International Conference (Bio)Degradable Polymers from Renewable Resources Vienna, November 18 – 21, 2007
ABSTRACTS
Polish Academy of Sciences Scientific Centre in Vienna The Conference is held under auspices of the
European Polymer Federation
Sponsors
Polish Academy of Sciences Polska Akademia Nauk
Ministry of Science and Higher Education, Poland Ministerstwo Nauki i Szkolnictwa Wyzszego˙
Federal Ministry of Transport, Innovation and Technology, Austria Bundesministerium für Verkehr, Innovation und Technologie
ACS PUBLICATIONS HIGH QUALITY. HIGH IMPACT. CONTENTS
Conference Committees and Organizers ...... 5
Conference Programme ...... 6
Conference Venues...... 8
Overview of Abstracts ...... 9
Abstracts of Invited Lectures...... 13
Abstracts of Poster Contributions ...... 33
Author Index ...... 108
List of Participants ...... 111
SCIENTIFIC COMMITTEE Ann-Christine Albertsson (Sweden) – co-Chair Gerhart Braunegg (Austria) – co-Chair Francesco Ciardelli (Italy) Danuta Ciechanska (Poland) Andrzej Dworak (Poland) Zbigniew Florjanczyk (Poland) Shiro Kobayashi (Japan) Izabella Krucinska (Poland) Andrej Krzan (Slovenia) Christopher K. Ober (USA) Gabriel Rokicki (Poland) Tadeusz Spychaj (Poland) Robert F. Stepto (UK) Piotr Tomasik (Poland) Jean-Pierre Vairon (France) Danuta Zuchowska (Poland)
Chairman of the Conference Stanislaw Penczek
Chairman of the Organizing Committee Stanislaw Slomkowski
Conference Secretary Andrzej Nadolny
CO-ORGANIZERS OF THE CONFERENCE
Polish Academy of Sciences, Scientific Centre in Vienna, Austria
International Network (Bio)degradable Polymers from Renewable Resources
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Lodz, Poland
Institute of Biotechnology and Biochemical Engineering, Graz University of Technology, Graz, Austria
5 CONFERENCE PROGRAMME
TIME VENUE
Sunday, November 18 Scientific Centre
17:00 – 21:00 Registration and Welcome Party
Monday, November 19 Studio 44
8:00 – 9:15 Registration 9:15 – 9:25 Opening: Stanislaw Penczek and Stanislaw Slomkowski
Chair: Maria Nowakowska 9:25 – 10:00 I-01 Ramani Narayan: BioPlastics and Biodegradable Plastics – Role in sustainability, Reducing Carbon Footprint and Environmental Responsibility 10:00 – 10:20 Coffee break
Chair: Zbigniew Florjanczyk 10:20 – 10:55 I-02 Ann-Christine Albertsson: (Bio)Degradable Polymers from Renewable Resources 10:55 – 11:30 I-03 Andrzej Duda: Controlled Polymerization of Cyclic Esters 11:30 – 11:50 Coffee break
Chair: Mariastella Scandola 11:50 – 12:25 I-04 Philippe Dubois: Polylactide-based Materials: from Micro- to Nanocompositions 12:25 – 13:00 I-05 Andrzej Galeski: Physical Modification of Polylactide 13:00 – 14:30 Buffet lunch
Chair: Andrzej Dworak 14:30 – 15:05 I-06 Richard A. Gross: New Biocatalytic Routes to Monomers, Macromers and Polymers 15:05 – 15:40 I-07 Francesco Ciardelli: Modification of Biorelated Macromolecules through Grafting of Short and Long Side Chains 15:40 – 16:15 I-08 Yves Gnanou: Dextran Based Block Copolymers: Synthesis and Self Assembly in Solution 16:30 – 18:30 Poster session, Wine and cheese Authors-in-attendance time: 16:30 – 17:30 odd numbers, 17:30 – 18:30 even numbers 6 TIME VENUE
Tuesday, November 20 Studio 44
Chair: Danuta Ciechanska 9:00 – 9:35 I-09 Piet J. Lemstra: Petro vs. Bio-based Plastics 9:35 – 10:10 I-10 Jan Feijen: Injectable Biodegradable Hydrogels for Protein Delivery 10:10 – 10:40 Coffee break
Chair: Izabella Krucinska 10:40 – 11:15 I-11 Martin Moeller: Polyether - Polyester Conjugates for Biodegradable Hydrophilic Microgels and Hyperbranched Polymers 11:15 – 11:50 I-12 Emo Chiellini: Hydro- and Oxo-Biodegradable Polymers from Fossil Feedstock vs. Their Counterparts from Renewable Resources 11:50 – 12:25 I-13 Gerhart Braunegg: Polyhydroxyalkanoates (PHAs): Biodegradable Polyesters from Agricultural Waste and Surplus Materials
Renaissance Penta Vienna Hotel
19:00 – 23:00 Conference Dinner
Wednesday, November 21 Scientific Centre
Chair: Andrej Krzan 9:00 – 9:35 I-14 Marek M. Kowalczuk: (Bio)degradation of Polymeric Materials Containing PHA and their Synthetic Analogues 9:35 – 10:10 I-15 Andreas Greiner: Novel Biodegradable Polymers and Scaffolds for Tissue Engineering 10:10 – 10:40 Coffee break
Chair: Gerhart Braunegg 10:40 – 11:15 I-16 Maria Nowakowska: Novel Photosensitizers Based on Polysaccharides 11:15 – 11:50 I-17 Piotr Tomasik: The Polarized Light-Induced Enzymatic Formation and Degradation of Biopolymers 11:50 – 12:00 Closing remarks
7 CONFERENCE VENUES
Scientific Centre of the Polish Academy of Sciences in Vienna Boerhaavegasse 25, A-1030 Wien and Studio 44, Austrian Lotteries Rennweg 44, A-1038 Wien
Schützeng.
ARTIS Hotel
Kleistgasse 1 71 Boerhaaveg.
Stanislausg. Aspangstr. Eslarng. 2 Rennweg S7
Kleistg.
Aspangstr. 50m
1 – Scientific Centre 2 – Studio 44 entrance: Kleistgasse
8 OVERVIEW OF ABSTRACTS
Invited Lectures I-01 R. Narayan: BioPlastics and Biodegradable Plastics – Role in sustainability, Reducing Carbon Footprint and Environmental Responsibility ...... 14 I-02 A.-C. Albertsson: (Bio)Degradable Polymers from Renewable Resources ...... 15 I-03 A. Duda: Controlled Polymerization of Cyclic Esters ...... 16 I-04 M. Murariu, A. Da Silva Ferreira, M. Pluta, M. Alexandre, L. Bonnaud, and P. Dubois: Polylactide-based Materials: from Macro- to Nanocomposites ...... 17 I-05 A. Galeski, E. Piorkowska, and M. Pluta: Physical Modification of Polylactide ...... 18 I-06 R. A. Gross: New Biocatalytic Routes to Monomers, Macromers and Polymers ...... 20 I-07 F. Ciardelli, S. Bronco, M. Bertoldo, F. Signori, M. B. Coltelli, and G. Zampano: Modification of Biorelated Macromolecules through Grafting of Short and Long Side Chains ...... 21 I-08 C. Houga, J.-F. Lemeins, R. Borsali, D. Taton, and Y. Gnanou: Dextran-Based Block Copolymers: Synthesis and Self-Assembly in Solution ...... 22 I-09 P. J. Lemstra: Petro vs. Bio-based Plastics ...... 24 I-10 C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen: Injectable Biodegradable Hydrogels for Protein Delivery ...... 25 I-11 H. Keul, M. Hans, M. Erberich, J. Meyer, and M. Moeller: Polyether- Polyester Conjugates for Biodegradable Hydrophilic Microgels and Hyperbranched Polymers ...... 26 I-12 E. Chiellini: Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock vs their Counterparts from Renewable Resources ...... 27 I-13 G. Braunegg, A. Atlic, M. Koller, and C. Kutschera: Polyhydroxyalkanoates (PHAs): Biodegradable Polyesters from Agricultural Waste and Surplus Material ...... 28 I-14 M. M. Kowalczuk: (Bio)degradation of Polymeric Materials Containing PHA and their Synthetic Analogues ...... 29 I-15 Y. Chen, R. Dersch, M. Gensheimer, U. Bourdiot, S. Agarwal, J. H. Wendorff, and A. Greiner: Novel Biodegradable Polymers and Scaffolds for Tissue Engineering ...... 30 I-16 M. Nowakowska, K. Szczubiałka, S. Zapotoczny, and Ł. Moczek: Novel Photosensitizers Based on Polysaccharides ...... 31 I-17 A. Molenda-Konieczny, M. Fiedorowicz, and P. Tomasik: The Polarized Light-induced Enzymatic Formation and Degradation of Biopolymers ...... 32
Poster Contributions P-01 A. Piegat and M. El Fray: Biodegradation of Polyester Nanocomposites ...... 34 P-02 P. Rychter, G. Adamus, and M. M. Kowalczuk: ESI-MS Studies of Slow-release Conjugate of 2,4-D with a-PHB for Agricultural Applications ...... 35 P-03 P. Wozniak, S. Sosnowski, and S. Slomkowski: Polymer-inorganic Hybrid Materials for Tissue Engineering ...... 36 P-04 E. Vidovic,´ D. Klee, and H. Höcker: Biodegradable Hydrogels Based on Poly(vinyl alcohol)-graft- [poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)] ...... 37 P-05 J. B. Chardhuri, M. G. Davidson, M. J. Ellis, M. D. Jones, and X. Wu: Fabrication of Honeycomb-Structured Polylactide and Poly(lactide-co-glycolide) Films and their Use for Osteoblast-Like Cell Culture ...... 38 P-06 H. Nilsson, A. Olsson, M. Lindström, and T. Iversen: Bark Suberin as a Renewable Source of Long-chain ω-Hydroxyalkanoic Acids ...... 39
9 P-07 A. Tiwari and A. P. Mishra: Studied on Electrical Conducting Biopolymer-poly(thiazole) Copolymers ...... 40 P-08 A. Zemaitatitis, R. Klimaviciute, and R. Kavaliauskaite: Antibacterial Activity of Cationic Starch-iodine Derivatives...... 41
P-09 A. Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra: Chitosan-co-polyaniline/WO3.nH2O Nanocomposites: Green Polymer Composite for Sensor Applications ...... 42 P-10 K. Wilpiszewska, S. Spychaj, and T. Spychaj: Chemical Modification of Starch with Hexamethylene Diisocyanate Amide Derivatives ...... 43 P-11 K. Wilpiszewska and T. Spychaj: Starch Plasticisation via Twin-screw Extrusion ...... 44 P-12 C. Duncianu and C. Vasile: Study of Interpolymeric Complexes Based on Polymers from Renewable Sources ...... 45 P-13 A. Pandey and B. Garnaik: Homopolymerization and Copolymerization of L, L-Lactide in Presence of Novel Zinc Proline Organocmetallic Catalyst...... 46 P-14 F. Faÿ, I. Linossier, and K. Vallée-Réhel: Poly(lactic acid) Microcapsules Containing Bioactive Molecules: Study of Activity ...... 47 P-15 W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk: Degradation Study of Polymers from Renewable Resources and their Blends in Industrial Composting Pile ...... 48 P-16 D. Macocinschi, D. Filip, and S. Vlad: Polyurethanes from Renewable Resources as Candidates for Friendly Environment New Materials ...... 49 P-17 P. Dacko, M. Sobota, H. Janeczek, J. Dzwonkowski, J. Goł˛ebiewski, and M. M. Kowalczuk: Viscoelastic and Thermal Proprieties of the Biodegradable Polymer Materials Containing Polylactide, Aliphatic-Aromatic Polyester and Synthetic Poly[(R,S)-3-hydroxybutyrate] Received via Injection Moulding ...... 50 P-18 V. Sedlarik, N. Saha, J. Bobalova, and P. Saha: Biodegradation of Blown Films Based on Polylactide Acid in Natural Conditions ...... 51 P-19 M. Bertoldo, F. Cognigni, F. Signori, S. Bronco, and F. Ciardelli: Molecular Modification of Gelatine by Reaction with Isocyanates ...... 52 P-20 M.-B. Coltelli, F. Signori, C. Toncelli, C. E. Rondán, S. Bronco, and F. Ciardelli: Biodegradable and Compostable PLA-based Formulations to Replace Plastic Disposable Commodities ...... 53 P-21 C. Peptu, V. Harabagiu, B. C. Simionescu, G. Adamus, and M. M. Kowalczuk: Mass Spectrometry Studies of Cyclic Esters Ring Opening Oligomerization in the Presence of Disperse Red 1 ...... 54 P-22 D. Ciolacu and F. Ciolacu: Supramolecular Structure – a Key Parameter for Cellulose Biodegradation ...... 55 P-23 M. Kawalec, G. Adamus, H. Janeczek, P. Kurcok, M. M. Kowalczuk, and M. Scandola: Kinetics of Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates ...... 56 P-24 R. P. Dumitriu and C. Vasile: Novel Biodegradable Matrices for Drug Delivery ...... 57 P-25 M. Michalak, M. Kawalec, C. Peptu, P. Kurcok, and M. M. Kowalczuk: Divergent Synthesis of β-Cyclodextrin-Cored Star -Poly([R,S]-3-hydroxybutyrate) ...... 58 P-26 J.-R. Sarasua, E. Zuza, A. López-Arraiza, N. Imaz, and E. Meaurio: Crystallinity and Crystalline Confinement of the Amorphous Phase in Polylactides ...... 59 P-27 D. Filip, A. I. Cosutchi, C. Hulubei, and S. Ioan: Liquid Crystal Template Applied for Polyimide-Cellulose Derivative Thin Films ...... 60 P-28 I. Spiridon, M. Ichim, and N. Anghel: Biomass Compounds with Pharmacological Applications ..... 61 P-29 M. Socka, M. Florczak, and A. Duda: Homo- and Copolymerization of Cyclic Aliphatic Esters with Suppression of Transesterification ...... 62 P-30 C.-I. Liu and C.-Y. Huang: Acid Modification and Application of Biodegradable Polymer-Starch ..... 63
10 P-31 H.-K. Lao, E. Renard, V. Langlois, X. Pennanec, M. Cuart, K. Vallee-Rehel, and I. Linossier: Characterization of the Radical Polymeric Grafting of Hydroxylethyl Methacrylate onto Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) ...... 64 P-32 J. Jaworska, Y. Hu, J. Wei, J. Kasperczyk, P. Dobrzynski,´ and S. Li: Degradation Process of Bioresorbable PGLC Terpolymers...... 65 P-33 G. Bogoeva-Gaceva, M. Avella, V. Srebrenkoska, A. Grozdanov, A. Buzarovska, M. E. Errico, and G. Gentile: Sustainable Green Polymer Composites Based on PLA...... 66 P-34 A. Błasinska´ and J. Drobnik: Accelerated Wound Repair by Di-O-butyrylchitin, the Polymer for New Non-Woven Dressing Material ...... 67 P-35 A. Šišková, W. Sikorska, M. Musioł, M. M. Kowalczuk, and W. J. Kowalski: Characterization of Biodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means of Electrospray Ionization-mass Spectrometry after a Partial Depolymerization ...... 68 P-36 M. Scandola, E. Zini, and M. L. Focarete: Commercial Biodegradable Polymers Reinforced with Flax Fibers ...... 69 P-37 K. G˛ebarowska, J. Kasperczyk, P. Dobrzynski,´ M. Scandola, and E. Zini: Investigation of Novel Shape-Memory Polymers’ Chain Microstructure ...... 70 P-38 M. Scandola, C. Gualandi, M. L. Focarete, P. Dobrzynski, M. Kawalec, and P. Wilczek: Bioresorbable Electrospun Non-woven Scaffolds ...... 71 P-39 J. M. Cardamone: Keratin Coating for Wool Fiber ...... 72 P-40 K. S. Mikkonen, M. P. Yadav, S. Willför, K. B. Hicks, and M. Tenkanen: Films from Spruce Galactoglucomannan Blended with Poly (Vinyl Alcohol), Corn Arabinoxylan and Konjac Glucomannan...... 73 P-41 B. Zywicka,˙ E. Zaczynska,´ A. Czarny, S. Pielka, J. Karas,´ and M. Szymonowicz: Activation of Transcription Nuclear Factor NF-κB and Induction of Inflammatory Cytokines in Immune Response on Resorbable Biomaterials ...... 74 P-42 M. Szymonowicz, B. Zywicka,˙ S. Pielka, L. Solski, D. Haznar, and J. Pluta: Influence of the Gelatin-Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and Tissue Reaction ...... 75 P-43 M. Szymonowicz, A. Marcinkowska, B. Zywicka,˙ S. Pielka, A. Gamian, D. Haznar, and J. Pluta: Cellular Response after Stimulation of the Gelatin-Alginate Matrixes...... 76 P-44 R. Makuška and R. Kulbokaitë: Synthesis and Properties of Chitosan – Poly(ethylene glycol) Comb Copolymers ...... 77 P-45 M. Koller, P. Hesse, A. Atlic,´ C. Hermann-Krauss, C. Kutschera, and G. Braunegg: Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose ...... 78 P-46 U. Janèiauskaite and R. Makuška: Synthesis and Study of Chitosan – Oligosaccharide Graft Copolymers ...... 79 P-47 M. Koller, P. Hesse, A. Atlic,´ C. Hermann-Krauss, C. Kutschera, and G. Braunegg: Selection of Carbon Feed Stocks for Cost-Efficient Polyhydroxyalkanoate (PHA) Production...... 80 P-48 W.-L. Lu, C.-I. Liu, and C.-Y. Huang: Properties and Degradation of PVA/Starch Blends with a PVA-g-MA Compatibilizer ...... 81 P-49 L. Santonja-Blasco, J. D. Badia, R. Moriana, and A. Ribes-Greus: Thermal and Mechanical Behaviour of a Commercial Poly(lactid acid) Submitted to Soil Burial Test ...... 82 P-50 J. D. Badia, R. Moriana, L. Santonja-Blasco, and A. Ribes-Greus: A Thermogravimetric Approach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid)...... 83 P-51 R. Moriana, L. Santonja-Blasco, J. D. Badia, and A. Ribes-Greus: Comparative Study about the Biodegradability and the Mechanical Performance of Different Biocomposites Based on Thermoplastic Starch Reinforced with Cotton Fibre ...... 84
11 P-52 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Improving the Processing Ability and Mechanical Strength of Starch/PVA Blends through Plasma and Acid Modification ...... 85 P-53 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Biodegradation of Starch and PVA/Starch Blend Enhanced by Rhizopus Arrhizus ...... 86 P-54 M. Kowalczyk and E. Piorkowska: Biodegradable Blends of Polylactide and Natural Rubber ...... 87 P-55 G. Adamus and M. M. Kowalczuk: Synthetic Analogues of PHA Anionic Ring-opening Polymerization of β-alkoxy Substituted β-lactones ...... 88 P-56 D. Ciechanska, J. Wietecha, J. Kazimierczak, D. Wawro, and E. Grzesiak: Biopolymer-based Fluorescent Sensors for Quality Control of Food Products ...... 89 P-57 S. Povolo and S. Casella: Polyhydroxyalkanoates Production by Isolates from a Polluted Salt-lagoon ...... 90 P-58 M. Sobota, H. Janeczek, P. Dacko, and M. M. Kowalczuk: Thermal Properties for Blend of Poly[(L)-lactide] and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate] ...... 91 P-59 I. Poljanšek, B. Brulc, M. Gricar,ˇ E. Žagar, A. Kržan, and M. Žigon: Synthesis of Poly(aspartic acid)-b-Polylactide Block Copolymer ...... 92 P-60 K. Krasowska, M. Rutkowska, and M. M. Kowalczuk: Compostability of Aliphatic-aromatic Copolyester and their Blends under Natural Weather Depending Conditions ...... 93 P-61 A. Konieczna-Molenda, M. Molenda, M. Fiedorowicz, and P. Tomasik: Illumination of Cellulose with Linearly Polarized Visible Light ...... 94 P-62 W. Tomaszewski, A. Duda, M. Szadkowski, J. Libiszowski, and D. Ciechanska:´ Poly(l-lactide) Nano- and Micro-fibers by Electrospinning: Influence of Poly(l-lactide) Molecular Weight ...... 95 P-63 G. C. Chitanu, I. Popescu, A. G. Anghelescu-Dogaru, and I. Dumistracel: Biomedical Applications of Maleic Anhydride Copolymers and Their Derivatives ...... 96 P-64 D. M. Suflet, G. C. Chitanu, and V. Trandafir: Complexation of Phosphorylated Cellulose with Collagen ...... 97 P-65 I. M. Pelin, G. C. Chitanu, V. Trandafir, and Z. Vuluga: Effect of Collagen on Sparingly Soluble Inorganic Salts Separation ...... 98 P-66 I. Popescu, M. I. Popa, and G. C. Chitanu: Supramolecular Systems from Natural Polymers and Maleic Polyelectrolytes ...... 99 P-67 M. Gadzinowski, B. Miksa, and S. Slomkowski: Polylactide-polyglycidol Block Copolymer as a New Nanoparticles Forming Material ...... 100 P-68 M. Pluta and A. Galeski: Structure Evolution in Amorphous Poly(L/DL-lactide) upon Plain Strain Compression ...... 101 P-69 M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, and P. Dubois: Structure and Physical Properties of PLA/Calcium Sulfate Composites...... 102 P-70 M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak: Materials of Functional Properties Based on Biodegradable Polymers ...... 103 P-71 D. Babic, Z. Kacarevic-Popovic, G. Mikova, and I. Chodak: Influence of Gamma-radiation on PCL/PHB Blends ...... 104 P-72 S. Agarwal and L. Ren: Synthesis and Properties Evaluation of a New Class of Degradable Polymers: Poly(vinyl-co-ester)s ...... 105 P-73 A. Gregorova and R. Wimmer: Dynamic-Mechanical and Thermal Properties of Biodegradable Composites from Polylactic Acid (PLA) Reinforced with Wood Fibres ...... 106 P-74 T. Eren and B. Taslica: New Derivatives of Methyl Oleate ...... 107
12 ABSTRACTS OF INVITED LECTURES
13 I-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 BioPlastics and Biodegradable Plastics -- Role in sustainability, Reducing Carbon Footprint and Environmental Responsibility
Ramani Narayan
Department of Chemical Engineering & Materials Science, Michigan State University, East Lansing MI 48824
BioPlastics offers the intrinsic value proposition for managing our carbon in a sustainable manner and provide a carbon neutral footprint in complete harmony with the natural biological carbon cycle. Biodegradable plastics offers the potential to manage single use, short-life, disposable packaging and consumer goods in a environmentally responsible manner. Plastics recycling and waste to energy operations also offer environmentally responsible approaches to managing plastic waste. Many questions arise: What is a biobased plastic? Why and how are they sustainable and environmentally responsible? How does one identify and measure biobased content? How does one document and quantify the positive environmental attributes of biobased plastics? What about biodegradable plastics? Is degrading the plastic the goal? Or is it more important to ensure that these degraded fragments are completely consumed/assimilated by the microorganisms within a reasonable and short time in the specified disposal environment? Composting is one such environment under which biodegradability occurs. In the composting environment, the nature of the environment, the degree of microbial utilization (biodegradation), and the time frame within which it occurs are specified in an ASTM standard. What are the environmental consequences and risks associated with degradable or partially biodegradable plastics without ensuing complete biodegradability? What is the relationship between biobased and biodegradable, biobased but not biodegradable? How does one document the reduced carbon footprint (LCA) and obtain carbon credits. The answers to these fundamental questions provide the basis and scientific rationale for designing and engineering biobased, and biodegradable plastics, and lay the foundation for standards and regulations world-wide. Life Cycle Assessment (LCAs) of these renewable/biobased materials often show reduced environmental impact and energy use when compared to petroleum-based materials, which we will review, and learn. We will look at successful technology exemplars that showcase the above “bio” model. Keywords: bioplastics; biodegradable plastics; carbon footprint ______[1] Narayan, Ramani, Biobased and Biodegradable Materials, Rationale, Drivers, & Technology Exemplars, ACS (An American Chemical Society Publication) Symposium Ser 939, Ch 18, pg 282, 2006
14 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-02 (Bio)Degradable Polymers from Renewable Resources
Ann-Christine Albertsson
Fibre and Polymer Technology, School of Chemical Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm, Sweden
During the last years, the interest in renewable and biodegradable materials has increased tremendously in the global community. The global market for renewable and biodegradable materials is anticipated to increase immensely in the near future following the raising societal awareness of the climate situation and the expected results of a continued consumer mentality. Still, the use of renewable and biodegradable materials has not been realized to any significant extent and few really renewable materials are available on the market. Increasing the fundamental knowledge of the degradation and environmental interactions of materials based on renewable and biodegradable polymers are the keys to fulfilling the increasing demand of new materials. There is also a need for new materials and more discriminating tools to predict the safety and degradation performance of the new materials throughout the life cycle of the material and products. Indicator products and chromatographic fingerprinting are thus powerful tools for the degradation state prediction [1- 3]. The material should have right mechanical properties and, if degradable, a suitable degradation time for the given application and it should totally degrade to non-toxic water soluble degradation products. The environment where the material is going to be used has a large influence on the degradation and release rate. Materials of the future need to be developed and made to function in all aspects of its existence, including production, use and waste management. Forestry and agricultural biomass holds huge potential as a renewable source of reactants and materials, being cheap and abundant. Hemicelluloses present such a material group, available for the production of functional materials, mainly hydrogels [4] and barrier films [5-6]. PLA is another interesting candidate and one of the very few polymeric materials today that are available from renewable resources, e.g. by fermentation of agricultural waste.
Keywords: degradable; bioresorbable polymers; renewable, green materials
______[1] M. Hakkarainen; A.-C. Albertsson Adv. Polym. Sci. , 169 , 177 (2004). [2] M. Hakkarainen; A. Höglund; K. Odelius; A.-C. Albertsson J. Am. Chem. Soc. , 129, 6308 (2007). [3] L. Burman; A.-C . Albertsson; M. Hakkarainen Adv. Polym. Sci. (2007) http://dx.doi.org/10.1007/12_2007_114. [4] M.S. Lindblad; E. Ranucci; A.-C. Albertsson Macromol. Rapid Comm. , 22 (12) , 962 (2001). [5] J. Hartman, A.-C. Albertsson, J. Sjoberg Biomacromolecules , 7(6) , 1983 (2006). [6] J. Hartman, A.-C. Albertsson, M.S. Lindblad, J. Sjöberg, J.Appl. Polym. Sci. , 100(4) , 2985-2991 (2006).
15 I-03 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Controlled Polymerization of Cyclic Esters
Andrzej Duda
Centre of Molecular and Macromolecular Studies Polish Academy of Sciences, Sienkiewicza 112, Lodz, Poland
Ring-Opening Polymerization (ROP) of cyclic esters will be discussed, stressing that independently on the initiator/catalyst used, i.e.: covalent metal alkoxide [1], carboxylate [2, 3], or acetyloacetonate [3], polymerization proceeds on the alkoxide species. Preparative applications of the most often used catalysts: aluminum tris-isopropoxide and tin(II) bis- octoate will be presented in more detail, on the example of synthesis of linear and star-like poly( ε-caprolactone)s and polylactides [1-5] as well as poly[(R)-lactide]/poly[(S)-lactide] stereocomplexes [6, 7]. It will be also shown that initiation with aluminum alkoxides that bear bulky, bidendate phenolate-type ligands at the metal atom, results in an efficient suppression of both intra- and intermolecular transesterification [6, 8, 9]. The latter finding enabled preparation of the (S,S )- LA and ε-caprolactone (CL) di- and triblock copolymers via the poly(CL) (PCL) block growth initiation with the living poly[(S,S )-LA] (PLA*) [9]. In the previous attempts to prepare block copolymers this way only random copolyesters were obtained because the PLA* + CL cross-propagation rate was lower than that of the PLA-CL* + PLA transesterification. Finally, it will be revealed that inversion of the initiator configuration may lead to a substantial change of the reactivity ratios [10]. It is a well-known fact that CL homopolymerization rate constant ( kCC ) exceeds considerably that of ( S,S )-LA homopolymerization ( kLL ). For example, in polymerizations initiated with (S)-(+)-2,2’-[1,1’- binaphtyl-2,2’-diylbis-(nitrylomethylidyno)]-diphenolate aluminum isopropoxide (SBO2Al- i O Pr): kCC /kLL ≈ 60 (THF, 80 °C). However, the LA comonomer is consumed first from the CL/( S,S )-LA mixture. The corresponding reactivity ratios are equal to: rL = 322 and rC = 19. The observed phenomena can be explained assuming that the cross-propagation rate constant kLC is relatively low. Change of the initiator configuration, from S to R, results in consumption of both comonomers with a comparable rate ( rL = 1.5 i rC = 1.9).
Keywords: aliphatic polyesters; lactide; ε-caprolactone; living polymerization; star-shaped polymers; stereocomplexes; block copolymers; reactivity ratios; transesterification
______[1] A. Kowalski, J. Libiszowski, A. Duda, S. Penczek, Macromolecules 33, 1964 (2000) . [2] A. Kowalski, J. Libiszowski, T. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38 , 8170 (2005). [3] A. Kowalski, J. Libiszowski, K. Majerska, A. Duda, S. Penczek, Polymer 48 , 3952 (2007). [4] T. Biela, A. Duda, H. Pasch, K. Rode, J. Polym. Sci., Part A: Polym. Chem. , 43 , 6116 (2005). [5] T. Biela, I. Polanczyk, J. Polym. Sci., Part A: Polym. Chem. , 44 , 4214 (2006). [6] A. Duda, K. Majerska, J. Am. Chem. Soc . 126 , 1026 (2004). [7] T. Biela, A. Duda, S. Penczek, Macromolecules 39 , 3710 (2006). [8] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38 , 2027 (2005). [9] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28 , 1385, (2007). [10] M. Florczak, A. Duda, in preparation.
16 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-04 Polylactide-based Materials: from Macro- to Nanocomposites
M. Murariu 1, A. Da Silva Ferreira 1, M. Pluta², M. Alexandre 1, L. Bonnaud 1, and Ph. Dubois 1
1Laboratory of Polymeric and Composite Materials, Materia Nova Research Center & University of Mons-Hainaut, Place du Parc 20, 7000- Mons, Belgium 2Department of Polymer Physics, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
The market for biodegradable polymers is growing every year and important demands can be expected for those applications where biodegradability offers clear advantage for customers and environment. In this context, polylactide (PLA) is undoubtedly one of the most promising candidates; it is not only biodegradable but also produced from renewable resources (sugar beets, corn starch, etc.). Because PLA has been recently considered as alternative in replacing petrochemical polymers, there is a strong demand to enlarge the range of PLA properties. For further applications, the profile of PLA properties and its price can be changed by combining this matrix with different dispersed phases: fillers or reinforcements, (nano)additives, other polymers. Therefore, several types of mineral (nano)fillers (e.g., clays, calcium phosphate, hydroxyapatite, etc.) can be incorporated into PLA in order to obtain (nano)composite materials. For some applications where the property of transparency is not strictly needed, the use of PLA with mineral (micro)fillers can be an interesting solution to reduce the global cost and to improve some specific properties such as rigidity, heat deflection temperature, processability, isotropic shrinkage, etc. In this objective, two products with the same source as origin, i.e., issued from the production and use of lactic acid, PLA and one main byproduct - calcium sulphate, have been first mixed by melt-compounding to prepare new polymer composites. The calcium sulphate microfiller was previously dried during one hour at 500 °C, to isolate the anhydrite II form (AII), which was specifically used for any further melt-compounding processes. Various amounts of AII (10 to 50 wt%) were mixed together with PLA pellets at 190 °C. Interestingly, remarkable AII filler dispersion could be achieved even at high filler loadings resulting in a very good stiffness vs. toughness compromise. Other properties like durability, thermal stability and gas barrier properties have been evaluated as well and proved efficient with respect to the starting unfilled PLA. The thermo-mechanical performances of these novel PLA/gypsum compositions have been further tuned up via the addition of plasticizers, toughening polymeric agents and nanofillers like organo-clays. Indeed, the field of polymer nanocomposites based on clays, such as montmorillonite, has given rise to a steadily increasing interest from scientists and industrials, as the nanoscale distribution of such high aspect ratio fillers brings up some large improvements to the polymer matrix in terms of mechanical, fire retardant, rheological, gas barrier and optical properties, especially at low clay content (as tiny as 1 wt%). As a result, novel ternary formulation, i.e, PLA filled with both AII and selected organo-clays, have been produced by melt blending yielding unequal thermo-mechanical properties, e.g., significantly improved flame retardancy behavior.
Keywords: biodegradable; polyesters; nanocomposites; organoclays; blends.
______M. Murariu, A. Da Silva Ferreira, Ph. Degée, M. Alexandre, Ph. Dubois, Polymer, 48 , 2613 (2007) M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, Ph. Dubois, J. Polym. Sci. B: Polym. Phys., 45 , 2770-2780 (2007) G. Gorrasi, V. Vittoria, M. Murariu, A. Da Silva Ferreira, M. Alexandre, Ph. Dubois, Biomacromolecules, in press (2007)
17 I-05 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Physical Modification of Polylactide
A.Galeski, E.Piorkowska, and M.Pluta
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Lodz, Poland
Light weight and durability, valuable feature of plastics, become serious flaws when they turn to waste: post-consumer polymer packaging degrade slowly and they occupy large space in plastics waste disposal. One of the solutions are biodegradable polymers that are transformed quickly by enzymes into water and carbon dioxide. Most interesting is polylactide (PLA) that can be produced from renewable resources: agricultural products and side products of food production. Potential applications of PLA are: foil packaging, foil fibers, injection mouldings and extruded profiles. Due to a broad range of applications PLA must be subjected to serious modifications in order to accomplish the best performance. Chemical modification is achieved by introducing a fraction of lactide of opposite chirality or by copolymerization with selected biodegradable co-monomers. Simpler and easier way is by physical modification. In our research we explored various means of physical modifications: by thermal treatment, plastification, filling with natural fibrous fillers and particulate mineral fillers, compounding with various organo- modified nanoclays and by molecular orientation resulting from cavity-free plastic deformation [1-10]. The driving force of the investigation was an expected improvement of mechanical and physical properties of PLA and PLA based systems. Plastic deformation in cavity-free manner (channel die) of amorphous copolymer P(L/DL)LA, 70/30 (i.e. unable to crystallize thermally), was studied at the temperature from 60 to 90 oC. Evolution of structure and modification of mechanical properties were investigated as a function of compression ratio. Transformation of amorphous P(L/DL)LA to crystalline texture oriented in the direction of plastic flow without a trace of lamellar structure was clearly detected. Formed crystalites (α crystallographic form) were small up to 9 nm in the transverse direction to the flow, while the crystallinity was not exceeding 9% at highest compression ratios. Significant increase of Tg and few fold increase of tensile strength of 120 MPa as compared to 33 MPa for unoriented PLA. Improvement of deformability of PLA both amorphous and crystalline was achieved by elaborating of a new plasticizer – poly(propylene glycol) (PPG). PPG is soluble in PLA and is not exuded by a crystallizing front of spherulites and remains dissolved in the amorphous phase of PLA. Improvement of deformability depends on the amount of plasticizer and is very effective for amorphous PLA. However, in the case of crystalline PLA PPG is concentrated in the amorphous phase between crystalline lamellae and plasticizes PLA very efficiently: by a decrease of yield stress, an increase of strain at fracture up to 100%, and an increase of tensile impact strength from 36 to 60 kJ/m2 for 10wt.% of plasticizer. Improvement of mechanical properties of crystalline PLA by plastification demonstrated the use of crystalline PLA at o temperature higher than its Tg, up to the melting point of crystals (+160-170 C), i.e. cups for hot drinks, plates for hot food, micro-oven heating etc. Filling PLA with natural fibrous fillers such as hemp fibers, grinded cacao shells, grinded apple pomace, oat chaff and other leads to the increase of tensile modulus. Plasticizing such systems with PPG or poly(ethylene glycol) allows the recovery of drawability. Studies of nanocomposites of PLA with organo-modified nanoclay showed that the dispersion of nanoclay depends on the nature of organo-modification and it is best with Cloisite 30B. Exfoliation of nanoclay can be increased by increasing the mixing time with fixed other compounding parameters. It indicates that the main mechanism of exfoliation is stripping clay
18 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-05 platelets one by one. Nanocomposites were characterized by thermal, rheological, structural and mechanical studies. It was found that the molar mass of PLA decreases during mixing, nevertheless the main parameter influencing the performance of PLA nanocomposites is their phase structure. The best exfoliated PLA nanocomposite showed the best barrier properties for gas diffusion. The barrier properties of PLA nanocomposites are especially important because of possible application of PLA for food and drink packaging. The presented results illustrate a broad range of physical modifications including plastification, molecular orientation, filling with fibrous and particulate natural fillers as well as nanofillers. The role of those factors is extending beyond to interaction during mechanical loading to modification of supermolecular structure and all physical properties of PLA based systems. ______ [1] Z.Kulinski, E.Piorkowska, Polymer, 46, 10290 10300 (2005). [2] A.Gałęski, E.Piórkowska, M.Pluta, Z.Kuliński, R.Masirek, Polimery, 50, 562 569 (2005). [3] Z.Kulinski, E.Piorkowska, K.Gadzinowska, M.Stasiak, Biomacromolecules, 7, 2128 2135 (2006). [4] E.Piorkowska, Z.Kulinski, A.Galeski, R.Masirek, Polymer, 47, 7178 7188 (2006). [5] R.Masirek, E.Piorkowska, A.Galeski, M.Mucha, J.Appl.Polym.Sci. 105, 282–290 (2007). [6] R.Masirek, Z.Kulinski, D.Chionna, E.Piorkowska, M.Pracella, J.Appl.Polym.Sci. 105, 255–268 (2007). [7] M.Kozlowski, R.Masirek, E.Piorkowska and M.Gazicki Lipman, Appl.Polym.Sci. 105, 269–277 (2007). [8] E.Lezak, Z.Kulinski, R.Masirek, E.Piorkowska, M.Pracella, K.Gadzinowska, Composites Polym.Sci,. in print. [9] E.Piórkowska, A.Gałęski, Z.Kuliński, Polish patent application URP, 2006, Nr. P376080, Worls patent application. [10] M.Pluta, A.Galeski, Biomacromolecules, 8, 9 16 (2007). [11] M.Pluta, J Polym Sci Part B:Polym Phys, 44, 392 (2006). [12] M. Pluta, M. Murariu, A. S. Ferreira, M. Alexandre, A.Galeski and Ph. Dubois, J.Polym.Sci. Phys Ed. in print (2007). [13] M. Pluta, J.K. Jeszka, G. Boiteux, Europ.Polym.J. 43, 2819 2835 (2007). [14] Pluta M, Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B Polym.Phys., 44 (2): 299 311, (2006). [15] Pluta M, Polymer , 45 (24): 8239 8251, (2004). [16] Pluta M., Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B Polym.Phys., 44 (2): 312 325, (2006). [17] Galeski A, Piorkowska E, Pluta M, Kulinski Z, Masirek R, Polimery, 50 (7 8): 562 569 (2005). [18] Pluta M, Galeski A, J.Appl.Polym.Sci., 86 (6): 1386 1395, (2002). [19] Pluta M, Galeski A, Alexandre M, Paul MA, Dubois P, J.Appl.Polym.Sci., 86 (6): 1497 1506, (2002).
19 I-06 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 New Biocatalytic Routes to Monomers, Macromers and Polymers Richard A. Gross
NSF I/UCRC for Biocatalysis and Bioprocessing of Macromolecules, Department of Chemical and Biological Sciences; Polytechnic University, Six Metrotech Center, Brooklyn, NY 11201 New and versatile biocatalytic methods were developed that offer mild and efficient options for macromer and polymer synthesis. Lipase B from Candida antartica (CALB), physically immobilized on hydrophobic macroporous resins, is a remarkable catalyst for both ring opening and step condensation reactions. CALB catalysis enabled the synthesis of aliphatic polyolpolyesters and polycarbonates by using a wide range of building blocks including sugar alcohols such as glycerol and sorbitol. Lipase regioselectivity enables direct copolymerizations of polyols with diols and diacids to give non crosslinked high molecular weight materials with controlled branching. The mild reaction conditions (50 to 90 oC) allowed incorporation of chemically and/or thermally sensitive co monomers such as silicones. For example, poly(ester amides) were prepared containing silicone chain segments and carbohydrates were directly linked to silicones (“sweet silicones”), the latter giving materials with interesting surfactant properties. Enzymatic routes to new monomers and their polymerization will also be discussed. For example, fatty acids were transformed by an engineered Candida tropicalis strain to their corresponding α,ω dicarboxylic acids, α carboxyl ω hydroxyl fatty acids, or a mixture of these products. Enzyme catalyzed copolymerizations of these fatty acid derived monomers resulted in new functional copolyesters. Also, sophorolipids were prepared by microbial fermentation of Candida bombicola were converted by metathesis polymerization to functional biomaterials. Cutinases from different micro organisms have been evaluated for polymer synthesis and modification reactions. It was discovered that cutinases also possess impressive catalytic activity for lactone ring opening and diacid/diol polycondensation reactions. In addition to polymer synthesis, cutinases have been revealed that have interesting activities for polymer modification and hydrolysis. As examples, the results of cutinase catalyzed hydrolysis of PET and de acetylation of poly(vinyl acetate) will be presented. Keywords: Enzyme catalysis, lipase, cutinase, polyesters, polycarbonates, immobilization
______ Hunsen, M.; Azim, A.; Mang, H.; Wallner, S. R.; Ronkvist, A.; Xie, W.; Gross, R. A. A Cutinase with Polyester Synthesis Activity. Macromolecules ; 2007 ; 40 (2); 148 150 (2007). Gao, W.; Hagver, R.; Shah, V.; Xie, W.; Gross, R. A.; Ilker, M. F.; Bell, C.; Burke, K. A.; Coughlin, E. B. Glycolipid Polymer Synthesized from Natural Lactonic Sophorolipids by Ring Opening Metathesis Polymerization. Macromolecules ;40 (2); 145 147 ( 2007 ). Hu, J; Gao, W.; Kulshrestha, A.; Gross, R.A. "Sweet polyesters": Lipase catalyzed condensation Polymerizations of alditols, Macromolecules 39 (20): 6789 6792 (2006). Kulshrestha, A. S.; Gao, W.; Gross, R.A. “Glycerol Copolyesters: Control of Branching and Molecular Weight Using a Lipase Catalyst”, Macromolecules , ( 2005 ); 38 (8); 3193 3204. Sahoo, B.; Brandstadt, K. F.; Lane, T. H.; Gross, R. A. “Sweet Silicones": Biocatalytic Reactions to Form Organosilicon Carbohydrate Macromers Org. Lett .; 7(18); 3857 3860 (2005). Mei, Y.; Miller, L.; Gao, W.; Gross, R. A.; Imaging the Distribution and Secondary Structure of Immobilized Enzymes Using Infrared Microspectroscopy Biomacromolecules ; 4(1); 70 74 ( 2003 ).
20 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-07 Modification of Biorelated Macromolecules through Grafting of Short and Long Side Chains
Francesco Ciardelli 1,2 , Simona Bronco 1, Monica Bertoldo 1, Francesca Signori 2, Maria Beatrice Coltelli 3 , and Giovanni Zampano 2
1PolyLab-CNR, Pisa, Italy 2Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126, Pisa 3C.I.P.,Mestre,Venezia Italy
Macromolecules of natural origin are either characterized by a hyprophobicity and low content of polar reactive groups ( as polyesters ) or by a high number of functional hydrogen bonding side chains . In order to improve the possible use of this materials as bioplastics , the chemical modification of the side chains and/or the combination with other macromolecules are highly necessary. Following our previous and current work in the functionalization [1] and blending [2] of polyolefins we are now attempting similar routes for proteins, polysaccharides and polylactic acid to improve their suitability in the development of innovative multiphase materials combining renewability and biodegradability with advanced thermomechanical and functional properties. As far a proteins are concerned we combined an experimental approach [3] with a molecular dynamic modelling [4] to study the modification of molecular and supramolecular structure of Collagen and Gelatine. In the experimental approach gelatine was successfully modified according to different routes namely crosslinking with 1,6 diisocyanatohexane (HDI) [5], side chain binding of hydrophobic florescent groups with 1 naphtylisocyanate (NpI) and grafting of isocyanate terminated polypropylenglycole monobutyl ether chains (PPG). The modified gelatine derivatives showed that the modification procedures all based on the reaction of isocyanate with reactive side chains provides materials with a large variety of water swelling and solubility properties. The controlled modification of cellulose fibres by grafting with a synthetic polymer was also investigated. The first step was the controlled esterification of cellulose fibre surface with α bromoisobutyrylbromide (BIBB), an ATRP initiator. Ethyl acrylate (EA) was grafted polymerised from functionalised cellulose under ATRP conditions with or without the presence of a sacrifical free radical initiator (ethyl α bromoisobutyrate). The adopted polymerisation methods allowed to control grafting degree, grafted polymer chain length and, in perspective, grafted polymer structure, namely random and block copolymers. Finally in case of polylactic acid the number of reactive groups in the original homopolymer was increased by transesterification with citric acid.
______ [1] S. Coiai, E. Passaglia, M. Aglietto, F. Ciardelli, Macromolecules , 37 , 8414 (2004). [2] M. B. Coltelli, M. Angiuli, E. Passaglia, V. Castelvetro, F. Ciardelli, Macromolecules , 39 , 2153 (2006). [3] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules , 38 , 1385 (2005). [4] (a). Bronco, S.; Cappelli, C ,Monti, S. J. Phys. Chem . B , 108, 10101(2004).; (b) Monti,S., Bronco, S.; Cappelli, C J. Phys. Chem . B ,109 ,11389(2005) . [5] M. Bertoldo, S.Bronco, T. Gragnoli, F. Ciardelli, Macromolecular Bioscience , 7, 328 338 (2007).
21 I-08 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Dextran-Based Block Copolymers: Synthesis and Self-Assembly in Solution Clément Houga, Jean-François Lemeins, Redouane Borsali, Daniel Taton, and Yves Gnanou Université BORDEAUX I-ENSCPB-CNRS, Laboratoire de Chimie des Polymères Organiques, 16 Avenue Pey Berland, 33607 PESSAC cedex, France Naturally occurring polysaccharides such as cellulose, dextran, etc… are an abundant source of raw materials that attract an increasing interest due to their biodegradability and renewable character. A convenient and classical means to tailor the physicochemical properties of these natural macromolecules is to modify their backbone by graft copolymerisation. A number of applications have thus been developed from such graft copolymers but seldom as nanodevices or nanosystems. An attractive route to obtain nanostructures with well defined morphologies is to let block copolymers to self assemble in a selective solvent, but the synthesis of polysaccharide based block copolymers has so far presented challenging difficulties. In this work, we describe the first synthesis of dextran b polystyrene diblock copolymers from a dextran based ATRP macroinitiator and the preliminary results of the self assembly of such diblocks in water. Dextran is a highly water soluble polysaccharide composed of α D glucopyranosyl units mainly linked by (1→6) bonds and exhibiting a low degree of branching. The first step in our synthetic endeavor was to introduce an appropriate ATRP site at the anomeric extremity of a 1 commercial dextran of Mn= 6600 g.mol . This terminal anomeric aldehyde was subjected to reductive amination, using a specifically designed coupling agent fitted with ω amino and α tertiary bromide groups. Before growing the polystyrene (PS) block by ATRP from the tertiary bromide ended dextran, the OH groups of the latter were silylated to make it soluble in regular organic solvents. Next, styrene was polymerized from the corresponding silylated dextran based ATRP macroinitiator. ATRP experiments were carried out in toluene using CuBr/PMDETA as catalyst. Five diblock copolymers whose DPn of the PS block ranged from 5 to 775 were synthesized from the same dextran based precursor and characterized by SEC using THF as eluent. Finally, these (silylated dextran) b PS block copolymers were readily desilylated under acidic conditions (Scheme 1), affording the targeted amphiphilic dextran b PS block copolymers. i) Toluene Me3SiO PMDETA HO O CuBr O Me3SiO HO Me3SiO Styrene HO HO Me3SiO O O O Me SiO O ii) HCl HO 3 HO Me3SiO n n O O HO Me3SiO HO OH H OSiMe3 Me3SiO H HO N N Me3SiO N HO Br N Br H Me3SiO H O O Next, the self assembling properties in water of these diblock copolymers were investigated. Block copolymers with the smallest content in PS could be directly dissolved in water at ~90°C. The nanoparticules thus formed adopted a micelle like spherical shape with a diameter of 56
22 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-08 nm, as determined by dynamic light scattering (DLS) and 50 nm from atomic force microscopy (AFM). Samples with larger contents in PS could not be directly transferred in water; they were first dissolved in a DMSO/THF mixture before slowly substituting water for the organic phase, the latter being totally removed by dialysis. For instance, a sample with a 87% content in PS exhibited a vesicular morphology as seen by Transmission Electron Microscopy (TEM). DLS and static light scattering measurements on the same sample afforded a ratio of 1 for Rg/RH, thus confirming the formation of a vesicle. The self-assembly in water of other diblock copolymers led to a variety of stable morphologies (vesicles ovoides, etc.) whose size strongly depended on the overall composition.
23 I-09 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Petro vs. Bio-based Plastics
P. J. Lemstra
Eindhoven University of Technology/Dept SKT, Eindhoven, The Netherlands
Currently, approximately 200 million tonnes of plastics are produced annually, viz. 30 kg/capita in the world. In view of the unbalanced distribution regarding the consumption of plastics, appr. 150 kg/capita in the Western world and Japan, and less than an average of 10 kg/capita in Asia, expectations are running high regarding the future growth of plastics. Some EU studies predict the plastic consumption to grow even by a factor of 10 in the year 2100, viz. 2000 million tonnes/annum!
Plastics are based on oil and currently appr. 5% of the world oil production is used to make plastics. If the consumption of plastics increases in this Century as forecasted by several studies then we might need up to 50% of the current oil production to produce plastics. In view of oil depletion towards the end of this Century, this growth can not be realized based on oil.
Bio-based plastics are promoted as an alternative to replace petro-based plastics and many marketing studies predict that bioplastics will grow with at least 20% per annum. The European Bioplastics society (www.european-bioplastics.org), however, predict a much faster growth, close to 900.000 tonnes/annum by 2010, of which 800.000 tonnes based on bioplastics based on renewable sources (Thermoplastic Starch/TPS, PLA and PHB).
At this point in time, however, one has to conclude that the expectations regarding the growth of bio-based plastics as alternatives for petro-based plastics is below any forecast. The main problem with bio-based polymers is their poor processability, notably of biopolymers which have grown intra-cellular and possess a very high molar mass (to reduce the osmotic pressure) such as PHB and starch, and/or they lack the physical/mechanical properties of synthetic counterparts, viz. PLA vs. PET.
Bio-based plastics might have a growth potential if proper legislation is implemented and but alternative sources to make plastics are also coming up soon, e.g. ethylene derived from bio- ethanol (Braskem) and feedstock (monomers) from gas (Sasol, BP, Shell).
In this lecture, some fact and figures will be presented aiming to forecast the (near) future.
Keywords: petro-based plastics; bio-based polymers; forecast
24 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-10 Injectable Biodegradable Hydrogels for Protein Delivery
C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen
University of Twente, Faculty of Science and Technology, Institute for BioMedical Technology (BMTi), Department of Polymer Chemistry and Biomaterials (PBM), P.O.Box 217, 7500 AE Enschede, The Netherlands
Injectable biodegradable hydrogels that are formed in situ from aqueous polymer solutions under physiological conditions are of particular interest for tissue engineering and protein delivery applications. In situ formed hydrogels provide many advantages. For instance, they allow easy homogenous encapsulation of cells and/or proteins, preparation of complex shapes, as well as minimally invasive implantation. However, current injectable hydrogels often require photo-irradiation, auxiliary crosslinking agents, and/or organic solvents, which may damage the cells or proteins of interest. In the past few years, we have developed several novel types of rapidly in situ forming biodegradable hydrogels.
Stereocomplexed hydrogels . Based on stereocomplex formation between enantiomeric PLLA and PDLA blocks, in situ forming hydrogels have been prepared from eight-arm poly(ethylene glycol)-poly(L-lactide) (PEG-PLLA) and poly(ethylene glycol)-poly(D-lactide) (PEG-PDLA) star block copolymers, wherein the gelation time (from instantaneous to 1 h) and storage modulus (up to 14 kPa in PBS at 37 °C) were shown to depend on PLA block length and polymer concentration [1, 2]. These stereocomplexed hydrogels have been used for in vitro and in vivo protein release [3, 4].
Michael addition hydrogels . Highly elastic hydrogels were rapidly formed in situ under physiological conditions by Michael type addition upon mixing aqueous solutions of dextran- vinyl sulfone (dex-VS) and multi-functional PEG-SH at a concentration of 10 to 20 w/v% [5]. These dextran hydrogels have a low initial swelling and are degradable under physiological conditions with degradation time varying from 3 to 21 days depending on the DS, concentration, dextran molecular weight and PEG-SH functionality. Dextran hydrogels with slower degradation (degradation time ranging from 3 to over 21 weeks) could be obtained from thiol functionalized dextran (dex-SH) and PEG tetra-acrylate [6].
Enzymatic hydrogels . Dextran-tyramine (Dex-TA) conjugates have been designed to prepare hydrogels via enzymatic oxidative crosslinking [7]. Interestingly, hydrogels were rapidly formed under physiological conditions from Dex-TA at or above a concentration of 2.5 wt% in the presence of H 2O2 and horseradish peroxidase (HRP). The swelling/degradation studies showed that under physiological conditions, Dex-TA hydrogels are rather stable with less than 25% loss of gel weight in 5 months. Hydrogels with faster degradation could be achieved by linking tyramine to dextran via an ester group.
Keywords: hydrogels, biodegradable, drug delivery systems
______[1] C. Hiemstra et al., Macromol. Symp. , 224 , 119 (2005). [2] C. Hiemstra et al., J. Biomacromolecules 7, 2790 (2006). [3] C. Hiemstra et al., J. Control. Release , 116 , e19 (2006). [4] C. Hiemstra et al., J. Control. Release , 119 , 320 (2007). [5] C. Hiemstra et al., Macromolecules , 40, 1165 (2007). [6] C. Hiemstra et al., J. Biomacromolecules , 8, 1548 (2007). [7] R. Jin et al., J. Biomaterials , 28 , 2791 (2007).
25 I-11 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polyether- Polyester Conjugates for Biodegradable Hydrophilic Microgels and Hyperbranched Polymers
Helmut Keul, Marc Hans, Michael Erberich, Jörg Meyer, and Martin Moeller
Institute of Technical and Macromolecular Chemistry, RWTH Aachen, and DWI an der RWTH Aachen e.V., Pauwelsstr. 8, D-52056 Aachen, Germany
Anionic polymerization of protected glycidols with mono- and multifunctional initiators results in polymers with linear, graft, or star-shaped architectures. Removal of the protection groups leads to polyglycidols which are used as multifunctional macroinitiators for the ring opening polymerization of ε-caprolactone. Core-shell polymers with a hydrophilic polyether core and a hydrophobic polyester shell are obtained. These amphiphilic core shell polymers are able to encapsulate guest molecules or catalytically active hydrophilic species. In this respect, polyether-polyester conjugates are attractive materials for drug delivery systems, because of the biodegradability of the polyester arm building blocks and the biocompatibility of the polyether core. Regarding biomedical applications increasing interest has been devoted to enzyme catalyzed polymerization of lactones. In this respect, a comparison between chemical and enzymatic catalysis using multifunctional macroinitiators for the ring opening polymerization of ε-caprolactone was performed.[1] Polyglycidols with two orthogonal protective groups were obtained via anionic ring- opening copolymerization of allyl glycidyl ether (AGE), tert. butyl glycidyl ether ( tBuGE), and ethoxyethyl glycidyl ether (EEGE). Poly(AGE-co -tBuGE), poly(AGE-co -EEGE), and poly(EEGE-co -tBuGE) were obtained with controlled degree of polymerization, narrow molecular weight distribution and a predetermined ratio of repeating units. The following conversions were achieved by selective removal of only one protection group: using aqueous hydrochloric acid, poly(AGE-co -EEGE) was converted to poly(AGE-co -GE); using trifluoroacetic acid, poly(AGE-co -tBuGE) was converted to poly(AGE-co -glycidyl trifluoroacetate); and by using Pd/C and p-toluene sulfonic acid poly(AGE-co -tBuGE) was converted to poly(GE-co -tBuGE). A selective removal of only one protection group from poly(EEGE-co -tBuGE) was not possible.[2] Free hydroxymethyl groups of the polymers were partially converted in a polymer analogous reaction to give multifunctional polyglycidols or by using bifunctional reagents to result in amphiphilic microgels.
R2O HO
O selective deprotection O O O m+n m+n
OR1 OR1
P(tBuGE)-co-P(AGE): R1 = -C(CH3)3; R2 = -CH2-CH=CH2 P(tBuGE)-co-P(EEGE): R1 = -C(CH3)3; R2 = -CH(CH3)-O-CH2CH3 co P(AGE)- -P(EEGE): R1 = -CH2-CH=CH2; R2 = -CH(CH3)-O-CH2CH3 Keywords: biodegradable polymers; chemical and enzymatic ring-opening polymerization, grafting from ______[1] M. Hans, P. Gasteier, H. Keul, M. Moeller, Macromolecules 39, 3184 (2006). [2] M. Erberich, H. Keul, M. Moeller, Macromolecules 40, 3070 (2007).
26 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-12 Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock vs their Counterparts from Renewable Resources
Emo Chiellini
INSTM Unit - Department of Chemistry and Industrial Chemistry, University of Pisa, via Risorgimento 35, 56126 Pisa, Italy BIOlab, via Vecchia Livornese 1291, 56122 Loc. S. Piero a Grado (Pi)
Synthetic and semisynthetic polymeric materials were originally developed for their durability and resistance to all forms of degradation as promoted by physical, chemical and biological means or combinations therefrom. Special performances are achieved in relevant items produced under conditions guaranteeing for the maintenance of molecular weight and functionality of the raw polymeric materials both during processing and under service conditions. The polymeric materials had been and are currently widely accepted because of their ease of processability and amenability to provide a large variety of cost effective items that helped enhance the comfort and quality of life both in modern industrial society and in developing countries. However all those good features, that make the polymeric materials so convenient and useful to the human life and societal needs, have contributed to create a serious plastic waste burden sometime exageratedly amplified by mass media and public opinionists. On the other hand future expectations for polymeric materials demand in the next two decades are in favour of two to three fold increase in production as a consequence of the increase of the plastic consumption in developing countries and countries in transition. The design, production and consumption of polymeric materials for commodity and specialty plastic items have certainly to face all the constraints and regulations already in place or to be issued in the near future, dealing with the management of primary and post-consume plastic waste. In this respect the formulation of environmentally sound degradable polymeric materials and relevant plastic items will constitute a key option among those available for the management of primary and post-consume plastic waste. The technologies based on the recovery of free energy content through recycling, including also the energy recovery by incineration will be flanked by the increasing option of environmentally degradable polymeric materials and plastics. These should be entitled to replace the conventional commodity plastics in those segments in which recycling is difficult and labour-intensive with hence an heavy penalisation on the cost-performance of the “recycled’ items. Moreover one has to take into account the downgrading of the original material properties occurring both during the service life of the items as well as during their reprocessing stages once they enter the post-consume rank. The strategies that are nowadays receiving a considerable deal of attention both at fundamental and applied level imply design of new biobased polymeric materials, introduction of hybrid polymeric formulations and revisiting and reengineering well-consolidated polymeric materials of synthetic and natural origin. In this connection the present contribution is aimed at providing an outline of the polymeric materials consisting of macromolecules characterized by a full carbon as well as an heteronuclear backbone. Whilst the latter are included into the class of hydro-biodegradable systems, the former in order to be converted to oxo-biodegradable systems need to be eventually reengineered to polymer grades susceptible to controlled and modulated environmental oxidation followed by fragmentation and then ultimately by biodegradation to carbon dioxide, water and cell biomass under aerobic conditions. Case studies specifically focused on polyvinyl alcohol (as a water soluble thermoplastic) and oxo-biodegradable polyethylene (as a water-insoluble thermoplastic) will be presented in comparison to hydro-biodegradable counterparts.
27 I-13 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polyhydroxyalkanoates (PHAs): Biodegradable Polyesters from Agricultural Waste and Surplus Material
G. Braunegg , A. Atlic, M. Koller, and C. Kutschera
Graz University of Technology, Institute of Biotechnology and Biochemical Engineering, 8010Graz, Petersgasse 12, Austria
Polyhydroxyalkanoates (PHAs) are biodegradable polyesters that are stored intracellular in granules when growth of the producing bacteria is limited by essential nutritional compounds like the nitrogen or phosphate source of the growth and production medium [1]. Under such conditions the PHA content in the cells can increase to more than 80% of the cell dry weight formed, and the quality of the polyesters stored can be influenced by feeding precursors for synthesis of copolyesters or terpolyesters. A drawback for this development is the fact that in most cases production costs for PHAs are still higher than costs for conventional resins. Biotechnological polymer production occurs in aerobic processes, therefore only about 50% of the main carbon sources, and even a lower percentage of the precursors used for production of co-polyesters end up in the products wanted. To overcome this problem, cheap carbon and nitrogen sources for microbial growth and PHA synthesis are needed to lower the production costs. Such sources are available as agricultural waste and surplus materials, for example lactose in cheese-whey or glycerol liquid phase (GLP) from the biodiesel production process to be used as a cheap carbon source (Fig. 1), or meat and bone meal (MBM) to be used as nitrogen source after hydrolysis [2]. Based on these renewable resources new technologies for polymer production can be developed, integrating the principles of “Cleaner Production” and “Life Cycle Analysis” into the strategies for process design [3].
a b 16 2 25 25 14 1,8 1,6 20 20 12 1,4 15 15 10 1,2 8 1 10 10 6 0,8 0,6 [g/L] 3-PHV Glycerol[g/L] 4 5 5 0,4 Protein,PHA [g/L] PHA, 3-PHB [g/L] 3-PHB PHA, 2 0,2 0 0 0 0 0 24 48 72 96 120 144 168 0 24 48 72 96 120 144 168 Time [h] Time [h]
Figure 1: Production of poly-(3HB-co -3HV) from glycerol liquid phase (GLP) with Haloferax mediterranei . (a) Patterns of glycerol, protein and PHA; (b) polyester formation during the process
Keywords: polyhydroxyalkanoates; sustainable production; waste materials
______[1] G. Braunegg, G. Lefebvre, K.F. Genser, J. Biotechnol. 65 , 127 (1998). [2] M. Koller, G. Braunegg, R. Bona, C. Herrmann, P. Horvat, J. Martinz, J. Neto, L. Pereira, M. Kroutil, P. Varila, Biomacromolecules 6, 561 (2005). [3] G. Braunegg, R. Bona, M. Koller, Polymer-Plastics Technology and Engineering 43 , 1779 (2004).
28 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-14 (Bio)degradation of Polymeric Materials Containing PHA and their Synthetic Analogues Marek M. Kowalczuk Polish Academy of Sciences, Centre of Polymer and Carbon Materials, 34 M. Curie-Skłodowska St, 41-800 Zabrze, Poland Anionic ring opening polymerization (ROP) of β butyrolactone (the monomer which could be obtained using synthetic gas derived from coal or waste biomass gasification) has been reported over twenty years ago.[1] The polymer chain growth proceeds regio selectively and stereo selectively entirely via carboxylate anions. Propagation on carboxylate active centers (much less sensitive to impurities than any other anionic species) enables scaling up the anionic ROP process of β butyrolactone to atactic poly[(R,S) 3 hydroxybutyrate] (a PHB), a synthetic amorphous analog of n PHB. Synthetic a PHB undergoes heterogeneous enzymatic attack (by PHB depolymerse) in the presence of second crystalline polymer which can be in form of component of binary blend or block in a PHB containing block copolymer. Moreover, the heterogeneous enzymatic hydrolysis of a PHB occurred both when the crystalline component was itself susceptible to enzymatic attack as well as when it was non biodegradable by the PHB depolymerase employed. The enzymatic degradation of a PHB can be induced also by its blending with amorphous polymers with high glass transition temperature, e.g. atactic poly(L,D lactic acid). The plain a PHB could be degraded to the mixture of monomer, dimer and trimer in the presence of PHA depolymerases purified from Paucimonas lemoignei ( PhaZ7 ) as well as Acidovorax Sp. TP4 ( PhaZ aci ).[2, 3] Review of innovative results concerned with (bio)degradation of atactic PHB will be presented. Novel results concerned with evaluation of the environmental degradation of polyester blends containing a PHB will be discussed.[4] Moreover, the ability to control thermal degradation and stability of a PHB as well as of its blends via concentration of the carboxylate polymer end groups will be demonstrated.[5] Acknowledgement. This research was supported by Eureka E! 3420 project and by Marie Curie Transfer of Knowledge Fellowships of the European Community’s Sixth Framework Programme under the contract number MTKD CT 2004 509232.
Keywords: biodegradable polymers; atactic poly(3 hydroxybutyrate) ______ [1] Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651 1656; [2] Handrick, R.; Reinhardt, S.; Focarete, M.L.; Scandola, M.; Adamus, G.; Kowalczuk, M.; Jendrossek, D. J. Biol. Chem. 2001, 276, 36215 36224. [3] Wang, Y.; Inagawa, Y.; Osanai, Y.; Kasuya, K.; Saito, T.; Matsumura, S.; Doi, Y.; Inoue, Y. Biomacromolecules 2002, 3, 894 898. [4] Rychter, P.; Biczak, R.; Herman, B.; Smylla, A.; Kurcok, P.; Adamus, G.; Kowalczuk, M. Biomacromolecules 2006, 7, 3125 3131. [5] Kawalec, M.; Adamus, G.; Kurcok, P.; Kowalczuk, M.; Foltran, I.; Focarete, M. L.; Scandola, M. Biomacromolecules 2007, 8, 1053 1058.
29 I-15 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Novel Biodegradable Polymers and Scaffolds for Tissue Engineering
Y. Chen, R. Dersch, M. Gensheimer, U. Bourdiot, S. Agarwal, J.H.Wendorff, and A. Greiner
Philipps-University Marburg, Department of Chemistry and Scientific Center for Materials Science, Hans-Meerwein-Str., D-35032 Marburg, Germany
Biodegradable polymers are important for subcutane medical applications such as drug delivery, implants, suture materials, and tissue engineering. For bone tissue engineering new biodegradable polymers with excellent mechanical properties may be required as well as special scaffold design.
Here we will present new synthetic routes to new biodegradable polyesters and their invitro degradation behaviour [1-7]. Speciality scaffold design based on electrospun polylactide nanofibers [8] will be reported as well as their compatibility to mesenchym stem cells for applications in tissue engineering [9]. Bacteria containing electrospun nanofibers will be reported as a potentially new biohybrid material for applications in tissue engineering [10].
Acknowledgements The authors are indebted to Deutsche Forschungsgemeinschaft for financial support.
Keywords: tissue engineering; bioresorbable polymers; biocompatibility, nanofibers, electrospinning ______[1] G. Haderlein, H. Petersen, C. Schmidt, J. H. Wendorff, A. Schaper, D. B. Jones, J. Visjager, P. Smith, A. Greiner; Macromol. Chem. Phys. 200 , 2080 (1999) [2] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Chem. Mater. 15 , 694 (2003) [3] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Biomacromolecules 4, 974 (2003) [4] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Polymer 44 , 5513-5520 (2003) [5] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Chem Mater. 15 , 694(2003). [6] L. Ren, S. Agarwal, Macromol. Chem. Phys., 2007, 208, 245. [7] S. Agarwal, Polymer J ., 2006, 39, 163. [8] Greiner, J. H. Wendorff, Angew. Chem., Int. Ed. 46 , 5670 (2007). [9] U. Boudriot, R. Dersch, A. Greiner, J. H. Wendorff, Artificial Organs 30 , 785 (2006). [10] M. Gensheimer, M. Becker, Astrid Brandis-Heep, J. H. Wendorff, R. K. Thauer, A. Greiner, Adv. Mat. 19 , 2480 (2007).
30 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-16 Novel Photosensitizers Based on Polysaccharides
Maria Nowakowska , Krzysztof Szczubiałka, Szczepan Zapotoczny, and Łukasz Moczek
Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Ingardena 3, Poland
There is a growing interest in the development of novel polymeric photosensitizers. Because of the environmental concerns the possibility of using the systems based on natural polymers is considered. We have chosen polysaccharides as the most abundant natural polymers in biosphere. They have a lot of advantages; they are cheap, can be easily modified and are biodegradable. Polysaccharides such as cellulose, dextran, starch and chitosan were modified by covalent attachment of required chromophores: naphthalene, anthracene, Rose Bengal, porphyrin and chlorophyll [1-7] The lecture describes the synthesis, characterization, photophysical/photochemical properties of these photosensitizers as well as their potential applications. All the photosensitizers are soluble in water. Due to the presence of hydrophobic substituents, the modified polysaccharide chains adopted a pseudomicellar conformation in the aqueous solutions allowing an efficient solubilization of hydrophobic compounds sparingly soluble in water. The obtained photosensitizers absorb light from the near UV-visible spectral region, including solar light. Photophysical studies demonstrated that the attachment of the chromophores to the polymeric chain does not influence considerably their properties. The aggregation of chromophores is limited while the efficiency of the energy migration is high and the energy transfer to the suitable acceptors is efficient. It was found that these photosensitizers can induce various photochemical reactions. The mechanisms of these processes are dependent on the type of chromophore present in the system and the type of reactant. Two main mechanisms of the primary photochemical process were identified and utilized in our studies: the photoinduced electron transfer from the electronically excited chromophores of the photosensitizer to the reactant (molecule of organic compound and/or oxygen) and energy transfer to the molecule of reactant (molecule of organic compound and/or oxygen). These processes result in the formation of very reactive species such as radical-ions, hydroxyl radicals or singlet oxygen which induce secondary photochemical reactions. It was demonstrated that the photosensitizers based on polysaccharides can induce the oxidation of pollutants and toxins present in water such as polynuclear aromatics, chlorinated organic compounds, cyanides, or pesticides. Finally, the fate of the photosensitizers after their prolonged irradiation in aqueous solution was studied. It was found that they undergo slow photo-assisted degradation.
Keywords: photosensitizers, polysaccharides, pollutants
______[1] M. Nowakowska, M. Sterzel, K. Szczubiałka, J. E. Guillet, Macromol.Rapid Commun. , 23 , 972 (2002). [2] M. Nowakowska, S. Zapotoczny, M. Sterzel, E. Kot, Biomacromolecules 5, 1009 (2004). [3] M. Nowakowska, M. Sterzel, S. Zapotoczny, Photochem.Photobiol . 81 , 1227 (2005). [4] M. Nowakowska, M. Sterzel, S. Zapotoczny, E. Kot, Appl.Catal. B: Environ. 57 , 1 (2005). [5] M. Nowakowska, M. Sterzel, K. Szczubiałka, J.Polym.Environ. 14 , 59 (2006). [6] Ł. Moczek, M. Nowakowska, Biomacromolecules 8, 433 (2007). [7] M. Nowakowska, Ł. Moczek, unpublished results .
31 I-17 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 The Polarized Light-induced Enzymatic Formation and Degradation of Biopolymers
Anna Molenda-Konieczny, Maciej Fiedorowicz, and Piotr Tomasik Departament of Chemistry, Agricultural University, Balicka Street, 122, 30-149 Cracow, Poland It has been reported [1] that moonlight stimulated decomposition of polysaccharides in plants. That phenomenon was interpreted [2] in terms of the activation of hydrolases with polarized light of the moon. Subsequent studies [3 7] showed that white, linearly polarized light decomposes starch, provided starch is crystalline. Definitely, no enzymes were involved in that process. Initially, side branches of amylopectin undergo scission followed by repolymerization of resulting short chains into linear amylose like polysaccharide. Studies with polarized color light [8] showed that red light stimulated depolymerization whereas green light stimulated repolymerization. Independently, focus on effect of the polarized light upon enzymatic reactions of polysaccharides resulted in interesting discoveries. Thus, white, linearly polarized light activated α amylolysis of starch [9], hydrolysis of xylane with xylanase [10], hydrolysis of chitin with chitinase and chitosan with chitosanase [11], hydrolysis of cellulose with cellulase [12], and interestingly influenced production of cyclodextrins with cyclodextrin glycosyltransferase [13]. Effect of duration of illumination of cyclodextrin glucosyltransferase with polarized light had certain effect upon the yield and isomer ration of three isomeric cyclodextrins. Application of the polarized light required 1 2 hour illumination of the enzymes in a small reaction vessel followed by admixture of so activated enzymes to a bioreactor. Further reaction did not require any illumination. These studies are under development.
Keywords: chitin; chitosan; cyclodextrins, starch; ______ [1] E.S. Semmens, Nature 159 , 613 (1947). [2] A.E. Navez, B.B. Rubenstein, J. Biol. Chem . 80 , 503 (1928). [3] M. Fiedorowicz, P. Tomasik, C.Y. Lii, Carbohydr. Polym . 45 , 75 (2001). [4] M. Fiedorowicz, C.Y. Lii, P. Tomasik, Carbohydr Polym . 50, 57 (2002). [5] M. Fiedorowicz, K. Rębilas, Carbohydr. Polym. 50 , 315 (2002). [6] M. Fiedorowicz, G. Khachatryan, J. Sci. Food Agric. 84 , 36 (2004). [7] M. Fiedorowicz, G. Khachatryan, V.P. Yuryev, L.A. Wasserman, From starch containing sources to isolation of starches and their applications , Eds: V.P. Yurev, H. Ruck, P. Tomasik, Nova Science Publishers, New York, 2004, ISBN:1 59454 014 4. [8] H. Staroszczyk, M. Fiedorowicz, P. Janas, P. Tomasik, Polimery 52 (11 12), 63 (2007). [9] M. Fiedorowicz, G. Khachatryan, J. Agric. Food. Chem . 51 , 7815 (2003). [10] [M. Fiedorowicz, A. Konieczna Molenda, V.M.F. Lai, P. Tomasik, in preparation. [11] [M. Fiedorowicz, A. Konieczna Molenda, W. Zhong, P. Tomasik, Carbohydr. Res. submitted. [12] [A. Konieczna Molenda, Macromol. Symp.. accepted. [13] [M. Fiedorowicz, A.Konieczna Molenda, G. Khachatryan, P. Tomasik Polish Patent, Appl. P 379950 (2006).
32 ABSTRACTS OF POSTER CONTRIBUTIONS
33 P-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Biodegradation of Polyester Nanocomposites
Agnieszka Piegat and Miroslawa El Fray
Szczecin University of Technology, Polymer Institute, Division of Biomaterials and Microbiological Technologies, ul. Pulaskiego 10, 70-322 Szczecin
Poly(ethylene terephthalate) (PET) is a thermoplastic polyester widely used in fibres and packing industry. PET is known as a material resistant to hydrolysis, therefore several modifications have been made with the aim to render PET biodegradation. One of commercially produced aliphatic-aromatic copolyester of PET is Biomax® [1]. This material is fully biodegradable under composting conditions, because of the copolymerization of PET with poly(lactic acid) (PLA), a common polymer from renewable resources. Other modifiers of such origin are poly(glycolic acid) (PGA), poly(3-hydroxybutyrate) (PHB) [2], polysaccharides like starch or cellulose [3]. Another group of biodegradable monomers from renewable resources are dimer fatty acids, e.g. dilinoleic acid (DLA), obtained by dimerization of unsaturated fatty acids derived from vegetable oils. This group of monomers is widely used as modifier for polyurethanes, adhesives but also for thermoplastic elastomers (TPE), where they form the soft phase. Their chemical and physical properties can be tuned by the soft/hard segments ratio. For PET/DLA copolymers, higher susceptibility to degradation was observed for copolymers with higher amount of DLA soft segments [5]. In this work, we report on PET modification with DLA and TiO 2 nanoparticles. Such physical modification with nanoparticles enhances not only mechanical properties, but also controls the degradation profile [6]. The addition of ceramic components is already know as an effective modification with the aim to obtain more controlled degradation conditions of polymer/ceramic composites. Such solution was already applied for biodegradable poly(L,L- lactide-co-glycolide) (PLGA), where addition of tricalcium phosphate reduced acidity of degradation products and changed hydrophilicity of the material, what had strong influence on the porosity of obtained scaffolds [7]. PET/DLA copolymers containing TiO 2 nanoparticles (0.2 and 0.4 wt%) were degraded in PBS for 6 months. TiO2 nanoparticles incorporated into copolymer matrix demonstrated a strong influence on such properties as: absorption, crystallinity and molecular weight of composites. The decrease in Mn after 6 months was 68.8% for the neat PET/DLA copolymer, whereas only 41% for the same copolymer containing 0.2 wt% TiO 2 and 55% for this one containing 0.4 wt% TiO 2. Changes of thermal properties for PET/DLA were mainly observed in the hard segments region, showing decrease of melting temperature from 130.6 to 102.4˚C. The melting temperature of nanocomposites decreased by 6˚C and 18.4˚C for 0.2 and 0.4 wt% TiO 2 nanoparicles, respectively. Also the absorption level was highest for copolymer without TiO 2 nanoparticles. These results confirm that both DLA and TiO 2 nanoparticles are effective modifiers of PET enabling preparation of materials with controlled mechanical properties and degradation time.
Acknowledgements: This work was partially financed from research project 3T08E03628.
Keywords: biodegradation, polymer/ceramic nanocomposites, PET modification ______[1] V. Nagarajan, M. Singh, H. Kane, M. Khalili, M. Bramucci, J Polym Environ 281 , 14 (2007) [2] D. Kint, S. Munoz-Guerra, Polym Int , 1999, 48 , 346 [3] B.G. Girija, R.R.N. Sailaja, Giridhar Madras, Polym Degr Stability 147, 90 (2005) [4] M. El Fray, Nanostructured Elastomeric Biomaterials for Soft Tissue Reconstruction, Publishing House of the Warsaw University of Technology, Warszawa 2003, 1-144 [5] A. Piegat, M. El Fray, Polimery , in press [6] M. El Fray, A.R. Boccaccini. Materials Letters, 2300 , 59 (2005) [7] F. Yang, W. Cui, Z. Xiong, L. Liu, J. Bei, S. Wang, Polym Degr Stability 3065 , 91 (2006)
34 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-02 ESI-MS Studies of Slow-release Conjugate of 2,4-D with a-PHB for Agricultural Applications
P. Rychter 1, G. Adamus 2, and M. M. Kowalczuk 1,2
1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University of Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 Polish Academy of Sciences, Centre of Polymer and Carbon Materials 34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland Depending on the natural conditions, only about 10% of the applied agrochemicals reach their objectives. This process leads to undesirable side effects causing increase of the active agent concentration levels in surrounding environment. From the point of view of public health, application of hazardous pesticides in agriculture should be limited. Biodegradable polymers to be used as a matrix for agrochemicals may constitute one of the possible way to solve this problem. The advantages of control release of agricultural chemical systems are prolongation of action of such agrochemicals (by providing continuous, low amounts of biocides maintaining appropriate dosage for the desired period of time), decrease of cost and pollution [1,2]. In this communication the results concerned with synthesis of conjugate of selected herbicide i.e. 2,4 dichlorophenoxyacetic acid (2,4 D) covalently bounded with atactic oligo[(R,S) 3 hydroxybutyrate] will be demonstrated. Herbicide 2,4 D belongs to the phenoxyacetic acids group of pesticides and is one of the most common and widely used for control of broad leafed weeds and grasses in plantation crops such as sugar cane, oil palm and weeds along highways. As previously reported, poly([R,S] 3 hydroxybutyrate) as well as its degradation products are non toxic for natural environment [3]. Moreover, [R,S] 3 hydroxybutyric acid oligomers are biocompatible and can be potentially applied to formulation of chemical conjugates for delivery of active agent, improving its taken up by cells in vitro [4]. The ring opening anionic polymerization of [R,S] β butyrolactone initiated with activated 2,4 dichlorophenoxyacetic acid salts as well as [R,S] β butyrolactone oligomerization induced by 2,4 D have been selected as methods of synthesis of 2,4 D oligo 3 hydroksybutyrate conjugates. Evaluation of the subtle structure of the conjugates obtained, based on sequencing of individual macromolecular ions with the aid of ion trap multistage mass spectrometry (ESI MS n), will be presented. Keywords: slow release formulations; biodegradable polymers; biocides ______ [1] J. Zhao, R.M. Wilkins, J. Agric. Food Chem. 53 , 4076 (2005) [2] M.G. Mogul, H. Akin, N. Hasirci, D.J. Trantolo, J.D. Gresser, D.L. Wise, Resources, Conservation and Recycling 16 , 289 (1996) [3] P. Rychter, R. Biczak, B. Herman, A. Smylla, P. Kurcok, G. Adamus, M. Kowalczuk, Biomacromolecules 7, 3125 (2006) [4] V. Piddubnyak, P. Kurcok, A. Matuszowicz, M. Glowala M., A. Fiszer Kieszkowska, Z. Jedliński, M. Juzwa, Z. Krawczyk, Biomaterials 25 , 5271 (2004)
35 P-03 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polymer-inorganic Hybrid Materials for Tissue Engineering
Pawel Wozniak, Stanislaw Sosnowski, and Stanislaw Slomkowski
Centre of Molecular and Macromolecular Studies, Polish Academy of Science, Sienkiewicza 112, 90-363 Lodz, Poland
There is a great interest in manufacturing objects with surface properties adaptable to environment (e.g. exposing hydrophilic or hydrophobic surface elements to hydrophilic or hydrophobic exterior). Such properties are very desirable in fabrication of scaffolds for tissue engineering. Since we are interested in scaffolds for hard tissue building cells our efforts were concentrated on modification of silica and glass (nanosilica and model glass plates) in a way allowing changes of their interfacial hydrophilic/hydrophobic properties in contact with hydrophilic or hydrophobic liquids. The mentioned above nanosilica has been used as a filler increasing mechanical strength of polymer scaffolds made from polylactide and poly(lactide- co -glycolide). Modification of silica and of glass plates was did consist of grafting 3-glycidoxypropyl trimethoxysilane (GPS) onto silica (reaction with hydroxyl groups on silica surface). In this way epoxide groups were introduced. The next step included grafting of biocompatibile polymers. Living poly(ethylene oxide) was grafted onto silica in reaction with epoxide groups. Active centers created in this way initiated polymerization of lactide. In result hydrophilic poly(ethylene oxide) and hydrophobic poly(L-cactide) chains were tethered to the surface. Depending on hydrophilicity of the liquid being in contact with modified silica the hydrophilic or hydrophobic chains were in expanded conformation. The resulting materials were characterized by photoelectron spectroscopy, wetting angle measurements and (in case of nanosilica) by 13 C CP MAS NMR. Mechanical properties of poly(L-lactide) and poly(lactide-co -glycolide) with modified silica fillers were investigated.
Schematic illustration of modification of silica surface.
Keywords: silica; (3-glycidoxypropyl)trimethoxysilane; surface modification; poly(ethylene oxide); poly(L- lactide)
Financial support of BIOMAT project and Ministry of Science and Higher Education is acknowledged.
36 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-04 Biodegradable Hydrogels Based on Poly(vinyl alcohol) graft [poly(D,L lactide)/poly(D,L lactide co glycolide)]
Elvira Vidović 1, Doris Klee 2, and Hartwig Höcker 2
1Faculty of Chemical Engineering and Technology, University of Zagreb, 10000 Zagreb, Croatia 2Department of Textile and Macromolecular Chemistry, RWTH Aachen, 52056 Aachen, Germany
In this work a synthetic procedure is described towards a class of poly(vinyl alcohol)-graft - [poly(D,L-lactide)/poly(D,L-lactide-co -glycolide)] copolymers which are sensitive to hydro- lysis and therefore can be used for the development of controllably biodegradable hydrogels. Poly(D,L-lactide) and poly(D,L-lactide-co -glycolide) with various composition were obtained by reacting 2-hydroxyethyl methacrylate with D,L-lactide or glycolide dimers, followed by the transformation of the terminal hydroxyl group into carboxylate with the assistance of succinic anhydride. Coupling of those polyesters (PES) onto poly(vinyl alcohol) (PVA) was performed via the carboxylate group in dimethyl sulfoxide using N,N-carbonyldiimidazole. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator [1,2]. The resulting copolymers, in the course O O R z O of synthesis, were characterized with O O respect to their molar composition by O O O 1 q-z n means of H NMR spectra. Furthermore, O R O OH p polymer networks were detected and O O C studied qualitatively by means of IR AIBN R = H or CH 3 o CH 3 50 C spectroscopy. The influence of the glyco- lide content in the polyester grafts and of the number of ester units in the grafts on PVA backbone thermal behavior and swellability were studied, as well as surface properties of hydrogels. Differential scanning calori- PES graft chain metry showed a single glass transition crosslinking site temperature that occurs in the range between 51 °C and 69 °C indicating the absence of phase separation. Thermogravimetry analysis of the networks showed the main loss in weight in the temperature range between 290 °C and 370 °C. The high swellability in water is characteristic of all hydrogels. Hydrophilicity, an important property of hydrogels relevant to their biomedical applications, was identified by the captive-bubble contact angle method. Hydrogels display the values of contact angle between 37 and 45 ° which are significantly higher in comparison with the polylactide sample (57°).
Keywords: biodegradable hydrogels; poly(vinyl alcohol); poly(D,L-lactide); poly(D,L-lactide-co -glycolide); swellability; thermal properties; contact angle ______[1] C.R. Nuttelman, S.M. Henry, K.S. Anseth, Biomaterials 23, 3617 (2002). [2] E. Vidovic, Dissertation , RWTH-Aachen, Germany (2006).
37 P-05 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Fabrication of Honeycomb-Structured Polylactide and Poly(lactide-co - glycolide) Films and their Use for Osteoblast-Like Cell Culture
Julian B. Chardhuri 1, Matthew G. Davidson 2, Marianne J. Ellis 1, Matthew D. Jones 2, and Xujun Wu 1, 2
1Centre for Regenerative Medicine, Department of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7AY 2Department of Chemistry, University of Bath, Claverton Down, Bath, UK, BA2 7AY
Biodegradable polymers have been widely applied in tissue engineering and drug delivery systems [1,2]. Recently, honeycomb-structured thin films have been reported to be good candicates as scaffolds for cell culture [3]. In the present study, polylactide (PLA) and poly(lactide-co -glycolide) [PLGA] were used to prepare honeycomb-structured thin films by using a water droplet templating method. The influence factors on pattern formation, such as solvents, humidity and ethanol sterilization were investigated. To study cell attachment and proliferation on honeycomb-structured films, MG63 osteoblastic-like cell lines were cultured. Cellular responses on PLA and PLGA with various compositions are discussed.
Keywords : honeycomb-structured film; Water droplet template; Polylactide; Poly(lactide-co -glycolide); Tissue engineering ______[1] Langer, R. and Vacanti, J. P. Science, 1993. 260 (5110): p. 920-926. [2] Srivastava, R. K., Albertsson, A.-C. Biomacromolecules, 2006, 7, p. 2531-2538. [3] Fukuhira, Y., Kitazon, E., Hayashi, T., Kaneko, H., Tanaka, M., Shimomura, M., Sumi, Y., Biomaterials, 2006. 27 (9): p. 1797-1802.
38 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-06 Bark Suberin as a Renewable Source of Long chain ω Hydroxyalkanoic Acids Helena Nilsson, Ann Olsson, Mikael Lindström, and Tommy Iversen STFI-Packforsk AB, Box 5604, SE-114 86 Stockholm, Sweden Production of paper pulp and timber results in by product streams of which some have potential commodity values. One example is bark, a low value by product today mainly used for energy production. The outer bark of birch species in northern Europe contain about 30% of the natural aliphatic polyester suberin [1]. cis 9,10 Epoxy 18 hydroxyoctadecanoic acid (1) is the principal monomer comprising about 100 g/kg dry outer bark in Betula verrucosa . This epoxy acid, together with straight chain even numbered C 16 – C 24 ω hydroxy fatty acids, can be isolated in high yield from alkali hydrolyzed birch outer bark, by extraction followed by selective precipitation by acidification. Lipase catalyzed polymerizations may sometimes allow straightforward synthesis strategies for polyesters from sensitive monomers that do not survive more conventional polymerization catalysts and this has, for example, been used for the preparation of polyesters from epoxy containing monomers. In this study we report polycondensations of cis 9,10 epoxy 18 hydroxyoctadecanoic ( 1) acid isolated from birch outer bark using immobilized Candida antarctica lipase B (Novozyme 435) as catalyst. The polycondensation performed in both toluene and bulk gave the polyester ( 2) with fairly high molecular weights. For example, a M w of 15 000 was obtained after 3 hours reaction time (Mw/M n 2.2) by bulk polymerization in an open vial without any drying agent present. O HO COOH (CH2)8 (CH2)7 1
O O O
HO CO (O CO)n O COOH (CH2)8 (CH2)7 (CH2)8 (CH2)7 (CH2)8 (CH2)7
2
39 P-07 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Studied on Electrical Conducting Biopolymer-poly(thiazole) Copolymers
Ashutosh Tiwari 1 and A. P. Mishra 2
1National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India 2Department of Science and Technology, Technology Bhawan, New Maharauli Road, New Delhi –110 016, India
Water-soluble, biodegradable and electrical conducting copolymer of arabinogalactan- poly(thiazole) was synthesized by adopting oxidative-radical polymerization method. UV-vis and FTIR spectra were used to characterize the resulting copolymer. Electrical conductivity and biodegradable behavior of copolymer was studied and optimized the composition to get appropriate material for technological applications as varying concentration of thiazole (THA), pH of the material and temperature. The electrical conductivity of the copolymer was physically regulated via varying pH and temperature and could have interesting features on these effects, as are semiconductors. Therefore materials have potential application for the biosensor especially for the specific detection of microorganisms and hazardous gases. Moreover, conducting biopolymer-based materials could be usefully exploited as multifunctional electronic materials for technological applications. The materials might be of great importance in the fabricating various sensor devices for in vivo and in vitro applications.
Keywords: arabinogalactan-polythiazole copolymer; electrical conductivity; biodegradability
Fig. Co-polymerization of biopolymers with synthetic polymer
40 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-08 Antibacterial Activity of Cationic Starch-iodine Derivatives
Algirdas Zemaitatitis, Rima Klimaviciute, and Rasa Kavaliauskaite
Kaunas University of Technology, Radvilenu 19, Kaunas LT-50524, Lithuania Different compounds, such as phenol, halogen or derivatives of aldehydes, as well as quaternary ammonium salts exhibit bactericidal properties and are used as disinfectants. It is known, that cationic polymers with quaternary ammonium groups have higher antimicrobial activity than corresponding low molecular weight compounds. Starch is a valuable material for the production of cationic polysaccharides because of its high chemical activity and peculiarities of structure. For this reason considerable efforts are now being made in the research and development of modified polysaccharides as the basic material for new applications. The aim of this study was to synthesize cationic (CS) or cross linked cationic (CCS) starch chlorides and their iodine derivatives and to examine their antimicrobial activity. CS or CCS with preserved micro granules, the degree of substitution from 0.2 to 0.6 and the reaction efficiency from 82% to 93% might be obtained during catalytically etherification of starch or cross linked starch with a 2,3 epoxypropyltrimethylammonium chloride. In the ion exchange reaction with inorganic iodide in water, CS or CCS chloride (CSCl or CCSCl) was converted to CS or CCS iodide (CSI or CCSI). The chemical analysis confirmed that iodide substituted for at least 95% of chloride counter ions. In aqueous solutions having KI, cationic starches rapidly bind iodine and form polymer– iodine complexes. Investigations of iodine binding by different cationic starches at equilibrium showed that starches with quaternary ammonium groups were able to bind about 300 wt % of iodine from I 2 KI solution and form complexes CSI I m or CCSI I m, where m ≤ 4. Maximum two molecules of iodine could be incorporated , i.e., polymeric complexes of pentaiodide could be formed. The stability of cationic starch–iodine complexes depended on the quantity of involved iodine. Cationic starch triiodides ( CSI I 2 or CCSI I 2) were the most stable complexes. The antibacterial activity of different starch derivatives against Enterococcus faecalis, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella typhimurium, Staphylococcus aureus, Escherichia coli, Lysteria monocytogenes was studied by measuring the inhibition zone diameter (agar diffusion plate test). It was found, that the diameter of inhibition zone depended on both the counter ion of CS or CCS and examined microorganisms. In general, cationic starches were bacteriostatic rather than bactericidal. The studied cationic starches can be arranged in the following order according to their increasing antibacterial activity: CCSI < CCSCl ≤ CSCl. However, cationic starch–iodine complexes were the most effective and showed an excellent prolonged antibacterial activity. CCSI I 2 obtained from CCS with DS>0.2 were bactericides and 0,1 mg/mL of them killed 100% of E. Coli . The higher activity of cationic starch–iodine complexes has been interpreted in terms of their stability in water at the presence of iodine acceptors.
Keywords: highly cationic starch; cationic starch iodine complexes; antibacterial activity
41 P-09 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Chitosan-co -polyaniline/WO 3.nH 2O Nanocomposites: Green Polymer Composite for Sensor Applications
Ashutosh Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra
National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India
A monodispersed WO 3.nH 2O nanoparticles embedded chitosan-co -polyaniline have been prepared by one pot chemical precursor method. UV-visible, FTIR XRD and SEM analytical tools were used to confirm the formation of nanocomposite. The composition of WO 3.nH 2O precursor to chitosan-co -polyaniline was tailored in order to develop materials of controlled electrical conductivity. The electrical conductivity of the chitosan-co - polyaniline/ WO 3.nH 2O was stimulated with the exposure of HCl and NH 3. Under controlled conditions, hybrid material showed electrical conductivity in the range of 6.82 X 10 -4 Scm -1 at room temperature. The intercalations of cationic biopolymer based electrically conducting copolymer apart with layered nanostructured inorganic solids provide multifunctional nature, which have combined significant special features towards thermal-mechanical stability, biocompatibility, solubility, porosity and redox surface property. Layered conducting biopolymer based host could be interesting regarded as an alternative to obtain eco-friendly interlayer transition metal oxide bio-nanocomposites for technological applications.
co co Chitosan- -polyaniline WO 3.nH 2O Chitosan- -polyaniline/WO 3.nH 2O
Figure: Layered structure of Chitosan-co -polyaniline/ WO 3.nH 2O nanocomposite
Keywords: chitosan-co -polyaniline, WO 3.nH 2O nanocomposites, electrical conductivity, green polymer composite, sensor applications
42 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-10 Chemical Modification of Starch with Hexamethylene Diisocyanate Amide Derivatives
Katarzyna Wilpiszewska, Stanislawa Spychaj, and Tadeusz Spychaj
Polymer Institute, Szczecin University of Technology, ul. Pulaskiego 10, 70-322 Szczecin, Poland
The growing interest in materials from renewable resources is observed [1]. Starch is a biodegradable and easily available biopolymer. In Europe 45% of its total production is used for nonfood applications (mostly paper industry) [2]. However, starch plastics are not widely used because of some drawbacks, like: brittleness or sensitivity to water [3]. Chemical modification of starch could, at least partially, prevent mentioned problems. Recently paper describing synthesis of urethane and urea derivatives of hexamethylene diisocyanate (HMDI) and their usage for starch chemical modification has been published [4]. Preparing starch plastics is in fact achieving a compromise between a few contradictory features, such as: degree of substitution, level of hydrophobisation, susceptibility to biodegradation, and melt flow features. In this contribution chemical modification of potato starch with amide derivatives of HMDI in a two-step process has been presented. At the first stage starch modifiers, i.e. isocyanate amide derivatives were synthesised in the equimolar reaction between HMDI and monocarboxylic acids, containing 2 to 18 carbon atoms in alkyl chain. HMDI was used as it is relatively environmentally friendly [5]. FTIR spectra of the obtained HMDI derivatives revealed the presence of bands for NCO, in the range of ~2300 cm -1 and amide groups at ca. 1700 cm -1. At the second step the starch was modified with the synthesised HMDI derivatives, in N-methylpyrrolidone (NMP) slurry. Some properties of the obtained starch polymers were investigated and compared, i.e. efficiency of substitution, IR spectra, hydrophobic/hydrophilic features, rheometric characteristics in temperature range up to 200°C, as well as moldability (hot press melt flow). Physicochemical properties of starch products depend greatly on degree of substitution and alkyl chain length attached. The influence of the alkyl chain length attached to polysaccharide as well as degree of substitution on some physicochemical and thermal properties were evaluated. The hydrophilic/hydrophobic properties of the modified starches evaluated by the measurement of their swelling indices in water were compared.
Keywords: thermoplastic starch; chemical modification of starch; urethane-amide starch derivatives ______[1] Fakirov, S. & Bhattachatyya, S., Ed. Handbook of engineering biopolymers: homopolymers, blends, and composites. Munich, Hanser Verlag (2007). [2] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27 , 67 (2004). [3] G. Engelmann, E. Bonatz, I. Bechthold, G. Rafler. Starch , 53 , 560 (2001). [4] K. Wilpiszewska, T. Spychaj. Carboh. Polym. doi:10.1016/j.carbopol.2007.04.023 (2007). [5] T. Ohkita, S. Lee. J. Adh. Sci. Technol. 18, 905 (2004).
43 P-11 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Starch Plasticisation via Twin-screw Extrusion
Katarzyna Wilpiszewska and Tadeusz Spychaj
Polymer Institute, Szczecin University of Technology, ul. Pulaskiego 10, 70-322 Szczecin, Poland
The growing interest in materials from renewable resources is observed. Starch is potentially useful material for technical uses because of its biodegradability, availability and relatively low cost. In Europe 45% of total starch production is used for nonfood applications (mostly for paper industry) [1]. Granular starch cannot be processed with conventional technologies because its melting point (T m = 220-240°C) and T g are higher than its degradation temperature (ca. 220°C) – it degrades before melting [2]. The addition of plasticiser (commonly used glycerol) decreases Tg of starch, preventing its decomposition [3]. Moreover, the kind of plasticiser influences the mechanical and thermal properties of starch material [4]. Extrusion is the most widespread method for producing thermoplastic starch. In this contribution the preliminary results of starch twin-screw extrusion with ε-caprolactam in the presence of glycerol with water admixture has been presented. Some microorganisms could utilise ε-caprolactam as the sole source of carbon, nitrogen and energy [5]. The extruded mixture contained: 9 – 17 wt. % ε-caprolactam, 11- 47 wt. % glycerol (with water admixture) and 40-70 wt. % starch. The main processing parameters, i.e. temperature regime, rotational speed as well as die pressure were changed. Their effect on extrusion operating as well as extruded product is discussed. Some properties of obtained starch products were investigated and compared, i.e. hydrophobic/hydrophilic features and elongation at break. Water uptake of extruded starch materials depends greatly on polysaccharide content and rises with its increase. For comparison starch extruding with glycerol itself has been also performed. The influence of starch/plasticizers content in the system on the water uptake and mechanical properties was evaluated. Comparison of plasticised starch extrudates containing 70 wt. % of starch and 30 wt. % of plasticiser(s) shows that material with ca. 18 wt. % ε-caprolactam and 11 wt. % glycerol + 1 wt. % water swells in water up to 270 % whereas starch plasticised with 30 wt. % glycerol (no water addition) up to 140 %. The probable reason for this finding is both the presence of additional water as well as amide bond in the lactam ring.
Keywords: thermoplastic starch; starch extrusion; starch plasticisation ______[1] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27 , 67 (2004). [2] T. Czigany, G. Romhany, J.G. Kovacs. Chapter 3 in: Fakirov, S. & Bhattachatyya, S., Ed. Handbook of engineering biopolymers: homopolymers, blends, and composites. Munich, Hanser Verlag, pp. 81-108 (2007). [3] S.H.D. Hulleman, F.H.P. Janssen, H.Feil. Polymer , 39 , 2043 (1998). [4] K. Wilpiszewska, T. Spychaj. Polimery , 51 , 325 (2006). [5] C.C. Wang, C.M. Lee. J. Hazard. Mat. 145 , 136 (2007).
44 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-12 Study of Interpolymeric Complexes Based on Polymers from Renewable Sources
Catalina Duncianu and Cornelia Vasile
„Petru Poni” Institute of Macromolecular Chemistry, 41 A, Gr.Ghica Voda Alley, 700487, Iasi, Romania
The hydrogen-bonded interpolymeric complexes (IPC) have attracted great interest due to their unique physical and chemical properties in comparison with pure components and their wide applications in pharmaceutics as drug delivery carriers. Intermacromolecular interactions via hydrogen bonds between a natural, renewable, non-toxic polymer e.g. alginic acid (AgA) and syntethic polymers e.g. polyethyleneglycol (PEG), poly (N-isopropyl acrylamide) (PNIPAM), polyacrylamide (PAM) in diluted and semi-diluted solutions were investigated by means of viscometry, potentiometry and conductometry. Thermodynamic functions have been evaluated. It has been established that the alginic acid at a pH = 4 forms interpolymeric complexes with all three synthetic polymers but their strengths vary with chemical structure and temperature.
Keywords: interpolymeric complexes, alginic acid, polyethyleneglycol, poly (N-isopropyl acrylamide), polyacrylamide,
45 P-13 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Homopolymerization and Copolymerization of L, L-Lactide in Presence of Novel Zinc Proline Organocmetallic Catalyst
A. Pandey and B. Garnaik
Polymer Science and Engineering Division, National Chemical Laboratory, Pune 411008, India
Poly (L, L-lactide) (PLA) and its copolymers from renewable resources have been studied extensively because of their vast potential applications in many fields. Ring-opening polymerization (ROP) of L, L-lactide to form poly (L, L-lactide) s by single-site metal alkoxide precursors has attracted considerable recent attention since the properties of PLA are determined by molecular weight, molecular weight distribution, and most importantly by its microstructure analysis. Many metal complexes such as Al, Li, Mg, Fe, Sn, and Zn etc. have been used as initiators/catalysts for ring opening polymerization (ROP) of cyclic esters [1-2]. However, in many cases, backbiting reaction/transesterification take place as side reactions, resulting in the formation of macrocycles with a wide range of molecular weight distribution. Using a bulky legands (both isomers of L- and D-proline ) coordinatively attached with active metal center (zinc) and provided an asteric barrier for prevention of undesired side reactions and minimized the undesired backbiting/transesterification reactions. The homopolymerization of (L, L-lactide) and copolymerization by using PEG as macroinitiator were conducted in presence of zinc proline catalyst. The kinetic and thermodynamic parameters of ROP of L, L-lactide using zinc proline were studied. Polylactides were characterized by various techniques such as GPC, DSC, FT IR, NMR, XRD and MALDI ToF etc. The configurational sequence determination of PLA polymers were carried out by 13 C NMR quantitative analysis and compared by 13 CP/MAS NMR. The results of ROP of L, L- lactide using zinc proline ( L- and D-proline) will be highlighted .
13 Figure 1. C NMR (500 MHz) of polylactide(CDCl 3)
Keywords : renewable resources; zinc proline; polylactide; configurational sequence
______[1] K. S. Fun, B. Teo, S.G. Teoh, K. Chinnakali, Acta Crystallog. C51 , 244 (1995). [2] Bradley M. Chamberlain, Ming. Cheng, David. R. Moore, Tina. M. Ovitt, B. Emil Lobkovsky, Geoffrey W. Coate, J.C.A.S . 123, 3229 (2001).
46 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-14 Poly(lactic acid) Microcapsules Containing Bioactive Molecules: Study of Activity
F. Faÿ, I. Linossier, and K. Vallée-Réhel
Laboratoire de Biotechnologie et Chimie Marines EA 3884, Université de Bretagne-Sud, BP92116, 56321 Lorient cedex, France
In order to prevent the development of marine biofilm on immersed surfaces, it is required to conceive preventing systems. Actually, this is realized by the blending of poly(methylmethacrylate-co-butylmethacrylate) resins (PMMA-PBMA) with two types of biocides : an organic biocide used in agriculture (herbicides, pesticides) and a mineral biocide such as cuprous oxide. However, due to severe environmental degradations, the use of toxic molecules and non degradable polymers is questioned. These concerns have created a considerable interest to produce a new generation of protective systems based on biodegradable polymers [1,2] and non toxics molecules. Two essential properties have been clearly identified as discriminating factors of antifouling efficiency: erosion which is controlled by biodegradable polymer such as polyester or poly(ester-anhydride) and presence of biocides at the coating surface during immersion [3]. In this work, two active molecules were studied. The first is a bactericide molecule, called chlorhexidine. Chlorhexidine is a bisdiguanide antiseptic widely used in dentistry as an anti- plaque agent and has demonstrated good antibacterial activity against a wide range of bacteria. The second is a quorum sensing autoinducer for the bacterial cell-to-cell communication (furanone). However, previous works are shown that hydrosoluble molecules were too rapidly released. These characteristics implicate their microencapsulation. In a first part, this study presents i) the encapsulation of a commercial furanone (tetronic acid) and chlorhexidine by using biodegradable polymer (PLA), prepared by the water-in-oil-in- water solvent evaporation method ; ii) their characterization for their size, morphology and encapsulation efficiency : imaging of the particles was performed by scanning electron (SEM) and confocal laser microscopies (CLSM) ; iii) their incorporation in paint formulation. The second part reports the influence of encapsulation : i) on biocide release determined by EDX analysis and UV-spectrometry ; ii) on the growth, adhesion and viability of several marine bacteria.
Keywords : PLA, encapsulation, antifouling ______[1] F.Faÿ, I. Linossier, V. Langlois, E. Renard, K. Vallée-Réhel, Biomacromolecules . 7, 857 (2006). [2] F. Faÿ, I. Linossier, V. Langlois, K. Vallée-Rehel, Biomacromolecules . 8, 1751 (2007). [3] M. Thouvenin, J.J. Peron, C. Charreteur, Ph. Guerin, J.Y. Langlois, K. Vallee-Rehel, Prog. Org. Coat ., 44 , 75 (2002).
47 P-15 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Degradation Study of Polymers from Renewable Resources and their Blends in Industrial Composting Pile
W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk
Centre of Polymer and Carbon Materials, M.C.-Skłodowskiej 34, 41-819 Zabrze, Poland
New trends in solid waste management and rapid changes in public legislation made scientist in increase activities on the design of new generation of biodegradable polymers as important biomaterials for environmental, biomedical and pharmaceutical applications [1, 2]. For the last few years, intensive research and development of new materials for packaging has been also observed [3]. The most commercially available plastics are non-degradable and their recycling is not feasible economically in many cases due to the deterioration of mechanical properties and excessive cost. Selective use of biodegradable packaging materials in certain applications may provide a solution to the above-mentioned environmental problems. Polyesters, produced from renewable resources and susceptible to hydrolysis under the industrial composting conditions offer ecological advantages as compared to thermoplastics polymers and elastomers produced from fossil carbon sources [4]. Additionally, traditional packing waste needs to have the PE it is coated with removed in the repulping process during the recycling in paper-mill. In the paper the results of degradation behavior of polymer blends of a-PHB, poly[(D,L)-lactide] and additionally BTA in natural environment such as industrial composting pile, consisting of leaves - 40%, branches - 30% and grass - 30%, have been presented. The macroscopic observations of surface changes, the weight loss, changes of molecular weight, polydispersity and composition of the tested materials were monitored during experiments performed. The obtained results revealed that the investigated blends was degradable in the industrial compost pile and in this environment the hydrolytic degradation was occurred. Moreover the biodegradable polyesters systems are promised materials, which can be use as paper coatings for multilayer packaging materials.
This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD-CT-2004-509232. The financial support of Polish Ministry of Science and Higher Education: R&D project no. R05 055 02 is also acknowledged.
Keywords: renewable resources; biodegradable polymers; industrial composting pile
______[1] Biodegradable Plastics: North America, Europe, Asia, Market-Technology Report PO119, New York, 2001. [2] B. Kessler and B. Witholt, Macromol. Symp . 130 , 245 (1998). [3] M. Kowalczuk, Plastic Review , 4(26) , 48 (2003). [4] G. Adamus, P. Dacko, M. Musioł, W. Sikorska, M. Sobota, R. Biczak, B. Herman, P. Rychter, K. Krasowska, M. Rutkowska, M. Kowalczuk, Polimery , 51 , 539 (2006).
48 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-16 Polyurethanes from Renewable Resources as Candidates for Friendly Environment New Materials
D. Macocinschi, D. Filip, and S. Vlad
“Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania
Because of the importance of biomaterials in medical applications, their development has been a long-term area of research and has become one of the principal challenges to polymer scientists. In the present study new types of polyurethane-cellulose derivative biomaterials based on urethane prepolymers functionalized with hydroxypropylcellulose are presented. In the literature are reported studies on materials with better haemocompatibility, biocompatibility and amphiphilic microphase-separated domain structures [1-4]. Few biodegradable elastomers have been synthesized, and new materials are required to meet the need for an increasingly diverse range of physical properties. It is worthy of note that block- polyurethanes based on cellulose derivatives were found to be biodegradable and haemocompatibles. Biodegradable elastomers are expected to be suitable for any application requiring the use of a flexible, elastic material, such as soft tissue engineering. The remarkable chemical versatility characteristic to polyurethane materials combined with polymers derived from nature like cellulose derivatives resulting in bulk and surface properties is evidenced by means of different techniques like DSC, TGA, FT-IR, AFM, mechanical tensile tests. The influence of various factors on the developed morphologies and the microstructural changes is investigated. Both polyester and polyether macrodiols have been used to prepare these polyurethanes. The aim of this study is to find also alternative methods for improving biostability while maintaining the excellent biocompatibility and other properties. In these applications a balance between the surface hydrophilic and hydrophobic qualities is essential for achieving enhanced bioproperties.
Keywords : renewable resources; biodegradable polyurethanes; morphology.
______[1]. T. Hanada, Yu-J. Li, T. Nakaya , Macromol. Chem. Phys. , 202 , 97 (2001). [2] A. Vaidya, M. K. Chaudhury, J.Colloid Interf. Sci. , 249 , 235 (2002) [3] R. W. Thring, M.N. Vanderlaan, S. L. Griffin, Biomass Bioenerg, 13 , 125 (1997). [4] You-X. Wang, J. L. Robertson, W. B. Spillman Jr., R. O. Claus , Pharm Res 21 , 1362 (2004).
49 P-17 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Viscoelastic and Thermal Proprieties of the Biodegradable Polymer Materials Containing Polylactide, Aliphatic Aromatic Polyester and Synthetic Poly[(R,S) 3 hydroxybutyrate] Received via Injection Moulding
P. Dacko 1, M. Sobota 1, H. Janeczek 1, J. Dzwonkowski2, J. Gołębiewski 2, and M. M. Kowalczuk 1 1Centre of Polymer and Carbon Materials, 41 819 Zabrze, Poland 2Institute for Plastics Processing METALCHEM, PL 87 100 Toruń, Poland
The injection moulding is one of most important technologies in the processing of plastics and of biodegradable polymer materials. In this method the material is plastified to the viscous flow state in the plastifying system and then introduced under pressure to the form, where it solidifies or hardens at the change of the temperature. The influence of temperature and pressure during the process on plastics, especially on polymer compositions, can make essential structural changes of initial components and consequently seriously influence on proprieties of final materials. The main goal this work was to examine the viscoelastic and thermal proprieties of biodegradable polymer materials containing the amorphous poly lactide (PLA b), aliphatic aromatic copolyester of terephthalic and adipic acids and butanediol (BTA), and synthetic poly[(R,S) 3 hydroxybutyrate] (a PHB), received via injection moulding The a PHB (Mn = 6000, IP = 1,3) was synthesized by bulk polymerization of (R,S) – β butyrolactone at room temperature, using tetrabutylammonium acetate as the initiator [1]. The BTA ( Mn =34000, Mw/Mn = 2,1) was obtained from BASF, and the PLA b (GALASTIC, PABR L 68, 12 % D( ) content units, Mn = 53000, Mw/Mn = 2,7) obtained from Galactic S.A. Both polymers were used as received. Results, obtained by means of DMTA and DSC showed that polymer compositions received from PLA b and BTA mixtures via injection moulding are two phase systems. This suggestion is confirmed by presence of two maxima on the temperature dependence of the mechanical loss coefficient tg δ (DMTA) and two glass transition temperatures Tg 1 in the negative area of temperatures and Tg2 – in the positive area of temperatures (DSC). It is characteristic that BTA and PLA b mixtures show values of Tg 1 lower than for pure BTA (Tg = 25,6 °C) in spite that Tg of PLA b amounts 52,9 °C. Values of Tg 2 practically do not change with the PLA b content change in the composition. DSC data show that maximum degree of compatibility becomes visible at the weight ratio BTA/PLA b equal 50/50. PLA b mixtures with containing a small amount of a PHB (5% and 10%) create compositions that show one glass transition temperature, and this is confirmed by presence of single peaks on the temperature dependence of tg δ. The introduction of a PHB to BTA/PLA b mixtures leads to enlarged compatibility of components and to improving of their mechanical proprieties.
This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD CT 2004 509232. The financial support of Polish Ministry of Science and Higher Education: R&D project no. R05 055 02 is also acknowledged.
Keywords: biodegradable polymer materials, compatibility, mechanical properties
______ [1] Kurcok P., Śmiga M., Jedliński Z . J. Polym. Sci. Polym. Chem. 40 , 2184 (2002).
50 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-18 Biodegradation of Blown Films Based on Polylactide Acid in Natural Conditions
Vladimir Sedlarik 1, Nabanita Saha 1, Jana Bobalova 2, and Petr Saha 1
1 Polymer Centre, Faculty of Technology, Tomas Bata University in Zlin, Nam. T. G. Masaryka 275, 76272 Zlin, Czech Republic 2 Innovation Centre, University Institute, Tomas Bata University in Zlin, Mostni 5139, 76001 Zlin, Czech Republic
The environmental pollution by non degradable plastic waste attracts attention to the development of biodegradable polymers made from renewable resources [1]. Polylactic acid (PLA) is polymer which fulfills these conditions. [1]. In the environment it can be degraded within less than two years in contrast to conventional plastics such as PE or PS [2]. Nowadays, the development of PLA based materials is commercially available in applications including medical items production or compostable packaging. In this work, we deal with the assessment of biodegradation course of blown film base of PLA in composting environment. The main attention is paid to mechanical properties of investigated samples and their changes during the time of biodegradation. Beside that, mass loss, and observation of structural changes of PLA films are the subsequent aims of this paper. The material investigated in this work is commercially available polymeric blend of PLA and biodegradable co polyester Bioflex® 219F, density 1380 kg.m 3, melting point 155°C, softening temperature Vicat A 72°C. The film preparation was performed on mono extrusion blown moulding machine at the temperature range of 170 175°C. The L/D ration was 26. The thickness of resulting film was about 45 µm. The rectangular shape specimens were cut off the film and introduced into the composting environment. The composting conditions were kept in accordance to the standard ČSN EN ISO 14855. The total time of biodegradation assessment was 6 weeks. The influence of microbial attack on mechanical properties, physico chemical structure, mass loss and surface morphology was studied weekly. The results obtained during 6 weeks of composting indicate relatively good accessibility to biological degradation. Figure 1 shows the macroscopic surface changes of the blown films after 6 weeks of the testing. The interesting results were also found in the course of mechanical, thermal and physico chemical properties and mass loss, which will be presented at the conference in detail. (a) (b) Figure 1: Optical micrographs of PLA based blown film before (a) and after 6 weeks (b) of composting Keywords: biodegradable polyester; composting; mechanical properties; blown films Authors are grateful to the Ministry of Education, Youth and Sports of the Czech Republic for financial support (Grant No. MSM7088352101 and 1PO5ME736). ______ [1] L. Chen, X. Qui, M. Deng, Z. Hong, R. Luo, X. Chen, X. Jing, Polymer 46 , 5723 (2005). [2] M. Pluta, Polymer 45 , 8239 (2004).
51 P-19 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Molecular Modification of Gelatine by Reaction with Isocyanates
Monica Bertoldo 1, Federica Cognigni 2, Francesca Signori 2, Simona Bronco 1, and Francesco Ciardelli 1,2
1PolyLab-CNR, via Risorgimento 35, 56126 Pisa, Italy 2Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126, Pisa, Italy
Gelatine is a very common denaturated protein of collagen widely available at low cost [1]. Its chain is formed by various aminoacid residues, some of which bearing nucleophyl groups, which can react with isocyanates. In addition, the amide groups of the protein main chain are polarizable groups and are expected to catalyze urethane and urea group formation[2]. Several mono- and di- isocyanate derivatives were used to study the reaction of modification of gelatine to obtain structurally modified derivatives for biomedical, adhesive, paint, photographic and films. In this work gelatine was successfully modified according to different routes namely crosslinking with 1,6-diisocyanatohexane (HDI), side chain binding of hydrophobic florescent groups with 1-naphtylisocyanate (NpI) and grafting of isocyanate terminated polypropylenglycole monobutyl ether chains (PPG). Dimethylsulfoxide was used as reaction solvent as, to our knowledge, is the only solvent that dissolves gelatine but does not react with isocyanates under mild conditions. HDI and NpI were commercial products, whereas the terminal isocyanate derivative of PPG (PPG-NCO) was synthesized in this project. The preparative reaction was carried out with an excess of PPG in order to minimize the amount of unreacted HDI which was then removed by evaporation under reduced pressure at 70°C. Gelatine was then reacted with different amount of HDI, NpI or PPG-NCO in DMSO at 40°C. Isocyanate species went to a non detectable concentration after raction times of the order of minutes as evidenced by FT-IR analysis of the reaction mixtures. Therefore, the presence of somewhat autocatalytic effect on the reaction environment seemed to be confirmed. In the case of NpI, the occurring of a quantitative bonding of naphtyl groups to gelatine was assessed by UV-Vis spectroscopy analysis through the well detectable adsorption band of the naphtyl group. A calibration performed with propyl 1-naphthylcarbamate allowed to quantify the bonding yields, which could be modulated to a considerable extent on the bassi of the reactive components molar ratios . Modified gelatine showed a reduced hydrophilic character with respect to the pristine proteineven if modulable solubility: in particular NpI modified gelatine is swallable but not soluble, whereas gelatin-g-PPG is more soluble then the the pristine protein.. The three modification procedures all based on the reaction of isocyanate functionality with recative side chains of gelatine provide useful route to biopolymer based materials with a large variety of water swelling and solubility properties. ______[1] B. Brodsky, J. A. Werkmeister, J. A. M. Ramshaw, in Biopolymers, (Polyamides and Complex Proteinaceous Materials II), A. Steinbuchel, Ed. Wiley-VCH Verlag GmbH, Weinheim, Germany, 2003 , Vol. 8, 119-147. [2] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules 2005, 38(4), 1385-1394 [3] M. Bertoldo, S. Bronco, T. Gragnoli, F. Ciardelli, Macromol. Biosci . in press.2007
52 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-20 Biodegradable and Compostable PLA-based Formulations to Replace Plastic Disposable Commodities
M.-B. Coltelli 1, F. Signori 2, C. Toncelli 3, C. Escrig Rondán 4, S. Bronco 3, and F. Ciardelli 2,3
1Centro Italiano Packaging and DCCI; 2 DCCI-Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35-I-56126 Pisa, Italy ; 3CNR-INFM- PolyLAB Pisa and DCCI ; 4AIMPLAS, C/ Gustave Eiffel, 4 València Parc Tecnològic, 46980 Paterna-Valencia, Spain
For several traditional applications, in particular those related to agriculture and fresh food packing, the use of a 100 % biodegradable plastics could represent a convenient alternative to polyolefin based materials. In this perspective, poly(lactic acid) (PLA), (a biodegradable linear aliphatic polyester), is receiving much attention thanks to its peculiar thermomechanical behavior, which makes it a possible polypropylene substitute, and its availability from renewable resources. However, standard grade PLA presents high E- modulus (E-Mod: 2.5-3.0 GPa) and high brittleness (elongation at break < 5%). Although the copolymerization of lactides with various cyclic monomers resulted highly effective in the reduction of PLA brittleness, blending of PLA (hard component) with low molecular weight additives [1] or elastomeric-like polymers [2] (soft component) appears a more sustainable approach to tailor the properties of the final material. In this framework, our work has been focusing on the preparation and the characterization of binary PLA-based blends, where poly(butylene adipate-co -terephtalate) (PBAT), a commercially available biodegradable polyester, was selected as the soft component. Process conditions were firstly assessed, and then thermal, rheological and mechanical behavior of the prepared blends in all the composition range were investigated, in search of a composition with properties similar to those of standard poly(propylene) (PP). Among the prepared blends, those richer in PLA showed more suitable properties, mainly in terms of E-Mod and elongation at break (EaB). Remarkably, we identified a promising PLA-based formulation to obtain a 100 % biodegradable PP-like material. The fine tailoring of the mechanical parameters, especially in terms of E-Mod and EaB, required to better mimic target PP behavior, was carried out by means of different reactive blending approaches, in order to improve PLA/PBAT phase compatibility by the promotion of PLA-PBAT block or graft copolymer synthesis during the blending process. The PLA-PBAT block or graft copolymers are meant to dislocate at the PLA/PBAT interfaces, thanks to their structure which combine features of the two homopolymers, thus lowering the interfacial tension. Two approaches were investigated, e.g. the use of a transesterification catalyst and the radical promoted grafting reaction. Indeed, the transesterification catalyst was expected to produce macromolecules containing random distributed short and long segments from PLA and PBAT, while the use of a peroxide initiator was expected to provide some inter-chains grafting extension to a branched macromolecular structure containing very long PLA and PBAT segments. Note that the addition of increasing amount of a non toxic, biodegradable low molecular weight plasticizer as third component to the selected blend was investigated, to further tailor mechanical performances. The obtained results indicate that the followed approaches were successful to generate PLA-based biodegradable polymeric blends fitting a wide spectrum of thermomechanical characteristics.
Keywords: PLA; biodegradable polymer blends; reactive blending ______[1] I. Pillin, N. Montrelay, Y. Grohens Polymer 47 , 4676 (2006) . [2] L. Jiang, M. P. Wolcott, J. Zhang, Biomacromolecules 7, 199 (2006).
53 P-21 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Mass Spectrometry Studies of Cyclic Esters Ring Opening Oligomerization in the Presence of Disperse Red 1
C. Peptu 1, V. Harabagiu 2, B.C. Simionescu 2, G. Adamus 3, and M. M. Kowalczuk 1,3
1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University of Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 "Petru Poni" Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, 700487 Iasi, Romania 3 Polish Academy of Sciences, Centre of Polymer and Carbon Materials, 34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland Azobenzene containing polymers are used as polymeric dyes, molecular probes, electrooptic liquid crystals, and materials for nonlinear optics and optical storage [1]. One of their major commercial applications is the preparation of ophthalmic lenses [2]. Poly(ε caprolactone) (PCL) and polylactides (PLA) crystalline polymers are well known as hydrophobic, biocompatible and biodegradable materials [3]. They are prepared mainly by ring opening polymerization (ROP) of cyclic esters. The catalysts used in ROP are generally derivatives of metals, such as Al, Sb, Sn, Ge, and might leave impurities. The bulk polymerization without using catalysts avoids the contamination of the products, being preferred in application where high purity is required. The polymerization in absence of metal catalysts can be initiated by various active hydrogen containing compounds, such as amines [4], alcohols [5], amino acids [6] or cyclodextrins [7]. The presentation deals with the synthesis and characterization of low molecular weight poly(ε caprolactone) and poly(D,L lactide) end functionalized with Disperse Red 1, considering that they could prove interesting optical applications. Well defined oligomers were obtained by bulk polymerization initiated only by the means of hydroxyl groups. Structural details were provided by classical characterization techniques like NMR, GPC, and mass spectrometry MALDI and ESI techniques. Characterization by tandem mass spectrometry of the resulting polymer products, with respect to their structure, end groups content and composition, showed that these are best described as endcapped azobenzene oligomers with linear structure. Acknowledgment. This research project has been supported by a Marie Curie Early Stage Training Fellowship of the European Community’s Sixth Framework Program under the contract number MEST CT 2005 021029. Keywords: poly(ε caprolactone), poly(D,L lactide), azobenzene olygomers ______ [1] S. K. Yesodha et al.; Prog. Polym. Sci . 29, 45 (2004). [2] R. A. Evans et al.; Nature Materials, 4, 249 (2005). [3] A. Albertsson and I. K. Varma; Biomacromolecules, 4, 1466 (2003). [4] W. Tian; European Polymer Journal , 39, 1935 (2003). [5] P.Cerrai, M.Tricoli, F. Andruzzi, M. Paci ; Polymer , 30 , 338 (1989). [6] J. Liu and L. Liu; Macromolecules , 37 , 2674 (2004). [7] Y. Takashima, M. Osaki, A. Harada; J. Am. Chem. Soc ., 126 , 13588 (2004).
54 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-22 Supramolecular Structure – a Key Parameter for Cellulose Biodegradation
Diana Ciolacu 1 and Florin Ciolacu 2
1 “Petru Poni” Institute of Macromolecular Chemistry, Dept. of Chemistry-Physics of Polymers, 41A, Gr. Ghica-Voda Alley, 700487, Iasi, Romania 2 “Gh. Asachi” Technical University of Iasi, Dept. of Natural and Synthetic Polymers, Blvd. Mangeron, 700050, Iasi, Romania
One of the major obstacles that have to be cleared for the full understanding of the enzymatic degradation of cellulose is the influence of parameters such as accessibility, crystallinity and supramolecular structure of the substrata. For a better understanding of the cellulose biodegradation it was chosen three different cellulosic substrata, like microcrystalline cellulose, cotton cellulose and spruce dissolving pulp in order to be biodegraded. The kinetics of the enzymatic hydrolysis of these celluloses by Trichoderma reesei has been investigated. The experiments proved the fact that both the morphological structure and the crystalline one are crucial to the process and the ratio of the reactions. In this paper the effect of cellulose polymorphism on its biodegradability, was also evaluated. It was studied the celluloses with different crystalline forms and a variety of structural features, like cellulose I, II and III, obtained from cotton cellulose, in order to obtain the most accessible cellulose substratum. The insoluble cellulose fraction remaining after enzymatic hydrolysis was examined by X-ray diffraction method and it was established the degree of crystallinity and the average crystallite size. The roentgenograms of the residues resulted after different times of hydrolysis shown a slight increase in the crystallinity index, during the process. This fact can be attributed both to a preference in the attack over the domains poorly organized and also to their higher speed of hydrolysis. The enzymatic degradation is also proved by the decrease in the degree of polymerization of hydrolyzed samples.
Keywords: enzymatic degradation, Trichoderma reesei , cellulose allomorphs, kinetic
55 P-23 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Kinetics of Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates
M. Kawalec 1, G. Adamus 1, H. Janeczek 1, P. Kurcok 1, M. M. Kowalczuk 1, and M. Scandola 2 1 Centre of Polymer and Carbon Materials, Polish Academy of Sciences , 34 M. Curie-Skłodowskiej St., 41-819 Zabrze, Poland 2 Department of Chemistry “G. Ciamician”, University of Bologna, via Selmi 2, 40126 Bologna, Italy
Controlling of thermal properties of thermoplastics is of great importance from technological point of view since thermoplastics are processed mainly in melt. Knowledge of degradation mechanism allows one to predict and control thermal resistance of the plastic. The control of thermal properties means also decrease of thermal stability in order to obtain valuable short chain products even in mild conditions. Considering poly([R] 3 hydroxybutyrate) (PHB), which is a very well known thermoplastic bioresorbable material, there were many papers published on its thermal degradation mechanism [1,2] and the problem seemed to be examined thoroughly. It was reported that the PHB thermal degradation mechanism pathway led via intramolecular cis elimination were trans crotonate terminated polymer chains and trans crotonic acid were generated as the main degradation products. Moreover, it was also reported that the same degradation products were found when synthetic analogues of PHB have been degraded [3]. However, our recent studies of PHB degradation mechanism [4,5] revealed competitive degradation reaction proceeding even at moderate temperatures which is induced by basic agents. In this work kinetics of degradation of poly([R,S] 3 hydroxybutyrate)/acetate, as well as poly([R] 3 hydroxybutyrate)/acetate systems has been investigated by DSC and TG techniques. The results have enabled the determination of the activation energy of these processes. Moreover, the obtained results have allowed for explanation of the influence of carboxylate groups concentration as well as the counterion size on the kinetics of poly 3 hydroxybutyrate degradation. The authors would like to acknowledge financial support of projects: Eureka E! 3420, MTKD-CT-2004-509232 and Regional Stipend Fund for PhD Students under the European Social Fund (EFS-2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD). Keywords: degradation, kinetics of degradation, energy of activation, E1cB, thermal analysis, PHB; poly(3 hydroksybutyrate); poly(3 hydroxyalkanoates), ______ [1] A.C. Bertoli, M.D. Schmidt, Macromol. Symp. 252 , 197 (2005). [1] N. Grassie, E.J. Murray, P.A. Holmes, Polym. Degrad. Stab. 6, 47 (1984). [2] F.D. Kopinke, M. Remmler, K. Mackenzie, Polym. Degrad. Stab . 52 , 25 (1996). [3] P. Kurcok, M. Kowalczuk, G. Adamus, Z. Jedliński, R.W. Lenz, J. M. S.-Pure Appl. Chem. A32 , 875 (1995). [4] M. Kawalec, G. Adamus, P. Kurcok, M. Kowalczuk, , I. Foltran, L. Focarete, M. Scandola, Biomacromolecules 8, 1053 (2007). [5] M. Scandola, M.L. Focarete, I. Foltran, M. Kowalczuk, P. Kurcok, M. Kawalec, G. Adamus, PCT Patent application (filed on March 20, 2006) at No. PCT/IB2006/000898.
56 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-24 Novel Biodegradable Matrices for Drug Delivery
Raluca P. Dumitriu and Cornelia Vasile
“Petru Poni” Institute of Macromolecular Chemistry, Department of Physical Chemistry, 41A Gr. Ghica Voda Alley, 700487, Iasi, Romania
Nowadays the development of biodegradable polymeric hydrogels is gaining growing attention. Synthesis of hydrogels based on polysaccharides has attracted biomedical researchers due to their excellent biocompatibility and biodegradability. [1] In an attempt to obtain biodegradable materials with sensitivity to external stimuli, like pH and/or temperature, biopolymers from renewably resources were associated with thermo-sensitive macromolecules. [2,3,4] Such “smart” hydrogels can regulate drug release through responding to environmental stimuli by swelling and deswelling. New biodegradable hydrogels containing a natural polysaccharide, alginic acid and a synthetic thermo-responsive polymer, N-isopropylacryl amide (NIPAM) were obtained and characterized by swelling kinetic studies in different media and scanning electron microscopy (SEM). The studies performed allowed us to ascertain that the semi-interpenetrating networks obtained possess thermo- and pH-responsive properties dependent on composition and crosslinking degree. SEM micrographs showed a porous structure with pores dimensions dependent on the composition of the hydrogels.
4000
3500
3000
2500
2000
1500
Swelling ratio (%) ratio Swelling 1000 T = 25 0C 500 NIPAM/ALG 75/25 (a) NIPAM/ALG 75/25 (b) 0 0 50 100 150 200 250 Time (min)
Fig.1. SEM micrograph of 75/25 NIPAM/ALG Fig. 2. Swelling kinetic study in various media hydrogel . at 25 0C: a) twice distilled water; b) ethanol.
Keywords: biodegradable polymers; hydrogels; drug delivery
______[1] C. Xiao, G. Zhou, Polym. Degr. Stab . 81 , 297 (2003). [2] S.Y. Kim, S.M. Cho, Y.M. Lee, S.J. Kim, J. Appl. Polym. Sci. 78 , 1381 (2000). [3] E. Marsano, E. Bianchi, A. Viscardi, Polymer 45 , 157 (2004). [4] J. Shi, N.M. Alves, J.F. Mano , Macromol. Biosci. 6, 358 (2006).
57 P-25 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Divergent Synthesis of β Cyclodextrin Cored Star Poly([R,S] 3 hydroxybutyrate) M. Michalak 1, M. Kawalec 2, C. Peptu 1, P. Kurcok 1,2 , and M. M. Kowalczuk 1 1 Institute of Chemistry and Environment Protection, Jan Dlugosz University, 13/15 Armii Krajowej Ave., 42 200 Częstochowa, Poland 2 Centre of Polymer and Carbon Materials , Polish Academy of Sciences, 34 M. Curie Skłodowskiej St., 41 819 Zabrze, Poland Poly([R,S] 3 hydroxybutyrate) is a synthetic analogue of natural polyester poly([R] 3 hydroxybutyrate) which is produced and stored by many prokaryotic organisms as carbon and energy source [1]. The synthetic analogue can be obtained, among other ways, via ring opening polymerization (ROP) of β butyrolactone [2 5]. Recent work of preparation of star poly([R,S] 3 hydroxybutyrate) have arose from a task of increasing the content of carboxylic groups of atactic poly([R,S] 3 hydroxybutyrate) while keeping polymer’s high molecular weight. Obtaining of a biodegradable, non toxic polymer has been the second requirement for the material. Cyclodextrins [6] are cyclic oligosaccharides which have the characteristic size of a truncated cone. Commonly, they are constituted by 6, 7 or 8 glucose rings linked to each other by a 1 4 α glucosidic bond and they are named α , β and γ cyclodextrins, respectively. Nowadays β cyclclodextrin is produced in larger quantities and it is the cheapest available. Moreover, 7 anhydro glucose units offer total number of 21 hydroxy groups, which can be modified, per single cyclodextrin molecule. Furthermore, this hydroxycarbon is biodegradable, non toxic and it is from renewable sources. Thus, bearing in mind general purposes it has been contrived to prepare a star shaped polymer by applying polycarboxylate molecules for initiation of anionic polymerization of β butyrolactone. As the core, β cyclodextrin polycarboxylate derivative has been chosen. The method describes synthesis of poly(carboxysuccinate) β cyclodextrin in similar manner as it was reported previously [7]. The degree of esterification of the derivative has been determined by potentiometric and NMR analyses (spectra prove substitution of C2 OH as well as C3 OH mainly and hardly C6 OH). After it was titrated, the final polycarboxylate derivative has been used for initiation of β butyrolactone polymerization in DMF solution. The resulting star poly(3 hydroxybutyrate)s have been analysed with 1H, 13C NMR, MALDI TOF and SEC techniques after they were isolated from reaction mixtures. The detailed data on synthesis and properties of star poly([R,S] 3 hydroxybutyrate will be presented in this communication. The authors would like to acknowledge financial support of project Regional Stipend Fund for PhD Students under the European Social Fund (EFS 2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD). Keywords: biodegradable polymers; PHB, poly(3 hydroxybutyrate), star polymers, anionic polymerization, β cyclodextrin ______ [1] Y. Doi, Microbial Polyesters ; VCH Publishers: Weinheim, 1990. [2] L. R. Rieth, D. R. Moore, E. B. Lobkovsky, G. W. Coates, J.Am.Chem.Soc. 124 , 15239(2002). [3] Z. Jedliński, P. Kurcok, M. Kowalczuk, J. Kasperczyk, Makromol. Chem. 187 , 1651 (1986). [4] H. Abe, I. Matsubara, Y. Doi, Y. Hori, A. Yamaguchi Macromolecules 27 , 6018 (1994). [5] P. Kurcok, M. Śmiga, Z. Jedliński, J.Polym. Sci. Polym. Chem. 40 , 2184 (2002). [6] J. Szejtli, Cyclodextrin Technology ; Kluwer Academic Publishers, 1988. [7] R. Dicke, Cellulose 11 , 255 (2004).
58 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-26 Crystallinity and Crystalline Confinement of the Amorphous Phase in Polylactides
Jose-Ramon Sarasua, E. Zuza, A. López-Arraiza *, N. Imaz, and E. Meaurio University of the Basque Country (EHU-UPV), School of Engineering, Bilbao 48013, Sp. *present address: Mondragon University, MGEP, 20500 Mondragón, Sp. In many aspects there is still a lack of understanding of the fundamentals of physical chemistry that govern the segmental relaxation of polymer chains in both non confined and confined environments. Nonetheless, it is well established that constraints of polymer chains caused by crystallinity lead to an increase in the temperature of the glass transition, for chains find a growing hindrance to relax. Since macromolecules are longer than the crystal lamellae are thick, they can cross the phase boundaries and cause various degrees of coupling; on weak coupling, the dynamics of the non crystalline segments shows usually a broadening of the glass transition range, yet on stronger coupling the non crystalline material may also show a distinct glass transition, at higher temperature of the bulk amorphous phase due to a rigid amorphous phase. [1] Stereo regular polylactides such as poly (L lactide) (PLLA) or poly (D lactide) result from polymerization of optically pure lactides and are semicrystalline. Optically non active polylactides (PDLLA) can be regarded as random or atactic copolymers, show a random moiety distribution, and are completely amorphous [2]. In this work three phases, comprising mobile amorphous fraction (MAF, χMA ), rigid amorphous fraction (RAF, χRA ) and crystalline fraction ( χc) were determined in PLLA. It will be shown that RAP fraction not only elevates Tg but also increases the dynamic fragility (m) of polylactide chains around the Tg [3]. These results agree with reported cases in which topologycal constraints inhibit longer range dynamics and suggest a smaller length scale of cooperativity in confined environments [4].
0
Figure 1 -1 strong Angell’s plot of fully amorphous polylactide -2
(▲PDLLA) and semicrystalline polylactides
log a -3 crystallized by annealing after water quenching (● PLLA WQA) and by slow -4 cooling from the melt (■ PLLA SC). fragile -5 0.90 0.92 0.94 0.96 0.98 1.00 T /T g
Keywords: polylactide, crystalline confinement; dynamic fragility. ______ [1] Wunderlich, B. Prog. Polym. Sci. 28 , 383 450 (2003). [2] Sarasua, J. R.; Prud'homme R. E.; Wisniewski, M.; Le Borgne A.; Spassky, N. Macromolecules 31 , 3895 (1998); Meaurio, E.; Zuza, E.; Sarasua, J. R. Macromolecules 38 , 9221 (2005). [3] Angell, C. A. Journal of Non-Crystalline Solids 131 , 13 31 (1991); Science 67 , 1924 (1995). [4] Qin, Q.; McKenna, B. Journal of Non Crystalline Solids 352 , 2977 2985 (2006).
59 P-27 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Liquid Crystal Template Applied for Polyimide-Cellulose Derivative Thin Films
D. Filip, A.I. Cosutchi, C. Hulubei, and S. Ioan
“Petru Poni” Institute of Macromolecular Chemistry Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania
Thin polyimide films are the most commonly employed liquid crystal alignment layers. Two techniques [1] are used to produce LC alignment on polyimide films : standard method of rubbing and polarized UV irradiation of polyimides which result in anisotropy of the surface. Thin solid films prepared from lyotropic solutions of cellulose derivatives can be used also as alignment layers for liquid crystals [2]. For hydroxypropylcellulose solid thin films prepared from lyotropic solutions it was found that the band size constitutes a controlling factor in the anisotropy of the material properties. Tailoring the surface topography and altering the structure of polyimide enable to control orientation at the surface which is important in adhesion properties. Spatially ordered polymer microstructures from LC templates in a pattern-forming state is obtained. A new approach of polymerization and patterning of thin films based on partially aliphatic polyimides is achieved. The synthesis of the polyimides was reported previously [3]. The precursor lyotropic solution of hydroxypropylcellulose was used as liquid crystal template. The films were exposed to UV irradiation and the photosensitive properties have been investigated. The detailed structures of the resulting films were studied by polarized optical microscopy, atomic force microscopy and scanning electron microscopy.
Keywords: polyimide; liquid crystalline cellulose derivative. ______[1] D. Andrienko, Y. Kurioz, M. Nishikawa, Y. Reznikov, J.L. West, Jpn. Appl. Phys . 39 , 1217 (2000). [2] M. H. Godinho, J. G. Fonseca, A. C. Ribeiro, L. V. Melo, P. Brogueira, Macromolecules 35 , 5932 (2002). [3] E. Hamciuc, R. Lungu, C. Hulubei, M. Bruma, J. Macromol. Sci. Part A: Pure and Appl. Chem. , 43 , 247 (2006).
60 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-28
Biomass Compounds with Pharmacological Applications
Iuliana Spiridon 1, Maria Ichim 2 and Narcis Anghel 1
1“Petru Poni” Institute of Macromolecular Chemistry, Grigore Ghica-Voda no. 41, Iasi, Romania 2S. C. “Bioing“ S. A.,Calea 13 Septembrie no. 105, Bucuresti, Romania
Plants vary within and among species in the types and concentrations of phytochemicals due to variables in plant growth, soil, weather conditions and the age of the plant. Phenolic phytochemicals are the largest category of phytochemicals and the most widely distributed in the plant kingdom. Polyphenolic compounds, one of the most numerous and best studied groups of plant biomass, are well known to exhibit various biological and pharmacological effects. It is quite possible that several of these components could contribute to the antidepressant activity, either directly, or indirectly by making other compounds in the extract more active or more bioavailable (this latter possibility reflects the concept known as synergy). In our paper, the results obtained using the polymeric compounds separated from some biomass species to prepare a formula with therapeutic effect on nervous central system are presented.
Keywords : polymers; polyphenols; antidepressant
61 P-29 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Homo- and Copolymerization of Cyclic Aliphatic Esters with Suppression of Transesterification
Marta Socka, Marcin Florczak, and Andrzej Duda Centre of Molecular and Macromolecular Studies Polish Academy of Sciences, Sienkiewicza 112, Lodz, Poland Aliphatic polyesters [... −(C nH2n C(=O)O) m−...] become a new, emerging class of polymers that reveal interesting properties, like biocompability, ability to hydrolytical and biological degradation accompanied with useful mechanical and thermal parameters. Moreover, some of those monomers and/or polymers can be obtained from the renewable resources. The most convenient method for aliphatic polyesters synthesis is the ring opening polymerization (ROP) of the corresponding cyclic esters. This method provides sufficient control of polymerization of lactones, lactides, and cyclic carbonates, giving polymers of the required molecular weights and fitted with the desired end groups. In the appropriately chosen polymerization conditions the side reactions, like termination and transfer to the monomer could be eliminated [1]. Moreover, application of initiators that bear bulky, sterically demanding ligands, such as aromatic Schiff’s base (SB) derivatives (e.g. (R) (−) or ( S) (+) 2,2’ [1,1’ binaphtyl 2,2’ i diylbis (nitrylomethylidyne)] diphenolate aluminium isopropoxide (SBO 2Al O Pr)), leads to a considerable suppression of the inter and intramolecular transestrification (see e.g. papers [2] [4] and references cited therein) as well as disproportionation of the end groups. i The present contribution reports on application of SBO 2Al O Pr in the controlled ROP of ε caprolactone (CL), L,L lactide (LA), and cyclic carbonates (2.2 dimethyltrimethylene carbonate (DTC) and trimethylene carbonate (TMC)). H C 3 O O O H3C O O O O O O O O H3C O CH3 ( CL ) ( LA ) ( TMC ) ( DTC ) i It will be shown that SBO 2Al O Pr initiation of LA copolymerization with CL or cyclic carbonates leads to a particularly interesting results. Namely, the corresponding diblock and multiblock copolymers could be prepared for the first time employing the ‘living poly(LA) block first’ synthetic route [3,4]. Keywords: aliphatic polyesters; L,L lactide; ε caprolactone; 2.2 dimethyltrimethylene carbonate; trimethylene carbonate; living polymerization; block copolymers; transesterification ______ [1] A. Duda, S. Penczek, “Mechanisms of Aliphatic Polyester Formation”, in Biopolymers, Vol. 3b: Polyesters II – Properties and Chemical Synthesis , ed. by A. Steinbüchel, Y. Doi, Wiley VCH, Weinheim, 371 ( 2002). [2] A. Duda, K. Majerska, J. Am. Chem. Soc . 126 , 1026 (2004). [3] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38 , 2027 (2005). [4] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28 , 1385, (2007).
62 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-30 Acid Modification and Application of Biodegradable Polymer-Starch
Chia-I Liu and Chi-Yuan Huang Dep.of Materials Engineering, Tatung University, No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan
The blends with acid hydrolysis starch present a smooth face, because acid would break the molecular chains of starch. XRD and DSC analysis also confirmed crystallinity decrease and then increase as concentration of acid increased. MFI of blends could reach to 300g/10min as additive of 0.3M CA starch was 70wt%. 1. Experimental 1.1 Acid hydrolysis of starch with ultrasonic treatment A different concentration of Citric acid (reagent grade)(0.1M, 0.3M, 0.5M) water were ap plied to hydrolysis tapioca starch (food grade). The modified starch were added into tapioca starch/ glycerol the blends, and the additive was 30wt%, 50wt%, 70wt% ,separately. A sin gle screw extruder was employed to compound the blends at four step temperatures of 90, 100, 70, 40°C and the rotating speed was 20rpm. 2. Results and discussions 2.1. SEM observation of blends with acid hydrolysis starch: the cryo fractured surfaces of (a)blends presents (b) a smooth (c) face as the (d) content of (e) acid hydrolysis (f) starch (g) increased (Fig.1). (h) It indicated that acid would break the molecular chains of starch and the granule of starch was easy to melt in the process [1]. 2.2. DSC analysis of acid hydrolysis starch: The melting peak of 0.1M CA starch shift to a low temperature, but the melting peak of 0.3M and 0.5M CA starch shift to high temperature (Fig.2). It indicated that higher concentration acid would process a higher relative crystallinity. 2.3. XRD analysis of acid hydrolysis starch: The XRD pattern of 0.1M CA starch present weak peaks but the patterns in 0.3M and 0.5M CA starch appeared strong peaks at 2θ about 15°, 17°, 18° and 23°(Fig.3). 2.4. MFI analysis of blends with acid hydrolysis starch: the MFI of blends appear an increase as additive of acid hydrolysis starch increase. Especially, the blend with 70wt% 0.3M CA starch, the MFI of blend could reach to 300g/10min (Fig.4). (a) (b) (c) (d) (e) (f) (g) (h)
Figure 1. SEM morphology of blends with different c(h) ontent of acid hydrolysis starch: 0.1M CA-starch (a)30wt% (b) 50wt% (c) 70wt%; 0.3M CA-starch (d)30wt% (e) 50wt% (f) 70wt%; 0.5M CA-starch (g)30wt% (h) 50wt%.
350 0.0 350 Tapioca starch Hydrolysis starch 0.1M CA-starch -0.5 Tapioca starch 300 0.1M CA-starch 0.3M CA-starch 300 0.1M CA-starch 0.5M CA-starch 0.3M CA-starch 0.3M CA-starch 0.5M CA-starch -1.0 250 250 0.5M CA-starch
-1.5 200 200 -2.0 150 150
-2.5 Intensity 100
Heat ( Flow w/g) 100 -3.0 Melt FlowIndex (g/10min) Melt 50 50 -3.5
0 -4.0 0 50 100 150 200 250 10 20 30 40 50 60 70 80 90 30 40 50 60 70 Temperature ( OC) 2 theta Content (wt%) Fig. 2. DSC curves in different con Fig. 3. XRD curves in different con Fig. 4 .MFI curves in different con centration of acid hydrolysis starch. centration of acid hydrolysis starch. centration of acid hydrolysis starch. Keywords: biodegradation, acid hydrolysis, recrystallinity ______ [1] N. Atichokudomchai, S. Shobangob, S. Varavinit, Starch , 52 , 283(2000).
63 P-31 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Characterization of the Radical Polymeric Grafting of Hydroxylethyl Methacrylate onto Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
Hoi-Kuan Lao 1,2 , Estelle Renard 2, Valérie Langlois 2, Xaviera Pennanec 1, Mylène Cuart 1, Karine Vallee-Rehel 1, and Isabelle Linossier 1
1LBCM, EA 3884, Université de Bretagne-Sud, BP92116, 56321 Lorient Cedex, France 2SPC, ICMPE, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais, France
Polyhydroxyalkanoates (PHAs) are biosynthesized by a wide range of microorganisms as intracellular energy and carbon storage materials. These materials have been evaluated for a variety of medical applications, which include controlled release, surgical sutures, wound dressings, lubricating powders, orthopaedic uses and as a pericardial substitute. However, the surfaces of PHB and PHBHV are quite inert and hydrophobic. They have no physiological activity which is unfavourable for adhered cell growth in tissue engineering. Therefore, as for many polymer surfaces, the cytocompatibility should be improved by either chemical modification with functional groups or modification of the surface topography. Graft polymerization is a well-known method for the modification of chemical structure to obtain properties for specific applications such as bone scaffolds [1]. Many methods are used such as plasma, ozone treatment and gamma radiation [1-3]. In order to improve the general wettability of the PHBHV, graft copolymerization of 2- hydroxyethylmethacrylate (HEMA) was achieved. We have previously proposed a simple way of grafting HEMA onto PHBHV, this synthesis was carried out in aqueous solution with the benzoyl peroxide as chemical initiator [4].
In the framework of free radical grafting of vinylic monomer, it is generally speculate that the graft polymerization on PHBHV is conducted by formation of primary radicals from hydrogen abstraction of the methine protons on the PHBHV backbone, which can react with HEMA [5]. No literature data ascertain this hypothesis. In order to determine the localization of the grafted chains 2D 1H-NMR was carried out to elucidate the mechanism pathway. The free radical polymerization is known to lead to broad molecular weight: the determination of the molecular weight of the grafted chains by free radical grafting (UV, ozone, or chemical initiation …) was not explored yet. Indeed, it is difficult to access to these data and it is supposed to be the same order of magnitude of the homopolymer formed during the grafting procedure. Molecular weight of the grafted chain from the degradation of the PHBHV was characterized to ascertain the real size of the grafted PHEMA. Enzymatic biodegradability was investigated in order to know if the grafted polymer is still degradable.
______[1] Grondahl, L., Chandler-Temple, A.,Trau, M., Biomacromolecules 6 , 2197 (2005). [2] Kang, I. K.,Choi, S. H.,Shin, D. S.,Yoon, S. C., Int. J. Biol Macromol. 28 , 205 (2001). [3] Ke, Y.,Wang, Y.,Ren, L.,Lu, L.,Wu, G.,Xiaofeng,Chen, C. J., J. Appl. Polym. Sci. 104 , 4088 (2007). [4] Lao, H. K.,Renard, E.,Linossier, I.,Langlois, V.,Vallee-Rehel, K., Biomacromolecules 8 , 416 (2007). [5] Chen, C.,Peng, S.,Fei, B.,Zhuang, Y.,Dong, L.,Feng, Z.,Chen, S.,Xia, H., J. Appl. Polym. Sci. 88 , 659 (2003).
64 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-32 Degradation Process of Bioresorbable PGLC Terpolymers J. Jaworska 1, Y. Hu 2, J. Wei 2, J. Kasperczyk 1, P. Dobrzyński 1, and S. Li 2,3 1Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 Str.Curie-Sklodowska, 41-808 Zabrze, Poland 2Department of Materials Science, Fudan University, Shanghai 200433, China 3Research Center on Artificial Biopolymers, Max Mousseron Institute on Biomolecules, UMR CNRS 5247, Faculty of Pharmacy, University Montpellier I, 34093 Montpellier, France
Introduction Bioresorbable and compatible with human tissues aliphatic polyesters undergo hydrolytic and enzymatic degradation in biological environment to nontoxic components eliminated via the Krebs cycle. They are considered in a variety of medical and pharmaceutical applications in controlled drug delivery systems and in tissue engineering. In this work, we report a study on the hydrolytic degradation of PGLC terpolymers in order to elucidate the effect of the chain microstructure. On the basis of changes in chain microstructure the choice of appriopriate terpolymer to desired medical application is possible. Experimental methods Terpolymers of glycolide, lactide, and ε caprolactone have been prepared by the ring opening polymerization held in a bulk using zirconium and tin initiators. Obtained terpolymers were pressed and allowed to degrade in a phosphate buffer solution pH=7,4 in 37°C for a different period of time. The composition and chain microstructure of obtained terpolymers and degradation products have been determined by 1H and 13 C NMR. Results and discussion A series of glycolide, lactide and caprolactone terpolymers, were synthesized using Zr(acac) 4 or Sn(oct)2 as initiators in order to obtain various chain microstructure. The results revealed that the degradation rate depends not only on the terpolymer composition but also on its chain microstructure. For example in the case of high concentration of lactide units in terpolymer chains at the beginning of degradation, longer L sequences and alternating CGC and CLC segments in ordered domains are resistant for degradation but degradation of G L, G C and L C ‘mixed’ segments occurs faster. In consequence stable level of all monomeric units during degradation is observed. Such stable level is noticed also in the case of high amount of caproyl units in terpolymer chains. Alternating CGC and CLC sequences, which are resistant for degradation, influence on the content of G and L units in polymer chain and prevent decrease of glycolide and lactide units concentration in terpolymer chain during degradation process. Conclusions Chain microstructure of terpolymer influence its degradation and can be investigated by NMR method. According to various microstructures of the chain (random and block terpolymers) clear differences in degradation mechanism have been observed. On the basis of changes in chain microstructure it is possible to chose appriopriate terpolymer to desired application. Acknowledgements Joint French Polish CNRS PASc. Grant No. 18256 and Regional Scholarship EFS 2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD Keywords: hydrolytic degradation; bioresorbable polymers, NMR, microstructure
65 P-33 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Sustainable Green Polymer Composites Based on PLA
1 2 3 1 G. Bogoeva-Gaceva , M. Avella , V. Srebrenkoska , A. Grozdanov , A. Buzarovska 1, M. E. Errico 2, and G. Gentile 2
1Faculty of technology and Metallurgy, Rugjer Boskovic 16, 1000 Skopje,R.Macedonia 2Institute for Chemistry and Technologyof Polymers-ICTP, Via Campi Flegrei 34, 80078 Pozzuoli,Napoli, Italy 3Kompozitna Oprema, Industriska bb, Prilep, R.Macedonia
In the framework of the ECO-PCCM project [http://elchem.ihtm.bg.ac.yu/ECO-PCCM/], sustainable green polymer composites based on thermoplastic biodegradable polymer matrix (Polylactide acid – PLA) reinforced with natural fibers (kenaf) and agricultural fillers (rice straw) have been analyzed [1,2]. Production of green-composites has been performed by conventional techniques, such as melt mixing (T=170 oC t=10min) and compression molding (T=185 oC t= 10min). Characterization includes analysis of mechanical behavior (tensile test, flexural test, impact resistance), thermal stability (by TGA) and morphological analysis (by SEM). The obtained results for the studied composites with both reinforcements, have shown increased modulus, both tensile and flexural ( EPLA/kenaf d=60mm ρ=40kg/m3 = 1,1 GPa, EPLA/kenaf d=50mm ρ=40kg/m3 = 0,08 GPa). Tensile and flexural strength were slightly decreased. SEM analysis indicated on the satisfied durability of the PLA polymer based composites.
Fig. 1 SEM of PLA/RS/CA “neat” Fig. 2 SEM of PLAx1/RS/CA composite composites (75/20/5 wt%, x150). obtained with recycled PLA (75/20/5 wt%, x200).
Keywords: green composites; recycling; mechanical properties
______[1] G.Bogoeva-Gaceva, D.Dimeski, Z.Manov, V.Srebrenkoska, A.Grozdanov, A.Buzarovska, M.Avella, IUMACRO’07, IUPAC and ACS Conference on Macromolecules for a Safe, Sustainable and Healthy World 2nd Strategic Polymer Symposium, NewYork USA , June 10-13 (2007). [2] M.Avella, G.Bogoeva-Gaceva, A.Buzarovska, M.E.Errico, G.Gentile, A.Grozdanov, J.Appl.Polym.Sci., 104 , 3192 (2007)
66 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-34 Accelerated Wound Repair by Di O butyrylchitin, the Polymer for New Non Woven Dressing Material A. Błasińska 1 and J. Drobnik 2 1Department of Fiber Physics and Textile Metrology, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland 2Department of Connective Tissue Metabolism, Medical University of Lodz, Narutowicza 60, 90-136 Lodz, Poland. Di O butyrylchitin (DBC) is the technologically friendly chitin derivative, obtained after introduction of the two butyryl groups to chitin at position C 3 and C 6 [1,2]. Well solubility of DBC in common solvents and high biocompatiblity makes this polymer the good candidate for application in biological subjects [3,4]. The present study is aimed at testing DBC action on a healing process, as well as, explaining the mechanisms of its’ effect. Moreover, the comparison of DBC action with other dressing materials effects (butyrylchitin, regenerated chitin and chitosan) is planned. Experiments were made on male Wistar rats. Polypropylene nets (2cmX3cm) were implanted subcutaneously to the rats. The implants alone served as control but in other groups the nets were covered with the dressing material made of investigated polymers: DBC 1 and DBC 2 with intrinsic viscosity [η]DMAc/25deg.C equal 1.75dl/g and 2.08dl/g respectively, butyrylchitin, regenerated chitin and chitosan. Four weeks after implantation samples were taken for biochemical analysis. DBC dressings were showed to increase granulation tissue weight and glicosaminoglycans content in the scar. Total collagen content was not changed but the soluble fraction of the protein (not polymerized collagen) was reduced. One can state the improvement of collagen polymerization by DBC. Number of fibroblasts isolated from the wounds and cultured on DBC films was elevated but reduction of died cells was seen. Contrary to DBC, chitosan reduced glicosaminoglycans level in the wound and increased water content in the granulation tissue. Some general effects of DBC were observed. Thus the polymer decreased body weight of rats and reduced body temperature. Beneficial effects of DBC dressings on wound repair have been documented. The most promisable effects were obtained after application of DBC 1 with intrinsic viscosity [η] DMAc/25deg.C =1.75 dl/g. Thus the DBC elevated the granulation tissue mass in the wound and increased glycosaminoglycans content and polymerization of collagen level. One can explain the observed phenomenon by direct influence of DBC on the cells in the wound (increased cells number and weight of granulation tissue). The effects of the butyrylchitin and regenerated chitin on repair were not better as compared to DBC (di O butyrylchitin). Keywords: dibutyrylchitin; non wovens; wound healing ______ [1] L. Szosland, G. Janowska, Method for preparation of dibutyrylchitin, Patent PL169077B1 (1996). [2] L. Szosland, Di O butyrylchitin, in Chitin Handbook ; Muzzarelli, R.A.A., Peter, M.G., Eds. 53 60, (1997). [3] L. Szosland, I. Krucińska, R. Cisło, D. Paluch, J. Staniszewska Kuś, L. Solski, M. Synthesis of dibutyrylchitin and preparation of new textiles made from dibutyrylchitin and chitin for medical applications, Fibres & Textiles in Eastern Europe , 9(34), 54 57 (2001). [4] A. Chilarski, L. Szosland, I. Krucińska, A. Błasińska, R. Cisło, Non wovens made from dibutyrylchitin as novel dressing materials accelerating wound healing, Proceedings of 6 th International Conference of the European Chitin Society, EUCHIS’04 , Poznań, Poland (2004) .
67 P-35 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Characterization of Biodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means of Electrospray Ionization-mass Spectrometry after a Partial Depolymerization
Alena Šišková 1, Wanda Sikorska 2, Marta Musioł2 , Marek M. Kowalczuk 2, and Witold J. Kowalski 1
1Institute of Chemistry and Environmental Protection, Faculty of Mathematics and Natural Sciences, Jan Dlugosz University, 13/15 Armi Krajowej, 42–200 Czestochowa, Poland 2Polish Academy of Sciences, Centre of Polymer and Carbon Materials, 34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland
Synthetic polymers are highly complex multicomponent materials. Their different heterogeneities can be summarized in a term “molecular heterogeneity“, meaning different aspects of molar mass, chemical composition, functionality type and molecular architecture distribution. Among the distributed properties in the case of co- and terpolymers are, e. g., sequence and length of incorporation (alternating, random or block) distributions [1]. Copolyesters containing aliphatic and aromatic repeating units formed of terephthalic acid, adipic acid and 1, 4-butanediol, (e.g., Ecoflex trade-mark series) present different degrees of (bio)- degradability and are interesting materials for medicinal and environmental applications. We intended to characterize these materials by means of the electrospray ionization coupled with mass spectrometry (ESI-MS), and chromatographic methods. The first step included a reduction of their molecular mass in order to enable the MS analysis by means of the accessible equipment [2,3]. Depolymerization processes of selected Ecoflex samples were carried out in selected conditions: in methanolic and aqueous solutions, at ambient and elevated temperatures, in basic media (tetrabutylammonium hydroxide). The degradation products were analyzed by means of steric exclusion chromatography (SEC) and the obtained fractions were submitted to 1H NMR and ESI-MS spectrometry. The highly reproductible partial depolymerization procedures gave rise to an assumption that the subsequent application of ESI-MS would significantly contribute to determination of the molecular architecture of studied polyesters.
Acknowledgement: This work was supported by the European Community, Marie Curie Actions: MEST-CT-2005- 021029, „POLY-MS”.
Keywords: partial depolymerization; molecular size fractionation; repeating units incorporation sequence
______[1] H. Pasch and B. Trathnigg, HPLC of polymers, Sprinter-Verlag, Berlin, Heidelberg, New York, (1999). [2] U. Witt et.al. Biodegradation of aliphatic-aromatic copolyesters: evaluation of the final biodegradability and ecotoxicological impact of degradation intermediates, Chemosphere 44,289-299 (2001). [3] F. Pardal, G. Tersac, Kinetics of poly (ethylene terephthalate) glycolysis by diethylene glycol. I. Evolution of liquid and solid phases, Polymer Degradation and Stability 91, 2840-2847 (2006).
68 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-36 Commercial Biodegradable Polymers Reinforced with Flax Fibers
Mariastella Scandola, Elisa Zini, and Maria L. Focarete
University of Bologna, “G.Ciamician” Department of Chemistry, via Selmi 2, 40126 Bologna, Italy
Increasing environmental concern over waste disposal has recently promoted research towards new biodegradable materials for a wide range of applications. In particular composites made of natural fibers and biodegradable polymers are presently considered new environmentally friendly materials suitable for lightweight structural parts [1]. At the end of their service life, biocomposites can be completely degraded in compositing units (in specific cases also in the environment) or alternatively they can be incinerated for energy recovery. Two biodegradable commercial polymers were used as the matrix in biocomposite manufacturing: a bacterial poly(3-hydroxybutyrate-co -3-hydroxyhexanoate), Nodax TM [average 3-hydroxyhexanoate content: 12 mol %] and cellulose acetate, CA (degree of substitution 2.5, food-grade plasticizer content: 34 wt%), while the reinforcing fibers were flax fibers, bleached with hydrogen peroxide in the presence of NaOH and Na 2CO 3. Two series of composites were prepared: long fiber (LF) and short-fiber (SF) composites. LF composites were obtained by high temperature compression molding alternated polymer films and fiber mats (five-layered sandwich), and contained 5mm-long fibers randomly distributed in the plane of the sheet. Mechanical investigations of LF composites indicated that long flax fibers are able to reinforce both polymeric matrices. SF composites were obtained by high temperature mechanical mixing polymer and fibers, followed by compression molding into sheets. In these composites the fibers were shortened during processing and their length was in the range 100-220 µm. The tensile modulus of SF composites increased, as expected, with increasing fiber content in both CA and Nodax TM composites. The tensile strength of SF composites, instead, only increased in the CA composites. In order to observe a reinforcing effect of the Nodax TM copolyester, a chemical modification (acetylation) had to be applied to the fiber surface to improve fiber-matrix adhesion, a technique that has been previously adopted [2,3] and does not substantially affect fiber biodegradability [4]. The Nodax TM biocomposites showed a remarkable increase of crystallization rate from the melt, attributed to heterogeneous nucleation of the vegetable fibers, that exhibited a transcrystalline polymer layer at their surface. From a practical standpoint, this results in faster composite solidification and reduces processing time.
Acknowledgments: we thank Mazzucchelli 1849 s.p.a. (Castiglione Olona, Italy) and Procter and Gamble Company (West Chester, OH, USA) for the gift of plasticized CA and of Nodax TM respectively and Linificio e Canapificio Nazionale s.p.a for kindly providing the flax fibers.
Keywords: biocomposites; biodegradable polymers; mechanical properties; natural fibers ______[1] A.K. Bledzki, J. Gassan, Prog. Polym. Sci. 24 , 221 (1999). [2] M. Baiardo, E. Zini, M. Scandola, Composites Part A: Appl. Sci. Manu. 35 , 703 (2004). [3] E. Zini, M. Baiardo, M. Scandola, Macromol. Biosci. 4, 286 (2004). [4] G. Frisoni, M. Baiardo, M. Scandola, D. Lednikà, M.C. Cnockaert, J. Mergaert, J. Swings, Biomacromolecules 2, 476 (2001).
69 P-37 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Investigation of Novel Shape Memory Polymers' Chain Microstructure Katarzyna Gębarowska 1, Janusz Kasperczyk 1, Piotr Dobrzyński 1, Mariastella Scandola 2, and Elisa Zini 2
1Centre of Polymer and Carbon Chemistry, Polish Academy of Sciences, Zabrze, Poland 2University of Bologna, Department of Chemistry, Bologna, Italy
Introduction Synthetic biodegradable lactide, glycolide and trimethylene carbonate (TMC) based materials can possess the ability to recover from intermediate shape to primal when applying e.g. severe temperature change. Such property is called shape-memory behaviour. [1] Shape- memory polymers (SMP) find wide application in medical field, for instance in manufacturing surgical pins, selfexpanding stents, etc. [2,3] The knowledge of microstructure of polymer chain dependence with shape-memory behaviour may be crucial in elaborating the process of obtaining material that exhibit appropriate mechanical parameters and temperature (in the range of body temperature) of transition form intermediate to primal state.
Experimental The investigations of chain microstructure of LL -lactide/glycolide/TMC terpolymers`, 1 13 obtained on zirconium initiator (Zr(acac) 4), were performed by means of H and C nuclear magnetic resonance spectroscopy. All terpolymer`s samples differed in the initial comonomeric unit contents. Results Results of 1H NMR spectra enabled to calculate the content of all comonomeric units: lactidyl LL, glycolidyl GG and carbonyl T. Much more information was obtained from 13 C NMR spectra. The most sensitive spectral region, best for detailed analysis of groups and sequences appearing in terpolymer`s chain, were methine carbon region from lactide and methylene carbon regions from glycolide and TMC. Therefore very detailed resonance lines assignment was performed. Furthermore, the 13 C NMR spectra allowed to evaluate percentage molar content of long polymer blocks and mixed segments. It was found that depending on the comonomeric unit ratio, different long blocks and mixed segments appear in terpolymer chain microstructure. Conclusions NMR spectroscopy is a very useful tool for analysing LL -lactide/glycolide/TMC terpolymer`s microstructure. According to obtained results it is to state that different monomeric unit content influences the polymer chain microstructure and, therefore, shape- memory behaviour of investigated materials.
Acknowledgements Financial support: EU6FP Excellence – BIOMAHE, FP-6-509232
Keywords : shape-memory polymers; biodegradable materials; NMR ______[1] Jeonga, B.; Gutowska, A.; Trends in Biotechnology 2002, 20, 305–311. [2] Wache, H. M.; Tartakowska, D. J.. Heinrich, A. Wagner, M. H.; J. Mat. Sci.: Mat.Med. 2003, 14,109-12. [3] Kawai, T. I in.; Plastic molded articles with shape memory property, US Patent 4, 950, 258.
70 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-38 Bioresorbable Electrospun Non-woven Scaffolds
Mariastella Scandola 1, Chiara Gualandi 1, Maria L. Focarete 1, Piotr Dobrzynski 2, Michal Kawalec 2, and Piotr Wilczek 3
1 University of Bologna, Dept of Chemistry “Ciamician”, via Selmi 2, 40126 Bologna, Italy 2Centre of Polymer and Carbon Materials, M.Curie-Skłodowskiej 34, 41819 Zabrze, Poland 3Foundation for Development of Cardiac Surgery, ul. Wolnosci 345a 41800 Zabrze Poland
Polymeric scaffolds obtained by electrospinning, in the form of non-woven mats, are promising materials for applications in the tissue engineering field [1], owing to their close similarity to the extra-cellular matrix, in terms of topology. Electrospun porous scaffolds, made of hydrolysable polymers, can efficiently support cell growth [1] and their bioabsorbability in vivo may be properly designed, through an accurate tuning of the rates of scaffold hydrolysis and tissue regeneration. In the electrospinning process for scaffold fabrication, a careful tuning of the processing parameters allows the obtainment of nanofibres with desired diameter and orientation. This aspect is important because it is well known that the micro/nano-architecture of the scaffold may affect cell behaviour. A random copolymer of poly(lactide-co-glycolide) (PLGA, molar ratio: 50:50), synthesized using a low-toxicity zirconium-based initiator [2], was used. Non-woven mats of PLGA were fabricated through electrospinning, after optimization of the processing parameters (solution composition, applied voltage, solution flow rate and needle-to-collector distance) in order to obtain defectless fibres (average diameter of 800 nm). Electrospun PLGA mats were subjected to an in vitro degradation study in phosphate buffer (pH=7.4) at 37°C. The molecular weight of PLGA was found to decrease from the very beginning of the degradation experiment, whereas the samples showed weight loss only after 20 days of exposure to buffer solution. All collected GPC curves were mono-modal, yielding no evidence of autocatalytic effect during degradation. After 20 days also fibre morphology, investigated by SEM analyses, began to change from smooth to porous. After 50 days the scaffold lost about 50% of its initial weight . In addition, endothelial cell growth supplement (ECGS) was suspended in the eletrospinning polymer solution and nanofibrous mats were obtained. A preliminary study on the effect of ECGS incorporation in the scaffold was conducted using mesenchymal stem cells from bone marrow.
Keywords: scaffold; tissue engineering; electrospinning; bioabsorbable polymers
______[1] A.G. Mikos et al., Tissue engineering , 12 , 1197 (2006). [2] P. Dobrzynski et al., Macromolecules , 34 , 5090-5098 (2001).
71 P-39 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Keratin Coating for Wool Fiber
Jeanette M. Cardamone
U.S. Department of Agriculture, Agricultural Research Service, Eastern Regional Research Center, 600 East Mermaid Lane, Wyndmoor, PA 19038, USA
Keratin as the major structural fibrous protein comprising wool, hair, feathers, and nail is rich in amino acids and cystine disulfide bonds which provide flexibility and tenacity to hair and wool. We applied alkali to break peptide and disulfide bonds and obtained keratin protein in the form of keratin hydrolysate (KH) and powder (KP) with molecular weight of 6 to 30 kDa. Then we used the unaffected glutamine and lysine amino acids of the protein as sites for enzyme-mediated crosslinking of wool, of KH and KP. We showed that keratin hydrolysate imparted shrink-resistant properties to wool textiles; the hydrolysate application is an eco- friendly alternative to chlorine-Hercosett treatment, which can be a source of AOX (Adsorbable Organic Halogens). The control of the dimensional stability of wool fabric by applying KH and KP proceeded through a mechanism involving in-situ crosslinking mediated by transglutaminase enzyme through the formation of isopeptide linkages between glycine and lysine residues of keratin peptide. Scanning electron and confocal fluoresence microscopy showed keratin protein localized on the surface of wool to smooth the fiber surface, thereby preventing the scales from interlocking. Wool material, including hydrolysates and powders crosslinked by transglutaminase enzyme-mediation, will provide a rich resource for the production of modified keratin-based biomaterials.
72 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-40 Films from Spruce Galactoglucomannan Blended with Poly (Vinyl Alcohol), Corn Arabinoxylan and Konjac Glucomannan
Kirsi S. Mikkonen 1,2 , Madhav P. Yadav 3, Stefan Willför 4, Kevin B. Hicks 3, and Maija Tenkanen 1
1Department of Applied Chemistry and Microbiology, University of Helsinki, P.O. Box 27, 00014 Helsinki, Finland 2Department of Food Technology, University of Helsinki, P.O. Box 66, 00014 Helsinki, Finland 3Eastern Regional Research Center, ARS, United States Department of Agriculture, 600 East Mermaid Lane, Wyndmoor, PA 19038, USA 4Process Chemistry Centre, Åbo Akademi University, Porthansgatan 3, 20500 Åbo, Finland
O-acetyl-galactoglucomannans (GGM) are the main hemicelluloses in softwoods and can be recovered as by-products from process water of mechanical pulping of spruce wood [1]. GGM can be used as raw material for biodegradable films, but the tensile strength and elongation at break of GGM films are rather low [2]. The aim of this study was to improve the mechanical properties of GGM-based films by blending GGM with poly (vinyl alcohol) (PVOH), corn arabinoxylan (CAX), and konjac glucomannan (KGM). In addition, thermal behavior of the blend films was examined using dynamic mechanical analysis (DMA) and the film structure was studied with scanning electron microscopy (SEM). GGM was recovered from process water of thermomechanical pulping of spruce [1] and CAX from fiber fractions from commercial corn wet milling (CFG-1) [3]. PVOH (98-99% hydrolyzed, Mw 146,000-186,000) was from Sigma and KGM from Baoji, China. Blend ratios of GGM to PVOH, CAX, and KGM were 1:0, 3:1, 1:1, 1:3, and 0:1. Films were prepared by casting and drying aqueous solutions of polymer blends (10 g/l) and glycerol (Sigma) (4 g/l). Tensile strength and elongation at break of films were determined at 21ºC and 65% RH using an updated Instron 1122 mechanical property tester (Instron Corp., Norwood, MA, USA) with TestWorks 4 data acquisition software (MTS Systems Corp., Minneapolis, MN, USA). Dynamic mechanical analysis was done on a Rheometrics RSA II solids analyzer (Piscataway, NJ, USA) for film specimens dried under vacuum for 30 min prior to testing. Images of cross-sections of freeze-fractured films were collected using a Quanta 200 scanning electron microscope (FEI Co., Hillsboro, OR, USA). Adding other polymers increased the elongation at break of GGM blend films. The tensile strength of films increased with increasing amount of PVOH and KGM, but the effect of CAX was the opposite. The mechanical properties of GGM:CAX 1:3 and 0:1 films could not be measured, because CAX was very sensitive to changes in ambient RH and these films were difficult to handle at 65% RH, which was used for mechanical testing. DMA showed two separate loss modulus peaks for blends of GGM and PVOH, but a single peak for all other films. SEM confirmed good miscibility of GGM with CAX and KGM. In contrast, for blend films from GGM and PVOH, SEM showed phase separation. Blending GGM with KGM was found to be an applicable way to improve the mechanical properties of GGM-based films.
Keywords: spruce galactoglucomannan; poly (vinyl alcohol); corn arabinoxylan; konjac glucomannan; films; mechanical properties; dynamic mechanical analysis; scanning electron microscopy ______[1] S. Willför, P. Rehn, A. Sundberg, K. Sundberg, B. Holmbom, Tappi J. 2, 27 (2003). [2] K. Mikkonen, H. Helén, R. Talja, S. Willför, B. Holmbom, L. Hyvönen, M. Tenkanen, Proceedings of the 9th European Workshop on Lignocellulosic and Pulp (EWLP), Vienna, Austria, 27-30 August 2006, 130 (2006). [3] M.P. Yadav, D.B. Johnston, A.T. Hotchkiss Jr, K.B. Hicks, Food Hydrocolloids, 21 , 1022 (2007).
73 P-41 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007
Activation of Transcription Nuclear Factor NF κB and Induction of Inflammatory Cytokines in Immune Response on Resorbable Biomaterials B. śywicka 1, E. Zaczyńska 2, A. Czarny 2, S. Pielka 1, J. Karaś 3, and M. Szymonowicz 1 1Department of Experimental Surgery and Biomaterials Research, Wroclaw Medical University; ul. Poniatowskiego 2, 53 326 Wrocław, Poland 2Institute of Immunology and Experimental Therapy, Polish Academy of Science, ul Weigla, Wrocław, Poland 3Institute of the Glass and Ceramics, ul Postępu 9,Warszawa, Poland Implantation materials grafted intratissularly overtaking determined functions in the living organism should not show unfavorable influence on the immunological system and should disturb its homeostasis in the least possible degree. Growth of the level of inflammatory cytokines is observed in the tissues surrounding the implant. But in pathophysiology of implants there are not compatible data whose tissue markers play a key role in the evoked inflammatory process. Activation of the immune response on an external stimulator requires coordinated expression of numerous factors. So, a question appears if there are key modulators of immune and inflammatory reaction, observation of which could be the purpose of the more efficient estimation of biocompatibility of implantation materials. Transcription nuclear factor NF kappa B plays the role of one of more important potential immunoregulators. It regulates the expression of many genes connected mainly with the course of inflammatory process, proliferation and cells differentiation including inflammatory cytokines II 1, IL 6, TNF α, IL 8; it is also connected with appearing of giant cells of the foreign body type. In our study we evaluated three kinds of resorbable materials prepared on the basis of calcium phosphate (CaSO 4 .1/2H 2O with 0.5%mass. KHSO 4). One of them was enhanced by poli(alchol vinyl), with the aim to increase its mechanical resistance. The second one was enriched with the growth activator of bone tissue tri calcium phosphate and the third calcium phosphate was used as control. These modifications could cause the local activation of leukocytes to produce the mediators of inflammatory processes, which leads to long term complications. The present study was designed to determine in vitro whether gypsum materials treatment of leukocytes from peripheral human blood (PBL) results in changes in activation of NF κB and production of cytokines. The immunocytochemical localization and expression of NF κB in leukocytes was assessed using anti c Rel antibody. The NF κB activation was expressed as the percentage of NF κB(+)cells after 24 and 72 hour incubation. The level of cytokines IL 6, IL 8 and TNF α in the supernatants from leukocytes culture with tested materials was determined by an immunoabsorbent assay (ELISA) after 24 and 72 hours. On the basis of the performed tests it was observed that calcium sulphate materials without modifications activated nuclear factor NF κB after 24 hour incubation (p<0.05) and not significantly decreased its expression after 72 hours (p>0.05). Calcium sulphate materials with addition of tri calcium phosphate did not activate NF κB, while calcium sulphate with poli (alchol vinyl) turned out toxic for leucocytes both after 24 and 72–hour incubation. The level of IL 6, IL 8, TNF α after stimulation for 24 and 72 hours with gypsum materials was compared to untreated leukocytes (p<0.05). The monitoring of the stimulation of NF κB mediator could give us the answer about cells reaction for the new biomaterials and it could prove to be the sensitive test for their selection. Keywords : NF κB, TNF α, IL 6, IL 8, peripheral human leukocytes
74 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-42 Influence of the Gelatin Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and Tissue Reaction M. Szymonowicz 1, B. śywicka 1, S. Pielka 1, L. Solski 1, D. Haznar 2, and J. Pluta 2
1Department of Experimental Surgery and Biomaterials Research, Medical University Poniatowskiego 2, 50-326 Wroclaw, Poland 2Department of Drug Form Technology, Medical University Szewska 38, 50-139 Wroclaw, Poland Porous biodegradable matrixes for implantation are interesting drug forms in pharmaceutical technology. Owing to their structure, sponges are likely to be used as drug carriers of modified releasing or used in tissues engineering as a cell carrier. Introduction of material belonging to a different species into a living organism causes systemic and local tissue reaction with a different degree of intensity dependent on the time and size of the contact area. The aim of the study was to evaluate the influence of gelatin-alginate matrixes with calcium lactate on blood hematologic parameters and the assessment of the local tissue reaction, and biodegradation and resorption after implantation into soft tissues. Gelatin-alginate matrices in a form of a sponge were used in the study. Sponge was prepared of mixture of gelatin and sodium alginate in 20:1 proportion with an addition of 3% of glycerol as well cross-linking agent calcium lactate. The samples sponge were implanted into back muscles of the rat for the following periods: 1, 2, 3, 5, 7 and 14 days. After time a blood for analysis was collected as well as the implanted samples with surrounding tissues. In the whole blood were designated: the value of hematocrit (Ht), hemoglobin concentration (Hb), red cells count (RBC) and red cells indexes: mean red cell volume (MCV), mean hemoglobin mass in red cell (MCH), mean hemoglobin concentration in red cells (MCHC). White cells count (WBC) was also determined. Results were analyzed by use of Statistica 5.5 software. Mean values RBC, HCT, Hb (p<0,01, p<0,001), MCV, MCH (p<0,05) and MCHC (p<0,05, p<0,01) to 3 days reduction to control group were observed. The result values are not higher then the reference values. The parameter values from 5 days to 14 days was in relation to the control group values. Values WBC in the blood were close and comparable to the values in the control group in all the times of the investigation. In the macroscopic assessment during the post mortem there were no any changes in the implantation sites. Collected samples were the subject of histological assessment. After 24h the strong inflammation were observed which lasted also up to 48h after implantation. At the implantation site the small leftovers of the sponge were noticed and exudation with the numerous inflammatory cells. In results, after 3 and 5 days the thin layer of the connective tissue with new, young vascularisation was formed. After 7 and 10 days the small portion of the implanted samples were observed which were surrounded by connective tissue with numerous fibroblasts and some lymphocytes, polymorphonuclear and plasma cells. There were also visible collagen and single muscle fibers. The small leftovers of the sponges surrounded by the tissue were visible until 14 days after implantation. On the basis of those all results we can stated that the sponge were surrounded and infiltrated by the tissues and partially undergone resorption. Also we can stat that the tested sponges did not produce the foreign body reaction. The study was supported by the project no. 1260 of the Wroclaw Medical University. Keywords: gelatin-alginate sponge white calcium lactate, blood parameters, implantation, soft tissue reaction, biodegradation and bioresorbable polymers
75 P-43 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Cellular Response after Stimulation of the Gelatin Alginate Matrixes
M. Szymonowicz 1, A. Marcinkowska 2, B. śywicka 1, S. Pielka 1, A. Gamian 2, D. Haznar 3, and J. Pluta 3
1Department of Expermental Surgery and Biomaterials Research, Medical University, Poniatowskiego 2, 50 326 Wroclaw, Poland 2Department of Medical Biochemistry, Medical University, 50 368 Wroclaw, Chalubińskiego 10, Poland 3Department of Drug Form Technology, Medical University, Szewska 38, 50 139 Wroclaw, Poland
Polymeric biomaterials have been used in medicine. Among the biomedical polymers there is family of resorbable sponges. The used of scaffolds settled as specific carriers for cells which after implantation into the system makes supporting the tissue and creates good conditions for the tissue regeneration. The evaluation with use of cells culture are quick sensitive tests for the assessment of the biological impurities in the tested sample. The aim of the work was to evaluate the changes in morphology and biological cells viability after directing its temporary contact with gelatin-alginate matrixes in testing in vitro. Four kinds of gelatin-alginate matrixes in a form of a sponge were used in the study. In order to obtain a form of sponge liofilization of foam originated from foaming of mixture of sterile solution of gelatin (20%), natrium alginate (2% or 4%) and glycerol (3% or 5%) selected in an appropriate ratio was performed. Biological material consisted of quickly proliferinghuman carcinoma cells of the lymphoblastic T lymphoma cells Jurkat grow in the suspension of medium, whereas epithelial lung carcinoma cells- A549 (adhering to the bed in the culture), show the superficial growth on substrate and slowly prolifering human umbilical vein endothelial wells – Huvec (adhering to the bed in the culture). The cells culture were performed In culture bottles at 37 with 5%CO for 24 hours addend . Next, cells were taken for temporary contact with sponges. The quantitative changes in selected of cells growth fixation after 24 hours and morphological changes observed after 24, 48 hours. For this purpose the dyed methods with neutral and trypane blue were used. Shape, adhesion to the bed, agglutination, vacuolization and lysis of the cells were determined. Division, proliferation, colonization (to build, construct colony) ability to reproduce and survival rate of cells were observed. Viability measured by means of MTT. In all cultures, after 18 hours the sponges were completely dissolved, and culture medium was clear. The cells were evaluated microscopically. No agglutination, vacuolization, separation from the bed neither lysis of the cell’s walls were observed. Proliferation of the cell was correct and the cells formed proper colonies. They demonstrated the proper structure, ability to growth and no significantly different when comparing to control group. No difference between cells after contact with sponges was observed, as well. Dead cells were not observed. In case of Jurkat, A549, Huvec cells shoved viability comparable with control group. Viability of those cells was over 90%. The survival rate of cells after contact with sponges was comparable. The longest time of viability of cells after contact with sponge and 4% of natrium alginate and 3% glycerol. On the basis of received results it was gelatin-alginate matrixes did not have anty cytotoxicy effects.
The study was supported by the project no. 1260 of the Wroclaw Medical University.
Keywords: gelatin-alginate sponge, cells cultured, aglutynation, proliferation, viability cells.
76 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-44 Synthesis and Properties of Chitosan – Poly(ethylene glycol) Comb Copolymers
Ričardas Makuška and Rūta Kulbokait÷ Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania
Chitosan, a naturally occurring linear cationic polysaccharide, has been widely employed as a drug delivery system, wound dressing, anticoagulants, and scaffolds for tissue engineering owing to its biocompatibility, biodegradability, and low toxicity. Recently prepared comb like chitosan derivatives containing methoxy poly(ethylene glycol) (MPEG) grafts [1, 2] may find application in household and personal care products maintaining appropriate rheological properties and conditioning contact surfaces. Derivatisation of chitosan with a functionalized MPEG-2000 resulted in variety of chitosan- MPEG comb copolymers differing in graft location, degree of substitution and molecular weight. Chitosan-2-N-MPEG comb copolymers were synthesized by reductive amination of chitosan using MPEG aldehyde [1]. Chitosan-O-MPEG copolymers were synthesized using MPEG iodide or MPEG dichlorotriazine as alkylating agent and silver oxide as a catalyst [2]. Oxidation of N-phthaloyl chitosan by the use of TEMPO radical led to 5-formyl-2-N- phthaloylchitosan which was proper precursor for preparation of chitosan-6-N-MPEG [3]. A serious problem is purification of chitosan comb copolymers from unreacted MPEG. To avoid this, the method of “click” chemistry (a copper-catalysed Huisgen reaction) was employed which usually gives nearly quantitative yields of the main products at mild conditions generating virtually no by-products. Azidated chitosan was prepared by reacting azidated epichlorohydrin with chitosan. MPEG azide was made by mesylation of MPEG followed by nucleophilic substitution using sodium azide. Alkyne containing derivatives were synthesized by reacting MPEG or N-phthaloyl chitosan with propargyl bromide. Chitosan-MPEG derivatives with the degree of substitution (DS) of chitosan ca. 20 % were water soluble in a wide pH range. 2-N-PEGylated chitosans were high-molecular-weight products (M w up to 2 million) with the DS of chitosan varying from 23 to 89 %. Solution viscosity of these chitosan copolymers was moderate and had tendency to decrease for the derivatives with high DS down to 0.29 dL/g. O-substituted chitosans were the products with low molecular weight, M w ranging from several to twenty thousand. Positively charged chitosan brush polyelectrolytes adsorb readily to negatively charged silica or mica surfaces. The rate of chitosan adsorption is much higher compared to its derivatives, though according to adsorbed amount chitosan derivatives are preponderant. The adsorption of O-PEGylated chitosans is sufficiently large to give rise to a brush structure that generates strong steric repulsive forces. Thus, chitosan-6-O-MPEG oligomers act as a steric stabilizer and can be used for modification of surface properties. The adsorption layers of N-PEGylated chitosans are heavily hydrated and much less compact than the layers of chitosan. Chitosan-2- N-MPEG graft copolymers could be used as protein-repellent vectors [4].
Keywords: Chitosan derivatives; PEGylation; brush polyelectrolytes; “click” chemistry; chitosan adsorption.
______[1] N. Gorochovceva et all., Eur. Polym. J ., 41 , 2653 (2005). [2] N. Gorochovceva, R. Makuska, Eur. Polym. J. , 40, 685 (2004). [3] R. Makuska, N. Gorochovceva, Carbohydrate Polymers , 64 , 319 (2006). [4] Y. Zhou et all., J. Colloid Interface Sci. , 305 , 62 (2007).
77 P-45 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose M. Koller, P. Hesse, A. Atlić, C. Hermann Krauss, C. Kutschera, and G. Braunegg Graz University of Technology; Inst. of Biotechnology & Biochemical Engineering, Petersgasse 12, A-8010 Graz, Austria The increasing demand for polymeric compounds acting as packaging materials for the safe distribution of goods is undisputed. Contemporary strategies for disposing of end of pipe plastics cause serious global problems such as increasing piles of waste. Incineration of petrol based polymers not only generates noxious compounds, but also elevates the atmospheric CO 2 concentration. This aggravates frequently discussed problems such as greenhouse effect and global warming. Recycling systems do not function as effectively as required for a real solution of the problem. Although data for remaining amounts of mineral oil are changing quickly due to advanced methods for tracing and discharging, the reserves of fossil feed stocks are limited. In May 2005, the price per barrel of mineral oil amounted to US $ 55; recently, this value has rocketed up to US $ 74 (July 2007). Utilizing alternative polymeric materials such as polyhydroxyalkanoates (PHAs) unites two major advantages: Firstly, they can be produced from renewable resources such as carbohydrates, making them independent from the availability of fossil feed stocks. Secondly, when being composted, these biopolymers undergo a biodegradation process by the action of various microbes resulting merely in CO 2 and H2O, the starting materials for the photosynthetic regeneration of carbohydrates by green plants. Thus, the mass stream for carbon in the biotechnological production lines for PHAs is embedded into a closed circle. This is clearly in contrast to the life cycle of classic polymers, where carbon fixed in the bowels of earth since millions of years is converted to CO 2 which is released in the atmosphere. Because recent studies point out that PHA production from purified sugars has been optimized to a high degree, further improvement of the fermentation technologies by using cheaper carbon sources as basis feed stocks is urgently needed.The work at hand studies the utilization of whey, the major by product from cheese and casein production, as feed stock for the biotechnological production of PHA. Whey is not only a cheap raw material, but 13500000 tons of whey per year which contain 620000 tons of lactose (D gluco pyranose 4 β D galactopyranoside) constitutes a surplus product in the EU, causing a huge disposal problem for the dairy industry. Hence, the utilization of whey lactose for PHA production unites the diminishing of a waste problem and the increase of cost efficiency in the bioinspired production of ecologically benign materials. The work at hand presents and compares kinetic data and polymer characteristics for three different microbial strains that turned out to be capable of PHA accumulation from whey lactose (the eubacterial species Pseudomonas hydrogenovora and Hydrogenophaga pseudoflava as well as Haloferax mediterranei ). Advantages and drawbacks of the organisms as potential PHA producers from whey on industrial scale are compared. The industrial significance of the study is underlined by economic appraisals for the investigated processes. Keywords : Biodegradable polymers; Renewable resources; polyhydroxyalkanoates; whey ______ [1] G. Braunegg et al., Polym. Plast. Technol.Eng. 43 (6), 1779 (2004) [2] M. Koller et al., Biomacromol. 23 (5), 561 (2005) [3] M. Koller et al., Bioproc. Biosyst. Eng . 29 (5 6), 367 (2006) [4] M. Koller et al., Macromol. Biosci . 15 (6), 218 (2007).
78 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-46 Synthesis and Study of Chitosan – Oligosaccharide Graft Copolymers
Ugn÷ Jančiauskaite and Ričardas Makuška Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania
Grafted brush polyelectrolytes are of immense technological importance, both for rheology control and for modification of surface properties. The latter application includes such vastly different areas as control of colloidal stability, non-specific protein adsorption, cleaning applications and lubrication. Comb polyelectrolytes partially or fully made from naturally occurring building blocks are of particular interest. The proper representatives of such polyelectrolytes are chitosan comb copolymers combining charge regulating positively charged backbone with flexible and affined to polysaccharides grafts of inulin or dextran. The presence of oligomeric hydrophilic side chains is expected to influence the adsorption of the polyelectrolytes on negatively charged surfaces, to affect the forces acting between the coated surfaces and to have impact on the attachment of the macromolecules of proteins or glycoproteins. Two types of dextran containing comb polyelectrolytes were synthesized attaching dextran-1500 (FLUKA, M r 1500) or dextran-6000 (FLUKA, M r 6000) to amine or C(6)-OH groups of chitosan (FLUKA, M r 400000). The synthesis of chitosan-N-dextran graft copolymers was done by the method of reductive amination resulting in high-molecular- weight products. Peculiar property of these polyelectrolytes was necessity to use freeze- drying process in order to obtain soluble products. Degree of substitution (DS) of chitosan in the copolymers varied from 16 to 62 %. Chitosan derivatives with higher DS had lower intrinsic viscosity [µ], moreover, grafting of dextran-6000 resulted in lower viscosity of aqueous solutions. Chitosan-O-dextran graft copolymers were synthesized by reacting dextran with tosylated derivatives of N-phthaloyl chitosan. Unfortunately, deprotection of amino group functionality in these copolymers always resulted in low-molecular-weight products. Inulin, a known reserve carbohydrate of Cychorium intybus, consists mainly of beta (2-1) fructosyl fructose units with normally, but not always, a glucopyranose at the reducing end [1]. Two different methods were chosen to graft inulin oligomer (ORAFTI, M r up to 2000) to chitosan. The first one is EDC induced coupling between chitosan and inulin succinate the latter being prepared by the reaction between inulin and succinic anhydride in dry DMF [2]. The second method is based on the reaction between chitosan and inulin activated with cyanuric chloride. Graft-copolymers were purified by dialysis against water and precipitated. Chitosan – inulin derivatives were white powders easily soluble in water possessing low intrinsic viscosity. FTIR and 1H NMR spectra of the products were consistent with the presumable structure of chitosan – inulin graft copolymers.
Acknowledgement: Financial support from the Lithuanian State Science and Studies Foundation (project TECHNOSACHARIDAS, N-04/2007) is gratefully acknowledged. ORAFTI is acknowledged for a kind donation of inulin.
Keywords: chitosan derivatives; dextran copolymers; inulin derivatives; comb polyelectrolytes.
______[1] C.V. Stevens, A. Meriggi, K. Booten, Biomacromolecules, 2, 1 (2001) [2] X.Y. Wu, P.I. Lee, J. Appl. Polym. Sci. 77 , 833 (2000).
79 P-47 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Selection of Carbon Feed Stocks for Cost Efficient Polyhydroxyalkanoate (PHA) Production
M. Koller, P. Hesse, A. Atlić, C. Hermann Krauss, C. Kutschera, and G. Braunegg
Graz University of Technology; Inst. of Biotechnology and Biochemical Engineering, Petersgasse 12, A 8010 Graz, Austria
Raw materials require the major part of biopolymer production costs; this share contributes with up to 50% to the entire process expenses. Recent studies indicate that PHA production from pure sugars such as glucose or sucrose has already been optimized to a high degree. Therefore it is of importance to enhance cost efficiency of PHA production by substituting pure substrates by cheaper carbon feed stocks or by integrating PHA production into energetically autarkic production lines of the carbon sources. Whey from dairy industry The utilization of polluting whey combines an economic progress with solving an ecological hazard. Whey was applied as carbon source for three wild type PHA producers: Haloferax mediterranei , Ps. hydrogenovora and Hydrogenophaga pseudoflava. Among these strains, H. mediterranei constitutes an outstanding candidate for PHA production on whey. This is due to its high robustness and stability; the risk of microbial contamination during cultivation is negligible, saving a lot of energy for sterility precautions. The strain grows on whey with a -1 max. specific growth rate max. of 0.11 h . PHA was accumulated at a max. specific production rate of 0.08 g/g h. Conversion yield for whey to PHA amounted to 0.3 g/g. The production of PHA copolyesters without co substrates, the excellent polymer characteristics together with a cheap isolation method make the strain of special interest [1,2,3]. Raw glycerol liquid phase from Biodiesel production H. mediterranei was also used for PHA-production on glycerol liquid phase (GLP), a side stream of the biodiesel production from plant oils and tallow, containing about 70 wt.-% glycerol. In all Europe, the total production of biodiesel is estimated for 2008 with 2,649.000 metric tons. GLP nowadays constitutes a surplus material. Its utilization leads to an enormous cost advantage compared with commercially available pure glycerol, possessing a market value of 900 € per metric ton (year 2002). On bioreactor scale, H. mediterranei was able to grow on GLP at a specific growth rate of 0,06 h -1 and produced PHA (76% of cell mass) at a specific rate of 0,08 g/g·h. The yield for PHA from glycerol was calculated with 0,23 g/g, resulting in a final concentration of 16,2 g/L PHA [1,2,3]. Sugar cane sucrose A different approach is provided by the utilization of carbon sources that feature a considerable market value and do not constitute waste materials, but are produced within a process integrating the fabrication of the carbon substrate and PHA. This will soon be realized in the south-central region of Brazil: starting from sugar cane, saccharose, ethanol and PHB are produced by Wautersia eutropha . The needed energy for polymer production is directly available from burning bagasse, a major by product of the sugar production. Due to the autarkic energy supply and the at-house availability of the carbon source saccharose, the production costs per kilogram PHB are estimated with less than US$ 3 [3, 4].
Keywords: biodegradable polyesters; polyhydroxyalkanoates; whey; raw glycerol phase; sugar cane sucrose ______ [1] M. Koller et al., Macromol. Biosci . 15 (6), 218 (2007). [2] M. Koller et al., Biomacromol . 23 (5), 561 (2005) [3] M. Koller et al.,article in press [4] R. Nonato et al., Appl. Microbiol. Biotechnol .57 , 1 (2001)
80 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-48 Properties and Degradation of PVA/Starch Blends with a PVA-g-MA Compatibilizer
Wan-Ling Lu 1, Chia-I Liu 2, and Chi-Yuan Huang 2
1Dep. of Raw Materials and Yarn Formation,Taiwan Textile Research Institute,Taipei,Taiwan 2Dep.of Materials Engineering, Tatung University, No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan
It can enhance the strain to 100~200 % by dissolving Polyvinyl alcohol (PVA) into one or two time water in the starch/PVA blend system. Adding a compatibilizer (MA-g-PVA) also has a well display in the strain at the break. 1. Experimental 1.1 MA grafting polymerization onto PVA: the general experimental procedure and an example were as follows: PVA 5g and MA 5g were dissolved in 95g DMSO after being stirred in an atmosphere of nitrogen. The reaction temperature was adjusted as needed (such as 60°C), then 0.5g of potassium persulfate was added as a initiator. The reaction lasted for 5h. The reaction mixture was concentrated to about 20%, and was then added to chloroform to precipitate the polymer. 1.2 Blend: in the series A, MA and PVA were dissolved in GA with 120°C for 30min before compounding. In series B and C, MA and PVA were dissolved individually in 300g or 150g distilled water with 70°C for 30min before compounding. For D series, MA-g-PVA (MA Grafting polymerization onto PVA) and PVA were dissolved in 300g distilled water with 70; for 30min before compounding. Then, the tapioca starch and GA were mixed with above composition. 2. Results and discussions 2.1 FTIR Spectra: FTIR spectra, Figure 1, were obtained from MA-g-PVA and PVA films by a JASCO Micro-IR. The IR spectra showed that the characteristic peaks of –COO– at 1720 cm -1 and –C=C– at 1640 cm -1 [1] at Figure .1 could confirm MA graft onto PVA. 2.2 Tensile Strength Measurement:There was a significant distinction of tensile strength for blends in Figure 2. The starch presented stiffness and brittleness in this blends. It was the reason that the maximum stress of A series was much higher than those of B, C and D series blends. Water is a good plasticizer for PVA/starch blends in this work. The strain of B series by adding 150g water was increased above 20 times (Figure 8). Adding 300g water, the strain of C5 was up to about 192 %. Thinking about the graft degree of MA-g-PVA (compatibilizer), the quantity of adding compatibilizer was converted into the amount of adding MA in the blends. The maximum stress range between D series blends was about 1.5 MPa and the strange range between D series blends was about 30 %.
(a) 220 16 80 A series 200 A series B series B series 14 B series 180 C series C series C series 160 D series D series 12 D series (b) 140 70 10 120
%T -1 -1 100 -COO- 1720 cm -C=C- 1640 cm 8
Strain(%) 80 Stress (MPa) 6 60 60 Weight%) Loss (wt
4 40
20 2 0 50 0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18 -2 0 2 4 6 8 10 12 14 16 18 4000 3000 2000 1000 400 MA (g) MA (g) MA (g) Wavenumber [cm -1] Fig. 1.The IR spectra of (a)pure Fig. 2.The tensile strength Fig. 3.The strain at break of Fig. 4.The weight loss PVA and (b)MA-g-PVA. of four series starch /PVA four series starch /PVA measurement of starch/PVA blends. blends. blends. Keywords: Polyvinyl alcohol (PVA) 、maleic anhydride (MA), compatibilizer, MA-g-PVA, SEM micrographs. ______[1] W. Y. Chiang, C. M. Hu, J. Appl. Polym. Sci., 30 , 3895(1985).
81 P-49 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Thermal and Mechanical Behaviour of a Commercial Poly(lactid acid) Submitted to Soil Burial Test L. Santonja-Blasco, J.D. Badia, Rosana Moriana, and A. Ribes-Greus Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior de Ingeniería del Diseño. Universidad Politécnica de Valencia, Camino de Vera s/n 46022 Valencia The replacement of petroleum based polymers, with biodegradable ones is an actual goal because of the increasingly aware in the environmentally friendly materials [1]. Poly(lactic acid) (PLA) an aliphatic, biodegradable and compostable polyester, can be obtained from renewable resources such as starch to yield articles for being used in industrial packaging or in agriculture field, as mulching films. A commercial PLA, supplied by Natureworks.DDL, Minnetonka, U.S.A, was buried in soil in order to characterize non controlled further disposal when it is used in packaging and its service life when it is used as mulching film. Samples were submitted to accelerated soil burial test in a culture oven at 28 ± 0.5ºC during 690 days according to the DIN 53739 standard [2]. Samples were extracted at 0, 30, 150, 300, 450 and 690 days and thermally characterized by means of Differential Scanning Calorimetry(Mettler Toledo DSC822), HR/CR=10ºC/min from 0 200ºC, under N 2 atmosphere and by Dynamic Mechanical Thermal Analysis experiments in a Mark IV DMTA (Rheometric Scientifics) using dual cantilever clamping by bending mode. Specimens were heated from 35 to 150ºC in isothermal mode at 2ºC/min in the frequency range:0.1 39 Hz. DSC thermograms show that when degradation time advances two melting peaks are formed at 450 days. The lamellae thickness distribution calculated by means of Thompson equation [3] is in a range from 75 to 115 Ǻ. In the curves of the samples without degradation it is observed a wide shoulder that becomes narrower when degradation time in soil advances. When 450 days are reached, the lamellae distribution is presented by two separated peaks, however at 690 days both peaks are less pronounced and the distribution is wider. DMTA spectra performed at 1 Hz have been compared, in terms of loss tangent (tan δ) and storage modulus (E’). The relaxation temperature related to glass transition has been calculated by means of the temperature at the maximum of the fitting of the experimental loss modulus (E’’) data to Fuoss Kirkwood [4] model. During degradation in soil: E’ value increases, the temperature related to the glass transition shifts to higher temperatures and the recrystallization occurs at lower temperatures. PLA has increased its crystallinity, due to the linkages weakening in the amorphous phase. Degradation in soil improves a faster linkage of the amorphous phase of the PLA, enhancing segregation of the crystallite size distribution until 690 days when seems to be homogenised. It also provides a higher E’ increased and recrystalization is produced at lower temperatures. Acknowledges: Ministerio de Educación y Ciencia and the European Region Development Fund for the economical support through the Project CTM2004 04977/TECNO and for the concession of pre doctoral grants FPI and FPU. Keywords: poly (lactid acid); DSC; DMA; degradation in soil ______ [1] A. C. Albertsson, S. Karlsson, Acta Polymerica , 1995 , 46, 114. [2] DIN 53739 Testing of plastics. 1984. [3] Hoffman, J. D., Davis, G. T. & Lauritzen, J. I. in Treatise on Solid State Chemistry (ed. Hannay, N. B.) 497−614 (Plenum, 1976). [4] R.M. Fuoss, J.G. Kirkwood, J. Am. Chem. Soc . 1941 , 63, 385.
82 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-50 A Thermogravimetric Approach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid)
J. D. Badia, Rosana Moriana, L. Santonja-Blasco, and A. Ribes-Greus Instituto de Tecnología de Materiales. Escuela Técnica Superior de Ingeniería del Diseño. Universidad Politécnica de Valencia. Camino de Vera s/n, 46022, Valencia, Spain Poly(lactic acid) (PLA) is a green polymer, due to it can be obtained from renewable resources and can be compostable when its service life has finished. The knowledge of the degradation mechanisms involving the disposal stage of PLA must be assessed, in order to assure the complete life cycle of a biodegradable material. PLA with a 3.8% of meso lactide content samples (supplied by Natureworks.DDL, Minnetonka, U.S.A) were submitted to accelerate soil burial test in a culture oven Heraeus 12 at 28 ± 0.5ºC during 450 days following the DIN 53739 standard[1]. Specimens extracted at 0, 30, 150, 300 and 450 were analyzed by thermogravimetry. Measures were carried out in a Mettler Toledo TGA/SDTA 851, from 25 to 750ºC at a heating rate of 20ºC/min, under Ar atmosphere. The DTG temperature peak (T peak ), the degradation onset (T on ) and endset (T end ), as well as the activation energy of the degradation process (Ea) were selected as characterization parameters to analyze the degradation in soil influence on poly(lactic acid). A f (α) = (1 α) n (with n=1) degradation kinetic model was previously hypothesized to employ the kinetics models proposed by Broido[2] and Chang[3] for calculating the Ea of the degradation mechanism. These results were compared to the Ea values obtained by the method developed by Coats and Redfern [4] to prove the consistence of the kinetic study. Criado[5] mastercurves were plotted from experimental data to confirm the degradation kinetic model assumed. For the samples submitted to an accelerated biodegradation process, no accentuated changes were observed at the thermal stability of the polymer. No linear trend was established for the activation energy evolution along the degradation in soil time, evidencing an oscillating behaviour, with an initial Ea decrease until 150 days of exposure in soil, followed by an Ea increase until the end of the experiment. The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the European Regional Development Fund for the economical support through the Project CTM2004 04977/TECNO and for the concession of the pre doctoral grants through the programmes FPI and FPU.
Keywords: poly (lactic acid);biodegradation in soil; thermogravimetry; kinetic analysis ______ [1] DIN 53739 Testing of plastics . (1984). [2] Broido, A . J.Polym.Sci. Part-2, 27 ,1768, (1969). [3] Chang, W.L. , J. Appl. Polym. Sci, 53 , 1759, (1994). [4] AW. Coats, Redfern JP. Nature , 201 , 68. (1964). [5] Criado,J.M., Thermochimica Acta , , 24 ,86, (1978).
83 P-51 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Comparative Study about the Biodegradability and the Mechanical Performance of Different Biocomposites Based on Thermoplastic Starch Reinforced with Cotton Fibre
Rosana Moriana, L. Santonja-Blasco , J. D. Badia, and A. Ribes-Greus
Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior de Ingeniería del Diseño. Universidad Politécnica de Valencia. Camino de Vera s/n 46022 Valencia
The substitution of traditional polymeric-based composite materials with synthetic matrixes (epoxy, unsaturated polyester, or phenolics) reinforced with fillers such as glass, carbon or aramid fibres, by environmentally-friendly composites with a biodegradable matrix and natural fibres is therefore considered critical, due to an increasing environmental consciousness and demands of legislative authorities [1]. Recent advances in natural fibre development and composite science allow improving materials from renewable sources. The current challenge is to design materials with structural and functional stability during use, together with enhanced degradability during disposal in landfills to reach to close the material loop without environmental hazard [2]. The purpose of this work is to study different composites reinforced with a cotton fibre in order to analyse the influence of the matrix employed. Thermal Analysis has been performed to evaluate the potential applications of these blends, their characterisation, as well as the study of their degradation processes.
The polymeric matrices are based on thermoplastic starch-based materials commercialized under the Mater-Bi KE 03B1 and Mater-Bi NF01U trade marks, [Novamont North America (USA) ]. Cotton is the natural fibre employed as reinforcement [Yute S.L.(Spain) ]. The thermo-mechanical properties of Mater-Bi have been investigated to assess its suitability as a matrix material for the fabrication of biocomposites, to guarantee the improvement of the mechanical properties after reinforcing with the biofibres, and to investigate the viscoelastic behaviour in the studied materials. The biodegradability of the unfilled matrix, the natural fibres and the composite with 10% in weight of cotton, were simulated by an accelerated soil burial test (DIN 53739) [3]. Thermogravimetric analysis was used to study the thermal stability of the employed materials, to fully investigate their thermal decomposition process and to monitor their degradation process in soil. A deep kinetic analysis of the decomposition process has been performed, with the determination of the activation energies and the discussion of the reaction mechanism.
The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the European Regional Development Fund for the economical support through the Project CTM2004- 04977/TECNO and for the concession of the pre-doctoral grants through the programmes FPI and FPU.
Keywords: biocomposites; renewably polymers; mechanical properties; thermal analysis. ______[1] C. Bastioli, C. Facci, Biodegradable Plastic Conference , Frankfurt. (1999 ). [2] A.K. Mohanty; M. Misra; T.D. Drzal, Ed.; Natural Fibers, Biopolymers and Biocomposites , Taylor & Francis edition, Boca Raton, (2005). [3] DIN 53739 Testing of plastics. Influence of Fungi and Bacteria. Visual Evaluation. Change in Mass and Physical Properties, (1984).
84 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-52 Improving the Processing Ability and Mechanical Strength of Starch/PVA Blends through Plasma and Acid Modification
Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu
Department of Materials Engineering, Tatung University, 40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.
In this investigation, maleic anhydride (MA), and citric acid (CA) used as the processing additive and plasma treatment to improve the processing ability and mechanical strength of biodegradable starch/PVA blends were studied. The melt flow index of starch/glycerol/PVA (300g/60g/80g) was increased from 2.3g/10min to 32.7 g/10min by adding 3g of MA and to 130 g/10min by adding MA and plasma treatment. The mechanical strength of starch/glycerol/PVA increases from 3.48 to 6.21 MPa by adding 1.5g of MA and 1.5g of CA, while it increases to 6.26 MPa by plasma treatment. Esterization reaction occurred when MA was dissolved into glycerol and glycerol grafted onto plasma pretreatment PVA. This was caused the improved compatibility between starch and PVA. Thermogravimetric analysis, x- ray diffraction, and scanning electron microscopy were used to study the morphology during plasma and acid modification. Keywords: biodegradable; maleic anhydride; citric acid; starch; thermogravimetric analysis (TGA)
85 P-53 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Biodegradation of Starch and PVA/Starch Blend Enhanced by Rhizopus Arrhizu s
Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu
Department of Materials Engineering, Tatung University, 40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.
Biodegradation of starch and PVA/starch blend improved by Rhizopus arrhizus was examined. PVA, tapioca starch, and PVA/starch blend were buried in soil for sixteen weeks in order to study the different biodegradation rates among these three materials. The PVA/starch blend consisted of PVA (20%), glycerol (15%), and native tapioca starch (65%). Burial tests were performance in three different soil conditions: (a) general compost (b) adding fungus in compost, and (c) adding fungus in compost after sterilization. The complete biodegradation time of PVA/starch blend were in the order as (b) test (burial time of 10 weeks) < (c) test (12 weeks) < (a) test (16 weeks). The biodegradation of starch has the same tendency among these burial soil conditions, but degradation time was shortening to 6, 8 and 10 weeks. Thermogravimetric analysis, x-ray diffraction, and scanning electron microscopy were used to determine the morphology and degradation process of each material. Overall, adding Rhizopus arrhizus in combination with other microorganisms can initiate the biodegradation and increase the degradation rate for starch and its blend in the burial tests. Keywords: biodegradable; fungus; starch; thermogravimetric analysis (TGA)
86 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-54 Biodegradable Blends of Polylactide and Natural Rubber
Marcin Kowalczyk and Ewa Piorkowska
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
Blends of polylactide (PLA) with two poly(1,4-cis-isoprene)s, differing in molecular weight, were prepared with the aim to improve drawability through promotion of craze plasticity. Morphology and mechanical properties of the blends were examined. Compression moulded and quenched films of PLA and the blends containing of 5-25 wt% of rubber were o amorphous, as it followed from DSC studies. T g of PLA, at about 55 C, remained unaffected by the presence of rubber. SEM, TEM and DMTA studies revealed that the blends were phase separated, with rubber particles dispersed within PLA matrix. Tensile test, performed on an Instron at the drawing rate of 5%/min and 50%/min, demonstrated that incorporation of rubber decreased significantly a yield stress. Significant improvement of elongation at break and tensile impact strength was achieved in the blends with 5 wt% of rubber. SEM and SAXS examination of deformed specimens demonstrated that at early stages of deformation crazes were initiated, presumably by rubbery particles. Further deformation involved also shear banding. Such a way of modification of PLA mechanical properties is a promising alternative to plasticization.
Keywords: polylactide ; biodegradable blends; mechanical properties
87 P-55 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Synthetic Analogues of PHA Anionic Ring-opening Polymerization of βββ-alkoxy Substituted βββ-lactones
G. Adamus and M. M. Kowalczuk Polish Academy of Sciences, Centre of Polymer and Carbon Materials, 34 M. Curie-Sklodowska St, 41-800 Zabrze, Poland Polyhydroxyalkanoates (PHAs) are thermoplastic aliphatic polyesters produced by microorganisms as energy storage materials. They represent an interesting group of biodegradable polymers that have recently received much attention, particularly as environmentally friendly materials produced from renewable resources. Among the variety of PHAs, poly[(R) 3 hydroxybutyrate], PHB, is of particular importance. Synthetic analogues of this biopolymer of potential industrial importance are obtainable by direct copolymerization of epoxides with carbon monoxide [1] or via ring opening polymerization (ROP) of β butyrolactone to isotactic, atactic (a PHB) and syndiotactic poly 3 hydroxybutyrate. [2 6] Recently, systematic investigations have been conducted on the catalytic synthesis of β lactones through the carbonylation of epoxides, since epoxides are easy to synthesize, inexpensive, and readily available in an enantiomerically pure form. This specific synthetic method opens a new opportunities for exploring the utility of the β lactones (and in particular precursors of synthetic analogues of natural poly(3 hydroxyalkanoate)s i.e. β substituted β lactones) as monomers for the synthesis of new polymers with desired properties. [7] The aim of the present communication is to report the ability of novel β alkoxy substituted β lactones i.e.: β (methoxymethyl) β propiolactone (MOMPL) and β (ethoxymethyl) β propiolactone (EOMPL) to undergo anionic ROP. Polymerization was conducted in the presence of activated carboxylates i.e. supramolecular complex of potassium + acetate and tetrabutylammonium acetate (Bu 4N Ac) as well as by tetrabutylammonium hydroxide. The subtle structure of the polyesters obtained has been established on the basis of ESI MS n experiments. Acknowledgement. This research project was supported by Polish Ministry of Science and Higher Education project No 3 T08E 022 30 and by Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD CT 2004 509232.
Keywords: ; biodegradable polymers; poly(3 hydroxy 4 methoxybutyrate), poly(3 hydroxy 4 ethoxybutyrate) ______ [1] Allmendinger, M.; Eberhardt, R.; Luinstra, G.; Rieger, B. J.Am.Chem.Soc. 2002, 124, 5646. [2] (a) Zhang, Y.; Gross, R.A.; Lenz, R.W. Macromolecules 1990, 23, 3206 3212; (b) Tanahashi, N.; Doi, Y.; Macromolecules 1991, 24, 5732 5733; (c) Hori, Y.; Suzuki, M.; Yamaguchi, A.; Nishishita, T. Macromolecules 1993, 26, 5533 5534; (d) Abe, H.; Doi, Y. Macromolecules 1996, 29, 8683 8688. [3] Rieth, L.R.; Moore, D.R.; Lobkovsky, E.B.; Coates, G.W. J.Am.Chem.Soc. 2002, 124, 15239 15248. [4] (a) Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651 1656; (b) Abe, H.; Matsubara, I.; Doi, Y.; Hori, Y.; Yamaguchi, A. Macromolecules 1994, 27, 6018 6025. [5] Kurcok, P.; Śmiga, M.; Jedliński, Z.; J.Polym. Sci. Polym. Chem. 2002, 40, 2184 2189. [6] (a) Kemnitzer, J.E.; McCarthy, S.P.; Gross, R.A. Macromolecules 1993, 26, 1221 1229; (b) Kricheldorf, H.R.; Eggerstedt, S. Macromolecules 1997, 30, 5693 5697 . [7] Church, T.L.; Getzler, Y.D.Y.L.; Byrne, C.M.; Coates, G.W Chemical Communications 2007, 7, 657 674.
88 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-56 Biopolymer-based Fluorescent Sensors for Quality Control of Food Products
D. Ciechanska 1, J. Wietecha 1, J. Kazimierczak 1, D. Wawro 1, and E. Grzesiak 2
1 Institute of Biopolymers and Chemical Fibres with the incorporated Pulp and Paper Research Institute, 19/27 M. Sklodowskiej-Curie St., 90-570 Lodz, Poland 2 Institute of Dyes and Organic Products, 2/4 Chemikow St., 95-100 Zgierz, Poland
The research was aimed at development of simple and quick method for checking microbiological quality of food, especially meat and milk products, using fluorescent indicators. The method consists in hydrolysis of substituted derivatives of fluorescein and rhodamine, which, in normal conditions, show no fluorescence. Fluorescein has the absorption maximum at 490 nm and emission maximum at 514 nm and rhodamine at 498 nm and 520nm, respectively. Upon the action of hydrolytic enzymes (esterases, lipases and proteases) released by active food-deteriorating microorganisms the functional groups of fluorescein and rhodamine derivatives will become unblocked and start emitting fluorescence. The rate of hydrolysis reaction of various derivatives is proportional to the enzymes concentration and, therefore, to the number and vitality of enzyme-producing microorganisms. At the early stage of research, a wide range of fluorescent dyes derivatives such as diacetylfluorescein, dibutyrylfluorescein, diacetyleosin, diacetylerythrosin, dilauroylfluorescein, dibenzoylfluorescein and diacetylrhodamine has been investigated in order to assess their suitability for sensors preparation. Based on the investigations two selected derivatives – diacetylfluorescein (FDA) and dibutyrylfluorescein (FDB) were deposited on surfaces of suitable polymer carriers. The progress of FDA and FDB hydrolysis due to action of enzymes of specified activity was monitored by intensity of fluorescence emitted by sensors under UV light source. Fluorescein derivatives proved to be hydrolysed by both lipases and proteases but in the case of lipases the reaction rate was significantly higher. It was also found out that diacetylfluorescein was the most susceptible to the hydrolytic action of the above enzymes. In vitro tests of fluorescent sensors were carried out using meat and milk samples of various degrees of microbiological contamination, which had been previously stored for 0-5 days at ambient temperature.
This work was carried out as part of research project Nr. 3 T09B 137 28, which has been supported financially by the Ministry of Science and Higher Education.
89 P-57 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polyhydroxyalkanoates Production by Isolates from a Polluted Salt-lagoon
S. Povolo and S. Casella Dipartimento di Biotecnologie Agrarie, University of Padova, Viale dell’Università, 16, Legnaro (PD), Italy Polyhydroxyalkanoates (PHAs) are a family of biodegradable polyesters having a number of possible industrial applications. They are synthesised as intracellular carbon and energy storage material by a wide variety of bacteria. The main obstacle to PHA diffusion is its high production cost greatly depending, among others, upon the cost of the fermentation substrate to be utilised as a carbon source. The use of agricultural waste materials could play an important role in economic production of PHA [1]. Starch or hydrolysed starch, cellulose and hemicellulose along with sucrose and cheese whey have been proposed as economical sources [2]. Polymer production was studied in many bacteria and recently also in moderately halophilic bacteria, which grow optimally with 3 15% (w/v) NaCl [3]. Nevertheless, investigations on the phenotypic characteristics of some type strains belonging to the genus Halomonas has revealed poly(β hydroxybutyrate) [PHB] accumulation for several species. In contrast to the culture requirements of extremely halophilic archaea, sodium chloride concentrations of 0.5 and 4.5% (w/v) provided the highest cell densities and PHB accumulation in the case of H. boliviensis [4]. The production of PHB by H. boliviensis from hydrolyased starch and from sucrose was also described [5]. The objective of the present work was to isolate from the salt lagoon of Sottomarina (Venice, Italy) bacteria able to degrade different carbon sources such as glycerol and lactose and producing PHA at the same time. Specially, we worked on the isolation of bacteria growing at 8 % (w/v) NaCl. Some isolates, were identified by 16S rDNA sequence analysis as belonging to the genus Halomonas . Here we report preliminary results on the bacterial conversion of glycerol and lactose to PHA by the selected isolates. Keywords: moderate halophile; Poly(β hydroxybutyrate) (PHB) accumulation; carbon source ______ [1] M. Koller, R. Bona, G. Braunegg, C. Hermann, P. Horvat, M. Kroutil, M. Martinz J. Neto, L. Pereira, P. Varila. Biomacromolecules 6, 561 565 (2005). [2] S.Y. Lee. Trends in Biotechnol. 14 , 431 438 (1996). [3] J.A. Mata, J. Martìnez Cànovas, E. Quesada, V. Bèjar. Yt. Appl. Microbiol. 25 , 360 375 (2002). [4] J. Quillaguamán, O. Delgado, B. Mattiasson, R. Hatti Kaul Enzyme Microb. Technol. 38 ,148–154 (2006). [5] J. Quillaguamàn, M. Muños, B. Mattiasson, R. Hatti Kau. Appl. Microbiol. Biotechnol . 74 , 981–986 (2007).
90 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-58 Thermal Properties for Blend of Poly[(L)-lactide] and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate] Michał Sobota, Henryk Janeczek, Piotr Dacko, and Marek M. Kowalczuk
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34, Marii Sklodowskiej Curie St., 41-819 Zabrze, Poland The field of biodegradable polymers is a fast growing area of polymer science because of crude oil, natural gas which are sources for traditional plastics reached price level where biodegradable polymers can be profitable at common applications instead of non biodegradable plastics. In addition, composting, which is used for disposal of food and yard waste is the most suitable for the disposal of biodegradable materials. Therefore promising oppurtiunity are appeared for packaging materials which could be prepare from biodegradable polymers. Polyesters such as: poly[(L) lactide] (PLA), poly[hydroxyalkanoate] (PHA) are most popular representants of biodegradable polymers which are applied in medical, pharmcological and packaging industries. However biodegradable polymers are promising materials, many of them are modified on diference ways for improve of physical properties and processability.[1,2] One of the method modification polymer is blending of two or more polymers, which is an attractive approach because of the low cost and simplicity. The aim of the work is thermal investigation for melted blends of PLA and atactic poly[(R,S) 3 hydroxybutyrate] (a PHB) by differential scanning calorimetry (DSC). Molecular weight of PLA (Mn= 100000, Mw/Mn= 2,0) and a PHB (Mn= 80000, Mw/Mn= 1.2) were determined by GPC performed in chlorofome with polystyrene standards. DSC thermograms for the blends and pure PLA showed differences in rate of crystallization, process is accelerated by the addition of a PHB component. Time of isothermal (115°C) crystallization for blends after processing decreased compare to neat PLA, even in sample which is 5% w/w a PHB content.
Acknowledgment This work was supported by: Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD CT 2004 509232. Polish Ministry of Science and Higher Education: R&D project no. R05 055 02. Regional Fund for PhD Students (Regionalny Fundusz Stypendiów Doktoranckich) of the European Social Fund. ______ [1] Jedliński Z, Kurcok P, Lenz RW. J Macromol Sci Pure Appl Chem 1995;A32:797. [2] Datta R, Tsai S P, Bonsignore P, Moon S H, Frank JR. FEMS Microbiol Rev 1995;16:221.
91 P-59 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Synthesis of Poly(aspartic acid) b Polylactide Block Copolymer Ida Poljanšek, Blaž Brulc, Maja Gričar, Ema Žagar, Andrej Kržan, and Majda Žigon
National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
The aim of our work is the preparation and study of novel functional polymers and polymeric materials with tailored properties for application in drug delivery systems. The research on functional polymers is oriented towards synthesis and characterization of biodegradable and biocompatible polyesteramides as carriers for controlled drug release based on natural monomers lactic and aspartic acids [1,2]. The current synthetic work is focused on the block copolymers made of these two monomers because side-chain carboxylic groups enable the formation of complexes of the copolymer with metal ions. In this study poly( β-benzyl L-aspartate)s and their block copolymers with L,L-lactide with varying molar mass averages and low polydispersity indices (PDI = 1.00–1.09) were prepared. NMR and FT-IR spectroscopy was used to elucidate the products chemical composition, and size-exclusion chromatography coupled to multi-angle laser photometer (SEC-MALLS) was used for the determination of the absolute molar mass averages of the products. The benzylic protected aspartic acid N-carboxyanhydride (Asp-NCA) was chosen as the monomer for the preparation of the polyamide block. Benzylic protection prevented side reaction leading to branched polymers whose degree of branching could not be controlled. Polymerization of aspartic acid NCAs was carried out in dry N,N-dimethylformamide at room temperature and at slightly elevated temperatures (up to 40 °C) in a dry argon atmosphere using triethylamine or n-pentylamine as the initiator. The polymerization mechanism is strongly dependent on the initiator used since triethylamine exhibits a basic and n-pentylamine a more nucleophilic character [3]. Molar mass averages of poly( β-benzyl L- aspartate)s were in both cases in the order of 10 3–10 4 g mol -1 (depending on the ratio of monomer to initiator used), while polymers were practically monodisperse (PDI = 1.00–1.05). The next step was the copolymerization of poly( β-benzyl L-aspartate) and L,L-lactide using stannous(II) octoate as the catalyst [4]. The reactive amino end group of protected poly(aspartate) block acts as a co-initiator. The linear block copolymers of well defined structures were synthesized in solution in a dry nitrogen atmosphere and at temperatures between 50 and 75 °C by lactide ring-opening polymerization. The chemical composition of the block copolymers i.e., the length of lactide block depends on the feed ratio, temperature and time of reaction. The copolymers synthesized in this manner were linear, but those prepared at temperatures at 65 °C and above exhibited some degree of branching due to partial hydrolysis of pendant benzylic ester groups.
Keywords: biodegradable polymers; block-copolymers; characterization
______[1] K. Uhrich, S. Cannizzaro, R. Langer, K. Shakesheff, Chem. Rev. 99 , 3181 (1999). [2] C. S. Ha, J. A. Gardella, Chem. Rev. 105 , 4205 (2005). [3] H. Sekiguchi, Pure Appl. Chem. 53 , 1689 (1981). [4] A. Kowalski, J. Libiszowski, R. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38 , 8170 (2005).
92 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-60 Compostability of Aliphatic-aromatic Copolyester and their Blends under Natural Weather Depending Conditions
Katarzyna Krasowska 1, Maria Rutkowska 1, and Marek M. Kowalczuk 2
1Gdynia Maritime University, Department of Chemistry and Industrial Commodity Science, 81-87 Morska Str., Gdynia, Poland 2Polish Academy of Sciences, 34 M. Sklodowskiej-Curie Str., Zabrze, Poland
Recently, there is growing demand of biodegradable polymers. They have acquired an important place in modern life. Products from biodegradable polymers have been implemented in the medical field, pharmacy, gardening, agriculture and packaging. Selective use of biodegradable polymers in certain applications might help to reduce the environmental impact of plastic wastes. Generally three categories of biodegradable polymers can be distinguished: (1) natural polymers produced by plants, animals, and microorganisms such as cellulose, starch, chitin and polyhydroxyalkanotes, (2) synthetic polymers such as polylactide, polycaprolactone, (3) convenient blends of natural and synthetic polymers. Among these biodegradable polymers, polyesters are the most promising materials. On the one hand aliphatic polyesters constitute the most attractive class of artificial polymers, which can degrade in contact with living organisms but on the other hand aromatic polyesters exhibit excellent material properties but proved to be almost resistant to microbial attack. To combine good material properties with biodegradability, a new group of copolyesters have been developed as biodegradable polymers. This group includes the aliphatic-aromatic copolyester of 1,4-butandiol with adipic and terephtalic acids. According to DIN and ASTM standards this polymer is biodegradable, atoxic and useful in composting process. The development of these group of the aliphatic-aromatic copolyesters biodegradable in natural environments is the key to solving problems caused by plastic wastes. But very often environmental degradation can only occur in favourable environments, where the biodegradation is expected to happen. In this way the aim of the present study was an examination of the compostability of copolyester of 1,4-butandiol with adipic and terephtalic acids (Ecoflex , BASF) and their blends under natural weather depending conditions. Environmental degradation of pure Ecoflex and and their blends such as Ecoflex / copolyester of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV) and Ecoflex / Ramie woven fabric took place in the compost pile consisted of the activated sludge, burnt lime and straw preapared under natural conditions of sewage farm The compostability of investigated polymers under natural conditions was based on the examination of the changes of surface and weight of polymers after degradation. The characteristic parameters of compost were also investigated and their influence on the rate of composting process was discussed. The results of the present study revealed that Ecoflex and their blends are degraded in compost with activated sludge under natural conditions. The rate of composting process depends on the nature of environment and the kind of degraded polymer. Generally the biodegradation rates of investigated polymers in compost with activated sludge decreased in order: Ecoflex /PHBV>Ecoflex >Ecoflex /Ramie woven fabric.
Keywords: copolyester of 1,4-butandiol with adipic and terephtalic acids, PHBV, Ramie woven fabric, compost with activated sludge
93 P-61 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Illumination of Cellulose with Linearly Polarized Visible Light A. Konieczna-Molenda 1, M. Molenda 2, M. Fiedorowicz 1, and P. Tomasik 1
1Department of Chemistry, University of Agriculture, Balicka 122 Str., 30-149 Cracow, Poland 2Faculty of Chemistry, Jagiellonian University, Ingardena 3 Str., 30-060 Cracow, Poland Cells and plants react to the polarized light [1,2]. Reports on effects of the polarized light upon the activation of enzymes [3], enhancement rate of enzymatic hydrolysis of starch polysaccharides [4] and rearrangement of the molecular structure of starch polysaccharides [5] were published recently. This work provides results of our study on the changes in physicochemical properties of cellulose induced by illumination with the polarized light. Water suspensions of commercially available cellulose, containing long polysaccharide chains, were illuminated with visible polarized light for 20 and 50 hrs. Another cellulose samples suspended in water and kept in the dark served as reference. After termination of illumination, cellulose was filtered off and dried. Crystalline structure [6], thermal properties (DSC) [7], susceptibility to oxidation [8] and degree of polymerization (DP by viscometry) [9] of the samples were determined. Additionally, kinetic of enzymatic as well as acid hydrolysis of cellulose was estimated. Illumination of cellulose with linearly polarized light (50 hrs) increased degree of polymerization of 15%. Such effect was not observed for illuminated at shorter time as well as for non illuminated samples. The DSC measurements indicated different water content in the samples of illuminated and nonilluminated cellulose prepared under the same conditions. The illuminated cellulose incorporated the highest, about 18%, water content. Only for that sample the heat effect related to water freezing was observed. X ray diffraction patterns demonstrated that the illumination resulted in an increase in the cellulose crystallinity. After prolonged illumination, the cellulose was resistant to the oxidation. Illuminated cellulose revealed lower susceptibility to enzymatic and acid catalysed hydrolysis ______ [1] T.Kubasowa, M.Fenyo, Z.Somosy, L.Gazso, I.Kertesz; Photochem. and Photobiol., Vol.48, No. 4, 1988, pp. 505–509. [2] K.M.Hartmann, A.Mollwo; Proc. Symp. Biologic Effects of Light , Basel, Switzerland, 1 3.11.1998. [3] M.Fiedorowicz, A.Konieczna–Molenda and G.Khachatryan; Starch: – Progress in structural studies, modifications and applications . Eds P.Tomasik, V.Yuryev, E.Bertoft, Polish Society of Food Technologist’ Małopolska Branch, 2007. [4] M.Fiedorowicz, G.Khachatryan, A.Konieczna Molenda, V.P.Yuryev, L.A. Wassermann; Starch: Achievements in Understanding of Structure and Functionality. Edts.: Vladimir Yuryev, Piotr Tomasik and Eric Bertoft . Nova Science Publishers, New York, 2006. [5] M.Fiedorowicz, G.Chaczatrian; J. Sci. Food Agric., 2004, 84 (1), 36 42. [6] K.Choo Won, K.Dae Sik, K.Seung Yeon, M.Marquez, Yong L.J; Polymer 47 (2006) 5097 5107. [7] A.Kochanowski, R.Dziembaj, M.Molenda, A.Izak, E.Bortel; J. Therm. Anal. Cal. 88(2) (2007) 499 502. [8] L.M.Proniewicz, C.Paluszkiewicz, A.Wesełucha Birczyńska, H.Majcherczyk, A.Barański, A.Konieczna; J. Molec. Struc. 596 (2001) 163 169. [9] A.Barański, A.Konieczna–Molenda, J.M. Łagan, L.M. Proniewicz; Restaurator 24 (2003) 36-45.
94 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-62
Poly( L lactide) Nano and Micro fibers by Electrospinning: Influence of Poly( L lactide) Molecular Weight W. Tomaszewski 1, A. Duda 2, M. Szadkowski 1, J. Libiszowski 2, and D. Ciechańska 1 1Institute of Biopolymers and Chemical Fibres, Sklodowskiej-Curie 19/27, 90-570 Lodz, Poland 2 Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
Aim of the work The present contribution aims at reporting on studies of nanofibers and nanofibrous mats parameters obtained from poly( L-lactide)s (PLA’s) of various molecular weights. Materials PLA’s were prepared by the controlled ring-opening polymerization of the L.L-dilactide (LA) monomer. The polymerization was carried out in THF as a solvent at 80 °C with tin(II) bis - octanoate (2-ethylhexanoate) as a coinitiator. For the resulting, isolated by precipitation into methanol PLA’s, the following molecular weights ( Mn, SEC, LLS detector) were determined: 22 ×10 3, 62 ×10 3, 132 ×10 3. Preparation of fibrous mats by electrospinning The spinning solutions contained from 1 to 12 wt-% of PLA in a solvent composed of 90/10 wt% CHCl 3/DMSO mixture. The electrospinning apparatus was equipped with 12 points spinning head sliding along a rotating tube, with diameter of about 8 cm, as collecting electrode. The air gap and voltage were 15 cm and 20 kV, respectively. The electrospun products were flat fibrous sheets, about 0.1 mm thick. Analytical methods Microscopy. The electrospun products were observed by a scanning electron microscope Quanta 200(W), FEI Co., USA. Thermal characterization. T he thermal transitions were measured by a differential scanning calorimeter DSC-2, Perkin-Elmer, USA. Viscometry. The viscosity of the spinning solutions were measured by a Brookfield viscometer Tensile tests. The tensile properties were measured by classic (tensile tester, Instron 5544, USA) and special ball piercing (modified Instron apparatus) methods. Results The nano- and micro-fibrous mats with diameters of fibers in the range from 0.1 to 1.7 µm were manufactured by electrospinnig from solution. Molecular weights of the applied PLA’s, viscosities of the spinning solutions, and the fibers thickness were correlated. The microscopic, thermal and tensile characteristics of the resulting mats were examined.
This work was carried out as a part of the research project no. 3 T08E 036 29 supported by the Ministry of Science and Higher Education, Poland
Keywords: poly( L-lactide); nanofibrous mats; electrospinning; mechanical properties
95 P-63 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Biomedical Applications of Maleic Anhydride Copolymers and Their Derivatives
Gabrielle C. Chitanu 1, Irina Popescu 1, Adina G. Anghelescu-Dogaru 1, and Irina Dumistracel 2
1“Petru Poni” Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, 700487, Iasi, Romania 2S. C. Antibiotice S.A. - Iasi, Valea Lupului 1, Iasi, Romania
The use of maleic anhydride copolymers or their derivatives for medical or pharmaceutical purposes is already known, some of such applications being of current use. An important research effort was dedicated to this topic, the pioneering results of Breslow [1] and Maeda [2] are worthy to be mentioned as well as the contributions of Hirano and co-workers [3], Hodnett et al. [4], Azori, Pato and co-workers [5], Rubessa and co-workers [6], Heller et al. [7], A. Urtti and his group [8]. The application of maleic anhydride copolymers in the biomedical and pharmaceutical topic is promoted by several advantages from which can be mentioned their regular, reproducible chemical structure, their variable hydrophobicity/hydrophilicity, that can be tailored by choosing the suitable comonomer, and their chemical versatility, due to the anhydride cycle, which allows to attach different low molecular compounds by mild reactions. Not on the last place is the pH dependent solubility of the conjugates based on maleic anhydride copolymers, which is particularly suitable for the controlled delivery of drugs in different segments of the gastrointestinal tract. In the first section of our contribution all these aspects are reviewed in a systematical and organized manner. The second part of our work presents several of our results aiming the obtaining of maleic anhydride (MA) copolymers based derivatives or systems for biomedical purpose. They are described: - Synthesis and characterization of macromolecular disinfecting systems from MA copolymers and OH- containing disinfectants such as thymol or eugenol - Synthesis and characterization of menthol-containing polymers for dental use - Synthesis and characterization of amidic derivatives of MA copolymers and preparation of microparticles loaded with bioactive molecules - Some data on the polymer degradation in aqueous solution.
Acknowledgement The financial support of Romanian National Authority for Scientific Research, CEEX projects no. 14/2005 and 277/2006 is gratefully acknowledged.
Keywords: bioactive polymers; polymer degradation; maleic anhydride copolymers; polymer-drug conjugates ______[1] D. S. Breslow, Pure Appl. Chem. , 46 , 103 (1976). [2] H.Maeda, Adv. Drug Delivery Rev. , 6, 181 (1991). [3] Hirano, T.; Ohashi, S.; Morimoto, S; Tsuda, K. Makromol. Chem. , 187 , 2815 (1986); Hirano, T.; Todoroki, T.; Kato, S; Yamamoto, H.; Calicetti, P.; Veronese, F.; Maeda H.; Ohashi, S. J. Control. Release, 28 , 203 (1994); Hirano, T.; Todoroki, T.; Morita, R.; Kato, S; Ito, Y.; Kim, K.-H.; Shukla, P. G.; Veronese, F.; Maeda H.; Ohashi, S. J. Control. Release, 48 , 131 (1997). [4] E.M. Hodnett, A. Wai Wu, and F.A. French, Eur. J. Med. Chem. , 13 , 577 (1978) and subsequent papers. [5] See for example: M. Azori, in: “Polymers in Medicine III”, ed. by C. Migliaresi, Elsevier Sci. Publishers, B.V., Amsterdam, 1988, p. 189-199. [6] C. Flego, M. Lovrecich, and F. Rubessa, Drug. Develop. Ind. Pharm. , 14 , 1185 (1988) and subsequent papers [7] J. Heller, R.W. Baker, R.M. Gale, J.O. Rodin, J. Appl. Polym. Sci. 22 , 1991 (1978). [8] U. Finne, K. Kyyrönen, A. Urtti, J. Control. Release 10 , 189 (1989).
96 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-64 Complexation of Phosphorylated Cellulose with Collagen
Dana M. Suflet 1, Gabrielle C. Chitanu 1, and Viorica Trandafir 2
1“Petru Poni” Institute of Macromolecular Chemistry , Aleea Grigore Ghica Voda 41A, 700487, Iasi , Romania 2National Research and Development Institute for Textile and Leather, str. Ion Minulescu 93, sector 3, Bucuresti, Romania
Polysaccharides are of the most abundant biopolymers possessing structural diversity and functional versatility. They are polyglucans type polymers, containing glucose repeating units only; however a broad variety of structures appears, resulting from the stereochemistry of the anomeric C-atom, from the regiochemistry of the glycosidic linkage and from the pattern of branching. Chemical derivatization of polysaccharides has a determinant effect on their macroscopic properties, such as solubility, stability, and viscosity characteristics. If the functionalization leads to polysaccharide derivatives bearing ionic or ionizable groups they will behave as polyelectrolytes. Among these, the strong polyelectrolytes containing phosphoric groups can be obtained mainly by derivatization [1, 2]. Collagen is the most abundant protein in higher animals, and its function has been considered to maintain the body skeleton. Collagen is usually employed in drug delivery systems or as material for constructing artificial organs. The interaction of collagen with other natural or synthetic polyelectrolytes is interesting at least from two points of view. The first concerns the way in which the polymers interact with nonflexible protein molecules, an understanding of which could provide a better explanation of the interaction mechanism of polyelectrolytes with ionic colloidal particles. The second concerns the extent to which biochemical activity is maintained in the resulting complexes, the answer to which is central to the molecular design of composite collagen-polymer systems [3]. In this work we report original results regarding the interaction of phosphorylated cellulose [4] with collagen in aqueous salt-free or added salt containing systems. The collagen-phosphorylated cellulose systems were investigated firstly in aqueous solution, by potentiometric, conductometric and turbidimetric titration, according to the recommended procedures [2, 5, 6]. The elemental analysis, FT-IR spectra, electron microscopy and termogravimetric method were used in characterization of complexes formed in different conditions.
Acknowledgement : The financial support of Romanian National Authority for Scientific Research, CEEX project no. 16/2005 is gratefully acknowledged.
Keywords: natural polymers; polysaccharides; collagen; intermacromolecular complexes
______[1] D. Klemm, B. Philipp, T. Heinze, U. Heinze, W. Wagenknecht, Comprehensive Cellulose Chemistry, Wiley Verlag GmbH, D-69469 Weinheim (F.R.G.), 2, 1998. [2] H. Dautzenbeg, W. Jaeger, J. Köetz, B. Philipp, Ch. Seidel, D. Stscherbina, in Polyelectrolytes. Formation, Characterization and Application , Hansel Publishers, Munich, 1994. [3] A. Tsuboi, T. Izumi, M. Hirata, J. Xia, P.L. Dubin, E. Kokufuta, Langmuir , 12 , 6295 (1996). [4] M.D. Suflet, G.C. Chitanu, V.I. Popa, React. Funct. Polym ., 66 (11), 1240 (2006). [5] Y. Li, P.L. Dubin, H.A. Havel, S.L. Edwards, H. Dautzenberg, Macromolecules , 28 , 3098 (1995). [6] Y.-P. Wen, P.L. Dubin, Macromolecules , 30 , 7856 (1997).
97 P-65 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Effect of Collagen on Sparingly Soluble Inorganic Salts Separation
Irina M. Pelin 1, Gabrielle C. Chitanu 1, Viorica Trandafir 2, and Zina Vuluga 3
1“Petru Poni” Institute of Macromolecular Chemistry, aleea Grigore Ghica Voda 41A, Iasi 700487, Romania 2National Research and Development Institute for Textile and Leather, str. Ion Minulescu 93, sector 3, Bucuresti, Romania 3National Research and Development Institute for Chemistry and Petrochemistry – ICECHIM, Splaiul IndependenŃei 202, Bucuresti, Romania
Collagen is a natural polyelectrolyte (polyampholyte) obtained by extraction from different animal sources. It proves good properties, from which it should be mentioned biocompatibility, bioabsorbability and hipoimmunogenicity, that make it proper in many biomedical applications as hemostats, sealants, implant coatings, artificial skin, bone graft substitutes, corneal shields and injectables for plastic surgery [1]. The interest in developing bone substitutes has been growing and numerous papers describe new methods of preparation. The bones contain a carbonated and partially substituted apatite, based on nanocrystal aggregates associated with collagen. In most cases, collagen processing involves aqueous preparations, and the obtaining of hydroxyapatite (HAp) takes place also in water. In our paper we investigated the interaction in aqueous solutions between the precursors of HAp: ammonium dihydrogen phosphate and calcium nitrate tetrahydrate, in presence of various amounts of collagen as crystallization regulator. As mineralizing agent a 12.5% ammonium hydroxide solution was used. The influence of collagen was followed by potentiometric, conductometric and turbidimetric titration. The particles of HAp were characterized by FTIR spectroscopy, X-ray diffraction and scanning or transmission electron microscopy.
Acknowledgement : The financial support of Romanian National Authority for Scientific Research, CEEX project no. 16/2005 is gratefully acknowledged.
Keywords: collagen, hydroxyapatite, crystallization regulators, biomaterials
______[1] W. Friess, M. Schlapp, Eur. J. Pharm. Biopharm. 51, 259 (2001).
98 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-66 Supramolecular Systems from Natural Polymers and Maleic Polyelectrolytes
Irina Popescu 1, Marcel I. Popa 2, and Gabrielle C. Chitanu 1
1“Petru Poni” Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda nr. 41-A, 700487, Iasi, Romania 2“Gh. Asachi” Technical University, Faculty of Chemical Engineering and Environment Protection, Bd. D. Mangeron 71, Iasi, Romania
Polyelectrolyte complexes (PEC) result from the interaction of macromolecules carrying opposite charged groups. They have been proposed for several purposes, from which we mention the design of drug delivery systems, anticoagulant coatings, and membranes or even as skin substitutes. The preparation of PEC from natural polymers, such as polysaccharide or polypeptides has the additional advantage of being non-toxic, biocompatible, and bioabsorbable. Chitosan is a cationic polysaccharide obtained by deacetylation of chitin, which is the major constituent of the shells of crustacean and insects. As the other natural polymers it is renewable, highly biocompatible, very low toxic in the oral and implant administrations and biodegradable. By derivatization or complexation of chitosan a variety of new functional materials can be obtained. In our work the formation of PEC by interaction between chitosan and maleic acid copolymers (MP) as strong/weak dibasic polyanions was investigated. The salt form of maleic acid copolymers with: vinyl acetate, N-vinylpyrrolidone, styrene and methyl methachrylate and the hydrochloride form of chitosan were used, all macromolecular partners being carefully purified by diafiltration and freeze-drying. The interaction of chitosan with MP in aqueous solution was followed by potentiometric, conductometric and turbidimetric titration by varying the polyelectrolytes concentration and the mixing order [1, 2]. The effect of the added low molecular salt on the complex formation was also investigated. The precipitated complexes were analysed by FT infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry. Preliminary layer-by-layer experiments were performed to obtain thin films from maleic polyelectrolytes and chitosan [3]. Chitosan behavior in the interaction with maleic polyelectrolytes was compared with other natural polymers such as collagen.
Acknowledgement : The financial support of Romanian National Authority for Scientific Research, CEEX project no. 16/2005 is gratefully acknowledged.
Keywords: chitosan; maleic polyelectrolytes; intermacromolecular complexes; supramolecular systems
______[1] B. Philipp, H. Dautzenberg, K.-J. Linow, J. Kötz, W. Dawydoff, Prog. Polym. Sci. 14 , 91 (1989). [2] A. F. Thünemann, M. Müller, H. Dautzenberg, J.-F. Joanny, H. Löwen, Adv. Polym. Sci . 166 , 113 (2004). [3] O. N. Oliveira, J.-A. He, V. Zucolotto, S. Balasubramanian, L. Li, H. S. Nalwa, J. Kumar, S. K. Tripathy, “Layer by layer polyelectrolyte-based thin films for optoelectronic and photonic applications”, chapter in “Handbook of polyelectrolytes and their applications”, Ed. By S. K. Tripathy, J. Kumar and H. S. Nalwa, American Scientific Publishers, 2002, USA.
99 P-67 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Polylactide-polyglycidol Block Copolymer as a New Nanoparticles Forming Material
Mariusz Gadzinowski, Beata Miksa, and Stanislaw Slomkowski
Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
A novel kind of block copolymer: polyglycidol-b-polylactide was synthesized by living anionic polymerization and used for the nanoparticles preparation. The main advantage of using polyglycidol is presence of functional hydroxyl groups in the hydrophilic polyglycidol chain. Synthesis includes four main steps: a) protection of glycidol hydroxyl group, b) polymerization of protected monomer, c) extension of polyether chain by polymerization of L-lactide initiated by active centers on the living polyglycidol chain and d) deprotection of glycidol hydroxyl groups. Potassium tert-buthoxide has been used as an intiator. Polymerizations were carried on in THF. Copolymer blocks lengths were determined by 1H-NMR spectroscopy and a very good agreement between calculated (assuming quantitative initiation and complete monomer conversion) and measured molecular weight of blocks was observed. In water macromolecules of all synthesized polyglycidol-b-polylactides (with various molecular weight: PGL4000-PLA3000, PGL2000–PLA3000, PGL4000-PDLA3000) did self-assembly into nanoparticles with diameters ranging from 22 to 31 nm. There was developed a method for preparation of polyglycidol-b-polylactide loaded with ovalbumin (OVA). This method consists on dialysis of copolymer and ovalbumin solution in DMSO carried on against water. Diameter of nanoparticles with OVA was equal 31 nm. The high loading with OVA (from 77-200 mg protein per gram of nanoparticles, depending on the PGL/PLA ratio in the copolymer chain) has been achieved.
100 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-68 Structure Evolution in Amorphous Poly(L/DL-lactide) upon Plain Strain Compression
Miroslaw Pluta and Andrzej Galeski
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
Plastic deformation of amorphous, thermally non-crystallizable poly(L/DL-lactide) 70/30 (P(L/DL)LA) was induced by a plain strain compression in a channel-die at different o o temperatures, above T g from 60 C to 90 C. Samples undeformed (reference) and deformed to different compression ratios (CR), from 4.6 to 23.0, were studied by an X-ray diffraction, thermally modulated differential scanning calorimetry, light microscopy and mechanical methods – viscoelastic and tensile tests. The effects of the compression ratios and deformation temperatures on the final structure and properties of the P(L/DL)LA were evaluated. It was revealed that plastic deformation transformed of an amorphous P(L/DL)LA (thermally non- crystallizable), to a crystalline fibrillar texture oriented in the flow direction. Fibrillar texture was formed in spite of the tendency of the plane strain compression to form single crystal-like texture. The crystallite size in the transverse direction was small, up to 90 Å at the highest CR. No evidence of lamellar organization and features of supermolecular structure were detected by SAXS and light microscopy, respectively. The oriented samples exhibited low crystallinity degree at the level of 6-9% at the highest CR. The main transformation mechanism was shear and orientation induced crystallization. The crystalline phase was in the α crystallographic modification of poly(lactide) typically formed in more stereoregular poly(lactide) by thermal treatment. The glass transition increased with the increase of CR reflecting the increase of orientation of the polymer chains. Tensile strength of deformed samples were improved considerably in comparison to the reference sample.
101 P-69 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Structure and Physical Properties of PLA/Calcium Sulfate Composites
Miroslaw Pluta 1, Marius Murariu 2, Amália Da Silva Ferreira 3, Michaël Alexandre 2, Andrzej Galeski 1, and Philippe Dubois 3
1Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland 2Materia Nova asbl, Parc Initialis, Av. Nicolas Copernic 1, B-7000 Mons, Belgium 3Centre of Innovation and Research in Materials & Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials (LPCM), University of Mons-Hainaut, Académie Universitaire Wallonie- Bruxelles, Place du Parc 20, B-7000 Mons, Belgium
Starting from calcium sulfate (gypsum) as fermentation by-product of lactic acid production process, high performance composites have been produced by melt-blending polylactide (PLA, L/D isomer ratio of 96 : 4) and beta - anhydrite II (AII) filler i.e., calcium sulfate hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting for potential use as biodegradable rigid packaging. Physical characterization of selected composites filled with 20 and 40 wt% AII has been performed and compared to processed unfilled PLA with similar amorphous structure. State of dispersion of the filler particles and interphase characteristic features have been investigated using light microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching a slight increase of PLA crystallizability during melt-crystallization and upon heating from the glassy, amorphous state (DSC). It was found by thermo-mechanical measurements (DMTA) that the AII filler increased pronouncedly storage modulus (E’) of the composites in comparison with PLA in a broad temperature range: e.g. addition of 40 wt% AII increased E’ more than 90% at 25 °C, and surprisingly, more than 200% at 80 °C. The X-ray investigations showed stable/unchanged crystallographic structure of AII during processing with molten PLA and in the composite system. The notable thermal and mechanical properties of PLA– AII composites are accounted for by the good filler dispersion throughout the polyester matrix confirmed by morphological studies, system stability and favourable interactions between components.
102 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-70 Materials of Functional Properties Based on Biodegradable Polymers
M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak
Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
Modern plastic materials constitute frequently polymer blends and composites obtained by mixing polymers with fillers, adhesion promoters, processing aids etc. Incorporation of such additives brings about a novel properties to a matrix polymer, thus broadening a field of possible applications. Recent shortages in the petrochemical products delivery and high oil prices caused a revival of renewable resources, which is higly advantageous for a sustainable development. Polymers and fillers deriving from agriculture recently have focused substantial interest of the research teams and industry. Thermoplastic composites with natural fibers (biocomposites) have been increasingly used in automotive industry, insulating materials and in constructions. Further modification may be obtained by addition of functional fillers. Properties of biodegradable polymers filled with natural fibers and flame retardants have been presented in this paper. Polylactic acid (PLA) and poly(hydroxybutyrate) (PHB) were used as matrix polymers, whereas flax (F) and hemp fibers (H) were used for reinforcement. Different flame retardants (FR) were used for modification of the fire resistance of biocomposites. Flammability was evaluated by UL 94 horizontal and vertical Bunsen burner tests according to IEC 6007 and IEC 60695. Mechanical properties of biocomposites were tested by means of the tensile and bending methods. Selected results have been presented in Table 1 and Table 2.
Table 1. Horizontal burn method Material Burning time Behaviour Class (0-25 mm), min PLA 0:16 burning, flaming drips, cotton ignition PLA/F30/20FR 1:45 burning stops, no flaming drips HB PLA/H30/20FR 0:02 burning stops, no flaming drips HB PLA/H30/20FR/10M 1:00 burning stops, no flaming drips HB PLA/H30/20FR/20M 2:20 burning stops, no flaming drips HB PLA/H30/20FR/30M 1:20 burning stops, no flaming drips HB
Table 2. Vertical burn method Material Burning time Behaviour Class (50 mm), sec PLA 5 buring intensively, flaming drips, cotton ignition - PLA/F30/20FR 0 no flaming drips V-0 PLA/H30/20FR 0 no flaming drips V-0 PLA/H30/20FR/10M 20 no flaming drips V-1 PLA/H30/20FR/20M 15 no flaming drips V-1 PLA/H30/20FR/30M 40 no flaming drips V-1
Acknowledgements This research was financially supported by FP6-IP-SME Project 515769-2 BIOCOMP. Keywords: biodegradable polymers; fire resistance; mechanical properties
103 P-71 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Influence of Gamma-radiation on PCL/PHB Blends
D. Babic 1, Z. Kacarevic-Popovic 1, G. Mikova 2, and I. Chodak 2
1Institute of Nuclear Sciences Vinca, Laboratory Gamma, Belgrade, Serbia 2Polymer Institute of the Slovak Academy of Sciences, Bratislava, Slovakia
The influence of high energy radiation to polymer blend made of polycaprolactone (PCL) and polyhydroxybutyrate (PHB) was studied. The PCL/PHB blend was prepared in 50:50 component ratio with different amounts of triallylcyanurate (TAC) up to 5%. The samples have been irradiated with the radiation doses of 25 and 50 kGy with the Co-60 gamma rays. Mechanical properties were studied by stress-strain measurements. Heat properties and supermolecular structure were followed by thermal characterization with DSC method. Molecular structure was characterized by FTIR. Changes in structural and mechanical properties are correlated with the influence of TAC content and absorbed radiation dose. The effects to end-use properties of this material were discussed. As this material is of interest for use in biodegradable application the changes of biodegradability of the radiation treated blends has been followed as well.
104 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-72 Synthesis and Properties Evaluation of a New Class of Degradable Polymers: Poly(vinyl-co-ester)s
Seema Agarwal and Liqun Ren
Philipps Universitaet Marburg, Hans-Meerwein Strasse, 35032 Marburg, Germany
Generally, a high molecular weight polymer based on the C-C backbone like vinyl polymers tends to be resistant to hydrolysis, oxidative cleavage, resistant to the enzymatic attack etc. and are therefore not (bio)degradable, whereas heteroatom-containing polymer backbones confer (bio)degradability. In this work efforts have been made to bring degradable ester linkages onto the poly vinyl polymer backbones like poly (methyl methacrylate)(PMMA) and poly(N-isopropyl acrylamide)(PNIPAAM) for the generation of new class of degradable materials poly(vinyl-co-ester)s. A combination of radical ring-opening polymerisation of cyclic ketene acetals and conventional free-radical polymerisation of vinyl monomers have been utilised for bringing ester linkages onto the C-C backbones. An in sight into the microstructure of the resulting materials is achieved using different 1D and 2D NMR techniques. The introduction of ester linkages generated different new materials with a range of properties like varied lower critical solution temperatures (LCSTs), improved thermal stability, elasticity etc. besides making them degradable thereby increasing their utility areas for various biomedical applications. Synthesis, characterization and properties of some new materials like (poly(MMA-co-ester)s and poly(NIPAAM-co-ester)s will be presented.
105 P-73 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 Dynamic-Mechanical and Thermal Properties of Biodegradable Composites from Polylactic Acid (PLA) Reinforced with Wood Fibres
A. Gregorova and R. Wimmer
Green Composites Group, Universität für Bodenkultur Wien, Peter Jordanstrasse 82, 1190 Vienna, Austria
Biodegradable polymers have received an increased interest for utilization due to increasing environmentally aware consumers, increased price of crude oil and global warming. Nowadays, biodegradable polymers are used with a number of applications, such as therapeutic aids, medicines, coatings, food products and packaging materials. Poly(lactic acid) (PLA) is a biodegradable hydrolysable aliphatic polyester of lactic acid, which can be obtained from renewable resources. PLA is becoming increasingly popular as a biodegradable engineering plastic due to its high mechanical strength, and easy to process compared to other biopolymers. However, the addition of plasticizers is necessary because of rigidity and brittleness f PLA. The goal of this work was to compare the dynamic-mechanical and thermal properties of 5% softwood and hardwood filled PLA films prepared by solution casting method in chloroform. Softwood and hardwood fibres with particles from 100-500 µm were modified by various methods such as hydrolysis, esterification, oligoesterification, NaOH impregnation, and silane impregnation. Dynamic-mechanical-analysis (DMA) and differential-scanning-calorimetry (DSC) showed that different types of wood fibres modification have a tremendous effect on the results in terms of changes in storage and loss moduli, as well as crystallinity.
Keywords: biodegradable polymers; wood fibres, dynamic-mechanical properties, differential scanning calorimetry
106 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-74 New Derivatives of Methyl Oleate
Tarik Eren and Banu Taslica
Department of Chemistry, Bogazici University, Bebek, Istanbul, 34342, Turkey
Abstract: The purpose of this work is to synthesize new free radically polymerizable monomers based on methyl oleate. The chemistry consists of reaction of the unsaturated fatty ester with N-bromosuccinimide (NBS) in the presence of excess amount of a nucleophile. The nucleophiles used were acrylic acid ( 1), methacrylic acid ( 2), methacrylamide ( 3) and maleic acid-mono(dibutylamine) salt ( 4). Monomers are the addition products of bromine and the nucleophile to the oleate double bond. These new monomers were characterized by spectroscopic techniques. New phosphonate derivative of methyl oleate was also synthesized. Bromoacrylated methyl oleate was reacted with trimethyl phosphite (TMP) by Arbuzov reaction to produce the phosphonate ( 5) derivative. 1,4- addition of TMP to the acrylate double bonds of bromoacrylated methyl oleate was observed as main product instead of the expected Michaelis-Arbuzov product.
NBS, RT, 1 day [1] O
OH
NBS, RT, 1 day [2] O OH
COOCH3 NBS, RT, 6 h, Acetone [3] O
NH2
1. NBS, RT, 1 day, CH2Cl2 [4] O O
HO O H3NC4H9 2 2. H
[1] [2] [3] [4]
Br X O O NH O COOCH3 O C O C O C O C O HC CH2 C CH2 C CH2 HC C C OH H X CH3 CH3
Fig. Synthesis of new derivatives of 10-bromo, 9-acrylate methyl stearate ( 1); 10-bromo, 9- methacryloxy methyl stearate (2); 10-bromo, 9-methacrylamido methyl stearate ( 3); mono-9- (10-bromo methyl stearate)yl ester (4) (corresponding regioisomers are not shown).
107 AUTHOR INDEX
Aa van der L. J. 25 (I-10) Dumistracel I. 96 (P-63) Adamus G. 35 (P-02), 54 (P-21), 56 (P-23), Dumitriu R. P. 57 (P-24) 88 (P-55) Duncianu C. 45 (P-12) Agarwal S. 30 (I-15), 105 (P-72) Dzwonkowski J. 50 (P-17) Albertsson A.-C. 15 (I-02) El Fray M. 34 (P-01) Alexandre M. 17 (I-04), 102 (P-69) Ellis M. J. 38 (P-05) Anghel N. 61 (P-28) Erberich M. 26 (I-11) Anghelescu-Dogaru A. G. 96 (P-63) Eren T. 107 (P-74) Atlic´ A. 28 (I-13), 78 (P-45), 80 (P-47) Errico M. E. 66 (P-33) Avella M. 66 (P-33) Faÿ F. 47 (P-14) Babic D. 104 (P-71) Feijen J. 25 (I-10) Badia J. D. 82 (P-49), 83 (P-50), 84 (P-51) Fiedorowicz M. 32 (I-17), 94 (P-61) Bawa S. S. 42 (P-09) Filip D. 49 (P-16), 60 (P-27) Bertoldo M. 21 (I-07), 52 (P-19) Florczak M. 62 (P-29) Błasinska´ A. 67 (P-34) Focarete M. L. 69 (P-36), 71 (P-38) Bobalova J. 51 (P-18) Frackowiak S. 103 (P-70) Bogoeva-Gaceva G. 66 (P-33) Gadzinowski M. 100 (P-67) Bonnaud L. 17 (I-04) Galeski A. 18 (I-05), 101 (P-68), 102 (P-69) Borsali R. 22 (I-08) Gamian A. 76 (P-43) Bourdiot U. 30 (I-15) Garnaik B. 46 (P-13) Braunegg G. 28 (I-13), 78 (P-45), 80 (P-47) Gensheimer M. 30 (I-15) Bronco S. 21 (I-07), 52 (P-19), 53 (P-20) Gentile G. 66 (P-33) Brulc B. 92 (P-59) G˛ebarowska K. 70 (P-37) Buzarovska A. 66 (P-33) Gnanou Y. 22 (I-08) Cardamone J. M. 72 (P-39) Goł˛ebiewski J. 50 (P-17) Casella S. 90 (P-57) Gregorova A. 106 (P-73) Chardhuri J. B. 38 (P-05) Greiner A. 30 (I-15) Chen Y. 30 (I-15) Gricarˇ M. 92 (P-59) Chiellini E. 27 (I-12) Gross R. A. 20 (I-06) Chitanu G. C. 96 (P-63), 97 (P-64), 98 (P-65), Grozdanov A. 66 (P-33) 99 (P-66) Grzesiak E. 89 (P-56) Chodak I. 104 (P-71) Gualandi C. 71 (P-38) Ciardelli F. 21 (I-07), 52 (P-19), 53 (P-20) Hans M. 26 (I-11) Ciechanska´ D. 89 (P-56), 95 (P-62) Harabagiu V. 54 (P-21) Ciolacu D. 55 (P-22) Haznar D. 75 (P-42), 76 (P-43) Ciolacu F. 55 (P-22) Hermann-Krauss C. 78 (P-45), 80 (P-47) Cognigni F. 52 (P-19) Hesse P. 78 (P-45), 80 (P-47) Coltelli M.-B. 21 (I-07), 53 (P-20) Hicks K. B. 73 (P-40) Cosutchi A. I. 60 (P-27) Hiemstra C. 25 (I-10) Cuart M. 64 (P-31) Houga C. 22 (I-08) Czarny A. 74 (P-41) Höcker H. 37 (P-04) Da Silva Ferreira A. 17 (I-04), 102 (P-69) Hu Y. 65 (P-32) Dacko P. 48 (P-15), 50 (P-17), 91 (P-58) Huang C.-Y. 63 (P-30), 81 (P-48), 85 (P-52), Davidson M. G. 38 (P-05) 86 (P-53) Dersch R. 30 (I-15) Hulubei C. 60 (P-27) Dijkstra P. J. 25 (I-10) Ichim M. 61 (P-28) Dobrzynski´ P. 65 (P-32), 71 (P-38), 70 (P-37) Imaz N. 59 (P-26) Drobnik J. 67 (P-34) Ioan S. 60 (P-27) Dubois P. 17 (I-04), 102 (P-69) Iversen T. 39 (P-06) Duda A. 16 (I-03), 62 (P-29), 95 (P-62) Iwanczuk A. 103 (P-70)
108 Janeczek H. 50 (P-17), 56 (P-23), 91 (P-58) Molenda M. 94 (P-61) Janèiauskaite U. 79 (P-46) Molenda-Konieczny A. 32 (I-17) Jaworska J. 65 (P-32) Moriana R. 82 (P-49), 83 (P-50), 84 (P-51) Jin R. 25 (I-10) Murariu M. 17 (I-04), 102 (P-69) Jones M. D. 38 (P-05) Musioł M. 48 (P-15), 68 (P-35) Kacarevic-Popovic Z. 104 (P-71) Narayan R. 14 (I-01) Karas´ J. 74 (P-41) Nilsson H. 39 (P-06) Kasperczyk J. 65 (P-32), 70 (P-37) Nowakowska M. 31 (I-16) Kavaliauskaite R. 41 (P-08) Olsson A. 39 (P-06) Kawalec M. 56 (P-23), 58 (P-25), 71 (P-38) Pandey A. 46 (P-13) Kazimierczak J. 89 (P-56) Pelin I. M. 98 (P-65) Keul H. 26 (I-11) Pennanec X. 64 (P-31) Klee D. 37 (P-04) Peptu C. 54 (P-21), 58 (P-25) Klimaviciute R. 41 (P-08) Piegat A. 34 (P-01) Koller M. 28 (I-13), 78 (P-45), 80 (P-47) Pielka S. 74 (P-41), 75 (P-42), 76 (P-43) Konieczna-Molenda A. 94 (P-61) Piorkowska E. 18 (I-05), 87 (P-54) Kowalczuk M. M. 29 (I-14), 35 (P-02), 48 (P-15), Pluta J. 75 (P-42), 76 (P-43) 50 (P-17), 54 (P-21), 56 (P-23), 58 (P-25), Pluta M. 17 (I-04), 18 (I-05), 101 (P-68), 68 (P-35), 88 (P-55), 91 (P-58), 93 (P-60) 102 (P-69) Kowalczyk M. 87 (P-54) Poljanšek I. 92 (P-59) Kowalski W. J. 68 (P-35) Popa M. I. 99 (P-66) Kozlowska A. 103 (P-70) Popescu I. 96 (P-63), 99 (P-66) Kozlowski M. 103 (P-70) Povolo S. 90 (P-57) Krasowska K. 93 (P-60) Ren L. 105 (P-72) Kržan A. 92 (P-59) Renard E. 64 (P-31) Kulbokaitë R. 77 (P-44) Ribes-Greus A. 82 (P-49), 83 (P-50), 84 (P-51) Kurcok P. 56 (P-23), 58 (P-25) Rondán C. E. 53 (P-20) Kutschera C. 28 (I-13), 78 (P-45), 80 (P-47) Rutkowska M. 93 (P-60) Langlois V. 64 (P-31) Rychter P. 35 (P-02) Lao H.-K. 64 (P-31) Rydz J. 48 (P-15) Lemeins J.-F. 22 (I-08) Saha N. 51 (P-18) Saha P. 51 (P-18) Lemstra P. J. 24 (I-09) Santonja-Blasco L. 82 (P-49), 83 (P-50), Li S. 65 (P-32) 84 (P-51) Libiszowski J. 95 (P-62) Sarasua J.-R. 59 (P-26) Lindström M. 39 (P-06) Scandola M. 56 (P-23), 69 (P-36), 70 (P-37), Linossier I. 47 (P-14), 64 (P-31) 71 (P-38) Liu C.-I. 63 (P-30), 81 (P-48) Sedlarik V. 51 (P-18) López-Arraiza A. 59 (P-26) Signori F. 21 (I-07), 52 (P-19), 53 (P-20) Lu W.-L. 81 (P-48) Sikorska W. 48 (P-15), 68 (P-35) Macocinschi D. 49 (P-16) Simionescu B. C. 54 (P-21) Makuška R. 77 (P-44), 79 (P-46) Singh S. P. 42 (P-09) Malhotra B. D. 42 (P-09) Slomkowski S. 36 (P-03), 100 (P-67) Marcinkowska A. 76 (P-43) Sobota M. 48 (P-15), 50 (P-17), 91 (P-58) Meaurio E. 59 (P-26) Socka M. 62 (P-29) Meyer J. 26 (I-11) Solski L. 75 (P-42) Michalak M. 58 (P-25) Sosnowski S. 36 (P-03) Mikkonen K. S. 73 (P-40) Spiridon I. 61 (P-28) Mikova G. 104 (P-71) Spychaj S. 43 (P-10) Miksa B. 100 (P-67) Spychaj T. 43 (P-10), 44 (P-11) Mishra A. P. 40 (P-07) Srebrenkoska V. 66 (P-33) Moczek Ł. 31 (I-16) Suflet D. M. 97 (P-64) Moeller M. 26 (I-11) Szadkowski M. 95 (P-62)
109 Szczubiałka K. 31 (I-16) Wilczek P. 71 (P-38) Szymonowicz M. 74 (P-41), 75 (P-42), 76 (P-43) Willför S. 73 (P-40) Šišková A. 68 (P-35) Wilpiszewska K. 43 (P-10), 44 (P-11) Taslica B. 107 (P-74) Wimmer R. 106 (P-73) Taton D. 22 (I-08) Wozniak P. 36 (P-03) Tenkanen M. 73 (P-40) Wu J.-Y. 85 (P-52), 86 (P-53) Tiwari A. 40 (P-07), 42 (P-09) Wu X. 38 (P-05) Tomasik P. 32 (I-17), 94 (P-61) Yadav M. P. 73 (P-40) Tomaszewski W. 95 (P-62) Yang S.-Y. 85 (P-52), 86 (P-53) Toncelli C. 53 (P-20) Zaczynska´ E. 74 (P-41) Trandafir V. 97 (P-64), 98 (P-65) Zampano G. 21 (I-07) Vallee-Rehel K. 64 (P-31) Zapotoczny S. 31 (I-16) Vallée-Réhel K. 47 (P-14) Zemaitatitis A. 41 (P-08) Vasile C. 45 (P-12), 57 (P-24) Zhong Z. 25 (I-10) Vidovic´ E. 37 (P-04) Zhou W. 25 (I-10) Vlad S. 49 (P-16) Zini E. 69 (P-36), 70 (P-37) Vuluga Z. 98 (P-65) Zuza E. 59 (P-26) Wawro D. 89 (P-56) Zywicka˙ B. 74 (P-41), 75 (P-42), 76 (P-43) Wei J. 65 (P-32) Žagar E. 92 (P-59) Wendorff J. H. 30 (I-15) Žigon M. 92 (P-59) Wietecha J. 89 (P-56)
110 LIST OF PARTICIPANTS
Adamus Grazyna, Dr. Chodak Ivan, Prof. Polish Academy of Sciences, Centre of Polymer and Carbon Polymer Institute, Slovak Academy of Sciences; Comosite Materials Thermoplastics 34 M. Curie-Sklodowska St; 41-800 Zabrze; POLAND Dubravska 9; 84236 Bratislava; SLOVAKIA E-mail: [email protected] E-mail: [email protected] Phone: +48-32-2716077; Fax: +48-32-2712969 Phone: +421-2-54771603 Agarwal Seema, Dr. Ciardelli Francesco, Prof. Philipps universitaet Marburg; Department of Chemistry University of Pisa; Department of Chemistry and Industrial Hans-Meerwein Strasse; 35032 Marburg; GERMANY Chemistry E-mail: [email protected] via Risorgimento, 35; 56126 Pisa; ITALY Phone: +49-6421-2825755; Fax: +49-6421-2825785 E-mail: [email protected] Albertsson Ann-Christine, Prof. Phone: +39-050-2219229; Fax: +39-050-2219229 KTH, Royal Institute of Technology; Department of Polymer Ciechanska Danuta, Dr. Technology Institute of Biopolymers and Chemical Fibres with the S-100 44 Stockholm; SWEDEN Incorporated Pulp and Paper Research Institute E-mail: [email protected] Sklodowskiej-Curie 19/27; 90-570 Lodz; POLAND Phone: +46-8-7908274; Fax: +46-8-7908274 E-mail: [email protected] Babic Dragan, Dr. Phone: +48-42-6376510; Fax: +48-42-6376501 Institute of Nuclear Sciences Vinca; Laboratory of Radiation Chemistry and Physics Ciolacu Diana Elena, Dr. Mike Petrovica Alasa 12-14; 11001 Belgrade; SERBIA Petru Poni Institute of Macromolecular Chemistry; Chemistry - E-mail: [email protected] Physics of Polymers Phone: +381-11-2453986; Fax: +381-11-3440100 Grigore-ghica Voda Alley, 41A; 700487 Iasi; ROMANIA E-mail: [email protected] Blasinska Anna, Dr. Technical University of Lodz; Department of Fiber Physics and Dacko Piotr, Dr. Textile Metrology Centre of Polymer and Carbon Materials Zeromskiego 116; 90-924 Lodz; POLAND M. Curie-Skłodowskiej 34; 41-819 Zabrze; POLAND E-mail: [email protected] E-mail: [email protected] Braunegg Gerhard, Prof. Davidson Matthew G, Prof. Technische Universität Graz; Institut für Biotechnologie University of Bath; Department of Chemistry Petersgasse 12; 8010 Graz; AUSTRIA Claverton Down; BA27AY Bath; UNITED KINGDOM E-mail: [email protected] E-mail: [email protected] Phone: +43-316-8738412; Fax: +43-316-8738412 Phone: +44-1225-386443 Brulc Blaž, Mr. National Institute of Chemistry; Laboratory of Polymer Dubois Philippe, Prof. Chemistry and Technology Université de Mons-Hainaut Hajdrihova 19; 1000 Ljubljana; SLOVENIA Place du Parc, 20; B-7000 Mons; BELGIUM E-mail: [email protected] E-mail: [email protected] Phone: +386-1-4760207 Phone: +32-65-373480; Fax: +32-65-373480 Cardamone Jeanette M, Dr. Duda Andrzej, Prof. U.S. Department of Agriculture; Fats, Oils and Animal Centre of Molecular and Macromolecular Studies, Polish Coproducts Research Unit Academy of Sciences; Department of Polymer Chemistry 600 E. Mermaid Lane; 19038 Wyndmoor; UNITED STATES Sienkiewicza 112; 90-363 Lodz; POLAND E-mail: [email protected] E-mail: [email protected] Phone: +215-2336680; Fax: +215-2336795 Phone: +48-42-6819815; Fax: +48-42-6847126 Chen Su-Chen, Ms. Dumitriu Raluca Petronela, Ms. Taiwan Textile Research Institute; Department of Raw Materials Romanian Academy, "Petru Poni" Institute of Macromolecular and Yarn Formation Chemistry; Physical Chemistry of Polymers No.6, Chengtian Rd., Tucheng; 23674 Taipei; TAIWAN, Gr. Ghica Voda Alley, 41A; 700487 Iasi; ROMANIA PROVINCE OF CHINA E-mail: [email protected] E-mail: [email protected] Phone: +40-232-217454; Fax: +40-232-211299 Phone: +886-22670321 ext.223 Chiellini Emo, Prof. Duncianu Catalina Natalia, Ms. Universita di Pisa; Dip. Chimica e Chimica Industriale Institute of Macromolecular Chemistry Petru Poni; Department Via Risorgimento 35; 56126 Pisa; ITALY of Physical Chemistry of Polymers E-mail: [email protected] Gr. Ghica Voda Alley 41A; 700487 Iasi; ROMANIA Phone: +39-50-2219299; Fax: +39-50-2219299 E-mail: [email protected] Phone: +40-232-217454; Fax: +40-232-211299 Chitanu Gabrielle Charlotte, Dr. Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactive Dworak Andrzej, Prof. and Biocompatible Polymers Department Polish Academy of Sciences; Institute of Coal Chemistry Aleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIA Sowinskiego 5; 44-121 Gliwice; POLAND E-mail: [email protected] E-mail: [email protected] Phone: +40-232-217454; Fax: +40-232-211299 Phone: +48-32-2380780; Fax: +48-32-2380780 111 El Fray Miroslawa, Prof. Gregorova Adriana, Dr. Szczecin University of Technology; Polymer Institute Universität für Bodenkultur Wien; Institut für Holzforschung Pulskiego 10; 70-322 Szczecin; POLAND Peter-Jordan-Straße 82; A-1190 Wien; AUSTRIA E-mail: [email protected] E-mail: [email protected] Phone: +48-91-4494828; Fax: +48-91-4494098 Greiner Andreas, Prof. Fay Fabienne, Dr. Universitat Marburg; Materials Science Center Université Bretagne Sud; Laboratoire de Biotechnologie et Hans-Meerwein-Strasse, Gebäude H; D-35032 Marburg; chimie Marine GERMANY Centre de Recherche BP92116; 56321 Lorient; FRANCE E-mail: [email protected] E-mail: [email protected] Phone: +49-6421-2825573; Fax: +49-6421-2825573 Feijen Jan, Prof. Gross Richard A., Prof. University of Twente; Institute for BioMedical Technology The Polytechnic University; Department of Chemical and P.O. Box 217;; 7500 AE Enschede; NETHERLANDS Biological Sciences E-mail: [email protected] Six Metrotech Center; NY 11201 Brooklyn; UNITED STATES Phone: +31-53-4893367; Fax: +31-53-4893367 E-mail: [email protected] Phone: +718-2603984; Fax: +718-2603984 Filip Daniela, Dr. Institute of Macromolecular Chemistry; Physical Chemistry of Grozdanov Anita, Dr. Polymers Faculty of Technology and Metallurgy; Department of Polymer Aleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIA Engineering E-mail: [email protected] Rugjer Boskovic 16; 1000 Skopje; MACEDONIA E-mail: [email protected] Florjanczyk´ Zbigniew, Prof. Phone: +389-2-3064588 ext.237; Fax: +389-2-3065389 Warsaw University of Technology; Department of Polymer Gulle Heinz, Dr. Chemistry and Technology, Faculty of Chemistry Baxer Aktiengesellschaft; R&D Biosurgery Fibrin Platform Noakowskiego 3; 00-664 Warsaw; POLAND Industriestrasse 67; 1220 Vienna; AUSTRIA E-mail: [email protected] E-mail: [email protected] Phone: +48-22-2347303; Fax: +48-22-2347303 Phone: +43-1-20100259 Forstner Reinhard, Dr. Haan Robert, Mr. Upper Austrian Research G.m.b.H Purac Biochem bv; Process Technology Franz-Fritsch-Strasse 11; 4600 Wels; AUSTRIA Arkelsedijk 46; 4206AC Gorinchem; NETHERLANDS E-mail: [email protected] E-mail: [email protected] Phone: +43-7242-20881022; Fax: +43-7242-20881020 Phone: +31-183-695695; Fax: +31-183-695607 Gadzinowski Mariusz, Dr. Ichim Maria, Dr. Center of Molecular and Macromolecular Studies Polish Institutul De Inginerie, Biotehnologie Si Protectia Mediului Academy of Sciences; Department of Engineering of Polymer Prof. Ion Bogdan nr.10; 010539 Bucuresti; ROMANIA Materials E-mail: [email protected] Sienkiewicza 112; 90-363 Lodz; POLAND Phone: +40-21-2113754; Fax: +40-21-2102659 E-mail: [email protected] Iversen Tommy, Dr. Phone: +48-42-6803235 STFI-Packforsk Galeski Andrzej, Prof. Drottning Kristinas väg 61; SE-11486 Stockholm; SWEDEN Centre of Molecular and Macromolecular Studies; olymer E-mail: tommy.iversen@stfi.se Physics Department Phone: +46-8-6767000 ext.210; Fax: +46-8-4115518 Sienkiewicza 112; 90363 Lodz; POLAND Janciauskaite Ugne, Ms. E-mail: [email protected] Vilnius University; Polymer Chemistry Phone: +48-42-6803250; Fax: +48-42-6803261 Naugarduko 24; LT-03225 Vilnius; LITHUANIA Garnaik Baijayantimala, Dr. E-mail: [email protected] National Chemical Laboratory; Polymer Science and Phone: +370-5-2337811; Fax: +370-5-2330987 Engineering Division Jaworska Joanna, Ms. Dr.Homi Bhabha Road; 411008 Pune; INDIA Polish Academy of Sciences; Centre of Polymer and Carbon E-mail: [email protected] Materials Phone: +91-20-25902071 ext.2071; Fax: +91-20-25902615 Sklodowskiej-Curie 34; 41-819 Zabrze; POLAND ext.2615 E-mail: [email protected] G˛ebarowska Katarzyna, Ms. Phone: +48-32-2712214 ext.164 Centre of Polymer and Carbon Materials Polish Academy of Kawalec Michal, M.Sc. Sciences Centre of Polymer and Carbon Materials Polish Academy of Skłodowskiej-Curie 34; 41-819 Zabrze; POLAND Sciences E-mail: [email protected] 34, Marii Skłodowskiej-Curie St.; 41-819 Zabrze; POLAND Phone: +48-60983359 E-mail: [email protected] Gnanou Yves, Dr. Phone: +48-32-2716077 ext.121 Université Bordeaux I; Laboratoire de Chimie des Polymères Klimaviciute Rima, Dr. Organiques (LCPO-CNRS) Kaunas University of Technology; Organic Technology 16, ave Pey-Berland; 33607 Pessac; FRANCE Radvilenu 19; LT-50524 Kaunas; LITHUANIA E-mail: [email protected], [email protected] E-mail: [email protected] Phone: +33-5-40006987; Fax: +33-5-40006987 Phone: +370-37-456081; Fax: +370-37-456081 112 Koller Martin, Dr. Lao Hoi-Kuan, Dr. Graz University of Technology; Institute of Biotechnology and LBCM - Laboratoire de Biotechnologie et Chimie Marine; Biochemical Engineering Universite de Bretagne Sud Petersgasse 12; 8010 Graz; AUSTRIA Rue Saint Maude; 56321 Lorient; FRANCE E-mail: [email protected] E-mail: [email protected] Phone: +43-316-8738905 Phone: +33-2-97874594 Lee Chia, Ms. Konieczna-Molenda Anna, Dr. Tatung University University of Agriculture; Department of Chemistry No. 40, Cung-Shan N. RD., Sec. 3; 10453 Taipei; TAIWAN, Balicka 122; 30-149 Cracow; POLAND PROVINCE OF CHINA E-mail: [email protected] E-mail: [email protected] Kowalczuk Marek M., Prof. Lemstra Piet J., Prof. Centre of Polymer and Carbon Materials, Polish Academy of Eindhoven University of Technology; Polymer Technology Sciences PO Box 513, Helix STO 0.37; 5600 MB Eindhoven; M. Curie-Sklodowskiej 34; 41-819 Zabrze; POLAND NETHERLANDS E-mail: [email protected] E-mail: [email protected] Phone: +48-32-2716077; Fax: +48-32-2716077 Phone: +31-40-2473650; Fax: +31-40-2473650 Kowalczyk Marcin, M.Sc. Liu Chia-I, Ms. Centre of Molecular and Macromolecular Studies, Polish Tatung University; Department of Materials Engineering Academy of Sciences; Polymer Physics 40, Chung-Shan N. Rd.,3rd Sec.; 10453 Taipei; TAIWAN, Sienkiewicza 112; 90363 Lodz; POLAND PROVINCE OF CHINA E-mail: [email protected] E-mail: [email protected] Phone: +48-42-6803237 Lu Wan-Ling, Dr. Taiwan Textile Research Institute; Raw Materials and Yarn Kowalski Witold J., Prof. Formation Jan Długosz University, Faculty of Mathematics and Natural No.6 Chengtian Rd.; 23674 Tucheng; TAIWAN, PROVINCE OF Sciences; Institute of Chemistry and Enivironmental Protection CHINA Armii Krajowej 13/15; PL-42-200 Czestochowa; POLAND E-mail: [email protected] E-mail: [email protected] Phone: +886-2-22670321 ext.245 Phone: +48-502-616458 Macocinschi Doina, Dr. Kozlowska Anna, Dr. Institute of Macromolecular Chemistry; Physical Chemistry of Wroclaw University of Technology Polymers Wybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLAND Aleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIA E-mail: [email protected] E-mail: [email protected] Phone: +48-71-3206216 Makuska Ricardas, Prof. Kozlowski Marek, Prof. Vilnius University; Polymer Chemistry Wroclaw University of Technology; Faculty of Environmental Naugarduko 24; LT-03225 Vilnius; LITHUANIA Engineering E-mail: [email protected] Wybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLAND Phone: +370-5-2337811; Fax: +370-5-2330987 E-mail: [email protected] Meyer Sibylle, Ms. Phone: +48-71-3206538; Fax: +48-71-3282980 Wiley-VCH Verlag Boschstrasse 12; 69469 Weinheim; GERMANY Krasowska Katarzyna, Dr. E-mail: [email protected] Gdynia Maritime University; Department of Chemistry and Industrial Commodity Science Mikkonen Kirsi, M.Sc. Morska 81-87; 81-225 Gdynia; POLAND University of Helsinki; Department of Applied Chemistry and E-mail: [email protected] Microbiology Phone: +48-58-6901367; Fax: +48-58-6206701 Latokartanonkaari 11; 00014 Helsinki; FINLAND E-mail: kirsi.s.mikkonen@helsinki.fi Krucinska Izabella, Prof. Phone: +358-9-19158417; Fax: +358-9-19158475 Technical University of Lodz; Textile Engineering and Marketing Mishra Astbhuja Prasad, Dr. Zeromskiego 116; 90-924 Lodz; POLAND Ministry of Science and Technology; Department of Science E-mail: [email protected], [email protected] and Technology Phone: +48-42-6313300; Fax: +48-42-6313300 Technology Bhawan, New Maharauli Road; 110016 New Delhi; INDIA Krzan Andrej, Dr. E-mail: [email protected] National Institute of Chemistry; Laboratory for Polymer Phone: +91-11-26590325 Chemistry and Technology; Hajdrihova 19, POB 660; 1001 Ljubljana; SLOVENIA Moeller Martin, Prof. E-mail: [email protected] DWI an der RWTH Aachen e. V. Phone: +386-1-4760204; Fax: +386-1-4760204 Pauwelsstrasse 8; 52074 Aachen; GERMANY E-mail: [email protected] Kurcok Piotr, Dr. Phone: +49-241-8023300; Fax: +49-241-8023301 Centre of Polymer and Carbon Materials, Polish Academy Nadolny Andrzej J., Dr. Sciences Scientific Centre of the Pol. Acad. Sci. in Vienna 34, Marii Sklodowskiej Curie St.; 41-819 Zabrze; POLAND Boerhaavegasse 25; 1030 Wien; AUSTRIA E-mail: [email protected] E-mail: [email protected] Phone: +48-32-2716077 ext.261; Fax: +48-32-2712969 Phone: +43-1-7135929 ext.303 113 Narayan Ramani, Prof. Rapa Maria, Ms. Michigan State University; Chemical Engineering Division Commercial Society Incerplast S.A.; Research Development 2527 Engineering Building; MI 48824-122 East Lansing; Ziduri Mosi 23; 021203 Bucuresti; ROMANIA UNITED STATES E-mail: [email protected] E-mail: [email protected] Phone: +40-21-2525250 Phone: +517-4320775; Fax: +517-4320775 Raquez Jean-Marie, Dr. Nilsson Helena, M.Sc. University of Mons-Hainaut/Materia Nova; Laboratory of STFI-Packforsk; Packaging and Logistics Polymeric Composites and Materials Drottning Kristinas väg 61; 11486 Stockholm; SWEDEN Place du Parc 20; 7000 Mons; BELGIUM E-mail: helena.nilsson@stfi.se E-mail: [email protected] Phone: +46-8-6767253 Phone: +32-65-373771 Rokicki Gabriel, Prof. Nowakowska Maria, Prof. Warsaw University of Technology; Department of Polymer Jagiellonian University; Department of Physical Chemistry and Chemistry and Technology, Faculty of Chemistry Electrochemistry, Faculty of Chemistry ul. Noakowskiego 3; 00-664 Warszawa; POLAND Ingardena 3; 30-060 Krakow; POLAND E-mail: [email protected] E-mail: [email protected] Phone: +48-22-2347562; Fax: +48-22-2347562 Phone: +48-12-6632050; Fax: +48-12-6632050 Rutkowska Maria, Prof. Pandey Asutosh Kumar, Mr. Gdynia Maritime University; Department of Chemistry National Chemical Laboratory; Polymer Chemistry Morska 83; 81-225 Gdynia; POLAND Dr.Homi Bhabha Road; 411008 Pune; INDIA E-mail: [email protected] E-mail: [email protected] Phone: +48-58-6901585; Fax: +48-58-6206701 Phone: +91-20-25902071 ext.2071 Rychter Piotr, M.Sc. Pelin Irina Mihaela, Ms. Chemistry and Environmental Protection; Mathematics and Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactive Environment and Biocompatible Polymers Department Armii Krajowej Av., 13/15; 42-200 Czestochowa; POLAND Aleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIA E-mail: [email protected] E-mail: [email protected] Phone: +48-34-3615154; Fax: +48-34-3665322 Phone: +40-232-217454; Fax: +40-232-211299 Sahli Stefan, Dr. Penczek Stanislaw, Prof. Sika Technology AG; Corporate Research and Analytics Centre of Molecular and Macromolecular Studies, Polish Tüffenwies 16; 8048 Zürich; SWITZERLAND Academy of Sciences E-mail: [email protected] Sienkiewicza 112; 90-363 Lodz; POLAND Phone: +41-44-4365827; Fax: +41-44-4365850 E-mail: [email protected] Santonja-Blasco Laura, Ms. Phone: +48-42-6819815; Fax: +48-42-6819815 Universidad Politecnica Valencia Peptu Cristian, M.Sc. Camino De Vera S/n; 46022 Valencia; SPAIN Institute of Chemistry and Environmental Protection Jan E-mail: [email protected] Dlugosz Czestochowa Phone: +34-96-3879817 ext.71806 13/15 Armii Krajowej Av.; 42-200 Czestochowa; POLAND Sarasua Jose-Ramon, Prof. E-mail: [email protected] University of the Basque Country; Materials Science ETS Ingenieria Bilbao, Alameda de Urquijo s/n; 48013 Bilbao; Piorkowska Ewa Malgorzata, Prof. SPAIN Centre of Molecular and Macromolecular Studies; Polymer E-mail: [email protected] Physics Department Phone: +34-94601427; Fax: +34-94601418 Sienkiewicza 112; 90363 Lodz; POLAND E-mail: [email protected] Scandola Mariastella, Prof. Phone: +48-42-6803223; Fax: +48-42-6803261 University of Bologna; G. Ciamician Chemistry Department Via Selmi 2; 40126 Bologna; ITALY Pluta Miroslaw, Dr. E-mail: [email protected] Centre of Molecular and Macromolecular Studies, Polish Sedlarik Vladimir, Dr. Academy of Sciences; Department of Polymer Physics Faculty of Technology, Tomas Bata University in Zlín; Polymer Sienkiewicza 112; 90-363 Lodz; POLAND Centre E-mail: [email protected] T.G. Masaryka 275; 76272 Zlín; CZECH REPUBLIC Phone: +48-42-6803237; Fax: +48-42-6847126 E-mail: [email protected] Popescu Irina, Ms. Phone: +420-57603801; Fax: +420-57603144 Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactive Signori Francesca, Dr. and Biocompatible Polymers Department University of Pisa; Dipartimento di Chimica e Chimica Aleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIA Industriale E-mail: [email protected] via Risorgimento 35; I-56126 Pisa; ITALY Phone: +40-232-217454; Fax: +40-232-211299 E-mail: [email protected] Phone: +390-50-2219212; Fax: +390-50-2219320 Povolo Silvana, Dr. Universita degli Studi di Padova; Biotechnologie Agrarie Sikorska Wanda, Dr. Viale dell’Universita, 16; 35020 Legnaro; ITALY Centre of Polymer and Carbon Materials E-mail: [email protected] M.C.-Skłodowskiej 34; 41-819 Zabrze; POLAND Phone: +39-49-8272926; Fax: +39-49-8272929 E-mail: [email protected] 114 Slomkowski Stanislaw, Prof. Tomasik Piotr, Prof. Centre of Molecular and Macromolecular Studies, Polish Agricultural University in Krakow; Department of Chemistry Academy of Sciences Balicka 122; 30-149 Krakow; POLAND Sienkiewicza 112; 90-363 Lodz; POLAND E-mail: [email protected] E-mail: [email protected] Phone: +48-12-6624335; Fax: +48-12-6624335 Phone: +48-42-6826537; Fax: +48-42-6826537 Vairon Jean-Pierre, Prof. Sobota Michal, M.Sc. Université Pierre et Marie Curie; UMR 7610 - Chimie Des Centre of Polymer and Carbon Materials, Polish Academy of Polymeres Sciences Case 185, 4 Place Jussieu; F-75252 Paris Cédex 05; FRANCE 34, Marii Sklodowskiej Curie St. Poland; 41-819 Zabrze; E-mail: [email protected] POLAND Phone: +33-1-44275502; Fax: +33-1-44275502 E-mail: [email protected] Vidovic Elvira, Dr. Phone: +48-32-2716077 ext.121 University of Zagreb; Faculty of Chemical Engineering Socka Marta, M.Sc. Marulicev trg, 19; 10000 Zagreb; CROATIA Centre of Molecular and Macromolecular Studies, Polish E-mail: [email protected] Academy of Sciences; Department of Polymer Chemistry Phone: +385-1-4597128; Fax: +385-1-4597142 Sienkiewicza, 112; 90-363 Lodz; POLAND Weber Hedda, Dr. E-mail: [email protected] Competence Centre Wood; Wood and Pulp Chemistry Phone: +48-42-6803219 ext.219 Werkstrasse 2; 4860 Lenzing; AUSTRIA Spiridon Iuliana, Dr. E-mail: [email protected] Petru Poni Institute of Macromolecular Chemistry; Natural Phone: +43-7672-7013181; Fax: +43-7672-9183181 Polymers Aleea Gr. Ghica Voda 41A; 700487 Iasi; ROMANIA Woldum Henriette Sie, M.Sc. E-mail: [email protected] Chew Tech I/S Phone: +40-232-217454; Fax: +40-232-211299 Dandyvej 19; DK-7100 Vejle; DENMARK E-mail: [email protected] Spychaj Tadeusz, Prof. Szczecin University of Technology; Polymer Institute Wozniak Pawel, M.Sc. Pulaskiego 10; 70-322 Szczecin; POLAND Centre of Molecular and Macromolecular Studies, Polish E-mail: [email protected] Academy of Science; Department of Engineering of Polymer Phone: +48-91-4494684; Fax: +48-91-4494685 Materials Sienkiewicza, 112; 90-363 Lodz; POLAND Stanford John L., Prof. E-mail: [email protected] University of Manchester; School of Materials Grosvenor Street; m17hs Manchester; UNITED KINGDOM Wu Xujun, Mr. E-mail: [email protected] University of Bath; Center for Regenerative Medicine, Phone: +44-161-2003573 Department of Chemical Engineering& Department of Stepto Robert F., Prof. Chemistry University of Manchester and UMIST; Polymer Science and Claverton Down; BA27AY Bath; UNITED KINGDOM Technology Group E-mail: [email protected] Groswenor St.; M1 7HS Manchester; UNITED KINGDOM Wu Jing-Yi, Ms. E-mail: [email protected] Tatung University; Department of Materials Engineering Chung-Shan N. Rd., 3rd Sec.; 10452 Taipei; TAIWAN, Suflet Dana Mihaela, Dr. PROVINCE OF CHINA Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactive E-mail: [email protected] and Biocompatible Polymers Department Phone: +886-2-25925252; Fax: +886-2-25866050 Aleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIA E-mail: dsufl[email protected] Yang Sung-Yeng, Mr. Phone: +40-232-217454; Fax: +40-232-211299 Tatung University 40, Chung-Shan N. Rd., 3rd Sec.; 10453 Taipei; TAIWAN, Szymonowicz Maria, Dr. PROVINCE OF CHINA Wrocław Medical University; Department of Experimental E-mail: [email protected] Surgery and Biomaterials Research Poniatowskiego 2; 50-326 Wroclaw; POLAND Zittrich Boris, Mr. E-mail: [email protected] Postnova Analytics GmbH Phone: +48-71-7840135 Max-Planck-Str. 14; 86899 Landsberg am Lech; GERMANY E-mail: [email protected] Šišková Alena, M.Sc. Jan Dlugosz University, Faculty of Mathematiscs and Natural Phone: +49-8191-428181; Fax: +49-8191-428175 Sciences; Institute of Chemistry and Environmental Protection Zuchowska˙ Danuta, Prof. Armii Krajowej 13/15; PL-42-200 Czestochowa; POLAND Wroclaw University of Technology; Faculty of Chemistry E-mail: [email protected] Wybrzeze S. Wyspianskiego 27; 50-370 Wroclaw; POLAND Taslica Banu, M.Sc. E-mail: [email protected] Bogazici University; Department of Chemistry Phone: +48-71-3203633; Fax: +48-71-3203633 Bebek; 34342 Istanbul; TURKEY Zywicka˙ Bogusława, Dr. E-mail: [email protected] Wroclaw Medical University; Department of Experimental Phone: +90-212-3587572; Fax: +90-212-2872467 Surgery and Biomaterials Research Tiwari Ashutosh, Dr. Poniatowskiego 2; 53-326 Wrocław; POLAND National Physical Laboratory; Division of Engineering Materials E-mail: [email protected] Dr. K. S. Krishnan Road; 110012 New Delhi; INDIA Phone: +48-71-7840136 E-mail: [email protected] Phone: +91-11-32507819 115