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BIOPLASTICS


By:
Mugdha Nigam
ME Biotech
Bio-Plastics
   Bio-based Plastics
    Major focus is on “origin of life” or where
    did Carbon come from..

   Biodegradable Plastics
    Focus is on “end of life or disposal”
    Defined by EN13432 and ASTM D6400
What are Biodegradable
plastics?
   Biodegradable or Compostable plastics are those
    that meet all the scientifically recognized
    standards of biodegradability of plastics and
    plastic products independent of their carbon
    origin.
   According to ASDM D6400, biodegradability is measured on
    Mineralization, Disintegration and Safety of the material.
    - atleast 90% conversion to CO2, water and biomass via
    microbial assimilation.
    - should occur within a time period of 180 days or less.
    - no impacts on plants.
    - etc……
Drivers for Bioplastics
   Reduced environmental impact.
   Disposal issues – Landfills.
   Concerns about human health.
   Legislative initiatives.
Lifecycle of Bioplastics
Types of Bioplastics (Kaeb, 2009)
Starch and Starch blends
   Virgin starch is brittle and difficult to be
    processed. This problem is mainly caused by
    the presence of strong inter‐ and intra‐
    molecular hydrogen bonds between the
    starch macromolecules.
 Thermoplasticized starch
 Cross-linked starch
 Starch esters
 Starch – Biopolymer blends
 High density
 Low resistance to oil and solvents
 Easy to process bur vulnerable to
  degradation.
 Sensitive to moisture
 High water vapour permeability
Cellulose based Bioplastics
 Cellulose-based bioplastics are typically chemically-
  modified plant cellulose materials such as cellulose acetate
  (CA).
 Common cellulose sources include wood pulp, hemp and
  cotton.
 These biodegradable plastics can be processed on
  conventional injection molding machines or on extruders
  adapted to their specific processing properties.
 The thermal resistance is somewhat lower, but the
  permeability to steam and oxygen is relatively high
  compared to that of standard plastics. The material is
  resistant to oils and fats and, for a short while, even to weak
  acids and alkalies.
Polylactic Acid (PLA)
   PLA is an aliphatic
    polyester.
   The conformational ratio
    of L- and D- lactic acid in
    the polyester decides
    the material properties.
   Degrades within 4 to 6
    weeks .
   High stability
   Transparency
The biology of
Polyhydroxyalkanaotes (PHA)
   The carbon sources are assimilated, converted into
    hydroxyalkanoate (HA) compounds and finally polymerized into
    high molecular weight PHAs and stored as water insoluble
    granules in the cell cytoplasm.

   PHAs are an excellent storage compound because their
    presence in the cytoplasm, even in large quantities does not
    disturb the osmotic pressure of the cell.

   These granules may be surrounded by a phospholipid
    monolayer that contains specific granule associated proteins.

   PHA granules are intriguingly maintained in an amorphous state
    in vivo.
A) Transmission Electron micrograph of Ralstonia eutropha H16 containing 70
   wt% P(3HB) granules cultured in mineral medium containing palm kernel oil as
   the sole carbon source for 48h.
B) Nile Blue stained R. eutropha cells containing P(3HB) granules cultivated for
   72h in mineral medium containing palm kernel oil as the sole carbon source.
Chemical Composition of
PHAs
   approximately 150 different constituents of
    PHAs have been identified as homopolymers
    or as copolymers.
 Good thermoplastic material.
 Wide temperature range
 Lower crystallinity
 Tendency of shrinkage
 UV resistance
• Short chain-length PHAs (SCL-PHA):
                         contains 3-5 carbon atoms.
  Monomer size
                       • Medium chain-length PHAs (MCL-
                         PHA): contains 6-14 carbon atoms



                      • Homopolymer: The polymerization begins with the
                        linkage of a small molecule or monomer through ester
Number of different     bonds to the carboxylic group of the next monomer. A
                        homopolymer is produced when single monomeric units
                        are linked together. i.e P(3HB).
monomers in PHAs      • Heteropolymer: When two or more different monomeric
                        units are linked together, a copolymer is formed. i.e
                        P(3HB-co-4HB).




                      • Natural PHAs: produced naturally by
                        microorganisms from general substrates. i.e Poly(3-
                        hydroxybutyrate) P(3HB)
Biosynthetic origin   • Semisynthetic PHAs: requires addition of unusual
                        precursors such as 3-mercaptopropionic acid to
                        promote the biosynthesis of poly(3-hydroxybutyrate-
                        co-3-mercaptopropionic) [P(3HB-co-3MP)]
Wild type and recombinant strains used for pilot and large scale production of PHA
Strain and Process Development for industrial production of PHA
Commercially important
PHAs
   Poly(3-hydroxybutyrate)
    [P(3HB)]

   Poly(3-hydroxybutyrate-
    co-3-hydroxyvalerate)
    [P(3HB-co-3HV)]

   Poly(3-hydroxybutyrate-
    co-4-hydroxybutyrate)
    [P(3HB-co-4HB)]

   Poly(3-hydroxybutyrate-
    co-3-hydroxyhexanoate)
    [P(3HB-co-3HHx)]
Comparison of mechanical properties of different PHAs with common plastics
In general
 SCL PHAs are highly crystalline and have poor
   tensile strength.
 MCL PHAs are amorphous and very
   elastomeric.


   P(3HB-co-3HHx) is an interesting copolymer.
   3HHx units addition(5 mol%) into the 3HB
    sequence reduces the melting point from 180 °C to
    less than 155 °C, thus significantly improving the
    thermal processability and physical properties.
   Aeromonas caviae and A. hydrophila are the only
    found organisms to naturally produce this polymer.
Applications of PHA in various fields

                               All materials for short life packing like
Packaging Industry
                               food utensils, films, electronic
                               appliances


Printing and Photography       PHA are polyesters that can be easily
                               stained.
Chemical Industry
                               Heat sensitive matrices, latex gels.
                               Nonwoven matrices to remove facial
                               oil.

Textile Industry
                               PHA can processed into fibers.
Medical Implants
                               Medical implant materials, drug
                               controlled release matrices.
Healthy food additives         PHA oligomers used as food
                               supplements to obtain ketone bodies.
Biofuels & additives
                               Hydrolysed to form combustible HA
                               methyl esters.
Protein Purification &
                               PhaP used to purify recombinant
Specific Drug delivery
                               proteins and along with specific
                               ligands, can achieve targeting to
                               dieseased tissue.
Advantages
 Lower fossil fuels consumption.
 Less dependency on non-renewable
  resources.
 Lower CO and other green house gas
           2


  emissions in the atmosphere.
 Decrease in waste generation.
 Water saving.
Disadvantages
   Bio-based plastics are made from plant
    sources like corn and maize. With already
    increasing demand of food supply, Plastic
    production from plants could create a steep
    cut-short.
   Some bioplastics don’t readily decompose.
    They require high temperature in especially
    built pilot plants. Thus, they may not be so
    economical.
   GMOs are used to increase productivity of
    PHA and PLA.
Future developments prospects
   High cell density within short period of time.
   Controllable lysis of cells containing PHA
    granules.
   Controllable PHA molecular weight.
   Use of PHA monomers as biofuels
    additives.
   PHA blending with starch, cellulose.
   PHA as building blocks for new polymers.
References
   Lei Pei et al, Biotechnology of
    Biopolymers, 2010.
   Guo-Qiang Chen, Chemical Society
    Reviews, 2009.
   Ching-Yee Loo and Kumar
    Sudesh, Malayasian Polymer Journal, 2007.
   Erwin T.H. Vink et al, Polymer degradation and
    stability, 2002.
   Franziska Hempel et al, Microbial Cell
    Factories, 2011.
   bioplastics MAGAZINE
    www.bioplasticsmagazine.com/
Bioplastics   copy

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Bioplastics copy

  • 2. Bio-Plastics  Bio-based Plastics Major focus is on “origin of life” or where did Carbon come from..  Biodegradable Plastics Focus is on “end of life or disposal” Defined by EN13432 and ASTM D6400
  • 3. What are Biodegradable plastics?  Biodegradable or Compostable plastics are those that meet all the scientifically recognized standards of biodegradability of plastics and plastic products independent of their carbon origin.  According to ASDM D6400, biodegradability is measured on Mineralization, Disintegration and Safety of the material. - atleast 90% conversion to CO2, water and biomass via microbial assimilation. - should occur within a time period of 180 days or less. - no impacts on plants. - etc……
  • 4. Drivers for Bioplastics  Reduced environmental impact.  Disposal issues – Landfills.  Concerns about human health.  Legislative initiatives.
  • 6. Types of Bioplastics (Kaeb, 2009)
  • 7. Starch and Starch blends  Virgin starch is brittle and difficult to be processed. This problem is mainly caused by the presence of strong inter‐ and intra‐ molecular hydrogen bonds between the starch macromolecules.  Thermoplasticized starch  Cross-linked starch  Starch esters  Starch – Biopolymer blends
  • 8.
  • 9.  High density  Low resistance to oil and solvents  Easy to process bur vulnerable to degradation.  Sensitive to moisture  High water vapour permeability
  • 10. Cellulose based Bioplastics  Cellulose-based bioplastics are typically chemically- modified plant cellulose materials such as cellulose acetate (CA).  Common cellulose sources include wood pulp, hemp and cotton.  These biodegradable plastics can be processed on conventional injection molding machines or on extruders adapted to their specific processing properties.  The thermal resistance is somewhat lower, but the permeability to steam and oxygen is relatively high compared to that of standard plastics. The material is resistant to oils and fats and, for a short while, even to weak acids and alkalies.
  • 11. Polylactic Acid (PLA)  PLA is an aliphatic polyester.  The conformational ratio of L- and D- lactic acid in the polyester decides the material properties.  Degrades within 4 to 6 weeks .  High stability  Transparency
  • 12.
  • 13. The biology of Polyhydroxyalkanaotes (PHA)  The carbon sources are assimilated, converted into hydroxyalkanoate (HA) compounds and finally polymerized into high molecular weight PHAs and stored as water insoluble granules in the cell cytoplasm.  PHAs are an excellent storage compound because their presence in the cytoplasm, even in large quantities does not disturb the osmotic pressure of the cell.  These granules may be surrounded by a phospholipid monolayer that contains specific granule associated proteins.  PHA granules are intriguingly maintained in an amorphous state in vivo.
  • 14. A) Transmission Electron micrograph of Ralstonia eutropha H16 containing 70 wt% P(3HB) granules cultured in mineral medium containing palm kernel oil as the sole carbon source for 48h. B) Nile Blue stained R. eutropha cells containing P(3HB) granules cultivated for 72h in mineral medium containing palm kernel oil as the sole carbon source.
  • 15. Chemical Composition of PHAs  approximately 150 different constituents of PHAs have been identified as homopolymers or as copolymers.
  • 16.  Good thermoplastic material.  Wide temperature range  Lower crystallinity  Tendency of shrinkage  UV resistance
  • 17. • Short chain-length PHAs (SCL-PHA): contains 3-5 carbon atoms. Monomer size • Medium chain-length PHAs (MCL- PHA): contains 6-14 carbon atoms • Homopolymer: The polymerization begins with the linkage of a small molecule or monomer through ester Number of different bonds to the carboxylic group of the next monomer. A homopolymer is produced when single monomeric units are linked together. i.e P(3HB). monomers in PHAs • Heteropolymer: When two or more different monomeric units are linked together, a copolymer is formed. i.e P(3HB-co-4HB). • Natural PHAs: produced naturally by microorganisms from general substrates. i.e Poly(3- hydroxybutyrate) P(3HB) Biosynthetic origin • Semisynthetic PHAs: requires addition of unusual precursors such as 3-mercaptopropionic acid to promote the biosynthesis of poly(3-hydroxybutyrate- co-3-mercaptopropionic) [P(3HB-co-3MP)]
  • 18. Wild type and recombinant strains used for pilot and large scale production of PHA
  • 19. Strain and Process Development for industrial production of PHA
  • 20. Commercially important PHAs  Poly(3-hydroxybutyrate) [P(3HB)]  Poly(3-hydroxybutyrate- co-3-hydroxyvalerate) [P(3HB-co-3HV)]  Poly(3-hydroxybutyrate- co-4-hydroxybutyrate) [P(3HB-co-4HB)]  Poly(3-hydroxybutyrate- co-3-hydroxyhexanoate) [P(3HB-co-3HHx)]
  • 21. Comparison of mechanical properties of different PHAs with common plastics
  • 22. In general  SCL PHAs are highly crystalline and have poor tensile strength.  MCL PHAs are amorphous and very elastomeric.  P(3HB-co-3HHx) is an interesting copolymer.  3HHx units addition(5 mol%) into the 3HB sequence reduces the melting point from 180 °C to less than 155 °C, thus significantly improving the thermal processability and physical properties.  Aeromonas caviae and A. hydrophila are the only found organisms to naturally produce this polymer.
  • 23. Applications of PHA in various fields All materials for short life packing like Packaging Industry food utensils, films, electronic appliances Printing and Photography PHA are polyesters that can be easily stained. Chemical Industry Heat sensitive matrices, latex gels. Nonwoven matrices to remove facial oil. Textile Industry PHA can processed into fibers. Medical Implants Medical implant materials, drug controlled release matrices. Healthy food additives PHA oligomers used as food supplements to obtain ketone bodies. Biofuels & additives Hydrolysed to form combustible HA methyl esters. Protein Purification & PhaP used to purify recombinant Specific Drug delivery proteins and along with specific ligands, can achieve targeting to dieseased tissue.
  • 24. Advantages  Lower fossil fuels consumption.  Less dependency on non-renewable resources.  Lower CO and other green house gas 2 emissions in the atmosphere.  Decrease in waste generation.  Water saving.
  • 25. Disadvantages  Bio-based plastics are made from plant sources like corn and maize. With already increasing demand of food supply, Plastic production from plants could create a steep cut-short.  Some bioplastics don’t readily decompose. They require high temperature in especially built pilot plants. Thus, they may not be so economical.  GMOs are used to increase productivity of PHA and PLA.
  • 26. Future developments prospects  High cell density within short period of time.  Controllable lysis of cells containing PHA granules.  Controllable PHA molecular weight.  Use of PHA monomers as biofuels additives.  PHA blending with starch, cellulose.  PHA as building blocks for new polymers.
  • 27. References  Lei Pei et al, Biotechnology of Biopolymers, 2010.  Guo-Qiang Chen, Chemical Society Reviews, 2009.  Ching-Yee Loo and Kumar Sudesh, Malayasian Polymer Journal, 2007.  Erwin T.H. Vink et al, Polymer degradation and stability, 2002.  Franziska Hempel et al, Microbial Cell Factories, 2011.  bioplastics MAGAZINE www.bioplasticsmagazine.com/