CN101818094A

CN101818094A - Clean energy efficient sulphohydrocarbon ester ash-free antiwear agent and preparation method thereof

Info

Publication number: CN101818094A
Application number: CN201010174933A
Authority: CN
Inventors: 赵益民; 王小雄
Original assignee: LANZHOU HUIFENG BIOLOGY SCIENCE AND TECHNOLOGY Co Ltd
Current assignee: LANZHOU HUIFENG BIOLOGY SCIENCE AND TECHNOLOGY Co Ltd
Priority date: 2010-05-15
Filing date: 2010-05-15
Publication date: 2010-09-01

Abstract

The invention relates to a clean energy efficient sulphohydrocarbon ester ash-free antiwear agent. The antiwear agent is sulphohydrocarbon ester of shown in structure general formula; wherein R1 and R2 are the same or different C3-15 linear chain or branched chain alkyl, structural formula of R3 is, wherein R4, R5 and R6 are the same or different H or C1-C12 linear chain or branched chain alkyl, R7 is C5-C10 linear chain or branched chain alkyl, aralkyl, cyclones and alpha, beta-unsaturated carboxylic ester. The antiwear agent has the advantages of low odour, good heat stability and good corrosion resistance and can reduce pollution to air. The antiwear agent also has excellent extreme pressure property, abrasion resistance, rust protection and anti-emulsification property and higher bearing capacity and can be applicable to vehicle gear oil, industrial gear oil, hydraulic oil and internal combustion engine oil.

Description

Clean energy efficient sulphohydrocarbon ester ash-free antiwear agent and preparation method thereof

Technical field

The invention belongs to the lubricating oil additive technical field, relate to a kind of product of using as anti-wear agent of being applied in the lubricating oil.Exactly be a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent, the invention still further relates to the preparation method of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent.

Background technology

At present, the wear preventive additive of widely used lubricating oil, fat mainly contains benzyldithio toluene (T322), tritolyl phosphate (T306), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple ester amine salt (T307) of sulphur phosphoric acid also has additive such as NSPN to have abrasion resistance preferably.But because they at room temperature just have unpleasant stink, when surface of friction produces high temperature, cause the volatilization of oil and additive to enter in the atmosphere in addition, cause serious atmospheric pollution.And,, cause a large amount of greasy filth to generate and cause sealing leak because thermostability is relatively poor.United States Patent (USP) (US5037587) discloses the multi-functional wear preventive additive of a kind of S-P type, is to adopt

With sulphur phosphoric acid and epoxy compounds is raw material, makes as solvent reaction with benzene, and its structure is (1) structure; German Patent (DE4317980) discloses the multi-functional wear preventive additive of a kind of S-P type, is by sulphur phosphoric acid and α, β-insatiable hunger carboxylicesters reaction and make, and its structure is (2) structure.These two kinds of agent all have characteristics such as low toxicity, anticorrosive and heat-resistant quality be good, and are little but its shortcoming is a fastness to wear.Under 54.5 ℃, load 196 newton and the condition that turned round 60 minutes, the wear scar diameter of structure (1) is 0.68 millimeter; The wear scar diameter of structure (2) is 0.85 millimeter.

Summary of the invention

The purpose of this invention is to provide a kind of low smelly, heat-resistant quality, anticorrosive and clean energy efficient sulphohydrocarbon ester ash-free antiwear agent that abrasion resistance is good; Another object of the present invention provides a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method.

The said clean energy efficient sulphohydrocarbon ester ash-free antiwear agent of the present invention is a kind of general formula is (3)

Sulfo-hydrocarbon ester;

R1, R2 are the alkyl of identical or different C3-15 straight or branched in the formula (3), and the structural formula of R3 is formula (4).

R4, R5 and R6 are identical or different H or the straight or branched alkyl of C1-C12 in the formula (4), and R7 is C5-C10 straight or branched alkyl, aralkyl, cyclenes and α, β-undersaturated carboxylicesters.

The said clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method of the present invention is: with general formula is the double bond compound of (6) for the alkylthio phosphoric acid of (5) and general formula, be 1.0: 0.8～2.2mol in molar ratio, in nitrogen protection, reacted under 50～80 ℃ the condition 2～8 hours; Add catalyzer again, catalyst levels is 0.5～5% of a reactant gross weight, then in nitrogen protection, reacts under 100～140 ℃ the condition 3～20 hours; The solid matter that is cooled to room temperature, removes by filter in the system obtains crude product, then crude product is carried out underpressure distillation, removes light constituent, makes faint yellow or the incarnadine oily liquids; Be ash-free antiwear agent of the present invention.

(5) R1, R2 are the straight or branched alkyl of identical or different C3-C15 in the formula; (6) R4, R5 and R6 are identical or different H or the straight or branched alkyl of C1-C12 in the formula, and R7 is C5-C10 straight or branched alkyl, aralkyl, cyclenes and α, β-undersaturated carboxylicesters.

Used general formula prepares according to the described method of U.S. Pat P5080813 for the alkylthio phosphoric acid of (5).

General formula for the alkylthio phosphoric acid of (5) and general formula be the mol ratio of the double bond compound of (6) be preferably 1.0: 1.0～1.4; Optimal reaction temperature behind the adding catalyzer is 100～120 ℃; Optimum reacting time is 8～20 hours.

Among the clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method of the present invention, catalysts can be used acid and alkaline two types; An acidic catalyst is Lewis acids such as aluminum trichloride (anhydrous), tin protochloride, silicotungstic acid, FERRIC CHLORIDE ANHYDROUS, can also be storng-acid cation exchange resin; Basic catalyst has sodium ethylate, tertiary amine etc., judges (acid number is more little favourable more) according to the acid number result of different catalysts gained reactor product:

An acidic catalyst is preferably storng-acid cation exchange resin; Basic catalyst is preferably tertiary amine.

Among the clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method of the present invention, the optimum amount of catalysts is that to be the alkylthio phosphoric acid of (5) and general formula be 1～4% of the double bond compound gross weight of (6) to general formula.

Clean energy efficient sulphohydrocarbon ester ash-free antiwear agent provided by the invention is to be raw material synthetic lubricating oil additive with sulfide and hydrocarbon ester class.It has advantages such as low odor, thermostability and corrosion resistance are good, can reduce the pollution to air.Also have good extreme pressure property, resistance to abrasion, rust-preventing characteristic, demulsification performance and advantages of high bearing capacity simultaneously, its abrasion resistance surpasses the S-P type wear preventive additive of reported in literature, and the abrasion resistance than T307, T305, T202 is good simultaneously.Can be used for automotive gear oil, industrial gear oil, hydraulic efficiency oil and oil engine wet goods, is a kind of ashless additive that cleans energy-saving multifunction.

Embodiment

The per-cent that following embodiment relates to is weight percent.Used general formula is the alkylthio phosphoric acid of (5), as: two butyl thiophosphoric acids, fourth octylsulfo phosphoric acid etc. are to prepare according to the described method of U.S. Pat P5080813.

Embodiment 1

Take by weighing the two butyl thiophosphoric acids of 60.5 grams; 37.0 the gram nonene is blended in the four-hole reaction flask of 250ml; use nitrogen protection; reaction is 4 hours in the time of 75 ℃; add 4 gram storng-acid cation exchange resins again and make catalyzer; reaction is 8 hours in the time of 115 ℃; be cooled to room temperature; the catalyzer storng-acid cation exchange resin that removes by filter in the system obtains crude product, then crude product is carried out underpressure distillation, removes light constituent; obtain the pale yellow oily liquid body; this pale yellow oily liquid body is numbered A1, records S content 16.9%, P content is 8.2%; acid number 0.8mg/l, yield are 97.3%.

Embodiment 2

Take by weighing 88.5 gram fourth octylsulfo phosphoric acid; 28.0 gram vinylbenzene; join in the 250ml four-hole reaction flask that prolong, agitator and nitrogen protection are housed; 60 ℃ of reactions 8 hours; add 3 gram aluminum trichloride (anhydrous)s again and make catalyzer; 105 ℃ of reactions 20 hours; the catalyzer aluminum chloride that is cooled to room temperature, removes by filter in the system obtains crude product; then crude product is carried out underpressure distillation, remove light constituent and obtain the garnet oily liquids, this liquid is numbered A2; recording S content is 13.2%; P content is 6.4%, and acid number 16.8mg/l, yield are 96.2%.

Embodiment 3

Take by weighing 120 gram fourth hexyl thiophosphoric acids; 31.5 gram vinyl-acetic ester; join in the 250ml four-hole reaction flask that prolong, agitator and nitrogen protection are housed; under protection of nitrogen gas; be heated to 50 ℃ of reactions 6 hours; add 4.5 gram tertiary amines again and make catalyzer; 100 ℃ of reactions 12 hours, be cooled to room temperature and obtain crude product, then crude product is carried out underpressure distillation; remove light constituent and obtain the incarnadine viscous liquid; this liquid is numbered A3, records S content 13.0%, P content 6.2%; acid number 3.3mg/l, yield are 98.1%.

Embodiment 4

Take by weighing the two octylsulfo phosphoric acid of 68.4 grams; add 40.0 gram vinyl-acetic esters in 250ml four-hole reaction flask; under nitrogen protection, react; temperature was 75 ℃ of reactions 5 hours; the silicotungstic acid catalyst that adds 2.8 grams again; 140 ℃ of reactions 5 hours; the catalyzer silicotungstic acid that is cooled to room temperature, removes by filter in the system obtains crude product; then crude product is carried out underpressure distillation, remove light constituent and obtain the incarnadine clear liquid, this liquid is numbered A4; record S content 12.9%; P content 6.0%, acid number 6.1mg/l, yield are 95.0%.

Embodiment 5

Take by weighing 54 gram fourth octylsulfo phosphoric acid; add 60.0 gram cyclopentadiene in 250ml four-hole reaction flask; under nitrogen protection, react; temperature was 70 ℃ of reactions 7 hours; the rare earth HY type molecular sieve catalyst that adds 1.14 grams again; 110 ℃ of reactions 15 hours; the catalyzer rare earth HY type molecular sieve that is cooled to room temperature, removes by filter in the system obtains crude product; then crude product is carried out underpressure distillation, remove light constituent and obtain red clear liquid, this liquid is numbered A5; record S content 13.6%; P content 6.7%, acid number 4.1mg/l, yield are 94.0%.

Embodiment 6

Take by weighing 90 grams, the third octylsulfo phosphoric acid; add 65.0 gram vinyl-acetic esters and cinnamic mixture in 250ml four-hole reaction flask; under nitrogen protection, react; temperature was 80 ℃ of reactions 3 hours; the ferric chloride catalyst that adds 6 grams again; 120 ℃ of reactions 8 hours; the catalyzer iron trichloride that is cooled to room temperature, removes by filter in the system obtains crude product; then crude product is carried out underpressure distillation, remove light constituent and obtain red clear liquid, this liquid is numbered A6; record S content 11.4%; P content 5.8%, acid number 6.3mg/l, yield are 91.0%.

Embodiment 7

Take by weighing 80 grams, the third octylsulfo phosphoric acid, the mixture that adds 65.0 gram vinyl-acetic esters and nonene reacts under nitrogen protection in 250ml four-hole reaction flask; temperature was 80 ℃ of reactions 7 hours, and the sodium ethylate that adds 6 grams again is as catalyzer, 120 ℃ of reactions 8 hours; be cooled to room temperature and obtain crude product; then crude product is carried out underpressure distillation, remove light constituent and obtain orange clear liquid, this liquid is numbered A7; record S content 12.4%; P content 5.8%, acid number 10.5mg/l, yield are 92.5%.

Embodiment 8

Take by weighing the two octylsulfo phosphoric acid of 56 grams; add 64.0 gram dibutyl maleinates in 250ml four-hole reaction flask; under nitrogen protection, react; temperature was 80 ℃ of reactions 5 hours; the tin protochloride catalyzer that adds 2 grams again; 110 ℃ of reactions 6 hours; the catalyzer tin protochloride that is cooled to room temperature, removes by filter in the system obtains crude product, then crude product is carried out underpressure distillation, removes light constituent; obtain orange clear liquid; this liquid is numbered A8, records S content 10.8%, P content 5.2%; acid number 43.0mg/l, yield are 91.1%.

Experimental example 1

The liquid that is numbered A1, A2, A3, A4, A5, A6, A7, A8 is added to respectively in the 150BS base oil, be mixed with and contain the lubricating oil that additive concentration is 1% (weight), by the anti-supporting capacity of four-ball tester measuring, wear-resistant situation, copper corrosion situation and oil soluble energy, and and T305, T307, T202 carries out performance comparison.The results are shown in Table 1.

Performance by table 1 is relatively found out: the lubricating oil that is added with anti-wear agent A1, A2, A6, A7 has good extreme pressure, wear-resistant, antirust and oil soluble, show anti-wear agent of the present invention be a kind of superior performance clean the energy-saving multifunction ashless additive.Wherein anti-wear agent A4 is modulated to simulation L-37 bench testing in the recombiner, marks 1.25 fens, and the mill spot is 0.56mm.

The performance of synthetic phosphorus containing agent of table 1 the present invention and existing phosphorus containing agent relatively

Claims

1. clean energy efficient sulphohydrocarbon ester ash-free antiwear agent, it is characterized in that: described ash-free antiwear agent is that general structure is:

Sulfo-hydrocarbon ester;

Wherein: R1, R2 are the alkyl of identical or different C3-15 straight or branched, and the structural formula of R3 is a following formula:

Wherein: R4, R5 and R6 are identical or different H or the straight or branched alkyl of C1-C12, and R7 is C5-C10 straight or branched alkyl, aralkyl, cyclenes and α, β-undersaturated carboxylicesters.

2. clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method is characterized in that: with general formula be:

Alkylthio phosphoric acid and general formula be:

Double bond compound, be 1.0: 0.8～2.2mol in molar ratio, in nitrogen protection, reacted under 50～80 ℃ the condition 2～8 hours; Add catalyzer again, catalyst levels is 0.5～5% of a reactant gross weight, then in nitrogen protection, reacts under 100～140 ℃ the condition 3～20 hours; The solid matter that is cooled to room temperature, removes by filter in the system obtains crude product, then crude product is carried out underpressure distillation, removes the product that light constituent makes.

3. a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method as claimed in claim 2 is characterized in that: described catalyzer is aluminum trichloride (anhydrous) or tin protochloride or silicotungstic acid or FERRIC CHLORIDE ANHYDROUS or storng-acid cation exchange resin or rare earth HY type molecular sieve or sodium ethylate or tertiary amine.

4. as claim 2 or 3 described a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation methods, it is characterized in that: described catalyst levels is 1～4% of a reactant gross weight.

5. a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method as claimed in claim 4 is characterized in that: described mol ratio is 1.0: 1.0～1.4.

6. a kind of clean energy efficient sulphohydrocarbon ester ash-free antiwear agent preparation method as claimed in claim 5 is characterized in that: the optimal reaction temperature behind the adding catalyzer is 100～120 ℃; Optimum reacting time is 8～20 hours.