biodegradable polymers 03 08
TRANSCRIPT
-
8/13/2019 Biodegradable Polymers 03 08
1/16
-
8/13/2019 Biodegradable Polymers 03 08
2/16
2
COCO22 footprintfootprint
Dr. Jim Lunt, Tianan Biologic Material Co. Ltd, Ningbo, China, 2nd European
Bioplasti cs Conference, November 21-22, 2007
BioplasticBioplastic OriginOrigin
Raw materials forRaw materials forRaw materials forRaw materials forRaw materials forRaw materials forRaw materials forRaw materials for bioplasticsbioplasticsbioplasticsbioplasticsbioplasticsbioplasticsbioplasticsbioplastics
Hans van der Pol, PURAC, 2nd European BioplasticsConference
Paris, 21. November 2007
BioplasticsBioplastics
Biobased and biodegradable (PLA, PHA,Biobased and biodegradable (PLA, PHA,Biobased and biodegradable (PLA, PHA,Biobased and biodegradable (PLA, PHA,
starch): shortstarch): shortstarch): shortstarch): short----life, disposable productslife, disposable productslife, disposable productslife, disposable products
Biobased and durable (castor oil basedBiobased and durable (castor oil basedBiobased and durable (castor oil basedBiobased and durable (castor oil based
NylonNylonNylonNylon 11111111, 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)
RememberRememberRememberRemember: Biobased plastics are not: Biobased plastics are not: Biobased plastics are not: Biobased plastics are not
always biodegradable andalways biodegradable andalways biodegradable andalways biodegradable and BiodegradableBiodegradableBiodegradableBiodegradable
plastics are not always biobasedplastics are not always biobasedplastics are not always biobasedplastics are not always biobased
-
8/13/2019 Biodegradable Polymers 03 08
3/16
3
Green PolyethyleneGreen PolyethyleneDegradability and biodegradabilityDegradability and biodegradability
There are five different types of degradable polymersThere are five different types of degradable polymersThere are five different types of degradable polymersThere are five different types of degradable polymers ::::
Biodegradable polymersBiodegradable polymersBiodegradable polymersBiodegradable polymers are those that are capable ofare those that are capable ofare those that are capable ofare 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 predominantinorganic compounds or biomass in which the predominantinorganic compounds or biomass in which the predominantinorganic compounds or biomass in which the predominant
mechanism is the enzymatic action of micromechanism is the enzymatic action of micromechanism is the enzymatic action of micromechanism is the enzymatic action of micro----organisms that can beorganisms that can beorganisms that can beorganisms 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 (90909090 totototo 180180180180
days), reflecting available disposal conditions.days), reflecting available disposal conditions.days), reflecting available disposal conditions.days), reflecting available disposal conditions.
Compostable polymersCompostable polymersCompostable polymersCompostable polymers are those that are degradable underare those that are degradable underare those that are degradable underare those that are degradable under
composting conditions. To meet this definition they must breakcomposting conditions. To meet this definition they must breakcomposting conditions. To meet this definition they must breakcomposting conditions. To meet this definition they must break
down under the action of microdown under the action of microdown under the action of microdown 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 aerobicmethane, water, inorganic compounds or biomass under aerobicmethane, water, inorganic compounds or biomass under aerobicmethane, water, inorganic compounds or biomass under aerobic
conditions) and the mineralization rate must be high and compatibleconditions) and the mineralization rate must be high and compatibleconditions) and the mineralization rate must be high and compatibleconditions) 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.
OxoOxoOxoOxo----degradable polymersdegradable polymersdegradable polymersdegradable polymers are those that undergo controlledare those that undergo controlledare those that undergo controlledare those that undergo controlled
degradation through the incorporation of prodegradant additivesdegradation through the incorporation of prodegradant additivesdegradation through the incorporation of prodegradant additivesdegradation 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 oxidativeprocess). These polymers undergo accelerated oxidativeprocess). These polymers undergo accelerated oxidativeprocess). These polymers undergo accelerated oxidative
degradation initiated by natural daylight, heat and/or mechanicaldegradation initiated by natural daylight, heat and/or mechanicaldegradation initiated by natural daylight, heat and/or mechanicaldegradation initiated by natural daylight, heat and/or mechanical
stress, and embrittle in the environment and erode under thestress, and embrittle in the environment and erode under thestress, and embrittle in the environment and erode under thestress, and embrittle in the environment and erode under theinfluence of weathering.influence of weathering.influence of weathering.influence of weathering.
Photodegradable polymersPhotodegradable polymersPhotodegradable polymersPhotodegradable polymers are those that break downare those that break downare those that break downare those that break down
through the action of ultraviolet (UV) light, which degrades thethrough the action of ultraviolet (UV) light, which degrades thethrough the action of ultraviolet (UV) light, which degrades thethrough the action of ultraviolet (UV) light, which degrades the
chemical bond or link in the polymer. This process can bechemical bond or link in the polymer. This process can bechemical bond or link in the polymer. This process can bechemical bond or link in the polymer. This process can be
assisted by the presence of UVassisted by the presence of UVassisted by the presence of UVassisted by the presence of UV----sensitive additives in thesensitive additives in thesensitive additives in thesensitive additives in the
polymer.polymer.polymer.polymer.
WaterWaterWaterWater----soluble polymerssoluble polymerssoluble polymerssoluble polymers are those that dissolve in water withinare those that dissolve in water withinare those that dissolve in water withinare those that dissolve in water within
a designated temperature range and then biodegrade in contacta designated temperature range and then biodegrade in contacta designated temperature range and then biodegrade in contacta designated temperature range and then biodegrade in contact
with microorganisms.with microorganisms.with microorganisms.with microorganisms.
Problems presented by degradableProblems presented by degradable
but not biodegradable polymersbut not biodegradable polymers A plastic may be degradable but not biodegradable or it may beA plastic may be degradable but not biodegradable or it may beA plastic may be degradable but not biodegradable or it may beA plastic may be degradable but not biodegradable or it may be
biodegradable but not compostable (it breaks down too slow ly tobiodegradable but not compostable (it breaks down too slowly tobiodegradable but not compostable (it breaks down too slow ly tobiodegradable 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 andPlastic debris around the globe can erode (degrade) away andPlastic debris around the globe can erode (degrade) away andPlastic debris around the globe can erode (degrade) away and
end up as microscopic granular or fiber like fragments, and thatend up as microscopic granular or fiber like fragments, and thatend up as microscopic granular or fiber like fragments, and thatend 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 TransportToxic Chemicals TransportToxic Chemicals TransportToxic Chemicals Transport::::
Plastic pieces can attract toxic residues and function as aPlastic pieces can attract toxic residues and function as aPlastic pieces can attract toxic residues and function as aPlastic pieces can attract toxic residues and function as a
transport mediumtransport mediumtransport mediumtransport medium
Toxic pesticides were detected in high concentrations inToxic pesticides were detected in high concentrations inToxic pesticides were detected in high concentrations inToxic pesticides were detected in high concentrations in
degraded polypropylene (PP) resin pellets collected from fou rdegraded polypropylene (PP) resin pellets collected from fourdegraded polypropylene (PP) resin pellets collected from fou rdegraded polypropylene (PP) resin pellets collected from four
Japanese coasts.Japanese coasts.Japanese coasts.Japanese coasts.
-
8/13/2019 Biodegradable Polymers 03 08
4/16
4
EuropeEurope bioplasticsbioplastics boomboom
Growth of up toGrowth of up toGrowth of up toGrowth of up to 100100100100% over% over% over% over 2005200520052005 levels inlevels inlevels inlevels inbiobiobiobio----packaging field.packaging field.packaging field.packaging field.
Increasing numbers of chain stores thatIncreasing numbers of chain stores thatIncreasing numbers of chain stores thatIncreasing numbers of chain stores thathave introduced biohave introduced biohave introduced biohave introduced bio----packaging.packaging.packaging.packaging.
Bioplastics are thought to represent aBioplastics are thought to represent aBioplastics are thought to represent aBioplastics are thought to represent atechnological potential of abouttechnological potential of abouttechnological potential of abouttechnological potential of about 10101010% of the% of the% of the% of thepresent plastics market ofpresent plastics market ofpresent plastics market ofpresent plastics market of 40404040 million tons inmillion tons inmillion tons inmillion tons inEurope.Europe.Europe.Europe.
http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf
tons/year
Consumers Acceptance ResearchConsumers Acceptance Research
The milk comes fromThe milk comes fromThe milk comes fromThe milk comes from
mother naturemother naturemother naturemother nature
Now, so does the bottleNow, so does the bottleNow, so does the bottleNow, so does the bottle
MarketingMarketing ApproachApproach
-
8/13/2019 Biodegradable Polymers 03 08
5/16
5
First legal incentives in EUFirst legal incentives in EU
member statesmember states Germany: Certified compostable plasticGermany: Certified compostable plasticGermany: Certified compostable plasticGermany: Certified compostable plastic
packaging is exempted from recyclingpackaging is exempted from recyclingpackaging is exempted from recyclingpackaging is exempted from recycling
obligations until yearobligations until yearobligations until yearobligations until year 2012201220122012
French Agri Law/ Italy: One way plastic bagsFrench Agri Law/ Italy: One way plastic bagsFrench Agri Law/ Italy: One way plastic bagsFrench Agri Law/ Italy: One way plastic bags
must be biodegradable frommust be biodegradable frommust be biodegradable frommust be biodegradable from 2010201020102010 onononon
PotentialPotentialApplicationsApplications
http://www.european-bioplastics.org/media/files/docs/en-pub/060526_European_Bioplastics.pdf
-
8/13/2019 Biodegradable Polymers 03 08
6/16
6
h tt p: // ww w. eu ro pe an -b io pl ast ics .o rg /m ed ia/ fi le s/ do cs /e n- pu b/ 06 05 26 _E ur op ean _B io pl as ti cs .p df h tt p: // ww w. eu ro pe an -b io pl as ti cs .o rg /m ed ia /f il es/ do cs /e n- pu b/ 06 05 26 _E ur op ea n_ Bi op la st ic s. pd f
Cosmetics packagingCosmetics packaging
-
8/13/2019 Biodegradable Polymers 03 08
7/16
7
Durable productsDurable productsTOYOTATOYOTAEcoEco--plasticsplasticsforfor
Interior PartsInterior Parts
FormaldehydeFormaldehyde--Free BiodegradableFree Biodegradable
Wood CompositesWood Composites
RenewableRenewableRenewableRenewable
BiodegradableBiodegradableBiodegradableBiodegradable
FormaldehydeFormaldehydeFormaldehydeFormaldehyde----freefreefreefree
EnvironmentallyEnvironmentallyEnvironmentallyEnvironmentally----friendlyfriendlyfriendlyfriendly
Main disadvantageMain disadvantage
PricePricePricePrice
Synthetic plasticsSynthetic plasticsSynthetic plasticsSynthetic plastics > 4444 Euro/kgEuro/kgEuro/kgEuro/kg
-
8/13/2019 Biodegradable Polymers 03 08
8/16
8
PolylacticPolylactic acidacid
PLAPLA
Polylactic acid (PLA):Polylactic acid (PLA):Polylactic acid (PLA):Polylactic acid (PLA):
Linear aliphatic polyesterLinear aliphatic polyesterLinear aliphatic polyesterLinear aliphatic polyester
Produced by :Produced by :Produced by :Produced by : po ly polypolypoly----condensation of naturally produced lactic acid (cocondensation of naturally produced lactic acid (cocondensation of naturally produced lactic acid (cocondensation of naturally produced lactic acid (co----
product of corn), or byproduct of corn), or byproduct of corn), or byproduct 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 biodegradableCompared to the others biodegradableCompared to the others biodegradableCompared to the others biodegradablepolyesters, PLA is the product that at thepolyesters, PLA is the product that at thepolyesters, PLA is the product that at thepolyesters, PLA is the product that at thepresent has one of the highest potentialpresent has one of the highest potentialpresent has one of the highest potentialpresent has one of the highest potentialdue to its avai lability on the market and itsdue to its avai lability on the market and itsdue to its avai lability on the market and itsdue to its avai lability on the market and itslow price.low price.low price.low price.
PolylacticPolylactic Acid (PLA)Acid (PLA)
PolylacticPolylactic Acid (PLA)Acid (PLA) PLA propertiesPLA propertiesPLA propertiesPLA propertiesPLA propertiesPLA propertiesPLA propertiesPLA 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 (60606060ooooC)C)C)C)
slow degradationslow degradationslow degradationslow degradation
Properties can be tailored blending PLA withProperties can be tailored blending PLA withProperties can be tailored blending PLA withProperties can be tailored blending PLA withPHBV, starch and other biodegradablePHBV, starch and other biodegradablePHBV, starch and other biodegradablePHBV, starch and other biodegradablepolymers (PCL, PBAT, PBS).polymers (PCL, PBAT, PBS).polymers (PCL, PBAT, PBS).polymers (PCL, PBAT, PBS).
-
8/13/2019 Biodegradable Polymers 03 08
9/16
9
Homopolymer of lHomopolymer of lHomopolymer of lHomopolymer 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 (37373737%)%)%)%)
high tensile strength, low elongation and high modulushigh tensile strength, low elongation and high modulushigh tensile strength, low elongation and high modulushigh tensile strength, low elongation and high modulus
Poly(dlPoly(dlPoly(dlPoly(dl----lactide) (DLPLA)lactide) (DLPLA)lactide) (DLPLA)lactide) (DLPLA)
Amorphous copolymer exhibiting a random distributionAmorphous copolymer exhibiting a random distributionAmorphous copolymer exhibiting a random distributionAmorphous copolymer exhibiting a random distributionof 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, andLower tensile strength, higher elongation, andLower tensile strength, higher elongation, andLower tensile strength, higher elongation, and Rapid degradation time.Rapid degradation time.Rapid degradation time.Rapid degradation time.
Heat stable PLAHeat stable PLAHeat stable PLAHeat stable PLAHeat stable PLAHeat stable PLAHeat stable PLAHeat stable PLAIncreased optical purityIncreased optical purityIncreased optical purityIncreased optical purity
SelfSelfSelfSelf----nucleation bynucleation bynucleation bynucleation by stereocomplexstereocomplexstereocomplexstereocomplexformationformationformationformation
Increase of melting point fromIncrease of melting point fromIncrease of melting point fromIncrease of melting point from 160160160160C toC toC toC to 170170170170CCCC ---- 230230230230CCCC
Increase of glass transition temperature fromIncrease of glass transition temperature fromIncrease of glass transition temperature fromIncrease of glass transition temperature from 55555555C toC toC toC to 60606060CCCC----70707070CCCC
ApllicationsApllicationsApllicationsApllications----
---- Text il es,Textiles,Textiles,Textiles, industrial yarnsindustrial yarnsindustrial yarnsindustrial yarns
- HotHotHotHot fillablefillablefillablefillablebottlesbottlesbottlesbottles
- Ove nabl eOvenableOvenableOvenable packagingpackagingpackagingpackaging
FastFastFastFastFastFastFastFast CrystallisingCrystallisingCrystallisingCrystallisingCrystallisingCrystallisingCrystallisingCrystallisingPLAPLAPLAPLAPLAPLAPLAPLANucleation byNucleation byNucleation byNucleation by stereocomplexstereocomplexstereocomplexstereocomplexformationformationformationformation
HeterogenousHeterogenousHeterogenousHeterogenous nucleating agentsnucleating agentsnucleating agentsnucleating agents
CrystallisationCrystallisationCrystallisationCrystallisation halfhalfhalfhalf----times less thantimes less thantimes less thantimes less than 1111 min achievablemin achievablemin achievablemin achievable
App li cat ions :Applications:Applications:Applications: Engineering plasticsEngineering plasticsEngineering plasticsEngineering plastics
---- Automobile partsAutomobile partsAutomobile partsAutomobile parts
HouseholdHouseholdHouseholdHousehold
Greenhouse gasGreenhouse gas
emissions fromemissions from
cradle tocradle to
polymer factorypolymer factorygategate
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 PLAProperties and uses of PLAProperties and uses of PLAProperties and uses of PLAProperties and uses of PLAProperties and uses of PLAProperties and uses of PLAProperties and uses of PLA
Mechanical properties between that ofMechanical properties between that ofMechanical properties between that ofMechanical properties between that of
polystyrene and PET.polystyrene and PET.polystyrene and PET.polystyrene and PET.
Packag ingPackagingPackagingPackaging
Packaging foamPackaging foamPackaging foamPackaging foam Fi lmsFilmsFilmsFilms
Containers (biodegradable)Containers (biodegradable)Containers (biodegradable)Containers (biodegradable)
Coatings for papers and boardsCoatings for papers and boardsCoatings for papers and boardsCoatings for papers and boards
FibresFibresFibresFibres
ClothingClothingClothingClothing
Carpet tiles (Interface Inc.)Carpet tiles (Interface Inc.)Carpet tiles (Interface Inc.)Carpet tiles (Interface Inc.)
NappiesNappiesNappiesNappies
Bo ttl esBottlesBottlesBottles
Biodegradable bottlesBiodegradable bottlesBiodegradable bottlesBiodegradable bottles NatureWorks
-
8/13/2019 Biodegradable Polymers 03 08
10/16
10
PLAPLA processabilityprocessability
Rigid thermoformsRigid thermoformsRigid thermoformsRigid thermoforms
Clear, short term life, refrigeratedClear, short term life, refrigeratedClear, short term life, refrigeratedClear, short term life, refrigerated
trays and lids (fruits, vegetabletrays and lids (fruits, vegetabletrays and lids (fruits, vegetabletrays 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 andConsumer displays andConsumer displays andConsumer displays and
electronic packaging.electronic packaging.electronic packaging.electronic packaging.
Disposable articles (plates andDisposable articles (plates andDisposable articles (plates andDisposable articles (plates andcups).cups).cups).cups).
Applications of PLA in packagingApplications of PLA in packaging
Body of Sony WalkmanBody of Sony WalkmanBody of Sony WalkmanBody of Sony Walkman
Blisterpack for SonyBlisterpack for SonyBlisterpack for SonyBlisterpack for Sony
consumer electronicsconsumer electronicsconsumer electronicsconsumer electronics Bioriented filmsBioriented filmsBioriented filmsBioriented films
Shrink wrap for consumerShrink wrap for consumerShrink wrap for consumerShrink wrap for consumergoods packaging.goods packaging.goods packaging.goods packaging.
Twist wrap candy andTwist wrap candy andTwist wrap candy andTwist wrap candy andflower wrap.flower wrap.flower wrap.flower wrap.
Laminations toLaminations toLaminations toLaminations topaperboard for food andpaperboard for food andpaperboard for food andpaperboard for food andnon food packaging.non food packaging.non food packaging.non food packaging.
Windows for envelopesWindows for envelopesWindows for envelopesWindows for envelopesand cartons.and cartons.and cartons.and cartons.
BottlesBottlesBottlesBottles
Short shelfShort shelfShort shelfShort shelf----life milk and oillife milk and oillife milk and oillife milk and oilpackaging.packaging.packaging.packaging.
-
8/13/2019 Biodegradable Polymers 03 08
11/16
11
Use ofUse of BioplasticsBioplastics in Durablein Durable
Products in JapanProducts in Japan
2002200220022002: Fujitsu fir stly 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
PCPCPCPC
2002200220022002: Sony used PLA in housing of Walkman: Sony used PLA in hous ing of Walkman: Sony used PLA in housing of Walkman: Sony used PLA in hous ing of Walkman
2003200320032003: Toyota used PLA in cover o f spear tire and flo or mat: Toyota used PLA in cover of spear tire and flo or mat: Toyota used PLA in cover of spear tire and floor mat: Toyota used PLA in cover of spear tire and flo or mat
2004200420042004: 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
2005200520052005: Fujitsu used flame: Fujitsu used flame: Fujitsu used flame: Fujitsu used flame----retarding PLA compositeretarding PLA compositeretarding PLA compositeretarding PLA composite
(petroleum(petroleum(petroleum(petroleum----based plastic alloy) in PC housingbased plastic alloy) in PC housingbased plastic alloy) in PC housingbased plastic alloy) in PC housing
2006200620062006: 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 o f PLA/Kenaf: NEC and NTT DoCoMo started the use of PLA/Kenaf
comp. in ECOcomp. in ECOcomp. in ECOcomp. in ECO----cellular phonecellular phonecellular phonecellular phone2007200720072007: 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 carsin boards in carsin boards in carsin boards in cars
Masatosh Iji, Nano Electronics Research Laboratories NEC Corporation, 2nd
European BioplasticsConference , Paris, 21. November 2007
PLA biodegradabilityPLA biodegradability PLA is presumed to be biodegradable although the role ofPLA is presumed to be biodegradable although the role ofPLA is presumed to be biodegradable although the role ofPLA is presumed to be biodegradable although the role of
hydrolysis vs. enzymatic depolymerization in this processhydrolysis vs. enzymatic depolymerization in this processhydrolysis vs. enzymatic depolymerization in this processhydrolysis vs. enzymatic depolymerization in this processremains open to debate.remains open to debate.remains open to debate.remains open to debate.
Composting conditions are found only in industrial units withComposting conditions are found only in industrial units withComposting conditions are found only in industrial units withComposting conditions are found only in industrial units witha high temperature (abovea high temperature (abovea high temperature (abovea high temperature (above 50505050C) and a high relativeC) and a high relativeC) and a high relativeC) and a high relativehumidity (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 foundWeaknesses of PLA based packaging systems are foundWeaknesses of PLA based packaging systems are foundWeaknesses of PLA based packaging systems are found
for indicators likefor indicators likefor indicators likefor indicators like acidification and eutrophication.acidification and eutrophication.acidification and eutrophication.acidification and eutrophication.
In a midIn a midIn a midIn a mid----term perspective PLA recycling should be theterm perspective PLA recycling should be theterm perspective PLA recycling should be theterm perspective PLA recycling should be the
target.target.target.target.
PLA packaging solutions promise benefits regardingPLA packaging solutions promise benefits regardingPLA packaging solutions promise benefits regardingPLA packaging solutions promise benefits regarding
consumption of nonconsumption of nonconsumption of nonconsumption of non----renewable resources and climaterenewable resources and climaterenewable resources and climaterenewable resources and climate
changechangechangechange....
-
8/13/2019 Biodegradable Polymers 03 08
12/16
12
PolyhydroxyalkanoatePolyhydroxyalkanoate
PHAPHA
PolyhydroxyalkanoatesPolyhydroxyalkanoates (PHA)(PHA)
Biodegradation to COBiodegradation to CO22 and Hand H22OO
Sunlight CropSugar solution
Fermentation
O O
CH3 H
O
*n
PHAPlastic product
PolyhydroxyalkanoatesPolyhydroxyalkanoates (PHA)(PHA)
Aliphatic polyesters naturally produced via a microbialAliphatic polyesters naturally produced via a microbialAliphatic polyesters naturally produced via a microbialAliphatic polyesters naturally produced via a microbialfermentation 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 copolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate co----hydroxyalkanoates such ashydroxyalkanoates such ashydroxyalkanoates such ashydroxyalkanoates such aspolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate co----hydroxyvalerates (PHBV), orhydroxyvalerates (PHBV), orhydroxyvalerates (PHBV), orhydroxyvalerates (PHBV), orpolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate co----hydroxyhexanoate (PHBHx),hydroxyhexanoate (PHBHx),hydroxyhexanoate (PHBHx),hydroxyhexanoate (PHBHx),polyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate co----hydroxyoctonoate (PHBO) andhydroxyoctonoate (PHBO) andhydroxyoctonoate (PHBO) andhydroxyoctonoate (PHBO) andpolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate copolyhydroxybutyrate co----hydroxyoctadecanoate (PHBOD).hydroxyoctadecanoate (PHBOD).hydroxyoctadecanoate (PHBOD).hydroxyoctadecanoate (PHBOD).
-Fully biodegradable in soil, water and compostFully biodegradable in soil, water and compostFully biodegradable in soil, water and compostFully biodegradable in soil, water and compost-Semicrystalline thermoplastic,Semicrystalline thermoplastic,Semicrystalline thermoplastic,Semicrystalline thermoplastic, brittlebrittlebrittlebrittle
-Most commercial grades are injection molding gradesMost commercial grades are injection molding gradesMost commercial grades are injection molding gradesMost commercial grades are injection molding grades
-Good printabilityGood printabilityGood printabilityGood printability
-Good resistance to grease and oilsGood resistance to grease and oilsGood resistance to grease and oilsGood resistance to grease and oils
-Withstands hot liquids, HDT >Withstands hot liquids, HDT >Withstands hot liquids, HDT >Withstands hot liquids, HDT > 120120120120CCCC
PropertiesPropertiesPropertiesPropertiesPropertiesPropertiesPropertiesProperties
----PHB is a natural polymer. It is an intracellularPHB is a natural polymer. It is an intracellularPHB is a natural polymer. It is an intracellularPHB is a natural polymer. It is an intracellularstorage product of bacteria and algae. Afterstorage product of bacteria and algae. Afterstorage product of bacteria and algae. Afterstorage product of bacteria and algae. Afterfermentation, PHB can be obtained by solventfermentation, PHB can be obtained by solventfermentation, PHB can be obtained by solventfermentation, PHB can be obtained by solventextraction.extraction.extraction.extraction.
-
8/13/2019 Biodegradable Polymers 03 08
13/16
13
PHAs Commercially Available PolymersPHAs 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.htmMirel Bio-Plastic Resins
MirelMirel ((MetabolixMetabolix)) 6060 days at seadays at sea
Mirel Bio-Plastic Resins - 2nd European BioplasticsConference
Paris, 21. November 2007
-
8/13/2019 Biodegradable Polymers 03 08
14/16
14
StarchStarch
Thermoplastic StarchThermoplastic Starch Constituting aboutConstituting aboutConstituting aboutConstituting about 80808080 per cent of the bioplasticsper cent of the bioplasticsper cent of the bioplasticsper cent of the bioplastics
market, thermoplastic starch currently representsmarket, thermoplastic starch currently representsmarket, thermoplastic starch currently representsmarket, thermoplastic starch currently representsthe most important and widely used bioplastic.the most important and widely used biop lastic.the most important and widely used bioplastic.the most important and widely used biop lastic.
Flexibiliser and plasticiser such as sorbitol andFlexibiliser and plasticiser such as sorbitol andFlexibiliser and plasticiser such as sorbitol andFlexibiliser and plasticiser such as sorbitol andglycerine are added so that starch can also beglycerine are added so that starch can also beglycerine are added so that starch can also beglycerine are added so that starch can also beprocessed thermoprocessed thermoprocessed thermoprocessed thermo----plastically.plastically.plastically.plastically.
By varying the amounts of these additives, theBy varying the amounts of these additives, theBy varying the amounts of these add itives, theBy varying the amounts of these additives, thecharacteristic of the material can be ta ilored tocharacteristic of the material can be ta ilored tocharacteristic of the material can be ta ilored tocharacteristic of the material can be ta ilored 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, amyloseStarch consists of two types of molecules, amyloseStarch consists of two types of molecules, amyloseStarch consists of two types of molecules, amylose
(normally(normally(normally(normally 20202020----30303030%%%%) and amylopectin (normally) and amylopectin (normally) and amylopectin (normally) and amylopectin (normally 70707070----80808080%).%).%).%).
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 asNative starch must be modified to find applications such asNative starch must be modified to find applications such asNative starch must be modified to find applications such asdestructured starch.destructured starch.destructured starch.destructured starch.
To obtain starch gelatinization with the combination of waterTo obtain starch gelatinization with the combination of waterTo obtain starch gelatinization with the combination of waterTo 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 destructionThe starch swells, forming a viscous paste with destructionThe starch swells, forming a viscous paste with destructionThe starch swells, forming a viscous paste with destruction
of most of interof most of interof most of interof most of inter----macromolecule hydrogen links.macromolecule hydrogen links.macromolecule hydrogen links.macromolecule hydrogen links. A reduction of both, the melting temperature (Tm) and theA reduction of both, the melting temperature (Tm) and theA reduction of both, the melting temperature (Tm) and theA 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
-
8/13/2019 Biodegradable Polymers 03 08
15/16
15
By decreasing the moisture content (less thanBy decreasing the moisture content (less thanBy decreasing the moisture content (less thanBy decreasing the moisture content (less than 20202020 wt%), thewt%), thewt%), thewt%), themelting temperature tends to be close to the degradationmelting temperature tends to be close to the degradationmelting temperature tends to be close to the degradationmelting temperature tends to be close to the degradationtemperature (Tm=temperature (Tm=temperature (Tm=temperature (Tm=220220220220----240240240240C )C )C )C )
To overcome this last issue, we add a nonTo overcome this last issue, we add a nonTo overcome this last issue, we add a nonTo overcome this last issue, we add a non----volatilevolatilevolatilevolatileplasticizer to decrease Tm, such as glycerol or othersplasticizer to decrease Tm, such as glycerol or othersplasticizer to decrease Tm, such as glycerol or othersplasticizer to decrease Tm, such as glycerol or otherspolyols (sorbitol, polyethylene glycol).polyols (sorbitol, polyethylene glycol).polyols (sorbitol, polyethylene glycol).polyols (sorbitol, polyethylene glycol).
These plasticized starches (PLS) are also commonly calledThese plasticized starches (PLS) are also commonly calledThese plasticized starches (PLS) are also commonly calledThese plasticized starches (PLS) are also commonly calledthermoplastic starches or TPS.thermoplastic starches or TPS.thermoplastic starches or TPS.thermoplastic starches or TPS.
http://www.biodeg.net/biomaterial.html
Starch blendsStarch 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 withMost of the researches are focused on the blending of TPS wi thMost of the researches are focused on the blend ing of TPS withMost of the researches are focused on the blending of TPS wi thbiodegradable polyesters: polycaprolactone (PCL)],biodegradable polyesters: polycaprolactone (PCL)],biodegradable polyesters: polycaprolactone (PCL)],biodegradable polyesters: polycaprolactone (PCL)],polyesteramide (PEA), polyhydroxybutyratepolyesteramide (PEA), polyhydroxybutyratepolyesteramide (PEA), polyhydroxybutyratepolyesteramide (PEA), polyhydroxybutyrate----cocococo----hydroxyvaleratehydroxyvaleratehydroxyvaleratehydroxyvalerate(PHBV), polybutylene succinate(PHBV), polybutylene succinate(PHBV), polybutylene succinate(PHBV), polybutylene succinate----adipate (PBSA), poly(butyleneadipate (PBSA), poly(butyleneadipate (PBSA), poly(butyleneadipate (PBSA), poly(butyleneadipateadipateadipateadipate----cocococo----terephtalate) (PBAT), polylactic acid (PLA) orterephtalate) (PBAT), polylactic acid (PLA) orterephtalate) (PBAT), polylactic acid (PLA) orterephtalate) (PBAT), polylactic acid (PLA) orpoly(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 interestingThese polyesters commercially available show some interestingThese polyesters commercially available show some interestingThese polyesters commercially available show some interesting
and reproducible properties such as a more hydrophobicand reproducible properties such as a more hydrophobicand reproducible properties such as a more hydrophobicand reproducible properties such as a more hydrophobiccharacter, a lower water permeability and some improvedcharacter, a lower water permeability and some improvedcharacter, a lower water permeability and some improvedcharacter, a lower water permeability and some improvedmechanical properties, compared to PLS.mechanical properties, compared to PLS.mechanical properties, compared to PLS.mechanical properties, compared to PLS.
Commercially Available Starch andCommercially Available Starch and
blendsblendsOriginSupplierTrade name
GermanyStanelco/Biotec/AdeptStarpol
ItalyNovamontMater-bi
USACereplast, Inc.Cereplast
USATeinnovations, Inc.PSM
GermanyBiopolymer TechnologiesBiopar
JapanEvercornEvercorn
AustraliaPlanticPlantic
Starpol NS is a co polyester starch blend and plasticizer free material
StarpolTM Wrap 100 Starpol 2000
-
8/13/2019 Biodegradable Polymers 03 08
16/16
PLA/corn starch blend corn or potato starch
sy.com/-www.bio
IPRC Biodegradable PolymersIPRC Biodegradable Polymers
R&DR&D IPRC is conducting a R&D projects to evaluate blendsIPRC is conducting a R&D projects to evaluate blendsIPRC is conducting a R&D projects to evaluate blendsIPRC is conducting a R&D projects to evaluate blends
properties, processing, product development andproperties, processing, product development andproperties, processing, product development andproperties, processing, product development andbiodegradability 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 aHelping the Israel Plastics Indus try to introduce bioplastics, as aHelping the Israel Plastics Indus try to introduce bioplastics, as aHelping the Israel Plastics Indus try to introduce bioplastics, as areplacement for synthetic non renewable source polymers usingreplacement for synthetic non renewable source polymers usingreplacement for synthetic non renewable source polymers usingreplacement for synthetic non renewable source polymers usingconventional processing.conventional processing.conventional processing.conventional processing.
Developing new biodegradable blends in order to achieve similarDeveloping new biodegradable blends in order to achieve similarDeveloping new biodegradable blends in order to achieve similarDeveloping 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: biodegradableImproving properties using nanotechnology: biodegradableImproving properties using nanotechnology: biodegradableImproving properties using nanotechnology: biodegradablenanocomposites.nanocomposites.nanocomposites.nanocomposites.
Summary and conclusionsSummary and conclusions
All recycling options can be used, includingAll recycling options can be used, includingAll recycling options can be used, includingAll recycling options can be used, includingcomposting.composting.composting.composting.
High market potential (High market potential (High market potential (High market potential (10101010% of plastic consumption).% of plastic consumption).% of plastic consumption).% of plastic consumption).
Main benefits: COMain benefits: COMain benefits: COMain benefits: CO2222 emission reduction, reductionemission reduction, reductionemission reduction, reductionemission reduction, reductionof 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 acceptanceHigh consumer acceptanceHigh consumer acceptanceHigh consumer acceptance