CN111057111B - Sulfur-substituted phosphonate compound and preparation method and application thereof - Google Patents
Sulfur-substituted phosphonate compound and preparation method and application thereof Download PDFInfo
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- CN111057111B CN111057111B CN201811201077.XA CN201811201077A CN111057111B CN 111057111 B CN111057111 B CN 111057111B CN 201811201077 A CN201811201077 A CN 201811201077A CN 111057111 B CN111057111 B CN 111057111B
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- cardanol
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- agent
- branched alkyl
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- -1 Sulfur-substituted phosphonate compound Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 30
- 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 25
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 25
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 25
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 25
- 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 24
- 238000004073 vulcanization Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000006863 thiophosphorylation reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 229940100684 pentylamine Drugs 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims 9
- 238000006366 phosphorylation reaction Methods 0.000 claims 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000000865 phosphorylative effect Effects 0.000 claims 1
- 238000005486 sulfidation Methods 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 2
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 description 77
- 125000004434 sulfur atom Chemical group 0.000 description 31
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920000098 polyolefin Chemical group 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 244000226021 Anacardium occidentale Species 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 8
- 235000020226 cashew nut Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- NAKDJXIEBCHXIZ-UHFFFAOYSA-N dihydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)C1=CC=CC=C1 NAKDJXIEBCHXIZ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- VUBOQPNQIMKEKI-UHFFFAOYSA-N 3,8-dithiatricyclo[5.1.0.02,4]oct-5-en-4-ol Chemical compound C12SC2C=CC2(O)C1S2 VUBOQPNQIMKEKI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 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
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 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
- 239000008096 xylene Substances 0.000 description 2
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 1
- LNMBCRKRCIMQLW-UHFFFAOYSA-N 2-tert-butylsulfanyl-2-methylpropane Chemical compound CC(C)(C)SC(C)(C)C LNMBCRKRCIMQLW-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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 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
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655309—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a three-membered ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a thiophosphonate sulfide compound, a preparation method and application thereof. The structure of the thiophosphonate sulfide compound is shown as a general formula (I):the definition of each group is shown in the specification. The thiophosphonate sulfide compound can be used as an extreme pressure antiwear agent and applied to lubricating oil and lubricating grease. The thiophosphonate sulfide compound has outstanding bearing capacity and excellent wear resistance and antifriction performance.
Description
Technical Field
The present invention relates to a thiophosphonate sulfide compound, and more particularly, to a thiophosphonate sulfide compound suitable for use as an antiwear agent.
Background
Lubrication is generally divided into fluid lubrication and boundary lubrication, and extreme pressure antiwear agents are indispensable additives in the boundary lubrication state, and can be adsorbed on or react with a metal surface to form an adsorption film or a reaction film so as to prevent abrasion or even fusion welding of the metal surface and improve the lubricity and the wear resistance of oil products. Mainly comprises a sulfur-containing extreme pressure antiwear agent, a chlorine-containing extreme pressure antiwear agent, a phosphorus-containing extreme pressure antiwear agent, a nitrogen-containing extreme pressure antiwear agent, a metal salt extreme pressure antiwear agent, a boron-containing extreme pressure antiwear agent and the like, the sulfur-phosphorus agent containing sulfur and phosphorus is widely used because of the characteristics of high bearing capacity, good compatibility, good multiple effects and the like.
Among extreme pressure antiwear agents currently widely used in the lubricating oil field are tricresyl phosphate (T306), ammonium thiophosphate (T307), phosphorothioate (IRGALUBE 353), ammonium phosphate (IRGALUBE 349), etc., but their antiwear and antifriction properties are to be further improved. CN 106317109a discloses a phosphorothioate extreme pressure antiwear agent, which is used as hydraulic oil or lubricating oil additive, and has better anti-rust performance, better antiwear performance, thermal stability, filterability and hydrolytic stability, but the antiwear and antifriction performance is not better than the prior art. CN 101724492B discloses a zinc thiophosphate type extreme pressure antiwear agent, which has better bearing capacity, oxidation stability and antiwear performance compared with T405, but the compared T405 additive belongs to an oiliness agent, and does not have bearing capacity and antiwear performance of the extreme pressure antiwear agent, so that the actual antiwear performance and bearing capacity of the extreme pressure antiwear agent cannot be measured.
The cardanol is a main component of cashew nut shell oil, is a natural phenolic compound, is an important agricultural and sideline product in cashew nut production, and has wide sources and huge reserves. The friction modifier which is prepared from the natural compounds with abundant sources and low cost and has better synthesis performance than the existing products is adopted, and meets the definition of green chemistry and the strategic requirements of national sustainable development.
Disclosure of Invention
The invention provides a thiophosphonate sulfide compound, a preparation method and application thereof.
The structure of the thiophosphonate sulfide compound is shown as a general formula (I):
in the general formula (I), the radical R 0 Selected from H, C 6 ～C 20 Aryl, C 1-300 Straight or branched alkyl (preferably phenyl, C 1 ～C 14 Alkylphenyl radicals C 1 ～C 20 Linear or branched alkyl); each group R 1 、R 2 、R 3 、R 4 、R 5 Are the same as or different from each other and are each independently selected from H, C 1 ～C 20 A linear or branched alkyl group and a group of the formula (II), each group R 1 、R 2 、R 3 、R 4 、R 5 At least one group of the formula (II);
in the general formula (II), the radical R 1 ' selected from single bond, C 1-20 Straight-chain or branched alkylene (preferably selected from single bond and C 1-4 Linear or branched alkylene groups); group R in n repeating units 2 ' same or different from each other, each independently selected from C of 2, 3 or 4 1-20 Straight or branched alkyl (preferably C independently selected from 2, 3 or 4 valences each 1-4 Linear or branched alkyl); group R in n repeating units 3 ' same or different from each other, each independently selected from single bond, C of 2 or 3 valences 1-20 Straight or branched alkyl (preferably C each independently selected from single bond, 2-valent or 3-valent C 1-4 Linear or branched alkyl); group R in n repeating units 4 ' same or different from each other, each independently selected from single bond, C of 2 or 3 valences 1-20 Straight or branched alkyl (preferably C each independently selected from single bond, 2-valent or 3-valent C 1-4 Linear or branched alkyl); group R in n repeating units 5 ' same or different from each other, each independently selected from C of 2, 3 or 4 1-20 Straight or branched alkyl (preferably C independently selected from 2, 3 or 4 valences each 1-4 Linear or branched alkyl); group R in n repeating units 6 ' are identical or different from each other and are each independently selected from single bonds, C 1-20 Straight-chain or branched alkylene groups (preferably each independently selected from single bond, C 1-4 Linear or branched alkylene groups); group R 7 ' selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C 1-4 Linear or branched alkyl); n is an integer between 1 and 10 (preferably an integer between 1 and 3); m in n repeating units, equal to or different from each other, are each independently selected from integers between 0 and 10 (preferably integers between 0 and 5); m' in the n repeating units are the same or different from each other and are each independently selected from integers between 0 and 10 (preferably integers between 0 and 5); in each repeating unit of formula (II), when m is greater than 0, m S atoms are bonded to the group R 2 '、R 5 ' bonding; when m 'is greater than 0, m' S atoms are bonded to the R group 3 '、R 4 ' bonding; in each repeating unit of formula (II), when the radical R 3 When 'is a single bond, m' S atoms and the group R 2 ' bonding, when the radical R 4 When 'is a single bond, m' S atoms and the group R 5 'bonding'.
In the general formula (I), it is preferred that each group R 1 、R 3 、R 5 Are identical or different from each other and are each independently selected from hydrogen, C 1-4 Linear or branched alkyl; each group R 2 、R 4 Are identical or different from each other and are each independently selected from hydrogen, C 1-300 Straight or branched hydrocarbon radicals (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 (II), wherein at least one group is selected from the group represented by the general formula (II).
In the general formula (I), it is further preferred that each group R 1 、R 3 、R 5 Are identical or different from each other and are each independently selected from hydrogen, C 1-4 Linear or branched alkyl; each group R 2 、R 4 One of the groups is selected from the group represented by the general formula (II), and the other group is selected from hydrogen.
The thiophosphonate sulfide compound of the present invention may be selected from the following specific compounds or a mixture thereof in any ratio.
The method for producing a thiophosphonate compound of the present invention comprises the steps of vulcanizing and thiophosphorylating a phenol compound represented by the general formula (X);
in the general formula (X), each group R 1 ”、R 2 ”、R 3 ”、R 4 ”、R 5 "same as or different from each other, each independently selected from hydrogen, C 1-300 Straight or branched hydrocarbon radicals (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 groups represented by the general formula (Y);
wherein the radicals R 1 "' is selected from single bond, C 1-20 Straight-chain or branched alkylene (preferably selected from single bond and C 1-4 Linear or branched alkylene groups); group R in m repeating units 2 "' are the same or different from each other and are each independently selected from a single bond, C 1-20 Straight-chain or branched alkylene groups (preferably each independently selected from single bond, C 1-4 Linear or branched alkylene groups); group R 3 "' is selected from hydrogen, C 1-20 Straight or branched alkyl (preferably selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 4 "' are the same or different from each other and are each independently selected from hydrogen, C 1-20 Straight or branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); group R in m repeating units 5 "' are the same or different from each other and are each independently selected from hydrogen, C 1-20 Straight or branched alkyl (preferably each independently selected from hydrogen, C 1-4 Linear or branched alkyl); m is a positive integer (preferably a positive integer between 1 and 10, more preferably a positive integer between 1 and 3).
According to the preparation method of the present invention, in the general formula (X), preferably, each group R 1 ”、R 3 ”、R 5 "same as or different from each other, each independently selected from hydrogen, C 1-4 Linear or branched alkyl; each group R 2 ”、R 4 "same as or different from each other, each independently selected from hydrogen, C 1-20 A linear or branched alkyl group and a group represented by the general formula (Y), wherein at least one group is selected from the group represented by the general formula (Y).
According to the preparation method of the present invention, in the general formula (X), it is further preferable that each group R 1 ”、R 3 ”、R 5 "same as or different from each other, each independently selected from hydrogen, C 1-4 Linear or branched alkyl; each group R 2 ”、R 4 One of the groups is selected from the group represented by the general formula (Y), and the other group is selected from hydrogen.
According to the production method of the present invention, the phenol compound represented by the general formula (X) may be subjected to a vulcanization reaction and then to a vulcanization reaction of the vulcanization product (the vulcanization product of the phenol compound represented by the general formula (X)), or the phenol compound represented by the general formula (X) may be subjected to a vulcanization reaction and then to a vulcanization reaction of the vulcanization product (the vulcanization product of the phenol compound represented by the general formula (X)).
According to the production method of the present invention, the vulcanization reaction includes a step of reacting a phenol compound represented by the general formula (X) or a thiophosphorylated product of the phenol compound represented by the general formula (X) with a vulcanizing agent. The vulcanizing reaction causes electrophilic addition reaction between the vulcanizing agent and a carbon-carbon double bond (olefinic bond), and forms a monosulfur cyclized product when there are 1 carbon-carbon double bond in the molecule, and forms a monosulfur cyclized product and a polysulfide cyclized product when there are a plurality of carbon-carbon double bonds in the molecule. The vulcanizing agent is preferably an inorganic vulcanizing agent and/or an organic vulcanizing agent, and the inorganic vulcanizing agent can be sulfur or Na 2 S、K 2 S、ZnS、H 2 One or more of S and SCl; the organic vulcanizing agent can be selected from one or more of di-tert-butyl sulfide (DBPS), dimethyl disulfide (DMDS), dimethyl sulfide (DMS), ethyl Mercaptan (EM), n-butyl mercaptan (NBM) and tert-nonyl polysulfide (TNPS); the vulcanizing agent is more preferably sulfur or Na 2 S and one or more of thiols. In the vulcanization reaction, the general formula (X) The mole ratio of phenolic compound to vulcanizing agent shown is 1:1 to 6, more preferably 1:2 to 4. The temperature of the vulcanization reaction is 100-240 ℃, preferably 140-190 ℃; generally, the longer the reaction time, the higher the conversion, and the conversion of the reaction and the economy of the reaction are combined, and the reaction time is generally from 0.5 to 10 hours, preferably from 3 to 5 hours.
According to the preparation method of the present invention, a catalyst may be added or not added in the vulcanization reaction, and preferably, a catalyst is added. The catalyst is preferably selected from C 1～6 For example, one or more of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, tripropylamine, butylamine, pentylamine, hexylamine, aqueous ammonia, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, zinc oxide, sodium carbonate, potassium carbonate and zinc carbonate can be used. The mass of the catalyst is 0.01 to 10%, preferably 0.1 to 5% of the mass of the phenol compound represented by the general formula (X).
According to the production method of the present invention, after the completion of the vulcanization reaction, the reaction product may be subjected to a purification treatment including one or more of water washing, distillation, filtration, drying and recrystallization methods, without particular limitation; when the organic amine and/or inorganic base catalyst is added to the sulfiding reaction, the purification treatment method includes one or more of acid washing, water washing, distillation, filtration, drying and recrystallization methods.
According to the preparation method of the present invention, preferably, the structure of the thiophosphorylation agent is as shown in formula (Z):
wherein R is 0 Selected from H, C 6 ～C 20 Aryl, C 1-300 Straight or branched alkyl (preferably phenyl, C 1 ～C 14 Alkylphenyl radicals C 1 ～C 20 Linear or branched alkyl); the group A is selected from F, cl, br, I, OH (preferably Cl, br). In particular, the thiophosphorylation agent mayThe thiophosphoryl chloride, thiophosphoryl dichloride and C are selected 1-300 One or more of linear or branched alkyl thiophosphonic dichloride and phenyl thiophosphonic dichloride (preferably phenyl thiophosphonic dichloride).
According to the production method of the present invention, preferably, the vulcanization product of the phenol compound represented by the general formula (X) or the condition under which the phenol compound represented by the general formula (X) is reacted with the thiophosphorylation agent is: the molar ratio between the thiophosphorylation agent and the phenol compound shown in the general formula (X) is 1:1 to 10 (preferably 1:1 to 5); the reaction temperature is 50 ℃ -150 ℃ (preferably 60 ℃ -100 ℃); generally, the longer the reaction time, the higher the conversion, and the reaction time is usually 0.5 to 10 hours (preferably 3 to 5 hours). In the thiophosphorylation reaction, a catalyst may or may not be added, and preferably a catalyst is added. The catalyst is preferably C 1～10 For example, one or more of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine and ammonia may be used. The catalyst is preferably added in an amount of 0.1 to 60% by mass, more preferably 10 to 40% by mass, based on the mass of the phenol compound. In the thiophosphorylation 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 toluene and/or xylene may be used, for example. The solvent is used in an amount of 50 to 500% (preferably 100 to 300%) based on the mass of the phenol compound represented by the general formula (X). The catalyst, solvent may be removed by one or more methods including acid washing, water washing, distillation, filtration, drying, and recrystallization, and is not particularly limited.
According to the production method of the present invention, after the completion of the reaction of the vulcanized product of the phenol compound represented by the general formula (X) or the phenol compound represented by the general formula (X) with the thiophosphorylation agent, the reaction product may be subjected to a purification treatment, the method of which includes one or more of washing with water, distillation, filtration, drying and recrystallization methods, without particular limitation.
The phenolic compound shown in the general formula (X) is preferably derived from natural plant cashew nuts, and contains a large amount of cashew nut shell oil in cashew nut shells, wherein the main component is meta-phenol, which is commonly called cardanol, and the structure is as follows:
wherein R is C 15 H (31+x) X is 0, -2, -4 or-6.
The thiophosphonate sulfide compound can be used as an extreme pressure antiwear agent and applied to lubricating oil and lubricating grease.
The preparation method of the thiophosphonate sulfide compound is simple, convenient to operate, green and easily available in raw materials, high in product yield and high in purity.
The thiophosphonate sulfide compound has outstanding bearing capacity and excellent wear resistance and antifriction performance.
Drawings
FIG. 1 is an infrared spectrum of the product of example 3.
Detailed Description
The invention will now be further illustrated by, but is not limited to, the following examples.
According to the invention, as said C 1-300 Examples of the linear or branched alkyl group include C 1-20 Straight or branched alkyl (preferably C) 1-10 Linear or branched alkyl, more preferably C 1-4 Linear or branched alkyl) or polyolefin-based. The polyolefin group may specifically be, for example, a polyolefin group having a number average molecular weight Mn of 300 to 3000. In this case, the number average molecular weight Mn of the polyolefin group is preferably 500 to 2000, more preferably 500 to 1500. According to the present invention, the polyolefin-based (substantially) is saturated (exhibits a long-chain alkyl structure), but depending on the kind of polyolefin as a starting material or the production method of the polyolefin, the polyolefin-based may contain a small amount of olefinic double bonds in the molecular chain (such as residues or introduced during the production of the polyolefin), which does not affect the achievement of the effect of the present invention, nor is the present invention intended to be clarified, and the present inventionSuch polyolefin groups are still classified as "alkyl".
In this specification, the term "single bond" is sometimes used in the definition of a group. By "single bond" is meant that the group is absent. For example, assume the structural formula-CH 2 -A-CH 3 Wherein the group A is defined as selected from single bonds and methyl groups. In view of this, if A is a single bond, this means that the group A is absent, in which case the formula is correspondingly reduced to-CH 2 -CH 3 。
In the context of the present specification, the expression "number +valence +group" or the like means a group obtained by removing the number of hydrogen atoms represented by the number from a basic structure (such as a chain, a ring, or a combination thereof, etc.) to which the group corresponds, preferably a group obtained by removing the number of hydrogen atoms represented by the number from carbon atoms (preferably saturated carbon atoms and/or non-identical carbon atoms) contained in the structure. For example, "3-valent linear or branched alkyl group" refers to a group obtained by removing 3 hydrogen atoms from a linear or branched alkane (i.e., the basic chain to which the linear or branched alkyl group corresponds), while "2-valent linear or branched heteroalkyl group" refers to a group obtained by removing 2 hydrogen atoms from a linear or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further from a non-identical carbon atom). For example, the 2-valent propyl group may be-CH 2 -CH 2 -CH 2 -*、The 3-valent propyl group can be +.>The 4-valent propyl group can be +.>Wherein represents the binding end in the group that can be bonded to other groups.
According to the invention, in each repeating unit of formula (II), when m is greater than 0, m S atoms are bonded to the R group 2 '、R 5 ' bonding; when (when)When m 'is greater than 0, m' S atoms and the group R 3 '、R 4 ' bonding; in each repeating unit of formula (II), when the radical R 3 When 'is a single bond, m' S atoms and the group R 2 ' bonding, when the radical R 4 When 'is a single bond, m' S atoms and the group R 5 'bonding'.
According to the invention, in each repeating unit of formula (II), when m is 0, there is no S atom with the group R 2 '、R 5 ' bonding; when m' is 0, there is no S atom or group R 3 '、R 4 ' bonding; in each repeating unit of formula (II), when the radical R 3 When 'non-single bond, m' S atoms and R group 3 ' bonding, when the radical R 4 When 'non-single bond, m' S atoms and R group 4 'bonding'.
According to the invention, in each repeating unit of formula (II), the radical (S) m 、(S) m ’、R 2 '、R 3 '、R 4 '、R 5 ' conform to the key formation rules.
According to the invention, m S atoms are bonded to the radicals R 2 '、R 5 ' bonding refers to the terminal S atom of m S atoms (or only one S atom present) with the group R 2 '、R 5 ' bonding (when m is 1, there is only one S atom, this S atom being then bonded to the group R 2 '、R 5 'bonding'; m' S atoms and radicals R 3 '、R 4 'bonding means that the terminal S atom of m' S atoms (or only one S atom is present) is bonded to the group R 3 '、R 4 'bonding (when m' is 1, there is only one S atom, this S atom being then bonded to the group R 3 '、R 4 'bonding').
According to the invention, in each repeating unit of formula (II), in the radical R 2 '、R 3 '、R 4 '、R 5 ' when bound to each other, the bond can be formed by the group R 2 '、R 3 '、R 4 '、R 5 Any of the binding ends of' form a covalent bond. In each repeating unit of formula (II), in the radical (S) m Or (S) m’ And R is R 2 '、R 3 '、R 4 '、R 5 ' when bonding with each other, the two components canTo be combined with the radicals R 2 '、R 3 '、R 4 '、R 5 Any of the binding ends of' form a covalent bond.
According to the invention, in each repeating unit of formula (II), when the radical R 3 '、R 4 When ' non-single bond, m ' is greater than 0, m ' S atoms and the group R 3 '、R 4 ' bond, R 3 '、R 4 ' each independently selected from C of 3 valency 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 '、R 4 When 'non-single bond, m' is 0, there is no S atom or group R 3 '、R 4 ' bond, R 3 '、R 4 ' each independently selected from C of valence 2 1-20 Straight or branched alkyl (preferably each independently selected from C of valence 2 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 '、R 4 When' non-single bond, m is greater than 0, R 2 '、R 5 ' each independently selected from C of 3 valency 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 '、R 4 When' non-single bond, m is 0, R 2 '、R 5 ' each independently selected from C of valence 2 1-20 Straight or branched alkyl (preferably each independently selected from C of valence 2 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 ' is a single bond, R 4 When ' non-single bond, m ' is greater than 0, m ' S atoms and the group R 2 '、R 4 ' bond, R 4 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 ' is a single bond, R 4 When 'non-single bond, m' is 0, there is no S atom or group R 2 '、R 4 ' bond, R 4 ' C selected from 2 valences 1-20 Straight or branched alkyl (preferably each independently selected from C of valence 2 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 ' is a single bond, R 4 When' non-single bond, m is greater than 0, R 2 ' C selected from 4-valent atoms 1-20 Straight or branched alkyl (preferably selected from C of valence 4 1-4 Linear or branched alkyl), R 5 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 ' is a single bond, R 4 When' non-single bond, m is 0, R 2 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably selected from C of 3 valency 1-4 Linear or branched alkyl), R 5 ' C selected from 2 valences 1-20 Straight or branched alkyl (preferably selected from C2 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 ' non-single bond, R 4 When ' is a single bond and m ' is greater than 0, m ' S atoms and the group R 3 '、R 5 ' bond, R 3 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 ' non-single bond, R 4 When 'is a single bond and m' is 0, there is no S atom or group R 3 '、R 5 ' bond, R 3 ' C selected from 2 valences 1-20 Straight or branched alkyl (preferably each independently selected from C of valence 2 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 ' non-single bond, R 4 When' is a single bond and m is greater than 0, R 2 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably selected from C of 3 valency 1-4 Linear or branched alkyl), R 5 ' C selected from 4-valent atoms 1-20 Straight or branched alkyl (preferably selected from C of valence 4 1-4 Linear or branched alkyl); when the radical R 3 ' non-single bond, R 4 When' is a single bond and m is 0, R 2 ' C selected from 2 valences 1-20 Straight or branched alkyl (preferably selected from C2 1-4 Linear or branched alkyl), R 5 ' C selected from 3 valences 1-20 Straight or branched alkyl (preferably selected from C of 3 valency 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 '、R 4 When ' are single bonds and m ' is greater than 0, m ' S atoms and the group R 2 '、R 5 ' bond, when m is greater than 0, R 2 '、R 5 ' each independently selected from C of 4 valency 1-20 Straight or branched alkyl (preferably each independently selected from C having a valence of 4 1-4 Linear or branched alkyl) when m is 0, R 2 '、R 5 ' each independently selected from C of 3 valency 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl).
According to the invention, in each repeating unit of formula (II), when the radical R 3 '、R 4 When 'are single bonds, m' is 0 and m is greater than 0, R 2 '、R 5 ' each independently selected from C of 3 valency 1-20 Straight or branched alkyl (preferably each independently selected from C of 3 valency 1-4 Linear or branched alkyl); when the radical R 3 '、R 4 When 'are single bonds, m' is 0, and m is 0, R 2 '、R 5 ' each independently selected from C of valence 2 1-20 Straight or branched alkyl (preferably each independently selected from C of valence 2 1-4 Linear or branched alkyl).
In each repeating unit of formula (II) according to the invention, structures that may be formed include, for example: * -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -*、
The main raw materials used are as follows:
cashew nut shell oil, shanghai Material racing technology Co., ltd, industrial products
Sulfur powder, national medicine group chemical reagent Co., ltd., analytical grade
Sodium bicarbonate, national pharmaceutical Congress chemical reagent Co., ltd., analytical grade
Phenyl thiophosphonic dichloride, national pharmaceutical systems chemical reagent Co., ltd
Triethylamine, national medicine group chemical reagent Co., ltd., analytical grade
Extreme pressure antiwear agent T306, xingpu, institute of petrochemistry, industrial products; extreme pressure antiwear agent T307, an industrial product of Xingpu, institute of petroleum industry; extreme pressure antiwear agent IRGALUBE 353, an industrial product of EFuton Corp; extreme pressure antiwear agent IRGALUBE349, manufactured by EFuton, inc.
Example 1 preparation of sulfurized cardanol
62g of cardanol (about 0.2 mol) and 12.8g of sulfur powder (0.4 mol) were put into a 250ml three-necked reaction flask, and stirring and heating were started. The reaction temperature was maintained at 190℃and the reaction was continued for 3 hours. Cooling after the reaction is finished, and filtering to obtain dark brown red viscous liquid, namely the vulcanized cardanol, wherein the product conversion rate is 89.3%.
EXAMPLE 2 preparation of Dicardanol phenylthiophosphonate
20g of cardanol, 4g of triethylamine and 20g of toluene are added into a reaction bottle, heating and stirring are started, 7.5g of phenyl thiophosphonic dichloride is added, the reaction temperature is maintained at 70 ℃, and the reaction is carried out for 5 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. The reaction product was washed with distilled water to neutrality, the organic phase was distilled under reduced pressure at 100Pa at 150℃for 1h, and the water and solvent were removed to give a brown yellow transparent liquid with a reaction conversion of 94.8%.
Example 3 preparation of phenyl thiophosphonic acid cashew phenol disulfide
25g of the sulfurized cardanol obtained in example 1, 8g of triethylamine and 50g of toluene were charged into a reaction flask, and 5g of phenylthiophosphonic dichloride was added thereto with stirring under heating, and the reaction temperature was maintained at 90℃for 4 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. Washing the reaction product with distilled water to neutrality, and distilling the organic phase under reduced pressure at 100Pa and 150deg.C for 1 hr to remove water and solvent to obtain brown yellow transparent liquid with reaction conversion rate of 95.1%.
Example 4 preparation of phenyl thiophosphonic acid cashew phenol disulfide
25g of the sulfurized cardanol obtained in example 1, 8g of triethylamine and 60g of toluene were charged into a reaction flask, and 3.5g of phenylthiophosphonic dichloride was added thereto with stirring under heating, and the reaction temperature was maintained at 80℃for 5 hours. And cooling after the reaction is finished to obtain brownish red transparent liquid. The reaction product was washed with distilled water to neutrality, the organic phase was distilled under reduced pressure at 100Pa at 150℃for 1h, and the water and solvent were removed to give a brown yellow transparent liquid with a reaction conversion of 93.9%.
Example 5 preparation of phenyl thiophosphonic acid cashew phenol disulfide
65g of the cardanol phenylthiophosphonate obtained in example 2 and 8.5g of sulfur powder were put into a 250ml three-necked reaction flask, and stirring and heating were started. The reaction temperature was maintained at 190℃and the reaction was continued for 3 hours. And cooling after the reaction is finished, and filtering to obtain brownish red viscous liquid, namely phenyl thiophosphonic acid disulfide cardanol ester, wherein the product conversion rate is 90.6%.
Comparative example 1
70.8g of di (2-ethylhexyl) dithiophosphoric acid and 7.08g of p-toluenesulfonic acid are poured into a flask under the protection of nitrogen, the flask is placed in a constant temperature water bath (the temperature is controlled at 100 ℃), stirring is started, 31.2g of total methyl itaconate is added dropwise in 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, and the oil phase is dried, filtered and finally distilled under reduced pressure to obtain the dimethyl diisooctyl dithiophosphate-2-methyl succinate.
Example 6
The products of examples 3, 4, and 5, T306, T307, IRGALUBE 353, IRGALUBE349, and the product of comparative example 1 were dissolved in mineral oil 150SN, respectively, to prepare a composition having a mass fraction of 0.5%. These compositions were tested for antiwear properties using an SRV vibration friction tester under the following conditions: 100N, 200N, 300N, frequency 50Hz, amplitude 1mm,30℃for 1h. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the thiophosphonate sulfide of the present invention has outstanding antiwear, antifriction and extreme pressure properties.
Example 7
The product prepared in example 3 was subjected to infrared spectrum analysis, the spectrum is shown in FIG. 1, and the analysis results are shown in Table 2.
TABLE 2 Infrared analysis results of example 3 products
Claims (9)
1. A method for preparing a sulfurised thiophosphonate compound comprises the steps of causing cardanol to undergo sulfuration reaction and sulfuration phosphorylation reaction; firstly, the cardanol is subjected to a vulcanization reaction, and then the vulcanization product is subjected to a sulfuration phosphorylation reaction; or the cardanol is subjected to sulfuration and phosphorylation reaction, and then the sulfuration and phosphorylation reaction product is subjected to sulfuration reaction; the vulcanization reaction is a reaction between cardanol or a thiophosphorylation product of cardanol and a vulcanizing agent; the sulfuration phosphorylation reaction is the sulfuration product of the cardanol or the reaction of the cardanol and the sulfuration phosphorylating agent; the vulcanizing agent is sulfur; the thiophosphorylation agent is phenyl thiophosphono dichloride; the molar ratio of the cardanol to the vulcanizing agent is 1: 1-6, wherein the temperature of the vulcanization reaction is 100-240 ℃.
2. The preparation method according to claim 1, wherein the molar ratio of cardanol to vulcanizing agent is 1: 2-4, wherein the temperature of the vulcanization reaction is 140-190 ℃.
3. A process according to claim 1, wherein a catalyst is added to the sulfiding reaction, the catalyst being selected from the group consisting of C 1～6 Organic amines and inorganic bases of (a).
4. The process according to claim 1, wherein a catalyst selected from one or more of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, tripropylamine, butylamine, pentylamine, hexylamine, aqueous ammonia, sodium hydroxide, potassium hydroxide, zinc hydroxide, sodium oxide, potassium oxide, zinc oxide, sodium carbonate, potassium carbonate and zinc carbonate is added to the sulfidation reaction.
5. The preparation method according to claim 1, wherein the reaction conditions of the cardanol vulcanization product or cardanol and the thiophosphorylation agent are as follows: the molar ratio between the thiophosphorylation agent and cardanol is 1:1 to 10; the reaction temperature is 50-150 ℃.
6. The preparation method according to claim 1, wherein the reaction conditions of the cardanol vulcanization product or cardanol and the thiophosphorylation agent are as follows: the molar ratio between the thiophosphorylation agent and cardanol is 1:1 to 5; the reaction temperature is 60-100 ℃.
7. A process according to claim 1, wherein a catalyst is added to the thiophosphorylation reaction, said catalyst being selected from the group consisting of C 1～10 Organic and inorganic ammonium.
8. The process according to claim 1, 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 thiophosphorylation reaction.
9. The thiophosphonate sulfide compound produced by the process according to any one of claims 1 to 8, for use as an extreme pressure antiwear agent for lubricating oils or greases.
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