EP0649457B1 - Base oils with a high viscosity index and improved low-temperature behaviour - Google Patents
Base oils with a high viscosity index and improved low-temperature behaviour Download PDFInfo
- Publication number
- EP0649457B1 EP0649457B1 EP93915753A EP93915753A EP0649457B1 EP 0649457 B1 EP0649457 B1 EP 0649457B1 EP 93915753 A EP93915753 A EP 93915753A EP 93915753 A EP93915753 A EP 93915753A EP 0649457 B1 EP0649457 B1 EP 0649457B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base oils
- aliphatic
- esters
- carbon atoms
- hydroxyl groups
- 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
- 239000002199 base oil Substances 0.000 title claims abstract description 51
- 150000002148 esters Chemical class 0.000 claims abstract description 53
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001279 adipic acids Chemical class 0.000 claims abstract 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000539 dimer Substances 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010725 compressor oil Substances 0.000 claims description 3
- 239000010720 hydraulic oil Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010705 motor oil Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 claims 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 7
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 6
- 229940100539 dibutyl adipate Drugs 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 230000000447 dimerizing effect Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Natural products OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007799 cork Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- AOHAPDDBNAPPIN-UHFFFAOYSA-N myristicinic acid Natural products COC1=CC(C(O)=O)=CC2=C1OCO2 AOHAPDDBNAPPIN-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 108010002493 Arachin Proteins 0.000 description 1
- LSPHULWDVZXLIL-UHFFFAOYSA-N Camphoric acid Natural products CC1(C)C(C(O)=O)CCC1(C)C(O)=O LSPHULWDVZXLIL-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 235000013830 Eruca Nutrition 0.000 description 1
- 241000801434 Eruca Species 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- PVNIQBQSYATKKL-UHFFFAOYSA-N Glycerol trihexadecanoate Natural products CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- LSPHULWDVZXLIL-QUBYGPBYSA-N camphoric acid Chemical compound CC1(C)[C@H](C(O)=O)CC[C@]1(C)C(O)=O LSPHULWDVZXLIL-QUBYGPBYSA-N 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
- WNPXRNJEBMRJGV-UHFFFAOYSA-N chembl1399590 Chemical compound COC1=CC=CC(C=2N=C3C=CC=CC3=C(N3C(CCCC3)C)N=2)=C1O WNPXRNJEBMRJGV-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 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
- 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
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
- C10M105/44—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
- C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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Definitions
- the present invention relates to base oils with a high viscosity index and improved low-temperature behavior, which contain complex esters and adipic acid esters of unbranched monofunctional alcohols, and a process for the preparation of such base oils and their use as hydraulic, compressor and motor oils.
- esters both as a base oil and as an additive in lubricants.
- the synthetic esters were mostly used as base oil when high demands were made on the viscosity-temperature behavior and a low pour point, as was the case with aircraft turbine oils.
- esters based on oleochemicals have become increasingly important, as they are not only powerful but also biodegradable.
- the esters on the basis of oleochemistry are divided into 5 groups: mono-, glycerol, dicarboxylic acid, polyol and complex esters.
- the dicarboxylic acid esters are derived primarily from adipic, trimethyladipinic, sebacic, azelaic, dodecanedioic and brassylic acid, the C6 ⁇ 12 dicarboxylic acid derivatives in particular being of increasing importance since they have a very good viscosity Have temperature behavior.
- the so-called viscosity index (VI) which is determined at 40 and 100 ° C according to DIN 51562 and calculated according to DIN ISO 2909, is usually given as the key figure of the viscosity-temperature ratio in the lubricating oil sector. High VI values indicate that slight viscosity fluctuations are observed at different temperatures.
- Most of the above dicarboxylic acid esters have high VI values.
- linear dicarboxylic acid esters of adipic acid with VI values of 200 and higher show an extraordinarily low temperature dependence of the viscosity.
- a disadvantage of the dicarboxylic acid esters of adipic acid mentioned is their low viscosity, which means that they are not suitable for all fields of application.
- Both the adipic acid esters and the complex esters have an acceptable cold behavior insofar as the pour point, that is to say the temperature which results when 3 ° C. is added to the temperature at which the sample is no longer flowable after cooling Values around -30 ° C.
- the pour point that is to say the temperature which results when 3 ° C. is added to the temperature at which the sample is no longer flowable after cooling Values around -30 ° C.
- the base oil has an even lower pour point.
- the object of the present invention was to provide base oils with improved low-temperature behavior (pour point), which moreover have higher viscosities than the known adipic acid esters. Furthermore, these base oils should have very good viscosity-temperature behavior and VI values above 200.
- base oils from certain complex esters and the dicarboxylic acid esters of adipic acid show better cold behavior with a high viscosity index.
- the base oils according to the invention are products which are liquid at room temperature (20 to 25 ° C.).
- the complex esters and adipic acid esters contained in the base oils according to the invention are so-called full esters for the purposes of the invention, which means that these esters should not have any free hydroxyl or carboxyl group per molecule. Rather, complex esters and adipic acid esters are sought which have no or only small hydroxyl or acid numbers, preferably in the range below 3, because of the esterification, which is never complete in practice.
- the adipic acid esters contained in the base oils according to the invention are known compounds which are formed by esterification of the adipic acid with unbranched aliphatic monofunctional alcohols.
- Adipic acid esters derived from saturated alcohols are preferred. Since the adipic acid esters should be as liquid as possible, those are particularly preferred which are derived from saturated alcohols having 1 to 4 carbon atoms, in particular from methanol, ethanol, propanol and / or butanol. From this group, dibutyl adipate is of outstanding importance, especially since it also has an excellent VI.
- the complex esters contained in the base oils according to the invention are also compounds known per se.
- these complex esters can also be easily prepared by esterification reactions of the dicarboxylic acids, polyols and monocarboxylic acids.
- aliphatic, cycloaliphatic or aromatic dicarboxylic acids are oxalic, malonic, amber, glutaric, adipic, pimeline, cork, azelaic, sebacic, undecanedicarbonic, eicosanedicarbonic, maleic, fumaric, citraconic, Mesaconic, itaconic, cyclopropane, cyclobutane, cyclopentadicarboxylic acid, camphoric acid, hexahydrophthalic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalic acid, diphenyl-o, o'-dicarboxylic acid and dimer fatty acids are suitable.
- Dimer fatty acids for the purposes of the invention are dicarboxylic acids which are prepared by dimerizing mono- or polyunsaturated monocarboxylic acids in the presence of catalysts.
- dimer fatty acids preference is given to those which have been prepared by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms and in particular those which have been prepared by dimerizing oleic acid.
- aliphatic dicarboxylic acids particularly those with 6 to 10 carbon atoms and in particular the saturated representatives thereof are preferred. From the group of aromatic dicarboxylic acids, phthalic acid is particularly suitable.
- their anhydrides can also be used to prepare the complex esters.
- dicarboxylic acids preference is given to aliphatic dicarboxylic acids having 6 to 10 carbon atoms, phthalic acid and / or dimer fatty acid as the basis for the complex esters, the dimer fatty acid having been prepared by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms .
- aliphatic polyols on which the complex esters are based are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Glycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, xylitol, mannitol and / or sorbitol.
- polyols are particularly preferred branched polyols which preferably have tertiary C atoms (that is to say those which do not bear a hydrogen atom) in the vicinity of the primary hydroxyl groups, such as trimethylolpropane, pentaerythritol, neopentyl glycol, dipentaerythritol and / or mixtures thereof.
- Examples of aliphatic monocarboxylic acids with 6 to 22 carbon atoms from which the complex esters are made are: caprylic, pelargon, capric, undecane, lauric, laurolein, tridecane, myristic, myristolein , Pentadecane, palmitin, palmitolein, heptadecane, stearin, petroselin, petroselaidin, oil, eladin, linole, linolaidin, linolen, nonadecane, arachin, arachidone, behen, eruca - and / or brassidic acid.
- the straight-chain representatives thereof are preferred from this group of saturated and / or unsaturated monocarboxylic acids.
- the complex esters contained in the base oils according to the invention are preferably constructed such that the static average of the 2 to 6 hydroxyl groups of the polyols is 25 to 75% with dicarboxylic acids and 75 to 25% with monocarboxylic acids.
- the% number of esterified hydroxyl groups it is formally assumed how many hydroxyl groups are present in the reaction mixture forming the complex ester and that 25 or 75% of this reaction mixture is esterified with dicarboxylic acids or monocarboxylic acids.
- the base oils according to the invention preferably contain the complex esters in amounts of 25 to 75% by weight and the adipic acid esters in amounts of 75 to 25% by weight, based on the base oil.
- the base oils according to the invention have a pour point which is significantly lower than the pour points of the individual complex esters or adipic acid esters. Because of the significantly lower pour point, the cold behavior of the base oils according to the invention is much better since the base oils are no longer flowable at a lower temperature. This opens up areas of application with these base oils that have so far remained closed to the individual complex esters or adipic acid esters. Furthermore, the base oils according to the invention have a significantly higher viscosity than the pure adipic acid esters, so that they are suitable for broader fields of application than the low-viscosity adipic acid esters.
- the base oils according to the invention have better viscosity-temperature behavior than the pure complex esters, so that the field of application also widens here.
- any desired viscosities of the base oil can be set. It is thus possible to adjust a low-viscosity base oil by adding higher amounts of the low-viscosity adipic acid ester, which also has an extremely high viscosity index.
- the base oils according to the invention can additionally contain mono-, glycerol and / or polyol esters or also mineral oils.
- the amount of these additional esters or mineral oils depends on the respective area of application.
- the base oils according to the invention can be additized in order to further optimize them for their application.
- Suitable additives are, for example, oxidation inhibitors, such as sulfur, phosphorus, phenol derivatives or amines, detergents such as naphthenates, stearates, sulfonates, phenolates, phosphates, phosphonates or methacrylate copolymers, extreme pressure additives such as sulfur and chlorine compounds, anti-foaming agents, demulsifiers, corrosion inhibitors or also friction coefficient reducer.
- the known viscosity index improvers such as polyalkylstyrenes, polyolefins, polymethacrylic acid esters, polyisobutenes and diene polymers can also be added to the base oils according to the invention, but this makes the base oils according to the invention more sensitive to shear. On the whole, the base oils according to the invention already show such good viscosity-temperature behavior that an addition of a viscosity index improver is not necessary. Another advantage of the base oils according to the invention is that they are no longer as sensitive to shear as mineral oils to which viscosity index improvers have to be added.
- the base oils according to the invention can be used in a wide range of applications. However, due to their quality profile, use as hydraulic, compressor and motor oils is particularly preferred.
- Table I the mixing ratios, V40 and the pour point of the base oils are summarized. The amounts of ester are given in parts by weight (T).
- Table I Base oils and characteristics Base oil Most complex DBA * V40 in mm / s Pour point in ° C VI I. 61 T Example A 1) 39 T. 46.58 -51 255 II 50 T Example A 1) 50 T 28.68 -51 243 III 25 T Example A 1) 75 T. 10.68 -51 219 IV 29 T Example A 2) 71 T. 19.51 -51 282 V 43 T Example A 3) 57 T.
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Abstract
Description
Gegenstand der vorliegenden Erfindung sind Grundöle mit hohem Viskositätsindex und verbessertem Kälteverhalten, die Komplexester und Adipinsäureester von unverzweigten monofunktionellen Alkoholen enthalten, sowie ein Verfahren zur Herstellung derartiger Grundöle und deren Verwendung als Hydraulik-, Kompressoren- und Motorenöle.The present invention relates to base oils with a high viscosity index and improved low-temperature behavior, which contain complex esters and adipic acid esters of unbranched monofunctional alcohols, and a process for the preparation of such base oils and their use as hydraulic, compressor and motor oils.
Es ist seit langem bekannt, synthetische Ester sowohl als Grundöl als auch als Additiv in Schmiermitteln zu verwenden. Im Vergleich zu den billigeren, aber umweltbedenklicheren Mineralölen wurden die synthetischen Ester meist dann als Grundöl verwendet, wenn hohe Anforderungen an das Viskositäts-Temperaturverhalten und ein niedriger Pourpoint verlangt wurde, wie bei Flugzeugturbinenölen. In jüngster Zeit gewinnen insbesondere Ester auf fettchemischer Basis immer größere Bedeutung, da sie nicht nur leistungsstark, sondern auch biologisch abbaubar sind. In der Regel werden die Ester auf fettchemischer Basis in 5 Gruppen eingeteilt: Mono-, Glycerin-, Dicarbonsäure-, Polyol- und Komplexester. Die Dicarbonsäureester leiten sich aus technologischen und wirtschaftlichen Gründen vor allem von der Adipin-, Trimethyladipin-, Sebacin-, Azelain-, Dodecandi- und Brassylsäure ab, wobei insbesondere die C₆₋₁₂-Dicarbonsäurederivate zunehmende Bedeutung besitzen, da sie ein sehr gutes Viskositäts-Temperaturverhalten haben. Als Kennzahl des Viskositäts-Temperaturverhältnis wird auf dem Schmierölsektor meist der sogenannte Viskositätsindex (VI) angegeben, der bei 40 und 100 °C gemäß DIN 51562 ermittelt und nach DIN ISO 2909 ausgerechnet wird. Hohe VI-Werte zeigen an, daß geringe Viskositätsschwankungen bei unterschiedlichen Temperaturen beobachtet werden. Die meisten der obengenannten Dicarbonsäureester haben hohe VI-Werte. So zeigen insbesondere lineare Dicarbonsäureester der Adipinsäure mit VI-Werten von 200 und höher eine außerordentlich geringe Temperaturabhängigkeit der Viskosität.It has long been known to use synthetic esters both as a base oil and as an additive in lubricants. Compared to the cheaper, but more environmentally friendly mineral oils, the synthetic esters were mostly used as base oil when high demands were made on the viscosity-temperature behavior and a low pour point, as was the case with aircraft turbine oils. Recently, esters based on oleochemicals have become increasingly important, as they are not only powerful but also biodegradable. As a rule, the esters on the basis of oleochemistry are divided into 5 groups: mono-, glycerol, dicarboxylic acid, polyol and complex esters. For technological and economic reasons, the dicarboxylic acid esters are derived primarily from adipic, trimethyladipinic, sebacic, azelaic, dodecanedioic and brassylic acid, the C₆₋₁₂ dicarboxylic acid derivatives in particular being of increasing importance since they have a very good viscosity Have temperature behavior. The so-called viscosity index (VI), which is determined at 40 and 100 ° C according to DIN 51562 and calculated according to DIN ISO 2909, is usually given as the key figure of the viscosity-temperature ratio in the lubricating oil sector. High VI values indicate that slight viscosity fluctuations are observed at different temperatures. Most of the above dicarboxylic acid esters have high VI values. In particular, linear dicarboxylic acid esters of adipic acid with VI values of 200 and higher show an extraordinarily low temperature dependence of the viscosity.
Nachteilig an den genannten Dicarbonsäureestern der Adipinsäure ist aber deren niedrige Viskosität, wodurch sie nicht für alle Anwendungsfelder geeignet sind.A disadvantage of the dicarboxylic acid esters of adipic acid mentioned is their low viscosity, which means that they are not suitable for all fields of application.
Höhere Viskositäten als Adipinsäureester zeigen Komplexester, die aus mehrfunktionellen Carbonsäuren und Polyolen und Monocarbonsäuren aufgebaut sind. Diese Komplexester zeigen aber leider nicht ein so gutes Viskositäts-Temperaturverhalten und damit niedere VI-Werte als die Dicarbonsäureester der Adipinsäure.Higher viscosities than adipic acid esters show complex esters which are composed of polyfunctional carboxylic acids and polyols and monocarboxylic acids. Unfortunately, these complex esters do not show such good viscosity-temperature behavior and thus lower VI values than the dicarboxylic acid esters of adipic acid.
Sowohl die Adipinsäureester als auch die Komplexester weisen zwar ein akzeptables Kälteverhalten insofern auf, als der Pourpoint, das heißt diejenige Temperatur, die sich beim Addieren von 3 °C zu der abgelesenen Temperatur ergibt, bei der die Probe nach Abkühlung nicht mehr fließfähig ist, bei Werten um -30 °C liegt. Für einige Anwendungsgebiete, ist es jedoch von Vorteil, wenn das Grundöl einen noch niedrigeren Pourpoint aufweist.Both the adipic acid esters and the complex esters have an acceptable cold behavior insofar as the pour point, that is to say the temperature which results when 3 ° C. is added to the temperature at which the sample is no longer flowable after cooling Values around -30 ° C. For some areas of application, however, it is advantageous if the base oil has an even lower pour point.
Aufgabe der vorliegenden Erfindung war es, Grundöle mit verbessertem Kälteverhalten (Pourpoint) bereitzustellen, die zudem höhere Viskositäten aufweisen als die bekannten Adipinsäureester. Des weiteren sollten diese Grundöle über ein sehr gutes Viskositäts-Temperaturverhalten verfügen und VI-Werte über 200 haben.The object of the present invention was to provide base oils with improved low-temperature behavior (pour point), which moreover have higher viscosities than the known adipic acid esters. Furthermore, these base oils should have very good viscosity-temperature behavior and VI values above 200.
Überraschenderweise zeigen Grundöle aus bestimmten Komplexestern und den Dicarbonsäureestern der Adipinsäure ein besseres Kälteverhalten bei gleichzeitig hohem Viskositätsindex.Surprisingly, base oils from certain complex esters and the dicarboxylic acid esters of adipic acid show better cold behavior with a high viscosity index.
Gegenstand der vorliegenden Erfindung sind Grundöle, die
- I. Komplexester aus
- a) aliphatischen, cycloaliphatischen und/oder aromatischen Dicarbonsäuren mit 2 bis 36 C-Atomen
- b) aliphatischen Polyolen mit 2 bis 6 Hydroxylgruppen
- c) aliphatischen Monocarbonsäuren mit 6 bis 22 C-Atomen und
- II. Adipinsäureester von unverzweigten aliphatischen monofunktionellen Alkoholen
- I. complex esters
- a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with 2 to 36 carbon atoms
- b) aliphatic polyols with 2 to 6 hydroxyl groups
- c) aliphatic monocarboxylic acids with 6 to 22 carbon atoms and
- II. Adipic acid esters of unbranched aliphatic monofunctional alcohols
Im Sinne der Erfindung handelt es sich bei den erfindungsgemäßen Grundölen um bei Raumtemperatur (20 bis 25 °C) flüssige Produkte. Die in den erfindungsgemäßen Grundölen enthaltenen Komplexester und Adipinsäureester stellen im Sinne der Erfindung sogenannte Vollester dar, dies bedeutet, daß diese Ester pro Molekül über keine freie Hydroxyl- oder auch Carboxylgruppe verfügen sollen. Vielmehr werden Komplexester und Adipinsäureester angestrebt, die keine bzw. aufgrund der in der Praxis nie vollständigen Veresterung nur kleine Hydroxyl- bzw. Säurezahlen, vorzugsweise im Bereich unter 3, aufweisen.For the purposes of the invention, the base oils according to the invention are products which are liquid at room temperature (20 to 25 ° C.). The complex esters and adipic acid esters contained in the base oils according to the invention are so-called full esters for the purposes of the invention, which means that these esters should not have any free hydroxyl or carboxyl group per molecule. Rather, complex esters and adipic acid esters are sought which have no or only small hydroxyl or acid numbers, preferably in the range below 3, because of the esterification, which is never complete in practice.
Die in den erfindungsgemäßen Grundölen enthaltenen Adipinsäureester sind an für sich bekannte Verbindungen, die durch Veresterung der Adipinsäure mit unverzweigten aliphatischen monofunktionellen Alkoholen entstehen. Bevorzugt werden Adipinsäureester, die sich von gesättigten Alkoholen ableiten. Da die Adipinsäureester möglichst flüssig sein sollten, werden solche ganz besonders bevorzugt, die sich von gesättigten Alkoholen mit 1 bis 4 C-Atomen, insbesondere von Methanol, Ethanol, Propanol und/oder Butanol ableiten. Aus dieser Gruppe kommt dem Dibutyladipat eine herausragende Bedeutung zu, zumal es zusätzlich über einen hervorragenden VI verfügt.The adipic acid esters contained in the base oils according to the invention are known compounds which are formed by esterification of the adipic acid with unbranched aliphatic monofunctional alcohols. Adipic acid esters derived from saturated alcohols are preferred. Since the adipic acid esters should be as liquid as possible, those are particularly preferred which are derived from saturated alcohols having 1 to 4 carbon atoms, in particular from methanol, ethanol, propanol and / or butanol. From this group, dibutyl adipate is of outstanding importance, especially since it also has an excellent VI.
Auch die Komplexester, die in den erfindungsgemäßen Grundölen enthalten sind, sind an für sich bekannte Verbindungen. So wird beispielsweise in der deutschen Patentschrift DE-C-19 07 768 die Verwendung derartiger Komplexester als Gleitmittel für thermoplastische Kunststoffe beschrieben. Diese Komplexester lassen sich ebenfalls leicht durch Veresterungsreaktionen der Dicarbonsäuren, Polyolen und Monocarbonsäuren herstellen. Als aliphatische, cycloaliphatische oder aromatische Dicarbonsäuren sind Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Kork-, Azelain-, Sebacin-, Undecandicarbon-, Eicosandicarbon-, Malein-, Fumar-, Citracon-, Mesacon-, Itacon-, Cyclopropan-, Cyclobutan-, Cyclopentadicarbonsäure, Camphersäure, Hexahydrophthalsäure, Phthalsäure, Terephthalsäure, Isophthalsäure, Naphthalsäure, Diphenyl-o,o'-Dicarbonsäure und Dimerfettsäuren geeignet. Dimerfettsäuren im Sinne der Erfindung sind Dicarbonsäuren, die durch Dimerisierung von einfach oder mehrfach ungesättigten Monocarbonsäuren in Gegenwart von Katalysatoren hergestellt werden. Von den Dimerfettsäuren werden solche bevorzugt, die durch Dimerisierung von einfach ungesättigten Monocarbonsäuren mit 12 bis 22 C-Atomen hergestellt worden sind und insbesonders solche, die durch Dimerisierung von Ölsäure hergestellt worden sind. Von den aliphatischen Dicarbonsäuren werden besonders solche mit 6 bis 10 C-Atomen und insbesondere die gesättigten Vertreter hiervon bevorzugt. Aus der Gruppe der aromatischen Dicarbonsäuren eignet sich insbesondere Phthalsäure. Anstelle der Dicarbonsäuren können auch deren Anhydride zur Herstellung der Komplexester eingesetzt werden. Insgesamt gesehen werden aus der Gruppe der Dicarbonsäuren bevorzugt aliphatische Dicarbonsäuren mit 6 bis 10 C-Atomen, Phthalsäure und/oder Dimerfettsäure als Basis für die Komplexester bevorzugt, wobei die Dimerfettsäure durch Dimerisierung von einfach ungesättigten Monocarbonsäuren mit 12 bis 22 C-Atomen hergestellt worden sind.The complex esters contained in the base oils according to the invention are also compounds known per se. For example, in the German patent DE-C-19 07 768 the use of such More complex described as a lubricant for thermoplastics. These complex esters can also be easily prepared by esterification reactions of the dicarboxylic acids, polyols and monocarboxylic acids. As aliphatic, cycloaliphatic or aromatic dicarboxylic acids are oxalic, malonic, amber, glutaric, adipic, pimeline, cork, azelaic, sebacic, undecanedicarbonic, eicosanedicarbonic, maleic, fumaric, citraconic, Mesaconic, itaconic, cyclopropane, cyclobutane, cyclopentadicarboxylic acid, camphoric acid, hexahydrophthalic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalic acid, diphenyl-o, o'-dicarboxylic acid and dimer fatty acids are suitable. Dimer fatty acids for the purposes of the invention are dicarboxylic acids which are prepared by dimerizing mono- or polyunsaturated monocarboxylic acids in the presence of catalysts. Of the dimer fatty acids, preference is given to those which have been prepared by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms and in particular those which have been prepared by dimerizing oleic acid. Of the aliphatic dicarboxylic acids, particularly those with 6 to 10 carbon atoms and in particular the saturated representatives thereof are preferred. From the group of aromatic dicarboxylic acids, phthalic acid is particularly suitable. Instead of the dicarboxylic acids, their anhydrides can also be used to prepare the complex esters. Overall, from the group of dicarboxylic acids, preference is given to aliphatic dicarboxylic acids having 6 to 10 carbon atoms, phthalic acid and / or dimer fatty acid as the basis for the complex esters, the dimer fatty acid having been prepared by dimerizing monounsaturated monocarboxylic acids having 12 to 22 carbon atoms .
Als aliphatische Polyole, die den Komplexestern zugrunde liegen, sind beispielsweise Ethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, 1,4-Butandiol, 2,3-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, Glycerin, Trimethylolpropan, Erythrit, Pentaerythrit, Dipentaerythrit, Xylit, Mannit und/oder Sorbit zu nennen. Besonders bevorzugt von diesen Polyolen sind verzweigte Polyole, die vorzugsweise in Nachbarstellung zu den primären Hydroxylgruppen tertiäre C-Atome (das heißt solche, die kein Wasserstoffatom tragen) aufweisen, wie Trimethylolpropan, Pentaerythrit, Neopentylglykol, Dipentaerythrit und/oder Mischungen hiervon.Examples of aliphatic polyols on which the complex esters are based are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Glycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, xylitol, mannitol and / or sorbitol. Of these polyols are particularly preferred branched polyols which preferably have tertiary C atoms (that is to say those which do not bear a hydrogen atom) in the vicinity of the primary hydroxyl groups, such as trimethylolpropane, pentaerythritol, neopentyl glycol, dipentaerythritol and / or mixtures thereof.
Als Beispiele für aliphatische Monocarbonsäuren mit 6 bis 22 C-Atomen, aus denen die Komplexester aufgebaut sind, sind zu nennen: Capryl-, Pelargon-, Caprin-, Undecan-, Laurin-, Laurolein-, Tridecan-, Myristin-, Myristolein-, Pentadecan-, Palmitin-, Palmitolein-, Heptadecan-, Stearin-, Petroselin-, Petroselaidin-, Öl-, Eladin-, Linol-, Linolaidin-, Linolen-, Nonadecan-, Arachin-, Arachidon-, Behen-, Eruca- und/oder Brassidinsäure. Bevorzugt aus dieser Gruppe der gesättigten und/oder ungesättigten Monocarbonsäuren werden die geradkettigen Vertreter hiervon.Examples of aliphatic monocarboxylic acids with 6 to 22 carbon atoms from which the complex esters are made are: caprylic, pelargon, capric, undecane, lauric, laurolein, tridecane, myristic, myristolein , Pentadecane, palmitin, palmitolein, heptadecane, stearin, petroselin, petroselaidin, oil, eladin, linole, linolaidin, linolen, nonadecane, arachin, arachidone, behen, eruca - and / or brassidic acid. The straight-chain representatives thereof are preferred from this group of saturated and / or unsaturated monocarboxylic acids.
Die in den erfindungsgemäßen Grundölen enthaltenen Komplexestern sind vorzugsweise so aufgebaut, daß die 2 bis 6 Hydroxylgruppen der Polyole im statischen Mittel zu 25 bis 75 % mit Dicarbonsäuren und zu 75 bis 25 % mit Monocarbonsäuren verestert sind. Bei Berechnung der %-Zahl an veresterten Hydroxylgruppen geht man ganz formal davon aus, wieviel Hydroxylgruppen in dem Komplexester bildenden Reaktionsansatz vorhanden sind und das von diesem Reaktionsansatz 25 bzw. 75 % mit Dicarbonsäuren bzw. Monocarbonsäuren verestert sind. Bei den dabei entstehenden Komplexestern ist es daher im statistischen Mittel völlig unerheblich, ob die Dicarbonsäure 2 Hydroxylgruppen eines Polyols oder verbrückend 2 Hydroxylgruppen von zwei Polyolen verestert.The complex esters contained in the base oils according to the invention are preferably constructed such that the static average of the 2 to 6 hydroxyl groups of the polyols is 25 to 75% with dicarboxylic acids and 75 to 25% with monocarboxylic acids. When calculating the% number of esterified hydroxyl groups, it is formally assumed how many hydroxyl groups are present in the reaction mixture forming the complex ester and that 25 or 75% of this reaction mixture is esterified with dicarboxylic acids or monocarboxylic acids. In the complex esters formed in the process, it is therefore completely irrelevant on a statistical average whether the dicarboxylic acid esterifies 2 hydroxyl groups of one polyol or bridging 2 hydroxyl groups of two polyols.
Die erfindungsgemäßen Grundöle enthalten bevorzugt die Komplexester in Mengen von 25 bis 75 Gew.-% und die Adipinsäureester in Mengen von 75 bis 25 Gew.-% - bezogen auf Grundöl.The base oils according to the invention preferably contain the complex esters in amounts of 25 to 75% by weight and the adipic acid esters in amounts of 75 to 25% by weight, based on the base oil.
Ganz besonders bevorzugt werden Grundöle, die in Mengen von 25 bis 75 Gew.-% Dibutyladipat und in Mengen von 25 bis 75 Gew.-% Komplexester aus
- a) Dimerfettsäuren, Adipin-, Pimelin-, Kork-, Azelain-, Sebacin- und/oder Phthalsäure und
- b) Neopentylglykol, Trimethylolpropan, Pentaerythrit, Dipentaerythrit und/oder Mischungen hiervon und
- c) Capryl-, Caprin-, Laurin-, Myristin-, Palmitin-, Stearin- und/oder Ölsäure
- a) Dimer fatty acids, adipic, pimeline, cork, azelaic, sebacic and / or phthalic acid and
- b) neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and / or mixtures thereof and
- c) caprylic, capric, lauric, myristic, palmitic, stearic and / or oleic acid
Die erfindungsgemäßen Grundöle weisen einen Pourpoint auf, der deutlich niedriger liegt als die Pourpoints der einzelnen Komplexester bzw. Adipinsäureester. Aufgrund des deutlich niedrigeren Pourpoints ist also das Kälteverhalten der erfindungsgemäßen Grundöle sehr viel besser, da erst bei einer niedrigeren Temperatur die Grundöle nicht mehr fließfähig sind. Damit eröffnet sich mit diesen Grundölen Anwendungsgebiete, die den einzelnen Komplexestern bzw. Adipinsäureestern bislang verschlossen blieben. Des weiteren zeigen die erfindungsgemäßen Grundöle eine deutlich höhere Viskosität als die reinen Adipinsäureester, so daß sie für breitere Anwendungsfelder geeignet sind als die niedrigviskosen Adipinsäureester. Außerdem weisen die erfindungsgemäßen Grundöle ein bessers Viskositäts-Temperaturverhalten auf als die reinen Komplexester, so daß auch hier das Anwendungsfeld breiter wird. Als besonders günstig erweist sich bei den erfindungsgemäßen Grundölen auch die Tatsache, daß die Komplexester und die Adipinsäureester in weiten Mengenbereichen miteinander vermischt werden können, und trotzdem stets das verbesserte Kälteverhalten (Pourpoint) auftritt. Damit können unter Ausnutzung der verschiedenen Viskositäten der Komplexester und das Adipinsäureester beliebige Viskositäten des Grundöls eingestellt werden. So ist es möglich, durch höhere Zugabemengen des niederviskosen Adipinsäureesters insgesamt ein niedrigviskoseres Grundöl einzustellen, das zudem einen extrem hohen Viskositätsindex besitzt.The base oils according to the invention have a pour point which is significantly lower than the pour points of the individual complex esters or adipic acid esters. Because of the significantly lower pour point, the cold behavior of the base oils according to the invention is much better since the base oils are no longer flowable at a lower temperature. This opens up areas of application with these base oils that have so far remained closed to the individual complex esters or adipic acid esters. Furthermore, the base oils according to the invention have a significantly higher viscosity than the pure adipic acid esters, so that they are suitable for broader fields of application than the low-viscosity adipic acid esters. In addition, the base oils according to the invention have better viscosity-temperature behavior than the pure complex esters, so that the field of application also widens here. The fact that the complex esters and the adipic acid esters can be mixed with one another in wide ranges of amounts and the improved low-temperature behavior (pour point) always proves to be particularly favorable in the base oils according to the invention. Using the different viscosities of the complex esters and the adipic acid ester, any desired viscosities of the base oil can be set. It is thus possible to adjust a low-viscosity base oil by adding higher amounts of the low-viscosity adipic acid ester, which also has an extremely high viscosity index.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Grundölen mit hohem Viskositätsindex und verbessertem Kälteverhalten, dadurch gekennzeichnet, daß Komplexester aus
- a) aliphatischen, cycloaliphatischen und/oder aromatischen Dicarbonsäuren mit 2 bis 36 C-Atomen
- b) aliphatischen Polyolen mit 2 bis 6 Hydroxylgruppen
- c) aliphatischen Monocarbonsäuren mit 6 bis 22 C-Atomen mit Adipinsäureester von unverzweigten aliphatischen monofunktionellen
- a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with 2 to 36 carbon atoms
- b) aliphatic polyols with 2 to 6 hydroxyl groups
- c) aliphatic monocarboxylic acids with 6 to 22 carbon atoms with adipic acid esters of unbranched aliphatic monofunctional
Falls gewünscht können die erfindungsgemäßen Grundöle zusätzlich Mono-, Glycerin- und/oder Polyolester enthalten oder aber auch Mineralöle. Die Menge an diesen zusätzlichen Estern bzw. Mineralölen richtet sich nach dem jeweiligen Anwendungsgebiet. Des weiteren können die erfindungsgemäßen Grundöle additiviert werden, um sie für ihre Anwendung weiter zu optimieren. Geeignete Additive sind beispielsweise Oxidationsinhibitoren, wie Schwefel-, Phosphor-, Phenolderivate oder auch Amine, Detergenzien wie Naphthenate, Stearate, Sulfonate, Phenolate, Phosphate, Phosphonate oder Methacrylatcopolymere, Extrem-Pressure-Additive wie Schwefel- und Chlorverbindungen, Schaumverhüttungsmittel, Demulgatoren, Korrosionsinhibitoren oder auch Reibwertverminderer. Wenn man möchte, kann man den erfindungsgemäßen Grundölen auch die bekannten Viskositäts-Indexverbesserer wie Polyalkylstyrole, Polyolefine, Polymethacrylsäureester, Polyisobutene und Dienpolymere zugeben, aber dadurch werden die erfindungsgemäßen Grundöle empfindlicher gegen Scherung. Im großen und ganzen zeigen die erfindungsgemäßen Grundöle schon ein so gutes Viskositäts-Temperaturverhalten, so daß ein Zusatz von Viskositätsindexverbesserer nicht notwendig ist. So ist auch ein weiterer Vorteil der erfindungsgemäßen Grundöle darin zu sehen, daß sie nicht mehr so empfindlich gegen Scherung sind wie Mineralöle, denen Viskositätsindexverbesserer zugesetzt werden müssen.If desired, the base oils according to the invention can additionally contain mono-, glycerol and / or polyol esters or also mineral oils. The amount of these additional esters or mineral oils depends on the respective area of application. Furthermore, the base oils according to the invention can be additized in order to further optimize them for their application. Suitable additives are, for example, oxidation inhibitors, such as sulfur, phosphorus, phenol derivatives or amines, detergents such as naphthenates, stearates, sulfonates, phenolates, phosphates, phosphonates or methacrylate copolymers, extreme pressure additives such as sulfur and chlorine compounds, anti-foaming agents, demulsifiers, corrosion inhibitors or also friction coefficient reducer. If desired, the known viscosity index improvers such as polyalkylstyrenes, polyolefins, polymethacrylic acid esters, polyisobutenes and diene polymers can also be added to the base oils according to the invention, but this makes the base oils according to the invention more sensitive to shear. On the whole, the base oils according to the invention already show such good viscosity-temperature behavior that an addition of a viscosity index improver is not necessary. Another advantage of the base oils according to the invention is that they are no longer as sensitive to shear as mineral oils to which viscosity index improvers have to be added.
Die erfindungsgemäßen Grundöle können in weiten Einsatzgebieten eingesetzt werden. Besonders bevorzugt ist jedoch aufgrund ihres Qualitätsprofils die Verwendung als Hydraulik-, Kompressoren- und Motorenöle.The base oils according to the invention can be used in a wide range of applications. However, due to their quality profile, use as hydraulic, compressor and motor oils is particularly preferred.
1) Komplexester aus Trimethylolpropan, Ölsäure, Dimerfettsäure 171,84 g Trimethylolpropan, entsprechend 1,42 mol, 685,2 g technische Ölsäure (Zusammensetzung in Gew.-%: C₁₆' 5; C₁₇ 1; C₁₈ 2; C₁₈' 67; C₁₈" 12; C₁₈"' 1; >C₁₈ 2;mit einer Säurezahl SZ gemäß DIN 53402 von 198), entsprechend 2,4 mol, und 327,77 g C₁₈-Dimerfettsäure mit einer SZ von 193, entsprechend 1,1 Mol, wurden in Anwesenheit von 0,33 g Zinnoxalat miteinander bei steigender Temperatur bis 240 °C verestert. Die Veresterung wurde beendet als die Säurezahl des erhaltenen Komplexesters unter 1 war. Der Komplexester wrude mit Bleicherde bei 90 °C gebleicht und anschließend abfiltriert.
- Kenndaten:
- Verseifungszahl VZ (gemäß DIN 53401) 185 Jodzahl JZ (gemäß DGF-C-V 11b) 85 VI (gemäß DIN 51562 und berechnet nach DIN ISO 2909) = 186 Pourpoint (gemäß DIN ISO 3016) -31°C.
- Key data:
- Saponification number VZ (according to DIN 53401) 185 Iodine number JZ (according to DGF-CV 11b) 85 VI (according to DIN 51562 and calculated according to DIN ISO 2909) = 186 pour point (according to DIN ISO 3016) -31 ° C.
2) Komplexester aus Trimethylolpropan, Ölsäure und Dimerfettsäure Analog Beispiel 1 wurden 159,05 g Trimethylolpropan, entsprechend 1,325 mol, 570 g technische Ölsäure der Säurezahl 198, entsprechend 2 mol, und 411,0 g C₁₈-Dimerfettsäure der Säurezahl 183, entsprechend 1,3 mol umgesetzt und aufbereitet. Man erhielt einen Komplexester mit folgenden Kenndaten:
VZ = 180; JZ = 85; VI = 200; Pourpoint -32°C.2) Complex esters of trimethylolpropane, oleic acid and dimer fatty acid Analogously to Example 1, 159.05 g of trimethylolpropane, corresponding to 1.325 mol, 570 g technical oleic acid having an acid number of 198, corresponding to 2 mol, and 411.0 g of C₁₈ dimer fatty acid having an acid number of 183, corresponding to 1, 3 mol implemented and processed. A complex ester was obtained with the following characteristics:
VZ = 180; JZ = 85; VI = 200; Pour point -32 ° C.
320,25 g Dipentaerythrit, entsprechend 1,26 mol, 172,5 g Isononansäure, entspreched 1,1 mol, 646,5 g C8/10 Fettsäure (Zusammensetzung in Gew.-%: 69-75 C₈; 23-27 C₁₀; Rest C₆ und C₁₂; Säurezahl 368), entsprechend 4,2 mol, und 121,75 g Phthalsäureanhydrid, entsprechend 0,8 mol, wurden analog Beispiel 1 hergestellt und aufbereitet. Man erhielt einen Komplexester mit folgenden Kenndaten: VZ = 360; JZ < 1, VI = 100; Pourpoint -15°C.320.25 g dipentaerythritol, corresponding to 1.26 mol, 172.5 g isononanoic acid, corresponding to 1.1 mol, 646.5 g C 8/10 fatty acid (composition in% by weight: 69-75 C₈; 23-27 C₁₀ ; Balance C₆ and C₁₂; acid number 368), corresponding to 4.2 mol, and 121.75 g of phthalic anhydride, corresponding to 0.8 mol, were prepared and prepared analogously to Example 1. A complex ester was obtained with the following characteristics: VZ = 360; JZ <1, VI = 100; Pour point -15 ° C.
Die Komplexester A 1) bis 3) wurden mit unterschiedlichen Mengen Dibutyladipat mit den Kenndaten: VI = > 250; Pourpoint = -31°C vermischt. In Tabelle I sind die Mischungsverhältnisse, V₄₀ und der Pourpoint der Grundöle zusammengefaßt. Die Mengen an Ester sind in Gewichtsteilen (T) angegeben.
Aus Tabelle I ist ersichtlich, daß Grundöle mit dem niederviskosen Dibutyladipat und den hochviskosen Komplexestern zum einen eine höhere Viskosität haben als reines Dibutyladipat und zum anderen sehr viel niedere Pourpoints aufweisen als die reinen Ausgangsstoffe.From Table I it can be seen that base oils with the low-viscosity dibutyl adipate and the high-viscosity complex esters on the one hand have a higher viscosity than pure dibutyl adipate and on the other hand have much lower pour points than the pure starting materials.
Claims (9)
- Base oils containingI. complex esters ofa) aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids containing 2 to 36 carbon atoms,b) aliphatic polyols containing 2 to 6 hydroxyl groups,c) aliphatic monocarboxylic acids containing 6 to 22 carbon atoms andII. adipic acid esters of unbranched aliphatic monohydric alcohols.
- Base oils as claimed in claim 1, characterized in that they contain adipic acid esters of saturated alcohols preferably containing 1 to 4 carbon atoms.
- Base oils as claimed in claim 1, characterized in that they contain complex esters in which 25 to 75% of the hydroxyl groups of the polyols are esterified with the dicarboxylic acids and 75 to 25% of the hydroxyl groups of the polyols are esterified with the monocarboxylic acids.
- Base oils as claimed in claim 1, characterized in that they contain complex esters of aliphatic dicarboxylic acids containing 6 to 10 carbon atoms, phthalic acid and/or dimer fatty acid, the dimer fatty acid having been obtained by dimerization of monounsaturated C₁₂₋₂₂ monocarboxylic acids.
- Base oils as claimed in claim 1, characterized in that they contain complex esters of branched polyols preferably containing tertiary carbon atoms adjacent the primary hydroxyl groups, such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and/or mixtures thereof.
- Base oils as claimed in claim 1, characterized in that they contain complex esters of linear monocarboxylic acids.
- Base oils as claimed in claim 1, characterized in that they contain the complex esters in quantities of 25 to 75% by weight and the adipic acid esters in quantities of 75 to 25% by weight, based on base oil.
- A process for the production of base oils with a high viscosity index and improved low-temperature behavior, characterized in that complex esters ofa) aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids containing 2 to 36 carbon atoms,b) aliphatic polyols containing 2 to 6 hydroxyl groups,c) aliphatic monocarboxylic acids containing 6 to 22 carbon atomsare mixed with adipic acid esters of unbranched, aliphatic monohydric alcohols.
- The use of the base oils claimed in claim 1 as hydraulic, compressor and motor oils.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4222341A DE4222341A1 (en) | 1992-07-08 | 1992-07-08 | Base oils with a high viscosity index and improved cold behavior |
| DE4222341 | 1992-07-08 | ||
| PCT/EP1993/001686 WO1994001516A1 (en) | 1992-07-08 | 1993-06-30 | Base oils with a high viscosity index and improved low-temperature behaviour |
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| Publication Number | Publication Date |
|---|---|
| EP0649457A1 EP0649457A1 (en) | 1995-04-26 |
| EP0649457B1 true EP0649457B1 (en) | 1996-05-29 |
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| EP93915753A Expired - Lifetime EP0649457B1 (en) | 1992-07-08 | 1993-06-30 | Base oils with a high viscosity index and improved low-temperature behaviour |
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|---|---|
| US (1) | US5503762A (en) |
| EP (1) | EP0649457B1 (en) |
| JP (1) | JPH07508783A (en) |
| AT (1) | ATE138681T1 (en) |
| DE (2) | DE4222341A1 (en) |
| ES (1) | ES2087751T3 (en) |
| WO (1) | WO1994001516A1 (en) |
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| EP0727454A3 (en) * | 1995-02-10 | 1998-12-09 | Nippon Zeon Co., Ltd. | Oil-soluble polyester, additive for lubricating oil, and lubricating oil composition |
| CN1069918C (en) * | 1995-08-22 | 2001-08-22 | 亨凯尔公司 | Smokeless two-cycle engine lubricants |
| CA2250964C (en) * | 1996-04-16 | 2004-09-14 | Thomas Friedrich Bunemann | Hydraulic fluids |
| US5942475A (en) * | 1996-09-06 | 1999-08-24 | Exxon Chemical Patents Inc. | Engine oil lubricants formed from complex alcohol esters |
| US5922658A (en) * | 1996-09-06 | 1999-07-13 | Exxon Chemical Patents Inc. | Two-cycle engine oil formed from a blend of a complex alcohol ester and other basestocks |
| DE69816843T2 (en) * | 1997-10-01 | 2004-04-15 | Unichema Chemie B.V. | COMPLEXASTER, THESE COMPOSITIONS AND THEIR USE |
| US8183190B2 (en) * | 2003-08-20 | 2012-05-22 | Cognis Ip Management Gmbh | Complex polyol esters with improved performance |
| GB0410649D0 (en) * | 2004-05-13 | 2004-06-16 | Ici Plc | Antiwear automotive formulations |
| WO2006086752A1 (en) * | 2005-02-10 | 2006-08-17 | Inolex Investment Corporation | High temperature lubricant compositions and methods of making the same |
| DE102006027602A1 (en) * | 2006-06-13 | 2007-12-20 | Cognis Ip Management Gmbh | Lubricant compositions containing complex esters |
| GB0822256D0 (en) * | 2008-12-05 | 2009-01-14 | Croda Int Plc | Gear oil additive |
| BRPI0900280A2 (en) * | 2009-02-17 | 2010-10-26 | Promax Produtos Maximos S A | ecological, biodegradable and antifreeze lubricant fluid composition for hydraulic systems |
| US20100216678A1 (en) * | 2009-02-24 | 2010-08-26 | Abhimanyu Onkar Patil | Lubricant compositions containing glycerol tri-esters |
| JP5489838B2 (en) * | 2010-04-22 | 2014-05-14 | コスモ石油ルブリカンツ株式会社 | Industrial hydraulic oil composition |
| CN105452327B (en) * | 2013-07-31 | 2017-06-06 | 富士胶片株式会社 | The manufacture method of complex polyester composition, lubricant compositions, lubricant and complex polyester composition |
| EP3048093B1 (en) | 2013-09-20 | 2019-02-20 | Moresco Corporation | Ether-containing monoester compound and use thereof |
| US10208269B2 (en) | 2013-12-23 | 2019-02-19 | Exxonmobil Research And Engineering Company | Low viscosity ester lubricant and method for using |
| JP6748519B2 (en) * | 2015-09-15 | 2020-09-02 | 三洋化成工業株式会社 | Viscosity index improver composition and lubricating oil composition |
| EP3255128B1 (en) | 2016-06-08 | 2021-12-01 | Peter Greven GmbH & Co. KG | Complex esters and their use |
| US10336958B2 (en) | 2016-08-30 | 2019-07-02 | Resinate Materials Group, Inc. | Sustainable base oils for lubricants |
| ES2989124T3 (en) * | 2019-07-16 | 2024-11-25 | Oleon N V | Low pour point dimeric fatty acid derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2499983A (en) * | 1948-12-16 | 1950-03-07 | Rohm & Haas | Polyester lubricants |
| US2588194A (en) * | 1950-12-22 | 1952-03-04 | Standard Oil Dev Co | Synthetic lubricant |
| US3016353A (en) * | 1954-12-15 | 1962-01-09 | Exxon Research Engineering Co | Ester type synthetic lubricants |
| NL100929C (en) * | 1955-03-04 | |||
| US2944973A (en) * | 1955-11-14 | 1960-07-12 | Union Carbide Corp | Di-ester fluids with improved water tolerance |
| US3000917A (en) * | 1957-03-15 | 1961-09-19 | Drew & Co Inc E F | Linear mixed ester lubricants |
| US3048608A (en) * | 1959-03-18 | 1962-08-07 | Heyden Newport Chemical Corp | Neopentyl glycol esters |
| US3047504A (en) * | 1959-12-31 | 1962-07-31 | Exxon Research Engineering Co | Process for treating complex esters to improve viscosity stability |
| US3223636A (en) * | 1961-05-23 | 1965-12-14 | Exxon Research Engineering Co | Lead corrosion inhibitor |
| DE1594423A1 (en) * | 1964-02-11 | 1969-10-02 | Exxon Research Engineering Co | Lubricating oil |
| US3778454A (en) * | 1970-02-18 | 1973-12-11 | Ethyl Corp | Complex ester |
| SU464127A3 (en) * | 1972-03-31 | 1975-03-15 | Стауффер Кемикал Компани (Фирма) | Lubricant for gas turbine engines |
| DE2262266C2 (en) * | 1972-12-20 | 1982-04-01 | Neynaber Chemie Gmbh, 2854 Loxstedt | Use of an ester mixture as a lubricant for the shaping processing of thermoplastic materials |
| GB1460665A (en) * | 1974-02-11 | 1977-01-06 | Ciba Geigy Ag | Transmission device |
| FR2307867A1 (en) * | 1975-04-16 | 1976-11-12 | Inst Francais Du Petrole | NEW COMPOSITIONS OF COMPLEX ESTERS AND THEIR USE AS LUBRICANT BASE CONSTITUENTS |
| DE2551173C2 (en) * | 1975-11-14 | 1985-09-12 | Henkel KGaA, 4000 Düsseldorf | Neutral complex esters |
| US4113642A (en) * | 1976-11-11 | 1978-09-12 | Henkel Kommanditgesellschaft Auf Aktien | High viscosity neutral polyester lubricants |
| DE3635490A1 (en) * | 1986-10-18 | 1988-04-21 | Basf Ag | USE OF POLYCARBONIC ACID ESTERS IN FULL OR PART SYNTHETIC LUBRICANTS AND LUBRICANTS CONTAINING THESE ESTERS |
| JP2801703B2 (en) * | 1989-09-01 | 1998-09-21 | 花王株式会社 | Refrigerating machine oil |
| DE629687T1 (en) * | 1990-01-31 | 1995-12-14 | Tonen Corp | Esters as lubricants for haloalkane freezers. |
-
1992
- 1992-07-08 DE DE4222341A patent/DE4222341A1/en not_active Withdrawn
-
1993
- 1993-06-30 EP EP93915753A patent/EP0649457B1/en not_active Expired - Lifetime
- 1993-06-30 AT AT93915753T patent/ATE138681T1/en not_active IP Right Cessation
- 1993-06-30 ES ES93915753T patent/ES2087751T3/en not_active Expired - Lifetime
- 1993-06-30 US US08/367,197 patent/US5503762A/en not_active Expired - Fee Related
- 1993-06-30 JP JP6502904A patent/JPH07508783A/en active Pending
- 1993-06-30 DE DE59302760T patent/DE59302760D1/en not_active Expired - Fee Related
- 1993-06-30 WO PCT/EP1993/001686 patent/WO1994001516A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| EP0649457A1 (en) | 1995-04-26 |
| JPH07508783A (en) | 1995-09-28 |
| DE59302760D1 (en) | 1996-07-04 |
| DE4222341A1 (en) | 1994-01-13 |
| WO1994001516A1 (en) | 1994-01-20 |
| ATE138681T1 (en) | 1996-06-15 |
| ES2087751T3 (en) | 1996-07-16 |
| US5503762A (en) | 1996-04-02 |
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