DE2340454A1 - LUBRICANT CONTAINING MINERAL OIL AND AZELAIC ACID THIS LUBRICANT - Google Patents

Description

containing lubricant

The invention relates to a lubricant containing mineral oil or petroleum and azelaic acid.

If materials with extremely low pour points and high viscosity indices are required for lubrication, mineral oils are the best choice proved unsatisfactory. Synthetic lubricating oils, such as polyolefins (e.g. polydecene or polyoctene), or acids of organic esters are used, but these are synthetic Lubricants, compared to mineral oils, are extremely expensive and have relatively narrow viscosity ranges and are unfavorable Show swelling properties for sealing materials.

It has now been found that a lubricant with excellent Low temperature properties and high viscosity index by mixing an azelaic acid diester with mineral oil or petroleum lubricating oils. The mixtures obtained show

OHQlNM- INSPECTS)

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compared to the percentage of the high pour point mineral oil component, surprisingly low pour points. The blends of the invention can have viscosity and seal swelling properties have, which can vary within a wide range.

The invention therefore relates to a lubricant which can be used as a hydraulic oil, as a low-temperature gear oil or as a high-temperature bearing lubricant and which contains 20 to 50 parts by volume (more preferably 25 to 40 parts by volume, in particular 30 to 35 parts by volume) of an azelaic acid diester and 50 to 80 parts ( preferably 60 to 75 parts, especially 60 to 65 parts) of a mineral oil having a viscosity in the range from 50 to 3000 SUS (Saybolt Universal seconds) at 37.8 ° C (100 ⁰ F). Preferably the mineral oil consists essentially of low pour point, high viscosity index paraffinic lubricating oils (e.g., either a common solvent refined material, e.g. Duosol, or dewaxed lubricating oils (which may be hydrogen refined) or dewaxed hydrocracked lubricating oils having a paraffinic viscosity density constant). The lubricant can also contain the usual additives. For example, the bearing lubricant can contain additives that modify friction or wear, extreme pressure additives (EP additives), pour point depressants, antioxidants or viscosity index improvers. Multipurpose gear oils and hydraulic oils may contain additional additives such as rust inhibitors and synthetic sulphurized sperm oil substitutes (sulphurized fat materials) and additional extreme pressure additives (EP additives).

The preferred azelaic acid diester contains ester groups which contain 6 to 16, preferably 8 to 12 carbon atoms. A preferred ester is that available from Emora Industries under the name "Emory 4238-R, which is a mixture represents from diesters which have the same empirical formula and the same molecular weight, but are in the Differentiate chain structure (i.e. contain isomeric alkyl ester groups). These diesters have the following molecular formula:

A09808 / 0952

^C 29 ^H 56 ° 4 ^{or e} ^ ⁿ molecular weight of 46 8 and can be expressed by the following general formula

O O

R-CH ₂ OC- {CH ₂ ) ₇ -C-OCH ₂ -R 'in which R and R ^{1 are} C ^ H ^ groups.

In both cases, the alkyl groups R and R ¹ are branched-chain groups that have an average of three methyl groups per chain

a) from 5 CH-j groups and one quaternary carbon atom

(-C-) or
3d /) 4 CH ₂ groups and 2 tertiary carbon atoms (-CH)

built up jseiiu iDiss Azelaic acid is the only acid component , and the TSster hydrolyzes to a mixture of primary Alcohols with 10 carbon atoms, which are how out the NKR spectrum found, three methyl groups per carbon chain caufwexseru iDi-e analysis of the combined alcohol inventory— divide ialb's oil mixture by capillary gas chromatography showed the presence of 7 to 8 major alcohol components and about a good number present in very small quantities Components.

Another, less preferred ester used in the inventions mixtures according to the invention, can also be used the azelaic acid li-2-ethylhexyl ester.

Although mixtures of alcohols and similar esters of others organic dicaaiboinsatir-en (e.g. phthalic acid) can be produced fccam-en ,, see the azelaic acid esters given for the mentioned mixed «» lubricants and in particular the Azelaic acid diesters with alkyl groups with 10 carbon atoms away from their cheapness, their high viscosity index and theirs , Low Stacfcpianktes preferred.

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In general, naphthenic distillates are a lubricating oil component not preferred according to the invention. In certain cases, however, mixtures of paraffinic and naphthenic can be used Lubricating oils can be used together with the azelaic acid diester when a very high viscosity index is not required is.

A naphthenic distillate is a distillate fraction (or a moderately acid-treated distillate fraction or a solvent refined fraction or an acid-treated raffinate) that is usually obtained from a vacuum distillation of a crude oil which has been obtained by the viscosity-density constant (VGC) classification method (viscosity- gravity constant classification method) has been classified as naphthenic (including a "relatively naphthenic" material). Preferably used crudes of the "Grade A" ( "Grade A") (wax free) and in particular GUIF Coastal such Refugio-, Mirando and Black Bayou oils _v low viscosity oils density constant (VGC value) can be obtained from mid- Continental crude oils, but removal of wax (by extraction or isomerization) may be required to obtain an oil that has a low pour point [e.g. less than -1.11 ° C (30 ° F) amounts to]. Such naphthenic fractions have a VGC-value in the range from 0.820 to 0.899 and typically have a viscosity in the range from 150 to 12,000 SUS at 3 7.8 ° C (100 ⁰ F) (eg, a SUS-value of 500 to 6000). In certain cases, the crude oil (and distillate) can have a VGC of up to 0.94 (such crudes are referred to as "weakly aromatic") and a furfural hydrate extract (e.g., about 50 % yield) of a distillate from a crude oil Grade A (Grade A) can be used to produce a wax-free, low VGC fraction (around 0.83) that can be used in low-pour point mixtures with paraffinic oils. Paraffinic oils (or lubricating oils) are those oils that have a VGC of 0.819 or less and an ASTM viscosity index of 65 or greater.

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In general, the preferred mineral oils include solvent refined ones paraffinic distillates or bright stocks, hydrogen-refined paraffinic distillates or Brightstocks, hydroisomerized paraffinic distillates, hydrocracked paraffinic distillates (the can be stabilized by solvent extraction or by hydrorefining). Napthenic ones are less preferred Distillates (preferably with a low naphthenic acid content), naphthenic refined with solvents and / or acids Distillates and hydrorefined naphthenic distillates and mixtures of two or more oils this kind.

A particularly preferred ingredient of this type is a hydrocracked one Petroleum with a Viscosity Density Constant (VGC) of 0.819 or less.

Typical properties of stabilized are shown in the following table hydrocracked oils specified, which are used according to the invention together with an azelaic acid diester in mixtures can.

Properties of hydrocracked oils

Viscosity ASTM-Vis-

(SUS), 37.7 ° C viscosity density% weight aniline point (100 F) index API aromatics ^ C ( ⁰ F)

100 103 34.2 12 104.4 (220)

200 107 33.3 11 112.8 (235)

500 107 31.5 13 121.1 (250)

All oils were dewaxed by cooling in a solvent and stabilizing • by extraction with furfuraldehyde to a pour point of -17.8 ° C ( ⁰ ° F).

Other oils of this type have an aromatic content of 6% by weight Or less.

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The term "hydrocracked paraffinic oil" (or lubricating oil), As used herein, it means by hydrocracking a petroleum material (that according to the VGC classification can be either paraffinic or naphthenic) obtained product having a lube oil viscosity range product) that has a VGC value below 0.820. I.e. hydrocracking (similar to extracting with heavy solvents) results in a low VGC value (which is therefore "paraffinic" is) than the VGC of the feed materials. For example, a feed introduced into a hydrocracking facility can be used be a distillate fraction of a Lagomedio crude that at 37.8 ° C (100 ° F) has a viscosity of 191 SUS, an API gravity of 27.5 and a VGC of 0.837 (and which would therefore be classified as "relatively naphthenic). The hydrocracked oil can boil in the same range as the feed material introduced and can have a viscosity at 37.8 ° C (100 ° F) of 93.5 SUS, an API density of 36.5 and a VGC of 0.91 (i.e. classified as "paraffinic") exhibit. After dewaxing, the ASTM viscosity index of the product can be 120. Such a hydrocracked oil, that has a "paraffinic" VGC also falls under the term "hydrocracked paraffinic oil".

Useful additives that can be used in the lubricants of the invention are those commonly found in Bearing lubricants, hydraulic oils and gear lubricating oils can be used.

The preferred antioxidants include zinc organothiophosphates (e.g. zinc dialkyldithiophosphates), substituted phenols and polyalkylphenols with methylene bridges (e.g. di-tert-butyl-pcresol, 2,6-di-tert-butylphenol, 4,4-methylenebis (2,6-di-1ert-butylphenol) etc. Amines, e.g. phenylenediamine, 2,6-di-tert-butyl-oc-dimethylamino-p-cresol, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-diisopropyl-p-phenylenediamine etc., Used will.

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The concentration of the antioxidant can be used in mixtures containing the azealic acid diester and one refined with a solvent dewaxed paraffinic lubricating oil, usually reduced when 85 to 100% of that with solvent refined lubricating oil can be replaced by the stabilized hydrocracked oil.

In certain blends of this type that contain a solvent refined paraffinic lubricating oil, one can use For a given viscosity index, use the polymeric additive in a lower concentration when using the lubricating oil partially or completely replaced by a hydrocracked (preferably stabilized hydrocracked) lubricating oil

When the lubricating system, in which the lubricant to be used has rubber seals, it is preferred that the mixture of the diester and the mineral oil an aniline point in the range from 65.6 to 76.7 ° C (150 to 170 ⁰ F ) to ensure that the seals are in a suitably swollen state. When using silicone rubber seals, the preferred aniline point is in the range of 90.5 to 101.6 ° C (195 to 215 ° F).

It is further preferred that the basic nitrogen content of the mixture be as low as possible, preferably below 5 ppm nitrogen, more preferably less than 1 ppm nitrogen, since it has been found that basic nitrogen compounds are present in lubricating oils have an unfavorable effect on the lubricating oil layer.

Sulfurized fat materials can be used as additives in the invention Gear oils are used to improve the high pressure properties to improve and control the slip-back behavior. The preferred sulfurized fat materials include Tallow fatty acids, sulphurized sperm oil and synthetic sulphurised sperm oil substitutes (e.g. sulphurised mixtures made from lard oil and an olefin) to control the slip-back properties Neutralized acid phosphates and acid phosphates (Ortholeum 162 or 535) can also be added.

Λ09808 / 0952

The chemical products that are obtained by reacting sulfur or sulfur monochloride with glycerine (such as bacon oil) and olefins (or polyolefin oils) are particularly favorable slip-back and / or high-pressure additives. Such cosulphurized (sulphurized) compositions are generally suitable as a substitute for sulphurized sperm oil and can be prepared by sulphuring a mixture of 90 to 30 parts by weight of lard oil and 10 to 70 parts of an aliphatic olefin containing 6 to 128 carbon atoms (preferably 12 to 60 carbon atoms) contains. The sulfurization is carried out using elemental sulfur. Sulfur monochloride can be used for simultaneous sulfurization and chlorination. The sulfurization can involve heating to 166 to 229.5 ° C (330 to 445 ° F) for 20 minutes to 10 hours followed by gas bubbling [preferably for 30 minutes to 20 hours at a temperature of 51.7 to 171 ° C (125 to 340 F)] to remove hydrogen sulfide. In a Verwertdung sulfur monochloride, the preferred reaction temperature in the range of 65.6 to 121.1 is C (150 to 250 ⁰ F) (where one optionally operating under positive pressure). The sulfurized oils can contain 5 to 25% by weight of sulfur based on the mixture of the olefin and the lard oil (ie 5 to 25 parts by weight of sulfur per 100 parts by weight of the olefin / lard oil mixture).

E.g. an effective reduction in the slip-back ratio can be achieved by adding 0.1 to 10% by weight of a composition to a mineral oil which essentially from a sulfur-containing chemical reaction product a mixture of lard oil and a polyisobutylene containing 12 to 32 carbon atoms.

Such a cosulphurized mixture is obtained as follows:

2260 ml of winter strained lard oil are mixed with 400 ml of tetraisobutylene in a 5 l flask equipped with a vibration mixer. The mixture is then heated to 121.1 ° C (250 ⁰ F) using the vibratory mixer at maximum speed.

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speed is operated. Then add 239 grams of sulfur and raise the temperature of the mixture to 190.5 ° C (375 ° F) over 2 hours. The mixture is then cooled to 93.3 ° C (200 ° F) and air is passed through the mixture at a moderate rate (without splashing or vigorous agitation) for 1 hour using a glass tube. The sulfurized oil obtained is analyzed and found to contain 8.23% sulfur. Then, 10 g of the sulfurized oil in 100 g of a commercially available, solvent refined paraffinic lubricating oil having a viscosity of 40.45 SUS at 98.9 ° C (210 ⁰ F) and an ASTM viscosity index of 104, 12% Aromatics (determined according to the ASTM method D2OO7), dissolved. The oil solution obtained remains clear when examined overnight at 2.22 ° C (36 ° F) and for 1 week at room temperature without any separation occurring.

In general, the additives used should not greatly increase the pour point of the lubricant or significantly lower its viscosity index. Preferably the lubricant should have an ASTM pour point below -17.8 ° C (0 ° F), more preferably below -37.2 ° C (-35 F), most preferably from -40 to -62.2 ° C (-40 to -80 ° F) and an ASTM viscosity index of at least 90, more preferably at least 105, most preferably at least 130. The pour point and the viscosity index can be adjusted by the selection of the type and the amount of the diester, the mineral lubricating oil and the use of conventional pour point depressants and / or viscosity index improvers. In order to achieve such a low pour point, when a bright stock is part of the mixture, it is preferred that the extraction and dewaxing be controlled so as to obtain a bright stock with a pour point of -17.8 ° C (0 ° F) or lower [e.g. -20.6 to -23.3 ° C (-5 to -10 ⁰ F)].

Very generally preferred diesters have a maximum viscosity are ex (ASTM Method D227O, Method B) of 130, more preferred of at least 190, and a maximum pour point (ASTM-

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A method D97) of -40, ⁰ ° C (-40 ⁰ F) [more preferably -48.3 to 65, ⁰ ° C (-55 to -85 ° F)].

For high-pressure temperature applications, additives should be selected that have high boiling or sublimation points. E.g. di-tert-butyl-p-cresol (DBPC) represents high temperature lubricants is a poor phenolic antioxidant as it sublimes at 121.1 ° C (250 ° F).

The following examples are intended to explain the invention further without, however, restricting it.

example 1

Two bearing lubricants (for lubrication purposes at high operating temperatures) we are formulated as follows:

Part by weight component Oil 1 Oil 2

paraffinic lubricating oil 100 SUS ⁺⁾ 9.50

paraffinic lubricating oil 500 SUS ⁺⁾ 52.00 56.50

paraffinic bright stock 2600 SUS ⁺⁾ - 5.00

Azelaic acid esters of alcohols with

with 10 carbon atoms 33.00 33.00

anti-wear additive

(Lubrizol 757) 1.00 I ₁ OO

Dispersant and pour point depressant (Acryloid 983) 4, OO 4.00

phenolic antioxidant (ethyl 702) 0.50 0.50

SUS viscosity at 37.8 ° C (100 ⁰ F)

Lubricating oils having the following properties were obtained

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430.2 528.5 73.7 81.33 163 158 27.1 27.1 218 (425) 238 (460) -48.3 (-55) -51.1 (-6O) 0.11 0.17 86,000 169,000

- 11 -

Oil 1 oil 2

SUS viscosity at 37.8 ° C (100 ⁰ F)
SUS viscosity at 98.9 ° C (210 ⁰ F)
Viscosity index (ASTM)
Density (API)
Flash point, ⁰ C ( ⁰ F)
Actual pour point
Total acid number
Brookfield viscosity at -40.0 ° C (-40 ⁰ F)

All data were determined by ASTM methods, with the exception of the Brookfield viscosity (determined by the CRCL45 method). These lubricants are especially for automotive ventilation fans suitable because they enable low-noise operation (e.g. reduced squeaking) and at high temperatures have good resistance to oxidation.

Example 2

There were two blends of the ester and solvent refined dewaxed paraffinic lubricants.

The mixture I consisted of 65% by volume of a paraffinic lubricating oil having an SUS viscosity of 100 at 37.8 ° C (100 ⁰ F) (available under the designation "Sunvis 11") and 35% by volume of Azelainsäureesters. The mixture showed a viscosity at 37.8 ° C (100 ⁰ F) of 138 SUS at 98.9 ° C (210 ° F) of 45.3 SUS and an ASTM viscosity index of the 159th

Mixture II consisted of 65% by volume of a paraffinic lubricating oil having a viscosity of 150 SUS at 37.8 ° C (100 ° F) and 35% by volume of the azelaic acid ester (Emory 4238R). The mixture had a viscosity of 170.8 SUS at 98.9 ° C (210 ° F) of 48.1 SUS and an ASTM viscosity index of 154 at 37.8 ° C (100 ⁰ F).

The usual additives (e.g. add those used in Example 1) to obtain a lubricant for a wick-lubricated bearing (Permawick).

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Claims (11)

Claims 1.) Lubricants containing a minor amount of lubricant additives and a major amount of a mixture of 20 to 50 parts by volume of an azelaic acid diester and 50 to 80 parts by volume of a mineral oil with a viscosity at 37.8 ° C of 50 to 3000 SUS (Saybolt Universal Seconds). 2.) Lubricant according to claim 1, characterized in that there is at least one as an additive A friction-modifying agent, a wear-reducing agent, • a high-pressure additive, a pour point depressant, an antioxidant and / or a viscosity index improver contains. 3.) Lubricant according to claim 1, characterized in that it is a paraffinic mineral oil Contains mineral oil with a low pour point and a high viscosity index. 4.) Lubricant according to claim 3, characterized in that the paraffinic lubricating oil has an ASTM pour point of not more than -15.0 ⁰ C and an ASTM viscosity index of at least 90. 5.) Lubricant according to claim 4, characterized in that it is a paraffinic lubricating oil solvent refined paraffinic distillate 409808/0952 hydroisomerized paraffinic distillate and / or a hydro-refined petroleum distillate with a paraffinic one Contains viscosity density constants. 6.) Lubricant according to claim 5, characterized in that at least one of the lubricating oils has dewaxed an ASTM pour point of -2.6 ° C or less. 7.) Lubricant according to claim 1, characterized in that the azelaic diester of the following general formula O O ti Il R-CH ₂ -OC- (CH ₂ ) ₇ -C-OCH ₂ -R corresponds in which R is an alkyl group having 5 to 15 carbon atoms and R ^{1 is} an alkyl group having 5 to 15 carbon atoms. 8.) Lubricant according to claim 7, characterized in that the two groups R and R * 9 carbon contain atoms. 9.) Lubricant according to claim 8, characterized in that the mixture is 30 to 35 parts by volume of the diester and 65 to 70 parts by volume of a solvent refined and dewaxed paraffinic lubricating oil, or of a dewaxed hydrocracked lubricating oil with a VLs- ΧΛ09808 / 0952 viscosity density constants (VGC value) in the paraffinic range or a mixture of these lubricating oils. 10.) Use of a lubricant according to one of claims 1 to 7 as a hydraulic oil, as a bearing lubricant or Gear oil. 11.) Use of the lubricant according to claim 8 as a lubricant for a wick-lubricated bearing. 409808/0952