JPS59159896A - Sulfur-based extreme pressure additive - Google Patents

Abstract

PURPOSE:To provide an extreme pressure additive which is equal to or superior to conventional sulfur-basded extreme additives in extreme pressure and oiliness effects and is pale colored and odorless, prepared by reacting mercaptan and sulfur with unsaturated oil or fat or unsaturated fatty acid ester in the presence of a basic catalyst. CONSTITUTION:The additive is obtained by reacting mercaptan (e.g. n-butyl mercaptan or octyl 3-mercaptopropionate) and sulfur with an unsaturated vegetable or animal oil or fat (e.g. lard, beef tallow, soybean oil or rapeseed oil) and/or an unsaturated fatty acid ester (e.g. methyl ester of rapeseed fatty acid or methyl oleate) in the presence of a basic catalyst (e.g. di-n-butylamine or di- n-octylamine). It is equal to or superior to conventional sulfurized vegetable and animal oil and fat or sulfurized fatty acid esters in extreme pressure and oiliness effects and is pale colored and odorless.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sulfur-based extreme pressure additive that is light in color and has little odor.

Sulfur-based extreme pressure additives are additives added to metal working oils such as cutting oils, grinding oils, and plastic working oils to reduce friction between two metal surfaces, reduce wear, and prevent seizure. This has the effect of extending the life of the tool chisel and improving finishing accuracy.

Conventionally, as sulfur-based extreme pressure additives, sulfurized animal and vegetable oils and fats or sulfurized fatty acid esters, which are obtained by reacting unsaturated animal and vegetable oils and fats or unsaturated fatty acid esters with sulfur at a high temperature of 170 to 220° C., have been put into practical use. The sulfide reacts with the metal surface at high temperatures at high-load contact surfaces during metal processing, producing a film with low shearing force, exhibiting an extreme pressure effect that prevents wear, seizure, and fusion, and also prevents machining. Even when the contact surface temperature is low, such as immediately after starting, the polar group of the ester structure adsorbs to the metal surface and exhibits a so-called oily effect, which reduces friction. However, it is difficult to see through the work point, and it has a unique odor that makes workers feel uncomfortable. On the other hand, as light-colored sulfur-based extreme pressure additives, polysulfides such as sia nrF ruborisulfide, diaryl polysulfide, and alkylaryl polysulfide are also used in practical use. rare.

As a result of various studies to solve these difficulties, the present inventors have found that by adding mercaptans together with sulfur and reacting them, it is possible to achieve extreme pressure and oiliness effects equivalent to those of conventional sulfurized animal and vegetable oils or sulfurized fatty acid esters. The present inventors have discovered that it is possible to obtain a sulfur-based extreme pressure additive that is light in color and has little odor, and has completed the present invention.

That is, the present invention provides a sulfur-based extreme pressure additive, which is obtained by reacting unsaturated animal and vegetable oils and fats and/or unsaturated fatty acid esters with mercaptans and sulfur in the presence of a basic catalyst. It is something.

The unsaturated animal and vegetable oils and fats and unsaturated fatty acid esters used in the present invention have one or more unsaturated bonds in one molecule, and may be used alone or in combination.
Examples of unsaturated animal and vegetable oils and fats include liver fat, beef tallow, soybean oil, rapeseed oil, and pepper oil. Examples of unsaturated fatty acid esters include methyl rapeseed oil, rice bran millet, methyl 671 oleate, butyl oleate, and oleic acid. Oil etc. can be mentioned.

As the mercaptans, for example, alkyl mercaptans having 4 to 20 carbon atoms, mercapto fatty acid esters, etc. can be used, and examples of the former include, for example, n-butyl mercaptan, inbutyl mercaptan, tert-
Butyl mercaptan, n-octyl mercaptan, te
Examples of the latter include butyl dioglycolate, ethyl thiopropionate, octyl 3-mercaptopropionate, and the like. Among them, n-butyl mercaptan, terL-butyl mercaptan, n-octyl mercaptan, and octyl 3-mercaptopropionate are most common.

Salt 7.1. (For the catalyst No. 41, a primary to tertiary amine or polyamine having 1 to 20 carbon atoms or a known vulcanization accelerator may be used.

Examples of primary to tertiary amines include n-butylamine,
Isobutylamine, sec'-7'thylamine, 2-n-hexylamine, n-octylamine, diisobutylamine, diisobutylamine, di-5ec-butylamine, di-2-ethylhexylamine, di-n-octylamine, triisobutylamine , triisobutylamine, tri-see-butylamine, tri-2-ethylhexylamine, tri-n-octylamine, etc., and as polyamines, for example, triethylenediamine,
Examples include hexamedylenetetramine and the like.

Further, examples include cyclo-\xylbenzthiazylsulfenamide, N,N'-schedylthiazyl sulfenamide, 2-
Penduthiadzuyl sulfide, tetramethylthiuram disulfide, dipentameg renziuram tetrasulfide, bipenylin pipecolyldithiocarbamate,
Zinc dimethyl didiocarbamate, sink-zin
-Known vulcanization accelerators such as butyl didiocarbamate can also be used. -Addition of catalyst? is usually 0.1 to 2.0 mol%, preferably 0.5 to 1 mol% based on mercapkuns.
．． If it is less than 0.1 mol%, the reaction will not proceed sufficiently, and if it exceeds 2.0 mol%, it will cause a bad odor and lower the flash point of the product, which is not preferable.

The amounts of mercapsulants and sulfur used in unsaturated animal and vegetable oils and fats and/or unsaturated fatty acid esters are usually 0.3 to 2.0 and 0, respectively, relative to the unsaturated bonds in the animal and vegetable oils and/or fatty acid esters. .5 to 6.0 equivalents,
Preferably they are 0.50-1.0 equivalent and 0.7-4.0 equivalent. If the amount of mercaptans used is less than 0.3 equivalents, it will be difficult to obtain a light-colored extreme pressure additive with little odor; if it exceeds 2.0 equivalents, unreacted mercaptans will remain in the extreme pressure additive, resulting in a foul-smelling J3 Each of these is undesirable because it causes stress. If the amount of sulfur used in IJy is less than 0.5 equivalent t2, the resulting lateral pressure additive will have a low sulfur content and a sufficient extreme pressure effect will not be obtained, and if it exceeds 6.0 equivalent, unreacted Each is undesirable because sulfur precipitates.

When obtaining the extreme pressure additive of the present invention, by changing the expiry of mercaptans and sulfur, it is possible to obtain extreme pressure additives with different sulfur contents of 4+i, and to obtain one with less corrosivity to copper plates. When desired, it is preferable to set the molar ratio of sulfur to mercaptans to 2.0 or less.6 When it is desired to further reduce the phagocytosis of copper plates, for example, after dropping mercaptans,
In order to reduce active sulfur, 2,5-bis(octyldithio)-1,3゜4-thiadiazole, 2,5-dimercapto-1,3,4-deadiazole, etc. are added to mercaptans. It is sufficient to add .0 to 2.0% by weight. In addition, if necessary, for example, penzotriazole, 2,5-bis(n-octyldithio)
It is also possible to add 0.1 to 1.0% by weight of a copper plate deactivator such as -1,3',4-deadiazole to reduce the corrosion resistance of the copper plate by as little as /1v.

The extreme pressure additive according to the present invention can be prepared by adding mercaptans dropwise to an unsaturated animal or vegetable oil and/or unsaturated fatty acid ester, sulfur, and a salt-depleted catalyst (21) while heating and stirring, and then adding the mercaptans dropwise at 130 to 170°C. ~5 o'clock I+)), preferably at 150-160'C for 2-4 hours, by-produced saturated hydrocarbons are removed by vacuum distillation or aeration, and hydrogen sulfide is
Method of obtaining unsaturated animal and vegetable oils and fats and/or unsaturated fats and oils by heating to 0 to 100°C and removing them by aeration. Uj M
It can be similarly obtained by either a method of adding sulfur to the ester, mercaptans and a basic catalyst, or a method of charging these raw materials simultaneously and reacting them.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Lard (saponification value 190, iodine value 76.0, saponification value 190, iodine value 76.0,
Molecular weight: 886. Number of unsaturated bonds per molecule: 2.65) 8
86 g (1,0 mol), sulfur 168.7 g (5,2
7 mol=], 9 g equivalent), di-n-octylamine5.
8 g (0,024 mol) was added, and while heating and stirring, 531.1 g (
2.63 mol - 0.9 g equivalent) was added dropwise.

Next, after reacting at 160°C for 3 hours, reduced IE distillation was performed to remove the saturated hydrocarbon fraction, and the reaction was further heated at 80°C.
The sulfur-based extreme pressure additive of the present invention was obtained by removing hydrogen sulfide by aeration. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 2 Lard 886g (1.0 mol), sulfur 85. og(2,
66 mol-1, OO equivalent), di-n-octylamine 2
．． 91? -(0,012, El), tert-dodecyl mercaptan 267.7 g (1,33 mol-0,
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1 except that 50 equivalents) was used. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 3 Lard 886 g (1.0 mol), sulfur 28'2.5 g
(8,83 moles - 3,33 equivalents Q), di-n-octylamine 8.7 g (0,036 moles), tert-dodecyl mercaptan 531.6 g (2,63 moles -0
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1, except that 9 g of sulfur-based extreme pressure additive was used. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 4 Lard 886g (1.0mol), sulfur 62.9g (1.0mol)
97 mol=0.74 equivalent), di-n-butylamine3.
1 g (0,024 mol), n-butyl mercaptan 177.2 g (1,97 mol = 0.74 per E, 2
．． A sulfur-based extreme pressure twisted 1JII agent of the present invention was obtained in the same manner as in Example 1 except that 4.3 g (0,033 mol) of 5-bis(n-octyldithio)-1,3,4-thiadiazole was used. Ta. The obtained lateral pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 5 Lard 886g (1.0 mol), sulfur 77.7g (
2,j3 mol=0.92 equivalent)-n-butylamine1.
8 g (0,024 mol), n-octyl mercaptan 354.4 g (2,43 mol = 0.92 equivalent (J)
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1, except that 5.0 g (0,033 mol) of 2,5-dimercapto-1,3,4-thiadiazole was used. The obtained extreme pressure additive had good lateral pressure and oily effects, was light in color, and had little odor.

Example 6 Lard 1186 g <1. ．． 0 mole), sulfur 85.9
g (2,68 moles - 1,01 equivalents), di-n-butylamine 3.2 g (0,025 moles), octyl 3-mercaptopropionate 531.6 g (2,44 moles - 0
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1, except that 92 equivalents) was used. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 7 Rice bran methyl (saponification value 191, iodine value 102, molecular weight 21) 4. Number of unsaturated bonds per molecule 1.2) 294
H (111 mol), sulfur 64.0 g (2.0 mol-1,
67 equivalents), 3.1 g (0
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example I, except that 202.0 g (1.0 mol - 0.83 mol) of Kusha IJ-F decyl mercaptan was used. . The obtained extreme pressure additive has good extreme pressure and oiliness 9J
It had fruit, was pale in color, and had little odor.

Example 8 Butyl oleate (saponification value 86, iodine value 170, molecule @ 338. Number of unsaturated bonds per molecule 1.0) 338
g (1,0 mol), sulfur 64.0 + 7 (2,0 mol -2
,0 Dang Zhao), di-n-butylamine 3.1 g (0,02
4 mol), kunyariddecylmelka-f)yn 20
2. A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1, except that Og (1,0T nyl=1.0/9) was used. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Example 9 R-F 886 g (1.0% R), sulfur Vr 85°Og
(2,66T Nyl-1,00 mol), tributylamine 2.0 g ((1,011 mol), turn-relid decylmercapkun 267.7 g (1,325 mol-
A sulfur-based extreme pressure additive of the present invention was obtained in the same manner as in Example 1 except that 0.50 equivalents) was used. The obtained extreme pressure additive had good extreme pressure and oiliness (9)), and was light in color and had little odor.

Example 10 Seed 886 g (1.0 mol), tertiary dodecyl mercaptan 531, Ig (2.63 mol - 0.9 g per j) were placed in a 2a round bottom flask connected to a hydrogen sulfide absorber.
, di-r)-octylamine (5.3 g (0,022 mol)) was added, and after heating to 90'C without stirring, sulfuric acid* was added.
After adding 168.7 g (5.27 mol - 1.9 g equivalent) and reacting at 150°C for 3 hours, post-treatment was performed in the same manner as in Example 1 to obtain the sulfur-based extreme pressure addition of the present invention. obtained the drug.

The obtained extreme pressure additive has good extreme pressure and oily effect,
It was also light in color and had little odor.

Example 11 Hydrogen sulfide absorption! 886 g (1.0 mol) of lard, 168.7 g (5
, 27 moles - 1.9 g (100 g), tartary lead decyl mercaptan 531.1 g (2,63 moles - 0.9 g), di-n-octylamine 5.3 g (0,022
After slowly warming the stomach and reacting at 1'C for 3 hours, post-treatment was carried out in the same manner as in Example 1 to obtain the sulfur-based extreme pressure additive of the present invention. The obtained extreme pressure additive had good extreme pressure and oily effects, was light in color, and had little odor.

Test Example 1 Copper plate corrosion test results, sulfur content, hue, oil effect test words of the sulfur-based lateral pressure additive of the present invention obtained in Examples 1 to 11, sulfurized oil and dialkyl polysulfide for comparison (2) Results (friction coefficient) and extreme pressure effect test results (high-speed four-ball test results, Soda type four-ball test results) are shown in Table 1. In (3), sulfurized fat and oil (sulfurized lard (Δ)) synthesized by the conventional method without using mercaptans (sulfur content 1
0.0%), lard sulfide (B) (sulfur (4) gold content 1
5.0%) and rice bran methyl sulfide were used, and di-tert-dodecyl trisulfide and di-tert-nonylben-sulfide were used as dialkyl polysulfides.

When the test results were compared and evaluated for samples with almost the same corrosivity to copper plates, it was found that the sulfur f+ type extreme pressure additive of the present invention has oiliness and extreme It had a pressure effect and the hue was quite pale and good.

Incidentally, although the dialkylpolyruphide had a very good hue, it was very poor in oily effect.

The test method is described below.

(1) Copper plate corrosion test It was carried out according to JIS K-2513.

Sample addition amount: 5% Base oil: 500 neutral oil (100c at 40℃
st) Test temperature: QQ''C Test time = 1 hour or 3 hours Hue Measured according to JIS K-2580 (Petroleum product color test method).

sulfur content Measured according to JIS L2541.

Oil Effect Test Each extreme pressure additive was added in an amount of 5% by weight to the base oil, and its g-friction coefficient was measured using a pendulum friction tester.

Maximum swing angle: 20.5 radians Test temperature: Room temperature base oil Nisbindl oil (7 cst at 40°C)
Extreme pressure effect test/high speed four-ball test 5% by weight of each extreme pressure additive was added to the base oil, and ASTM
The fusion load, average Hertzian load, and wear scar diameter were measured according to D-2783.

Base oil Nisbindle oil (7'cst at 40°C) Spindle rotation speed: 1770 rpm Test steel ball: 2 inch steel ball for ball bearings (JIS advanced) Test time: fused load 1 (and measurement of average Hertzian load: 10 seconds wear) Measurement of scar diameter: Load when measuring wear scar diameter for 30 minutes: 15 kg Soda four-ball test Add extreme pressure additives to base oil at 5% and 10% by weight, respectively.
Added, JIS K-2'51! ] (Lubricating oil load-bearing capacity test method) The passing limit load was measured.

Base oil Nisbindle oil (7cst at 40°C) Spindle rotation speed: 75 Q rpm Test steel ball 1 inch steel ball for double ball bearing (JIS advanced) Test time -60 seconds

Claims (1)

[Claims] ° A sulfur-based extreme pressure additive obtained by reacting unsaturated animal and vegetable oils and fats and/or unsaturated fatty acid esters with mercaptans and sulfur in the presence of a basic catalyst.