Technical performance

of biodegradable polymers
as compared to polyolefins
Markus Gahleitner, Petar Doshev
Borealis Polyolefine GmbH, Linz, Austria
© 2010 Borealis AG

Outline

• Biopolymers – the visions

CO2 balance improvement vs. technical performance
Volume development in relation to conventional polymers
• Technical capabilities of 3 most discussed biodegradable polymers
Thermoplastic starch (TPS)
Poly(lactic acid) (PLA)
Poly(hydroxy alkanoate) (PHA)
• Possible developments & alternatives
Stabilization systems & bio-based impact modifiers
Bio-based Polyethylene (PE) & Polypropylene (PP)
Increased recycling & efficiency efforts
© 2010 Borealis AG

01 June 2012

Presentation title
 Biopolymers –
solving the CO2 dilemma ?

Bos H., Meesters K., Conijn S., Corré W., Patel M.,
© 2010 Borealis AG

3
Sustainability aspects of biobased applications,
01 June 2012 Wageningen UR Food & Biobased Research, 2010
Presentation title

Biopolymers will only succeed if they

perform technically!
+ less energy use
+ biodegradable
- less carrying
strength (load)
- high puncture
sensitivity
- not reusable
- not recyclable

+ high carrying
strength (load)
+ multiple use
possible
+ puncture resistant
+ recycling easy
- not biodegradable
© 2010 Borealis AG

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- not bio-based
01 June 2012

Presentation title
 Volume development of Bio-Plastics …

Shen L., Haufe J., Patel M.K., Product overview and market projection of emerging bio-
based plastics (PRO-BIP 2009, Final Report), Utrecht University 2009
© 2010 Borealis AG

01 June 2012

Presentation title

… in relation to conventional polymers

3E+05 1,00%
• Less than 1 wt% of globally Polymers total
produced polymers are bio-
Biodeg.polymers
degradable types
2E+05 Biodeg. fraction 0,80%
• TPS, PLA & PHA make up >
95% of these
• Growth inhibited by four
Global prod. / kt/a

2E+05 0,60%
factors:
• ressource questions
(food competition) 1E+05 0,40%

• production volume
(investment problem)
5E+04 0,20%
• cost issues
• performance limits
0E+00 0,00%
1998 2000 2002 2004 2006 2008 2010 2012
© 2010 Borealis AG

01 June 2012

Presentation title
 Thermoplastic starch (TPS)

• Production from various

starch sources
(composition determines
properties) and plasticisers
• Glycerol in combination
with water commonly used,
but also other options
(ethylene glycol, urea, …)
• Mechanics & glass
transition (Tg) strongly
affected by plasticiser
content Shen L., Haufe J., Patel M.K., Product overview and market
projection of emerging bio-based plastics (PRO-BIP 2009,
© 2010 Borealis AG

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Final Report), Utrecht University 2009
01 June 2012

Presentation title

Overall TPS performance

Flex.mod.
moulded

Ageing
• Only TPS allows (modulus, 1
NIS +23°C
moulded
production of soft films, day)
LDPE
but without transparency
HDPE
• High Tg of starch
(50-80°C) reduced by Density Tg
TPS
plasticiser, but materials
remain brittle due to
inhomgeneities
Tens.mod.
• Massive processing & Haze film
film
ageing effects
Puncture film
© 2010 Borealis AG

01 June 2012

Presentation title
 TPS Ageing –
Glycerol loss & Retrogradation
16 wt% glycerol / 14% water content
• Weight loss from
plasticiser diffusion &
evaporation only explains
part of the ageing process
• Practical problem for
carrier bags from TPS –
massive flexibility loss &
embrittlement within weeks
• Extension @ break
reduced from 50 to 5%
within one week (Tábi) Tábi T., Kovács J.G., Examination of injection moulded
thermoplastic maize starch, eXPRESS Polymer Letters
Vol.1, No.12 (2007) 804–809
© 2010 Borealis AG

01 June 2012

Presentation title

Processing problems
by TPS degradation
40 wt% glycerol content
• High sensitivity to
„standard“ processing
temperatures limits
applicability
• Parallel to degradation,
also reduction in
mechanical
performance
• Massive influence of
raw material (amylose
content, particle size, Rodriguez-Gonzalez F.J., Ramsay B.A., Favis B.D.,
water content, …) Rheological and thermal properties of thermoplastic
starch with high glycerol content, Carbohydr.Polym. 58
© 2010 Borealis AG

(2004) 139–147
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01 June 2012

Presentation title
 Poly(lactic acid) (PLA)

• Most „popular“ biopolymer,

strongest volume increase
• Production from starch or sugar,
eventually even cellulose
possible
• Fermentation as cost-controlling
step (yield critical)
• Purification & Stereocontrol
determines possibility to
crystallise (glassy PLA has low
heat resistance)
Shen L., Haufe J., Patel M.K., Product overview and
market projection of emerging bio-based plastics
(PRO-BIP 2009, Final Report), Utrecht University 2009
© 2010 Borealis AG

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01 June 2012

Presentation title

Overall PLA performance

Flex.mod.
pure

• Very stiff & rather brittle MFR stability Flex.mod.

(PS-like performance) (5x) 20% talc

PP
• Heat resistance defined
PLA
by crystallinty
(Tg ~ 62°C, Tm ~ 172°C) Density
NIS +23°C
pure
• No efficient bio-based
elastomers available
(EMA/EBA show limited NIS +23°C
biodegradability only) HDT 20% talc 10%
elastomer
• Compounding limited by
HDT pure
degradation effects in
melt
© 2010 Borealis AG

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01 June 2012

Presentation title
 Post-crystallization in PLA

• Efficiency of nucleation limited

by inherently low crystal
growth rate (related to
stereostructure resp. monomer
quality)
• No „specific“ nucleating agents
developed, PO-types used
• Post-crystallization significant
above ~ 50°C

Annealing at 80°C after injection moulding

Harris A.M., Lee E.C., Improving Mechanical Performance of
Injection Molded PLA by Controlling Crystallinity,
J.Appl.Polym.Sci. 107 (2008)2246–2255
© 2010 Borealis AG

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01 June 2012

Presentation title

PLA degradation
in multiple extrusion
• Next to MFR increase,
significant degradation &
mechanical performance loss
in multiple extrusion
• Obvious hydrolysis reduces
toughness even further –
critical even for re-processing
of industrial scraps
• Recent conclusion from an PLA Natureworks 2002D, multiple extrusion on
EU FP7 project: TSE at 190°C
„PLA is hardly recyclable“ Zenkiewicz M., Richert J., Rytlewski P., Moraczewski
K., Stepczynska M., Karasiewicz T., Characterisation
of multi-extruded poly(lactic acid), Polym.Testing 28
(2009) 412–418
© 2010 Borealis AG

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01 June 2012

Presentation title
 Poly(hydroxy alkanoates) (PHA)

• „Sleeping giant“ among biodegradable

polymers; low production volume
• Monomers & polymer are generated by
bacteria or genetically engineered plants
(like starch as energy storage)
• Good genetic understanding of synthesis
allows selective co-polymer production from
wide variety of biomass sources
© 2010 Borealis AG

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01 June 2012

Presentation title

Overall PHA performance

Flex.mod.
pure

• Better overall MFR stability Flex.mod.

(5x) 20% talc
mechanics, easier to
PP
crystallise than PLA
PHA
• Toughness strongly
NIS +23°C
dependent on Density
pure
comonomer content
• High mold shrinkage &
CLTE (~ 80% above NIS +23°C
PP) HDT 20% talc 10%
elastomer
• Low melt stability
HDT pure
© 2010 Borealis AG

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01 June 2012

Presentation title
 PHA degradation in molten state

• Autocatalytic degradation
reaction causes crystallinity
reduction and mechanical
losses
• Stabilization by addition of
plasticiser (e.g. PEG)
reduces stiffness significantly
(loss over time not studied)

[P(HB-co-HV)] with 8 wt% HV (Aldrich); degr. at 175°C

Cyras V.P., Vázquez A., Rozsa C.,Galego Fernandéz N., Torre L.,
Kenny J.M., Thermal Stability of P(HB-co-HV) and Its Blends with
Polyalcohols: Crystallinity, Mechanical Properties, and Kinetics of
© 2010 Borealis AG

Degradation, J.Appl.Polym.Sci. 77 (2000) 2889–2900

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01 June 2012

Presentation title

Possible developments & alternatives

• Stabilization systems & bio-based impact modifiers

Limited research efforts, but for both PLA & PHA learnings from
PET stabilization possible
TPS will require more systematic approach and more stable
plasticiser system (Mw effects!)
• Bio-based Polyethylene (PE) & Polypropylene (PP)
Developments ongoing – overall carbon footprint to be watched
Mechanics & processing identical
Risk of „greenwashing“ of conventional products –
certification required
• Increased recycling & efficiency efforts for conventional TPs
© 2010 Borealis AG

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01 June 2012

Presentation title
 Improving sustainability
of polymer applications

Export Export

49 % Disposal
Converter
demand of
12.1 Mt
Construction
EU25+N/CH 28% Packaging
Consumer
PC
Automotive
38%
demand
Waste
48.5 Mt 7% 24.9 Mt
E/E 6%
Others
51 % Recovery
21.0 %
12.8 Mt
Import Import

40% short service 5.3Mt 7.5Mt

21% 30%
life and 60% long
Recycling Energy
Data: PlasticsEurope 2009 recovery
© 2010 Borealis AG

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01 June 2012

Presentation title

Most European countries

could do better …
Recycling (1 - 33%) Energy Recovery (0 - 83%)

Switzerland
Sweden
Denmark
Germany
Belgium
Austria
Luxemburg
Netherlands
Norway
France
Italy
Portugal
Spain
Slovakia
Finland
Czechia
United Kingdom
Slovenia Key messages:
Ireland
Hungary
Latvia • Countries doing well in energy recovery
Poland
Estonia
also do well in recycling
Lithuania
Malta
• Landfills are obviously still far too cheap
© 2010 Borealis AG

Cyprus
20
Greece
June 1, 2012

Presentation title
0 20 40 60 80 100
 Recycling 2.0:
Shopping Carts from Recycled PP
• Presented at K2010 – development
of the company's first pro-recyclates
grades PP4R 500 and PP4R 100 for
combination with recycled PP
• Carts are made of a combination of
67% high impact PP4R 500 PP and
33% recycled PP – 15% carbon
footprint reduction
• Baskets: 75% recycled PP and 25% PP4R
100 – 30% carbon footprint reduction
• Cooperation with Italian moulder Sistemi 2000
© 2010 Borealis AG

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01 June 2012

Presentation title

Energy demand of packaging materials

150
Energy demand / MJ/kg

Recoverable Per volume – Polymers have

100
heating value a clear advantage
Recycling
bonus

400
50
Energy demand / MJ/l

300

0
200
Recycling
bonus

Recoverable
m
ss
PE

PS

PP

te
r
pe

iu
la
la

heating value
Pa

in
np
G

100
m
Ti

lu
A

Per weight – Polymers need 0

no additional raw material

m
ss
PE

PS

PP

te
r
pe

iu
la
la
Pa

in
np
G

m
Ti

lu
A
© 2010 Borealis AG

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June 1, 2012

Presentation title
 RF490MO performance enables carbon
& water footprint reduction

Kg CO2 per cap Litres water per cap

-35% Aluminium
0.215 -95% 0,50
Old cap design
-25% 0,45
New cap design
0,40
-25%
0.015 0,35
0,30
0,25
0.010
0,20 -65%
0,15
0.005 -25%
0,10
0,05
0.000 0,00
Carbon dioxide Cooling water Process water
• Key drivers
• Shift from aluminium to plastic caps
© 2010 Borealis AG

* Assumptions on cap weights: Aluminium 3g; PP 4,5g / 3,4g

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Source: Based on Plastics Europe Study "Contribution of plastics to energy • Innovative cap design enabled by RF490MO
consumption and greenhouse gas emissions in Europe"

The background for cars:

Saving weight = Saving fuel
100%
• About 90% of lifespan energy
demand of a car in the useage 80% 36% PP 70% PP
phase
60%
• ~ 200 kg plastics replace 350-
500 kg other materials in a car 40%

• More than 750 l fuel saved in a 20%

car‘s lifespan
0%
• EU 27+2: 25 mio tons of fuel 1990 2005
and 60 mio tons of CO2 saved
per year Steel Cast iron Plastics
Rubber Paint Glass
Aluminium Others
© 2010 Borealis AG

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June 1, 2012

Presentation title
 Saving weight „under the hood“ –
Polypropylene replacing Polyamide
High crystallinity PP + glass
fibres + special stabilization
XMOD™ GB306SAF
Air intake manifold

• Combined action of crystallinity and

stabilizer for high long-term heat
resistance
• 20% Minimum cost saving &
15% Weight saving
• - 5 dB Sound damping
• ~3 times lower CO2 emissions
• not dependent on humidity
© 2010 Borealis AG

… and there‘s much more potential

• Polymers providing and saving drinking water – filtration and

pipelines
• Polymers collecting sustainable energy – in wind turbines and
solar collectors
• Polymers providing and
protecting infrastructure –
as bridges and
flood barriers
© 2010 Borealis AG

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June 1, 2012

Presentation title
 End of presentation
Markus Gahleitner
February 2012

The information contained herein is to our knowledge accurate and reliable as of the date of publication. Borealis extends no warranties
and makes no representations as to the accuracy or completeness of the information contained herein, and assumes no responsibility
regarding the consequences of its use or for any printing errors.
© 2010 Borealis AG

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01 June 2012

Presentation title