presentation outline - soci
TRANSCRIPT
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Robert Haan, Senior Polymer Technician
PURAC Biochem, Gorinchem, The Netherlands
Unique Purac Lactides for improved PLA production and properties
PLA technology developed with Sulzer Chemtech
Bioplastic Processing & Properties
Thursday 23 April 2009. Loughborough University, UK
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Presentation outline
• PURAC
• PLA from Puralact® L-Lactide and D-Lactide
• Purac Business model: Partnerships
• PLA processing: Improving properties
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PURAC• Since 1935
• Subsidiary of CSM
• World leader in the field of Lactic acid and Lactic acid derivates
• Headquarters and R&D in The Netherlands
• Experience with lactides and PLA since late 1960s
• 3-5 kton/year lactide plant in Spain since 2008
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PURAC Locations
PURAC plants
PURAC sales offices
PURAC Headquarters (The Netherlands)
PURAC Thailand
Blair-Nebraska, USA
Campos – Rio, Brazil
Gorinchem - Netherlands
Montmelo, Spain Map Tha Put, Thailand
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Lactic Acid A World of Applications
Cosmetics
Medical
Pharma
Food
FeedIndustrial
Detergents
Bioplastics
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PLA is actually a family of (co-) polymers of D- and L-Lactic units
>10% D in L or>10% L in DAmorphousNo Tm
D-Lactic Unit L-Lactic Unit
PLLA 180 °C
scPLA 230 °C
160 °C PLA
A-PLA
Incr
easi
ng
T
m a
nd
cr
ysta
llin
ityStereo-block PLA 200 °C
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• Blending of Lactides or blending of PLLA and PDLA
• 1-10% sc-PLA in PLA acts as nucleating agent: HDT >100°C
• 80-100% sc-PLA (40-50% PDLA in PLA): Tm > 200°C and HDT >150°C
Why PURAC L-lactide and D- lactide?
Flexibility with Puralact® L and D
Puralact® L and D increases
PLA product portfolio
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PURAC Business Model
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Production chain of PLA
Production
Carbo-
hydrates
Production
Lactic Acid
Polymeri-
zation
Production
Lactide
Final
Conversion
Lactic Acid LactideCarbohydrate
PURACPOSITION
PURAC (Thailand)
LACTIC ACID LactideLactide
PLA Resin
PLA2PLA1
PLA4PLA3
Transport
PURAC PARTNERS
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Plant in Thailand is running at full capacity
Capacity 100.000 tons of non-GMO lactic acid
20 months construction period
Running at full capacity since March 2008
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The PURAC PLA Solution
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Partnership between PURAC, Sulzer and Synbra for PLA foams
PLA
BIOFOAM
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Sulzer polymerization and devolatilization technology
• Puralact® D and L from Purac Spain
• Polymerization of Lactide
• Devolatilization of Lactide residual monomer
• Fast track development since early 2008
• 5 kton/year production scale at Synbra at the end of 2009
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Conversion to thermo
dynamic equilibrium
Sulzer polymerization and devolatilization plant
-Catalyst
-Initiator
Sulzer static mixer polymerization unit
Catalyst deactivator
Removal of Lactide residual monomer
GranulationCrystalline PLA granulate
180-220°C
Melting of Lactide
Drying and crystallization
>99% yield
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Characteristics of Sulzer-PURAC PLA polymerization process
- Static mixer system
- Intensive mixing
- Efficient polymerization reactors
- Target residence time: <1 hour
- Viscosity increases from mPas (Lactide) to kPas (PLA) !!
- Efficient heat removal (exothermal reaction gives ~130°C adiabatic temperature rise)
Sulzer static mixer polymerization unit
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Properties of PLA influenced by recipe and processing
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Properties to improve for Amorphous PLA
Heat Deflection Temperature 50-60ºCPoor resistance to heat
Sticking of pellets during transport,storage, and processing
Deformation during transport and use of trays, preforms, cups, etc.
Poor Impact ResistanceEngineering applications
Gas Barrier PropertiesBottles
Packaging film
Improvable properties of PLA are limiting range of applications
Hot coffee in PLA cup for cold drinks
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How to process PLA?
• Can be processed on common process equipment
• Melt temperature ~180-200°C (~240°C for sc-PLA)
• Drying (<250 ppm H2O)
• Crystallized granulate
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Faster crystallization from the melt with PDLA nucleating agent
10 min at 140°CMelt at 140<T<180°C
Pure PLLA
5 min at 140°C
Crystallized at 140°C after 10 minutes
Melt at 140<T<180°C
PLLA with 5% PDLA
5 min at 140°C
Polarization optical microscopy, magnification 100x
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What has happened with PLA during cooling from the melt?
Tg Cold crystallization
Melting
DSC- 1st heating
- Heat with 10K/min
Sc-PLA
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Stiffness of PLA bars by increasing temperature
1,00E+06
1,00E+07
1,00E+08
1,00E+09
1,00E+10
0 50 100 150
Temp [°C]
Stiffnes
s (E
' / P
a) Limit for HDT
HDT ~60°C HDT ~150°C
Cold crystallization
Increasing PDLA content
PDLA improves the crystallinity of PLA and increases the HDT
=OK
=Failed
DMTA
- Heat with 2K/min
HDT
HDT
Glass MoltenRubber
HDT
F
FDMTA
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PDLA is efficient nucleating agent over a broad temperature range
0
5
10
80 90 100 110 120 130 140
temperature / °C
cry
sta
lliza
tio
n h
alf
-tim
e /
min
Injection moulding grade PLA (HDT= ~60°C)
5% PDLA (HDT= >100°C)
0.7% EBS (optimum (HDT= ~60°C)
5% Talc (HDT= ~60°C)
-Melt material
-Cool with 500 K/min till required temperature
-Measure t½ as function of time
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Sc-PLA improves HDT
NowFuture with sc-PLA??
Yes!!!
By mixing 40 % PDLA with PLA we can make cups that can be used till 190°C without distortion. (e.g. Fried chips)
Coffee 70°C
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Frying of chips
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Disclaimer: Nothing contained herein shall be taken as an inducement or recommendation to manufacture or use any of the described materials or processes in violation of existing or future patents of PURAC or any other party."