1. A New-to-the-World Surfactant Makes Water Work Like an Organic Solvent
Ron A. Masters, PhD
Research Associate, Stepan Company

2. Outline Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements

3. Stepan Derivatives Overview
Hallcomid
Onyxide
Steposol

4. Metathesis Derivatives Program: Drivers
Improve Performance
Reduce/Stabilize Feedstock Cost
Stabilize Feedstock Supply
Meet New Sustainability Targets
Nobel Prize-winning Technology
Conversion of Indigenous Vegetable Oils
Ideal Feeds for Derivatization Competencies
Large-Scale Supply – Elevance Renewable Sciences

5. Metathesis Derivatives Program: Overview
Hundreds of Molecules
Organized Team/Program
Synthesis
- Properties Characterization
Performance Tests
Looking for the “Wow”
N,N-Dimethyl 9-Decenamide
- New to the World, new CAS #
- Short Chain, Monounsaturated
- Solvent ? Surfactant ?

6. Metathesis Derivatives Program: Overview
Hundreds of Molecules
Organized Team/Program
Synthesis
- Properties Characterization
Performance Tests
Looking for the “Wow”
N,N-Dimethyl 9-Decenamide
- New to the World, new CAS #
- Short Chain, Monounsaturated
- Solvent ? Surfactant ? “ene”

7. Outline Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements

8. Molecule: Reaction, Chemistry, Properties
Amide 97% minimum (99% Typical)
Water % maximum (0.0 – 0.1% Typical)
Residual Ester 1.0% maximum (0.2 – 0.6% Typical)
Iodine Value – (g/100g)
Color (Gardner) 1 maximum (0 Typical)
Other Residuals 100ppm maximum each
Boiling Point (C) (LVP-VOC Exempt)
Flash Point (C) (PMCC)
Cloud Point (C) (Low HLB Nonionic)
Kauri-Butanol Value > (ASTM D1133)
Hansen Solubility Parameters D: 16.58, P: 9.58, H: (Experimental*)
Estimated HLB (Griffin or Davies)
* Using Hansen software and screening across a large set of test solvents

9. Molecule: Reaction, Chemistry, Properties
Amide 97% minimum (99% Typical)
Water % maximum (0.0 – 0.1% Typical)
Residual Ester 1.0% maximum (0.2 – 0.6% Typical)
Iodine Value – (g/100g)
Color (Gardner) 1 maximum (0 Typical)
Other Residuals 100ppm maximum each
Boiling Point (C) (LVP-VOC Exempt)
Flash Point (C) (PMCC)
Cloud Point (C) (Low HLB Nonionic)
Kauri-Butanol Value > (ASTM D1133)
Hansen Solubility Parameters D: 16.58, P: 9.58, H: (Experimental*)
Estimated HLB (Griffin or Davies)
* Using Hansen software and screening across a large set of test solvents

10. Molecule: Reaction, Chemistry, Properties
Amide 97% minimum (99% Typical)
Water % maximum (0.0 – 0.1% Typical)
Residual Ester 1.0% maximum (0.2 – 0.6% Typical)
Iodine Value – (g/100g)
Color (Gardner) 1 maximum (0 Typical)
Other Residuals 100ppm maximum each
Boiling Point (C) (LVP-VOC Exempt)
Flash Point (C) (PMCC)
Cloud Point (C) (Low HLB Nonionic)
Kauri-Butanol Value > (ASTM D1133)
Hansen Solubility Parameters D: 16.58, P: 9.58, H: (Experimental*)
Estimated HLB (Griffin, Davies, Oil)
* Using Hansen software and screening across a large set of test solvents

11. Molecule: Reaction, Chemistry, Properties
As-Is: Consider as a Solvent
- Ag solvent for pesticides
- Co-solvent in low/no VOC Industrial Paint Strippers
- Carrier solvent ?
- generally “No”
-C=C- bond not reactive, will not polymerize
b.p. too high – Non-Evaporative at RT, won’t cure
(possible at T= C , DHvap = 205 J/g)
Formulated in Water: Consider as a Surfactant
- Micellizes at about 0.05 to 0.10 %
- Solubility limit of about 0.15%
- Low HLB nonionic, but more powerful than alkoxylates
- Makes water work like an organic solvent in many cases

12. Molecule: Reaction, Chemistry, Properties
Chemical Stability: As-Is and Formulated
Air Headspace
(Oxidative)
For All Data
Amide is stable between pH 3-12, not beyond. -C=C- bond is stable as well.
Aqueous solutions demonstrate stability with peroxide at pH 3. Avoid NaOCl.

13. As-Is Properties: Kauri-Butanol >1000
What does this mean ?
Test Solvent
Kauri Resin
Kauri resin is soluble in butanol, less soluble in other solvents
Add test solvent to dilute the butanol solution of resin
At some added amount the resin precipitates due to insolubility
The more added to the endpoint, the higher the Kb value
Resins are common tackifiers for adhesives and coatings
High Kb value = good cleaning and removal performance

14. As-Is Properties: Kauri-Butanol >1000
Saturated Analog ≈ 300 Kb value
What does this mean ?
Test Solvent
Kauri Resin
Kauri resin is soluble in butanol, less soluble in other solvents
Add test solvent to dilute the butanol solution of resin
At some added amount the resin precipitates due to insolubility
The more added to the endpoint, the higher the Kb value
Resins are common tackifiers for adhesives and coatings
High Kb value = good cleaning and removal performance

15. As-Is Properties: Hansen Map
Large Hansen “Radius”
12.9 Units
N,N-Dimethyl 9-Decenamide is fully miscible with solvents within green line area

16. As-Is Properties: Hansen Map
“ene”
“ane”
Evidence For Some Type of Interaction Between -C=C- and Carbonyl
Ethylene Carbonate is miscible with N,N-Dimethyl 9-Decenamide, not Decanamide !

17. Formulated Properties: HLB
Calculated for alcohol ethoxylates of similar solubility (Griffin)
Calculated via group contribution (Davies)
Experimentally determined via oil emulsification
Lard Lanolin Oil Rapeseed Oil
HLB Required:
All methods estimate HLB to be ≈6.
Greater than 5, less than 9 based on oil emulsification test

18. Formulated Properties: CMC & Solubility
N,N-Dimethyl 9-Decenamide, although very hydrophobic, can micellize in water

19. Formulated Properties: CMC & Solubility
N,N-Dimethyl 9-Decenamide
“ene”
Is Different From
N,N-Dimethyl Decanamide
“ane”
“ane” main use is as an Ag solvent for Stepan customers to make pesticide formulations

20. Outline Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements

21. Let’s Watch Solution Behavior
Soluble in water to about 0.15% (vs. 0.05% for “ane”)
Can dissolve up to 19% added water, but not hygroscopic
Formulate similar to a Low-HLB Nonionic
Use charged (anionic or cationic) or mid/high HLB cosurfactant(s)
On its own, at 0.1 wt.%, Draves Wetting (ASTM D ) is nearly instant
Better than saturated analog
Better than similar Low-HLB alkoxylates
Remarkably fast release of air from the surface
“Fluffing” of the fibers observed
Let’s Watch

22. Let’s Watch Solution Behavior
Soluble in water to about 0.15% (vs. 0.05% for “ane”)
Can dissolve up to 19% added water, but not hygroscopic
Formulate similar to a Low-HLB Nonionic
Use charged (anionic or cationic) or mid/high HLB cosurfactant(s)
On its own, at 0.1 wt.%, Draves Wetting (ASTM D ) is nearly instant
Better than saturated analog
Better than similar Low-HLB alkoxylates
Remarkably fast release of air from the surface
“Fluffing” of the fibers observed
Let’s Watch

23. Let’s Watch Solution Behavior
Soluble in water to about 0.15% (vs. 0.05% for “ane”)
Can dissolve up to 19% added water, but not hygroscopic
Formulate similar to a Low-HLB Nonionic
Use charged (anionic or cationic) or mid/high HLB cosurfactant(s)
On its own, at 0.1 wt.%, Draves Wetting (ASTM D ) is nearly instant
Better than saturated analog
Better than similar Low-HLB alkoxylates
Remarkably fast release of air from the surface
“Fluffing” of the fibers observed
Let’s Watch

24. Before Weighted Skeins Dropped
These are solutions near the specified 0.1 wt%, but at solubility limits:
0.13% % % %

25. Weighted Skeins Dropped: 0 Seconds
Note the huge volume of air released from the Decenamide
(left-most cylinder), and the skein has sunk due to momentum

26. Weighted Skeins Dropped: 2 Seconds
Some air remains, buoying the skein for the Decenamide for a brief moment. All others were buoyant at 0 seconds and remain buoyant.

27. Weighted Skeins Dropped: 4 Seconds
The Decenamide skein has sunk. All others remain buoyant.
Note the “fluffing” observed for both amides, Decene and Decane.

28. Weighted Skeins Dropped: 10 Seconds
The Decenamide skein has sunk. All others remain buoyant.
Note the “fluffing” observed for both amides, Decene and Decane.

29. Weighted Skeins Dropped: 12 Seconds
The Decanamide saturated analog skein begins to sink at 12 seconds, long after the Decenamide. “ene” is different than “ane”

30. Weighted Skeins Dropped: 16 Seconds
The Decanamide saturated analog skein has sunk at 16 seconds, long after the Decenamide. C12/C13 EO3 and C6 EO1 remain buoyant.

31. Weighted Skeins Dropped: 20 Seconds
Still waiting on the other skeins to sink. The C12/13 EO3 will take more than a minute, and the C6 EO1 does not sink.

32. Solution Behavior: “ene” faster than “ane”
Cotton Cellulose Fiber
“ane”
Dilute Solution Looped Configuration “enes” could explain what is observed
Volume and speed of air displaced depends on strength of adsorption, diffusion rate, and molecular area1
1 Detergency: Theory and Technology, Surfactant Science Series: v. 20, W. Gale
Cutler and Erik Kisser, 1987, pp 314-5

33. Solution Behavior: Intra-H-Bonding ?
ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted
H-O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”
“ene”
“ane”
C=O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”

34. Solution Behavior: Intra-H-Bonding ?
ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted
H-O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”
“ene”
“ane”
C=O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”

35. Solution Behavior: Intra-H-Bonding ?
ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted
H-O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”
“ene”
“ane”
C=O stretch broadened to lower frequency (cm-1) for “ene” compared to “ane”
Let’s Watch
“Making Water Work Like an Organic Solvent”

36. Outline Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements

37. “Making Water Work Like an Organic Solvent”
Applications: Chewing Gum Dissolution/Disintegration
Formulated Aqueous, pH % w/MEA % w/Na2CO3
As-Is 100%
Aqueous Commercial Cleaners
pH pH 10.5
INITIAL
22C
50 hours
N,N-Dimethyl 9-Decenamide
d-Limonene NMP DCM Degreaser Cleaner
“Making Water Work Like an Organic Solvent”

38. Applications: Nail Polish Removers
Requires >50% Acetone and/or Ethyl Acetate
Typically contain 90+% Organic Solvent
85% Water
5% N,N-Dimethyl 9-Decenamide
5% MEA OR
87% Water
3% N,N-Dimethyl 9-Decenamide
1.5% Citrus Fragrance
0.3% Sodium Carbonate
Balance: High HLB co-emulsifier
Patent Pending blend with great synergy and new mechanism(s)
WO (A1)
“Making Water Work Like an Organic Solvent”

39. Applications: Pre-Wash Stain Remover
Typically Requires Peroxide or Hypochlorite
Decenamide + Citrus + Carbonate +
Co-Emulsifier
Commercial Peroxide Product
95% Water
1% N,N-Dimethyl 9-Decenamide
0.5% Citrus Fragrance
0.1% Sodium Carbonate
Balance: High HLB co-emulsifier
Patent Pending blend with great synergy and new mechanism(s)
WO (A1)
Mechanism: De-Chelation of Chromophores (UV-Vis)

40. Applications: Permanent Marker Remover
Typically Requires IPA or Acetone: Not Good for Surfaces
Commercial Marker Remover Product
Decenamide + Citrus + Carbonate +
Co-Emulsifier
95% Water
1% N,N-Dimethyl 9-Decenamide
0.5% Citrus Fragrance
0.1% Sodium Carbonate
Balance: High HLB co-emulsifier
Patent Pending blend with great synergy and new mechanism(s)
WO (A1)
Mechanism: De-Chelation of Chromophores (UV-Vis)

41. Applications: Oven Cleaning
Typically Requires Caustic: pH 12-14
Commercial Oven Cleaner with Caustic and Organic Solvents pH 12.5
Aerosol Can
85% Water
5% Decenamide
5% MEA
pH 11.5
Some alkalinity required, but not caustic → Safer pH

42. Applications: Aerosol Tests
Passes 1-Month 50C Stability in Flairosol® Package
STEPOSOL® CITRI-MET diluted 1:4
Water-based Graffiti Remover
DI Water
STEPOSOL® CITRI-MET diluted 1:14
Bug/Tar Remover, Spot Remover, APC
Commercial Retail APC
Spray patterns similar to retail APC
STEPOSOL® CITRI-MET at 1:4 dilution slightly more viscous – tighter pattern
DI water produces a more “misty” aerosol from this package

43. Applications: Aerosol Tests (continued)
Aerosol Droplet Size Distributions (mm)*
The strongest cleaner has the larger PSD Analysis a
* PSD Data obtained by Spray Analytics, Lincolnshire IL

44. Applications: Aerosol Tests (continued)
Aerosol Droplet Size Distribution Analysis (mm)*
1. Lower ST allows liquid to spread easier a smaller droplet PSD 1
2. Lower ST can ease flow through nozzle a lower fluid pressure a
larger droplet PSD 1
It was observed that DI water required more force on the trigger to generate the aerosol spray from this package, so
#2 above dominates
1 Atomization Concept and Theory, Graco Inc. Minneapolis, MN 2014
* PSD Data obtained by Spray Analytics, Lincolnshire IL

45. More on the Flairosol® Package
No-Propellant, Refillable Package by AFA Dispensing Group
Not an endorsement or recommendation
Noted to Stepan via the industry as a new item
Allows for easy fill/refill and testing of various cleaners
Storage/Use stability and longevity testing
Spray patterns

46. Applications: Materials Compatibility
In-Vitro EpiDerm Test
6% N,N-Dimethyl 9-Decenamide
3% MEA
Anionic/Nonionic co-emulsifiers
0.60 Hours for ET50, Moderate Irritant
Similar to other surfactants
SKIN
Immersion Tests: ASTM D543-95
Neat and formulated
PET, HDPE, PP all OK
Avoid PC (any amines/amide), PVC, Nylon
Plastics
Gaskets and Seals
Immersion Tests
Neat and formulated
Teflon, Silicone, Peroxide Cured EPDM OK
Avoid Viton and Elastomers

47. Applications: Materials Compatibility
In-Vitro EpiDerm Test
6% N,N-Dimethyl 9-Decenamide
3% MEA
Anionic/Nonionic co-emulsifiers
0.60 Hours for ET50, Moderate Irritant
Similar to other surfactants
SKIN
Immersion Tests: ASTM D543-95
Neat and formulated
PET, HDPE, PP all OK
Avoid PC (any amines/amide), PVC, Nylon
Plastics
Gaskets and Seals
Immersion Tests
Neat and formulated
Teflon, Silicone, Peroxide Cured EPDM OK
Avoid Viton and Elastomers

48. Applications: Materials Compatibility
In-Vitro EpiDerm Test
6% N,N-Dimethyl 9-Decenamide
3% MEA
Anionic/Nonionic co-emulsifiers
0.60 Hours for ET50, Moderate Irritant
Similar to other surfactants
SKIN
Immersion Tests: ASTM D543-95
Neat and formulated
PET, HDPE, PP all OK
Avoid PC (any amines/amide), PVC, Nylon
Plastics
Gaskets and Seals
Immersion Tests
Neat and formulated
Teflon, Silicone, Peroxide Cured EPDM OK
Avoid Viton and Elastomers

49. Acknowledgements SATA Elevance Renewable Sciences Spray Analytics
Stepan Company Team
Senior Management, Program Manager, Sales Management
Home & Prof. Care R&D Products Manager
Synthesis, Analytical, and Applications Lab Colleagues
Many more too numerous to mention
Customers who have commercialized products

50. It is nice to have MET-10U today
THANK YOU !
It is nice to have MET-10U today
POWER OF THE DOUBLE BOND TM
All images and clip art in this presentation are the work of the author and Stepan Company Employees.
Presentation logo provided by SATA for this presentation.