EP0003032B1 - Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base - Google Patents

Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base Download PDF

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Publication number
EP0003032B1
EP0003032B1 EP78101731A EP78101731A EP0003032B1 EP 0003032 B1 EP0003032 B1 EP 0003032B1 EP 78101731 A EP78101731 A EP 78101731A EP 78101731 A EP78101731 A EP 78101731A EP 0003032 B1 EP0003032 B1 EP 0003032B1
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EP
European Patent Office
Prior art keywords
acid
pentaerythritol
ester
esters
carboxylic acid
Prior art date
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Expired
Application number
EP78101731A
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German (de)
English (en)
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EP0003032A1 (fr
Inventor
Karl-Heinz Dr. Hentschel
Rolf Dr. Dhein
Hans Dr. Rudolph
Karl Dr. Nützel
Klaus Dr. Morche
Wolfgang Dr. Krüger
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Bayer AG
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Bayer AG
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Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0003032A1 publication Critical patent/EP0003032A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential

Definitions

  • the present application relates to carboxylic acid esters of pentaerythritol and their use in lubricants.
  • Lubricating oils based on carboxylic acid esters generally outperform mineral oils with the same basic viscosities at higher flash points, lower volatility and better viscosity-temperature characteristics (measured by the viscosity index, "VI").
  • VI index the viscosity index
  • esters which also contain monoalcohols, dicarboxylic acids and / or monocarboxylic acids as esterification components in addition to diols / polyols, are known. Although they allow ester oils of increased intrinsic viscosity to be provided, it is known to the person skilled in the art that their preparation is difficult because of the proportions of acid or partial esters of dicarboxylic acids remaining after the esterification reaction, which are difficult to remove by refining or distillation.
  • DE-OS 2302918 also proposes the use of carboxylic acids with 14 to 22 carbon atoms per molecule, which are preferably branched in the a-position to the carboxyl group, for the production of high-viscosity ester oils, but the underlying monocarboxylic acids are not easily obtainable and require additional synthesis steps. Under strongly oxidative conditions, such oils still show noticeable evaporation losses. These oils do not quite reach the required high viscosity index values of over 140.
  • a pentaerythritol ester lubricating oil which contains 2-ethylhexanoic and isostearic acid in a molar ratio of 1: 3.
  • the pour point specified is -45 ° C., but the viscosity index is only 133 and is therefore also below 140.
  • DE-OS 2 528 526 discloses lubricating oil formulations for gas turbines and jet engines based on pentaerythritol or trimethylolpropane esters of 2-18, but are preferred Saturated monocarboxylic acids containing 5-10 carbon atoms.
  • Examples of such monocarboxylic acids include cyclohexyl carboxylic acid is also mentioned, trimethylol and pentaerythritol esters of cyclohexyl carboxylic acid are described in detail in J. of Chem. and Eng. Data 7, 547 ff. (1962). From the data listed there it can be seen that pentaerythritol esters with 1-2 moles of cyclohexylcarboxylic acid per mole of ester have up to approximately 32 total pour points down to a total carbon number of the acid portion of the esters. The viscosity-temperature behavior of these esters depends on the number of molecules of cyclohexylcarboxylic acid contained per molecule of ester.
  • the viscosity indices of the pentaerythritol esters containing 1 mol of cyclohexylcarboxylic acid in the examples mentioned are between 118 and 129, and the VI's of the esters containing 2 mol of cyclohexylcarboxylic acid per ester molecule are only between 88 and 90.
  • a further increase in the total carbon number of the acid content of these esters to about 34 has different effects on the lubrication parameters, depending on the type of monocarboxylic acids used.
  • the use of only one medium-chain fatty acid (C s ) in addition to the cyclohexyl acid gives an oil with a pour point of -20 ° C and a VI of 127, while the use of a mixture of 1 mol of tetradecanoic acid with 1 mol of cyclohexyl carboxylic acid and 2 mol of hexanoic acid results in an ester oil. with a pour point of + 4 ° C and a VI of 129.
  • ester oils with a high viscosity index and low volatility are obtained from readily available raw materials based on pentaerythritol esters of "isostearic acid", cyclohexylcarboxylic acid and other aliphatic, saturated C 6 -C 16 -monocarboxylic acids, if the total number of carbon atoms per molecule Pentaerythritol ester is between 47 and 51 and at least 22 equivalent% of the alcoholic hydroxyl groups present in pentaerythritol are esterified with "isostearic acid” and cyclohexylcarboxylic acid.
  • Isostearic acid is a mixture of weakly methyl-branched C 18 fatty acids which contains, for example, the 16-methylheptadecanoic acid as described in the company font "Unem 5680" is described by Unilever-Emery. Ester oils from pentaerythritol and the “isostearic acid” as the sole acid component are solid substances at room temperature.
  • At least 22 equivalent% of the 4 primary alcoholic hydroxyl groups present in the pentaerthritol molecule should be esterified with "isostearic acid” and likewise at least 22 equivalent% of hydroxyl groups with cyclohexylcarboxylic acid, but at most 80 equivalent% of the 4 hydroxyl groups with the "isostearic acid” / Cyclohexylcarboxylic acid mixture may be implemented.
  • the molar ratio "isostearic acid” to cyclohexylcarboxylic acid in the finished ester may vary between 1.0: 1.0 and 1.0: 2.1.
  • a third acid component of the pentaerythritol esters according to the invention are aliphatic saturated, preferably straight-chain monocarboxylic acids which contain 6-16 carbon atoms. It is preferred that all the hydroxyl groups present in the pentaerythritol be esterified as completely as possible, but the hydroxyl number of the finished ester oil may vary within a range of 0-8 mgKOH / g.
  • Pentaerythritol can be used in both pure and technical quality.
  • the “isostearic acid” is a mixture of weakly branched saturated monocarboxylic acids, such as the name “Unimac 5680" is commercially available.
  • the cyclohexylcarboxylic acid is used in pure form or with a low content of benzoic acid for the preparation of the esters according to the invention.
  • Examples of other suitable aliphatic saturated monocarboxylic acids are caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid and palmitic acid.
  • the esterification reaction for the preparation of the esters according to the invention is carried out in bulk or with an azeotrope-forming solvent at temperatures of 50-260, preferably 140-220 ° C. under inert gas.
  • inert gas nitrogen, carbon dioxide or noble gases can be used as the inert gas.
  • Compounds such as organic sulfonic acids, sulfuric acid, phosphoric acid, their acidic salts such as hydrogen sulfates and dihydrogen phosphates, phosphonic acid esters or dialkyltin oxides can be used in catalytic amounts in the reaction. 0.8 to 1.3, preferably 1-1.2 equivalents of acid groups are used per equivalent of OH groups.
  • Aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene or halogen-containing hydrocarbons such as carbon tetrachloride or chloroform are suitable as azeotropic solvents.
  • the mixture is esterified either gradually, using the less volatile monocarboxylic acids first, then adding a small excess of the volatile monocarboxylic acids after reaching an acid number of ⁇ 5 mg KOH / g and bringing the reaction to an end, or by reacting pentaerythritol together with all the monocarboxylic acid components until the final acid number of the ester oil derived from the excess amount of monocarboxylic acids.
  • Solvents, excess acid and catalyst are removed by suitable operations such as filtration, high vacuum distillation, stripping, thin-layer evaporation and treatment with alkali or methanol.
  • esters according to the invention can be used as a base oil for the production of liquid or paste-like lubricants. They are also suitable for blending with other synthetic or mineral base lubricating oils.
  • ester oils according to the invention are notable for high flash points and low evaporation losses with higher basic viscosities than for comparison esters, but also for very high viscosity indices, as the following examples show:
  • Comparative Example 4 shows that the replacement of the isostearic acid with another aliphatic monocarboxylic acid with 18 carbon atoms leads to a significantly higher pour point and thus to significantly poorer flow properties of the oils.
  • the oils according to the invention are less degraded with the elimination of liquid constituents than, for example, pentaerythritol tetra (2-hexyl) decanoate, a state of the art according to DT-OS 2 302 918 corresponding oil, as the following table shows:
  • Table 2 shows the comparison of the properties of the two pentaerythritol esters A and B with the largest total carbon number from the Journal of Chemical and Engineering Data 7, 547 ff. (1962) and the ester oil according to the invention of the example.
  • esters A and B known from the literature do not expect that the use of fatty acids with 10 or more carbon atoms, which is necessary to increase the total carbon number, results in esters with pour points of -10 ° C. and viscosity indices greater than 130.
  • Replacing the pelargonic acid in ester B with a mixture of caproic acid and myristic acid (ester A) leads to an increase in the pour point to values above ° C.
  • Esters of 10 carbon atoms more and a C 1s fatty acid, bound has a viscosity index value of almost 150 and a pour point around -10 ° C.
  • Comparative Examples 2 and 3 show that similarly composed ester oils with less than 47 or more than 5 carbon atoms per molecule no longer result in the combination of a good pour point and a high viscosity index, like the oil according to the invention.
  • the comparison oil 2 with an average of 45 carbon atoms / molecule has a low pour point, but its viscosity index of 109 is significantly lower than that of the comparison oil 3 and the oil according to the invention.
  • Oil 3 which contains an average of 53 carbon atoms per molecule has only a VI of 129 (20 units lower than the oil according to the invention) and is also in the pour point between -10 and 0 ° C. and thus higher than in the oil according to the invention.
  • the preparation is carried out analogously to Comparative Example 1, starting from 163.2 g of pentaerythritol, 307.2 g of cyclohexane carboxylic acid, 340.8 g of "isostearic acid” and 23 g of tri-n-butyl phosphate with a reaction time of 20 h in the first stage, addition of 336 g of lauric acid and a reaction time of 6 h in the second stage. After extraction with methanol and final distillation, the final acid number is 0.1 and the yield is 859 g.
  • the preparation is carried out analogously to Example 1, starting from 108.8 g of pentaerythritol, 245.8 g of cyclohexane carboxylic acid, 159.0 g of "isostearic acid” and 10 g of tri-n-butyl phosphate with a reaction time of 10 h in the first stage, adding 176.0 g lauric acid and a reaction time of 6 h in the second stage. After extraction with methanol and final distillation, the final acid number is 0.3; the yield is 560 g.
  • the preparation is carried out analogously to Example 1, starting from 136 g of pentaerythritol and 256 g of cyclo hexane carboxylic acid, 284 g stearic acid and 4.5 g dibutyltin oxide in the first step with a reaction time of 6 h, addition of 240 g lauric acid and a reaction time of 4 h in the second step.
  • the final acid number after extraction with dilute sodium hydroxide solution is approximately 0.5, the yield 690 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (3)

1. Huiles esters consistant en:
a) pentaérythritol,
b) acide cyclohexylcarboxylique,
c) acide "isostéarique", et
d) au moins un autre acide monocarboxy- lique aliphatique saturé en C6―C16,
caractérisées en ce que le nombre total des atomes de carbone par molécule d'ester est de 47 à 51, 22 à 54 équivalents % des groupes hy- droxy alcooliques présents dans le pentaérythritol sont estérifiés par l'acide cyclohexylcarboxylique, 22 à 40 équivalents % par l'acide "isostéarique" et 20 à 56 équivalents 96 par des acides monocarboxyliques en C6―C16, l'ester contenant l'acide cyclohexylcarboxylique à l'état estérifié en quantité au moins équivalente à celle de l'acide "isostéarique".
2. Utilisation des esters selon la revendication 1 en tant qu'huiles lubrifiantes de base.
3. Utilisation des esters selon la revendication 1 dans des mélanges avec d'autres lubrifiants synthétiques ou minéraux.
EP78101731A 1977-12-29 1978-12-16 Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base Expired EP0003032B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2758780 1977-12-29
DE19772758780 DE2758780A1 (de) 1977-12-29 1977-12-29 Carbonsaeureester des pentaerythrits

Publications (2)

Publication Number Publication Date
EP0003032A1 EP0003032A1 (fr) 1979-07-25
EP0003032B1 true EP0003032B1 (fr) 1980-09-17

Family

ID=6027672

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78101731A Expired EP0003032B1 (fr) 1977-12-29 1978-12-16 Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base

Country Status (4)

Country Link
US (1) US4212816A (fr)
EP (1) EP0003032B1 (fr)
JP (1) JPS5496667A (fr)
DE (2) DE2758780A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1132602A (fr) * 1979-09-10 1982-09-28 Pier P. Rossi Procede d'obtention et emploi comme huiles lubrifiantes d'esters d'alcools polyvalents
US4313890A (en) * 1980-01-29 1982-02-02 Union Carbide Corporation Polyol ester functional fluids
US4477383A (en) * 1982-05-05 1984-10-16 National Distillers And Chemical Corporation Di- and tripentaerythritol esters of isostearic acid
JPH0631365B2 (ja) * 1985-12-27 1994-04-27 東燃株式会社 トラクシヨン流体
JPH0774350B2 (ja) * 1986-06-02 1995-08-09 東燃料株式会社 合成トラクシヨンフル−ド
US5259978A (en) * 1987-07-23 1993-11-09 Toa Nenryo Kogyo, K.K. Traction fluid composition comprising a cyclohexyl diester and branched poly-α-olefin
JPS62177099A (ja) * 1987-07-30 1987-08-03 Toa Nenryo Kogyo Kk トラクシヨン用フル−ド
JPH01299891A (ja) * 1988-05-26 1989-12-04 Asahi Glass Co Ltd チェーン用潤滑油組成物
US5080834A (en) * 1990-10-18 1992-01-14 Lce Partnership Branched ether esters as viscosity index modifiers
ATE184310T1 (de) * 1992-06-03 1999-09-15 Henkel Corp Polyol/ester-gemisch als schmiermittel für wärmeträgerflüssigkeiten in kälteanlagen
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
ATE195545T1 (de) 1992-06-03 2000-09-15 Henkel Corp Schmiermittel auf basis von polyolester für kälteübertragungsmittel
US6183662B1 (en) 1992-06-03 2001-02-06 Henkel Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
CA2137263C (fr) * 1992-06-03 2003-10-14 Nicholas E. Schnur Lubrifiants a base de polyol pour compresseurs frigorifiques fonctionnant a haute temperature
JP2613526B2 (ja) * 1992-07-04 1997-05-28 花王株式会社 冷凍機作動流体用組成物
US5318711A (en) * 1993-01-21 1994-06-07 Quaker Chemical Corporation Method for lubricating metal-metal contact systems in metalworking operations with cyclohexyl esters
EP0760845B1 (fr) * 1994-05-23 2003-08-27 Cognis Corporation Procede pour augmenter la resistivite electrique de lubrifiants bases sur des esters et destines en particulier a une utilisation avec des refrigerants bases sur des hydrocarbures fluores
US20010019120A1 (en) 1999-06-09 2001-09-06 Nicolas E. Schnur Method of improving performance of refrigerant systems
US6884761B2 (en) * 2001-12-18 2005-04-26 Bp Corporation North America Inc. High temperature stable lubricant mixed polyol ester composition containing an aromatic carboxylic acid and method for making the same
US7166491B2 (en) * 2003-06-11 2007-01-23 Fry's Metals, Inc. Thermoplastic fluxing underfill composition and method
FR2917615B1 (fr) * 2007-06-21 2009-10-02 Oreal Composition cosmetique comprenant deux polyesters.
WO2018110142A1 (fr) * 2016-12-13 2018-06-21 花王株式会社 Huile de base lubrifiante et composition lubrifiante comprenant ladite huile de base lubrifiante
JP2018095840A (ja) 2016-12-13 2018-06-21 花王株式会社 潤滑油基油、および該潤滑油基油を含有する潤滑油組成物
JP7216563B2 (ja) * 2019-02-12 2023-02-01 花王株式会社 グリース基油、および該グリース基油を含有するグリース組成物
CN111848403A (zh) * 2019-04-26 2020-10-30 南京纽邦生物科技有限公司 一种季戊四醇四异硬脂酸酯的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2991297A (en) * 1958-07-02 1961-07-04 Celanese Corp Process for preparing synthetic lubricants
FR95543E (fr) * 1966-03-28 1971-01-22 Nyco Sa Composition a base d'esters synthétiques utilisable notamment comme fluide de transmission hydraulique.
US3476685A (en) * 1967-05-08 1969-11-04 Texaco Inc Synthetic lubricating composition
US4053491A (en) * 1973-01-22 1977-10-11 Henkel Kommanditgesellschaft Auf Aktien Branched-chain aliphatic ester oils
FR2254633B1 (fr) * 1973-12-12 1976-10-08 Inst Francais Du Petrole

Also Published As

Publication number Publication date
JPS5496667A (en) 1979-07-31
DE2860183D1 (en) 1980-12-18
EP0003032A1 (fr) 1979-07-25
US4212816A (en) 1980-07-15
DE2758780A1 (de) 1979-07-12

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