EP2609178A1 - Huiles d'esters - Google Patents

Huiles d'esters

Info

Publication number
EP2609178A1
EP2609178A1 EP11754976.6A EP11754976A EP2609178A1 EP 2609178 A1 EP2609178 A1 EP 2609178A1 EP 11754976 A EP11754976 A EP 11754976A EP 2609178 A1 EP2609178 A1 EP 2609178A1
Authority
EP
European Patent Office
Prior art keywords
acid
ester oil
oil according
ester
monoalcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11754976.6A
Other languages
German (de)
English (en)
Inventor
Patrick LÄMMLE
Bernardo Walterspiel
Mathias Woydt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PANOLIN Holding AG
Original Assignee
PANOLIN Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PANOLIN Holding AG filed Critical PANOLIN Holding AG
Publication of EP2609178A1 publication Critical patent/EP2609178A1/fr
Withdrawn legal-status Critical Current

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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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/069—Linear chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/081—Biodegradable compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to ester oil, in particular for producing a hydraulic oil and / or a lubricant, comprising an esterification product of at least one monoalcohol with at least one multiple carboxylic acid. Furthermore, the invention relates to an ester oil, in particular for producing a hydraulic oil and / or a lubricant, comprising an esterification product of at least one monocarboxylic acid with at least one dialcohol. In addition, the invention relates to processes for the preparation of ester oils and the use of ester oils. State of the art
  • Lubricants or lubricants are used in particular for friction and wear reduction, for corrosion protection, for sealing, for cooling, as well as for vibration damping or power transmission in mechanical systems. Depending on the intended application lubricants are used in solid, liquid or gaseous state.
  • liquid lubricants are widely used in various technical fields and are used, inter alia, as engine oils, turbine oils; Hydraulic fluids or gear oils.
  • One known class of liquid lubricating oils are ester-based lubricating oils containing as main component organic reaction products of carboxylic acids with alcohols. The demands on modern ester oils are manifold. For example, an ester oil must satisfy the requirements imposed by the intended application in terms of density, viscosity, viscosity index, pour point, yield point, flash point, seal compatibility, aging resistance, toxicity and / or biodegradability.
  • esters based on branched Guerbet alcohols as a lubricant and carrier medium for hydraulic fluids.
  • the esters with branched alcohols can also be produced from renewable raw materials.
  • ester mixtures eg. B. as hydraulic oils, consisting of the reaction product of a branched alcohol with a multiple carboxylic acid.
  • Branched alcohols in particular 2-alkyl-branched alcohols are mentioned, which are preferably Guerbet alcohols.
  • Renewable resources are not mentioned.
  • lubricants for example gear, industrial and engine oils and hydraulic oils.
  • the base oils are in the form of mixtures Hydrocarbons (mineral oil, PAOs) with high-viscosity esters (HVE) before, which also have additives to improve the viscosity index.
  • Hydrocarbons mineral oil, PAOs
  • HVE high-viscosity esters
  • Reaction products of carboxylic acids and alcohols are disclosed. These do not come from renewable raw materials.
  • known esters are comparatively complicated to produce and correspondingly less economical.
  • ester oils have been known for some time, the economical and environmentally compatible production of optimized and flexible ester oils is still a major challenge. Presentation of the invention
  • the object of the invention is to provide an ester oil belonging to the technical field mentioned at the outset which is as cost-effective and environmentally compatible as possible and, in particular, has optimum properties for applications as a lubricating oil.
  • a first solution of the problem is defined by the features of claims 1 and 41.
  • a first aspect of the invention relates to ester oil, in particular for producing a hydraulic oil and / or lubricant, comprising an esterification product of at least one monoalcohol with at least one polycarboxylic acid, wherein the monoalcohol and / or the polycarboxylic acid originate from renewable raw materials.
  • a monoalcohol is reacted with a polycarboxylic acid to form an ester oil, wherein the monoalcohol and / or the polycarboxylic acid are derived from renewable resources.
  • the monoalcohol and / or the polycarboxylic acid can also be derived from mixtures of renewable and fossil raw materials. It is therefore not mandatory for the monoalcohol and / or the polycarboxylic acid to consist exclusively of .
  • the monoalcohol and / or the polycarboxylic acid are derived essentially exclusively from renewable raw materials.
  • a renewable raw material or a renewable raw material is understood in particular to mean an organic compound which is obtained by direct isolation and / or by refinement from organic raw materials, the organic raw materials being taken primarily from the living nature.
  • Suitable organic raw materials are, for example, plants.
  • Renewable resources are not to be confused with non-renewable raw materials from fossil sources. The latter are z.
  • Renewable raw materials can be distinguished from non-renewable raw materials from fossil sources, in particular by the proportion of the radioactive u C carbon isotope in the raw material. Due to their age, raw materials from fossil sources have essentially no 14 C carbon isotopes, while renewable raw materials have a characteristic fraction of the uC carbon isotope. u C-carbon isotopes are constantly formed by nuclear reactions in the upper Earth's atmosphere and enter the biosphere via the carbon cycle. There is essentially a balance between new formation and permanent radioactive decay. Accordingly, in living organisms of the biosphere (plants, animals) in about the same distribution ratio of radioactive carbon ( 14 C) to non-radioactive carbon ( 12 C and 3 C), as it is present in the atmosphere.
  • the novel ester oils, based on the carbon fraction, are preferably at least 25 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol%, particularly preferably at least 70 mol% formed from renewable raw materials.
  • Lubricants with a minimum content of 25 mol% of the total formulation of renewable raw materials (nwR) are referred to in Europe as Biolubes.
  • Biolubes With further eco-labels lubricants are awarded if, based on the carbon content, preferably at least 50 mol%, more preferably at least 60 Mol%, particularly preferably at least 70 mol% consist of renewable raw materials.
  • criteria relating to toxicology must also be met. In other regions, other criteria must be taken into account.
  • Biopreferred which is known in the USA, requires certain proportions of renewable raw materials, but no statements are made about their toxicity.
  • the radiocarbon method used to determine the proportion of 1 C carbon isotopes is well known to those skilled in the art (ASTM D6866 or DIN EN 15440).
  • the chemically treated samples are z. B. by Libby's counting tube method, by liquid scintillation spectrometry and / or by mass spectrometric detection in accelerators. It is also possible to take account of short-term and long-term fluctuations in the production of 1 C carbon isotopes in the course of geological history.
  • a particularly suitable and standardized method for determining the proportion of renewable resources in a product to be tested is z. As defined in the standard ASTM D6866-08.
  • the organic content of the product derived from renewable raw materials shall be determined in relation to the total organic content of the product. Inorganic carbon and substances without carbon content are not taken into account.
  • the method is based on liquid scintillation spectrometry.
  • the measured ratio of 14 C to 12 C in the product to be tested is determined relative to a standard compound (oxalic acid).
  • lubricant is to be understood in particular to mean an intermediate which serves to reduce friction and wear, as well as for power transmission, cooling, vibration damping, sealing action and / or for corrosion protection.
  • the lubricant of interest in this context is a fluid.
  • a specific lubricant is z.
  • B. a hydraulic fluid.
  • a hydraulic fluid is in particular a fluid which can be used for the transmission of energy (volume flow, pressure) in a hydraulic system.
  • the hydraulic fluid is a hydraulic oil, which in particular is not miscible with water.
  • novel ester oils according to the first aspect in which the monoalcohol and / or the polycarboxylic acid originate from renewable raw materials, are particularly advantageous.
  • ester oils have advantageous properties with regard to use as lubricants and hydraulic oils.
  • ester oils also have good lubricating properties and a high Luftabscheide866. It has also been found that the ester oils have a long life or aging resistance compared with known lubricating oils.
  • the inventive ester oils have a high flash point, so that even use at higher oil sump and component temperatures is safely possible.
  • the flow limit (pour point) of the ester oils is relatively low, as a result of which the ester oils can also be used at low temperatures.
  • the flow limit for a liquid product indicates the temperature at which it is just still able to flow when cooled.
  • the inventive ester oils can be used in a wide temperature range.
  • the viscosity of the novel ester oils is also in an optimum range for lubricating oils and hydraulic fluids. An adjustment of the viscosity by mixing with another, for. B. thicker, oil is not required.
  • the inventive ester oils can be used even at elevated temperatures without causing viscosity changes in the ester oil, as is the case with blended oils due to the different evaporation properties of the individual oil components.
  • the viscosity index (VI), which characterizes the temperature dependence of the kinematic viscosity of a lubricating oil, in the inventive Ester oils relatively high.
  • the ester oils thus show a relatively small temperature-dependent viscosity change, which is very advantageous for most applications in practice, since they can be used in a wide temperature range with relatively constant properties.
  • the evaporation losses (NOACK) of the ester oils according to the invention are also relatively low.
  • the use of renewable resources allows a particularly environmentally friendly and economical production.
  • the inventive ester oils are able to convince at the same time in terms of toxicology and biodegradability.
  • the ester oils according to the invention have a relatively rapid and easy biodegradability.
  • the multiple carboxylic acid is derived from renewable raw materials.
  • the polycarboxylic acid can be prepared from vegetable oils which are already available worldwide in large quantities. From renewable raw materials or vegetable oils can also be a variety of different polycarboxylic acids win in relatively simple chemical process steps. In addition, compliance with current environmental regulations or labels is made possible. But it is also possible in principle, for. B. from fossil raw materials synthesized multiple carboxylic acid, if appropriate.
  • the polycarboxylic acid is saturated. In other words, preferably only single bonds are present between the carbon atoms of the polycarboxylic acid.
  • Ester oils with such polycarboxylic acids have been found to be particularly resistant to oxidation and more stable, which benefits the life or aging resistance of the ester oils.
  • the polycarboxylic acid is unbranched.
  • the polycarboxylic acid preferably has an unbranched carbon chain, which is in particular linear. This has proven to be advantageous for a variety of applications.
  • the polycarboxylic acid may also be branched. Whether an unbranched or a branched polycarboxylic acid is more advantageous depends inter alia on the monoalcohols used for the ester oil and the desired material properties of the ester oil. The use of branched polycarboxylic acids may lower the yield point and increase the flash point, which may be advantageous for specific applications.
  • ester oils with branched polycarboxylic acids may have higher seal compatibilities.
  • the polycarboxylic acid has 6 to 13 carbon atoms, more preferably 8 to 13 carbon atoms.
  • such polycarboxylic acids can be economically obtained from renewable raw materials and, on the other hand, enable the production of a wide range of ester oils which are particularly suitable as lubricants or hydraulic oils.
  • the polycarboxylic acid comprises a dicarboxylic acid.
  • dicarboxylic acid which are particularly suitable as lubricants and hydraulic oils.
  • dicarboxylic acids from renewable raw materials, eg. As vegetable oils, easily possible, which is beneficial to the economy.
  • the dicarboxylic acid comprises in particular adipic acid (1,6-hexanedioic acid, HOOC-C 4 H 8 -COOH), suberic acid (octanedioic acid, HOOC-C 6 H 12 -COOH), azelaic acid (nonanedioic acid, HOOC-C 7 H u -COOH) , Sebacic acid (decanedioic acid, HOOC-C 8 H 16 -COOH), dodecanedioic acid (HOOC-C 10 H 20 -COOH) and / or brassylic acid (HOOC-CiiH 22 -COOH).
  • adipic acid (1,6-hexanedioic acid, HOOC-C 4 H 8 -COOH
  • suberic acid octanedioic acid, HOOC-C 6 H 12 -COOH
  • azelaic acid nonanedioic acid
  • These unbranched dicarboxylic acids with 6, 8, 9, 10, 12 or 13 carbon atoms can be produced from renewable raw materials or vegetable oils.
  • these dicarboxylic acids with a variety of recoverable from renewable raw materials monoalcohols for lubricants or hydraulic oils suitable ester oils can be produced.
  • polycarboxylic acids with three or even more carboxylic acid groups.
  • dicarboxylic acids can be used which z. B. less than 6 carbon atoms or more than 13 carbon atoms.
  • branched derivatives of adipic acid, suberic acid, azelaic acid, dodecanedioic acid and / or brassylic acid can be used.
  • the properties of the ester oils can be controlled even more precisely and, on the other hand, the production process can be further optimized with regard to economic efficiency.
  • the at least two different polycarboxylic acids originate from renewable raw materials.
  • the at least one monoalcohol originates from renewable raw materials.
  • the inventive ester oils can be produced particularly economically by fatty acids from vegetable oils.
  • a variety of different monoalcohols can be obtained oleochemically from fatty acids by known chemical reactions.
  • the at least one monoalcohol is saturated.
  • preferably only single bonds are present between the carbon atoms of the at least one monoalcohol.
  • both the polycarboxylic acid and the at least one monoalcohol are saturated.
  • the oxidation and aging resistance can be greatly improved.
  • the at least one monoalcohol may also be monounsaturated or polyunsaturated.
  • the at least one monoalcohol is unbranched.
  • the at least one monoalcohol advantageously has an unbranched carbon chain, which in particular is linear.
  • the monoalcohol is also referred to in this case as n-monoalcohol. This has proven to be advantageous for a variety of applications. This is especially true when combined with unbranched polycarboxylic acids and especially with unbranched dicarboxylic acids.
  • the at least one monoalcohol may also be branched.
  • the use of branched monoalcohols may lower the yield point and increase the flash point, which may be advantageous for specific applications.
  • ester oils with branched monoalcohols may have higher seal compatibilities.
  • Branched monoalcohols have proved advantageous, in particular in combination with unbranched polycarboxylic acids and in particular unbranched dicarboxylic acids.
  • Branched polycarboxylic acids, in particular branched dicarboxylic acids, are advantageously used in combination with unbranched monoalcohols.
  • Branched monoalcohols advantageously have an iso-end branching. This means, in particular, that a methyl group is arranged or branched off at the second position of the end of the carbon chain remote from the alcohol group.
  • Ester oils comprising monoalcohols with terminal iso branches have proven to be advantageous in practice, in particular for lubricants and hydraulic oils, and at the same time can be produced relatively inexpensively from renewable raw materials.
  • the at least one monoalcohol has 6-24, preferably 8-16, carbon atoms.
  • the at least one monoalcohol 9, 1 1, 12, 14 and / or 16 carbon atoms.
  • such monoalcohols can be obtained economically from renewable raw materials and, on the other hand, enable the production of a wide range of ester oils which are particularly suitable as lubricants or hydraulic oils. This especially in combination with a multiple carboxylic acid or a dicarboxylic acid having 6 to 13 carbon atoms.
  • the at least one monoalcohol is a fatty alcohol and in particular an unbranched fatty alcohol from the group 2-octanol (C 8 H 18 0), 1-nonanol (C 9 H 20 O), 1-undecanol (C ⁇ Hz ⁇ ), 1- Dodecanol (C 12 H 26 O), 1-tetradecanol (C u H 30 O) and / or cetyl alcohol (also known as 1-hexadecanol; C 16 H 34 0).
  • Such monoalcohols are particularly economically available from renewable raw materials and particularly suitable for the novel ester oils. It may also be advantageous to use mixtures of two or even more different fatty alcohols. Such mixtures are also referred to as cuts.
  • Fatty alcohols are commonly available as blends or cuts of different carbon chain lengths.
  • the following cuts are particularly suitable: C8 - C10 fatty alcohols and / or C16 - C18 fatty alcohols.
  • the following ester products can be formed: di-alkyl (C8-10) nonanedioate [CAS #: 92969-93-2], di-alkyl (C16-18) nonanedioate [CAS * 92969-94-3], mono- alkyl (C8-10) nonanedioate [CAS * 92969-95-4] and / or monoalkyl (C16-18) nonanedioate [CAS *: 92969-96-5].
  • the at least one monoalcohol comprises methyltetradecanol (13-methyl-1-tetradecanol; C 15 H 33 0). This is a saturated iso-end-branched monoalcohol.
  • the monoalcohols mentioned in the last two paragraphs have been found to be particularly advantageous in combination with polycarboxylic acids, in particular dicarboxylic acids having 6 to 13 carbon atoms, more preferably 8 to 13 carbon atoms proved.
  • Particularly suitable are combinations with adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and / or brassylic acid.
  • the polycarboxylic acid is particularly preferably a dicarboxylic acid having 12 carbon atoms, in particular 1, 12-dodecanedioic acid, and the at least one monoalcohol is an alcohol having 13 carbon atoms, more preferably 1-tridecanol and / or isotridecanol.
  • Such ester oils have proven to be particularly advantageous for lubricants and hydraulic oils in terms of preparation and properties.
  • the esterification product of the dicarboxylic acid dodecanedioic acid and the monoalcohol isotridecanol has proved particularly suitable in connection with lubricants and / or hydraulic oils.
  • ester oils according to the invention may also be more advantageous.
  • a second aspect of the invention relates to an ester oil, in particular for producing a hydraulic oil and / or a lubricant, comprising an esterification product of at least one monocarboxylic acid with at least one dialcohol, wherein the dialcohol and / or monocarboxylic acid originate from renewable raw materials.
  • a dialcohol with a monocarboxylic acid converted to an ester oil, wherein the dialcohol and / or the monocarboxylic acid derived from renewable resources.
  • dialcohol and / or the monocarboxylic acid can also be derived from mixtures of renewable and fossil raw materials. It is therefore not mandatory that the dialcohol and / or the monocarboxylic acid originate exclusively from renewable raw materials. In a preferred variant, however, the dialcohol and / or monocarboxylic acid are derived essentially exclusively from renewable raw materials.
  • Dialcohol is understood in this context, in particular an organic compound having exactly two hydroxyl groups. Dialcohols may also be referred to as diols and / or dihydric alcohols.
  • ester oils according to the second aspect have proven to be unexpectedly advantageous.
  • ester oils are suitable for lubricants and hydraulic oils.
  • the ester oils also have good lubricating properties and a high Luftabscheide866. It has also been found that the ester oils have a long life or aging resistance compared with known lubricating oils.
  • inventive ester oils have a high flash point, so that use at higher temperatures is also possible without risk.
  • the flow limit of the ester oils is relatively low, whereby the ester oils can be used even at low temperatures.
  • the inventive ester oils can be used in a wide temperature range.
  • the viscosity of the novel ester oils is also in an optimum range for lubricating oils and hydraulic fluids. An adjustment of the viscosity by mixing with another, for. B. thicker, oil is not required.
  • the inventive ester oils can be used even at elevated temperatures without causing viscosity changes in the ester oil, as is the case with blended oils due to the different evaporation properties of the individual oil components. Even a most disadvantageous addition of viscosity modifying thickeners is not required in the novel ester oils due to the relatively high viscosity and the high viscosity index (VI), which characterizes the temperature dependence of the kinematic viscosity of a lubricating oil.
  • VI viscosity index
  • the ester oils Due to the relatively high viscosity index (VI), the ester oils exhibit a relatively small temperature-dependent change in viscosity, which is very advantageous for most applications, since they can be used in a broad temperature range with relatively constant properties.
  • VI viscosity index
  • the use of renewable resources allows a particularly environmentally friendly and economical production.
  • the inventive ester oils are able to convince at the same time in terms of toxicology and biodegradability.
  • the ester oils according to the invention have a relatively rapid and easy biodegradability.
  • monocarboxylic acids are used directly for the preparation of the ester oils in the second aspect of the invention.
  • Monocarboxylic acids are available with a wide variety of structures on the market, with which the properties of the ester oils can be adjusted relatively easily by the use of specific monocarboxylic acids.
  • fatty acids which are obtainable directly from renewable raw materials or vegetable oils can also be used as monocarboxylic acids. This has proven to be particularly economical.
  • the dialcohol preferably originates from renewable raw materials. This has proven to be advantageous, in particular with regard to the economic efficiency of the production exposed. Dialcohols can be z. B. in a conventional manner oleochemically produce. For example, a variety of different polycarboxylic acids can be obtained from vegetable oils by oxidative cleavage, which can then be converted by reduction into dialcohols. Corresponding vegetable oils are already available worldwide in large quantities. From renewable raw materials or vegetable oils can thus be obtained in relatively simple chemical process steps, a variety of different polycarboxylic acids, which can be converted to corresponding dialcohols. In addition, compliance with current environmental regulations or labels is made possible. But it is also possible in principle, for. B. use of fossil raw materials petrochemically produced dialcohols, if appropriate.
  • the dialcohol is saturated.
  • the dialcohol can also be monounsaturated or polyunsaturated.
  • the dialcohol is unbranched.
  • the dialcohol preferably has an unbranched carbon chain, which in particular is linear. This has proven to be particularly advantageous for a variety of applications of ester oil.
  • the dialcohol is branched, in particular methyl or branched one or more times. This means in particular that the dialcohol has a carbon chain, from which at least one methyl group (-CH 3 ) branches off.
  • the dialcohol z. B. be a trimethylhexanediol (TMH).
  • Whether an unbranched or a branched dialcohol is more advantageous depends inter alia on the monocarboxylic acids used for the ester oil and the desired Substance properties of the ester oil from.
  • the use of branched dialcohols may lower the yield point and increase the flash point, which may be advantageous for specific applications.
  • ester oils with branched dialcohols may have higher seal compatibilities.
  • methyl branches have proved to be particularly advantageous.
  • the dialcohol has 5 to 14 carbon atoms.
  • such dialcohols can be economically obtained from renewable raw materials and, on the other hand, enable the production of a wide range of ester oils which are particularly suitable as lubricants or hydraulic oils.
  • dialcohols having less than 5 or more than 14 carbon atoms.
  • this can also be advantageous.
  • the dialcohol is a terminal dialcohol.
  • the alcohol groups are located at the ends of the carbon chain of the alcohol. This can be combined with monocarboxylic acids form ester oils, which are particularly suitable as lubricants and hydraulic oils.
  • the production of terminal dialcohols from renewable raw materials, eg. As vegetable oils easily possible, which is beneficial to the economy.
  • the dialcohol advantageously comprises one or more representatives from the series 1, 6-hexanediol (HO-C 6 H 12 -OH), 1, 7-heptanediol (HO-C 7 H u -OH), 1, 8-octanediol ( HO-C 8 H 16 -OH), 1, 9-nonanediol (HO-C 9 H 18 -OH), 1, 10-decanediol (HO-C 10 H 20 -OH), 1, 12-dodecanediol (HO- C 12 H 24 -OH), 1, 13-tridecanediol (HO-C 13 H 26 -OH) and / or their isomers.
  • isomers are meant, in particular, compounds having the same empirical formula, which, however, differ with regard to linking and / or spatial arrangement of the individual atoms.
  • dialcohols having 6, 7, 8, 9, 10, 12 and 13 carbon atoms, a plurality of ester oils can be formed which are can be economically produced from renewable raw materials and which are particularly well suited for lubricants and hydraulic oils.
  • alcohols having three or even more hydroxyl groups In principle, it is also conceivable to use alcohols having three or even more hydroxyl groups. Also, other than the above representatives of dialcohols can be used which z. B. less than 5 carbon atoms or more than 14 carbon atoms.
  • the properties of the ester oils can be controlled even more precisely and, on the other hand, the production process can be further optimized with regard to economic efficiency.
  • the at least two different dialcohols are derived from renewable raw materials.
  • the at least one monocarboxylic acid originates from renewable raw materials.
  • the inventive ester oils can be produced, for example, particularly economically in a few process steps via fatty acids from vegetable oils.
  • the fatty acids can be used directly without having to be reacted in additional reaction steps to alcohols or other derivatives. Since in each case at least two moles of monocarboxylic acid per mole of dialcohol can be implemented, a relatively high proportion of renewable raw materials in the reaction product or the ester oil can also be achieved by the use of monocarboxylic acids from renewable raw materials. This also simplifies compliance with current environmental regulations or labels.
  • both the dialcohol and the monocarboxylic acid originate from renewable raw materials.
  • the above-mentioned advantages can be further improved.
  • monocarboxylic acids from fossil raw materials, if this appears expedient.
  • the at least one monocarboxylic acid is saturated.
  • between the carbon atoms of the at least one monocarboxylic acid are preferred only Single bonds before.
  • the oxidation resistance and stability of the ester oil can be improved.
  • both the dialcohol and the at least one monocarboxylic acid are saturated.
  • the oxidation and aging resistance can be greatly improved.
  • the at least one monocarboxylic acid is unbranched.
  • the at least one monocarboxylic acid advantageously has an unbranched carbon chain, which in particular is linear. This has proved to be advantageous, in particular with regard to an optimum viscosity of the ester oil for a large number of applications. This in particular in a combination with unbranched dialcohols.
  • the at least one monocarboxylic acid may also be branched.
  • Particularly suitable are monocarboxylic acids which are methyl-branched one or more times.
  • the monocarboxylic acid particularly preferably has an iso end branching.
  • the use of such branched monocarboxylic acids may under certain circumstances lower the yield point and increase the flash point, which may be advantageous for specific applications.
  • ester oils with branched monocarboxylic acids may have higher sealing compatibilities.
  • Branched monocarboxylic acids have proven to be advantageous, in particular in combination with unbranched dialcohols and in particular unbranched dialcohols.
  • Branched dialcohols, in particular branched dialcohols are advantageously used in combination with unbranched monocarboxylic acids.
  • the at least one monocarboxylic acid has 6 to 18 carbon atoms, preferably 9 to 16 carbon atoms.
  • Such monocarboxylic acids can be on the one hand economically recover from renewable resources, eg. B. in the form of fatty acids from vegetable oils, and on the other hand allow the production of a wide range of Ester oils which are particularly suitable as lubricants or hydraulic oils. This especially in combination with dialcohols having 5 to 14 carbon atoms.
  • the at least one monocarboxylic acid is a fatty acid and in particular comprises at least one monocarboxylic acid one or more representatives from the set of caprylic acid (C 7 H 15 -COOH; as octanoic acid hereinafter), pelargonic acid (C 8 H 17 -COOH; also known as Nonanoic acid), capric acid (C 9 H 19 -COOH, also referred to as decanoic acid), undecanoic acid (C 10 H 2 rCOOH), lauric acid ( ⁇ ,, ⁇ ⁇ - ⁇ , also referred to as dodecanoic acid), tridecanoic acid (C 12 H 25 -COOH), myristic acid (C 13 H 27 -COOH, also referred to as tetradecanoic acid), hexanecanoic acid (C 15 H 31 -COOH, also referred to as palmitic acid), octanecanoic acid (C 17 H 35 -COOH, also referred to as
  • the monocarboxylic acids mentioned in the last paragraph have proved to be advantageous in particular in combination with polyalcohols, in particular dialcohols, with 5-14 carbon atoms.
  • Particularly suitable are combinations with one or more representatives from the series 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1 , 13-Tridecanediol and / or their isomers.
  • the monocarboxylic acid is a cyclic monocarboxylic acid, in particular a saturated cyclic monocarboxylic acid.
  • This can be obtained directly from linseed oil, which is contained in the seeds of flax, by alkaline isomerization [see Beal et al .; JAOCS 42, 1 1 15 - 1 1 19 (1965)].
  • the dialcohol is particularly preferably a dialcohol having 12 carbon atoms, in particular 1,12-dodecanediol, and the at least one monocarboxylic acid is a monocarboxylic acid having 13 carbon atoms, more preferably 1-tridecanoic acid and / or isotridecanoic acid.
  • ester oils have proven to be particularly advantageous for lubricants and hydraulic oils in terms of preparation and properties.
  • the ester oil according to the invention is preferably formed from at least 25 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol%, particularly preferably at least 70 mol% from renewable raw materials.
  • the inventive ester oil is formed, except for unavoidable impurities, exclusively from renewable raw materials.
  • a molecular weight of the esterification product is advantageously at least 400 g / mol, in particular at least 550 g / mol.
  • ester oils are particularly suitable, in particular, as lubricants and hydraulic oil. This is probably due to the fact that the substance properties (viscosity, viscosity index, flash point or yield point) which are particularly relevant for lubricants and hydraulic oils in the case of such ester oils are all within a practically optimum to optimum range.
  • ester oils having a lower molecular weight than 500 g / mol are also possible. However, this may be detrimental to certain applications of the ester oils.
  • the esterification product has at least 30 carbon atoms and / or at most 50 carbon atoms.
  • the esterification product has at least 30 carbon atoms and / or at most 50 carbon atoms.
  • the ester oils contain esterification products having at least 30 carbon atoms and / or at most 50 carbon atoms. This can be in an unexpected way at the same time lower the flow limits and increase the viscosity.
  • ester oils may also contain esterification products which have less than 30 carbon atoms and / or more than 50 carbon atoms. This may even be indicated for specific applications.
  • novel ester oils can be used in particular as a lubricant and / or hydraulic oil. This applies both to ester oils according to the first aspect and to ester oils according to the second aspect.
  • Lubricants and / or hydraulic oils which comprise an ester oil according to the invention preferably have a proportion of ester oil of at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, very particularly preferably at least 93% by weight. %, even more preferably at least 96% by weight, based on the total weight of the lubricant.
  • the lubricants or hydraulic fluid may then no longer have the aforementioned advantageous properties.
  • the lubricant and / or the hydraulic fluid contains additives for improving the properties.
  • Antioxidants, anti-wear additives, metal deactivators, corrosion inhibitors and / or defoamers are advantageously used as additives.
  • antioxidants in particular aminic antioxidants and / or phenolic antioxidants are advantageous.
  • Suitable aminic antioxidants are alkylated diphenylamines (alkylated DPA) and / or N-phenyl-alpha-naphthylamine (PANA).
  • a proportion of the aminic antioxidants is in particular 0.01-3% by weight, particularly preferably 0.1-0.5% by weight.
  • BHT butylhydroxytoluene
  • 2,6-di-tert-butyl-phenol (2,6-DTBP) and / or derivatives of 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) are mentioned as phenolic antioxidants.
  • propionate advantageous.
  • Particularly suitable derivatives are octadecyl 3- (3,5-di-fe / t-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate for example, 6,6'-di-tert-butyl-2,2'-methylene di-p-cresol [CAS * 1 19-47-1] and 4,4'-methylene-bis-2 are advantageous 6 di-tert-butyl-phenol [CAS *: 1 18-82-1].
  • a proportion of the phenolic antioxidants is in particular 0.01-5% by weight, particularly preferably 0.3-0.7% by weight.
  • the lubricant and / or the hydraulic fluid contain both aminic antioxidants and phenolic antioxidants.
  • ashless anti-wear additives are used. Wear protection additives such as zinc dithio-phosphates are therefore preferably not used. Suitable anti-wear additives are, in particular, amine phosphates, alkylated phosphates, such as. Tricresyl phosphate, triphenyl phosphorothionate and / or sulfonated esters. A proportion of the anti-wear additives is advantageously 0.01-3% by weight, in particular 0.6-1.0% by weight.
  • metal deactivators in particular benzotriazole, tolutriazole and corresponding Mannich bases and / or derivatives of 2,5-dimercapto-1, 3,4-thiadiazole have proven to be advantageous.
  • a proportion of the metal deactivators is advantageously 0.01-1% by weight, preferably 0.02-0.1% by weight.
  • Suitable corrosion inhibitors are, for example, alkylated succinylic acid and / or derivatives thereof, such as. B. semi-esters, hemiamides and / or amine phosphates.
  • the proportion of corrosion inhibitors is in particular from 0.01 to 3 wt .-%, preferably 0.1 to 0.4 wt .-%.
  • defoamers are particularly suitable: alkyl polyacrylates, Metaycrylat derivatives and / or polydimethyl-siloxanes (PDMS).
  • An advantageous proportion is 0.001-0.1% by weight, preferably 0.01-0.03% by weight.
  • antioxidants are in particular chemically compatible with the novel ester oils.
  • the stated proportions also provide optimum effects without compromising the performance of the lubricants and / or hydraulic fluids. In principle, however, additional and / or other additives can also be used. It is also possible to dispense with some or all of the additives mentioned.
  • the monocarboxylic acids, polycarboxylic acids, monoalcohols and / or dialcohols used for the preparation of the ester oils are preferably prepared from fatty acids from renewable raw materials. Particularly suitable are palm oil and / or fatty acids such as oleic acid (C18: 1, 9Z, co-9), linoleic acid (C18: 2, 9Z, 12Z, ⁇ -6), gadoleic acid (C20: 1, 1Z, co-9 ), Erucic acid (C22: 1, 1 3Z, ⁇ -9), petroselinic acid (C 1 8: 1; 6Z; ⁇ -6), arachidonic acid (C20: 4, 51, 8Z, 1 1 Z, 14Z, ⁇ -6 ) and / or generally omega-6 fatty acids.
  • palm oil and / or fatty acids such as oleic acid (C18: 1, 9Z, co-9), linoleic acid (C18: 2, 9Z, 12Z, ⁇ -6), gadoleic acid (C
  • the number following the name of the fatty acid after the letter "C” in parentheses indicates the number of carbon atoms. Separated by a colon, the number of double bonds in the fatty acid and information on the position and configuration (Z, E) of the double bonds in the carbon chain follows. Also listed is the ⁇ -type of the fatty acid or the position of the first double bond relative to the last and of the carboxy group furthest spaced carbon atom ("o") in the carbon chain.
  • Particularly suitable for the preparation of the monocarboxylic acids, polycarboxylic acids, monoalcohols and / or dialcohols used for the ester oils are also hydroxyfatty acids, in particular ricinoleic acid (C 18: 1; 9Z; 1 2R; 1 2-hydroxy; ⁇ -9), lesquerolic acid (C20: 1 Z 1 1; 14-hydroxy) and / or vernolic acid (C 18: 1; 9Z; 13-epoxy; ⁇ -9).
  • ricinoleic acid C 18: 1; 9Z; 1 2R; 1 2-hydroxy; ⁇ -9
  • lesquerolic acid C20: 1 Z 1 1; 14-hydroxy
  • / or vernolic acid C 18: 1; 9Z; 13-epoxy; ⁇ -9.
  • Such sources of raw materials in particular allow an economical production of ester oils for lubricants and hydraulic oils.
  • a variety of vegetable oils and / or animal fats are known to those skilled in the art, from which the fatty acids mentioned
  • Fig. 1 is a diagram showing the friction coefficients (f) as a function of
  • FIG. 4a, b Four diagrams which show the friction coefficient (f), the normal force (F N ) and deflection (stroke dx) in that of FIG. 1 Vibration Fretting Test with Trimethylolpropane Ester (TMP-C8 / C10) as a function of time.
  • Fatty acids such as oleic acid, linoleic acid, gadoleic acid, erucic acid, petroselinic acid, arachidonic acid or generally ⁇ -6-fatty acids can be, for. B. win in a conventional manner via alkaline saponification of the corresponding triacylglycerides.
  • the appropriate fats or oils are boiled with bases.
  • the resulting salts can then be neutralized with acids, whereby free fatty acids or mixtures of free fatty acids are obtained.
  • a separation of the different fatty acids in the mixtures takes place z. B. by a distillative separation process.
  • Oleic acid may, for. B. from olive oil, peanut oil, avocado oil, goose fat, palm oil, lard, sesame oil, Hammeltalg, beef tallow and sunflower oil are obtained. Linoleic acid is available, for example, from safflower oil, sunflower oil, soybean oil, corn oil and olive oil. Gadoleinic acid is contained in jojoba oil, while erucic acid is found in various types of rapeseed and sea kale. Furthermore, petroselinic acid can be obtained from coriander oil and arachidonic acid from animal fats or fish oil.
  • Rizinolic acid may, for. Example, by hydrolysis of castor oil in which the substance occurs in the form of triglycerides can be obtained.
  • Lesquerolic acid is available, in particular, from the oil of Lesquerella fendleri seeds, while vernolic acid is obtainable by extraction from the seeds of Vernonia galamensis, a plant of the sunflower family.
  • Adipic acid from renewable raw materials can be obtained for example from xylose derivatives (C 5 sugar), by decarbonylation of furfuryl alcohol (furfural, C 5 H 4 0 2 ). It is also possible to obtain from glucose (C 6 sugar), in the form of sorbitol or from D-glucose [KM Drahts et al., J. Am. Chem. Soc. 1994, Vol. 1 16, pp.
  • adipic acid can be obtained via an oxidative cleavage of an ⁇ -6-fatty acid, such as.
  • elaidic acid or trans-9-octadecenoic acid [CAS * 1 12-79-8; Ci 8 H 34 0 2 ], which corresponds to the trans isomer of oleic acid, applies mutatis mutandis the same.
  • Azeal acid is also in the same way from gadoleic acid or eicosenoic acid [CAS * 26764-41-0; C20: 1; ⁇ -9; MW - 310.51] obtainable by oxidative cleavage.
  • oxidative cleavage (described in the same manner as in the case of the azealic acid)
  • pelargonic acid is used as monocarboxylic acid and brassylic acid or tridecanedioic acid [CAS * 505-52-2; C 13 H 24 0 4 .
  • M w 244.3] as a saturated C 13 dicarboxylic acid formed.
  • Suberic acid can be obtained petrochemically by ozonolysis of cyclooctene. On the basis of renewable raw materials, it can be obtained mainly from cork bark and potato peels.
  • Cork powder can be split by oxidation with HN0 3 to cork acid. Also possible is the oxidative cleavage of ricinoleic acid, palm oil and oleic acid, in which in addition to azelaic also suberic acid is formed, [see, for. BRG Kadesh; J. Am. Oil Chemists' Soc. Vol. 56, pp. 845A-849A (1979) and references therein].
  • Capric acid itself, for example, comes in Triglycerides bound in vegetable oils and is also contained in palm oil, coconut oil and in the fat of goat's milk.
  • mixtures with C 1 -C 4 -alcohols which are rich in C 10 -alcohols are also commercially available [CAS * 93821-1 1-5 or 68526-85-2].
  • various mixtures with 1-tridecanol are commercially available.
  • BASF a mixture of 1-tridekanol with 1-dodecanol [CAS #: 90583-91-8] or Shell under the name "Neodol 25" a mixture of C 10 -C 17 alcohols, which is also the C 13 -Alkohole includes.
  • myristic acid C 14 0 [CAS * 544- 63-81] are obtained, which is contained in coconut oil to about 15 - 21% and in palm kernel oil to about 14 - 18%.
  • General fatty alcohols
  • fatty alcohols can be obtained directly from vegetable raw materials.
  • fatty alcohols can be prepared, for example, by reduction of corresponding esters with sodium (Bouveault-Blanc reaction).
  • fatty alcohols can be prepared by hydrogenation on copper or copper / cadmium catalysts. Frequently, fatty alcohols are produced petrochemically from petroleum today and are accordingly available commercially. From renewable raw materials, fatty alcohols can be prepared in particular by hydrogenation of fatty acids from vegetable oils. The fatty acids are reduced, for example with lithium aluminum hydride in a conventional manner to the corresponding fatty alcohols.
  • 1.6-hexane diol
  • the z. B. from the oxidative cleavage of mono- and dicarboxylic acids and alcohols are taking advantage of different material properties such.
  • Dicarboxylic acid esters can be prepared in a manner known per se by reacting dicarboxylic acids with monoalcohols with elimination of water.
  • the esterification can in particular be acid-catalyzed (Fischer esterification) and is well known to the person skilled in the art.
  • 2 mol of monoalcohols are reacted with 1 mol of dicarboxylic acid for the preparation of dicarboxylic acid esters.
  • the diesters listed in the table below have proven to be particularly advantageous in the field test for hydraulic oils. All diesters can be made from 100% renewable raw materials. In the last column, the maximum proportion of renewable raw materials from the dicarboxylic acid (S) and from the monoalcohols (A) in the diester is indicated in each case.
  • Dialcohol esters or diol esters can be obtained by reacting dialcohols with monocarboxylic acids.
  • monocarboxylic acids for the preparation of diol esters, in particular 2 mol monocarboxylic acids are reacted with 1 mol of diol.
  • the diesters listed in the table below have proven to be particularly advantageous in the field test for hydraulic oils.
  • the diol esters can also be produced 100% from renewable raw materials. In the last column, the maximum proportion of renewable raw materials from the diol (A) and from the monocarboxylic acids (S) is indicated in the diol ester.
  • diesters described above are merely examples that may be modified within the scope of the invention.
  • This can be compared to the unbranched variants lower the flow limits and slightly increase the viscosity.
  • z. B. 1, 6-hexanediol also be prepared by branched diols from the series neopentyl glycol, 2,2,4-trimethyl-1, 3-pentanediol and / or 2-butyl-2-ethyl-1, 3-propanediol.
  • Hydraulic oils Hydraulic oils according to the invention advantageously have at least 93% by weight of a base oil.
  • a hydraulic oil has the composition described in Table 1 below.
  • Table 2 below shows various viscometric properties of selected diesters.
  • the diesters having more than 30 carbon atoms have relatively high viscosity layers (compare ⁇ 40 ⁇ ( ⁇ values), which is particularly advantageous when used as hydraulic oil or lubricant.)
  • the values in the column OECD 301 B / F indicates the biodegradability according to the known OECD-test procedure, in the column UBA- the numbers assigned by the German Federal Environment Agency are given.
  • ester base oils trimethylolpropane esters (TMP-C8 / C10), diisotridecyl adipate (DITA), di (isotridecyl) dodecanedioate (C12D13, three samples), di (isotridecyl) decandioate (C10D13, three samples), and Di (isotridecyl) nonanedioate (C9D13) and the fully-formulated hydraulic oil "PANOLIN HLP Synth" based on DITA (available from Panolin, Switzerland) are compared in comparison experiments.
  • DITA diisotridecyl adipate
  • DIITA di (isotridecyl) dodecanedioate
  • C10D13 di (isotridecyl) decandioate
  • the table also contains information on an ester of a diol and two carboxylic acids, namely neopentyl glycol di (isostearate) (D5C 18).
  • the lubricants used have the viscometric properties contained in Table 3.
  • the C12D13 esters and the C10D 13 esters three independently prepared samples were considered.
  • the C9D 13 ester and the D5C18 ester each tested one sample.
  • the columns “CCS- 25 " c [mPas] "and” CCS_ 20 “c [mPas]” contain information from the so-called “Cold Crank Simulator” according to ASTM D5293 at -25 ° C and -20, respectively ° C.
  • the column HTHS [mPas] indicates the so-called "high temperature high shear viscosity" (HTHS) at elevated temperature.
  • HTHS high temperature high shear viscosity
  • Table 4 contains ecotoxicological information for orientation purposes and taken from safety data sheets.
  • the column "Aquatic toxicity [mg / l]" contains information on the toxicity tests according to the known test methods according to OECD 201, 202 and 203.
  • the NOACK values of the tested esters are also lower than or equal to the NOACK value of the commercially available hydraulic oil "PANOLIN HLP Synth” (available from Panolin, Switzerland), which is a fully formulated hydraulic oil based on DITA. If one compares the NOACK values of the investigated esters with "PANOLIN HLP Synth", it can be expected that the NOACK value for a hydraulic oil fully formulated from a tested ester will be well below 2.0 - 4.3%. For the environment this means less oil consumption, ie entry into the environment, and less recharging costs for the user, which reduces operating costs and, once again, benefits the environment by conserving resources.
  • Another advantage of the examined esters is the high flash point of up to 280 ° C, which is about 40 ° higher than that of the "PANOLIN HLP Synth". This is a significant safety gain and additionally opens up the possibility of further increasing the flash point into the area of flame-retardant hydraulic fluids by means of suitable additives.
  • the C12D 13 base oil is viscometric, so z. B. at the kinematic viscosity at 40 ° C, without the addition of polymeric viscosity index improvers or thickeners, comparable to PANOLIN HLP Synth. This results in a better foam behavior, since the air bubbles are not hindered by the macromolecules on the rise. Furthermore, it can be assumed that the low-temperature viscosities of a polymer-free or polymer-reduced formulation based on C12D 13 are lower. This significantly improves oil penetration at low temperatures. The lubricating film build-up in all lubrication points of the construction machine and its accessories is faster and with lower pump performance (energy efficiency).
  • esters studied show higher viscosity indices, increased viscosity levels, increased flash points and also lower NOACK evaporations over diisotridecyl adipate (DITA).
  • DITA diisotridecyl adipate
  • FIG. 1 shows the results of vibrational fretting tests (SRV, model III) with the five unadditized ester base oils diisotridecyl adipate (DITA), trimethylol propane ester (TMP-C8 / C10), di (isotridecyl) nonanedioate (C9D13), di (isotridecyl) dodecanedioate (C12D 13) and di (isotridecyl) decanedioate (C 10D 13).
  • DITA diisotridecyl adipate
  • TMP-C8 / C10 trimethylol propane ester
  • C9D13 di (isotridecyl) nonanedioate
  • C12D 13 di (isotridecyl) dodecanedioate
  • C 10D 13 di (isotridecyl) decanedioate
  • test tests were carried out according to the standard ASTM D7421-08 (feeding load) at a typical operating temperature for hydraulic oils of + 80 ° C.
  • the frequency was 50 Hz at a deflection of 1 mm (in the positive x direction) and 2 mm (in the negative x direction).
  • the normal force was increased by 100 N every 2 minutes during the trials. It shows that extending the chain length of the dicarboxylic acid also improves the frying load-bearing capacity of the base oil.
  • values greater than P 3'938 MPa are reached, as at 2 ⁇ 00 N or after 40 minutes, no adhesive failure occurs.
  • the C9D13 diesters and C12D 13 diesters surpass the feeding load limit of the trimethylol propane ester (TMP-C8 / C10) and, even as unadditized base oils, significantly lower the mixing / limiting friction coefficient at high pressures.
  • TMP-C8 / C10 trimethylol propane ester
  • Fig. 2a shows graphs showing the coefficient of friction (f) and the normal force (F N ) (top) and the deflection (stroke dx) and the normal force (F N ) (bottom) of diisotridecyl adipate in the positive x direction as a function of time represent.
  • Fig. 2b accordingly shows diagrams showing the friction coefficient (f) and the normal force (F N ) (above) and also the deflection (stroke dx) and the normal force (F N ) (below) of diisotridecyl adipate in the negative x direction as a function to reflect the time.
  • Figures 3a, b are graphs showing the corresponding data for diisotridecyl dodecanedioate (C12D13), while Figures 4a, b show in an analogous manner the graphs for trimethylolpropane ester (TMP-C8 / C10).
  • the investigated esters di (isotridecyl) nonanedioate (C9D 13), di (isotridecyl) dodecanedioate (C12D 13) and di (isotridecyl) decanedioate (C10D13) are said to be used for eco-friendly lubricants, preferably at least 25% by weight of carbon Mol%, more preferably at least 50 mol%, even more preferably at least 60 mol%, particularly preferably at least 70 mol% consist of renewable raw materials.
  • renewable raw materials nwR
  • the proportion is measured by radiocarbon methods (ASTM D6866 or DIN EN 15440: 201 1-05).
  • ASTM D6866 or DIN EN 15440: 201 1-05 This means that the ester C12D13 is already a biolube if only the acid component (dodecanedioic acid, proportion nwR of 31.6%) comes from renewable raw materials.
  • C10D13 (27.8% share nwR) and C9D13 (25.7% share nwR) also meet this criterion.
  • C6D13 (DITA, 18.79% nwR) alone can not be considered a biolube.
  • a lubricant based on DITA meets this requirement if it contains additional esters of renewable raw materials in low additions, which can compensate for the proportion of renewable raw materials.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une huile d'ester, notamment pour la fabrication d'une huile hydraulique et/ou d'un lubrifiant, contenant un produit d'estérification d'au moins un monoalcool avec au moins un acide polycarboxylique, qui est, selon un premier aspect, caractérisée en ce que le monoalcool et/ou l'acide polycarboxylique sont issus de matières premières renouvelables. L'invention concerne également une huile d'ester, notamment pour la fabrication d'une huile hydraulique et/ou d'un lubrifiant, contenant un produit d'estérification d'au moins un acide monocarboxylique avec au moins un dialcool, qui est, selon un second aspect, caractérisée en ce que le dialcool et/ou l'acide monocarboxylique sont issus de matières premières renouvelables.
EP11754976.6A 2010-08-25 2011-08-25 Huiles d'esters Withdrawn EP2609178A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH01378/10A CH703629A8 (de) 2010-08-25 2010-08-25 Esteröle.
PCT/CH2011/000194 WO2012024808A1 (fr) 2010-08-25 2011-08-25 Huiles d'esters

Publications (1)

Publication Number Publication Date
EP2609178A1 true EP2609178A1 (fr) 2013-07-03

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EP11754976.6A Withdrawn EP2609178A1 (fr) 2010-08-25 2011-08-25 Huiles d'esters

Country Status (6)

Country Link
US (1) US20130190217A1 (fr)
EP (1) EP2609178A1 (fr)
BR (1) BR112013004432A2 (fr)
CA (1) CA2809150A1 (fr)
CH (1) CH703629A8 (fr)
WO (1) WO2012024808A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN104718315A (zh) * 2012-08-22 2015-06-17 因温斯特技术公司 脂族二羧酸混合物调配物
CA2924253C (fr) * 2013-10-31 2018-06-19 Amril Ag Fluides de traitement de puits respectueux de l'environnement comprenant un ester
DE102015122273A1 (de) * 2015-12-18 2017-06-22 Minebea Co., Ltd. Verfahren zur Herstellung eines Basisfluids für Schmiermittelzusammensetzungen zur Verwendung in fluiddynamischen Lagersystemen
US10190067B2 (en) * 2016-02-24 2019-01-29 Washington State University High performance environmentally acceptable hydraulic fluid

Citations (1)

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EP0552554A1 (fr) * 1992-01-22 1993-07-28 The British Petroleum Company P.L.C. Compositions d'huile lubrifiante

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US2507401A (en) * 1948-01-19 1950-05-09 Wagner Electric Corp Brake fluid
US2823113A (en) 1954-02-03 1958-02-11 Manila Mine Dev Corp Process of treating vanadium and molybdenum ores
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US3878112A (en) * 1974-05-23 1975-04-15 Westinghouse Electric Corp Lubricant-refrigerant system for centrifugal refrigeration compressors
JP2901413B2 (ja) 1992-04-22 1999-06-07 北村機電株式会社 巻鉄心用帯材の切り抜き装置
US5629190A (en) 1992-08-10 1997-05-13 Rhone-Poulenc Chimie Polypeptides possessing a nitrilase activity and method of converting nitriles to carboxylates by means of said polypeptides
EP0612831B1 (fr) * 1992-12-07 1998-03-25 Idemitsu Kosan Company Limited Huile hydraulique ignifuge
DE10343623A1 (de) * 2003-09-20 2005-04-28 Celanese Chem Europe Gmbh Carbonsäureester auf Basis von Limonanalkohol [3-(4'-Methylcyclohexyl)butanol] mit niedrigem Stockpunkt
DE102004034202A1 (de) 2004-07-14 2005-11-10 Sasol Germany Gmbh Dicarbonsäure-Estermischungen und deren Verwendung
DE102006001768A1 (de) 2006-01-12 2007-07-19 Cognis Ip Management Gmbh Verwendung von Estern mit verzweigten Alkylgruppen als Schmiermittel
DE102006027602A1 (de) 2006-06-13 2007-12-20 Cognis Ip Management Gmbh Schmierstoffzusammensetzungen enthaltend Komplexester
US20080004475A1 (en) 2006-06-28 2008-01-03 Basf Aktiengesellschaft Process for the production of neopentylglycol using formaldehyde with a low methanol content

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EP0552554A1 (fr) * 1992-01-22 1993-07-28 The British Petroleum Company P.L.C. Compositions d'huile lubrifiante

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Title
See also references of WO2012024808A1 *

Also Published As

Publication number Publication date
WO2012024808A1 (fr) 2012-03-01
BR112013004432A2 (pt) 2016-05-31
CH703629A8 (de) 2012-04-30
CA2809150A1 (fr) 2012-03-01
CH703629A2 (de) 2012-02-29
US20130190217A1 (en) 2013-07-25

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