CN102099326B - 9,10,12-三酰氧基十八烷酸烷基酯和富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物及其制备方法 - Google Patents
9,10,12-三酰氧基十八烷酸烷基酯和富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物及其制备方法 Download PDFInfo
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- CN102099326B CN102099326B CN200980127702.3A CN200980127702A CN102099326B CN 102099326 B CN102099326 B CN 102099326B CN 200980127702 A CN200980127702 A CN 200980127702A CN 102099326 B CN102099326 B CN 102099326B
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- Prior art keywords
- acid alkyl
- octadecanoic acid
- rich
- octadecanoic
- trihydroxy
- 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.)
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 42
- 239000000194 fatty acid Substances 0.000 title claims abstract description 42
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 235000021355 Stearic acid Nutrition 0.000 title claims abstract description 29
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 21
- 239000012530 fluid Substances 0.000 claims abstract description 27
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 20
- DJKUVMZEGIWUTP-UHFFFAOYSA-N 9,10,12-trihydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CC(O)C(O)CCCCCCCC(O)=O DJKUVMZEGIWUTP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000314 lubricant Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 16
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- -1 9,10,12-trihydroxy-octadecanoic acid fatty acid Chemical class 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052802 copper Inorganic materials 0.000 abstract description 17
- 239000010949 copper Substances 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 abstract description 11
- 239000004359 castor oil Substances 0.000 abstract description 6
- 235000019438 castor oil Nutrition 0.000 abstract description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract description 6
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 5
- 229960003656 ricinoleic acid Drugs 0.000 abstract description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011630 iodine Substances 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 3
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- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 238000005555 metalworking Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 25
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
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- 150000002632 lipids Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000002024 ethyl acetate extract Substances 0.000 description 6
- 238000007385 chemical modification Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 239000000284 extract Substances 0.000 description 2
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- WHMMVHORNLUTCC-UHFFFAOYSA-N methyl 9,10,12-trihydroxyoctadecanoate Chemical class CCCCCCC(O)CC(O)C(O)CCCCCCCC(=O)OC WHMMVHORNLUTCC-UHFFFAOYSA-N 0.000 description 2
- RFSHKURIZIMTEQ-UHFFFAOYSA-N methyl 9,10,12-tripropoxyoctadecanoate Chemical class CCCCCCC(OCCC)CC(OCCC)C(OCCC)CCCCCCCC(=O)OC RFSHKURIZIMTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- AAAYGLDLAQWORT-UHFFFAOYSA-N propyl 9,10,12-trihydroxyoctadecanoate Chemical compound CCCCCCC(O)CC(O)C(O)CCCCCCCC(=O)OCCC AAAYGLDLAQWORT-UHFFFAOYSA-N 0.000 description 2
- PUGHUQFNJNVXGE-UHFFFAOYSA-N propyl 9,10,12-tripropoxyoctadecanoate Chemical compound CCCCCCC(OCCC)CC(OCCC)C(OCCC)CCCCCCCC(=O)OCCC PUGHUQFNJNVXGE-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- JDFSCKJIBGVQIE-UHFFFAOYSA-N methyl 9,10,12-trihexoxyoctadecanoate Chemical class CCCCCCOC(CCCCCC)CC(OCCCCCC)C(OCCCCCC)CCCCCCCC(=O)OC JDFSCKJIBGVQIE-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- 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
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-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic 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
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- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
- C10M2207/2895—Partial esters containing free hydroxy groups used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/301—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 used as base material
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Abstract
本发明涉及将在蓖麻油中以85-90%的程度存在的蓖麻油酸的化学结构改性成为三酰氧基烷基酯衍生物。因此,富含9,10,12-三羟基十八烷酸的脂肪酸混合物由蓖麻油制备,并被转化为其烷基酯,接着通过羟基的酰化以得到富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物。从粗产物纯化9,10,12-三酰氧基十八烷酸烷基酯,并通过1HNMR研究来表征。也评估粗产物的酸值(A.V.)、羟值(H.V.)、碘值(I.V.)、粘度、粘度指数(V.I.)、倾点、闪点、铜片腐蚀,并发现其为用于液压流体、金属工作流体及其他工业流体的潜在的基本原料。
Description
技术领域
本发明涉及具有优良的润滑性能的新的化学改性的蓖麻油脂肪酸化合物即富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸烷基酯和富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物及其制备方法。
发明背景
植物油诸如油菜籽油和油的高油品种被认为是制备取代常规矿物油基润滑油和合成酯的生物润滑剂进料的潜在的候选[Randies,S.J.等人;J.Synthetic Lubrication.,9:145(1992);Asadauskas,S.等人;Lub.Eng.,52:877(1996)]。植物油基的衍生产品是有吸引力的石油衍生产品的替代品,因为它们具有增强的生物降解性、较低的毒性,它们来自可再生的含油种子来源。酯键提供固有的润滑,并使油粘附到金属表面。此外,植物油比矿物油基流体具有较高的对于污染物和添加剂的溶解能力。文献中关于润滑剂基本原料的报告的大部分工作是基于可食用的油。
主要的非食用油(即蓖麻油)作为制造许多功能衍生物的工业原料发挥作用[J.Am.Oil Chem.Soc.51,65(1974),J.Am.Oil Chem.Soc.48,759(1971)]。蓖麻油是一种公知的润滑剂,由于其中羟基脂肪酸(12-羟基-9-顺式-十八碳烯酸(octadecenoic acid)或蓖麻油酸)以85-90%的程度存在(Chemical Business,1991,55-60)。J.Synthetic Lubrication24,181(2007)报告了蓖麻油的物理化学特性。
蓖麻油在40℃和100℃下具有不受欢迎的非常高的粘度。蓖麻油也在大约200℃及以上的温度下脱水。
化学改性的蓖麻油的流变学特性比矿物油和其他植物油基润滑剂 好得多。主要由于其在低温下的物理特性,在12位具有用C6、C12、C16和C18脂肪酸酯化的羟基的蓖麻油基酯是令人感兴趣的(Eur J LipidSci.Technol.2003,105,214-218)。具有游离羟基的酯在提高石油燃料的润滑能力方面是有效的。制备蓖麻油酸和12-羟基十八烷酸的甲酯和乙酯,测定其物理化学性质,结果表明,除了粘度、密度和十六烷值之外,游离羟基的存在并没有影响它们的参数并且不限制其酯作为燃料的用途(Eur J.lipid Sci.Technol.,2006,108,629-635)。改性大豆油以将不饱和位点转化为C2至C10二酯,其具有作为液压流体、金属工作流体及其他工业流体的效用(US 6,583,302)。没有关于制备用作润滑剂基本原料的富含这些三羟基脂肪酸的混合物的衍生物的报告。
发明目标
本发明的主要目标是从富含9,10,12-三羟基十八烷酸的脂肪酸混合物开始制备不同的润滑剂基本原料。
本发明的另一目标是使用直链或支链醇,转化富含9,10,12-三羟基十八烷酸的脂肪酸混合物成为其烷基酯。
本发明的另一目标是通过与2-8个碳链长度的酸酐反应,转化富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸混合物成为其相应的三酰氧基衍生物。
提供这些酯的物理化学性质也是本发明的目标。
本发明的另一目标是从富含三酰氧基脂肪酸烷基酯的产品分离所有三酰氧基脂肪酸烷基酯,并通过1H NMR研究阐明其结构。
本发明的再另外的一个目标是制备具有适于工业应用的广泛的粘度范围和低温特性的环保蓖麻油基润滑剂基本原料。
发明内容
因此,本发明涉及一类新的化学改性的蓖麻油基润滑剂基本原料及其制造方法。根据本发明,从蓖麻油开始制备12-羟基-9-顺式-十八碳烯酸基润滑剂基本原料。因此,在酸催化剂的存在下,使用过氧化氢二羟基化蓖麻油,接着皂化以获得羟基脂肪酸和非羟基脂肪酸的混合物。9,10,12-三羟基十八烷酸是产品中存在的主要的脂肪酸。
具体实施方式
因此,本发明提供了通式1的9,10,12-三羟基十八烷酸烷基酯和9,10,12-三酰氧基十八烷酸烷基酯:
R1=H,CH3(CH2)m-CO-其中,m=1-4
通式1。
在本发明的实施方式中,其中,化合物9,10,12-三酰氧基十八烷酸烷基酯用作潜在的润滑剂基本原料,用于制备在液压流体、金属工作流体及其他工业流体中应用的润滑剂制剂。
因此,本发明提供了制备式1的9,10,12-三酰氧基十八烷酸烷基酯的方法,步骤包括:
(a)向蓖麻油加入乙酸和硫酸,接着在12-20℃下加入过氧化氢持续2至2.5小时;
(b)将反应混合物倒入水中,并用水不混溶的溶剂如苯、氯仿和乙酸乙酯萃取混合物,以获得残留物;
(c)在碱金属氢氧化物如氢氧化钠和氢氧化钾的存在下,加热步骤(b)获得的产物,并用HCl中和以获得富含9,10,12-三羟基十八烷酸的脂肪酸混合物;
(d)用醇酯化富含9,10,12-三羟基十八烷酸的脂肪酸混合物,以获得富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸烷基酯的混合物;
(e)在取决于溶剂沸点的温度范围内,在二甲氨基吡啶DMAP的存在下,在使用的选自水共沸物形成溶剂如二甲苯、甲苯的溶剂中,用酸酐酰化步骤(d)获得的富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸烷基酯的混合物,持续完全转化所需的一段时间,以获得富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物,从混合物纯化9,10,12-三酰氧基十八烷酸烷基酯。
在一个实施方式中,本发明提供了一种方法,其中,富含9,10,12-三羟基十八烷酸的脂肪酸混合物含有大约87.0%的9,10,12-三羟基十八烷酸。
本发明的再另外的一个实施方式提供了一种方法,其中,在作为催化剂的分别为0.1-0.2%和1-2%浓度的氯化亚锡或硫酸的存在下,用于酯化9,10,12-三羟基十八烷酸的羧基的醇可以选自甲醇、丙醇和2-乙基己醇。
在一个实施方式中,本发明提供了一种方法,其中,可以使用1∶2至1∶27的摩尔比的脂肪酸混合物和醇而进行酯化。
在另一实施方式中,本发明提供了一种方法,其中,酯化反应可以在60至190℃的温度下进行。
在另一实施方式中,本发明提供了一种方法,其中,酯化反应可以进行持续6-8小时。
在本发明的一个实施方式中,其中,在175至180℃下、0.1%浓度的DMAP的存在下,用于9,10,12-三羟基十八烷酸的羟基的酰化的酐可以选自丙酸酐、丁酸酐、戊酸酐和己酸酐。
在一个实施方式中,本发明提供了一种方法,其中,富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物可以用作潜在的润滑剂基本原料,用于制备在液压流体、金属工作流体及其他工业流体中应用的润滑剂制剂。
在一个实施方式中,本发明提供了一种方法,其中,从富含9,10,12- 三酰氧基十八烷酸烷基酯的产物分离9,10,12-三酰氧基十八烷酸烷基酯,并通过1H NMR阐明其结构。
在一个实施方式中,本发明提供了一种方法,其中,9,10,12-三酰氧基十八烷酸烷基酯可以由容易获得的9,10,12-三羟基十八烷酸通过酯化接着酰化来制备。
自古以来植物油如蓖麻油已被用作润滑剂。这些材料,类似于合成酯,比矿物油具有更好的生物可降解性,也是可再生的。植物油具有一些缺点,诸如比合成酯较高的倾点和较低的粘度指数。由于不饱和键的存在,它们具有有限的粘度范围和较低的氧化稳定性。因此这样的植物油不能满足现代机械润滑的所有要求。因此,在本发明中,天然蓖麻油的化学结构通过化学改性被改性成为十八烷酸三酯。富含9,10,12-三羟基十八烷酸的脂肪酸混合物由蓖麻油制备,并被转化为其烷基酯,接着通过羟基的酰化以得到富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物。评估这些产品的酸值(A.V.)、羟值(H.V.)、碘值(I.V.)、粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,并发现其为用于液压流体、金属工作流体及其他工业流体的潜在的基本原料。富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物的粘度和倾点特性优于蓖麻油。
根据本发明,环氧化具有87.0%蓖麻油酸(12-羟基-9-顺式-十八碳烯酸)的蓖麻油,原位用乙酸将环氧环开环,接着用碱皂化,接着中和,以得到富含9,10,12-三羟基十八烷酸的脂肪酸混合物。
在接下来的步骤中,在酸催化剂的存在下,使用直链或支链醇(C1至C8),转化富含9,10,12-三羟基十八烷酸的脂肪酸混合物的羧基成为其烷基酯。
在本发明的一个实施方式中,开发通过与酸酐(C3-C6)反应从9,10,12-三羟基十八烷酸烷基酯的混合物制备富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物的有效的方法。产品中的主要成分(即9,10,12-三羟基十八烷酸烷基酯和9,10,12-三酰氧基十八烷酸烷基酯)的结构如下:
R1=H,CH3(CH2)m-CO- 其中,m=1-4
评估三酰氧基衍生物的物理化学特性诸如酸值(A.V.)、羟值(H.V.)、碘值(I.V.)、粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀。三酰氧基衍生物显示的性能使得它们可用作对于生物可降解润滑剂应用诸如液压流体、金属工作流体及其他工业流体的基本原料。在没有添加传统的添加剂的情况下,这些产品的某些性能达到或超过对于某些润滑剂应用的一些规范。
下面的实施例是为了进一步说明本发明,没有任何意图将本发明限于本文所述的具体实施方式。
实施例1
富含9,10,12-三羟基十八烷酸甲酯的脂肪酸的制备:
将蓖麻油(200g)放入2升的R.B.烧瓶中,并向此加入冰醋酸(700g)、硫酸(13.3g),冷却反应混合物至15-20℃。向冷却的搅拌的悬浮液,在2小时期间逐滴加入50%的过氧化氢(393g)。完全加入过氧化氢后,缓慢升高反应混合物的温度至40℃,并使其搅拌另外的5小时。在反应时间结束时,将内容物倒入冷水中,并使其过夜。用乙酸乙酯(2×1000ml)萃取有机相,并用水冲洗乙酸乙酯萃取物直至水相的pH为中性。将乙酸乙酯萃取物通过无水硫酸钠床,使用旋转蒸发仪除去溶剂以在真空干燥后回收中间产物(260g)。将中间产物(260g) 放入5升的R.B.烧瓶,并向此加入3N氢氧化钠溶液(2666ml),在80℃下机械搅拌2小时。经过2小时后,用1∶1盐酸水溶液(800ml)中和内容物,并使悬浮液的温度下降至大约30℃,并搅拌额外的20分钟。过滤沉淀物,并在真空干燥器中干燥以回收富含9,10,12-三羟基十八烷酸的脂肪酸混合物(150g)。将该产物放入2升R.B.烧瓶,并向其加入于甲醇(500ml)中的2%的硫酸,在60℃下搅拌内容物6小时。通过定时测定酸值监测该反应过程。反应完成后,使用旋转蒸发仪蒸发部分甲醇,并将残留物放入乙酸乙酯(1升)中,用蒸馏水洗涤(5×250ml)直至中性pH。将乙酸乙酯提取物通过无水硫酸钠床,浓缩,并真空干燥,以回收具有2.2的A.V.、460的H.V.和2.0的I.V.的产物(120g)。
通过柱色谱纯化9,10,12-三羟基十八烷酸甲酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.9[t,-CH3],1.2-1.7[m,12x-CH2-],2.3[t,-CO-CH2-],3.5-3.9[m,3x(-CH-OH),-O-CH3].
实施例2
富含9,10,12-三丙氧基十八烷酸甲酯的脂肪酸甲酯混合物的制备:
将实施例1制备的富含9,10,12-三羟基十八烷酸的脂肪酸甲酯(300g)放入1升的R.B.烧瓶,并向其加入丙酸酐(681g)、二甲氨基吡啶(DMAP,300mg)和二甲苯(100ml),在180℃下磁力搅拌内容物6小时。通过TLC监测该反应过程。反应完成后,减压蒸馏二甲苯及未转化的丙酸酐和丙酸,并将残留物放入乙酸乙酯中。乙酸乙酯提取物经蒸馏水洗涤,并通过无水硫酸钠,真空浓缩,以回收具有0.3的A.V.、3.3的H.V.和2.0的I.V.的产物(270g)。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 32.42 |
在100℃下的粘度cSt: | 5.18 |
粘度指数 | 84 |
倾点(℃) | -33 |
闪点(℃) | 252 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三丙氧基十八烷酸甲酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.9[t,-CH3],1.1-1.8[m,12x-CH2,3x-CH3],2.2-2.4[m,4x(-CO-CH2-)],3.6[s,-O-CH3],4.8-5.2[m,3x(-O-CH)].
实施例3
富含9,10,12-三丁酰氧基十八烷酸甲酯的脂肪酸甲酯混合物的制备:
根据实验2,通过将富含9,10,12-三羟基十八烷酸甲酯的脂肪酸甲酯混合物(97g)与丁酸酐(260g)反应制备标题化合物(190g),具有0.1的A.V.、2.4的H.V.和2.0的I.V.。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 24.2 |
在100℃下的粘度cSt: | 4.66 |
粘度指数 | 109 |
倾点(℃) | -42 |
闪点(℃) | 252 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三丁酰氧基十八烷酸甲酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.9[m,4x(-CH3)],1.2-1.8[m,15x-CH2-],2.2-2.3[m,4x(-CO-CH2-)],3.6[s,-O-CH3],4.8-5.2[m,3x(-O-CH)].
实施例4
富含9,10,12-三戊酰氧基十八烷酸甲酯的脂肪酸甲酯混合物的制备:
根据实验2,通过将富含9,10,12-三羟基十八烷酸甲酯的脂肪酸甲酯混合物(90g)与戊酸酐(352g)反应制备标题化合物(210g),具有0.3的A.V.、1.9的H.V.和2.0的I.V.。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 12.63 |
在100℃下的粘度cSt: | 3.21 |
粘度指数 | 129 |
倾点(℃) | -54 |
闪点(℃) | 252 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三戊酰氧基十八烷酸甲酯,并通过1H研究确定标题化合物的结构。
1HNMR(CDCl3,δppm):0.8-1.0[m,4x-CH3],1.2-1.7[m,18x-CH2-],2.2-2.4[m,4x-CO-CH2-],3.6[s,-O-CH3],4.8-5.2[m,3x(-O-CH)].
实施例5
富含9,10,12-三己氧基十八烷酸甲酯的脂肪酸甲酯混合物的制备:
根据实验2,通过将富含9,10,12-三羟基十八烷酸甲酯的脂肪酸甲酯混合物(45g)与己酸酐(162g)反应制备标题化合物(113g),具有0.3的A.V.、2.0的H.V.和2.0的I.V.。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 35.37 |
在100℃下的粘度cSt: | 6.2 |
粘度指数 | 127 |
倾点(℃) | -39 |
闪点(℃) | 252 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三己氧基十八烷酸甲酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.9-1.0[m,4x-CH3],1.2-1.4[m,21x-CH2-],2.2-2.4[m,4x-CO-CH2-],3.6[s,-O-CH3],4.8-5.1[m,3x-O-CH].
实施例6
富含9,10,12-三羟基十八烷酸丙酯的脂肪酸混合物的制备:
将实施例1制备的富含9,10,12-三羟基十八烷酸的脂肪酸混合物(400g)放入1升的R.B.烧瓶,并向其加入1-丙醇(108g)和氯化亚锡(400mg),在96℃下搅拌内容物8小时。通过定时测定酸值监测该反应过程。反应完成后,使用旋转蒸发仪蒸发部分1-丙醇,并将残留物放入乙酸乙酯(600ml)中,用蒸馏水洗涤(5×500ml)。将乙酸乙酯提取物通过无水硫酸钠床,浓缩,并真空干燥,浓缩物通过碱性氧化铝柱,以回收具有2.5的A.V.、420的H.V.和5.0的I.V.的产物(405g)。
通过柱色谱纯化9,10,12-三羟基十八烷酸丙酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.9-1.0[m,2x-CH3],1.2-1.7[m,13x-CH2-],2.3[t,-CO-CH2-],3.3-3.4,3.5-3.7,3.7-3.9[3m,3x-CH-OH],4.0[t,-O-CH2-].
实施例7
富含9,10,12-三丙氧基十八烷酸丙酯的脂肪酸丙酯混合物的制备:
将实施例6制备的富含9,10,12-三羟基十八烷酸丙酯的脂肪酸丙酯(200g)放入1升的R.B.烧瓶,并向其加入丙酸酐(313.6g)、DMAP(200mg)和二甲苯(100ml),在180℃下磁力搅拌内容物6小时。通过TLC监测该反应过程。反应完成后,减压蒸馏二甲苯及未转化的丙酸酐和丙酸,并将残留物放入乙酸乙酯(600ml)中。乙酸乙酯提取 物经蒸馏水洗涤,并通过无水硫酸钠,真空浓缩,浓缩物通过碱性氧化铝柱,以回收具有0.3的A.V.、0.5的H.V.和5.0的I.V.的产物(190g)。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 40.57 |
在100℃下的粘度cSt: | 6.38 |
粘度指数 | 106 |
倾点(℃) | -18 |
闪点(℃) | 228 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三丙氧基十八烷酸丙酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.8-1.0[m,5x-CH3],1.1-1.7[m,13x-CH2-],2.2-2.4[m,4x-CO-CH2-],4.0[t,-O-CH2-],4.8-5.2[m,3x-O-CH-].
实施例8
富含9,10,12-三戊酰氧基十八烷酸丙酯的脂肪酸丙酯混合物的制备:
将实施例6制备的富含9,10,12-三羟基十八烷酸丙酯的脂肪酸丙酯(200g)放入1升的R.B.烧瓶,并向其加入戊酸酐(447g)、DMAP(200mg)和二甲苯(100ml),在180℃下磁力搅拌内容物6小时。通过TLC监测该反应过程。反应完成后,减压蒸馏二甲苯及未转化的戊酸酐和戊酸,并将残留物放入乙酸乙酯(600ml)中。乙酸乙酯提取物经蒸馏水洗涤,并通过无水硫酸钠,真空浓缩,浓缩物通过碱性氧化铝柱,以回收具有0.2的A.V.、0.7的H.V.和5.0的I.V.的产物(198g)。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 44.51 |
在100℃下的粘度cSt: | 7.2 |
粘度指数 | 126 |
倾点(℃) | -24 |
闪点(℃) | 238 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三戊酰氧基十八烷酸丙酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.85-1.0[m,5x-CH3],1.2-1.7[m,19x-CH2-],2.2-2.4[m,4x-CO-CH2-],4.0[t,-O-CH2-],4.8-5.2[m,3x-O-CH-].
实施例9
富含9,10,12-三羟基十八烷酸2-乙基己酯的脂肪酸混合物的制备:
将富含9,10,12-三羟基十八烷酸的脂肪酸混合物(200g)放入1升的R.B.烧瓶,并向其加入2-乙基己醇(156g)、氯化亚锡(200mg)和二甲苯(100ml),在190℃磁力下搅拌内容物8小时。通过TLC监测该反应过程。反应完成后,减压蒸馏过量的2-乙基己醇、二甲苯。将残留物放入乙酸乙酯(600ml)中,用水洗涤有机相直至中性pH。使用旋转蒸发仪蒸发溶剂,以回收具有0.9的A.V.和5.0的I.V.的产物(180g)。
通过柱色谱纯化9,10,12-三羟基十八烷酸2-乙基己酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.8-0.9[m,3x-CH3],1.1-1.7[m,l6x-CH2-],2.3[t,-CO-CH2-],3.6[m,-CH-OH],3.7[m,-OCH2-],4.2-4.3[m,2x-CH-OH].
实施例10
富含9,10,12-三丙氧基十八烷酸2-乙基己酯的脂肪酸2-乙基己酯混合物的制备:
将实施例9制备的富含9,10,12-三羟基十八烷酸2-乙基己酯的脂肪酸2-乙基己酯(150g)放入1升的R.B.烧瓶,并向其加入丙酸酐(257g)、二甲氨基吡啶(150mg)和二甲苯(100ml),在180℃下磁力搅拌内容物6小时。通过TLC监测该反应过程。反应完成后,减压蒸馏二甲苯及未转化的丙酸酐和丙酸,并将残留物放入乙酸乙酯中。乙酸乙酯提取物经蒸馏水洗涤,并通过无水硫酸钠,真空浓缩,以回收产物(257g)。产物具有0.9的A.V.、1.5的H.V.和5.0的I.V.。评估产物的粘度、粘度指数(V.I.)、倾点、闪点和铜片腐蚀,下面的表格提供数据。
性质 | 值 |
在40℃下的粘度cSt | 76.22 |
在100℃下的粘度cSt: | 10.62 |
粘度指数 | 125 |
倾点(℃) | -30 |
闪点(℃) | 262 |
铜片腐蚀 | 1a |
通过柱色谱纯化9,10,12-三丙氧基十八烷酸2-乙基己酯,并通过1H研究确定标题化合物的结构。
1H NMR(CDCl3,δppm):0.8-0.9[m,6x-CH3],1.1-1.7[m,16x-CH2-],2.3-2.4[m,4x-CO-CH2-],3.9[m,-O-CH2-],4.8-5.2[m,3x-O-CH-]
本发明的优点:
在本专利中,制备具有优良的润滑性能特性的新颖化学改性的蓖麻油脂肪酸衍生物。这些产品具有良好的粘度指数、高闪点和低倾点。由于缺乏不饱和性,它们具有优良的热和氧化稳定性。它们是用于金属工作流体、液压流体及其他工业流体的潜在的基本原料。
Claims (12)
3.一种制备权利要求1所述的式1的9,10,12-三酰氧基十八烷酸烷基酯的方法,其中,步骤包括:
(a)向蓖麻油加入乙酸和硫酸,接着在12-20℃下加入过氧化氢持续2至2.5小时;
(b)将反应混合物倒入水中,并用水不混溶的溶剂萃取混合物,以获得残留物;
(c)在碱金属氢氧化物的存在下,加热步骤(b)获得的产物,并用HC1中和以获得富含9,10,12-三羟基十八烷酸的脂肪酸混合物;
(d)用醇酯化富含9,10,12-三羟基十八烷酸的脂肪酸混合物,以获得富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸烷基酯的混合物;
(e)在取决于溶剂沸点的温度范围内,在二甲氨基吡啶DMAP的存在下,在使用的选自水共沸物形成溶剂的溶剂中,用酸酐酰化步骤(d)获得的富含9,10,12-三羟基十八烷酸烷基酯的脂肪酸烷基酯的混合物,持续完全转化所需的一段时间,以获得富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物,从混合物纯化9,10,12-三酰氧基十八烷酸烷基酯。
4.根据权利要求3的方法,其中,所述富含9,10,12-三羟基十八烷酸的脂肪酸混合物含有87.0%的9,10,12-三羟基十八烷酸。
5.根据权利要求3的方法,其中,在作为催化剂的分别为0.1-0.2%和1-2%浓度的氯化亚锡或硫酸的存在下,所述用于酯化9,10,12-三羟基十八烷酸的羧基的醇选自甲醇、丙醇和2-乙基己醇。
6.根据权利要求3的方法,其中,使用1:2至1:27的摩尔比的脂肪酸混合物和醇进行所述酯化。
7.根据权利要求3的方法,其中,所述酯化反应在60至190℃的温度下进行。
8.根据权利要求3的方法,其中,所述酯化反应进行持续6-8小时。
9.根据权利要求3的方法,其中,在175至180℃下、0.1%浓度的DMAP的存在下,所述用于酰化9,10,12-三羟基十八烷酸的羟基的酸酐选自丙酸酐、丁酸酐、戊酸酐和己酸酐。
10.根据权利要求3的方法,其中所述水共沸物形成溶剂选自二甲苯和甲苯。
11.根据权利要求3的方法,其中,所述富含9,10,12-三酰氧基十八烷酸烷基酯的脂肪酸烷基酯的混合物用作潜在的润滑剂基本原料,用于制备在液压流体、金属工作流体及其他工业流体中应用的润滑剂制剂。
12.根据权利要求3的方法,其中,从富含9,10,12-三酰氧基十八烷酸烷基酯的产物分离9,10,12-三酰氧基十八烷酸烷基酯,并通过1H NMR阐明其结构。
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Thomas H. Kalantar et al..Transformations of Hydroxy Cyclic Sulfates: Stereospecific Coversion into 2,3,5-Trisubstituted Tetrahydrofurans.《Acta Chemica Scandinavica》.1993,第307-313页. |
Transformations of Hydroxy Cyclic Sulfates: Stereospecific Coversion into 2,3,5-Trisubstituted Tetrahydrofurans;Thomas H. Kalantar et al.;《Acta Chemica Scandinavica》;19931231;第308页左栏第1段,化合物6,图1 * |
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