CN111057101B - Phosphoramidate compound and preparation method and application thereof - Google Patents
Phosphoramidate compound and preparation method and application thereof Download PDFInfo
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- CN111057101B CN111057101B CN201811201045.XA CN201811201045A CN111057101B CN 111057101 B CN111057101 B CN 111057101B CN 201811201045 A CN201811201045 A CN 201811201045A CN 111057101 B CN111057101 B CN 111057101B
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- cardanol
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- -1 Phosphoramidate compound Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 11
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 11
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 11
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- NQXBGROVTFATAB-UHFFFAOYSA-N n-[chloro(dimethylaminooxy)phosphoryl]oxy-n-methylmethanamine Chemical group CN(C)OP(Cl)(=O)ON(C)C NQXBGROVTFATAB-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 2
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 26
- 125000000217 alkyl group Chemical group 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 150000002431 hydrogen Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 244000226021 Anacardium occidentale Species 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000020226 cashew nut Nutrition 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 2
- SAZNCXWJWABJOR-UHFFFAOYSA-N 4-methylidenebenzotriazole Chemical compound C=C1C=CC=C2N=NN=C12 SAZNCXWJWABJOR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SBBZURPHBXCUCR-UHFFFAOYSA-N CCCCCCCCCCCCCCCC1=CC=CC(OP(ON(C)C)(ON(C)C)=O)=C1 Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(OP(ON(C)C)(ON(C)C)=O)=C1 SBBZURPHBXCUCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DOLNHNMENUZESU-UHFFFAOYSA-N bis(dimethylamino) hydrogen phosphate Chemical compound CN(C)OP(O)(=O)ON(C)C DOLNHNMENUZESU-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- WDPNDMPWBDGXDB-UHFFFAOYSA-N dichloro-hydroxy-imino-$l^{5}-phosphane Chemical compound NP(Cl)(Cl)=O WDPNDMPWBDGXDB-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QHCVPJWQCGJDFA-UHFFFAOYSA-N n-dichlorophosphorylaniline Chemical class ClP(Cl)(=O)NC1=CC=CC=C1 QHCVPJWQCGJDFA-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000008298 phosphoramidates Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IVTHSFJXIARUFL-UHFFFAOYSA-N triazanium;thiophosphate Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=S IVTHSFJXIARUFL-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- COTPAMORPWZHKE-UHFFFAOYSA-H trizinc;thiophosphate;thiophosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=O.[O-]P([O-])([O-])=S COTPAMORPWZHKE-UHFFFAOYSA-H 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/16—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-nitrogen bond
-
- 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
- C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
Landscapes
- 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)
- Lubricants (AREA)
Abstract
The invention provides an phosphoramidate compound, a preparation method and application thereof. The phosphoramidate compound has a structure shown in a general formula (I):the definition of each group is shown in the specification. The phosphoramidate compound has outstanding bearing capacity and excellent wear resistance, and can be used as an extreme pressure antiwear agent and applied to lubricating oil and lubricating grease.
Description
Technical Field
The invention relates to an phosphoramidate compound, in particular to an phosphoramidate compound which is suitable for being used as an extreme pressure antiwear agent.
Background
Lubrication is generally divided into fluid lubrication and boundary lubrication, and extreme pressure antiwear agents are indispensable additives in the boundary lubrication state, and can be adsorbed on or react with a metal surface to form an adsorption film or a reaction film so as to prevent abrasion or even fusion welding of the metal surface and improve the lubricity and the wear resistance of oil products. Mainly comprises a sulfur-containing extreme pressure antiwear agent, a chlorine-containing extreme pressure antiwear agent, a phosphorus-containing extreme pressure antiwear agent, a nitrogen-containing extreme pressure antiwear agent, a metal salt extreme pressure antiwear agent, a boron-containing extreme pressure antiwear agent and the like, the sulfur-phosphorus agent containing sulfur and phosphorus is widely used because of the characteristics of high bearing capacity, good compatibility, good multiple effects and the like.
Among extreme pressure antiwear agents currently widely used in the lubricating oil field are tricresyl phosphate (T306), ammonium thiophosphate (T307), phosphorothioate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), etc., but their antiwear and antifriction properties are to be further improved. CN 106317109a discloses a phosphorothioate extreme pressure antiwear agent, which is used as hydraulic oil or lubricating oil additive, and has better anti-rust performance, better antiwear performance, thermal stability, filterability and hydrolytic stability, but the antiwear and antifriction performance is not better than the prior art. CN 101724492B discloses a zinc thiophosphate type extreme pressure antiwear agent, which has better bearing capacity, oxidation stability and antiwear performance compared with T405, but the compared T405 additive belongs to an oiliness agent, and does not have bearing capacity and antiwear performance of the extreme pressure antiwear agent, so that the actual antiwear performance and bearing capacity of the extreme pressure antiwear agent cannot be measured.
The cardanol is a main component of cashew nut shell oil, is a natural phenolic compound, is an important agricultural and sideline product in cashew nut production, and has wide sources and huge reserves. The friction modifier which is prepared from the natural compounds with abundant sources and low cost and has better synthesis performance than the existing products is adopted, and meets the definition of green chemistry and the strategic requirements of national sustainable development.
Disclosure of Invention
The invention provides an phosphoramidate compound, a preparation method and application thereof.
The phosphoramidate compound has a structure shown in a general formula (I):
in the general formula (I), each group R 0 Are the same as or different from each other and are each independently selected from H, C 1 ～C 10 Straight-chain or branched alkyl, C 6 ～C 10 Aryl, (preferably C) 1 ～C 4 Straight-chain or branched alkyl, phenyl, C 1 ～C 4 Alkyl substituted phenyl); each group R 1 、R 2 、R 3 、R 4 、R 5 Are the same as or different from each other and are each independently selected from H, C 1 ～C 20 A linear or branched alkyl group and a group of the formula (II), each group R 1 、R 2 、R 3 、R 4 、R 5 At least one group of the formula (II);
wherein the radicals R 1 ' selected from single bond, C 1-20 Straight-chain or branched alkylene (preferably selected from single bond and C 1-4 Linear or branched alkylene groups); group R in m repeating units 2 ' are identical or different from each other and are each independently selected from single bonds, C 1-20 Straight-chain or branched alkylene groups (preferably each independently selected from single bond, C 1-4 Linear or branched alkylene groups); group R 3 ' selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 4 ' same or different from each other, each independently selected from hydrogen, C 1-20 Straight or branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 5 ' same or different from each other, each independently selected from hydrogen, C 1-20 Straight or branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); m is a positive integer (preferably a positive integer between 0 and 10, more preferably a positive integer between 1 and 3).
According to the invention, it is preferred that, in the general formula (I), the radical R 1 、R 3 、R 5 Each independently selected from H, C 1 ～C 4 Linear or branched alkyl; group R 2 、R 4 Each independently selected from H, C 1 ～C 20 A linear or branched alkyl group and a group of formula (II), wherein at least one group is a group of formula (II).
According to the invention, it is preferred that, in the general formula (I), the radical R 1 、R 3 、R 5 Each independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; group R 2 、R 4 One of the groups is a group represented by formula (II), and the other is H.
According to the present invention, it is preferable that in the general formula (I), the total carbon number of the group represented by the formula (II) is 2 to 30, preferably 6 to 20, more preferably 10 to 18.
The phosphoramidate compounds of the present invention may be selected from the following specific compounds or mixtures thereof in any ratio:
the process for producing an phosphoramidate compound of the present invention comprises a step of reacting a phenol compound represented by the general formula (X) with a phosphatation agent and optionally a hydrotreating step;
in the general formula (X), each group R 1 ”、R 2 ”、R 3 ”、R 4 ”、R 5 "same as or different from each other, each independently selected from H, C 1 ～C 20 A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y);
wherein the radicals R 1 "' is selected from single bond, C 1-20 Straight-chain or branched alkylene (preferably selected from single bond and C 1-4 Linear or branched alkylene groups); group R in m repeating units 2 "' are the same or different from each other and are each independently selected from a single bond, C 1-20 Straight-chain or branched alkylene groups (preferably each independently selected from single bond, C 1-4 Linear or branched alkylene groups); group R 3 "' is selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 4 "' are the same or different from each other and are each independently selected from hydrogen, C 1-20 Straight chainOr branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 5 "' are the same or different from each other and are each independently selected from hydrogen, C 1-20 Straight or branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); m is a positive integer (preferably a positive integer between 0 and 10, more preferably a positive integer between 1 and 3).
According to the preparation method of the present invention, in the general formula (X), preferably, the group R 1 ”、R 3 ”、R 5 "same as or different from each other, each independently selected from hydrogen, C 1-4 Linear or branched alkyl; group R 2 ”、R 4 "same as or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y).
According to the preparation method of the present invention, in the general formula (X), it is further preferable that the group R 1 ”、R 3 ”、R 5 "same as or different from each other, each independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; group R 2 ”、R 4 One of the groups is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the preparation method of the present invention, preferably, the structure of the phosphazene is as shown in formula (Z):
wherein each R 0 Each independently selected from H, C 1 ～C 10 Straight-chain or branched alkyl, C 6 ～C 10 Aryl, (preferably C) 1 ～C 4 Straight-chain or branched alkyl, phenyl, C 1 ～C 4 Alkyl substituted phenyl); the group A is selected from F, cl, br, I, H, OH (preferably Cl, br). Specifically, the phosphazene can be amino phosphoryl chloride or C 1 ～C 10 Alkyl amino phosphoryl chlorideOne or more, preferably C, of the phenylaminophosphoryl chlorides 1 ～C 10 Alkyl amino phosphoryl chloride.
According to the production method of the present invention, preferably, the conditions under which the phenol compound represented by the general formula (X) is reacted with the phosphazene are: the molar ratio between the phosphazene and the phenol compound shown in the general formula (X) is 1:1 to 10 (preferably 1:1 to 3); the reaction temperature is 50 ℃ -150 ℃ (preferably 60 ℃ -100 ℃); generally, the longer the reaction time, the higher the conversion, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the reaction of the phenol compound represented by the general formula (X) with the phosphazene, a catalyst may be added, or a catalyst may not be added, and a catalyst is preferably added. The catalyst is preferably C 1～10 For example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia may be used. The catalyst is preferably added in an amount of 0.1 to 60% by mass, more preferably 10 to 40% by mass, based on the mass of the phenol compound represented by the general formula (X). In the reaction of the phenol compound represented by the general formula (X) with the phosphazene, a solvent may be added, or a solvent may not be added, and it is preferable to add a solvent. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and toluene and/or xylene may be used, for example. The solvent is used in an amount of 50 to 500% (preferably 100 to 300%) based on the mass of the phenol compound represented by the general formula (X). The catalyst, solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying, and recrystallization, and is not particularly limited.
According to the production method of the present invention, after the reaction of the phenol compound represented by the general formula (X) with the phosphazene is completed, the reaction product may be subjected to a purification treatment, the method of which includes one or more of washing with water, distillation, filtration, drying and recrystallization methods, and is not particularly limited.
According to the production method of the present invention, the optional hydrotreating step may be performed by first hydrotreating the phenol compound represented by the general formula (X) and then reacting with the phosphazene, or may be performed by first reacting the phenol compound represented by the general formula (X) with the phosphazene and then hydrotreating the reaction product thereof. The hydrotreating step can increase the saturation of the reaction product.
According to the preparation method of the invention, the process conditions of the hydrotreatment are preferably as follows: the hydrogen pressure is 1.0-6.0 MPa (preferably 3.0-4.0 MPa), the temperature is 60-260 ℃ (preferably 180-220 ℃), and the time is 0.5-10 h (preferably 3-5 h). Preferably, a hydrogenation catalyst is added during the hydrotreating process. The hydrogenation catalyst may be any known hydrogenation catalyst in the art, and is not particularly limited. The hydrogenation catalyst is preferably a transition metal or carrier supported transition metal catalyst, for example, palladium carbon catalyst and Raney nickel can be selected. The addition amount of the hydrogenation catalyst is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, of the phenol compound represented by the general formula (X).
The phenolic compound shown in the general formula (X) is preferably derived from natural plant cashew nuts, and contains a large amount of cashew nut shell oil in cashew nut shells, wherein the main component is meta-phenol, which is commonly called cardanol, and the structure is as follows:
wherein R is C 15 H (31 +x), x is 0, -2, -4 or-6.
The phosphoramidate compound of the invention can be used as an extreme pressure antiwear agent and applied to lubricating oil and lubricating grease.
The preparation method of the phosphoramidate compound has the advantages of simplicity, convenience in operation, green and easily obtained raw materials, high product yield and high purity.
The phosphoramidate compound of the present invention has outstanding bearing capacity and excellent antiwear performance.
Drawings
FIG. 1 is an infrared spectrum of the product of example 3.
Detailed Description
The invention will now be further illustrated by, but is not limited to, the following examples.
The raw materials used are as follows:
cashew nut shell oil, shanghai Material racing technology Co., ltd, industrial products
Palladium-carbon catalyst (metallic palladium supported on activated carbon) with palladium content of 5% and available from New materials Co., ltd. In Shaanxi Ruike
Sodium bicarbonate, national pharmaceutical Congress chemical reagent Co., ltd., analytical grade
Bis (dimethylamino) chlorophosphate, national pharmaceutical chemicals Co., ltd., analytically pure
Triethylamine, national medicine group chemical reagent Co., ltd., analytical grade
Toluene, national medicine group chemical reagent Co., ltd., analytical grade
Petroleum ether, national medicine group chemical reagent Co., ltd., analytical grade
Dibutyl phosphite, national pharmaceutical systems chemical reagent Co., ltd., chemical purity
P-dodecylphenol, national medicine group chemical reagent Co., ltd., chemical purity
N, N-dibutenyl methylene benzotriazol carbofuran reagent Co, chemical purity
Extreme pressure antiwear agent T306, xingpu, institute of petroleum industry, industrial products
Extreme pressure antiwear agent T307, xingpu, institute of petro-chemical industry, industrial products
Extreme pressure antiwear agent IRGALUBE 349, manufactured by EFuton Corp., industrial products
EXAMPLE 1 preparation of m-pentadecyl phenol
100g of cardanol and 1.5g of palladium-carbon catalyst are put into a 200ml high-pressure reaction kettle, the high-pressure kettle is closed, hydrogen is introduced to 3.5MPa, stirring and heating are started, and the reaction is carried out for 4.5 hours at the temperature of 200 ℃. Cooling to 60 ℃ after the reaction is finished, taking out a viscous reaction mixture, carrying out reduced pressure distillation for 1h at 100Pa and 160 ℃, and cooling to obtain a milky solid. Dissolving the product with petroleum ether, crystallizing and purifying to obtain m-pentadecyl phenol with purity over 98% and reaction conversion rate of 83.6%.
Example 2 preparation of cardanol bis (dimethylamino) phosphate
20g of cardanol, 4g of triethylamine and 20g of toluene are added into a reaction bottle, heating and stirring are started, 12g of bis (dimethylamino) chlorophosphoric acid is added, the reaction temperature is maintained at 70 ℃, and the reaction is carried out for 5 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150deg.C for 1 hr to remove water and solvent to obtain brownish red viscous liquid with reaction conversion rate of 91.2%.
EXAMPLE 3 preparation of (3-pentadecylphenyl) bis (dimethylamino) phosphate
20g of the m-pentadecyl phenol obtained in example 1, 8g of triethylamine and 50g of toluene were charged into a reaction flask, and 5.5g of bis (dimethylamino) chlorophosphoric acid was added while stirring with heating, and the reaction temperature was maintained at 90℃for 4 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150 deg.C for 1 hr to remove water and solvent to obtain brown yellow product with reaction conversion rate of 92.8%.
EXAMPLE 4 preparation of (3-pentadecylphenyl) bis (dimethylamino) phosphate
20g of the m-pentadecyl phenol obtained in example 1, 8g of triethylamine and 60g of toluene were charged into a reaction flask, heating and stirring were started, 4g of bis (dimethylamino) chlorophosphate was added, and the reaction temperature was maintained at 80℃for 5 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150 deg.C for 1 hr to remove water and solvent to obtain brown yellow product with reaction conversion rate of 91.9%.
EXAMPLE 5 preparation of (4-dodecylbenzene) phenol bis (dimethylamino) phosphate
20g of p-dodecylphenol, 8g of triethylamine and 60g of toluene are added into a reaction flask, heating and stirring are started, 4g of bis (dimethylamino) chlorophosphoric acid is added, and the reaction temperature is maintained at 80 ℃ for 5 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150 deg.C for 1 hr to remove water and solvent to obtain brown yellow product with reaction conversion rate of 94.8%.
Comparative example 1
19.4g of dibutyl phosphite and 25.6g of N, N-dibutyrylene methylene benzotriazole are poured into a flask, the flask is placed in a constant temperature water bath (the temperature is controlled at 80 ℃), stirring is started, 1.35g of hydrochloric acid solution containing 0.5g of HCl is dropwise added, the temperature is raised to 120 ℃, stirring reaction is continued for 2 hours, and after the reaction is finished, the (N-butyl-N-butenyl) methylene benzotriazole dibutyl phosphite is obtained through reduced pressure distillation.
Example 6
The products of examples 2, 3, 4, and 5, T306, T307, IRGALUBE 349, and the product of comparative example 1 were dissolved in mineral oil 150SN, respectively, to prepare a composition having a mass fraction of 0.5%. These compositions were tested for antiwear properties using an SRV vibration friction tester under the following conditions: 100N, 200N, 300N, frequency 50Hz, amplitude 1mm,30℃for 1h. The test results are shown in Table 1.
TABLE 1
Example 7
The product prepared in example 3 was subjected to infrared spectrum analysis, the spectrum is shown in FIG. 1, and the analysis results are shown in Table 2.
TABLE 2 Infrared analysis results of example 3 products
Claims (5)
1. A preparation method of phosphoramidate compound comprises the steps of reacting cardanol or m-pentadecyl phenol with a phosphazene; the phosphazene is bis (dimethylamino) chlorophosphoric acid; the reaction conditions of the cardanol or the m-pentadecyl phenol and the phosphazene are as follows: the mol ratio between the phosphazene and cardanol or m-pentadecyl phenol is 1:1 to 10; the reaction temperature is 50-150 ℃.
2. The process according to claim 1, wherein the cardanol or m-pentadecyl phenol is reacted with a phosphazene under the following conditions: the mol ratio between the phosphazene and cardanol or m-pentadecyl phenol is 1:1 to 3; the reaction temperature is 60-100 ℃.
3. A process according to claim 1, wherein a catalyst is added to the reaction of cardanol or m-pentadecyl phenol with the phosphazene, said catalyst being C 1～10 Organic and inorganic ammonium.
4. An phosphoramidate compound produced according to the process of any one of claims 1 to 3 for use as an extreme pressure antiwear agent.
5. An phosphoramidate compound produced by the process according to any one of claims 1 to 3 for use as an extreme pressure antiwear agent for lubricating oils or greases.
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| US2385713A (en) * | 1944-02-03 | 1945-09-25 | Monsanto Chemicals | Amidophosphates |
| GB1070314A (en) * | 1964-01-31 | 1967-06-01 | Shell Int Research | Improvements in or relating to lubricant compositions |
| JPH0827170A (en) * | 1994-07-13 | 1996-01-30 | Ikari Yakuhin Kk | Organophosphorus agent and herbicide, germicide and insecticide containing the same agent as active component |
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| "A facile synthesis of benzo[b]furan derivatives including naturally occurring neolignans via regioselective of ortho-cresols using the bis(dimethylamino)phosphoryl group as a directing group";Mitsuaki Watanabe等;《Chem.Pharm.Bull.》;19910131;第39卷(第1期);第41-48页 * |
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