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EP3375850A1 - High-temperature lubricant for the food industry - Google Patents

High-temperature lubricant for the food industry Download PDF

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Publication number
EP3375850A1
EP3375850A1 EP18000086.1A EP18000086A EP3375850A1 EP 3375850 A1 EP3375850 A1 EP 3375850A1 EP 18000086 A EP18000086 A EP 18000086A EP 3375850 A1 EP3375850 A1 EP 3375850A1
Authority
EP
European Patent Office
Prior art keywords
oil
temperature
group
mixture
food
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.)
Granted
Application number
EP18000086.1A
Other languages
German (de)
French (fr)
Other versions
EP3375850B1 (en
Inventor
Karl EGERSDÖRFER
Thomas Kilthau
Martin Schmidt-Amelunxen
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.)
Klueber Lubrication Muenchen GmbH and Co KG
Original Assignee
Klueber Lubrication Muenchen SE and Co KG
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 Klueber Lubrication Muenchen SE and Co KG filed Critical Klueber Lubrication Muenchen SE and Co KG
Priority to PL18000086T priority Critical patent/PL3375850T3/en
Publication of EP3375850A1 publication Critical patent/EP3375850A1/en
Application granted granted Critical
Publication of EP3375850B1 publication Critical patent/EP3375850B1/en
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02Well-defined hydrocarbons
    • C10M105/06Well-defined hydrocarbons aromatic
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04Detergent property or dispersant property
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/62Food grade properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76Reduction of noise, shudder, or vibrations
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/38Conveyors or chain belts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/04Aerosols
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02Reduction, e.g. hydrogenation

Definitions

  • the invention relates to a high-temperature lubricant, in particular a high-temperature oil based on an aromatic ester, such as a trimellitic acid ester and mixtures of various trimellitic acid esters, heteroaromatics, estolides and a fully hydrogenated or hydrogenated polyisobutylene or a mixture thereof.
  • the high-temperature lubricant may be a high-temperature grease when a thickening agent is added to the above-mentioned components.
  • the invention further relates to the use of these high temperature lubricants for lubricating implements used in the processing of food.
  • the lubricants must fulfill a variety of other tasks: they must cool, reduce friction, wear and power transmission, protect against corrosion and at the same time have a sealing effect.
  • Synthetic esters are often used as base oils for high-temperature applications since they have very good oxidative, hydrolytic and thermal stability.
  • the lubricants In order to meet the diverse requirements of high-temperature applications, the lubricants must have, among other things, high stability, low friction coefficients and high wear resistance. In order to ensure uniform lubrication even at high temperatures, a liquid lubricant film must remain between metal parts during the entire processing process. Therefore, the lubricant must evaporate only slightly at the maximum processing temperature, form little residue and form as few cracking residues as possible.
  • High processing temperatures often occur during food processing, such as cooking, baking, boiling, roasting, braising, sterilizing, frying and steaming.
  • various tools are used. To lubricate these tools high temperature resistant lubricants are necessary.
  • a food-grade lubricant H1 should be suitable if the lubricant can come into direct or indirect contact with foodstuffs, food and groceries.
  • Preferred applications in the food industry include chains in ovens and other high temperature applications, as well as conveyor hangers, especially trolleys and their bearings.
  • lubricants are subject to regulatory requirements such as NSF / H1 or NSF / H2 certification.
  • the classification "H1” is to be obtained from lubricants that are in "incidental food contact", that is to say in an occasional technically unavoidable contact with foodstuffs. However, intentional or permanent contact should also be excluded when using “H1” lubricants.
  • An “H2” classification can produce lubricants that are non-toxic and non-carcinogenic. When using “H2” lubricants, however, any contact with the food must be excluded.
  • the food-compatible lubricants used hitherto have a good oxidation resistance and an acceptable pour point, their residue behavior after complete evaporation does not correspond to the high demands demanded in high-temperature applications.
  • the resulting cracking residues form deposits, which must be removed again after some time. As a rule, the operation of the plant must be stopped and the residue removed or the components replaced.
  • the object of the present invention is to provide a high-temperature oil and a high-temperature grease, which meets the standards of NSF / H1 lubricant and moreover has satisfactory tribological properties.
  • the lubricant should show a good lubricating effect at high temperature over a long period of time.
  • the Vercrackungs Wegwarnote should not be laked, but be redissolvable by fresh oil.
  • the high-temperature lubricant should have a good hydrolytic stability, be resistant to corrosion and wear, and have a good oxidation resistance and adapted to the requirements of low-temperature behavior.
  • the high-temperature oil according to the invention and the high-temperature fat according to the invention are both suitable for an H1 classification and are distinguished by outstanding performance.
  • the high-temperature oil or high-temperature grease according to the invention exhibits high thermal stability combined with a long service life and good lubricating properties.
  • the high-temperature oil and the high-temperature fat of the present invention comprise as an ester compound a trimellitic acid ester or a mixture of various trimellitic acid esters, wherein the alcoholic group of the ester is a linear or branched alkyl group having 8 to 16 carbon atoms.
  • the properties of the lubricant for example the viscosity, the viscosity-temperature behavior, the oxidation resistance and residue behavior can be adjusted.
  • the aromatic ester comprises a sterically hindered alcohol as alcohol component, preferably an alcohol having 8 to 16 carbon atoms, in particular 10 to 13 carbon atoms, in particular trimellitic tri (iso-C 10 ) ester (1) and trimellitic acid tri (iso-C 13 ) ester (2).
  • the mixing ratio of (1) to (2) is 99: 1 to 1:99, more preferably, the mixing ratio of (1): (2) is 87.12.
  • the high-temperature oil according to the invention or the high-temperature fat according to the invention may contain a second oil which comprises an aromatic.
  • an aromatic means a monocyclic, bicyclic or tricyclic ring system having four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings being aromatic in a bi- or tricylic ring system.
  • a bicyclic ring system which preferably has 10 carbon atoms.
  • the aromatic is substituted with one or more aliphatic substituents.
  • the aromatic is particularly preferably substituted by one to four aliphatic substituents and in particular by two or three aliphatic substituents.
  • An alkyl group according to the invention is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 to 17 and especially 6 to 15 carbon atoms.
  • An alkyl group may be linear or branched and is optionally substituted with one or more of the abovementioned substituents.
  • the viscosity, measured at 40 ° C, of the aliphatically substituted naphthalene is preferably 30 to 600 mm 2 / s, more preferably 30 to 300 m 2 / s.
  • estolides can also be used as component a).
  • Preferred viscosities, measured at 40 ° C are between 30 and 500 mm 2 / sec. Viscosities of 30 to 140 mm 2 / sec are particularly preferred.
  • Estolides are ester compounds which are acid or enzymatically catalyzed from fatty acids, preferably oleic acid or dicarboxylic acids.
  • the acid function attacks the double bond of an adjacent fatty acid molecule, resulting in a higher molecular weight ester compound.
  • the terminal acid group is then usually esterified with an alcohol, preferably 2-ethyl-hexanol, and then the remaining double bonds are hydrogenated or with carboxylic acid, e.g. Acetic acid esterified.
  • Other alcohols such as e.g. Isoamyl alcohol or Guebert alcohols are also conceivable for the esterification of the terminal acid group.
  • estolides can also be synthesized via a condensation of hydroxycarboxylic acids, for example oleic or stearic acid derivatives.
  • the chain length of the hydroxycarboxylic acids or unsaturated acids used can range from C 6 to C 54 .
  • the acids may contain other functional groups such as amines, ethers, sulfur-containing groups.
  • an esterification with alpha-olefins or ß-Farnesen is conceivable.
  • the high-temperature oil or high-temperature grease according to the invention furthermore comprises a polyisobutylene.
  • a polyisobutylene By suitable choice of the polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, the properties of the oil and fat according to the invention, for example their kinematic viscosity, can be influenced in a desired manner.
  • the polyisobutylene can be used in hydrogenated or fully hydrogenated form, as well as a mixture of hydrogenated and fully hydrogenated polyisobutylene can be used. Fully hydrogenated polyisobutylenes are preferably used.
  • the polyisobutylene is present in an amount of 6 to 45 wt .-% in the composition, preferably 10 to 45 wt .-%, in particular 15 to 45 wt .-% are used.
  • the polyisobutylene has a number average molecular weight of 115 to 10,000 g / mol, preferably from 160 to 5000 g / mol.
  • the high-temperature oil or high-temperature grease according to the invention comprise further from 0.1 to 5 wt .-%, additives which are used individually or in combination and are selected from the group consisting of anti-corrosion additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants.
  • the high-temperature fat according to the invention further comprises a thickener.
  • the thickener in the high-temperature grease of the lubricant composition according to the invention is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatophenylmethane, 4,4'-diisocyanatodi phenyl, 4,4'-diisocyanato-3,3'-dimethylphenyl, 4,4'-diisocyanato-3,3'-dimethylphenylmethane, which may be used singly or in combination with an amine of the general formula R ' 2 -NR , or a diamine of the general formula R ' 2 -NR-NR' 2 , wherein R is an aryl, alky
  • antioxidants can reduce or even prevent the oxidation of the oil or fat according to the invention, in particular when it is used. Oxidation can lead to undesirable free radicals and, as a result, decomposition reactions of the high-temperature lubricant can occur.
  • the addition of antioxidants turns the high-temperature oil or grease stabilized.
  • antioxidants are the following food-compatible compounds: diaromatic amines, phenolic resins, thiophenol resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alpha-naphthylamine, phenyl-betanaphthylamine, octylated / butylated diphenylamine, di-alpha-tocopherol, di-tert-butyl-phenyl, benzenepropanoic acid and mixtures of these components.
  • the high temperature oil or grease may contain corrosion inhibiting additives, metal deactivators or ion complexing agents.
  • corrosion inhibiting additives metal deactivators or ion complexing agents.
  • These include triazoles, imidazolines, N-methylglycine (sarcosine), benzotriazole derivatives, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; N-methyl-N (1-oxo-9-octadecenyl) glycine, mixture of phosphoric acid and mono- and Diisooctylester reacted with (C 11-14 ) alkylamines, mixture of phosphoric acid and mono- and Diisooctylester reacted with tert-alkylamine and primary (C 12-14 ) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates.
  • IRGAMET® 39 IRGACOR® DSS G, amine O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 and CI-498.
  • anti-wear additives are amines, amine phosphates, phosphates, thiophosphates, phosphorothionates and mixtures of these components.
  • Commercially available anti-wear additives include IRGALUBE® TPPT, IRGALUBE® 232, IRGALUBE® 349, IRGALUBE® 211 and ADDITIN® RC3760 Liq 3960, FIRC-SHUN® FG 1505 and FG 1506, NA-LUBE® KR-015FG, LUBEBOND®, FLUORO ® FG, SYNALOX® 40-D, ACHESON® FGA 1820 and ACHESON® FGA 1810.
  • the oil or the fat may contain food grade solid lubricants such as PTFE, BN, Na pyrophosphate, Zn oxide, Mg oxide, Zn pyrophosphate, Na thiosulfate, Mg carbonate, Ca carbonate, Ca stearate, Zn oxide. Sulfide or a mixture thereof.
  • the high-temperature oil or fat according to the invention may contain, as another food-compatible base oil, an oil, preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides and / or poly-alpha-olefins.
  • an oil preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides and / or poly-alpha-olefins.
  • the high temperature oil or fat according to the invention contains an estolide, preferably the main constituents of the estolide being obtained by chemical or enzymatic processes starting from native oils from the group of sunflower oil, rapeseed oil, castor oil, linseed oil, corn oil, diest oil, soybean oil, linseed oil , Peanut oil, "Lesqueralle” oil, palm oil, olive oil or mixtures of the aforementioned oils.
  • native oils from the group of sunflower oil, rapeseed oil, castor oil, linseed oil, corn oil, diest oil, soybean oil, linseed oil , Peanut oil, "Lesqueralle” oil, palm oil, olive oil or mixtures of the aforementioned oils.
  • the high-temperature oil or fat according to the invention due to its physical and chemical properties, can be used excellently for lubricating working devices for processing foodstuffs. Due to its good temperature resistance, it can also be used at high use temperatures up to 260 ° C, preferably at temperatures of 150 to 250 ° C, e.g. Chains in ovens.
  • the invention further relates to a process for the preparation of the above-described high-temperature oil or grease, in which the base oils and the additives are mixed together.
  • trimellitic acid esters Two trimellitic acid esters are placed in a stirred tank. At 100 ° C, the polyisobutylene and optionally a further oil is added with stirring. Subsequently, the mixture is stirred for 1 h to obtain a homogeneous mixture. The anti-wear agents and the antioxidant are added to the kettle at 60 ° C with stirring. After about 1 hour, the finished oil can be filled into the containers provided.
  • Table 1 shows the compositions of the high temperature oils and the redissolvability of the oil residue after complete evaporation of the oil, depending on the added amount of polyisobutylene. ⁇ u> Table 1 ⁇ / u> Ex.1 Ex. 2 Example 3 Example 4 Example 5 Example 6 Example 7 Fully hydrogenated polyisobutylene 24.41 22.0 19,53 17.1 14.63 12.2 9.76 C 10 - branched trimellitic acid ester (1) 71.52 73.91 76.35 78.76 81.2 83.61 86.02 C 13 branched trimellitic acid esters (2) 0.72 0.74 0.77 0.79 0.82 0.84 0.87 Viscosity 40 ° C mm 2 / s 426.8 375.5 328.7 292.7 259 228.8 202.8 Solubility of the residue after 72h / 250 ° C.
  • Examples 8 to 10 show, in comparison with Comparative Examples 1 to 3, the excellent properties of the food grade high temperature oil of the present invention in view of solubility when different components a) are used as the oil.
  • composition of the oils (all data are in% by weight)
  • Example 8 Comparative Example 1 Trimellitate 1 70.0 52,65 Trimellitate 2 0.7 44.0 hydrogenated PIB 25.95 0.0 Amine Antioxidant 0.5 0.5 phenolic antioxidant 1.5 1.5 Wear protection EP / WA 1.0 1.0 Corrosion protection 0.25 0.25 Metal deactivator 0.1 0.1 solvent resistance very good (4) bad (1) Table 3 Example 9 Comparative Example 2 Trimellitate 1 0.0 52,65 Trimellitate 2 0.0 44.0 alkylated naphthalene 70.65 0.0 hydrogenated PIB 26.0 0.0 Amine Antioxidant 0.5 0.5 phenolic antioxidant 1.5 1.5 Wear protection EP / WA 1.0 1.0 Corrosion protection 0.25 0.25 Metal deactivator 0.1 0.1 solvent resistance very good (4) bad (1) Table 4 Example 10 Comparative Example 3 Trimellitate 1 0.0 52,65 Trimellitate 2 0.0 44.0 Estolid 1 40.4 0.0 Estolid 2 23.25 0.0 hydrogenated PIB 33,00 0.0 Amine Antioxidant 0.5 0.5 phenolic antioxidant 1.5 1.5 Wear protection EP /
  • Table 5 describes the food-compatible high-temperature fats according to the invention by way of example. ⁇ u> Table 5 ⁇ / u> Bsp.11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Trimellitate 1 46.3 0.0 46.3 39.0 46.3 46.3 Trimellitate 2 17.1 0.0 17.1 20.0 17.7 17.7 Estolid 1 0.0 38.4 0.0 0.0 0.0 0.0 0.0 Estolid 2 0.0 25.6 0.0 0.0 0.0 0.0 0.0 alkylated naphthalene 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 fully hydrogenated PIB 25.0 25.0 25.0 25.0 25.0 25.0 25.0
  • the samples were annealed at 250 ° C for 72 hours. The residue was redissolved with the respective base oil of the fat pattern. In all examples the re-solubility was good.
  • the thickeners used in Examples 11 to 16 are Li complex (Ex 11 and 12), Al complex (Ex 13), bentonite (Ex 14), Ca single (Ex 15), Li-Simple (Ex. 16) and Urea (Ex.17).
  • ⁇ u> Continued Table 5 ⁇ / u> Bsp.17 Trimellitate 1 46.3 Trimellitate 2 18.7 Estolid 1 0.0 Estolid 2 0.0 alkylated naphthalene 0.0 fully hydrogenated PIB 25.0 Antioxidant 1.0 thickener 9.0
  • solubility of the residues not only depends on the degree of hydrogenation of the polyisobutylene, but also on the mixing ratio of the two esters. Both esters must be used in combination to ensure the H1 capability of the high temperature oil.
  • the mixing ratios are freely selectable, starting from a 1: 1 mixture begin the preferred areas. Particularly preferred is the ratio of 87.12 (iso-C 10 / iso-C 13 ).
  • the above-described food grade high temperature oils and high temperature greases can also be used to lubricate implements that are subject to similar lubricant requirements. These include the cosmetics and pharmaceutical industries as well as the animal feed industry.
  • the high-temperature lubricants according to the invention can be used for lubricating implements in food processing, as hydraulic oils for the food industry, for transport and timing chains in the food industry, and for devices for the processing of cereals, flour and animal feed and for ovens.

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  • General Chemical & Material Sciences (AREA)
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  • Lubricants (AREA)

Abstract

Die Erfindung betrifft einen lebensmittelverträglichen Hochtemperaturschmierstoff, insbesondere ein Hochtemperaturöl und ein Hochtemperaturfett umfassend folgende Komponenten:
a) mindestens ein Öl ausgewählt aus einem Trimellitsäureester oder einem Gemisch aus verschiedenen Trimellitsäureestern, Alkylaromaten, vorzugsweise ein aliphathisch substituiertes Naphthalin oder Estoliden;
b) einem hydrierten oder vollhydrierten Polyisobutylens oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen und;
c) Additive einzeln oder in Kombination.
The invention relates to a food-grade high-temperature lubricant, in particular a high-temperature oil and a high-temperature fat comprising the following components:
a) at least one oil selected from a trimellitic acid ester or a mixture of different trimellitic esters, alkylaromatics, preferably an aliphatically substituted naphthalene or estolides;
b) a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene and;
c) additives individually or in combination.

Im Fall des Hochtemperaturfetts wird ein Verdickungsmittel zugegeben.In the case of high-temperature fat, a thickening agent is added.

Description

Die Erfindung betrifft einen Hochtemperaturschmierstoff, insbesondere ein Hochtemperaturöl auf Basis eines aromatischen Esters, wie eines Trimellitsäureesters und Mischungen verschiedener Trimellitsäureester, Heteroaromaten, Estoliden und einem vollhydrierten oder hydrierten Polyisobutylen oder einer Mischung daraus. Des weiteren kann der Hochtemperaturschmierstoff ein Hochtemperaturfett sein, wenn den oben genannten Komponenten noch ein Verdickungsmittel zugegeben wird. Die Erfindung betrifft ferner die Verwendung dieser Hochtemperaturschmierstoffe zum Schmieren von Arbeitsgeräten, die bei der Verarbeitung von Lebensmitteln verwendet werden.The invention relates to a high-temperature lubricant, in particular a high-temperature oil based on an aromatic ester, such as a trimellitic acid ester and mixtures of various trimellitic acid esters, heteroaromatics, estolides and a fully hydrogenated or hydrogenated polyisobutylene or a mixture thereof. Furthermore, the high-temperature lubricant may be a high-temperature grease when a thickening agent is added to the above-mentioned components. The invention further relates to the use of these high temperature lubricants for lubricating implements used in the processing of food.

Neben der Schmierwirkung müssen die Schmierstoffe noch eine Vielzahl weiterer Aufgaben erfüllen: Sie müssen kühlen, Reibung, Verschleiß und Kraftübertragung verringern, vor Korrosion schützen und gleichzeitig eine dichtende Wirkung aufweisen.In addition to the lubricating effect, the lubricants must fulfill a variety of other tasks: they must cool, reduce friction, wear and power transmission, protect against corrosion and at the same time have a sealing effect.

Herkömmliche Schmierstoffe sind für Hochtemperaturanwendungen nicht geeignet, da sie bei hohen Temperaturen beispielsweise über Oxidations- und/oder thermische Zersetzungsreaktionen und Polymerisationen zerstört werden und ihre schmierenden Eigenschaften stark eingeschränkt werden. Bei Zersetzungsreaktionen wird der Schmierstoff in niedermolekulare flüchtige Komponenten gespalten. Deren Verdampfen führt zu unerwünschten Viskositätsänderungen, Ölverlust und zur übermäßigen Dampfbildung. Hieraus resultiert ein Verlust der Schmierwirkung. Auch durch Polymerisation verlieren die Schmierstoffe ihre Schmierwirkung aufgrund der Bildung unlöslicher Polymerisationsprodukte.Conventional lubricants are not suitable for high temperature applications because they are destroyed at high temperatures, for example by oxidation and / or thermal decomposition reactions and polymerizations and their lubricating properties are severely limited. In decomposition reactions, the lubricant becomes volatile in low molecular weight Components split. Their evaporation leads to undesirable viscosity changes, oil loss and excessive vapor formation. This results in a loss of lubricity. Also by polymerization, the lubricants lose their lubricating effect due to the formation of insoluble polymerization products.

Das Entfernen dieser Verschmutzungen erhöht die Wartungsarbeiten und produziert chemische Abfallstoffe, die aufwendig entsorgt werden müssen. Aufgrund der vermehrten Reinigungs- und Wartungsarbeiten erhöhen sich die Ausfallzeiten. Insgesamt führt die Verwendung von ungeeigneten Schmierstoffen bei Hochtemperaturanwendungen zu höheren Kosten, da die Arbeitsgeräte verschmutzen und ein höherer Bedarf an Schmierstoffen besteht. Darüber hinaus sinkt die Produktqualität.The removal of these contaminants increases the maintenance work and produces chemical waste, which must be disposed of consuming. Due to the increased cleaning and maintenance work, the downtime increases. Overall, the use of unsuitable lubricants in high-temperature applications leads to higher costs, as the tools pollute and there is a greater need for lubricants. In addition, the product quality decreases.

Als Basisöle für Hochtemperaturanwendungen werden oftmals synthetische Ester eingesetzt, da diese über eine sehr gute oxidative, hydrolytische und thermische Stabilität verfügen.Synthetic esters are often used as base oils for high-temperature applications since they have very good oxidative, hydrolytic and thermal stability.

Um den vielfältigen Anforderungen bei Hochtemperaturanwendungen gerecht zu werden, müssen die Schmierstoffe unter anderem eine hohe Stabilität, niedrige Reibungsbeiwerte und hohe Verschleißfestigkeiten aufweisen. Um eine gleichmäßige Schmierung auch bei hohen Temperaturen gewährleisten zu können, muss während des gesamten Verarbeitungsprozesses ein flüssiger Schmierfilm zwischen Metallteilen bestehen bleiben. Deshalb darf der Schmierstoff bei der maximalen Verarbeitungstemperatur nur wenig verdampfen, wenig Rückstände bilden und möglichst wenig Vercrackungsrückstände bilden.In order to meet the diverse requirements of high-temperature applications, the lubricants must have, among other things, high stability, low friction coefficients and high wear resistance. In order to ensure uniform lubrication even at high temperatures, a liquid lubricant film must remain between metal parts during the entire processing process. Therefore, the lubricant must evaporate only slightly at the maximum processing temperature, form little residue and form as few cracking residues as possible.

Hohe Verarbeitungstemperaturen treten oftmals bei der Lebensmittelverarbeitung auf, wie beim Kochen, Backen, Sieden, Rösten, Schmoren, Sterilisieren, Braten und Dämpfen. Bei diesen Vorgängen kommen diverse Arbeitsgeräte zum Einsatz. Zur Schmierung dieser Arbeitsgeräte sind hochtemperaturbeständige Schmierstoffe notwendig.High processing temperatures often occur during food processing, such as cooking, baking, boiling, roasting, braising, sterilizing, frying and steaming. In these processes, various tools are used. To lubricate these tools high temperature resistant lubricants are necessary.

An die Basisöle zum Schmieren von Arbeitsgeräten für die Verarbeitung von Lebensmitteln werden besondere Anforderungen in Bezug auf ihre Umweltverträglichkeit und Toxizität gestellt. Grundsätzlich sollte ein lebensmittelverträglicher Schmierstoff H1 tauglich sein, wenn der Schmierstoff mittelbar oder unmittelbar mit Nahrungs-, Genuss- und Lebensmitteln in Kontakt kommen kann. Zu den bevorzugten Anwendungsbereichen in der Lebensmittelindustrie gehören Ketten in Backöfen und anderen Hochtemperaturanwendungen, sowie Transportgehänge, insbesondere Trolleys und deren Lager.To the base oils for lubricating equipment for the processing of Foods are subject to special environmental and toxicity requirements. In principle, a food-grade lubricant H1 should be suitable if the lubricant can come into direct or indirect contact with foodstuffs, food and groceries. Preferred applications in the food industry include chains in ovens and other high temperature applications, as well as conveyor hangers, especially trolleys and their bearings.

Diese Schmierstoffe unterliegen gesetzlichen Vorschriften, wie der Zertifizierung nach NSF/H1 oder NSF/H2.These lubricants are subject to regulatory requirements such as NSF / H1 or NSF / H2 certification.

Die Einstufung "H1" ist von Schmierstoffen zu erzielen, die in "incidental food contact", das heißt in einem gelegentlichen technisch unvermeidbaren Kontakt mit Lebensmitteln, stehen. Ein beabsichtigter oder dauerhafter Kontakt ist jedoch auch bei der Verwendung von "H1"-Schmierstoffen auszuschliessen. Eine "H2"-Klassifikation können Schmierstoffe erzielen, die nicht toxisch und nicht kanzerogen sind. Bei der Verwendung von "H2"-Schmierstoffen ist dennoch jeglicher Kontakt mit dem Lebensmittel auszuschliessen.The classification "H1" is to be obtained from lubricants that are in "incidental food contact", that is to say in an occasional technically unavoidable contact with foodstuffs. However, intentional or permanent contact should also be excluded when using "H1" lubricants. An "H2" classification can produce lubricants that are non-toxic and non-carcinogenic. When using "H2" lubricants, however, any contact with the food must be excluded.

Nachteilig an den bekannten lebensmittelverträglichen Schmierstoffen, die im Hochtemperaturbereich eingesetzt werden, ist, dass sie oftmals ein nicht zufriedenstellendes, technisches Leistungsvermögen aufweisen. So verfügen die bisher verwendeten lebensmittelverträglichen Schmierstoffe zwar über eine gute Oxidationsbeständigkeit und einen akzeptablen Pourpoint, ihr Rückstandsverhalten nach vollständiger Verdampfung entspricht jedoch nicht den bei Hochtemperaturanwendungen geforderten hohen Ansprüchen. Die entstandenen Vercrackungsrückstände bilden Ablagerungen, die nach einiger Zeit wieder entfernt werden müssen. In der Regel muss der Betrieb der Anlage eingestellt und der Rückstand abgelöst oder die Bauteile ausgetauscht werden. Es besteht also ein Bedarf an einem Hochtemperaturschmierstoff, bei dem die Verdampfung einzelner Grundölbestandteile des Öls stark reduziert werden und bei konstant höheren Temperatur über einen langen Zeitraum die Schmierwirkung nicht verloren geht.A disadvantage of the known food-grade lubricants that are used in the high temperature range, is that they often have an unsatisfactory, technical performance. Although the food-compatible lubricants used hitherto have a good oxidation resistance and an acceptable pour point, their residue behavior after complete evaporation does not correspond to the high demands demanded in high-temperature applications. The resulting cracking residues form deposits, which must be removed again after some time. As a rule, the operation of the plant must be stopped and the residue removed or the components replaced. There is therefore a need for a high-temperature lubricant in which the evaporation of individual base oil components of the oil are greatly reduced and at constant higher temperature over a long period of time, the lubricating effect is not lost.

Die Aufgabe der vorliegenden Erfindung besteht darin, einen Hochtemperaturöl und ein Hochtemperaturfett bereitzustellen, der den Standards eines NSF/H1 Schmierstoffes entspricht und darüber hinaus zufriedenstellende tribologische Eigenschaften aufweist. Insbesondere soll der Schmierstoff bei hoher Temperatur über einen langen Zeitraum eine gute Schmierwirkung zeigen. Des weiteren sollen die gebildeten Vercrackungsrückstände nicht verlacken, sondern durch Frischöl wieder anlösbar sein. Ferner soll der Hochtemperaturschmierstoff eine gute hydrolytische Stabilität aufweisen, korrosions- und verschleißresistent sein, sowie eine gute Oxidationsbeständigkeit und ein an die Anforderungen angepasstes Tieftemperaturverhalten aufweisen.The object of the present invention is to provide a high-temperature oil and a high-temperature grease, which meets the standards of NSF / H1 lubricant and moreover has satisfactory tribological properties. In particular, the lubricant should show a good lubricating effect at high temperature over a long period of time. Furthermore, the Vercrackungsrückstände should not be laked, but be redissolvable by fresh oil. Furthermore, the high-temperature lubricant should have a good hydrolytic stability, be resistant to corrosion and wear, and have a good oxidation resistance and adapted to the requirements of low-temperature behavior.

Diese Aufgabe wird erfindungsgemäß durch ein lebensmittelverträgliches Hochtemperaturöl umfassend folgende Komponenten gelöst:

  1. a) 93,9 bis 45 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe bestehend aus einem Gemisch aus Trimellitsäure-tri(iso-C10)ester (1) und Trimellithsäure-tri(iso-C13)ester (2), wobei das Mischungsverhältnis von (1) zu (2) bei 99:1 bis 1:99, Alkylaromaten, vorzugsweise aliphatisch substituiertes Naphthalin, Estoliden;
  2. b) 6 bis 45 Gew.-% eines Polymers, nämlich eines hydrierten oder vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen;
  3. c) 0,1 bis 5 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidanten, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen.
This object is achieved by a food-compatible high-temperature oil comprising the following components:
  1. a) 93.9 to 45 wt .-% of at least one oil selected from the group consisting of a mixture of trimellitic acid tri (iso-C 10 ) ester (1) and trimellitic tri (iso-C 13 ) ester (2 ), wherein the mixing ratio of (1) to (2) at 99: 1 to 1:99, alkylaromatics, preferably aliphatically substituted naphthalene, estolides;
  2. b) 6 to 45 wt .-% of a polymer, namely a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene;
  3. c) 0.1 to 5 wt .-% of additives individually or in combination, selected from the group consisting of corrosion protection additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants.

Das erfindungsgemäße lebensmittelverträgliche Hochtemperaturfett umfaßt:

  1. a) 91,9 bis 30 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe bestehend aus einem Gemisch aus Trimellitsäure-tri(iso-C10)ester (1) und Trimellithsäure-tri(iso-C13)ester (2), wobei das Mischungsverhältnis von (1) zu (2) bei 99:1 bis 1:99, Alkylaromaten, vorzugsweise aliphatisch substituiertes Naphthalin, Estoliden;
  2. b) 6 bis 45 Gew.% eines Polymers, nämlich eines hydrierten oder vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen;
  3. c) 0,1 bis 5 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidanten, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen und
  4. d) 2 bis 20 Gew.-% Verdickungsmittel.
The food-grade high-temperature fat according to the invention comprises:
  1. a) 91.9 to 30 wt .-% of at least one oil selected from the group consisting of a mixture of trimellitic acid tri (iso-C 10 ) ester (1) and trimellitic acid tri (iso-C 13 ) ester (2 ), wherein the mixing ratio of (1) to (2) at 99: 1 to 1:99, alkylaromatics, preferably aliphatically substituted naphthalene, estolides;
  2. b) 6 to 45% by weight of a polymer, namely a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene;
  3. c) 0.1 to 5 wt .-% of additives individually or in combination, selected from the group consisting of anti-corrosion additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants and
  4. d) 2 to 20 wt .-% thickener.

Überraschend wurde gefunden, dass das erfindungsgemäße Hochtemperaturöl und das erfindungsgemäße Hochtemperaturfett sowohl geeignet für eine H1-Klassifizierung sind, als auch sich durch eine hervorragende Leistungsfähigkeit auszeichnen. So zeigt das erfindungsgemäße Hochtemperaturöl bzw. Hochtemperaturfett eine hohe thermische Stabilität kombiniert mit einer hohen Lebensdauer und guten Schmiereigenschaften.Surprisingly, it has been found that the high-temperature oil according to the invention and the high-temperature fat according to the invention are both suitable for an H1 classification and are distinguished by outstanding performance. Thus, the high-temperature oil or high-temperature grease according to the invention exhibits high thermal stability combined with a long service life and good lubricating properties.

Das erfindungsgemäße Hochtemperaturöl und das erfindungsgemäße Hochtemperaturfett umfassen als eine Esterverbindung einen Trimellitsäureester oder ein Gemisch aus verschiedenen Trimellitsäureestern, wobei die Alkoholgruppe des Esters eine lineare oder verzweigte Alkylgruppe mit 8 bis 16 Kohlenstoffatomen ist. Je nach Wahl des aromatischen Esters können die Eigenschaften des Schmierstoffs, beispielsweise die Viskosität, das Viskositäts-Temperatur-Verhalten, die Oxidationsbeständigkeit und Rückstandsverhalten angepasst werden.The high-temperature oil and the high-temperature fat of the present invention comprise as an ester compound a trimellitic acid ester or a mixture of various trimellitic acid esters, wherein the alcoholic group of the ester is a linear or branched alkyl group having 8 to 16 carbon atoms. Depending on the choice of the aromatic ester, the properties of the lubricant, for example the viscosity, the viscosity-temperature behavior, the oxidation resistance and residue behavior can be adjusted.

Gemäß einer besonders bevorzugten Ausführungsform der Erfindung umfasst der aromatische Ester einen sterisch gehinderten Alkohol als Alkoholkomponente, vorzugsweise einen Alkohol mit 8 bis 16 Kohlenstoffatomen, insbesondere 10 bis 13 Kohlenstoffatomen, insbesondere Trimellitsäure-tri(iso-C10)ester (1) und Trimellitsäure-tri(iso-C13)ester (2). Das Mischungsverhältnis von (1) zu (2) liegt bei 99:1 bis 1:99, besonders bevorzugt ist das Mischungsverhältnis von (1) : (2) von 87,12.According to a particularly preferred embodiment of the invention, the aromatic ester comprises a sterically hindered alcohol as alcohol component, preferably an alcohol having 8 to 16 carbon atoms, in particular 10 to 13 carbon atoms, in particular trimellitic tri (iso-C 10 ) ester (1) and trimellitic acid tri (iso-C 13 ) ester (2). The mixing ratio of (1) to (2) is 99: 1 to 1:99, more preferably, the mixing ratio of (1): (2) is 87.12.

Das erfindungsgemäße Hochtemperaturöl bzw. das erfindungsgemäße Hochtemperaturfett können ein zweites Öl enthalten, das einen Aromaten umfasst.The high-temperature oil according to the invention or the high-temperature fat according to the invention may contain a second oil which comprises an aromatic.

Unter einem Aromaten wird erfindungsgemäß ein monocyclisches, bicyclisches oder tricyclisches Ringsystem mit vier bis fünfzehn Kohlenstoffatomen verstanden, wobei das monocyclische Ringsystem aromatisch ist oder zumindest einer der Ringe in einem bi- oder tricylischen Ringsystem aromatisch ist. Bevorzugt wird ein bicyclisches Ringsystem, das vorzugsweise 10 Kohlenstoffatome aufweist, eingesetzt.According to the invention, an aromatic means a monocyclic, bicyclic or tricyclic ring system having four to fifteen carbon atoms, the monocyclic ring system being aromatic or at least one of the rings being aromatic in a bi- or tricylic ring system. Preference is given to using a bicyclic ring system which preferably has 10 carbon atoms.

Bevorzugt ist der Aromat mit einem oder mehreren aliphatischen Substituenten substituiert. Besonders bevorzugt ist der Aromat mit ein bis vier aliphatischen Substituenten und insbesondere mit zwei oder drei aliphatischen Substituenten substituiert.Preferably, the aromatic is substituted with one or more aliphatic substituents. The aromatic is particularly preferably substituted by one to four aliphatic substituents and in particular by two or three aliphatic substituents.

Eine Alkylgruppe ist erfindungsgemäß eine gesättigte aliphatische Kohlenwasserstoffgruppe mit 1 bis 30, vorzugsweise 3 bis 20, noch bevorzugter 4 bis 17 und insbesondere 6 bis 15 Kohlenstoffatomen. Eine Alkylgruppe kann linear oder verzweigt sein und ist wahlweise mit einem oder mehreren der oben genannten Substituenten substituiert.An alkyl group according to the invention is a saturated aliphatic hydrocarbon group having 1 to 30, preferably 3 to 20, more preferably 4 to 17 and especially 6 to 15 carbon atoms. An alkyl group may be linear or branched and is optionally substituted with one or more of the abovementioned substituents.

Praktische Versuche haben gezeigt, dass Gemische unterschiedlich substituierter Naphthaline, das heißt Gemische aus Naphthalinen, die einen unterschiedlichen Substitutionsgrad und unterschiedliche aliphatische Substituenten aufweisen, besonders geeignet sind. Durch Variation der Mischungszusammensetzung können in diesem Fall die Eigenschaften, wie beispielsweise die Viskosität, des Hochtemperaturschmierstoffs besonders einfach eingestellt werden. Aliphatisch substituierte Naphthaline zeichnen sich ferner durch hervorragende Lösungseigenschaften und hohe thermo-oxidative Stabilität aus.Practical experiments have shown that mixtures of differently substituted naphthalenes, ie mixtures of naphthalenes, which have a different degree of substitution and different aliphatic substituents, are particularly suitable. In this case, by varying the mixture composition, the properties, such as the viscosity, of the high-temperature lubricant can be set particularly easily. Aliphatic-substituted naphthalenes are also characterized by excellent dissolution properties and high thermo-oxidative stability.

Die Viskosität, gemessen bei 40 °C, des aliphathisch substituierten Naphthalins beträgt vorzugsweise 30 bis 600 mm2/s, bevorzugter 30 bis 300 m2/s.The viscosity, measured at 40 ° C, of the aliphatically substituted naphthalene is preferably 30 to 600 mm 2 / s, more preferably 30 to 300 m 2 / s.

Des weiteren können auch Estolide als Komponente a) verwendet werden. Bevorzugte Viskositäten, gemessen bei 40°C liegen zwischen 30 und 500 mm2/sec. Besonders bevorzugt sind Viskositäten von 30 bis 140 mm2/sec.Furthermore, estolides can also be used as component a). Preferred viscosities, measured at 40 ° C are between 30 and 500 mm 2 / sec. Viscosities of 30 to 140 mm 2 / sec are particularly preferred.

Unter Estoliden versteht man Esterverbindungen, die säure- oder enzymatischkatalysiert aus Fettsäuren bevorzugt Ölsäure oder Dicarbonsäuren hergestellt werden. Dabei greift die Säurefunktion die Doppelbindung eines benachbarten Fettsäuremoleküls an, so dass eine höher molekularere Esterverbindung entsteht. Die endständige Säuregruppe wird dann üblicherweise mit einem Alkohol, bevorzugt 2-Ethyl-hexanol verestert und anschließend werden die restlichen Doppelbindungen hydriert oder mit Carbonsäure z.B. Essigsäure verestert. Andere Alkohol wie z.B. Isoamylalkohol oder Guebert Alkohole sind ebenfalls für die Veresterung der endständigen Säuregruppe denkbar.Estolides are ester compounds which are acid or enzymatically catalyzed from fatty acids, preferably oleic acid or dicarboxylic acids. The acid function attacks the double bond of an adjacent fatty acid molecule, resulting in a higher molecular weight ester compound. The terminal acid group is then usually esterified with an alcohol, preferably 2-ethyl-hexanol, and then the remaining double bonds are hydrogenated or with carboxylic acid, e.g. Acetic acid esterified. Other alcohols such as e.g. Isoamyl alcohol or Guebert alcohols are also conceivable for the esterification of the terminal acid group.

Weitere Estolide können auch über eine Kondensation von Hydroxycarbonsäuren, z.B. Ölsäure- oder Stearinsäurederivate synthetisiert werden. Die Kettenlänge der verwendeten Hydroxycarbonsäuren oder ungesättigte Säuren können von C6 bis C54 reichen. Die Säuren können weitere funktionelle Gruppen z.B. Amine, Ether, schwefelhaltige Gruppen enthalten. Darüber hinaus ist auch eine Veresterung mit alpha-Olefinen oder ß-Farnesen denkbar.Other estolides can also be synthesized via a condensation of hydroxycarboxylic acids, for example oleic or stearic acid derivatives. The chain length of the hydroxycarboxylic acids or unsaturated acids used can range from C 6 to C 54 . The acids may contain other functional groups such as amines, ethers, sulfur-containing groups. In addition, an esterification with alpha-olefins or ß-Farnesen is conceivable.

Das erfindungsgemäße Hochtemperaturöl bzw. das Hochtemperaturfett umfassen des weiteren ein Polyisobutylen. Durch geeignete Wahl des Polyisobutylens, insbesondere im Hinblick auf Hydrierungsgrad und Molekulargewicht, können die Eigenschaften des erfindungsgemäßen Öls und Fettes, beispielsweise deren kinematische Viskosität, in erwünschter Weise beeinflusst werden. Das Polyisobutylen kann in hydrierter oder vollhydrierter Form eingesetzt werden, ebenso kann eine Mischung aus hydriertem und vollhydriertem Polyisobutylen verwendet werden. Bevorzugt werden vollhydrierte Polyisobutylene eingesetzt. Das Polyisobutylen ist in einer Menge von 6 bis 45 Gew.-% in der Zusammensetzung vorhanden, bevorzugt werden 10 bis 45 Gew.-%, insbesondere 15 bis 45 Gew.-% eingesetzt.The high-temperature oil or high-temperature grease according to the invention furthermore comprises a polyisobutylene. By suitable choice of the polyisobutylene, in particular with regard to the degree of hydrogenation and molecular weight, the properties of the oil and fat according to the invention, for example their kinematic viscosity, can be influenced in a desired manner. The polyisobutylene can be used in hydrogenated or fully hydrogenated form, as well as a mixture of hydrogenated and fully hydrogenated polyisobutylene can be used. Fully hydrogenated polyisobutylenes are preferably used. The polyisobutylene is present in an amount of 6 to 45 wt .-% in the composition, preferably 10 to 45 wt .-%, in particular 15 to 45 wt .-% are used.

Gemäß einer weiteren bevorzugten Ausführungsform weist das Polyisobutylen ein zahlenmittleres Molekulargewicht von 115 bis 10.000 g/mol, vorzugsweise von 160 bis 5000 g/mol auf.According to a further preferred embodiment, the polyisobutylene has a number average molecular weight of 115 to 10,000 g / mol, preferably from 160 to 5000 g / mol.

Das erfindungsgemäße Hochtemperaturöl bzw. das Hochtemperaturfett umfassen des weiteren von 0,1 bis 5 Gew.-%, Additive, die einzeln oder in Kombination eingesetzt werden und aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidaten, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen, ausgewählt werden.The high-temperature oil or high-temperature grease according to the invention comprise further from 0.1 to 5 wt .-%, additives which are used individually or in combination and are selected from the group consisting of anti-corrosion additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants.

Das erfindungsgemäße Hochtemperaturfett umfasst des weiteren ein Verdickungsmittel. Das Verdickungsmittel in dem erfindungsgemäßen Hochtemperaturfett der Schmierstoffzusammensetzung ist entweder ein Reaktionsprodukt aus einem Diisocyanat, vorzugsweise 2,4-Diisocyanatotoluol, 2,6-Diisocyanatotoluol, 4,4'-Diisocyanatodiphenylmethan, 2,4'-Diisocyanatophenylmethan, 4,4'-Diisocyanatodi-phenyl, 4,4'-Diisocyanato-3-3'-dimethylphenyl, 4,4'-Diisocyanato-3,3'-dimethylphenylmethan, die einzeln oder in Kombination verwendet werden können, mit einem Amin der allgemeinen Formel R'2-N-R, oder einem Diamin der allgemeinen Formel R'2-N-R-NR'2, wobei R ein Aryl-, Alkyl- oder Alkylenrest mit 2 bis 22 Kohlenstoffatomen ist und R' identisch oder verschieden ein Wasserstoff, ein Alkyl-, Alkylen- oder Arylrest ist, oder mit Gemischen aus Aminen und Diaminen
oder
wird aus gewählt aus Al-Komplexseifen, Metall-Einfachseifen der Elemente der ersten und zweiten Hauptgruppe des Perriodensystems, Metall-Komplexseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems, Bentonite, Sulfonate, Silikate, Aerosil, Polyimide oder PTFE oder einer Mischung der vorgenannten Verdickungsmittel.
The high-temperature fat according to the invention further comprises a thickener. The thickener in the high-temperature grease of the lubricant composition according to the invention is either a reaction product of a diisocyanate, preferably 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatophenylmethane, 4,4'-diisocyanatodi phenyl, 4,4'-diisocyanato-3,3'-dimethylphenyl, 4,4'-diisocyanato-3,3'-dimethylphenylmethane, which may be used singly or in combination with an amine of the general formula R ' 2 -NR , or a diamine of the general formula R ' 2 -NR-NR' 2 , wherein R is an aryl, alkyl or alkylene radical having 2 to 22 carbon atoms and R 'identically or differently a hydrogen, an alkyl, alkylene or aryl radical is, or with mixtures of amines and diamines
or
is selected from among Al complex soaps, metal soaps of the first and second main group elements of the perriodic system, metal complex soaps of elements of the first and second main group of the periodic table, bentonites, sulfonates, silicates, aerosil, polyimides or PTFE or a mixture of the foregoing thickener.

Um den gesetzlichen Bestimmungen bezüglich der Verwendung von Schmierstoffen zum Schmieren von Arbeitsgeräten für die Verarbeitung von Lebensmitteln zu entsprechen, ist es zweckmäßig, wenn die eingesetzten Additive eine H1-Klassifikation aufweisen.In order to comply with the legal requirements regarding the use of lubricants for lubricating equipment for processing food, it is useful if the additives used have an H1 classification.

Der Zusatz von Antioxidantien kann die Oxidation des erfindungsgemäßen Öls oder Fetts, insbesondere bei seinem Einsatz, verringern oder gar verhindern. Bei einer Oxidation können unerwünschte freie Radikale entstehen und infolgedessen vermehrt Zersetzungsreaktionen des Hochtemperaturschmierstoffes auftreten. Durch die Zugabe von Antioxidantien wird das Hochtemperaturöl bzw. das -fett stabilisiert.The addition of antioxidants can reduce or even prevent the oxidation of the oil or fat according to the invention, in particular when it is used. Oxidation can lead to undesirable free radicals and, as a result, decomposition reactions of the high-temperature lubricant can occur. The addition of antioxidants turns the high-temperature oil or grease stabilized.

Erfindungsgemäß besonders geeignete Antioxidantien sind die folgenden lebensmittelverträglichen Verbindungen:
diaromatische Amine, Phenolharze, Thiophenolharze, Phosphite, butyliertes Hydroxytoluol, butyliertes Hydroxyanisol, Phenyl-alpha-naphthylamin, Phenyl-betanaphthylamin, octyliertes/butyliertes Diphenylamin, di-alpha-Tocopherol, di-tert-butyl-Phenyl, Benzolpropansaure und Mischungen dieser Komponenten.
Particularly suitable antioxidants according to the invention are the following food-compatible compounds:
diaromatic amines, phenolic resins, thiophenol resins, phosphites, butylated hydroxytoluene, butylated hydroxyanisole, phenyl-alpha-naphthylamine, phenyl-betanaphthylamine, octylated / butylated diphenylamine, di-alpha-tocopherol, di-tert-butyl-phenyl, benzenepropanoic acid and mixtures of these components.

Kommerziell erhältliche lebensmittelverträgliche Additive sind:

  • IRGANOX® 1010 (Benzolpropansäure, 3,5-bis(1, 1-Dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propandiylester; IRGANOX® L06 (alkyliertes Phenyl-alpha-naphthylamin oder N-Phenyl-ar-(1,1,3,3-tetramethylbutyl)-1-naphthalenamin;
  • IRGANOX® L01 (dioctyliertes Diphenylamin);
  • IRGANOX® L57 (Mischung aus alkylierten Diphenylaminen);
  • IRGANOX® L06;
  • IRGANOX® L 115;
  • IRGANOX® L150 (Mischung aus aminischen und phenolischen Antioxidantien mit hohem Molekulargewicht);
  • IRGANOX® L64 (Mischung aus Mono- und Dialkyl- butyl/octyl -diphenylamin);
  • IRGANOX® 1035; (Mischung bestehend aus Thiodiethylenbis(3,5-di-tert-butyl-4-hydroxyhydrocinnamat);
  • IRGANOX® 1010;
  • IRGANOX® L101 (Mischung bestehend aus Tetrakis[methylen-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat]methan);
  • IRGANOX® L109 (Benzolpropansäure, 3,5-bis(1,1-dimethyl)-4-hydroxy-1,6-Hexandiylester);
  • IRGANOX® L57;
  • IRGANOX® L109;
  • Irgalube® TPPT;
  • IRGANOX® L115 (Benzolpropansäure, 3,5-Bis(1,1-dimethylethyl)-4-hydroxy-, thiodi-2, 1- Ethandiylester);
  • IRGANOX® E201 (flüssiges DL-alpha-tocopherol, 2H-1-Benzopyran-6-ol,3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-Trimethyltridecyl);
  • IRGAFOS® 168 (Mischung enthaltend Tris(2,4-di-tert-butylphenyl)Phosphat); ADDITIN® RC7130 (N-Phenyl-1-naphthylamin);
  • Na-LUBE® A0142 (flüssiges Diphenylamin basiertes Antioxidant);
  • VANLUBE® 961 (Mischung aus octyliertem und butyliertem Diphenylamin oder Benzolamin, N-Phenyl, Reaktionsprodukt aus 2,4-Trimethylpentan und 2-Methylpropen);
  • VANLUBE® PCX (Mischung enthaltend 1-Hydroxy-4-methyl-2-6-di-tert-Butylbenzol); Hexamethylenbis(3,5-di-tert-butyl-4-Hydroxyhydrocinnamt);
  • Irgafox® 168; Reaktionsprodukt aus N-Phenylbenzolamin mit 2,4,4-Trimethylpenten; Thiodiethylenbis(3,5-di-tert-butyl-4-hydroxyhydro-Cinnamatmethan); Bis(4-(1,1,3,3-tetramethylbutyl)phenyl)amin;
  • 3,5-Bis(1,1-dimethylethyl)-4-hydroxyester;
  • Thiodi-2,1-Ethandiylester.
Commercially available food-grade additives are:
  • IRGANOX® 1010 (benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-2,2-bis [[3- [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] 1-oxopropoxy] methyl] -1,3-propanediyl ester; IRGANOX® L06 (alkylated phenyl-alpha-naphthylamine or N-phenyl-ar (1,1,3,3-tetramethylbutyl) -1-naphthalenamine;
  • IRGANOX® L01 (dioctylated diphenylamine);
  • IRGANOX® L57 (mixture of alkylated diphenylamines);
  • IRGANOX® L06;
  • IRGANOX® L 115;
  • IRGANOX® L150 (mixture of high molecular weight amine and phenolic antioxidants);
  • IRGANOX® L64 (mixture of mono- and dialkylbutyl / octyldiphenylamine);
  • IRGANOX® 1035; (Mixture of thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate);
  • IRGANOX® 1010;
  • IRGANOX® L101 (mixture consisting of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane);
  • IRGANOX® L109 (benzenepropanoic acid, 3,5-bis (1,1-dimethyl) -4-hydroxy-1,6-hexanediyl ester);
  • IRGANOX® L57;
  • IRGANOX® L109;
  • Irgalube® TPPT;
  • IRGANOX® L115 (benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, thiodi-2, 1-ethanediyl ester);
  • IRGANOX® E201 (liquid DL-alpha-tocopherol, 2H-1-benzopyran-6-ol, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl);
  • IRGAFOS® 168 (mixture containing tris (2,4-di-tert-butylphenyl) phosphate); ADDITIN® RC7130 (N-phenyl-1-naphthylamine);
  • Na-LUBE® A0142 (liquid diphenylamine based antioxidant);
  • VANLUBE® 961 (mixture of octylated and butylated diphenylamine or benzene amine, N-phenyl, reaction product of 2,4-trimethylpentane and 2-methylpropene);
  • VANLUBE® PCX (mixture containing 1-hydroxy-4-methyl-2-6-di-tert-butylbenzene); Hexamethylene bis (3,5-di-tert-butyl-4-Hydroxyhydrocinnamt);
  • Irgafox® 168; Reaction product of N-phenylbenzolamine with 2,4,4-trimethylpentene; Thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydro-Cinnamatmethan); amine (4- (1,1,3,3-tetramethylbutyl) phenyl) up;
  • 3,5-Bis (1,1-dimethylethyl) -4-hydroxy ester;
  • Thiodi-2,1-ethanediyl.

Weiterhin kann das Hochtemperaturöl bzw. das -fett Korrosionsschutzadditive, Metalldesaktivatoren oder Ionen-Komplexbildner enthalten. Hierzu zählen Triazole, Imidazoline, N-Methylglycin (Sarcosin), Benzotriazolderivate, N,N-Bis(2-ethylhexyl)-ar-methyl-1H-benzotriazol-1-methanamin; n-Methyl-N(1-oxo-9-octadecenyl)glycin, Gemisch aus Phosphorsäure und Mono-und Diisooctylester umgesetzt mit (C11-14)-Alkylaminen, Gemisch aus Phosphorsäure und Mono-und Diisooctylester umgesetzt mit tert-Alkylamin und primären (C12-14)-Aminen, Dodekansäure, Triphenylphosphorthionat und Aminphosphate. Kommerziell erhältliche Additive sind die folgenden: IRGAMET® 39, IRGACOR® DSS G, Amin O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, Cl-429 und CI-498.Furthermore, the high temperature oil or grease may contain corrosion inhibiting additives, metal deactivators or ion complexing agents. These include triazoles, imidazolines, N-methylglycine (sarcosine), benzotriazole derivatives, N, N-bis (2-ethylhexyl) -ar-methyl-1H-benzotriazole-1-methanamine; N-methyl-N (1-oxo-9-octadecenyl) glycine, mixture of phosphoric acid and mono- and Diisooctylester reacted with (C 11-14 ) alkylamines, mixture of phosphoric acid and mono- and Diisooctylester reacted with tert-alkylamine and primary (C 12-14 ) amines, dodecanoic acid, triphenyl phosphorothionate and amine phosphates. Commercially available additives are as follows: IRGAMET® 39, IRGACOR® DSS G, amine O; SARKOSYL® O (Ciba), COBRATEC® 122, CUVAN® 303, VANLUBE® 9123, CI-426, CI-426EP, CI-429 and CI-498.

Weitere denkbare Verschleißschutzadditive sind Amine, Aminphosphate, Phosphate, Thiophosphate, Phosphorthionate und Mischungen dieser Komponenten. Zu den kommerziell erhältlichen Verschleißschutzadditiven gehören IRGALUBE® TPPT, IRGALUBE® 232, IRGALUBE® 349, IRGALUBE® 211 und ADDITIN® RC3760 Liq 3960, FIRC-SHUN® FG 1505 und FG 1506, NA-LUBE® KR-015FG, LUBEBOND®, FLUORO® FG, SYNALOX® 40-D, ACHESON® FGA 1820 und ACHESON® FGA 1810.Further conceivable anti-wear additives are amines, amine phosphates, phosphates, thiophosphates, phosphorothionates and mixtures of these components. Commercially available anti-wear additives include IRGALUBE® TPPT, IRGALUBE® 232, IRGALUBE® 349, IRGALUBE® 211 and ADDITIN® RC3760 Liq 3960, FIRC-SHUN® FG 1505 and FG 1506, NA-LUBE® KR-015FG, LUBEBOND®, FLUORO ® FG, SYNALOX® 40-D, ACHESON® FGA 1820 and ACHESON® FGA 1810.

Des weiteren können das Öl bzw. das Fett lebensmitteltaugliche Festschmierstoffe wie PTFE, BN, Na-Pyrophosphat, Zn-Oxid, Mg-Oxid, Zn-Pyrophosphat, Na-Thiosulfat, Mg-Carbonat, Ca-Carbonat, Ca-Stearat, Zn-Sulfid oder eine Mischung daraus enthalten.In addition, the oil or the fat may contain food grade solid lubricants such as PTFE, BN, Na pyrophosphate, Zn oxide, Mg oxide, Zn pyrophosphate, Na thiosulfate, Mg carbonate, Ca carbonate, Ca stearate, Zn oxide. Sulfide or a mixture thereof.

Praktische Versuche haben gezeigt, dass das erfindungsgemäße Hochtemperaturöl bzw. -fett bis zu einer Temperatur von 250°C keine oder zu vernachlässigende Zersetzungserscheinungen aufweist. Hierunter wird verstanden, dass sich weniger als 10% des Schmierstoffs zersetzen.Practical experiments have shown that the high-temperature oil or fat according to the invention up to a temperature of 250 ° C has no or negligible decomposition phenomena. By this is meant that less than 10% of the lubricant decomposes.

Das erfindungsgemäße Hochtemperaturöl bzw. -fett kann als ein weiteres lebensmittelverträgliches Grundöl ein Öl, vorzugsweise ausgewählt aus der Gruppe bestehend aus Mineralöl, aliphatischen Carbonsäure- und Dicarbonsäureestern, Fettsäuretriglyzeriden und/oder Poly-alpha-olefinen enthalten.The high-temperature oil or fat according to the invention may contain, as another food-compatible base oil, an oil, preferably selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides and / or poly-alpha-olefins.

In einer besonderen Ausführungsform enthält das erfindungsgemäße Hochtemperaturöl bzw. -fett ein Estolid, wobei vorzugsweise die Hauptbestandteile des Estolides gewonnen werden durch chemische oder enzymatische Prozesse ausgehend von nativen Ölen aus der Gruppe Sonnenblumenöl, Rapsöl, Rizinusöl, Leinöl, Maisöl, Diestelöl, Sojabohnenöl, Leinsamenöl, Erdnussöl, "Lesqueralle"-Öl, Palmöl, Olivenöl oder Mischungen aus den vorgenannten Ölen.In a particular embodiment, the high temperature oil or fat according to the invention contains an estolide, preferably the main constituents of the estolide being obtained by chemical or enzymatic processes starting from native oils from the group of sunflower oil, rapeseed oil, castor oil, linseed oil, corn oil, diest oil, soybean oil, linseed oil , Peanut oil, "Lesqueralle" oil, palm oil, olive oil or mixtures of the aforementioned oils.

Praktische Versuche haben gezeigt, dass das erfindungsgemäße Hochtemperaturöl bzw. -fett aufgrund seiner physikalischen und chemischen Eigenschaften hervorragend zum Schmieren von Arbeitsgeräten für die Verarbeitung von Lebensmitteln verwendet werden kann. Aufgrund seiner guten Temperaturbeständigkeit kann er auch bei hohen Einsatztemperaturen bis 260°C, vorzugsweise bei Temperaturen von 150 bis 250°C eingesetzt werden, z.B. Ketten in Backöfen.Practical tests have shown that the high-temperature oil or fat according to the invention, due to its physical and chemical properties, can be used excellently for lubricating working devices for processing foodstuffs. Due to its good temperature resistance, it can also be used at high use temperatures up to 260 ° C, preferably at temperatures of 150 to 250 ° C, e.g. Chains in ovens.

Die Erfindung betrifft ferner ein Verfahren zur Herstellung des oben beschriebenen Hochtemperaturöls bzw. -fetts, bei dem die Grundöle und die Additive miteinander vermischt werden.The invention further relates to a process for the preparation of the above-described high-temperature oil or grease, in which the base oils and the additives are mixed together.

Die Erfindung wird nun anhand der nachfolgenden Beispiele näher erläutert.The invention will now be explained in more detail with reference to the following examples.

Beispiele 1 bis 7Examples 1 to 7 Herstellung eines erfindungsgemäßen Hochtemperaturöls für die Lebensmittelind ustrieProduction of a high-temperature oil according to the invention for the food industry

Es werden zwei Trimellitsäureester in einem Rührkessel vorgelegt. Bei 100°C wird unter Rühren das Polyisobutylen und ggf. ein weiteres Öl hinzugegeben. Anschließend wird das Gemisch 1 h gerührt, um eine homogene Mischung zu erhalten. Die Verschleißschutzmittel und das Antioxidationsmittel werden bei 60°C unter Rühren in den Kessel zugegeben. Nach ca. 1 Stunde kann das fertige Öl in die vorgesehenen Gebinde abgefüllt werden.Two trimellitic acid esters are placed in a stirred tank. At 100 ° C, the polyisobutylene and optionally a further oil is added with stirring. Subsequently, the mixture is stirred for 1 h to obtain a homogeneous mixture. The anti-wear agents and the antioxidant are added to the kettle at 60 ° C with stirring. After about 1 hour, the finished oil can be filled into the containers provided.

Zusammensetzung der Hochtemperaturöle:Composition of high-temperature oils:

Tabelle 1 zeigt die Zusammensetzungen der Hochtemperaturöle und die Wiederanlösbarkeit des Ölrückstandes nach vollständiger Verdampfung des Öls in Abhängigkeit von der zugegebenen Menge an Poyisobutylen. Tabelle 1 Bsp.1 Bsp. 2 Bsp. 3 Bsp. 4 Bsp. 5 Bsp. 6 Bsp. 7 vollhydriertes Polyisobutylen 24,41 22,0 19,53 17,1 14,63 12,2 9,76 C10- verzweigter Trimellitsäureester (1) 71,52 73,91 76,35 78,76 81,2 83,61 86,02 C13-verzweigter Trimellitsäureester (2) 0,72 0,74 0,77 0,79 0,82 0,84 0,87 Viskosität 40°C mm2/s 426,8 375,5 328,7 292,7 259 228,8 202,8 Anlösbarkeit des Rückstandes nach 72h/250°C 4 3 3 2 1 (Lack) 1 (Lack) 1 (Lack) 4 = Rückstand nach vollständiger Verdampfung sehr gut anlösbar
3 = Rückstand nach vollständiger Verdampfung gut anlösbar
2 = Rückstand nach vollständiger Verdampfung partiell anlösbar
1 = Rückstand nach vollständiger Verdampfung nicht anlösbar
Table 1 shows the compositions of the high temperature oils and the redissolvability of the oil residue after complete evaporation of the oil, depending on the added amount of polyisobutylene. <u> Table 1 </ u> Ex.1 Ex. 2 Example 3 Example 4 Example 5 Example 6 Example 7 Fully hydrogenated polyisobutylene 24.41 22.0 19,53 17.1 14.63 12.2 9.76 C 10 - branched trimellitic acid ester (1) 71.52 73.91 76.35 78.76 81.2 83.61 86.02 C 13 branched trimellitic acid esters (2) 0.72 0.74 0.77 0.79 0.82 0.84 0.87 Viscosity 40 ° C mm 2 / s 426.8 375.5 328.7 292.7 259 228.8 202.8 Solubility of the residue after 72h / 250 ° C. 4 3 3 2 1 (paint) 1 (paint) 1 (paint) 4 = residue after complete evaporation very good dissolvable
3 = residue readily dissolvable after complete evaporation
2 = residue partially soluble after complete evaporation
1 = residue can not be dissolved after complete evaporation

Alle Angaben sind in Gewichts-%. Der Rest auf 100 Gew.-% ergibt sich durch die Zugabe von Additiven, insbesondere aminische und/oder phenolische Antioxidanten, Korrosionschutzadditive, Verschleißschutzadditiven EP/AW sowie Metalldesaktivatoren.All figures are in% by weight. The remainder to 100% by weight results from the addition of additives, in particular aminic and / or phenolic antioxidants, corrosion protection additives, wear protection additives EP / AW and metal deactivators.

Diese Ergebnisse zeigen, dass es bis zu einer kinematischen Viskosität bei 40°C von 292,7 mm2/s möglich ist, die nach vollständiger Verdampfung entstandenen Rückstände mit frischem Öl wieder anzulösen. Die Zusammmensetzung nach Beispiel 1 zeigt die besten Eigenschaften hinsichtlich Viskosität und Wiederanlösbarkeit.These results show that, up to a kinematic viscosity at 40 ° C. of 292.7 mm 2 / s, it is possible to re-dissolve the residues that have formed after complete evaporation with fresh oil. The composition according to Example 1 shows the best properties in terms of viscosity and re-solubility.

Die nachfolgenden Beispiele 8 bis 10 zeigen im Vergleich zu den Vergleichsbeispielen 1 bis 3 die hervorragenden Eigenschaften des erfindungsgemäßen lebensmittelverträglichen Hochtemperaturöls, im Hinblick auf die Anlösbarkeit, wenn unterschiedliche Komponenten a) als Öl verwendet werden.The following Examples 8 to 10 show, in comparison with Comparative Examples 1 to 3, the excellent properties of the food grade high temperature oil of the present invention in view of solubility when different components a) are used as the oil.

Beispiele 8 bis 10Examples 8 to 10 Zusammensetzung der Öle (alle Angaben sind in Gew.-%)Composition of the oils (all data are in% by weight)

Tabelle 2Table 2 Beispiel 8Example 8 Vergleichsbeispiel 1Comparative Example 1 Trimellitat 1Trimellitate 1 70,070.0 52,6552,65 Trimellitat 2Trimellitate 2 0,70.7 44,044.0 hydriertes PIBhydrogenated PIB 25,9525.95 0,00.0 aminisches AntioxidantAmine Antioxidant 0,50.5 0,50.5 phenolisches Antioxidantphenolic antioxidant 1,51.5 1,51.5 Verschleißschutz EP/WAWear protection EP / WA 1,01.0 1,01.0 KorrossionsschutzCorrosion protection 0,250.25 0,250.25 Metall-DesaktivatorMetal deactivator 0,10.1 0,10.1 Anlösbarkeitsolvent resistance sehr gut (4)very good (4) schlecht (1)bad (1) Tabelle 3Table 3 Beispiel 9Example 9 Vergleichsbeispiel 2Comparative Example 2 Trimellitat 1Trimellitate 1 0,00.0 52,6552,65 Trimellitat 2Trimellitate 2 0,00.0 44,044.0 alkyliertes Naphthalinalkylated naphthalene 70,6570.65 0,00.0 hydriertes PIBhydrogenated PIB 26,026.0 0,00.0 aminisches AntioxidantAmine Antioxidant 0,50.5 0,50.5 phenolisches Antioxidantphenolic antioxidant 1,51.5 1,51.5 Verschleißschutz EP/WAWear protection EP / WA 1,01.0 1,01.0 KorrossionsschutzCorrosion protection 0,250.25 0,250.25 Metall-DesaktivatorMetal deactivator 0,10.1 0,10.1 Anlösbarkeitsolvent resistance sehr gut (4)very good (4) schlecht (1)bad (1) Tabelle 4Table 4 Beispiel 10Example 10 Vergleichsbeispiel 3Comparative Example 3 Trimellitat 1Trimellitate 1 0,00.0 52,6552,65 Trimellitat 2Trimellitate 2 0,00.0 44,044.0 Estolid 1Estolid 1 40,440.4 0,00.0 Estolid 2Estolid 2 23,2523.25 0,00.0 hydriertes PIBhydrogenated PIB 33,0033,00 0,00.0 aminisches AntioxidantAmine Antioxidant 0,50.5 0,50.5 phenolisches Antioxidantphenolic antioxidant 1,51.5 1,51.5 Verschleißschutz EP/WAWear protection EP / WA 1,01.0 1,01.0 KorrossionsschutzCorrosion protection 0,250.25 0,250.25 Metall-DesaktivatorMetal deactivator 0,10.1 0,10.1 Anlösbarkeitsolvent resistance sehr gut (4)very good (4) schlecht (1)bad (1)

In Tabelle 5 werden nachfolgend die erfindungsgemäßen lebensmittelverträglichen Hochtemperaturfette beispielhaft beschrieben. Tabelle 5 Bsp.11 Bsp. 12 Bsp. 13 Bsp. 14 Bsp. 15 Bsp. 16 Trimellitat 1 46,3 0,0 46,3 39,0 46,3 46,3 Trimellitat 2 17,1 0,0 17,1 20,0 17,7 17,7 Estolid 1 0,0 38,4 0,0 0,0 0,0 0,0 Estolid 2 0,0 25,6 0,0 0,0 0,0 0,0 alkyliertes Naphthalin 0,0 0,0 0,0 0,0 0,0 0,0 vollhydriertes PIB 25,0 25,0 25,0 25,0 25,0 25,0 Antioxidant 1,0 1,0 1,0 1,0 1,0 1,0 Verdickungsmittel 10,6 10,0 10,6 15,0 10,0 10,0 Table 5 below describes the food-compatible high-temperature fats according to the invention by way of example. <u> Table 5 </ u> Bsp.11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Trimellitate 1 46.3 0.0 46.3 39.0 46.3 46.3 Trimellitate 2 17.1 0.0 17.1 20.0 17.7 17.7 Estolid 1 0.0 38.4 0.0 0.0 0.0 0.0 Estolid 2 0.0 25.6 0.0 0.0 0.0 0.0 alkylated naphthalene 0.0 0.0 0.0 0.0 0.0 0.0 fully hydrogenated PIB 25.0 25.0 25.0 25.0 25.0 25.0 Antioxidant 1.0 1.0 1.0 1.0 1.0 1.0 thickener 10.6 10.0 10.6 15.0 10.0 10.0

Um die Wiederanlösbarkeit zu bestimmen, wurden die Proben bei 250°C für 72 Stunden getempert. Der Rückstand wurde mit der jeweiligen Grundöl des Fettmusters wieder angelöst. In allen Beispielen war die Wiederanlösbarkeit gut.To determine the re-solubility, the samples were annealed at 250 ° C for 72 hours. The residue was redissolved with the respective base oil of the fat pattern. In all examples the re-solubility was good.

Bei den in den Beispielen 11 bis 16 verwendeten Verdickungsmitteln handelt es sich um Li-Komplex (Bsp. 11 und 12), Al-Komplex (Bsp. 13), Bentonit (Bsp. 14), Ca-Einfach (Bsp. 15), Li-Einfach (Bsp. 16) und Harnstoff (Bsp.17). Fortsetzung Tabelle 5 Bsp.17 Trimellitat 1 46,3 Trimellitat 2 18,7 Estolid 1 0,0 Estolid 2 0,0 alkyliertes Naphthalin 0,0 vollhydriertes PIB 25,0 Antioxidant 1,0 Verdickungsmittel 9,0 The thickeners used in Examples 11 to 16 are Li complex (Ex 11 and 12), Al complex (Ex 13), bentonite (Ex 14), Ca single (Ex 15), Li-Simple (Ex. 16) and Urea (Ex.17). <u> Continued Table 5 </ u> Bsp.17 Trimellitate 1 46.3 Trimellitate 2 18.7 Estolid 1 0.0 Estolid 2 0.0 alkylated naphthalene 0.0 fully hydrogenated PIB 25.0 Antioxidant 1.0 thickener 9.0

Des weiteren wurde die Wiederanlösbarkeit des Ölrückstandes nach vollständiger Verdampfung bei zwei verschiedenen Temperaturen (220°C/120h) und (250°C/72h) in Abhängigkeit des Mischungsverhältnisses der beiden Trimellitsäureester (1) und (2) untersucht. Die Konzentration des vollhydrierten PIB wurde bei 25 Gew.-% konstant gehalten. Es wurde überraschenderweise gefunden, dass für beide Temperaturen die Wiederanlösbarkeit vom Mischungsverhältnis der beiden Trimellitsäureester abhängt. Bei einem Mischungsverhältnis von 0,02, d.h. einem hohen Anteil des iso-C13-Trimellitsäureester gegenüber dem iso-C10-Ester, ist der Rückstand mit Frischöl nicht wieder anlösbar, jedoch steigt die Anlösbarkeit mit zunehmendem Gehalt an iso-C10-Trimellithsäureester deutlich an, wie der Abbildung 1 zu entnehmen ist. Bei einem Mischungsverhältnis von 1:1 wird ein Sättigungspunkt erreicht. Die Werte sind auch in der Tabelle 6 gezeigt. Tabelle 6 Verhältnis iso-C10/iso-C13 Anlösbarkeit der Rückstandes nach vollständiger Verdampfung (Alterung) 250°C/72h 220°C/120h 0,02 1 1 0,33 2 3 1,00 3 4 2,97 3 4 87,12 3 4 4 = Rückstand nach vollständiger Verdampfung sehr gut anlösbar
3 = Rückstand nach vollständiger Verdampfung gut anlösbar
2 = Rückstand nach vollständiger Verdampfung partiell anlösbar
1 = Rückstand nach vollständiger Verdampfung nicht anlösbar
Furthermore, the remissibility of the oil residue after complete evaporation at two different temperatures (220 ° C / 120h) and (250 ° C / 72h) depending on the mixing ratio of the two trimellitic acid esters (1) and (2) was examined. The concentration of fully hydrogenated PIB was kept constant at 25% by weight. It was surprisingly found that for both temperatures the re-solubility depends on the mixing ratio of the two trimellitic acid esters. At a mixing ratio of 0.02, ie a high proportion of the iso-C 13 trimellitic ester compared to the iso-C 10 ester, the residue can not be redissolved with fresh oil, but the solubility increases with increasing content of iso-C 10 - Trimellithsäureester clearly like the illustration 1 can be seen. At a mixing ratio of 1: 1, a saturation point is reached. The values are also shown in Table 6. <u> Table 6 </ u> Ratio iso-C10 / iso-C13 Solubility of the residue after complete evaporation (aging) 250 ° C / 72h 220 ° C / 120h 0.02 1 1 0.33 2 3 1.00 3 4 2.97 3 4 87.12 3 4 4 = residue after complete evaporation very good dissolvable
3 = residue readily dissolvable after complete evaporation
2 = residue partially soluble after complete evaporation
1 = residue can not be dissolved after complete evaporation

Es konnte also gezeigt werden, dass die Anlösbarkeit der Rückstände nicht nur von dem Hydrierungsgrad des Polyisobutylens, sondern auch vom Mischungsverhältnis der beiden Ester abhängt. Beide Ester müssen in Kombination verwendet werden, um die H1-Fähigkeit, des Hochtemperaturöls zu gewährleisten. Die Mischungsverhältnisse sind frei wählbar, ab einer 1:1 Mischung beginnen die bevorzugten Bereiche. Besonders bevorzugt ist das Verhältnis von 87,12 (iso-C10/iso-C13).It could therefore be shown that the solubility of the residues not only depends on the degree of hydrogenation of the polyisobutylene, but also on the mixing ratio of the two esters. Both esters must be used in combination to ensure the H1 capability of the high temperature oil. The mixing ratios are freely selectable, starting from a 1: 1 mixture begin the preferred areas. Particularly preferred is the ratio of 87.12 (iso-C 10 / iso-C 13 ).

Die vorstehend beschriebenen lebensmittelverträglichen Hochtemperaturöle und Hochtemperaturfette können auch zur Schmierung von Arbeitsgeräten verwendet werden, die ähnlichen Einschränkungen hinsichtlich der Anforderungen an die Schmierstoffe unterliegen. Dazu gehören die Kosmetik- und Arzneimittelindustrie sowie die Tierfutterindustrie.The above-described food grade high temperature oils and high temperature greases can also be used to lubricate implements that are subject to similar lubricant requirements. These include the cosmetics and pharmaceutical industries as well as the animal feed industry.

Im Hinblick auf die Lebensmittelindustrie können die erfindungsgemäßen Hochtemperaturschmierstoffe zum Schmieren von Arbeitsgeräten bei der Lebensmittelverarbeitung, als Hydrauliköle für die Lebensmittelindustrie, für Transport- und Steuerketten in der Lebensmittelindustrie, sowie für Vorrichtungen für die Verarbeitung von Getreide, Mehl und Tierfutter sowie für Backöfen verwendet werden.With regard to the food industry, the high-temperature lubricants according to the invention can be used for lubricating implements in food processing, as hydraulic oils for the food industry, for transport and timing chains in the food industry, and for devices for the processing of cereals, flour and animal feed and for ovens.

Bei einigen Anwendungen ist die Verwendung in Form eines Sprays vorteilhaft.In some applications, use in the form of a spray is advantageous.

Claims (7)

Lebensmittelverträgliches Hochtemperaturöl umfassend folgende Komponenten: a) 93,9 bis 45 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe bestehend aus einem Gemisch aus Trimellitsäure-tri(iso-C10)ester (1) und Trimellithsäure-tri(iso-C13)ester (2), wobei das Mischungsverhältnis von (1) zu (2) bei 99:1 bis 1:99 liegt, Alkylaromaten, Estoliden; b) 6 bis 45 Gew.-% eines Polymers, ausgewälht aus der Gruppe bestehend aus einem hydrierten oder vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen; c) 0,1 bis 5 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidanten, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen. Food-compatible high-temperature oil comprising the following components: a) 93.9 to 45 wt .-% of at least one oil selected from the group consisting of a mixture of trimellitic acid tri (iso-C 10 ) ester (1) and trimellitic tri (iso-C 13 ) ester (2 ), wherein the mixing ratio of (1) to (2) is 99: 1 to 1:99, alkylaromatics, estolides; b) from 6 to 45% by weight of a polymer selected from the group consisting of a hydrogenated or fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene; c) 0.1 to 5 wt .-% of additives individually or in combination, selected from the group consisting of corrosion protection additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants. Lebensmittelverträgliches Hochtemperaturfett umfassend folgende Komponenten: a) 91,9 bis 30 Gew.-% mindestens eines Öls, ausgewählt aus der Gruppe bestehend aus einem Gemisch aus Trimellitsäure-tri(iso-C10)ester (1) und Trimellithsäure-tri(iso-C13)ester (2), wobei das Mischungsverhältnis von (1) zu (2) bei 99:1 bis 1:99 liegt, Alkylaromaten, Estoliden; b) 6 bis 45 Gew.% eines Polymers, ausgewälht aus der Gruppe bestehend aus einem hydrierten, vollhydrierten Polyisobutylen oder einer Mischung aus hydrierten oder vollhydrierten Polyisobutylen; c) 0,1 bis 5 Gew.-% Additive einzeln oder in Kombination, ausgewählt aus der Gruppe bestehend aus Korrosionsschutzadditiven, Antioxidanten, Verschleißschutzadditiven, UV-Stabilisatoren, anorganischen oder organischen Feststoffschmierstoffen und d) 2 bis 20 Gew.-% Verdickungsmittel. Food-grade high-temperature fat comprising the following components: a) 91.9 to 30 wt .-% of at least one oil selected from the group consisting of a mixture of trimellitic acid tri (iso-C 10 ) ester (1) and trimellitic acid tri (iso-C 13 ) ester (2 ), wherein the mixing ratio of (1) to (2) is 99: 1 to 1:99, alkylaromatics, estolides; b) from 6 to 45% by weight of a polymer selected from the group consisting of a hydrogenated fully hydrogenated polyisobutylene or a mixture of hydrogenated or fully hydrogenated polyisobutylene; c) 0.1 to 5 wt .-% of additives individually or in combination, selected from the group consisting of anti-corrosion additives, antioxidants, anti-wear additives, UV stabilizers, inorganic or organic solid lubricants and d) 2 to 20 wt .-% thickener. Hochtemperaturöl bzw. Hochtemperaturfett nach Anspruch 1 oder 2 bei dem die alkylaromatische Verbindung ein aliphatisch substituiertes Naphthalin ist.High-temperature oil or high-temperature grease according to claim 1 or 2, wherein the alkylaromatic compound is an aliphatic-substituted naphthalene. Hochtemperaturöl bzw. Hochtemperaturfett nach Anspruch 1 oder 2, bei dem die Komponente a) als weiteres lebensmittelverträglichen Öls eine Verbindung ausgewählt aus der Gruppe bestehend aus Mineralöl, aliphatischen Carbonsäure- und Dicarbonsäureestern, Fettsäuretriglyzeriden und Poly-alpha-olefinen umfasstHigh-temperature oil or high-temperature fat according to claim 1 or 2, wherein the component comprises a) as a further food-compatible oil, a compound selected from the group consisting of mineral oil, aliphatic carboxylic acid and dicarboxylic acid esters, fatty acid triglycerides and poly-alpha-olefins Hochtemperaturfett nach Anspruch 2, bei dem die Komponente d) ausgewählt wird aus der Gruppe bestehend aus Harnstoff, Al-Komplexseifen, Metall-Einfachseifen der Elemente der ersten und zweiten Hauptgruppe des Perriodensystems, Metall-Komplexseifen der Elemente der ersten und zweiten Hauptgruppe des Periodensystems, Bentonite, Sulfonate, Silikate, Aerosil, Polyimide, PTFE oder einer Mischung der vorgenannten Verdickungsmittel.A high temperature grease according to claim 2, wherein component d) is selected from the group consisting of urea, Al complex soaps, metal soaps of the elements of the first and second main groups of the perriodic system, metal complex soaps of the elements of the first and second main group of the periodic table, Bentonites, sulfonates, silicates, aerosil, polyimides, PTFE or a mixture of the aforementioned thickeners. Verwendung des Hochtemperaturöls bzw. Hochtemperaturfetts nach einem der vorherigen Ansprüche zum Schmieren von Arbeitsgeräten in der Lebensmittelverarbeitung, als Hydrauliköl in der Lebensmittelindustrie, für Transport- und Steuerketten, für Vorrichtungen für die Verarbeitung von Getreide, Mehl und Tierfutter, sowie in Backöfen.Use of the high-temperature oil or high-temperature grease according to one of the preceding claims for lubricating work tools in food processing, as hydraulic oil in the food industry, for transport and timing chains, for devices for processing grain, flour and animal feed, and in ovens. Verwendung des Hochtemperaturöls nach einem der vorherigen Ansprüche als Öl in Form eines Sprays.Use of the high-temperature oil according to one of the preceding claims as oil in the form of a spray.
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CN107001968A (en) 2017-08-01
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EP3234080A2 (en) 2017-10-25
KR20170083612A (en) 2017-07-18
EP3375850B1 (en) 2021-10-27
EP3375851A1 (en) 2018-09-19
WO2016096075A2 (en) 2016-06-23
MX2017007681A (en) 2018-01-23
CN107001968B (en) 2020-07-17
KR101931511B1 (en) 2019-03-13
US20170321143A1 (en) 2017-11-09
BR112017012562B1 (en) 2022-04-05
ES2901414T3 (en) 2022-03-22
JP6400211B2 (en) 2018-10-03
WO2016096075A3 (en) 2016-09-01
DK3375850T3 (en) 2022-01-17
BR112017012562A2 (en) 2018-01-02

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