The use of adducts of n alkylalkanolamines (aaa’s

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

18th International

Colloquium Tribology

Technische Akademie Esslingen

January 10 – 12, 2012

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

The Lower the Oil/Water Interfacial Tension, the

More Stable the Oil/Water Emulsion

Energy difference between O/W emulsion and two

separate oil & water phases

E = (water/oil)Awater/oil - TSmixing

ASA = Alkene Succinnic Anhydride

Olefin can also be derived from polyisobutylene or polypropylene

1) PIBSA/ASA Derivatives

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 and

ammonium 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 and

ammonium 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 and

ammonium carboxylates

Tertiary AAA with two EO may yield bridging ester/carboxylates in addition to

hemiester internal carboxylates with one unreacted hydroxyl group

Reaction of ASA with sufficient secondary AAA favors amide

ASA/AAA Adducts; mixed amide, ester and

ammonium carboxylates

Analysis of AAA/ASA Adducts

1 2

3

ester amide

BAE/salt

80% Amide / 20% Ester

ASA Olefin Approximate Cost

OSA 1-octene $2.25 / pound

DDSA propylene tetramer

2 regioisomers $2.35 / pound

HDSA -hexadecene

isomerized $1.75 / pound

ODSA -octadecene

isomerized $1.75 / pound

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)

DMAE (3º, 1 hydroxy group) Hemiester Internal Carboxylate

(Ammonium)

MDEA (3º, 2 hydroxy groups) Bridged Ester/Carboxylate, Hemiester

Internal Carboxylate (Ammonium

MAE, EAE, BAE (2º) Amide/Carboxylate (Ammonium)

BAE/BDEA (2º/3º) Amide/Carboxylate (Ammonium)

(Ammonium Tertiary)

The ASA Starting Material

Adding AAA to ASA maximizes bridged ester/amide; larger molecules

Adding ASA to AAA maximizes amide/carboxylate; smaller molecules

Tag ASA AAA Stoichiometry & Order of

Addition

A C20 – C24 BAE 1 AAA to ½ ASA; T < 60 ºC

B C20 – C24 BAE ½ ASA to 1 AAA; T < 60 ºC

C DDSA BAE ½ ASA to 1 AAA; T < 60 ºC

D ODSA BAE ½ ASA to 1 AAA; T < 60 ºC

E ODSA BAE/BDEA ½ ASA to 1 BAE/BDEA; T < 60 ºC

F OSA BDEA 1 ASA to 1 AAA; T < 60 ºC

G OSA Bis(DMAPA) 1 bis(DMAPA) to 1 ASA

H C20 – C24 Bis(DMAPA) 1 bis(DMAPA) to 1 ASA

Observations in a Medium Oil Semi-Synthetic (MOSS)

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

Alkanolamide

Substitute Resulting Coolant Concentrate

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

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

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

Observations in a Medium Oil Semi-Synthetic (MOSS)

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

0

10

20

30

40

50

60

70

80

0.00% 10.00% 20.00% 30.00% 40.00% 50.00% 60.00%

Solution Composition (%)

Su

rfa

ce t

en

sio

n (

dy

nes/

cm

)

Surface Tension of Aqueous Solutions of Some AAA’s

20

15

13

12

10

HLB

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.