CN1045108C - Extreme pressure antiwear additive composition - Google Patents

Abstract

This invention relates to extreme pressure antiwear additive compositions. The composition is compounded by antiwear agent (A) and chlorinated paraffin. Antiwear agent (A) is a thiophosphoramidate.

The extreme pressure antiwear additive composition of the present invention has low odor and excellent extreme pressure antiwear performance.

Description

Extreme pressure antiwear additive composition

式中R为芳基。US 5080813公开了一种含有硫磷酸胺盐的润滑油组分，硫磷酸胺盐具有优良的抗磨性能，可以作为金属工作液添加剂，但其水解安定性差，在常温下有难闻的臭味。A.M.Кулиев在介绍含SPN润滑油添加剂时提到，具有

结构的化合物可以作为抗氧添加剂(R、R′、R″为烷基或芳基)，但没有涉及抗磨性能(A.M.Кулиев“ХИМИЯ ИTEXHОЛОΓИЯ ПPИCAДОК К MACЛAMИTОПЛИBAM”P.47)。USP 4564709和EP 0529388公开了一种制备烷基多硫化物的方法，该法是采用金属氧化物如氧化锌、氧化锰、氧化镁、氧化铝作催化剂，以烷基硫醇和硫黄为原料，在N₂气保护下直接反应制得的，该方法环境污染较少，用该法制得的烷基多硫化物添加剂有高的极压性，但油膜强度较低，磨损较大。The invention belongs to the technical field of lubricating oil and grease additives, in particular relates to an ashless extreme pressure anti-wear additive containing sulfur, phosphorus and nitrogen (SPN). At present, among the widely used extreme pressure agents and antiwear agents for lubricating oils and greases, some have good extreme pressure and antiwear properties, such as isobutylene sulfur (T321), dibenzyl disulfide (T322), trimethyl phosphate Phenol ester (T306), thiophosphoric acid-formaldehyde-amine condensate (T305), thiophosphoric acid complex ester amine salt (T307), etc. In addition, when the friction surface generates high temperature, the oil and additives will volatilize into the atmosphere, causing serious air pollution. Therefore, it is not suitable for lubricating oil additives such as metal cutting fluids. It is not suitable for occasions where there are strict restrictions on lubricant odor when working at room temperature. SU 874957 has reported a kind of vehicle lubricating oil containing mineral oil and thiophosphoric acid diester urea, and the structural formula of used additive is

In the formula, R is an aryl group. US 5080813 discloses a lubricating oil component containing phosphoric acid amine salt. Ammonium phosphoric acid salt has excellent anti-wear properties and can be used as an additive for metal working fluids, but its hydrolysis stability is poor and it has an unpleasant odor at room temperature . AM Кулиев mentioned in the introduction of lubricating oil additives containing SPN, with

The compounds of the structure can be used as antioxidant additives (R, R', R" are alkyl or aryl groups), but do not involve anti-wear properties (AMКулиев "ХИМИЯ ИTEXHОЛОΓИЯ ПPИCAДОК К MACЛAMИTОПЛИBAM" P.47). USP 4564709 and EP 0529388 disclose A method for the preparation of alkyl polysulfides is proposed, which uses metal oxides such as zinc oxide, manganese oxide, magnesium oxide, and aluminum oxide as catalysts, and uses alkyl mercaptan and sulfur as raw materials, directly under N ₂ gas protection It is prepared by reaction, and this method has less environmental pollution. The alkyl polysulfide additive prepared by this method has high extreme pressure performance, but the oil film strength is low and the wear is relatively large.

The object of the present invention is to provide an ashless extreme pressure antiwear additive composition containing sulfur, phosphorus and nitrogen, which has excellent extreme pressure performance, better antiwear performance and low odor.

The present invention is achieved through the following technical solutions.

的硫代磷酰胺酯及其部分脱硫产物。A式中，X选自

基团中的一种；R₁、R₂为相同或不同的C₄～C₂₄直链或支链的烷基、芳基或芳烷基，R₃、R₄为C₂～C₈的烷基或环烷基，R₅具有-(CH₂)_n-结构，其中n＝2～5，R₆为H、-CH₃或-C₂H₅，R₇为H、-CH₃或

抗磨剂(A)是按照申请号为95106741.9的中国专利申请所述方法制备的。氯化石蜡的氯含量为29-72重％，抗磨剂(A)与氯化石蜡的重量比为1∶0.5～5，组合物(D)在润滑油、脂中的用量为0.1～10重％。The extreme pressure anti-wear additive composition (D) in the present invention is compounded by the anti-wear additive (A) and chlorinated paraffin. Antiwear agent (A) is a kind of general formula

Thiophosphoramidate and its partially desulfurized products. In formula A, X is selected from

One of the groups; R ₁ and R ₂ are the same or different C ₄ to C ₂₄ linear or branched alkyl, aryl or aralkyl, R ₃ and R ₄ are C ₂ to C ₈ Alkyl or cycloalkyl, R ₅ has -(CH ₂ ) _n -structure, where n=2~5, R ₆ is H, -CH ₃ or -C ₂ H ₅ , R ₇ is H, -CH ₃ or

The antiwear agent (A) is prepared according to the method described in Chinese patent application No. 95106741.9. The chlorine content of the chlorinated paraffin is 29-72% by weight, the weight ratio of the anti-wear agent (A) to the chlorinated paraffin is 1:0.5-5, and the amount of the composition (D) in lubricating oil and grease is 0.1-10 Heavy%.

The present invention has the following characteristics:

1. The present invention is compounded by anti-wear agent (A) and chlorinated paraffin, (A) itself is a kind of good anti-wear additive, and its anti-wear performance is better than currently commonly used anti-wear agents such as dialkyl Zinc dithiophosphate (ZDDP), phosphorothioate-formaldehyde-amine condensate (T305), phosphorothioate complex ester amine salt (T307).

2. The composition (D) of the present invention is an excellent extreme pressure and antiwear additive. This is because the combination of antiwear agent (A) and sulfur-based or chlorine-based extreme pressure additives has a good synergistic effect. Chlorinated paraffin is an extreme pressure additive commonly used in metalworking oils at present. The composition (D) prepared by compounding it with A has significantly improved oil film strength, enhanced extreme pressure properties, reduced wear, and greatly improved lubricating ability. Utilizing the feature of the antiwear agent (A), the extreme pressure and antiwear level of the extreme pressure and antiwear additive composition (D) can be adjusted to meet the different requirements of different working conditions on the properties of lubricating oil and grease.

3. The extreme pressure and antiwear additive composition (D) of the present invention has low odor characteristics. Since antiwear agent (A) and chlorinated paraffin are low-odor additives, compared with currently widely used sulfurized olefin (T321), sulfuric acid-formaldehyde-amine condensate (T305), and sulfuric acid double ester amine salt (T307) , the former has no obvious odor below 150°C, which can reduce air pollution, while the latter has an unpleasant odor at room temperature, which seriously pollutes the air.

The following examples will further illustrate the present invention.

Examples of the present invention are about the main test index in "lubricant bearing capacity assay method" (four-ball method, GB3142-82):

1.P _B : Maximum non-jamming load [kg or Newton (N)], which indicates the highest load at which the steel ball does not jam under test conditions, commonly known as P _K point, which represents the strength of the oil film.

2. P _D : sintering load [kg or Newton (N)], which means the minimum load to sinter the steel ball under the test conditions, and it means the limit working capacity of the lubricant.

3. ZMZ: comprehensive wear value, which is an index of the lubricant's ability to resist extreme pressure, which is equal to the mathematical average of several calibration loads. $\mathrm{ZMZ}=\frac{A+B/2}{10}=\frac{A_1+A_2+B/2}{10}$ In the formula: A: When P _D is greater than 400kg, A is 315kg and less than 315kg for grade 9 schools

The sum of positive loads; when _PD is less than or equal to 400kg, A is 10-level correction

sum of loads;

B: When P _D is greater than 400kg, B starts from 400kg until sintering

The arithmetic mean of the corrected load at all levels, when _PD is less than or equal to 400kg,

B is zero;

A ₁ : before point P _B , that is, the sum of the part of the correction load on the compensation line;

A ₂ : After point P _{and B} , the sum of the corrected load before 315kg.

Instance 1

Antiwear additive A ₁ was prepared according to the method described in Chinese patent application No. 95106741.9. Weigh 0.5M O, O'-diisooctyl dithiophosphoric acid (abbreviated as sulfuric acid, self-made according to US 5080813 example 1 method), mix with 0.2M carbon tetrachloride (chemically pure, Tianjin Chemical Reagent No. 1 Factory), Feed _N2 gas, add 0.55M di-n-butylamine (chemically pure, Beijing Chemical Reagent No. 3 Factory) dropwise at 0-5°C, then raise the temperature, react at 150-160°C for 1 hour, let stand, settle, separate, The crude product was obtained, and then washed three times each with 1N dilute hydrochloric acid, _1NNa2CO3 and water _equal to the volume of the crude product, and dried with 30 g of anhydrous _MgSO4 for 8 hours to obtain a dark red liquid _A1 . Example 2

In 97 grams of 650SN base oil, add 1 gram of A ₁ , 2 grams of chlorinated paraffin (chlorine content 48% by weight, Shenyang Chemical Plant), heated to 50 ° C, stirred and dissolved, cooled to room temperature, and prepared additive-containing composition D ₁ lubricating oil, its four-ball evaluation results are shown in Table 3.

As can be seen from Table 3: A ₁ and chlorinated paraffin showed obvious synergistic effect.

Table 1

Note: Four-ball machine 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).