Transcript Slide 1

DuPont™ Cerenol™
A New Family of Sustainable and Environmentally Friendly Materials
The 12th Annual Green Chemistry and Engineering Conference
June 24-26, 2008, Washington DC
Hari B Sunkara
DuPont Central & Research Development
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Agenda
• Introduction
– DuPont sustainability goals
– PDO based polymers and products
• DuPont™ Cerenol™
– Products, processes and properties
• Cerenol™ vs Commercial Polyols
• Cerenol™ Based Products
– Hytrel® RS Thermoplastic Elastomers
– Performance Coatings
3
Sustainable Growth Trends
• Growth in developing countries
• Increased food production
• Renewable energy and materials
• Greater safety and security
• Increased connectivity
4
DuPont 2015 Sustainability Goals
Marketplace goals
• Double R&D investment in
environmentally smart market
opportunities.
• Grow annual revenue $2 billion or
more from products that create
energy-efficiency and/or reduce
greenhouse gas emissions.
• Double annual revenue to $8
billion from non-depletable
resources.
• Introduce at least 1,000 new safety
products or services.
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DuPont Applied BioSciences uses science to bring
breakthrough biotechnology-based products to the world.
• DuPont Tate and Lyle Bio PDO™
manufacturing facility
• Businesses
– BioMaterials
– BioFuels
– BioSpecialties
– BioMedical
• Key Products
– PDO-based polymers and products
– Biobutanol/Cellulosic ethanol
– Peptides
– Medical adhesives & embolics
– Omega-3 fatty acids
6
Bio-PDO™ serves as a building block for diverse
applications and markets
Ingredient Brand
Markets
Examples of final
product brands
Textile Fibers
• Smartstrand
Carpet Fibers
Resins, Films,
etc.
Bio-PDO™
• Zemea™
• Susterra™
Direct
Applications
Specialty
Applications
Elastomers
• Zemea™ & SusterraTM are registered trademarks of the DuPont Tate & Lyle Bio Products
Company
Stretch Fibers
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Agenda
• Introduction
– DuPont sustainability goals
– PDO based polymers and products
• DuPont™ Cerenol™
– Products, processes and properties
• Cerenol™ vs Commercial Polyols
• Cerenol™ Based Products
– Hytrel® RS Thermoplastic Elastomers
– Performance Coatings
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Cerenol™ is a family of high performance renewably
sourced polyols
Biomass Feed Stock
Cerenol™
Bio-PDO™
• Zemea™
• Susterra™
Products
Structure
H
Homopolymer (H-Series)
Copolyetherglycol (G-Series)
Polyetherglycol ester (E-Series)
H
[
ROCO
[
O
C
O
C
C
O
C
C
C
Bio Content
]OH
n
C
O
O
n
C
100%
] OH
OCOR
70-80%
50-60%
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Cerenol™ uses an environmentally Friendly
Process
Cerenol™ batch manufacturing
facility
Process benefits
• Renewably sourced ingredient
• One step polycondensation process
• Safer manufacturing process
• Less energy consumption
• Less GHG emission
• Low toxic product
• Inherent Biodegradability
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Cerenol™ Commercial Homopolymers
• Typical Property Ranges
Property
Cerenol
H650
Cerenol
H1000
Cerenol
H1400
Cerenol
H2000
Cerenol
H2400
Molecular weight
600 - 700
900 - 1100
1300 - 1450
1900- 2100
2300 - 2500
Hydroxl number
187.0 - 160.3
124.7 -102.0
86.3 - 77.4
59.1 - 53.4
48.8 - 44.9
0.02 max
0.02 max
0.02 max
0.02 max
0.02 max
~2
~2
~2
~2
~2
-2.0 - 2.0
-2.0 - 2.0
-2.0 - 2.0
-2.0 - 2.0
-2.0 - 2.0
50 max
50 max
50 max
50 max
50 max
Melting point (Tm), oC
9 - 11
12 - 14
15 - 17
16 - 18
17 - 19
Density @ 40 oC, g/cc
1.019
1.018
1.017
1.016
1.016
Viscosity @40 oC, cP
100 - 150
190 - 260
310 - 420
720 - 850
950 - 1100
Unsaturation, meq/g
OH Functionality
Alkalinity, meq/30 kg
Color, APHA
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Cerenol™ has led to multiple inventions on
products, processes and uses
• Filed applications on product,
process and applications
• Filed applications by market
Specialty
polymers
Product &
Processes
Product
Applications
Functional
fluids
Coatings
& Inks
Personal care
Fibers
>90 US Patent Applications Filed
60 Granted/Published
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Agenda
• Introduction
– DuPont sustainability goals
– PDO based polymers and products
• DuPont™ Cerenol™
– Products, processes and properties
• Cerenol™ vs Commercial Polyols
• Cerenol™ Based Products
– Hytrel® RS Thermoplastic Elastomers
– Performance Coatings
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Cerenol™ compares best to high performance
polyether diols
• Petroleum Based Synthetic Polyether Diols
– Polyethylene glycol (PEG)
– Polypropylene glycol (PPG)
– Polyethylene-propylene glycols (EO/PO)
– Polytetramethylene ether glycol (PTMEG)
• Vegetable Oil based Polyols (Oleochemical Polyols)
– Soy bean oil based polyols
– Castor oil
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Cerenol™ is an ideal soft segment for
thermoplastic elastomers
• Properties of Cerenol™ vs. other Polyols
Properties
Structure
PPG
CH3
HO CH2-CH- O H
CHn3
Cerenol™
PTMEG
HO-CH2-CH2-CH2-O H
n
HO-CH2-CH2-CH2-CH2O H
n
Biobased
Polyol
Raw material
source
Non renewable
Renewable
Non renewable
Renewable
Hydroxyl type
Secondary
Primary
Primary
Secondary
Low
High
High
Low
Liquid
Liquid/solid
Solid
Liquid
Amorphous
Semi crystalline
Semi crystalline
Polydispersity
Narrow
Broad
Broad
Melting point
No melt
Low
High
Low
Low
Low
Viscosity
Very low
Low
High
High
Oxidative stability
Inferior
Superior
Superior
Inferior
Low
Low
Low
High
Reactivity
Physical state
Crystallinity
Tg
Properties
variability
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Cerenol™ is relatively amorphous and easy
processable polyol
• Properties of Cerenol™ vs Fossil fuel based Polyols
a
Polyol
Tg
o
C
Tm
o
C
Viscosity
60oC
cP
Tc
o
C
Crystallization
half timea
minutes
MWD
PEG
2000
-72
54
130
30.8
ND
< 1.2
PTMEG
2000
- 85
27
575
5.7
T0.85
1.7-1.9
Cerenol
H2000
- 77
17
340
none
16.4
1.7-18
at -5 deg C
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Cerenol™ has comparable Thermo-oxidative
stability vs. PTMEG in spite the higher ether links
• Cerenol™ vs PTMEG
TGA in Air
Isothermal at 175 oC in air
PTMEG-1400
Cerenol-1400
120
–––––––
–––––––
120
PTMEG 1400
Cerenol 1400
16.00min
99.12%
100
100
16.00min
97.99%
Weight (%)
% Weight loss in air
80
80
60
60
58.54min
50.00%
59.01min
50.00%
40
40
92.24min
20.00%
20
20
0
0
0
50
100
150
200
250
300
Temperature, C
350
400
450
92.12min
20.00%
0
500
20
40
60
80
100
Time (min)
120
140
160
180
20
Universal V4.2E
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Cerenol™ is an excellent ingredient for both thermoset and
thermoplastic polymers
• Properties of Cerenol™ vs. Biobased polyols
Typical Properties
Cerenol™
H2000
Biobased Polyol
Biobased
Polyol
Molecular weight
2010
1700
1100
56
56
235
Primary
Secondary
Secondary
2
2 (average)
4.4 (average)
1840
4500
8900
1.02 (40 oC)
1.00
1.01
50 APHA (Max)
<1G
<2G
> 230
> 130
>130
Acid value, mg KOH/g
0.003
0.30
1.7
Water, ppm
<500
500
3000
Hydroxyl number, mg KOH/g
Hydroxyl type
OH Functionality
Viscosity @ 25 oC, cP
Density, g/mL
Color
Flash point,
oC
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Cerenol™ reduces the environmental footprint vs.
PTMEG (cradle to gate life cycle analysis)
40%
80%
70%
60%
50%
40%
30%
20%
10%
0%
PTMEG
3
CERENOL
(Industry average4)
1Industry
Average: 39% Reppe, 26% GEMINOX, 21% Davy, 14% Mitsubishi
100%
relative to fossil PTMEG industry average, (%)
90%
Greenhouse Gas Emissions (Fossil + Nuclear)
Greenhouse Gas Emissions
100%
relative to fossil PTMEG industry average, (%)
Total Non-Renewable Energy (Fossil + Nuclear)
Fossil Energy
90%
42%
80%
70%
60%
50%
40%
30%
20%
10%
0%
PTMEG
3
(Industry average4)
CERENOL
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Agenda
• Introduction
– DuPont sustainability goals
– PDO based polymers and products
• DuPont™ Cerenol™
– Products, processes and properties
• Cerenol™ vs. Commercial Polyols
• Cerenol™ Based Products
– Hytrel® RS Thermoplastic Elastomers
– Performance Coatings
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Cerenol™ Based Products from DuPont
• DuPont™ Hytrel® RS Thermoplastic Elastomer
– 25-60% Renewable content
– Comparable performance to standard grades of Hytrel®
• Performance Coatings for new automotive primers and clearcoats
– Cerenol™ is used as an additive
– Improved flexibility and chip resistance
• Imron® polyurethane
enamels
-– Superior durability, gloss and color retention
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Cerenol™ is more compatible with PBT Hard
segment than PTMEG
Soft segment content (%wt)
60
CLEAR
MELT
PTMEG
40
Cerenol™
20
PHASED
MELT
1000
1500
2000
Polyether Polyol Mn (g/mol)
2500
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Cerenol™ enhances performance of COPE resins
Less Stiffness at - 40oC
E' Modulus [MPa]
3000
2500
2000
Renewable
1500
1000
Standard
500
0
-80
-60
-40
-20
Temperature [°C]
0
20
40
Elastic deformation [%] = f (Total deformation)
Improved elastic recovery
150
Renewable
100
Standard
50
Measured at 50,100,200 and 300[%]
at 23ºC, 50mm/min on 80mm of a Tensile 1BA.
Values reported after 1st cycle
0
0
50
100
150
200
Total deformation [%]
250
300
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Cerenol™ vs. PTMEG-COPE Aging Performance
45DUV
polymer
55DHEAT
polymer
80%
60%
40%
20%
0%
10
20
30
40
Days @ 135°C in air
Cerenol™ Sample
100%
100%
80%
80%
Elongation Retention
Retention of Tensile Strength
Retention of Elongation
100%
0
OILPolymer
45D
(NON UV STABILIZED)
(LOW HEAT STABILIZER)
60%
40%
20%
0%
60%
40%
20%
0%
0
10
20
30
40
Days QUV Exposure
0
200
400
600
800
Hrs @ 120ºC in ASTM Oil #3
PTMEG Sample
Changing from PTMEG to Cerenol™ as a soft segment does not impact
aging despite the increase in ether linkages
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Cerenol™ in Performance Coatings
(US Patents: 6,875,514; 7,169,475; 7,268,182)
Control
Cerenol™
formulation
Durability of Clear coats
120%
100%
80%
60%
40%
20%
0%
Lab
V7500S
• Improvement in chip resistance
3.50%
% 20° Gloss ret. 1 year
%20Gloss ret. 48.7 months
% DOI ret. 3 year
7%
10.50%
V7500S
% 20 Gloss ret. 3 yr
%DOI ret. 1 year
%DOI ret. 48.7 months
• Improvement in flexibility
• 4+ years of Florida exposure
• Hardness retention
• Comparable or better retention of
gloss and DOI
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Cerenol™ in Performance Coatings
• Adhesion Improvement
• Decrease in coating dry time
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Contact information
• www.cerenol.dupont.com
• www.renewable.dupont.com