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Novel modified oils enabled by metathesis
Frederyk Ngantung
May 2017
Copyright 2017, Elevance Renewable Sciences, Inc. All rights reserved in this presentation as a whole and the individual slides and content thereon.
AgendaOlefin metathesis of plant oils
Novel modified oils
Summary
2
• Achieved with hydrocarbon feedstocks ONLY• High pressure and temperatures
• Achieved with renewable oils (lipids, fats)• Low pressure and temperatures
Propylene
Ethylene 2-butene
Propylene
A
B
C
D
B DA C
Traditional Metathesis Catalyst Proprietary Metathesis Catalyst
1-decene
9-dodecenoic acid methyl ester
Methyl oleate
1-butene
A B
C D
BD
C A
Olefin metathesis of plant oils
3
Robert Grubbs and Richard Schrock’s advances in new metathesis catalysts enabled the use of plant oil feedstock
Nobel Prize-Winning Catalysis
Novel renewable building blocks
4
Plant oil metathesis enables new building blocks never before accessible at scale
Unsaturated C10 Methyl Ester
Unsaturated C12 Methyl Ester
C18 Diester and Diacid
Elevance Proprietary Olefin Metathesis Process
Plant Oil Feedstock
BiorefineryGresik, Indonesia
Capacity: 180,000 MT
Elevance is the first company to commercialize plant oil metathesis at scale.
Modified oil
Oil
AgendaOlefin metathesis of plant oils
Novel modified oils
Summary
5
Many variables are available to manipulate oil structures via metathesis
6
Plant Oil
Metathesis
Modified oils
Various types of oils:SoyCanolaPalmJatropha……
Various process conditions1 2 Tailored materials with tunable: Architectures Viscosities Functionality
Rheology of plant oils is manipulated via metathesis
7
•Viscosity vs temperature was measured on a stress controlled rheometer (DHR-2) using a 40-mm, parallel plates geometry• Constant shear rate (100s−1) was chosen in the common Newtonian region
Temperature, ⁰C
Vis
cosity (
Pa
.s)
Oligomerized Oils
MTAGs
Plant Oils
Plant oil structures can be manipulated via metathesis
8
Plant Oil
General Triglyceride (TAG)
Cross-Metathesis
- olefins
MTAGs1
Self-Metathesis
- olefins
Oligomerized oils2
MTAG is a new type of oil which can be further derivatized through its terminal double bond
9
Plant oils MTAG
Structure
Dynamic viscosity (25o C)
Average molecular
weight
Terminal double bond
(%)
45-60 cPs 120-150 cPs
800-1,000 1,400-2,700
10-30%
Unique site for derivatization
Fatty acid composition
0%
Well defined by nature Unique unsaturated mid-chain, dibasic
+ oligomers
Palm MTAG is solid at room temperature
10
Dynamic viscosity at 25oC (cPs)
NA - solid
NA – solid
60
120
Dynamic viscosity at 50oC (cPs)
25
30
25
50
Palm MTAG
Canola MTAG
Thermal stability of MTAG is similar to that of its corresponding unmodified plant oil
TGA was carried out on TGAQ500 (TA Instruments, DE, USA)
11
0
50
100
150
200
250
300
350
400
450
Canola Canola MTAG Soy Soy MTAG Palm Palm MTAG
Oxidative Decomposition
Temperature at 10% weight lost (oC) Temperature at 50% weight lost (oC)
Plant oil structures can be manipulated via metathesis
12
Plant Oil
General Triglyceride (TAG)
Cross-Metathesis
- olefins
MTAG1
Self-Metathesis
- olefins
Oligomerized oils2
Oligomerized oil is a new type of high molecular weight oil
13
Source: Croda and Oleon
Stand oil
Blown oil
Oligomerized oils
• Produced at high temperatures without air• Carbon-carbon crosslinking• Pale and low acidity• Made from linseed and soybean
• Produced at high temperatures with air• Oxygen is incorporated into the crosslinking bond• Dark and high acidity• Made from linseed, soy, canola, castor
• Elevance’s metathesis technology on plant oils• Tunable molecular weight and viscosity• Light color with no odor • No polar group; ease of emulsification
Oligomerized oil is a tunable pre-polymer that has low viscosity and sufficient reactivity
14
Plant oils Blown oil
Average molecular
weight (Mw)
Iodine value
Terminal double bond
(%)
Gardner color
45-50 cPs(@ 25⁰C)
15,000
110-180Semi-drying to drying
84Non-drying
0% 0%
1-10 6
Oligomerized oils
Dynamic viscosity
100 - 3200 cPs(@ 40⁰C)Tunable
5400(@ 25⁰C)
800-1,000 2,500 - 30,000+Tunable
Tunable
0-10%Unique site for derivatization
4Lighter than
linseed/blown oil
Oligomerized oil has uncompromised low temperature property
15
Wax appearance temperature (oC)
-13 -2.5 -4 -9
Soy OligomerizedOil 1
OligomerizedOil 2
Blown soybean oil
Gardner color 1 4 4 6
Thermal stability of oligomerized oil is similar to that of plant oil and blown oil
TGA was carried out on TGAQ500 (TA Instruments, DE, USA)16
0
50
100
150
200
250
300
350
400
450
Soy Oligomerized oil 1 Oligomerized oil 2 Blown soybean oil
Oxidative Decomposition
Temperature at 10% weight lost (oC) Temperature at 50% weight lost (oC)
Potential application for MTAG and oligomerized oils
17
Personal care Polyurethane
Paints and coatings
Alkyd resins
Lubricating oilsMetal treating
AgendaOlefin metathesis of plant oils
New modified oils
Summary
18
Leverage complementary
capabilities
Creating differentiated
growth opportunities
Reduce development investment
and risk
Progressing mutual
sustainabilitygoals
Collaborative business model
19
Summary: Elevance offers novel modified oils enabled by metathesis
20
• Novel modified oils via metathesis offer a valuable option to plant oils
• MTAG is a novel oil that can be further derivatized through its unique terminal double bond
• Oligomerized oil is a tunable pre-polymer that has low viscosity and uncompromised low temperature property
• Elevance is actively seeking partners to evaluate and commercialize our novel modified oil for new applications
Acknowledgments
21
• Georgeta Hategan
• Jeremiah Favero
• Dr. Paul Bertin
• Dr. Steve Cohen
• Jeff Duncan
• Michelle Morie-Bebel
• Rusty Pittman
Thank you
Dr. Frederyk NgantungDirector, Business Development+1-630-633-6722+1-415-272-9452Frederyk.Ngantung@elevance.com
Back up slides
C10 and C12 unsaturated methyl esters
24
Unique mid-chain unsaturated esters unlock new performance possibilities
Difunctional (ester & olefin) High purity BiobasedUnique internal & alpha olefins
Derivatize with known ester chemistry
Derivatize with known olefin chemistry
Unsaturation of mid-chain esters offer new properties & reactivity: better solvency, low-temp operability (pour point), higher CMC, better stability, etc.