High Throughput Approach for Agricultural...
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High Throughput Approach for Agricultural Formulation Optimization
P. F. Augusto, K. Harris, M. I. Michen, L. G. Madrigal, S.-S. Ng, L. B. Quencer, C. J. Tucker, J. Mu The Dow Chemical Company April 25th, 2013
High Throughput Research at Dow
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Sample
Preparation Properties Performance
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Su
rfa
ce T
en
sio
n (
mN
/m)
0.001 0.01 0.1Concentration (wt%)
Tergitol A Tergitol B Tergitol C Tergitol D Tergitol E Tergitol F Tergitol G Tergitol H Tergitol I Tergitol J
Do
w C
lea
nin
g In
de
x
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2-EH - 10% 2-EH - 15% 2-octanol - 10%2-octanol - 15%
Dowanol PnB - 10%Dowanol PnB - 15%
PnHex - 10%PnHex - 15%
Tide-Snow
Solvent
All PairsTukey-Kramer 0.05
RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)
0.3975770.3593280.82126914.49079
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Summary of Fit
SolventErrorC. Total
Source 8
126 134
DF 56.08695 84.98491 141.07186
Sum of Squares 7.01087 0.67448
Mean Square 10.3944
F Ratio <.0001Prob > F
Analysis of Variance
2-EH - 10%2-EH - 15%2-octanol - 10%2-octanol - 15%Dowanol PnB - 10%Dowanol PnB - 15%PnHex - 10%PnHex - 15%Tide-Snow
Level 15 15 15 15 15 15 15 15 15
Number 14.4771 14.2851 15.2826 14.3529 14.2351 13.9370 13.3073 15.4482 15.0918
Mean0.212050.212050.212050.212050.212050.212050.212050.212050.21205
Std Error 14.057 13.865 14.863 13.933 13.815 13.517 12.888 15.029 14.672
Lower 95% 14.897 14.705 15.702 14.773 14.655 14.357 13.727 15.868 15.511
Upper 95%
Means for Oneway Anova
Oneway Anova
Oneway Analysis of Dow Cleaning Index By Solvent
Symyx XCM
Har
dwar
e S
oftw
are
• Catalysis, synthesis and polymerization (new materials) • Liquid formulations (agricultural, home and personal care, electronic materials) • Coatings and adhesives (water-borne and reactive) • Thermoset and thermoplastic formulation and application
Dow is a leading innovator in high throughput with an initial investment of > $100 million in the early 2000s
Combinatorial Design of Experiments
Formulation Constraints
Experimental Constraints
DOE: Understanding Reproducibility and
Modeling Needs
Library Studio
Experimental Variables
Design Parameters
Formulation Components
Equations
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Informatics Is Critical
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Dow has various information research groups that work to develop and integrate the best hardware and software options for HTR
Mining & Modeling
Combinatorial DOE
Automated Formulation
System
Data Collection & Processing
Data Analysis & Visualization
Phase Diagrams
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Other Screens Rheology, chemical/thermal stability, cleaning, solubility, cloud point, wetting, etc.
Instructed Volume
Experimental Design
Ternary Phase Diagram
Output • Number of phases • Volume fraction of
each phase • Optical clarity of each
phase
Visualization Software
Automated Liquid Handler Phase Characterization
Phase Identification and Characterization Apparatus
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• Heating/cooling programmable controller • Mixing capabilities: Variable time/speed control • Birefringence filters • Digital imagery with side and back lighting • Analyzes for optical clarity, color and uniformity • 6-plate deck (~45 min/ plate)
Vial Tray Deck Vortex mixer
Vial in gripper
Wrist shaker
Imaging Chamber
Temperature Scanning Turbiometry (TST)
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• Samples are video recorded and software detects opacity changes
• Device ramps 48 samples through a temperature sweep using various min/ max temperatures and adjustable heating rates
HTR Performance Evaluation Capabilities
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• Solubility/compatibility • Surface tension/CMC • Foam generation and stability • Wetting • Solubilization • Emulsion stability • Rheology • Freeze/thaw stability • Optical clarity • Application-specific screens
Nonionics Tested StructureA 2-Ethyl-hexyl- (PO)2(EO)4B 2-Ethyl-hexyl- (PO)3(EO)7C 2-Ethyl-hexyl- (PO)1(EO)8D 2-Ethyl-hexyl- (PO)9(EO)9E 2-Ethyl-hexyl- (PO)11(EO)11F Undecyl-(PO)1.5(EO)7G Undecyl-(PO)2(EO)7H Undecyl-(PO)3(EO)7I TERGITOL NP-9J TERGITOL 15-S-9
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Sur
face
Ten
sion
(mN
/m)
0.001 0.01 0.1Concentration (wt%)
TERGITOL ATERGITOL BTERGITOL CTERGITOL DTERGITOL ETERGITOL FTERGITOL GTERGITOL HTERGITOL ITERGITOL J
Nonionics Tested StructureA 2-Ethyl-hexyl- (PO)2(EO)4B 2-Ethyl-hexyl- (PO)3(EO)7C 2-Ethyl-hexyl- (PO)1(EO)8D 2-Ethyl-hexyl- (PO)9(EO)9E 2-Ethyl-hexyl- (PO)11(EO)11F Undecyl-(PO)1.5(EO)7G Undecyl-(PO)2(EO)7H Undecyl-(PO)3(EO)7I TERGITOL NP-9J TERGITOL 15-S-9
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Sur
face
Ten
sion
(mN
/m)
0.001 0.01 0.1Concentration (wt%)
TERGITOL ATERGITOL BTERGITOL CTERGITOL DTERGITOL ETERGITOL FTERGITOL GTERGITOL H
TERGITOL ATERGITOL BTERGITOL CTERGITOL DTERGITOL ETERGITOL FTERGITOL GTERGITOL HTERGITOL ITERGITOL J
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0
Clo
ud p
oint
(°C
)
1.00.80.60.40.20.0Concentration (M)
Na2SO4
S-7S-9S-12S-15S-20S-30S-40
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Cla
rity
(vol
ts)
1086420Na2SO4 concentration (wt %)
S-7S-9S-12S-15S-20S-30S-40
1% TERGITOL 15-S
Agrochemical Formulation Development
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When traditional formulation approaches are limited… High throughput methods speed up new formulation development • Reformulation to meet new regulatory requirements • Aromatic solvent replacement • Multi-active compatibility • Tank mix compatibility • Customized projects
Example: Reformulation of Emulsifiable Concentrate
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Example of a failed emulsion: Example of a good emulsion:
Hei
ght
Hei
ght
Opacity Opacity
Height level 1
Height level 2
Height level 3
Uniform opacity at different height levels
Different opacity at different height levels
CIPAC MT36
40% AI 51% Solvent 9% Emulsifier
96 formulations
in 45 min
Items Room Temp
0ºC, 1wk
54ºC, 2 wks
Active content (%) 30.31 30.30 30.18
Phase separation (%) 0 0 6.0 (water separation)
Viscosity (mPas) 186.7 147.5 124.2 Emulsion stability (diluted
200 times,1h) qualified qualified qualified
Persistent foaming (mL) 0 0 0 Particle Size (d50), µm 1.41 1.90 1.64
0 2 4 6
DOW EO/PO butyl ether copolymer
DOW EO/PO copolymer
phosphate ester
polyether
Particle size (µm)
Stability of EW 30% Chlorpyrifos
54ºC, 2 weeks
0ºC, 1 week
Initial
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Chlorpyrifos 30%
Solvent Oil 150# 15% DOW EO/PO butyl ether copolymer
4%
Defoamer 0.5% Propylene Glycol 5% Xanthan Gum 0.2% Water ~100
Typical EW Formulation
Summary
• High throughput formulation tools are utilized to accelerate research in a variety of application areas
• High throughput technique allows formulators to cover more experiments addressing unpredictability associated with active ingredients characteristics
• When traditional agrochemical formulation approaches fail, high throughput formulation strategies allow large scale, systematic screening of additives in a short time period
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