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

Transcription

1 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

2 Outline Metathesis Derivatives Program Molecule: Reaction, Chemistry, Properties Solution Behavior Applications Cleaning Personal Care Summary and Acknowledgements

3 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

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: 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

6 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

7 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?

8 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

9 Outline Metathesis Derivatives Program Molecule: Reaction, Chemistry, Properties Solution Behavior Applications Cleaning Personal Care Summary and Acknowledgements

10 Molecule: Reaction, Chemistry, Properties Amide 97% minimum (99% Typical) Water 0.5% maximum ( % Typical) Residual Ester 1.0% maximum ( % Typical) Iodine Value (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

11 Molecule: Reaction, Chemistry, Properties Amide 97% minimum (99% Typical) Water 0.5% maximum ( % Typical) Residual Ester 1.0% maximum ( % Typical) Iodine Value (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

12 Molecule: Reaction, Chemistry, Properties Amide 97% minimum (99% Typical) Water 0.5% maximum ( % Typical) Residual Ester 1.0% maximum ( % Typical) Iodine Value (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

13 % Remaining Molecule: Reaction, Chemistry, Properties Chemical Stability: As-Is and Formulated % Emulsified at 80C, ph 3 6% Emulsified at 80C, ph % As-Is at 54C Air Headspace For All Data Days (x3 for As-Is) 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.

14 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

15 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

16 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

17 Molecule: Properties: Kauri-Butanol >1000 Saturated Analog, ane, 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

18 Molecule: Properties: Hansen Map Large Hansen Radius 12.9 Units N,N-Dimethyl 9-Decenamide is fully miscible with solvents within green line area

19 Ethylene Carbonate is miscible with N,N-Dimethyl 9-Decenamide, not Decanamide! Molecule: Properties: Hansen Map ene ane Evidence For Some Type of Interaction Between -C=Cand Carbonyl

20 Molecule: 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

21 Surface Tension (mn/m) Window of Opportunity: CMC & Solubility CMC calculates ppm Solubility Limit 1500 ppm Concentration (wt. %) N,N-Dimethyl 9-Decenamide, although very hydrophobic, can micellize in water

22 Window of Opportunity: CMC & Solubility N,N-Dimethyl 9-Decenamide ene Is Different From N,N-Dimethyl Decanamide ane 0 N,N-Dimethyl Decanamide N,N-Dimethyl 9-Decenamide

23 Outline Metathesis Derivatives Program Molecule: Reaction, Chemistry, Properties Solution Behavior Applications Cleaning Personal Care Summary and Acknowledgements

24 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

25 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

26 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

27 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%

28 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

29 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.

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

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

32 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

33 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.

34 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.

35 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 area 1 1 Detergency: Theory and Technology, Surfactant Science Series: v. 20, W. Gale Cutler and Erik Kisser, 1987, pp 314-5

36 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 area 1 1 Detergency: Theory and Technology, Surfactant Science Series: v. 20, W. Gale Cutler and Erik Kisser, 1987, pp 314-5

37 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

38 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

39 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 Making Water Work Like an Organic Solvent ane C=O stretch broadened to lower frequency (cm-1) for ene compared to ane Let s Watch

40 Making Water Work Like an Organic Solvent Chewing Gum: Dissolution/Disintegration Formulated Aqueous, ph 11.5 As-Is 5% w/mea 3% w/na 2 CO 3 100% As-Is 100% As-Is 100% As-Is 100% Aqueous Commercial Cleaners ph 13 ph 10.5 INITIAL 22C 50 hours N,N-Dimethyl 9-Decenamide d-limonene NMP DCM Degreaser Cleaner

41 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 H 2 O 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

42 Making Water Work Like an Organic Solvent Solution Behavior: Minimize Hydrophobe Contact with H 2 O Hydrophobe in H 2 O 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 H 2 O RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION > N,N-Dimethyl 9-Decenamide H-bonded to H 2 O N,N-Dimethyl 9-Decenamide H-bonded hypothesized cyclic configuration

43 Making Water Work Like an Organic Solvent Solution Behavior: Minimize Hydrophobe Contact with H 2 O Hydrophobe in H 2 O 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 H 2 O RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION > N,N-Dimethyl 9-Decenamide H-bonded to H 2 O N,N-Dimethyl 9-Decenamide H-bonded hypothesized cyclic configuration

44 Making Water Work Like an Organic Solvent Solution Behavior: Minimize Hydrophobe Contact with H 2 O Hydrophobe in H 2 O 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 H 2 O RELATIVE SURFACE AREA EXPOSED TO WATER MOLECULES IN SOLUTION > N,N-Dimethyl 9-Decenamide H-bonded to H 2 O N,N-Dimethyl 9-Decenamide H-bonded hypothesized looped conformation

45 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

46 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

47 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

48 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) WO (A1) Making Water Work Like an Organic Solvent

49 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) WO (A1) Making Water Work Like an Organic Solvent

50 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) WO (A1) Making Water Work Like an Organic Solvent

51 Applications: Blood Stain Remover Typically Requires Peroxide or Hypochlorite Commercial Peroxide 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)

52 Applications: Blood Stain Remover Typically Requires Peroxide or Hypochlorite Commercial Peroxide 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)

53 Applications: 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)

54 Applications: 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)

55 Applications: Oven Cleaning Typically Requires Caustic: ph Commercial Oven Cleaner with Caustic and Organic Solvents ph % Water 5% Decenamide 5% MEA ph 11.5 Some alkalinity required, but not caustic Safer ph

56 Applications: Materials Compatibility SKIN 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 Plastics Gaskets and Seals Immersion Tests: ASTM D 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

57 Applications: Materials Compatibility SKIN 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 Plastics Gaskets and Seals Immersion Tests: ASTM D 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

58 Applications: Materials Compatibility SKIN 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 Plastics Gaskets and Seals Immersion Tests: ASTM D 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

59 Outline Metathesis Derivatives Program Molecule: Reaction, Chemistry, Properties Solution Behavior Applications Cleaning Personal Care Summary and Acknowledgements

60 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

61 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.