CN100338200C - Process for preparing lubricating oil additive containing nano microparticles - Google Patents
Process for preparing lubricating oil additive containing nano microparticles Download PDFInfo
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- CN100338200C CN100338200C CNB2004100311844A CN200410031184A CN100338200C CN 100338200 C CN100338200 C CN 100338200C CN B2004100311844 A CNB2004100311844 A CN B2004100311844A CN 200410031184 A CN200410031184 A CN 200410031184A CN 100338200 C CN100338200 C CN 100338200C
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- salt
- microemulsion
- consumption
- alkali
- acid
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 35
- 239000000654 additive Substances 0.000 title abstract description 15
- 230000000996 additive effect Effects 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000011859 microparticle Substances 0.000 title 1
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 68
- 239000003513 alkali Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000002199 base oil Substances 0.000 claims abstract description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000012467 final product Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 17
- -1 allyl butyrate imide Chemical class 0.000 claims description 15
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002480 mineral oil Substances 0.000 claims description 13
- 235000010446 mineral oil Nutrition 0.000 claims description 13
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 9
- 150000003973 alkyl amines Chemical class 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 150000004291 polyenes Chemical class 0.000 claims description 9
- 235000013311 vegetables Nutrition 0.000 claims description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- 229960001124 trientine Drugs 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 241000158728 Meliaceae Species 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005069 Extreme pressure additive Substances 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000005461 lubrication Methods 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 5
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- WERKSKAQRVDLDW-ANOHMWSOSA-N [(2s,3r,4r,5r)-2,3,4,5,6-pentahydroxyhexyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO WERKSKAQRVDLDW-ANOHMWSOSA-N 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 5
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims 3
- 239000002585 base Substances 0.000 claims 3
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 21
- 150000007530 organic bases Chemical class 0.000 description 9
- 229920000136 polysorbate Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 210000000582 semen Anatomy 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- Lubricants (AREA)
Abstract
The present invention provides a preparation method of a lubricating oil extreme pressure abrasion resistance additive containing nanometer particulates., which comprises: 1) a metal salt solution or a metal acid solution is mixed with a lubricating oil dispersing agent, an emulsifier and base oil, and is heated to 30 DEG C to 120 DEG C, an auxiliary dispersing agent is dropped until microemulsion is clear and transparent, and the microemulsion of salts and acid is obtained; 2) alkali with the equal equivalent weight of the salts or the acid in the microemulsion is mixed with the dispersing agent, the emulsifier and the base oil, the mixture is heated to 30 DEG C to 120 DEG C, and the auxiliary dispersing agent is dropped until the microemulsion is clear and transparent, to obtain alkali microemulsion; 3) the two kinds of microemulsion are mixed, and are stirred under the conditions of the temperature of 25 DEG C to 100 DEG C and the stirring speed of 100 to 2000 revolutions per minute for 0.5 to 8 hours, and a final product is obtained. In the preparation method provided by the present invention, the nanometer particulates are directly generated in lubricating oil, the problem of solid and liquid separation caused by agglomerate is avoided, and the obtained additive has good stability and extreme pressure abrasion resistance in the base oil.
Description
Technical field
Preparation process lubricant oil additive of the present invention specifically, is the preparation method who contains the lubrication oil anti-wear extreme pressure additive of nanoparticle.
Technical background
Past, the research that nanotechnology is used to improve the lubricating oil extreme pressure anti-wear obtained tangible progress for over ten years.From the kind of additive, can be divided into Inorganic Nanometer Antiwear Agents, the organic and inorganic matrix material anti-wear agent of finishing, and ashless nano antiwear agent.Inorganic Nanometer Antiwear Agents generally adopts two-step approach, promptly utilizes various physics and chemical process to prepare the ultra-fine grain of metal, metal oxide, metallic sulfide etc., they is distributed in the base oil as additive goes again.Many metal oxides such as Lithium Oxide 98min, zirconium white, titanium oxide and silicon oxide etc., very high fusing point and hardness are arranged itself, it is the presoma of preparation pottery, be used for the anti-caking power that lubricating oil can significantly improve lubricating oil, and the nanometer superfine powder body of preparation can not resemble the problem that has easy oxidation the metal powder.Introduced the good result that nano size rare earth hydroxide has obtained as lubricating oil additive among the CN 1218103A; US 6,243, and 669 have introduced the natural crystal that will contain multiple metal oxide handles the nanometer state, add after the specific catalyst as lubricating oil additive again, but do not introduce anti-wear effect in detail.CN1362500A has introduced mixture with a kind of borate and ester as lubricating oil additive, does not also introduce anti-wear effect.The problem that above-mentioned additive all exists nanoparticle to reunite.
Summary of the invention
The invention provides the preparation method of the lubrication oil anti-wear extreme pressure additive that contains nanoparticle, this method directly generates nanoparticle in lubricating oil, and nanoparticle is remained among the liquid pearl of microemulsion of high dispersing, avoid reunion, and then avoided the solid-liquid separation problem that causes because of reunion.
Preparation process lubricant oil additive provided by the invention comprises following three kinds of methods:
First method comprises:
1) with metal-salt or acid solution and lubricating oil dispersant, emulsifying agent, base oil mixes, and is heated to 30 ℃～120 ℃, drips dispersion aids to the microemulsion clear, obtains the microemulsion of salt or acid;
2) will with the salt in the above-mentioned microemulsion or the alkali of sour equivalent, mix with dispersion agent, emulsifying agent and base oil, be heated to 30 ℃～120 ℃, drip dispersion aids to the microemulsion clear, obtain alkaline microemulsion;
3) above-mentioned two kinds of microemulsions being mixed, is 25 ℃～100 ℃ in temperature, and stir speed (S.S.) is to stir 0.5～8 hour under 100～2000 rev/mins the condition, obtains final product.
Specifically, first method can be carried out according to following steps:
Step 1: with metal-salt or acid solution and lubricating oil dispersant, emulsifying agent, base oil mixes, and stirs, and is heated to 30 ℃～120 ℃, and preferred 40 ℃～100 ℃, drip dispersion aids to the microemulsion clear, obtain the microemulsion of salt or acid.
Wherein, said metal-salt or acid are water-soluble zirconates, water-soluble aluminum salt, boric acid or their mixture, preferred zirconium tetrachloride, tri-chlorination zirconium, aluminum chloride, aluminum nitrate, boric acid, and the concentration of the aqueous solution is 5～20%, preferred 8～15%.
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture.
Said dispersion aids is an alcohols, as: Pentyl alcohol, n-hexyl alcohol, n-dodecanol or their mixture.
Said emulsifying agent is (Si Ben-60), sorbitol monooleate (Si Ben-80), polyoxyethylene (20) sorbitol anhydride mono-laurate (tween 20), polyoxyethylene sorbitan monoleate (tween-80) or their mixture.
Said base oil is mineral oil, ucon oil, vegetables oil or their mixture.40 ℃ of viscosity of mineral oil, ucon oil, vegetables oil are 5～50mm
2/ s, preferred 20～40mm
2/ s.Ucon oil is ester class oil, polyethers, synthetic hydrocarbon or their mixture.Vegetables oil is Oleum Gossypii semen, rapeseed oil, peanut oil or their mixture.
Weight in metal-salt or acid solution is 1 part, and the consumption of base oil is 10～40 parts, preferred 20～30 parts; The consumption of lubricating oil dispersant is 1～6 part, preferred 2～4 parts; The consumption of emulsifying agent is 1～6 part, preferred 2～4 parts;
Step 2: will with the alkali of above-mentioned salt or sour equivalent, mix with dispersion agent, emulsifying agent and base oil, stir, be heated to 30 ℃～120 ℃, drip dispersion aids to the microemulsion clear, obtain alkaline microemulsion.
Said alkali can be organic bases or mineral alkali, and organic bases is C2～C16 alkylamine or polyamines polyene, or their mixture, and alkylamine can be primary amine, secondary amine or tertiary amine, as ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine etc.; Polyamines polyene can be a diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.; Mineral alkali can be sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia etc.Mineral alkali is that concentration is 1～30 weight %, preferred 8～25% the aqueous solution, and organic bases can directly use.
The implication of dispersion agent, emulsifying agent, dispersion aids and base oil is identical with step 1.
Weight in alkali or alkali lye is 1 part, and the consumption of base oil is 10～40 parts, preferred 20～30 parts; The consumption of lubricating oil dispersant is 1～6 part, preferred 2～4 parts; The consumption of emulsifying agent is 1～6 part, preferred 2～4 parts.
Step 3: above-mentioned two kinds of microemulsions are mixed, heated and stirred 0.5～8 hour, preferred 1～4 hour, stir speed (S.S.) was 100～2000 rev/mins, preferred 300～1500 rev/mins, 25 ℃～100 ℃ of Heating temperatures, obtain final product by preferred 55～80 ℃.
Second method comprises:
1), obtains the microemulsion of salt or acid with the step 1 of method one;
2) will with the salt in the above-mentioned microemulsion or the alkali of sour equivalent, the speed of dividing with 0.001～0.02mol/ joins in the above-mentioned microemulsion, in temperature is 25 ℃～100 ℃, and stir speed (S.S.) is to stir under 100～2000 rev/mins the condition to obtain final product in 0.5～8 hour.
Specifically, second method can be carried out according to following steps:
Step 1: with metal-salt or acid solution and lubricating oil dispersant, emulsifying agent, base oil mixes, and stirs, and is heated to 30 ℃～120 ℃, and preferred 40 ℃～100 ℃, drip dispersion aids to the microemulsion clear, obtain the microemulsion of salt or acid.
The implication of metal-salt or acid solution, dispersion agent, emulsifying agent, dispersion aids and base oil and consumption are identical with the step 1 of method one.
Step 2: will with the salt in the above-mentioned microemulsion or the alkali of sour equivalent, with 0.001～0.02mol/ branch, the speed that preferred 0.005～0.015mol/ divides joins in the above-mentioned microemulsion, heated and stirred 0.5～8 hour, preferred 1～4 hour, stir speed (S.S.) was 100～2000 rev/mins, preferred 300～1500 rev/mins, 25 ℃～100 ℃ of Heating temperatures, obtain final product by preferred 55 ℃～80 ℃.
Said alkali can be organic bases or mineral alkali, and organic bases is C2～C16 alkylamine or polyamines polyene, or their mixture, and alkylamine can be primary amine, secondary amine or tertiary amine, as ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine etc.; Polyamines polyene can be a diethylenetriamine, triethylene tetramine, triethylene tetramine etc.; Mineral alkali can be sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia etc.It is 1～30 weight % that mineral alkali is mixed with concentration in use, preferred 8～25% the aqueous solution, and organic bases can directly use.According to the form (liquid, solid-state or gaseous state) of alkali can take to drip, gradation adds or the mode of ventilation with 0.001～0.02mol/ branch, the speed that preferred 0.005～0.015mol/ divides joins in the microemulsion of salt or acid.
The third method comprises:
1) alkali is mixed with dispersion agent, emulsifying agent and base oil, stir, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain alkaline microemulsion to the microemulsion clear;
2) will with the metal-salt or the acid solution of alkali equivalent in the above-mentioned microemulsion, be added dropwise in the above-mentioned microemulsion with 10～60 droplets/minute speed, in temperature is 25 ℃～100 ℃, and stir speed (S.S.) is to stir 0.5～8 hour under 100～2000 rev/mins the condition, obtains final product.
Specifically, the third method can be carried out according to following steps:
Step 1: alkali is mixed with dispersion agent, emulsifying agent and base oil, stir, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain alkaline microemulsion to the microemulsion clear.
Said alkali can be organic bases or mineral alkali, and organic bases is C2～C16 alkylamine or polyamines polyene, or their mixture, and alkylamine can be primary amine, secondary amine or tertiary amine, as ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine etc.; Polyamines polyene can be a diethylenetriamine, triethylene tetramine, triethylene tetramine etc.; Mineral alkali can be sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia etc.Mineral alkali is that concentration is 1～30 weight %, preferred 8～25% the aqueous solution, and organic bases can directly use.
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture.
Said dispersion aids is an alcohols, as: Pentyl alcohol, n-hexyl alcohol, n-dodecanol or their mixture.
Said emulsifying agent is (Si Ben-60), sorbitol monooleate (Si Ben-80), polyoxyethylene (20) sorbitol anhydride mono-laurate (tween 20), polyoxyethylene sorbitan monoleate (tween-80) or their mixture.
Said base oil is mineral oil, ucon oil, vegetables oil or their mixture.40 ℃ of viscosity 5～50mm of mineral oil, ucon oil, vegetables oil
2/ s, preferred 20～40mm
2/ s.Ucon oil is ester class oil, polyethers, synthetic hydrocarbon or their mixture.Vegetables oil is Oleum Gossypii semen, rapeseed oil, peanut oil or their mixture.
Weight in alkali or alkali lye is 1 part, and the consumption of base oil is 10～40 parts, preferred 20～30 parts; The consumption of lubricating oil dispersant is 1～6 part, preferred 2～4 parts; The consumption of emulsifying agent is 1～6 part, preferred 2～4 parts, obtains alkaline microemulsion.
2) will with the metal-salt or the acid solution of alkali equivalent in the above-mentioned microemulsion, with 10～60 droplets/minute, preferred 20～40 droplets/minute speed is added dropwise in the above-mentioned microemulsion, heated and stirred 0.5～8 hour, preferred 1～4 hour, stir speed (S.S.) was 100～2000 rev/mins, preferred 300～1500 rev/mins, 25 ℃～100 ℃ of Heating temperatures, obtain final product by preferred 55～80 ℃.
Said metal-salt or acid are water-soluble zirconates, water-soluble aluminum salt, boric acid or their mixture, preferred zirconium tetrachloride, tri-chlorination zirconium, aluminum chloride, aluminum nitrate, boric acid, and concentration of aqueous solution is 5～20%, preferred 8～15%.
In the lubricating oil additive according to three kinds of methods preparation provided by the invention, comprising particle diameter is the insoluble nanoparticle of 1～100nm, and these nanoparticles are reaction product of metal-salt or acid and alkali.This additive has good dispersiveness and stable in base oil, and extreme pressure, resistance to abrasion are preferably arranged.
The lubrication oil anti-wear extreme pressure additive that contains nanoparticle provided by the invention, the consumption in lubricating oil are 0.1～10 weight %.
Embodiment
Example 1
Method one
The zirconium tetrachloride aqueous solution of 2ml 13.2% is joined 1.5g Si Ben-80,1g tween 20,2g allyl butyrate imide, 25g mineral oil (40 ℃ of viscosity 22mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip Pentyl alcohol down to the microemulsion clear, 68 ℃ of Heating temperatures; Aqueous sodium hydroxide solution with 1ml 9% joins 1.5g Si Ben-80,1g tween 20,1.8g allyl butyrate imide, 25g mineral oil (40 ℃ of viscosity 22mm again
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip Pentyl alcohol down to the microemulsion clear, and Heating temperature is 89 ℃; Two kinds of microemulsions are mixed, heated and stirred is 2.5 hours under the normal pressure again, and stir speed (S.S.) is 360 rev/mins, and 55 ℃ of Heating temperatures get the clear product A, adopts the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 2
Method one
The aluminum chloride aqueous solution of 2ml 9.8% is joined 3g Si Ben-80,2g tween-80,1.6g petroleum sodium sulfonate 25g mineral oil (40 ℃ of viscosity 35.46mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-hexyl alcohol down to the microemulsion clear, and Heating temperature is 50 ℃; Sodium silicate aqueous solution with 1ml 12.5% joins 3g Si Ben-80,2g tween-80,1.6g petroleum sodium sulfonate, 25g mineral oil (40 ℃ of viscosity 35.46mm again
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-hexyl alcohol down to the microemulsion clear, and Heating temperature is 77 ℃; Two kinds of microemulsions are mixed, heated and stirred is 1.5 hours under the normal pressure again, and stir speed (S.S.) is 500 rev/mins, and Heating temperature is 73 ℃, gets the clear product B, adopts the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 3
Method one
The boric acid aqueous solution of 2ml 11.6% is joined 2g Si Ben-60,3g tween 20,2g calcium mahogany sulfonate, 25g mineral oil (40 ℃ of viscosity 40mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-hexyl alcohol down to the microemulsion clear, and Heating temperature is 42 ℃; Lithium hydroxide aqueous solution with 1ml 8.9% joins 3g Si Ben-60,2g tween 20,2g calcium mahogany sulfonate, 25g mineral oil (40 ℃ of viscosity 40mm again
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-hexyl alcohol down to the microemulsion clear, and Heating temperature is 83 ℃; Two kinds of microemulsions are mixed, heated and stirred is 3 hours under the normal pressure again, and stir speed (S.S.) is 1050 rev/mins, and 66 ℃ of Heating temperatures get the clear products C, adopts the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 4
Method two
The zirconium tetrachloride aqueous solution of 2ml 10.9% is joined 1.8g Si Ben-60,2.6g tween-80,3g allyl butyrate imide, 25g rapeseed oil (40 ℃ of viscosity 20.6mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip Pentyl alcohol down to the microemulsion clear, and Heating temperature is 48 ℃; The ammoniacal liquor of 1ml 24% speed with 60 droplets/minute is added dropwise in the above-mentioned microemulsion, heated and stirred is 3.5 hours under the normal pressure again, and stir speed (S.S.) is 400 rev/mins, Heating temperature is 69 ℃, get clear product D, adopt the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 5
Method three
The potassium hydroxide aqueous solution of 1ml 8.8% is joined 2.1g Si Ben-80,2.8g tween 20,2.6g allyl butyrate imide, synthetic hydrocarbon (the 40 ℃ of viscosity 35.6mm of 25g
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip Pentyl alcohol down to the microemulsion clear, and Heating temperature is 50 ℃; Again the zirconium tetrachloride aqueous solution of 2ml 11.3% speed with 30 droplets/minute is added dropwise in the above-mentioned microemulsion, heated and stirred is 2.5 hours under the normal pressure, stir speed (S.S.) is 1300 rev/mins, Heating temperature is 65 ℃, get the clear product E, adopt the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 6
Method one
The zirconium tetrachloride aqueous solution of 3ml 12.1% is joined 2.8g Si Ben-60,3.6g tween 20,1.5g petroleum sodium sulfonate, 25g Oleum Gossypii semen (40 ℃ of viscosity 22.8mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-dodecanol down to the microemulsion clear, and Heating temperature is 48 ℃; Again the 1ml di-n-butyl amine is joined 3g Si Ben-60,2g tween 20,1.5g petroleum sodium sulfonate, 25g Oleum Gossypii semen (40 ℃ of viscosity 22.8mm
2In/s) the mixture, heated and stirred is even under the normal pressure; With two kinds of liquid mixing, heated and stirred 3.5 hours, stir speed (S.S.) are 630 rev/mins again, and Heating temperature is 75 ℃, get the clear product F, adopt the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Example 7
Method two
The zirconium tetrachloride aqueous solution of 2ml 10.1% is joined 6.0g Si Ben-80,4.0g tween-80,4g petroleum sodium sulfonate, 50g polyethers (40 ℃ of viscosity 30mm
2In/s) the mixture, heated and stirred is even under the normal pressure, stirs to drip n-hexyl alcohol down to the microemulsion clear, and Heating temperature is 68 ℃; The 100ml ammonia is fed in this microemulsion, and heated and stirred 1.5 hours, stir speed (S.S.) are 1500 rev/mins, and Heating temperature is 35 ℃, get the clear product G, adopt the GB3142-82 method to measure its supporting capacity, the results are shown in Table 1.
Table 1 contains the extreme pressure and antiwear behavior of the lubricating oil of different concns additive
| Numbering | Form | Oil film strength P B(N) | Sintering load P D(N) | ZMZ |
| 1 2 3 4 5 6 7 8 9 10 11 | Base oil P P+2.5 ‰ A P+5 ‰ A P+10 ‰ A P+15 ‰ A P+5 ‰ B P+5 ‰ C P+5 ‰ D P+5 ‰ E P+5 ‰ F P+5 ‰ G | 333 421 588 412 608 412 421 588 588 588 588 | 1568 1568 1568 1960 1960 1960 1960 1568 1568 1568 1568 | 23.65 29.90 37.32 40.05 45.36 / / / / / / |
Claims (19)
1. preparation method who contains the lubrication oil anti-wear extreme pressure additive of nanoparticle comprises:
1) metal-salt or acid solution are mixed with lubricating oil dispersant, emulsifying agent and lubricant base, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain the microemulsion of salt or acid to the microemulsion clear; Said metal-salt or acid are water-soluble zirconates, water-soluble aluminum salt, boric acid or their mixture, and concentration of aqueous solution is 5～20 weight %; Weight in metal-salt or acid solution is 1 part, and the consumption of base oil is 10～40 parts, and the consumption of lubricating oil dispersant is 1～6 part, and the consumption of emulsifying agent is 1～6 part;
2) will mix with dispersion agent, emulsifying agent and base oil with the salt in the above-mentioned microemulsion or the alkali of sour equivalent, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain alkaline microemulsion to the microemulsion clear; Said alkali is C2～C16 alkylamine or polyamines polyene, or concentration is the aqueous solution of the mineral alkali of 1～30 weight %; Weight in alkali or alkaline solution is 1 part, and the consumption of base oil is 10～40 parts, and the consumption of lubricating oil dispersant is 1～6 part, and the consumption of emulsifying agent is 1～6 part;
3) above-mentioned two kinds of microemulsions being mixed, is 25 ℃～100 ℃ in temperature, and stir speed (S.S.) is to stir 0.5～8 hour under 100～2000 rev/mins the condition, obtains final product;
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture, said emulsifying agent is, sorbitol monooleate, Tween-20, polyoxyethylene sorbitan monoleate or their mixture, said dispersion aids is Pentyl alcohol, n-hexyl alcohol, n-dodecanol or their mixture, and said base oil is mineral oil, ucon oil, vegetables oil or their mixture.
2. according to the described preparation method of claim 1, it is characterized in that said metal-salt or acid are selected from zirconium tetrachloride, tri-chlorination zirconium, aluminum chloride, aluminum nitrate, boric acid.
3. according to the described preparation method of claim 1, it is characterized in that said metal-salt or aqueous acid concentration are 8～15 weight %.
4. according to the described preparation method of claim 1, it is characterized in that, said alkali is selected from ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, or concentration is the aqueous solution of 8～25% sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia.
5. according to the described preparation method of claim 1, it is characterized in that, in the step 1, is 1 part in the weight of metal-salt or acid solution, and the consumption of base oil is 20～30 parts, and the consumption of lubricating oil dispersant is 2～4 parts, and the consumption of emulsifying agent is 2～4 parts.
6. according to the described preparation method of claim 1, it is characterized in that, in the step 2, is 1 part in the weight of alkali or alkali lye, and the consumption of base oil is 20～30 parts, and the consumption of lubricating oil dispersant is 2～4 parts, and the consumption of emulsifying agent is 2～4 parts.
7. according to the described preparation method of claim 1, it is characterized in that in the step 3, heated and stirred 1～4 hour, stir speed (S.S.) are 300～1500 rev/mins, Heating temperature is 55～80 ℃.
8. preparation method who contains the lubrication oil anti-wear extreme pressure additive of nanoparticle comprises:
1) metal-salt or acid solution are mixed with lubricating oil dispersant, emulsifying agent and lubricant base, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain the microemulsion of salt or acid to the microemulsion clear; Said metal-salt or acid are water-soluble zirconates, water-soluble aluminum salt, boric acid or their mixture, and concentration of aqueous solution is 5～20 weight %; Weight in metal-salt or acid solution is 1 part, and the consumption of base oil is 10～40 parts, and the consumption of lubricating oil dispersant is 1～6 part, and the consumption of emulsifying agent is 1～6 part;
2) will with the salt in the above-mentioned microemulsion or the alkali of sour equivalent, the speed of dividing with 0.001～0.02mol/ joins in the above-mentioned microemulsion, in temperature is 20 ℃～100 ℃, and stir speed (S.S.) is to stir 0.5～8 hour under 100～2000 rev/mins the condition, obtains final product; Said alkali is C2～C16 alkylamine or polyamines polyene, or concentration is the aqueous solution of the mineral alkali of 1～30 weight %, or ammonia;
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture, said emulsifying agent is, sorbitol monooleate, Tween-20, polyoxyethylene sorbitan monoleate or their mixture, said dispersion aids is Pentyl alcohol, n-hexyl alcohol, n-dodecanol or their mixture, and said base oil is mineral oil, ucon oil, vegetables oil or their mixture.
9. according to the described preparation method of claim 8, it is characterized in that said metal-salt or acid are selected from zirconium tetrachloride, tri-chlorination zirconium, aluminum chloride, aluminum nitrate, boric acid.
10. according to the described preparation method of claim 8, it is characterized in that said metal-salt or aqueous acid concentration are 8～15 weight %.
11. according to the described preparation method of claim 8, it is characterized in that, said alkali is ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, or concentration is the aqueous solution of 8～25% sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia, or ammonia.
12., it is characterized in that in the step 1, the consumption of base oil is 20～30 parts according to the described preparation method of claim 8, the consumption of lubricating oil dispersant is 2～4 parts, the consumption of emulsifying agent is 2～4 parts.
13., it is characterized in that, in the step 2 according to the described preparation method of claim 8, the speed that alkali is divided with 0.005～0.015mol/ feeds or is added dropwise in the microemulsion of salt or acid, stir speed (S.S.) is 300～1500 rev/mins, and heated and stirred 1～4 hour, Heating temperature are 55～80 ℃.
14. a preparation method who contains the lubrication oil anti-wear extreme pressure additive of nanoparticle comprises:
1) alkali is mixed with dispersion agent, emulsifying agent and lubricant base, stir, be heated to 30 ℃～120 ℃, drip dispersion aids, obtain alkaline microemulsion to the microemulsion clear; Said alkali is C2～C16 alkylamine or polyamines polyene, or concentration is the aqueous solution of the mineral alkali of 1～30 weight %; Weight in alkali or alkali lye is 1 part, and the consumption of base oil is 10～40 parts, and the consumption of lubricating oil dispersant is 1～6 part, and the consumption of emulsifying agent is 1～6 part;
2) will with the metal-salt or the acid solution of alkali equivalent in the above-mentioned microemulsion, be added dropwise in the above-mentioned microemulsion with 10～60 droplets/minute speed, in temperature is 25 ℃～100 ℃, and stir speed (S.S.) is to stir 0.5～8 hour under 100～2000 rev/mins the condition, obtains final product; Said metal-salt or acid are water-soluble zirconates, water-soluble aluminum salt, boric acid or their mixture;
Said lubricating oil dispersant is allyl butyrate imide, petroleum sodium sulfonate, calcium mahogany sulfonate or their mixture, said emulsifying agent is, sorbitol monooleate, Tween-20, polyoxyethylene sorbitan monoleate or their mixture, said dispersion aids is Pentyl alcohol, n-hexyl alcohol, n-dodecanol or their mixture, and said base oil is mineral oil, ucon oil, vegetables oil or their mixture.
15. according to the described preparation method of claim 14, it is characterized in that, said alkali is ethylamine, di-n-butyl amine, n-hexyl amine, dodecyl amine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, or concentration is the aqueous solution of 8～25% sodium hydroxide, potassium hydroxide, lithium hydroxide, water glass, ammonia.
16., it is characterized in that said metal-salt or acid are selected from zirconium tetrachloride, tri-chlorination zirconium, aluminum chloride, aluminum nitrate, boric acid according to the described preparation method of claim 14.
17., it is characterized in that the concentration of said metal-salt or aqueous acid is 5～20 weight % according to the described preparation method of claim 14.
18., it is characterized in that according to the described preparation method of claim 14, in the step 1, be 1 part in the weight of alkali or alkali lye, the consumption of base oil is 20～30 parts, and the consumption of lubricating oil dispersant is 2～4 parts, and the consumption of emulsifying agent is 2～4 parts.
19. according to the described preparation method of claim 14, it is characterized in that, in the step 2, will with the metal-salt or the acid solution of alkali equivalent in the alkaline microemulsion, be added dropwise in the alkaline microemulsion with 20～40 droplets/minute speed, heated and stirred 1～4 hour, stir speed (S.S.) are 300～1500 rev/mins, 55～80 ℃ of Heating temperatures.
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| CN101462914B (en) * | 2009-01-12 | 2011-12-07 | 山西建烨工贸有限公司 | Environment protective emulsive explosive composite emulsifying agent |
| CN102041140B (en) * | 2010-01-19 | 2013-04-24 | 江苏惠源石油科技有限公司 | Anti-micro pitting gear oil composite additive |
| CN101974361A (en) * | 2010-08-20 | 2011-02-16 | 泰安天健应用技术推广中心 | Multifunctional nanocomposite antiwear agent |
| CN102925251A (en) * | 2012-11-27 | 2013-02-13 | 沈阳工业大学 | Method for preparing nano-borate particles in liquid-state lubricating oil |
| CN115383534A (en) * | 2022-09-13 | 2022-11-25 | 成都青洋电子材料有限公司 | Production process of monocrystalline silicon wafer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4915895A (en) * | 1987-11-30 | 1990-04-10 | General Motors Corporation | Method for making a composite tread for track-laying vehicles |
| CN1218104A (en) * | 1998-10-08 | 1999-06-02 | 中国科学院兰州化学物理研究所 | Nano size rare earth fluoride lubricant oil additive |
| CN1320683A (en) * | 2000-04-26 | 2001-11-07 | 青岛立大集团股份有限公司 | Rare-earth additive of lubricating oil and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4915895A (en) * | 1987-11-30 | 1990-04-10 | General Motors Corporation | Method for making a composite tread for track-laying vehicles |
| CN1218104A (en) * | 1998-10-08 | 1999-06-02 | 中国科学院兰州化学物理研究所 | Nano size rare earth fluoride lubricant oil additive |
| CN1320683A (en) * | 2000-04-26 | 2001-11-07 | 青岛立大集团股份有限公司 | Rare-earth additive of lubricating oil and its preparing process |
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