Polyamides from renewable resources' past, present and future From Dr. Harald Haeger Vice President Process and Product Development BU Performance Polymers German-Russian Forum Biotechnology Hannover, 10.10.2011
Polyamides from
renewable resources'past, present and future
From Dr. Harald Haeger
Vice President Process and Product Development
BU Performance Polymers
German-Russian Forum Biotechnology
Hannover, 10.10.2011
Dr. Harald Häger, Seite | 2
Outline
• Introduction
• Monomers from renewable resources
• Polyamide synthesis
• Applications examples for polyamides from renewable
resources
• LCA analysis of PA610
• Summary outlook
Dr. Harald Häger, Seite | 3
Bio-renewable or petrochemically
based: Only polyamides are
offering a wide range of products
in both sectors;
Most bio-degradable polymers are
competing with polyolefins in the
commodity sector.
PP, PS, PE,
PVC, etc.PE, PVC, PLA,
PHB, etc
PMMA, PA6,
PA66, PBT,
PET, PC
PA1010, PA610,
PTT, etc
PEEK,
PPSU,
PEI, PPA,
PA12
Bio-
PPA
PA11
PA1012
Engineering
plastics
High
performance
polymers
Based on petro-
chemical feedstock
Based on bio-
renewable feedstock
Polyamides based on renewable feedstock are readily
available and actively asked for from our customers
Dr. Harald Häger, Seite | 4
Source: KH Hill, Pure Appl Chem 2000
Natural Fats and Oils (castor, rape seed, palm kernel oil, …)
By using suitable technologies fatty acids derivates
can be converted to versatile polyamide building
blocks
Oleic acid
Ozono-
lysis
Dimeri-
sation
Azelaic
acid
Dimer
fatty acid
Ricinoleic acid
Caustic
oxidation
Thermo-
lysis
Sebacic
Acid
-
Aminoundeca
noic acid
Biocatalysis
C10, C12,
C14….
diacids
Fatty acid (C10,
C12, C14, …)
Diamines are accessible via the corresponding diacids!
Dr. Harald Häger, Seite | 5
Preparation of Polyamides
a) Diacids and Diamines
n HOOC-R-COOH + n H2N-R’-NH2 HO-[-OC-R-CO-NH-R’-NH-]n-H + (2n-1) H2O Examples: Polyamide 66: Hexamethylenediamine, Adipic acid
Polyamide 612: Hexamethylene diamine, Dodecanoic diacid
b) Lactams
n --CO-NH-- HO-[-OC-- --NH-]n-H Examples: Polyamide 6: Caprolactame
Polyamide 12: Laurolactame
Dr. Harald Häger, Seite | 6
Polyamides based on renewable resources
PA612,
Up to 65% based on
bio-renewables
N N
O10 10
On
H H
PA1012,
45% to100% based on
bio-renewables
N N
O10 8
On
H H
PA1010,
100% based on
bio-renewables
N N
O6 8
On
H H
PA610,
62% based on
bio-renewables
HT-Polyamides
40% to 60% based on
bio-renewable monomers
microcristalline-
Polyamides
40% to 50% based on
bio-renewable monomers
N N
O6 10
On
H H
Dr. Harald Häger, Seite | 7
Results are indicating that PA610 GF30 could
replace PA612 GF30
0,50,6
0,7
0,8
0,9
1
1,1
1,2
1,31,4
E-Modulus
Tensile strength
Tensile strength
after wet ageing
Tensile strength after
ageing @140°C for 5000 h
elongation @ break
Impact strength
unnotched @ 23°C
Impact strength
unnotched @ 0°CImpact strenght
unnotched @ -30°C
Impact strength unnotched
@ 23°C wet ageing*
Impact strength notched
@ 23°C wet ageing*
Impact strength unnotched
@ 23°C ageing at 140°C for 3000 h
Vicat A
Vicat B
water absorption
saturation
VESTAMID D GF30
VESTAMID® Terra HS GF30
Dr. Harald Häger, Seite | 8
Melting point and water absorption of different
polymers
350
200
150
250
300
8 10 122 4 60 0
Me
ltin
g p
oin
t [
°C ]
Water absorption [ % ] Test (acc. ISO62) in water by +23°C
PPA
PEEK
PA46
PA6
PA66
PA
612
LCP
PES
PPSU
PSU
PA12
PA11
PBT
PET
PPS
PEI
610
30 % glass fiber
reinforced polymersVESTAMID
HTplus
M3000
PA10T with a successful combination of excellent mechanical and thermal properties and low water uptake
Dr. Harald Häger, Seite | 9
Product characteristics
PA10T basic properties
+ =
• next generation PPA
• up to 50% renewable
• lower water absorption
• better dimensional stability
• higher hydrolysis resistance
• improved processing window
Vestamid HTplus with 30% filler
Tmp 290 °C
Tg 125 °C
HDT 290 °C
Tensile Strength 190 MPa
Tensile Modulus 9500 MPa
moisture uptake
dimensional stability
hydrolysis resistance
chemical resistance
stiffness
tensile strength
elongation at break
impact strength unnotched
impact strength notched
processability
VESTAMID HTplus M1000 VESTAMID HTplus M3000
Dr. Harald Häger, Seite | 10
PA10T a successful combination of excellent
mechanical and thermal properties and low water
uptake
Dr. Harald Häger, Seite | 11
VESTAMID® HTplus for LED - whiter, brighter, longer
lasting
76
78
80
82
84
86
88
90
92
94
96
VESTAMID HTplus PA10T PA6T
0 96 144 192
% reflectance, 85°C, 85% r.h.
Dr. Harald Häger, Seite | 12
• high degree of reflectivity
• superior aging behavior
• excellent UV-stability
• high dimensional stability due to low water absorption
• broader processing window compared to PA6T/X
• good bondage to metal and silicone
Why use VESTAMID®HTplus PA10T grade?
VESTAMID® HTplus for LED - whiter, brighter, longer
lasting
Dr. Harald Häger, Seite | 13
PA 610 1 Polymerisation – standard procedereGaBi 4 process plan: Reference quantities
The names of the basic procces are shown.
DE: PA610-Polymerisation, klass. Herstellung EV
CH: treatment, sewage,
to wastewater treatment,
Class 5
X m³
DE: PA 610
Rohgranulat
Weitergabe EV1 kg
CPM ThE supply steam
CPM Power supply
transport land (lorry)
DE
transport land (lorry)
DE
DE: Water deionized PE
RER: tap water, at user
Water (surface water) PE
DE: Nitrogen (gaseous)
PE
HMDA Transport
nach Marl (per Landweg)
FR:
Hexamethylenediamine
(HMDA; from butadiene
via adiponitrilte) PE
_transport sea
(ocean ship)
DE: Sebacic acid
(by product 2-Octanol)
(via ricinus oil) PE
Sebacinsäure Transport
von China, über Shanghai
nach Marl, ca. 19.000 km
ges. per Schiff/Land
(500 Land, 18.500 Schiff)X kg
X kg
X kg
X kg
X kg
X kg
X MJ
X kg
X kg
Xkg
0,729 kg
X MJ
CPM Power supplyCPM Power supplyX MJ
GLO: Compressed air 7 bar
(high power consumption) PE [b]RER: tap water, at user
GLO: Cooling Water
Recycling EV
X Nm³
X kg
RER: heat, natural gas,
at industrial fumace > 100kW
X MJ
X kg
X kg
Dr. Harald Häger, Seite | 14
PA 610 Compounding to GF30GaBi 4 process plan: Reference quantities
The names of the basic procces are shown.
DE: PA610-Konfektionierung EV
DE: PA 610 Granulat
verkaufsfertig
Weitergabe EV1 kg
X MJ
_CPM Power supply
GLO: Compressed air 7 bar
(high power consumption) PE [b]
0,075 Nm³
Glasfasern gemahlen
Transport
nach Marl (per Landweg)
_glass fiber milled
X kg
X kg
X kg
Power supply mix,
Infracor (Marl)
_transport land (lorry)
DE
DE: Nitrogen (gaseous)
PE
DE: PA 610 Rohgranulat
Weitergabe EV
_CPM ThE supply steam
(5 bar)
X kg
X kg
X MJ
Dr. Harald Häger, Seite | 15
PA 610 GF 30 (renewable materials) Carbon Footprint
4,61,7
2,9
0
1
2
3
4
5
6
7
8
class.
polymeri
zation
compou
nding
GF 30
PA 610
GF 30
GaBi-
Referen
ce PA 6
GF 30
7,3
CO2-Equiv. / kg PA 610
-37%
3,51,7
1,8
0
1
2
3
4
5
6
7
8
compou
nding
GF 30
PA 610
GF 30
GaBi-
Referen
ce PA 6
GF 30
7,3
Optim.
polymeri
sation
CO2-Equiv. / kg PA 610
-52%
LCA by Evonik Reference data (fossil)
Dr. Harald Häger, Seite | 16
Conclusion and Outlook
• Currently polyamides from renewable resources are mainly based
on castor seeds!
• The monomer synthesis id still based on a 70 year old chemistry.
• There are first signs in the market that dodecanoic diacid can be
made also from renewable resources.
• At least for long chain polyamides, fatty acid derivatives will be an
important feedstock for the future.
• Biotechnology is an interesting and already proven method to
produce -diacids from n-alkanes or fatty acid derivatives
• New polyamides based on renewables are offering an very
interesting potential for new applications