1. Expanding the application opportunities of
biopolymers
Ir. Gerald G.J. Schennink
Senior scientist Biobased Products - Wageningen UR
gerald schennink@wur nlgerald.schennink@wur.nl
Eindhoven – 28 Oktober 2010
Contents
„ Introduction WUR-FBR-Biobased Products
„ Bioplastics„ Bioplastics
z Biodegradable
z Biobasedz Biobased
„ Classification of bioplastics
L d l„ Latest developments
z BPM
z Biobased polymers
z Heat stable PLA
z Composites & foams
„ Conclusions
2. What is going on ?
AfbreekbaarDuurzaam
Composteerbaarp
Biobased
Wageningen UR (University & Research centre)g g
„ Three pillars:
z Wageningen University
z Van Hall Larenstein Univ. of Appl. Sci
z DLO Applied Research Institutesz DLO - Applied Research Institutes
„ Annual budget about 650 m euros
„ About 6500 employeesp y
„ 9000 BSc/MSc; 1200 PhD (>100 countr.)
„ Extensive international network
„ Active partner in Food Valley
to explore the potential of nature…to explore the potential of nature
to improve the quality of life…
3. Wageningen University & Research Centre
Supervisory
Board „ > 6000 employees
Five Sciences Groups
„ University: academic research
Research Centres contract
Life long learning Statutory tasks units
Executive
Board
„ Five Sciences Groups„ Research Centres: contract
R&D
IAC, PHLO, WMS
y
Rikilt, CIDC
Board
of Directors
Board
of Directors
Board
of Directors
Board
of Directors
Board
of Directors
Board
of Directors
Agrotechnology &
Food Sciences
Plant
Sciences
Animal
Sciences
Social
Sciences
Environmental
Sciences
Polymer Research facilities at WUR-FBRy
„ Processing
Extrusion (single/double screw)z Extrusion (single/double screw)
z Co-extrusion; 1-5 layers sheet/blown film
z Injection moulding
Cz Compression moulding
z Thermo forming
„ Analysisy
z Thermal (DSC, TGA, HDT)
z Mechanical (tension, bending, compression, DMTA, impact, falling
dart))
z Rheological (capillary, dynamic)
z Structural (SAXS, FTIR, SEM)
z Chemical (ss-NMR HPSEC-MALLS GPC GC)z Chemical (ss NMR, HPSEC MALLS, GPC, GC)
z Biodegradation (controlled composting, pilot-scale composting,
aquatic tests)
4. Biopolymers
Biobased vs. biodegradable
Biodegradable plasticsg p
„ Biodegradation: degradation catalyzed by biological
activity leading to mineralization and/or biomassactivity leading to mineralization and/or biomass
„ Biodegradability: degree to which biodegradation leads to„ Biodegradability: degree to which biodegradation leads to
mineralization and/or biomass
„ Mineralization: the conversion of (organic) constituents in
naturally occurring gasses, water and inorganicnaturally occurring gasses, water and inorganic
constituents
5. Biodegradable plastics
„ Environment determines type and speed of degradation
z Industrial compostingz Industrial composting
z Home composting
z Degradation in Soil
Fresh aterz Fresh water
z Marine water
z Anaerobic digesting
Standardisation and certification is very important!„ Standardisation and certification is very important!
z Demands for combination of biodegradable products & industrial composting are
described in EN 13432
Biobased plastics
„ Renewable or biobased polymers are polymers
from which the raw materials originate directly orfrom which the raw materials originate directly or
indirectly from nature
Cl ifi i f bi b d l„ Classification of biobased polymers:
z (Modified) natural polymers
z Directly from micro-organisms or gene-modified crops
z From biobased feed stock (eg via fermentation)
„ Biobased plastics biodegradable plastics
6. Why biobased?y
„ Less dependency of crude oil
„ Durability, less CO2 production
„ (sometimes) better properties( ) p p
„ (sometimes) biodegradability
„„ ……..
Biodegradable vs. biobased materialsg
Finished product
N bi d d bl Bi d d blNon-biodegradable Biodegradable
Ecoflex (BASF)Traditional PE
Raw
Non
renewable
Ecoflex (BASF)
Bionolle (Showa Denko)
Traditional PE
Biodeg
h
PET
wmater
PLA (Natureworks)
Eco – LDPE (Braskem)
starch
based
blends
rials
Renewable
PLA (Natureworks)
Rilsan (Arkema)
Sorona (Dupont)
PHBV (Tianan)
7. Cl ifi ti f bi (d d bl ) l tiClassification of bio(degradable)plastics
Available biodegradable plasticsg p
M t i t t f bi d d bl l tiMost important groups of biodegradable plastics
„ Cellulose and cellulose derivatives„ Cellulose and cellulose derivatives
„ Starch based plastics (thermoplastic starch)
„ Polyesters
z Poly lactic acid (PLA)
z Poly caprolactone (PCL)
z Polyhydroxy alkanoates (PHA, PHBV)
z Several (co-)polyesters
„ Materials based on industrial proteins
„ Blends of various bioplastics (eg thermoplastic starch & polyesters)„ Blends of various bioplastics (eg thermoplastic starch & polyesters)
8. Cellulose derivatives (cellulose diacetate)( )
„ Advantages
z Good mechanical properties
„ Disadvantages
z Price (>4€/kg)p p
(like PS)
z Good thermal resistance
z Glossy transparent
Price ( 4€/kg)
z Use plasticiser
z Glossy transparent
appearance
z Renewable
„ Processing
z It is advised to dry the material
z Suitable for:
• Injection moulding
• Sheet extrusion (thermo formingSheet extrusion (thermo forming
• Fibre extrusion
z Processing temperature 190-240°C
Th l d d ti iblz Thermal degradation possible
Polylactic acid (PLA)y ( )
„ Advantages
z Good mechanical properties
„ Disadvantages
z Only compostable inz Good mechanical properties
(like PET)
z Transparent
z Only compostable in
industrial composting facilities
z Water sensitivity during processing
z Price (1.8-2.0 €/kg)
z Renewable
y g p g
„ Processing
z Material needs to be dried
z Suitable for:
Fil t i ( d th f i )• Film extrusion (and thermo forming)
• Blow molding
• Injection moulding
Fib t i• Fibre extrusion
z Processing temperature 170-210°C
9. Starch based plasticsp
„ Advantages
z Good mechanical properties
„ Disadvantages
z Humidity dependentz Good mechanical properties
(LDPE to PS)
z Excellent gas barrier
properties
z Humidity dependent
z Not completely transparent
properties
z Anti-static
z Fast biodegradable
„ Processing
z Processed as delivered (no drying)
z Suitable for:
• Film blowing (incl multilayer)
• Injection mouldingInjection moulding
• Sheet extrusion (and thermo forming)
• Foam extrusion
z Processing temperature 120 180°Cz Processing temperature 120-180 C
Poly hydroxy alkanoates (PHA’s)y y y ( )
„ Advantages
z Mechanical properties can
„ Disadvantages
z Expensive (for now > 4€/kg)
z Mechanical properties can
be varied
z Hydrophobic (low water
bilit )
z Harvested from micro organisms
z Low melt strength
vapour permeability)
z Rather high HDT (>100°C)
z Renewable
Processing„ Processing
z Suitable for:
• Injection mouldingInjection moulding
• Sheet extrusion (and thermo forming)
• (under development) film blowing, film
castingcasting
10. Synthetic (co)polyesters and polyester amidesy ( )p y p y
„ Not renewable (not yet)„ Not renewable (not yet)
„ Mechanical properties possible from PE to PP
„ Compostable
„ Suitable for films and extrusion (in most cases not(
for injection moulding)
Production capacity biodegradable polymers (2007)
„ PLA materials ton/year
z Natureworks LLC Natureworks polymer USA 70.000 (140.000 in 2009)
z Hisun Corp. Hisun China 4.000 (expanding)
z Purac Lactide customers Europe/Asia ……. (starting up)
„ Starch based materials
z Novamont SpA Mater-bi Italy 60.000
z Rodenburg Solanyl The Netherlands 40.000
z Biotec GmbH Bioplast Germany 10.000
z Biop Biopar Germany 4.000
z Plantic Plantic Australiaz Plantic Plantic Australia …..
z Biograde Biograde Australia …..
z Cereplast Corp. USA >>
„ Cellulose based materials
z Innovia films Natureflex England 10.000
z Celanese Clarifoil England …..g
z FKUR Biograde Germany 4.000
„ PHB
z Tianan Enmat China 4.000
z Biomer Biomer Germany 1.000
z PHB Industrial SA Biocycle Brazil …. (starting up)
T ll Mi l USA ( t ti )z Telles Mirel USA …. (starting up)
„ Biodegradable polyesters
z BASF Ecoflex Germany 8.000 (expanding in 2010)
z Showa Denko Bionolle Japan 3.000
z Solvay/Perstorp CAPA England ……
z Mitsibishi Chemical GS Pla Japan 3.000Mitsibishi Chemical GS Pla Japan 3.000
„ Others
z Limagrain Cereales Biolice France ….
z (Idroplast Hydrolene (PVA) Italy …. )
11. P d t & lProducts & examples
Examples of (existing) packaging applicationsp ( g) p g g pp
12. Examples of (existing) agricultural applicationsp ( g) g pp
L t t d l tLatest developments
13. Biobased Performance Materials Programme (BPM)
„ BPM is a programme sponsored by the Dutch Ministry of Agriculture,
Nature and Food Quality (LNV)Nature and Food Quality (LNV)
z Aim is to create an internationally appealing programme
z Dominant language in BPM communication will be English
„ Programme fills an important gap in Biobased research i e ; dedicated„ Programme fills an important gap in Biobased research i.e.; dedicated
research into biobased performance materials
„ Is unique in its construction:
z Industrial partners participate from all parts of the value chain, varying
from raw materials producers, polymer producers and processors until
end users
BPM: Selected proposals November 2009
Chemical cluster
1. NOPANIC: Novel renewable polyamides and non-isocyanate
polyurethanes for coating applications
• Target: To develop scientific and applied knowledge for the generation of isocyanate free
polyurethane
2. MOBIOSOL: Modification of semi-crystalline polyesters with bio-based
building blocks by solid state polycondensation and by melt
copolymerization
• Target: To develop scientific and applied knowledge for the generation water-dispersible,
hydrolytically and thermally stable, (bio)degradable/non-biodegradable, biomass-based,
de-inkable, non-curing, polyesters
3 BIOCRES: Biobased Composite resins3. BIOCRES: Biobased Composite resins
• Target: To develop scientific and applied knowledge for the generation of well functioning
composite resins based upon (styrene-free) unsaturated polyesters can be generated.
4. ACTION: Acrylic and Styrenic Monomers from Biomassy y
• To develop scientific and applied knowledge for the generation of efficient synthesis routes
to acrylic and stryrenic monomers
14. BPM: Selected proposals November 2009
Material cluster
5. HI-PLA: High impact polylactic acid
T t T d l i tifi d li d k l d f th ti f PLA ith• Target: To develop scientific and applied knowledge for the generation of PLA with
improved of elasticity properties and melt-processability
6. FLOSTARBLEND: Blending technology for flour / starch by-product
based bioplasticsbased bioplastics
• Target: To develop scientific and applied knowledge for the generation of co-continuous
and/or nanolayered morphology consisting out of the renewable based blend system
TPS/PLA/PVAc.
7. STRAIN ENHANCED PLA: Strain-induced crystallization of PLA and its
application for production of PLA bottle
• Target: To develop scientific and applied knowledge for the improvement of mechanicalg p pp g p
properties of PLA by strain-induced crystallization
8. FEASIBLE: Feasibility of End use Applications: SustaInaBiliLty and
techno-Economic aspects
• Target: Feasibility will be approached from an end user perspective taking into account
both the techno-economic feasibility as well as sustainability aspects. The project
generates specific information for the selected end applications.
Latest developments (at WUR BBP)p ( )
„ Novel biopolymers
z Replacement of oil based building blocks by renewablesReplacement of oil based building blocks by renewables
z Development of novel 100% biobased polymers (rubber from dandilion)
z Engineering plastics
z Powder coatings
„ Novel additives
z Compatibilisers
z PlasticisersPlasticisers
z Chain extenders
z Nucleating agents, PDLA (Improving heat stability of PLA)
z Composites
„ Novel processes
z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……)
z Recyclingz Recycling
z Blown films, chain extenders
z Foaming of PLA
15. Polymers from naturey
Latest developments (at WUR BBP)p ( )
„ Novel biopolymers
z Replacement of oil based building blocks by renewablesReplacement of oil based building blocks by renewables
z Development of novel 100% biobased polymers (rubber from dandilion)
z Engineering plastics
z Powder coatings
„ Novel additives
z Compatibilisers
z PlasticisersPlasticisers
z Chain extenders
z Nucleating agents, PDLA (Improving heat stability of PLA)
z Composites
„ Novel processes
z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……)
z Recyclingz Recycling
z Blown films, chain extenders
z Foaming of PLA
16. Solid Polymer Structure: AmorphousAmorphous vs. SemiSemi--crystallinecrystalline
Amorphous polymersAmorphous polymers
•• transparencytransparency
•• toughnesstoughness
SemiSemi--crystalline polymerscrystalline polymers
•• temperature resistancetemperature resistance
•• chemical resistancechemical resistance
•• no melting, only softeningno melting, only softening
PLAPLA-
2
PLA-1
Heat stable PLA
PLA is actually a family of (co-)polymers of D- and L-Lactic
units
Stereo-block PLA
sc-PLA
PLA
PLLA
A PLA
PLA
A-PLA
17. Heat stable PLA
Effect of D-isomer content in PLA chain on crystallinity & melting point
7
min
190
°C
S h lit th t (135°C)
5
6
thrate/mm/m
160
170
180
intPLA(Tm)/
Spherulite growth rate (135°C)
melting point
3
4
Crystalgrowt 130
140
150
MeltingPoi
More D-comonomer:
• less crystallinity 0
1
2
100
110
120
How to increase PLA temperature resistance (HDT)?
• lower D-content in PLA
• less crystallinity
• lower melting point
0 2 4 6 8 10 12 14
D-lactic acid content in PLA / %
lower D content in PLA
• introduce crystallinity by adding nucleators or use fillers
• heat setting / annealing in mold (TF, IM)
• orientation, e.g. in film, fiber and foam
Heat stable PLA
Crystallization time (t½ in DSC) of PDLA nucleated PLA 6201D
10 NTR PLA 6201
Increasing
min
Increasing
PDLA
content
5
half-time/m
2.5%
5
stallizationh
2
5
5%
PDLA effective over wide temperature range
crys
1
h
2
h
40%
0
80 90 100 110 120 130 140
temperature / °C
h
temperature / C
18. Heat stable PLA
Effect of stretching on crystallinity of PLA
Fibre grade PLA stretched at 115C
60
70
40
50
g)
20
30
dH(J/g
0
10
Fibre grade
Fibre grade + Additive A
Fibre grade + Additive B
0
0 2 4 6 8 10 12 14
Draw ratio
Polymers from nature: heat stable PLAy
19. Latest developments (at WUR BBP)p ( )
„ Novel biopolymers
z Replacement of oil based building blocks by renewables
z Development of novel 100% biobased polymers (rubber from dandilion)
z Engineering plastics
z Powder coatings
„ Novel additives„ Novel additives
z Compatibilisers
z Plasticisers
z Chain extenders
z Nucleating agents, PDLA (Improving heat stability of PLA)
z Composites
„ Novel processes„ Novel processes
z Blending of renewable / synthetic polymers (PLA / PMMA, PLA / PC, ……)
z Recycling
z Blown films, chain extenders
z Foaming of PLA
z Thermoforming of heat stable products
z Composites
Trends in product developmentp p
Fi t ti fil th ti fil
„ Research topics
First generation film xth generation film
p
• Specialty products: (hot fill materials/microwavable materials
• Coextruded/laminated/blended structures (e.g. barrier bottles, films,
sheets)sheets)
• Foamed structures (3-D products)
• Reduction of the price of the material
„ Try to maximize the added value of biodegradable
materials by using a series of positive properties
20. Application: Thermoformed productspp p
„ High HDT„ High HDT
z PLA type
N l tiz Nucleation
z Processing
Application: 3D-foamed structurespp
„ Expandable bead techniquep q
z Good cell structure
z Density <30 g/lz Density 30 g/l
21. Application: PLA composite materialspp p
„ Large injection moulded panels„ Large injection moulded panels
z Excellent strength
z Good impactz Good impact
z Good processing
Concluding remarksg
S„ Sense
z Consumer trends ask for new (food)packaging/material concepts.
Natural polymers can add to a solutionNatural polymers can add to a solution
z Successful product developments make use of a series of positive
properties (not only biodegradability) of biodegradable plastics
z Biodegradable plastic product = polymer + additive + material
processing + inks, glues, tapes etc.
„ Non Sense
z Biodegradable plastics will overtake the market of Poly-ethyleneg p y y
(within several years)
