From castor oil to Specialty Polyamides:
the success of the diversification
Journées Annuelles des Hydrocarbures – Paris , October 2014
Patrice Perret Global Market Development Manager, Specialty Polyamides
Journées Annuelles des Hydrocarbures 2014, Paris – France, October 2014 2
Agenda
► Introduction ARKEMA
► Rilsan® PA11 the first bio-based high performance polyamide
► Product range expansion in bio-based Specialty Polyamides ► Conclusion
Journées Annuelles des Hydrocarbures 2014, Paris – France, October 2014 3
Arkema - In a snapshot
► Global producer of specialty chemicals
► Sales of € 6.5 bn
► Worldwide no1 to no3 on 90% of our sales
► 14,000 employees in 40 countries
► 85 industrial plants
► 10 research centers
40% 34%
Sales by region
26%
Europe
Asia and Row
North America
33% 34% Coating Solutions
High Performance
Materials
Sales by segment
Industrial Specialties
33%
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Three business segments
4
Global and integrated industrial niches
Solutions for decorative paints, industrial coatings and high-growth acrylic applications
World of high value and innovative solutions
● Thiochemicals ● Fluorochemicals ● PMMA (Altuglas International) ● Hydrogen peroxide
● Acrylics ● Coating resins ● Photocure resins (Sartomer) ● Rheology additives (Coatex)
● Specialty polyamides ● Fluoropolymers ● Adorption/filtration (CECA) ● Organic peroxides
Industrial Specialties Coating Solutions High Performance Materials
● Specialty polyamides ● Fluoropolymers ● Adorption/filtration (CECA) ● Organic peroxides
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ARKEMA Sustainable Strategy Ready to take up the environmental challenges, with R&D innovation to contribute to the development of:
►Bio-sourced materials Be the leader in bio-based high performance PA
based on castor oil chemistry
Combine renewable and ethical
No competition with food No deforestation Grown on poor soil in semi arid areas
►Lightweight materials and structures High temperature PA to replace metal and rubber
Thermoplastic composites
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Agenda
► Introduction ARKEMA
► Rilsan® PA11 the first bio-based high performance polyamide
► Product range expansion in bio-based Specialty Polyamides ► Conclusion
Journées Annuelles des Hydrocarbures 2014, Paris – France, October 2014 7
Arkema high performance polyamides ►Rilsan® PA11 : a 100% bio-sourced polymer…
POLYMER SYNTHESIS
castor seeds
castor plants - renewable resource -
HARVESTING
GRINDING
castor oil
amino 11 - monomer -
MONOMER SYNTHESIS
Rilsan® - Polyamide 11 -
C
ON
H
nPA11
H20
Hydrobromuration
Methanolisis / Cracking / Hydrolysis
C
OOH
H2N
n
11-aminoundecanoic acid
C
OOH
H2N
n
UNDECYLENIC ACID
C
OOH
H2N
n Br
Amination
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Moving to technical applications from 1960’ in Automotive, Oil & Gas,…
More than 40 years of experience in most severe environments for Fuel lines, Air brake, O&G flexibles, ….
Starting of the Rilsan® PA11 manufacturing in 1950’
Base resin: 100% from castor oil First applications in textile markets
60 years of experience in Rilsan® PA11 !
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Moving to technical applications from 1960’ in Automotive, Oil & Gas,…
Rilsan® PA11 polyamide : The First and Unmatched 100% bio-based PA - and still the reference
Intrinsic high performance of long
chain PA11 Outstanding chemical resistance Very low moisture absorption High hydrolysis resistance High impact strength at low T°C
Starting of the Rilsan® PA11 manufacturing in 1950’
60 years of experience in Rilsan® PA11 !
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Rilsan® PA11 still the long-chain PA reference
Flexibility Processability Ageing resistance Chemical resistance Abrasion resistance Low Temperature impact
Applications Oil & Gas Sports Automotive Air brake Electric
Rilsan® PA11
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► Non renewable cumulative energy demand
Cradle to gate LCA (base polymer)
Data sources: PA11, PA12: Arkema internal LCA / PA6, PA6.6: Plastics Europe
PA11 benefits vs PA12, PA6 or PA6.6
• Global warming reduced by 40 up to 52 %
• For 100 t polymer, up to 470 t CO2 saved (equivalent to up to 3.5 million km by car)
• Similar NR-CED for PA11
• PA 11 is 100 % bio-sourced
► Climate Change /Global warming impact
PA11 PA12 PA6.6 PA6
Glo
bal w
arm
ing
(kg
eqC
O2
/ kg) up to - 52 % from - 40 %
PA6 PA11 PA6.6 PA12Non
Ren
ewab
le C
umul
ativ
e En
ergy
D
eman
d (M
J / k
g)
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Moving to technical applications from 1960’ in Automotive, Oil & Gas,…
Expansion of product range
- Long Chain PAx.y - Elastomer
- Transparent PA - HT flexible PPA
Arkema Specialty polyamides : The largest product range of bio-based PA of the world
Starting of the Rilsan® PA11 manufacturing in 1950’
How to boost their applications ?
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Agenda
► Introduction ARKEMA
► Rilsan® PA11 the first bio-based high performance polyamide
► Product range expansion in bio-based Specialty Polyamides ► Conclusion
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Arkema’s Long-Chain PAx.y Product range
►Polyamide 11
►Polyamide 12
►Polyamide 10.12 400 & 11
►Polyamide 10.10 & 200 & 211
►Polyamide 6.12 90
►Polyamide 6.10 70
Polyamide : Biobased long chain PA / Polyamide : Fossil based long chain PA
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Polymerization of PAxy Polyamides
► PA10.12 from Decamethylene Diamine (DA10) & Dodeconioic Diacid (DC12)
► PA10.10 from Decamethylene Diamine (DA10) & Sebacic Acid (DC10)
► PA6.10 from Hexamethylene Diamine (DA6) & Sebacic Acid (DC10)
with DC10 & DA10 coming from the castor oil chemistry
DA X DC Y
PA X.Y
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Specialty Polyamides: A Building Block chemistry
HMDA monomer
DC12 monomer
DC 10 monomer
DA 10 monomer
DC 10 monomer
PA10.10
POLYMERIZATION
PA6.10 PA10.12
POLYMERIZATION POLYMERIZATION
®
MONOMER SYNTHESIS
Castor oil
Castor plant
HARVESTING
Castor seed
GRINDING
A 11 monomer
POLYMERIZATION
PA11
With the best monomer integration
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Technical positioning of base resins
Renewable Carbon
62
0
100
45
100
00
20
40
60
80
100
PA610 PA612 PA1010 PA1012 PA11 PA12
% R
enew
able
Car
bon
Melting point
140
160
180
200
220
240
PA610 PA612 PA1010 PA1012 PA11 PA12
Moisture Absorption
0
0,2
0,4
0,6
0,8
1
1,2
1,4
PA610 PA612 PA1010 PA1012 PA11 PA12
Moi
sutr
e up
take
%
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Technical Positioning of base resin
► Biobased long chain Polyamides
-a continuum of performance opening a large opportunity to match the customer needs
- Plasticized & Reinforced grades have been developed for specific applications
400
600
800
1000
1200
1400
1600
1800
2000
170 180 190 200 210 220 230Melting Point °C
Tens
ile M
odul
us (M
Pa) c
ond
PA6.10
PA6.12
PA10.10PA12
PA10.12
PA11
Tensile Modulus vs Melting Point
0
5
10
15
20
1000 1200 1400 1600 1800 2000Tensile Modulus (MPa) cond
Cha
rpy
Not
ched
23°
C c
ond
PA6.10 PA6.12
PA10.10
PA12PA10.12
PA11
Impact Strengths vs Tensile Modulus
► Biobased long chain Polyamides
- similar characteristics than petroleum derivated PA
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Hiprolon® PA10.10 Thermal resistance Mechanical resistance Chemical resistance Processability
Rigidity Thermal resistance Chemical resistance Processability
Hiprolon® A wide range of long-chain combinations
Hiprolon® PA10.12 Flexibility Mechanical resistance Chemical resistance Processability
Applications Monofilaments Sports Automotive
Applications Automotive Hydraulic &
Pneumatic Cable
In tank
Applications Automotive Electronics Automotive
Fuel line MLT
Hiprolon® PA6.10
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Thermoplastic Elastomer – TPE Poly Ether Block Amide (eXtreme)
Two phases structure Polyamide – Rigid Block Polyether – Soft Chain
Most of properties controlled by: Nature of PA and polyether PE / PA ratio Flexibility
Elastomer Pebax® Rnew
Pebax® Rnew - Biobased Polyamide 11 as rigid segment
Polyamide 11 Polyether
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Wide range of hardness
Thermoplastic Polyurethane (TPU)
TPO
PolyEther Block Esters (COPE)
Polyamides
Shore D 72D 70D 63D 55D 40D 35D 25D
Shore A 90A 85A 75A 50A
Caoutchouc / Rubber
Pebax® Rnew range
Renewable Carbon content
19%
Renewable Carbon content
75%
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Energy Return
TPU (80 shore A)
Energy Loss Factor = 0.4~0.5
Ideal case (theoretical)
Energy Loss Factor = 0
Elongation
HIGH ENERGY
LOSS
Load
Extension Relaxation
Pebax® Rnew (80 shore A)
Energy Loss factor = 0.1~0.2
Elongation
LOW ENERGY
LOSS
Load Elongation
Load
NO ENERGY
LOSS
Extension Relaxation
Extension Relaxation
Pebax® Rnew has a high energy absorption
But also a lower energy loss factor than TPU
and so a BEST Energy Return*
* Capacity of a material to retain a maximum of energy during extension phase and to deliver back a maximum of it (“return”) during relaxation phase.
Pebax® Rnew
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First engineering thermoplastic Elastomer range made from Renewable resources used in sport
20 to 95% renewable resources
Running shoes Ski boots
Pebax® Rnew
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Rilsan® Clear : a cycloaliphatic based PA with high transparency
Weather resistance Long lifetime under UV exposition.
Chemical resistance Much better than PC & PMMA
Toughness Still ductile at –30°C.
Lightness 20% lighter than PC & PMMA
Transparency More transparent than glass
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Rilsan® Clear Rnew based on castor oil chemistry
► Rilsan® Clear G830 Rnew & G850 Rnew Glossy finish, Flexibility
Easy processing, lightness, high Tg
Chemical & Mechanical resistance
► Rilsan® Clear G120 Rnew Lightness / Transparency
Good dimensional stability (Low moisture absorption)
Excellent chemical resistance
Excellent mechanical properties (impact, scratch)
Rilsan® Clear Rnew
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150°C
110-120°C
250°C
110-120°C
150°C
220-200°C Metal
Metal & Rubber
Complex solutions (i.e. reinforced Rubber / FKM)
Cooling: PA11 HPPA MLT solution PA12 Special Grade Air Intake TEEE, PA6, PA6-Alloy, Rubber
Metal / Rubber Solution Flexible Thermoplastic Solution
-
no solution
no solution
220-200°C
Rilsan® HT: a Breakthrough in Metal Replacement
This new PPA family creates opportunities to replace metal in tubing applications that were previously unthinkable
Rilsan® HT New class of flexible PPA
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PA 11
1000
1500
2000
2500
3000
3500
170 190 210 230 250 270 290 310 330
Melting point (°C)
Flex
ural
mod
ulus
(MPa
) PA 6
(neat resins)
Rigid
500
Flexible
Rilsan® HT - The First Flexible PPA
Unprecedented Flexibility Optimum properties of long-chain PA11 and classic PPA
Rilsan® HT Rilsan® PA11 Classic PPA ↑ higher /
better
0
1
2
3
4
0
1
2
3
4
Flexibility
Processing
Temperature Resistance
Thermooxidative Resistance
Chemical Resistance
Oil ResistanceDensity
Renewable Carbon Content
Impact
Elongation at Break
Moisture Uptake
Processing
Temperature Resistance
Thermo- oxidative Resistance
Chemical Resistance
Oil Resistance Density
Renewable Carbon Content
Impact
Elongation at Break
Moisture Uptake
Flexibility
PA 6 6/6T
66/6T
6I/6T
46
Classic PPA
9T
PA 11 PA 11
Rilsan® HT
New class of flexible PPA
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Thermal ageing rating of long chain PA extrusion grades
120°C 130°C 140°C 150°C 160°C 170°C 180°C 190°C 200°C 210°C 220°C
Service temperature 1000h cont.
Peak temperature Melting point 175h cont.
Flex
ibili
ty
255 °C
* Life time based on mechanical test (cold impact) on 8*1 mm tubes, after continuous dry air heat ageing
255 °C
RILSAN® PA11 HIPROLON®PA10.12
RILSAN® T PA10.10
RILSAN® HT more flexible
RILSAN® HT flexible
RILSAMID®PA12
►Service & Peak temperatures *
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Rilsan® HT Powertrain Applications
Rilsan® HT Flexible Tubing
The genuine alternative to metal tubing assemblies
Air / Vacuum Mngt. Exhaust Gas Recirculation
EGR
Oil / Hydraulic Fluid Mngt. Brake System
Air / Pressure Mngt. Air Intake
Air / Vacuum Mngt. Brake Booster
Oil Mngt./Transport Transmission Oil Cooling, TOC
Aggressive Media Mngt. Blow-By
Aqueous Media Mngt. Cooling & SCR / AdBlue®
Air management (pressure & vacuum management) Oil management (hydraulic fluids, lubricants) Aqueous Media Management (Cooling, SCR) Aggressive Media Management (Blow By, PCV)
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Agenda
► Introduction ARKEMA
► Rilsan® PA11 the first bio-based high performance polyamide
► Product range expansion in bio-based Specialty Polyamides ► Conclusion
Journées Annuelles des Hydrocarbures 2014, Paris – France, October 2014 31
Renewable without
compromises
Product range expansion in biobased PA
Type PEBA Bio-content 20 to 95%
Specificity High performance thermoplastic elastomer
Type PA11 Bio-content Up to 100% Specificity Long history of high
performance applications. Best in class for low temperature impact properties (-40°C).
Type Amorphous PA Bio-content >50%
Specificity Higher transparency than glass
New range of high performance bio-based PA.
Specificity
60 to 100% Bio-content
PA6.10, PA10.10, PA10.12
Type
Type Bio-based PPA Bio-content Up to 70%
Specificity Resistant to high temperature environment. Metal Replacement
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Arkema – Specialty polyamides
Thank you for your attention