CN1191338C - Prepn of extreme pressure antiwear agent for lubricant oil - Google Patents
Prepn of extreme pressure antiwear agent for lubricant oil Download PDFInfo
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- CN1191338C CN1191338C CN 02116921 CN02116921A CN1191338C CN 1191338 C CN1191338 C CN 1191338C CN 02116921 CN02116921 CN 02116921 CN 02116921 A CN02116921 A CN 02116921A CN 1191338 C CN1191338 C CN 1191338C
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- acid
- clay
- carboxylic acid
- described preparation
- product
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Abstract
The present invention relates to a method for preparing extreme-pressure antiwear agents for lubricants. The method comprises the following steps: modified organic clay soil reacts with C4-C24 carboxylic acid compounds at a temperature of 100 to 160 DEG C when solvents exist, and products are separated and recovered. The method of the present invention utilizes hydroxyl radicals at the periphery of a sheet layer of the clay soil to carry out an esterification reaction with anhydride or carboxylic acid so as to connect the sheet layer of the clay soil with long carbon chains. The prepared extreme-pressure antiwear agent has the advantages of good dispersivity, high resistance to extreme pressure wear, no inclusion of elements, such as sulphur, phosphorus, chlorine, etc., simple synthetic method and wide prospect for development and application, and can be applied to industrial lubricants, such as cutting oil, rolling oil, punching oil, etc.
Description
Technical field
The invention belongs to lubricating oil additive, specifically, is a kind of preparation method of extreme pressure anti-wear additives.
Technical background
Be the material of sulfur-bearing, phosphorus, chlorine at present at lubricating oil field practical and effective extreme pressure anti-wear additives, though good effect is arranged, but also can exert an adverse impact to environment, so development no sulphur, phosphorus, chlorine or low-sulfur, phosphorus, free from chloride product are the direction that develops of extreme-pressure anti-friction additive from now on.
Clay is widespread in nature, and is still organically-modified no matter be inorganic as a kind of inorganic materials, all is used widely.Because the laminated structure of clay uniqueness, interlayer has the ion such as the Na that can be exchanged
+, K
+, Mg
2+Deng, can be given clay with the organic character of parent by the ion of other large volume such as ammonium, phosphine, oxygen, the exchange of sulfonium plasma.The neutral polar molecule also can embed between clay seam, thereby clay is organised.
Organo-clay is used very wide, as: CN1052094A carries out the interlayer ion exchange with the mixture reaction of wilkinite and quaternary amine or quaternary amine and tertiary amine, and products therefrom can be used as the anti-sedimentation agent of grease thickener, paint etc.CN1238353A discloses the preparation method of clay-rubber nm-class composite material.CN1255510A has introduced the preparation method of the matrix material of polyolefine and clay.US4810734 has introduced and a kind of clay and polymkeric substance has been combined with ionic linkage, thereby makes clay be dispersed in method in the polymeric matrix.Above-mentioned patent is all utilized the laminated structure of clay, and clay is dispersed in the polymeric matrix, and mechanical property is greatly improved.Especially in CN1212716, describe the exchangable ion that utilizes between clay seam in detail, after particularly ammonium cation exchanges as ion, further generate polymkeric substance-organoclay composite in several modes with polymkeric substance.On the other hand, utilize the reaction of hydroxyl on the lamella edge and coupling agent, as the supporting process that generates matrix material, in relevant patent, also have related, as above-mentioned CN1238353A.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of novel extreme pressure anti-wear additives, this method directly utilizes the hydroxyl on the clay layer to react, and is synthetic easy.
The preparation method of extreme pressure anti-wear additives provided by the invention comprises: with organo-clay and C
4-C
24Carboxylic acid compound reacts under 100-160 ℃ in the presence of solvent, the Separation and Recovery product.
Specifically with organo-clay and C
4-C
24, preferred C
12-C
22Carboxylic acid compound in 100-160 ℃, under preferred 100-130 ℃, react 4-40 hour in the presence of solvent, and preferred 6-30 hour, steam solvent, usefulness base oil stripping product gets final product.
Said clay is selected from wilkinite, polynite, attapulgite etc.Organically-modified is to use ion, as the ion that can be exchanged between ammonium, phosphine, oxygen, sulfonium etc. and clay seam, as Na
+, K
+, Mg
2+Deng carrying out ion-exchange, give clay with the organic property of parent.Said organo-clay can be the commercial goods, also can be according to conventional method of modifying self-control.Comparatively general method of modifying is that clay and alkylamine or aminocarboxylic acid, hydrochloric acid are added in the distilled water, is warmed up to 30-90 ℃, and the best be 60-80 ℃, fully stirs, and with muddy liquid centrifugation, uses the distilled water repetitive scrubbing to arrive no Cl
-Detect,, obtain product isolate vacuum-drying at room temperature.
Said carboxylic acid compound is selected from C
4-C
24Carboxylic acid, acid anhydrides and carboxylic acid and the adduction product of acid anhydrides, preferably carbon number is C
12-C
22, preferred oleic acid, sebacic acid, Succinic Acid, hexosamine, lauric acid (C
12), tetradecanoic acid (C
14), palmitinic acid (C
16) and erucic acid (C
22).
Organic solvents such as selected solvent can toluene, dimethylbenzene, benzene, ethanol, ethylene glycol, methyl-phenoxide, preferably reflux temperature is at 100-160 ℃ organic solvent.
The present invention synthesizes the raw material of extreme pressure anti-wear additives with the organo-clay conduct.Because clay is a silicate minerals, silicon itself has very high fusing point, and the clay particle degree is little, the secondary interface of engaging friction preferably.In organic solvent, by solvent " swelling ", the clay of multilayered structure is scattered in the solvent with monolithic layer through organically-modified clay.Utilize hydroxyl and the acid anhydrides or the carboxylic acid generation esterification at lamella edge, make clay layer connect long carbochain, can improve oil soluble, and resistance to abrasion and extreme pressure property also are improved.
The extreme pressure anti-wear additives of the inventive method preparation has dispersiveness and extreme pressure anti-wear preferably, elements such as sulfur-bearing, phosphorus, chlorine not, and simple synthetic method has very wide development and application prospect, can be applicable to machining oil, ROLLING OIL, punching press wet goods industrial lubricant.
Embodiment
Example 1
With 4.00 gram quaternary ammonium salt modified wilkinites of the U.S. and 4.00 gram oleic acid and maleic anhydride adducts, 200 gram toluene, add in the there-necked flask, refluxed 36 hours, pressure reducing and steaming toluene, with 150SN base oil stripping product A, add in the 150SN base oil with 1%, 3%, 8% dosage respectively, measure oil film strength P according to the GB3142-82 method
BBe respectively 539N, 539N, 637N, sintering load is respectively 1568N, 1960N, 1960N.3% product long term wear wear scar diameter d
30Kg 60min(75 ℃, 1200rpm)=0.39mm.And 150SN base oil long term wear wear scar diameter d
30Kg 60min(75 ℃, 1200rpm)=0.75mm.The results are shown in Table 1.
Example 2
With 4.00 homemade quaternary ammonium salt modified wilkinite of gram and 11.12 oleic acid, 250 gram toluene refluxed 12 hours, and pressure reducing and steaming toluene is dissolved in 150SN with product, product numbering B, the oil film strength P of 3%B
BBe 539N, sintering load P
DBe 1568N.The results are shown in Table 1.
Example 3
Produce quaternary ammonium salt modified wilkinite and 4.00 gram sebacic acid with the 4.00 gram U.S., 250 gram toluene, back flow reaction 12 hours, pressure reducing and steaming toluene is dissolved in 150SN with product, numbering C, the P of 2.7%C
BBe 539N, P
DBe 2450N.The results are shown in Table 1.
Example 4
With 10.00 gram Ca base montmorillonites, 20 gram stearylamines, the hydrochloric acid of the 200ml of 1: 10 dilution proportion, normal temperature stirred 4 hours down, filtered, and was washed with distilled water to no Cl
-Detect, oven dry is pulverized, and obtains organically-modified clay.
Get 10 gram products and 3 gram Succinic Acid, reaction is 8 hours under refluxing toluene, and pressure reducing and steaming toluene is dissolved in the 150SN base oil with product with 3%, and numbering D surveys its P
BBe 666N, P
DBe 2450N.The results are shown in Table 1.
Get 10 gram products and 10 gram erucic acid reacts 6 hours under reflux in toluene, pressure reducing and steaming toluene is dissolved in 150SN with product with 3%, numbers E, surveys its P
BBe 539N, P
DBe 1960N.The results are shown in Table 1.
Example 5
Get 10 gram attapulgites, 10 gram hexosamines, 200ml are with the hydrochloric acid of dilution in 1: 10, and normal temperature stirred 4 hours down, filter, and washing, oven dry is pulverized.
Get the attapulgite of 3 gram modifications, 6 gram maleic acid anhydrides were reflux in toluene 6 hours, and pressure reducing and steaming toluene is dissolved in 150SN with product with 3%, and numbering F surveys its P
BBe 441N, P
DBe 1960N.
Example 6
With the quaternary ammonium salt modified wilkinite of 5 grams, 10 gram sebacic acid, in ethylene glycol solution,, leave standstill after-filtration in 110 ℃ of reactions 8 hours, use distilled water wash, evaporate to dryness.Be dissolved among the 150SN with 3% product, numbering G surveys its P
BBe 490N, P
DBe 1960N.The results are shown in Table 1.
The performance of table 1 a synthetic extreme pressure anti-wear additives
| Product (or base oil) | Dosage, % | Oil film strength P B，N | Sintering load P D.N |
| The 150SN base oil | -- | 441 | 1568 |
| A | 1 | 539 | 1568 |
| A | 3 | 539 | 1960 |
| A | 8 | 637 | 1960 |
| B | 3 | 539 | 1568 |
| C | 2.7 | 539 | 2450 |
| D | 3 | 666 | 2450 |
| E | 3 | 539 | 1960 |
| F | 3 | 441 | 1960 |
| G | 3 | 490 | 1960 |
Claims (8)
1. the preparation method of extreme pressure antiwear agent for lubricant oil comprises: with organo-clay and C
4-C
24Carboxylic acid compound reacted 4-40 hour down in 100-160 ℃ in the presence of organic solvent, the Separation and Recovery product.
2. according to the described preparation method of claim 1, it is characterized in that, organo-clay and C
12-C
22Carboxylic acid compound under 100-130 ℃, reacted 6-30 hour in the presence of solvent, steamed solvent, with base oil stripping product.
3. according to claim 1 or 2 described preparation methods, it is characterized in that said clay is selected from wilkinite, polynite, attapulgite.
4. according to claim 1 or 2 described preparation methods, it is characterized in that, the preparation method of said organo-clay comprises: clay and alkylamine or aminocarboxylic acid, hydrochloric acid are added in the distilled water, be warmed up to 30-90 ℃, fully stir, with muddy liquid centrifugation,, obtain product with isolate washing, drying.
5. according to the described preparation method of claim 1, it is characterized in that said carboxylic acid compound is selected from the adduction product of carboxylic acid, acid anhydrides and carboxylic acid and acid anhydrides.
6. according to the described preparation method of claim 1, it is characterized in that said carboxylic acid compound is selected from oleic acid, sebacic acid, Succinic Acid, hexosamine, lauric acid, tetradecanoic acid, palmitinic acid and erucic acid.
7. according to the described preparation method of claim 1, it is characterized in that said organic solvent is selected from toluene, dimethylbenzene, benzene, ethanol, ethylene glycol and methyl-phenoxide.
8. according to the described preparation method of claim 1, it is characterized in that said organic solvent is a reflux temperature at 100-160 ℃ organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02116921 CN1191338C (en) | 2002-04-26 | 2002-04-26 | Prepn of extreme pressure antiwear agent for lubricant oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02116921 CN1191338C (en) | 2002-04-26 | 2002-04-26 | Prepn of extreme pressure antiwear agent for lubricant oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453346A CN1453346A (en) | 2003-11-05 |
| CN1191338C true CN1191338C (en) | 2005-03-02 |
Family
ID=29257052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02116921 Expired - Lifetime CN1191338C (en) | 2002-04-26 | 2002-04-26 | Prepn of extreme pressure antiwear agent for lubricant oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1191338C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328361C (en) * | 2004-11-30 | 2007-07-25 | 中国石油化工股份有限公司 | Method for preparing water base extreme pressure lubricating liquid |
| PL2633009T3 (en) | 2010-10-26 | 2016-10-31 | Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy- carboxylic acids, and uses thereof | |
| CN103240126B (en) * | 2012-02-03 | 2015-05-20 | 中国石油化工股份有限公司 | Iron ore-containing heavy oil hydrogenation catalyst, and preparation method and application thereof |
| CN103285930B (en) * | 2012-02-22 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst containing yellow iron and Synthesis and applications thereof |
| CN103285929B (en) * | 2012-02-22 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst of aluminiferous ore and Synthesis and applications thereof |
| CN108192709A (en) * | 2018-01-30 | 2018-06-22 | 中国科学院宁波材料技术与工程研究所 | Lubricant oil composite, preparation method and application with excellent antifriction antiwear |
-
2002
- 2002-04-26 CN CN 02116921 patent/CN1191338C/en not_active Expired - Lifetime
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|---|---|
| CN1453346A (en) | 2003-11-05 |
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