CN1045108C - Extreme-pressure anti-friction additive composite - Google Patents

Abstract

The present invention relates to a composite of extreme-pressure antiwear additives, which is compounded from an antiwear agent (A) and chlorcosane, wherein the antiwear agent (A) is thiophosphoramide ester. The composite of the extreme-pressure antiwear additives of the present invention has the advantages of low odour and superior extreme-pressure antiwear performance.

Description

Extreme-pressure anti-friction additive composite

The invention belongs to lubricating oil, fat additives technical field, exactly is the ashless extreme-pressure anti-friction additive about sulfur-bearing phosphorus nitrogen (SPN).At present, widely used lubricating oil, in the extreme pressure agent and anti-wear agent of fat, though some has extreme pressure property and resistance to abrasion preferably, as sulfide isobutene (T321), dibenzyl disulfide (T322), tritolyl phosphate (T306), the condenses of sulphur phosphoric acid-formaldehyde-amine (T305), the multiple ester amine salt (Huang Wenxuan such as (T307) of sulphur phosphoric acid, Han Changning compiles " lubricating oil and fuel dope handbook "), but because they at room temperature just have unpleasant stink, in addition when surface of friction produces high temperature, cause the volatilization of oil and additive to enter in the atmosphere, cause serious atmospheric pollution, therefore, uncomfortable cooperation also is not suitable for use in working at normal temperatures to the tighter occasion of lubricant smell restriction as the lubricating oil additive of this class operating mode of metal working fluid.SU 874957 has reported a kind of automobile oil that contains mineral oil and thiophosphoric acid dibasic acid esters uride, and the structural formula of additive therefor is

R is an aryl in the formula.US 5080813 discloses a kind of lubricating oil component that contains the sulphur phosphate amine salt, and the sulphur phosphate amine salt has good abrasion resistance, can be used as the working metal solution additive, but its hydrolysis stability is poor, and unpleasant stink is arranged at normal temperatures.A.M. К у л и e в mentions when introduction contains the SPN lubricating oil additive, has

The compound of structure can be used as antioxidant additive (R, R ', R " for alkyl or aryl), but does not relate to abrasion resistance (A.M. К у л и e в " Х И М И Я И TEXH О Л О Γ И Я П P И CA Д О К К MAC Л AM И T О П Л И BAM " P.47).USP 4564709 and EP 0529388 disclose a kind of method for preparing alkyl polysulfide, and this method is employing metal oxide such as zinc oxide, manganese oxide, magnesium oxide, aluminum oxide is made catalyzer, is raw material with alkyl sulfhydryl and Sulfur, at N ₂Direct reaction makes under the gas shiled, and this method environmental pollution is less, and the alkyl polysulfide additive that makes with this method has high extreme pressure property, but oil film strength is lower, and it is bigger to wear and tear.

The purpose of this invention is to provide a kind of outstanding extreme pressure property that has, preferably the ashless extreme-pressure anti-friction additive composite of the sulfur-bearing phosphorus nitrogen of abrasion resistance and low odor.

The present invention is achieved through the following technical solutions.

The said extreme-pressure anti-friction additive composite of the present invention (D) is to be composited by wear preventive additive (A) and clorafin.Anti-wear agent (A) is that a kind of general formula is

Thio-phosphamide ester and partial desulfurization product thereof.In the A formula, X is selected from

A kind of in the group; R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or-C ₂H ₅, R ₇For H ,-CH ₃Or

Anti-wear agent (A) is to be 95106741.9 Chinese patent application described method preparation according to application number.The cl content of clorafin is the heavy % of 29-72, and anti-wear agent (A) is 1: 0.5～5 with the weight ratio of clorafin, and the consumption of composition (D) in lubricating oil, fat is 0.1～10 heavy %.

The present invention has following characteristics:

1. the present invention is composited by anti-wear agent (A) and clorafin, (A) itself be exactly a kind of good wear preventive additive, its abrasion resistance is better than anti-wear agent at present commonly used such as zinc dialkyl dithiophosphate (ZDDP), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple ester amine salt (T307) of sulphur phosphoric acid.

2. the present composition (D) is a kind of good extreme-pressure anti-friction additive.This be because anti-wear agent (A) and sulphur system or chlorine to be extreme-pressure additive compound has good synergism.Clorafin is present metal working with oil extreme-pressure additive commonly used, the composition (D) that it makes after compound with A, and oil film strength obviously improves, and extreme pressure property strengthens, wearing and tearing decline, lubricity improves greatly.Utilize these characteristics of anti-wear agent (A), the extreme-pressure anti-wear level that can regulate extreme-pressure anti-friction additive composite (D) is to satisfy the different requirements of different operating modes to lubricating oil, fat performance.

3. extreme-pressure anti-friction additive composite of the present invention (D) has low smelly characteristics.Because anti-wear agent (A) and clorafin belong to low smelly additive, compare with present widely used olefine sulfide (T321), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple ester amine salt (T307) of sulphur phosphoric acid, the former is not also having tangible stink below 150 ℃, can reduce pollution to air, and the latter just has unpleasant stink at normal temperatures, and is serious to atmospheric pollution.

The following examples will the invention will be further described.

Example of the present invention about " load carrying capacity of lubricant assay method " (four ball methods, GB3142-82) the main test index in:

1.P _B: last non seizure load [kilogram or newton (N)], it is illustrated in, and steel ball does not block the maximum load of stinging under the test conditions, is commonly called as P _KPoint is represented oil film strength.

2.P _D: sintering load [kilogram or newton (N)], be illustrated under the test conditions, make steel ball generation agglomerating minimum load, the maximal work ability of its expression lubricant.

3.ZMZ: integrated abrasion value is an index of the anti-extreme pressure ability of lubricant, and it equals the mathematical mean of several times correcting load. $\mathrm{ZMZ}=\frac{A+B/2}{10}=\frac{A_1+A_2+B/2}{10}$ In the formula: A: work as P _DDuring greater than 400kg, A is that 315kg reaches 9 grades of schools less than 315kg

The summation of positive carry; Work as P _DWhen being less than or equal to 400kg, A is 10 grades of corrections

The summation of load;

B: work as P _DDuring greater than 400kg, B is from 400kg, before sintering

The arithmetical av of correcting loads at different levels, work as P _DWhen being less than or equal to 400kg,

B is zero;

A ₁: P _BBefore the point, i.e. the summation of that part of correcting load on the compensation wire;

A ₂: P _BAfter the point, the summation of that part of correcting load before the 315kg.

Example 1

According to application number is that 95106741.9 the described method of Chinese patent application prepares wear preventive additive A ₁Take by weighing 0.5M O, O '-diisooctyl phosphorodithioic acid (be called for short sulphur phosphoric acid, make by oneself), mix, feed N with the tetracol phenixin (chemical pure, Tianjin chemical reagent one factory) of 0.2M according to US 5080813 examples 1 method ₂Gas at 0-5 ℃ of Di-n-Butyl Amine (chemical pure, Beijing chemical reagent three factories) that drips 0.55M, heats up then, 150-160 ℃ of reaction 1 hour, leaves standstill, and sedimentation, separation obtain crude product, use then and the isopyknic 1N dilute hydrochloric acid of crude product, 1NNa ₂CO ₃Respectively give a baby a bath on the third day after its birth time with water, restrain anhydrous MgSO with 30 ₄Dry 8 hours, make the garnet liquid A ₁Example 2

In 97 gram 650SN base oils, add 1 gram A ₁, 2 gram clorafins (the heavy % of chlorinity 48, chemical plant, Shenyang) are heated to 50 ℃ of stirring and dissolving, and cool to room temperature makes and contains compositions of additives D ₁Lubricating oil, its four ball commentary the results are shown in Table 3 surely.

As can be seen from Table 3: A ₁Show obvious synergistic effect with clorafin.

Table 1

Annotate: four-ball tester rotating speed: 1500rpm

Claims (2)

1. the extreme-pressure anti-friction additive composite of a lubricating oil, fat is characterized in that it is to be composited by wear preventive additive (A) and clorafin, and anti-wear agent (A) is that a kind of general formula is The thio-phosphamide ester of-S-X, X is selected from the A formula

A kind of in the group, R ₁, R ₂Be identical or different C ₄～C ₂₄The alkyl of straight or branched, aryl or aralkyl, R ₃, R ₄Be C ₂～C ₈Alkyl or cycloalkyl, R ₅Have-(CH ₂) _n-structure, n=2～5 wherein, R ₆For H ,-CH ₃Or C ₂H ₅, R ₇For H ,-CH ₃Or

The cl content of clorafin is 29～72 heavy %, and anti-wear agent (A) is 1: 0.5～5 with the weight ratio of clorafin, and the consumption of composition (D) in lubricating oil, fat is 0.1～10 heavy %.

2. according to the said extreme-pressure anti-friction additive composite of claim 1, the preparation method who it is characterized in that this compositions of additives is: (A) mixes according to the above ratio with clorafin with anti-wear agent, stirred 0.5～1 hour at 30～80 ℃, promptly get extreme-pressure anti-friction additive composite (D).