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POLYMERS Dept.

Biodegradable coating materials from water dispersable co-polyesters obtained by chemical recycling of pet wastes (BIOCOPET)
Polymer Technology
Modified polymers
Elastomers
 















BIOCOPET    

ABOUT the PROJECT
  • Project title: BIODEGRADABLE COATING MATERIALS FROM WATER DISPERSIBLE CO-POLYESTERS OBTAINED BY CHEMICAL RECYCLING OF PET WASTES
  • Acronym: BIOCOPET
  • Project number: 31-044
  • Financing: Governmental budget - Ministerul Educației, Cercetării și Tineretului, Programul 4 - PARTENERIATE IN DOMENIILE PRIORITARE
  • Project category: PC
  • Project budget (including other sources): 2.000.000 lei*
  • Contract budget (only governmental source): 2.000.000 lei
  • Contract period: 36 months (September 2007 – September 2010)
  • Contracting Authority: National Center of Programme Management (CNMP)
  • Coordinator: National Institute of Research and Development for Chemistry and Petrochemistry-ICECHIM
  • Project abstract:
    This project relates to biodegradable coating materials obtained from water dispersible co polyesters, which might be used for coating fertilizers granules. In order to avoid problems caused by the rapid dissolving process of most of the fertilizers in the moisture in the soil, often at a rate that exceeds the rate at which it can be used by plants, various slow and controlled release fertilizers have been developed. Due to the slow process of biodegradation of the polyester-coating proposed by this project, the efficacy of the fertilizers increases, because the coated fertilizers release the substances which act as plant nutrients in a delayed manner and it can thus display its action over a prolonged period. The coated fertilizers granules have to exhibit a relatively low tendency to stick and cake, even at elevated temperatures, and a good resistance to mechanical stress which occurs typically when being transferred and transported and in particular, when being applied by means of rapidly operating modern machinery. In general, it should be possible for the polymers used as coatings to be applied to the fertilizer starting granules without resorting to the use of organic solvents. Such coatings are preferable from an environmental standpoint, since they are carried in water. They have superior water barrier characteristics, can be applied in relatively thin coating layers and they are also easier to handle. The co-polyesters prepared in accordance with the present proposal must exhibit good film-forming properties,which means only small amounts of co-polyester to be required for producing a stable layer, ensuring economical advantages. In the mean time, the co-polyesters prepared according to the present proposal must disintegrate within an appropriate and measurable period of time when exposed to environment factors. On the other hand, the polymers used for the coating must not show undue hardness and brittleness, since the coating would otherwise be damaged, or could even chip off, when the coated fertilizer granules are exposed to mechanical stress as is the case, for example, during repackaging or, in particular, during mechanical spreading. The proposed method of production utilizes recycled or reclaimed poly-ethylene terephthalate (PET) from plastic articles such as beverage bottles, as a raw material, following a chemical processing route. By reacting PET with either an alcohol or with an acid, it is possible to reduce the average chain length of the PET molecules. The chemical structure of PET backbone is modified using suitable co monomers which can provide both biodegradability and water dispersability for the resulted co-polyester. Preferably, the co-polyesters are produced through a melt polycondensation method. Thus, aromatic dicarboxylic acid component, (either as acids, esters, or mixtures thereof, aliphatic dicarboxylic acid component, (either as acids, esters, or mixtures thereof), other optional glycol component and optionally a polyfunctional branching agent, are combined in the presence of a catalyst at a temperature high enough and under full vacuum, such that the monomers combine to form esters and diesters, then oligomers, and finally polymers. The polymeric product at the end of the polymerisation process is a molten product. Various monomer components can be charged to a polymerisation vessel along with polymerisation catalysts, for example, manganese and antimony catalyst, and subjected to poly condensation conditions to produce linear polyester in which the units are randomly distributed along the molecular chain. Specific catalyst or combination or sequence of catalysts used must be selected. The melt process conditions, particularly the amounts of monomers used, depend on the polymer composition that is desired. The proposed procedure will provide achieving of ecological products, with low emission of organic volatile compounds upon the environment, with high performance properties and with large area of applications. In addition, this procedure uses PET wastes as raw materials, which is an important economical and ecological advantage. It provides the opportunity of recycling great amounts of poly-ethylene terephthalate derived from packaging materials, an attractive source of raw materials which can replace those derived from oil, providing thus resources –conservation.

PARTNERS
  • Coordonator Proiect (P1)
    National Research & Development Institute for Chemistry & Petrochemistry ICECHIM - Polymers Dept
    Spl. Independentei 202, sector 6, 06021, Bucuresti
    Director proiect - Ing. Stela Iancu; stela_iancu@yahoo.com
  • PARTNER 2 (P2)
    Universitatea Politehnica Bucuresti UPB
    Spl. Independentei 296, sector 6, 06031, Bucuresti
    Director P2 - PhD. Sorina Garea
  • PARTNER 3 (P3)
    Center of Organic Chemistry "C.D.Nenitescu" of Romanian Academy
    Spl.Independentei nr 202B Cod 060023 Bucresti
    Director P3 - PhD. Emeric Bartha; bimre@cco.ro
  • PARTNER 4 (P4)
    Institute of Phisical Chemistry "I.G.Murgulescu" of Romanian Academy,
    Spl.Independentei nr 202 Cod 060021, Bucuresti
    Director P4 - PhD Dan-Florin Anghel; adan@icf.ro
  • PARTNER 5 (P5)
    National Institute of Research and Development for Pedology, Agrochemistry and Environment Protection,ICPA
    Bld. Mărăști, nr. 61 Cod 011464 Bucharest
    Director P5 - PhD ANCA-ROVENA LĂCĂTUȘU; anca@icpa.ro
OBJECTIVES

General objectives:
  • designing, working out and testing an integrated procedure, connected to the specific priorities and objectives of European fields of research, adjusted to national priorities and resources
  • a process for synthesis of a biodegradable coating material exhibiting a reduced negative impact upon environment
  • opportunity of generating of such coatings from water-dispersions which provides a non-toxic technology (avoiding emissions of organic volatile compounds), eco-friendly and safety
  • possibility of using such biodegradable coating materials for sheeting granulated fertilizers in order to improve their efficacy because the coated fertilizers release the nutrients in a delayed manner and it can thus display its action over a prolonged period of time
  • saving the natural resources which can reduce the raw materials supply (especially those derived from oil) and provide renewable resources, due to recycling and returning to industry of high potential valuable products
  • possibility of using toghether with PET wastes of some other raw materials resulted from biomass (renewable resources such as sugars and starches)
Specific objectives:
  • Scientific and technical substantiation of the project -Designing laboratory scale models
  • Developing and experimenting the laboratory scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
  • Testing the laboratory scale technology for yielding biodegradable coating materials from water dispersible co polyesters resulted from chemical recycling of PET wastes
  • Results dissemination by means of publishing scientific papers and developing scientific communications, display and demonstration of technology workability and usefulness, patent protection.
  • Developing and experimenting the pilot scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
  • Testing the pilot scale technology
  • Developing the detailed handbook for technology description and feasibility study.
EXPECTED R&D RESULTS :
  • Studies, analysis regarding synthetic routes for achieving biodegradable coating materials from water dispersible co polyesters by chemical recycling of PET wastes S
  • Experimental models at laboratory scale for polyesters preparation derived from PET waste and for getting their water dispersions
  • Laboratory scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
  • Results dissemination by means of publishing scientific papers and developing scientific communications
  • Presentation and demonstration of technology workability and usefulness
  • Patent elaboration
  • Developing and experimenting the pilot scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
  • Developing the detailed handbook for technology description and
  • Feasibility study

PHASES
  • Step I Studies and analysis for the identification of the main principles of developing biodegradable coatings, using as raw materials PET wastes.
  • Step II Developing and experimenting the laboratory scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
  • Step III Testing the laboratory scale technology for yielding biodegradable coating materials from water dispersible co polyesters in order to yield slow release nutrients, results dissemination, display and demonstration of technology workability and usefulness, patent protection
  • Step IV Developing and testing the pilot scale technology for yielding coating biodegradable materials, developing the detailed handbook for technology description and feasibility study

  • OBJECTIVES ACHIEVED IN STEP I/2007
  • 1. Evaluation of scientific approaches for achieving biodegradable coating materials from water dispersible copolyesters produced by chemical recycling of PET wastes
    Revue of scientic publications regarding the following aspects:
    • - procedures for obtaining water dispersable copolyesters using as raw material PET wastes
    • - possibilities of using such copolyesters as coating materials for fertilizers
    • - identification of analytical methods for characterization of biodegradable copolyesters, water dispersable starting from PET wastes
    • - technical and scientific evaluations regarding preparation of copolyester aqueous dispersions - study regarding microorganisms involved in polyesters biodegradation
  • 2. Design of laboratory scale models
    Designing laboratory scale experimental models regarding:
    • - synthesis routes for biodegradable water dispersible co polyesters yielded from PET wastes
    • - utilization of these copolyesters as coating materials for fertilizers.
    • - preparing of aqueous copolyesters dispersions
    • - experimental model for testing the nitrogen release kinetics in greenhouse from coated granulated fertilizers. Establishing the connections between autotrofic microorganisms (bacteria and fungi) and the polyesters from soil

    OBJECTIVES ACHIEVED IN WP II/2008
  • 1. Developing the laboratory scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
    • 1.1 Synthesis of biodegradable polyesters, water dispersible. There were obtained 12 experimental copolyesters structures in order to select those chemical structures which are able to provide best properties of biodegradability and hydrophilicity and to establish the most suitable reaction parameters.
    • 1.2 Preparation of aqueous copolyester dispersions. The representative copolyesters prepared at laboratory scale were dispersed in water without involving any external surfactant, thus resulting 6 water dispersions.
  • 2. Experimenting the laboratory scale technology for yielding coating biodegradable materials, generated from aqueous co polyesters dispersions, starting from PET wastes
    • 2.1 Physico-chemical and structural characterization of copolyesters
      • 2.1.1 Determination of basic chemical and physical characteristics of yielded polyesters:melting range, content of acid and hydroxil groupes, medium molecular weight, relative viscosity determined at various polymer concentrations in solution, intrinsec viscosity and thermostability
      • 2.1.2 Complex structural characterization of co polyesters:1H-RMN and 13C-RMN spectroscopy, FTIR spectroscopy and DSC (differential scanning chalorimetry) measurements.
      • 2.1.3 Coplyesters characterisation regarding their water affinity: measuremenrs of tensioactive properties, viscosity, turbidity, UV-VIS and FTIR-ATR spectroscopy, optic microscopy
    • 2.2 Characterization of water copolyesters dispersions: stability, morphology and rheometry using conductometric, rheologic measurements and optic microscopy with image capture
    • 2.3 Laboratory scale testing of co polyesters biodegradability. Testing the copolyester effect upon the magnitude and structure of heterotrophic microorganisms communities in soil (toxicology)

CONTACT
  • stela_iancu@yahoo.com


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