isofol esters · in figure 2 (brugger test). in summary, due to the superior properties of isofol...

ISOFOL EstersBranched Guerbet Esters

Sasol Performance Chemicals

2

ContentsISOFOL Esters – Branched Guerbet Esters

1. About us . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2. General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3. Introdution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4. Properties of ISOFOL alcohols . . . . . . . . . . . . . . . . . . . . 6

5. Comparing properties of various esters . . . . . . . . . 8–11

6. Properties of ISOFOL 2426S based Esters . . . . . 12

7. Potential formulations applying ISOFOL based Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

Contents

3

About usISOFOL Esters – Branched Guerbet Esters

1. About usSasol’s Performance Chemicals business unit markets a broad portfolio of organic and inorganic commodity and speciality chemicals. Our business employs about 1300 people in four key business divisions: Organics, Inorganics, Wax and PCASG (Phenolics, Carbon, Ammonia and Speciality Gases). Our offices in 18 countries serve customers around the world with a multi-faceted portfolio of state-of-the-art chemical products and solutions for a wide range of applications and industries.

Our key products include surfactants, surfactant intermediates, fatty alcohols, linear alkyl benzene (LAB), short-chain linear alpha olefins, ethylene, petrolatum, paraffin waxes, synthetic waxes, cresylic acids, high-quality carbon solutions as well as high-purity and ultra-high-purity alumina. Our speciality gases sub-division supplies its customers with high-quality ammonia, hydrogen and CO2 as well as liquid nitrogen, liquid argon, krypton and xenon gases.

Our products are as individual as the industrial applications they serve, with tailor-made solutions creating real business value for customers. Ongoing research activities result in a continuous stream of innovative product concepts that help our customers position themselves successfully in future markets.

Our products are used in countless applications in our daily lives to add value, security and comfort. Typical examples include detergents, cleaning agents, personal care, construction, paints and coatings, leather and metal processing, hot-melt adhesives, bitumen modification and catalyst support for automotive catalysts and other diverse specialty applications including oil and gas recovery, aroma production, plastic stabili-sation, and polymer production. Every day, our researchers explore ways to improve our products and develop innovations that improve the quality of people’s lives.

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General information / IntroductionISOFOL Esters – Branched Guerbet Esters

5

ISOFOL Esters – Branched Guerbet Esters General information / Introduction

2. General informationThis brochure relates to various esters based on branched alcohols and their application. Specific attention is given to alcohols derived by hydroformylation of olefins obtained by Fischer-Tropsch (FT) process from synthesis gas. Ester based on these alcohols are characterized by unique features like high flash point, excellent low temperature proper-ties, very low tendency to evaporate combined with good load carrying capacity, oxidative and hydrolytic stability. The combined features of these discussed products are key to high performance in formulations for many industrial applications like hydraulic fluids, crankcase oils, gear oils and greases to name only a few.

3. IntroductionEsters with the general formula R1O-C(=O)-R2, in which R1 and R2 independently of one ano-ther represent linear or branched or cyclic alkyl groups. The esters are for example formed by an esterification of linear and/or branched alcohols or mixtures of linear and/or branched alcohols and linear and/or branched and/or cyclic acids and are well known in industry [see IP.com publication 000011798: M. van der Merwe, D. Schär, D. Elberfeld in branched alcohols and alcohol mixtures, their derivatives and use obtained from homologation of FT-feed stocks, 2003]. Hence, multiple processes have been developed to access Guerbet alcohols [see for instance: a) P. Burk, J. Molecular Catalysis 1985, 33, 1-15; b) WO 9104242 1991; c) A. Wick, E. U. Mahnke, WO 2011054483] and applications of the alcohols and their corresponding esters have been found in the past [see for instance: DE 4341794; DE 19525109, DE 19960099].

For the various applications a multitude of esters are needed with different properties. New esters having improved properties like lower pour point, increased flash point, better viscosity temperature behavior and good spreading properties are needed to optimize the performance of the formulations in the final application.

6

Properties of ISOFOL alcoholsISOFOL Esters – Branched Guerbet Esters

Known Guerbet-based, mono branched alcohols are e.g. ISOFOL 16, ISOFOL 20, ISOFOL 24 and the FT-based multi- branched ISOFOL 2426S (see table 1). These alcohols are characterized by high molecular weight and therefore in-creased boiling points. Due to the 2-alkyl branching these alcohols also exhibit low pour points (e.g. ISOFOL 20 -20 °C). With increasing chain length the viscosity increases from

46 cSt @ 20 °C for ISOFOL 16 to approximately 141 cSt @ 20 °C for ISOFOL 2426S. Flash point of these Guerbet alcohols also rise with increasing chain length (see figure 1). Interes-tingly, the FT-based Guerbet alcohol ISOFOL 2426S exhibits a significantly lower pour point (-34 °C) compared to the corresponding ISOFOL 24, due to the methyl-branched structure of the ISOFOL 2426S.

The thermo-oxidative stability (1hr/180°C; air 19 mL/min) is comparable for all Guerbet alcohols (see figure 1). The volatile

loss is decreasing with higher chain length. Lowest loss of volatiles were observed with ISOFOL 2426S (below 60%).

4. Properties of ISOFOL alcohols

ISOFOL 16 ISOFOL 20 ISOFOL 24 ISOFOL 2426S

Appearance Clear, colorless Clear, colorless Clear, colorless Clear, colorless

Average g/mol ~ 242 ~ 298 ~ 354 ~ 354–382 Molecular weight

Water % 0.1 max 0.1 max 0.1 max 0.1 max

Hydroxyl value mg KOH/g 225-235 184-190 154-160 140-155

Carbonyl value mg KOH/g 0.3 max. 0.3 max. 0.3 max. <0.5

Ester value mg KOH/g 0.3 max. 0.5 max 0.5 max 0.5 max

Acid number mg KOH/g 0.05 max. 0.05 max. 0.05 max. <0.1

Iodine number mg Iod/100mg 0.5 max. 0.5 max. 0.5 max. <0.6

Color Hazen 10 max. 10 max. 10 max. 15 max.

Boiling point °C 294 324 >300 >300

Pour point °C -69 -21 -3 -34

Flash point °C 156 180 230 204

Kin. Viscosity @ 20°C cSt ~ 46 ~ 72 ~ 102 ~ 141 (ASTM D 7042)

Table 1: Properties of various ISOFOL-type alcohols (typical values)

7

Properties of ISOFOL alcoholsISOFOL Esters – Branched Guerbet Esters

Figure 1: Physico-chemical properties of ISOFOL alcohols

Also the loading capacity of all pure, non-doped ISOFOL alcohols exhibited excellent capacities beneath 30 N/mm² compared to data needed in formulated products as shown in figure 2 (brugger test).

In summary, due to the superior properties of ISOFOL alcohols and especially ISOFOL 2426S, these alcohols are ideal for minimum quantity lubrication, starting material for lubricant esters, components for rolling and stamping oils, base alco-hols for extended surfactants and as coupling agents in metal

working fluids. However, the multi-branched Guerbet alcohol ISOFOL 2426S exhibits very unique features like good lubrica-ting effect, low volatility, increased flash point, excellent low temperature properties together with high oxidative stability and good biodegradability.

Loading capacity (15 sec drop time)

ISOFOL 2426S N/mm² 25

ISOFOL 24 N/mm² 24,6

ISOFOL 20 N/mm² 21,4

ISOFOL 16 N/mm² <15

Figure 2: Loading capacity of various ISOFOL Guerbet alcohols

Recommendations [NOLD: 30 N/mm² for hydraulic fluids and engine oils; 50 N/mm² for greases and 70 N/mm² for gear oils]

Evaporation (after 24 hours @ 180 °C)

ISOFOL 16

100

80

60

40

20

0Vo

lati

le L

oss

[%]

ISOFOL 20 ISOFOL 24 ISOFOL 2426S

Thermo-oxidative Stability (180 °C, 19mL Air/min)

time [min]

250

200

150

100

50

0

cond

ucti

vity

[µS/

cm]

0 10 20 30 40 50 60

ISOFOL 16ISOFOL 20ISOFOL 24ISOFOL 2426S

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Comparing properties of various estersISOFOL Esters – Branched Guerbet Esters

Due to the above described superior properties of the multi-branched ISOFOL 2426S also the corresponding esters provide extraordinary properties for various applica-tions. Table 2 shows the properties of various ester based

on different alcohols and acids. Due to the high molecular weight of the ISOFOL 2426S also the corresponding adipic ester exhibits a high molecular weight of approximately 850 g/mol.

5. Comparing properties of various esters

LINPLAST REPROXAL ISOFOL ESTER ISOFOL ESTER 810TM 13XAN 1806S* 4606

Acid Component Trimellitic acid Adipic acid/ Modified Adipic acid anhydride Sebacic acid Adipic acid

Alcohol Component Linear C8/C10 MARLIPAL O13 ISOFOL 18T ISOFOL 2426S

Average Molecular Weight g/mol 587 520 665 ~ 850

Density at 20°C g/cm3 0.972 0.910 0.885 0.887

Refractive Index n20d - 1.484 1.457 1.458 1.464

Water Content % 0.1 max. 0.05 max. 0.1 max. 0.1 max.

Acid Number mg KOH/g 0.2 max. 0.1 max. 0.1 max. 0.2 max.

Iodine Number mg Iod/100 mg 0.5 max. 1.0 max. 0.5 max. 0.5 max.

Table 2: Basic properties of different esters (typical values)

In correspondence to the properties of the ISOFOL 2426S also the ISOFOL ESTER 4606 exhibits a high flash point of more than 290 °C, together with an unique low pour point of -48 °C. Other ester also exhibit a low pour point e.g. linear

alcohol based LINPLAST 810 TM has a pour point of roughly -48 °C, however at a lower flash point (275 °C). Interestingly, the hydrolytic stability of all discussed esters is comparable, providing a good potential biodegradability (see Table 3 and 4).

* Development product

9


LINPLAST REPROXAL ISOFOL ESTER ISOFOL ESTER 810TM 13XAN 1806S* 4606

Color APHA Hazen 80 max. 80 max. 80 max. 80 max.

Pour Point °C -48 -54 -45 -48

Kinem. Viscosity @20°C mm2/s 135 53 73 170 (ASTM D 7042)

Kinem. Viscosity @ 40°C mm2/s 50 24.5 31 65 (ASTM D 7042)

Kinem. Viscosity @ 100°C mm2/s 7.8 5.0 6.3 10.6 (ASTM D 7042)

Viscosity Index - 122 137 155 152

5% Weight Loss °C 280 250 254 253

D-Peak °C 320 290 310 298

Flash Point °C 275 240 250 >290

TG Noack % 1.1 6.7 4.7 1.1

Hydrolytical Stability % hydrolysed 26.5 35.0 32.6 28.6 (7d/150°C)

Table 3: Physico-chemical properties of different esters (typical values)

Properties (24hrs/180°C), LINPLAST REPROXAL ISOFOL ESTER ISOFOL ESTER non-stabilized 810TM 13XAN 1806S* 4606

Volatile loss [%] 17.2 56.8 38.2 21.0

Appearance of fresh oil on drop formation

a) fast spreading

b) easily spreading

c) non-spreading

d) caves in

e) stays convex

Solubility of residue on comminuting with fresh oil

a) dissolving (XX) non-solvable (--) XX XX XX XX

Table 4: Physico-chemical properties of different esters (typical values)



10


The beneficial properties of such a multi-branched ester like ISOFOL ESTER 4606 are even more pronounced, if it is compared to a corresponding ester based on the same acid component trimellitic acid anhydride. In Table 5 the stan-dard LINPLAST 810TM is compared to ISOFOL ESTER 2493 and ISOFOL ESTER 4693. As shown the overall properties like acid number, iodine number, density and other are comparable, however, the ISOFOL 2426S based ester provides a higher molecular mass. The ISOFOL 2426S based trimel-litic acid ester shows an increased flash point, significant

lower weight loss together with a low pour point. Indeed the viscosity of this ester differs significantly compared to the other esters (Table 5). At 20 °C the ISOFOL ESTER 4693 exhibits a kinematic viscosity of more than 800 mm²/s whereas the ISOFOL ESTER 2493 is at roughly 500 mm²/s. Both esters show comparable (25.9 mm²/s for ISOFOL ESTER 4693 and 19.9 mm²/s for ISOFOL ESTER 2493) viscosity at 100°C. It is important to note that the lowest weight loss is obtained for ISOFOL ESTER 4693 (Table 6).

LINPLAST 810TM ISOFOL ESTER 2493* ISOFOL ESTER 4693*

Acid Component Trimellitic acid Trimellitic acid Trimellitic acid anhydride anhydride anhydride

Alcohol Component Linear C8/C10 ISOFOL 24 ISOFOL 2426S

Average Molecular Weight g/mol ~ 587 ~ 1220 ~ 1266

Density at 20°C g/cm3 0.972 0.905 0.911

Refractive Index n20d - 1.484 1.478 1.480

Water Content % 0.1 max. 0.15 max. 0.15 max.

Acid Number mg KOH/g 0.2 max. 0.2 max. <0.5

Iodine Number mg Iod/ 100 mg 0.5 max. 0.5 max. 0.5 max.

Color APHA Hazen 80 max. 80 max. 80 max.

Pour Point °C -48 -33 -42

Kinem. Viscosity @20°C mm2/s 135 498 840

Kinem. Viscosity @ 40°C mm2/s 50 168 253

Kinem. Viscosity @ 100°C mm2/s 7.8 19.9 25.9

Viscosity Index - 122 137 129

5% Weight Loss °C 280 280 265

D-Peak °C 320 365 365

Flash Point °C 275 280 >295

TG Noack % 1.1 0.7 0.7

Table 5: Physico-chemical properties of ISOFOL ESTER 2493 and ISOFOL ESTER 4693 (typical values).

At elevated temperatures the viscosity of ISOFOL ESTER 4693 is dropping massively to values which can compete e.g. with LINPLAST 810TM. Related to all presented trimellitate ester ISOFOL ESTER 4693 shows the highest flash point and

lowest volatile loss. The resistance to hydrolysis is best for all discussed trimellitates. This performance enables application of ISOFOL ESTER 4693 as base fluid in grease formulations.


11


Properties (24hrs/180°C), LINPLAST 810TM ISOFOL ESTER 2493* ISOFOL ESTER 4693* non-stabilized

Volatile loss [%] 17.2 16.1 15.5 Appearance of fresh oil on drop formation

a) fast spreading

b) easily spreading

c) non-spreading

d) caves in

e) stays convex

Table 6: Properties of ISOFOL ESTER 2493 and ISOFOL ESTER 4693 (typical values)


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Properties of ISOFOL 2426S based EstersISOFOL Esters – Branched Guerbet Esters

Table 7, Figure 2 and 3 show the properties of various esters of ISOFOL 2426S and different acid components.

6. Properties of ISOFOL 2426S based Esters

ISOFOL ESTER ISOFOL ESTER ISOFOL ESTER ISOFOL ESTER 4604* 4606 4693* 46100*

Acid component Succinic acid Adipic acid Trimellitic acid Carbonic acid anhydride

Alcohol component ISOFOL 2426S ISOFOL 2426S ISOFOL 2426S ISOFOL 2426S

Average Carbon number – 52-56 54-58 81-87 49-53

Average Molecular weight g/mol 790-818 ~850 ~1266 ~790

Acid number mg KOH/g <0.5 <0.5 <0.5 <0.5

Iodine number mg I/100 mg 0.5 max. 0.5 max. 0.5 max. 0.5 max.

Water % 0.15 max. 0.15 max. 0.15 max. 0.15 max.

Color APHA Hazen <80 <80 <80 <80

Refractive Index n20/D – 1.464 1.464 1.480 1.463

Density @ 20°C g/cm3 0.889 0.887 0.911 0.874

Dyn. Viscosity @ 20°C mPas 158 151 8969 148 (calculated)

Kin. Viscosity @ 20°C mm²/s 177 170 840 169 (ASTM D7042)

Kin. Viscosity @ 40°C mm²/s 65.1 64.9 253 62.8 (ASTM D7042)

Kin. Viscosity @ 100°C mm²/s 10.09 10.56 25.5 9.64 (ASTM D7042)

Viscosity Index – 140 152 129 136

Pour point (ISL) °C -48 -48 -42 -33

Solidification point (ISL) °C -51 -51 -41 -34

Flash point °C >285 >290 >295 >280

5% Weight loss °C 257 258 267 258

D -Peak °C 303 301 365 303

TG-Noack % 1.2 1.1 0.7 1.5

Hydrolytical Stability % hydrolysed 35.7 28.4 20.9 15.9 (7d/150°C)

Table 7: Properties of different esters based on ISOFOL 2426S (typical values)


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Properties of ISOFOL 2426S based EstersISOFOL Esters – Branched Guerbet Esters


In Figure 3 the pour point and the flash point of different ISOFOL based esters are shown. ISOFOL ESTER 4693 has the highest flash point comparing the esters and ISOFOL ESTER 4604 or

ISOFOL ESTER 4606 shows a remarkably low pour point below -50 °C.


In Figure 4 the thermal behavior and the different viscosity at different temperatures are shown. ISOFOL ESTER 4693 exhibits the lowest volatile loss, albeit that all other esters also have a volatile loss below roughly 30%. In terms of viscosity the ISOFOL ESTER 4693 shows the highest kinematic viscosity at lower temperature (20°C), whereas the ISOFOL ESTER 46100, ISOFOL ESTER 4604 and ISOFOL ESTER 4606 were comparable. At higher temperatures the viscosity is similar for all discussed ester.

In summary, also the viscosity of ISOFOL ESTER 4693 based on trimellitic acid anhydride are exhibiting to a good Viscosi-ty Index. Related to all presented esters ISOFOL ESTER 4693

shows the highest flash point and a very low volatile loss. The resistance to hydrolysis is second best for all discussed esters. This performance for instance enables the application of ISOFOL ESTER 4693 as base fluid in grease formulations.

The physico-chemical properties like good load carrying capa-city, very low tendency to evaporate, flash point above 280 °C, high oxidative and hydrolytic stability and excellent low tempe-rature properties of the discussed ISOFOL ESTER 4606 based on multi-branched Guerbet alcohol make it superior as part of formulations used in many applications like hydraulic fluids, crankcase oils, gear oils or air compression applications.

Flash point of different ISOFOL ESTER (IFE)

IFE 4604

300

250

200

150

100

50

0

Flas

h po

int

[°C]

IFE 4606 IFE 4693 IFE 46100

Pour point of different ISOFOL ESTER (IFE)

IFE 46040

-5

-10

-15

-20

-25

-30

-35

-40

-45

-50

-55Po

ur p

oint

[°C]

IFE 4606 IFE 4693 IFE 46100

Evaporation (after 24 hours @ 180 °C)

IFE 4604

35

30

25

20

15

10

5

0

Vola

tile

Los

s [%

]

IFE 4606 IFE 4693 IFE 46100

Viscosity of different ISOFOL ESTER

temperature [°C]

11000

10000

9000

250

200

150

100

50

0

Kin.

Vis

cosi

ty [c

St]

20 40 60 80 100

IFE 4604IFE 4606IFE 4693IFE 46100

14

Potential formulations applying ISOFOL based EstersISOFOL Esters – Branched Guerbet Esters

7. Potential formulations applying ISOFOL based Esters

Examples of basic formulations for greases applying these superior esters may comprise base fluids 65-95 wt.% (for example mineral oil / poly alpha olefins / ester and/or blends thereof), thickener 5-35 wt.% (for example Lithium-, Aluminium-, Barium-, Calcium-, Sodium soaps and/or bentonite and/or Clay and/or Silica), additives 0-10 wt.% (for example anticorrosion compounds, antioxidants, AW, EE).

Examples of basic formulations for gear oils applying these superior esters may comprise base fluid 50-95 wt.% (for example mineral oil and/or ester and/or blends thereof), viscosity index improver 0-35 wt.% (for example polymers) and additives 5-12 wt.% ( for example anti wear, EP, friction modifier, anti corrosion, anti foam).

Examples of basic formulations for engine oils applying these superior esters may comprise poly alpha olefins 23-80 wt.% (for example PAO 6 and/or PAO 8), esters 0-10 wt.%, viscosity index improver 0-0.5 wt.% (for example polymers), anti wear 0-2.5 wt.%, dispersant 0-7 wt.%, detergent 0-5 wt.%, antioxidant 0-1 wt.%, anti corrosion 0-0.3 wt.% and friction modifier 0-1 wt.%.

Examples of basic formulations for water miscible coolants applying these superior esters may comprise base fluids 30-40 wt.% (for example mineral oil and/or esters), emulsifiers (non-ionic) 10-15 wt.%, friction modifier 5-10 wt.%, anti corrosion (bacteriostatic) 20-25 wt.%, solubilizer 0-5 wt.%, emulsifiers and/or anti corrosion (others) 5-25 wt.%. extreme pressure additives 0-10 wt.%, biocides 2-5 wt.% and water 0-10 wt.%.

Examples of basic formulations for hydraulic fluids applying these superior esters may com-prise base fluid 0-99 wt.% (for example esters), additives 0-10 wt.% (for example antioxidant and/or anti wear and/or anti corrosion and/or defoamers).

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ISOFOL Esters – Branched Guerbet Esters Our global footprint

Sasol is a registered trademark of Sasol Ltd. Product trademarks displayed in this document are the property of the Sasol Group of Companies, except where it is clear from the context that not. Users of this document are not permitted to use these trademarks without the prior written consent of their proprietor. All rights not expressly granted are reserved.

Disclaimer: The information contained in this document is based on Sasol`s knowledge and experience at the time of its creation. We reserve the right to make any changes to this document or the products described therein, as a result of technological progress or developments. This information implies no liability or other legal responsibility on our part, including with regard to existing third-party patent rights. In particular, no guarantee or warranty of properties in the legal sense is implied. The customer is not exempted from the obligation to conduct careful inspection and testing of incoming goods. Reference to trademarks used by other companies is neither a recommendation, nor should it give the impression that products of other companies cannot be used. All our business transactions are governed exclusively by our General Business Conditions.

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isofol esters · in figure 2 (brugger test). in summary, due to the superior properties of isofol...

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