CN1066851A

CN1066851A - The preparation method of trialkyl-single thiophosphate ester of gear oil extreme pressure

Info

Publication number: CN1066851A
Application number: CN 91103460
Authority: CN
Inventors: 匡奕九; 骆远秀; 伏喜胜
Original assignee: Lanzhou Oil Refining Chemical General Plant China Petroleum Chemical General Co
Current assignee: Lanzhou Oil Refining Chemical General Plant China Petroleum Chemical General Co
Priority date: 1991-05-20
Filing date: 1991-05-20
Publication date: 1992-12-09

Abstract

The preparation method of gear oil extreme pressure agent trialkyl-single thiophosphate ester is reacted in the presence of solvent by monohydroxy compound, phosphorus trichloride and pyridine and to obtain trialkyl phosphite, makes trialkyl-single thiophosphate ester with sulfur reaction again.

Trialkyl-single thiophosphate ester shows good extreme pressure property, thermal oxidation stability and corrosion-resisting resisting resistance in extreme pressure industrial gear oil and automotive gear oil.The automotive gear oil that the compound uses of additive such as it and olefine sulfide make can pass through CRCL-37, L-42, four bench testings of L-60, L-33, reaches GL-5 gear of vehicle oil level.

Description

The preparation method of trialkyl-single thiophosphate ester of gear oil extreme pressure

The invention belongs to the preparation method of gear oil extreme pressure additive trialkyl-single thiophosphate ester and the application in gear oil thereof.

The kind of gear oil extreme pressure additive is a lot.At present, mainly contain two big classes: a class is a sulfur-containing extreme-pressure additive, and is effective especially under the high-speed friction condition; One class is phosphorous extreme pressure agent, and is effective especially under high torque friction condition.Sulfur-containing extreme-pressure additive is representative with the olefine sulfide.The kind of phosphorous extreme pressure agent is then very complicated, and is the crucial extreme-pressure additive of preparation extreme pressure gear oil.

The preparation method who the purpose of this invention is to provide a kind of phosphorous extreme pressure agent-trialkyl-single thiophosphate ester newly.

Trialkyl-single thiophosphate ester has excellent extreme-pressure anti-wear damage property, thermal oxidation stability and corrosion-resisting resisting resistance.Automotive gear oil with the compound use preparation of it and additives such as sulfur-containing extreme-pressure additive, oiliness improver can reach the GL-5 level that API uses classification.

Patent (USP4,770,800) has reported dialkyl phosphites and the Sulfur reaction obtains dialkyl group list sulfo-acid phosphoric acid ester, prepares the method for dialkyl group list sulfo-acid phosphate amine salt extreme pressure agent again with the organic amine salify.But the preparation method of The compounds of this invention is not narration in the literature.

The preparation method of trialkyl-single thiophosphate ester of the present invention is as described below.

React in the presence of solvent with aliphatics unit alcohol (I) and phosphorus trichloride (II), pyridine (III) and to obtain trialkyl phosphite (IV), use (IV) and Sulfur (V) reaction to obtain trialkyl-single thiophosphate ester (VI) again.Reaction process is as follows:

A, esterification

B, vulcanization reaction

R=C in the formula ₄～C ₁₈

Adopt 3 moles of C ₄～C ₁₈Alcohol (C preferably ₄～C ₁₂Alcohol) and 1 mole of phosphorus trichloride, 3 moles of pyridines in the presence of benzene or industrial naptha, react 0～80 ℃ of temperature of reaction, preferably 10～50 ℃.The reaction after-filtration is removed pyridine hydrochloride, boils off solvent, obtains trialkyl phosphite.React at 50～180 ℃ (preferably 120～150 ℃) with 1 mole of trialkyl phosphite and 0.6～1 molar sulphur bloom, in 2～10 hours reaction times, filter cleaner obtains the trialkyl-single thiophosphate ester product then.

Making us interested especially is that product of the present invention has good thermal oxidation stability, corrosion-resisting resisting resistance and extreme-pressure anti-wear damage property.Heavy with product 0.5～2%(of the present invention) be added in the solvent treatment mineral base oil, add additives such as olefine sulfide again, can make the GL-5 automotive gear oil that meets API use classification.

Example 1

Add propyl carbinol 148g, pyridine 158g, benzene 306g to 2000 milliliters of four-hole bottles that thermometer, reflux exchanger, sealed stirrer and dropping funnel are installed, under 10～50 ℃ of stirrings, drip the mixture of phosphorus trichloride 91.7g and benzene 91.7g, at room temperature reacted then 1 hour, at room temperature remove by filter pyridine hydrochloride again, filtrate is distilled, take out solvent, obtain 155.2g tributyl phosphorous acid ester product.The phosphorous 12.1%(of product is heavy), acid number is 0.1mgKOH/g.

Example 2

Use-case 1 instrument and method, but use benzene and the pyridine that when the preparation trialkyl phosphite, reclaims.Obtain 153.0g tributyl phosphorous acid ester, phosphorous 11.9%(is heavy), acid number is 0.2mgKOH/g.

Example 3

Use-case 1 instrument and method, but solvent benzol changes 40～150 ℃ of petroleum naphthas into.Obtain tributyl phosphorous acid ester 151.2g, phosphorous 11.5%(is heavy), acid number 0.2mgKOH/g.

Example 4

Use-case 1 instrument, add n-Octanol 130g, pyridine 79g, benzene 418g, the mixture of dropping phosphorus trichloride 45.8g and benzene 45.8g under 10～50 ℃ of stirrings, stirring reaction 1 hour at room temperature after adding, at room temperature remove by filter pyridine hydrochloride then, the filtrate distillation is taken out solvent benzol, obtain trioctylphosphine phosphorous acid ester product 126.7g, phosphorous 7.2%(is heavy), acid number 0.05mgKOH/g.

Example 5

Use-case 4 instruments and method are used the benzene and the pyridine of recovery instead, obtain 129.5g trioctylphosphine phosphorous acid ester product, and phosphorous 7.1%(is heavy), acid number 0.16mgKOH/g.

Example 6

Use-case 4 instruments and method, but n-Octanol changes isooctyl alcohol into, gets tri iso octyl phosphorite 124.0g, phosphorous 6.6%(is heavy), acid number 0.5mgKOH/g.

Example 7

Use-case 1 instrument, add lauryl alcohol 186g, pyridine 79g, benzene 530g, the mixture of dropping phosphorus trichloride 45.8g and benzene 45.8g under 10～50 ℃ of stirrings, at room temperature continue reaction 1 hour after adding, at room temperature remove by filter pyridine hydrochloride then, the filtrate distillation is taken out solvent benzol, obtain three lauryl phosphorous acid ester product 188.4g, the phosphorous 5.2%(of product is heavy), acid number 0.2mgKOH/g.

Example 8

To thermometer is housed, 250 milliliters of there-necked flasks of reflux exchanger and sealed stirrer add 125.0g example 1 product 16.0g sulfur flour, reacted 10 hours down at 80 ℃, filter and remove residue at room temperature then, obtain tributyl single thiophosphate ester product 137.1g, product sulfur-bearing 11.2%(is heavy), phosphorus 10.3%(is heavy), acid number 12.9mgKOH/g.

Example 9

Use-case 8 instruments add the tributyl phosphorous acid ester 125.0g that example 1 method makes, sulfur flour 12.5g, 150 ℃ of reactions 8 hours, filter cleaner under the room temperature got tributyl single thiophosphate ester product 135.5g, product sulfur-bearing 9.1%(is heavy), phosphorous 10.8%(is heavy), acid number 2.7mgKOH/g.

Example 10

Use-case 8 instruments and method, but change the tributyl phosphorous acid ester that example 1 product is an example 2.Get tributyl single thiophosphate ester 136.7g at last, sulfur-bearing 11.0%(is heavy), phosphorus 10.5%(is heavy), acid number 13.5mgKOH/g.

Example 11

Use-case 8 instruments add 104.5g example 4 products, the 8.0g sulfur flour, and 150 ℃ of reactions 4 hours, filter cleaner under the room temperature got trioctylphosphine single thiophosphate ester product 112.0g, sulfur-bearing 7.1%(is heavy), phosphorus 6.7%(is heavy), acid number 10.6mgKOH/g.

Example 12

Use-case 8 instruments add example 7 product 146.5g, sulfur flour 8.0g, and 150 ℃ of reactions 8 hours, filter and remove residue under the room temperature got three lauryl single thiophosphate ester product 151.2g, sulfur-bearing 4.91%(is heavy), phosphorus 4.71%(is heavy), acid number 14.6mgKOH/g.

Example 13

Use-case 8 instruments and method, temperature of reaction change 120 ℃ into, and the reaction times changes 5 hours into.Obtain tributyl single thiophosphate ester product 139.0g, sulfur-bearing 10.9%(is heavy), phosphorus 10.5%(is heavy), acid number 5.2mgKOH/g.

Example 14

With example-9, example-11, example-12 products respectively with 1%(heavily) being added to 100 ℃ of kinematic viscosity is 20mm ²Carry out in the mineral base oil of/S copper strip test (100 ℃ * 3h), (135 ℃ * 72h) and tetra-ball machine test, the results are shown in table-1 of baking oven oxidation tests.

Table-1 presentation of results trialkyl-single thiophosphate ester has good thermal oxidation stability, extreme-pressure anti-wear damage property and erosion resistance.Deposit-free generates after the baking oven oxidation test, and (PB) is more much higher than base oil for the last non seizure load of tetra-ball machine test, and the wear scar diameter of long term wear test is more much smaller than base oil, and the copper strip test result is also fairly good.

* PB-last non seizure load

d ^196N _60min-steel ball mill spot diameter under 196N * 1800rpm * 60min condition.

Example 15

With example-9 product with 1%(heavily) being added to 100 ℃ of kinematic viscosity is 20mm ²In the mineral base oil of/S, add additives such as sulfur-containing extreme-pressure additive, oiliness improver again, the automotive gear oil that makes has good high speed performance, high torsional performance, moisture-resistant gas corrosion performance and thermal oxidation stability energy, sees Table-2.

Find out from table-2 data, passed through CRCL-33, L-37, L-42 and four bench testings of L-60, reached the performance requriements of GL-5 automotive gear oil with product of the present invention and the synthetic automotive gear oil of other additive.

Claims

1, a kind of preparation method of gear oil extreme pressure additive, said gear oil extreme pressure agent is a trialkyl-single thiophosphate ester, it is characterized in that trialkyl-single thiophosphate ester is by monohydroxy compound, phosphorus trichloride and pyridine carry out esterification in the presence of solvent, the trialkyl phosphite that obtains carries out vulcanization reaction with sulfur flour again and makes, its component ratio is: monohydroxy compound: phosphorus trichloride: pyridine=3: 1: 3 (mole), trialkyl phosphite: sulfur flour=1: 0.8～1 (mole), esterification reaction temperature is 0～80 ℃, time is 0.5～2 hour, the vulcanization reaction temperature is 50～180 ℃, and the time is 1～10 hour.

2,, it is characterized in that monohydroxy compound is C according to the method for claim 1 ₄～C ₁₈Positive structure and isomery primary alconol.

3,, it is characterized in that the pyridine that pyridine and solvent benzol (or gasoline) reclaim in the time of can be with esterification and the benzene (or gasoline) of recovery according to the method for claim 1.

4, according to the method for claim 1, solvent benzol (or gasoline) consumption is oxy-compound, phosphorus trichloride and pyridine weight sum 0.5～2 times.