CURRENT RESEARCH AND DEVELOPMENT IN THE FIELD OF BIODEGRADABLE POLYMER MATERIALS IN THE INSTITUTE OF POLYMERS - BAS

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1 Bulgarian Academy of Science Institute of Polymers CURRENT RESEARCH AND DEVELPMENT IN THE FIELD F BIDEGRADABLE PLYMER MATERIALS IN THE INSTITUTE F PLYMERS - BAS M. Ignatova and N. Koseva s: ignatova@polymer.bas.bg koseva@polymer.bas.bg 3 rd International PLASTICE Conference ctober 1-2 nd 2013, Warsaw, Poland

2 Bulgarian Academy of Sciences Institute of Polymers Acad. G. Bonchev St., bl. 103A 1113 Sofia, Bulgaria Tel:/Fax: +359(2)

3 Institute of Polymers Structural organization The Institute of Polymers is an autonomous research unit that belongs to the Nanosciences, New Materials and Technologies Division of the Bulgarian Academy of Sciences INSTITUTE F PLYMERS Laboratory of Amphiphilic and Ionogenic Polymers Laboratory of Bioactive Polymers Laboratory of Conjugated Polymers Laboratory of Phosphorus- Containing Monomers and Polymers Laboratory of Polymerization Processes Laboratory of Structure and Properties of Polymers IP-BAS is a scientific entity with 60 employees. Research staff 49 Administration 6 ther - 5

4 Institute Institute of Polymers of Polymers Prospects Structural for Development organization Research staff Scientists- 4 full professors, 12 associate professors; 22 assistant professors Research supporting staff - 11 university or high technical school graduates. 12 PhD students are trained at IP-BAS. The young researcher staff has ever been considered one of the most important advantages of the Institute of Polymers and much efforts have been put into encouraging the young generation to built their career at home

5 Institute of Polymers Mission Statement and Research Priorities Mission - to do advanced research and education on polymers and polymer materials and to transform the generated knowledge into innovative materials and processes in response to the needs of industry and society. (i) Synthesis, modification and characterization of polymers (ii) Development of new polymer materials with tailored properties Materials for environmental monitoring, preservation and recovering Materials for pharmacy, medicine and biotechnology IP-BAS excellence in design and synthesis of polymers with valuable properties : biodegradable, biocompatible, stimuli sensitive, self-organizing, electroactive, etc. Materials for alternative energy production Materials for agriculture and food preservation A considerable part of the research includes investigations on biodegradable polymer materials design and application.

6 Biobased and (bio)degradable polymers Extracted from biomass Proteins Polysaccharides By polymerization of monomers derived from renewable sources Poly(lactic acid) and copolymers today Produced by bacterial fermentation Poly(hydroxyalkanoates) Microbial cellulose Plant origin Marine origin 10 days later Novel materials for biomedical, agricultural and food applications

7 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers electrospinning + capillary extrusion hydrogels beads PE + PE coprecipitation 120nm nanoparticles micro- and nanofibers

8 Chitosan, N-carboxyethylchitosan (polyelectrolyte complexes at ph 1-14) H H NH 2 H H NH 2 H CECh/PEI H NHCCH 3 H H + Institute of Polymers Research Priorities H NH 2 CCH 3 Laboratory of Bioactive Polymers CH 2 CH 2 H 2 N + H H C - H + NH 3 - C CH CH 2 CH 2 HN CH 2CH 2 + H H CECh/PDMAEMA CECh/PDMAEMA CECh/PAA CECh/PAMPS Chit/P(AMPS-co-AA) CECh/PDMAEMAQ50 CECh/PDMAEMAQ100 CECh/PDMAEMAQ100 Chit/PAMPS Chit/PAA ph E. Yancheva, D. Paneva, V. Maximova, L. Mespouille, Ph. Dubois, N. Manolova, I. Rashkov, Biomacromolecules 8: (2007) E. Yancheva, D. Paneva, D. Danchev, L. Mespouille, Ph. Dubois, N. Manolova, I. Rashkov, Macromol. Biosci. 7: (2007) CECh/PDMAEMA, blood

9 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers STEALTH NANPARTICLES FRM N-CARBXYETHYLCHITSAN H 3 C CH3 CH 3 CH 3 Br 114 n N C H H H NH CCH 3 H + NH 3 H H + NH H H 2 N + H C - H 3 C CH 3 - C CNa C HC CH2 C3Br n CH 3 CH 3 CH 3 CH CH 2 C CH 2 CH 2 CH 3 C CH 3 NH C CH 2 CH 2 CH Br m 114 H 3 C H 3 C H 3 C CH 2 CH 2 N + I - H 3 C C CH 3 CH 2 S 3 -, Na + R. Mincheva, D. Paneva, L. Mespouille, N. Manolova, I. Rashkov, Ph. Dubois, J. Polymer Sci. Part A., Polym. Chem., 47(4): (2009) R. Mincheva, F. Bougard, D. Paneva, M. Vachaudez, Ch. A. Fustin, J.-F. Gohy, N. Manolova, I. Rashkov Ph. Dubois, J. Polym. Sci, Part A, 47(8): (2009) R. Mincheva, F. Bougard, D. Paneva, M. Vachaudez, N. Manolova, Ph. Dubois, I. Rashkov, Biomacromolecules, 10: (2009)

10 Institute of Polymers Research Priorities Laboratory of Conjugated Polymers Biodegradable nanocomposites based on polyhydroxybutyrate (PHB) PHB is fully renewable biodegradable and biocompatible thermoplastic polymer produced by microorganisms. Preparation of PHB/montmorillonite (MMT) nanocomposites by solution intercalation method. Application of organomodified clay Cloisite 30B for preparation of the nanocomposites - weight ratio polymer/clay in the range form 0 wt.% up to 10 wt.% Characterization of the nanocomposites by DSC, XRD, IR, optical microscope and mechanical testing Till now the XRD results obtained show that, at filler loadings higher than 3 wt. %, intercalation of the clay with polymer matrix is observed. At lower clay concentrations, exfoliation dominates. Scheme of types of obtained nanocomposite structures

11 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers NANFIBRUS MATERIALS FRM BICMPATIBLE AND BIDEGRADABLE PLYMERS WITH TAILRED BILGICAL PRPERTIES N CNTACT WITH CELLS wound healing devices antibacterial non-woven textile haemostatic non-woven textile > 200 cells/100 μm2 ~ 5 cells/100 μm2 scaffolds for cell and tissue engineering fullerene-containing nanofibers 200 hν Destruction of tumor cells

12 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers Drug-Loaded Electrospun Polylactide Bundles screen????? - - needle jet Multi-needle electrode + SEM micrograph of drug-loaded PLA/PEG bundle + Al Al???? foil Taylor cone Multi-needle electrode collector?????? syringe???????????? needle syringe containing polymer solution Cl H N Cl - Na + Diclofenac sodium anti-inflammatory agent Benzalkonium chloride antibacterial Lidocaine hydrochloride local anesthetic CH 3 + CH 3 N CH 3 CH 2 N CH - 3 Cl R H + Cl - HN C 2 H 5 C 2 H 5 CH 3 CH Poly(L-lactide) C n CH 2 CH 2 m PEG А. Toncheva, M. Spasova, D. Paneva, N. Manolova, I. Rashkov, Journal of Bioactive and Compatible Polymers 26: (2011)

13 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers Tuning of the Surface Biological Behavior of Poly(L-Lactide)-Based Electrospun Materials by Polyelectrolyte Complex Formation Yancheva E., Paneva D., Manolova N., Mincheva R., Danchev D., Dubois Ph., Rashkov I., Biomacromolecules 11: (2010)

14 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers A laboratory know-how for electrospinning directly onto the injured tissue of patient's hand Non-traumatic wound dressing rashkov@polymer.bas.bg

15 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers Antitumor activity of electrospun nanofibrous materials containing quaternized chitosan, poly(l-lactide-co-d,l-lactide) and doxorubicin Apoptosis in HeLa human cervical cancer cells QCh/coPLA/DX Antitumor activity of electrospun implants against Graffi myeloid tumor copla Ignatova M., Manolova N., Toshkova R., Rashkov I., Gardeva E., Yossifova L., Alexandrov M., Biomacromolecules 11: (2010). Toshkova R., Manolova N., Gardeva E., Ignatova M., Yossifova L., Rashkov I., Alexandrov M., Int. J. Pharm. 400: (2010).

16 M. Spasova, N. Manolova, M. Naydenov, J. Kuzmanova, I. Rashkov, Journal of Bioactive and Compatible Polymers 26: (2011). Lab-scale technology for embedding of biopesticide (T. viride) in a fibrous membrane from biodegradable polymer chitosan Institute of Polymers Research Priorities Laboratory of Bioactive Polymers Stimulates the plant protection Impedes the development of plant pathogens Provides favorable conditions for plant growth a protective fibrous membrane Environmentally friendly plant protection systems based on chitosan

17 Institute of Polymers Research Priorities Laboratory of Bioactive Polymers Fusaruim Fusaruim Tricho-kit against Fusaruim Tricho-kit Cucumbers Control

18 Institute of Polymers Research Priorities Laboratory of Phosphorus-containing Monomers and Polymers Biocompatible/biodegradable phosphorus-containig polymers xidative chlorination Atherton-Todd reaction NHR'R P NR'R'' Polyphosphoramidate HR P H Poly(H-phosphonate) Addition reactions to С=О, С=С and C=N P CR'R''Y Polyphosphonate NH 2 R'.HCl P R' Polyphosphates Drug-Polymer Conjugates P - + Polysalt NH 3 R' Radioprotectors (Cysteamine, WR2721) Anticancer agents (bendamustine HCl) Antiviral agents (azidothymidine, AZT)

19 Institute of Polymers Research Priorities Laboratory of Phosphorus-containing Monomers and Polymers Chemical degradation of polymers by esters of H-phosphonic and phosphoric acids Chemical Degradation of Polyurethanes C NH CH 2 NH C ( CH 2 ) 4 C ( CH 2 ) C ( ) 4 CH 2 2 n Chemical Degradation of Polycarbonate Chemical Degradation of Polyamide The chemical transformation of polymer waste into new phosphor containing oligomers which can be used for preparation of polymers with new properties. The main aim of the recycling of polymer waste materials and used polymers is conservation of the natural resources and reduction of environmental stress. The degradation products can be used successfully for the preparation of rigid polyurethanes with improved exploitation characteristics (high density and good mechanical properties).

20 Institute of Polymers Tradition and Competence in Polymer Research and Innovations Scientific Equipment Differential scanning calorimeter DSC-8500 Perkin Elmer; TGA-4000 Perkin Elmer; Analytical ultracentrifuge ProteomeLab XL-I Beckman Coulter Universal modular rheometer RheoStress 600, Thermo Haake; GPC Waters equipment for determination of molecular weight and molecular weight distribution of polymers; DAWN DSP Wyatt for determining the absolute molecular mass and particles size via light scattering; AVS-310 Schott Gerate automatic viscometer; Stanton Redcroft apparatus for determining the limiting oxygen index; ptical microscopes Zetoplan NU-2, Reicher and DMLP Leica; Microwave reactor RotoSYNTH (Milestone s.r.l.); LDC-SJP-35 single screw extrusion pelletizer line; HZ-1005B dynamometer; HZ-1072A cantilever beam impact testing machine; IR spectrometers: Vector 22 Bruker and IRAffinity-1 Shimadzu FTIR; UV-VIS spectrometer DU 800 (Beckman Coulter); Electrospinning equipment The Institute is a co-owner of a Bruker Avance II+ 600 NMR spectrometer.

21 PRJECTS FUNDED BY EC FP-7 Projects PLINNVA - Strengthening the Research Capacity and Innovation Potential of the Institute of Polymers at the Bulgarian Academy of Sciences for Further Integration into the ERA, Coordination and Support Action, No PASPRT Plan of Action - a Strategic Portal to Research Excellence (CAPACITIES; REGPT-2; ) SEE-ERA-NET Pilot Joint Call - Immobilized Yeast Cells in Hydrogel Carriers for Bioproduction of Alcohols (SEE-ERA-NET; 2008) FP-6 Projects AUTBRANE: Automotive High Temperature Fuel Cell Membranes, No (SЕS6) CARISMA: Coordinated Action of Research on Intermediate and High Temperature Specialized Membrane Electrode Assemblies, No FUNDED BY STRUCTURAL FUNDS: Human Resources Development Programme: Support for the Development and Career of PhD Students, Post-doc Fellows and Young Scientists in the Field of Polymer Chemistry, Physics and Engineering P "Development of the Competitiveness of the Bulgarian Economy : Support to the application research at the IP-BAS for development polymer and composite materials. FUNDED BY THE NATINAL SCIENCE FUND Center of Excellence: NATINAL CENTER FR ADVANCED MATERIALS - UNIN Module 2: New materials for medicine and pharmacy Novel Hybrid Nanostructured Materials for Local Cancer Treatment New Polymeric Delivery Systems of Antitumor Platinum Coordination Compounds Polymeric Nanotraps for Immobilization and Delivery of Biomacromolecules Self-assembly of Conducting Nanofibers into Yarns During Electrospinning of Polyelectrolyte Solutions Novel Nanocomposites Polyolefin/Lamellar Silicate with Improved Thermal Stability and Enhanced Mechanical Properties New Antibacterial and Hemostatic Nanofibrous Wound Dressings Study of the Interaction Chitosan (Solutions, Microgels or Nanostructured Spheres) Beneficial/Pathogenic Microorganisms Agricultural Crops Novel Functional Nanostructured Materials for Electrochemical Detection of Pesticides in Foods Appliances Development and Technologies for Electrospinning of Biopolymers for Preparation of Nanofiber Materials (NANBIMAT) Hollow Polymeric Nanospheres and Nanocylinders PEM Hydrogen

22 Institute of Polymers International Collaboration IP-BAS has been fostering high-level bilateral cooperation with academic institutions from Europe and the rest of the world - Germany, France, Belgium, Switzerland, the Czech Republic, Poland, Spain, Italy, UK, Greece, Turkey, Romania, Russia, Ukraine, Belarus, Japan, USA. IP-BAS is a co-founder of the Central and East European Polymer Network which is an informal association of polymer institutes and polymer groups affiliated to national academies of sciences in eight Central- and East- European countries.

23 THER RESEARCH GRUPS IN BULGARIA WRKING IN THE FIELD F BIDEGRADABLE PLYMER MATERIALS UNIVERSITY F SFIA "ST. KLIMENT HRIDSKI" Faculty of Chemistry and Pharmacy, Department of Applied rganic Chemistry, Laboratory of Polymers, Head: Prof. Michail Evstatiev, DSc, ohtme@wmail.chem.uni-sofia.bg UNIVERSITY F CHEMICAL TECHNLGY AND METALLURGY, SFIA Faculty of Chemical Technology, Department of Polymer Engineering, Head: Prof. Nikolai Dishovsky, DSc, dishov@uctm.edu Faculty of Chemical and System Engineering, Department of Biotechnology, Head: Prof. Lyubov Yotova, PhD, lubov@uctm.edu

24 Branch organization Bulgarian Association Polymers (BAP) It represents 37 Bulgarian companies processing and marketing polymers and plastics. BAP is active affiliate of the Bulgarian Institute for Standardization and a member of the European Plastics Converters Association (EUPC). BAP actively monitors the alteration in the Bulgarian and European legislation concerning the plastics industry and business preserving interests, and also cooperates with the Bulgarian authorities in the country legislation making process. BAP implements a set of communication activities used to promote the image of the company and their products, and to support the introduction of new products to the market. The memorandum, signed between BAP and the Institute of Polymers-BAS, by the project PLINNVA, mapped the joint activities and the commitment of BAP to mediate for establishment of firm contacts between the Institute of Polymers and representatives of the polymer industry.

25 CMPANY EXTRAPACK Ltd. established in 1995 by five young enterprisers, whose efforts have been directed towards creating a company that is a leader in the polyethylene packaging production. In the spring of 2000 Extrapack made a "green field investment", launching a big modern plant, located in the West industry area of Veliko Turnovo town. At present it has over 400 employees with annual turnover of more than 18 millions of Euro. Products of the company: Non-biodegradable polymer bags, paper bags and biodegradable polymer bags luxury bags t-shirt bags photoprinted bags patch handle bags bags for gift flat bags garbage bags plastic envelopes Packages for industry foil and film small and large bags impulse sealers Plastic and paper cups, boxes, bottles, plates, knives, spoons and forks ther standard products (necessary and practical products for home, office or fast food: raincoat, tablecloth, bags for sandwiches, foil for painting). Extrapack Ltd. is the first company in Bulgaria with 100% automatized production of paper bags for shopping, and the only manufacturer of bags ECFLEX, produced from 100% compostable, biodegradable polymer. Extrapack Ltd. produces different plastic bags and packages made from DEGRALEN. For recycling purposes Extrapack Ltd. has built a plant with total capacity of over 500 kg/per hour. For contacts: EXTRAPACK factory Veliko Tarnovo 5000, Bulgaria Zapadna Promishlena Zona Tel. ( ) , Fax: ( ) EXTRAPACK Sofia branch Sofia 1712, Mladost 3, ul. eng. Georgi Belov 20a Tel. ( ) ; ; Fax ( ) , team@ep-bags.com

26 Bulgarian Academy of Science Institute of Polymers All researchers of the Institute of Polymers are members of the Bulgarian Polymer Society full member of the European Polymer Federation