The Power of "ene" in Water - Based Cleaners and Removers

8/16/2019 The Power of "ene" in Water - Based Cleaners and Removers

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The Power of "ene" in Water-Based

Cleaners and Removers:

A New-to-the-World Metathesis-BasedSurfactant Makes Water Work Like an

Organic Solvent

Ron A. Masters, PhD

Research Associate, Stepan Company


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Outline

• Metathesis Derivatives Program

• Molecule: Reaction, Chemistry, Properties

• Solution Behavior

•

Applications – Cleaning

– Personal Care

• Summary and Acknowledgements


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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


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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 ?


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Metathesis Derivatives Program: Overview

Hundreds of Molecules

- Organized Team/Program

- Synthesis

- Properties Characterization

- Performance Tests- Looking for the “Wow”


- New to the World, new CAS #

- Short Chain, Monounsaturated

- Solvent ? Surfactant ? “ene”


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Outline




•


– Personal Care



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Molecule: Reaction, Chemistry, Properties

Amide 97% minimum (99% Typical)

Water 0.5% maximum (0.0 – 0.1% Typical)

Residual Ester 1.0% maximum (0.2 – 0.6% Typical)Iodine Value 117 – 137 (g/100g)

Color (Gardner) 1 maximum (0 Typical)

Other Residuals 100ppm maximum each

Boiling Point (C) 297 (LVP-VOC Exempt)

Flash Point (C) 134 (PMCC)Cloud Point (C) -13 (Low HLB Nonionic)

Kauri-Butanol Value >1000 (ASTM D1133)

Hansen Solubility Parameters D: 16.58, P: 9.58, H: 8.45 (Experimental*)

Estimated HLB 6 (Griffin or Davies)

* Using Hansen software and screening across a large set of test solvents


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Estimated HLB 6 (Griffin or Davies)



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Estimated HLB 6 (Griffin, Davies, Oil)



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Molecule: Reaction, Chemistry, PropertiesChemical Stability: As-Is and Formulated

0.00

20.00

40.00

60.00

80.00

100.00

120.00

0 2 4 11 18 25

% R e m a i n i n g

Days (x3 for As-Is)

6% Emulsified at 80C, pH 3

6% Emulsified at 80C, pH 11

100% As-Is at 54C

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.

Air Headspace

For All Data


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Molecule: Properties: Kauri-Butanol >1000

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

Test Solvent


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Kauri Resin







Test Solvent


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Kauri Resin







Test Solvent


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Kauri Resin







Test Solvent

Saturated Analog, “ane”, ≈ 300 Kb value


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Molecule: Properties: Hansen Map

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

Large

Hansen“Radius”

12.9 Units


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Molecule: Properties: Hansen Map

Ethylene Carbonate is miscible with N,N-Dimethyl 9-Decenamide, not Decanamide !

“ene”

“ane”

Evidence For

Some Type of

InteractionBetween -C=C-

and Carbonyl


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Molecule: Properties: HLB

All methods estimate HLB to be ≈6.

Greater than 5, less than 9 based on oil emulsification test

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: 5 9 6


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Window of Opportunity: CMC & Solubility

N,N-Dimethyl

9-Decenamide

“ene”

Is DifferentFrom

N,N-Dimethyl

Decanamide

“ane” 01020

30

40

50

60

70

80

0 5000 10000

N,N-Dimethyl Decanamide



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Outline




•


– Personal Care



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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 HLBcosurfactant(s)

•

On its own, at 0.1 wt.%, Draves Wetting (ASTM D2281-68) 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


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•



•




–


Let’s Watch


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•



•




–


Let’s Watch


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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%


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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


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Some air remains, buoying the skein for the Decenamide for a brief

moment. All others were buoyant at 0 seconds and remain buoyant.


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The Decenamide skein has sunk. All others remain buoyant.

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


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The Decenamide skein has sunk. All others remain buoyant.

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


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The Decanamide saturated analog skein begins to sink at 12

seconds, long after the Decenamide. “ene” is different than “ane”


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The Decanamide saturated analog skein has sunk at 16 seconds, long

after the Decenamide. C12/C13 EO3 and C6 EO1 remain buoyant.


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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.


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Solution Behavior: “ene” faster than “ane”Cotton

Cellulose

Fiber

“ene”

“ane”

Volume and speed of air displaced depends on strength of adsorption,

diffusion rate, and molecular area11

Detergency: Theory and Technology, Surfactant Science Series: v. 20, W. GaleCutler and Erik Kisser, 1987, pp 314-5

Nothing in this view to

suggest a difference


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Solution Behavior: “ene” faster than “ane”Cotton

Cellulose

Fiber

Dilute Solution

LoopedConfiguration

“enes” could

explain what is

observed

“ane”

Volume and speed of air displaced depends on strength of adsorption,

diffusion rate, and molecular area11

Detergency: Theory and Technology, Surfactant Science Series: v. 20, W. GaleCutler and Erik Kisser, 1987, pp 314-5


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Solution Behavior: Intra-H-Bonding ?ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted

H-O stretch broadened tolower frequency (cm-1) for

“ene” compared to “ane”

C=O stretch broadened to

lower frequency (cm-1) for


“ene”

“ane”


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ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted

H-O stretch broadened tolower frequency (cm-1) for





“ene”

“ane”

Solution Behavior: Intra-H-Bonding ?


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ATR-FTIR SPECTRA: Dilute Solution, Bulk Water Subtracted

H-O stretch broadened to






“Making Water Work Like an Organic Solvent” Let’s Watch

“ene”

“ane”

Solution Behavior: Intra-H-Bonding ?

“Making Water Work Like an Organic Solvent”


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Making Water Work Like an Organic Solvent

Chewing Gum: Dissolution/Disintegration

INITIAL

22C

50 hours

Formulated Aqueous, pH 11.5

5% w/MEA 3% w/Na2CO3

As-Is

100%As-Is

100%

As-Is

100%As-Is

100%

Aqueous Commercial Cleaners

pH 13 pH 10.5

N,N-Dimethyl 9-Decenamide d-Limonene NMP DCM Degreaser Cleaner



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Conformational Analysis: Ab-Initio Calculations Pending

N,N-Dimethyl 9-Decenamide - Linear

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

N,N-Dimethyl 9-DecenamideH-bonded in a hypothesized

looped configuration

• 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 H –C-C-, but much less than water H-O-

• Perhaps the lowest energy conformation in dilute aqueous solution for H-C=C- ? TBD



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Solution Behavior: Minimize Hydrophobe Contact with H2O

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

hypothesized cyclic configuration

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 H2

O

RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION

>



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hypothesized cyclic configuration



O


>



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hypothesized looped conformation



O


>

l l l h


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Applications: Nail Polish RemoversRequires >50% Acetone and/or Ethyl Acetate

Typically contain 90+% Organic Solvent

87% Water3% N,N-Dimethyl 9-Decenamide

1.5% Citrus Fragrance0.3% Sodium Carbonate

Balance: High HLB co-emulsifier


5% MEA


Patent Pending

blend with great

synergy and new

mechanism(s)WO2013162926(A1)

OR

l l l h


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5% MEA


Patent Pending

blend with great

synergy and new


OR

A li i il li h


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5% MEA


Patent Pending

blend with great

synergy and new


OR

A li i “W l ” H d Cl


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Applications: “Waterless” Hand Cleaners Requires >50% Emulsified Petroleum Distillates or Soy Methyl Ester






5% MEA


Patent Pending

blend with great

synergy and new


OR

A li i “W l ” H d Cl


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5% MEA


Patent Pending

blend with great

synergy and new


OR

A li ti “W t l ” H d Cl


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5% MEA


Patent Pending

blend with great

synergy and new


OR

A li ti Bl d St i R


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Applications: Blood Stain Remover

Typically Requires Peroxide or Hypochlorite




Mechanism: De-Chelation of Chromophores (UV-Vis)

Patent Pending

blend with great

synergy and new


Commercial

Peroxide

Product

Decenamide +

Citrus +

Carbonate +

Co-Emulsifier

A li ti Bl d St i R


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Applications: Blood Stain Remover

Typically Requires Peroxide or Hypochlorite





Patent Pending

blend with great

synergy and new


Commercial

Peroxide

Product

Decenamide +

Citrus +

Carbonate +

Co-Emulsifier

A li ti M k R


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Applications: Marker Remover

Typically Requires IPA or Acetone: Not Good for Surfaces

95% Water

1% N,N-Dimethyl 9-Decenamide0.5% Citrus Fragrance

0.1% Sodium Carbonate



Patent Pending

blend with greatsynergy and new


Commercial

Marker

Remover

Product

Decenamide +

Citrus +

Carbonate +

Co-Emulsifier

A li ti M k R


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Applications: Marker Remover

Typically Requires IPA or Acetone: Not Good for Surfaces

95% Water

1% N,N-Dimethyl 9-Decenamide0.5% Citrus Fragrance

0.1% Sodium Carbonate



Patent Pending

blend with greatsynergy and new


Commercial

Marker

Remover

Product

Decenamide +

Citrus +

Carbonate +

Co-Emulsifier

A li ti O Cl i


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Applications: Oven Cleaning

Typically Requires Caustic: pH 12-14

Some alkalinity required, but not caustic → Safer pH

85% Water5% Decenamide

5% MEA

pH 11.5

Commercial

Oven Cleaner

with Caustic

and Organic

Solvents

pH 12.5

Applications Materials Compatibility


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Applications: Materials Compatibility

SKIN

Plastics

Gaskets

and

Seals

• 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

• Immersion Tests: ASTM D543-95- Neat and formulated

• PET, HDPE, PP all OK

• Avoid PC (any amines/amide), PVC, Nylon

• Immersion Tests- Neat and formulated

• Teflon, Silicone, Peroxide Cured EPDM OK

•

Avoid Viton and Elastomers



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SKIN

Plastics

Gaskets

and

Seals


- 3% MEA









•




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SKIN

Plastics

Gaskets

and

Seals


- 3% MEA









•


Outline


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Outline




• Applications

– Cleaning

– Personal Care

•

Summary and Acknowledgements

Acknowledgements


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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


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THANK YOU !

It is nice to have

MET-10U today

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.

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The Power of "ene" in Water - Based Cleaners and Removers