CN106699806A - Low-impurity content zinc dialkyl dithiophosphate and preparation method and application thereof - Google Patents
Low-impurity content zinc dialkyl dithiophosphate and preparation method and application thereof Download PDFInfo
- Publication number
- CN106699806A CN106699806A CN201510783549.7A CN201510783549A CN106699806A CN 106699806 A CN106699806 A CN 106699806A CN 201510783549 A CN201510783549 A CN 201510783549A CN 106699806 A CN106699806 A CN 106699806A
- Authority
- CN
- China
- Prior art keywords
- zinc
- dialkyl dithiophosphate
- impurity content
- acid
- low impurity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012535 impurity Substances 0.000 title claims abstract description 88
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 68
- 239000011701 zinc Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 45
- -1 alkyl phenol Chemical compound 0.000 claims description 38
- LICUQAFOHXHWQC-UHFFFAOYSA-N [S].OP(O)(O)=O Chemical compound [S].OP(O)(O)=O LICUQAFOHXHWQC-UHFFFAOYSA-N 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 239000002199 base oil Substances 0.000 claims description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004246 zinc acetate Substances 0.000 claims description 13
- 150000003752 zinc compounds Chemical class 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000013459 approach Methods 0.000 claims description 6
- 230000001050 lubricating effect Effects 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003694 hair properties Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 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
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000002019 disulfides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 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
- 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 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- 238000003113 dilution method Methods 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 150000008282 halocarbons Chemical class 0.000 claims 1
- 150000003751 zinc Chemical class 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 208000005374 Poisoning Diseases 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 48
- 125000000217 alkyl group Chemical group 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229960005137 succinic acid Drugs 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical class [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 3
- 229960000250 adipic acid Drugs 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 241000249820 Lipotes vexillifer Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000625 Poly(1-decene) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- JMTIXSZQYHAMLY-UHFFFAOYSA-N [P].[Zn] Chemical compound [P].[Zn] JMTIXSZQYHAMLY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without 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
- C10M137/04—Phosphate esters
- C10M137/06—Metal salts
-
- 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
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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
The invention discloses low-impurity content zinc dialkyl dithiophosphate (ZDDP). In the zinc dialkyl dithiophosphate, phosphorus is volatile impurity phosphorus and available phosphorus; the molar percentage content of the volatile impurity phosphorus measured through a 31P-NMR spectrum does not exceed 7.2% of the total phosphorus content of the zinc dialkyl dithiophosphate. The invention further provides a preparation method of the low-impurity content zinc dialkyl dithiophosphate. The zinc dialkyl dithiophosphate provided by the invention has low impurity content and high available phosphorus content, has excellent volatility resistance and better oxidation resistance, wear resistance, corrosion resistance and other properties, and can effectively reduce the using mount in engine and transmission lubricating oil and reduce the risk of poisoning failure of an exhaust gas treatment catalyst.
Description
Technical field
The present invention be more particularly directed to a kind of zinc dialkyl dithiophosphate of low impurity content, its preparation method and application, category
In engine and transmission lubricant field.
Background technology
Zinc dialkyl dithiophosphate (ZDDP) as the wear-resistant anti-rotten multifunction additive of antioxygen, in lubricating oil
More than 60 years, be function admirable and most comprehensive multifunction additive, in the prior art still without a kind of additive energy
Replace ZDDP completely.Research in recent years find, the p and ses in zinc dialkyl dithiophosphate can cause Particulate Emission and
Other pollutant emissions increase.Additionally, the easily accumulation of phosphorous volatile matter is in the active metal catalyst position of exhaust catalytic converter
On point, cause catalyst poisoning, cause catalytic efficiency to reduce, exhaust emissions is unqualified.With the hair of GF-4 standards
Cloth, phosphorus content requirement is less than 0.08%, while also requiring to improve oxidation stability, wear resistance etc..In order to meet
Anti-oxidant, wear-resistant and control deposit requirement, it is necessary to more additives are added in formula, or improves addition
The performance of agent single dose.
Known references, such as US4263150, US4289635, US4308154, US4417990, EP0666264,
The disclosure such as US3328335, US3843530, US4957649, production and commercialized ZDDP, the skill of common concern
Art index is the content and zinc-phosphorus ratio of zinc and phosphorus, and its phosphorus content refers to total phosphorus content in ZDDP products, comprising waving
The content of hair property foreign matter of phosphor and available phosphorus.The common structure containing phosphorus impurities includes (RO)2P(S)SR、(RS)3P(S)、
[(RO)2P(S)]2S、(RO)2P(S)H、(RO)3P(S)、(RO)2P(S)OH、[(RO)2P(O)]2S etc.【Lin Yichao, ripple
Spectroscopy magazine, 13 (4) in 1996:365-370】, these are not only mistakened as being available phosphorus content containing phosphorus impurities, also significantly
Reduce the quality of ZDDP.Meanwhile, research shows, the impurity containing P in ZDDP is volatile because without metal,
Easily cause catalyst poisoning.Then, there is no document report to cross at present can effectively control phosphorous impurity content in ZDDP
Method.
The content of the invention
In view of deficiency of the prior art, the dialkyl group two it is a primary object of the present invention to provide a kind of low impurity content
D2EHDTPA zinc, with the impurity content far below commercial product, ZDDP active ingredients high, can reduce its
Consumption in engine and transmission lubricant.
The present invention also aims to provide a kind of side of the zinc dialkyl dithiophosphate for synthesizing the low impurity content
Method, to reduce the impurity content of ZDDP single doses, volatile component particularly therein improves available phosphorus content, together
The performances such as Shi Youhua its antioxygen, wear-resistant and anti-corruption.
Application the present invention also aims to provide the zinc dialkyl dithiophosphate of the low impurity content.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of zinc dialkyl dithiophosphate of low impurity content, the dialkyl disulfides are provided in certain embodiments
It is volatile impurity phosphorus and available phosphorus for the phosphorus in trbasic zinc phosphate, wherein the mole percent level of the volatile impurity phosphorus
No more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate.
Further, in the zinc dialkyl dithiophosphate of the low impurity content, Mole percent of the non-salt containing phosphorus impurities
Than content no more than 7.2%, preferably more than 7.0% of total phosphorus content in the zinc dialkyl dithiophosphate, especially
Preferably shorter than 6.5%.
Further, in the zinc dialkyl dithiophosphate of the low impurity content, zinc dialkyl dithiophosphate
Mass content is 10-99%.
A kind of method of the zinc dialkyl dithiophosphate for synthesizing the low impurity content is provided in certain embodiments,
Including：
Reacted to comprising sulphur phosphoric acid is introduced in diluent, zinc compound, the mixture of organic metal salt, and
The reaction is kept in first temperature range, zinc compound and the first catalyst is added and is formed slurry；
In the range of second temperature, reacted to addition sulphur phosphoric acid in the slurry, and in the second temperature scope
The reaction is kept, the second catalyst is added and is proceeded reaction, reactant mixture is post-treated, obtains described low miscellaneous
The zinc dialkyl dithiophosphate of matter content.
The zinc dialkyl dithiophosphate of any one foregoing low impurity content is provided in certain embodiments or by foregoing
The zinc dialkyl dithiophosphate of low impurity content obtained in any one method is used as the wear-resistant anti-rotten multifunction additive of antioxygen
Purposes.
A kind of compositions of additives, the dioxane comprising any one foregoing low impurity content are provided in certain embodiments
Base zinc dithiophosphate or as obtained in foregoing any one method low impurity content zinc dialkyl dithiophosphate.
Further, the zinc dialkyl dithiophosphate of the low impurity content is effective in the compositions of additives
Addition is 0.001%-5%.
A kind of lubricating composition, the dioxane comprising any one foregoing low impurity content are provided in certain embodiments
Base zinc dithiophosphate or as obtained in foregoing any one method low impurity content zinc dialkyl dithiophosphate.
In certain embodiments there is provided the zinc dialkyl dithiophosphate comprising foregoing low impurity content, by foregoing
Any one in the zinc dialkyl dithiophosphate of low impurity content, foregoing lubricating composition obtained in a kind of method
Device.
Further, described device includes engine or transmission device, but not limited to this.
Compared with prior art, the present invention at least has following good effect：
(1) zinc dialkyl dithiophosphate that the present invention is provided has a low impurity content, available phosphorus content high, together
When also there is excellent anti-volatile, the more preferably performance such as antioxygen, wear-resistant and anti-corruption, and be effectively reduced in engine and
The risk of usage amount and reduction catalyst poisoning in transmission lubricant；
(2) method provided using the present invention can synthesize the zinc dialkyl dithiophosphate of described low impurity.
Specific embodiment
The above quite roughly outlines the features of the present invention and technological merit, to more fully understand subsequent this hair
Bright detailed description.Other feature of the present invention and advantage is described below, they constitute claims of the present invention
Theme.It should be appreciated that disclosed principle and specific embodiment can be easily used as to change or designing reality
Apply the basis of other systems of identical purpose of the invention.It should also be appreciated that such equivalents are without departing from appended
The present invention proposed in claim.With reference to result, it is considered as the present invention to be better understood from following description
Feature assembled about it and operating method novel feature, and other objects and advantages.
One aspect of the present invention provides a kind of zinc dialkyl dithiophosphate of low impurity content, in particular low to wave
Zinc dialkyl dithiophosphate of the hair property containing phosphorus impurities.
More specifically, among the zinc dialkyl dithiophosphate of the low impurity content that the present invention is provided, volatile impurity
The mole percent level of phosphorus particularly, is led to no more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate
Cross31The phosphorous impurity content of non-salt that P-NMR spectrums are measured is more preferably small no more than 7.2%, preferably more than 7.0%
In 6.5%.
The zinc dialkyl dithiophosphate of low impurity content of the invention, in particular improving antioxygen, wear-resistant and anti-corruption has
Imitate the zinc dialkyl dithiophosphate of the relative amount of composition.
The non-salt of the ZDDP of low impurity content of the invention has containing phosphorus impurities well below commercially produced product, and ZDDP
Effect composition is high, can reduce its consumption in engine and transmission lubricant.
Another aspect provides a kind of synthesis low zinc dialkyl dithiophosphate method containing phosphorus impurities,
It can include：
Reacted by sulphur phosphoric acid is introduced at least one diluent, zinc compound and organic metal salt mixture,
Under suitable temperature conditionss, such as at 0-100 DEG C, to introducing additional amount of ZnO in batches in above-mentioned reactant mixture,
And add the first catalyst to form slurry at the appropriate time；Then in suitable temperature, such as 50-150 DEG C, upwards
State and add additional amount of sulphur phosphoric acid in slurry, while after the reaction certain hour is kept in the temperature range, then add
Enter the second catalyst to react, the post-treated dialkyl dithio phosphorus for obtaining the low impurity content of reactant mixture
Sour zinc product.
In synthetic method of the invention, at least one organic metal salt is used to suppress impurity generation and closed as zinc impregnation
The auxiliary dispersants of thing, its species may include carboxylic metallic salt, organic phosphate, alkyl-thio-phosphate, dialkyl group
One kind of metal dithiophosphate or its mixture.Zinc compound is comprising in zinc oxide, zinc hydroxide or zinc carbonate
Any one or its mixture, it is preferable to zinc oxide.In preferred embodiment more, the organic gold for using
Category salt can be organic phosphate/alkyl-thio-phosphate/dialkyl dithiophosphate, such as ZDDP.Other one
In a little more preferred embodiments, the organic metal salt for using can selected from organic phosphate, alkyl-thio-phosphate,
The ZDDP of dialkyl dithiophosphate mixing.In other more preferred embodiment, used is organic
Slaine also can be by (instant) the reaction generation in original position.
In synthetic method of the invention, temperature is preferably controlled in 0-100 DEG C when adding zinc compound, especially preferably
40-80 DEG C, more preferably 42-65 DEG C, impurity generation can be reduced and prevent from generating the aggregate of zinc compound.
It is to add the second catalyst, second catalysis in suitable temperature and time in synthetic method of the invention
Agent may be selected from but be not limited to water, metal salt of organic carboxylic acid, organic carboxyl acid ammonium salt a kind of or its mixture, for example, can be excellent
Selected from salts of carboxylic acids, acetic acid ammonium salt and its mixture or the aqueous solution, more preferably from zinc acetate and zinc acetate aqueous solution.
In some embodiments of the invention, the aqueous solution of zinc acetate can be added, the wherein consumption of zinc acetate about zinc total moles are used
The 0.1-50% of amount.Wherein, the addition of the second catalyst, the generation and/or decomposition that can substantially reduce impurity has been generated
Impurity.
It is that reactant mixture is post-processed in suitable temperature in synthetic method of the invention, temperature can be with excellent
Elect 50-120 DEG C, especially preferably 80-95 DEG C, the impurity that generation can be avoided unnecessary as.
In some embodiments of the present invention, synthesized ZDDP is used as lubricant oil concentrate and lubricating oil
Additive.These lubricant oil concentrates and lubricating oil can be added in engine and transmission device.
In of the invention one more specific case study on implementation, aforementioned synthetic methods may include steps of：
Reacted by sulphur phosphoric acid is introduced in diluent, zinc compound and organic metal salt mixture；
The reaction is kept in the first temperature range, while to above-mentioned mixed comprising diluent, zinc compound and slaine
Other quantity zinc compound and catalyst are introduced in compound to form slurry；
In second temperature scope, to additional amount of sulphur phosphoric acid is added in above-mentioned slurry, while in the temperature range
Keep the reaction；
The second catalyst is added to form zinc dialkyl dithiophosphate in the second temperature scope.
Post processing above reactant obtains zinc dialkyl dithiophosphate product.
In synthetic method of the invention, foregoing diluent may be selected from but be not limited to base oil, alkane, aromatic hydrocarbons, halo
One kind in hydrocarbon, alcohol, ether, ketones solvent or both and more than.Wherein base oil can be natural oil, artificial oil
Or their mixture.
Wherein, natural oil may be selected from but be not limited to animal oil and vegetable oil (such as castor oil, lard), liquid petroleum and
The mineral oil of alkane, the hydrofinishing of cycloalkanes and mixing alkane-naphthene types, solvent treatment or acid treatment, from coal
The oil of the lubricant viscosity of charcoal or shale also serves as useful base oil.
Wherein, artificial oil may be selected from but be not limited to hydrocarbon ils and the hydrocarbon ils of halogen substitution, such as polymerization and the mutually alkene (example of polymerization
Such as, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1- hexenes), poly- (1- octenes),
Poly- (1- decene))；Alkylbenzene is (for example, detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethyl hexyls
Base) benzene)；Polyphenyl (for example, biphenyl, terphenyl, polyphenol of alkylation)；Diphenyl ether and alkylation with alkylation
Diphenyl sulfide and its derivative, analog and homologue.Gas from Fiscber-Tropscb synthesis hydrocarbon to liquid technique artificial oil also
It is useful, they are commonly referred to gas to liquid, or " GTL " base oils.
Wherein oneself warp of terminal hydroxyl passes through the modified oxyalkylene polymer such as esterification, etherificate and interpretation and their derivative
Thing constitutes another kind of known artificial oil.Their example includes being prepared by the polymerization of ethylene oxide or propylene oxide
Polyoxyalkylene polymers, and polyoxyalkylene polymers alkyl and aryl ether (for example, molecular weight be 1000 methyl-
Poly- Isopropanediol ether or molecular weight are the diphenyl ether of the polyethylene glycol of 1000-1500)；With their list and polybasic carboxylic acid
Ester, such as acetic acid esters, the oxygen-containing acid diesters of the C13 of C3-C8 fatty acid esters and TEG of mixing.
Another kind of suitable synthetic lubricant fluid includes dicarboxylic acids (such as phthalic acid, butanedioic acid, alkyl succinic acid
With alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer,
Malonic acid, alkyl malonic acid, alkenyl malonic etc.) with various alcohol (such as butanol, hexanol, lauryl alcohol, 2- ethyls
Hexanol, ethylene glycol, diethylene glycol monoether, propane diols etc.) ester.
Can be used as the ester of artificial oil also include by C5-C12 monocarboxylic acids and polyalcohol and polyol ester such as neopentyl glycol,
Trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol be made those.
Oil based on silicon such as poly- alkyl, poly- aryl, poly-alkoxyl or poly- aryloxy group silicone oil and silicic acid ester oil constitute another
The useful syntholube of class；This oil includes tetraethyl orthosilicate, the isopropyl ester of silicic acid four, silicic acid four (2- ethylhexyls)
Ester, silicic acid four (4- methyl -2- ethylhexyls) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4- methyl -2- second
Base hexyl) disiloxane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Other synthetic lubricant fluid bags
Include phosphorous sour liquid ester (such as diethyl ester of tricresyl phosphate, trioctyl phosphate, decylphosphonic acid) and poly-
Tetrahydrofuran.
In synthetic method of the invention, foregoing organic metal salt can be carboxylic metallic salt, organic phosphate, alkyl
Thiophosphate, one kind of dialkyl dithiophosphoric acid slaine or its mixture, the carboxylic acid group include C1-C18
The hydroxy-acid group of alkyl, aryl and halogen, sulphur, phosphorus heteroatoms substituted hydrocarbon radical etc.；The dialkyl dithiophosphoric acid base
Any commercialized sulphur phosphoric acid and its mixture are may be selected from, is generated also selected from by any C3-C18 alcohol, alkyl phenol
Single or mix sulphur phosphoric acid；The metal is including sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc etc..
Foregoing sulphur phosphoric acid may be selected from any commercialized sulphur phosphoric acid and its mixture, also selected from by any alkyl, cycloalkanes
It is single or mixed that the alcohol and phosphorus pentasulfide of base, aralkyl or alkaryl and the basic alkyl with similar structures are generated
Close sulphur phosphoric acid；The alcohol includes straight chain and side chain and the primary, secondary, tertiary and quaternary alcohol and its mixture of isomerization.It is so-called
Basic hydrocarbon refers to the base containing substitution, and such as ether, ester group, nitro and halogen, these groups do not influence this alkyl substantially
That hydrocarbon of hydrocarbon characteristic.
Described alkyl may be selected from but be not limited to isopropyl, isobutyl group, normal-butyl, sec-butyl, various amyl groups, heptyl,
2- ethylhexyls, double isobutyl groups, iso-octyl, nonyl, docosyl, decyl, dodecyl, three decyls etc..Institute
The alkane phenyl for enumerating is etc. butylbenzene base, penta phenyl, dodecylphenyl, heptan phenyl.Cycloalkyl is also similarly have
, and they mainly include cyclohexyl and relatively low alkyl-cyclohexyl group.Most substituted hydrocarbon radicals can also be used,
Such as chloro amyl group, dichloro- phenyl and dichloro- decyl.
The preparation method of foregoing sulphur phosphoric acid can be all known commercialized production methods, or
The synthetic method being widely known by the people in the patents such as US4263150, US4289635, US4308154, US4417990.
Above-mentioned patent is incorporated into present specification by being cited these disclosures herein.I.e. by phosphorus pentasulfide with
The mixture phase reaction of a kind of alcohol, a kind of phenol, the mixture of alcohol or alcohol and phenol prepares this sulphur phosphoric acid.Every mole five vulcanization
Alcohol of two phosphorus with 4-5 moles or phenol participate in reaction, and the temperature of this reaction can be in about 50 DEG C~about 200 DEG C of scope
Inside carry out.
Foregoing first catalyst includes acid, ammonium carboxylate salt and carboxylic metallic salt；Sour preferred aliphatic series acid or alicyclic carboxylic acid,
Can be monocarboxylic acid and polybasic carboxylic acid, generally contain from 1 to about 3 carboxyl, preferably containing only 1 carboxyl.Carboxylic acid can
With containing from about 2 to about 40 carbon atoms, preferably containing from about 2 to about 20 carbon atoms, preferably containing about 2 to about
8 carbon atoms.Preferred carboxylic acid is the carboxylic acid with general formula R COOH, and R is aliphatic series or cycloaliphatic hydroxyl group in formula.
Suitable acid includes ethanol, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid/dodecanoic acid, stearic acid
With 20 acid, and olefinic acid, such as oleic acid, linoleic acid, linolenic and linoleic dimer.Preferred polynary carboxylic
Acid can be butanedioic acid, alkane tomb and alkenyl succinic, hexanedioic acid, decanedioic acid and citric acid etc..The ammonium carboxylate salt
And carboxylic metallic salt, including aforementioned carboxylic acid ammonium salt and carboxylic metallic salt.The preferred acetic acid of catalyst, ammonium acetate and
Zinc acetate.
Foregoing first temperature range at 0-100 DEG C, preferably 40-80 DEG C, more preferably 42-65 DEG C.
Foregoing second temperature scope at 50-150 DEG C, preferably 60-125 DEG C, more preferably 70-90 DEG C.
Foregoing second catalyst may be selected from water, carboxylic metallic salt, ammonium carboxylate salt one kind or its mixture.Carboxylic metallic salt,
Carboxylic acid in ammonium carboxylate salt may be selected from aliphatic acid or alicyclic carboxylic acid, can be monocarboxylic acid and polybasic carboxylic acid, generally contain
From 1 to about 3 carboxyl, preferably containing only 1 carboxyl.Carboxylic acid can contain from about 2 to about 40 carbon atoms, preferably contain
From about 2 to about 20 carbon atoms, preferably containing about 2 to about 8 carbon atoms.Preferred carboxylic acid is with formula
The carboxylic acid of RCOOH, R is aliphatic series or cycloaliphatic hydroxyl group in formula.Suitable acid includes ethanol, propionic acid, butyric acid, penta
Acid, caproic acid, octanoic acid, n-nonanoic acid, capric acid, lauric acid/dodecanoic acid, stearic acid and 20 acid, and olefinic acid, such as oleic acid,
Linoleic acid, linolenic and linoleic dimer.Preferred polybasic carboxylic acid can be butanedioic acid, alkane tomb and alkenyl amber
Acid, hexanedioic acid, decanedioic acid and citric acid etc..Wherein preferred scheme is salts of carboxylic acids and acetic acid ammonium salt and its mixture
Or the aqueous solution, preferred scheme is zinc acetate and zinc acetate aqueous solution.The water of the preferred zinc acetate of the catalyst of the above second
Solution, zinc acetate consumption is the 0.1-50% molar concentrations of the total consumption of zinc.
Foregoing post-processing approach can have various, for example：
Post-processing approach optionally vacuum can strip the reactant mixture, and temperature is 50-120 DEG C, preferably 80-95 DEG C；
Post-processing approach optionally can filter the reactant mixture to remove solid particle；
Post-processing approach can dilute the reactant mixture optionally with base oil, thus produce the low impurity content
Zinc dialkyl dithiophosphate.
ZDDP of the invention or its mixture can be applied in the formula of lubricating oil, lubricating grease, the ZDDP compounds
With low impurity content, available phosphorus content high, except with wear-resistant, antioxygen and anti-corrosion property, also resists with excellent
Volatility etc..
Technical scheme is described in more detail below by way of some embodiments, but the embodiment is not constituted
Limitation of the present invention.
Explanation：All percentage compositions are molar content below, are bases31P-NMR is calculated.
Embodiment 1 and embodiment 2 (comparative example)
Two classes obtained by commercially available approach mix the commercialization sample ZDDP1 that secondary alkyl ZDDP, multiple commercial vendors are produced
And ZDDP2, any change is not added with, directly test.Test to obtain impurity phosphorus content average out to 7.38% and 7.65%, alkali
Formula ZDDP contents average out to 23% and 27%.
Embodiment 3
The present embodiment refers to EP0866113 using the homemade secondary alkyl sulfide phosphoric acid of mixing, its preparation method, its alcohol knot
Structure and ratio are identical with embodiment 1 and embodiment 2.
By 10g base oils (150N), 0.5gZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler,
In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature
At 40-60 DEG C, 7.0g ZnO are dividedly in some parts, add 0.07g glacial acetic acid.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.
Completion of dropwise addition, after reaction 2h, adds the 3g saturated acetic acid zinc aqueous solution.After reacting 2h again, 95 DEG C are warming up to, subtracted
Pressure distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.
Test foreign matter of phosphor be 4.1%, alkali formula ZDDP contents be 24%.
Embodiment 4
The present embodiment refers to EP0866113 using the homemade secondary alkyl sulfide phosphoric acid of mixing, preparation method, average each alcohol
Containing about 4.5 carbon atoms, its alcohol structure and ratio are identical with sulphur phosphoric acid used in embodiment 1.
By 10g base oils (150N), 0.5g ZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler,
In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature
At 40-60 DEG C, 6.35g ZnO are dividedly in some parts, add 0.07g glacial acetic acid.75 degree are warmed up to, 45g sulphur phosphoric acid is added dropwise.
Completion of dropwise addition, after isothermal reaction 4h, is warming up to 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol.Subsequent silicon
Diatomaceous earth drainage, removes solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 6.2%, alkali formula ZDDP contents
2%.
Embodiment 5
The present embodiment contains about 4.5 carbon atoms, preparation side using the homemade secondary alkyl sulfide phosphoric acid of mixing, average each alcohol
Method refers to EP0866113, and its alcohol structure and ratio are identical with sulphur phosphoric acid used in embodiment 1.
By 10g base oils (150N), 0.5gZnO and 5g mix secondary alkyl sulfide phosphoric acid be added to be equipped with puddler,
In four neck round-bottom flasks of thermometer, condenser pipe and dropping funel, in dispersed with stirring at 45 DEG C.Then keep temperature
At 40-60 DEG C, 6.35gZnO is dividedly in some parts, adds 0.07g glacial acetic acid.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.
Completion of dropwise addition, after reaction 2h, adds the 3g saturated acetic acid zinc aqueous solution.After reacting 2h again, 95 DEG C are warming up to, subtracted
Pressure distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.
Test foreign matter of phosphor be 5.9%, alkali formula ZDDP contents 13.4%.
Embodiment 6 (comparative example)
The present embodiment uses homemade pair of Xin Baiji sulphur phosphoric acid, its preparation method to refer to EP0866113.
21g base oils (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold
In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at,
7.51g ZnO are dividedly in some parts, 0.07g glacial acetic acid is added.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition,
After reaction 4h, 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol are warming up to.Subsequent diatomite drainage, removes
Solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 6.4%, alkali formula ZDDP contents be 16.5%.
Embodiment 7
The present embodiment uses homemade pair of Xin Baiji sulphur phosphoric acid identical with embodiment 6.
21g base oils (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold
In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at,
7.51g ZnO are dividedly in some parts, 0.07g glacial acetic acid is added.75 DEG C are warmed up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition,
After reaction 2h, 1.36g deionized waters are added.After reacting 2h again, 95 DEG C are warming up to, vacuum distillation 30min is removed
The impurity such as water and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 5.1%,
Alkali formula ZDDP contents are 36.3%.
Embodiment 8 (comparative example)
The present embodiment refers to EP0866113 using homemade mixing primary alkyl sulphur phosphoric acid, its preparation method.
21g base oils (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold
In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at,
6.93g ZnO are dividedly in some parts, 0.08g glacial acetic acid is added.75 DEG C are warmed up to, 47g sulphur phosphoric acid is added dropwise.Completion of dropwise addition,
After reaction 4h, 95 DEG C, vacuum distillation 30min, the impurity such as water removal and alcohol are warming up to.Subsequent diatomite drainage, removes
Solid impurity, obtains ZDDP products.Test foreign matter of phosphor be 8.1%, alkali formula ZDDP contents be 25.5%.
Embodiment 9
The present embodiment homemade mixes primary alkyl sulphur phosphoric acid using identical with embodiment 8.
21g base oils (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with puddler, thermometer, cold
In four neck round-bottom flasks of solidifying pipe and dropping funel, in dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at,
7.8g ZnO are dividedly in some parts, 0.12g glacial acetic acid is added.75 DEG C are warmed up to, 47g sulphur phosphoric acid is added dropwise.Completion of dropwise addition,
After reaction 2h, the 2.6g saturated acetic acid zinc aqueous solution is added.After reacting 2h at 80 DEG C again, 95 DEG C, decompression are warming up to
Distillation 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP products.Survey
Try foreign matter of phosphor be 6.7%, alkali formula ZDDP contents be 39.3%.
Embodiment 10-18
As seen from the above embodiment, the ZDDP impurity contents synthesized by the method for the present invention are much smaller than commercial product, greatly
The big quality that improve ZDDP.
Embodiment described above has been described in detail to technical scheme, it should be understood that the above is only
Be specific embodiment of the invention, be not intended to limit the invention, it is all done in spirit of the invention it is any
Modification, supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of zinc dialkyl dithiophosphate of low impurity content, phosphorus in the zinc dialkyl dithiophosphate is to wave
Hair property foreign matter of phosphor and available phosphorus, it is characterised in that：The mole percent level of the volatile impurity phosphorus is no more than described
The 7.2% of total phosphorus content in zinc dialkyl dithiophosphate；
Preferably, in the zinc dialkyl dithiophosphate of described low impurity content, Mole percent of the non-salt containing phosphorus impurities
7.2%, preferably shorter than 6.5% is no more than than content；
It is further preferred that in the zinc dialkyl dithiophosphate of described low impurity content, dialkyl dithiophosphoric acid
The mass percentage content of zinc salt is 10-99%.
2. the preparation method of the zinc dialkyl dithiophosphate of low impurity content as claimed in claim 1, it is characterised in that
Including：
Reacted to comprising sulphur phosphoric acid is introduced in diluent, zinc compound, the mixture of organic metal salt, and
The reaction is kept in first temperature range, zinc compound and the first catalyst is added and is formed slurry；
In the range of second temperature, reacted to addition sulphur phosphoric acid in the slurry, and in the second temperature scope
The reaction is kept, the second catalyst is added and is proceeded reaction, reactant mixture is post-treated, obtains described low miscellaneous
The zinc dialkyl dithiophosphate of matter content；
Preferably, first temperature range is 0-100 DEG C, more preferably especially preferably 40-80 DEG C, 42-65 DEG C；
And/or, it is preferred that the second temperature scope be 50-150 DEG C, especially preferably 60-125 DEG C, more preferably
It is 70-90 DEG C.
3. the preparation method of the zinc dialkyl dithiophosphate of low impurity content according to claim 2, its feature exists
In：
The diluent comprising any one in base oil, alkane, aromatic hydrocarbons, halogenated hydrocarbons, alcohol, ether, ketones solvent or
Combination more than both persons；
And/or, the zinc compound includes the group of any one or more in zinc oxide, zinc hydroxide or zinc carbonate
Close；
And/or, the organic metal salt includes carboxylic metallic salt, organic phosphate, alkyl-thio-phosphate, dialkyl group
The combination of any one or more in metal dithiophosphate；
Preferably, the carboxylic acid group employed in the organic metal salt includes C1-C18 alkyl, aryl, halogen,
Any one or more in sulphur, phosphorus heteroatoms substituted hydrocarbon radical；
Preferably, metallic element contained in the organic metal salt include sodium, potassium, magnesium, calcium, barium, iron, cobalt,
Any one or more in nickel, copper, zinc.
4. according to any one of claim 2-3 the zinc dialkyl dithiophosphate of low impurity content preparation side
Method, it is characterised in that the sulphur phosphoric acid includes any commercialized sulphur phosphoric acid, is given birth to by any C3-C18 alcohol, alkyl phenol
Into single or mix sulphur phosphoric acid in the combination of any one or more；
The alcohol includes the group of any one or more in the primary, secondary, tertiary and quaternary alcohol of straight chain, side chain and isomerization
Close.
5. the preparation method of the zinc dialkyl dithiophosphate of low impurity content according to claim 2, its feature exists
The combination of any one or more in first catalyst includes acid, ammonium carboxylate salt, carboxylic metallic salt, it is excellent
Selected from selected from aliphatic acid or alicyclic carboxylic acid, or, it preferably is selected from acetic acid, ammonium acetate or zinc acetate；
And/or, second catalyst includes any one or more in water, carboxylic metallic salt, ammonium carboxylate salt
Combination, the combination of any one or more preferably being selected from salts of carboxylic acids, acetic acid ammonium salt or its aqueous solution, more preferably
From zinc acetate and/or zinc acetate aqueous solution, the more preferably aqueous solution of zinc acetate is more highly preferred to, described second
The consumption of catalyst is the 0.1-50% of zinc total moles consumption.
6. the preparation method of the zinc dialkyl dithiophosphate of low impurity content according to claim 2, its feature exists
The post-processing approach used in the method is at least selected from vacuum air- extraction, filtration method, dilution method；
Wherein, the temperature conditionss for being used in the vacuum air- extraction are 50-120 DEG C, preferably 80-95 DEG C；
Wherein, the filtration method includes：The reactant mixture is filtered to remove solid particle；
Wherein, the dilution method includes：The reactant mixture is diluted using base oil.
7. the zinc dialkyl dithiophosphate of low impurity content as claimed in claim 1 or by any in claim 2-6
The zinc dialkyl dithiophosphate of low impurity content is used as the wear-resistant anti-rotten multifunction additive of antioxygen obtained in item methods described
Purposes.
8. a kind of compositions of additives, it is characterised in that the dialkyl disulfides comprising low impurity content described in claim 1
For trbasic zinc phosphate or low impurity content obtained in the method as any one of claim 2-6 dialkyl dithiophosphoric acid
Zinc；
Preferably, the zinc dialkyl dithiophosphate of the low impurity content effectively adding in the compositions of additives
Dosage is 0.001%-50%.
9. a kind of lubricating composition, it is characterised in that the dialkyl group two comprising low impurity content described in claim 1
The dialkyl dithio phosphorus of D2EHDTPA zinc or low impurity content obtained in the method as any one of claim 2-6
Sour zinc；
Preferably, the zinc dialkyl dithiophosphate of the low impurity content effectively adding in the lubricating composition
Dosage is 0.001%-5%, especially preferably 0.005%-4%.
10. zinc dialkyl dithiophosphate comprising low impurity content described in claim 1, by claim 2-6
Any one of addition obtained in method described in the zinc dialkyl dithiophosphate of low impurity content, claim 8
The device of any one in lubricating composition described in agent composition, claim 9；
Preferably, described device includes engine or transmission device.
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