Post on 12-Jul-2020
Transformation of a Synthetic Chemist into an Oil Chemist
Dharma R. Kodali, Ph.D., FAOCSBioproducts and Biosystems Engineering
University of Minnesota
AOCS Annual MeetingA.E. Bailey Award Lecture
MinneapolisMay 07, 2018
Presentation - Outline
I Introduction: - Research Chronology
K.U. PINY B.U. Industry (Cargill/GM) U.M.
II Learnings: - at P.I.N.Y. and Boston UniversityA. Molecular Probes to study the micro-environmentB. Synthesis and molecular packing of Glycerol derivativesC. Single crystal structures of mixed chain TAGD. Influence of TAG structure on glycerol conformation
III Industrial Applications: -at Cargill, GM and U of MA. Low VOC Paints and CoatingsB. Synthetic LubricantsC. Cholesterol free animal fatsD. Bio-plasticizers
IV Summary
Research Chronology
1976-80 Ph.D. Kurukshetra University1980-81 New York Poly, New York1981-91 Boston University, Boston1991-03 Cargill, MPLS2003-04 General Mills, MPLS2005- Univ. of Minnesota, MPLS
Andhra
Kurukshetra
New Delhi
New York
Boston
Minneapolis
Potential Anti-inflammatory AgentsPh.D. Thesis: >140 new compounds synthesized
Kurukshetra University1976-1980
Fluorescent Molecular Probes
J.C.S. Chem. Comm. 759-760, 1981.J.C.S. Chem. Comm. 758-759, 1981.
Ar = Aromatic
P.I.N.Y.1980-81
ExcimerMonomerCyclodextrins
Micelle
Lipids – Synthesis, Molecular Packing and Properties
1-acetyl-3-palmitoyl-sn-glycerol
1-palmitoyl-3-acetyl-sn-glycerol
Stereospecific Glycerol Derivatives
Boston University 1981 -91
J. Am. Oil Chem. Soc., 61, 1078-1084, (1984).
2 2 n 3
3 2 14
2 2 14 3
n = 2, 4, 6, 8, 10, 12, 14,16
1,2-dipalmitoyl-3-acyl-sn-glycerols (PPX)
Stereospecific sn-Glycerol Derivatives
sn- Tri- , Di-, and Mono-acylglycerols: TAG, DAG and MAGOOX, OXO, SXS and other homologues
Polymorphism – Molecular PackingAbility to crystallize into more than one crystal state
Subcell
β β' α
Characterization: XRD, IR, and Raman
Properties: melting temperature, enthalpy, stability, volume, bloom, hardness, texture, mouth feel, graininess,lubricity, air-entrapment
Polymorphism – PP10
42.5 °C
Liquid
47 °C
37 °C
β 56Å β2’ 37Åβ3’ 37Å
β1’ 111Å
39 °C
α 40.4Å
21 °C
Ref: Larsson K.(1963)
Single Crystal structures of TAG (C10, C12)
Glycerol //
End Methyl Plane
Trilauroyl (C12) Glycerol
β
Crystal Structures – PP2
Proc. Natl. Acad. Sci. 89, 8083, 1992.
β
12
3
1
3
2
Glycerol ┴
Crystal Structure – PP14 (myrsitoyl)
J Lipid Res. 42, 338-345, 2001
β'2
PP
P
P M M
P PP
Hybrid O ┴
P M M
30?
OOPOOS
OPOOSO
Glycerol //Glycerol ┴
Influence of Glycerol Conformation
TAG Enthalpy(Kcal/mol) Melting Temp (°C)OPO 30 22OOP 21 18OSO 32 25OOS 22.5 23
End Methyl Plane
β
SymmetricAsymmetric
β
Industrial Applications – Market DriversValue creation - Alchemy
CostPerformanceAvailability (Supply / Demand)
Regulations (Availability/Pollution)
EHS (Environment, Health and Safety)
Green Image (Renewable, biodegradable)
Understanding application functionality, market value and opportunity
New Product DevelopmentStructure / Properties / Functionality
Chemical Structureand Composition
Physical Structure and Properties
ApplicationsFunctionality
Leverage the connection
Create the desired functionality through Modification of Structure and or Composition.
Molecular PropertyReactivityUnsaturation (Mono/Poly)Chain lengthSap. ValueAcid ValuePeroxide Value PolaritySolvencyHydrophobicityMol. WeightMol. PackingHeterogeneity
Derived FunctionalityAppearance/ColorViscosity Volatility (VOC)Low Temp. (m.p./f.p., Flow)Drying (film formation)AdhesionTack/Rub-offLubricityOxidative Stability(shelf-life)CompatibilityBiodegradability
Properties VS. Functionality
New Product Development – Fats & Oils
COMMERCIALIZED PRODUCTS & TECHNOLOGIES Dilulin – Reactive diluent – Paints Coatings Agripure – A family of synthetic lubricants Moldlube NS – Steel mold lubricant Odyssey 500 – High stability oils CTO – 300 – Formulated lubricant AS-900 – Metal Working Fluid Stabilization of bottled oils
NON-COMMERCIALIZED TECHNOLOGIES Cholesterol free animal fats Cyclopropanated Oils Fertilizer coatings Asphalt release agents Biotechnology – designer TAG EOE, CBE Trans free fats – Maltodextrin encapsulation, oleogels, longer FA TAG Bioplasticizers
Cargill Inc. GM and U of M 1991 - present
New Product Development
Industrial Applications:
A) Paints and CoatingsB) Lubricants C) Cholesterol free animal fatsD) Bio-plasticizers
Cargill Inc. GM and U of M 1991 - present
A) Conventional Solvent Based Coatings
VOLATILES(HYDROCARBON SOLVENTS)
40 - 65%NON VOLATILES
(RESIN + PIGMENTS + DRIERS)
35 - 60%
LIQUID SOLID3 MIL 1 MILDrying
VOC
Resin
Reactive Diluent - Dilulin(Reduction of VOC)
OO
O OO
O
OO
O OO
O
Linseed Oil DILULINUS 5,693,715 US 5,288,805
B) Lubricants – Fats and Oils
Advantages
Excellent boundary lubricationGood viscosity and viscosity indexHigh flash pointBiodegradable, nontoxic Environmentally friendly, renewable
Limitations
Poor oxidative stabilityPoor low temperature flow properties
Low Temp. VS. Oxidative Stability
Property C18:0 TAG
Saturated
C18:1 TAG
Mono-Unsat
C18:2 TAG
Di-Unsat
C18:3 TAG
Tri-Unsat
Melt Temp (° C) 74 5 -11 -24
Oxidation Rate Low1
Moderate10
High100
Very High200
Cyclopropanated Oils
Carbene :CH2
Simmons-Smith Rx
CH2I2, Zn(Cu)
US 6,051,539
Saturated Oil, liquid -40 °CHigh Oxidative stability
O OOO O
O
Vegetable Oil
Transesterification of High Oleic Oils
+
-OH
Bio‐based Synthetic Polyol Esters
TMPPE
NPG
High Oleic Oil
US 6,278,006 US 6,943,262
Heterogeneous Oils - Cont’d
+
+
O
O
O
O
O
O
Salient Features of Bio-Synthetic Esters
Excellent Low Temperature Fluidity (-25°C) Excellent Oxidative Stability Very High VI (180 - 210) Range of Viscosities (18 - 46 cSt @ 40°C) Low volatility ( < 7%) Good Boundary Lubrication Readily Biodegradable Cost Effective
is a Family of Bio-based synthetic estersAP – 512, 560,570
Industrial Lubrication and Tribology, 54, 165-170, 2002.
C) Cholesterol-free Animal FatsConcept
Polar Hydrophilic head group
NonpolarOleophilic body
U.S. 5,880,300 and 6,303,803
PHOSPHOLIPIDS(Lecithin)
CHOLESTEROL
Concept
Water Animal Fat/Oil
Cholesterol
PHOSPHOLIPIDS
(Lecithin, a biproduct of SBO processing)
PHOSPHOLIPIDBILAYERS
Cholesterol Removal
Bilayers withcholesterol
Centrifuge Cholesterolremoved oil
Phospholipidswith cholesterol
Results
Number of Treatments
% Ch
oles
tero
l Rem
oved
Lecithin : Tallow =1:5
0102030405060708090
100
0 1 3 5
D) Bioplasticizers – Commercial Opportunity
• Plasticizers market size - $20 Billion/yr
• >90% of Plasticizers used in flexible PVC
• Currently used Petroleum derived “Phthalate” plasticizers have EHS concerns. With time they leach out and cause hormonal disruption and reproductive damage.
• Cost effective bioplasticizrs have a great opportunity
Glycerol Epoxy Estolide Fatty Acid Esters
Glycerol Fatty AcidEsters Ac2O
Glycerol Epoxy Estolide FattyAcid Esters
R = glycerol derivativen = 0-6 m = 0-3
AcOH
H2O2+ Cat.
Glycerol EpoxyFatty AcidEsters
AcOH
Summary of Plastisol Evaluation
Gelation
PlastisolViscosity
Plastisol Aging
EfficiencyCold Flex
Volatility
Compatibility
DINPBioplasticizer
Cost of the bioplasticizer is about $0.75/lb similar to commercial phthalates
Summary
Skills to modify structure – Synthesis, Characterization
Structure - Properties - Functionality relationship to create new products
Functional properties that are lacking can be brought in through chemical modification to make value added products useful in coatings, lubricants and plasticizers
Cost, Performance, Environmental factors and Regulations are major driving forces for using oils and their derivatives in industrial applications
Acknowledgements
SP Singh SN Sawhney O. Prakash J. Emert D. Small
T. Redgrave D. Atkinson D. Fahey M. Badr J. Hamilton
K. Li F. Kaneko M.Kobayashi J. Evans P. Addis
L. DeBonte M. Grass B. Woldt M. Nathan S. Nivens
Z. Fan R. Duclos J. Powell K. Krishnan M. Goto
K. Sato J. Yano L. Lei H.T. Davis L. Dassanayake
S. Ueno S. Kandula L. Stolp S. Bhamidipati R. Catena
W. Byrdwell R. Tomer P. Phalon I. Prakash G. Dhindsa
Metabolism – OOS and OSO
TAG
2-MAG +FA
lipase
Absorp. Enterocytes
TAGpackage into
Chylomicrons
Lipoproteins
% in
ject
ed (
CPM
)
Time (min)J. Biol. Chem. 263, 5118, 1988.
[VLDL to LDL to HDL]
Low Temp. VS. Oxidative Stability
Property C18:0 TAG
C18:1 TAG
C18:2 TAG
C18:3 TAG
Melt Temp (° C) 74 5 -11 -24Oxidation Rate Low
1Moderate
10High100
Very High200
Poor
Excellent
Perf
orm
ance
Sats Monos Polys