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18th International                        Colloquium Tribology                   Technische Akademie Esslingen            ...
Common Emulsifiers/Dispersants   •   Synthetic/Petroleum Sulfonates       •   e.g., Underbased Sodium MW = 460 Alkylaryl S...
Semi-Synthetic Concentrate (low oil coolant)     •   100 SUS Naphthenic Oil                 72 g/Kg     •   60% Sulfonated...
Today’s Talk    •   Petroleum Sulfonates         •   e.g., Sulfonated100SUS Naphthenic Oil    •   1) PIBSA/ASA Derivatives...
Why is Liquid/Liquid Interfacial Tension Important        Oil in water emulsions are destabilized by large increase       ...
Why is Liquid/Liquid Interfacial Tension Important     Energy difference between O/W emulsion and two                separ...
1) PIBSA/ASA Derivatives              ASA = Alkene Succinnic Anhydride   Olefin can also be derived from polyisobutylene o...
Applications of ASA Derivatives    •   Reaction of ASA with cellulose hydroxyls; paper sizing    •   Ammonium carboxylate ...
ASA/AAA Adducts; mixed amide, ester andammonium carboxylates           Simple Hydrolysis followed by Neutralization with A...
ASA/AAA Adducts; mixed amide, ester andammonium carboxylates       Tertiary AAA with one EO provides hemiester internal ca...
ASA/AAA Adducts; mixed amide, ester andammonium carboxylates      Tertiary AAA with two EO may yield bridging ester/carbox...
ASA/AAA Adducts; mixed amide, ester andammonium carboxylates           Reaction of ASA with sufficient secondary AAA favor...
Analysis of AAA/ASA Adducts
80% Amide / 20% Ester                3                BAE/salt    1 2  ester amide
The ASA Starting Material           ASA                Olefin          Approximate Cost           OSA               1-octe...
The ASA Starting Material               AAA                 ASA/AAA Type (Direct Reaction)        MEA, AMP, MIPA (1º)     ...
Stoichiometry & Order ofTag     ASA           AAA                                            AdditionA     C20 – C24      ...
Observations in a Medium Oil Semi-Synthetic (MOSS)                                 Alkanolamide                           ...
Observations in a Medium Oil Semi-Synthetic (MOSS)                               Syn-Ester                               S...
AAA/ASA Conclusions                          Replace TOFA/DIPA Amide   •   A = BAE bridged C20/C24 ASA works best   •   B ...
2) Alkanolamides
BAE Lactamide as Emulsifier(MOSS; BAE Lactamide can replace Boramide)      • Oil                                          ...
New AAA’s for Metalworking   3) Alkanolamines in the Emulsion
A Practical Possibility                          LD50(female rat) >> 2000 mg/kg
Surface Tension of Aqueous Solutions of Some AAA’s                             80                             70          ...
Biostability & Emulsion Stability Connected?
The RBC (Red Blood Cell)Lysis Assay
Conclusions    •   ASA/AAA derivatives prepared from normal starting        materials but by atypical reactions can be use...
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
The use of adducts of n alkylalkanolamines (aaa’s
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The use of adducts of n alkylalkanolamines (aaa’s

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The Use of Adducts of N-Alkylalkanolamines (AAA’s) with Alkenyl Succinic Anhydrides (ASA’s), AAA carboxamides and structurally unique AAA’s as Emulsifiers in Metalworking Fluids.

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Transcript of "The use of adducts of n alkylalkanolamines (aaa’s"

  1. 1. 18th International Colloquium Tribology Technische Akademie Esslingen January 10 – 12, 2012The Use of Adducts of N-Alkylalkanolamines (AAA’s) withAlkenyl Succinic Anhydrides (ASA’s), AAA carboxamides and structurally unique AAA’s as Emulsifiers in Metalworking Fluids
  2. 2. Common Emulsifiers/Dispersants • Synthetic/Petroleum Sulfonates • e.g., Underbased Sodium MW = 460 Alkylaryl Sulfonate • PIBSA/ASA Derivatives • e.g., Hydrolyzed PIBSA ammonium salts • Tall Oil Fatty Acid Carboxylates • e.g., Neutralized Fatty Acids (KOH) • Alkanolamides • e.g., DIPA Amide of TOFA • Nonionic Surfactants (PAG’s) • e.g., EO/PO block copolymers • High & Low HLB Fatty Esters • e.g., Triacyl Glyceride & TOFA PEG Ester
  3. 3. Semi-Synthetic Concentrate (low oil coolant) • 100 SUS Naphthenic Oil 72 g/Kg • 60% Sulfonated Naphthenic Oil 72 g/Kg • DEA Fatty Acid Amide 72 g/Kg • Tall Oil Fatty Acid (5% Rosin) 72 g/Kg • BASF 17R4 Nonionic Surfactant 24 g/Kg • Triethanolamine (85%) 100 g/Kg • Alkanolamine (emulsifier?) 40 g/Kg • Water Balance
  4. 4. Today’s Talk • Petroleum Sulfonates • e.g., Sulfonated100SUS Naphthenic Oil • 1) PIBSA/ASA Derivatives • Novel ASA/AAA derivatives • Tall Oil Fatty Acid Carboxylates • e.g., Neutralized Fatty acids • 2) Alkanolamides • AAA Amides • 3) Alkanolamines in the Emulsion • Novel AAA’s • Nonionic Surfactants (PAG’s) • e.g., EO/PO block copolymers • High & Low HLB Fatty Esters • e.g., Triacyl Glyceride & TOFA PEG Ester
  5. 5. Why is Liquid/Liquid Interfacial Tension Important Oil in water emulsions are destabilized by large increase in oil/water surface area E = Gwater+ Goil + water/glassAwater/glass+ water/airAwater/air+ water/oilAwater/oil
  6. 6. Why is Liquid/Liquid Interfacial Tension Important Energy difference between O/W emulsion and two separate oil & water phases E = (water/oil)Awater/oil - TSmixing The Lower the Oil/Water Interfacial Tension, the More Stable the Oil/Water Emulsion
  7. 7. 1) PIBSA/ASA Derivatives ASA = Alkene Succinnic Anhydride Olefin can also be derived from polyisobutylene or polypropylene
  8. 8. Applications of ASA Derivatives • Reaction of ASA with cellulose hydroxyls; paper sizing • Ammonium carboxylate corrosion inhibitors • Ammonium carboxylate functional fluid emulsifiers • Imide dispersants in fuels and engine lubricants • ASA amide/carboxylate adhesives • Functionalized starch based food emulsifiers
  9. 9. ASA/AAA Adducts; mixed amide, ester andammonium carboxylates Simple Hydrolysis followed by Neutralization with AAA; anionic surfactants; fatty acid analogs Reaction with primary amine with removal of water to yield imide; common fuel & lube dispersants additives
  10. 10. ASA/AAA Adducts; mixed amide, ester andammonium carboxylates Tertiary AAA with one EO provides hemiester internal carboxylate; commonly used emulsifier in explosive formulations Secondary AAA may yield some hemiester internal carboxylate, but amide formation usually predominates
  11. 11. ASA/AAA Adducts; mixed amide, ester andammonium carboxylates Tertiary AAA with two EO may yield bridging ester/carboxylates in addition to hemiester internal carboxylates with one unreacted hydroxyl group
  12. 12. ASA/AAA Adducts; mixed amide, ester andammonium carboxylates Reaction of ASA with sufficient secondary AAA favors amide
  13. 13. Analysis of AAA/ASA Adducts
  14. 14. 80% Amide / 20% Ester 3 BAE/salt 1 2 ester amide
  15. 15. The ASA Starting Material ASA Olefin Approximate Cost OSA 1-octene  $2.25 / pound propylene tetramer DDSA  $2.35 / pound 2 regioisomers -hexadecene HDSA  $1.75 / pound isomerized -octadecene ODSA  $1.75 / pound isomerized Blended C20 – C24 isomerized  $2.30 / pound Blended C16 & C18 isomerized  $1.70 / pound
  16. 16. The ASA Starting Material AAA ASA/AAA Type (Direct Reaction) MEA, AMP, MIPA (1º) Imide (Neutral) Hemiester Internal Carboxylate DMAE (3º, 1 hydroxy group) (Ammonium) Bridged Ester/Carboxylate, Hemiester MDEA (3º, 2 hydroxy groups) Internal Carboxylate (Ammonium MAE, EAE, BAE (2º) Amide/Carboxylate (Ammonium) Amide/Carboxylate (Ammonium) BAE/BDEA (2º/3º) (Ammonium Tertiary)
  17. 17. Stoichiometry & Order ofTag ASA AAA AdditionA C20 – C24 BAE 1 AAA to ½ ASA; T < 60 ºCB C20 – C24 BAE ½ ASA to 1 AAA; T < 60 ºCC DDSA BAE ½ ASA to 1 AAA; T < 60 ºCD ODSA BAE ½ ASA to 1 AAA; T < 60 ºCE ODSA BAE/BDEA ½ ASA to 1 BAE/BDEA; T < 60 ºCF OSA BDEA 1 ASA to 1 AAA; T < 60 ºCG OSA Bis(DMAPA) 1 bis(DMAPA) to 1 ASAH C20 – C24 Bis(DMAPA) 1 bis(DMAPA) to 1 ASAAdding AAA to ASA maximizes bridged ester/amide; larger moleculesAdding ASA to AAA maximizes amide/carboxylate; smaller molecules
  18. 18. Observations in a Medium Oil Semi-Synthetic (MOSS) Alkanolamide Resulting Coolant Concentrate Substitute Lubrizol DF-1 * clear concentrate H unstable even with 3% NON & DGA A clear concentrate (best) B clear w/ 3.4% Nonionic (10 HLB) G unstable even with 3% NON & DGA E unstable even with 3% NON & DGA C unstable even with 3% NON & DGA ASA/AAA Comments H Hemiamide Internal C20/24 (pure, basic) A MW, bridged, C20/24 B Max Amide, C20/24 G Hemiamide Internal C8 (pure, basic) E Max Amide, C18, low 2º C Max Amide, C12 NON = blend of low & high HLB nonionic surfactants low HLB ethoxylated octylphenol and a high HLB ethoxylated nonylphenol (HLB 7.8 + HLB 12.9)/2 = HLB 10.35 average DGA = diglycolamine
  19. 19. Observations in a Medium Oil Semi-Synthetic (MOSS) Syn-Ester Substitute Resulting Coolant Concentrate GY-301 clear concentrate H clear concentrate A hazy concentrate, soft gel B hazy concentrate, very little gel G hazy before water, turns to soluble oil E clear concentrate F unstable even with 3% non & DGA C unstable even with 3% non & DGA D clear concentrate (best overall) ASA/AAA Comments H Hemiamide Internal (pure, basic) A MW, bridged, C20/24 B Max Amide, C20/24 G Hemiamide Internal (pure, basic) E Max Amide, C18, low 2º F Hemiester Ammonium C Max Amide, C12 D Max Amide, C18
  20. 20. AAA/ASA Conclusions Replace TOFA/DIPA Amide • A = BAE bridged C20/C24 ASA works best • B = BAE maximum amide with C20/C24 ASA works OK Replace Ammonium Monoalkylsuccinate (Syn-Ester) • D = BAE maximum amide with C18 ASA works best • H = bis(DMAPA) + C24/C20 ASA pure hemiamide works well • E = BAE/BDEA maximum amide with C18 ASA (low 2º) works well • G = bis(DMAPA) + C8 ASA pure hemiamide works OK In general, ASA + secondary AAA based compounds with maximum amide levels were found to be good biostatic enhancing emulsifier replacements for sulfonates or alkanolamides
  21. 21. 2) Alkanolamides
  22. 22. BAE Lactamide as Emulsifier(MOSS; BAE Lactamide can replace Boramide) • Oil 20% • Rapeseed Fatty Acid Diethanolamide 6% • Sodium Petroleum Sulphonate 4% • Sylvatal 25/30 (distilled tall oil) 6% • Oxazolidine (bactericide) 3% • IPBC 30 (fungicide) 0.5% • DEA-Boramide or BAE Lactamide 14% • JCol 2520 (alcohol ethoxylate) 1% • Water to 100% * JCol produced by J1Technologies, Trafford park, Manchester, UK
  23. 23. New AAA’s for Metalworking 3) Alkanolamines in the Emulsion
  24. 24. A Practical Possibility LD50(female rat) >> 2000 mg/kg
  25. 25. Surface Tension of Aqueous Solutions of Some AAA’s 80 70 HLBSurface tension (dynes/cm) 20 60 50 15 40 13 12 30 10 20 10 0 0.00% 10.00% 20.00% 30.00% 40.00% 50.00% 60.00% Solution Composition (%)
  26. 26. Biostability & Emulsion Stability Connected?
  27. 27. The RBC (Red Blood Cell)Lysis Assay
  28. 28. Conclusions • ASA/AAA derivatives prepared from normal starting materials but by atypical reactions can be useful emulsifiers in emulsion lubricants. • AAA Amides containing novel N-alkyl groups allow for, through novel distribution of hydrophobic and hydrophilic groups, enhanced emulsification. • Novel AAA’s with novel distribution of hydrophobic and hydrophilic groups, may enhance emulsification. • Certain aspects of biostability may be related to emulsification.
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