CN112759612B - Lubricating oil biodegradation accelerant and preparation method thereof - Google Patents
Lubricating oil biodegradation accelerant and preparation method thereof Download PDFInfo
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- CN112759612B CN112759612B CN201911000341.8A CN201911000341A CN112759612B CN 112759612 B CN112759612 B CN 112759612B CN 201911000341 A CN201911000341 A CN 201911000341A CN 112759612 B CN112759612 B CN 112759612B
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 31
- 238000006065 biodegradation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 25
- 235000002906 tartaric acid Nutrition 0.000 claims description 25
- 239000011975 tartaric acid Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000013067 intermediate product Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 13
- 230000002140 halogenating effect Effects 0.000 claims description 13
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- -1 1-ethyl- (3-dimethylaminopropyl) Chemical group 0.000 claims description 11
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 230000006340 racemization Effects 0.000 claims description 9
- 238000010517 secondary reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 7
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- MZSPRSJAOSKAAT-ZDUSSCGKSA-N 4-(3-methylbut-2-enyl)-L-tryptophan Chemical compound CC(C)=CCC1=CC=CC2=C1C(C[C@H]([NH3+])C([O-])=O)=CN2 MZSPRSJAOSKAAT-ZDUSSCGKSA-N 0.000 claims description 4
- MZSPRSJAOSKAAT-UHFFFAOYSA-N 4-Dimethylallyltryptophan Natural products CC(C)=CCC1=CC=CC2=C1C(CC(N)C(O)=O)=CN2 MZSPRSJAOSKAAT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 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 claims description 4
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052796 boron Chemical group 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 9
- 150000007530 organic bases Chemical class 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002199 base oil Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- 125000005233 alkylalcohol group Chemical group 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 3
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 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 3
- 229940043348 myristyl alcohol Drugs 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 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
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 101150092791 PAO4 gene Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010696 ester oil Substances 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a lubricating oil biodegradation accelerant and a preparation method thereof, the lubricating oil biodegradation accelerant is a compound shown in the following formula I, wherein X is phosphorus or boron, R 1 One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R 2 Is selected from C 8 ‑C 18 Alkyl group of (1). When the compound of the formula I is used as a biodegradation accelerator, the biodegradation rate of lubricating oil can be effectively improved, and the compound has the advantages of low price of synthetic raw materials, mild reaction, suitability for large-scale industrial production and good industrial development potential.
Description
Technical Field
The invention relates to the field of lubricating oil additives, in particular to a lubricating oil biodegradation accelerant and a preparation method thereof.
Background
Lubricating oil is a necessary working medium in the normal operation of mechanical equipment and the manufacturing and processing processes of materials, and along with the rapid development of industry, the demand of the lubricating oil is more and more increased. During the storage, transportation and use of the lubricating oil, the situations of leakage, overflow and improper discharge of various polluted environments can not be avoided. Although the acute toxicity of the lubricating oil to organisms is very small, and there are reports about poisoning caused by contacting the lubricating oil, the lubricating oil entering the environment seriously pollutes the land, rivers and lakes due to poor biodegradability, and meanwhile, the ecological balance can be influenced by the accumulation of the lubricating oil in the environment, so that a biodegradation accelerator is urgently needed to improve the biodegradation rate of the lubricating oil.
In recent years, the influence of waste and leaked lubricating oil on the environment has attracted much attention, and in order to solve the problem, research is mainly focused on two aspects, namely, research and development of easily biodegradable lubricating base oil, such as biodegradable vegetable oil or ester synthetic oil, for example, a biodegradable lubricating oil composition is reported in patent CN102408939B, a biodegradable industrial gear oil composition is reported in patent CN105132104a, and the like; another aspect is the development of environmentally friendly additives for readily biodegradable base oils, for example, patent CN103642557B reports a chemical formula C 20 H 37 NO 3 Amide-type lubricating oil biodegradation accelerator.
However, there are still few reports on the biodegradation accelerator for lubricating oil, and the degradation effect on mineral oil or poly-alpha-olefin 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
It is a primary object of the present invention to overcome at least one of the above-mentioned drawbacks of the prior art and to provide a lubricant biodegradation accelerator and a method for preparing the same, which can synthesize a lubricant additive for accelerating the biodegradation of a lubricant in high yield from a conventionally available tartaric acid raw material. The method has the advantages of low raw material price, mild reaction conditions, strong biodegradation promoting capability and great industrialization potential.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a compound of formula I as shown below:
wherein X is phosphorus or boron, R 1 One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R 2 Is selected from C 8 -C 18 Alkyl group of (1).
According to one embodiment of the invention, R 1 Selected from methyl or isopropyl, R 2 Is selected from C 12 Alkyl or C 14 An alkyl group.
According to one embodiment of the invention, R 1 Is methyl, R 2 Is C 14 Alkyl and X is phosphorus.
The present invention also provides a process for the preparation of a compound of formula I as described above, comprising:
tartaric acid and a compound shown as a formula II are mixed in a first solvent for carrying out a primary reaction to obtain a first intermediate product, wherein R is 3 Is methyl, ethyl, tert-butyl or benzyl;
reacting a halogenating agent with a compound of formula III (R) 2 OH) compound is mixed in a second solvent and placed in a reactor for secondary reaction, obtaining a second intermediate product, wherein the halogenating agent is selected from phosphorus trichloride, phosphorus tribromide,One or more of phosphorus oxychloride, phosphorus oxybromide, boron tribromide and boron trichloride;
mixing the first intermediate product in a third solvent, adding the mixture into the reactor, and carrying out three times of reaction with the second intermediate product to obtain a third intermediate product;
and carrying out hydrolysis reaction on the third intermediate product to obtain the compound shown in the formula I.
According to one embodiment of the present invention, the first solvent is selected from one or more of dichloromethane, chloroform, acetone, ethyl acetate, N-dimethylformamide, dimethyl sulfoxide and acetonitrile; the second solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile; the third solvent is one or more selected from tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile.
According to one embodiment of the present invention, the molar ratio of the tartaric acid to the compound of formula II is 1:5 to 5:1, and the concentration of the tartaric acid in the primary reaction system is 0.2 mol/l to 1.0 mol/l.
According to an embodiment of the present invention, the method further comprises adding a condensing agent selected from one or more of Dicyclohexylcarbodiimide (DCC), 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (edihcl), 4-dimethylallyl tryptophan (DMAT) to the primary reaction system, wherein the molar ratio of the tartaric acid to the condensing agent is 1:3 to 3:1.
according to an embodiment of the invention, a racemization inhibitor is added into the primary reaction system, the racemization inhibitor is selected from one or more of 1-hydroxybenzotriazole, N-hydroxysuccinimide (HOSu), 1-hydroxy-7-azobenzotriazol (HOAt), 3-hydroxy-1,2,3-benzotriazin-4 (3H) -one (HOBt), and the molar ratio of tartaric acid to the racemization inhibitor is 1:3 to 3:1.
according to one embodiment of the invention, the molar ratio of tartaric acid to the halogenating agent is (0.95-1.05): 1 and the molar ratio of the halogenating agent to the compound of formula III is 1:3-3:1.
According to one embodiment of the invention, the reaction temperature of the primary reaction is-20 ℃ to 40 ℃, and the reaction time of the primary reaction is 1h to 48h; the reaction temperature of the secondary reaction is-20 ℃ to 40 ℃, and the reaction time of the secondary reaction is 0.1h to 30h; the temperature of the third reaction is-20 ℃ to 40 ℃, and the reaction time of the third reaction is 0.1h to 30h.
The invention also provides application of the compound shown in the formula I as a lubricating oil biodegradation accelerator.
According to the technical scheme, the compound of the formula I and the application thereof as the lubricating oil biodegradation accelerant have the advantages and positive effects that:
the invention provides a novel compound of formula I and a preparation method thereof, wherein the synthetic route 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 compound 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.
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 example 1 of the present invention;
FIG. 2 is a synthesis scheme of example 2 of the present invention;
FIG. 3 is a synthetic scheme of example 3 of the present invention.
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 be limiting. 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 numerical ranges, combinations of values between the endpoints of each of the ranges, between the endpoints of each of the ranges and individual values, and between individual values can result in one or more new numerical ranges, and such numerical ranges should be considered as being specifically disclosed herein.
The present invention provides a compound of formula I as shown below:
wherein X is phosphorus or boron, R 1 One or more selected from methyl, isopropyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R 2 Is selected from C 8 -C 18 Alkyl group of (1).
The lubricating oil according to the present invention is typically a mineral oil, a vegetable oil, an ester oil, a polyalphaolefin, or the like. Although synthetic esters and vegetable oils are biodegradable lubricating oils that are currently advocated for use, mineral oils, polyalphaolefins, and the like generally dominate the lubricant base oil market due to their low cost and good performance. How to improve the degradation rate of the lubricating oil difficult to degrade is of great significance. In the case of mineral oils, they are difficult to degrade, not only because of their structure, but also because they are poorly soluble in water. The compound of the formula I is used as an amino acid type surfactant taking tartaric acid as a framework, is favorable for 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 some embodiments, preferably, the aforementioned R 1 Selected from methyl or isopropyl, R 2 Is selected from C 12 Alkyl or C 14 An alkyl group. More preferably, R 1 Is methyl, R 2 Is C 14 Alkyl and X is phosphorus.
The invention also provides a preparation method of the compound of the formula I, which 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 R 3 Is 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 to 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 to 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 48h. 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) 2 OH) 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. C 8 -C 18 The alkyl 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 to 3:1, preferably 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 30h. 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 30h. 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-pass 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 after dripping until the reaction is finished. After the reaction, carrying out suction filtration, washing, drying, filtering, spin-drying and other steps 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 using weak base such as lithium hydroxide, and the final compound of 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 tartaric acid raw material which is easy to obtain, 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 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.
Example 1
This example illustrates the synthesis of 2,2' - ((2-dodecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutanoic acid) (see structure I-a).
1) 100mL of DMF, tartaric acid (33.3 mmol,5 g), L-valine methyl ester hydrochloride (73.2 mmol, 12.27g), 1-hydroxybenzotriazole (79.9mmol, 10.8g) and pyridine (8 mL) are sequentially added into a reactor, the temperature is reduced to 0 ℃, DCC (79.9mmol, 16.5g) is added, and the reaction is carried out 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) Dissolving phosphorus trichloride (40mmol, 5.48g) in 5mL of n-hexane, cooling to 4 ℃, dissolving triethylamine (40mmol, 4.04g) in 25mL of trichloroethylene, adding lauryl alcohol (27mmol, 5 g) in 40mL of trichloroethylene, and slowly dropping into the reaction kettle. After the addition, the temperature was raised to room temperature and stirring was continued for 1 hour.
3) Taking the white solid (30mmol, 10.44g) 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, 11.81g) was dissolved in 200mL of a mixed solution of tetrahydrofuran: water =2:1, and a lithium hydroxide solid (200mmol, 5 g) was added thereto, reacted at room temperature overnight, the tetrahydrofuran was removed by rotary evaporation, acidified to pH =4 with a 10% hydrochloric acid solution, and suction-filtered to obtain a white solid. Acetone recrystallization afforded 2,2' - ((2-dodecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutanoic acid) (formula I-a).
The above synthesis is detailed in FIG. 1.
Wherein the compound has the following nuclear magnetic test result of formula I-a:
1 H NMR(400MHz,CDCl 3 )δ11.75(br,2H),8.01(s,2H),4.71(d,J＝6.8Hz,2H),4.32(d,J＝7.2Hz,2H),3.76(t,J＝6.4Hz,2H),2.03-1.88(m,2H),1.77-1.59(m,4H),1.33-1.17(m,16H),0.99(d,J＝7.2Hz,12H),0.80(t,J＝7.0Hz,3H)；.HRMS(FT-ICRMS)calcd for C 26 H 45 N 2 O 9 P(M-2H):280.1437,found:280.1441.
the compound obtained was identified as the target compound 2,2' - ((2-dodecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutanoic acid) (see structural formula I-a).
Example 2
This example illustrates the synthesis of 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutanoic acid) (see structure I-b).
1) 100mL of DMF, tartaric acid (33.3 mmol,5 g), L-valine methyl ester hydrochloride (73.2 mmol, 12.27g), 1-hydroxybenzotriazole (79.9mmol, 10.8g) and pyridine (8 mL) are sequentially added into a reactor, the temperature is reduced to 0 ℃, DCC (79.9mmol, 16.5g) is added, and the reaction is carried out 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 deg.C, 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, 10.44g) 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, 11.81g) was dissolved in 200mL of a mixed solution of tetrahydrofuran: water =2:1, and a lithium hydroxide solid (200mmol, 5 g) was added thereto, reacted at room temperature overnight, the tetrahydrofuran was removed by rotary evaporation, acidified to pH =4 with a 10% hydrochloric acid solution, and suction-filtered to obtain a white solid. Acetone recrystallization afforded 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutyric acid) (formula I-b)
The above synthesis is detailed in FIG. 2.
Wherein the compound has the following nuclear magnetic test result of formula I-b:
1 H NMR(400MHz,CDCl 3 )δ11.79(br,2H),8.11(s,2H),4.77(d,J＝6.4Hz,2H),4.37(d,J＝7.0Hz,2H),3.75(t,J＝6.4Hz,2H),2.05-1.89(m,2H),1.79-1.57(m,4H),1.34-1.18(m,16H),0.98(d,J＝7.2Hz,16H),0.81(t,J＝7.0Hz,3H)；.HRMS(FT-ICRMS)calcd for C 28 H 49 N 2 O 9 P(M-2H):294.1593,found:294.1601.
the compound was identified as 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-bis (3-methylbutyric acid) of interest (see structural formula I-b).
Example 3
This example illustrates 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-dipropionic acid (see structure I-c).
1) To the reactor were added sequentially 100mL of DMF, tartaric acid (33.3 mmol,5 g), L-alanine methyl ester hydrochloride (73.2 mmol,10.2 g), 1-hydroxybenzotriazole (79.9 mmol,10.8 g), and pyridine (8 mL), and then the mixture was cooled to 0 ℃ and DCC (79.9 mmol,16.5 g) was added and reacted 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 deg.C, 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: water =2:1, and a lithium hydroxide solid (200mmol, 5 g) was added thereto, reacted at room temperature overnight, the tetrahydrofuran was removed by rotary evaporation, acidified to pH =4 with a 10% hydrochloric acid solution, and suction-filtered to obtain a white solid. Acetone recrystallization afforded 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-dipropionic acid (shown in formula I-c).
The above synthesis is detailed in FIG. 3.
Wherein the compound of formula I-c has the following nuclear magnetic test results:
1 H NMR(400MHz,CDCl 3 )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 C 24 H 41 N 2 O 9 P(M-2H):266.1280,found:266.1287.
the compound obtained is identified as target compound 2,2' - ((2-tetradecyloxy) -1,3,2-dioxolane-4,5-dicarbonyl) -diamino-dipropionic acid (see structural formula I-c).
Test example
The compounds obtained in the above examples 1 to 3 were added to the lubricating oil in a proportion of 1% as biodegradation accelerators, respectively, and the biodegradation accelerating function of the lubricating oil was remarkable as measured by the method OECD302B, and the results of the biodegradation rates thereof are shown in table 1 below.
TABLE 1
| Lubricating oil name | Example 1 | Example 2 | Example 3 | Blank group |
| HVI 350 | 71.7％ | 79.4％ | 83.9％ | 23.5％ |
| PAO4 | 76.5％ | 84.3％ | 85.7％ | 25.7％ |
| PAO10 | 68.4％ | 71.3％ | 77.4％ | 22.3％ |
As can be seen, the compound of formula I synthesized by the invention has good biodegradation effect when being used as a lubricating oil additive. And the compound has low price of synthetic raw materials and mild reaction, is suitable for large-scale industrial production and has good industrial development potential.
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 (11)
1. A compound of formula I as shown below:
wherein X is phosphorus, R 1 One or more selected from methyl, isopropyl, 2-methylpropyl and 1-methylpropyl, R 2 Is selected fromC 8 -C 18 The alkyl group of (1).
2. A compound of claim 1, wherein R is 1 Selected from methyl or isopropyl, R 2 Is selected from C 12 Alkyl or C 14 An alkyl group.
3. A compound of claim 1, wherein R is 1 Is methyl, R 2 Is C 14 Alkyl and X is phosphorus.
4. A process for the preparation of a compound of formula I as claimed in any one of claims 1 to 3, comprising:
tartaric acid and a compound shown in a formula II are mixed in a first solvent for carrying out a primary reaction to obtain a first intermediate product, wherein R is 3 Is methyl, ethyl, tert-butyl or benzyl;
reacting a halogenating agent with a compound of formula III (R) 2 OH) compound is mixed in a second solvent and placed in a reactor for secondary reaction to obtain a second intermediate product, wherein the halogenated reagent is selected from one or more of phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, phosphorus oxybromide, boron tribromide and boron trichloride;
mixing the first intermediate product in a third solvent, adding the mixture into the reactor, and carrying out three times of reaction with the second intermediate product to obtain a third intermediate product;
and carrying out hydrolysis reaction on the third intermediate product to obtain the compound shown in the formula I.
5. The method according to claim 4, wherein the first solvent is one or more selected from the group consisting of dichloromethane, chloroform, acetone, ethyl acetate, N-dimethylformamide, dimethylsulfoxide and acetonitrile; the second solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, normal hexane, trichloroethylene and acetonitrile; the third solvent is one or more selected from tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile.
6. The method according to claim 4, wherein the molar ratio of tartaric acid to the compound of formula II is 1:5 to 5:1, and the concentration of tartaric acid in the primary reaction system is 0.2 mol/l to 1.0 mol/l.
7. The method according to claim 4, further comprising adding a condensing agent selected from one or more of dicyclohexylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, and 4-dimethylallyl tryptophan to the primary reaction system, wherein the molar ratio of the tartaric acid to the condensing agent is 1:3 to 3:1.
8. the preparation method of claim 7, further comprising adding a racemization inhibitor to the primary reaction system, wherein the racemization inhibitor is selected from one or more of 1-hydroxybenzotriazole, N-hydroxysuccinimide, 1-hydroxy-7-azobenzotriazol, and 3-hydroxy-1,2,3-benzotriazin-4 (3H) -one, and the molar ratio of the tartaric acid to the racemization inhibitor is 1:3 to 3:1.
9. the method of claim 4, wherein the molar ratio of tartaric acid to the halogenating agent is (0.95-1.05): 1, and the molar ratio of the halogenating agent to the compound of formula III is 1:3-3:1.
10. The preparation method according to claim 4, wherein the reaction temperature of the primary reaction is-20 ℃ to 40 ℃, and the reaction time of the primary reaction is 1h to 48h; the reaction temperature of the secondary reaction is-20 ℃ to 40 ℃, and the reaction time of the secondary reaction is 0.1h to 30h; the temperature of the third reaction is-20 ℃ to 40 ℃, and the reaction time of the third reaction is 0.1h to 30h.
11. Use of a compound of formula I according to any one of claims 1 to 3 as a lubricating oil biodegradation accelerator.
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