EP0003032B1 - Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base - Google Patents
Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base Download PDFInfo
- Publication number
- EP0003032B1 EP0003032B1 EP78101731A EP78101731A EP0003032B1 EP 0003032 B1 EP0003032 B1 EP 0003032B1 EP 78101731 A EP78101731 A EP 78101731A EP 78101731 A EP78101731 A EP 78101731A EP 0003032 B1 EP0003032 B1 EP 0003032B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- pentaerythritol
- ester
- esters
- carboxylic acid
- 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
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 title claims description 30
- 239000010687 lubricating oil Substances 0.000 title claims description 7
- 150000001733 carboxylic acid esters Chemical class 0.000 title description 4
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims description 50
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 48
- 150000002148 esters Chemical class 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000010696 ester oil Substances 0.000 claims description 13
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 13
- -1 saturated aliphatic monocarboxylic acid Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 18
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 17
- 239000003921 oil Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000005639 Lauric acid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- VOPQPXBWECOXHO-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;cyclohexanecarboxylic acid Chemical class OCC(CO)(CO)CO.OC(=O)C1CCCCC1 VOPQPXBWECOXHO-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NCGQPNAQUYGWMI-UHFFFAOYSA-N [3-heptanoyloxy-2,2-bis(heptanoyloxymethyl)propyl] heptanoate Chemical compound CCCCCCC(=O)OCC(COC(=O)CCCCCC)(COC(=O)CCCCCC)COC(=O)CCCCCC NCGQPNAQUYGWMI-UHFFFAOYSA-N 0.000 description 1
- CFRNDJFRRKMHTL-UHFFFAOYSA-N [3-octanoyloxy-2,2-bis(octanoyloxymethyl)propyl] octanoate Chemical compound CCCCCCCC(=O)OCC(COC(=O)CCCCCCC)(COC(=O)CCCCCCC)COC(=O)CCCCCCC CFRNDJFRRKMHTL-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002027 dodecanoic acid esters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- XFHYIYJBUXIFPF-UHFFFAOYSA-N hexan-2-yl decanoate Chemical compound CCCCCCCCCC(=O)OC(C)CCCC XFHYIYJBUXIFPF-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 150000004667 medium chain fatty acids Chemical class 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
Definitions
- the present application relates to carboxylic acid esters of pentaerythritol and their use in lubricants.
- Lubricating oils based on carboxylic acid esters generally outperform mineral oils with the same basic viscosities at higher flash points, lower volatility and better viscosity-temperature characteristics (measured by the viscosity index, "VI").
- VI index the viscosity index
- esters which also contain monoalcohols, dicarboxylic acids and / or monocarboxylic acids as esterification components in addition to diols / polyols, are known. Although they allow ester oils of increased intrinsic viscosity to be provided, it is known to the person skilled in the art that their preparation is difficult because of the proportions of acid or partial esters of dicarboxylic acids remaining after the esterification reaction, which are difficult to remove by refining or distillation.
- DE-OS 2302918 also proposes the use of carboxylic acids with 14 to 22 carbon atoms per molecule, which are preferably branched in the a-position to the carboxyl group, for the production of high-viscosity ester oils, but the underlying monocarboxylic acids are not easily obtainable and require additional synthesis steps. Under strongly oxidative conditions, such oils still show noticeable evaporation losses. These oils do not quite reach the required high viscosity index values of over 140.
- a pentaerythritol ester lubricating oil which contains 2-ethylhexanoic and isostearic acid in a molar ratio of 1: 3.
- the pour point specified is -45 ° C., but the viscosity index is only 133 and is therefore also below 140.
- DE-OS 2 528 526 discloses lubricating oil formulations for gas turbines and jet engines based on pentaerythritol or trimethylolpropane esters of 2-18, but are preferred Saturated monocarboxylic acids containing 5-10 carbon atoms.
- Examples of such monocarboxylic acids include cyclohexyl carboxylic acid is also mentioned, trimethylol and pentaerythritol esters of cyclohexyl carboxylic acid are described in detail in J. of Chem. and Eng. Data 7, 547 ff. (1962). From the data listed there it can be seen that pentaerythritol esters with 1-2 moles of cyclohexylcarboxylic acid per mole of ester have up to approximately 32 total pour points down to a total carbon number of the acid portion of the esters. The viscosity-temperature behavior of these esters depends on the number of molecules of cyclohexylcarboxylic acid contained per molecule of ester.
- the viscosity indices of the pentaerythritol esters containing 1 mol of cyclohexylcarboxylic acid in the examples mentioned are between 118 and 129, and the VI's of the esters containing 2 mol of cyclohexylcarboxylic acid per ester molecule are only between 88 and 90.
- a further increase in the total carbon number of the acid content of these esters to about 34 has different effects on the lubrication parameters, depending on the type of monocarboxylic acids used.
- the use of only one medium-chain fatty acid (C s ) in addition to the cyclohexyl acid gives an oil with a pour point of -20 ° C and a VI of 127, while the use of a mixture of 1 mol of tetradecanoic acid with 1 mol of cyclohexyl carboxylic acid and 2 mol of hexanoic acid results in an ester oil. with a pour point of + 4 ° C and a VI of 129.
- ester oils with a high viscosity index and low volatility are obtained from readily available raw materials based on pentaerythritol esters of "isostearic acid", cyclohexylcarboxylic acid and other aliphatic, saturated C 6 -C 16 -monocarboxylic acids, if the total number of carbon atoms per molecule Pentaerythritol ester is between 47 and 51 and at least 22 equivalent% of the alcoholic hydroxyl groups present in pentaerythritol are esterified with "isostearic acid” and cyclohexylcarboxylic acid.
- Isostearic acid is a mixture of weakly methyl-branched C 18 fatty acids which contains, for example, the 16-methylheptadecanoic acid as described in the company font "Unem 5680" is described by Unilever-Emery. Ester oils from pentaerythritol and the “isostearic acid” as the sole acid component are solid substances at room temperature.
- At least 22 equivalent% of the 4 primary alcoholic hydroxyl groups present in the pentaerthritol molecule should be esterified with "isostearic acid” and likewise at least 22 equivalent% of hydroxyl groups with cyclohexylcarboxylic acid, but at most 80 equivalent% of the 4 hydroxyl groups with the "isostearic acid” / Cyclohexylcarboxylic acid mixture may be implemented.
- the molar ratio "isostearic acid” to cyclohexylcarboxylic acid in the finished ester may vary between 1.0: 1.0 and 1.0: 2.1.
- a third acid component of the pentaerythritol esters according to the invention are aliphatic saturated, preferably straight-chain monocarboxylic acids which contain 6-16 carbon atoms. It is preferred that all the hydroxyl groups present in the pentaerythritol be esterified as completely as possible, but the hydroxyl number of the finished ester oil may vary within a range of 0-8 mgKOH / g.
- Pentaerythritol can be used in both pure and technical quality.
- the “isostearic acid” is a mixture of weakly branched saturated monocarboxylic acids, such as the name “Unimac 5680" is commercially available.
- the cyclohexylcarboxylic acid is used in pure form or with a low content of benzoic acid for the preparation of the esters according to the invention.
- Examples of other suitable aliphatic saturated monocarboxylic acids are caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid and palmitic acid.
- the esterification reaction for the preparation of the esters according to the invention is carried out in bulk or with an azeotrope-forming solvent at temperatures of 50-260, preferably 140-220 ° C. under inert gas.
- inert gas nitrogen, carbon dioxide or noble gases can be used as the inert gas.
- Compounds such as organic sulfonic acids, sulfuric acid, phosphoric acid, their acidic salts such as hydrogen sulfates and dihydrogen phosphates, phosphonic acid esters or dialkyltin oxides can be used in catalytic amounts in the reaction. 0.8 to 1.3, preferably 1-1.2 equivalents of acid groups are used per equivalent of OH groups.
- Aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene or halogen-containing hydrocarbons such as carbon tetrachloride or chloroform are suitable as azeotropic solvents.
- the mixture is esterified either gradually, using the less volatile monocarboxylic acids first, then adding a small excess of the volatile monocarboxylic acids after reaching an acid number of ⁇ 5 mg KOH / g and bringing the reaction to an end, or by reacting pentaerythritol together with all the monocarboxylic acid components until the final acid number of the ester oil derived from the excess amount of monocarboxylic acids.
- Solvents, excess acid and catalyst are removed by suitable operations such as filtration, high vacuum distillation, stripping, thin-layer evaporation and treatment with alkali or methanol.
- esters according to the invention can be used as a base oil for the production of liquid or paste-like lubricants. They are also suitable for blending with other synthetic or mineral base lubricating oils.
- ester oils according to the invention are notable for high flash points and low evaporation losses with higher basic viscosities than for comparison esters, but also for very high viscosity indices, as the following examples show:
- Comparative Example 4 shows that the replacement of the isostearic acid with another aliphatic monocarboxylic acid with 18 carbon atoms leads to a significantly higher pour point and thus to significantly poorer flow properties of the oils.
- the oils according to the invention are less degraded with the elimination of liquid constituents than, for example, pentaerythritol tetra (2-hexyl) decanoate, a state of the art according to DT-OS 2 302 918 corresponding oil, as the following table shows:
- Table 2 shows the comparison of the properties of the two pentaerythritol esters A and B with the largest total carbon number from the Journal of Chemical and Engineering Data 7, 547 ff. (1962) and the ester oil according to the invention of the example.
- esters A and B known from the literature do not expect that the use of fatty acids with 10 or more carbon atoms, which is necessary to increase the total carbon number, results in esters with pour points of -10 ° C. and viscosity indices greater than 130.
- Replacing the pelargonic acid in ester B with a mixture of caproic acid and myristic acid (ester A) leads to an increase in the pour point to values above ° C.
- Esters of 10 carbon atoms more and a C 1s fatty acid, bound has a viscosity index value of almost 150 and a pour point around -10 ° C.
- Comparative Examples 2 and 3 show that similarly composed ester oils with less than 47 or more than 5 carbon atoms per molecule no longer result in the combination of a good pour point and a high viscosity index, like the oil according to the invention.
- the comparison oil 2 with an average of 45 carbon atoms / molecule has a low pour point, but its viscosity index of 109 is significantly lower than that of the comparison oil 3 and the oil according to the invention.
- Oil 3 which contains an average of 53 carbon atoms per molecule has only a VI of 129 (20 units lower than the oil according to the invention) and is also in the pour point between -10 and 0 ° C. and thus higher than in the oil according to the invention.
- the preparation is carried out analogously to Comparative Example 1, starting from 163.2 g of pentaerythritol, 307.2 g of cyclohexane carboxylic acid, 340.8 g of "isostearic acid” and 23 g of tri-n-butyl phosphate with a reaction time of 20 h in the first stage, addition of 336 g of lauric acid and a reaction time of 6 h in the second stage. After extraction with methanol and final distillation, the final acid number is 0.1 and the yield is 859 g.
- the preparation is carried out analogously to Example 1, starting from 108.8 g of pentaerythritol, 245.8 g of cyclohexane carboxylic acid, 159.0 g of "isostearic acid” and 10 g of tri-n-butyl phosphate with a reaction time of 10 h in the first stage, adding 176.0 g lauric acid and a reaction time of 6 h in the second stage. After extraction with methanol and final distillation, the final acid number is 0.3; the yield is 560 g.
- the preparation is carried out analogously to Example 1, starting from 136 g of pentaerythritol and 256 g of cyclo hexane carboxylic acid, 284 g stearic acid and 4.5 g dibutyltin oxide in the first step with a reaction time of 6 h, addition of 240 g lauric acid and a reaction time of 4 h in the second step.
- the final acid number after extraction with dilute sodium hydroxide solution is approximately 0.5, the yield 690 g.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2758780 | 1977-12-29 | ||
DE19772758780 DE2758780A1 (de) | 1977-12-29 | 1977-12-29 | Carbonsaeureester des pentaerythrits |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0003032A1 EP0003032A1 (fr) | 1979-07-25 |
EP0003032B1 true EP0003032B1 (fr) | 1980-09-17 |
Family
ID=6027672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78101731A Expired EP0003032B1 (fr) | 1977-12-29 | 1978-12-16 | Esters d'acides carboxyliques de pentaerythrite et leur application comme huile lubrifiante de base |
Country Status (4)
Country | Link |
---|---|
US (1) | US4212816A (fr) |
EP (1) | EP0003032B1 (fr) |
JP (1) | JPS5496667A (fr) |
DE (2) | DE2758780A1 (fr) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1132602A (fr) * | 1979-09-10 | 1982-09-28 | Pier P. Rossi | Procede d'obtention et emploi comme huiles lubrifiantes d'esters d'alcools polyvalents |
US4313890A (en) * | 1980-01-29 | 1982-02-02 | Union Carbide Corporation | Polyol ester functional fluids |
US4477383A (en) * | 1982-05-05 | 1984-10-16 | National Distillers And Chemical Corporation | Di- and tripentaerythritol esters of isostearic acid |
JPH0631365B2 (ja) * | 1985-12-27 | 1994-04-27 | 東燃株式会社 | トラクシヨン流体 |
JPH0774350B2 (ja) * | 1986-06-02 | 1995-08-09 | 東燃料株式会社 | 合成トラクシヨンフル−ド |
US5259978A (en) * | 1987-07-23 | 1993-11-09 | Toa Nenryo Kogyo, K.K. | Traction fluid composition comprising a cyclohexyl diester and branched poly-α-olefin |
JPS62177099A (ja) * | 1987-07-30 | 1987-08-03 | Toa Nenryo Kogyo Kk | トラクシヨン用フル−ド |
JPH01299891A (ja) * | 1988-05-26 | 1989-12-04 | Asahi Glass Co Ltd | チェーン用潤滑油組成物 |
US5080834A (en) * | 1990-10-18 | 1992-01-14 | Lce Partnership | Branched ether esters as viscosity index modifiers |
ATE184310T1 (de) * | 1992-06-03 | 1999-09-15 | Henkel Corp | Polyol/ester-gemisch als schmiermittel für wärmeträgerflüssigkeiten in kälteanlagen |
US6183662B1 (en) | 1992-06-03 | 2001-02-06 | Henkel Corporation | Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures |
ATE194641T1 (de) * | 1992-06-03 | 2000-07-15 | Henkel Corp | Polyolester als schmiermittel für hochtemperatur- kältekompressoren |
ATE195545T1 (de) * | 1992-06-03 | 2000-09-15 | Henkel Corp | Schmiermittel auf basis von polyolester für kälteübertragungsmittel |
US5976399A (en) | 1992-06-03 | 1999-11-02 | Henkel Corporation | Blended polyol ester lubricants for refrigerant heat transfer fluids |
JP2613526B2 (ja) * | 1992-07-04 | 1997-05-28 | 花王株式会社 | 冷凍機作動流体用組成物 |
US5318711A (en) * | 1993-01-21 | 1994-06-07 | Quaker Chemical Corporation | Method for lubricating metal-metal contact systems in metalworking operations with cyclohexyl esters |
WO1995032266A1 (fr) * | 1994-05-23 | 1995-11-30 | Henkel Corporation | Procede pour augmenter la resistivite electrique de lubrifiants bases sur des esters et destines en particulier a une utilisation avec des refrigerants bases sur des hydrocarbures fluores |
US20010019120A1 (en) | 1999-06-09 | 2001-09-06 | Nicolas E. Schnur | Method of improving performance of refrigerant systems |
US6884761B2 (en) * | 2001-12-18 | 2005-04-26 | Bp Corporation North America Inc. | High temperature stable lubricant mixed polyol ester composition containing an aromatic carboxylic acid and method for making the same |
US7166491B2 (en) * | 2003-06-11 | 2007-01-23 | Fry's Metals, Inc. | Thermoplastic fluxing underfill composition and method |
FR2917615B1 (fr) * | 2007-06-21 | 2009-10-02 | Oreal | Composition cosmetique comprenant deux polyesters. |
CN110036095B (zh) * | 2016-12-13 | 2022-01-04 | 花王株式会社 | 润滑油基础油和含有该润滑油基础油的润滑油组合物 |
JP2018095840A (ja) | 2016-12-13 | 2018-06-21 | 花王株式会社 | 潤滑油基油、および該潤滑油基油を含有する潤滑油組成物 |
JP7216563B2 (ja) | 2019-02-12 | 2023-02-01 | 花王株式会社 | グリース基油、および該グリース基油を含有するグリース組成物 |
CN111848403A (zh) * | 2019-04-26 | 2020-10-30 | 南京纽邦生物科技有限公司 | 一种季戊四醇四异硬脂酸酯的制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2991297A (en) * | 1958-07-02 | 1961-07-04 | Celanese Corp | Process for preparing synthetic lubricants |
FR95543E (fr) * | 1966-03-28 | 1971-01-22 | Nyco Sa | Composition a base d'esters synthétiques utilisable notamment comme fluide de transmission hydraulique. |
US3476685A (en) * | 1967-05-08 | 1969-11-04 | Texaco Inc | Synthetic lubricating composition |
US4053491A (en) * | 1973-01-22 | 1977-10-11 | Henkel Kommanditgesellschaft Auf Aktien | Branched-chain aliphatic ester oils |
FR2254633B1 (fr) * | 1973-12-12 | 1976-10-08 | Inst Francais Du Petrole |
-
1977
- 1977-12-29 DE DE19772758780 patent/DE2758780A1/de not_active Withdrawn
-
1978
- 1978-12-16 DE DE7878101731T patent/DE2860183D1/de not_active Expired
- 1978-12-16 EP EP78101731A patent/EP0003032B1/fr not_active Expired
- 1978-12-20 US US05/971,389 patent/US4212816A/en not_active Expired - Lifetime
- 1978-12-27 JP JP16026278A patent/JPS5496667A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
JPS5496667A (en) | 1979-07-31 |
US4212816A (en) | 1980-07-15 |
DE2860183D1 (en) | 1980-12-18 |
DE2758780A1 (de) | 1979-07-12 |
EP0003032A1 (fr) | 1979-07-25 |
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