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

A New-to-the-World Surfactant Makes Water Work Like an Organic Solvent

Ron A. Masters, PhDResearch Associate, Stepan Company

Outline

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

Stepan Derivatives Overview

Hallcomid

OnyxideSteposol

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”

N

O

Outline


Molecule: Reaction, Chemistry, Properties

O

O

N

N

O

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

Molecule: Reaction, Chemistry, Properties

O

O

N

N

O

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, 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, 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

emai

ning

Days (x3 for As-Is)

6% Emulsified at 80C, pH 36% Emulsified at 80C, pH 11100% 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(Oxidative)For All Data

As-Is Properties: Kauri-Butanol >1000

What does this mean ?

Kauri ResinO

H

Kauri resin is soluble in butanol, less soluble in other solventsAdd test solvent to dilute the butanol solution of resinAt some added amount the resin precipitates due to insolubilityThe more added to the endpoint, the higher the Kb valueResins are common tackifiers for adhesives and coatings High Kb value = good cleaning and removal performance

Test Solvent

As-Is Properties: Kauri-Butanol >1000

What does this mean ?

Kauri Resin

Kauri resin is soluble in butanol, less soluble in other solventsAdd test solvent to dilute the butanol solution of resinAt some added amount the resin precipitates due to insolubilityThe more added to the endpoint, the higher the Kb valueResins are common tackifiers for adhesives and coatings High Kb value = good cleaning and removal performance

Test Solvent

Saturated Analog ≈ 300 Kb value

As-Is Properties: Hansen Map

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

Large Hansen

“Radius” 12.9 Units

As-Is Properties: Hansen Map

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

“ene”

“ane”

N

O

O

N

O

OO

Evidence For Some Type of

Interaction Between -C=C- and Carbonyl

Formulated 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

Formulated Properties: CMC & Solubility

25

30

35

40

45

50

55

60

0.005 0.05 0.5 5 50

Surfa

ce T

ensi

on (m

N/m

)

Concentration (wt. %)

CMC calculates ≈ 500 - 1000 ppmSolubility Limit ≈ 1500 ppm

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”0

1020304050607080

0 5000 10000

N,N-Dimethyl Decanamide

N,N-Dimethyl 9-Decenamide

“ane” main use is as an Ag solvent for Stepan customers to make pesticide formulations

Outline


“Making Water Work Like an Organic Solvent”

Applications: 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

O

H

H

H

H

O

N

H

O

H

N

O

N

O

H

HCl

Cl O

H

O

N

H

HO

H

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

Applications: Nail Polish RemoversRequires >50% Acetone and/or Ethyl AcetateTypically contain 90+% Organic Solvent

87% Water3% N,N-Dimethyl 9-Decenamide1.5% Citrus Fragrance0.3% Sodium CarbonateBalance: High HLB co-emulsifier

85% Water5% N,N-Dimethyl 9-Decenamide5% MEA

“Making Water Work Like an Organic Solvent”

Patent Pending blend with great synergy and new mechanism(s)WO2013162926(A1)

OR

Applications: Pre-Wash Stain RemoverTypically Requires Peroxide or Hypochlorite


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


Commercial Peroxide Product

Decenamide + Citrus + Carbonate +Co-Emulsifier

Applications: Permanent Marker RemoverTypically Requires IPA or Acetone: Not Good for Surfaces


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


Commercial Marker Remover Product

Decenamide + Citrus + Carbonate +Co-Emulsifier

Applications: Oven CleaningTypically Requires Caustic: pH 12-14

Some alkalinity required, but not caustic → Safer pH

85% Water5% Decenamide5% MEApH 11.5

Commercial Oven Cleaner with Caustic and Organic Solvents pH 12.5

Aerosol Can

Applications: Aerosol TestsPasses 1-Month 50C Stability in Flairosol® Package

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

STEPOSOL® CITRI-MET diluted 1:4 Water-based Graffiti RemoverDI Water

Commercial Retail APCSTEPOSOL® CITRI-MET diluted 1:14 Bug/Tar Remover, Spot Remover, APC

Applications: Aerosol Tests (continued)Aerosol Droplet Size Distributions (mm)*

* PSD Data obtained by Spray Analytics, Lincolnshire IL

Liquid Dx(10) Dx(50) Dx(90) ST (mN/m) KeyDI Water 40.0 65.6 107.9 72 ------Retail Cleaner 40.6 71.7 130.6 29 oooo

CITRI-MET diluted 1:14 36.5 73.7 170.3 27.6 mmmm

CITRI-MET diluted 1:4 45.4 122.6 624.0 28.2 uuuu

The strongest cleaner has the larger PSD Analysis a

Applications: Aerosol Tests (continued)Aerosol Droplet Size Distribution Analysis (mm)*

* PSD Data obtained by Spray Analytics, Lincolnshire IL

Liquid Dx(10) Dx(50) Dx(90) ST (mN/m) KeyDI Water 40.0 65.6 107.9 72 ------Retail Cleaner 40.6 71.7 130.6 29 oooo

CITRI-MET diluted 1:14 36.5 73.7 170.3 27.6 mmmm

CITRI-MET diluted 1:4 45.4 122.6 624.0 28.2 uuuu

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 dominates1 Atomization Concept and Theory, Graco Inc. Minneapolis, MN 2014

http://wwwd.graco.com/training/concept_and_theory/Atomization%20v2.pdf

More on the Flairosol® PackageNo-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

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

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 haveMET-10U today

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.

POWER OF THE DOUBLE BOND TM

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

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