CN112760151B - Biodegradable lubricating grease composition and preparation method thereof - Google Patents
Biodegradable lubricating grease composition and preparation method thereof Download PDFInfo
- Publication number
- CN112760151B CN112760151B CN201911000961.1A CN201911000961A CN112760151B CN 112760151 B CN112760151 B CN 112760151B CN 201911000961 A CN201911000961 A CN 201911000961A CN 112760151 B CN112760151 B CN 112760151B
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- grease composition
- lubricating
- base oil
- reaction
- lubricating grease
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- 239000004519 grease Substances 0.000 title claims abstract description 69
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002199 base oil Substances 0.000 claims abstract description 42
- 238000006065 biodegradation reaction Methods 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- 229910052796 boron Chemical group 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 14
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 14
- 239000008158 vegetable oil Substances 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 11
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012990 dithiocarbamate Substances 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229920013639 polyalphaolefin Polymers 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010696 ester oil Substances 0.000 claims description 5
- 239000013556 antirust agent Substances 0.000 claims description 4
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- YSIQDTZQRDDQNF-UHFFFAOYSA-L barium(2+);2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 YSIQDTZQRDDQNF-UHFFFAOYSA-L 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000013067 intermediate product Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 235000002906 tartaric acid Nutrition 0.000 description 9
- 239000011975 tartaric acid Substances 0.000 description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- 230000002140 halogenating effect Effects 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- -1 preferably Chemical compound 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 230000006340 racemization Effects 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- HJBLUNHMOKFZQX-UHFFFAOYSA-N 3-hydroxy-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N(O)N=NC2=C1 HJBLUNHMOKFZQX-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YIRRTBMIVUEJBM-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCCCCCCC)[Ba]CCCCCCCCC Chemical compound C1(=CC=CC2=CC=CC=C12)S(=O)(=O)O.C(CCCCCCCC)[Ba]CCCCCCCCC YIRRTBMIVUEJBM-UHFFFAOYSA-N 0.000 description 1
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- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 101150092791 PAO4 gene Proteins 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- PQGVTLQEKCJXKF-RGMNGODLSA-N ethyl (2s)-2-amino-3-methylbutanoate;hydron;chloride Chemical compound Cl.CCOC(=O)[C@@H](N)C(C)C PQGVTLQEKCJXKF-RGMNGODLSA-N 0.000 description 1
- JCXLZWMDXJFOOI-WCCKRBBISA-N ethyl (2s)-2-aminopropanoate;hydrochloride Chemical compound Cl.CCOC(=O)[C@H](C)N JCXLZWMDXJFOOI-WCCKRBBISA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KUGLDBMQKZTXPW-JEDNCBNOSA-N methyl (2s)-2-amino-3-methylbutanoate;hydrochloride Chemical compound Cl.COC(=O)[C@@H](N)C(C)C KUGLDBMQKZTXPW-JEDNCBNOSA-N 0.000 description 1
- IYUKFAFDFHZKPI-DFWYDOINSA-N methyl (2s)-2-aminopropanoate;hydrochloride Chemical compound Cl.COC(=O)[C@H](C)N IYUKFAFDFHZKPI-DFWYDOINSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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Abstract
The invention provides a biodegradable lubricating grease composition and a preparation method thereof, wherein the lubricating grease composition comprises, by mass, 70% -90% of lubricating base oil, 4% -30% of lithium-based thickening agent and 0.1% -5% of additive, wherein the additive comprises a biodegradation accelerator, and is represented by a compound shown as the following formula I:
wherein X is phosphorus or boron, R1One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8‑C18Alkyl group of (1). The lubricating grease composition disclosed by the invention has excellent degradation performance, ensures environmental friendliness, has little influence on other performances, still has good colloid stability, excellent mechanical stability and excellent antioxidant effect, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of lubricating grease, in particular to a biodegradable lubricating grease composition and a preparation method thereof.
Background
The lubricating grease is a necessary working medium in the normal operation of mechanical equipment and the manufacturing and processing process of materials, and the demand of the lubricating grease is more and more increased along with the rapid development of the industry. During the storage, transportation and use of the lubricating grease, the situations of leakage, overflow and improper discharge of various polluted environments can not be avoided. Although the acute toxicity of the lubricating grease to organisms is very small, there are only reports about poisoning caused by contacting with the lubricating grease, but the lubricating grease entering the environment has poor biodegradability and seriously pollutes the land, rivers and lakes, and meanwhile, the lubricating grease is not easy to recycle like the lubricating grease, so the research on the lubricating grease with biodegradability becomes a breakthrough for solving the problem of ecological environment.
In recent years, the influence of waste and leaked lubricating grease on the environment has attracted people's attention, and in order to solve the problem, research is mainly focused on two aspects, namely research and development of lubricating base oil which is easy to biodegrade, such as biodegradable vegetable oil or ester synthetic oil, for preparing lubricating grease, and development of environment-friendly additives of the lubricating base oil which is easy to biodegrade.
However, there are still few reports on the biodegradation accelerator for lubricating oils, and the degradation effect of lubricating greases using mineral oil or polyalphaolefin as the main base oil is not ideal.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The present invention is directed to overcoming at least one of the drawbacks of the prior art, and providing a biodegradable grease composition and a method for preparing the same, wherein the grease composition employs a novel biodegradation accelerator, so that the grease composition has excellent degradation performance, has little influence on other performances while ensuring environmental friendliness, still has good colloid stability, excellent mechanical stability, and excellent antioxidant effect, and has good industrial application prospects.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a lubricating grease composition, which comprises, by mass, 70-90% of lubricating base oil, 4-30% of a lithium-based thickening agent and 0.1-5% of an additive, wherein the additive comprises a biodegradation accelerator, and is represented by a compound of the following formula I:
wherein X is phosphorus or boron, R1One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8-C18Alkyl group of (1).
According to one embodiment of the invention, R1Selected from methyl or isopropyl, R2Is selected from C12Alkyl or C14An alkyl group.
According to one embodiment of the invention, R1Is methyl, R2Is C14Alkyl and X is phosphorus.
According to one embodiment of the invention, the lubricating base oil is selected from one or more of mineral oils, vegetable oils, ester oils, polyalphaolefins.
According to one embodiment of the present invention, the lubricating base oil comprises a vegetable oil, the vegetable oil comprising not more than 40% by mass of the grease composition.
According to one embodiment of the invention, the kinematic viscosity of the lubricating base oil at 100 ℃ is 5mm2/s～60mm2/s。
According to one embodiment of the invention, the lithium-based thickener is obtained by reacting fatty acid with lithium hydroxide, wherein the lithium hydroxide accounts for 3.8-9.8% of the mass of the grease composition, and the fatty acid is selected from C12-C20A fatty acid.
According to one embodiment of the invention, the additive further comprises one or more of an antioxidant, a rust inhibitor and an extreme pressure anti-wear agent.
According to one embodiment of the invention, the antioxidant is selected from one or more of 2, 6-di-tert-butyl-p-cresol and phenyl-alpha-naphthylamine, the antirust agent is selected from one or more of dinonyl barium naphthalene sulfonate and barium petroleum sulfonate, and the extreme pressure antiwear agent is selected from one or more of thiosemicarbazide and dialkyl dithiocarbamate.
The invention also provides a preparation method of the lubricating grease composition, which comprises the following steps:
33 to 66 percent of lubricating base oil and C12-C20Adding fatty acid into the reaction kettle, and uniformly stirring;
heating the reaction kettle to 60-95 ℃, and adding a mixture of lithium hydroxide and water for saponification reaction;
continuously heating to 120-180 ℃ for dehydration reaction;
adding the rest lubricating base oil, cooling to 100-130 ℃, adding the biodegradation accelerator, and uniformly stirring to obtain the lubricating grease composition.
According to one embodiment of the present invention, the saponification reaction time is 25min to 120 min.
According to one embodiment of the invention, the method further comprises the steps of adding an antioxidant into the reaction kettle after the dehydration reaction, and continuously heating to 190-220 ℃ for high-temperature refining.
According to one embodiment of the present invention, the time for the high-temperature refining is 5min to 20 min.
According to one embodiment of the invention, the method further comprises the step of adding the antirust agent and/or the extreme pressure antiwear agent into the reaction kettle after the temperature is reduced to 100-130 ℃.
According to the technical scheme, the lubricating grease composition and the preparation method thereof have the advantages and positive effects that:
the additive of the biodegradable lubricating grease composition provided by the invention is added with a novel biodegradation accelerator, and the biodegradation accelerator has excellent degradation performance, ensures environmental friendliness, has little influence on other performances, and still has good colloid stability, excellent mechanical stability and excellent antioxidant effect. The lubricating grease composition can be used under various harsh working conditions such as high temperature, high speed, high load, much water and the like, and the preparation method is simple and has good industrial application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a synthesis scheme of the biodegradation accelerator of preparation example 1.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a biodegradable lubricating grease composition, which comprises, by mass, 70-90% of lubricating base oil, 4-30% of a lithium-based thickening agent and 0.1-5% of an additive, wherein the additive comprises a biodegradation accelerator, and the additive is represented by a compound shown as the following formula I:
wherein X is phosphorus or boron, R1One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8-C18Alkyl group of (1).
According to the invention, the lubricating grease is a thick grease-like semisolid which is used for a friction part of a machine and has the functions of lubricating and sealing, and is also used for a metal surface to fill a gap and prevent rust. It is mainly prepared by blending base oil and a thickening agent. At present, mineral oil, vegetable oil, ester oil, poly alpha-olefin and the like are mainly adopted as base oil. Although synthetic ester and vegetable oil are biodegradable lubricating oil advocated to be used at present, mineral oil, poly-alpha-olefin and the like generally occupy the leading position of the lubricating oil base oil market due to low cost and good performance, and how to improve the degradation rate of the difficultly degraded lubricating oil has important significance for producing environment-friendly lubricating grease. In the case of mineral oils, they are difficult to degrade, in addition to their structure being detrimental to degradation, and also because they are difficult to dissolve in water. The lubricating grease composition adopts a biodegradation accelerator compound shown in the formula I as an additive, and the compound shown in the formula I as an amino acid type surfactant with tartaric acid as a framework is beneficial to improving the solubility of oil in water, has the advantages of low irritation, low toxicity and the like, and is easy to biodegrade. In addition, the structure of the compound also contains phosphorus or boron, which is beneficial to being absorbed by microorganisms to provide nutrients, and further improves the biodegradation rate. In addition, by adding a proper amount of the biodegradation accelerator and matching with the base oil and the lithium-based thickening agent, on the premise of ensuring environmental friendliness, other properties are not affected, so that the lubricating grease composition has a good industrial application prospect.
In some embodiments, preferably, the aforementioned R1Selected from methyl or isopropyl, R2Is selected from C12Alkyl or C14An alkyl group. More preferably, R1Is methyl, R2Is C14Alkyl and X is phosphorus.
In some embodiments, the aforementioned biodegradation promoting agent is preferably present in an amount of 0.2% to 2% of the lubricating composition.
In some embodiments, the lubricating base oil is selected from one or more of mineral oil, vegetable oil, ester oil, polyalphaolefins. In some embodiments, the aforementioned lubricating base oil comprises a vegetable oil, the vegetable oil comprising no more than 40% by mass of the grease composition. The existing lubricating grease generally adopts the technical scheme that the proportion of vegetable oil in base oil is improved, so that the biodegradability of the lubricating grease is relatively improved, but certain influence is caused on the performance of the lubricating grease. The grease composition of the present invention has good biodegradability even when the vegetable oil content is low, indicating that the biodegradation accelerator has excellent degradability for base oils that are difficult to degrade, such as mineral oil.
In some embodiments, the lubricating base oil has a kinematic viscosity of 5mm at 100 ℃2/s～60mm2/s。
In some embodiments, the lithium-based thickener is obtained by reacting a fatty acid with lithium hydroxide, wherein the lithium hydroxide accounts for 3.8% -9.8% of the mass of the grease composition, and the fatty acid is selected from C12-C20A fatty acid.
In some embodiments, the additive further comprises one or more of an antioxidant, a rust inhibitor, and an extreme pressure antiwear agent.
In some embodiments, antioxidants include, but are not limited to, 2, 6-di-tert-butyl-p-cresol, phenyl-alpha-naphthylamine, and the like, rust inhibitors include, but are not limited to, barium dinonylnaphthalenesulfonate, barium petroleum sulfonate, and the like, and extreme pressure anti-wear agents include, but are not limited to, aminothioesters, dialkyldithiocarbamates, and the like. Further, the additives may also include other types and functions of additives than those described above according to production needs, and the present invention is not limited thereto.
The invention also provides a preparation method of the compound shown in the formula I and a method for preparing a lubricating grease composition by using the compound shown in the formula I.
The preparation method of the compound of the formula I comprises the following steps:
(1) tartaric acid and amino acid ester hydrochloride, namely a compound shown in the following formula II are mixed in a first solvent for carrying out a reaction, namely a first intermediate product is obtained through amidation reaction, wherein R3Is methyl, ethyl, tert-butyl or benzyl, for example, the compound of formula II can be L-valine methyl ester hydrochloride, L-alanine ethyl ester hydrochloride, L-valine ethyl ester hydrochloride, and the like.
In some embodiments, the first solvent is selected from one or more of dichloromethane, chloroform, acetone, ethyl acetate, N-Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), and acetonitrile, preferably, N-Dimethylformamide (DMF) or Dimethylsulfoxide (DMSO).
In some embodiments, further comprising adding a condensing agent and a racemization inhibitor to the amidation reaction. Condensing agents include, but are not limited to, Dicyclohexylcarbodiimide (DCC), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCL), 4-Dimethylallyltryptophane (DMAT), and the like, preferably Dicyclohexylcarbodiimide (DCC); the molar ratio of tartaric acid to condensing agent is 1: 3-3: 1, preferably 1: 2-3. Racemization inhibitors include, but are not limited to, 1-hydroxybenzotriazole (HOBt), N-hydroxysuccinimide (HOSu), 1-hydroxy-7-azobenzotriazol (HOAt), 3-hydroxy-1, 2, 3-benzotriazin-4 (3H) -one (HOBt), etc., preferably 1-hydroxybenzotriazole (HOBt). The molar ratio of tartaric acid to racemization inhibitor is 1: 3-3: 1, preferably 1: 2-3.
In some embodiments, the molar ratio of tartaric acid to the compound of formula II is 1:5 to 5:1, preferably 1 (2 to 3). The concentration of tartaric acid in the primary reaction system is 0.2 mol/l to 1.0 mol/l, preferably 0.2 mol/l to 0.5 mol/l.
In some embodiments, the reaction temperature of the first reaction is-20 ℃ to 40 ℃, and the reaction time of the first reaction is 1h to 48 h. It will be appreciated that the reaction time can be relatively reduced by lowering the temperature and by suitably extending the reaction time and by raising the temperature so that the reaction end point is more easily reached. For example, when the reaction temperature is 0 ℃, the reaction time is about 12 hours. In some embodiments, the method further comprises adding an organic base to the primary reaction system to neutralize acidity, wherein the organic base may be Triethylamine (TEA), Tetramethylethylenediamine (TMEDA), triethylenediamine (DABCO), pyridine, trimethylamine, or the like, but the present invention is not limited thereto. For example, an appropriate amount of pyridine is added. And after the reaction is finished, washing, drying, filtering and spin-drying the product to obtain a white solid, namely a first intermediate product.
(2) The halogenating agent is reacted with an alkyl alcohol, i.e., of formula III (R)2OH) compound is mixed in a second solvent and placed in a reactor for secondary reaction to obtain a second intermediate product. It is understood that the steps (1) and (2) are not limited to a sequence, and the step (2) may be performed first and then the step (1) may be performed, or both may be performed simultaneously.
In some embodiments, the aforementioned halogenating agent is selected from one or more of phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus oxybromide, boron tribromide, boron trichloride, and is preferably phosphorus trichloride. The alkyl alcohol, i.e. the compound of formula III, may be lauryl alcohol, myristyl alcohol, etc. C8-C18Alkyl alcohol of (1).
In some embodiments, the molar ratio of tartaric acid to halogenating agent is (0.95-1.05): 1, preferably 1: 1; the molar ratio of the halogenating agent to the compound of formula III is 1: 3-3: 1, preferably 1: 1.5.
In some embodiments, the second solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene, and acetonitrile; preferably trichloroethylene.
In some embodiments, the reaction temperature of the secondary reaction is-20 ℃ to 40 ℃, and the reaction time is 0.1h to 30 h. For example, the reaction is carried out at 4 ℃ for 1 hour. In some embodiments, the method further comprises adding an organic base to the secondary reaction system to allow the reaction to proceed under weak base conditions, wherein the organic base added may be Triethylamine (TEA), Tetramethylethylenediamine (TMEDA), triethylenediamine (DABCO), pyridine, trimethylamine, or the like, but the invention is not limited thereto. Preferably, an appropriate amount of triethylamine is added.
According to the invention, the halogenating reagent can be dissolved during the reaction, and a small amount of organic base is added into the reactor, wherein a part of the second solvent is placed in the reactor, then the alkyl alcohol is dissolved into the other part of the second solvent, the mixture is slowly dripped into the reactor containing the halogenating reagent, and after the dripping is finished, the mixture is continuously stirred and reacts to obtain a second intermediate product for standby.
(3) And (3) mixing the first intermediate product obtained in the step (1) in a third solvent, adding the mixture into a reactor, and carrying out three times of reaction with the second intermediate product obtained in the step (2) to obtain a third intermediate product.
In some embodiments, the third solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene, and acetonitrile. Preferably dichloromethane.
In some embodiments, the temperature of the three reactions is-20 ℃ to 40 ℃, and the reaction time of the three reactions is 0.1h to 30 h. For example, the reaction is carried out at 0 ℃ for 12 hours. In some embodiments, the method further comprises adding an organic base to the three-time reaction system to allow the reaction to proceed under weak base conditions, wherein the organic base added may be Triethylamine (TEA), Tetramethylethylenediamine (TMEDA), triethylenediamine (DABCO), pyridine, trimethylamine, or the like, but the invention is not limited thereto. Preferably, an appropriate amount of pyridine is added.
According to the invention, in the reaction, the first intermediate product is dissolved in the third solvent, a small amount of organic base is added, the obtained mixed solution is slowly dripped into the reactor containing the second intermediate product after the reaction in the step (2), and the reaction is continued until the reaction is finished after the dripping. After the reaction, carrying out the steps of suction filtration, washing, drying, filtering, spin drying and the like to obtain a white solid, namely a third intermediate product.
(4) And (4) carrying out hydrolysis reaction on the third intermediate product obtained in the step (3) to obtain the compound of the formula I. Wherein the hydrolysis reaction can be carried out by adopting weak base such as lithium hydroxide, and the final compound of the formula I is obtained by recrystallization after the hydrolysis reaction. The yield can reach about 60% through determination.
The compound of the formula I is synthesized by the method, the synthetic route of the compound adopts a common and easily-obtained tartaric acid raw material, the yield is high, the reaction condition is mild, the raw material price is low, and the method is suitable for large-scale industrial production. The compound is suitable for being used as a lubricating oil biodegradation accelerant, can greatly improve the degradation rate of mineral oil, polyalpha-olefin and other lubricating base oil which are difficult to biodegrade, and has great industrialization potential.
The preparation method of the grease composition comprises the following steps:
first, a part of the lubricating base oil raw material used, generally 33% to 66%, of the lubricating base oil and C are mixed12-C20Adding fatty acid into the reaction kettle, and uniformly stirring; then, heating the reaction kettle to 60-95 ℃, and adding a mixture of lithium hydroxide and water to perform saponification reaction for 25-120 min; continuously heating to 120-180 ℃ for dehydration reaction; adding the rest lubricating base oil after removing water, cooling to 100-130 ℃, adding the biodegradation accelerator, uniformly stirring, grinding for 2-3 times by a three-roller machine, and then forming grease to obtain the lubricating grease composition.
In some embodiments, the invention further comprises adding an antioxidant into the reaction kettle after the dehydration reaction, and continuously heating to 190-220 ℃ for high-temperature refining, wherein the time for high-temperature refining is 5-20 min.
In some embodiments, the invention also comprises adding other additives, such as antirust agent and extreme pressure antiwear agent, into the reaction kettle after the temperature is reduced to 100-130 ℃, so as to be suitable for different production purposes.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, all reagents used in the invention are analytically pure.
Preparation example 1
This preparation example serves to illustrate the synthesis of the biodegradation accelerator of the present invention, i.e., 2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (see structural formula I-c).
1) To the reactor were added sequentially 100mL of DMF, tartaric acid (33.3mmol, 5g), L-alanine methyl ester hydrochloride (73.2mmol, 10.21g), 1-hydroxybenzotriazole (79.9mmol, 10.8g), pyridine (8mL), cooled to 0 deg.C, DCC (79.9mmol, 16.5g) was added, and the reaction was allowed to proceed overnight. The reaction mixture is filtered by suction, the solid is washed by 300mL ethyl acetate, the organic phases are combined, the saturated sodium bicarbonate solution is washed twice, the 10% hydrochloric acid solution is washed twice, the saturated saline solution is washed once, the anhydrous magnesium sulfate is dried for 2h, and the white solid is obtained after filtration and spin drying.
2) Phosphorus trichloride (40mmol, 5.48g) was dissolved in 5mL of n-hexane, the temperature was reduced to 4 ℃, triethylamine (40mmol, 4.04g) was dissolved in 25mL of trichloroethylene, myristyl alcohol (27mmol, 5.78g) was dissolved in 40mL of trichloroethylene, and the solution was slowly added dropwise to the reactor. After the addition, the temperature was raised to room temperature and stirring was continued for 1 hour.
3) Taking the white solid (30mmol, 9.61g) obtained in the step 1), adding 50mL of dichloromethane and 8mL of pyridine, cooling to 0 ℃, slowly dropping the reaction liquid obtained in the step 2) into the reactor, reacting at room temperature overnight after dropping, filtering to remove the solid, washing the filtrate twice with 10% hydrochloric acid solution, washing once with saturated saline solution, drying for 2h with anhydrous magnesium sulfate, filtering, and spin-drying to obtain the white solid.
4) The above white solid (20mmol, 11.25g) was dissolved in 200mL of a mixed solution of tetrahydrofuran and water 2:1, and a lithium hydroxide solid (200mmol, 5g) was added thereto, reacted at room temperature overnight, and then the tetrahydrofuran was removed by rotary evaporation, acidified to pH 4 with a 10% hydrochloric acid solution, and filtered by suction to obtain a white solid. Acetone is recrystallized to obtain 2, 2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (shown in a formula I-c).
The above synthesis is detailed in FIG. 1.
Wherein the compound has the following nuclear magnetic test results of formula I-c:
1H NMR(400MHz,CDCl3)δ11.91(br,2H),8.11(s,2H),4.75(d,J＝7.0Hz,2H),4.59-4.34(m,2H),3.71(t,J＝6.8Hz,2H),1.59-1.40(m,4H),1.33-1.17(m,26H),0.84(t,J＝7.2Hz,3H)；.HRMS(FT-ICRMS)calcd for C24H41N2O9P(M-2H):266.1280,found:266.1287.
the obtained compound is identified as the target compound 2, 2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (shown in structural formula I-c).
Example 1
The raw material components in the embodiment are as follows: lubricating base oil (500SN, Thailand) 828g (viscosity at 100 ℃ C. is 10.9 mm)2(s), 8.3g of lithium hydroxide, and 103.5g of dodecahydroxystearic acid; 12g of 2, 6-di-tert-butyl-p-cresol; 9g of barium petroleum sulfonate; 8g of dialkyl dithiocarbamate; 8g of the biodegradation accelerator of preparation example 1;
firstly, 500g of base oil and 103.5g of dodecahydroxystearic acid are added into a grease making kettle, and the mixture is mixed and stirred uniformly. When the temperature is raised to 88 ℃, 80.7g of lithium hydroxide aqueous solution (containing 8.3g of lithium hydroxide and 72.4g of water) is added for saponification reaction for 30 min;
then, heating to 130 ℃ for dehydration reaction, adding 12g of 2, 6-di-tert-butyl-p-cresol after removing water, and continuously heating to 215 ℃ for high-temperature refining for 15 min;
after high-temperature refining, adding the rest 278g of base oil, cooling to 120 ℃, then adding 9g of barium petroleum sulfonate, 8g of dialkyl dithiocarbamate and 8g of biodegradation accelerator in preparation example 1, and uniformly stirring; grinding for 2-3 times by a three-roller machine to form grease. The product properties are shown in table 1.
Example 2
The raw material components in the embodiment are as follows: 1037g (viscosity at 100 ℃ C. of 10.9 mm) of lubricating base oil (500SN, Thailand)2S), 11.4g of lithium hydroxide and 141.8g of dodecahydroxystearic acid; 15g of 2, 6-di-tert-butyl-p-cresol; 11g of barium petroleum sulfonate; 10g of dialkyl dithiocarbamate; 10g of the biodegradation accelerator of preparation example 1;
first, 690g of base oil and 141.8g of dodecahydroxystearic acid were added to a grease preparing kettle, and mixed and stirred uniformly. When the temperature is raised to 88 ℃, 101.9g of lithium hydroxide aqueous solution (wherein, 11.4g of lithium hydroxide and 90.5g of water are contained) is added to carry out saponification reaction for 30 min;
then, heating to 130 ℃ for dehydration reaction, adding 15g of 2, 6-di-tert-butyl-p-cresol after removing water, and continuously heating to 220 ℃ for refining at high temperature for 10 min;
after high-temperature refining, adding the remaining 347g of base oil, cooling to 118 ℃, then adding 11g of barium petroleum sulfonate and 10g of dialkyl dithiocarbamate and 10g of biodegradation accelerator in preparation example 1, and uniformly stirring; grinding for 2-3 times by a three-roller machine to form grease. The product properties are shown in table 1.
Example 3
The raw material components in the embodiment are as follows: 708g (viscosity at 100 ℃ 10 mm) of lubricating base oil (PAO10, Exxon Mobil)2(s), 5.7g of lithium hydroxide, 71.5g of dodecahydroxystearic acid; 10.8g of 2, 6-di-tert-butyl-p-cresol; 6.3g of barium petroleum sulfonate; 7.2g of dialkyldithiocarbamate; 7.2g of the biodegradation accelerator of preparation example 1;
firstly, 475g of base oil and 71.5g of dodecahydroxystearic acid are added into a grease making kettle, and the mixture is mixed and stirred uniformly. When the temperature is raised to 91 ℃, 46.4g of lithium hydroxide aqueous solution (containing 4.7g of lithium hydroxide and 41.7g of water) is added for saponification reaction for 35 min;
then, heating to 130 ℃ for dehydration reaction, adding 10.8g of 2, 6-di-tert-butyl-p-cresol after removing water, and continuously heating to 215 ℃ for refining for 15min at high temperature;
after high-temperature refining, adding the rest 233g of base oil, cooling to 115 ℃, then adding 6.3g of barium petroleum sulfonate, 7.2g of dialkyl dithiocarbamate and 7.2g of biodegradation accelerator in preparation example 1, and uniformly stirring; grinding for 2-3 times by a three-roller machine to form grease. The product properties are shown in table 1.
Example 4
The raw material components in the embodiment are as follows: 708g (viscosity at 100 ℃ C. of 3.9 mm) of lubricating base oil (PAO4, Exxon Mobil)2S) hydrogen oxidation of5.67g of lithium, 70.77g of dodecahydroxystearic acid; 12g of 2, 6-di-tert-butyl-p-cresol; 7g of barium petroleum sulfonate; 8g of dialkyl dithiocarbamate; 8g of the biodegradation accelerator of preparation example 1;
first, 534g of base oil and 70.77g of dodecahydroxystearic acid were put into a grease making kettle, and mixed and stirred uniformly. When the temperature is raised to 92 ℃, 50.79g of lithium hydroxide aqueous solution (containing 5.67g of lithium hydroxide and 45.12g of water) is added to carry out saponification for 25 min;
then, heating to 135 ℃ for dehydration reaction, adding 12g of 2, 6-di-tert-butyl-p-cresol after removing water, and continuously heating to 220 ℃ for refining at high temperature for 10 min;
after high-temperature refining, the rest 267g of base oil is added, the temperature is reduced to 125 ℃, then 7g of barium petroleum sulfonate and 8g of dialkyl dithiocarbamate and 8g of biodegradation accelerator in preparation example 1 are added, and the mixture is stirred uniformly; grinding for 2-3 times by a three-roller machine to form grease. The product properties are shown in table 1.
Comparative example 1
A grease was prepared by the method of example 1 except that the biodegradation accelerator of preparation example 1 was not added. The product properties are shown in table 1.
TABLE 1
As can be seen from table 1 above, after the biodegradation accelerator of the present invention is added, the degradation performance of the grease is significantly improved, and other performances are not affected, thus the grease composition of the present invention has good degradation performance, ensures environmental friendliness, has little effect on other performances, still has good colloid stability, excellent mechanical stability and excellent antioxidant effect, and has good industrial application prospects.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (14)
1. The biodegradable lubricating grease composition is characterized by comprising, by mass, 70% -90% of lubricating base oil, 4% -30% of lithium-based thickening agent and 0.1% -5% of additive, wherein the sum of the content of the components of the lubricating grease composition is 100%, wherein the additive comprises a biodegradable accelerator, and is represented by a compound of the following formula I:
wherein X is phosphorus or boron, R1One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8-C18Alkyl group of (1).
2. A grease composition according to claim 1, wherein R is1Selected from methyl or isopropyl, R2Is selected from C12Alkyl or C14An alkyl group.
3. A grease composition according to claim 1, wherein R is1Is methyl, R2Is C14Alkyl and X is phosphorus.
4. A grease composition according to claim 1, wherein the lubricating base oil is selected from one or more of mineral oils, vegetable oils, ester oils, polyalphaolefins.
5. A grease composition according to claim 4, wherein the lubricating base oil comprises a vegetable oil, the vegetable oil constituting no more than 40% by mass of the grease composition.
6. Grease composition according to claim 1, characterized in that the lubricating baseThe kinematic viscosity of the base oil at 100 ℃ is 5mm2/s~60mm2/s。
7. The grease composition of claim 1, wherein the lithium-based thickener is obtained by reacting a fatty acid with lithium hydroxide, the lithium hydroxide accounts for 3.8-9.8% of the mass of the grease composition, and the fatty acid is selected from C12-C20A fatty acid.
8. The grease composition of claim 1, wherein the additive further comprises one or more of an antioxidant, a rust inhibitor, and an extreme pressure antiwear agent.
9. The lubricating grease composition of claim 8, wherein the antioxidant is selected from one or more of 2, 6-di-tert-butyl-p-cresol and phenyl-alpha-naphthylamine, the rust inhibitor is selected from one or more of barium dinonylnaphthalene sulfonate and barium petroleum sulfonate, and the extreme pressure antiwear agent is selected from one or more of thioaminoate and dialkyl dithiocarbamate.
10. A method of preparing a grease composition according to any one of claims 1 to 9, comprising the steps of:
33% -66% of lubricating base oil and C12-C20Adding fatty acid into the reaction kettle, and uniformly stirring;
heating the reaction kettle to 60-95 ℃, and adding a mixture of lithium hydroxide and water for saponification reaction;
continuously heating to 120-180 ℃ for dehydration reaction;
adding the rest lubricating base oil, cooling to 100-130 ℃, adding the biodegradation accelerator, and uniformly stirring to obtain the lubricating grease composition.
11. The method according to claim 10, wherein the saponification reaction time is 25min to 120 min.
12. The preparation method of claim 10, further comprising adding an antioxidant into the reaction kettle after the dehydration reaction, and continuously heating to 190-220 ℃ for high-temperature refining.
13. The method according to claim 12, wherein the time for the high-temperature refining is 5 to 20 min.
14. The preparation method of claim 10, further comprising adding an antirust agent and/or an extreme pressure antiwear agent into the reaction kettle after the temperature is reduced to 100-130 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120065110A1 (en) * | 2009-02-18 | 2012-03-15 | The Lubrizol Corporation | Compounds and a Method of Lubricating an Internal Combustion Engine |
| CN103254951A (en) * | 2012-02-17 | 2013-08-21 | 中国石油化工股份有限公司 | Additive composition, diesel oil composition, and method for increasing oxidation stability of biodiesel |
| CN110317668A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of lubricating grease and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120065110A1 (en) * | 2009-02-18 | 2012-03-15 | The Lubrizol Corporation | Compounds and a Method of Lubricating an Internal Combustion Engine |
| CN103254951A (en) * | 2012-02-17 | 2013-08-21 | 中国石油化工股份有限公司 | Additive composition, diesel oil composition, and method for increasing oxidation stability of biodiesel |
| CN110317668A (en) * | 2018-03-28 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of lubricating grease and preparation method thereof |
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