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Bioplastics Bioplastics Bioplastics Bioplastics Bioplastics Bioplastics Bioplastics Bioplastics

The future of The future of
plastics industry plastics industry
" "
" "
What are What are bioplastics bioplastics??
Polymers based on renewable raw materials Polymers based on renewable raw materials Polymers based on renewable raw materials Polymers based on renewable raw materials
- -- - bio/new carbon (ASTM D bio/new carbon (ASTM D bio/new carbon (ASTM D bio/new carbon (ASTM D 6866 6866 6866 6866, based on , based on , based on , based on
C CC C14 14 14 14) ) ) )
Biodegradable polymers with approved Biodegradable polymers with approved Biodegradable polymers with approved Biodegradable polymers with approved
biodegradability in compost (EN biodegradability in compost (EN biodegradability in compost (EN biodegradability in compost (EN 13432 13432 13432 13432, , , ,
ASTM D ASTM D ASTM D ASTM D 6400 6400 6400 6400- -- -99 99 99 99) )) )
Most of bioplastics are based on agricultural Most of bioplastics are based on agricultural Most of bioplastics are based on agricultural Most of bioplastics are based on agricultural
feedstocks feedstocks feedstocks feedstocks
Why Why bioplastics bioplastics??
Depletion of fossil resources Depletion of fossil resources Depletion of fossil resources Depletion of fossil resources
Synthetic p Synthetic p Synthetic p Synthetic plastics are building up in landfill lastics are building up in landfill lastics are building up in landfill lastics are building up in landfill
Use of non Use of non Use of non Use of non- -- -renewable sources contributes to renewable sources contributes to renewable sources contributes to renewable sources contributes to
global warming. global warming. global warming. global warming.
Closing the carbon loop by composting and Closing the carbon loop by composting and Closing the carbon loop by composting and Closing the carbon loop by composting and
energetic recovery, bioplastics make a energetic recovery, bioplastics make a energetic recovery, bioplastics make a energetic recovery, bioplastics make a
positive contribution to climate positive contribution to climate positive contribution to climate positive contribution to climate
protection (CO protection (CO protection (CO protection (CO
2 22 2
footprint). footprint). footprint). footprint).
http://www.biocycle.com.br/site.htm
Biodegradable Biodegradable bioplastic bioplastic life cycle (LCA) life cycle (LCA)
2
CO CO
2 2
footprint footprint
Dr. Jim Lunt, Tianan Biologic Material Co. Ltd, Ningbo, China, 2nd European
Bioplastics Conference, November 21-22, 2007
Bioplastic Bioplastic Origin Origin
Raw materials for Raw materials for Raw materials for Raw materials for Raw materials for Raw materials for Raw materials for Raw materials for bioplastics bioplastics bioplastics bioplastics bioplastics bioplastics bioplastics bioplastics
Hans van der Pol, PURAC, 2nd European BioplasticsConference
Paris, 21. November 2007
Bioplastics Bioplastics
Biobased and biodegradable (PLA, PHA, Biobased and biodegradable (PLA, PHA, Biobased and biodegradable (PLA, PHA, Biobased and biodegradable (PLA, PHA,
starch): short starch): short starch): short starch): short- -- -life, disposable products life, disposable products life, disposable products life, disposable products
Biobased and durable (castor oil based Biobased and durable (castor oil based Biobased and durable (castor oil based Biobased and durable (castor oil based
Nylon Nylon Nylon Nylon 11 11 11 11, ethanol based green PE, soy , ethanol based green PE, soy , ethanol based green PE, soy , ethanol based green PE, soy
based polyurethane) based polyurethane) based polyurethane) based polyurethane)
Remember Remember Remember Remember: Biobased plastics are not : Biobased plastics are not : Biobased plastics are not : Biobased plastics are not
always biodegradable and always biodegradable and always biodegradable and always biodegradable and Biodegradable Biodegradable Biodegradable Biodegradable
plastics are not always biobased plastics are not always biobased plastics are not always biobased plastics are not always biobased
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Green Polyethylene Green Polyethylene
Degradability and biodegradability Degradability and biodegradability
There are five different types of degradable polymers There are five different types of degradable polymers There are five different types of degradable polymers There are five different types of degradable polymers : :: :
Biodegradable polymers Biodegradable polymers Biodegradable polymers Biodegradable polymers are those that are capable of are those that are capable of are those that are capable of are those that are capable of
undergoing decomposition into carbon dioxide, methane, water, undergoing decomposition into carbon dioxide, methane, water, undergoing decomposition into carbon dioxide, methane, water, undergoing decomposition into carbon dioxide, methane, water,
inorganic compounds or biomass in which the predominant inorganic compounds or biomass in which the predominant inorganic compounds or biomass in which the predominant inorganic compounds or biomass in which the predominant
mechanism is the enzymatic action of micro mechanism is the enzymatic action of micro mechanism is the enzymatic action of micro mechanism is the enzymatic action of micro- -- -organisms that can be organisms that can be organisms that can be organisms that can be
measured by standardized tests, in a specified time ( measured by standardized tests, in a specified time ( measured by standardized tests, in a specified time ( measured by standardized tests, in a specified time (90 90 90 90 to to to to 180 180 180 180
days), reflecting available disposal conditions. days), reflecting available disposal conditions. days), reflecting available disposal conditions. days), reflecting available disposal conditions.
Compostable polymers Compostable polymers Compostable polymers Compostable polymers are those that are degradable under are those that are degradable under are those that are degradable under are those that are degradable under
composting conditions. To meet this definition they must break composting conditions. To meet this definition they must break composting conditions. To meet this definition they must break composting conditions. To meet this definition they must break
down under the action of micro down under the action of micro down under the action of micro down under the action of micro- -- -organisms (bacteria, fungi, algae), organisms (bacteria, fungi, algae), organisms (bacteria, fungi, algae), organisms (bacteria, fungi, algae),
achieve total mineralization (conversion into carbon dioxide, achieve total mineralization (conversion into carbon dioxide, achieve total mineralization (conversion into carbon dioxide, achieve total mineralization (conversion into carbon dioxide,
methane, water, inorganic compounds or biomass under aerobic methane, water, inorganic compounds or biomass under aerobic methane, water, inorganic compounds or biomass under aerobic methane, water, inorganic compounds or biomass under aerobic
conditions) and the mineralization rate must be high and compatible conditions) and the mineralization rate must be high and compatible conditions) and the mineralization rate must be high and compatible conditions) and the mineralization rate must be high and compatible
with the composting process. with the composting process. with the composting process. with the composting process.
Oxo Oxo Oxo Oxo- -- -degradable polymers degradable polymers degradable polymers degradable polymers are those that undergo controlled are those that undergo controlled are those that undergo controlled are those that undergo controlled
degradation through the incorporation of prodegradant additives degradation through the incorporation of prodegradant additives degradation through the incorporation of prodegradant additives degradation through the incorporation of prodegradant additives
(additives that can trigger and accelerate the degradation (additives that can trigger and accelerate the degradation (additives that can trigger and accelerate the degradation (additives that can trigger and accelerate the degradation
process). These polymers undergo accelerated oxidative process). These polymers undergo accelerated oxidative process). These polymers undergo accelerated oxidative process). These polymers undergo accelerated oxidative
degradation initiated by natural daylight, heat and/or mechanical degradation initiated by natural daylight, heat and/or mechanical degradation initiated by natural daylight, heat and/or mechanical degradation initiated by natural daylight, heat and/or mechanical
stress, and embrittle in the environment and erode under the stress, and embrittle in the environment and erode under the stress, and embrittle in the environment and erode under the stress, and embrittle in the environment and erode under the
influence of weathering. influence of weathering. influence of weathering. influence of weathering.
Photodegradable polymers Photodegradable polymers Photodegradable polymers Photodegradable polymers are those that break down are those that break down are those that break down are those that break down
through the action of ultraviolet (UV) light, which degrades the through the action of ultraviolet (UV) light, which degrades the through the action of ultraviolet (UV) light, which degrades the through the action of ultraviolet (UV) light, which degrades the
chemical bond or link in the polymer. This process can be chemical bond or link in the polymer. This process can be chemical bond or link in the polymer. This process can be chemical bond or link in the polymer. This process can be
assisted by the presence of UV assisted by the presence of UV assisted by the presence of UV assisted by the presence of UV- -- -sensitive additives in the sensitive additives in the sensitive additives in the sensitive additives in the
polymer. polymer. polymer. polymer.
Water Water Water Water- -- -soluble polymers soluble polymers soluble polymers soluble polymers are those that dissolve in water within are those that dissolve in water within are those that dissolve in water within are those that dissolve in water within
a designated temperature range and then biodegrade in contact a designated temperature range and then biodegrade in contact a designated temperature range and then biodegrade in contact a designated temperature range and then biodegrade in contact
with microorganisms. with microorganisms. with microorganisms. with microorganisms.
Problems presented by degradable Problems presented by degradable
but not biodegradable polymers but not biodegradable polymers
A plastic may be degradable but not biodegradable or it may be A plastic may be degradable but not biodegradable or it may be A plastic may be degradable but not biodegradable or it may be A plastic may be degradable but not biodegradable or it may be
biodegradable but not compostable (it breaks down too slowly to biodegradable but not compostable (it breaks down too slowly to biodegradable but not compostable (it breaks down too slowly to biodegradable but not compostable (it breaks down too slowly to
be called compostable or leaves toxic residue). be called compostable or leaves toxic residue). be called compostable or leaves toxic residue). be called compostable or leaves toxic residue).
Plastic debris around the globe can erode (degrade) away and Plastic debris around the globe can erode (degrade) away and Plastic debris around the globe can erode (degrade) away and Plastic debris around the globe can erode (degrade) away and
end up as microscopic granular or fiber like fragments, and that end up as microscopic granular or fiber like fragments, and that end up as microscopic granular or fiber like fragments, and that end up as microscopic granular or fiber like fragments, and that
these fragments have been steadily accumulating in the oceans. these fragments have been steadily accumulating in the oceans. these fragments have been steadily accumulating in the oceans. these fragments have been steadily accumulating in the oceans.
Toxic Chemicals Transport Toxic Chemicals Transport Toxic Chemicals Transport Toxic Chemicals Transport: :: :
Plastic pieces can attract toxic residues and function as a Plastic pieces can attract toxic residues and function as a Plastic pieces can attract toxic residues and function as a Plastic pieces can attract toxic residues and function as a
transport medium transport medium transport medium transport medium
Toxic pesticides were detected in high concentrations in Toxic pesticides were detected in high concentrations in Toxic pesticides were detected in high concentrations in Toxic pesticides were detected in high concentrations in
degraded polypropylene (PP) resin pellets collected from four degraded polypropylene (PP) resin pellets collected from four degraded polypropylene (PP) resin pellets collected from four degraded polypropylene (PP) resin pellets collected from four
Japanese coasts. Japanese coasts. Japanese coasts. Japanese coasts.
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Europe Europe bioplastics bioplastics boom boom
Growth of up to Growth of up to Growth of up to Growth of up to 100 100 100 100% over % over % over % over 2005 2005 2005 2005 levels in levels in levels in levels in
bio bio bio bio- -- -packaging field. packaging field. packaging field. packaging field.
Increasing numbers of chain stores that Increasing numbers of chain stores that Increasing numbers of chain stores that Increasing numbers of chain stores that
have introduced bio have introduced bio have introduced bio have introduced bio- -- -packaging. packaging. packaging. packaging.
Bioplastics are thought to represent a Bioplastics are thought to represent a Bioplastics are thought to represent a Bioplastics are thought to represent a
technological potential of about technological potential of about technological potential of about technological potential of about 10 10 10 10% of the % of the % of the % of the
present plastics market of present plastics market of present plastics market of present plastics market of 40 40 40 40 million tons in million tons in million tons in million tons in
Europe. Europe. Europe. Europe.
http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf
tons/year
Consumers Acceptance Research Consumers Acceptance Research
The milk comes from The milk comes from The milk comes from The milk comes from
mother nature mother nature mother nature mother nature
Now, so does the bottle Now, so does the bottle Now, so does the bottle Now, so does the bottle
Marketing Marketing Approach Approach
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First legal incentives in EU First legal incentives in EU
member states member states
Germany: Certified compostable plastic Germany: Certified compostable plastic Germany: Certified compostable plastic Germany: Certified compostable plastic
packaging is exempted from recycling packaging is exempted from recycling packaging is exempted from recycling packaging is exempted from recycling
obligations until year obligations until year obligations until year obligations until year 2012 2012 2012 2012
French Agri Law/ Italy: One way plastic bags French Agri Law/ Italy: One way plastic bags French Agri Law/ Italy: One way plastic bags French Agri Law/ Italy: One way plastic bags
must be biodegradable from must be biodegradable from must be biodegradable from must be biodegradable from 2010 2010 2010 2010 on on on on
Potential Potential
Applications Applications
http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf
6
http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf
Cosmetics packaging Cosmetics packaging
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Durable products Durable products
TOYOTA TOYOTA Eco Eco- -plastics plastics for for
Interior Parts Interior Parts
Formaldehyde Formaldehyde- -Free Biodegradable Free Biodegradable
Wood Composites Wood Composites
Renewable Renewable Renewable Renewable
Biodegradable Biodegradable Biodegradable Biodegradable
Formaldehyde Formaldehyde Formaldehyde Formaldehyde- -- -free free free free
Environmentally Environmentally Environmentally Environmentally- -- -friendly friendly friendly friendly
Main disadvantage Main disadvantage
Price Price Price Price
Synthetic plastics Synthetic plastics Synthetic plastics Synthetic plastics < < < < 1 1 1 1 Euro/kg Euro/kg Euro/kg Euro/kg
PLA PLA PLA PLA 3 33 3- -- -4 4 4 4 Euro/kg Euro/kg Euro/kg Euro/kg
Starch compounds Starch compounds Starch compounds Starch compounds 2 22 2- -- -4 4 4 4 Euro/kg Euro/kg Euro/kg Euro/kg
PHA PHA PHA PHA > > > > 4 4 4 4 Euro/kg Euro/kg Euro/kg Euro/kg
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Polylactic Polylactic acid acid
PLA PLA
Polylactic acid (PLA): Polylactic acid (PLA): Polylactic acid (PLA): Polylactic acid (PLA):
Linear aliphatic polyester Linear aliphatic polyester Linear aliphatic polyester Linear aliphatic polyester
Produced by : Produced by : Produced by : Produced by :
poly poly poly poly- -- -condensation of naturally produced lactic acid (co condensation of naturally produced lactic acid (co condensation of naturally produced lactic acid (co condensation of naturally produced lactic acid (co- -- -
product of corn), or by product of corn), or by product of corn), or by product of corn), or by
Catalytic ring opening of the lactide group. Catalytic ring opening of the lactide group. Catalytic ring opening of the lactide group. Catalytic ring opening of the lactide group.
Compared to the others biodegradable Compared to the others biodegradable Compared to the others biodegradable Compared to the others biodegradable
polyesters, PLA is the product that at the polyesters, PLA is the product that at the polyesters, PLA is the product that at the polyesters, PLA is the product that at the
present has one of the highest potential present has one of the highest potential present has one of the highest potential present has one of the highest potential
due to its availability on the market and its due to its availability on the market and its due to its availability on the market and its due to its availability on the market and its
low price. low price. low price. low price.
Polylactic Polylactic Acid (PLA) Acid (PLA)
Polylactic Polylactic Acid (PLA) Acid (PLA)
PLA properties PLA properties PLA properties PLA properties PLA properties PLA properties PLA properties PLA properties
Unmodified PLA has several limitations: Unmodified PLA has several limitations: Unmodified PLA has several limitations: Unmodified PLA has several limitations:
brittleness (aging) brittleness (aging) brittleness (aging) brittleness (aging)
low heat distortion temperatures ( low heat distortion temperatures ( low heat distortion temperatures ( low heat distortion temperatures (60 60 60 60
o oo o
C) C) C) C)
slow degradation slow degradation slow degradation slow degradation
Properties can be tailored blending PLA with Properties can be tailored blending PLA with Properties can be tailored blending PLA with Properties can be tailored blending PLA with
PHBV, starch and other biodegradable PHBV, starch and other biodegradable PHBV, starch and other biodegradable PHBV, starch and other biodegradable
polymers (PCL, PBAT, PBS). polymers (PCL, PBAT, PBS). polymers (PCL, PBAT, PBS). polymers (PCL, PBAT, PBS).
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Homopolymer of l Homopolymer of l Homopolymer of l Homopolymer of l - -- -lactide (LPLA or PLLA): lactide (LPLA or PLLA): lactide (LPLA or PLLA): lactide (LPLA or PLLA):
semicrystalline polymer ( semicrystalline polymer ( semicrystalline polymer ( semicrystalline polymer (37 37 37 37%) %) %) %)
high tensile strength, low elongation and high modulus high tensile strength, low elongation and high modulus high tensile strength, low elongation and high modulus high tensile strength, low elongation and high modulus
Poly(dl Poly(dl Poly(dl Poly(dl- -- -lactide) (DLPLA) lactide) (DLPLA) lactide) (DLPLA) lactide) (DLPLA)
Amorphous copolymer exhibiting a random distribution Amorphous copolymer exhibiting a random distribution Amorphous copolymer exhibiting a random distribution Amorphous copolymer exhibiting a random distribution
of both isomeric forms of lactic acid, of both isomeric forms of lactic acid, of both isomeric forms of lactic acid, of both isomeric forms of lactic acid,
Lower tensile strength, higher elongation, and Lower tensile strength, higher elongation, and Lower tensile strength, higher elongation, and Lower tensile strength, higher elongation, and
Rapid degradation time. Rapid degradation time. Rapid degradation time. Rapid degradation time.
Heat stable PLA Heat stable PLA Heat stable PLA Heat stable PLA Heat stable PLA Heat stable PLA Heat stable PLA Heat stable PLA
Increased optical purity Increased optical purity Increased optical purity Increased optical purity
Self Self Self Self - -- -nucleation by nucleation by nucleation by nucleation by stereocomplex stereocomplex stereocomplex stereocomplex formation formation formation formation
Increase of melting point from Increase of melting point from Increase of melting point from Increase of melting point from 160 160 160 160C to C to C to C to 170 170 170 170C C C C - -- - 230 230 230 230C CC C
Increase of glass transition temperature from Increase of glass transition temperature from Increase of glass transition temperature from Increase of glass transition temperature from 55 55 55 55C to C to C to C to 60 60 60 60C CC C- -- -70 70 70 70C CC C
Apllications Apllications Apllications Apllications- -- -
- -- - Textiles, Textiles, Textiles, Textiles, industrial yarns industrial yarns industrial yarns industrial yarns
- Hot Hot Hot Hot fillable fillable fillable fillable bottles bottles bottles bottles
- Ovenable Ovenable Ovenable Ovenable packaging packaging packaging packaging
Fast Fast Fast Fast Fast Fast Fast Fast Crystallising Crystallising Crystallising Crystallising Crystallising Crystallising Crystallising Crystallising PLA PLA PLA PLA PLA PLA PLA PLA
Nucleation by Nucleation by Nucleation by Nucleation by stereocomplex stereocomplex stereocomplex stereocomplex formation formation formation formation
Heterogenous Heterogenous Heterogenous Heterogenous nucleating agents nucleating agents nucleating agents nucleating agents
Crystallisation Crystallisation Crystallisation Crystallisation half half half half - -- -times less than times less than times less than times less than 1 1 1 1 min achievable min achievable min achievable min achievable
Applications: Applications: Applications: Applications:
Engineering plastics Engineering plastics Engineering plastics Engineering plastics
- -- - Automobile parts Automobile parts Automobile parts Automobile parts
Household Household Household Household
Greenhouse gas Greenhouse gas
emissions from emissions from
cradle to cradle to
polymer factory polymer factory
gate gate
NatureWorksPLA: Vink E.T.H. et all.
The eco-profiles for current and near-
future NatureWorks polylactide (PLA)
production. Industrial Biotechnology,
Volume 3, Number 1, 2007, Page 58-
81. Fossil based polymers:
PlasticsEurope;
www.lca.plasticseurope.org
Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA Properties and uses of PLA
Mechanical properties between that of Mechanical properties between that of Mechanical properties between that of Mechanical properties between that of
polystyrene and PET. polystyrene and PET. polystyrene and PET. polystyrene and PET.
Packaging Packaging Packaging Packaging
Packaging foam Packaging foam Packaging foam Packaging foam
Films Films Films Films
Containers (biodegradable) Containers (biodegradable) Containers (biodegradable) Containers (biodegradable)
Coatings for papers and boards Coatings for papers and boards Coatings for papers and boards Coatings for papers and boards
Fibres Fibres Fibres Fibres
Clothing Clothing Clothing Clothing
Carpet tiles (Interface Inc.) Carpet tiles (Interface Inc.) Carpet tiles (Interface Inc.) Carpet tiles (Interface Inc.)
Nappies Nappies Nappies Nappies
Bottles Bottles Bottles Bottles
Biodegradable bottles Biodegradable bottles Biodegradable bottles Biodegradable bottles
NatureWorks
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PLA PLA processability processability
Rigid thermoforms Rigid thermoforms Rigid thermoforms Rigid thermoforms
Clear, short term life, refrigerated Clear, short term life, refrigerated Clear, short term life, refrigerated Clear, short term life, refrigerated
trays and lids (fruits, vegetable trays and lids (fruits, vegetable trays and lids (fruits, vegetable trays and lids (fruits, vegetable
and deli). and deli). and deli). and deli).
Opaque dairy containers (yogurt, Opaque dairy containers (yogurt, Opaque dairy containers (yogurt, Opaque dairy containers (yogurt,
cheese, creams). cheese, creams). cheese, creams). cheese, creams).
Consumer displays and Consumer displays and Consumer displays and Consumer displays and
electronic packaging. electronic packaging. electronic packaging. electronic packaging.
Disposable articles (plates and Disposable articles (plates and Disposable articles (plates and Disposable articles (plates and
cups). cups). cups). cups).
Applications of PLA in packaging Applications of PLA in packaging
Body of Sony Walkman Body of Sony Walkman Body of Sony Walkman Body of Sony Walkman
Blisterpack for Sony Blisterpack for Sony Blisterpack for Sony Blisterpack for Sony
consumer electronics consumer electronics consumer electronics consumer electronics
Bioriented films Bioriented films Bioriented films Bioriented films
Shrink wrap for consumer Shrink wrap for consumer Shrink wrap for consumer Shrink wrap for consumer
goods packaging. goods packaging. goods packaging. goods packaging.
Twist wrap candy and Twist wrap candy and Twist wrap candy and Twist wrap candy and
flower wrap. flower wrap. flower wrap. flower wrap.
Laminations to Laminations to Laminations to Laminations to
paperboard for food and paperboard for food and paperboard for food and paperboard for food and
non food packaging. non food packaging. non food packaging. non food packaging.
Windows for envelopes Windows for envelopes Windows for envelopes Windows for envelopes
and cartons. and cartons. and cartons. and cartons.
Bottles Bottles Bottles Bottles
Short shelf Short shelf Short shelf Short shelf- -- -life milk and oil life milk and oil life milk and oil life milk and oil
packaging. packaging. packaging. packaging.
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Use of Use of Bioplastics Bioplastics in Durable in Durable
Products in Japan Products in Japan
2002 2002 2002 2002: Fujitsu firstly started to use PLA in a part (IR mask) in : Fujitsu firstly started to use PLA in a part (IR mask) in : Fujitsu firstly started to use PLA in a part (IR mask) in : Fujitsu firstly started to use PLA in a part (IR mask) in
PC PC PC PC
2002 2002 2002 2002: Sony used PLA in housing of Walkman : Sony used PLA in housing of Walkman : Sony used PLA in housing of Walkman : Sony used PLA in housing of Walkman
2003 2003 2003 2003: Toyota used PLA in cover of spear tire and floor mat : Toyota used PLA in cover of spear tire and floor mat : Toyota used PLA in cover of spear tire and floor mat : Toyota used PLA in cover of spear tire and floor mat
2004 2004 2004 2004: NEC used PLA/Kenaf comp. in dummy cards in PC : NEC used PLA/Kenaf comp. in dummy cards in PC : NEC used PLA/Kenaf comp. in dummy cards in PC : NEC used PLA/Kenaf comp. in dummy cards in PC
2005 2005 2005 2005: Fujitsu used flame : Fujitsu used flame : Fujitsu used flame : Fujitsu used flame- -- -retarding PLA composite retarding PLA composite retarding PLA composite retarding PLA composite
(petroleum (petroleum (petroleum (petroleum- -- -based plastic alloy) in PC housing based plastic alloy) in PC housing based plastic alloy) in PC housing based plastic alloy) in PC housing
2006 2006 2006 2006: NEC and NTT DoCoMo started the use of PLA/Kenaf : NEC and NTT DoCoMo started the use of PLA/Kenaf : NEC and NTT DoCoMo started the use of PLA/Kenaf : NEC and NTT DoCoMo started the use of PLA/Kenaf
comp. in ECO comp. in ECO comp. in ECO comp. in ECO- -- -cellular phone cellular phone cellular phone cellular phone
2007 2007 2007 2007: Mitubishi Motors will use PBS/bamboo comp. : Mitubishi Motors will use PBS/bamboo comp. : Mitubishi Motors will use PBS/bamboo comp. : Mitubishi Motors will use PBS/bamboo comp.
in boards in cars in boards in cars in boards in cars in boards in cars
Masatosh Iji, Nano Electronics Research Laboratories NEC Corporation, 2nd
European BioplasticsConference, Paris, 21. November 2007
PLA biodegradability PLA biodegradability
PLA is presumed to be biodegradable although the role of PLA is presumed to be biodegradable although the role of PLA is presumed to be biodegradable although the role of PLA is presumed to be biodegradable although the role of
hydrolysis vs. enzymatic depolymerization in this process hydrolysis vs. enzymatic depolymerization in this process hydrolysis vs. enzymatic depolymerization in this process hydrolysis vs. enzymatic depolymerization in this process
remains open to debate. remains open to debate. remains open to debate. remains open to debate.
Composting conditions are found only in industrial units with Composting conditions are found only in industrial units with Composting conditions are found only in industrial units with Composting conditions are found only in industrial units with
a high temperature (above a high temperature (above a high temperature (above a high temperature (above 50 50 50 50C) and a high relative C) and a high relative C) and a high relative C) and a high relative
humidity (RH) to promote chain hydrolysis. humidity (RH) to promote chain hydrolysis. humidity (RH) to promote chain hydrolysis. humidity (RH) to promote chain hydrolysis.
Weaknesses of PLA based packaging systems are found Weaknesses of PLA based packaging systems are found Weaknesses of PLA based packaging systems are found Weaknesses of PLA based packaging systems are found
for indicators like for indicators like for indicators like for indicators like acidification and eutrophication. acidification and eutrophication. acidification and eutrophication. acidification and eutrophication.
In a mid In a mid In a mid In a mid- -- -term perspective PLA recycling should be the term perspective PLA recycling should be the term perspective PLA recycling should be the term perspective PLA recycling should be the
target. target. target. target.
PLA packaging solutions promise benefits regarding PLA packaging solutions promise benefits regarding PLA packaging solutions promise benefits regarding PLA packaging solutions promise benefits regarding
consumption of non consumption of non consumption of non consumption of non- -- -renewable resources and climate renewable resources and climate renewable resources and climate renewable resources and climate
change change change change. .. .
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Polyhydroxyalkanoate Polyhydroxyalkanoate
PHA PHA
Polyhydroxyalkanoates Polyhydroxyalkanoates (PHA) (PHA)
Biodegradation to CO Biodegradation to CO
2 2
and H and H
2 2
OO
Sunlight Crop
Sugar solution
Fermentation
O O
C H
3 H
O
*
n
PHA Plastic product
Polyhydroxyalkanoates Polyhydroxyalkanoates (PHA) (PHA)
Aliphatic polyesters naturally produced via a microbial Aliphatic polyesters naturally produced via a microbial Aliphatic polyesters naturally produced via a microbial Aliphatic polyesters naturally produced via a microbial
fermentation of sugars (corn or cane) or vegetable oils. fermentation of sugars (corn or cane) or vegetable oils. fermentation of sugars (corn or cane) or vegetable oils. fermentation of sugars (corn or cane) or vegetable oils.
This family comprises mainly a homopolymer, This family comprises mainly a homopolymer, This family comprises mainly a homopolymer, This family comprises mainly a homopolymer,
polyhydroxybutyrate (PHB), and different copolyesters, polyhydroxybutyrate (PHB), and different copolyesters, polyhydroxybutyrate (PHB), and different copolyesters, polyhydroxybutyrate (PHB), and different copolyesters,
polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co- -- -hydroxyalkanoates such as hydroxyalkanoates such as hydroxyalkanoates such as hydroxyalkanoates such as
polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co- -- -hydroxyvalerates (PHBV), or hydroxyvalerates (PHBV), or hydroxyvalerates (PHBV), or hydroxyvalerates (PHBV), or
polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co- -- -hydroxyhexanoate (PHBHx), hydroxyhexanoate (PHBHx), hydroxyhexanoate (PHBHx), hydroxyhexanoate (PHBHx),
polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co- -- -hydroxyoctonoate (PHBO) and hydroxyoctonoate (PHBO) and hydroxyoctonoate (PHBO) and hydroxyoctonoate (PHBO) and
polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co polyhydroxybutyrate co- -- -hydroxyoctadecanoate (PHBOD). hydroxyoctadecanoate (PHBOD). hydroxyoctadecanoate (PHBOD). hydroxyoctadecanoate (PHBOD).
-Fully biodegradable in soil, water and compost Fully biodegradable in soil, water and compost Fully biodegradable in soil, water and compost Fully biodegradable in soil, water and compost
-Semicrystalline thermoplastic, Semicrystalline thermoplastic, Semicrystalline thermoplastic, Semicrystalline thermoplastic, brittle brittle brittle brittle
-Most commercial grades are injection molding grades Most commercial grades are injection molding grades Most commercial grades are injection molding grades Most commercial grades are injection molding grades
-Good printability Good printability Good printability Good printability
-Good resistance to grease and oils Good resistance to grease and oils Good resistance to grease and oils Good resistance to grease and oils
-Withstands hot liquids, HDT > Withstands hot liquids, HDT > Withstands hot liquids, HDT > Withstands hot liquids, HDT > 120 120 120 120C C C C
Properties Properties Properties Properties Properties Properties Properties Properties
- -- -PHB is a natural polymer. It is an intracellular PHB is a natural polymer. It is an intracellular PHB is a natural polymer. It is an intracellular PHB is a natural polymer. It is an intracellular
storage product of bacteria and algae. After storage product of bacteria and algae. After storage product of bacteria and algae. After storage product of bacteria and algae. After
fermentation, PHB can be obtained by solvent fermentation, PHB can be obtained by solvent fermentation, PHB can be obtained by solvent fermentation, PHB can be obtained by solvent
extraction. extraction. extraction. extraction.
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PHAs Commercially Available Polymers PHAs Commercially Available Polymers
Trade-name Supplier Origin
Mirel (PHB, PHBV) Telles - Metabolix USA
Biomer
Germany
Biofan Gunze Japan
Biogreen. Mitsubishi Gas Chemical Japan
ENMAT (PHBV) China
Biocycle (PHB, PHBV) PHB Brazil
Tianan
http://www.biocycle.com.br/site.htm
Mirel Bio-Plastic Resins
Mirel Mirel ((Metabolix Metabolix) ) 60 60 days at sea days at sea
Mirel Bio-Plastic Resins - 2nd European BioplasticsConference
Paris, 21. November 2007
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Starch Starch
Thermoplastic Starch Thermoplastic Starch
Constituting about Constituting about Constituting about Constituting about 80 80 80 80 per cent of the bioplastics per cent of the bioplastics per cent of the bioplastics per cent of the bioplastics
market, thermoplastic starch currently represents market, thermoplastic starch currently represents market, thermoplastic starch currently represents market, thermoplastic starch currently represents
the most important and widely used bioplastic. the most important and widely used bioplastic. the most important and widely used bioplastic. the most important and widely used bioplastic.
Flexibiliser and plasticiser such as sorbitol and Flexibiliser and plasticiser such as sorbitol and Flexibiliser and plasticiser such as sorbitol and Flexibiliser and plasticiser such as sorbitol and
glycerine are added so that starch can also be glycerine are added so that starch can also be glycerine are added so that starch can also be glycerine are added so that starch can also be
processed thermo processed thermo processed thermo processed thermo- -- -plastically. plastically. plastically. plastically.
By varying the amounts of these additives, the By varying the amounts of these additives, the By varying the amounts of these additives, the By varying the amounts of these additives, the
characteristic of the material can be tailored to characteristic of the material can be tailored to characteristic of the material can be tailored to characteristic of the material can be tailored to
specific needs. specific needs. specific needs. specific needs.
Raw material: corn, wheat, potatoes, tapioca, Raw material: corn, wheat, potatoes, tapioca, Raw material: corn, wheat, potatoes, tapioca, Raw material: corn, wheat, potatoes, tapioca,
beans, etc. beans, etc. beans, etc. beans, etc.
Starch consists of two types of molecules, amylose Starch consists of two types of molecules, amylose Starch consists of two types of molecules, amylose Starch consists of two types of molecules, amylose
(normally (normally (normally (normally 20 20 20 20- -- -30 30 30 30% %% %) and amylopectin (normally ) and amylopectin (normally ) and amylopectin (normally ) and amylopectin (normally 70 70 70 70- -- -80 80 80 80%). %). %). %).
Representative partial structure of amylose
Representative partial structure of amylopectin
http://www.lsbu.ac.uk/water/hysta.html
Native starch must be modified to find applications such as Native starch must be modified to find applications such as Native starch must be modified to find applications such as Native starch must be modified to find applications such as
destructured starch. destructured starch. destructured starch. destructured starch.
To obtain starch gelatinization with the combination of water To obtain starch gelatinization with the combination of water To obtain starch gelatinization with the combination of water To obtain starch gelatinization with the combination of water
(high content) and heat. (high content) and heat. (high content) and heat. (high content) and heat.
Gelatinization is the disruption of the granule organization. Gelatinization is the disruption of the granule organization. Gelatinization is the disruption of the granule organization. Gelatinization is the disruption of the granule organization.
The starch swells, forming a viscous paste with destruction The starch swells, forming a viscous paste with destruction The starch swells, forming a viscous paste with destruction The starch swells, forming a viscous paste with destruction
of most of inter of most of inter of most of inter of most of inter- -- -macromolecule hydrogen links. macromolecule hydrogen links. macromolecule hydrogen links. macromolecule hydrogen links.
A reduction of both, the melting temperature (Tm) and the A reduction of both, the melting temperature (Tm) and the A reduction of both, the melting temperature (Tm) and the A reduction of both, the melting temperature (Tm) and the
glass transition (Tg) is obtained. glass transition (Tg) is obtained. glass transition (Tg) is obtained. glass transition (Tg) is obtained.
http://www.biodeg.net/biomaterial.html
15
By decreasing the moisture content (less than By decreasing the moisture content (less than By decreasing the moisture content (less than By decreasing the moisture content (less than 20 20 20 20 wt%), the wt%), the wt%), the wt%), the
melting temperature tends to be close to the degradation melting temperature tends to be close to the degradation melting temperature tends to be close to the degradation melting temperature tends to be close to the degradation
temperature (Tm= temperature (Tm= temperature (Tm= temperature (Tm=220 220 220 220- -- -240 240 240 240C ) C ) C ) C )
To overcome this last issue, we add a non To overcome this last issue, we add a non To overcome this last issue, we add a non To overcome this last issue, we add a non- -- -volatile volatile volatile volatile
plasticizer to decrease Tm, such as glycerol or others plasticizer to decrease Tm, such as glycerol or others plasticizer to decrease Tm, such as glycerol or others plasticizer to decrease Tm, such as glycerol or others
polyols (sorbitol, polyethylene glycol). polyols (sorbitol, polyethylene glycol). polyols (sorbitol, polyethylene glycol). polyols (sorbitol, polyethylene glycol).
These plasticized starches (PLS) are also commonly called These plasticized starches (PLS) are also commonly called These plasticized starches (PLS) are also commonly called These plasticized starches (PLS) are also commonly called
thermoplastic starches or TPS. thermoplastic starches or TPS. thermoplastic starches or TPS. thermoplastic starches or TPS.
http://www.biodeg.net/biomaterial.html
Starch blends Starch blends
TPS has been widely used in blends with other polymers. TPS has been widely used in blends with other polymers. TPS has been widely used in blends with other polymers. TPS has been widely used in blends with other polymers.
A great number of patents have been published on this topic. A great number of patents have been published on this topic. A great number of patents have been published on this topic. A great number of patents have been published on this topic.
Most of the researches are focused on the blending of TPS with Most of the researches are focused on the blending of TPS with Most of the researches are focused on the blending of TPS with Most of the researches are focused on the blending of TPS with
biodegradable polyesters: polycaprolactone (PCL)], biodegradable polyesters: polycaprolactone (PCL)], biodegradable polyesters: polycaprolactone (PCL)], biodegradable polyesters: polycaprolactone (PCL)],
polyesteramide (PEA), polyhydroxybutyrate polyesteramide (PEA), polyhydroxybutyrate polyesteramide (PEA), polyhydroxybutyrate polyesteramide (PEA), polyhydroxybutyrate- -- -co co co co- -- -hydroxyvalerate hydroxyvalerate hydroxyvalerate hydroxyvalerate
(PHBV), polybutylene succinate (PHBV), polybutylene succinate (PHBV), polybutylene succinate (PHBV), polybutylene succinate- -- -adipate (PBSA), poly(butylene adipate (PBSA), poly(butylene adipate (PBSA), poly(butylene adipate (PBSA), poly(butylene
adipate adipate adipate adipate- -- -co co co co- -- -terephtalate) (PBAT), polylactic acid (PLA) or terephtalate) (PBAT), polylactic acid (PLA) or terephtalate) (PBAT), polylactic acid (PLA) or terephtalate) (PBAT), polylactic acid (PLA) or
poly(hydroxy ester ether (PHEE). poly(hydroxy ester ether (PHEE). poly(hydroxy ester ether (PHEE). poly(hydroxy ester ether (PHEE).
These polyesters commercially available show some interesting These polyesters commercially available show some interesting These polyesters commercially available show some interesting These polyesters commercially available show some interesting
and reproducible properties such as a more hydrophobic and reproducible properties such as a more hydrophobic and reproducible properties such as a more hydrophobic and reproducible properties such as a more hydrophobic
character, a lower water permeability and some improved character, a lower water permeability and some improved character, a lower water permeability and some improved character, a lower water permeability and some improved
mechanical properties, compared to PLS. mechanical properties, compared to PLS. mechanical properties, compared to PLS. mechanical properties, compared to PLS.
Commercially Available Starch and Commercially Available Starch and
blends blends
Origin Supplier Trade name
Germany Stanelco/Biotec/Adept Starpol
Italy Novamont Mater-bi
USA Cereplast, Inc. Cereplast
USA Teinnovations, Inc. PSM
Germany Biopolymer Technologies Biopar
Japan Evercorn Evercorn
Australia Plantic Plantic
Starpol NS is a co polyester starch blend and plasticizer free material
StarpolTM Wrap 100
Starpol 2000
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PLA/corn starch blend corn or potato starch
sy.com/ - www.bio
IPRC Biodegradable Polymers IPRC Biodegradable Polymers
R&D R&D
IPRC is conducting a R&D projects to evaluate blends IPRC is conducting a R&D projects to evaluate blends IPRC is conducting a R&D projects to evaluate blends IPRC is conducting a R&D projects to evaluate blends
properties, processing, product development and properties, processing, product development and properties, processing, product development and properties, processing, product development and
biodegradability with the objective of: biodegradability with the objective of: biodegradability with the objective of: biodegradability with the objective of:
Helping the Israel Plastics Industry to introduce bioplastics, as a Helping the Israel Plastics Industry to introduce bioplastics, as a Helping the Israel Plastics Industry to introduce bioplastics, as a Helping the Israel Plastics Industry to introduce bioplastics, as a
replacement for synthetic non renewable source polymers using replacement for synthetic non renewable source polymers using replacement for synthetic non renewable source polymers using replacement for synthetic non renewable source polymers using
conventional processing. conventional processing. conventional processing. conventional processing.
Developing new biodegradable blends in order to achieve similar Developing new biodegradable blends in order to achieve similar Developing new biodegradable blends in order to achieve similar Developing new biodegradable blends in order to achieve similar
properties of the synthetic polymers. properties of the synthetic polymers. properties of the synthetic polymers. properties of the synthetic polymers.
Developing technologies in order to control the biodegradability rate. Developing technologies in order to control the biodegradability rate. Developing technologies in order to control the biodegradability rate. Developing technologies in order to control the biodegradability rate.
Improving properties using nanotechnology: biodegradable Improving properties using nanotechnology: biodegradable Improving properties using nanotechnology: biodegradable Improving properties using nanotechnology: biodegradable
nanocomposites. nanocomposites. nanocomposites. nanocomposites.
Summary and conclusions Summary and conclusions
All recycling options can be used, including All recycling options can be used, including All recycling options can be used, including All recycling options can be used, including
composting. composting. composting. composting.
High market potential ( High market potential ( High market potential ( High market potential (10 10 10 10% of plastic consumption). % of plastic consumption). % of plastic consumption). % of plastic consumption).
Main benefits: CO Main benefits: CO Main benefits: CO Main benefits: CO
2 22 2
emission reduction, reduction emission reduction, reduction emission reduction, reduction emission reduction, reduction
of landfill mass, saving fossil resources. of landfill mass, saving fossil resources. of landfill mass, saving fossil resources. of landfill mass, saving fossil resources.
High consumer acceptance High consumer acceptance High consumer acceptance High consumer acceptance