CN111057103B - Thiophosphonate compound and preparation method and application thereof - Google Patents
Thiophosphonate compound and preparation method and application thereof Download PDFInfo
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- CN111057103B CN111057103B CN201811201076.5A CN201811201076A CN111057103B CN 111057103 B CN111057103 B CN 111057103B CN 201811201076 A CN201811201076 A CN 201811201076A CN 111057103 B CN111057103 B CN 111057103B
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- acylating agent
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000010687 lubricating oil Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-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
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 claims description 8
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 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
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 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
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 description 28
- 150000003254 radicals Chemical class 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 17
- -1 Alkylphenyl radicals Chemical class 0.000 description 16
- 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
- 125000002947 alkylene group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 244000226021 Anacardium occidentale Species 0.000 description 6
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 description 6
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 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
- 239000000203 mixture Substances 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
- 150000005840 aryl radicals Chemical class 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
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 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
- 238000010438 heat treatment 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
- 239000003607 modifier Substances 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
- 229910052763 palladium Inorganic materials 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
- 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
- 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
- 239000004215 Carbon black (E152) Substances 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
- 125000005037 alkyl phenyl group Chemical group 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
- 229930195733 hydrocarbon Natural products 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
- 229920000098 polyolefin Chemical group 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
- 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
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 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
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-
- 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
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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)
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 lubricating oil mainly comprises a sulfur-containing extreme pressure anti-wear agent, a chlorine-containing extreme pressure anti-wear agent, a phosphorus-containing extreme pressure anti-wear agent, a nitrogen-containing extreme pressure anti-wear agent, a metal salt extreme pressure anti-wear agent, a boron-containing extreme pressure anti-wear agent and the like, wherein the sulfur-phosphorus agent simultaneously contains sulfur and phosphorus and is widely applied due to the characteristics of high bearing capacity, good compatibility, good multi-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, shows better antirust performance and better antiwear performance, thermal stability, filterability and hydrolytic stability, but the antiwear performance and antifriction performance of the thiophosphate extreme pressure antiwear agent are not superior to those of the prior art. CN 101724492B discloses a zinc thiophosphate type extreme pressure antiwear agent, which has better bearing capacity, anti-oxidation stability and anti-wear performance compared with T405, but the compared T405 additive belongs to an oiliness agent and does not have the bearing capacity and anti-wear performance of the extreme pressure antiwear agent, so that the real anti-wear and anti-wear performance 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 of the invention is shown as the general formula (I):
in the general formula (I), the radical R 0 Selected from H, C 6 ～C 20 Aryl radical, C 1-300 Straight or branched chain alkyl (preferably phenyl, C) 1 ～C 14 Alkylphenyl radicals); each radical R 1 、R 2 、R 3 、R 4 、R 5 Are the same or different from each other and are each independently selected from H, C 1 ～C 20 Straight or branched alkyl and formula (II)The radicals shown, the radicals R 1 、R 2 、R 3 、R 4 、R 5 At least one group of (a) is a group represented by the formula (II);
wherein the radical R 1 ' is selected from a single bond, C 1-20 Straight or branched alkylene (preferably selected from the group consisting of single bond and C) 1-4 Straight or branched chain alkylene); radical R in m repeating units 2 ' same or different from each other, each independently selected from the group consisting of a single bond, C 1-20 Straight or branched alkylene (preferably each independently selected from single bond, C) 1-4 Linear or branched alkylene); radical R 3 ' selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C) 1-4 Straight or branched chain alkyl); radical R in m repeating units 4 ' same or different from each other, each independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4 Straight or branched chain alkyl); radical R in m repeating units 5 ' same or different from each other, each independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4 Straight 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 R 1 、R 5 Each independently selected from H, C 1 ～C 4 A linear or branched alkyl group; each radical R 2 、R 4 Each independently selected from C 1 ～C 20 Straight-chain or branched alkyl and a radical of the formula (II), R 3 Each independently selected from H and C 1 ～C 20 Straight or branched chain alkyl.
According to the invention, preferably, in the general formula (I), the radicals R 1 、R 5 Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; each radical R 2 At least one group of (A) is a group of formula (II), each group R 4 At least one group in (A) is a group of formula (II), R 3 Each independently selected from H and C 1 ～C 20 Straight or branched chain alkyl.
According to the invention, preferably, in the general formula (I), the radicals R 1 、R 5 Each independently selected from H, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; radicals R bound to the same benzene ring 2 、R 4 One group is a group represented by formula (II), and the other is H; r is 3 Each independently selected from H and C 1 ～C 20 Straight or branched chain alkyl.
The thiophosphonate ester 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 R 1 ”、R 2 ”、R 3 ”、R 4 ”、R 5 "equal to or different from each other, each independently selected from hydrogen, C 1-300 Straight or branched chain hydrocarbon radical (preferably C) 1-30 A linear or branched alkyl group or a polyolefin group having a number average molecular weight Mn of 300 to 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 R 1 ”'Selected from single bond, C 1-20 Straight or branched alkylene (preferably selected from the group consisting of single bond and C) 1-4 Linear or branched alkylene); radical R in m repeating units 2 "'s, which may be the same or different from each other, are each independently selected from the group consisting of a single bond, C 1-20 Straight or branched alkylene (preferably each independently selected from single bond, C) 1-4 Linear or branched alkylene); radical R 3 "' is selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C) 1-4 Straight or branched chain alkyl); radical R in m repeating units 4 "'s, equal to or different from each other, are each independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4 Straight or branched chain alkyl); radical R in m repeating units 5 "'s, equal to or different from each other, are each independently selected from hydrogen, C 1-20 Straight or branched chain alkyl (preferably each independently selected from hydrogen, C 1-4 Straight 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 R 1 ”、R 3 ”、R 5 "identical to or different from each other, each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R 2 ”、R 4 "equal to 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 process of the present invention, in the general formula (X), further preferably, the group R 1 ”、R 3 ”、R 5 "equal to or different from each other, each independently selected from hydrogen, C 1-4 A linear or branched alkyl group; radical R 2 ”、R 4 One 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 R 1 Is selected from C 1-4 Straight or branched alkyl, R 5 "is selected from hydrogen; radical R 3 Is selected from hydrogen、C 1-4 A linear or branched alkyl group; radical R 2 "is selected from hydrogen, R 4 "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 is 0 Selected from H, C 6 ～C 20 Aryl radical, C 1-300 Straight or branched alkyl (preferably phenyl, C) 1 ～C 14 Alkyl phenyl, C 1-30 Straight 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 agent 1-300 One 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 C 1～10 The 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 solvent isThe amount of the phenol compound 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 by one or more methods selected from water washing, distillation, filtration, drying and recrystallization, without particular limitation.
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 of 1.0-6.0 MPa (preferably 3.0-4.0 MPa), temperature of 60-260 deg.C (preferably 180-220 deg.C), and time of 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 C 15 H (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 m-pentadecylphenol by using petroleum ether, and then crystallizing and purifying to obtain the m-pentadecylphenol with the purity of more than 98 percent, wherein the reaction conversion rate is 83.6 percent.
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 phenylthiophosphonyl dichloride 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 bis (2-ethylhexyl) dithiophosphate 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 added dropwise within 1.5h, the reaction is continuously stirred 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 dithiophosphate-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 1h. 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 (11)
1. A thiophosphonate compound, the structure of which is shown in the general formula (I):
in the general formula (I), the radical R 0 Is selected from phenyl; each radical R 1 、R 3 、R 4 、R 5 Selected from H, each radical R 2 Is a linear pentadecyl group.
2. A method for preparing a thiophosphonate compound comprises a step of reacting cardanol with a thiophosphoryl acylating agent and a step of hydrotreating;
the structure of the sulfur-phosphorus acylating agent is shown as a formula (Z):
wherein R is 0 Is selected from phenyl; the group A is selected from Cl.
3. The method of claim 2, wherein the cardanol is reacted with a thiophosphoryl acylating agent under the following conditions: the mol ratio of the sulfur-phosphorus acylating agent to the cardanol is 1:1 to 10;
the reaction temperature is 50-150 ℃.
4. The method of claim 2, wherein the cardanol is reacted with a thiophosphoryl acylating agent under the following conditions: the mol ratio of the sulfur-phosphorus acylating agent to the cardanol is 1:1 to 5; the reaction temperature is 60-100 ℃.
5. The process according to claim 2, wherein a catalyst is added to the reaction, said catalyst being selected from the group consisting of C 1～10 Organic amine and inorganic ammonium of (1).
6. The method according to claim 2, wherein a catalyst selected from one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia is added to the reaction.
7. The method according to claim 2, wherein the step of hydrotreating comprises hydrotreating cardanol and then reacting it with a thiophosphoryl acylating agent, or reacting cardanol and a thiophosphoryl acylating agent and then hydrotreating the reaction product.
8. The method according to claim 2, wherein the hydrotreating process conditions are: hydrogen pressure is 1.0-6.0 MPa, temperature is 60-260 ℃, and time is 0.5-10 h.
9. The method according to claim 2, wherein the hydrotreating process conditions are: hydrogen pressure of 3.0-4.0 Mpa, temperature of 180-220 deg.C, and time of 3-5 h.
10. The thiophosphonate compound of claim 1 and the thiophosphonate compound prepared by the process of any one of claims 2 to 9 are useful as extreme pressure antiwear agents.
11. The thiophosphonate compound of claim 1 and the thiophosphonate compound prepared by the process of any one of claims 2 to 9 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 |
| US2769743A (en) * | 1952-04-18 | 1956-11-06 | Union Oil Co | Pest control utilizing pesticidal compositions of phosphorus |
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