CN1036716C - Phosphosulfides compounds - Google Patents
Phosphosulfides compounds Download PDFInfo
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- CN1036716C CN1036716C CN91112817A CN91112817A CN1036716C CN 1036716 C CN1036716 C CN 1036716C CN 91112817 A CN91112817 A CN 91112817A CN 91112817 A CN91112817 A CN 91112817A CN 1036716 C CN1036716 C CN 1036716C
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- UAQJVNPFHGOEAH-UHFFFAOYSA-N oxido-oxo-phosphosulfanylphosphanium Chemical class O=P(=O)SP(=O)=O UAQJVNPFHGOEAH-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000005864 Sulphur Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 23
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 238000005987 sulfurization reaction Methods 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 239000000460 chlorine Chemical group 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 5
- 229920001021 polysulfide Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical class [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- -1 sulfur phosphorus compound Chemical class 0.000 description 32
- 239000000126 substance Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 25
- 239000011701 zinc Substances 0.000 description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- 238000000921 elemental analysis Methods 0.000 description 24
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000004679 31P NMR spectroscopy Methods 0.000 description 20
- 230000000996 additive effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- GTCZFOKUGWSLLG-UHFFFAOYSA-N OS([P])(=O)=O Chemical compound OS([P])(=O)=O GTCZFOKUGWSLLG-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 2
- 150000002148 esters Chemical class 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
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 210000003097 mucus Anatomy 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Abstract
New phosphorus-sulphur compounds corresponding to the following general formula (I): (((R<1>-Sx-Oy-A-)rBv)pP(X)-Yt-)qZm in which, for example, R<1> denotes an alkyl or alkenyl group, A denotes the group -(CH2)n-O-, B denotes the group -P(S)-S-CH2-CH(CH3)-O-, X denotes an oxygen atom or a sulphur atom, Y denotes an oxygen atom, a sulphur atom or an oxygen- or sulphur-containing hydrocarbon chain, Z denotes a hydrogen, chlorine or sulphur atom or a polysulphide chain, a metal or an alkyl or alkenyl group, x = 1, 2 or 3, y = 0, 1 or 2, v = 0 or 1, r = 1 (if v = 0) or r = 2 (if v = 1), p = 2 or 3, t = 0 or 1, m = 0, 1 or 2, q = valency of Z if Z is a metal or q = 1 or 2; n being a number from 1 to 30. Use of the said compounds as additives for lubricating oils.
Description
The present invention relates to new sulfur phosphorus compound (organic compound that promptly contains sulphur and phosphorus) preparation method.The compound that the present invention obtains can be used as petroleum additive and uses, and particularly is used as antioxygen, wear-resistant, extreme pressure and corrosion resistant additive in lubricating oil.
Over past ten years, wear-resistantly be used in particular in machine oil, transmission fluid and the hydraulic liquid with additive extreme pressure.Developed many additive types, wherein some can reduce the loss of machinery greatly, thereby has prolonged its life-span.
The most effective in the additive of wear-resisting and extreme pressure, thereby also be that what to have maximum industrial development future is the dialkyldithiocarbamacompositions fat of dialkyl group and diaryl phosphorodithioate and metal, (particularly those zinc salts), the terpenes of alkylthio phosphoric acid ester, tricresyl phosphate (to the toluene ester), di(2-ethylhexyl)phosphate (dodecyl) ester, sulfo-, the spermaceti of sulfur-bearing oil and various chlorine compounds.Wherein some has been described in U.S. Pat-A-2364283,2364284,2365938,2410650,2438876,3190833.These generally are the heteroatomic compounds that contains just like sulphur and phosphorus, or contain single (as the terpenes and the dithiocarbamate of tricresyl phosphate (to the toluene ester), sulfur-bearing) or both bonded (as the dialkyl dithiophosphate and the alkylthio phosphoric acid ester of metal).Reference has French Patent FR-A-982719 and 1321821 and U.S. Pat-A-2750342 and 3944495.
Used in the past sulfur phosphorus compound has the amount of relative sulphur and phosphorus, and it is that the stoichiometry by reaction adds in its building-up process.Its special character of composing and extreme pressure wear-resistant with it, this character can not be improved by the technical specialist.
Found new thin phosphorus compound now, it can preferably prepare by phosphorus reagent commonly used and the reaction of (many) sulfurized alcohols as lubricated additive, and this makes it can improve the performance of the wear-resisting relatively and extreme pressure at random of described sulfur phosphorus compound.
Have following general formula (I) according to sulfur phosphorus compound of the present invention:
(((R
1-S
X-Oy-A-) rBv-)
PP (X)-Y
t-)
qZm is R wherein
1Be that an alkyl group (as methyl, ethyl or the tertiary butyl) or kiki alkenyl group are (as, CH
z=C (CH
3)-CH
2-), it can be the functionalized or non-functionalized group that contains l～30 carbon urine; A representative-(CH
2) the n-O-group, or (
) basic child, in the base, n is the integer of l～30, and R
2And R
3Can be identical or different, each be represented hydrogen atom or has the monoradical (as methyl, ethyl etc.) of the hydrocarbonylation basically of 1-30 carbon atom, R
2And R
3Can interconnect and form the polymethylene chain and common A representative-(OH
2) n-O-; The B representative
Group, wherein R
4And R
5Can be identical or different, and each monoradical of representing hydrogen atom or having the hydrocarbonylation basically of 1-30 carbon atom, and R
4And R
5Can interconnect and form a polymethylene chain: as R
4Be H R
5Be H or CH
3X is Sauerstoffatom or sulphur atom; Y is a Sauerstoffatom, sulphur atom or sulfur-bearing or oxygen containing hydrocarbon chain; Z is hydrogen atom, chlorine atom, sulphur atom, vulcanizes chain more, is selected from the metal as sodium, zinc, copper, molybdenum, lead, antimony and cadmium, the derivative that contains oxygen or sulfur-bearing or alkyl, alkenyl or the R of molybdenum
6Group, R
6Group can be the functionalized or non-functionalized group that contains 1-30 carbon atom, and X is equal to or greater than 1 integer, preferably equals 1,2 or 3; Y equals 0,1 or 2, and if y=D then (R
1-S
X-Oy-A-) r is just write as (R
1-S
X-A-) r; V equals 0 or 1 (if V=0 then just do not have the B group in by the chemical formula of compound of the present invention); If V=0, r then equal 1, if V=1 then r equals 2; P equals 2 or 3; T equals 0 or 1 (if t=0 then just do not have Y group in the general formula of The compounds of this invention); M equals 0 or 1 (if m=0 does not then just have the Z group in the chemical formula of The compounds of this invention); If with Z be a metal, q equals the valent integer of Z or equals 1 or 2 numerical value.
At R
1And R
5Definition in, term functionalization group is interpreted as referring to containing at least one such as the heteroatoms of chlorine or sulphur or contain at least one such as the chemical functional group that is selected from carboxyl, aldehyde, ketone, nitrile, hydroxyl and epoxide function, thereby several this functional group may reside in same R
1And R
6In the group.
Connect according to dissimilar sulfur phosphorus compounds of the present invention preferably following (term (many) sulfuration is meant or single compound that vulcanizes (X=1) or many sulfurations (X＞1)):
Many sulfurized dialkyl dithiophosphoric acid of general formula (II) or two alkenyl phosphorodithioic acid:
(R
1-S
X-(CH
2) n-O-)
2Promptly in general formula (I), wherein A is-(CH P (S)-SH
2) n-O, X is that S, Y are that S, Z are H, y=0, v=0, r=1, p=2, t=1, q=1, and m=1; And in general formula (II), x is equal to or greater than 2 numerical value, can be those as the reference example of general formula (II), wherein R
1Be the tertiary butyl, x=2, n=2,3,4,5 or 6, preferred n=2,3 or 6, and R
1Be CH
2=C (CH
3)-CH
2-, x=2, n=2,3,4,5 or 6, preferred n=3;
(many) sulfurized alcohols of general formula (III):
R wherein
7And R
8Can be identical or inequality, on behalf of a hydrogen atom or representative, each the monoradical of the hydrocarbonaceous basically of 1-30 carbon atom is arranged; And R
7And R
8Can interconnect and form a polymethylene chain; The A that formula (III) is equivalent in the general formula (I) is (CH
2) n-O, X be that S, Y are that S, Z are
, y=0, v=0, r=1, p=2, t=1, q=1, m=1; And in formula (III), x is equal to or greater than 1 number; Formula (III) examples for compounds has those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
7Be H and R
8Be H or CH
3
Many metal sulphides salt of general formula (IV):
((R
1-S
X-(CH
2) n-O-)
2P (S)-S-) qZ wherein Z is a metal, and q equals the valent value of Z; Be that A in the general formula (I) is-(CH
2) n-O-, X be that S, Y are that S, Z are a metal (as zinc), y=0, v=0, r=1, p=2, the valency of t=1 q=z and m=1; And in formula (IV), x is equal to or greater than 2 numerical value, suc as formula the examples of compounds of (IV) those is arranged, and wherein R is the tertiary butyl or CH
2=C (CH
3)-CH
2-, X=2,3,4,5 or 6, Z is Zn q=2;
(many) sulfurations dialkyl dithio phosphorus base phosphorodithioic acid and corresponding (many) metal sulphides salt of logical formula V:
Wherein Z is H or metal (as, zinc), and promptly the A in the general formula (1) is-(CH
2) n-O-, X be that S, Y are that S, Z are H or metal, y=0, v=1, r=2, p=2, t=1, q=1 (is H as Z) or q are valency (if Z is a metal) and the m=1 of Z; And (v), x is equal to or greater than 1 in formula; The formula V examples for compounds has those, wherein, and R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H, R
5For
HOr CH
3, Z is that Zn (and q=2) or Z are H (and q=1);
(many) sulfurized organic compounds of general formula (VI):
((R
1-S
X-(CH
2) n-O-)
2P (S)-S-R
6That is, the A in the general formula (I) is-(CH
2) n-O-, X be that S, Y are that S, Z are R
6, y=0, v=0, r=1, p=2, t=1, q=1 and m=1; And in formula (VI), x is equal to or greater than 1 number and R
6Be R
6The monoradical of-OH alcohol; Formula (VI) examples for compounds is those, wherein R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6 and R
6Be (CH
3)
3-C-S-(CH
2)
3-CH
2-;
(many) sulfurized organic compounds of general formula (VII):
Be that A in the general formula (1) is-(CH
2) n-O-, X is S, and Y is S, and Z is R
6, y=0, v=1, r=2, p=2, t=1, q=1 and m=1; And in formula (VII), x is equal to or greater than 1 numerical value, and formula (VII) examples for compounds is those, and wherein R is the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H, R
5Be H or CH
3And R
6Be (CH
3)
3-C-S-(CH
2)
3-CH
2-;
Many sulfurized dialkyl group phosphoric acid of general formula (VIII) and two alkenyl phosphoric acid and corresponding many sulfurized metal-salt:
((R
1-S
X-(CH
2) n-O-)
2P (O)-O-) qZ wherein Z is H or metal (for example zinc), and promptly the A in the general formula (I) is-(CH
2) n-O-, X=0, Y=0, Z are H or metal, y=0, v=0, r=1, p=2, t=1, q=1 (if Z is H) or q are valency (if Z is a metal) and the m=1 of Z; And in formula (VIII), x is equal to or greater than 2 numerical value, and formula (VIII) examples for compounds is those, its R
1Be the tertiary butyl or CH
2-C (CH
3)-CH
2-, x=2, n=2,3,4,5 or 6, Z is that Zn (and q=2) or Z are H (and q=1);
The metal-salt of (many) sulfurized dialkyl dithio phosphorus base phosphoric acid of general formula (IX) and corresponding (many) sulfo-s:
Wherein Z is a H or a metal (as zinc), and promptly the A in the general formula (I) is-(CH
2) n-O-, X=0, Y=0, Z are a H or a metal, y=0, and v=1, r=2, p=2, t=1, q=1 (if Z is H) or q are valency (if Z is a metal) and the m=1 of Z; And in formula (IX), x is equal to or greater than 1 numerical value; The examples of compounds of formula (IX) is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-(CH
2)-, x=1, n=2,3,4,5 or 6, R
4Be H, R
5Be H or CH
3, Z is that Zn (and q=2) or Z are H (and q=1);
(many) sulfo-s dialkyl group chloro phosphoric acid ester of general formula (X) and two alkenyl chloro phosphoric acid ester:
(R
1-S
X-(CH
2) n-O-)
2P (O)-Cl is that the A in the general formula (1) is (CH
2) n-O-, X=0, Z are Cl, y=0, v=0, r=1, p=2, t=0, q=1 and m=1; And in formula (X), x is equal to or greater than 2 numerical value, and the examples for compounds of formula (X) is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=2, n=2,3,4,5 or 6, preferred n=3 or 6;
(many) sulfurized dialkyl group chloro thiophosphatephosphorothioate of general formula (XI) and two alkenyl chloro thiophosphatephosphorothioates:
(R
1-S
X-(CH
2) n-O-)
2P (S)-Cl is that A is-(CH in the general formula (1)
2) n-O-, X is S, Z is Cl, y=0, v=0, r=1, p=2, t=0, q=1 and m=1; And in formula (XI), x is equal to or greater than 1 numerical value, and formula (XI) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1, or 2, n=2,3,4,5 or 6, and preferred n=3 or 6;
The organic compound of (many) sulfo-s of general formula (XII):
Be that A in the general formula (1) is-(CH
2) n-O-, X=0, Z are Cl, y=0, v=1, r=2, p=2, t=0, q=1 and m=1; And in formula (XII), x is equal to or greater than 1 numerical value, and formula (XII) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=(CH
3)-CH
3-, x=1 or 2, n=2,3,4, S or 6, R
4Be H and R
5Be H or CH
3
(many) sulfurized organic compound of general formula (XIII):
Be that A in the general formula (1) is-(CH
2) n-O-, X is S, Z is Cl, y=0, v=1, r=2, p=2, t=0, q=1 and m=1; And in formula (XIII), x is equal to or greater than 1 numerical value, and formula (XIII) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H and R
5Be H or CH
3
(many) sulfurized trialkyl phosphates of general formula (XIV) and three alkenyl phosphoric acid ester:
(R
1-S
X-(CH
2) n-O-)
3P (O) wherein X is equal to or greater than 2 numerical value, and promptly the A in the general formula (I) is-(CH
2) n-O-, x=0, y=0, v=0, r=1, p=3, t=0, q=1 and m=0; Formula (XIV) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=2, and n=2,3,4,5 or 6;
(many) sulfurized organic compound of general formula (XV):
Wherein x is equal to or greater than 1 numerical value, and promptly the A in the general formula (I) is-(CH
2) n-O-, x=0, y=0, v=1, r=2, p=3, t=0, q=1 and m=0; Formula (XV) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H and R
5Be H or CH
3
(many) sulfurized trialkyl thiophosphatephosphorothioate of general formula (XVI) or three alkenyl thiophosphatephosphorothioates:
(R
1-S
X-(CH
2) n-O-)
3P (S) wherein, X is equal to or greater than 1 numerical value, that is, the A in the general formula (I) is-(CH
2) n-O-, X is S, y=0, v=0, r=1, p=3, t=0, q=1 and m=0; Formula (XVI) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2 and n=2,3,4,5 or 6;
(many) sulfurized organic compound of general formula (XVII):
Wherein, x is equal to or greater than 1 numerical value, and promptly the A in the formula (I) is-(CH
2) n-O-, X is S, y=0, v=1, r=2, p=3, t=0, q=1 and m=0; Formula (XVII) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H and R
5Be H or CH
3
(many) sulfurized dialkyl phosphonates of general formula (XVIII) or two alkenyl phosphonic acid esters:
(R
1-S
X-(CH
2) n-O-)
2P (O)-H wherein x is equal to or greater than 1 numerical value, and promptly the A in the general formula (I) is-(CH
2) n-O-, X=0, Z are H, y=0, v=0, r=1, p=2, t=0, q=1 and m=1; Formula (XVIII) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6;
(many) sulfurized organic compound of general formula (XIX):
Wherein, x is equal to or greater than 1 numerical value, and promptly the A in the general formula (I) is-(CH
2) n-O-, x=0, Z are H, y=0, v=1, r=2, p=2, t=0, q=1 and m=1; Formula (XIX) examples for compounds is those, its R
1Be the tertiary butyl or CH
2=C (CH
3)-CH
2-, x=1 or 2, n=2,3,4,5 or 6, R
4Be H and R
5Be H or CH
3: (many) sulfurized organic compound of general formula (XX):
Wherein x is equal to or greater than 1 numerical value; With n is to be equal to or greater than 3 numerical value, and promptly the A in the general formula (I) is-(CH
2) n-O-, X is S, Y is
, R
7And R
8As above-mentioned defined, Z is S
w, w is equal to or greater than 1 numerical value, y=0, v=0, r=1, p=2, t=1, q=1 and m=1; Formula (XX) examples for compounds is those, its R
1Be CH
3, C
2H
5-, (CH
3)
3C-and CH
2=C (CH
3)-CH
2, x=1,2 or 3, n=3,4,5 or 6, R
7Be H, R
8Be H or CH
3, and w=1,2,3 or 4; And have the compound (the tBu=tertiary butyl) of following chemical formula more specifically:
((tBu-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
((tBu-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
2
((tBu-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
3
((tBu-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
((tBu-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
2
((tBu-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2)
2S
3
The preparation method of sulfur phosphorus compound of the present invention illustrates in an embodiment.Particularly, because its good antioxygen, erosion resistance and especially wear-resisting and extreme pressure characterisitic, according to each sulfur phosphorus compound of the present invention all can be advantageously mineral and/or synthetic lubricating oil in be used as additive, its concentration is 0.05～5% (weight).
Therefore, the present invention relates to lubricating composition, it is the sulfur phosphorus compound at least a of the present invention that adds the lubricating oil and 0.05～5% (weight) of main ratio.
Following embodiment illustrates the present invention and does not limit its scope.Embodiment 1: single sulfurized dialkyl dithiophosphoric acid (known product) synthetic.
In the first step, with 3000cm
3Straight alcohol add 6000cm
3Three neck reactors in, then add the sodium hydroxide of 372g (9.3 moles).After the dissolving, with mixture heating up to 50 ℃ and add the 2-methyl-propane-2-mercaptan of 837.6g (9.3 moles) gradually.After adding, kept again 30 minutes, then be cooled to 20 ℃ at 50 ℃.Add gradually then 878.8g (9.3 moles) just-the chloro propyl alcohol.Mixture was carried out pure reflux 6 hours, then cool to room temperature.
The NaCl that generates by removing by filter, and organic solution 2N HCl acidified aqueous solution.Collect organic phase and use the dichloromethane extraction water then.Merge organic moiety, wash with water, in anhydrous Na
2SO
4Last dry, and evaporation under reduced pressure and remove methylene dichloride.
Distill with purified product down by reduced pressure (PE=84 ℃/1mm crust), obtain the 1370g colorless product, its results of elemental analyses is as follows:
Carbon (% weight) H (% weight) S (% weight) measured value theoretical value measured value theoretical value measured value theoretical value (Fd) is (Fd) (Th) (Fd) (Th) 56.81 56.73 10.79 10.81 21.84 21.66 (Th)
By
13CNMR analyzes and determines that the chemical structure of giving the phase is:
(CH
3)
3C-S-(CH
2)
3-OH (single sulfurized alcohol)
In second step, with the single sulfurized alcohol 189.6g (1.28 moles) and the 400cm of above-mentioned preparation
3Chloroform add 2000cm
3Three neck reactors.With mixture heating up to 60 ℃, then add the P of 71.12g (0.32 mole) gradually
2S
5Dissolving P fully
2S
5After, mixture kept under 60 ℃ 1 hour again and with stirring.After under reduced pressure, removing chloroform, collect the 240g weak yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 43.21 43.05 7.97 7.94 32.71 32.86 8.02 7.94
13C NMR analyzes the chemical structure of the conclusive evidence material that gives, that is:
((CH
3)
3C-S-(CH
2)
3-O)
2P (S)-SH embodiment 2: single sulfurized zinc dialkyl dithiophosphate (known product) synthetic
With the dialkyl group thiophosphoric acid (30g, promptly 0.077 mole) of the partial vulcanization of top gained by adding 100cm therein
3Aqueous sodium hydroxide solution (NaOH=3.2g, promptly 0.08 mole) and be transformed into sodium salt.By with hexane continuous extraction and this sodium salt of purifying, then with the purification of aqueous solutions that reclaims with being dissolved in 30cm
3The 7H of the 12.66g of water (0.045 mole)
2OZnSO
4Solution-treated.Precipitate this sulfurized zinc dialkyl dithiophosphate then immediately.Use the chloroform extraction mixture, the organic phase of recovery is in anhydrous Na
2SO
4Last dry, evaporation under reduced pressure desolvates to remove then.Collect the sticking yellow liquid of 20.3g like this, it has following results of elemental analyses: C, (% weight) H, (% weight) S, (% weight) P, (% weight) Zn, (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 40.11 39.81 7.26 7.11 30.69 30.40 7.24 7.35 7.82 7.75 and, infrared
31P and
13C NMR analyzes the chemical structure of the zinc salt of determining the material that gives, that is:
(((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S)
2Zn embodiment 3: the dialkyl dithiophosphoric acid alcohol of single sulfo-synthetic.
The dialkyl dithiophosphoric acid (60g, promptly 0.154 mole) of the partial vulcanization of embodiment 1 gained is added 250cm
3Three neck reactors, then add the propylene oxide of 10g (0.172 mole) gradually, make temperature of reaction be no more than 30 ℃ simultaneously.Behind the excessive propylene oxide of vapourisation under reduced pressure, reclaim the 66g light yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 45.75 45.51 8.57 8.26 29.12 28.61 6.92 6.92
It is infrared,
31P and
13C NMR analyzes and has determined the chemical structure of expecting, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-OH embodiment 4: single sulfurized dialkyl dithio phosphorus base zinc dithiophosphate synthetic
One Dean is being housed---the 250cm of Rodney Stark separator
3In the three neck reactors; The yellow soda ash and the 100cm that add 1.7g (0.016 mole)
3Benzene.Make medium anhydrous in 1 hour the mixture reflux, then add the P of 3.66g (0.0165 mole)
2S
5The single sulfurized dialkyl dithiophosphoric acid alcohol that adds embodiment 3 preparations of 29.6 grams (0.066 mole) then gradually.Reflux mixture and keeping 3 hours then.
Then be cooled to 50 ℃ and add 20cm
3The ethanol that contains 0.4g (0.01 mole) sodium hydroxide.Reaction was carried out 1 hour.Filtration is to remove excessive P
2S
5, then add 50cm
3Contain 10g 7H
2OZnSO
4The aqueous solution of (0.0356 mole) also makes reaction carry out 2 hours, and follow violent stirring.Then at Na
2SO
4Last dry, filtration and evaporation under reduced pressure benzene etc.Reclaim light yellow mucus, it has following results of elemental analyses: C (% weight) H (% weight) S (% weight) P (% weight) Zn (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 40.01 39.91 7.27 7.04 30.89 31.36 8.95 9.10 3.06 3.20
Infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, that is: ((((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O)
2P (S)-S-)
2Zn embodiment 5: dialkyl dithiophosphoric acid three esters of single sulfo-synthetic
In the first step, 30g (0.2 mole) embodiment 1 prepared single sulfurized alcohol is dissolved in 60cm
3In the chloroform, then add 11.9g SOCl gradually
2(0.1 mole).The reflux mixture then adds 11.94g SOCl gradually then
2(0.1 mole) then kept reflux 2 hours again.After the cooling, the evaporative removal chloroform by the chlorine derivative of underpressure distillation (PE=92 ℃/1mm crust) purifying corresponding to single sulfurized alcohol, obtains 31.5g product (0.189 mole).
In second step, single sulfurized dialkyl dithiophosphoric acid 27.3g (0.07 mole) that embodiment 1 is prepared changes sodium salt into by embodiment 2 pointed methods.Sodium-salt aqueous solution with purifying mixes with 1g 4-butyl ammonium hydrogen sulfate (phase-transfer catalyst) then, then adds the halogen-containing derivative of the top the first step gained of 11.42g (0.07 mole), and it is dissolved in 10cm
3Methylene dichloride.With mixture reflux 10 hours, cooling, the organic phase of recovery washes with water, at Na
2SO
4Last dry, filter and vapourisation under reduced pressure.Reclaim the 35g product like this, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 48.78 48.43 8.57 8.65 31.02 30.81 6.04 5.96
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-S-C-(CH
3)
3Embodiment 6: single sulfurized dialkyl group chloro phosphoric acid ester synthetic.
Embodiment 6.1 (known product)
At a 500cm
3Add in the three neck reactors and be dissolved in 50cm
316g in the benzene (0.104 mole) POCl
3Then add single sulfurized alcohol gradually, 16g pyridine and 50cm by 30.8g (0.208 mole) embodiment 1 preparation
3The solution that benzene constituted.The gained mixture was at room temperature stirred 1 hour.The pyridinium chloride of gained is by removing by filter, and organic phase washes with water, at Na
2SO
4Last dry, and evaporation under reduced pressure.Obtain the 38g product, its results of elemental analyses is as follows:
C (% weight) H (% weight) S (% weight) P (% weight) Cl (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 44.89 44.61 8.02 7.97 17.44 17.03 8.11 8.23 9.65 9.43
Infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives:
((CH
3)
3C-S-(CH
2)
3-O-)
2P (O)-Cl embodiment 6.2:(product innovation)
On the basis of the prepared single sulfurized sulfo-phosphorus alcohol of embodiment 3, carry out the product that same experiment causes being equivalent to following structural formula: (((CH
3)
3C-S-(CH
2)
3-O)
2P (S)-S-CH
2-CH (CH
3)-O-)
2P (O)-Cl embodiment 7: single sulfurized dialkyl group zinc phosphate synthetic.Embodiment 7.1 (known product)
In the first step with 18g (0.048 mole) embodiment 6 first single sulfurized dialkyl group chloro phosphoric acid ester and 50cm
3The 2N sodium hydroxide solution carried out vigorous stirring 2 hours, then extracted mixture with toluene.The water that is reclaimed carries out acidifying with 2N hydrochloric acid, with the toluene extraction, washes with water, at Na
2SO
4Last dry, filter and evaporation under reduced pressure.Obtain the 15g yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 47.21 46.91 8.87 8.66 17.45 17.91 8.44 8.66
It is infrared,
31P and
13The chemical structure that C NMR analyzes single sulfurized dialkyl group phosphoric acid of determining the material that gives is:
((CH
3)
3C-S-(CH
2)
3-O-)
2P(O)-OH
In second step, single sulfurized dialkyl group phosphoric acid that the first step above the 15g (0.042 mole) is made is with being dissolved in 50cm
3The 2.35g potassium of methyl alcohol neutralizes.At room temperature keep stirring 30 minutes, then add 12.7g (0.045 mole) and be dissolved in 25cm
37H in the water
2O ZnSO
4At room temperature stirred the mixture 30 minutes, and then used alcohol extraction.The organic phase that reclaims washes with water, at Na
2SO
4Last dry, filter, then vapourisation under reduced pressure.Obtain the very sticking lacteous liquid of 15g, its results of elemental analyses is as follows:
C (% weight) H (% weight) S (% weight) P (% weight) Zn (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 43.52 43.10 7.55 7.70 16.26 16.45 8.14 7.95 8.11 8.39
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
2P (O)-O-)
2Zn embodiment 7.2 (product innovation)
On the basis of the chlorine derivative of the prepared single sulfurized sulfo-phosphorus alcohol of embodiment 3, carry out the product that same experiment (consulting embodiment 6.1) causes being equivalent to following structural formula: ((((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O-)
2P (O)-O-)
2Zn embodiment 8: single sulfurized trialkyl phosphates synthetic.Embodiment 8.1 (known product)
With 10g (0.065 mole) POCl
3Be dissolved in 50cm
3In the benzene.Mixture is cooled to 5 ℃, then goes into prepared single sulfurized alcohol in gradually, 30g pyridine and 50cm by 28.9g (0.195 mole) embodiment 1
3The solution that benzene constituted remains on temperature of reaction 5 ℃ simultaneously.After the adding, under this temperature, kept again 30 minutes.Then be heated to solvent refluxing and keep boiling 2 hours.Cooling solution filters, and organic phase washes with water, at Na
2SO
4Last dry, filter and vapourisation under reduced pressure.Obtain the 27g product, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 51.87 51.62 9.54 9.22 19.22 19.70 6.11 6.35
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
3P (O) embodiment 8.2 (product innovations)
On the basis of embodiment 3 prepared single sulfurized sulfo-phosphorus alcohol, carry out the product that same experiment causes being equivalent to following structural formula:
(((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O-)
3P (O) embodiment 9: the synthetic embodiment 9.1. of single sulfurized trialkyl thiophosphatephosphorothioate
Repeat the experiment of embodiment 8.1, and with the PSCl of same molar weight
3Replace POCl
3After reaction and the processing, collect the 24g product, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 50.12 49.97 9.01 8.92 25.12 25.43 6.11 6.15
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
3P (S) embodiment 9.2
On the basis of embodiment 3 prepared single sulfurized sulfo-phosphorus alcohol, carry out same experiment, obtain being equivalent to the product of following structural formula:
(((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O-)
3P (S) embodiment 10: the synthetic embodiment 10.1 of single sulfurized dialkyl phosphonate
30g (0.18 mole) embodiment 1 prepared single sulfurized alcohol is dissolved in 100cm
3Tetracol phenixin in.Then at room temperature, progressively add 8.25g (0.06 mole) and be dissolved in 50cm
3The PCl of tetracol phenixin
3Boil and under this temperature, kept 1 hour.Evaporation under reduced pressure with remove desolvate and by the liquid silica gel column chromatography by separating dialkyl phosphonate in the halogen-containing derivative.Obtain 18 gram products, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 49.32 49.08 9.21 9.06 18.62 18.74 8.95 9.06
Infrared,
31P and
13C NMR analyzes and determines to give the material chemical structure, that is:
((CH
3)
3C-S-(CH
2)
3-O-)
2P (O)-H embodiment 10.2
On single sulfurized sulfo-phosphorus alcohol basis of embodiment 3 preparations, carry out same experiment, cause being equivalent to the product of following structural formula: (((CH
3)
3C-S-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O-)
2P (O)-H
Use many sulfurized alcohol (x＞1) can repeat these experiments (or synthetic).Like this, can be adjusted in the sulfur content that is contained by in the additive of the present invention at random, thereby obtain having and to regulate wear-resisting and product extreme pressure characterisitic.Following examples have illustrated these character.Embodiment 11: many sulfurized alcohols synthetic
At a 500cm
3Three neck reactors in add 200cm
3Methyl alcohol adds 44g (1.1 moles) sodium hydroxide then.After the dissolving,, then progressively add 99g (1.1 moles) 2-methyl-2-propane-mercaptan with mixture heating up to 50 ℃.After adding, again temperature is remained on 50 ℃ 30 minutes.Then progressively add 33.2g (1.1 grammeatom) elementary sulfur, make it reaction till sulphur dissolves fully at 50 ℃ then.Then progressively add 92.5 the gram (1 mole) just-the chloro propyl alcohol.Heated mixt is to alcohol reflux 6 hours, cool to room temperature then.
Remove by filter the NaCl that is generated, evaporation under reduced pressure organic solution.Wash organic phase with water to remove the excessive sodium polysulphide of toluene extraction, at Na
2SO
4Last dry, and evaporation under reduced pressure.Resulting rough many sulfurized alcohols are used hexane wash-out impurity (tertiary butyl polysulfide) simultaneously with the liquid chromatography purifying on the silica gel, reclaim desired product with methanol-eluted fractions.Behind the evaporation methyl alcohol, reclaim many sulfurized of 173g tertiary butyl alcohol, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) measured value theoretical value measured value theoretical value measured value theoretical value 46.87 46.63 8.92 8.88 35.24 35.60
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining the material that gives, the statistics mixture of the sulfurized alcohol of promptly following summary structural formula:
(CH
3)
3C-S
2-(CH
2)
3-OH embodiment 12: many sulfurized dialkyl dithiophosphoric acid synthetic
-1000cm
3Add 150g (0.83 mole) embodiment 11 prepared many sulfurized alcohols and 400cm in the three neck reactors
3Chloroform.With mixture heating up to 60 ℃, then progressively add 46.11g (0.207 mole) P
2S
5At P
2S
5After the dissolving, kept mixture again 1 hour fully at 60 ℃, and with stirring.After under reduced pressure, removing chloroform, collect the 185g light yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 37.12 36.97 6.92 6.82 42.11 42.34 6.71 6.82
It is infrared,
31P and
13C NMR analyzes definite chemical structure of being expected, promptly
((CH
3)
3C-S
2-(CH
2)
3-O-)
2Synthesizing of P (S)-SH embodiment more than 13. sulfuration dialkyl dithiophosphoric acid alcohol.
Many sulfurations dialkyl dithiophosphoric acid (0.22 mole) that 100g embodiment 12 is obtained adds a 500cm
3Three neck reactors then progressively add 15g (0.26 mole) propylene oxide, make temperature of reaction be no more than 30 ℃ simultaneously.Under reduced pressure, reduce excessive propylene oxide, reclaim the 112g light yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 39.94 39.81 7.35 7.22 37.32 37.55 6.01 6.05
It is infrared,
31P and
13C NMR analyzes the chemical structure of the alcohol of determining the material that gives:
((CH
3)
3C-S
2-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-OH embodiment 14: many sulfurized zinc dialkyl dithiophosphate synthetic.
Repeat the experiment of embodiment 1 and 2 with embodiment 11 prepared many sulfurized alcohols.Then reaction and separating, obtain many sulfuration zinc dialkyl dithiophosphates, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) Zn (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 34.82 34.56 6.37 6.17 39.12 39.58 6.14 6.38 6.46 6.73
It is infrared,
31P and
13C NMR analyzes the chemical structure of the product of determining the material that gives, that is:
(((CH
3)
3C-S
2-(CH
2)
3-O-)
2P (S)-S)
2Zn embodiment 15: many sulfurized dialkyl dithio phosphorus base zinc dithiophosphate synthetic.
Use embodiment 13 prepared many sulfurized dialkyl dithiophosphoric acid alcohol to repeat the experiment of embodiment 4.Then reaction and separating, obtain many sulfurized dialkyl dithio phosphorus base zinc dithiophosphate, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) Zn (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 35.58 35.46 6.46 6.26 38.67 39.01 7.95 8.08 2.64 2.84
It is infrared,
31P and
13C NMR analyzes the chemical structure of determining product, that is: ((((CH
3)
3C-S
2-(CH
2)
3-O-)
2P (S)-S-CH
2-CH (CH
3)-O-)
3P (S)-S-)
2The extreme pressure of Zn additive of the present invention and the mensuration of wear-resisting property
The test that shows the wear-resisting and extreme pressure characterisitic of additive of the present invention is to carry out in the lubricant formulations of gear oil type.
According to the method for ASTM D2783, nationality helps the machine of four balls and has studied embodiment 2,3,4,5,8.1,9.1,10.1,11,14 and 15 additive, and its concentration is the sulphur content of mineral base oil SAE80W90 is equaled or to approach 0.2% (weight).Gained the results are shown in table 1.
Can see that especially functional additive of the present invention has good wear-resisting and extreme pressure characterisitic, it can be improved by the function of used sulphur content in synthetic.Can also see that concerning same sulphur concentration, polysulfide type additive (x=2 in this case) generally has better properties than single sulfur compound (x=1) additive, it can regulate these mechanical performance of products at random, according to the function of selecting x (1,2,3 etc.) value.This improvement is advantageously used in lubricating oil preparation, particularly gear oil.
Table 1
The wearing and tearing additive is added on 1 hour loading capacity of load-carrying welding load-carrying number (% weight) (% weight) (% weight) value 40Kgf 60Kgf 80Kgf before the amount S amount wearing and tearing load-carrying chucking of S amount agent of embodiment of the extreme pressure impression diameter (mm) in the oil in oil in additive
Kgf Kgf Kgf 392.4 588.6 784.8----28.0 274.7 50 490.5 150 1471.5 1.47 1.90 2.50 2 30.69 0.652 0.2 36.0 353.2 80 784.8 200 1962.0 0.36 0.68 0.98 14 39.21 0.510 0.2 55.4 543.5 126 1236.1 250 2452.5 0.33 0.60 0.87 4 30.89 0.647 0.2 42.9 420.8 100 981.0 200 1962.0 0.45 0.66 0.98 15 38.67 0.517 0.2 47.0 461.1 100 981.0 250 2452.5 0.37 0.65 0.90 3 29.12 0.755 0.22 34.9 342.4 80 784.8 200 1962.0 0.35 0.52 1.10 5 31.02 0.709 0.22 33.8 331.6 80 784.8 200 1962.0 0.36 0.55 1.07 8.1 19.22 1.116 0.22 35.9 352.2 80 784.8 200 1962.0 0.39 0.67 0.93 9.1 25.12 0.875 0.22 42.9 420.8 100 981.0 250 2452.5 0.37 0.61 0.90 10.1 18.62 1.182 0.22 50.6 496.4 126 1236.1 200 1962.0 0.42 0.48 1.20 11 35.24 0.624 0.22 37.2 364.9 80 784.8 200 1962.0 0.39 0.54 1.0916：：
(((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
The a-the first step prepares single sulfurized alcohol:
(CH
3)
3C-S-(CH
2)
3-OH
With 150cm
3Straight alcohol adds a 500cm
3In the three neck reactors, then add 18.6g (0.465 gram mole) sodium hydroxide.After the dissolving,, then progressively add the 2-methyl-2-propane mercaptan of 41.9g (0.465 gram mole) with mixture heating up to 50 ℃.After adding, temperature kept 30 minutes at 50 ℃ again, then was cooled to 20 ℃.Progressively add then 43.95g (0.465 gram mole) just-the chloro propyl alcohol, mixture heating up to alcohol reflux 6 hours, then is cooled to envrionment temperature.
Formed NaCl is by removing by filter organic solution 2N HCl acidified aqueous solution.Collect organic phase, use the dichloromethane extraction water then.Merge organic part, wash with water, in anhydrous Na
2SO
4Last dry, evaporation under reduced pressure is to remove methylene dichloride.
Contain mercaptan by distillation under the reduced pressure (PE=84 ℃/1 millibar) with purifying.Reclaim 68.5 gram colorless product, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) measured value theoretical value measured value theoretical value measured value theoretical value 56.81 56.73 10.79 10.81 21.84 21.66
It is infrared,
1H and
13C NMR analyzes the chemical structure of determining product.
In second step of b-, prepare single sulfurized dialkyl dithiophosphoric acid:
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-SH
At 250cm
3Add 19.0g (0.128 gram mole) prepared single sulfurized alcohol and 40cm in the first step in the reactor
3Chloroform.With mixture heating up to 60 ℃, then progressively add 7.11g (0.032 gram mole) P
2S
5After the dissolving, again mixture was kept 1 hour at 60 ℃ fully, and with stirring.Under reduced pressure remove chloroform, obtain the 24g light yellow liquid, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 43.21 43.05 7.97 7.94 32.71 32.86 8.02 7.94
It is infrared,
1H and
13What C NMR analyze to determine product gives the material chemical structure.
In the 3rd step of c-, prepare single sulfurized dialkyl dithiophosphoric acid alcohol:
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-OH
At a 100cm
3Add 22.0 (0.0564 gram moles) in the reactor at the prepared sulfur-bearing dialkyl dithiophosphoric acid of previous step, then add 2.8g (0.064 gram mole) oxyethane, stirring and quick cooling are to maintain the temperature at 25 ℃ simultaneously.Vapourisation under reduced pressure is removed excessive oxyethane, collect 24 gram mucus, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 44.09 44.22 8.12 8.06 29.32 29.53 7.03 7.14
It is infrared,
1H,
31P and
13C NMR analyzes the chemical structure of the product of determining the material that gives.
In the 4th step of d-, preparation is equivalent to the muriate of top single sulfurized dialkyl dithio phosphorus alcohol alcohol:
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-Cl
At 100cm
3Add 20.0g (0.046 gram mole) in the reactor and, then add the 20g chloroform, add 2.74g (0.023 gram mole) SOCl then very slowly at the prepared single sulfurized dialkyl dithiophosphoric acid alcohol of back
2, and temperature of reaction is maintained at about 20 ℃.Reflux mixture then adds the SOCl of same amount more very slowly
2After the cooling, under reduced pressure remove chloroform collecting about 20g product, it is infrared,
31P,
1H and
13C NMR analyzes the chemical structure of the product that is equivalent to the material that gives.
E-the 5th and final step prepare required compound:
(((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
In the reactor of previous step, add the 20g chloroform and contain chlorine derivative, then add 1g tetrabutylammonium chloride (phase-transfer catalyst), add 20cm at last very slowly with dissolving
3Contain 7g 9H
2O Na
2The aqueous solution of S (0.03 gram mole) is maintained at about temperature 20 ℃ simultaneously.With mixture reflux 1 hour, cooling also separated phase.The organic moiety that reclaims washes with water, in anhydrous Na
2SO
4Last dry, filter then, collect 19 gram products, its results of elemental analyses is as follows:
C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 44.89 44.31 7.99 7.85 32.47 33.30 7.01 7.15
It is infrared,
1H,
31P and
13C NMR analyzes the chemical structure of having determined product.Embodiment 17: synthetic compound
(((CH
3)
3C-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
Repeat the first step (a) of embodiment 16, and in reaction mixture, add 14.91g (0.465 gram mole) elementary sulfur to add up the compound that ground forms curing.After the reaction, the rough curing of gained alcohol is by the liquid chromatography purifying on silica gel, then with hexane drip washing removing impurity, and methanol-eluted fractions behind the vapourisation under reduced pressure, can reclaim the alcohol of the curing of needed purifying.Use the reagent of same molar ratio to continue experiment to obtain the 5th step (e) later product, its results of elemental analyses is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 38.97 38.60 7.05 6.84 41.02 41.90 6.01 6.23
It is infrared,
31P and
13C NMR analyzes the chemical structure of the product of determining to be equivalent to the material that gives.Embodiment 18: synthetic compound
(((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
2
The experiment of embodiment 16 was intactly repeated to for the 5th step, use 25cm
3Contain 7g 9H
2O Na
2S (0.03 gram mole) and 1g elementary sulfur (0.03 grammeatom) form the compound of curing with statistics ground.The product that obtains has following results of elemental analyses: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 43.22 42.73 7.85 7.57 34.89 35.68 6.73 6.90
It is infrared,
31P,
1H and
13C NMR analyzes the chemical structure determine to be equivalent to add up the product of the ground material that gives.Embodiment 19: synthetic compound
(((CH
3)
3C-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
3
Repeat the experiment of embodiment 17, with the dialkyl dithio phosphorus alcohol of the curing of preparation sulfur-bearing.Continue experiment, keep the whole mol ratios between reagent,, use 25cm up to the 5th step
3By 7g 9H
2O Na
2The aqueous solution that S (0.03 gram mole) and 2g elementary sulfur (0.06 grammeatom) are constituted is to form the desired three sulfurized compounds in statistics ground.The results of elemental analyses of products obtained therefrom is as follows: C (% weight) H (% weight) S (% weight) P (% weight) measured value theoretical value measured value theoretical value measured value theoretical value measured value theoretical value 36.86 36.26 6.78 6.42 44.71 45.42 5.34 5.85
It is infrared,
31P,
1H and
13C NMR analyzes the chemical structure determine to be equivalent to add up the product of the ground material that gives.The extreme pressure of the additive of embodiment 16～19 and the mensuration of wear-resisting property
Demonstration is a method according to ASTM D2783 according to the test of the extreme pressure of additive of the present invention and wear-resisting property.Use has the machine of four balls to carry out, and its concentration is to make the sulphur content of mineral oil SAE80W90 equal 0.22% (weight).Gained the results are shown in table 2.
These results show that additive of the present invention has good wear-resisting and extreme pressure characterisitic, and these can change by the function of element sulfur content used in synthetic.Show concerning equal sulphur concentration is arranged, to have the unitary compound ratio of polysulfide and have single sulfide unitary those are more effective especially, it may regulate these mechanical performance of products at random.This improvement can be advantageously used in the preparation of the lubricating oil of gear or metal rotation.
Table 2 additive is added on load-carrying welding load-carrying impression diameter before the S amount agent S amount wearing and tearing load-carrying welding of embodiment of the extreme pressure wearing and tearing in the oil in oil in additive, (mm) number, (% weight), (% weight), 1 hour weight-carrying capacity of (% weight) value
Kgf newton Kgf newton Kgf newton 40Kgf 60Kgf 80Kgf
392.4 newton 588.6 newton 784.8 newton--0-28.0 274.7 50 490.5 150 1471.5 1.47 1.90 2.50 16 32.47 0.68 0.22 33.8 331.6 80 784.8 200 1962.0 0.40 0.58 1.07 17 41.02 0.54 0.22 43.0 421.8 100 981.0 200 1962.0 0.39 0.55 0.98 18 34.89 0.63 0.22 36.0 353.2 80 784.8 200 1962.0 0.39 0.65 0.95 19 44.71 0.49 0.22 55.1 540.5 126 1236.1 250 2452.5 0.35 0.60 0.89
Claims (5)
1. the organic compound preparation method of following formula sulfur-bearing and phosphorus; ((R
1-S
X-(CH
2)
3-O-)
2P (S)-S-CH
2-CH
2)
2S
W
R wherein
1Be the tertiary butyl, x is 1-2, and w is 1-3, the method is characterized in that comprising:
(a) in the first step, choose wantonly help to reach in the presence of the certain proportion elementary sulfur of the x value that requires (greater than 1 o'clock) with mercaptan R
1SH with just-chloro propyl alcohol reaction and obtain one or curing alcohol of following formula
R
1-S
X-(CH
2)
3-OH
(b) in second step, with described one or curing alcohol and P
2S
5Reaction and obtain following formula
One or the curing dialkyl dithiophosphoric acid
(R
1-S
X-(CH
2)
3-O-)
2P(S)-SH
(c) in the 3rd step, with described one or curing dialkyl dithiophosphoric acid and reacting ethylene oxide and obtain one or curing dialkyl dithiophosphoric acid alcohol of following formula
(R
1-S
X-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-OH
(d) in the 4th step, with described one or curing dialkyl dithiophosphoric acid alcohol and SOCl
2Reaction and obtain the corresponding muriate of following formula
(R
1-S
X-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-Cl
And (e) in the 5th step, choose wantonly help to reach in the presence of the certain proportion elementary sulfur of the w value that requires (greater than 1 o'clock) with described muriate and Na
2S reaction and obtain desired compound.
2. method according to claim 1 wherein prepares following formula: compound
(((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
(a) in the first step, with 2-methyl-2-propane mercaptan with just-chloro propyl alcohol reaction and obtain a sulfurized alcohol of following formula
(CH
3)
3C-S-(CH
2)
3-OH
(b) in second step, with a described sulfurized alcohol and P
2S
5The reaction and obtain following formula one the sulfuration dialkyl dithiophosphoric acid
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-SH
(c) in the 3rd step, will be described a sulfuration dialkyl dithiophosphoric acid and reacting ethylene oxide and obtain one and vulcanize dialkyl group curing alcohol acid phosphate
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-OH
(d) in the 4th step, with a described sulfuration dialkyl dithiophosphoric acid alcohol and a SOCl
2Reaction and obtain the corresponding muriate of following formula
((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-Cl
And (e) in the 5th step, with described muriate and Na
2S reaction and obtain desired compound.
3. method according to claim 2 wherein prepares following formula: compound
(((CH
3)C-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
This method is in (a) the first step, addition element sulphur and obtain corresponding curing alcohol.
4. method according to claim 2 wherein prepares following formula: compound
(((CH
3)
3C-S-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
2
This method is in (e) the 5th step, addition element sulphur and obtain corresponding curing compound.
5. method according to claim 3 wherein prepares following formula: compound
(((CH
3)
3C-S
2-(CH
2)
3-O-)
2P(S)-S-CH
2-CH
2-)
2S
3
This method in (e) the 5th step, addition element sulphur and obtain corresponding three sulfuration compounds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9016530A FR2671084B1 (en) | 1990-12-27 | 1990-12-27 | NOVEL PHOSPHOSULFUR COMPOUNDS AND THEIR USE AS ADDITIVES FOR LUBRICATING OIL. |
| FR9016530 | 1990-12-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063493A CN1063493A (en) | 1992-08-12 |
| CN1036716C true CN1036716C (en) | 1997-12-17 |
Family
ID=9403867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91112817A Expired - Fee Related CN1036716C (en) | 1990-12-27 | 1991-12-27 | Phosphosulfides compounds |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1036716C (en) |
| FR (1) | FR2671084B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467769A (en) * | 2015-08-19 | 2017-03-01 | 雅富顿化学公司 | Phosphorus-containing compound and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4563114B2 (en) * | 2004-08-30 | 2010-10-13 | 出光興産株式会社 | Additive for lubricant |
| US9944879B2 (en) * | 2014-10-08 | 2018-04-17 | Afton Chemical Corporation | Phosphorous-containing compounds and uses thereof |
| KR102584012B1 (en) | 2016-10-31 | 2023-10-04 | 에프톤 케미칼 코포레이션 | Phosphorus-containing compounds and their uses |
| US10329511B2 (en) * | 2016-10-31 | 2019-06-25 | Afton Chemical Corporation | Lubricant compositions comprising thiophosphates and thiophosphate derivatives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591475A (en) * | 1968-12-09 | 1971-07-06 | Exxon Research Engineering Co | Preparation of unsymmetrical thiol-allene diadducts |
| US3944495A (en) * | 1974-02-19 | 1976-03-16 | Texaco Inc. | Metal dialkyldithiophosphates |
| US4154779A (en) * | 1976-03-04 | 1979-05-15 | Rhein-Chemie Rheinau Gmbh | Sulphurized phosphoric acid ester salts and method of preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA515666A (en) * | 1955-08-16 | S. Fletcher Beatrice | O,o,o',o'-tetraalkyl s,s'-oxydialkylene bis (thiophosphates) |
-
1990
- 1990-12-27 FR FR9016530A patent/FR2671084B1/en not_active Expired - Fee Related
-
1991
- 1991-12-27 CN CN91112817A patent/CN1036716C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591475A (en) * | 1968-12-09 | 1971-07-06 | Exxon Research Engineering Co | Preparation of unsymmetrical thiol-allene diadducts |
| US3944495A (en) * | 1974-02-19 | 1976-03-16 | Texaco Inc. | Metal dialkyldithiophosphates |
| US4154779A (en) * | 1976-03-04 | 1979-05-15 | Rhein-Chemie Rheinau Gmbh | Sulphurized phosphoric acid ester salts and method of preparation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467769A (en) * | 2015-08-19 | 2017-03-01 | 雅富顿化学公司 | Phosphorus-containing compound and application thereof |
| CN106467769B (en) * | 2015-08-19 | 2019-10-18 | 雅富顿化学公司 | Phosphorus-containing compound and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063493A (en) | 1992-08-12 |
| FR2671084A1 (en) | 1992-07-03 |
| FR2671084B1 (en) | 1993-04-09 |
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