A New-to-the-World Surfactant Makes
Water Work Like an Organic Solvent
Ron A. Masters, PhD
Research Associate, Stepan Company
Outline
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•
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•
•
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Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements
Stepan Derivatives Overview
Hallcomid
Steposol
Onyxide
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
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 ?
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”
Outline
•
•
•
•
•
•
Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements
Molecule: Reaction, Chemistry, Properties
Amide
Water
Residual Ester
Iodine Value
Color (Gardner)
Other Residuals
97% minimum
0.5% maximum
1.0% maximum
117 – 137
1 maximum
100ppm maximum each
Boiling Point (C)
Flash Point (C)
Cloud Point (C)
Kauri-Butanol Value
Hansen Solubility Parameters
Estimated HLB
(99% Typical)
(0.0 – 0.1% Typical)
(0.2 – 0.6% Typical)
(g/100g)
(0 Typical)
297
134
-13
>1000
D: 16.58, P: 9.58, H: 8.45
6
(LVP-VOC Exempt)
(PMCC)
(Low HLB Nonionic)
(ASTM D1133)
(Experimental*)
(Griffin or Davies)
* Using Hansen software and screening across a large set of test solvents
Molecule: Reaction, Chemistry, Properties
Amide
Water
Residual Ester
Iodine Value
Color (Gardner)
Other Residuals
97% minimum
0.5% maximum
1.0% maximum
117 – 137
1 maximum
100ppm maximum each
Boiling Point (C)
Flash Point (C)
Cloud Point (C)
Kauri-Butanol Value
Hansen Solubility Parameters
Estimated HLB
(99% Typical)
(0.0 – 0.1% Typical)
(0.2 – 0.6% Typical)
(g/100g)
(0 Typical)
297
134
-13
>1000
D: 16.58, P: 9.58, H: 8.45
6
(LVP-VOC Exempt)
(PMCC)
(Low HLB Nonionic)
(ASTM D1133)
(Experimental*)
(Griffin or Davies)
* Using Hansen software and screening across a large set of test solvents
Molecule: Reaction, Chemistry, Properties
Amide
Water
Residual Ester
Iodine Value
Color (Gardner)
Other Residuals
97% minimum
0.5% maximum
1.0% maximum
117 – 137
1 maximum
100ppm maximum each
Boiling Point (C)
Flash Point (C)
Cloud Point (C)
Kauri-Butanol Value
Hansen Solubility Parameters
Estimated HLB
(99% Typical)
(0.0 – 0.1% Typical)
(0.2 – 0.6% Typical)
(g/100g)
(0 Typical)
297
134
-13
>1000
D: 16.58, P: 9.58, H: 8.45
6
(LVP-VOC Exempt)
(PMCC)
(Low HLB Nonionic)
(ASTM D1133)
(Experimental*)
(Griffin, Davies, Oil)
* Using Hansen software and screening across a large set of test solvents
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=100-130C , 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
Molecule: Reaction, Chemistry, Properties
Chemical Stability: As-Is and Formulated
6% Emulsified at 80C, pH 3
6% Emulsified at 80C, pH 11
100% As-Is at 54C
Air Headspace
(Oxidative)
For All Data
% Remaining
120.00
100.00
80.00
60.00
40.00
20.00
0.00
0
2
4
11
18
Days (x3 for As-Is)
25
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.
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
As-Is Properties: Kauri-Butanol >1000
Saturated Analog ≈ 300 Kb value
Test Solvent
What does this mean ?
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
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
As-Is Properties: Hansen Map
“ene”
“ane”
Evidence For
Some Type of
Interaction
Between -C=Cand Carbonyl
Ethylene Carbonate is miscible with N,N-Dimethyl 9-Decenamide, not Decanamide !
Formulated Properties: HLB
Calculated for alcohol ethoxylates of similar solubility (Griffin)
Calculated via group contribution (Davies)
Experimentally determined via oil emulsification
Lard
HLB Required:
5
Lanolin Oil
9
Rapeseed Oil
6
All methods estimate HLB to be ≈6.
Greater than 5, less than 9 based on oil emulsification test
Formulated Properties: CMC & Solubility
Surface Tension (mN/m)
60
55
CMC calculates ≈ 500 - 1000 ppm
Solubility Limit ≈ 1500 ppm
50
45
40
35
30
25
0.005
0.05
0.5
5
50
Concentration (wt. %)
N,N-Dimethyl 9-Decenamide, although very hydrophobic, can micellize in water
Formulated Properties: CMC & Solubility
N,N-Dimethyl
9-Decenamide
“ene”
Is Different
From
N,N-Dimethyl
Decanamide
“ane”
N,N-Dimethyl Decanamide
N,N-Dimethyl 9-Decenamide
80
70
60
50
40
30
20
10
0
0
5000
10000
“ane” main use is as an Ag solvent for Stepan customers to make pesticide formulations
Outline
•
•
•
•
•
•
Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements
Outline
•
•
•
•
•
•
Stepan Core Derivative Technologies
Metathesis Derivatives Program
Molecule: Reaction, Chemistry, Properties
Aqueous Solution Behavior
Applications
Acknowledgements
Applications: Chewing Gum Dissolution/Disintegration
Formulated Aqueous, pH 11.5
5% w/MEA
3% w/Na2CO3
As-Is
100%
As-Is
100%
As-Is
100%
As-Is
100%
d-Limonene
NMP
DCM
Aqueous Commercial Cleaners
pH 13
pH 10.5
INITIAL
22C
50 hours
N,N-Dimethyl 9-Decenamide
Degreaser
“Making Water Work Like an Organic Solvent”
Cleaner
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)
WO2013162926(A1)
“Making Water Work Like an Organic Solvent”
Applications: Pre-Wash Stain Remover
Typically Requires Peroxide or Hypochlorite
Commercial
Peroxide
Product
95% Water
1% N,N-Dimethyl 9-Decenamide
0.5% Citrus Fragrance
0.1% Sodium Carbonate
Balance: High HLB co-emulsifier
Decenamide +
Citrus +
Carbonate +
Co-Emulsifier
Patent Pending
blend with great
synergy and new
mechanism(s)
WO2013162926(A1)
Mechanism: De-Chelation of Chromophores (UV-Vis)
Applications: Permanent Marker Remover
Typically Requires IPA or Acetone: Not Good for Surfaces
Commercial
Marker
Remover
Product
95% Water
1% N,N-Dimethyl 9-Decenamide
0.5% Citrus Fragrance
0.1% Sodium Carbonate
Balance: High HLB co-emulsifier
Decenamide +
Citrus +
Carbonate +
Co-Emulsifier
Patent Pending
blend with great
synergy and new
mechanism(s)
WO2013162926(A1)
Mechanism: De-Chelation of Chromophores (UV-Vis)
Applications: Oven Cleaning
Typically Requires Caustic: pH 12-14
Commercial
Oven Cleaner
with Caustic
and Organic
Solvents
pH 12.5
85% Water
5% Decenamide
5% MEA
pH 11.5
Aerosol Can
Some alkalinity required, but not caustic → Safer pH
Applications: Aerosol Tests
Passes 1-Month 50C Stability in Flairosol® Package
DI Water
Commercial Retail APC
STEPOSOL® CITRI-MET diluted 1:4
Water-based Graffiti Remover
STEPOSOL® CITRI-MET diluted 1:14
Bug/Tar Remover, Spot Remover, 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
Applications: Aerosol Tests (continued)
Aerosol Droplet Size Distributions (mm)*
Liquid
Dx(10)
DI Water
40.0
Retail Cleaner
40.6
CITRI-MET diluted 1:14 36.5
CITRI-MET diluted 1:4
45.4
Dx(50)
65.6
71.7
73.7
122.6
Dx(90)
107.9
130.6
170.3
624.0
The strongest cleaner has the larger PSD
ST (mN/m) Key
72
-----oooo
29
mmmm
27.6
uuuu
28.2
Analysis a
* PSD Data obtained by Spray Analytics, Lincolnshire IL
Applications: Aerosol Tests (continued)
Aerosol Droplet Size Distribution Analysis (mm)*
Dx(10)
Liquid
40.0
DI Water
40.6
Retail Cleaner
CITRI-MET diluted 1:14 36.5
45.4
CITRI-MET diluted 1:4
Dx(50)
65.6
71.7
73.7
122.6
Dx(90)
107.9
130.6
170.3
624.0
ST (mN/m) Key
72
-----oooo
29
mmmm
27.6
uuuu
28.2
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
http://wwwd.graco.com/training/concept_and_theory/Atomization%20v2.pdf
* PSD Data obtained by Spray Analytics, Lincolnshire IL
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
http://www.afadispensing.com/flairosol
Applications: Materials Compatibility
• In-Vitro EpiDerm Test
SKIN
- 6% N,N-Dimethyl 9-Decenamide
- 3% MEA
- Anionic/Nonionic co-emulsifiers
• 0.60 Hours for ET50, Moderate Irritant
• Similar to other surfactants
• Immersion Tests: ASTM D543-95
Plastics
- Neat and formulated
• PET, HDPE, PP all OK
• Avoid PC (any amines/amide), PVC, Nylon
Gaskets
and
Seals
• Immersion Tests
- Neat and formulated
• Teflon, Silicone, Peroxide Cured EPDM OK
• Avoid Viton and Elastomers
Applications: Materials Compatibility
• In-Vitro EpiDerm Test
SKIN
- 6% N,N-Dimethyl 9-Decenamide
- 3% MEA
- Anionic/Nonionic co-emulsifiers
• 0.60 Hours for ET50, Moderate Irritant
• Similar to other surfactants
• Immersion Tests: ASTM D543-95
Plastics
- Neat and formulated
• PET, HDPE, PP all OK
• Avoid PC (any amines/amide), PVC, Nylon
Gaskets
and
Seals
• Immersion Tests
- Neat and formulated
• Teflon, Silicone, Peroxide Cured EPDM OK
• Avoid Viton and Elastomers
Applications: Materials Compatibility
• In-Vitro EpiDerm Test
SKIN
- 6% N,N-Dimethyl 9-Decenamide
- 3% MEA
- Anionic/Nonionic co-emulsifiers
• 0.60 Hours for ET50, Moderate Irritant
• Similar to other surfactants
• Immersion Tests: ASTM D543-95
Plastics
- Neat and formulated
• PET, HDPE, PP all OK
• Avoid PC (any amines/amide), PVC, Nylon
Gaskets
and
Seals
• Immersion Tests
- Neat and formulated
• Teflon, Silicone, Peroxide Cured EPDM OK
• Avoid Viton and Elastomers
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
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.