2011 STLE Annual Meeting66th Annual Exhibition

Atlanta, GA

The Synergex ® Alkanolamines

Presentation Outline

1) Brief description of Taminco

2) Brief description of the Synergex® AAA’s

3) Material related to Volatility/VOC

4) Material related to Colloid stability

5) Material related to Biostability

6) AAA Derivatives of Interest

Taminco: The AMINe COmpany

leading supplier of aminesand

derived molecules1000 people

Round the Globe

N

Taminco at a glance - THE AMINE COMPANY

• Activity leading supplier of alkylamines and derivatives• Turnover € 715 million (2010)• Personnel ±800 people in 16 countries• Production 8 sites

• Europe: Gent – Belgium, Leuna – Germany• Asia: Shanghai, Yixing & Nanjing – China• Americas: Pace & St Gabriel-USA, Camaçari – Brazil

• Installed productioncapacity 1 million tonnes per annum

• Sales Offices USA, Mexico, Brazil, Argentina, England, Belgium, France, Germany, Italy, Hungary, India, Japan, China, Malaysia, Philippines, Australia

Amines& Solvents

SpecialtyDerivativesPerformanceChemicals

CropProtection

HerbicideSystemsFeedAdditives

Fields of activity – it’s all about amines!

The Synergex ® Product Line

• Synergex®: excellent supplementary biostability, low volatility & odor, good corrosion inhibition, colloid stabilization

• Synergex®-T: good supplementary biostability, tertiary amine, very low volatility & odor, colloid stabilization

• Synergex®-T-Plus: next-generation supplementary biostability at low concentration, tertiary amine, very low volatility & odor, myco-control stability, emulsifier

Synergex & the Metalworking Market

� Low/Zero VOC

� Longer Life Fluids

� Enhanced Colloid Stability

� High Performance

Fluid Longevity

1) Lower Vapor Pressure = Less Evaporation

2) Lower Vapor Pressure = Less VOC

3) Better Colloid Stability = Longer Life

4) Better Biostability = Longer Life

Vapor Pressure, VOC &Fluid Longevity

Lower Vapor Pressure = Less Evaporation

Evaporation Rates of someN-Alkylalkanolamines (RT)

Alkanolamine Hours % Remaining

AAA I (high MW, 1 -OH) 75 100%

AAA I (high MW, 2 -OH) 75 100%

AAA I (mid MW, 2 -OH) 75 100%

AAA I (mid MW, 1 -OH) 75 95%

AAA I (low MW, 1 -OH) 75 65%

AAA II (low MW, 1 -OH) 75 65%

AAA I (high MW, 1 -OH) 170 100%

AAA I (high MW, 2 -OH) 170 100%

AAA I (mid MW, 2 -OH) 170 100%

AAA I (mid MW, 1 -OH) 170 80%

AAA I (low MW, 1 -OH) 170 20%

AAA II (low MW, 1 -OH) 170 20%

Vapor Pressure, VOC &Fluid Longevity

Lower Vapor Pressure = Less VOC

VOC & the Definition of Volatility

• Volatility is a generic term referring to some type of tendency for a condensed phase material (usually a liquid) to transfer to the gas phase.

• Volatility can be assessed by odor, flammability, etc.

• For scientific & regulatory purposes, volatility must be quantified in a precise and accurate manor. The only reasonable scientific measurement of volatility is derived by equating it with vapor pressure.

• The vapor pressure of a liquid (material) depends on the composition of the liquid phase, the composition of gas phase and on the temperature.

Two Parameters: Log(P) = A/T + BDBAE (GMW = 173.30, CAS RN 102-81-8): Below is a table of the literature data that we could find for the boiling point of DBAE versus pressure. BP (oC) BP (oK) P (torr) P (KPa) Reference

230 503.15 760 101.3232 Bouilloux; Bull.Soc.Chim.Fr.; 1958; 1446. 227 500.15 738 98.3902 Burnett et al.; J.Amer.Chem.Soc.; 59; 1937; 2249. 118 391.15 17 2.2664 Leonard; Simet; J.Amer.Chem.Soc.; 77; 1955; 2855, 2857. 100 373.15 0.8 0.1067 Perrine; J.Org.Chem.; 18; 1953; 1356,1361. 85 358.15 3.5 0.46662 Hannig; Haendler; Arch.Pharm.(Weinheim Ger.); 290; 1957; 131,133.

^^ r2 = 0.999942 Apparent ∆Hvaporization = 55.86 KJ/mole & ∆Svaporization (1 Torr) = 166.39 J/(mole-K)

Real Relative Volatility

Measure as close to the use temperature as is possible

T Ramp TGA of Vantex-T (first derivative)

Relative Volatility requires the use of thermal methods

CompounddW/dt

@ 50 oCdW/dt

@ 80 oCdW/dt

@ 110 oCdW/dt

@ 140 oCdW/dt

@ 180 oCdW/dt

@ 210 oCBP

Methyl Palmitate ND0.005

>180 min0.11

(12 min)0.6

2.2 min3.1

0.4 min- 330 oC

TEA0.005

180 min0.005

150 min0.01

60 min0.129 min

1.01 min

3.20.5 min

335 oC

Glycerol0.005

180 min0.02

37 min0.146 min

0.622 min

3.30.4 min

8.30.1 min

290 oC

BDEA0.005

180 min0.08

14 min0.462 min

2.30.5 min

7.60.1 min

- 285 oC

2-methylhexadecane0.007

130 minutes0.10

11.5 min0.642 min

2.40.5 min

7.30.2 min

- 294 oC

Hexadecane0.01

120 min0.10

14 min0.622 min

2.60.5 min

8.50.1 min

- 285 oC

TXIB0.01

80 min0.166 min

0.801 min

4.20.4 min

- - 280 oC

AEPD0.03

40 min0.186 min

0.731.7 min

2.00.6 min

7.30.2 min

- 260 oC

DBAE0.158 min

0.941.3 min

3.70.33 min

9.50.1 min

- - 230 oC

TBA0.3

3 min2.1

0.6 min6.8

0.2 min13.1

0.1 min- - 215 oC

MEA0.403 min

2.40.5 min

7.40.2 min

140.1 min

- - 170 oC

AMP0.76

1.6 min3.2

0.4 min9.5

0.1 min- - - 165 oC

The derivative weight loss (% weight loss per minute) of 12 compounds of interest in industry at different temperatures after 1.25% (≈ 40 mg total weight, 0.5 mg weight loss) of material evaporated with nitrogen purge. The time in minutes where the derivative weight loss was taken is given below the weight loss value. A dash indicates that data was irrelevant owing to evaporation occurring too quickly, ND = “not detectable”. The BP (normal boiling point) is rounded to the nearest 5 oC.

Exemplary Derivative Weight Loss Ratios

What is the best way to measure volatility?

Thermal methods operated under conditions as close as possible to the use conditions work the best

Metalworking industryis on the right track.

ASTM E1868Weight Loss at 81 oC for 110 minutes

Still an issue when applied to purematerials versus formulated fluids.

Interfacial Tension &Colloid Stability

1) Emulsion Stability: low l/l interfacial tension

2) Wetting: low s/l interfacial tension

3) Foam (form & break): low g/l interfacial tension

Semi-Synthetic Concentrate (Reference)

• 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 40 g/Kg• Water Balance

Why is Liquid/Liquid Interfacial Tension Important

Oil in water emulsions are destabilized by large increase in oil/water surface area.

E = Gwater+ Goil + γwater/glassAwater/glass+ γwater/airAwater/air+ γwater/oilAwater/oil

The Lower the Oil/Water Interfacial Tension, the More Stable the Oil/Water Emulsion

∆E = (γwater/oil)∆Awater/oil - T∆Smixing

Why is Liquid/Liquid Interfacial Tension Important

Contact angle versus drop weight

Tate’s LawDrop Shape Analysis

Capillary Contact Angle(new method)

2πrγ = drop volume x ∆ρ = drop weight

0

10

20

30

40

50

60

Synergex Synergex T MAE DGA MEA TEA Water

Inte

rfac

ial T

ensi

on (d

ynes

/cm

)

5% wt/wt Alkanolamine(aq)

Versus Soybean Oil

Liquid/Liquid Interfacial Tension in dynes/cm

Correlation of Interfacial Tension Measurements

0

10

20

30

40

50

60

70

80

90

0 10 20 30 40 50 60 70 80 90

Tension (drop weight)

Ten

sion

(ne

wer

met

hod)

Drop weight versus bubble pressureDrop Weight versus Contact AngleBest Fit Line - Bubble PressureBest Fit Line - Contact Angle

600 grams of DI water300 grams of Synergex-T-Plus60 grams of Synergex-Tadd sebacic acid to suit

Overall Fluid Performance

1) low volatility = less evaporation

2) colloid stability = stable emulsions

3) low VOC = regulatory stability

4) AAA = biostability too

Full Synthetic Concentrate Starting Formula: Synergex®-T-Plus 3%

or

Synergex®-T 5% _____________________________________________________________________________

MDEA 10% - adjust Isononanoic acid 8% Polartech SGL 20% Phenoxyethanol up to 10% Water ≈ 50% • Addition of preferred corrosion inhibitors recommended

Note that diethanolamines like Synergex ®-T and Synergex ®-T-Plus are known to provide exceptional biostabilizing synergy in fully synth etic metalworking fluids (see; Golec, K.; Hill, E.C.; Kazemi, P.; Skold, R. O.; Tribology International 1989, 22(6), 375 – 382.)

or 50 ppm BIT in operating fluid

Emulsifiers and Dispersants

New Materials based on Synergex ® AAA’s

Model Formulation for Soluble Concentrate Using TecGARD 235 (PIBSA) Step 1 1. To a 250 ml beaker add

a. 40.0 g of 100 SUS naphthenic mineral oil b. 9.2 g of TG 235 c. 2.3 g of 45% KOH in water

2. Stir and heat up to 160 F for 15 minutes 3. Allow blend to cool Step 2 1. To the blend prepared in step 1, add:

a. 1.0 g Hexylene glycol b. 2.8 g Oleic acid c. 1.1 g Triethanol amine d. 2.5 g Tomadol 1-3

2. Stir for one to two minutes after each additive has been added. 3. Add 41.1 g 100 SUS naphthenic oil to the blend 4. Stir for 15 minutes Mixture should be bright and clear.

R

O

O

O

R

Neutral Dispersant Fuel/Lube Additive

RNH2

N

O

O

R

− H2O

R

O

O

O

1 BAE + 1 BDEA

R

O

O N OH

OHN

OH

Water Soluble O/W Emulsifier

OH

R

O

O

O

R

Anionic Surfactant Type

H2O

O

OH

Amine

R

O

OO

O

RR'R"NH

RR'R"NH

HO

O

The ReactionSequenceMake a difference.

PIBSA Type Emulsifiers/Dispersants

R

alpha-olefin

catalyst R

internal olefin

OOO

R

O

O

O∆

1 BAE + 1 BDEA

R

O

O N OH

OHN

OH

Water Soluble O/W Emulsifier

OH

ASA Derivativeswith better biostability

Synergex – ASA is as good an emulsifier as SulfonatedPetroleum Oil, PIBSA Derivatives and/or Rapeseed Acid Isopropanolamides.

From truckloads of amines to metalworking additives to a technology development partner

Taminco is a full service specialty amines provider

www.Taminco.comwww.SpecialtyAmines.com

THANK YOU !

Visit us at Booth 3

More information:

www.taminco.comwww.specialtyamines.comwww.SynergexAmine.com

Synergex

• Boiling Point = 200 oC

• Freezing Point = - 20 oC

• Amine mequiv per gram = 8.53

• mg KOH equiv. per gram = 478

• pKa = 10.03

Synergex-T• Boiling Point = 285 oC

• Melting Point = - 70 oC

• Amine mequiv per gram = 6.20

• mg KOH equiv. per gram = 347

• pKa = 8.91

Synergex-T-Plus

• Boiling Point = 140 oC @ 1 Torr

• Melting Point < - 25 oC

• Amine mequiv per gram = 4.61

• mg KOH equiv. per gram = 258

• pKa = 8.74