The Power of "ene" in Water-Based

Cleaners and Removers:

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

Outline

Metathesis Derivatives Program

Molecule: Reaction, Chemistry, Properties
Solution Behavior
Applications
Cleaning
Personal Care
Summary and Acknowledgements

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: 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: 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: 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

Metathesis Derivatives Program

Molecule: Reaction, Chemistry, Properties
Solution Behavior
Applications
Cleaning
Personal Care
Summary and 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

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
For All Data

% Remaining

120.00
100.00
80.00
60.00

40.00
20.00

0.00

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.

Molecule: 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

Molecule: 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

Molecule: 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

Molecule: Properties: Kauri-Butanol >1000

Saturated Analog, ane, 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

Molecule: Properties: Hansen Map

Large
Hansen
Radius
12.9 Units

N,N-Dimethyl 9-Decenamide is fully miscible with solvents within green line area

Molecule: 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 !

Molecule: 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

Window of Opportunity: 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

50

Concentration (wt. %)
N,N-Dimethyl 9-Decenamide, although very hydrophobic, can micellize in water

Window of Opportunity: 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

Outline

Metathesis Derivatives Program

Molecule: Reaction, Chemistry, Properties
Solution Behavior
Applications
Cleaning
Personal Care
Summary and Acknowledgements

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 D228168) 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

Lets 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 D228168) 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

Lets 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 D228168) 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

Lets Watch

Before Weighted Skeins Dropped

These are solutions near the specified 0.1 wt%, but at solubility limits:
0.13%
0.05%
0.02%
0.25%

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

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.

Weighted Skeins Dropped: 4 Seconds

The Decenamide skein has sunk. All others remain buoyant.

Note the fluffing observed for both amides, Decene and Decane.

Weighted Skeins Dropped: 10 Seconds

The Decenamide skein has sunk. All others remain buoyant.

Note the fluffing observed for both amides, Decene and Decane.

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

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.

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.

Solution Behavior: ene faster than ane

ane

Cotton
Cellulose
Fiber

ene

Nothing in this view to

suggest a difference
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

Solution Behavior: ene faster than ane

ane

Cotton
Cellulose
Fiber

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

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

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

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

Making Water Work Like an Organic Solvent Lets Watch

Making Water Work Like an Organic Solvent

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

Cleaner

Making Water Work Like an Organic Solvent

Conformational Analysis: Ab-Initio Calculations Pending
N,N-Dimethyl 9-Decenamide - Linear

N,N-Dimethyl 9-Decenamide
H-bonded in a hypothesized
looped configuration

N,N-Dimethyl 9-Decenamide H-bonded to H2O

FTIR, Draves, and Solution Behavior support this hypothesis, or at least a looped conformation
Unorthodox to suggest H-C=C- H-bond: more positive than HC-C-, but much less than water H-O Perhaps the lowest energy conformation in dilute aqueous solution for H-C=C- ?
TBD

Making Water Work Like an Organic Solvent

Solution Behavior: Minimize Hydrophobe Contact with H2O

Hydrophobe in H2O is a high energy condition

- Drives surfactant hydrophobe to surfaces
- Drives hydrophobe to micelle interior
- Drives hypothesized monomer conformation by
minimizing hydrophobe surface area contact with H2O
RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION

>
N,N-Dimethyl 9-Decenamide H-bonded to H2O

N,N-Dimethyl 9-Decenamide H-bonded

hypothesized cyclic configuration

Making Water Work Like an Organic Solvent

Solution Behavior: Minimize Hydrophobe Contact with H2O

Hydrophobe in H2O is a high energy condition

- Drives surfactant hydrophobe to surfaces
- Drives hydrophobe to micelle interior
- Drives hypothesized monomer conformation by
minimizing hydrophobe surface area contact with H2O
RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION

>
N,N-Dimethyl 9-Decenamide H-bonded to H2O

N,N-Dimethyl 9-Decenamide H-bonded

hypothesized cyclic configuration

Making Water Work Like an Organic Solvent

Solution Behavior: Minimize Hydrophobe Contact with H2O

Hydrophobe in H2O is a high energy condition

- Drives surfactant hydrophobe to surfaces
- Drives hydrophobe to micelle interior
- Drives hypothesized monomer conformation by
minimizing hydrophobe surface area contact with H2O
RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION

>
N,N-Dimethyl 9-Decenamide H-bonded to H2O

N,N-Dimethyl 9-Decenamide H-bonded

hypothesized looped conformation

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: 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: 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: Waterless Hand Cleaners

Requires >50% Emulsified Petroleum Distillates or Soy Methyl Ester

Typically contain 70+% 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: Waterless Hand Cleaners

Requires >50% Emulsified Petroleum Distillates or Soy Methyl Ester

Typically contain 70+% 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: Waterless Hand Cleaners

Requires >50% Emulsified Petroleum Distillates or Soy Methyl Ester

Typically contain 70+% 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: Blood 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: Blood 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: 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: 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

Some alkalinity required, but not caustic Safer pH

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

Outline

Metathesis Derivatives Program

Molecule: Reaction, Chemistry, Properties
Solution Behavior
Applications
Cleaning
Personal Care
Summary and Acknowledgements

Acknowledgements

AOCS and SCC

Professor Bob Lochhead
Elevance Renewable Sciences
Stepan Company Team

Senior Management including Randy Bernhardt, Rob Slone

Program Manager Bridget Weir
Sales Management including Nathan Shook
Consumer Product Development R&D Manager Chris Gariepy
Project Manager Wilma Gorman
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 template and AOCS logo provided by AOCS for this presentation.