JP2003526002A - Multifunctional lubricant based on phosphorus compounds and sulfur compounds - Google Patents

Abstract

(57) Abstract: An improved multifunctional lubricant containing at least one phosphorus compound (A) and at least one sulfur compound (B). PROBLEM TO BE SOLVED: To provide a phosphorus compound (A) having a general formula: (Where k is 2 or 3, m is a number in the range of 0 to 8, x is 1 or 2, and R is a straight-chain alkyl or alkenyl group having 10 to 20 carbon atoms. a phosphate ester or a salt of the ester of the representative), sulfur compound (B) is the following general formula: R'-S _y -R '(where, y is a number from 2 to 8, R' is 4 Represents a t-alkyl group or an alkenyl group having from 18 to 18 carbon atoms), and the mass ratio of (A) / (B) is from 0.01 / 1 to 1/1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION

The present invention relates to lubricants, in particular additives used in industrial lubricant formulations such as gearboxes, transmissions, bearings, compressors, turbines, hydraulic fluids and lubricant formulations for metal working or forming.

[0002]

[Prior art]

Additives for lubricants generally fall into three major groups. Boundary additives or agents d'onctuosites are generally compounds consisting of fatty chains and polar groups (eg fatty acids), which allow lubrication under low loads. This compound forms a monomolecular film on the surface to be lubricated, which reduces friction and wear. When the friction conditions become more severe, the temperature rise causes the so-called boundary additive or lubricant to come off, and to lubricate the contact surface, an antiwear agent (AW) is used.
Alternatively, extreme pressure additives (EP) are required. These additives AW and EP are generally compounds containing phosphorus and chlorine or sulfur. AW additives significantly reduce the wear between parts that contact one another under high load. The EP additive causes some wear, but can prevent welding and adhesion phenomena. An effective lubricant formulation must contain additives that can be lubricated in the above three areas: boundary, AW and EP, and is therefore called a lubrifiant multifonctionel.

Until the 1990s, chlorinated paraffins were widely used from the viewpoint of AW and EP, but due to their toxicity, their use tends to decrease. Sulfur compounds, such as polysulphides, sulphurised olefins or sulphurised fatty substances, have long been used due to their EP properties (ie lubrication under high load and / or high temperature conditions). When the sulfur compound is used alone, the EP characteristics are improved, but the wear is too large. Also, various sulfur derivatives are not suitable for lubricating yellow metals (metaux jaunes, copper, copper alloys, etc.) due to their corrosive action.

The AW action of phosphorus derivatives is well known. The phosphorus derivative is generally a phosphite or a phosphoric acid ester (a triester obtained by reacting PCl ₃ with an alcohol or a mixture of a monoester and a diester obtained by reacting P ₂ O ₅ with an alcohol). When the phosphorus compound is used alone, the wear resistance is significantly reduced, but it cannot be used when the friction conditions are very severe. The combined use of a sulfur compound and a phosphorus compound is disclosed in US Pat. No. 3,933,658.
Already recommended in German Patent No. 2,752,218 and JP 54-154,405, it is possible to obtain a lubricant for the properties of AW and EP. However, these known compositions are generally not lubricious and require the addition of fatty substances to prevent the stick-slip phenomenon and reduce friction under low loads and / or low temperature conditions. Furthermore, compositions based on phosphorus compounds and sulfur compounds cause the problem of corrosion of the brass brass, due to the presence of the sulfur compounds.

[0005]

[Problems to be Solved by the Invention]

The present inventors have proposed the corrosion of yellow metals (metaux jaunes, copper, copper alloys, etc.) by combining a phosphate ester based on an optionally ethoxylated linear fatty alcohol and a di-t-alkyl polysulfide. Excellent multifunctional lubricants that can be prevented (boundary, AW and EP) (polysulfide (A with no free sulfur)
STM D-1662 standard))) can be obtained.

[0006]

[Means for Solving the Problems]

The subject of the present invention is a multifunctional lubricant comprising at least one phosphorus compound (A) and at least one sulfur compound (B), the phosphorus compound (A) having the general formula:

[0007]

[Formula 3]

(Where k is 2 or 3, m is a number in the range 0-8, x is 1 or 2 and R is a straight chain alkyl group having 10-20 carbon atoms. or an alkenyl group) phosphate ester or a salt of the ester of the sulfur compound (B) is the following general formula: R'-S _y -R '(where, y is a number from 2 to 8, R Represents a t-alkyl group or an alkenyl group having 4 to 18 carbon atoms), and the mass ratio of (A) / (B) is 0.01 / 1 to 1 / 1, preferably 0.05 / 1 to
It is 0.4 / 1. It is in a multifunctional lubricant characterized by the above. Another subject of the invention is a mixture of at least one phosphate ester (A) or salt thereof as defined above and at least one polysulphide (B) (A) / (B).
In the additive for a multifunctional lubricant having a mass ratio of 0.01 / 1 to 1/1, preferably 0.05 / 1 to 0.4 / 1.

[0009]

Embodiments

As the phosphoric acid ester (A), k is equal to 2, m is 2 to 6, and R is 12 to 18.
Groups having 4 carbon atoms, especially lauryl, stearyl, oleyl or linoleyl groups are preferred. The phosphoric acid ester (A) is generally a mixture of monoester and diester in a ratio of 10/90 to 90/10, and can be used in an acidic state or an alkali metal salt, ammonium salt or alkanolamine salt state.

As the polysulfide (polysulfide) (B), y is a number of 3 to 5 and R'group is 4 to 4.
Those having 12 carbon atoms are preferred, especially di-t-butyl trisulfide, di-t-nonyl pentasulfide, di-t-dodecyl trisulfide and di-t-dodecyl pentasulfide. The additive of the present invention can be generally prepared by simply mixing the liquid compounds (A) and (B) at room temperature, and this operation can be carried out under heating.

The multifunctional lubricant of the present invention comprises the additive of the present invention in 1 to 100 parts (preferably, 100 parts of oil) of the additive in whole oil (huiles entieres) or soluble oil (emulsion and microemulsion). Is obtained by mixing at a ratio of 2 to 50 parts, more preferably 5 to 20 parts. These oils may be mineral, synthetic, animal or vegetable oils, and additives commonly used in lubricants, for example lubricants d'onctuosi.
te), a corrosion inhibitor, an emulsifier, an alkaline agent and the like.

[0012]

【Example】

Examples of the present invention will be described below, but the present invention is not limited to the following examples. Parts and ratios are expressed in weight units. The names and chemical properties of the compounds used in the examples are shown in [Table 1].

[0013]

[Table 1] * EO = ethylene oxide

Phosphate esters are commercially available from the Applicant and consist primarily of monoesters. Polysulfides TPS 20, TPS 32, TPS 37 and TPS 44 are commercially available from Atofina. The performance of the lubricant was evaluated by the following experimental procedure.

1. 4-ball extreme pressure test (ASTM D-2783): wear resistance obtained at maximum load value (generally ≧ 100 kg) before seizing up and extreme pressure resistance obtained at maximum welding load value (generally ≧ 315 kg) Evaluation. Conditions: 1500 revolutions / minute, increasing load every 10 seconds. 2. 4-ball abrasion test (ASTM D-4172): Evaluation of abrasion resistance obtained at the lowest value (generally ≤0.60 mm) at which abrasion damage occurs. Conditions: 1500 rpm, 40 kg, 3600 seconds, 75 ° C.

3. Ball disc test: Evaluation of lubricity or boundary property of a lubricant obtained with a friction coefficient value μ. This value μ should be as small as possible and is generally ≦ 0.05. This ball-disc test spins a disc at a constant speed under a constant load ball. Soak discs and balls in lubricant. The force sensor measures the coefficient of friction of the ball-disk lubricated contact. Conditions: 1 rev / min, 1 kg, 30 min, steel 100C6 balls on aluminum 3104 disc.

4. Corrosion Resistance to Copper Strips (ASTM D-130) This test evaluates the corrosion resistance of a formulation to copper strips (sulfur additives are prone to corrode yellow metal (46 brass) due to the presence of their free sulfur). . In this test, a polished copper plate was placed in a test tube containing 30 ml of the compound at 60 ° C. for 2 hours.
Soak for 4 hours. At the end of the test time, the copper plate is cleaned and compared with a standard corrosion strip (classification is from 1a with minimum corrosion to 4c with maximum corrosion).

Twenty-seven additive compositions made using the compounds in [Table 1] are summarized in [Table 2]. The present invention is only compositions 6-15,17. Others do not contain phosphorus compounds (Compositions 1-4) or sulfur compounds (Compositions 5, 16, 18, 20, 22, 24)
Or containing phosphorus compounds derived from non-linear alcohols (compositions 19, 21, 23, 2
5-27).

[0019]

[Table 2]

Examples 1-30 The compositions of Table 2 were diluted with 100 natural paraffin oil. The performance of the resulting formulation is summarized in Table 3. Dilution rate indicates the ratio of additive composition in the formulation.

[0021]

[Table 3]

[0022]

[Table 4] (Continued from [Table 3])

From the results of [Table 3] and [Table 4], the lubricants of Examples 24, 26, 28 and 30 containing the ester other than the present invention showed a high coefficient of friction (> 0.05), and the lubricity was improved. The lack of evidence proves that the choice of phosphate ester is decisive.
Furthermore, it can be seen that when the polysulfide does not have free sulfur, the corrosion of yellow metal (46 brass) is suppressed.

Examples 31-39 [Table 2] additive compositions 5, 7, 9, 12, 13, 16, 18, 26 and 27.
Were dispersed in water to make nine lubricants. The performance is summarized in [Table 5]. Examples 31 to 33 are prepared by simply dispersing the phosphorus compound in water. Example 34
~ 37 is the present invention, Examples 38-39 are not the present invention.

[0025]

[Table 5]

Examples 40-44 5% natural 100 paraffin oil, 9.5% polyethoxylated (4 EO) lauryl alcohol, 0.5% sodium dodecylbenzene sulfonate, 85
A non-added microemulsion (Example 40) was made with% water. Compositions 1, 2, 5 or 7 of Table 2 were each added to this microemulsion sample and the mixture was heated to 50 ° C. and homogenized. The performance of the obtained transparent lubricant at room temperature is summarized in [Table 6].

[0027]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C10N 10:02 C10N 10:02 30:12 30:12 40:00 40:00 A 40:02 40 : 02 40:04 40:04 40:08 40:08 40:12 40:12 40:20 40:20 Z 40:30 40:30 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, A , AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK , MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Dalbot-Houbert, Zill France 95130 Franconville Le Chevalier 14 Bis F term (reference) 4H104 BG12C BH03C BH04C BH05C FA01 LA06 PA01 PA02 PA05 PA07 PA09 PA20 PA21

Claims (12)

[Claims] 1. A multifunctional lubricant containing at least one phosphorus compound (A) and at least one sulfur compound (B), wherein the phosphorus compound (A) has the following general formula: (Wherein k is 2 or 3, m is a number in the range of 0 to 8, x is 1 or 2 and R is a linear alkyl or alkenyl group having 10 to 20 carbon atoms. Represents a phosphoric acid ester or a salt of this ester, wherein the sulfur compound (B) has the following general formula: R′—S _y —R ′ (where y is a number from 2 to 8 and R ′ is 4). Represents a t-alkyl group or an alkenyl group having 18 to 18 carbon atoms), and the mass ratio of (A) / (B) is 0.01 / 1 to 1/1. Characteristic multifunctional lubricant. 2. k is equal to 2, m is a number in the range 2 to 6 and R is 12 to.
The lubricant according to claim 1, which is a group having 18 carbon atoms. 3. The lubricant according to claim 1, wherein y is a number of 3 to 5 and R ′ is a t-alkyl group having 4 to 12 carbon atoms. 4. The lubricant according to claim 1, wherein the mass ratio of (A) / (B) is 0.05 / 1 to 0.4 / 1. 5. The compound (A) is a mixture of a phosphoric acid monoester and a phosphoric acid diester, k is equal to 2, m is a number from 4 to 5, R is a lauryl group, a stearyl group, an oleyl group or a linoleyl group. The lubricant according to any one of claims 1 to 4. 6. The sulfur compound (B) is di-t-butyl trisulfide, di-t.
-Nonyl pentasulfide, di-t-dodecyl trisulfide or di-t-dodecyl pentasulfide, The lubricant according to any one of claims 1 to 5. 7. The following general formula: [Formula 2] (Where k is 2 or equal to, m is a number in the range 0 to 8, x is equal to 1 or 2 and R represents a straight chain alkyl or alkenyl group having 10 to 20 carbon atoms. ) At least one phosphoric acid ester (A) or a salt of this ester, and the following general formula: R′—S _y —R ′ (where y is a number in the range of 2 to 8 and R ′ is 4). Represents a t-alkyl group or an alkenyl group having 18 carbon atoms) and at least one polysulfide (B), and the mass ratio of (A) / (B) is 0.01 / 1 to Additive for multifunctional lubrication characterized by being 1/1. 8. k is equal to 2, m is a number in the range 2-6, and R is 12-.
The additive according to claim 7, which is a group having 18 carbon atoms. 9. The additive according to claim 7, wherein y is a number of 3 to 5 and R ′ is a t-alkyl group having 4 to 12 carbon atoms. 10. The additive according to claim 7, wherein the mass ratio of (A) / (B) is 0.05 / 1 to 0.4 / 1. 11. A compound (A) is a mixture of a phosphoric acid monoester and a phosphoric acid diester, k is equal to 2, m is a number from 4 to 5, R is a lauryl group, a stearyl group, an oleyl group or a linoleyl group. The additive according to any one of claims 7 to 10. 12. The sulfur compound (B) is di-t-butyl trisulfide, di-
t-nonyl pentasulfide, di-t-dodecyl trisulfide and di-t-
The additive according to any one of claims 7 to 11, which is dodecyl pentasulfide.