CN106699806B - Zinc dialkyl dithiophosphate, preparation method and the application of low impurity content - Google Patents
Zinc dialkyl dithiophosphate, preparation method and the application of low impurity content Download PDFInfo
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- CN106699806B CN106699806B CN201510783549.7A CN201510783549A CN106699806B CN 106699806 B CN106699806 B CN 106699806B CN 201510783549 A CN201510783549 A CN 201510783549A CN 106699806 B CN106699806 B CN 106699806B
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- CN
- China
- Prior art keywords
- zinc
- acid
- preparation
- phosphorus
- dialkyl dithiophosphate
- Prior art date
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- 239000012535 impurity Substances 0.000 title claims abstract description 75
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 50
- 239000011701 zinc Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011574 phosphorus Substances 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- -1 alkyl zinc dithiophosphate Chemical compound 0.000 claims description 42
- LICUQAFOHXHWQC-UHFFFAOYSA-N [S].OP(O)(O)=O Chemical compound [S].OP(O)(O)=O LICUQAFOHXHWQC-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000002199 base oil Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000003752 zinc compounds Chemical class 0.000 claims description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
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- 239000011833 salt mixture Substances 0.000 claims description 4
- 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 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
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- 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
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- 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
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- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
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- 239000001361 adipic acid Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 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
- 150000004945 aromatic hydrocarbons Chemical class 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 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
- 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
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 239000000539 dimer Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 150000002019 disulfides Chemical class 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
- 230000000694 effects Effects 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
- 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
- 239000004519 grease Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 238000004519 manufacturing process Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 229910052759 nickel Inorganic materials 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
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 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
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-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
- 150000003751 zinc Chemical class 0.000 description 1
- 229960000314 zinc acetate Drugs 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
- 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)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a kind of zinc dialkyl dithiophosphate of low impurity content (ZDDP), the phosphorus in the zinc dialkyl dithiophosphate is volatile impurity phosphorus and available phosphorus, wherein passing through31The mole percent level for the volatile impurity phosphorus that P-NMR spectrum measures is no more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate.The present invention also provides the methods for the zinc dialkyl dithiophosphate for preparing the low impurity content.Zinc dialkyl dithiophosphate provided by the invention has low impurity content, high available phosphorus content, also there is excellent anti-volatile simultaneously, the more preferably performances such as antioxygen, wear-resistant and anti-corruption, and the usage amount in engine and transmission lubricant can be effectively reduced and reduce the risk of exhaust gas treatment catalyst poison deactivation.
Description
Technical field
The present invention is more particularly directed to a kind of zinc dialkyl dithiophosphate of low impurity content, preparation method and applications, belong to
In engine and transmission lubricant field.
Background technique
Zinc dialkyl dithiophosphate (ZDDP) is as the wear-resistant anti-rotten multifunction additive of antioxygen, in lubricating oil six
More than ten years are function admirable and most comprehensive multifunction additive, can replace completely still without a kind of additive in the prior art
ZDDP.Research in recent years finds that the p and s in zinc dialkyl dithiophosphate will lead to Particulate Emission and other pollutant emissions
Increase.In addition, phosphorous volatile matter is easily accumulated on the active metal catalyst site of exhaust catalytic converter, cause in catalyst
Poison causes catalytic efficiency to reduce, and exhaust emissions is unqualified.With the publication of GF-4 standard, phosphorus content is required less than 0.08%, together
When also require to improve oxidation stability, wear resistance etc..It, must in order to meet anti-oxidant, wear-resistant and control deposit requirement
More additives must be added in formula, or improve the performance of additive single dose.
Known references, such as US4263150, US4289635, US4308154, US4417990, EP0666264,
US3328335, US3843530, US4957649 etc. are open, produce and commercialized ZDDP, the technical indicator of common concern are zinc
With the content and zinc-phosphorus ratio of phosphorus, phosphorus content refers to phosphorus content total in ZDDP product, comprising volatile impurity phosphorus and effectively
The content of 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, Wave Spectrum magazine, 1996,13 (4): 365-370],
These are not only mistakened as being also greatly reduced the quality of ZDDP for available phosphorus content containing phosphorus impurities.Meanwhile studies have shown that ZDDP
In impurity containing P because be free of metal, it is volatile, easily cause catalyst poisoning.Then there is no literature reported on excessively can be effective at present
The method for controlling phosphorous impurity content in ZDDP.
Summary of the invention
In view of deficiency in the prior art, the main purpose of the present invention is to provide a kind of dialkyl group two of low impurity content
Thiophosphoric acid zinc, has an impurity content far below commercial product, high ZDDP effective component, can reduce its in engine and
Dosage in transmission lubricant.
The object of the invention is also to provide a kind of sides of zinc dialkyl dithiophosphate for synthesizing the low impurity content
Method, to reduce the impurity content of ZDDP single dose, volatile component especially therein improves available phosphorus content, while optimizing it
The performances such as antioxygen, wear-resistant and anti-corruption.
The object of the invention is also to provide the applications of the zinc dialkyl dithiophosphate of the low impurity content.
For realization 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 some 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 does not surpass
Cross 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate.
Further, in the zinc dialkyl dithiophosphate of the low impurity content, the non-salt Mole percent containing phosphorus impurities
It is no more than 7.2%, preferably more than 7.0% of total phosphorus content in the zinc dialkyl dithiophosphate than content, particularly preferably
Lower 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 zinc dialkyl dithiophosphate for synthesizing the low impurity content is provided in some embodiments,
Include:
To comprising diluent, zinc compound, organic metal salt mixture in introduce sulphur phosphoric acid and react, and the
The reaction is kept in one temperature range, is added zinc compound and the first catalyst and is formed slurry；
Sulphur phosphoric acid is added within the scope of second temperature, in Xiang Suoshu slurry to be reacted, and in the second temperature range
The reaction is kept, the second catalyst is added and continues to react, reaction mixture is post-treated, obtains the low impurity content
Zinc dialkyl dithiophosphate.
The zinc dialkyl dithiophosphate of any low impurity content above-mentioned is provided in some embodiments or by preceding
The zinc dialkyl dithiophosphate of low impurity content made from any method is stated as the wear-resistant anti-rotten multifunction additive of antioxygen
Purposes.
A kind of compositions of additives is provided in some embodiments, the dioxane comprising any low impurity content above-mentioned
The zinc dialkyl dithiophosphate of base zinc dithiophosphate or the low impurity content as made from aforementioned any method.
Further, the zinc dialkyl dithiophosphate of the low impurity content is effective in the compositions of additives
Additive amount is 0.001%-5%.
A kind of lubricating composition is provided in some embodiments, the dioxane comprising any low impurity content above-mentioned
The zinc dialkyl dithiophosphate of base zinc dithiophosphate or the low impurity content as made from aforementioned any method.
The zinc dialkyl dithiophosphate comprising low impurity content above-mentioned is provided in some embodiments, by aforementioned
A kind of dress of any one of the zinc dialkyl dithiophosphate of low impurity content made from method, lubricating composition above-mentioned
It sets.
Further, the 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 provided by the invention have low impurity content, high available phosphorus content, simultaneously
Also there is excellent anti-volatile, the more preferably performances such as antioxygen, wear-resistant and anti-corruption, and can effectively reduce in engine and transmission device
The risk of usage amount and reduction catalyst poisoning in lubricating oil；
(2) zinc dialkyl dithiophosphate of the low impurity can be synthesized using method provided by the invention.
Specific embodiment
Above content quite roughly outlines the features of the present invention and technological merit, to more fully understand this subsequent hair
Bright detailed description.Other features and advantages of the present invention are described below, they constitute the master of claims of the present invention
Topic.It should be appreciated that disclosed principle and specific embodiment can be easily used as changing or designing and implement the present invention
The basis of other systems of identical purpose.It should also be appreciated that such equivalents are without departing from institute in appended claims
The present invention of proposition.In conjunction with as a result, being better understood from description below is considered as that related its of feature of present invention assembles
With the novel feature and other objects and advantages of operating method.
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 low impurity content provided by the invention, volatile impurity
The mole percent level of phosphorus is no more than 7.2% of total phosphorus content in the zinc dialkyl dithiophosphate, in particular, passing through31The non-salt phosphorous impurity content that P-NMR spectrum measures is no more than 7.2%, preferably more than 7.0%, even more preferably less than 6.5%.
The zinc dialkyl dithiophosphate of low impurity content of the invention, in particular raising antioxygen, wear-resistant and anti-corruption have
Imitate the zinc dialkyl dithiophosphate of the relative amount of ingredient.
The ZDDP of low impurity content of the invention it is non-salt containing phosphorus impurities well below commercially produced product, and ZDDP effectively at
Divide height, its dosage in engine and transmission lubricant can be reduced.
The low zinc dialkyl dithiophosphate method containing phosphorus impurities is synthesized another aspect provides a kind of,
It may include:
Occurred and introducing sulphur phosphoric acid at least one diluent, zinc compound and organic metal salt mixture anti-
It answers, under the conditions of suitable temperature, such as at 0-100 DEG C, introduces additional amount of ZnO in Xiang Shangshu reaction mixture in batches,
And the first catalyst is added at the appropriate time to form slurry；Then in suitable temperature, such as 50-150 DEG C, Xiang Shangshu slurry
It is middle that additional amount of sulphur phosphoric acid is added, while the reaction is kept after a certain period of time in the temperature range, add the second catalysis
Agent reacts, the post-treated zinc dialkyl dithiophosphate product for obtaining the low impurity content of reaction mixture.
In synthetic method of the invention, use at least one organic metal salt that impurity is inhibited to generate and close as zinc impregnation
The auxiliary dispersants of object, type may include carboxylic metallic salt, organic phosphate, alkyl-thio-phosphate, dialkyl dithio
Or mixtures thereof one kind of phosphate metal salt.Zinc compound include any one of zinc oxide, zinc hydroxide or zinc carbonate or its
Mixture, it is preferable to zinc oxide.In preferred embodiment more, the organic metal salt used can be organic phosphorus
Hydrochlorate/alkyl-thio-phosphate/dialkyl dithiophosphate, such as ZDDP.In other more preferred embodiment
In, the organic metal salt used can be mixed selected from organic phosphate, alkyl-thio-phosphate, dialkyl dithiophosphate
ZDDP.In other more preferred embodiment, organic metal salt used can also be generated by (instant) reaction in situ.
In synthetic method of the invention, temperature is preferably controlled in 0-100 DEG C when zinc compound is added, especially preferably
40-80 DEG C, more preferably 42-65 DEG C, impurity can be reduced and generate and prevent to generate the aggregate of zinc compound.
It is that the second catalyst, second catalysis is added in suitable temperature and time in synthetic method of the invention
Agent may be selected from but not limited to or mixtures thereof water, metal salt of organic carboxylic acid, organic carboxyl acid ammonium salt one kind, for instance, it may be preferable to from carboxylic
Sour zinc salt, acetic acid ammonium salt and its mixture or aqueous solution, more preferably from zinc acetate and zinc acetate aqueous solution.Of the invention some
In embodiment, the aqueous solution of zinc acetate can be added, wherein the 0.1-50% of the dosage of zinc acetate about zinc total moles dosage.Its
In, the addition of the second catalyst can substantially reduce the generation of impurity and/or decompose the impurity generated.
It is to be post-processed in suitable temperature to reaction mixture, temperature can be excellent in synthetic method of the invention
It is selected as 50-120 DEG C, especially preferably 80-95 DEG C, can avoid generating extra impurity.
In some embodiments of the present invention, synthesized ZDDP is used as adding for lubricant oil concentrate and lubricating oil
Add agent.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 be may include steps of:
It is reacted and introducing sulphur phosphoric acid into diluent, zinc compound and organic metal salt mixture；
The reaction is kept in the first temperature range, while including the mixed of diluent, zinc compound and metal salt to above-mentioned
It closes in object and introduces other quantity zinc compound and catalyst to form slurry；
In second temperature range, additional amount of sulphur phosphoric acid is added in Xiang Shangshu slurry, while in the temperature range
Keep the reaction；
The second catalyst is added in the second temperature range to form zinc dialkyl dithiophosphate.
It post-processes the above reactant and obtains zinc dialkyl dithiophosphate product.
In synthetic method of the invention, aforementioned diluent may be selected from but not limited to base oil, alkane, aromatic hydrocarbons, halogenated hydrocarbons,
One of alcohol, ether, ketones solvent or both or more.Wherein base oil can be natural oil, synthetic oil or they
Mixture.
Wherein, natural oil may be selected from but not limited to animal oil and vegetable oil (such as castor oil, lard), liquid petroleum and chain
The mineral oil of alkane, cycloalkanes and mixing alkane-naphthene types hydrofinishing, solvent processing or acid processing, is originated from coal or page
The oil of the lubricant viscosity of rock also serves as useful base oil.
Wherein, synthetic oil may be selected from but not limited to the hydrocarbon ils that hydrocarbon ils and halogen replace, such as polymerization and the alkene (example mutually polymerizeing
Such as, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1- hexene), poly- (1- octene), poly- (the 1- last of the ten Heavenly stems
Alkene))；Alkylbenzene (for example, detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene)；Polyphenyl (for example,
Biphenyl, terphenyl, alkylated polyphenol)；With alkylated diphenyl ether and alkylated diphenyl sulfide and its derivative, analog
And homologue.For gas from Fiscber-Tropscb synthesis hydrocarbon to the synthetic oil of liquid technique or useful, they are commonly referred to as gas to liquid, or
" GTL " base oil.
Wherein oneself warp of terminal hydroxyl passes through the modified oxyalkylene polymer and interpretation such as esterification, etherificate and their derivative
Object constitutes another kind of known synthetic oil.Their example includes the polymerization by ethylene oxide or propylene oxide and the polyoxy for preparing
Change the alkyl and aryl ether of alkene polymer and polyoxyalkylene polymers (for example, the methyl-polyisopropylene glycol that molecular weight is 1000
The diphenyl ether for the polyethylene glycol that ether or molecular weight are 1000-1500)；List and multi-carboxylate with them, such as acetic acid esters,
The oxygen-containing acid diesters of C13 of mixed C3-C8 aliphatic ester and tetraethylene glycol.
Another kind of suitable synthetic lubricant fluid include dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid and
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.) and various alcohol (such as butanol, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, diethylene glycol
Monoether, propylene glycol etc.) ester.
Can be used as synthetic oil ester further include by C5-C12 monocarboxylic acid and polyalcohol and polyol ester such as neopentyl glycol,
Trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol those of are made.
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, silicic acid tetra-isopropyl, silicic acid four (2- ethylhexyl) ester, silicon
Sour four (4- methyl -2- ethylhexyl) esters, silicic acid four (to tert-butyl-phenyl) ester, six (4- methyl -2- ethylhexyl) two silicon oxygen
Alkane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Other synthetic lubricant fluids include phosphorous acid liquid ester (such as
Tricresyl phosphate, trioctyl phosphate, decylphosphonic acid diethyl ester) and polytetrahydrofuran.
In synthetic method of the invention, aforementioned organic metal salt can be carboxylic metallic salt, organic phosphate, alkyl sulfide
For or mixtures thereof phosphate, one kind of dialkyl dithiophosphoric acid metal salt, the carboxylic acid group includes C1-C18 alkyl, aryl
With the carboxylic acid group of halogen, sulphur, phosphorus heteroatoms substituted hydrocarbon radical etc.；The dialkyl dithiophosphoric acid base can be selected from any commercialization
Sulphur phosphoric acid and its mixture, also selected from by any C3-C18 alcohol, alkyl phenol generation single or mix sulphur phosphoric acid；It is described
Metal includes sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc etc..
Aforementioned sulphur phosphoric acid can be selected from any commercialized sulphur phosphoric acid and its mixture, also selected from by any alkyl, cycloalkanes
The single or mix sulphur that the alcohol of base, aralkyl or alkaryl and basic alkyl with similar structure and phosphorus pentasulfide generate
Phosphoric acid；The alcohol includes straight chain and branch and the primary, secondary, tertiary and quaternary alcohol and its mixture of isomerization.What so-called basic hydrocarbon referred to
It is the hydrocarbon such as the hydrocarbon characteristic that ether, ester group, nitro and halogen these groups do not influence this alkyl substantially containing substituent group.
The alkyl may be selected from but not limited to isopropyl, isobutyl group, normal-butyl, sec-butyl, various amyls, heptyl, 2-
Ethylhexyl, double isobutyl groups, iso-octyl, nonyl, docosyl, decyl, dodecyl, three decyls etc..The alkane phenyl enumerated
Including butylbenzene base, penta phenyl, dodecylphenyl, phenyl in heptan etc..Naphthenic base is similarly also useful, and they are mainly wrapped
Include cyclohexyl and lower alkyl-cyclohexyl group.Most substituted hydrocarbon radicals also can be used, such as chloro amyl, dichloro- phenyl and two
Chloro decyl.
The preparation method of aforementioned sulphur phosphoric acid can be all known commercialized production methods, be also possible to
Well-known synthetic method in the patents such as US4263150, US4289635, US4308154, US4417990.Pass through herein
It is cited these disclosures and above-mentioned patent is incorporated into present specification.Pass through phosphorus pentasulfide and a kind of alcohol, one kind
The mixture phase reaction of phenol, the mixture of alcohol or pure and mild phenol prepares this sulphur phosphoric acid.Every mole of phosphorus pentasulfide and 4-5 moles of alcohol
Or phenol participates in reaction, and the temperature of this reaction can carry out in the range of about 50 DEG C~about 200 DEG C.
Aforementioned first catalyst includes acid, ammonium carboxylate salt and carboxylic metallic salt；Sour preferred aliphatic series acid or alicyclic carboxylic acid, can
To be monocarboxylic acid and polybasic carboxylic acid, usually 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 contain about 2 to about 8 carbon atoms.Preferred carboxylic acid
It is the carboxylic acid with general formula R COOH, R is aliphatic series or cycloaliphatic hydroxyl group in formula.Suitable acid includes ethyl alcohol, 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, flax
Acid and linoleic acid dimer.Preferred polybasic carboxylic acid can be succinic acid, alkane tomb and alkenyl succinic, hexanedioic acid, decanedioic acid
With citric acid etc..The ammonium carboxylate salt and carboxylic metallic salt, ammonium salt and carboxylic metallic salt including aforementioned carboxylic acid.The catalyst
It is preferred that acetic acid, ammonium acetate and zinc acetate.
Aforementioned first temperature range is at 0-100 DEG C, and preferably 40-80 DEG C, more preferably 42-65 DEG C.
Aforementioned second temperature range is at 50-150 DEG C, preferably 60-125 DEG C, more preferably 70-90 DEG C.
Aforementioned second catalyst can be selected from or mixtures thereof water, carboxylic metallic salt, ammonium carboxylate salt one kind.Carboxylic metallic salt,
Carboxylic acid in ammonium carboxylate salt can be selected from aliphatic acid or alicyclic carboxylic acid, can be monocarboxylic acid and polybasic carboxylic acid, usually containing from 1 to
About 3 carboxyls, 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
Atom preferably contains about 2 to about 8 carbon atoms.Preferred carboxylic acid is the carboxylic acid with general formula R COOH, in formula R be aliphatic series or
Cycloaliphatic hydroxyl group.Suitable acid includes ethyl alcohol, 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 polybasic carboxylic acid can be
Succinic acid, alkane tomb and alkenyl succinic, hexanedioic acid, decanedioic acid and citric acid etc..Wherein Preferable scheme is that salts of carboxylic acids and
Acetic acid ammonium salt and its mixture or aqueous solution, preferred scheme are zinc acetate and zinc acetate aqueous solution.Above second catalyst
It is preferred that the aqueous solution of zinc acetate, zinc acetate dosage is the 0.1-50% molar concentration of the total dosage of zinc.
Post-processing approach above-mentioned can there are many, such as:
Post-processing approach optionally vacuum can strip the reaction mixture, and temperature is 50-120 DEG C, preferably 80-95 DEG C；
Post-processing approach can filter the reaction mixture optionally to remove solid particle；
Post-processing approach can dilute the reaction mixture optionally with base oil, thus produce the low impurity content
Zinc dialkyl dithiophosphate.
Or mixtures thereof ZDDP of the invention can be applied in the formula of lubricating oil, lubricating grease, which has
Low impurity content, high available phosphorus content also have excellent anti-volatile etc. except having wear-resistant, antioxygen and anti-corrosion property.
Technical solution of the present invention is described in more detail below by way of several embodiments, but the embodiment is not constituted
Limitation of the present invention.
Illustrate: following all percentage compositions are molar content, are bases31P-NMR is calculated.
Embodiment 1 and embodiment 2 (comparative example)
Two classes obtained by commercially available approach mix secondary alkyl ZDDP, the commercialization sample ZDDP1 that multiple commercial vendors are produced and
Any change is not added in ZDDP2, directly tests.Test to obtain impurity phosphorus content average out to 7.38% and 7.65%, alkali formula ZDDP content
Average out to 23% and 27%.
Embodiment 3
The present embodiment uses homemade mixing secondary alkyl sulphur phosphoric acid, and preparation method can refer to EP0866113, alcohol structure
It is identical with embodiment 1 and embodiment 2 with ratio.
10g base oil (150N), 0.5gZnO and 5g mixing secondary alkyl sulphur phosphoric acid are added to and are equipped with stirring rod, temperature
In four neck round-bottom flasks of meter, condenser pipe and dropping funel, it is dispersed with stirring at 45 DEG C.40-60 DEG C then is kept the temperature at,
7.0g ZnO is added portionwise, 0.07g glacial acetic acid is added.75 DEG C are warming up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, after reacting 2h,
3g saturated acetic acid zinc aqueous solution is added.After reacting 2h again, 95 DEG C are warming up to, is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.With
Diatomite drainage afterwards removes solid impurity, obtains ZDDP product.Test foreign matter of phosphor be 4.1%, alkali formula ZDDP content be 24%.
Embodiment 4
The present embodiment uses homemade mixing secondary alkyl sulphur phosphoric acid, and preparation method refers to EP0866113, and average each alcohol contains
About 4.5 carbon atoms, alcohol structure and ratio are identical as sulphur phosphoric acid used in embodiment 1.
10g base oil (150N), 0.5g ZnO and 5g mixing secondary alkyl sulphur phosphoric acid are added to and are equipped with stirring rod, temperature
In four neck round-bottom flasks of meter, condenser pipe and dropping funel, it is dispersed with stirring at 45 DEG C.40-60 DEG C then is kept the temperature at,
6.35g ZnO is added portionwise, 0.07g glacial acetic acid is added.75 degree are warming up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, isothermal reaction
After 4h, 95 DEG C are warming up to, is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains
ZDDP product.Test foreign matter of phosphor be 6.2%, alkali formula ZDDP content 2%.
Embodiment 5
The present embodiment uses homemade mixing secondary alkyl sulphur phosphoric acid, and average each alcohol contains about 4.5 carbon atoms, preparation method
With reference to EP0866113, alcohol structure and ratio are identical as sulphur phosphoric acid used in embodiment 1.
10g base oil (150N), 0.5gZnO and 5g mixing secondary alkyl sulphur phosphoric acid are added to and are equipped with stirring rod, temperature
In four neck round-bottom flasks of meter, condenser pipe and dropping funel, it is dispersed with stirring at 45 DEG C.40-60 DEG C then is kept the temperature at,
6.35gZnO is added portionwise, 0.07g glacial acetic acid is added.75 DEG C are warming up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition, after reacting 2h,
3g saturated acetic acid zinc aqueous solution is added.After reacting 2h again, 95 DEG C are warming up to, is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.With
Diatomite drainage afterwards removes solid impurity, obtains ZDDP product.Test foreign matter of phosphor be 5.9%, alkali formula ZDDP content 13.4%.
Embodiment 6 (comparative example)
The present embodiment uses homemade double Xin Baiji sulphur phosphoric acid, and preparation method can refer to EP0866113.
21g base oil (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with stirring rod, thermometer, condenser pipe
In four neck round-bottom flasks of dropping funel, it is dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, is added portionwise
0.07g glacial acetic acid is added in 7.51g ZnO.75 DEG C are warming up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition is warming up to 95 after reacting 4h
DEG C, it is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP product.It tests
Foreign matter of phosphor is 6.4%, and alkali formula ZDDP content is 16.5%.
Embodiment 7
The present embodiment uses and the identical homemade double Xin Baiji sulphur phosphoric acid of embodiment 6.
21g base oil (150N), 0.5gZnO and 25g sulphur phosphoric acid are added to and are equipped with stirring rod, thermometer, condenser pipe
In four neck round-bottom flasks of dropping funel, it is dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, is added portionwise
0.07g glacial acetic acid is added in 7.51g ZnO.75 DEG C are warming up to, 45g sulphur phosphoric acid is added dropwise.Completion of dropwise addition after reacting 2h, is added
1.36g deionized water.After reacting 2h again, 95 DEG C are warming up to, is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.Subsequent diatomite helps
Filter removes solid impurity, obtains ZDDP product.Test foreign matter of phosphor be 5.1%, alkali formula ZDDP content be 36.3%.
Embodiment 8 (comparative example)
The present embodiment uses homemade mixing primary alkyl sulphur phosphoric acid, and preparation method can refer to EP0866113.
21g base oil (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with stirring rod, thermometer, condenser pipe
In four neck round-bottom flasks of dropping funel, it is dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, is added portionwise
0.08g glacial acetic acid is added in 6.93g ZnO.75 DEG C are warming up to, 47g sulphur phosphoric acid is added dropwise.Completion of dropwise addition is warming up to 95 after reacting 4h
DEG C, it is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.Subsequent diatomite drainage, removes solid impurity, obtains ZDDP product.It tests
Foreign matter of phosphor is 8.1%, and alkali formula ZDDP content is 25.5%.
Embodiment 9
The present embodiment uses and embodiment 8 is identical homemade mixes primary alkyl sulphur phosphoric acid.
21g base oil (150N), 0.5gZnO and 23g sulphur phosphoric acid are added to and are equipped with stirring rod, thermometer, condenser pipe
In four neck round-bottom flasks of dropping funel, it is dispersed with stirring at 55 DEG C.40-60 DEG C then is kept the temperature at, is added portionwise
0.12g glacial acetic acid is added in 7.8g ZnO.75 DEG C are warming up to, 47g sulphur phosphoric acid is added dropwise.After reacting 2h, 2.6g is added in completion of dropwise addition
Saturated acetic acid zinc aqueous solution.Again after 80 DEG C of reaction 2h, 95 DEG C are warming up to, is evaporated under reduced pressure 30min, the impurity such as water removal and alcohol.With
Diatomite drainage afterwards removes solid impurity, obtains ZDDP product.Test foreign matter of phosphor is 6.7%, alkali formula ZDDP content is
39.3%.
Embodiment 10-18
As seen from the above embodiment, ZDDP impurity content synthesized by method of the invention is much smaller than commercial product, significantly
Improve the quality of ZDDP.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the zinc dialkyl dithiophosphate of low impurity content, characterized by comprising:
To comprising base oil, zinc compound, organic metal salt mixture in introduce sulphur phosphoric acid and react, and first temperature
It spends and keeps the reaction in range, add zinc compound and the first catalyst and form slurry, first temperature range is 42-
65 DEG C, the zinc compound is selected from any one of zinc oxide, zinc hydroxide or zinc carbonate or two or more combinations, described to have
Machine metal salt uses zinc dialkyl dithiophosphate, and first catalyst uses glacial acetic acid；
Sulphur phosphoric acid is added within the scope of second temperature, in Xiang Suoshu slurry to be reacted, and is kept in the second temperature range
The reaction adds the second catalyst and continues to react, and reaction mixture is post-treated, obtains the dialkyl group of low impurity content
Zinc dithiophosphate, second catalyst are selected from zinc acetate aqueous solution or water, and the second temperature range is 70-90 DEG C, institute
The dosage for stating the second catalyst is the 0.1-50% of zinc total moles dosage；
Phosphorus in the zinc dialkyl dithiophosphate of the low impurity content is volatile impurity phosphorus and available phosphorus, wherein dialkyl group
The mass percentage content of phosphordithiic acid zinc salt is 10-99%, and the non-salt mole percent level containing phosphorus impurities is lower than described two
The 6.5% of total phosphorus content in alkyl zinc dithiophosphate.
2. preparation method according to claim 1, it is characterised in that: the sulphur phosphoric acid is selected from by any C3-C18 alcohol, alkane
Any one of single or mix sulphur phosphoric acid that base phenol generates or two or more combinations；The alcohol is in straight chain, branch
Any one or more combinations.
3. preparation method according to claim 1, it is characterised in that: second catalyst is the aqueous solution of zinc acetate.
4. preparation method according to claim 1, it is characterised in that: the post-processing approach that the preparation method uses is selected from
Vacuum air- extraction, filtration method or dilution method.
5. the preparation method according to claim 4, it is characterised in that: the temperature condition used in the vacuum air- extraction for
50-120℃。
6. preparation method according to claim 5, it is characterised in that: the temperature condition used in the vacuum air- extraction for
80-95℃。
7. the preparation method according to claim 4, which is characterized in that the filtration method includes: to filter the reaction mixture
To remove solid particle.
8. the preparation method according to claim 4, which is characterized in that the dilution method includes: should using base oil dilution
Reaction mixture.
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| CN1144223A (en) * | 1995-09-01 | 1997-03-05 | 中国石化兰州炼油化工总厂 | Method for preparation of zinc dialkyl dithiophosphate |
| US6958409B1 (en) * | 2004-06-15 | 2005-10-25 | Chevron Oronite Company Llc | Process for reduced crude sediment in metal salts of hydrocarbyl dithiophosphoric acid |
| CN103820004A (en) * | 2014-02-17 | 2014-05-28 | 湖南至诚涂料有限公司 | Preparation method of anticorrosive powder paint and product thereof |
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|---|---|---|---|---|
| US3328335A (en) * | 1964-08-31 | 1967-06-27 | Mobil Oil Corp | Lubricating oils containing complex zinc salts |
| EP0666264A1 (en) * | 1994-02-07 | 1995-08-09 | Ethyl Petroleum Additives, Inc. | Process for producing metal salts of hydrocarbyl dithiophosphoric acid |
| CN1769405A (en) * | 2003-11-06 | 2006-05-10 | 雅富顿公司 | Process for producing zinc dialkyldithiophosphates exhibiting improved seal compatibility properties |
| CN101517048A (en) * | 2006-07-17 | 2009-08-26 | 卢布里佐尔公司 | Method of lubricating an internal combustion engine and improving the efficiency of the emissions control system of the engine |
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