EP0486575B1 - Basic oil for formulating hydraulic fluids - Google Patents
Basic oil for formulating hydraulic fluids Download PDFInfo
- Publication number
- EP0486575B1 EP0486575B1 EP90912376A EP90912376A EP0486575B1 EP 0486575 B1 EP0486575 B1 EP 0486575B1 EP 90912376 A EP90912376 A EP 90912376A EP 90912376 A EP90912376 A EP 90912376A EP 0486575 B1 EP0486575 B1 EP 0486575B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- ester
- acids
- esters
- oils
- 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.)
- Expired - Lifetime
Links
- 239000012530 fluid Substances 0.000 title abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 31
- 235000019198 oils Nutrition 0.000 claims abstract description 30
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 18
- 235000019484 Rapeseed oil Nutrition 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 12
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000007513 acids Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 38
- 239000003921 oil Substances 0.000 claims description 28
- 239000010720 hydraulic oil Substances 0.000 claims description 27
- 239000010696 ester oil Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 239000003549 soybean oil Substances 0.000 claims description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 9
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 claims description 8
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 235000010384 tocopherol Nutrition 0.000 claims description 8
- 239000011732 tocopherol Substances 0.000 claims description 8
- 229960001295 tocopherol Drugs 0.000 claims description 8
- 229930003799 tocopherol Natural products 0.000 claims description 8
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 235000021313 oleic acid Nutrition 0.000 claims description 5
- PHNGKIFUTBFGAG-UHFFFAOYSA-N 2-ethoxybenzene-1,4-diol Chemical compound CCOC1=CC(O)=CC=C1O PHNGKIFUTBFGAG-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002889 oleic acids Chemical class 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- -1 trimethylol propane ester Chemical class 0.000 claims description 2
- 240000002791 Brassica napus Species 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 235000016068 Berberis vulgaris Nutrition 0.000 description 7
- 241000335053 Beta vulgaris Species 0.000 description 7
- 239000002199 base oil Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- HFWHTGSLDKKCMD-UHFFFAOYSA-N 2,2-bis(octanoyloxymethyl)butyl octanoate Chemical compound CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC)COC(=O)CCCCCCC HFWHTGSLDKKCMD-UHFFFAOYSA-N 0.000 description 4
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 4
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 229940117969 neopentyl glycol Drugs 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BTGGRPUPMPLZNT-PGEUSFDPSA-N 2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC BTGGRPUPMPLZNT-PGEUSFDPSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000010499 rapseed oil Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019487 Hazelnut oil Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000012716 cod liver oil Nutrition 0.000 description 1
- 239000003026 cod liver oil Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000010468 hazelnut oil Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
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- 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
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/04—Hydroxy compounds
- C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/14—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring containing at least 2 hydroxy groups
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
- C10M129/20—Cyclic ethers having 4 or more ring atoms, e.g. furans, dioxolanes
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/02—Sulfurised compounds
- C10M135/06—Esters, e.g. fats
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/044—Cyclic ethers having four or more ring atoms, e.g. furans, dioxolanes
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- 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
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- 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
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/40—Fatty vegetable or animal oils
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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- C10M2223/042—Metal salts thereof
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10N2010/04—Groups 2 or 12
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- the invention relates to the field of hydraulic fluids, in particular hydraulic oils for hydrostatic power transmission.
- esters oils of the aforementioned type which are essential for practical use, i.e. H.
- oils based on purified rapeseed oils and / or soybean oils which are freed in particular of amylopectins and other mucilaginous oils, show two decisive weaknesses in practical use:
- esterols based on unsaturated fatty acid systems tend to thicken rapidly even at only moderately elevated operating temperatures of, for example, 50 to 80 ° C. Occasion the willingness of the olefinic double bonds of the ester-forming acids of the oil type affected here to react under the influence of atmospheric oxygen, which ultimately leads to an increase in viscosity. Although it is known in principle that such undesirable increases in viscosity can be dampened by adding antioxidants, especially in hydraulic oils, it has been shown that the antioxidants used up to now in hydraulic oils based on mineral oils have only inadequate performance in ester oils of the type concerned here.
- DE-A-34 19 415 describes the production of lubricants, formwork oils and drilling emulsions from environmentally friendly raw materials.
- vegetable, animal and synthetic esters of polyhydric alcohols in particular peanut oil, hazelnut oil, cod liver oil, linseed oil, olive oil, castor oil, rape oil, soybean oil and whale oil, are used as the oil base.
- Easily degradable, harmless auxiliary substances can be considered as additives.
- products from the wood processing industry e.g. cellulose derivatives, lignin sulfate
- sugar processing industry e.g. molasses
- essential oils are added as preservatives.
- emulsifiers for the stabilization and easier handling of corresponding emulsions, emulsifiers, stabilizers, protective substances, solubilizers, defoamers, antioxidants and preservatives are used.
- examples include tocopherol from vegetable oils as an additive.
- the present invention is based on the object of demonstrating effective remedies for the two main sources of error of the hydraulic oils described above on the basis of environmentally friendly base oils.
- the aim of the invention is in particular on the one hand the effective stabilization of such ester oils with substantial proportions of highly unsaturated fatty acid in the ester mixture against oxidative Thickening by adding selected antioxidants, on the other hand, the invention also wants to provide mixture components based on environmentally compatible ester oils, the use of which can substantially reduce the solidification point in the hydraulic oil effectively and over any period of use.
- these selected antioxidants are present in solution in a preferably high-boiling solvent, which in turn is soluble in the ester oils which form the main oil component and are based on rapeseed oil and / or soybean oil.
- the mixtures of substances according to the invention differ from the known hydraulic oils based on mineral oil, which are widely used in practice, by the selection of the Environmentally friendly ester oils of the type mentioned as a basic component of the hydraulic oil.
- the peculiarities of the invention are initially illustrated in the first embodiment of the invention described above, ie using the environmentally friendly base oils based on natural materials for the construction of the hydraulic oils.
- ester oils forming the main oil component are available inexpensively as commercial products.
- Suitable rapeseed oils are in particular the erucic acid-free types that are widespread today.
- Turnip oil in this category usually has a solidification point at - 16 ° C.
- the pour point or solidification point is significantly reduced.
- the ester-forming acids of these mixture components are selected in the two subclasses shown in such a way that they combine the desired viscosity improvement, in particular in the low temperature range, with high environmental compatibility. Accordingly, the use of fatty acids of natural origin in both ester subclasses is preferred in the sense of the inventive action.
- the first ester component based on the trimethylol derivatives mentioned uses, as the ester-forming carboxylic acids, comparatively low, in particular saturated, carboxylic acids with a maximum of 10 carbon atoms.
- a known natural starting material of this type are the so-called preliminary fatty acids, ie straight-chain saturated monocarboxylic acids with 6 to 10 carbon atoms.
- the esters in this group are characterized by particularly low solidification values and are therefore particularly suitable to improve the cold behavior of the main oil components in the desired sense.
- ester-forming carboxylic acids from the second group of the trimethylol derivatives described according to the invention are also suitable for the intended use, depending on the structure.
- the reason for this is the high concentration of the olefinically mono- and / or polyunsaturated carboxylic acids of rapeseed oil or soybean oil or technical oleic acid.
- the less represented ester component is present in amounts of at least 15% by weight, based on this ester mixture to be added to the main oil component.
- the setting point for example of rapeseed oil, is thus lowered in the range from -40 to -45 ° C.
- ester mixed components can be added to the main oil component up to the amount of approximately equal proportions of the ester mixture to be added - based on the main oil component - without fear of an undesired restriction of the required environmental compatibility.
- the stabilizers proposed according to the invention as antioxidants are known compounds from the class of phenolic inhibitors or corresponding compounds with a hydroquinone basic structure. However, the selection of these stabilizers cannot be taken for granted. It has been shown that by this made according to the invention A surprisingly strong inhibition of the ester oils or ester oil mixtures used according to the invention against the undesirable increase in viscosity due to aging in air can be achieved. The service life and usability of hydraulic oils based on natural materials can thus be extended to a previously unknown extent with largely constant material properties.
- hydraulic oils are not only supposed to have the previously high stability to low temperatures, but also a change in the viscosity of the base oil that is as small as possible is required immediately after its production on the one hand or after thermal stress in the presence of air on the other hand.
- the viscosity properties of the hydraulic oils are known to be described in the definition of different viscosity classes according to ISO 3448 or DIN 51519. Here means:
- the viscosity classes ISO-VG 22, ISO-VG 32 and ISO-VG 46 can be set with the substance mixtures according to the invention and maintained over long periods of use.
- the amount of the inhibitor class according to the invention added to the base oil is in the range from 0.5 to 5% by weight, based on the total ester oil mixture. It may be expedient to provide these inhibitors as an additive, dissolved in a solvent.
- Solvents include the solubility of the selected inhibitors over a wide temperature range and the homogeneous miscibility of this solvent in the ester oil mixture. The sufficient low volatility of this solvent is also preferred. Ester oils of various compositions can serve as solvents.
- sulfurized triglycerides sulfurized fatty acid alkyl esters, sulfurized sperm oils, phosphoric acid esters such as trioleyl alcohol phosphate or triaryl phosphate.
- Zinc dialkyldithiophosphate compounds such as zinc (di-2-ethylhexyldithiophosphate) are particularly suitable.
- a mixture of 69% beet oil, 30% trimethylolpropane tricaprylate and in each case 0.33% butylhydroxyanisole, tert-butylhydroquinone and tocopherol with an initial viscosity of 29 mm2 / s at 40 ° C. was stored in an open vessel at 200 ° C. for 106 hours. After this time the mixture had a viscosity of 50 mm2 / s at 40 ° C. The mixture is liquid at - 25 ° C.
- a mixture of 70% beet oil, 30% trimethylolpropane tricaprylate was stored at 200 ° C for 106 hours. After this time the mixture had a viscosity of 160 mm2 / s at 40 ° C. The mixture is solid at - 16 ° C.
- a mixture of 49% beet oil, 25% trimethylolpropane trioleate, 25% trimethylolpropane tricaprylate and in each case 0.33% butylated hydroxyanisole, tert-butylhydroquinone and tocopherol with an initial viscosity of 33 mm2 / s at 40 ° C was in an open vessel at 200 ° C during Stored for 110 hours. After this time the mixture had a viscosity of 52 mm2 / s at 40 ° C. The mixture is liquid at - 30 ° C.
- a mixture of 50% beet oil, 25% trimethylolpropane trioleate and 25% trimethylolpropane tricaprylate with an initial viscosity of 33 mm2 / s at 40 ° C was stored in an open vessel at 200 ° C for 110 hours. After this time the mixture had a viscosity of 130 mm2 / s at 40 ° C. The mixture is liquid at - 30 ° C.
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Abstract
Description
Die Erfindung betrifft das Gebiet der Hydraulikflüssigkeiten, insbesondere der Hydrauliköle für die hydrostatische Kraftübertragung.The invention relates to the field of hydraulic fluids, in particular hydraulic oils for hydrostatic power transmission.
In der Vergangenheit aber auch noch bis heute wird der überwiegende Teil der Hydrauliköle aus Mineralöl hergestellt. In Einsatzgebieten, in denen beispielsweise durch nicht zu verhindernde Leckagen Ölaustritte in die Umwelt als Möglichkeit einzubeziehen sind, wird zunehmend der Einsatz von Hydraulikölen gefordert, die als Ölbasis umweltfreundliche Esteröle, insbesondere solche auf Basis Rüböl und/oder Sojaöl enthalten. Typische Einsatzgebiete des hier betroffenen Bereiches sind die Maschinen und Arbeitsgeräte der Forstwirtschaft, der Landwirtschaft, Bagger und dergleichen. Gefordert wird hier heute der Einsatz von Hydraulikölen der Wassergefährdungsklasse 0. Hydrauliköle auf Esterbasis sind geeignet, diesen Anforderungen zu entsprechen.In the past, but still today, the majority of hydraulic oils are made from mineral oil. In areas of application in which, for example, leaks that cannot be prevented from escaping the environment are an option, the use of hydraulic oils that contain environmentally friendly ester oils, especially those based on rapeseed oil and / or soybean oil, is increasingly required. Typical areas of application of the area affected here are the machines and implements of forestry, agriculture, excavators and the like. The use of hydraulic oils of water hazard class 0 is required here today. Ester-based hydraulic oils are suitable to meet these requirements.
Die für den praktischen Einsatz wesentlichen Esteröle der zuvor genannten Art, d. h. Öle auf Basis gereinigter, insbesondere von Amylopektinen und anderen Schleimstoffen befreiter Rüböle und/oder Sojaöle, zeigen im praktischen Einsatz jedoch 2 entscheidende Schwächen:The ester oils of the aforementioned type which are essential for practical use, i.e. H. However, oils based on purified rapeseed oils and / or soybean oils, which are freed in particular of amylopectins and other mucilaginous oils, show two decisive weaknesses in practical use:
Die auf Basis ungesättigter Fettsäuresysteme aufgebauten Esterole neigen auch bei nur mäßig erhöhten Betriebstemperaturen von beispielsweise 50 bis 80 °C zur raschen Verdickung. Anlaß hierfür ist die Bereitschaft der olefinischen Doppelbindungen der esterbildenden Säuren des hier betroffenen Öltyps, unter Einfluß von Luftsauerstoff Reaktionen einzugehen, die letztlich zur Viskositätszunahme führen. Zwar ist grundsätzlich bekannt, daß gerade in Hydraulikölen durch Zusatz von Antioxidantien solche unerwünschten Viskositätssteigerungen zu dämpfen sind, es zeigt sich jedoch, daß die bisher in Hydraulikölen auf Mineralölbasis bevorzugt eingesetzten Antioxidantien in Esterölen der hier betroffenen Art nur eine unzureichende Leistung erbringen.The esterols based on unsaturated fatty acid systems tend to thicken rapidly even at only moderately elevated operating temperatures of, for example, 50 to 80 ° C. Occasion the willingness of the olefinic double bonds of the ester-forming acids of the oil type affected here to react under the influence of atmospheric oxygen, which ultimately leads to an increase in viscosity. Although it is known in principle that such undesirable increases in viscosity can be dampened by adding antioxidants, especially in hydraulic oils, it has been shown that the antioxidants used up to now in hydraulic oils based on mineral oils have only inadequate performance in ester oils of the type concerned here.
Eine weitere wichtige Einschränkung für Hydrauliköle auf Basis der genannten umweltfreundlichen Esteröle ist die unzureichende Kältestabilität. Gereinigtes Rüböl besitzt beispielsweise einen Erstarrungs- bzw. Stockpunkt von - 16 °C. Schon vor Erreichen des Erstarrungspunktes ist mit sinkenden Temperaturen ein bemerkenswerter Anstieg der Viskosität gegeben. Der beispielsweise im Winterbetrieb doch vergleichsweise hoch liegende Erstarrungspunkt des Rüböls bringt für den praktischen Einsatz der Hydrauliköle bei niederen Umgebungstemperaturen beträchtliche Probleme. Verständlicherweise kann diese Problematik im Betrieb dramatisch dadurch verstärkt werden, daß über eine oxidative Eindickung des Esteröls der zuvor geschilderten Art gleichzeitig auch die erhebliche Heraufsetzung des Erstarrungspunktes des Hydrauliköls ausgelöst wird. Der Zusatz von Stockpunktserniedrigern gibt hier keine Lösung des technischen Problems. Es ist bekannt, daß die Wirkung solcher Pour-Point-Depressants bei längerem Verweilen im zu behandelnden Öl verschwindet.Another important limitation for hydraulic oils based on the environmentally friendly ester oils mentioned is the inadequate low-temperature stability. Purified beet oil, for example, has a solidification or pour point of - 16 ° C. Even before the solidification point is reached, there is a remarkable increase in viscosity with falling temperatures. The solidification point of the beet oil, which is comparatively high in winter, for example, poses considerable problems for the practical use of hydraulic oils at low ambient temperatures. Understandably, this problem can be exacerbated dramatically in operation by the fact that an oxidative thickening of the ester oil of the type described above also triggers the considerable increase in the solidification point of the hydraulic oil. The addition of pour point depressants does not solve the technical problem here. It is known that the effect of such pour point depressants disappears when the oil to be treated remains for a long time.
In der DE-A-34 19 415 wird die Herstellung von Schmiermitteln, Schalölen und Bohremulsionen aus umweltfreundlichen Grundstoffen beschrieben. Hierzu werden als Ölgrundlage pflanzliche, tierische und synthetische Ester mehrwertiger Alkohole, insbesondere Erdnußöl, Haselnußöl, Lebertran, Leinöl, Olivenöl, Ricinusöl, Rüböl, Sojaöl und Walöl, eingesetzt. Als Zusätze kommen leicht abbaubare, unschädliche Hilfsstoffe in Frage. So werden zur Modifikation der Viskosität, Klebrigkeit und Haftfähigkeit von Schmiermitteln beispielsweise Produkte aus der holzverarbeitenden Industrie (z. B. Cellulosederivate, Ligninsulfat) oder höhermolekulare Substanzen der zuckerverarbeitenden Industrie (z. B. Melasse) verwendet. Als Konservierungsmittel werden insbesondere etherische Öle zugesetzt. Zur Stabilisierung und leichteren Handhabung von entsprechenden Emulsionen werden Emulgatoren, Stabilisatoren, Schutzstoffe, Solubilisatoren, Entschäumer, Antioxidantien und Konservierungsmittel eingesetzt. In Beispielen wird unter anderem als Additiv Tocopherol aus pflanzlichen Ölen genannt.DE-A-34 19 415 describes the production of lubricants, formwork oils and drilling emulsions from environmentally friendly raw materials. For this purpose, vegetable, animal and synthetic esters of polyhydric alcohols, in particular peanut oil, hazelnut oil, cod liver oil, linseed oil, olive oil, castor oil, rape oil, soybean oil and whale oil, are used as the oil base. Easily degradable, harmless auxiliary substances can be considered as additives. For example, products from the wood processing industry (e.g. cellulose derivatives, lignin sulfate) or higher molecular weight substances from the sugar processing industry (e.g. molasses) are used to modify the viscosity, stickiness and adhesiveness of lubricants. In particular, essential oils are added as preservatives. For the stabilization and easier handling of corresponding emulsions, emulsifiers, stabilizers, protective substances, solubilizers, defoamers, antioxidants and preservatives are used. Examples include tocopherol from vegetable oils as an additive.
Demgegenüber geht die vorliegende Erfindung von der Aufgabe aus, wirkungsvolle Abhilfe für die beiden vorstehend geschilderten Hauptfehlerquellen der Hydrauliköle auf Basis umweltfreundlicher Grundöle aufzuzeigen. Ziel der Erfindung ist insbesondere einerseits die wirkungsvolle Stabilisierung solcher Esteröle mit substantiellen Anteilen hochungesätttigter Fettsäure im Estergemisch gegen oxidative Verdickung durch Zusatz ausgewählter Antioxidantien, zum anderen will die Erfindung Mischungskomponenten ebenfalls auf Basis umweltverträglicher Esteröle zur Verfügung stellen, durch deren Mitverwendung eine substantielle Absenkung des Erstarrungspunktes im Hydrauliköl wirkungsvoll und über beliebig lange Benutzungszeiträume erzielt werden kann.In contrast, the present invention is based on the object of demonstrating effective remedies for the two main sources of error of the hydraulic oils described above on the basis of environmentally friendly base oils. The aim of the invention is in particular on the one hand the effective stabilization of such ester oils with substantial proportions of highly unsaturated fatty acid in the ester mixture against oxidative Thickening by adding selected antioxidants, on the other hand, the invention also wants to provide mixture components based on environmentally compatible ester oils, the use of which can substantially reduce the solidification point in the hydraulic oil effectively and over any period of use.
Gegenstand der Erfindung ist dementsprechend in einer ersten Ausführungsform ein Grundöl auf Naturstoffbasis für die Formulierung von Hydraulikölen mit Viskositäts- und Kältestabilität auf Basis von
- a) gereinigtem Rüböl und/oder Sojaöl als Öl-Hauptkomponente, sowie Antioxidantien und anderen Additiven, welches dadurch gekennzeichnet ist, daß es die folgenden Komponenten enthält:
- b) 0,5 bis 5 Gew.-% - bezogen auf Gesamtgemisch - an Antioxidantien ausgewählt aus der Gruppe Methoxyphenol, Ethoxyphenol, Butylhydroxyanisol, Butylhydroxytoluol, Methoxyhydrochinon, Ethoxyhydrochinon, tert.-Butylhydrochinon und/oder Tocopherol,
- c) Ester des Trimethylolethans, des Trimethylolpropans und/oder des Neopentylglykols mit Monocarbonsäuren der nachfolgenden Unterklassen:
- c1) gesättigte C₅₋₁₀-Monocarbonsäuren und/oder
- c2) Fettsäuren auf Basis Rüböl, Sojaöl und/oder technische Ölsäure,
- a) purified rapeseed oil and / or soybean oil as the main oil component, as well as antioxidants and other additives, which is characterized in that it contains the following components:
- b) 0.5 to 5% by weight, based on the total mixture, of antioxidants selected from the group consisting of methoxyphenol, ethoxyphenol, butylhydroxyanisole, butylhydroxytoluene, methoxyhydroquinone, ethoxyhydroquinone, tert-butylhydroquinone and / or tocopherol,
- c) esters of trimethylolethane, trimethylolpropane and / or neopentylglycol with monocarboxylic acids of the following subclasses:
- c1) saturated C₅₋₁₀ monocarboxylic acids and / or
- c2) fatty acids based on rape oil, soybean oil and / or technical oleic acid,
In einer weiteren Ausführungsform betrifft die Erfindung die Verwendung von Antioxidantien zusammen mit anderen Additiven zur Viskositätsstabilisierung und Absenkung des Stockpunktes von Hydraulikölen auf Basis von Rüböl und/oder Sojaöl, dadurch gekennzeichnet, daß
b) mindestens ein Antioxidans, ausgewählt aus:
Methoxyphenyol, Ethoxyphenol, Butylhydroxyanisol, Butylhydroxytoluol, Methoxyhydrochinon, Ethoxyhydrochinon, tert.-Butylhydrochinon und/oder Tocopherol,
zusammen mit
c) Estern des Trimethylolethans, des Trimethylolpropans und/oder des Neopentylglykols mit Monocarbonsäuren der nachfolgenden Unterklassen:
- c1) gesättigte C₅₋₁₀-Monocarbonsäuren und/oder
- c2) Fettsäuren auf Basis Rüböl, Sojaöl und/oder technische Ölsäuren, eingesetzt werden.
b) at least one antioxidant selected from:
Methoxyphenyol, ethoxyphenol, butylhydroxyanisole, butylhydroxytoluene, methoxyhydroquinone, ethoxyhydroquinone, tert-butylhydroquinone and / or tocopherol,
along with
c) esters of trimethylolethane, trimethylolpropane and / or neopentylglycol with monocarboxylic acids of the following subclasses:
- c1) saturated C₅₋₁₀ monocarboxylic acids and / or
- c2) fatty acids based on beet oil, soybean oil and / or technical oleic acids.
Gewünschtenfalls liegen dabei diese ausgewählten Antioxidantien in einem bevorzugt hoch siedenden Lösungsmittel gelöst vor, das seinerseits in den die Öl-Hauptkomponente bildenden Esterölen auf Basis Rüböl und/oder Sojaöl löslich ist.If desired, these selected antioxidants are present in solution in a preferably high-boiling solvent, which in turn is soluble in the ester oils which form the main oil component and are based on rapeseed oil and / or soybean oil.
Zu den näheren Einzelheiten über die Zusammensetzung der Hydrauliköle sei zunächst auf den einschlägigen Stand der Technik verwiesen. Genannt sei hier insbesondere "Ullmanns Enzyklopädie der technischen Chemie" 4. Auflage (Verlag Chemie, Weinheim) Band 13, Seite 85 ff., Hydraulikflüssigkeiten, sowie Dieter Klamann "Schmierstoffe und verwandte Produkte", Herstellung, Eigenschaf- ten, Anwendung, (Verlag Chemie, Weinheim) 1982, Seiten 147/148-11.9, Hydrauliköle.For further details on the composition of the hydraulic oils, reference is first made to the relevant prior art. Special mention should be made here of "Ullmann's Encyclopedia of Technical Chemistry" 4th edition (Verlag Chemie, Weinheim) Volume 13, page 85 ff., Hydraulic fluids, and Dieter Klamann "Lubricants and related products", manufacture, properties, application, (publisher Chemie, Weinheim) 1982, pages 147 / 148-11.9, hydraulic oils.
Von den vorbekannten und in der Praxis in weitem Umfang eingesetzten Hydraulikölen auf Mineralölbasis unterscheiden sich die erfindungsgemäßen Stoffgemische durch die Auswahl der umweltfreundlichen Esteröle der genannten Art als Grundkomponente des Hydrauliköls. Die Besonderheiten der Erfindung seien dabei zunächst an der zuvor dargestellten ersten Ausführungsform der Erfindung, d. h. anhand der umweltverträglichen Grundöle auf Naturstoffbasis für den Aufbau der Hydrauliköle dargestellt.The mixtures of substances according to the invention differ from the known hydraulic oils based on mineral oil, which are widely used in practice, by the selection of the Environmentally friendly ester oils of the type mentioned as a basic component of the hydraulic oil. The peculiarities of the invention are initially illustrated in the first embodiment of the invention described above, ie using the environmentally friendly base oils based on natural materials for the construction of the hydraulic oils.
Gereinigte und gegebenenfalls durch wenigstens partielle Entfärbung zusätzlich raffinierte, die Öl-Hauptkomponente bildende Esteröle stehen als Handelsprodukte preiswert zur Verfügung. Geeignete Rüböle sind insbesondere die heute verbreiteten Erucasäure-freien Typen.Purified and, if necessary, additionally refined by at least partial decolorization, the ester oils forming the main oil component are available inexpensively as commercial products. Suitable rapeseed oils are in particular the erucic acid-free types that are widespread today.
Rüböl dieser Kategorie besitzt üblicherweise einen Erstarrungspunkt bei - 16 °C. Durch den Zusatz der ausgewählten Ester des Trimethylolethans, des Trimethylolpropans und/oder des Neopentylglykols gelingt eine deutliche Senkung des Stock- bzw. Erstarrungspunktes. Die esterbildenden Säuren dieser Mischungskomponenten sind in den beiden dargestellten Unterklassen so ausgesucht, daß sie die angestrebte Viskositätsverbesserung, insbesondere im niederen Temperaturbereich mit hoher Umweltverträglichkeit vereinigen. Dementsprechend ist die Verwendung von Fettsäuren natürlichen Ursprungs in beiden Ester-Unterklassen im Sinne des erfindungsgemäßen Handelns bevorzugt.Turnip oil in this category usually has a solidification point at - 16 ° C. By adding the selected esters of trimethylolethane, trimethylolpropane and / or neopentylglycol, the pour point or solidification point is significantly reduced. The ester-forming acids of these mixture components are selected in the two subclasses shown in such a way that they combine the desired viscosity improvement, in particular in the low temperature range, with high environmental compatibility. Accordingly, the use of fatty acids of natural origin in both ester subclasses is preferred in the sense of the inventive action.
Die erste Esterkomponente auf Basis der genannten Trimethylolderivate setzt als esterbildende Carbonsäuren vergleichsweise niedere, insbesondere gesättigte Carbonsäuren mit maximal 10 C-Atomen ein. Ein bekanntes natürliches Ausgangsmaterial dieser Art sind die sogenannten Vorlauffettsäuren, d. h. geradkettige gesättigte Monocarbonsäuren mit 6 bis 10 C-Atomen. Die Ester dieser Gruppe zeichnen sich durch besonders niedere Erstarrungswerte aus und sind dementsprechend besonders geeignet, das Kälteverhalten der Öl-Hauptkomponenten im angestrebten Sinne zu verbessern.The first ester component based on the trimethylol derivatives mentioned uses, as the ester-forming carboxylic acids, comparatively low, in particular saturated, carboxylic acids with a maximum of 10 carbon atoms. A known natural starting material of this type are the so-called preliminary fatty acids, ie straight-chain saturated monocarboxylic acids with 6 to 10 carbon atoms. The esters in this group are characterized by particularly low solidification values and are therefore particularly suitable to improve the cold behavior of the main oil components in the desired sense.
Aber auch die esterbildenden Carbonsäuren aus der zweiten Gruppe der erfindungsgemäß beschriebenen Trimethylolderivate sind strukturbedingt für den beabsichtigten Einsatzzweck geeignet. Anlaß ist hier die hohe Konzentration der olefinisch einfach und/oder mehrfach ungesättigten Carbonsäuren des Rüböls oder des Sojaöls bzw. der technischen Ölsäure.However, the ester-forming carboxylic acids from the second group of the trimethylol derivatives described according to the invention are also suitable for the intended use, depending on the structure. The reason for this is the high concentration of the olefinically mono- and / or polyunsaturated carboxylic acids of rapeseed oil or soybean oil or technical oleic acid.
Es ist erfindungsgemäß bevorzugt, Mischungen dieser beiden Unterklassen von Trimethylolethan-, Trimethylolpropan- bzw. Neopentylglykol-Estern einzusetzen. In einer bevorzugten Ausführungsform liegt die jeweils geringer vertretene Esterkomponente in Mengen von wenigstens 15 Gew.-% - bezogen auf dieses der Öl-Hauptkomponente zuzusetzende Estergemisch - vor. Erfindungsgemäß kann es insbesondere bevorzugt sein, in diesem Estergemisch überwiegende Mengen der Trimethylolester auf Basis der niederen Fettsäuren mit maximal 10 C-Atomen einzusetzen. Erfindungsgemäß gelingt damit die Absenkung des Erstarrungspunktes beispielsweise von Rüböl in den Bereich von - 40 bis - 45 °C. Aufgrund ihrer hohen Umweltverträglichkeit können dabei der Öl-Hauptkomponente diese Estermischkomponenten bis zum Betrag etwa mengengleicher Anteile des zuzusetzenden Estergemisches - bezogen auf die Öl-Hauptkomponente - bedenkenlos zugesetzt werden, ohne eine unerwünschte Beschränkung der geforderten Umweltverträglichkeit befürchten zu müssen.It is preferred according to the invention to use mixtures of these two subclasses of trimethylolethane, trimethylolpropane or neopentylglycol esters. In a preferred embodiment, the less represented ester component is present in amounts of at least 15% by weight, based on this ester mixture to be added to the main oil component. According to the invention, it can be particularly preferred to use predominant amounts of the trimethyl esters based on the lower fatty acids with a maximum of 10 carbon atoms in this ester mixture. According to the invention, the setting point, for example of rapeseed oil, is thus lowered in the range from -40 to -45 ° C. Due to their high environmental compatibility, these ester mixed components can be added to the main oil component up to the amount of approximately equal proportions of the ester mixture to be added - based on the main oil component - without fear of an undesired restriction of the required environmental compatibility.
Die erfindungsgemäß als Antioxidantien vorgeschlagenen Stabilisierungsmittel sind an sich bekannte Verbindungen aus der Klasse der phenolischen Inhibitoren bzw. entsprechender Verbindungen mit Hydrochinon-Grundstruktur. Die Auswahl gerade dieser Stabilisatoren ist gleichwohl nicht selbstverständlich. Es hat sich gezeigt, daß durch diese erfindungsgemäß getroffene Auswahl eine überraschend starke Inhibierung der erfindungsgemäß eingesetzten Esteröle bzw. Esterölgemische gegen den unerwünschten Viskositätsanstieg durch Alterung an der Luft erzielt werden kann. Die Lebensdauer und die Gebrauchsfähigkeit der Hydrauliköle auf Naturstoffbasis kann damit bei weitgehend konstanten Stoffeigenschaften in einem bisher nicht gekannten Ausmaß verlängert werden.The stabilizers proposed according to the invention as antioxidants are known compounds from the class of phenolic inhibitors or corresponding compounds with a hydroquinone basic structure. However, the selection of these stabilizers cannot be taken for granted. It has been shown that by this made according to the invention A surprisingly strong inhibition of the ester oils or ester oil mixtures used according to the invention against the undesirable increase in viscosity due to aging in air can be achieved. The service life and usability of hydraulic oils based on natural materials can thus be extended to a previously unknown extent with largely constant material properties.
Hydrauliköle sollen bekanntlich nicht nur die zuvor hohe Kältestabilität aufweisen, gefordert ist darüber hinaus eine möglichst geringe Viskositätsänderung des Grundöls unmittelbar nach seiner Herstellung einerseits bzw. nach thermischer Belastung in Luftgegenwart andererseits. Die Viskositätseigenschaften der Hydrauliköle werden dabei bekanntlich in der Definition unterschiedlicher Viskositätsklassen nach ISO 3448 oder gemäß DIN 51519 beschrieben. Dabei bedeutet:
Je nach den erfindungsgemäß eingesetzten Mischungsverhältnissen der Esteröle und der Auswahl der erfindungsgemäß definierten Inhibitoren können mit den erfindungsgemäßen Stoffgemischen die Viskositätsklassen ISO-VG 22, ISO-VG 32 und ISO-VG 46 eingestellt und über lange Gebrauchszeiträume eingehalten werden.Depending on the mixing ratios of the ester oils used according to the invention and the selection of the inhibitors defined according to the invention, the viscosity classes ISO-VG 22, ISO-VG 32 and ISO-VG 46 can be set with the substance mixtures according to the invention and maintained over long periods of use.
Die Zusatzmenge der erfindungsgemäßen Inhibitorklasse zum Grundöl liegt im Bereich von 0,5 bis 5 Gew.-%, bezogen auf das Esteröl-Gesamtgemisch. Es kann dabei zweckmäßig sein, diese Inhibitoren in einem Lösungsmittel gelöst als Additiv zur Verfügung zu stellen. Die Anforderungen an das hier gewählte Lösungsmittel umfassen die Löslichkeit der ausgewählten Inhibitoren über einen weiten Temperaturbereich hinweg sowie die homogene Einmischbarkeit auch dieses Lösungsmittels in das Esterölgemisch. Weiterhin ist die hinreichende Schwerflüchtigkeit dieses Lösungsmittels bevorzugt. Als Lösungsmittel können Esteröle verschiedenartigster Zusammensetzung dienen.The amount of the inhibitor class according to the invention added to the base oil is in the range from 0.5 to 5% by weight, based on the total ester oil mixture. It may be expedient to provide these inhibitors as an additive, dissolved in a solvent. The requirements for the one selected here Solvents include the solubility of the selected inhibitors over a wide temperature range and the homogeneous miscibility of this solvent in the ester oil mixture. The sufficient low volatility of this solvent is also preferred. Ester oils of various compositions can serve as solvents.
Zur Formulierung des fertigen Hydrauliköls aus den erfindungsgemäß formulierten Grundölen bedarf es in bekannter Weise des Zusatzes weiterer Komponenten. So können den erfindungsgemäß beschriebenen Grundölen insbesondere die folgenden weiteren Komponenten zugesetzt werden:The formulation of the finished hydraulic oil from the base oils formulated according to the invention requires the addition of further components in a known manner. The following additional components can thus be added to the base oils described in accordance with the invention:
Hierbei handelt es sich insbesondere um geschwefelte Triglyceride, geschwefelte Fettsäurealkylester, geschwefelte Spermöle, Phosphorsäureester wie Trioleylalkoholphosphat oder Triarylphosphat.These are, in particular, sulfurized triglycerides, sulfurized fatty acid alkyl esters, sulfurized sperm oils, phosphoric acid esters such as trioleyl alcohol phosphate or triaryl phosphate.
Geeignet sind insbesondere Zinkdialkyldithiophosphatverbindungen wie Zink(di-2-ethylhexyldithiophosphat)
Beispielsweise ist das unter dem Handelsnamen "Edenor® 2410" von der Anmelderin vertriebene Produkt geeignet.For example, the product sold by the applicant under the trade name "Edenor® 2410" is suitable.
Im übrigen wird zu der speziellen Formulierung von Hydraulikölen, ihren Zusatzstoffen und den Mengen dieser Zusatzstoffe auf den eingehend referierten druckschriftlichen Stand der Technik zu dieser Materialklasse verwiesen.For the rest, with regard to the special formulation of hydraulic oils, their additives and the amounts of these additives, reference is made to the detailed, documented prior art relating to this material class.
Die nachfolgenden Beispiele beschreiben die erfindungsgemäß einstellbaren Effekte an ÖI-Hauptkomponenten auf Basis Rüböl und Sojaöl und vergleichen diese Ergebnisse mit entsprechenden Stoffgemischen, die jedoch der erfindungsgemäßen Definition nicht entsprechen.The following examples describe the effects which can be set according to the invention on main oil components based on rapeseed oil and soybean oil and compare these results with corresponding mixtures of substances which, however, do not correspond to the definition according to the invention.
Eine Mischung aus 69 % Rüböl, 30 % Trimethylolpropantricaprylat und jeweils 0,33 % Butylhydroxyanisol, tert.-Butylhydrochinon und Tocopherol mit einer Ausgangsviskosität von 29 mm²/s bei 40 °C wurde in einem offenen Gefäß bei 200 °C während 106 Stunden gelagert. Nach dieser Zeit hatte die Mischung eine Viskosität von 50 mm²/s bei 40 °C. Die Mischung ist bei - 25 °C flüssig.A mixture of 69% beet oil, 30% trimethylolpropane tricaprylate and in each case 0.33% butylhydroxyanisole, tert-butylhydroquinone and tocopherol with an initial viscosity of 29 mm² / s at 40 ° C. was stored in an open vessel at 200 ° C. for 106 hours. After this time the mixture had a viscosity of 50 mm² / s at 40 ° C. The mixture is liquid at - 25 ° C.
Eine Mischung von 70 % Rüböl, 30 % Trimethylolpropantricaprylat wurde 106 Stunden bei 200 °C gelagert. Nach dieser Zeit hatte die Mischung eine Viskosität von 160 mm²/s bei 40 °C. Die Mischung ist bei - 16 °C fest.A mixture of 70% beet oil, 30% trimethylolpropane tricaprylate was stored at 200 ° C for 106 hours. After this time the mixture had a viscosity of 160 mm² / s at 40 ° C. The mixture is solid at - 16 ° C.
Eine Mischung aus 49 % Rüböl, 25 % Trimethylolpropantrioleat, 25 % Trimethylolpropantricaprylat und jeweils 0,33 % Butylhydroxyanisol, tert.-Butylhydrochinon und Tocopherol mit einer Ausgangsviskosität von 33 mm² /s bei 40 °C wurde in einem offenen Gefäß bei 200 °C während 110 Stunden gelagert. Nach dieser Zeit hatte die Mischung eine Viskosität von 52 mm²/s bei 40 °C. Die Mischung ist bei - 30 °C flüssig.A mixture of 49% beet oil, 25% trimethylolpropane trioleate, 25% trimethylolpropane tricaprylate and in each case 0.33% butylated hydroxyanisole, tert-butylhydroquinone and tocopherol with an initial viscosity of 33 mm² / s at 40 ° C was in an open vessel at 200 ° C during Stored for 110 hours. After this time the mixture had a viscosity of 52 mm² / s at 40 ° C. The mixture is liquid at - 30 ° C.
Eine Mischung von 50 % Rüböl, 25 % Trimethylolpropantrioleat und 25 % Trimethylolpropantricaprylat mit einer Ausgangsviskosität von 33 mm²/s bei 40 °C wurde in einem offenen Gefäß bei 200 °C während 110 Stunden gelagert. Nach dieser Zeit hatte die Mischung eine Viskosität von 130 mm²/s bei 40 °C. Die Mischung ist bei - 30 °C flüssig.A mixture of 50% beet oil, 25% trimethylolpropane trioleate and 25% trimethylolpropane tricaprylate with an initial viscosity of 33 mm² / s at 40 ° C was stored in an open vessel at 200 ° C for 110 hours. After this time the mixture had a viscosity of 130 mm² / s at 40 ° C. The mixture is liquid at - 30 ° C.
Claims (7)
- A basic oil based on natural materials for the formulation of hydraulic oils having viscosity and low-temperature stability on the basis of
a) purified rapeseed oil and/or soybean oil as the main oil component and also antioxidants and other additives,
characterized in that it contains the following components:b) 0.5 to 5% by weight, based on the mixture as a whole, of antioxidants selected from the group consisting of methoxyphenol, ethoxyphenol, butyl hydroxyanisole, butyl hydroxytoluene, methoxyhydroquinone, ethoxyhydroquinone, tert. butyl hydroquinone and/or tocopherol,c) esters of trimethylol ethane, trimethylol propane and/or neopentyl glycol with monocarboxylic acids of the following subclasses:c1) saturated C₅₋₁₀ monocarboxylic acids and/orc2) fatty acids based on rapeseed oil, soybean oil and/or technical oleic acid,the ester components (c) being present in at most substantially equal quantities to the main oil component (a). - A basic oil as claimed in claim 1, characterized in that mixture component (c) is present in the form of an ester mixture of the carboxylic acids of subclasses (cl) and (c2) which consists of at least about 15% by weight, based on the ester mixture, of one ester subclass and, for the rest, of esters of the other subclass, predominant quantities of ester subclass (cl) being preferred.
- The use of antioxidants together with other additives for stabilizing the viscosity and lowering the pour point of hydraulic oils based on rapeseed oil and/or soybean oil, characterized in that
b) at least one antioxidant selected from:
methoxyphenol, ethoxyphenol, butyl hydroxyanisole, butyl hydroxytoluene, methoxyhydroquinone, ethoxyhydroquinone, tert. butyl hydroquinone and/or tocopherol,
together with
c) esters of trimethylol ethane, trimethylol propane and/or neopentyl glycol with monocarboxylic acids of the following subclasses:c1) saturated C₅₋₁₀ monocarboxylic acids and/orc2) fatty acids based on rapeseed oil, soybean oil and/or technical oleic acids,are used. - The use claimed in claim 3, characterized in that the trimethylol ethane, trimethylol propane and/or neopentyl glycol esters are added to the hydraulic oil in at most substantially equal quantities to the rapeseed oil and/or soybean oil.
- The use claimed in claims 3 and 4, characterized in that trimethylol ethane/trimethylol propane ester mixtures containing a relatively high percentage of esters of acids of subclass (cl) and, for the rest, esters of acids of subclass (c2) are added.
- The use claimed in claims 3 to 5, characterized in that esters or ester mixtures of acids of subclass (c1) of which the acid components are of natural origin and, more particularly, are corresponding head-fractionated fatty acids are used.
- The use claimed in claim 3, characterized in that the antioxidants (b) are present in solution in a preferably high-boiling solvent soluble in ester oils.
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DE3927155A DE3927155A1 (en) | 1989-08-17 | 1989-08-17 | ENVIRONMENTALLY FRIENDLY BASIC OIL FOR THE FORMULATION OF HYDRAULIC OILS |
DE3927155 | 1989-08-17 |
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EP0486575A1 EP0486575A1 (en) | 1992-05-27 |
EP0486575B1 true EP0486575B1 (en) | 1993-11-24 |
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CN110724582A (en) * | 2019-10-08 | 2020-01-24 | 山东瑞兴阻燃科技有限公司 | Tert-butylated triphenyl phosphate flame-retardant hydraulic oil and preparation method thereof |
EP4079830A1 (en) * | 2021-04-19 | 2022-10-26 | Marteen Sports World, S.L. | Biodegradable lubricant composition |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2305228A (en) * | 1940-05-14 | 1942-12-15 | Du Pont | Hydraulic fluid |
US2889354A (en) * | 1955-10-06 | 1959-06-02 | Monsanto Chemicals | Dicarboxylate esters of alcohol containing a quaternary carbon in the beta-position |
US3660289A (en) * | 1970-05-15 | 1972-05-02 | Universal Oil Prod Co | Reaction product of polyamine and carboxylic acids and fuels lubricating oils greases and plastics containing said product |
IT1010487B (en) * | 1974-05-08 | 1977-01-10 | Snam Progetti | ESTERS AS COMPONENTS OF LUBRIFI CANTI |
US3970574A (en) * | 1975-06-16 | 1976-07-20 | E. I. Du Pont De Nemours & Co. | Hydraulic brake fluid composition |
US4210543A (en) * | 1978-11-01 | 1980-07-01 | Olin Corporation | Use of hydrazidothioates as additives for functional fluids |
FI66899C (en) * | 1983-02-11 | 1984-12-10 | Kasvisoeljy Vaextolje Ab Oy | SMOERJMEDEL MED TRIGLYCERIDER SOM HUVUDKONPONENT |
DE3419415A1 (en) * | 1984-05-24 | 1985-11-28 | Hans 7432 Urach Schur | Production of lubricants, mould oils and drilling emulsions from environmentally friendly raw materials |
JPS63125598A (en) * | 1986-11-13 | 1988-05-28 | Kao Corp | Flame-retardant hydraulic oil |
DE3643935C2 (en) * | 1986-12-22 | 1995-07-06 | Henkel Kgaa | Synthetic polyol esters |
US5273672A (en) * | 1987-03-02 | 1993-12-28 | Idemitsu Kosan Company Limited | Lubricating oil composition containing a partial ester of a polyhydric alcohol and a substituted succinic acid ester |
-
1989
- 1989-08-17 DE DE3927155A patent/DE3927155A1/en not_active Withdrawn
-
1990
- 1990-08-08 DE DE90912376T patent/DE59003632D1/en not_active Expired - Fee Related
- 1990-08-08 ES ES90912376T patent/ES2060193T3/en not_active Expired - Lifetime
- 1990-08-08 CA CA002065011A patent/CA2065011A1/en not_active Abandoned
- 1990-08-08 JP JP2511445A patent/JPH05503949A/en active Pending
- 1990-08-08 BR BR909007600A patent/BR9007600A/en not_active Application Discontinuation
- 1990-08-08 EP EP90912376A patent/EP0486575B1/en not_active Expired - Lifetime
- 1990-08-08 WO PCT/EP1990/001296 patent/WO1991002784A1/en active IP Right Grant
-
1994
- 1994-11-21 US US08/342,996 patent/US5451334A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59003632D1 (en) | 1994-01-05 |
EP0486575A1 (en) | 1992-05-27 |
ES2060193T3 (en) | 1994-11-16 |
WO1991002784A1 (en) | 1991-03-07 |
JPH05503949A (en) | 1993-06-24 |
US5451334A (en) | 1995-09-19 |
BR9007600A (en) | 1992-06-30 |
CA2065011A1 (en) | 1991-02-18 |
DE3927155A1 (en) | 1991-02-21 |
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