CN111057103A - Thiophosphonate compound and preparation method and application thereof - Google Patents
Thiophosphonate compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN111057103A CN111057103A CN201811201076.5A CN201811201076A CN111057103A CN 111057103 A CN111057103 A CN 111057103A CN 201811201076 A CN201811201076 A CN 201811201076A CN 111057103 A CN111057103 A CN 111057103A
- Authority
- CN
- China
- Prior art keywords
- group
- straight
- independently selected
- radical
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 40
- 150000002431 hydrogen Chemical class 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 ester compound Chemical class 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 9
- 244000226021 Anacardium occidentale Species 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229920000098 polyolefin Chemical group 0.000 claims description 2
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical group ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 235000020226 cashew nut Nutrition 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 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 description 4
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 4
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000746 purification Methods 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KBFJHOCTSIMQKL-UHFFFAOYSA-N 3-methoxycarbonylbut-3-enoic acid Chemical compound COC(=O)C(=C)CC(O)=O KBFJHOCTSIMQKL-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000004566 IR spectroscopy Methods 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- DQNJHGSFNUDORY-UHFFFAOYSA-N bis(2-ethylhexoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCC(CC)COP(S)(=S)OCC(CC)CCCC DQNJHGSFNUDORY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 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
- NAKDJXIEBCHXIZ-UHFFFAOYSA-N dihydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)C1=CC=CC=C1 NAKDJXIEBCHXIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 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
- 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
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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with 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
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
- C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
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)
Abstract
The invention provides a thiophosphonate compound and a preparation method and application thereof. The structure of the thiophosphonate compound is shown as the general formula (I):
the definition of each group is shown in the specification. The thiophosphonate compound of the present invention may be used as extreme pressure antiwear agent and in lubricating oil and grease. The thiophosphonate compound of the present invention has outstanding bearing capacity and excellent antiwear and antifriction performance.
Description
Technical Field
The present invention relates to a thiophosphonate compound, and in particular to a thiophosphonate compound suitable for use as an antiwear agent.
Background
The lubrication is generally divided into fluid lubrication and boundary lubrication, and in the boundary lubrication state, an extreme pressure antiwear agent is an essential additive and can be adsorbed on a metal surface or react with the metal surface to form an adsorption film or a reaction film so as to prevent the metal surface from being scratched or even melted and welded and be used for improving the lubricity and the antiwear property of an oil product. The sulfur-phosphorus-containing extreme pressure antiwear additive 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, wherein the sulfur-phosphorus-containing extreme pressure antiwear additive simultaneously contains sulfur and phosphorus and is widely applied due to the characteristics of high bearing capacity, good compatibility, good multiple-effect and the like.
The extreme pressure antiwear agents widely used in the field of lubricating oil at present include tricresyl phosphate (T306), ammonium thiophosphate (T307), thiophosphate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), and the like, but their antiwear and antifriction properties need to be further improved. CN 106317109A discloses a thiophosphate extreme pressure antiwear agent, which is used as a hydraulic oil or lubricating oil additive and shows better antirust performance, better antiwear performance, thermal stability, filterability and hydrolytic stability, but the antiwear and antifriction performance of the thiophosphate extreme pressure antiwear agent is not superior to that of the prior art. CN 101724492B discloses a zinc thiophosphate type extreme pressure antiwear agent, which has better bearing capacity, anti-oxidation stability and antiwear property compared with T405, but the compared T405 additive belongs to an oiliness agent and does not have the bearing capacity and antiwear property of the extreme pressure antiwear agent, so that the real antiwear and antifriction properties and the 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 for cashew nut production, and is wide in source and huge in storage amount. The friction modifier with the advantages of rich sources and low cost is used as a raw material to synthesize the friction modifier with better performance than the existing product, and meets the definition of green chemistry and the strategic requirements of national sustainable development.
Disclosure of Invention
The invention provides a thiophosphonate compound and a preparation method and application thereof.
The structure of the thiophosphonate compound is shown as the general formula (I):
in the general formula (I), the radical R0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14Alkylphenyl radicals); each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from H, C1～C20A linear or branched alkyl group and a group of the formula (II), each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by the formula (II);
wherein the radical R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radical R in m repeating units5' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain 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, preferably, in the general formula (I), the radicals R1、R5Each independently selected from H, C1～C4A linear or branched alkyl group; each radical R2、R4Each independently selected from C1～C20Straight-chain or branched alkyl and a radical of the formula (II), R3Each independently selected from H and C1～C20Straight or branched chain alkyl.
According to the invention, preferably, in the general formula (I), the radicals R1、R5Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; each radical R2At least one group of (A) is a group of formula (II), each group R4At least one group in (A) is a group of formula (II), R3Each independently selected from H and C1～C20Straight or branched chain alkyl.
According to the invention, preferably, in the general formula (I), the radicals R1、R5Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; radicals R bound to the same benzene ring2、R4One group is a group represented by formula (II), and the other is H; r3Each independently selected from H and C1～C20Straight or branched chain alkyl.
The thiophosphonate compounds of the present invention may be selected from the following specific compounds or mixtures thereof in any proportion:
the process for producing a thiophosphonate compound of the present invention comprises a step of reacting a phenol compound represented by the general formula (X) with a thiophosphoryl acylating agent and optionally a step of hydrotreating;
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), 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 radical R1"' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2"'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); radical R in m repeating units5"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain 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 process of the present invention, in the general formula (X), preferably, the group R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-20A 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 process of the present invention, in the general formula (X), further preferably, the group R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4One group in "is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the preparation process of the present invention, in the general formula (X), more preferably, the group R1Is selected from C1-4Straight or branched alkyl, R5"is selected from hydrogen; radical R3"is selected from hydrogen and C1-4A linear or branched alkyl group; radical R2"is selected from hydrogen, R4"is selected from the group represented by the general formula (Y).
According to the preparation method of the invention, preferably, the structure of the sulfur-phosphorus acylating agent is shown as the formula (Z):
wherein R is0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14Alkyl phenyl, C1-30Straight or branched chain alkyl); the group A is selected from F, Cl, Br, I, OH (preferably Cl, Br). Specifically, the thiophosphoryl chloride, thiophosphonyl dichloride and C can be selected as the thiophosphoryl acylating agent1-300One or more of a straight-chain or branched alkyl thiophosphonyl dichloride and a phenyl thiophosphonyl dichloride (preferably a phenyl thiophosphonyl dichloride).
According to the production process of the present invention, it is preferable that the phenol compound represented by the general formula (X) is reacted with a thiophosphoryl acylating agent under the conditions: the molar ratio of the sulfur-phosphorus acylating agent to the phenol compound represented by the general formula (X) is 1: 1 to 10 (preferably 1: 1 to 5); the reaction temperature is 50-150 ℃ (preferably 60-100 ℃); in general, the conversion is higher as the reaction time is longer, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the reaction, a catalyst may or may not be added, and preferably a catalyst is added.The catalyst is preferably C1～10The organic amine and inorganic ammonium of (b) may be selected from, for example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia. The amount of the catalyst added is preferably 0.1 to 60%, more preferably 10 to 40% by mass of the phenol compound. In the reaction, a solvent may or may not be added, and preferably a solvent is added. The solvent is preferably one or more of toluene, xylene, petroleum ether and cyclohexane, and for example, toluene and/or xylene may be used. The amount of the solvent to be used is 50 to 500% (preferably 100 to 300%) by mass of the phenol compound represented by the general formula (X). The catalyst and the solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying and recrystallization, and are not particularly limited.
According to the preparation method of the present invention, after the reaction is completed, the reaction product may be subjected to a purification treatment, and the purification treatment may include one or more of water washing, distillation, filtration, drying and recrystallization methods, and is not particularly limited.
According to the production process of the present invention, the optional hydrotreating step may be carried out by hydrotreating the phenol compound represented by the general formula (X) and then reacting it with a sulfur-phosphorus acylating agent, or may be carried out by reacting the phenol compound represented by the general formula (X) with a sulfur-phosphorus acylating agent and then hydrotreating the reaction product thereof. The hydrotreating step can increase the saturation of the reaction products.
According to the preparation method of the invention, the process conditions of the hydrotreatment are preferably as follows: hydrogen pressure is 1.0-6.0 MPa (preferably 3.0-4.0 MPa), temperature is 60-260 deg.C (preferably 180-220 deg.C), and 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 hydrogenation catalyst known in the art, and is not particularly limited. The hydrogenation catalyst is preferably a transition metal or a transition metal catalyst supported on a carrier, and for example, a palladium carbon catalyst or Raney nickel can be selected. The amount of the hydrogenation catalyst to be added is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the mass of the phenol compound represented by the general formula (X).
The phenol compound represented by the general formula (X) of the present invention is preferably derived from a natural plant cashew nut, contains a large amount of cashew nut shell oil in the cashew nut shell, contains meta-phenol as a main component, is generally called cardanol, and has the following structure:
wherein R is C15H(31+x)And x is 0, -2, -4 or-6.
The thiophosphonate compound of the present invention may be used as extreme pressure antiwear agent and in lubricating oil and grease.
The preparation method of the thiophosphonate compound is simple, convenient to operate, green and easily available in raw materials, high in product yield and high in purity.
The thiophosphonate compound of the present invention has outstanding bearing capacity and excellent antiwear and antifriction performance.
Drawings
FIG. 1 is an IR spectrum of the product of example 3.
Detailed Description
The raw materials used were as follows:
cashew nut shell oil, Shanghai Bingsheng chemical science and technology Limited, Industrial products;
palladium carbon catalyst (palladium metal supported on activated carbon), new materials of Shaanxi ruike ltd, palladium content is 5%;
sodium bicarbonate, national pharmaceutical group chemical reagents ltd, analytically pure;
phenyl thiophosphonyl dichloride, national pharmaceutical group chemical reagents ltd, analytically pure;
triethylamine, chemical reagent of national drug group, ltd, analytically pure;
toluene, national pharmaceutical group chemical reagents ltd, analytically pure;
petroleum ether, national drug group chemical reagent limited, analytically pure;
extreme pressure antiwear agent T306, Prof, Inc., institute of petrochemical institute, Industrial products;
extreme pressure antiwear agent T307, institute of petrochemical institute, Xinpu corporation, Industrial products;
an extreme pressure antiwear agent IRGALUBE 353, Yafudun, Inc., an industrial product;
IRGALUBE 349, Yafuton corporation, Industrial products, extreme pressure antiwear agents.
EXAMPLE 1 preparation of m-pentadecylphenol
100g of cardanol and 1.5g of palladium-carbon catalyst are put into a 200ml high-pressure reaction kettle, the high-pressure kettle is sealed, 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 ℃. After the reaction is finished, the temperature is reduced to 60 ℃, the viscous reaction mixture is taken out, the pressure is reduced and the distillation is carried out for 1h under the conditions of 100Pa and 160 ℃, and the milky white solid is obtained after the cooling. Dissolving the metapentadecylphenol with petroleum ether, and then crystallizing and purifying to obtain the metapentadecylphenol with the purity of more than 98%, wherein the reaction conversion rate is 83.6%.
Example 2 preparation of Dicanacardol Phenylthiophosphonate
Adding 20g of cardanol, 4g of triethylamine and 20g of toluene into a reaction bottle, starting heating and stirring, adding 7.5g of phenyl thiophosphonyl dichloride, and reacting for 5 hours while maintaining the reaction temperature at 70 ℃. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, distilling the organic phase at 100Pa and 150 deg.c under reduced pressure for 1 hr to eliminate water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 96.6%.
EXAMPLE 3 preparation of bis (3-pentadecylphenyl) phenol phenylphosphinate
20g of m-pentadecylphenol prepared in example 1, 8g of triethylamine and 50g of toluene were charged into a reaction flask, heated and stirred, 5g of phenylthiophosphonodichloride was added, and the reaction temperature was maintained at 90 ℃ for 4 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, distilling the organic phase at 100Pa and 150 deg.c under reduced pressure for 1 hr to eliminate water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 95.8%.
EXAMPLE 4 preparation of bis (3-pentadecylphenyl) phenol phenylphosphinate
20g of m-pentadecylphenol prepared in example 1, 8g of triethylamine and 60g of toluene were charged into a reaction flask, heated and stirred, 3.5g of phenylthiophosphonyl dichloride was added, and the reaction temperature was maintained at 80 ℃ for 5 hours. And cooling after the reaction is finished to obtain a brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, distilling the organic phase at 100Pa and 150 deg.c under reduced pressure for 1 hr to eliminate water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 97.8%.
Comparative example 1
Under the protection of nitrogen, 70.8g of di (2-ethylhexyl) dithiophosphoric acid and 7.08g of p-toluenesulfonic acid are poured into a flask, the flask is placed in a constant-temperature water bath (the temperature is controlled at 100 ℃), stirring is started, 31.2g of itaconic acid methyl ester in total is dropwise added within 1.5h, the mixture is continuously stirred and reacts for 8h under the protection of nitrogen, after the reaction is finished, 10% sodium bicarbonate solution and petroleum ether are used for extraction, the oil phase is dried, filtered, and finally, the diisooctyl dithiophosphoric acid-2-methyl succinic acid dimethyl ester is obtained through reduced pressure distillation.
Example 5
The products of examples 2, 3 and 4, T306, T307, IRGALUBE 353, IRGALUBE 349 and the product of comparative example 1 were dissolved in mineral oil 150SN to prepare compositions with a mass fraction of 0.5%. The solution of the compositions is subjected to an abrasion resistance test, a test instrument is an SRV vibration friction tester, and the test conditions are as follows: 100N, 200N, 300N, frequency 50Hz, amplitude 1mm, 30 ℃ and 1 h. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the thiophosphonates of the present invention have outstanding antiwear, antifriction, extreme pressure properties.
Example 6
The product prepared in example 3 was analyzed by infrared spectroscopy, the spectra are shown in fig. 1, and the analysis results are shown in table 2.
Table 2 infrared analysis results of the product of example 3
Claims (16)
1. A thiophosphonate compound has a structure shown as a general formula (I):
in the general formula (I), the radical R0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14Alkylphenyl radicals); each radical R1、R2、R3、R4、R5Are the same or different from each other and are each independently selected from H, C1～C20A linear or branched alkyl group and a group of the formula (II), each group R1、R2、R3、R4、R5At least one group of (a) is a group represented by the formula (II);
wherein the radical R1' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2' same or different from each other, each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3' selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m repeating unitsGroup R in (1)5' same or different from each other, each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 0 and 10, more preferably a positive integer between 1 and 3).
2. Thiophosphonate compounds according to claim 1, characterised in that in the general formula (I) the radicals R1、R5Each independently selected from H, C1～C4A linear or branched alkyl group; each radical R2、R4Each independently selected from C1～C20Straight-chain or branched alkyl and a radical of the formula (II), R3Each independently selected from H and C1～C20Straight or branched chain alkyl.
3. Thiophosphonate compounds according to claim 1, characterised in that in the general formula (I) the radicals R1、R5Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; each radical R2At least one group of (A) is a group of formula (II), each group R4At least one group in (A) is a group of formula (II), R3Each independently selected from H and C1～C20Straight or branched chain alkyl.
4. Thiophosphonate compounds according to claim 1, characterised in that in the general formula (I) the radicals R1、R5Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; radicals R bound to the same benzene ring2、R4One group is a group represented by formula (II), and the other is H; r3Each independently selected from H and C1～C20Straight or branched chain alkyl.
5. The thiophosphonate ester compound as claimed in claim 1, wherein the thiophosphonate ester compound may be selected from the following specific compounds or mixtures thereof in any proportion:
6. a process for producing a thiophosphonate compound, which comprises a step of reacting a phenol compound represented by the general formula (X) with a thiophosphoryl acylating agent and optionally a step of hydrotreating;
in the general formula (X), each group R1”、R2”、R3”、R4”、R5"equal to or different from each other, each independently selected from hydrogen, C1-300Straight or branched chain hydrocarbon radical (preferably C)1-30A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300-3000), 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 radical R1"' is selected from a single bond, C1-20Straight or branched alkylene (preferably selected from single bond and C)1-4Linear or branched alkylene); radical R in m repeating units2"'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C1-20Straight or branched alkylene (preferably each independently selected from single bond, C)1-4Linear or branched alkylene); radical R3"' is selected from hydrogen, C1-20Straight or branched alkyl (preferably selected from hydrogen, C)1-4Straight or branched chain alkyl); radical R in m repeating units4"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkanesRadical); radical R in m repeating units5"'s, equal to or different from each other, are each independently selected from hydrogen, C1-20Straight or branched chain alkyl (preferably each independently selected from hydrogen, C1-4Straight or branched chain alkyl); m is a positive integer (preferably a positive integer between 0 and 10, more preferably a positive integer between 1 and 3).
7. The process according to claim 6, wherein in the formula (X), the group R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4"equal to or different from each other, each independently selected from hydrogen, C1-20A 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).
8. The process according to claim 6, wherein in the formula (X), the group R1”、R3”、R5"equal to or different from each other, each independently selected from hydrogen, C1-4A linear or branched alkyl group; radical R2”、R4One group in "is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
9. The process of claim 6, wherein the thiophosphoryl acylating agent has the formula (Z):
wherein R is0Selected from H, C6～C20Aryl radical, C1-300Straight or branched alkyl (preferably phenyl, C)1～C14An alkyl phenyl group; the group A is selected from F, Cl, Br, I, OH (preferably Cl, Br).
10. The method of claim 6, whereinThe said thiophosphoryl acylating agent is selected from thiophosphoryl chloride, thiophosphonyl dichloride and C1-300One or more of a straight-chain or branched alkyl thiophosphonyl dichloride and a phenyl thiophosphonyl dichloride (preferably a phenyl thiophosphonyl dichloride).
11. The process according to claim 6, wherein the reaction of the phenol compound represented by the general formula (X) with the thiophosphoryl acylating agent is carried out under the conditions: the molar ratio of the sulfur-phosphorus acylating agent to the phenol compound represented by the general formula (X) is 1: 1 to 10 (preferably 1: 1 to 5); the reaction temperature is 50 ℃ to 150 ℃ (preferably 60 ℃ to 100 ℃).
12. The process according to claim 6, wherein a catalyst is added to the reaction, the catalyst being selected from the group consisting of C1～10And inorganic ammonium (for example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, and ammonia may be used).
13. The process according to claim 6, wherein the optional hydrotreating step comprises either hydrotreating the phenol compound represented by the general formula (X) and then reacting it with the sulfur-phosphorus acylating agent, or reacting the phenol compound represented by the general formula (X) with the sulfur-phosphorus acylating agent and then hydrotreating the reaction product.
14. The process according to claim 6, wherein the hydrotreating process conditions are preferably: hydrogen pressure is 1.0-6.0 MPa (preferably 3.0-4.0 MPa), temperature is 60-260 deg.C (preferably 180-220 deg.C), and time is 0.5-10 h (preferably 3-5 h).
15. The process according to claim 6, wherein the phenol compound represented by the general formula (X) is derived from a natural plant cashew nut.
16. The thiophosphonate compound of any one of claims 1 to 5 and the thiophosphonate compound prepared by the process of any one of claims 6 to 15 are useful as extreme pressure antiwear agents (extreme pressure antiwear agents for lubricating oils or greases).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201076.5A CN111057103B (en) | 2018-10-16 | 2018-10-16 | Thiophosphonate compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201076.5A CN111057103B (en) | 2018-10-16 | 2018-10-16 | Thiophosphonate compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111057103A true CN111057103A (en) | 2020-04-24 |
| CN111057103B CN111057103B (en) | 2023-03-10 |
Family
ID=70296438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811201076.5A Active CN111057103B (en) | 2018-10-16 | 2018-10-16 | Thiophosphonate compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111057103B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2385713A (en) * | 1944-02-03 | 1945-09-25 | Monsanto Chemicals | Amidophosphates |
| US2769743A (en) * | 1952-04-18 | 1956-11-06 | Union Oil Co | Pest control utilizing pesticidal compositions of phosphorus |
| US3239464A (en) * | 1961-09-05 | 1966-03-08 | Sinclair Research Inc | Extreme pressure lubricant |
| GB1070314A (en) * | 1964-01-31 | 1967-06-01 | Shell Int Research | Improvements in or relating to lubricant compositions |
| US3558747A (en) * | 1967-01-30 | 1971-01-26 | Ethyl Corp | Dihydrocarbylhydroxyphenyl phosphorus-containing antioxidants |
| DE2204701A1 (en) * | 1972-02-01 | 1973-08-09 | Shell Int Research | Oxidn stabilised hydrocarbon oils - contg alkyl phenol (thio)phosphite esters |
| US4144247A (en) * | 1973-10-04 | 1979-03-13 | Edwin Cooper And Company Limited | Lubricating oil additives |
| 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 |
| US6660696B1 (en) * | 2002-05-24 | 2003-12-09 | Indian Oil Corporation Limited | Thermally stable phosphorothionates as antioxidant, antiwear, friction reducing and extreme pressure lubricant additives from cashew nut shell liquid |
| CN105503948A (en) * | 2016-01-19 | 2016-04-20 | 苏州科技学院 | Di(tetrabromo bisphenol A) phenylphosphonothioate compound and preparation method thereof |
| CN107541322A (en) * | 2016-06-26 | 2018-01-05 | 黄宇松 | It is a kind of at low temperature being capable of the anti-rotten automobile soft shaft lubricating grease of water resistant |
-
2018
- 2018-10-16 CN CN201811201076.5A patent/CN111057103B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2385713A (en) * | 1944-02-03 | 1945-09-25 | Monsanto Chemicals | Amidophosphates |
| US2769743A (en) * | 1952-04-18 | 1956-11-06 | Union Oil Co | Pest control utilizing pesticidal compositions of phosphorus |
| US3239464A (en) * | 1961-09-05 | 1966-03-08 | Sinclair Research Inc | Extreme pressure lubricant |
| GB1070314A (en) * | 1964-01-31 | 1967-06-01 | Shell Int Research | Improvements in or relating to lubricant compositions |
| US3558747A (en) * | 1967-01-30 | 1971-01-26 | Ethyl Corp | Dihydrocarbylhydroxyphenyl phosphorus-containing antioxidants |
| DE2204701A1 (en) * | 1972-02-01 | 1973-08-09 | Shell Int Research | Oxidn stabilised hydrocarbon oils - contg alkyl phenol (thio)phosphite esters |
| US4144247A (en) * | 1973-10-04 | 1979-03-13 | Edwin Cooper And Company Limited | Lubricating oil additives |
| 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 |
| US6660696B1 (en) * | 2002-05-24 | 2003-12-09 | Indian Oil Corporation Limited | Thermally stable phosphorothionates as antioxidant, antiwear, friction reducing and extreme pressure lubricant additives from cashew nut shell liquid |
| CN105503948A (en) * | 2016-01-19 | 2016-04-20 | 苏州科技学院 | Di(tetrabromo bisphenol A) phenylphosphonothioate compound and preparation method thereof |
| CN107541322A (en) * | 2016-06-26 | 2018-01-05 | 黄宇松 | It is a kind of at low temperature being capable of the anti-rotten automobile soft shaft lubricating grease of water resistant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111057103B (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111057103B (en) | Thiophosphonate compound and preparation method and application thereof | |
| CN111072702A (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN111057108B (en) | Phosphoramidate compound and preparation method and application thereof | |
| CN114478200A (en) | Phenol derivative and preparation method and application thereof | |
| CN111057110A (en) | Phosphoramidate compound and preparation method and application thereof | |
| CN111057101B (en) | Phosphoramidate compound and preparation method and application thereof | |
| CN111057107B (en) | Thiophosphonate compound, and preparation method and application thereof | |
| CN111057111B (en) | Sulfur-substituted phosphonate compound and preparation method and application thereof | |
| CN111072706B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN111057102B (en) | Organophosphorus compounds, preparation method and application thereof | |
| KR101278872B1 (en) | Norbornene dialkyl ester containing dialkyl dithiocarbamate compounds, antiwear additives and lubricant comprising the same | |
| CN113388438A (en) | Worm gear oil composition and preparation method and application thereof | |
| CN112552332B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN112552326B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN112552325B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN112552330B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN112760158B (en) | Gasoline engine lubricating oil composition and preparation method thereof | |
| CN112760161B (en) | Anhydrous calcium-based lubricating grease and preparation method thereof | |
| CN111072705B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN112552328B (en) | Silole derivative, preparation method and application thereof, and photoluminescent lubricating grease | |
| CN115975705A (en) | Gasoline engine oil composition and preparation method thereof | |
| JP2007070348A (en) | Method for producing sulfur-containing phosphate compound | |
| CN115960664A (en) | Worm gear oil composition and preparation method thereof | |
| CN115975702A (en) | Gasoline engine oil composition and preparation method thereof | |
| CN115975694A (en) | Hydraulic oil composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |