The use of adducts of n alkylalkanolamines (aaa’s

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

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

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

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

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

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

1) PIBSA/ASA Derivatives ASA = Alkene Succinnic Anhydride Olefin can also be derived from polyisobutylene or polypropylene

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

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

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

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

ASA/AAA Adducts; mixed amide, ester andammonium carboxylates Reaction of ASA with sufficient secondary AAA favors amide

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-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

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)

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

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

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

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

2) Alkanolamides

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

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 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 (%)

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 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.

The use of adducts of n alkylalkanolamines (aaa’s

by Taminco Specialty Amines on Jan 13, 2012

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