfunctionalized, telechelic polymers [1]. The current investigation starts with the synthesis of terthiophene as a model reaction and subseqeunt characterization by both ionization methods. Subsequently ethinyl end-groups were introduced into the terthiophene via Sonogashira reactions [2]. Polymerization of pure regioregular poly(3-hexyl)thiophene was achieved via GRIM- Grignard Metathesis polymerisation [3]. A defined ethinyl end-group structure 2 was generated by postfunctionalization via a second Grignard reagent acting as quenching agent. Hydrogen-bonding residues were introduced via the copper-catalyzed 1, 3-dipolar cycloaddition-“click” reaction [4]. The functionalized terthiophene could be characterized via LC-ESI-TOF mass spectroscopy and MALDI-TOF MS. It was shown that the ionization of PTHs higher than 4 kDa molecular weight is significantly more difficult by ESI-TOF than by MALDI-TOF. Nevertheless the molecular weight distribution of the PTPh (> 4 kDa) could be separated by gradient elution and subsequent detection via ESI-TOF. The ionization of the HPLC separated HT-P3HT (head-to-tail poly(3-hexyl)thiophene) was achieved by postcolumn injection of silver acetate, thus enabling an efficient analysis of the individual chains with different endgroup structure. A comparison of this analysis to the MALDI-data of the same polymers is provided. [1] Binder, W. H.; Bernstorff,S.; Kluger, C.; Petraru, L.; Kunz, M.J., Advanced Materials 2005, 17,(23), 28242828. [2] J.Lewis, N.J.Long; P.R. Raithby, G. P. Shields, W-Y Wong, M. Younus, J.Chem.Soc., Dalton Trans [3] 4283 (1997) [4] Jeffries-El, M.; Sauve, G.; McCullough, R. D., Macromolecules 2005, 38, (25), 10346-10352. [5] Binder, W. H.; Zirbs, R., Adv. Polym. Sci. 2007, 207.

120

Poster 17

CHARGE CARRIER TRANSPORT IN CONJUGATED POLYMERS Petr Toman (1), Stanislav Nešpůrek (1,2), Martin Weiter (2), Martin Vala (2), Wojciech Bartkowiak (3) (1) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 162 06 Prague 6, Czech Republic (2) Brno University of Technology, Purkyňova 118, 612 00 Brno, Czech Republic (3) Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland [email protected] Conjugated polymers attract considerable research interest because of their possible use in future molecular electronic devices. Thus, the knowledge of the charge transport mechanism and relations between molecular and macroscopic properties is very important. The charge carrier transport is usually considered as hopping within a geometrically and energetically disordered system. Our model describes the conjugated polymer chains as linear sequences of sites, in which the charge carrier can be localized. The site-to-site charge transfer integrals are randomized by the chain torsional disorder. Site energy disorder, resulting from intermolecular interactions of the charge carrier with dispersed polar species, is introduced as well. The polymer chain energy band structure and the on-chain motion are calculated solving the Schrödinger equation in the tight-binding approximation. The charge carrier localized on a given chain for a longer time looses quantum coherence due to its interaction with the phonon bath. This fact justifies the use of the quasi-classical Marcus concept in the modeling of the inter-chain hopping. The charge carrier residing on a given chain is supposed to be completely thermalized over all the on-chain states prior to the subsequent jump to one of the nearest neighboring chains. The results show a strong dependence of the charge carrier mobility on the degree of the energetic disorder. If the energetic disorder is increased by a polar additive, the mobility is reduced by several orders of magnitude. The calculated temperature dependence of the mobility shows essentially Arrhenius type behavior with a moderate subArrhenius deviation at the low energetic disorder and the low-temperature saturation at the high energetic disorder. This work was supported by the Grant Agency of the Academy of Sciences of the Czech Republic (Project No. IAA401770601) and by the Ministry of Education, Youth, and Sports of the Czech Republic and the Polish Ministry of Science and Higher Education (Project No. MEB 050815 – 2008/CZ-5, Czech-Polish cooperation). The computer time at the METACentrum (Prague and Brno) and at the Institute of Physics of the AS CR, v. v. i. (Project Luna) is gratefully acknowledged.

121

Poster 18

BLEND OR COPOLYMER? SPECTROELECTROCHEMICAL EVIDENCE OF COPOLYMERIZATION OR BLENDING TWO MONOMER: SYNTHESIS OF A DIPYRROMETHANE FUNCTIONALIZED MONOMER AND OPTOELECTROCHROMIC PROPERTIES OF ITS HOMOPOLYMER, COPOLYMER AND BLEND WITH EDOT Mine Sulak Ak, Metin Ak, Halil Çetişli, Ramazan Donat Pamukkale University, Department of Chemistry, 20020 Denizli, Turkey [email protected] Conducting polymers have attracted great interest due to their ease of synthetic accessibility and modified architecture which can control the polymer properties (i.e., electronic, optical, conductivity, etc.) [1]. These advanced systems can be modified to be amenable for use in the desired application by changing the structure of starting monomers. Blending and copolymerization are another frequently used methods in order to improve the properties of the polymers [2]. A dipyrromethane functionalized monomer; 5-(4-tert-butylphenyl) dipyrromethane (BPDP) was synthesized. Electrochemical polymerization, copolymerization and blending of BPDP with 3,4-ethylenedioxythiophene (EDOT) were achieved in LiClO4/AN. Spectral and electrochromic properties of producs are investigated. Spectral properties of copolymer and blend have great differences from each other and corresponding homopolymers. Effects of differentiation feed ratio of monomers on copolymers’ spectral properties are also investigated. [1] Terje A. Skotheim, Handbook of Conducting Polymers, II. Ed. Marcel Dekker, 1998. [2] O. Turkaslan, M. Ak, C. Tanyeli, I. M. Akhmedov and L. Toppare, “J. Polym. Sci., Part:A Polym. Chem., 45(19), 2007, 4496-4503.

122

Poster 19

THERMAL DEGRADATION AND PYROLYSIS-GC/MS STUDIES ON POLYSTYRENE/PVC BLENDS Z. Ahmad, N. A. Al-Awadi and F. Al-Sagheer Department of Chemistry, Kuwait University, Faculty of Science,PO Box 5969, Safat-13060, State of Kuwait [email protected]; [email protected] The effect of poly(vinyl Chloride) (PVC) on the thermal stability of polystyrene (PS) have been studied using different techniques. PS-PVC blends with different compositions in the film and the powder forms were prepared. The dynamic thermogravimetric studies on these blends were carried out under inert atmosphere from ambient to 800 °C at different heating rates. Thermal decomposition temperature of blends were found higher than that of pure PS which indicate stabilization effect of PVC on PS. The effect varies with the heating rates and the composition of the blends [1]. The pyrolysis-GC/MS studies were carried out on the these blends in a temperature range where the degradation was found maximum in the TGA studies. The absolute intensities of different volatile products measured from the chromatograms show that the production of benzene, styrene monomer, toluene, α-methyl styrene, naphthalene and 1-3 diphenyl propane dimer and the trimer decreased significantly in presence of PVC in the PS matrix where as the amount of cross-linked residue retained above 400 °C increased. The TGA results have been compared with the GC/MS data and the stabilizing effect of PVC on PS has been explained by the possible chemical interactions of the micro and macro -radicals produced from the polymer components and the changing morphology of blends with composition and degrading temperatures. [1] Z. Ahmad, N.A. Al-Awadi and F. Al-Sagheer, Polym. Degrad. & Stab., 92 (6), 1025-1033, 2007.

123

Poster 20

IN-SITU MONITORING OF REACTIVE EXTRUSION BY USING OF NIR-SPECTROSCOPY AND ULTRASONIC MEASUREMENTS S. Kummer, J. Müller, D. Fischer, B. Kretzschmar, K. Sahre Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Gerrmany [email protected] Inorganic oxides are a type of nanofillers in polymer matrices to produce polymers with specific tuneable material properties for specific applications. These fillers can be created by sol-gel chemistry. The sol-gel chemistry offers the possibility to produce in-situ nanofillers with particle sizes lower than 100 nm. Our concept was to carry out this reaction without solvent during extrusion by mixing of a precursor in a polymer matrix with subsequent hydrolysis to the inorganic oxide particles. In this way it is easier to control the particles size of the filler and to prevent agglomeration. The mentioned polymer properties are depending on the particle size and distribution. For process optimization it is necessary to monitor both during processing. Outstanding real time methods therefore are near infrared spectroscopy (NIR) and Ultrasonic measurements [1-2]. We added titanium-n-butoxide as precursor (liquid dosing) and water (liquid dosing) in molten polypropylene to produce TiO2-particles with low particle sizes in the molten state. TiO2 particle was generated by hydrolysis with the water directly in the extruder. The experiments was carried out in a Leistritz Micro 27 twin screw extruder (L/D44) at a temperature of 200 °C, with a flow rate of 6 kg/h, the screw speed was 150 U/min. The in-line NIR measurements were carried out by using the process spectrometer Sentroproc (1350 – 2050 nm) in transmission mode. The ultrasonic measurements (ultrasonic velocity and attenuation) were carried out with inhouse constructed ultrasonic probes (transmission) with commercial transducers in the spectral range from 3 to 10 MHz. The in-line NIR spectra show an increasing background scattering during the increasing of water dosing at different extrusion experiments. The ultrasonic attenuation spectra measured during the same extrusion experiments present an increase of the ultrasonic attenuation signal. We used scanning electron microscopy (SEM) to determine the particles size of TiO2 after the extrusion process. SEM images of samples with water dosing of 3 mol relating to the added Ti-n-butoxide show small TiO2 particles with particle sizes from 50 to 100 nm. In the case of adding 6 mol water SEM images show agglomerates with diameters up to 800 nm. So we could prove that the agglomeration is a result of the higher water dosing during extrusion. By multivariate data analysis (PLS) we could correlate the in-line NIR spectra and the in-line measured ultrasonic attenuation spectra with the particle sizes determined by SEM. In validation experiments we were able to predict in real time the particle size of TiO2 during reactive extrusion. [1] D. Fischer; K. Sahre; M. Abdelrhim; B. Voit; V.B. Sadhu; J. Pionteck; H. Komber J. Hutschenreuter [2] Comp.t Rendus Chem. 2006, 9, 1419. [3] I. Alig; D. Fischer; D. Lellinger; B. Steinhoff Macromol Symp 2005, 230, 51.

124

Poster 21

PARTICLE SIZE AND PARTICLE SIZE DISTRIBUTION OF NANOPARTICLES – A COMPARE OF CENTRIFUGAL SEPARATION ANALYSIS AND DYNAMIC LIGHT SCATTERING M. Mende (1), S. Schwarz (1), S. Zschoche (1), G. Petzold (1), K.-F. Arndt (2) (1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany (2) Dresden University of Technology, Institute of Physical Chemistry and Electrochemistry, Mommsenstr. 4, 01062 Dresden, Germany [email protected] Oppositely charged macromolecules dissolved in aqueous solutions are known to produce macromolecular aggregates in nano-dimension primarily based on long-range electrostatic interactions of opposite charges. They are also called polyelectrolyte complexes (PEC). Oppositely charged macromolecules dissolved in aqueous solutions are known to produce macromolecular aggregates in nano-dimension primarily based on long-range electrostatic interactions of opposite charges. They are also called polyelectrolyte complexes (PEC). The PEC formation, especially PEC size, depends on a number of parameters, particularly on the molecular weight and chemical structure of the polyions, distribution of charged groups along the chain, polymer concentration, molar ratio of the charged groups of the polycation and polyanion, ionic strength and pH of the medium. Stable dispersions of PECs are interesting for applications in cosmetic, pharmaceutical industry and for coatings. They are effectively flocculants and stabilizers. One criterion for the stability of dispersion is the particle size and particle size distribution, respectively. Our work contains the formation of PEC particles of cationic and anionic modified alternating maleic acid copolymers and their characterization by Dynamic Light Scattering (DLS) with the Zetasizer Nano S from Malvern Instruments (UK) and by Centrifugal Separation Analysis (CSA) with the LUMiSizer® from L.U.M. GmbH (Germany).

125

Poster 22

FORMATION, STABILITY, AND APPLICATION OF COMPLEX NANOPARTICLES BASED ON CHITOSAN Ecaterina Stela Dragan (1), Marcela Mihai (1), Simona Schwarz (2) (1) “Petru Poni” Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41 A, RO-700487 Iasi, Romania (2) Leibniz Institute of Polymer Research, Hohe Strasse 6, 01069 Dresden, Germany [email protected] Interpolyelectrolyte complex (IPEC) nanoparticles formed between chitosan having different molar masses (470, 670 and 780 kDa) and two random copolymers of 2-(acrylamido)-2methylpropanesulfonate (AMPS) with tert-butylacrylamide (TBA) [P(AMPS54-co-TBA46) and P(AMPS37-co-TBA63)] were prepared by the dropwise addition of polyanion onto the chitosan solution. The effect of polyelectrolyte characteristics and the molar ratio between charges on the morphology of the complex nanoparticles and on their colloidal stability was deeply investigated by turbidimetric titration (optical density at 500 nm), dynamic light scattering, and atomic force microscopy. It was found that the lowest sizes of the IPEC nanoparticles were obtained, with both polyanions, when the chitosan having the lowest molar mass (470 kDa) was used as a major component. In this case, the particle sizes varied in a narrow range, even after the complex stoichiometry; i.e., when the polyanion was added in excess, the colloidal stability of these IPEC dispersions was very high. A mechanism of complex formation as a function of the ratio between charges was proposed. According to this mechanism, the nonstoichiometric complex nanoparticles formed at molar ratios between charges, n-/n+, lower than 0.2, i.e., far from the complex stoichiometry, would have a high density of positive charges in excess not only because of the chitosan in excess, which forms the shell, but also because of the mismatch of opposite charges, due to both the differences in the flexibility of complementary polyions and the presence of the hydrophobic comonomer, TBA, in the polyanion structure. Nonstoichiometric IPECs prepared at n-/n+ around 0.2 proved to be more efficient than chitosan in the destabilization of kaolin from a model suspension, with a lower optimum concentration flocculation and a much larger flocculation window being found compared with chitosan.

126

Poster 23

CHARACTERIZATION OF POLYMERS BY FIELD-FLOW FRACTIONATION Evelin Moldenhauer, Dr. Thorsten Klein Postnova Analytics GmbH, Max-Planck-Str. 14, D-86899 Landsberg am Lech, Germany [email protected]; [email protected] Field-Flow Fractionation has been invented by Giddings [1] in 1966. It is similar to chromatography and is technically comparable to a GPC-MALS system, but without having the common disadvantages of these technologies. The column is replaced by a special separation channel without any stationary phase inside. FFF is a family of unique separation techniques comprising of various sub-systems. Every FFF technique utilizes the same basic separation principle, but employs different types of separation fields. Depending on the type of separation field used, these techniques are called Flow FFF, Sedimentation FFF, Thermal FFF, etc. Two FFF techniques are presented for polymer analysis, Asymmetrical Flow Field-Flow Fractionation (AF4) and Thermal Field-Flow Fractionation (TF3). The high separation potential of the FFF methods is shown by the examples of different polymer applications. Gum Arabic as a natural rubber is a complex mixture of polysaccharides and glycoproteins. The separation of different lots of Gum Arabic using the AF4 shows clear differences in their molar mass distribution. As a second example the molar mass and size distribution of an Alginate sample has been achived by using AF4. TF3 is a particularly important technique which can be used for the separation of high molar mass polymers, such as rubbers, poly(ethylene oxide) and polyvinyl acetate. [1] Giddings, J.C. Separation Sci., 1966, 1, 123-125.

127

Poster 24

SENSORIC PROPERTIES OF POLY(3,4ETHYLENEDIOXYTHIOPHENE)-POLY(STYRENE SULFONATE) TO VOLATILE COMPOUNDS Sergii Pochekailov (1), Stanislav Nešpůrek (1,2), Aleš Hamáček (3), Jan Řeboun (3) (1) Institute of Macromolecular Chemistry Academy of Sciences of the Czech Republic v. v. i. (2) Faculty of Chemistry, Brno University of Technology, Czech Republic (3) University of West Bohemia, Faculty of Electrical Engineering, Czech Republic [email protected] Poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) in the form of thin film was found to be sensitive to ethanol vapors and humidity. Electrical conductance is reversibly proportional to the level of humidity and to the concentration of alcohol vapours. This effect could be explained by the swelling of the polymer sensing layer in the presence of volatiles. During the swelling the probability of charge carriers hopping among polymer chains decreases, due to the decrease of the effective value of charge carrier transfer rate, and, therefore, the electrical conductance decreases. The response was stable and reproducible. The effect was utilized for the construction of ethanol commertial sensor. The electrical response, which was fast and fully reversible, was detected by impedance spectroscopy. The correction on air humidity was performed using humidity detector based on nickel phthalocyanine sulfuric acid sodium salt.

128

Poster 25

HUMIDITY SENSING PROPERTIES OF THIN POLYMERIC FILMS BASED ON CORE-SHELL PARTICLES AND MICROGEL COMPOSITES David Rais (1), Stanislav Nešpůrek (1), Jessica Hain (2), Andrij Pich (2), Hans-Juergen P. Adler (2), Jan Řeboun (3), Aleš Hamáček (3) (1) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic v. v. i., 16206 Prague, Czech Republic (2) Institute of Macromolecular Chemistry and Textile Chemistry, Dresden University of Technology, 01062 Dresden, Germany (3) The University of West Bohemia, Faculty of Electrical Engineering, 30614 Pilsen, Czech Republic [email protected] Some conductive polymers are suitable for the use in active sensing layers [1]. It is due to their sensitivity to environmental conditions and various gasses, their reversibility and stability. Conducting polymers (CPs) are generally insoluble; their disadvantage is lack of easy post-synthetic processing. Fortunately, some synthetic approaches to make them treatable are available. Carefully controlled new synthetic procedures made possible to prepare new conductive composite materials with defined chemical and supramolecular structures with new application possibilities. We present new groups of polymeric electrically conductive composites based on core-shell particles and microgels which change their electrical properties under varying environmental humidity and temperature. The particles of the coreshell composite materials consisted of poly(3,4-ethylenedioxythiophene) (PEDOT) or polypyrrole conducting polymers (shell) and insulating polystyrene copolymer (core). It is shown that the thickness of the CP film on the core strongly influences overall electrical conductivity of the composite film. This, in result, also determines the sensitivity of electrical response to humidity: In low-conductivity materials the conductivity increases with increasing humidity. Opposite effect was observed in the group of high-conductivity materials. It was established that in this case the humidity response was strongly influenced by water molecule intercalation among macromolecules in the grains of the composite. It resulted in the decrease of charge carriers hopping rate and therefore the conductivity decrease. The intercalation effect was further developed for microgel materials, which were composed of partially hydrophilic soft crosslinked copolymer matrix (in the form of uniformly sized sub-micrometer particles) containing. PEDOT in nanometer-sized needle-like inclusions. The humidity response in these materials was enhanced by swelling of their soft copolymer matrix. The responses of above mentioned sensing elements were measured in alternating current mode. Some of the materials showed good reversibility and stability. (1) Bai H. and Shi G., Sensors 7 (2007) 267-307

129

Poster 26

BEHAVIOUR OF NANOPARTICLES UNDER PHYSIOLOGICAL CONDITIONS – DISPERSION, CORONA EVOLUTION AND CELLULAR UPTAKE Nadine Haentzschel, Anna Bratek-Skicki, Sonia Ramírez-García, Francesca Baldelli, Anna Salvati,Iseult Lynch, Kenneth Dawson Centre for Bio Nano Interactions, School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland [email protected] During the last years, at lot of research has been done in the area of nanoparticles, with particular emphasis on the interactions of nanoparticles with living systems. Nanoparticles are interesting due to their small size and large surface area that allows a wide range of applications. But as nanoparticles are able to enter many compartments of living organisms that are usually not accessible for bulk materials, attention should be paid to safety issues in parallel with the development of novel applications in medicine, diagnostics and information technology. In the Centre for BioNano Interactions, our hypothesis is that the mechanisms of interaction of nanoparticles with cells are the same whether the interactions are intentional (nanomedicine) or unintended (nanosafety), and that if we can understand the fundamental interactions, we can begin to control them. The layer of proteins and other biomolecules that coat nanoparticles immediately upon contact with biological milieu (the protein corona) likely determines the uptake and transport route utilised by the nanoparticles, and so reading and modifying this is a key goal. The behaviour of several different kinds of nanoparticles (including polystyrene, silica or gold) when exposed to a physiological environment, e. g. cells or blood plasma, has been investigated in terms of the dispersion stability, the nature and evolution of the protein corona and their uptake by cells under a range of conditions. Typically, nanoparticles selectively bind between 6-20 different proteins from the some 3,700 proteins in plasma. Experiments to tailor the protein corona of various nanoparticles are now underway, such as physic-adsorbing or grafting various known transporter proteins to the nanoparticle surface, as this will alter the surface properties and the protein-protein interaction capacity, potentially resulting in altered protein coronas and hence altered “biological identities” for the nanoparticles.

130

Poster 27

STYRENE-BUTADIENE BLOCK COPOLYMERS WITH HIGH CIS-1,4 CONFIGURATION Han Zhu, Yixian Wu, Jiangwei Zhao, Qinglei Guo, Guanying Wu Beijing University of Chemical Technology, China [email protected] A novel butadiene-styrene block copolymer (cPS-b-cis-PB, BS) consisting of soft segment of polybutadiene (PB) with high cis-1,4 microstructure (cis-PB) and crystalline segment of polystyrene (cPS) could be synthesized by sequential copolymerization of styrene and butadiene with a Nd-based catalyst system. The GPC results of RI and UV curves reflect the existence of PS segments in copolymers. The fact that strong absorption at 746 cm-1 and weak absorptions at 969 cm-1 and 910 cm-1 indicates that there exist primarily cis-1,4 Bd units in the copolymer. The microstructure of the copolymer by the 1H-NMR and 13C-NMR spectra are presented by four monomer units, namely butadiene units with cis-1,4(C), trans-1,4(T), vinyl (V) configurations and styrene units (S). The very strong signal at 5.39 which assigned to the proton of CH in the cis-1,4 configuration, indicates that the copolymer contained primarily high cis-1,4 butadiene units. This result is supported by the undetectable signal at 5.43 (CH in the trans-1,4) and the very weak signal at 4.98 (CH2 in pendant vinyl group). The signals at 7.07 and 6.56 (3:2 integral) reflect the occurrence of vicinal effect between o-proton in neighbouring phenyl groups in styrene units. The very strong signal at 27.43, assigned to the CC1C and CC4C carbons, suggests that the primary cis-1,4 configuration are presented in Bd units. The presence of the diads CT1 and T4C at 32.7 and the triad CVT at 38.2 suggests that the T units are followed by V and C units. The presence of the diads C1S at 25.21, 35.72 and 45.70 indicates that the S units connect mainly to C units. Small fractions of vinyl and trans1,4 of Bd units occationally distributed among PB sequences. The contents of cis-1,4 and styrene (St) units in the copolymers are determined to be around 97% (mol) and 16 ~ 30% (mol) respectively. TEM micrograph indicates that St homosequence agglomerated and phase-separated morphology of PS domains ranging from 25nm to 50nm tethered by the elastomeric PB segments formed. The PS-b-cis-PB copolymer could be used as an effective compatilizer for binary PS/cis-PB blend. The cis-PB domains with size of 10~30 nm and with blurry borderline distributed homogeneously in PS matrix even at higher cis-PB content while the oval cis-PB domains with size of 100~300 nm and with clear borderline distributed in PS matrix due to the immiscibility of PS and cis-PB in the absence of PS-b-cis-PB copolymer. It was also found that PS could be greatly toughened by introduction of a small amount of cis-SB and the tensile strength and elongation at break could be even increased as well.

131

Poster 28

CLICK CHEMISTRY COMBINED WITH NITROXIDEMEDIATED RADICAL AND CATIONIC RING OPENING POLYMERIZATION: A VERSATILE METHOD FOR PREPARATION OF WELL–DEFINED BLOCK COPOLYMERS Saber Ibrahim (1), Brigitte Voit (2) (1) Germany National Research Center Giza, Cairo, Egypt (2) Leibniz Institute of Polymer Research Dresden, Germany [email protected] The azide/alkyne-“click”-reaction has had enormous impact within the field of polymer science. By using click chemistry not only new, but also more complex molecules and materials can be approached. Hundreds of publications have since followed which employ ‘‘click’’ chemistry to functionalize polymers and prepare intricately designed macromolecules: a number of reviews have recently been published [1-3]. For example, Matyjaszewski et al. have contributed a number of examples of construction of designed materials through a combination of controlled radical polymerization, mainly atom transfer radical polymerization (ATRP), and ‘‘click’’ chemistry. Complex materials such as high molecular weight stepgrowth polymers [4], graft copolymers, and multisegmented block copolymers have been prepared in this manner [5-7]. Well-defined diblock copolymers consisting of polystyrene (PS) and poly (2-methyl-2oxazoline) (PMeOX) or polyethyleneimine (PEI) were prepared using the nitroxide-mediated radical polymerization (NMRP) and Cationic Ring Opening Polymerization (CROP) methods, respectively. The number-average molecular weight and fraction of each segment were precisely controllable by adjusting the monomer/initiator ratio in feed. Polystyrene prepared by nitroxide-mediated radical polymerization bearing a benzyl chloride on the α-terminus was converted to an azide by SN2 displacement. Piperazine was protected to afford its N-Boc derivatives which was reacted with propargyl bromide to obtain N-t-Boc propargylpiperazine and finally deprotected with trifluroacetic acid to yield propargylpiperazine [6]. Poly2-methyl-2-oxazoline was created by cationic ring opening polymerization and terminated with propargylpiperazine. The block copolymer PS-bPMeOX was obtained by 1,3-dipolar cycloaddition reaction between azide group in PS and alkyne group in PMeOX in presence of Cu(I)-catalyst. Polystyrene-b-polyethylenimine (Ps-bPEI) was synthesized by the hydrolysis of the obtained block copolymer PS-b-PMeOX in alkaline medium overnight. The synthesis of diblock copolymers by combining predefined polymeric fragments via click chemistry was proved. Under the described conditions, the fragments could be completely linked with each other and diblock copolymers obtained exhibited a narrow molecular weight distribution. [1] [2] [3] [4] [5] [6] [7]

R.K. O'Reilly, M.J. Joralemon, K.L. Wooley and C.J. Hawker, Chem Mater 17 (2005), 5976. C.J. Hawker, V.V. Fokin, M.G. Finn and K.B. Sharpless, Aust J Chem 60 (2007), 381. P.L. Golas and K. Matyjaszewski, QSAR Comb Sci 26 (2007),1116. N.V. Tsarevsky, B.S. Sumerlin and K. Matyjaszewski, Macromolecules 38 (2005), 3558. N.V. Tsarevsky, S.A. Bencherif and K. Matyjaszewski, Macromolecules 40 (2007), 4439. H. Zheng, L.M. Weiner, O. Bar-Am, et al, Bioorg. & Med. Chem. 13 (2005), 773. S. Fleischman, H. Komber, D. Appelhans, B. I. Voit, Macromol. Chem. Phys. 208 (2007), 1050.

132

Poster 29

IN SITU ANALYSIS OF A BIMODAL SIZE DISTRIBUTION OF SUPERPARAMAGNETIC NANOPARTICLES A. F. Thünemann, P. Knappe, S. Rolf, S. Weidner Federal Institute for Materials Research and Testing, Richard-Willstätter-Straße 11, 12489 Berlin, Germany [email protected] The dispersed iron oxide nanoparticles of ferrofluids in aqueous solution are difficult to characterize due to their protective polymer coatings. We report[1] on the bimodal size distribution of superparamagnetic iron oxide nanoparticles found in the MRI contrast agent Resovist®, which is a representative example of commercial nanoparticle-based pharmaceutical formulations. The radii of the majority of the nanoparticles range from 4 to 13 nm (less then 1% of the particles display radii up to 21 nm). The maxima of the size distributions are at 5.0 and 9.9 nm. The analysis was performed with in situ characterization of Resovist via online coupling of asymmetrical flow field-flow fractionation (A4F) with small-angle X-ray scattering (SAXS) using a standard copper X-ray tube as a radiation source. A major advantage of A4F is a gentle separation based on different diffusion coefficients of particles without a stationary phase like in SEC which means very low sheer forces are applied to the analyte. By additionally measuring the hydrodynamic radius by DLS one can reasonably estimate the polymeric shell thickness. We recommend using the A4F-SAXS coupling as a routine method for analysis of dispersed nanoparticles with sizes in the range of 1 to 100 nm. It allows a fast and quantitative comparison of different batches without the need of sample preparation. [1] Thünemann, Rolf, Knappe, Weidner; Anal. Chem. 2009, 81(1), 296.

133

Poster 30

DESIGN AND CHARACTERISATION OF COMB-SHAPED COPOLYMERS Lionel Petton, Filip Du Prez Department of Organic Chemistry, Polymer Chemistry Research Group Ghent University, Krijgslaan 281 S4-bis, B-9000 Ghent, Belgium [email protected] Polymer chemists now have an increasing access to macromolecular engineering ‘tools’ [1], which allows for the synthesis of controlled polymers with complex structures and relatively high molecular weight. More specifically, Reversible addition-fragmentation chain transfer (RAFT) polymerisation was used [2]. The key advantage of the RAFT process is the possibility to polymerise a wide range of monomers under mild conditions. The RAFT copolymerisation of styrene with polyether macromonomers bearing methacrylate functions was carried out in solution with dibenzyl trithiocarbonate as chain transfer agent (CTA) [3]. The polymerisations were performed at 80°C using azobisisobutyronitrile (AIBN) as initiator and at 110°C using the thermal initiation of styrene. The kinetics as a function of the reaction conditions was studied. The structures were then characterised by NMR, GPC and DSC. Due to the difficulty to separate the copolymers from the unreacted macromonomer, 2D NMR [4] was used to confirm the presence of the copolymers. [1] [2] [3] [4]

Matyjaszewski, K. Prog. Polym. Sci. 2005, 30, 858. Moad, G.; Rizzardo, E.; Thang, S. H. Polymer 2008, 49, 1079. Couvreur, L.; Guerret, O.; Laffitte, J.-A.; Magnet, S. Polym. Prepr. 2005, 46, 219. McCord, E. F.; Dai, H.; Vega, A. J.; Lozada, E. U.; Vargeson, J. Polym. Prepr. 2003, 44, 291.

134

Poster 31

NEW PHOTOINITIATING SYSTEMS FOR LIVING/ CONTROLLED CATIONIC POLYMERIZATION AND CROSSLINKING OF VINYL ETHERS Muhammet U. Kahveci (1), M. Atilla Tasdelen (1), Mustafa Uygun (1), Wolfram Schnabel (2), Wayne D. Cook (3), Yusuf Yagci (1) (1) Istanbul Technical University, Faculty of Science and Letters, Department of Chemistry, Maslak, TR-34469, Istanbul, Turkey (2) Helmholtz Centre Berlin for Materials and Energy, 14109 Berlin, Germany (3) Monash University, Department of Materials Engineering, VIC 3800, Australia [email protected] Light-induced cationic polymerization overcomes volatile emissions, limitations due to molecular oxygen inhibition, toxicity, and problems associated to high viscosity. Furthermore, once initiated, cationically polymerizable monomers such as vinyl ethers (VEs) and epoxides undergo dark-polymerization in which they slowly polymerize without radiation. VEs are the most important cationically polymerizable monomers from the academically and industrial point of view. Cationic photopolymerization of typical vinyl ether monomers, such as isobutyl vinyl ether, di(ethylene glycol) divinyl ether, tri(ethylene glycol) divinyl ether, 1,4-butanediol divinyl ether, and 1,6-hexanediol divinyl ether by use of new photoinitiating system consisting of a photoinitiator with highly nucleophilic counter ion (i.e. diphenyliodonium halides) or carbon-halogen bond (i.e. vinyl halides), and a Lewis acid (such as zinc iodide or ytterbium triflate) has been studied. Photochemically generated protonic acid or carbocation reacts with VE monomer to form the corresponding halide-monomer adduct containing carbon-halogen bond which is activated by the coordinating effect of the Lewis acid. This activation leads to generation of suitable nucleophilic counterion by stabilizing the growing carbocation and, in turn, (quasi) living cationic polymerization. This approach was successfully employed in free radical promoted and sensitized systems (1), substituted vinyl halides type photoinitiating systems (2), and aqueous cationic photopolymerization systems (3). In the first system typical free radical photoinitiators such as 2, 2-dimethoxy-2-phenyl acetophenone (DMPA), benzophenone or thioxanthone were used to sensitize diphenyliodonium halides and thus to generate initiating adducts. In the second system, substituted vinyl halides, namely 1-bromo-1,2,2-tris(p-methoxyphenyl)ethene, 1-bromo-1-(pmethoxyphenyl)-2,2-diphenylethene, 1-bromo-1,2,2-triphenylethene, and 1-chloro-2,2-bis(pmethoxyphenyl)ethene was employed in photopolymerization of mono- and di-functional VEs in the presence of zinc iodide. The initiating system used in first system was employed also in the last system with a water-tolerant Lewis acid, ytterbium triflate. In these studies, behaviour close to living polymerization was observed according to time-conversion and conversion-Mn studies. Investigation of 1H NMR spectrum of the irradiated polymerization solution without the Lewis acid showed that the adduct was formed, which is cosistent with the mechanism of the thermal living cationic polymerization VEs proposed by Sawamoto and Higashimura. Experimental results fully support the idea that new photoinitiating systems in combination with a Lewis acid such as zinc halides or ytterbium triflate may be used to promote living cationic polymerization of alkyl VEs and curing of di-functional VEs.

135

Poster 32

NEW THIOXANTHONE PHOTOINITIATORS WITH EXTENDED ABSORPTION IN THE VISIBLE RANGE Ali Gorkem Yilmaz, Binnur Aydogan, Yusuf Yagci Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey [email protected] The free radical photopolymerization is in advanced state due to its applicability to a wide range of formulations based on (meth)- acrylates, unsaturated polyesters, and polyurethanes and the availability of photoinitiators having spectral sensitivity in the near-UV and visible range. The radical photopolymerization can be initiated either via bond cleavage (Type I) or hydrogen abstaction type (Type II) photoinitiators whose triplet states readily react with the H-donor compounds like tertiary amines, thiols, ethers and alcohols to yield the initiating radicals. Typical type II photoinitiators include benzophenone and derivatives, thioxanthones, benzil, and quinones, while alcohols, ethers, amines, and thiols are used as hydrogen donors. Among type II photoinitiators, thioxanthone (TX) derivatives in conjunction with tertiary amines are efficient photoinitiators with absorption characteristics that compare favorably with benzophenones. For the design of photoinitiators two issues are of high importance: i) visible light absorptivity and ii) water solubility. High wavelength absorbtion provides cost of lower energy and have found particular interest because of their use in many targeted applications such as dental filling materials. Water solubility, on the other hand, is another interest where water is used as a green solvent that has attractive properties such as non-toxicity, cheap cost, readily availability for coatings technology. In this work, we are presenting synthesis and characterization of two different photoinitiators, namely fluorene carboxylic acid thioxanthone (FLTXCOOH) and its sodium salt (FLTXCOONa) being oil and water soluble, respectively. Visible range absorbtion characteristics observed with both initiators make them particularly useful for industrial applications. The PhotoDSC studies performed with the dental formulation utilizing these initiators are also included.

136

Poster 33

SYNTHESIS OF BLOCK COPOLYMERS BY THE COMBINATION OF ATRP, PHOTOINDUCED COUPLING AND INIFERTER PROCESSES Halime Cengiz, Binnur Aydogan, Gokhan Temel, Nergis Arsu, Yusuf Yagci Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey [email protected] Benzophenone functional initiator for Atom Transfer Radical Polymerization (ATRP) was synthesized and characterized. Low molecular weight PMMA bearing benzophenone end function was obtained by ATRP using this initiator in the presence of CuBr/N, N, N’, N’’, N’’-pentamethyldiethylenetriamine (PMDETA) catalytic complex. The obtained polymer exhibited spectral characteristics and photochemical behavior of bare benzophenone. Photolysis of the solutions containing end functional PMMA in THF at λ = 350 nm in the presence of a hydrogen donor such as N, N-dimethylaniline leads to the formation of PMMA with double molecular weight and diphenyl dihydroxy ethane groups in the middle of the chain. In the final stage this polymer was used as inner iniferter in the polymerization of styrene leading to the formation of block copolymer.

137

Poster 34

PERFECTLY ALTERNATING AMPHIPHILIC POLYPHENYLENES BY COMBINATION OF CONTROLLED POLYMERIZATION AND SUZUKI COUPLING PROCESSES Elif L. Sahkulubey, Yasemin Yuksel Durmaz, Demet G. Colak, Yusuf Yagci Istanbul Technical University, Deparment of Chemistry, Maslak 34469, Istanbul, Turkey [email protected] Poly(p-phenylene)s ( PPs) are a promising class o high-performance polymers because of their excellent mechanical properties, thermal and thermo oxidative stability. Current methodologies for the direct synthesis of derivatized PPs are primarily based upon palladiummediated cross-coupling reactions due largely to their preservation of regiochemistry and nearly quantitative yields. In this work, the preparation amphiphilic polyphenylenes possessing completely and perfectly alternating hydrophilic poly(ethylene oxide) and hydrophobic polystyrene side chains is described. First, polystyrene macromonomers with suitable functionality for polyphenylation were prepared by Atom Transfer Radical Polymerization (ATRP). The antagonist macromonomer, polyethyleneoxide was synthesized by etherification reaction. Both macromonomers were reacted in the final stage via for Suzuki cross coupling in the presence of Pd(PPh3 )4 as catalyst to form desired amphiphilic copolymers.

138

Poster 35

ROMP-NMP-ATRP COMBINATION FOR THE PREPARATION OF3-MIKTOARM STAR TERPOLYMER VIA CLICK CHEMISTRY Aziz Gozgen, Aydan Dag, Hakan Durmaz, Okan Sirkecioglu, Gurkan Hizal, Umit Tunca Department of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkey [email protected] A combination of ring opening metathesis polymerization (ROMP) and click chemistry approach is first time utilized in the preparation of 3-miktoarm starterpolymer. The bromide end-functionality of monotelechelic poly(N-butyl oxanorbornene imide) (PNBONI-Br) is first transformed to azide and then reacted with polystyrene-b-poly(methyl methacrylate) copolymer with alkyne at the junction point (PS-b-PMMA-alkyne) via click chemistry strategy, producing PS-PMMA-PNBONI 3-miktoarm star terpolymer. PNBONI-Br was prepared by ROMP of N-butyl oxanorborneneimide (NBONI) 1 in the presence of (Z)-but-2ene-1,4-diyl bis(2-bromopropanoate)2 as terminating agent. PS-b-PMMA-alkyne copolymer was prepared successively vianitroxide-mediated radical polymerization (NMP) of St and atom transfer radical polymerisation (ATRP) of MMA.

139

Poster 36

SYNTHESIS AND CHARACTERIZATION OF TELECHELIC POLYMERS BY COMBINATION OF ATRP AND "CLICK" CHEMISTRY Suleyman Serdar Okcu, Yasemin Yuksel Durmaz, Yusuf Yagci Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey [email protected] Telechelic polymers can be used as crosslinkers, chain extenders and precursors for block and graft copolymers. A new method consisting of Atom Transfer Radical Polymerization (ATRP) and “Click” Chemistry processes for the preparation of hydroxyl functional telechelic copolymers (HO-PS-b-PMMA-OH or HO-PS-b-PtBA-OH) was described. The described method has also been applied for the heterotelechelic polymers (HO-PS-COOH) possessing hydroxyl and carboxylic functionality at chain ends. In the first step, hydroxyl and acetylene functional initiators were used in ATRP of styrene (St), and methyl methacrylate (MMA) or t-butylacrylate (t-BA) respectively. Bromide terminal group of hydroxyl functional polystyrene was then converted to azide group for the subsequent click reaction. This polymer was reacted with propargyl alcohol to incorporate hydroxyl functionality at the other chain end. The intermediates at various stages of the method and final polymer were characterized by spectral methods. Similar heterotelechelics of homopolystyrene was also prepared. In this case, click reaction of hydroxyl functional polystyrene and acetylene compound with acid functionality was successfully performed.

140

Poster 37

GRAFT COPOLYMERS BY THE COMBINATION OF ATRP AND PHOTOCHEMICAL ACYLATION PROCESS BY USING BENZODIOXINONES Yasemin Yuksel Durmaz, Volkan Kumbaraci, A. Levent Demirel, Naciye Talinli, Yusuf Yagci Istanbul Technical University, Department of Chemistry, Maslak 34469, Istanbul, Turkey [email protected] Synthesis of graft copolymers by combination of Atom Transfer Radical Polymerization (ATRP) and photoinduced reaction of benzodioxinone was reported. First, statistical copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were prepared by ATRP process. Then, the other component, namely benzodioxinone functional polystyrene (PS-B) was prepared independently by the etherification reaction of hydroxyl benzodioxinone (HDPD) with polystyrene (PS-Br) obtained by ATRP by using K2CO3 in acetone. Photolysis of poly(hydroxyethyl methacrylate-co-methyl methacrylate) (P(HEMAco-MMA)) and (PS-B) prepolymers in CH2Cl2 at λinc > 300 nm yielded graft copolymers. The graft copolymers and the intermediates were characterized in detail by using 1H NMR, GPC, UV, FT-IR, DSC, and AFM measurements.

141

Poster 38

ONE-POT DOUBLE CLICK REACTIONS FOR THE PREPARATION OF H-SHAPED ABCDE TYPE QUINTOPOLYMER Eda Gungor, Gurkan Hizal, Umit Tunca Department of Chemistry, Istanbul Technical University [email protected] H-shaped polymer, as one of complex macromolecular structures, where two side arms attached to the each end of a polymer backbone, has been generally accomplished through living anionic polymerization route by using chlorosilane or aromatic diolefins coupling agents.Because of its architectural difference, H-shaped polymers show different rheological properties, micellar properties, and self assembled structures when compared with other linear or branched block copolymers. In recent years, the use of the controlled/living radical polymerization (LRP) techniques in the synthesis of complex macromolecules has fast improved as a consequence of the variety of applicable monomers and more tolerant experimental conditions than the living ionic polymerization routes require. The combinations of reversible addition fragmentation chain transfer polymerization (RAFT), and the metal mediated living radical polymerization frequently called as atom transfer radical polymerization (ATRP) with living ring opening polymerization (ROP) have been widely used for the preparation of nonlinear polymers such as H-shaped polymers. We employed for the first time double click reactions: Cu (I) catalyzed azide-alkyne 1,3dipolar cycloaddition and Diels-Alder (4+2) reactions for the preparation of H-shaped polymer possessing pentablocks with different chemical nature (H-shaped quintopolymer) using one-pot technique. H-shaped quintopolymer consists of poly(ethylene glycol) (PEG)poly(methylmethacrylate) (PMMA) and poly(ε-caprolactone) (PCL)-polystyrene (PS) blocks as side chains and poly (tert-butylacrylate) (PtBA) as a main chain. For the preparation of Hshaped quintopolymer, PEG-b-PMMA and PCL-b-PS copolymers with maleimide and alkyne functional groups at their centers, respectively were synthesized and simply reacted in one-pot with PtBA with α-anthracene-ω-azide end functionalities in N,N-dimethylformamide (DMF) using CuBr/ N, N, N’, N”, N”-pentamethyldiethylenetriamine (PMDETA) as catalyst at 120°C for 48 h. The precursors and the target H-shaped quintopolymer were characterized comprehensively by 1H NMR, UV, FTIR, GPC and triple detection GPC.

142

Poster 39

SYNTHESIS OF BLOCK AND STAR COPOLYMERS BY PHOTOINDUCED RADICAL COUPLING PROCESS Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey [email protected], [email protected] The general design for the synthesis of AB diblock, and A2B and AB2 star copolymers based on the statistical coupling of poly(styrene) (PSt) and poly(methyl methacrylate) (PMMA) macromolecules containing photoreactive benzophenone is presented. For this purpose, mono- and bifunctional initiators for Atom Transfer Radical Polymerization (ATRP) bearing benzophenone group were synthesized and characterized. End- and mid-chain benzophenone functional PSt and PMMA with low molecular weights were obtained by ATRP using these initiators in the presence of CuBr/N, N, N’, N’’, N’’-pentamethyldiethylenetriamine (PMDETA) catalytic complex. Poly(styrene-block-methyl methacrylate) (PSt-b-PMMA) copolymers were prepared by photolysis of the solutions containing end functional PSt and PMMA in THF at λ = 350 nm for 60 min in the presence of a hydrogen donor such as Nmethyldiethanolamine (NMDEA). The proposed mechanism assumes hydrogen abstraction of photoexcited benzophenone moiety by NMDEA. Ketyl radicals resulting from abstraction reaction undergo radical-radical coupling to form benzpinacol structure at the core. Formation of A2B and AB2 type star copolymers upon irradiation of solutions containing appropriate combinations of end- and mid-chain functional polymers was also demonstrated.

143

Poster 40

SYNTHESIS AND CHARACTERIZATION OF WELL-DEFINED DIBLOCK COPOLYMERS OF POLY(N-ISOPROPYLACRYLAMIDE) AND POLY(VINYLACETATE) Cimen Ozguc and Turgut Nugay Department of Chemistry and The Polymer Research Center Bogazici University, Bebek 34342 Istanbul, Turkey [email protected] Poly(N-isopropylacrylamide) (PNIPAM) is a well known thermoresponsive polymer exhibiting a lower critical solution temperature (LCST) in aqueous solution at about 32 °C. This type of miscibility behavior implies that the polymer dissolves in water at temperatures below the LCST value and undergoes phase separation upon heating. This behavior of PNIPAM has applications in fields such as surface modification, drug delivery, reaction catalysis, stabilization and functionalization of metal nanoparticles etc. Many studies have been done to investigate the effect of copolymerization of NIPAM with suitable comonomers. Vinyl acetate, on the other hand, is another highly important monomer and its polymer has application areas in adhesives, paints, concrete additives to pharmaceuticals. Both monomers, individually, can be polymerized by using controlled/living free-radical polymerization techniques such as reversible addition-fragmentation chain-transfer (RAFT) process.Moreover, these methods are also suitable for the synthesis of poly(vinylacetate) (PVA) with controlled chain end functionality to enable the synthesis of block copolymers. In this study, the synthesis of well-defined diblock copolymers of poly(Nisopropylacrylamide) and poly(vinylacetate) was conducted by using macromolecular design via interchange of xanthates (MADIX). The synthesis of the chain transfer agent methyl (isopropoxycarbonothioyl)sulfanyl acetate (MIPCTSA) was carried out according to the procedure reported in the literature. The products in each step were then characterized with H1-NMR technique. The resultant spectra of xantate end-functionalized PVA and PNIPAM as well as PVA-b-PNIPAM give the signals of the methine proton of PVA (b) and the methine proton of the isopropyl group of PNIPAM (f) occuring at 4.8 - 5.0 and 3.9 - 4.1 ppm, respectively. The presence of both peaks in the final spectrum shows the incorporation of the second monomer in the copolymer structure, with the expected 1:1 molar ratio.The DSC thermogram of the block copolymer clearly exhibits the glass transition temperatures (Tg) of both PVA and PNIPAM, with the values closer to each other than with respect to the original Tg values of each polymer.This may be attributed to the well distribution of both polymer sequences in each other which is a characteristic of block copolymer structure. As a conclusion,it has been shown for the first time that xanthate end-functionalized PVA can be used successfully as macro chain transfer agent for the synthesis of PVA-b-PNIPAM. Both spectroscopic and thermal characterizations prove the presence of both monomers in the block copolymer structure. Acknowledgements: This work was supported by a grant from the Bogazici University Research Fund (09B504P).

144

Poster 41

SYNTHESIS AND CHARACTERIZATION OF ONE-COMPONENT POLYMERIC PHOTOINITIATOR BY SIMULTANEOUS DOUBLE CLICK REACTIONS AND ITS USE IN PHOTOINDUCED FREE RADICAL POLYMERIZATION Gokhan Temel, Binnur Aydogan, Nergis Arsu, Yusuf Yagci Department of Chemistry, Yildiz Technical University, Davutpasa, Istanbul, 34210, Turkey [email protected], [email protected] Polystyrene (PS-B-DMAB) possessing both benzophenone and dimethylamino moieties in the side chain was synthesized by combination of nitroxide-mediated radical polymerization (NMRP) and simultaneous double “Click reactions”. First, random copolymer of styrene (S) and chloromethylstyrene (CMS) with 32 mol% CMS content was prepared by NMRP process. Then, chloromethyl groups were converted to azide groups by reacting with NaN3 in DMF. The other two click components, namely propargyl benzophenone (Pr-B) and propargyl 4-(dimethylamino)benzoate (Pr-DMAB), were prepared independently by the etherification and esterification reactions, respectively. Then, in the final stage the obtained alkyne functional chromophoric and hydrogen donating molecules, Pr-B and Pr-DMAB, respectively were anchored to azide-modified polystyrene (PS-N3) in one-step by “Click chemistry”. The final polymer (PS-B-DMAB) and the intermediates were characterized in detail by spectral analysis and laser flash photolysis studies. The resulting polymer possesses absorption characteristics similar to the parent B. One-component photoinitiating nature of PS-B-DMAB was demonstrated by photopolymerization of mono- and multi-functional monomers, namely methyl methacrylate (MMA) and trimethylolpropane triacrylate (TMPTA), respectively.

145

Poster 42

THREE-ARM STAR RING OPENING METATHESIS POLYMERS VIA ALKYNE-AZIDE CLICK REACTION Aydan DAG, Hakan DURMAZ, Okan SIRKECIOGLU, Gurkan HIZAL, Umit TUNCA ITU [email protected] Click chemistry coined by Sharpless and coworkers has been a versatile definition for the chemical reactions possessing primarily high yield, regioselectivity, and tolerant to many other functional groups. Among these reactions, Cu catalyzed alkyne-azide cycloaddition reaction (Cu catalyzed Huisgen cycloaddition) has attracted much attention in synthetic polymer chemistry. As a consequence of both its mild reaction and high yielding conditions, this reaction has been widely applied for the synthesis of block, graft, star, miktoarm star, Hshaped, and dendrimeric type polymers, and bioconjugates. Ring opening metathesis polymerization (ROMP) of cycloolefins using catalytic systems developed by Schrock and Grubbs has afforded well-defined polymeric materials not obtainable before via classical polymerization routes. However, few studies for the synthesis of star homopolymers via ROMP have been reported. The click chemistry strategy is successfully applied for the preparation of three-arm star (A3) ring opening metathesis polymers. A well-defined monoazide end-functionalized poly(Nethyl oxanorbornene) and a poly(N-butyl oxanorbornene) obtained via ring opening metathesis polymerization using first generation Grubbs’ catalyst are simply clicked with the trisalkyne core affording the synthesis of target star polymers. The obtained star polymers are characterized via nuclear magnetic resonance spectroscopy and gel permeation chromatography (GPC). The deconvolution analyses of GPC traces reveal that the click reaction efficiency for the star formation strongly depends on the chemical nature and the molecular weight of ROM polymers.

146

Poster 43

TUNING THE LCST OF POLY(2-OXAZOLINE)S Stephan Huber (1), Rainer Jordan (1,2) (1) Wacker-Lehrstuhl für Makromolekulare Chemie, Department Chemie, Technische Universität München, Garching, Germany (2) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität Dresden, Germany [email protected] For the development of next-generation biomaterials and polymer therapeutics, hydrophilic and biocompatible [1] poly(2-oxazoline)s (POx) gained much interest. This is because POx, synthesized via living cationic polymerization, can be fine-tuned in terms of its composition, molecular architecture and functionality. Analogue to most of the water soluble polymers such as poly(N-isopropylacrylamide) (PNIPAAm), POx displays a lower critical solution temperature (LCST) which is a function of concentration, polymer molar mass and composition. For PNIPAAm this was used to adjust the LCST within the physiological range (i.e. human body temperature) for biomedical applications [2]. Recently, the influence of the terminal functionalization [3] as well as the composition of POx copolymers [4] was investigated. While Kataoka et al.[4] copolymerized 2-n- and 2-isopropyl-2-oxazoline with hydrophilic monomers (2-methyl-, 2-ethyl-2-oxazoline) to increase the LCST from 26 to 75°C, we investigated the LCST of copolymers with increasing hydrophobicity (2-isopropyl- with 2-n-propyl-, 2-n-butyl-, and 2-n-nonyl-2-oxazoline). The introduction of monomer units of stronger amphiphilic character results in a systematic decrease of the LCST from 46 for the poly(2-iso-propyl-2-oxazoline) homopolymer down to 9°C [5]. It is noteworthy that the LCST transition is spontaneous and defined within a temperature range of ≤1°C. Up to now the LCST of POx can be tuned from 9 to 75°C [4,5]. This temperature range renders the thermo-sensitive POx as potential polymers to be used as a adaptive or ‘smart material’ for biomedicine, catalysis, sensor or actuator technology. This work is financially supported by the Deutsche Forschungsgemeinschaft trough the SFB 563 and JO287/4-3. [1] [2] [3] [4]

F. C. Gärtner, R. Luxenhofer, B. Blechert, R. Jordan, M. Essler, J. Controlled Release 2007, 119, 291. E. Wischerhoff, T. Zacher, A. Laschewsky, E. Rekai, Angew. Chem., Int. Ed. 2000, 39, 4602. M. Meyer, H. Schlaad, Macromolecules 2006, 39, 3967. a) J. S. Park, K. Kataoka, Macromolecules 2007, 40, 3599. b) J. S. Park, K. Kataoka, Macromolecules 2006, 39, 6622. [5] S. Huber, R. Jordan, Colloid Polym. Sci. 2008, 286, 395. [6] S. Huber, N. Hutter, R. Jordan, Colloid Polym. Sci. 2008, 286, 1653.

147

Poster 44

SYNTHESIS OF BLOCK COPOLYMERS WITH POLY(PARAPHENYLENE) AND STIMULI-SENSITIVE SEGMENTS BY COMBINATION OF SPC AND NMRP S. Schmücker, A. Britze, D. Kuckling Universität Paderborn, Germany [email protected] The synthesis of rod-coil block copolymers composed of a poly(para-phenylene) (PPP) and a stimuli-sensitive segment is described. First, the rigid PPP block was synthesized via Suzuki polycondensation (SPC) in presence of a N-alkoxyamine termination reagent. A microwave system was applied for preparation of these macroinitiators affording reduced reaction times. Subsequent nitroxide-mediated radical polymerization (NMRP) was employed to introduce a defined stimuli-sensitive segment. Self-assembly of block copolymers in consequence of short range attractive forces (covalent bonds) and long range repulsive forces such as hydrophilic and hydrophobic interactions were observed. Hence, in aqueous media micellar structures are formed by parallel arrangement of hydrophobic PPP rods surrounded by coil-like stimuli-sensitive segments. By crossing the critical parameter e.g. critical temperature or critical pH-value a change in solubility behavior of the stimuli-sensitive block occurs and phase morphology changes. This behavior was investigated by light scattering methods, while polymers were characterized by size exclusion chromatography (SEC), NMR spectroscopy, MALDI-TOF mass spectrometry, IR and UVVis spectroscopy.

148

Poster 45

COMBINATORIAL ANIONIC SYNTHESIS OF FUNCTIONAL BLOCK COPOLYMERS WITH WELL-TAILORED COMPOSITIONS Robin Pettau, Klaus Kreger, Christian Erdelen, Hans-Werner Schmidt Macromolecular Chemistry I and Bayreuther Institut für Makromolekülforschung, Universität Bayreuth, D-95440 Bayreuth, Germany [email protected] The combinatorial approach increases the efficiency of experimentation since the output of a single experiment contains several chemically distinct compositions. Additionally anionic polymerization is a versatile technique for the synthesis of well defined block copolymers. Moreover it allows the design of complex polymer structures like comb shaped and star-block copolymers. By using monomers which contain protected reactive functions (e.g. –OH; NH2), functional block copolymers are accessible by polymer analogous reaction. Here we present a combinatorial approach to block copolymers by anionic polymerization utilizing a novel reactor setup. It features one main reactor (MR) and three secondary reactors (SRs) which are adequate for polymerizations on a lab scale range. This enables us to perform sequential anionic polymerization which is transformed into parallel synthesis based on the identical precursor. Thereby this setup can be used to synthesize series of four different block copolymers with each run. We can tailor these block copolymers either with respect to the end block length or by utilizing different kinds of monomers for the end blocks. We demonstrate that series of different AB- and ABC-block copolymers can be synthesized conveniently, suitable for further comparative investigation. Protected monomers for the first identical block and varying block length of the second block open up the access to functional block copolymers after cleavage of protection group and subsequent polymer analogous reaction with functional moieties. Depending on the block copolymer composition, the properties of the functional segment can be investigated.

149

Poster 46

PEROXIDE DERIVATIVES OF ALTERNATE COPOLYMERS FOR REVERSE MICELLE FORMATION O. Kudina, O. Budishewska, O. Khomenko, S. Voronov Lviv National Polytechnic University, Institute of Chemistry and Chemical Technology, department of Organic Chemistry [email protected] Regular polymeric surfactants with amphiphilic fragments, which are both hydrophilic and hydrophobic parts, are widely used because of their ability to form regular and reverse micelles with respect to disperse medium. Such polymeric surfactants can be used in different areas of modern nanotechnology, i.e. for metal nanoparticles formation. Via tert-butylperoxymethanol acylation using binary alternate copolymers maleic anhydrideco-1-dodecene (MA-DDC) or maleic anhydride-co-octylmethacrylate (MA-OMA) reactive peroxide regular copolymers with tert-buthylperoxymethylmaleate (PM), which contain primary-tertial peroxide fragments, were synthesized. MA-DDC, OMA-MA and their peroxide derivatives (MA-DDC-PM, OMA-MA-PM) after dissolving in benzene, form reverse micelles, which are able to solubilize hydrophilic substances. With the usage of malachite green solubilization technique in benzene solutions critical concentrations of micelle formation (CCM) were determined. Three levels of CCM for OMA-MA and OMA-MA-PM were discovered. Colloid surfactant association in liquid phase leads to organized associates formation of different structure and geometry subject to their concentration and different CCM. Reverse micelles in benzene solutions of MA-DDC-PM and OMA-MA-PM were used as nanoreactors for silver nanoparticles synthesis. Benzene OMA-MA-PM solutions were shown to solubilize [Ag(NH3)2]OH. Methanal was shown to be one of the products of tertbuthylperoxymethylmaleinate fragments thermal decomposition. That is why Ag+ reduction by methanal is believed to be the main reaction in the redox process.

150

Poster 47

LIVING RADICAL POLYMERIZATION OF METHYL METHACRYLATE USING CYCLOMETALATED COMPLEXE OF RUTHENIUM (II) N. Vargas (1), R. Le Lagadec (2), L. Alexandrova (1) (1) Departamento de Reología, Instituto de Investigaciones en Materiales, Circuito exterior s/n C.U. Apdo. postal 70-360 Delegación Coyoacán, 04510 México D.F. (2) Departamento de Química Inorgánica, Instituto de Química, Circuito exterior s/n C.U. Apdo. postal 70-360 Delegación Coyoacán, 04510 México D.F. [email protected] Atom transfer radical polymerization (ATRP) permits to obtain polymers and copolymers of low polydispersities and well-defined structures for a wide range of vinyl monomers [1-3]. Various complexes of different transition metals have been successfully applied as catalysts in ATRP [4-6]. The best results have been obtained using copper and ruthenium compounds [7,8]. Our research group has synthesized cyclometalated Ru (II) complexes. Here we report cyclometalated Ru (II) complex, cis-[Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6, for polymerization of methyl methacriyate. Polymers of controlled molecular weights and relatively low polydispersities around 1,3 were synthesized. The polymers obtained were characterized by GPC and NMR. Acknowledgments We are thankful to M.C. S. Lopez for GPC analysis, CONACyT and PAPIIT for financial support. [1] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Macromolecules 1995, 28, 1721. [2] J-S. Wang, K. Matyjaszewski, J. Am. Chem. Soc. 1995, 11, 5614. (b) J-S. Wang, K. Matyjaszewski, Macromolecules. 1995, 28, 7901. [3] F. Simal, A. Demonceau, A.F. Noels, Tetrahedron Lett. 1999, 40, 5689. [4] J.A.M. Brandts, P. van de Geijn, E.E. van Faassen, J. Boersma, G. Van Koten, J. Organomet. Chem. 1999, 584, 246. [5] M. A. Stump, D.M. Haddleton, A. McCamley, D. Duncalf, J. A. Segal, D. J. Irvine, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1997, 38(1), 508. [6] Y. Kotani, M. Kamigaito, M. Sawamoto, Macromolecules 1999, 32, 2420. [7] K. Matyjaszewski, T.P. Davis, Handbook of Radical Polymerization, Wiley Interscience, New York, USA, 2002. [8] M. Kato, M. Kamigaito, M. Sawamoto, T. Higashimura, Macromolecules 1995, 28, 1721.

151

Poster 48

LIVING RADICAL POLYMERIZATION OF VINYL ACETATE CONTROLLED BYCYCLOMETALATED COMPLEX OF RU(II) J. Olvera-Mancilla (1), Ronan Le Lagadec (2), L. Alexandrova (1) (1) Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito Exterior S/N, Ciudad Universitaria, Coyoacán, 04511 México Distrito Federal, México (2) Instituto de Química, Universidad Nacional Autónoma de México, Circuito exterior S/N, Ciudad Universitaria, Coyoacán, 04511 México Distrito Federal, México [email protected] Vinyl Acetate (VAc) is generally polymerized by a free radical mechanism. Radicals derived from VAc are highly reactive and thus undergo easily chain transfer and termination reactions, that is why this monomer is one of the most challenging to polymerize in a controlled fashion. Till the moment there have been only few successful attempts searches to polymerize [1, 2, 3]. Here we report radical polymerization of VAc catalyzed by two cyclometalated Ru(II) compounds [Ru(辗6-C6H6)(dmba)(NCMe)]+PF6- (a) and [Ru(phpy)3]+PF6- (b) where dmba and phpy are N,N-dimethylbenzylamine and phenylpyridine respectively. Both complexes are very active and mediate the polymerization in the presence of Al(Oi-Pr)3 as well as without it. The polymerization was notably faster in the presence of Al(Oi-Pr)3, but it was not very slow either without the additive. For example, conversion of ~50% was reached in 24 h in bulk polymerization mediated by a with Al(Oi-Pr)3. When no Al(Oi-Pr)3 was added conversion ~35% was reach in the same time. The complex b is more active than a, but demonstrate similar behavior in the presence and absence of Al(Oi-Pr)3. The complex a behaves differently in solution and bulk. Polymerization in solution was poorly controlled: Mn almost does not depend on conversion and Mw/Mn are quite broad. Meanwhile the level of control was significantly improved in bulk. Mn were only slightly higher than predicted by theory and depended linearly on conversion. The Mw/Mn was also getting lower with conversions. Polymerization mediated by complex b was investigated only in solution. Polymerizations induced by this complex were fast and poorly controlled: molecular weights don’t depend on conversions and Mw/Mn was ~1.4. Acknowledgments: We are thankful to M.C. S. Lopez for GPC analysis and CONACyT (Grand D 40135Q) for financial support. [1] Wakioka M, Baek K-Y, Ando T, Kamigaito M, Sawamoto M. Macromolecules. 2002, 35, 330-333. [2] Jianhui Xia, Hyung-jong Paik, and Krystof Matyjaszewski. Macromolecules. 1999, 32, 8310-8314. [3] Debuigne A, Caille J-R, Detrembleur C, Jerome R. Angew Chem Int Ed. 2005, 44, 1101-1104.

152

Poster 49

THE ROLE OF SOLVENT LIGATED METAL COMPLEXES ASSOCIATED WITH WEAKLY COORDINATING ANIONS IN ISOBUTYLENE POLYMERIZATION Yeong, Hui Yee (1), Voit, Brigitte (1), Li, Yang (2), Diebl, Bernd (2), Rach, Silvana (2), Kühn, Fritz E. (2), König, Hannah (3), Mühlbach, Klaus (3) (1) Leibniz-Institut für Polymerforschung Dresden e.V, Hohe Strasse 6, 01069 Dresden, Germany (2) Molekulare Katalyse, Fakultät für Chemie der Technischen Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany (3) BASF SE, Carl-Bosch-Str. 38, 67056 Ludwigshafen, Germany. [email protected] The application of solvent ligated metal complexes associated with weakly coordinating counteranions (WCAs) has been reported to allow a room temperature polymerization process resulting in highly reactive polyisobutylene (HR-PIB). The high content of terminal double bonds attained in HR-PIB is of high industrial importance [1,2,3,4]. Recently complexes were reported in literature applying manganese (II), copper (II) and molybdenum (III) metal ions which have demonstrated considerable catalytic roles in the polymerization of isobutylene [1,2,3]. For example, copper (II) compounds coordinated octahedrally with acetonitriles and bearing boron based WCAs can be applied as catalyst in a room temperature process which resulted in high yields of HR-PIB with high content of double bonds. The copper (II) compounds are - under certain conditions - even superior to the previously described manganese complexes, with respect to considerably shorter reaction times and the possibility to use non-chlorinated solvents [2]. In light of the recent interest shown in the room temperature catalytic process for the synthesis of HR-PIB and the industrial significance and attractiveness of HR-PIB, we have begun to further improve the polymerization and more importantly, to elucidate the mechanism of the catalytic process [4]. Systematic screening of the reaction conditions and the catalysts tailored according to our specifications were undertaken to understand the various factors influencing the catalytic process. These include the effects of the concentrations of the catalysts, the temperature, the solvents and so forth. Coupled with these, effects of the central metal atom and the counteranions in the catalytic system were also taken into consideration. Efforts were further undertaken to elucidate the mechanism of this room temperature process in order to better utilize this catalytic process to our advantage. So far, results have shown that polymer yield and quality of the HR-PIB differ accordingly to the conditions and complexes used and thus, presently we try to maximize the advantage of this current process based on our understanding on it. [1] (a)Vierle, M.; Zhang, Y.; Herdtweck, E.; Bohnenpoll, M.; Nuyken, O.; Kühn, F. E. Angew.Chem. Int. Ed. 2003, 42, 1307; (b)Radhakrishnan, N.; Hijazi, A.K.; Komber, H.; Voit, B.; Zschoche, S.; Kühn, F. E.; Nuyken, O.; Walter, M.; Hanefeld, P. J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 5636. [2] (a)Hijazi, A. K.; Yeong, H. Y.; Zhang, Y.; Herdtweck, E.; Nuyken, O.; Kühn, F. E., Macro-molecular Rapid Communications, 2007, 28, 670. (b)Li, Y.; Voon, L.T.; Yeong, H. Y.; Hijazi, A. K.; Radhakrishnan, N.; Köhler, K.; Voit, B.; Nuyken, O.; Kühn. F. E., Chem. Eur. J. 2008, 14, 7997-8003 [3] Hijazi, A. K.; Radhakrishnan, N.; Jain, K. R.; Herdtweck, E.; Nuyken, O.; Walter, H. M.; Hanefeld, P.; Voit, B.; Kühn, F. E. Angew. Chem. – Int. Ed. 2007, 46, 7290. [4] Nuyken, O.; Vierle, M.; Kühn, F. E.; Zhang, Y. Macromol. Symp. 2006, 236, 69.

153

Poster 50

KINETIC INVESTIGATION OF POLYISOBUTYLENE/POLYSYRENE COPOLYMERIZATION BEARING POLAR SIDE CHAINS Katharina Hackethal, Wolfgang H. Binder Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II, Institute of Chemistry Macromolecular Chemistry, TGZ III, Heinrich Damerow Strasse 4, D-06120 Halle [email protected] Supramolecular polymers represent an important concept for the engineering of defined material properties [1]. Thus, it is possible to design thermoplastic properties due to the presence of hydrogen bonds into a polymer chain by creating reversibly cross linked polymer with self-healing properties [2, 3]. The quasi-living cationic polymerization of isobutylene is often not compatible with highly polar moieties, mostly due to the incontrollable influence of polar moieties on the respective ion-equilibria. The aim of this research is directed towards the copolymerization of styrenederivatives bearing polar side groups and isobutylene via living cationic polymerization using monomers with hydrogen bonding moieties. Recent studies [4] have investigated the postfunctionalization of related styrene-polymers and have observed loss of control and livingness. In order to provide living conditions during the copolymerization reaction it is necessary to avoid the disturbance of the used polar moieties on the underlying ion equilibria of the living cationic polymerization reaction. We have investigated the synthesis of various pyridine-derivates with attached styrene-moieties, being reminiscent of the sterically-hindered pyridine bases conventionally used for the living cationic polymerization of isobutylene. The styrene monomers 4-(4-vinylphenethyl)-pyridine, 4-(4-vinylphenethyl)-2,6-dimethylpyridine and 2-(4-vinylphenethyl)-4,6-dimethyl-pyridine were synthesized and characterized by NMR-spectroscopy. These monomers (1 mol%, 2 mol%, 5 mol% and 7 mol%) were then copolymerized statistically with isobutylene in different amounts. The kinetic polymerization behaviour of the copolymerization was monitored with in-situ-ATR-FTIR-spectroscopy according to Storey et al. [5] also compared to the polymerization of isobutylene and isobutylene with added soluble 4-methylpyridine or 2,4,6-trimethylpyridine in amounts of 1 mol%, 2 mol%, 5 mol% and 7 mol%, respectively. In comparison to isobutylene homo-polymerization (kapp = 7 x 10-3 s-1), the copolymerization of 4-(4-vinylphenethyl)-pyridine with isobutylene results in kapp ranging from 19 x 10-3 s-1 (1 mol%) to 7 x 10-3 s-1 (7 mol%), being independent from the used pyridine concentration (kapp = 10-4 s-1 for 1 mol% and 2 mol% and kapp = 2 x 10-2 s-1 for 5 mol%). The final monomers and copolymers were characterized by NMR- spectroscopy and GPC analysis. The incorporation of the polar comonomers was proven via MALDI-TOF measurements. [1] 1 Binder, W. H.; Zirbs, R., Adv. Polym. Sci 2007, 207:1-78 [2] 2 (a) Bosman, A. W.; Sijbesma, R. P.; Meijer, E. W., Materials Today 2004, 7, (4), 34-39. (b) Lange, R. F. M.; Gurp, M. V.; Meijer, E. W., J. Polym. Sci. Part A: Polym. Chem. 1999, 37, (19), 3657-3670 [3] 3 Müller, M.; Seidel, U.; Stadler, R., Polymer 1995, 36, (16), 3143-3150 [4] 4 M. Tilliet, S. Lundgren, Ch. Moberg, V. Levacher, Adv. Synth. Catal. 2007, 349, (13), 2079-2084 [5] 5 Storey, R. F.; Thomas, Q. A., Macromolecules 2003, 36, (14), 5065-5071

154

Poster 51

SYNTHESIS AND CHARACTERIZATION OF POLY(10UNDECENE-1-OL) Matthias Johannsen, Ulrich Schulze, Dieter Jehnichen, Liane Häußler, Hartmut Komber, Brigitte Voit Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, D-01069 Dresden, Germany [email protected] The synthesis of poly(10-undecene-1-ol)s with metallocene catalysts and the investigation of the chemical structure was presented recently[1]. As result of our investigations we could find suitable polymerization conditions. The influence of the catalyst and polymerization conditions on the end group characteristics was analyzed. It was possible to find conditions for preparing poly(10-undecene-1-ol)s with terminal double bonds using unbridged catalysts activated with MAO. By variation of the polymerization conditions the chain length of the polymer backbone and the monomer conversion could be controlled. Thus polymers over a wide range of molar mass characterized by means of SEC and [1] H NMR were synthesized and the results will be presented. The main focus is on the characterization concerning the morphology and the thermal behavior of the poly(10-undecene-1-ol)s. DSC curves of the polymers show distinct endothermic peaks in the isotactic-rich as well as in the atactic poly(10-undecene-1ol). Two phase transitions were observed for most of the poly(10-undecene-1-ol)s. The occurrence of more than one melting peak was expected for the isotactic-rich poly(10undecene-1-ol) samples polymerized with rac-Me2Si[2-Me-4,5-BenzInd]2ZrCl2 (MBI) activated with methylalumoxan (MAO) according to investigations of Aubrey et al. [2] for higher isotactic-rich poly(1-olefin)s. The author reported that isotactic molecules are the reason for the higher temperature melting peak and atactic molecules, respectively atactic parts in mainly isotactic molecules, induce the lower temperature melting peak. However, for the atactic polymers synthesized with Me2Si[(t-Bu-N)(Me)4Cp]TiCl2 (Tin)/MAO and Cp2ZrCl2/MAO more than one melting peak was not expected a priori. WAXS investigations show that the poly(10-undencene-1-ol)s in isotactic-rich and atactic configurations shape frozen smectic structures. We assume that the long side chains supported by the polar groups cause an intermolecular phase separation, which results in an ordered layer structure. The layer distance of d= 2.57 nm corresponds to two elongated side chains of the polymer, that indicates an orthogonal arrangement of these side chains. A connection of the side chain by hydrogen bridges is indicated by the relative high melting points of the poly(10-undecene-1-ol)s compared with poly(1-olefin)s of corresponding side chain length ]3]. Additionally, one strong reflection in the scattering region around d ≈ 0.44 nm suggest a (pseudo-)hexagonal lateral order of the side chains. Further investigations are directed to clear-up this behavior. [1] U. Schulze, M. Johannsen, R. Haschick, H. Komber, B. Voit, submitted. [2] D.W. Aubrey, A. Barnatt J. Polym. Sci., Part A-2, 1968, 6, 241. [3] M. Arnold, J. Knorr, F. Köller, S. Bornemann, J. Macromol. Sci., Part A, 1999, 36, 1655.

155

Poster 52

SYNTHESIS, RHEOLOGY, AND CRYSTALLIZATION BEHAVIOR OF CYCLIC POLY(ε-CAPROLACTONE)S Elena Ostas (1), Wolfgang H. Binder (1), Kay Saalwächter (2), Kerstin Schäler (2), Thomas Thurn-Albrecht (3), Klaus Schröter (3) (1) Institute of Chemistry, Division of Technical and Macromolecular Chemistry, MartinLuther-Universität Halle-Wittenberg, D-06120 Halle (Saale), Germany (2) Institute of Physics – NMR, Martin-Luther-Universität Halle-Wittenberg, D-06120 Halle (Saale), Germany (3) Institute of Physics – Polymer Physics, Martin-Luther-Universität Halle-Wittenberg, D06099 Halle (Saale), Germany [email protected] Cyclic polymers are attractive model systems that can be used to explore the influence of topology on the dynamics in the molten and entangled state as well as on macromolecular self-organization processes such as the formation of the semicrystalline state [1-3]. The present work is focused on the synthesis of cyclic and comparable linear poly(εcaprolactone)s over a wide range of molecular weight (10000 – 100000 g/mol), and their characterization by GPC, DSC, melt-rheology and solid-state NMR. The main focus of this work concerns the investigation of the isothermal and non-isothermal crystallization behavior of the prepared polymers by low-field solid-state NMR and DSC respectively. Polymerization reactions were conducted via coordination-insertion ring opening mechanism using cyclic (2,2-dibutyl-1,2-dioxa-2-stannane) and linear (dibutyl-tin-dimethoxide) initiators [4] Cyclic polymers were obtained directly from the cyclic initiator, containing dibutyl stannanes inside the ring. Linear polymers were prepared either containing dibutyl stannanes inside the chain, or being devoid of Sn-species. Rheological experiments indicate that the cyclic polymers are less viscous by about a factor of 2 as compared to the linear counterparts of the same molecular weight. In a molecular weight range above 30000 g/mol we find that the crystallization of the cyclics proceeds somewhat slower, as judged from lower non-isothermal crystallization tempera¬tures on cooling. However, solid-state NMR data indicate higher crystallinities of the cyclics in comparison to linear polymers in the same molecular weight range under the condition of slower isothermal crystallization at 48°C. This suggests that cyclic polymers nucleate less efficiently, yet their enhanced overall mobility in the melt allows for the formation of thicker lamellae/larger crystallites. [1] Deffieux, A.; Borsali, R. In Macromolecular Engineering; Matyjaszewski, K., Gnanou, Y., Leibler, L., Eds.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany: 2007; Vol. 2, p 875-908. [2] Ungar, G.; Zeng, X. b. Chem. Rev. 2001, 101, 4157-4188. [3] Cosgrove, T.; Griffiths, P. C.; Hollingshurst, J.; Richards, R. D. C.; Semlyen, J. A. Macromolecules 1992, 25, 6761-6764. [4] Kricheldorf, H. R. E., S. Macromol.Chem.Phys 1998, 199, 283-290.

156

Poster 53

SUPRAMOLECULAR MATERIALS VIA A BIMETALLIC ROMP-CATALYST Steffen Kurzhals, Wolfgang H. Binder Martin-Luther University Halle-Wittenberg, Faculty of Natural Sciences II/Institute of Chemistry, Macromolecular Chemistry / TGZ III, Heinrich Damerow Str. 4, D-06120 Halle, Germany [email protected] Supramolecular polymers [1-4] are built from noncovalent interaction forces like hydrogen bondings or electrostatic forces. As a result, these structures display dynamic assembly and disassembly which is a major advantage of supramolecular polymers when compared to covalent bonded structures [1]. We report on the synthesis of telechelic and semi-telchelic polymers prepared via ring opening metathesis polymerization (ROMP) and the introduction of functional endgroups (e.g. hydrogen bonding moieties such as barbiturates) onto the polymer chains. Monomers used include norbornene-, cyclopropene- [5] and barrelene-based compounds [6]. The synthetic approach towards these telechelic polymers was achieved via a bimetallic Ru-initiator [7]. The introduction of acetoxy and barbiturate endgroups to produce semi-telechelic polymers via cross metathesis was achieved in high efficiencies by using symmetric quenching agents. Norbornene and cycloprene monomers were additionally used for the blockcopolymerization with Grubbs catalyst 1st, 2nd and 3rd generation, resulting in blockcopolymers with polydispersities around 1.7 and moderate yields. The crossover reaction during these blockcopolymerizations was monitored via MALDI-TOF and NMRspectroscopy. Analysis of chain growth via MALDI-TOF or NMR-spectroscopy after addition of exactly one equivalent of the second monomer suggest a dependency of the crossoverreaction on the chain length and nature of the living chain end. [1] Binder, W.; Zirbs, R., Supramolecular Polymers and Networks with Hydrogen Bonds in the Main- and SideChain. In Hydrogen Bonded Polymers, 2007; pp 1-78. [2] Kluger, C.; Binder, W. H., Functionalized poly(oxanorbornene)-block-copolymers: Preparation via ROMP/click-methodology. Journal of Polymer Science Part A: Polymer Chemistry 2007, 45, (3), 485-499. [3] Binder, W. H.; Kluger, C.; Josipovic, M.; Straif, C. J.; Friedbacher, G., Directing Supramolecular Nanoparticle Binding onto Polymer Films: Film Formation and Influence of Receptor Density on Binding Densities. Macromolecules 2006, 39, (23), 8092-8101. [4] Lehn, J.-M., Dynamers: dynamic molecular and supramolecular polymers. Prog. Polym. Sci. 2005, 30, (89), 814-831. [5] Binder, W. H.; Kurzhals, S.; Pulamagatta, B.; Decker, U.; Manohar Pawar, G.; Wang, D.; Kühnel, C.; Buchmeiser, M. R., Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers. Macromolecules 2008, 41, (22), 8405-8412. [6] Conticello, V. P.; Gin, D. L.; Grubbs, R. H., Ring-Opening Metathesis Polymerization of Substituted Bicyclo[2.2.2]octadienes: A New Precursor Route to Poly( 1,4-phenylenevinylene). J. Am. Chem. Soc. 1992, 114, 9708-9710. [7] Weck, M.; Schwab, P.; Grubbs, R. H., Synthesis of ABA Triblock Copolymers of Norbornenes and 7Oxanorbornenes via Living Ring-Opening Metathesis Polymerization Using Well-Defined, Bimetallic Ruthenium Catalysts. Macromolecules 1996, 29, (5), 1789-1793.

157

Poster 54

RING-OPENING METATHESIS POLYMERIZATION-DERIVED, POLYMER-BOUND CU-CATALYSTS FOR CLICKCHEMISTRY AND HYDROSILYLATION REACTIONS UNDER MICELLAR CONDITIONS Gajanan Pawar (1), Bhasker Bantu (1), Jochen Weckesser (2), Siegfried Blechert (2), Klaus Wurst (4), Michael R. Buchmeiser (1,3) (1) Leibniz-Institut für Oberflächenmodifizierung, Leipzig, Germany (2) Technische Universität Berlin, Germany (3) Institut für Technische Chemie, Universität Leipzig, Germany (4) Institut für Allgemeine, Anorganische und Theoretische Chemie, Universität Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria [email protected] Amphiphilic block copolymers have achieved wide attention, e.g., in the area of micellar catalysis [1-5] where, most recently, catalysts bound to amphiphilic block copolymers have become an important research topic due to the stability of these systems in aqueous media and the ease of product/catalyst separation [6]. In this study, we describe the synthesis of the amphiphilic block-copolymer poly(M1-co-M3)-b-poly(M2) via ring-opening metathesis polymerization (ROMP) from the hydrophilic monomer 5-2-[2-(2-methoxy-ethoxy)-ethoxy]ethoxymethyl-7-oxabicyclo[2.2.1]hept-2-ene (M2), and the hydrophobic monomers endo,exo5-decyloxymethyl-bicyclo[2.2.1]hept-2-ene (M1) and 1,3-di(1-mesityl)-4[(bicyclo[2.2.1]hept-5-en-2-ylcarbonyl)oxy]methyl-4,5-dihydro-1H-imidazol-3-ium carboxylate (M3). Poly(M1-co-M3)-b-poly(M2) was loaded with Cu and the resulting CuIloaded polymer was used for a series of catalytic reactions under micellar conditions, i.e. for the Cu-catalyzed [3-2] cycloaddition of azides to alkynes and hydrosilylation reactions. The polymer-bound Cu-catalyst was found to be an efficient catalyst for these reactions under the micellar condition. Turn-over numbers (TONs) in cycloaddition reactions were in the range of 200-375, those in hydrosilylation reactions reached 2000. The experimental details of these investigations are presented. [1] Krause, J. O.; Zarka, M. T.; Anders, U.; Weberskirch, R.; Nuyken, O.; Buchmeiser, M. R. Angew. Chem, 2003, 115, 6147; Angew. Chem., Int. Ed. 2003, 42, 5965. [2] Kotre, T.; Zarka, M. T.; Krause, J. O.; Buchmeiser, M. R.; Weberskirch, R.; Nuyken, O. Macromol. Symp. 2004, 217, 203. [3] Zarka M. T.; Bortenschlager M.; Wurst K.; Nuyken O.; Weberskirch, R. Organometallics 2004, 23, 4817. [4] Uozumi, Y.; Tanaka, H.; Shibatomi, K. Org. Lett. 2004, 6, 281. [5] B. Cornils, W. A. Herrmann, Aqueous Phase Organometallic Catalysis-Concept and Application; WileyVCH: Weinheim, Germany, 1998. [6] Zarka, M. T.; Nuyken, O.; Weberskirch, R. Macromol. Rapid Commun. 2004, 25, 858.

158

Poster 55

REGIOSELECTIVE CYCLOPOLYMERIZATION OF VARIOUS CHEMICALLY DIFFERENT 1,6-HEPTADIYNES BY RUIVBASED METATHESIS INITIATORS P. Santhosh Kumar (1), Klaus Wurst (3), Michael R. Buchmeiser (1, 2) (1) Leibniz-Institut für Oberflächenmodifizierung (e. V.) IOM, Permoserstr. 15, D-04318 Leipzig, Germany (2) Institut für Technische Chemie, Universität Leipzig, Linnéstr. 3, D-04103 Leipzig, Germany (3) Institut für Allgemeine, Anorganische und Theoretische Chemie, Universität Innsbruck, Innrain 52 a, A-6020 Innsbruck, Austria [email protected] Over the last decade, cyclopolymerisation-derived poly(acetylene)s have achieved wider attention. This is attributed to their simple design with the help of metathesis catalysts.[1-5] In this study, we describe the synthesis of such poly(acetylene)s via the cyclopolymerisation of sterically demanding dipropargyl diesters (M1-M3), dipropargyl ammonium salts (M4, M5), 3-(propargyloxy)-1-octyne (M6), dipropargyl amines (M9 and M10), and dipropargyl diethyl malonate (M11) by bis-trifluoroacetate or bis-penteafluorobenzoate modified Ru-based metathesis initiators (e.g. [Ru(CF3COO)2(3-mesityl-1-((1’R)-1’-phenylethyl)-4,5dihydroimidazolin-2-ylidene)(=CH-2-(2-PrO)C6H4)], [Ru(C6F5COO)2(IMesH2)(=CH-2-(2PrO)-C6H4)] (IMesH2=1,3-dimesityl-4,5-dihydro imidazolin-2-ylidene), [Ru(CF3COO)2(1,3dimesityl-4,5,6,7-tetrahydro-[1,3]-diazepin-2-ylidene)(=CH-2-(2-PrO)C6H4)],[6] 13C-NMR experiments revealed that all polymers (poly-M1 to poly-M11) synthesized by the action of any of the initiators consisted virtually solely (>95%) of five-membered repeat units along the polymer backbone. In the polymerization of N-ethyl-N,N-dipropargylamine (M9), an intermediate was isolated that reveals the role of heteroatoms in the 4-position of 1,6heptadiynes in cyclopolymerization, it would also explains for the observed ‘back-biting’ and the low polymerization propensity of Ru-alkylidenes for N-alkyl-N,N-dipropargylamines. A detailed mechanistic explanation of these findings is presented [7]. [1] [2] [3] [4] [5]

Fox, H. H.; Schrock, R. R., Organometallics 1992, 11, 2763. Buchmeiser, M. R., Adv. Polym. Sci. 2005, 176, 89. Anders, U.; Wagner, M.; Nuyken, O.; Buchmeiser, M. R., Macromolecules 2003, 36, 2668. Anders, U.; Nuyken, O.; Wurst, K.; Buchmeiser, M. R., Angew. Chem. 2002, 114, 4226. Vygodskii, Y. S.; Shaplov, A. S.; Lozinskaya, E. I.; Vlasov, P. S.; Malyshkina, I. A.; Gavrilova, N. D.; Kumar, P. S.; Buchmeiser, M. R., Macromolecules 2008, 41, 1919. [6] Kumar, P. S.; Wurst, K.; Buchmeiser, M. R., Organometallics 2009, in press. [7] Kumar, P. S.; Wurst, K.; Buchmeiser, M. R., J. Am. Chem. Soc. 2009, 131, 387.

159

Poster 56

DENDRITIC GLYCOPOLYMER LAYERS FOR THE INTERACTION WITH BIO-ACTIVE (MACRO-)MOLECULES Dietmar Appelhans, Monika Warenda, Anne Richter, Stefan Zschoche, Klaus-Jochen Eichhorn, Brigitte Voit Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany [email protected] The exploration of biological processes in nature requires the use of simple synthetic approaches to receive water-soluble polymers with (oligo-)saccharide surface groups, e.g., acting as carrier, inhibitor and recognition molecules. Chemically attached (oligo-)saccharides on polymer surfaces preferably act as non-ionic components in aqueous environment. The (oligo-)saccharides unify different properties/functions such as the combination of watersolubility with (a) the inhibition or activation of proteins, enzymes and viruses and (b) the reduction of immune reaction in biological processes. In this context, we are interested in the development of (oligo-)saccharide-shelled dendritic polyamines [1] as multifunctional macromolecules (A) for the establishment of biocompatible layers, mostly using thin layer technology, and their (non-)interaction properties towards bio-active (macro-)molecules and biological systems for bio-sensing, and (B) for its use in solution as carrier system [2] in (bio)medical applications. Here, we report on the preparation, characterization and stability of hyperbranched poly(ethylene imine)s with oligosaccharide substituents. Especially, the influence of interface layers on the formation of very thin (10-20 nm) up to thicker layers (≤ 400 nm) is presented and discussed which also possess different degree of swelling. Furthermore, such layers were used to investigate their interaction towards ATP and various Proteins. Interaction properties were determined by various techniques (ellipsometry, laser scanning microscopy, and AFM etc.). One result was that swollen dendritic glycopolymer layers show prefered proteinresistant properties meaning only the adsorption of isolated proteins on surfaces. Recent results will be considered too. [1] Chem. Eur. J. 2008, 14, 7030; Biomacromolecules 2009, 10, 1114 [2] Journal of Biophotonics 2009, in press

160

Poster 57

MULTIFUNCTIONAL MACROMOLECULES WITH OLIGOSACCHARIDE SHELL FOR (A) ENCAPSULATION STUDY AND (B) INCORPORATION IN HYDROGEL AS POTENTIAL CONTAINER MOLECULES Nikita Polikarpov, Jörg Kluge, Dietmar Appelhans and Brigitte Voit Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany [email protected] The exploration of biological processes in nature requires the use of simple synthetic approaches to receive water-soluble polymers with (oligo-)saccharide surface groups, e.g., acting as carrier, inhibitor and recognition molecules. Chemically attached (oligo-)saccharides on polymer surfaces preferably act as non-ionic components in aqueous environment. In this context, we are interested in the synthesis of hyperbranched poly(ethylene imine) (PEI) with various oligosaccharide architectures (Appelhans et al. Biomacromolecules 2009, accepted for publication) as multifunctional macromolecules for the encapsulation/release of different drugs and bio-active (macro-)molecules, including its carrier properties in biological environment, for the formation/stabilization of organic-inorganic hybrid materials and for the establishment of biocompatible layers for bio-sensing. As main goal we plan to develop hydrogels possessing oligosaccharide-modified PEI as multifunctional macromolecules for complexation and release of various (drug) molecules. For that purpose, firstly, encapsulation and release properties of oligosaccharide-decorated PEI towards different dye molecules (Rose Bengal and Indigo) and one statine molecule as drug are shown and discussed. This study gives us the chance to evaluate the encapsulation and release properties of the PEI derivatives for different test molecules in solution. In the next step, PEIs with different oligosaccharide architectures had been incorporated in hydrogels by non-covalent interaction and chemical fixation. Release studies revealed different binding stabilities of the PEI derivatives, fixed by non-covalent interactions, in hydrogels in dependence of various pH-values and salt concentrations. Also first results are shown and discussed for the chemical fixation of PEI derivatives in hydrogels. Thus, we are able to show and discuss which parameters are important for the accessability of PEI derivatives in hydrogels bringing us closer to realizing multifunctional macromolecules as container/release molecules in hydrogels.

161

Poster 58

PREPARATION AND CHARACTERIZATION OF (OLIGO-) SACCHARIDE MODIFIED HYPERBRANCHED POLY(ETHYLENE IMINE) LAYERS AND THEIR PROTEIN RESISTANT PROPERTIES M. Warenda, D. Appelhans, H. Komber, K-J. Eichhorn and B. Voit Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany [email protected] Recently, dendrimers and hyperbranched polymers with various (oligo-)saccharide architectures have been widely used as multifunctional materials. Naturally occurring (oligo-) saccharides when attached to the polymer surface can improve water solubility and reduce immune response. One of the most important and still definitely not disolved problem in medicine is biofouling onto materials which are in contact with organic fluids like human blood. In order to inhibit this undesired process, scientists have made efforts to develop protein resistant coating materials. Here, preparation and characterisation of hyperbranched poly(ethyleneimine) (PEI) modified with different (oligo-)saccarides such as maltose, maltotriose and maltoheptaose will be presented. PEI is a water soluble hyperbranched macromolecule which can be easily modified with carbohydrate molecules by one-pot synthetic approach as well-established working tool in our group [3, 4]. We can obtain three different structures by manipulation of the polymer: sugar ratio. Received macromolecules vary in degree of amine-group substitution that has an influence on material biocompatibility. For our experiments we used Si wafers coated with our modified hyperbranched polymer. The thin film preparation was carried out by spin coating technique. Poly(glycidyl methacrylate) was used for precoating and citric acid as a cross-linking agent for the formation of multi-layers. Film thickness was measured by ellipsometry and varied between 12-20 nm. Prepared (oligo-)saccharide modified poly(ethyleneimine) layers are very stable under different conditions like high temperature up to 200°C, water, PBS buffer and organic solutions, in broad pH range form acidic to basic and also ultrasounds treatment. We will show a good biocompability of this polymer with regard to its protein resistance ability. In our investigations we used Human Serum Albumin (HSA) and Lysozyme as proteins which differ in size and IEP value. The thickness of the adsorbed protein layers was measured in PBS by ellipsomteric method. The amount of adsorbed protein on the surface was calculated with De Feijter equation. [1] R. Haag, F. Kratz, Angew. Chem. Int. Ed. 45, 1198 (2006). [2] Y. Hu, J. K. Weiyuan, J. Biomater. Sci. Polymer Edn, 17, 3 (2006). [3] B. Klajnert, D. Appelhans, H. Komber, N. Morgner, S. Schwarz, S. Richter, B. Brutschy, M. Ionov, A. K. Tonkikh, M. Bryszewska, B. Voit, Chem. Eur. J. 14, 7030 (2008). [4] A. Köth, J. Koetz, D. Appelhans, B. Voit, Colloid Polym. Sci. 286, 1317 (2008).

162

Poster 59

NEW AMPHIPHILIC MULTISHELL STAR-BLOCKCOPOLYMERS AS BIODEGRADABLE ENCAPSULATION DEVICES FOR MEDICAL APPLICATION Florian Wolf, Daniel Wilms and Holger Frey Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany [email protected] A series of novel, potentially biocompatible/partially biodegradable star-block copolymers with the general block sequence poly(ethylene oxide)-b-poly(lactide)-b-poly(1,3dihydroxypropyl methacrylate) was synthesized. This hydrophilic-hydrophobic-hydrophilic star block copolymer system was obtained by the use of three orthogonal living polymerization techniques: 1) oxyanionic ring-opening polymerization (ROP) of an epoxide, 2) organo base catalyzed polymerization of a lactone and 3) atom transfer radical polymerization (ATRP) of a protected glycerol monomethacrylate. The core with and its first shell consists of hydrophilic Poly(ethylene glycol) attached to specifically designed initiators bearing six and eight hydroxyl functionalities, respectively. The polyether block was created via the controlled oxy anionic polymerization of ethylene oxide (EO) to form well defined (Mn 3,000-20,000; Mw/Mn105°. After formation of amphiphilic polymercolloidal complexes of grafted cationic polyelectrolytes PDADMAC and PMETAMS with anionic surfactant – sodium dodecylsulfate the modified Al are hydrophobic with contact angle θ~119-134° and θ~93-114° respectively. Thereby modification of Al by grafting of polymers and block-copolymers allows controlling its lyophilic properties in a wide interval.

200

Poster 97

STIMULI-RESPONSIVE POLYMER ARCHITECTURES IN CYLINDRICAL PORES VIA SURFACE-INITIATED LIVING RADICAL POLYMERIZATION F. Tomicki, M. Ulbricht Lehrstuhl für Technische Chemie II, Universität Duisburg-Essen, 45117 Essen, Germany [email protected] Poly(ethylene terephthalate) (PET) track-etched membranes (TEM) have been established as a model system for investigation of surface-initiated polymerizations in pores due to their uniform pore structure, narrow pore size distribution and robust, but moderately reactive structure [1]. Living polymerization techniques such as surface-initiated atom transfer radical polymerization (ATRP) are versatile in terms of adjustment of generated layer thickness, grafting density and monomer selection [2,3]. Earlier, our group had successfully functionalized PET TEM via surface initiated ATRP with homopolymers consisting of poly(N-isopropylacrylamide) (PNIPAAm) [4]. Recently, we had reported on ATRP grafting of both sequences of double-responsive hierarchical blockcopolymer layers of PNIPAAm and poly(acrylic acid) (PAA) [5]. Here, we report about recent investigations on surface functionalized PET TEM with N,Ndimethylaminoethyl methacrylate (DMAEMA) layers prepared under stationary and flowthrough conditions leading to double stimuli-responsive (pH, temperature) polyDMAEMA. Systematic investigations on the influence of pore diameter (curvature), grafting density and chain length have been accomplished. We have investigated the impact of reaction parameters on surface-initiated ATRP such as reaction time, catalyst system and functional group density. We further extended the range of accessible grafted polymers and block copolymers, for instance to poly(hydroxyethyl methacrylate) and poly(oligoethyleneglycol methacrylate) to create protein resistant surfaces. Recently, we have started to combine and utilize two different surface functionalization techniques such as photo-grafting and ATRP to modify PET TEM bearing both initiators on the same membrane surface. Both initiators could be widely indepently used for surface functionalization leading to more complex architectures. This will pave the road to tailored materials for controlled release or affinity separation by molecular imprinting. [1] [2] [3] [4] [5]

M. Ulbricht, Polymer, 47, 2006, 2217. K. Matyjaszewski, J. Xia, Chem. Rev., 101, 2001, 2921. Z. Bao, M. L. Bruening, G. L. Baker, Macromolecules, 39, 2006, 5851. A. Friebe, M. Ulbricht, Langmuir, 23, 2007, 10316. A. Friebe, M. Ulbricht, Macromolecules, 2009, in press.

201

Poster 98

MOLECULAR BRUSHES OF POLY(2-OXAZOLINE)S Ning Zhang, Rainer Jordan Wacker-Lehrstuhl für Makromolekulare Chemie, Dept. Chemie, TU München, Garching, Germany [email protected] We report on the synthesis and characterization of cylindrical molecular brushes based on poly(2-oxazoline)s (POx). The dual-functional monomer, 2-isopropenyl-2-oxazoline (IPOx), was first converted to a poly(2-isopropenyl-2-oxazoline), backbone by free radical (PIPOxR) or living anionic polymerization (PIPOxA). Quantitative reaction with methyl triflate yields a macroinitiator salt (PIPOxOTfR/A) for the preparation of molecular brushes via the grafting from approach by living cationic polymerization of 2-oxazolines (2-methyl-, 2-ethyl- and 2isopropyl-2-oxazoline). Characterization of the resulting molecular brushes by NMR and FTIR spectroscopy indicate a high side chain grafting density and quantitative reactions. Visualization of adsorbed molecular brushes by AFM corroborates this assumption. Furthermore, the lower critical solution temperatures of the POx molecular brushes were determined. The transition temperatures were found to be defined, reversible and with no noticeable hysteresis.

202

Poster 99

POLYMER BRUSHES ON DIAMOND Naima A. Hutter, Andreas Reitinger, José A. Garrido, Rainer Jordan Technische Universität München, Germany [email protected] In this project we develop electrochemical biosensors based on diamond electrodes modified with functional polymer brushes. Doped diamond is particularly suitable for biofunctionalization and biosensing as it exhibits several special properties, for example good biocompatibility and a large electrochemical potential window [1]. A variety of covalently bond polymer layers on diamond are fabricated through surface- or self-initiated polymerization methods which have recently been developed [2, 3]. The polymer brushes are soluble in aqueous solution and feature chemical functional side groups. Over these chemical moieties bioreceptors such as proteins can be attached via numerous already developed covalent or ionic coupling techniques resulting in a high loading. The smooth polymer matrix allows the biomolecules to keep their native structure. The linker functionalities are either introduced at the outset by the choice of monomer or - thanks to the high stability of the polymer brushes - by polymer analogue reactions. Structure and properties of the polymer brushes and biosensing capacities are monitored by IR spectroscopy, AFM measurements and amperometric detection techniques. [1] A. Härtl, E. Schmich, J. A. Garrido, J. Hernando, S. C. R. Catharino, S. Walter, P. Feulner, A. Kromka, D. Steinmuller, M. Stutzmann, Nature Materials 2004, 3, 736. [2] M. Steenackers, S. Q. Lud, M. Niedermeier, P. Bruno, D. M. Gruen, P. Feulner, M. Stutzmann, J. A. Garrido, R. Jordan, Journal of the American Chemical Society 2007, 129, 15655. [3] [M. Steenackers, A. Kueller, N. Ballav, M. Zharnikov, M. Grunze, R. Jordan, Small 2007, 3, 1764.

203

Poster 100

SELF-ASSEMBLY OF FUNCTIONAL POLYMER MULTILAYERED COMPOSITE MEMBRANES WITH ENHANCED PROTON CONDUCTIVITY AND METHANOL BARRIER PROPERTIES Serpil Yılmaztürk, Hüseyin Deligöz, Mesut Yılmazoğlu, Hakan Damyan, Faruk Öksüzömer, S.Naci Koç, Ali Durmuş, M.Ali Gürkaynak Istanbul University, Engineering Faculty, Chemical Engineering Department, 34320 Avcilar, Istanbul, Turkey [email protected] Fuel cells which directly convert chemical energy to electric energy have attracted a great attention due to increasing demand for clean and sustainable energy [1]. Nowadays, polymer electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) have been especially preferred in the applications required high power density such as vehicles, cell phones and notebooks. Perfluorosulfonic acid ionomers such as Nafion® are the most common membrane electrolytes used in these types of fuel cells due to their high proton conductivity and good chemical stability [2]. However, Nafion® also has some disadvantages such as (i) high methanol crossover through the membrane from the anode to the cathode causing a significant reduction in DMFC performance (ii) limited temperature range and (iii) high cost. Concerning these limitations and requirements, we tried to improve a series of polymer electrolyte membranes with adjustable surface properties by Layer-by-Layer (LbL) self assembly method which is explained by the sequential electrostatic adsorption of oppositely charged polyelectrolytes. Self-assembly is a promising and efficient method for obtaining multilayer thin films with finely tunable properties in a simple way. Here, we report the deposition of self-assembled polymeric multi-layers formed by LbL technique on Nafion® membrane to improve both proton conductivity and methanol barrier properties. The effect of deposition conditions such as pH, concentration and type of anionic and cationic polyelectrolytes, dipping time on proton conductivity (σ) and methanol permeability of the composite membranes were studied. Also, the effects of the charge and ionic form of polymeric layers were investigated. The formation of the self-assembled multilayered films on Nafion® was followed by UV–vis spectroscopy and it was found that the multi-layers growth linearly on the both sides Nafion membrane. To characterize LbL self-assembled composite membranes and optimize the LbL deposition conditions, the proton conductivity and methanol cross-over measurements were carried out by using AC impedance analyzer at room temperature in water and home-made glass apparatus, respectively. The results showed that deposition conditions and surface properties significantly affect the proton conductivity and methanol blocking properties of the composite membranes. In addition, the multilayered membranes prepared from polyelectrolytes with high charge density such as poly(vinyl sulfate potassium salt)(PVS) and poly(ethylene imine)(PEI) have exhibited highest σ values among all products. Our study indicated that LbL technique is a versatile method to prepare composite membranes with ultrathin and pore-free multilayer thin film which prevents the methanol permeation through the membrane. The reduction in methanol permeability is nearly 30%. Consequently, LbL self-assembled composite membranes with high proton conductivity and good barrier properties to methanol can be tailored by careful choice of the surface properties, preparation conditions and deposition number of the polyelectrolytes. The study was supported by TÜBĐTAK under the contract number of 107M449. [1] M. Hickner, Alternative polymer systems for proton exchange membranes (PEMs), Chem. Rev. 2004: 104; 4587. [2] L. Carrete, K.A. Friedrich, U. Stimming, Fuel cells—fundamentals and applications, Fuel Cells 2001: 1; 5. [3] A.A. Argun, J.N. Ashcraft, P.T. Hammond, Highly conductive, methanol resistant polyelectrolyte multilayers, Adv. Mater. 2008: 20; 1539.

204

Poster 101

PREPARATION OF CROSSLINKED POLY (2-BROMOETHYL METHACRYLATE) MICROSPHERES AND DECORATION OF THEIR SURFACES WITH FUNCTIONAL POLYMER BRUSHES BY SIP Bunyamin Karagoz, Deniz Gunes, Niyazi Bicak Istanbul Technical University, Department of Chemistry, Maslak 34469 Istanbul / Turkey [email protected] A suspension polymerization procedure is described for preparing crosslinked poly (2bromoethyl methacrylate) microspheres in relatively narrow size distributions (125-420 µm). The monomer, 2-bromoethyl methacrylate (BEMA) was newly synthesized by action of methacrylic acid on boron ester of 2-bromoethanol. In the polymerization process, ethylene glycol dimethacrylate (EGDMA) and methyl methacrylate (MMA) were employed as crosslinker and diluting comonomer respectively. Thus, a mixture of (BEMA) (0, 25 mol) – MMA (0.65 mol)-EGDMA (0.10 mol) was radically polymerized in aqueous suspension with 1/4 (v/v) [monomer] / [ water] ratio using poly(N-vinyl pyrrolidinone) as stabilizer. This procedure gave highly transparent microspheres with accessible bromoethyl group density of 1.55 mmol; g-1. Bromoalkyl groups, on the solid microparticles were employed as initiation sites for surface initiated atom transfer radical polymerization (ATRP) of glycidyl methacrylate(GMA) and ring opening polymerization (ROP) of 2-methyl 2-oxazoline to generate hairy grafts. Regarding with various modification possibilities of the bromo ethyl group the monomer BEMA and its spherical bead polymers would be key materials for functional polymers.

205

Poster 102

A FACILE AND GENERAL APPROACH TOWARDS HYDROPHILIC SILICONES Paul Böhm (1), Tammo J. Menke (2), Holger Frey (1) (1) Institute of Organic Chemistry, Organic and Macromolecular Chemistry, Duesbergweg 10-14, Johannes Gutenberg-University Mainz, D-55099 Mainz, Germany (2) Momentive Performance Materials GmbH, Chempark Leverkusen, D-51368 Leverkusen, Germany [email protected] Several synthetic routes to silicone-polymers with increased hydrophilic properties have been reported during the last 15 years. Most of the concepts include the combination of polydimethylsiloxanes (PDMS) and linear, hydrophilic polyethers like PEO, attached to the silicone either as linear copolymers or by grafting the polyether chains onto PDMS. Despite limited attention in the literature, hydrophilic silicones represent important compounds, particularly for application in contact lenses and for other biomedical purposes. Here we report on the development of various convenient one- or two-step synthetic approaches to novel hydrophilic silicones. Starting from different Si-H-functionalized polydimethylsiloxanes, silicones with hydrophilic grafts or amphiphilic ABA-triblock copolymers can be obtained using hydrosilylation chemistry to connect the hydrophilic structure to the silicone. The hydrophilic parts of the polymer consist of either glycerol sidechains or hyperbranched polyglycerol units. Thus, they contain at least two and (more likely) up to about 13 hydroxyl groups. Solubility and hydrophilicity can be readily tuned by variation of the number of Si-H bonds in the poly(dimethylsiloxane)-co-poly(methylhydrosiloxane)-copolymers with different amounts of Si-H-bonds.

206

Poster 103

DEVELOPMENT OF A NEW SILICONE FORMULATION FOR VERY HIGH SPEED COATING MACHINES T. Ireland, E. Pouget, L. Saint-Jalmes BLUESTAR Silicones, France [email protected] The use of very high-speed machines (up to 1600 m/min) for continuous silicone coating of flexible supports (paper, textile,…) is responsible for the apparition of high densities of misting during the process. After the analysis of the mechanism of formation of misting, we will present the different technologies developed by BLUESTAR Silicones to reduce the amount of misting. The first method deals with the addition of solid particles such as silica in the formulation. The second method deals with the addition of a viscoelastic silicone in the formulation that acts as a “glue”. The synthesis of a visco-elastic silicone by dehydrogenocondensation will be presented.

207

Poster 104

PHOTOPHYSICAL PROPERTIES OF PPP AND PPV DERIVATIVES BEARING POLYSTYRENE OR POLYCAPROLACTONE AS SIDE GROUPS Demet Goen Colak (1), Daniel Ayuk Mbi Egbe (2), Eckhard Birckner (3), Seda Yurteri (1), Ioan Cianga (1), Emine Tekin (4,5), Ulrich S. Schubert (4,5), Yusuf Yagci (1) (1) Istanbul Technical University, Department of Chemistry, Maslak 34469, Istanbul, Turkey (2) Institute for Print and Media Technology, Chemnitz University of Technology, Strasse der Nationen 62/B004, D-09111 Chemnitz, Germany (3) Institute of Physical Chemistry, University of Jena, Lessingstr. 10, 07743 Jena, Germany (4) Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands (5) Laboratory of Organic Chemistry and Macromolecular Chemistry, Friedrich-Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany [email protected], [email protected] Conjugated polymers have received a great attention on account of their unique optical, electrochemical or electrical properties and their potential use in a wide range of practical applications. Among a diversity of conjugated polymers poly(p-phenylene) (PPP) and poly(p-phenylene vinylene) (PPV) derivatives are one of the most promising classes and have been widely investigated in light-emitting diodes (LEDs) due to their relatively high photoluminescence (PL) and electroluminescence (EL) quantum efficiences. Attachment of relatively long and flexible side chains to the backbone of such rigid-rod polymers has been important as it allows solubility and subsequent processability which is required for most of the applications. The grafted side chains can also play an important role on optical and electronic properties of such materials. This contribution reports detailed photophysical investigations on PPP and PPV derivatives laterally decorated with polystyrene (PSt) and poly(ε-caprolactone) (PCL). Photophysical behaviour is governed by the basic chromophore units p-terphenylene and/or distyrylbenzene and steric effects caused by type and number of grafted macro-side chains. The polymers emit blue and exhibit very high relative and absolute photoluminescence quantum yield in dilute solution, thin film (spin-coated and inkjet-printed) and bulk state. This is ascribed to the presence of the lateral macromolecules, which suppress the strong π-π interactions and consequently excimers formation. The relatively high solid state fluorescence quantum yields suggest minimized fluorescence deactivation channels due to the presence of the macro-substituents, an aspect which favours the use of the present macromolecules in the design of high efficient light-emitting diodes.

208

Poster 105

CONJUGATED MICROPOROUS POLYMER NETWORKS Johannes Schmidt, Markus Antonietti, Arne Thomas Max Planck Institute of Colloids and Interfaces, Research Campus Golm, 14476 Potsdam-Golm [email protected] Microporous materials with very high surface areas are of considerable interest for fundamental research and industrial applications. Based on organic compounds, these materials combine the high surface areas and low densities of inorganic materials like zeolites or activated carbons with an excellent control of the chemical and physical properties known from organic synthesis. We synthesized microporous polymer networks with surface areas up to 1300 m2/g composed of purely organic materials. Porosity is created by using specially designed molecular architectures as 3D tectons and by generating stiff, covalent bonds between them. Two suitable tectons are 9,9‘-spirobifluorene or tri-substituted benzene. Different reaction routes, such as oxidative polymerization, Suzuki coupling or Yamamoto coupling can be used to connect these monomers into stiff polymer networks, exhibiting zeolite-like porosity and surface areas. Due to this different reaction types either homopolymers are obtained or by adding a second monomer copolymerisation is achieved. Through this approach a large variety of different functionalities can be easily incorporated into the porous polymer networks. The pores are accessible for gases, small organic molecules and metal ions. Thus metal nanoclusters can be created in the pores and the resulting polymer/metal nanocomposite shows a high catalytic activity in the hydrogenation of diphenylacetylene. Depending on the used monomers conjugation length, pore size and functionalities in the pore walls can be varied easily. This, in combination with the accessibility of the pores makes those porous polymer networks interesting as catalyst support, electronic devices and for gas storage or separation.

209

Poster 106

PHOTOINDUCED DECOMPOSITION OF DIBENZOYLDIETHYLGERMANE: APHOTOCHEMICAL ROUTE TO POLYGERMANES Yasemin Yuksel Durmaz (1), Manolya Kukut (1), Norbert Monszner (2), Yusuf Yagci (1) (1) Department of Chemistry, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey, (2) IvoclarVivadent AG, Bendererstrasse 2, FL-9494 Schaan, Liechtenstein [email protected] Photochemical synthesis of polygermanes was described. Thus, photolysis of bifuctional acyl germane photoinitiator, namely dibenzoyldiethylgermane (DBDEG) in CH3CN under visible light yielded oligo(diethylgermane)s. Photoinduced α-scission from the both sides of DBDEG and successive coupling of the resulting radicals resulted in the formation of oligogermanes. The structure of the photochemically formed oligogermane was confirmed by UV-vis, 1H NMR, 13C NMR spectral, and GPC measurements. The photoinitiation capability of the oligogermanes was demonstrated on the example of free radical polymerization of styrene.

210

Poster 107

TUNING OF THE NEUTRAL STATE COLOR OF THE πCONJUGATED DONOR-ACCEPTOR-DONOR TYPE POLYMER FROM BLUE TO GREEN VIA CHANGING THE DONOR STRENGTH ON THE POLYMER Simge Tarkuc (1,3), Yasemin Arslan Udum (2), Levent Toppare (1) (1) Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey (2) Institute of Science and Technology, Department of Advanced Technologies, Gazi University, 06570, Ankara, Turkey (3) Middle East Technical University, Northern Cyprus Campus, Kalkanli, Guzelyurt, TRNC, Mersin 10, Turkey [email protected] Two donor-acceptor-donor types of π-conjugated monomers were synthesized using Stille coupling reaction. Both monomers were found to produce electroactive polymers upon electrochemical oxidation. The effects of different donor substituents on the polymers’ electrochemical and spectroelectrochemical properties were examined. Optical characterization revealed that the band gaps of poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5,8-di(thiophen-2-yl)quinoxaline) (PDBQTh) and poly(2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(2,3-dihydrobenzo[b][1,4]dioxin-7-yl)-5(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-8-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7yl)quinoxaline) (PDBQEd) were 1.5 eV and 1.3 eV, respectively. PDBQEd reveals two distinct absorption bands as expected for this type of donor–acceptor-donor polymer at 423 and 738 nm, while PDBQTh has a single absorption band at 630 nm. The colorimetry analysis revealed that while PDBQTh has a blue color, PDBQEd showed a green color in the neutral state. The electron rich EDOT unit on DBQEd allows for the reversible n-doping of PDBQEd.

211

Poster 108

NEW AMPEROMETRIC ALCOHOL BIOSENSORS BASED ON POLYPYRROLE, POLY(3,4-ETHYLENEDIOXYTHIOPHENE) AND POLY(3,4-ETHYLENEDIOXYPYRROLE) Özlem Türkarslan, Levent Toppare Middle East Technical University, Department of Chemistry, 06531, Ankara, Turkey [email protected] Alcohol oxidase (AlcOx) was physically entrapped in polypyrrole (PPy), poly(3,4ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxypyrrole) (PEDOP) to construct amperometric alcohol biosensors. The responses of the enzyme electrodes were measured via monitoring oxidation current of H2O2 at +0.7 V in the absence of a mediator. Kinetic parameters, operational and storage stabilities, pH and temperature dependencies were determined. Sensitivities (Imax/Km) were calculated as 21.4, 22.2, 21.4 µA M-1 cm-2 for PPy, PEDOT and PEDOP based sensors respectively. Additionally the biosensors were tested in the presence of common interferents, which may be present in alcoholic beverages. The alcohol content of the beverages were checked with the AlcOx embedded PPy, PEDOT, PEDOP electrodes. Since the sensors should be specific, sensitive, stable, easy to use, portable and inexpensive, the alcohol sensors developed in this study are considered promising.

212

Poster 109

SYNTHESIS OF π-CONJUGATED HETEROCYCLIC FUSED POLYMER VIA DONOR-ACCEPTOR APPROACH AND ITS ELECTROCHROMIC APPLICATION Yasemin Arslan Udum (1), Simge Tarkuc (1,3), Levent Toppare (2) (1) Institute of Science and Technology, Department of Advanced Technologies, Gazi University, 06570, Ankara, Turkey (2) Middle East Technical University Northern Cyprus Campus, Kalkanli, Guzelyurt, TRNC, Mersin 10, Turkey (3) Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey [email protected] π-Conjugated monomer, namely 10,13-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)dibenzo [a,c]phenazine (TDP) was afforded by Pd-catalyzed cross coupling reaction of the dibromoquinoxaline derivative with tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5yl)stannane. A novel conducting polymer P(TDP) was synthesized electrochemically by direct anodic oxidation of TDP. The oxidation potential of TDP in dichloromethane (DCM) / TBABF6 (0.1M) was found to be 0.9 V. The polymer was characterized by cyclic voltammetry, UV–Vis-NIR spectroscopy and colorimetry. Spectroelectrochemical analysis of P(TDP) revealed electronic transitions at 470, 790 and 1600 nm corresponding to π-π* transition, polaron, and bipolaron band formations, respectively. P(TDP) was found to be green in the reduced state and transmissive gray in the oxidized state. P(TDP) was found to exhibit fast response times and high contrast ratios upon redox stepping, thereby proving them useful for electrochromic coatings. P(TDP) was used to construct dual-type polymer electrochromic devices (ECDs) against poly(3,4-ethylenedioxythiophene) (PEDOT). Spectroelectrochemical studies were carried out to examine the optical properties of the ECD's upon doping or dedoping to obtain information on the electronic structure. The response time that needed to perform switching between the redox states and the device’s stability during repeated cycles were evaluated by using double potential step chronoamperometry.

213

Poster 110

FLUORESCENCE SENSING OF GLUCOSE USING GLUCOSE OXIDASE MODIFIED BY PVA-PYRENE PREPARED VIA ‘CLICK CHEMISTRY’ Dilek Odaci (1), Bahadir N. Gacal (2), Burcin Gacal (2), Suna Timur (1), Yusuf Yagci (2) (1) Ege University, Faculty of Science, Department of Biochemistry, Bornova, 35100, Izmir, Turkey (2) Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, 34469, Istanbul, Turkey [email protected], [email protected] Poly(vinyl alcohol)-pyrene-glucose oxidase (PVA-Py-GOx), a water soluble polymer possessing both fluorescent and oxidant sites in the structure is synthesized by “click” chemistry and modification processes and characterized. The morphology of PVA-Py-Gox was characterized with atomic force microscopy (AFM), and an heterogenous morphology due to the incorporation of GOx was observed. The capability of PVA-Py-GOx to act as a bio-probe for fluroscence sensing of glucose is examined. The postulated fluroscence mechanism for glucose analysis is based on the consumption of glucose by dissolved oxygen and glucose oxidase present in the structure. Thus, the fluroscence intenstity of pyrene groups of the probe increases by the elimination of flurosence quenching by oxygen. Glucose concentration was measured quantitatively from 0.25 to 3.0 mM by the fluorescence measurement. The effect of pH and amount of enzyme was also studied.

214

Poster 111

COORDINATIVE SUPRAMOLECULAR ASSEMBLY OF LUMINESCENT FILMS BASED ON METALLO-POLYMERS WITH TERPYRIDYL- AND BENZIMIDAZOLYLPYRIDYL-ZINC MOIETIES Anna Maier, Irina Welterlich, A. Raman Rabindranath and Bernd Tieke Institut für Physikalische Chemie, Universität zu Köln, Luxemburger Str. 116, D-50939 Köln, Germany [email protected] New luminescent organized films are described, which were prepared upon multiple sequential adsorption of zinc hexafluorophosphate (Zn(PF6)2) and ditopic 2,7’-bisterpyridyl9,9-dihexylfluorene (type I films) on solid substrates. Alternatively, Zn(PF6)2 and polytopic polyfluorene-phenylene copolymers with pendent benzimidazolylpyridine groups were alternately adsorbed (type II films). Film formation is exclusively driven by coordinative interactions between the metal ions and the ligand groups. After twelve-fold alternate dipping into solutions of the zinc salt and the di- or polytopic ligands, homogeneous coordination polymer films of 10 to 50 nm in thickness were obtained. Type I films are colourless with absorption maximum at 382 nm and a strong light blue luminescence with maximum at 462 nm originating from the coordination polymer. Type II films are also colourless and exhibit a blue luminescence with maximum at 430 nm originating from the conjugated polymer backbone. A detailed study of the preparation of di- and polytopic ligands, zinc complexes, supramolecular assembly of the films, and the optical, electrochemical and structural properties of the films will be presented.

215

Poster 112

SYNTHESIS OF POLY (SULFOPROPYL METHACRYLATE) BASED COPOLYMERS FOR PROTON EXCHANGE MEMBRANE FUEL CELL Tuba Erdogan Bedri, Elif Erdal Unveren, Begum Elmas Chemistry Institute, TUBITAK Marmara Research Center, 41470, Gebze, Kocaeli, Turkey [email protected] The synthesis and characterization of novel membranes for proton exchange membrane fuel cell (PEMFC) continues to be the object of intensive research in the field of polymer science since the performance of a fuel cell is directly affected by membrane properties. Since, the composition and morphology of proton conducting polymers has close relationship with proton conductivity and tensile strength of membranes, the synthesis of new proton conducting polymers with different structures such as block, random or graft ionic copolymers is an active area of research. Especially, partially sulfonated block copolymers have attracted much attention as PEMFC materials due to their unique morphologies, and solid and solution properties that enhance the proton conductivity of the membrane. In this study, we synthesized poly (sulfopropyl methacrylate) based block and graft copolymers by atom transfer radical polymerization (ATRP). The membranes of partially sulfonated copolymers were prepared by solvent casting method for PEMFC. The structures and molecular characteristics of the ionic copolymers were studied by FT-IR and 1H NMR spectroscopy. The obtained membranes were characterized in terms of proton conductivity, ion exchange capacity (IEC), water uptake and thermal properties. Morphologies of the membranes were also investigated on a scanning electron microscope and atomic force microscope.

216

Poster 113

PREPARATION AND PROPERTIES OF HYPERBRANCHED POLYMER-BASED ELECTROLYTE MEMBRANES FOR FUEL CELLS Takahito Itoh, Takahiro Sakakibara, Yuki Takagi, Keita Hirai, Masashi Tamura, Takahiro Uno, Masataka Kubo, and Yuichi Aihara Division of Chemistry for Materials, Graduate School of Engineering, Mie University [email protected] Polymer electrolyte fuel cells (PEFCs) are the most promising candidates for electric vehicles and portable electrical power sources because of their high energy efficiency and environmentally benign technology. The present PEFCs are used at a relatively low temperature ( 150° and negligible hysteresis.

241

Poster 138

COATING AND FLEXIBLE MATERIALS FOR RADAR ABSORPTION AND EMI SHIELD Udayan De (1), Kriti Ranjan Sahu (1,2), N. Dutta Gupta (1,3) (1) Variable Energy Cyclotron Centre, Bidhannagar, Kolkata 700064, India (2) Egra SSB College, Egra, Purba Medinipur 721429, W Bengal, India (3) Dream Institute of Technology, Samali, Kolkata-700104, India [email protected] In this work, polymer-based hybrid materials have been developed and characterized over 700 MHz to 40 GHz range for potential applications as EMI (electromagnetic interference) Shields and as RAMs (Radar Absorbtion Materials). The major task in EMI Shielding is shielding of microwaves and radio-waves, often in a specified wavelength range. An explosive growth in the use of electrical and electronic devices has resulted in increased generation of EM waves and, hence, in a higher need for EMI Shielding to protect other devices. Strong EMI certainly has a negative effect, also, on human brain and health, in general. An EMI shield should cut off transmission to more than, something like - 20 dB. This can be done by either reflecting away the incident waves (as in metal shields) or by absorbing or by both. Radar Absorption Materials, on the other hand, demand minimum reflection or practically zero reflection of the radar beam from the shield, achievable by shielding materials having suitable absorbing bands. Composites of a polymeric binder with fine metallic turnings, powders of conducting inorganic compounds, ferroelectric powders and their combinations have been tested in a Vector Network Analyzer with respect to shielding and anti-reflection capabilities. Our substitution of expensive metal powders by fine metallic turnings, available as waste from mechanical workshops, for making the polymer composites reduces the cost substantially. Still, the best of these metal turnings composites show negligibly low Transmission (-24dB to -32dB in 08 to 12 GHz range). A polymeric composite of a conducting oxide, for example, shows a deep reflection minimum of -38.4 dB (at 9.71 GHz), important for RAM applications. The width of this minimum (9 to 10.5 GHz) could be increased by adding a third component. There is almost no reflection (-30 dB) also at 36 GHz. These RAM and shielding materials have been developed in ready-to-coat and ready-to-cast forms.

242

Poster 139

STRETCHING OF POLYELECTROLYTE MOLECULES ON THE HYDROPHOBIC SURFACE Konstantin Demidenok, Anton Kiriy, Manfred Stamm Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany [email protected] The abilities to control the size of conductive nanostructures and to manipulate them on a nanometer scale are priority subjects in the field of nanotechnology. One of the promising way for miniaturization is a template direct method. Polyelectrolytes molecules (PE) offers a range of interesting properties, such as, unique recognition, association and ability to assemble conductive polymers and metals. That is why PE are one of the most attractive templates. However, it is difficult to transform PE from their natural random-coil state into an extended state. The ability to reproducibly create and align well-stretched PE molecules very important for realizing nanoscale electronics. We developed a simple method creating highly aligned PE molecules, which enabled us to straighten and fix PE molecules on the surface without any surface modification or special equipment. The method relies upon stretching of the molecules or their bundles by shear forces while “drawing” by the PE solutions with the aid of capillary along a hydrophobic PDMS resin stamp, followed by a transfer of the resulting one-dimensional structures onto any surfaces with higher surface energy than that of PDMS. AFM pictures demonstrate that method is suitable for different kinds of PE molecules. The images of polystyrene sulfonic acid were statistically treated in order to determine the dependence of the height and morphology on the deposition conditions (concentration and velocity). A combination of this method with a deposition of conductive polymers (such as polypyrrole) on PSA already gave a positive result in the fabrication of conductive nanowires.

243

Poster 140

FABRICATION OF NANOASSEMBLIES BASED ON POLYMER BRUSHES AND METAL NANOPARTICLES Smrati Gupta (1), Marin Steenackers (2), Rainer Jordan (1) (1) Professur für Makromolekulare Chemie, Department Chemie, Technische Universität Dresden, Zellescher Weg 19, 01069 Dresden, Germany (2) Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany [email protected] Owing to the fascinating physical and chemical properties, metal nanoparticles (NPs) have been considered as promising materials for a wide spectrum of applications ranging from optoelectronics, sensors, catalysis, to medicine. Aggregation of nanoparticles due to high surface energy has been realized as the most prominent problem in all areas of applications outlined above. In order to avoid this problem, a number of studies have been reported in literature on their stabilization in solution/matrix. To this end, polymer-nanoparticle composites have been found the promising candidates, where NPs can render the unique optical properties to the resulting nanoassemblies and the polymer matrix can control hostguest interactions to ensure a well-defined spatial distribution of NPs. Here we exploit polymer brushes prepared by Self-Initiated Photografting and Photopolymerization (SIPGP) for immobilization of a variety of metal nanoparticles on macroscopic surfaces. Recently, we have shown that SIPGP can be used for a number of monomers on a variety of substrates where the formation of defined reactive interlayers such as SAMs is no longer necessary, and the direct grafting of monomers on surfaces can be realized in a one-step reaction. In the first step, polymer brushes were prepared and analyzed by a variety of analytical tools and later on in-situ synthesis of metal nanoparticles was carried out within these polymer brushes to achieve the nanoassemblies. To prove the immobilization of nanoparticles in the brushes, nanoassemblies were characterized using comprehensive methods including AFM, XPS and UV-VIS spectroscopy. The described approach offers an effective way toward the stabilization of NPs on the macroscopic surfaces and can be used for the fabrication of a wide range of polymer brushes nanoassemblies. [1] Steenackers, M.; Jordan, R.; Küller, A.; Grunze, M. Adv. Mater. 2009, 21, DOI: 10.1002/adma.200900500. [2] Gupta, S.; Uhlmann, P.; Agrawal, M.; Lesnyak, V.; Gaponik, N.; Simon, F.; Stamm, M.; Eychmüller A. J. Mater. Chem. 2008, 18, 214-220. [3] Gupta, S.; Uhlmann, P.; Agrawal, M.; Chapuis, S; Oertel, U.; Stamm, M. Macromolecules 2008, 41(8), 2874-2879.

244

Poster 141

ADAPTIVE LAYERS BASED ON SWITCHABLE CORE SHELL SILICA PARTICLES Anja Rollberg, Petra Uhlmann, P. Formanek, A. Janke, Manfred Stamm Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany [email protected] The creation of new multi-functional hybrid coatings based on commercial non fluorinated polymers and nanoparticles has received great attention during the last years. General aim of our research in this area is to develop new functional top-coats for applications e.g. in the automotive industry. This implies the production of core-shell-nanoparticle layers on a variety of substrates as polymers and metals with easy-to-clean (anti-soil and anti stain behaviour) and self cleaning properties. Additionally to these new surface functions the usage requirements of the new coating for foils comprehend scratch resistance, abrasion resistance and the sustainability of these effects. The block copolymers used for manufacturing the particle shell were synthesized by controlled living radical polymerization, especially via atom transfer radical polymerization (ATRP). These amphiphilic polymers with a narrow molecular weight distribution consist of an anchoring group to the substrate, a hydrophilic and a hydrophobic block. This offers the possibility to combine switching wettability behaviour and the anchoring to the foil in one molecule. The obtained core-shell particles were used to produce nanoparticle layers with a morphology determined by particle size and particle size distribution of the used particles: fumed silica OX50 (Evonik, Germany) and synthesized monodisperse silica particles causing an amplification of the intrinsic contact angle of the used triblock-and diblock copolymer system. The effect of molecular weight, anchoring block and polymer composition of the block-copolymers as well as the additional influence of surface morphology of the core-shellparticle layers (based on different roughness regimes of the different silica particles) on the wetting properties were investigated and compared. The developed new core-shell-particlesystems were characterised via REM, TEM electron loss spectroscopy, IR, MicroGlider and contact angle measurements. Acknowledgement: Financial support by the Federal Ministry of Education and Research (BMBF) is gratefully acknowledged. We thank Dr. P. Formanek and A. Janke, IPF DD e.V., for the TEM measurements.

245

Imprint Leibniz-Institut für Polymerforschung Dresden e.V. Hohe Str. 6 01069 Dresden, Germany www.ipfdd.de/apme09 [email protected] Layout Kerstin Wustrack Ulrike Schulze Cover picture Ch. Münch Manufacturer addprint AG, Dresden