CN114736237A - Preparation method of di-isooctyl zinc dithiophosphate - Google Patents
Preparation method of di-isooctyl zinc dithiophosphate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- RDTGTJWJGCWQJE-UHFFFAOYSA-N P(=S)(S)(O)O.C(CCCCC(C)C)[Zn]CCCCCC(C)C Chemical compound P(=S)(S)(O)O.C(CCCCC(C)C)[Zn]CCCCCC(C)C RDTGTJWJGCWQJE-UHFFFAOYSA-N 0.000 title claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 claims abstract description 17
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 4
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 66
- 239000010720 hydraulic oil Substances 0.000 description 33
- 239000011701 zinc Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010998 test method Methods 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
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 blending process Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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)
- Lubricants (AREA)
Abstract
The invention discloses a preparation method of di-isooctyl zinc dithiophosphate. Adding a first batch of isooctanol serving as a base material into a reactor additionally provided with a tail gas treatment device, adding phosphorus pentasulfide, and stirring; dropwise adding a second batch of isooctanol, controlling the dropwise adding rate, and after dropwise adding is finished, heating and carrying out heat preservation reaction; after the heat preservation is finished, steam stripping is carried out, then the hot solution is filtered, and the unreacted phosphorus pentasulfide is removed to prepare sulfuric phosphoric acid for later use; adding thiophosphoric acid and a catalyst into a reactor with a condenser pipe, adding zinc oxide, heating and stirring for reaction; after the reaction is finished, carrying out reduced pressure distillation on the reaction liquid to remove water, adding an adsorbent into the reaction liquid after water is removed, heating, stirring, and then adding a filter aid to filter to obtain a residual liquid; adding epoxy octane into the residual solution, heating, stirring for reaction, and filtering to obtain the zinc diisooctyl dithiophosphate. The product obtained by the preparation method has the advantages of excellent corrosion resistance and low impurity content.
Description
Technical Field
The invention relates to the technical field of hydraulic oil additives, in particular to a preparation method of zinc diisooctyl dithiophosphate.
Background
The hydraulic oil is an important component of the hydraulic system, realizes energy transfer, conversion and control in the hydraulic system, and plays roles of lubrication, rust prevention, cooling and shock absorption. The performance requirements of the hydraulic oil firstly need to have proper viscosity and good viscosity-temperature characteristics so as to ensure that power can be accurately and sensitively transmitted under the condition that the working temperature is changed and normal lubrication of hydraulic elements can be ensured; secondly, the steel plate is required to have good rust resistance and oxidation stability, difficult oxidation deterioration under high temperature condition, long service life and the like. The hydraulic oil in the current market is prepared by blending base oil and various additives.
The zinc dialkyl dithiophosphate serving as a common additive for zinc-containing antiwear hydraulic oil has a remarkable influence on the performance of the hydraulic oil. The zinc dialkyl dithiophosphate is used as a main additive of the antiwear hydraulic oil, and the addition amount of the zinc dialkyl dithiophosphate is larger than that of other additives. The anti-corrosion performance is an important index for measuring the quality of the hydraulic oil, and is also the index which is most concerned and most easily detected by users. The hydraulic oil additive with poor corrosion resistance can not play a role in resisting corrosion in a hydraulic system, which can cause the quality of oil products to be poor, the lubrication effect to be reduced, the damage to the hydraulic system is great, and serious accidents can be caused in serious cases. Therefore, the preparation of the additive with excellent corrosion resistance is of great significance.
The zinc dialkyl dithiophosphate produced in the current market hardly meets all the requirements of a hydraulic system on hydrolytic stability, corrosion resistance, oxidation resistance and the like of hydraulic oil, and the impurity content of the zinc dialkyl dithiophosphate has negative influence on all the performances, so that the research of the special additive for hydraulic oil with low impurity content is significant.
At present, in literature, various performances of hydraulic oil are mainly investigated from the aspects of base oil, blending process, additive composition and the like, and the influence of one additive on other performances of the hydraulic oil such as corrosion resistance and the like is not reported.
Patent document CN1144223A discloses a method for preparing di-isooctyl zinc dithiophosphate, which comprises using di-isooctyl zinc dithiophosphate and zinc oxide as raw materials, and reacting in a certain proportion under the action of accelerator concentrated ammonia water to synthesize the di-isooctyl zinc dithiophosphate with a pH value of 6-7. However, this process requires strong ammonia as catalyst, which not only increases the cost, but also results in poor corrosion resistance of the synthesized product.
Patent document CN102250139A discloses a method for preparing zinc alkyl thiophosphate, which comprises the steps of dispersing phosphorus pentasulfide into a high boiling point solvent, then vacuumizing, adding alcohol under vacuum condition, reacting to obtain thiophosphoric acid, and reacting thiophosphoric acid with zinc oxide to obtain the product. The preparation method needs 25-30% of excessive zinc oxide, so that the cost is high, and the subsequent waste residues also need high treatment cost.
Patent document CN91109043.6 discloses a preparation process of zinc dialkyl dithiophosphate with good hydrolytic stability, in which the raw material phosphorus pentasulfide is added into the reaction mixture in two times, and the first and second times are respectively added with P2S585 percent and 15 percent of the total weight, and the product prepared by the feeding mode has higher hydrolytic stability. However, after the product prepared by the preparation process is blended into the anti-wear hydraulic oil, the anti-corrosion performance is poor and the requirement cannot be met.
Therefore, how to provide a preparation method of the zinc diisooctyl dithiophosphate with excellent corrosion resistance and low impurity content is a problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the defects in the problems, the invention provides a preparation method of zinc diisooctyl dithiophosphate, which comprises the following steps:
adding a first batch of isooctanol serving as a base material into a reactor provided with a tail gas treatment device, adding phosphorus pentasulfide, and stirring;
step two, beginning to dropwise add a second batch of isooctyl alcohol, controlling the dropwise adding speed, and after the dropwise adding is finished, heating and carrying out heat preservation reaction;
step three, steam stripping is carried out after the heat preservation reaction is finished, then suction filtration is carried out while the reaction is hot, and unreacted phosphorus pentasulfide is removed to prepare sulfuric phosphoric acid for later use;
step four, adding thiophosphoric acid, a catalyst and zinc oxide into a reactor with a condenser pipe, heating after adding, and stirring for reaction;
after the reaction is finished, carrying out reduced pressure distillation on the reaction liquid to remove water, adding an adsorbent into the reaction liquid after water is removed, heating, stirring, and then adding a filter aid to filter to obtain a residual liquid;
and step six, adding epoxyoctane into the residual solution, heating, stirring for reaction, and filtering to obtain the zinc diisooctyl dithiophosphate.
As a further improvement of the invention, in the first step, the mass ratio of the first isooctanol to the phosphorus pentasulfide is 0.23:1-0.36: 1; the first batch of isooctanol and phosphorus pentasulfide are stirred for 5-10min at room temperature.
As a further improvement of the invention, in the second step, the mass ratio of the second batch of isooctyl alcohol to the phosphorus pentasulfide is 2.03:1-2.15: 1; controlling the dripping speed of the second batch of isooctanol to control the heating speed of the reaction solution to be 1.0-3.0 ℃/min, and controlling the temperature not to exceed 98 ℃; the second batch of isooctyl alcohol and phosphorus pentasulfide react for 3 to 4 hours at the temperature of 98 to 102 ℃.
As a further improvement of the invention, in the third step, the reaction liquid obtained in the second step is subjected to N introduction2Stripping for 2-3 h.
As a further improvement of the invention, in the fourth step, the catalyst is zinc sulfate, and the molar ratio of the zinc sulfate to the thiophosphoric acid is 0.005:1-0.015: 1; the molar ratio of the zinc oxide to the thiophosphoric acid is 0.55:1-0.60: 1; the zinc oxide is averagely added into the reaction system for 4 times at intervals of 30min, the temperature of the zinc oxide added for 4 times is 45 ℃, 55 ℃, 65 ℃ and 75 ℃ in sequence, and the temperature is raised to 93-97 ℃ after the zinc oxide is added, and the heat preservation reaction is carried out for 2.0 h.
As a further improvement of the invention, in the fifth step, after the reaction in the fourth step is finished, the reaction liquid is subjected to reduced pressure distillation at the temperature of 100 ℃ under the vacuum degree of-0.09 MPa to remove water, activated alumina is added into the reaction liquid after water is removed, the temperature is raised to 88-92 ℃, the mixture is stirred for 2.0 hours, and then filter aid is added to filter the mixture to obtain the residual liquid.
As a further improvement of the invention, the addition amount of the epoxy octane in the step six is 1.5-2.5% relative to the mass fraction of the reaction solution, after the epoxy octane is added into the residual solution, the temperature is raised to 88-92 ℃, the stirring is carried out for 4.0h, and the diisooctyl zinc dithiophosphate product is obtained by filtering.
Compared with the prior art, the invention has the following beneficial effects:
by the preparation method provided by the invention, the obtained zinc diisooctyl dithiophosphate has low impurity content, and when the zinc diisooctyl dithiophosphate is used in hydraulic oil, the corrosion resistance of the hydraulic oil is obviously improved, and other properties are also improved; the preparation method has the advantages of simple production process, low industrialization difficulty and low zinc oxide consumption, reduces the treatment of later-stage wastes and obviously reduces the production cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of zinc diisooctyl dithiophosphate, which comprises the following steps:
step one, adding a first batch of isooctanol serving as a base material into a reactor provided with a tail gas treatment device, adding phosphorus pentasulfide, and stirring at room temperature for 5-10 min. The mass ratio of the first isooctanol to the phosphorus pentasulfide is 0.23:1-0.36:1, preferably 0.28:1-0.32: 1. Since this step will generate hydrogen sulfide gas, in order not to pollute the environment, it is necessary to add a tail gas treatment device to the reactor, and the specific tail gas treatment device is not limited in the present invention.
And step two, dropwise adding a second batch of isooctanol into the reactor in the step one, controlling the dropwise adding speed, controlling the temperature rise of the reaction liquid to be 1.0-3.0 ℃/min, controlling the temperature not to exceed 98 ℃, and after the dropwise adding is finished, raising the temperature to 98-102 ℃ for heat preservation reaction for 3-4 h. In the second step, the mass ratio of the isooctanol and the phosphorus pentasulfide in the second step is 2.03:1-2.15:1, and preferably 2.08:1-2.12: 1. And step two, a coarse product of sulfuric and phosphoric acid can be obtained. The by-product can be reduced by controlling the dripping speed of the second isooctanol.
Step three, introducing N into the reaction liquid after the heat preservation reaction in the step two is finished2Stripping for 2-3h, then carrying out suction filtration while the solution is hot, and removing unreacted phosphorus pentasulfide to prepare thiophosphoric acid for later use. By N2The sulfuric phosphoric acid obtained in the third step can be separated from the hydrogen sulfide gas by steam stripping. And step three, the sulfuric phosphoric acid without impurities and waste gas is obtained and can be directly added into the subsequent reaction.
And step four, replacing a reactor with a condenser pipe, adding thiophosphoric acid and zinc sulfate into the reactor, then adding zinc oxide into the reactor in 4 batches at intervals of 30min every time, wherein the corresponding temperature is 45 ℃, 55 ℃, 65 ℃ and 75 ℃ when the zinc oxide is added for 4 times, heating to 93-97 ℃ after the zinc oxide is added, and carrying out heat preservation reaction for 2.0 hours. In the fourth step, zinc sulfate is selected as a catalyst, so that the reaction speed can be increased, and the purity of a reaction product can be increased. In the fourth step, the molar ratio of the zinc sulfate to the thiophosphoric acid is 0.005:1-0.015:1, preferably 0.008:1-0.012: 1; the molar ratio of zinc oxide to thiophosphoric acid is from 0.55:1 to 0.60:1, preferably from 0.57:1 to 0.59: 1.
And step five, after the reaction in the step four is finished, carrying out reduced pressure distillation on the reaction liquid at the vacuum degree of-0.09 MPa and the temperature of 100 ℃ to remove water, adding activated alumina into the reaction liquid after water removal, heating to 88-92 ℃, stirring for 2.0h, and then adding a filter aid to filter to obtain a residual liquid. The activated alumina can adsorb impurities and is helpful for improving the purity of the product, and the mass percent of the added activated alumina is 0.5-1.5%. And finally, during filtration, the diatomite or calcium oxide is used for assisting filtration, so that clear and transparent residual liquid can be obtained.
And step six, adding epoxyoctane into the residual liquid obtained in the step five, heating to 88-92 ℃, stirring for 4.0h, and finally filtering to obtain a diisooctyl zinc dithiophosphate product. In the above reaction, a trace amount of by-products such as monothiophosphate esters, which have a negative effect on corrosion resistance, is theoretically produced, and the effect of the by-products can be reduced or eliminated by adding octylene oxide. The mass percentage of the added epoxyoctane is 1.5-2.5%.
Example 1 preparation of zinc Diisooctyl dithiophosphate
30ml of first isooctanol is added into a four-neck flask as a bottom material, 70.0g of phosphorus pentasulfide solid is weighed and added into the flask, a tail gas treatment device is connected, and stirring is carried out for 6min at room temperature. Then, a second batch of isooctanol is dripped, the dripping speed is controlled, the temperature rise speed of the reaction solution is controlled to be 1.0 ℃/min, the temperature is controlled not to exceed 98 ℃, and 167.2g of isooctanol is added in total. After the isooctyl alcohol is dripped, the temperature is raised to 100 ℃ to start the heat preservation reaction for 3 hours. Starting to feed N after the heat preservation reaction is finished2Stripping for 2h, then carrying out suction filtration while the solution is hot, and removing unreacted phosphorus pentasulfide to prepare thiophosphoric acid for later use. A four-necked flask equipped with a condenser was replaced, and 200.0g of thiophosphoric acid and a catalyst ZnSO were added to the new reactor4Adding 25.9g ZnO (indirect method) into the reaction system at intervals of 30min for 4 times on average at a temperature of 45 ℃, 55 ℃, 65 ℃ and 75 ℃ for 4 times, heating to 95 ℃ after adding the ZnO, and keeping the temperature for reaction for 2.0 h. After the reaction is finished, carrying out reduced pressure distillation on the reaction liquid at the vacuum degree of-0.09 MPa and the temperature of 100 ℃ to remove water, adding 1.0g of activated alumina after the distillation is finished, keeping the temperature at 90 ℃ and stirring for 2.0h, and then adding a certain amount of filter aid to filter to obtain clear and transparent residual liquid. Adding 2.0g of epoxy octane into the residual solution, heating to 92 ℃, preserving the temperature, reacting for 4.0h, and finally filtering to obtain a light yellow transparent product. The product is noted as: product 1, its Zn% is 9.81%.
Example 2 preparation of zinc Diisooctyl dithiophosphate
The temperature rise rate of isooctanol dropping in example 1, which requires temperature control, was changed to 3 deg.C/min, and the rest remained the same as in example 1, to obtain a light yellow transparent product. The product is noted as: product 2, its Zn% is 9.17%.
Example 3 preparation of Zinc Diisooctyl dithiophosphate
ZnSO catalyst in example 14Conversion of solution to CH3The COOH solution, the rest remaining the same as in example 1, gave a yellowish transparent product. The product is noted as: product 3, its Zn% is 9.32%.
Example 4 preparation of Zinc diisooctyl dithiophosphate
The adsorbent in example 1 was changed to activated carbon, and the rest was kept the same as in example 1, to obtain a pale yellow transparent product. The product is noted as: product 4, its Zn%: 9.26 percent.
Example 5 preparation of zinc diisooctyl dithiophosphate
The procedure of example 1, in which octane oxide was added, was removed and the remaining part was the same as in example 1 to obtain a pale yellow transparent product. The product is noted as: product 5, its Zn% is 9.24%.
Example 6 preparation of Zinc Diisooctyl dithiophosphate
The synthesis of di-isooctyl zinc dithiophosphate products is carried out according to the method described in patent CN 107955035. The product is noted as: product 6, its Zn% is 9.08%.
Example 7 preparation of Zinc diisooctyl dithiophosphate
A di-isooctyl zinc dithiophosphate product synthesized according to the method described in patent CN 1144223A. The product is noted as: product 7, its Zn% is 9.15%.
Performance test
Products prepared in examples 1-7 were purified by nuclear magnetic P31The product content was calculated by spectroscopic measurements and the results are shown in Table 1 below.
TABLE 1 table of contents of products
| Product numbering | Effective content (%) | By-products (%) |
| Product 1 | 99.14 | 0.86 |
| Product 2 | 96.82 | 3.18 |
| Product 3 | 97.22 | 2.78 |
| Product 4 | 97.38 | 2.62 |
| Product 5 | 97.67 | 2.33 |
| Product 6 | 97.09 | 2.91 |
| Product 7 | 96.31 | 3.69 |
The corrosion resistance of the products prepared in examples 1 to 7 was tested according to the test method for copper sheet corrosion of petroleum products GB/T5096-.
TABLE 2 Corrosion resistance of the product
The products prepared in examples 1 to 7 were tested for thermal decomposition temperature according to "method for measuring thermal decomposition temperature of antioxidant and anticorrosive additive" SH/T0561-93, and the results are shown in Table 3 below.
TABLE 3 thermal decomposition temperature chart of products
| Product numbering | Temperature of thermal decomposition (. degree.C.) |
| Product 1 | 321.0 |
| Product 2 | 308.5 |
| Product 3 | 317.0 |
| Product 4 | 313.0 |
| Product 5 | 310.5 |
| Product 6 | 285.5 |
| Product 7 | 282.0 |
The products prepared in examples 1 to 7 were blended into hydraulic oil 1(1#), hydraulic oil 2(2#), hydraulic oil 3(3#), hydraulic oil 4(4#), hydraulic oil 5(5#), hydraulic oil 6(6#), and hydraulic oil 7(7#), respectively, according to the same formulation. The hydraulic oil is tested for thermal stability, hydrolytic stability, abrasion resistance and other properties.
The thermal stability of the hydraulic fluids prepared from the products of examples 1-7 was measured according to the test method for thermal stability of Hydraulic oil SH/T0209-92, and the results are given in Table 4 below.
TABLE 4 thermal stability of hydraulic oil products
X1Weight loss X of copper bar2Weight loss of steel bar
Y1Weight Y of deposit on steel bar2Total weight of sediment
Z1Percent change in kinematic viscosity Z2Percent change in acid number
The hydraulic oils prepared from the products of examples 1-7 were tested for water separation according to "Petroleum and synthetic liquids Water separation assay" GB/T7305-2003 with the results shown in Table 5 below.
Table 5 water separating performance table for hydraulic oil products
| Hydraulic oil batch number | Water separation performance |
| 1# | 42-38-0(03) |
| 2# | 42-38-3(30) |
| 3# | 41-36-3(29) |
| 4# | 39-37-4(35) |
| 5# | 40-38-2(30) |
| 6# | 37-25-18(60) |
| 7# | 38-24-18(60) |
The hydraulic fluids prepared from the products of examples 1-7 were tested for their hydrolytic stability according to "determination of hydrolytic stability of Hydraulic fluids" SH/T0301-1993, and the results are shown in Table 6 below.
TABLE 6 hydrolysis stability Performance of Hydraulic oil products
The hydraulic oils prepared from the products of examples 1 to 7 were tested for anti-wear properties in accordance with SH/T0819-.
TABLE 7 antiwear Performance Table for Hydraulic oil products
And (4) conclusion:
1. from tables 1-7, the overall performance of product 1 is best, also indicating that the process conditions of example 1 are optimal;
2. as can be seen from Table 1, the product obtained by the preparation method provided by the invention has high effective content and few impurities;
3. the adsorbent added in the preparation method provided by the invention can be filtered out in a filtering procedure, additional post-treatment is not needed, the operation is simple and convenient, the process is simple, and the production difficulty is reduced;
4. according to the table 2, the product obtained by the preparation method provided by the invention has better corrosion resistance, the copper sheet corrosion result can reach the level of 1a under the conditions of 100 ℃ and 3h, and other process conditions are obviously worse;
5. as can be seen from tables 3 to 7, the thermal stability, water separation performance, hydrolysis stability and abrasion resistance of the hydraulic oil prepared from the product obtained by the preparation method provided by the invention are improved;
6. according to the preparation method provided by the invention, the zinc oxide is excessive by 5-10%, the zinc oxide dosage is obviously less (25-30%) than that of the CN1144223A patent, the production cost is reduced, the generated waste residues are less, and the environment-friendly treatment pressure is reduced.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of di-isooctyl zinc dithiophosphate is characterized by comprising the following steps:
adding a first batch of isooctanol serving as a base material into a reactor provided with a tail gas treatment device, adding phosphorus pentasulfide, and stirring;
step two, beginning to dropwise add a second batch of isooctyl alcohol, controlling the dropwise adding speed, and after the dropwise adding is finished, heating and carrying out heat preservation reaction;
step three, steam stripping is carried out after the heat preservation reaction is finished, then suction filtration is carried out while the reaction is hot, and unreacted phosphorus pentasulfide is removed to prepare sulfuric phosphoric acid for later use;
step four, adding thiophosphoric acid, a catalyst and zinc oxide into a reactor with a condenser pipe, heating after adding, and stirring for reaction;
after the reaction is finished, carrying out reduced pressure distillation on the reaction liquid to remove water, adding an adsorbent into the reaction liquid after water is removed, heating, stirring, and then adding a filter aid to filter to obtain a residual liquid;
and step six, adding epoxyoctane into the residual solution, heating, stirring for reaction, and filtering to obtain the zinc diisooctyl dithiophosphate.
2. The method according to claim 1, wherein the mass ratio of the first isooctanol to the phosphorus pentasulfide in the first step is 0.23:1-0.36: 1; and stirring the first batch of isooctanol and phosphorus pentasulfide at room temperature for 5-10 min.
3. The method according to claim 1, wherein the mass ratio of the second isooctanol to the phosphorus pentasulfide in the second step is 2.03:1-2.15: 1; controlling the dropping rate of the second batch of isooctanol to control the heating rate of the reaction liquid to be 1.0-3.0 ℃/min and the temperature to be not more than 98 ℃; and the second batch of isooctyl alcohol and phosphorus pentasulfide react for 3 to 4 hours at the temperature of between 98 and 102 ℃ in a heat preservation way.
4. The method according to claim 1, wherein the reaction solution obtained in the second step in the third step is subjected to N-feeding2Stripping for 2-3 h.
5. The preparation method of claim 1, wherein the catalyst in the fourth step is zinc sulfate, and the molar ratio of the zinc sulfate to the thiophosphoric acid is 0.005:1-0.015: 1; the molar ratio of the zinc oxide to the thiophosphoric acid is 0.55:1-0.60: 1; the zinc oxide is evenly added into the reaction system for 4 times at intervals of 30min, the temperature of the zinc oxide added for 4 times is 45 ℃, 55 ℃, 65 ℃ and 75 ℃ in sequence, and after the zinc oxide is added, the temperature is raised to 93-97 ℃ for heat preservation reaction for 2.0 h.
6. The process according to claim 1, wherein in the fifth step, after the reaction in the fourth step is completed, the reaction solution is subjected to reduced pressure distillation at a temperature of 100 ℃ under a vacuum degree of-0.09 MPa to remove water, activated alumina is added to the reaction solution from which water has been removed, the temperature is raised to 88 ℃ to 92 ℃, the mixture is stirred for 2.0 hours, and then a filter aid is added to the mixture, and the mixture is filtered to obtain a residual solution.
7. The preparation method according to claim 1, wherein the addition amount of the cyclooctane oxide in the sixth step is 1.5-2.5% by mass relative to the reaction solution, the temperature is raised to 88-92 ℃ after the cyclooctane oxide is added to the residual solution, the mixture is stirred for 4.0h, and the product of the zinc diisooctyl dithiophosphate is obtained by filtering.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115403614A (en) * | 2022-09-22 | 2022-11-29 | 新乡市瑞丰新材料股份有限公司 | Preparation method of additive of low-acid-value anti-wear hydraulic oil |
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| CN102887918A (en) * | 2011-07-20 | 2013-01-23 | 中国石油天然气股份有限公司 | Preparation and application of dialkyl dithiophosphate hydroxyl derivative and boric acid ester thereof |
| CN107955035A (en) * | 2017-12-13 | 2018-04-24 | 新乡市瑞丰新材料股份有限公司 | The preparation method of the diisooctyl phosphordithiic acid salt additives of hydraulic oil |
| CN113214317A (en) * | 2021-05-07 | 2021-08-06 | 新乡市瑞丰新材料股份有限公司 | High-stability zinc dialkyl dithiophosphate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102887918A (en) * | 2011-07-20 | 2013-01-23 | 中国石油天然气股份有限公司 | Preparation and application of dialkyl dithiophosphate hydroxyl derivative and boric acid ester thereof |
| CN107955035A (en) * | 2017-12-13 | 2018-04-24 | 新乡市瑞丰新材料股份有限公司 | The preparation method of the diisooctyl phosphordithiic acid salt additives of hydraulic oil |
| CN113214317A (en) * | 2021-05-07 | 2021-08-06 | 新乡市瑞丰新材料股份有限公司 | High-stability zinc dialkyl dithiophosphate and preparation method thereof |
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| CN115403614A (en) * | 2022-09-22 | 2022-11-29 | 新乡市瑞丰新材料股份有限公司 | Preparation method of additive of low-acid-value anti-wear hydraulic oil |
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