CN1362500A - Additive for lubricant oil - Google Patents

Additive for lubricant oil Download PDF

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Publication number
CN1362500A
CN1362500A CN 01106035 CN01106035A CN1362500A CN 1362500 A CN1362500 A CN 1362500A CN 01106035 CN01106035 CN 01106035 CN 01106035 A CN01106035 A CN 01106035A CN 1362500 A CN1362500 A CN 1362500A
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China
Prior art keywords
ester
polyisobutene
acid
inorganic
lubricating oil
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CN 01106035
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Chinese (zh)
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CN1132917C (en
Inventor
王鼎聪
彭全铸
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to CN 01106035 priority Critical patent/CN1132917C/en
Publication of CN1362500A publication Critical patent/CN1362500A/en
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Publication of CN1132917C publication Critical patent/CN1132917C/en
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Abstract

The present invention relates to a lubricant additive. It is a colloid solution which comprioses one of borate and este of several mixtures and is dispersed in lubricant by means of polyolefine emulsifier and whose grain size is below 0.5 micron, and has high extreme pressure property, good antiwear property, resisting to corrosion and resisting to oxidation, can be made into antiwear hydraulic oil and gear oil, etc.

Description

A kind of lubricating oil additive
The present invention relates to a kind of antioxygen of lubricating oil, anti-corruption, wear preventive additive and preparation method thereof, be used to allocate antiwear hydraulic oil, the gear wet goods.
The quality of lubricating oil (agent) is decision machinery equipment serviceability and one of important factor that prolongs its work-ing life, and lubricating oil additive is the marrow of various senior lubricants (agent), can give the property that lubricating oil itself does not possess.As<the lubricant tribo-chemistry 〉. the .1994 of Sinopec press introduced in 10 months.The inorganic borate additive in lubricating oil extreme pressure and the research of abrasion resistance start from the beginning of the sixties.1964 Van Der Veer (Vandeuveer) Wo Bisi (Voorbees) synthesized borate additive for lubricating oil.After, gold people such as (King) has also delivered their research work.The Industrial products that the end of the seventies occurred borate additive, as: the OLOA-9750 gear oil additive of Cheveron company.
The borate that common people are familiar with comprises some alkali metal compounds such as potassium borate, Sodium Tetraborate, metaboric acid and sodium metaborate, and wherein, preceding two kinds of chemical combination have the similar molecular structure of thing, and the structure of back two kinds of compounds is also similar, all contains B 3O 6 3-Ion belongs to the plane six-ring on this ionic structure.Borate generally all has crystal water, and with the crystal water different amts, molecular structure also changes.Its crystal water can be heated and take off, even but borate itself under very high temperature, can not decompose yet.United States Patent (USP) 3,313,727 at the stable an alkali metal salt dispersion liquid in the preparation lubricating oil, and wherein the alkali metal borate of aquation is to be enough to keep particle stabilized dispersive amount of borate and emulsifier mix.These particles it is said that size almost all is lower than 1 micron, and major part is lower than 0.5 micron.Suitable alkali metal borate is to have the sodium of 1-4 water of hydration and the metaborate and the tetraborate of potassium.Also can there be neutral dispersion agent in these components, for example the alkenyl succinimide of alkali amine.CN1175621A discloses the preparation method of superfine borate additive for lubricating oil, adopts the ultrasonic emulsification method, and process is comparatively complicated.
From the work of having delivered, as the inorganic borate (or mixture) of extreme-pressure anti-friction additive by its empirical formula of forming of following several reflections:
xM 2.B 2O 3.yH 2o?????????????????????????????????????(A)
mNa 2O·nK 2O.pM 2O·B 2O 3·yH 2O????????????????????????(B)
MNa 2OnM 2OxB 2O 3YH 2In O (C) formula, M represents Na, or K, Li, alkali metals such as Rb, Cs.The mole number of crystal water is generally 0.5 to 4.5, the mole number and the B of metal oxide (or mixed metal oxide) 2O 3The ratio of your number of motorcycle is about 1: 1~and 2.
Additive is glassy fine particle with boratory form, and particle dia is less than 1 μ m, and majority should be less than 0.51 μ m, and too thick particle can not form stable solid-oil dispersion system, and effect is played at the engaging friction interface effectively.
Another main component is the blended dispersion stabilizer in the boronic acid containing salt additives prescription.The main effect of dispersion agent is to guarantee that boratory particulate is suspended in the oil uniformly and stably, and guarantees that borate can not separated out in crystallization under the situation that has moisture to exist.This class dispersion agent should have two class materials, and the one, hydrophobic anion surfactant contains elements such as II family element and sulphur in its molecule, and another is hydrophobic nonionogenic tenside.
Hydrophobic nonionic surface active agent mainly comprises the derivative of succinyl amine, polymethacrylate or tetramethylolmethane.Wherein most widely used general with the succimide class.
Generally there are two kinds of methods in preparation borate oil dispersion system: polishing and double decomposition
Polishing is a kind of method that is relatively easy to for preparing borate oil dispersion system.Its shortcoming is the difficult less boratory dispersion system of granularity that obtains.This method is not contain crystal water or some amount crystal water mesoboric acid salt mixes with base oil by a certain percentage, grinds in mortar in the presence of dispersion agent or uses the ball grinder barreling, and mill with vibration mill vibration or colloidal mill.
Double decomposition is with B (OH) 3, NaOH or Na 2CO 3, make B (OH) then 3The aqueous solution and the NaOH aqueous solution or Na 2CO 3Reactant aqueous solution, products therefrom emulsification in containing the oil of dispersion agent, intensification is at last dewatered and is made the borate oil dispersion.Can obtain the less borate dispersion of granularity with this method, but dehydration operation is difficult, borate is curding out in dehydration easily.The preparation borate additive for lubricating oil is that borate is made the aqueous solution among United States Patent (USP) and the CN1175621A, under the effect of neutral sulfonated petro-leum of dispersion agent and succimide, be scattered in the oil then, generate the emulsive borate microparticulate borate additive for lubricating oil of heating-up section dehydration suspensoid then by vigorous stirring.
The composition and preparation method thereof that the purpose of this invention is to provide the lubricating oil additive of a kind of antioxygen, anti-rotten, wear-resistant oil bag molten salt and inorganic ester aqueous colloidal dispersion.
In order to overcome the not high shortcoming of succinyl amine thermostability, the present invention is dispersed into colloid as dispersion emulsifier with borate and boric acid ester emulsification with polyolefine toxilic acid poly-hydroxy, this emulsifying agent has Heat stability is good than succinyl amine, the emulsifying power advantages of higher.The technology that existing preparation borate oil dispersion is is cumbersome, and polishing needs barreling in ball grinder for a long time, and mills with vibration mill vibration or colloidal mill, and double decomposition need be made aqueous product, dehydration then.The present invention adopts and makes borate and boric acid ester mixture, to reduce its fusing point, is dispersed in more than fusing point in the oil, and generation colloidal solution need not dewatering process and brute force is milled.
Lubricating oil additive of the present invention by dispersion agent, help emulsion, base oil, inorganic salt or inorganic ester to form, wherein inorganic salt and inorganic ester by dispersion agent, help emulsion, base oil to coat to form less than the dispersoid below 0.5 micron, consist of by weight:
Inorganic salt and inorganic ester 30~70%
Dispersion agent 5~25%
Help emulsion 1~5%
The base oil surplus
Wherein the weight ratio of inorganic salt and inorganic ester is 1: 0.2~5.
Lubricating oil additive of the present invention be a kind of oil bag molten salt and inorganic ester at dispersion agent, help the aqueous colloidal dispersion that is scattered under the emulsion effect in the base oil.Wherein inorganic salt are one or more mixtures of Sodium Tetraborate, potassium borate, sodium metaborate, potassium metaborate, sodium tetraborate.Inorganic ester is one or more mixtures of boric acid monoethanolamine, boric acid diethanolamine, triethanolamine borate, boric acid pentaerythritol ester, boric acid sorbitol ester, boric acid glycol ester, boric acid glycol ether ester, boric acid triethyleneglycol ester.
Dispersion agent is a kind of or many middle mixture of polyisobutene succinimide, polyisobutene toxilic acid glycol ether ester, polyisobutene toxilic acid triethyleneglycol ester, polyisobutene toxilic acid glyceryl ester, polyisobutene toxilic acid triethanolamine ester, polyisobutene toxilic acid diethanolamine ester, polyisobutene toxilic acid sorbitol ester, polyisobutene toxilic acid pentaerythritol ester, the molecular weight of polyisobutene is generally 600~3000, be preferably 800~2000, be preferably 900~1200.
Help emulsion to be selected from one or more mixtures of petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate, dodecyl alcohol acyl phosphoric acid ester.The kind of hydrophobic anion surfactant is a lot, and wherein the most frequently used is sulfonated petro-leum.Its lipophilic group is an alkylaryl, and polar group is sulfonic group (SO 3H), the group thermostability that this acidity is strong is fine.The hydrophilic radical of sulfonate is calcium salt, barium or magnesium salts.Sulfonate just is divided three classes by its metal content, and it is neutrality or low alkalinity sulfonate that metal content equals stoichiometric, and metal content is the alkaline sulfonate that is of about three times of chemical equivalents, and more than three times is overbased sulfonate.
The used oil medium of preparation additive can be the natural oil product, also can be synthetic oil product.Natural oil product can be a paraffinic based oil, also can be naphthene base crude oil.Synthetic oil product can be a polyolefine, the alkylaromatic hydrocarbon polymkeric substance.Base oil adopts a kind of or several mixtures of the subtracting two cut pressed oils, subtract three cut pressed oils of refinery, 150SN, 650SN, 120BS, 150BS.
Preparation process lubricant oil additive of the present invention is: inorganic salt or inorganic ester are heated to it more than fusing point, temperature is between 80~180 ℃, after making its fusing, slowly adding is heated to oil phase, the emulsifying agent of inorganic salt and inorganic ester uniform temp in advance and helps in the mixture of emulsion, under the mixture strength of on-line velocity 7~30 meter per seconds, mix and stir certain hour, mixing time 1 minute~60 minutes, stop to mix stirring, discharging at inorganic salt or more than the inorganic ester fusing point.In addition, preparation process lubricant oil additive of the present invention can also adopt continuous hybrid technique, and oil phase, inorganic salt or inorganic ester are heated to mixing temperature, quantitatively pass through in continuous mixing device.Mixed inorganic salt or inorganic ester coat with form membrane with oil phase, and the granularity of mixed inorganic salt or inorganic ester can reach below 0.5 micron.
Additive advantage of the present invention is a kind of or several mixtures of borate, silicate, boric acid ester, is scattered in the aqueous colloidal dispersion that forms oil bag molten state in the oil more than the fusing point of mixture.Do not need the reaction heating to dewater owing to anhydrous in this mixture, and mixture is that molten state does not need the ball mill brute force to smash borate when disperseing, and only needs general dispersing apparatus to meet the demands.Under condition of boundary lubrication, inorganic salt and inorganic ester become molten state and play the good lubrication effect, and the inorganic salt that work the effect of overstocking when non-boundary lubrication are scattered in the oil by dispersion agent again, and additive does not have destroyed, has prolonged the oil product usage period.Dispersion agent of the present invention, the effect, particularly inorganic salt and the inorganic ester that help emulsion all to have rust-preventive agent are again a kind of many metal antirusting agents, metals such as steel, iron, copper are all had the effect of rust-preventive agent.A kind of inorganic salt of the present invention also have the anti-corrosion additive effect, and the use temperature of oil product can be reached does not have tangible oxygenizement to take place more than 100 ℃.
Lubricating oil additive of the present invention can be widely used in various types of lubricating oil, and as gear oil, hydraulic pressure wet goods, wherein the addition in the lubricating oil is generally 15~80w%, better 25~60w%, best 35~50w%.
The composition and the preparation method of lubricating oil additive of the present invention are described below by embodiment.
Table 1 additive of the present invention is formed
Embodiment ????1 ????2 ????3 ????4
Inorganic salt and inorganic ester Kind Sodium Tetraborate boric acid monoethanolamine Potassium borate boric acid diethanolamine boric acid glycol ether ester Sodium metaborate sodium tetraborate triethanolamine borate Boric acid pentaerythritol ester potassium metaborate
Ratio/content ????1∶5 ????30 ????1∶2∶1 ????65 ????1∶1∶1 ????40 ????1∶1 ????55
Dispersion agent Kind Polyisobutene toxilic acid glycol ether ester polyisobutene toxilic acid glyceryl ester Polyisobutene toxilic acid triethyleneglycol ester polyisobutene toxilic acid pentaerythritol ester, Polyisobutene toxilic acid triethanolamine ester Polyisobutene toxilic acid diethanolamine ester polyisobutene toxilic acid sorbitol ester,
Ratio/content ????1∶1 ????5 ????2∶1 ????20 ????10 ????1∶1 ????15
Help emulsion Kind Petroleum sodium sulfonate Yelkin TTS Calcium mahogany sulfonate dodecyl alcohol acyl phosphoric acid ester Barium mahogany sulfonate phosphoric acid fat Petroleum sodium sulfonate
Ratio/content ????1∶1 ????2 ????2∶1 ????1 ????3∶1 ????4 ????5
Continuous table
Base oil Kind Subtract two cut pressed oil 120BS Subtract three cut pressed oils ????150SN ????650SN ????150BS
Ratio/content 3: 1 surpluses Surplus Surplus 5: 1 surpluses
Melt temperature ℃ ????80 ????180 ????100 ????120
Mixture strength m/s ????30 ????7 ????16 ????12
Mixing time min ????2 ????50 ????10 ????20
Annotate: ratio and content data are by weight in the table.The molecular weight of the polyisobutene among the embodiment 1 is 900.The molecular weight of the polyisobutene among the embodiment 2 is 1000.The molecular weight of the polyisobutene among the embodiment 3 is 950.The molecular weight of the polyisobutene among the embodiment 4 is 1050.
Table 2 additive performance of the present invention
Embodiment ????1 ????2 ????3 ????4
Outward appearance Transparent Transparent Transparent Transparent
20% mother liquor thinning oil outward appearance Transparent Transparent Transparent Transparent
Water-content Trace Trace Trace Trace

Claims (6)

1, a kind of lubricating oil additive, mainly by dispersion agent, help emulsion, base oil, inorganic salt and/or inorganic ester to form, it is characterized in that inorganic salt and inorganic ester by dispersion agent, help emulsion, base oil to coat to form dispersoid, it consists of:
Inorganic salt and inorganic ester 30~70%
Dispersion agent 5~25%
Help emulsion 1~5%
The base oil surplus.
2,, it is characterized in that described inorganic salt are one or more mixtures of Sodium Tetraborate, potassium borate, sodium metaborate, potassium metaborate, sodium tetraborate according to the described lubricating oil additive of claim 1.
3, according to the described lubricating oil additive of claim 1, it is characterized in that described inorganic fat is boric acid monoethanolamine, boric acid diethanolamine, triethanolamine borate, boric acid pentaerythritol ester, boric acid sorbitol ester, one or more mixtures of boric acid glycol ether ester, boric acid triethyleneglycol ester, boric acid glycol ester.
4,, it is characterized in that wherein said dispersion agent is a kind of or many middle mixture of polyisobutene succinimide, polyisobutene maleic acid glycol ester, polyisobutene toxilic acid glycol ether ester, polyisobutene toxilic acid triethyleneglycol ester, polyisobutene toxilic acid glyceryl ester, polyisobutene toxilic acid triethanolamine ester, polyisobutene toxilic acid diethanolamine ester, polyisobutene toxilic acid sorbitol ester, polyisobutene toxilic acid pentaerythritol ester according to the described lubricating oil additive of claim 1.
5,, it is characterized in that the wherein said emulsion that helps is to help emulsion to be selected from petroleum sodium sulfonate, calcium mahogany sulfonate, barium mahogany sulfonate, sodium stearate, sodium oleate, potassium stearate, potassium oleate, Yelkin TTS, phosphoric acid fat, fatty alcohol-polyoxyethylene ether (10), aliphatic acid polyethenoxy ether (15), alkylphenol polyoxyethylene (7), aliphatic amine polyoxyethylene ether (15), polyoxyethylene glycol (400), Yatall MA acid amides, sodium laurylsulfonate, dodecyl alcohol acyl phosphoric acid ester according to the described lubricating oil additive of claim 1.
6, according to the described lubricating oil additive of claim 1, it is characterized in that described base oil be subtract two cut pressed oils, subtract three cut pressed oils, a kind of or several mixtures of 150SN, 650SN, 120BS, 150BS.
CN 01106035 2001-01-05 2001-01-05 Additive for lubricant oil Expired - Lifetime CN1132917C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301319C (en) * 2004-12-29 2007-02-21 中国石油化工股份有限公司 Lubricating oil additive and preparation method
CN101985577A (en) * 2010-11-01 2011-03-16 彭美东 Linear cutting emulsified oil
CN101124307B (en) * 2005-02-22 2011-04-20 M-I有限公司 Additive for reducing torque on a drill string
CN102433210A (en) * 2011-10-27 2012-05-02 姜堰市华润化工厂 Water-based working liquid for electrical discharge wire cutting and preparation method thereof
CN102628000A (en) * 2012-03-22 2012-08-08 天津中澳星环保科技发展有限公司 Novel totally-synthetic processing fluid for wire-cutting metal by electric sparks
CN104017009A (en) * 2014-06-19 2014-09-03 天津舜能化学品有限公司 Boron-nitride-type borate lubricating oil additive and preparation method thereof
CN104178295A (en) * 2013-05-23 2014-12-03 天津市泽畅科技有限公司 Tungsten molybdenum alloy anti-wear additive used in engine oil
CN104263462A (en) * 2014-08-17 2015-01-07 青岛蓬勃石油技术服务有限公司 Purification dispersant for engine lubricating oil and preparation method thereof
CN104625672A (en) * 2014-12-24 2015-05-20 常熟市三骏精密刃具制造厂 Manufacturing method for metal slitting saw
CN105441168A (en) * 2015-11-30 2016-03-30 蚌埠市华科机电有限责任公司 Friction improved lubricating oil
CN113061480A (en) * 2021-03-31 2021-07-02 煤炭科学技术研究院有限公司 Protective liquid for hydraulic system and preparation method and application thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301319C (en) * 2004-12-29 2007-02-21 中国石油化工股份有限公司 Lubricating oil additive and preparation method
CN101124307B (en) * 2005-02-22 2011-04-20 M-I有限公司 Additive for reducing torque on a drill string
CN101985577B (en) * 2010-11-01 2012-10-10 彭美东 Linear cutting emulsified oil
CN101985577A (en) * 2010-11-01 2011-03-16 彭美东 Linear cutting emulsified oil
CN102433210B (en) * 2011-10-27 2013-09-25 姜堰市华润化工厂 Water-based working liquid for electrical discharge wire cutting and preparation method thereof
CN102433210A (en) * 2011-10-27 2012-05-02 姜堰市华润化工厂 Water-based working liquid for electrical discharge wire cutting and preparation method thereof
CN102628000A (en) * 2012-03-22 2012-08-08 天津中澳星环保科技发展有限公司 Novel totally-synthetic processing fluid for wire-cutting metal by electric sparks
CN102628000B (en) * 2012-03-22 2014-05-07 天津中澳星环保科技发展有限公司 Totally-synthetic processing fluid for wire-cutting metal by electric sparks
CN104178295A (en) * 2013-05-23 2014-12-03 天津市泽畅科技有限公司 Tungsten molybdenum alloy anti-wear additive used in engine oil
CN104017009A (en) * 2014-06-19 2014-09-03 天津舜能化学品有限公司 Boron-nitride-type borate lubricating oil additive and preparation method thereof
CN104263462A (en) * 2014-08-17 2015-01-07 青岛蓬勃石油技术服务有限公司 Purification dispersant for engine lubricating oil and preparation method thereof
CN104625672A (en) * 2014-12-24 2015-05-20 常熟市三骏精密刃具制造厂 Manufacturing method for metal slitting saw
CN105441168A (en) * 2015-11-30 2016-03-30 蚌埠市华科机电有限责任公司 Friction improved lubricating oil
CN113061480A (en) * 2021-03-31 2021-07-02 煤炭科学技术研究院有限公司 Protective liquid for hydraulic system and preparation method and application thereof
CN113061480B (en) * 2021-03-31 2022-09-20 煤炭科学技术研究院有限公司 Protective liquid for hydraulic system and preparation method and application thereof

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