JPS5817797B2 - Ladoyu to olefin no riyuka to sono seihin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel lubricant composition and its composition.
A mixture of 70 parts (by volume) of lard oil (representative of triglycerides) and 10 to 50 parts (preferably 12 to 30 parts by volume) of an ethylenically unsaturated hydrocarbon having 3 to 24 carbon atoms is sulfurized. It's about how to do it.

Sulfurization is carried out using elemental sulfur.

Simultaneous sulfurization and chlorination can also be carried out by reacting with sulfur monochloride.

The phosphorus sulfidation reaction can also be carried out by adding a small amount of phosphorus sulfide to the sulfiding mixture and then heating at 1800 to 25'O'F for 30 minutes to 10 hours to carry out the phosphorus sulfidation reaction.

The sulfurization or phosphorus sulfurization reaction is allowed to react at 330-445'F for 20 minutes to 10 hours, then at 125'F-250'F.
This also includes blowing gas for 30 minutes to 20 hours to remove hydrogen sulfide.

The simultaneous sulfidation and chlorination reaction takes place at 90-280"F.
from 0 minutes to 10 hours, then at 125-250”F for 3
Performed by blowing gas for 0 minutes to 20 hours, the sulfurized oil is 7.5 to 25% based on the mixture of olefin and lard oil.
% by weight of sulfur (or the amount of sulfur equivalent to 52C12).

Until now, sulfurized Matukola whale oil has been used in many lubricant formulations, such as gear oils, caterpillar and spur gears, automatic transmission fluids, launchpad lubricants, sintered blue pots, phosphorous bahit, and friction in permawick lubricants for bearings. It has been used as a modifier additive and as a metalworking oil additive.

Matukola whale oil is currently limited, and the present invention is aimed at replacing sulfurized Matukola whale oil.

Sulfurized olefins alone do not have the lubricity necessary for many applications, as evidenced by their high slip-on ratios.

Sulfurized naturally occurring triglycerides, such as lard oil, do not have adequate solubility in paraffinic base oils.

Sulfurized mixtures of triglycerides and ethylenically unsaturated hydrocarbons and preferably olefins have good lubricity;
It has been found that materials can be obtained that are soluble in lubricant base oils made from paraffinic crude oils.

When olefins and triglycerides are sulfurized separately and then mixed, different products are obtained and mixtures of separately sulfurized oils do not dissolve in paraffinic-based lubricating oils.

When one, slightly different triglyceride and olefin are sulfurized separately, then mixed with the unsulfurized components and re-exposed to sulfurization conditions, different products are also obtained.

The present invention uses 90 to 50 parts, preferably 88 to 70 parts (by volume).
of lard oil and 10 to 50, preferably 12 to 30 parts (by volume) of olefin, sulfiding the mixture, and then bubbling gas through the sulfurized mixture to remove hydrogen sulfide.

Pork fat oil (hereinafter sometimes referred to as triglycerides) and olefins are generally 65° to 340°F (18,3 to 171°F).
．． 1° C.) and add sulfur while the mixture is within this temperature range.

The preferred commercial lard oil is generally winter grade lard oil.

Pork fat oils suitable for use in the present invention are defined in Table 1.

Table 1 Properties Quality Preferred Suitable pork fat pork fat Free fatty acids (as oleic acid 2-5% 12-20%) Saponification number 192-198 192-198 Pour point (ASTM) 35-45 35-50 Viscosity 5 US (
100°'F) 200-210 200-210 fusion
Point 65-75 65-75 specific gravity (25°G
) 0.910-0.915 0.910-0.9
15 Iodine Number 60-75 60-75 The main difference between the less preferred grades, such as primary lard oil, and the preferred grades lies in the presence of saturates which reduce the solubility of the product.

The preferred specifications shown in Table 1 are the best winter filtered pork fat oil (the best winter pork fat oil) and the winter filtered pork fat oil (winter pork fat oil).
Numerous other naturally occurring lard oils, including those of superior quality, are suitable for use in the present invention.

The fatty acid portion of triglycerides generally consists essentially of acids containing from 9 to 22 carbon atoms.

At least about 4 of the fatty acid moieties present within the triglycerides
．． 5 moles contain at least one ethylenically unsaturated carbon-carbon double bond.

The fatty acid portion of the triglyceride should be hydrocarbon except for the carboxyl group.

Triglycerides such as castor oil, where the acid contains hydroxyl groups, are undesirable due to the poor solubility of these triglycerides in the oil.

Olefins suitable for use in the present invention generally have 3 to 2
Contains 4 carbon atoms.

For the convenience of carrying out the process of the invention in a non-pressurized open vessel, the olefin is at least 12, preferably 15, to prevent boiling loss of the olefin when heating the reaction mixture.
carbon atoms.

The olefin may be linear or branched.

Also suitable are any hydrocarbons having one ethylenically unsaturated carbon-carbon double bond and one aromatic or alicyclic ring.

Polycyclic hydrocarbons and hydrocarbons with double or triple double bonds do not provide desirable oil-soluble products.

True olefins are preferred.

Double bonds are not allowed within the ring and are observed to reduce the solubility of the product in paraffinic oils.

A suitable unsaturated hydrocarbon therefore has the following structural formula:

(In the formula, R1, R2, R3 are hydrogen or an alkyl group, and R4 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an alkaryl group).

β-olefins generally provide the best properties for the final product.

Regarding the properties of the final product, α containing 8 to 12 carbon atoms
-Olefins are preferred.

When a normally gaseous unsaturated hydrocarbon is used, the volume percent present is calculated from the apparent density of the unsaturated hydrocarbon if it were a normally liquid hydrocarbon.

The amount of sulfur is generally from 7.5 to 25 parts by weight based on the triglyceride and olefin mixture.

When an inert sulfurized product is desired, 7.5 to 11.0 parts by weight of sulfur, based on the triglyceride and olefin mixture, are used.

Under the conditions of use, this amount of sulfur is almost completely chemically bound to the inactive form.

7 based on a mixture of triglycerides and olefins
．． The resulting product containing 5 to 11 parts by weight is useful as a friction modifier for many applications, as well as as a metalworking fluid.

When sulfurized oils are used as metalworking oils, it is often desirable that they contain relatively large amounts of sulfur.

This is because the most important component for its function as an anti-stick agent is sulfur itself.

Generally, 16 to 25 parts by weight should be present in such metalworking fluids.

The sulfur present above 11 parts by weight is in active form.

The amount of sulfur in a sample of oil can be easily measured using X-ray fluorescence.

After measuring the total sulfur content, 100g of oil sample and 20g of copper powder were added.
g in a 250 m long beaker placed on a hot plate and equipped with a hygrometer and a lance-type stirrer operating at 1750 rpm.

The sample was heated to 350°F (176,7°C) within 5 minutes and then heated to 5°F (176,7°C ± 2.78°C) in the subsoil for 1 hour.
°C), then cooled and filtered through P paper to remove copper powder.

The sulfur content of the sample is determined once again by X-ray fluorescence.

This is inert sulfur. Sulfur loss (total sulfur amount - inactive sulfur amount) is the original active sulfur amount.

The amount of active sulfur in sulfurized oil used as a friction modifier is 2
．． It should not exceed 5 parts by weight.

The friction modifiers of this invention, which generally contain 7.5-11 parts by weight total sulfur, contain 1-2 parts by weight sulfur.

The sulfurized metal working oil additives of the present invention containing 16 to 25 parts by weight of sulfur contain 5 to 18 parts by weight of sulfur.

Generally, sulfur is heated to 250°F or more while stirring the mixture constantly.
Add to triglyceride-olefin mixture over 1-60 minutes while maintaining 330°F (121,1-165.6°C).

Temperature is not particularly critical, 250'F (121,1°
C) represents the softening point of sulfur, 330'F (165,6
C) represents the flash point of the triglyceride-olefin mixture when the olefin is a mixture containing 15 to 20 carbon atoms.

The high sulfur oil of the present invention is heated at 36'F (2.2C) for 16 hours.
It is soluble in paraffinic oils as exemplified by testing a sample of 1 (L9) in 100 g of oil for one week at room temperature.

Conversely, commercially available highly sulfurized triglycerides, such as sulfurized lard oil, and commercially available highly sulfurized whale oil separate from paraffinic oils after being tested under the above conditions.

Generally, for metalworking fluids, sulfurized oil is dissolved in paraffinic oil to form a 5-20 volume solution of sulfurized oil in paraffinic oil.

When using 52C12, which is usually a liquid, it is added to the tricryceride olefin mixture at ambient temperature and then heated above 90'F, (322°C) due to its enhanced chemical activity compared to elemental sulfur. can be reacted.

Generally, 0.5 to 3 parts by weight are used when carrying out the phosphosulfurization reaction of co-sulfurized triglyceride-olefin mixtures.

Therefore, phosphorous sulfide and sulfur are used to provide the required amounts of phosphorus and sulfur.

A preferred phosphorus sulfide is phosphorus tritetrasulfide.

The reaction conditions and time used for the phosphorus sulfurization reaction are from 180 to 2
50°F to 250cP, (82.2-121.1°C) for 30 minutes to 10 hours, then 125°F to 250cP, (51.7-1
71.1° C.) Gas blowing is performed for about 30 minutes to 2 hours.

After adding sulfur, heat the mixture.

If you want to maximize the amount of active sulfur present, below 330,
Temperatures as low as (165.6° C.) can be used.

The sulfurized oil of the present invention has a flash point of about 445'F, (229,4
C) 1, and this is therefore the maximum temperature that should be used in the heating step.

If desired, pressure equipment can be used to increase the maximum possible temperature, but for economical reasons the reaction is more easily carried out at normal pressure.

Additionally, there is little benefit to using humidity above 445°F (229.4°C).

For formulations when minimum active sulfur is desired, heating is
Should be carried out at temperatures above 185°F (185°C).

For formulations where the presence of large amounts of active sulfur is desired, heating should not be carried out above 345'F (173.9C).

Generally, heating is carried out for 20 minutes to 10 hours.

After the heating step, gas is blown into the sulfurized oil to remove H2S.

Any gas that dissolves H2S and does not react to any significant degree with the sulfurized oil can be used.

Suitable gases include air, nitrogen, carbon dioxide, gaseous perhalogenated hydrocarbons.

Air is clearly preferred from economic considerations.

Blowing can be simply carried out by bubbling gas into the sulfurized oil.

Alternatively, the oil can be sprayed into the gas or a falling curtain of oil can be used in the gas.

Generally blowing is 125°F to 250°F (51,7 to 1
21.1°C).

Sulfur is also known as elemental sulfur, sulfur monochloride (s2cr, )
It can be added as

Usually elemental sulfur is low in sulfur (7.5 to 11 parts by weight is preferred, but S2C2 is often preferred in metalworking fluid applications).

This is because chlorine also reacts with oil and has the role of improving the anti-stick properties of the product.

When using S2C■2, the temperature should be 280°F, unless a pressure device is used to maximize chlorine retention.
(137,8°C) (boiling point of S20I2).

The products of this invention have properties not possessed by sulfurized triglycerides, or sulfurized olefins, or mixtures of separately sulfurized triglycerides and separately sulfurized olefins.

Compatibility of sulfurized triglycerides with paraffinic lubricants:
C.There is a drawback that it is lacking.

Sulfurized olefins do not have adequate lubricity as evidenced by their low adhesion slip ratios.

(Static friction/dynamic friction when used as a lubricant additive).

The combination of adhesion/slip properties and compatibility is particularly important in automatic transmission fluids and limited slip differential fluids.

Automatic transmission fluids typically contain 75 to 98 parts by volume of paraffinic base oil and 2 to 25 parts by volume of additives.

Additives are necessary because any oil alone does not have all of the properties normally desired in automatic transmission fluids, such as viscosity, flash point, foaming, and lubricity.

To achieve these properties, oils must be enriched with various additives.

Usually a plurality of additives are used, each particular additive being aimed at improving one particular property of the hydrocarbon oil.

Compositions suitable for use as automatic transmission fluids typically have a temperature of at least 49.08 uS (210°F, 9
It has a viscosity of 8.9℃).

Further, the viscosity of the fluid must remain substantially constant during use of the fluid.

After use in a vehicle that is accelerated repeatedly enough to bring the temperature of the fluid to 300°F (148,9°C)
The fluid has a viscosity of 6.5 SuS (210°F, 98.9°C) and a flash point of at least 320°F (160,0°C) as measured by ASTM D-92.

The sulfurized oils of this invention are useful as friction modifiers in fluids because they reduce static friction rather than dynamic friction.

Generally, the sulfurized oil of the present invention is used in 1 to 5 volume parts of the total fluid.

A typical automatic conduction fluid has the following composition:

82.7 parts by volume of a solvent refined paraffinic lubricating oil with a viscosity of 40.3 SuS (210°F, 98.9°C) and a viscosity index of 101, 3 parts by volume of the sulfurized oil of Example 10, and 0.5 parts by volume of zinc dialkyldithiophosphate. 4,4'-methylenebis(2,
61 di-tertiary-butylene enol) 0.5 volume, barium phosphate 0. Overbased barium sulfonate 1
Volumetric, and hydrogenated naphthenic lubricating oil 15 volumetric as a seal swelling agent.

Example 1 300g of filtered pork fat oil for winter use was added to a 51-liter machine equipped with a vibratory mixer.
in a kettle with 300 g of α-olefin.

(Volume ratio of olefin to triglyceride 1:1.
56).

α-olefins are a mixture of predominantly linear mono-α-olefins containing 15 to 20 carbon atoms.

Heat the mixture to 250'F (121,1°C) and run the vibratory mixer at maximum speed.

Maintaining these conditions, 60 g of sulfur is added over several minutes.

Raise the temperature to 375'F (190,0C) and hold at this temperature for 2 hours.

Reduce the temperature to 200°F (93.3°C) and stir air into the mixture for 1 hour using a glass tube at a moderate speed below the rate at which splattering or agitation occurs to remove hydrogen sulfide. Let it bubble.

The resulting sulfurized oil was analyzed and found to contain 8.7 parts sulfur based on the total composition.

A 10 g portion of sulfurized oil is dissolved in 100 g of oil rAJ.

Oil rAJ has a viscosity of 40.3 seconds (Seybold Universal) (210°F, 98.9°C) and a viscosity index of 101
is a commercially available solvent refined paraffinic base oil containing 12% aromatics as measured by ASTM D-2007.

The oil sample remains clear with no separation after being tested overnight at 36'F (2.2C) and for a week at room temperature.

The solution does not corrode copper when tested at room temperature for 3 hours.

When tested at 212°F (100°C) for 3 hours, oil rA
Solution J slightly corrodes copper.

Make a solution of 3.65 wt. sulfurized oil in oil rBJ.

Oil IBJ is a commercially available solvent purified oil with a viscosity of 47.3 seconds (Seybold Universal) (210°F, 98.9°C), a viscosity index of 103, and contains group 13 aromatics as measured by ASTM D-2007. It is a paraffinic base oil.

This 3.65 weight solution was applied with a load of 20 kg for 60 minutes.
When tested in a standard four-ball abrasion tester at 1800 rpm and 130'F (54.4C), a 0.48 mm flaw is observed.

When this 3.65 weight solution is subjected to a Farex test with pressure increases in minute increments, a maximum load of 1750 pounds is obtained.

This Farex test was conducted at the Chicago, Illinois
The composition was tested in a Farex tester manufactured by Le Valley Corporation to demonstrate that the composition has extreme pressure lubricity.

Farex Test Apparatus An inch diameter steel bin rotates between two horizontally loaded steel V-blocks.

Pressure is applied in 250 pound increments at one minute intervals until the shear pin or steel bottle breaks due to lack of lubricant film.

Example 2 Example 1 is repeated except that 120 g of sulfur is added to the lard oil and alpha-olefin mixture.

Take a 10g portion of the sulfiding mixture and add it to 100g of oil rA.
Mix with J.

This mixture does not attack copper after being tested for 3 hours at room temperature, but it does attack copper after being tested for 3 hours at 212'F (100C).

A solution containing 2.96 weight of sulfide mixture in oil rBJ is prepared and subjected to Farex test and 4-ball abrasion test.

When pressure was increased in minute increments in the Farex test, the sample failed at 3500 pounds.

In the four-ball abrasion test, at 130° C. and a speed of 1800 rpm with a load of 20 kg, a scar of 0.61 mm was obtained after 60 minutes.

Example 3 2260 m7 of winter filtered lard oil are mixed with 400 mA of tetraisobutylene prepared as described in the following pages of the final example in a 51 kettle equipped with a vibratory mixer.

Heat the mixture to 250°F (121,1°C) and run the vibratory mixer at maximum speed.

Add sulfur (10wt) and bring the temperature of the mixture to 37°C for 2 hours.
Raise to 5°F (190,6°C).

The mixture was then cooled to 230°F (110,0°C),
Air is bubbled into the mixture with a glass tube for 1 hour at a moderate speed below the rate at which splattering and agitation occurs.

Analysis of the sulfurized oil produced reveals that it contains 8.23% sulfur.

A 10 g portion of this sulfurized oil is dissolved in 100 g of Oil 1-AJ overnight at 36°F (2.2°C) and after testing at room temperature for a week, the oil sample remains clear with no separation.

Example 4 4 50 ml of filtered lard oil for winter use (2550 ml) made by the method described on the page after the final example! of triisobutylene in a 51 kettle equipped with a vibratory mixer.

Heat the mixture to 25 oy (121.1° C.) and run the vibratory mixer at maximum speed.

These conditions are maintained while 266 g of sulfur is added over several minutes.

Increase temperature to 275°F (190,6°C) for 2 hours.

The mixture is then cooled to 230°F (110°C) and a flash of gas is bubbled into the mixture for one hour with a glass tube at a moderate rate below that at which splatter and agitation occurs.

Analysis of the sulfurized oil produced reveals that it contains 8.6 sulfur based on the total composition.

Take a 10 g portion of this sulfurized oil and dissolve it in 100 g of oil rAJ.

Even after one week of testing at 36°F (2.2°C) and overnight room mixing, the oil sample remains clear without separation.

Example 5 Winter filtered lard oil (2550 m, d) was mixed with 450 ml of a commercial mixture of C18 branched olefins containing mainly double bonds in the middle chain in a 51! Mix in a pot.

Heat the mixture to 250'F (121,1°C) and run the vibratory mixer at maximum speed.

Maintain these conditions while adding 265 g of sulfur.

Increase temperature to 375°F (190,6°C) for 2 hours.

The mixture is then cooled to 230'F (110C) and air is bubbled into the mixture with a glass tube for 1 hour at a moderate rate below the rate at which splatter and stirring occur.

Analysis of the sulfurized oil produced shows that it contains 8.58% sulfur.

Take a 10 g portion of this sulfurized oil and dissolve it in oil [AJlol.

The oil sample does not separate and remains clear even after testing overnight at 36'F (2.2C) and for a week at room temperature.

Example 6 A mixture (2646 g) of 85 vol. of winter filtered lard oil and 15 vol. of a mixture of predominantly linear α-olefins containing 15 to 20 carbon atoms was prepared using a vibratory mixer. Put it in the pot of 51.

Heat the mixture to 300°F (148,9°C) and
Add sulfur of I over 30 minutes.

Increase temperature to 335'F (168,3°C) for 35 minutes.

The mixture is then cooled to 212"F (100C) and air is bubbled into the mixture with a glass tube for 177 hours at a moderate rate below that at which splatter and stirring occur.

Analysis of the sulfurized oil produced revealed that it contained 16.33 weight sulfur.

This sulfurized oil is dissolved in oil rCJ to create a solution containing 28.5 parts by weight of sulfurized oil.

Oil "C" has a viscosity of 38.2 seconds (Saybold Universal) (210 OF?, 98.9°C), a viscosity index of -10 average molecular weight of 295, and a viscosity index of 21 as determined by ASTM D-2140 method.
aromatic carbon atom, 37 naphthenic carbon atom, 4
It is a commercially available naphthenic base oil containing 2 paraffinic carbon atoms.

A value of 3250 lbs (i+74 kg)' is obtained using the Noorex 1 minute kizami pressure increase test.

In the 4-ball welding test (Fed6503), 2 in oil rcJ
Welding was 800+kg using sulfurized oil solution with a weight ratio of 8.5
It happens.

0.81'ms in a four-ball wear test run at 1800 rpm, 130°F (54,4°C) and 25 kg for 30 minutes.
Scars can be seen.

Dissolve 10g of this sulfurized oil in 100g of oil rAJ,
When metal working oil is prepared, it is clear that it remains transparent even after being left at 36° C. (2.2° C.) for 16 hours and at room temperature for one week.

Conversely, commercially available pure whale oil and commercially available lard oil, both sulfurized to the same extent, are separated from the solution after the same test.

Example 7 Filtered pork fat oil for winter use (2550 ml) with 15 to 2 carbon atoms
A mixture of mainly linear α-olefins containing 0 250
Mix in a 51 kettle equipped with m1 and a vibratory mixer.

Heat the mixture to 178°F (81,1°C) and add 238g
Add sulfur monochloride (S2C) to the mixed oil over 15 minutes.

At the end of 15 minutes the temperature rises to 230°F (110°C).

The temperature is lowered to 194°F (90,0°C) and air is bubbled into the mixture with a glass tube for 14 hours at a moderate rate below the rate at which splatter and agitation occurs.

This air blowing serves to remove HCI as well as H2S.

The weight loss during this air blowing is O,'17%.

Analysis of this sulfurized oil revealed that it contained 3.96% sulfur and 3.9% by weight.
It can be seen that it contains 0% by weight of chlorine.

Example 8 This example illustrates the difference between sulfiding lard oil and olefins together and sulfurizing them separately and mixing them, and furthermore, this example illustrates the difference between sulfurizing lard oil and olefins together and sulfurizing them separately and mixing them. This shows that it is difficult to estimate.

a solution of winter filtered lard oil in 50 volumes of oil rAJ;
Examples of filtered lard oil for winter use with a volume of 5 and a volume of 15],
2. Make a solution of the mixture with the α-olefin used in 6.7 in 50 volumes of oil-operated rAJ.

These solutions do not differ in compatibility and both are clear at room temperature.

Both solutions solidify upon cooling to 36'F (2.2C).

Both solutions become clear when heated to room temperature.

Pour filtered pork fat oil for winter use (2699 g) into a 51 kettle equipped with a vibratory mixer.

Heat the lard oil to 300'F (148,9C) and run the vibratory mixer at maximum speed.

Add sulfur (270,9) over 30 minutes.

Raise the temperature to 375'F (190,6°C) and keep at 31
Keep time.

The temperature is then lowered to 200'F (93.3C) and air is bubbled through the sulfurized oil for 17 hours at a moderate rate below the rate at which splattering and agitation occurs.

Analysis of the sulfurized lard oil produced reveals that it contains 8.54% by weight of sulfur.

Charge 2356 g of the predominantly C15-C2o linear α-olefin blend used in Examples 1, 2, and 6.8 to a 51 kettle equipped with a vibration mixer.

Heat the α-olefin to 300'F (148,9C) and run the vibratory mixer at maximum speed.

Sulfur (236 g) is added over 30 minutes.

Raise the temperature to 335'F (168,3C) and then!
Hold for 30 minutes.

The temperature was then increased to 375''F'(190,6°C);
Leave it as is for 31 hours.

The temperature is then lowered to 200°F (93.3°C) and air is bubbled through the sulfurized oil for 17 hours at a moderate rate below the rate at which splattering or agitation occurs.

Analysis of the sulfurized α-olefins produced reveals that they contain 8.99% by weight of sulfur.

The compatibility of separately sulfurized lard oil and alpha-olefins in oil rAJ is tested.

When 10 g of sulfurized lard oil is dissolved in 100 g of oil rAJ, the solution becomes hazy after being tested overnight at 36'F.

When 10 g of sulfurized alpha-olefin is dissolved in 100 I oil rAJ and tested overnight at 36'F (2.2C), the solution remains clear and does not separate.

10 g of an 85:15% mixture of sulfurized lard oil and sulfurized α-olefin was dissolved in 1009 oil rAjK and heated to 36°F (2,
When tested overnight at 2°C, the solution becomes hazy.

When 10 g of a 70:30 mixture of sulfurized lard oil and sulfurized alpha-olefin is dissolved in 10 liters of oil rAJ and tested overnight at 36'F, the solution becomes hazy.

Haze is an indication of incompatibility between the additive and the paraffinic oil, which means that during use the additive forms a sludge and is therefore not available to perform its function. Become.

Conversely, when sulfided together, lard oil and alpha-olefins form a sulfurized product that is soluble in paraffinic lubricating oils at 36°F (2.2°C).

Example 9 This example demonstrates the use of an inert gas to remove H2S produced during the sulfidation reaction.

Filtered lard oil for winter use of 85 volume and 15- volume of 15 volume
A mixture (2666 g) with a predominantly linear α-olefin mixture containing 20 carbon atoms is charged to a 51 kettle equipped with a vibratory mixer operating at maximum speed.

These conditions are maintained during the addition of 534 g of sulfur over 30 minutes.

Raise the temperature to 335'F (168,3°C) for 35 minutes and add nitrogen gas at a moderate rate below the rate at which splattering and agitation occurs for 2 hours while maintaining the temperature of the mixture at 335'F (168,3°C). Whisk into the mixture.

Analysis of the sulfurized oil produced reveals that it contains 16.19g of sulfur.

Example 10 Filtered lard oil for winter use of 85 volume and 15- volume of 15 volume
A mixture (2644 g) with predominantly linear α-olefins containing 20 carbon atoms is charged to a 51 kettle equipped with a vibratory mixer.

Heat the mixture to 250°F (121,1°C) and
g of sulfur is added over a few minutes.

Increase temperature to 375'F (190,6C) for 2 hours.

The mixture is then cooled to 230°F (110°C) and air is bubbled into the mixture for 2 hours with a glass tube at a moderate rate below the rate at which splattering agitation occurs.

Analysis of the sulfurized oil produced reveals that it contains 8.35 parts by weight total sulfur and 0.59 parts by weight active sulfur.

Table 2 shows the "copper strip" test performed according to ASTM D-130.

A value of 2 or less is considered appropriate for these substances.

The weld points reported in Table 2 are based on the standard four-ball weld test (
Fed, 6503).

A value of 250 kg or more is considered suitable as a metal working oil.

The stick/slip ratio is the ratio of static friction to dynamic friction.

Values below 0.85 are considered adequate for most applications.

Examples 11-13 and Examples 14-25 Examples 11-13 and Examples 14-25 are shown in Table 3.

It is shown in Table 4. The solubility of each sulfurized triglyceride in at least one type of paraffinic oil is obtained by cosulfurizing the triglyceride with the amounts of olefins shown in Table 3.

In each of the examples shown in Table 3, the olefins used are a mixture of predominantly linear mono-alpha-olefins containing from 15 to 201 carbon atoms.

All solubility data shown in Tables 3 and 4 are indicated for oil 10
Based on 10g of sulfurized product in 0.9.

All performance data shown in Tables 3 and 4 are based on solutions of sulfided products in oil ICJ as previously defined.

In each example, the sulfurized product contained 0.3 sulfur in the total composition.
Dissolve in the amount of oil rCJ required to weigh 18 lbs.

Falex test when carried out on oil ICJ without additives shows 250 P, S, I (17,56 kg
/CIrL2) or less.

In Examples 11-13, Examples 19, 20, 24 and 25, the sulfurized product was a 100-100 O round bottom glass equipped with a thermometer, vibratory mixer, heating mantle, and water-cooled reflux condenser.・Made by putting it in a flask.

The temperature of the charge was raised to 250"F (121.1C) and 50g of sulfur was added over about 1 minute.

Raise the humidity to 375OF (190,6℃) and keep it at 52
The temperature was then lowered to 250°F (121.1°C).

The temperature was maintained at 250'F'' (121.1°C) for 2 hours and the sulfurized product was bubbled with air for 2 hours to remove hydrogen sulfide.

The product was analyzed for sulfur and the amount is shown in Tables 3 and 4.

In Examples 14 to 18, lard oil shown in Table 3 -C15C2
The zero-chain α-olefin mixture, or lard oil, or olefin was sulfurized as described above, and the sulfurized product was then subjected to the series of steps described above.

However, enough phosphorus trisulfide (P4S3) was added in place of sulfur so that in Examples 14 and 15.18, it became P in the double-layered part, and in Example 16.17, it became P in the single-layered part. And 22
A temperature of 0°F (104,4°C) is used for 5 hours.

The final product of Example 14 is P of 1.8 overlapping part, Example 15
In this case, P of the overlapping part is 1.5, and in Example 16.17, it is 0.86.
The weight placement part P in Example 18 contained 1.6 weight placement parts P.

For nominally double stacked P, the phosphorus sulfide mixture is more soluble than the phosphorus sulfide mixture or the phosphosulfide olefin.

In Examples 21 and 22, a cylinder reactor is used because propylene and hexene have low boiling points.

In these examples, 50
0g lard oil-olefin mixture is introduced together with 50g sulfur.

Seal the cylinder and heat to 375°F (190°C) for 2 hours with stirring.
, 6°C).

After 2 hours, remove the product from the cylinder and heat to 250'F (12
Place in a 1000 ml round bottom glass flask maintained at 1.1°C) and aerate for 2 hours.

After this the product is complete.

In Table 3, all of the Examples use the mixtures of lard oil of 85 parts by volume and olefins of 15 parts by volume shown in the table.

In Tables 3 and 4, CPS stands for centipoise and R
T represents room temperature and LWI represents the load wear index measured according to ASTM D-27-83.

OK means that the sulfurized products are soluble and no haze is observed.

S means that sulfidation products are separated from the oil.

SI, H means that slight haze was observed;
H means that haze was observed.

In Tables 3 and 4, the oil rDJ is a solvent refined bright stock having a viscosity of 169 SuS, a viscosity index of 95, and a coefficient of 23 aromatic compound.

Preparation of Tetraisobutylene Nitromethane (200 ml) and 5nC14 (5 mA) were stirred in a 30 round bottom flask (500 ml) equipped with a gas inlet tube, mechanical stirrer, reflux condenser, external bath and thermometer, while isobutyne was stirred at 35 °C. Pass through the mixture maintained at .

The isobutyne is fed into the flask at a rate sufficient to maintain no flow on the outlet side after air has been swept out of the flask.

After 26 minutes, the flow of isobutine is stopped and the contents of the flask are transferred to a separatory funnel.

The conversion of isobutine is quantitative.

After phase separation for 5 minutes, the nitromethane layer (202 ml
) from the bottom of the funnel.

In a standard procedure, the oil layer (235 m7) was washed twice with saturated aqueous sodium chloride solution, once with 5-carbon aqueous sodium hydroxide solution, and twice with saturated aqueous sodium chloride solution.

The oil layer is then dried over anhydrous calcium chloride and placed in a vacuum distillation apparatus.

All boiling point components below 0.5 mmHg and 80°C are removed by distillation.

The residual oil component (1 ooml) has the following properties.

Kinematic viscosity (210°F) = 4.25C8 (ASTMD-
445) Kinetic viscosity (100°F) = 22.42C8 (ASTMD
-445) VTF viscosity index = 98 ASTM viscosity index = 104 Distillate (100 mA) contains approximately 49 trimers and 49 ql)
was a tetramer (VPC).

It is believed that all dimer was lost to the trap (10 mA').

Batch drying loss is approximately 30 mA'. Table 3 Solubility Viscosity Oil rAJ Oil rB
J Performance example
Triglyceride Olefin Charge Product Sulfur R
T 36'F RT RT 36'F RT
Faretsuku adhesion/ abrasion welding LWIN volume%
Cps eps weight t% (22℃) 1 week (22'C) -4 hours psi slip mm psi11 lard oil 0 55 3760
0KHOK HHH1250121/
15 33.5 1100 8.98 0K OK
OK OK SI, HSI, H10000B
3 0.46 200 25.413 tt
25 20.0 610 9.56
0K OK OK 0K OK OK
750 0.74 0.46200 25.914
〃 (2%P) 0 9.5
SI,HHHH25000,840,443153
0,415 Pork fat oil (2 chips) 15 8.4 SI,
H8I, H0KSI, H22500,740,45,2
0030,216 Pork fat oil (1chiP') 0
8.59 S S S
S17 Pork fat oil (1%p) 15
8゜97 0K OK OK 0
K18 (2nd staff P) 100 10 5LHH
0KSI, H10000930,4116019,0 Table 4 Solubility (using lard oil) Viscosity Oil rAJ Oil rDJ Performance Examples
Olefin Charge Product Sulfur type RT
36'FRT RT 36〒 RT Styrene
Adhesion/Abrasion Welding LWIcps cps Amount % (22℃) 1 week (22℃) 1 week Cushion rnm psi19 C15-C
2o linear α-olefin 33.5 1100 8.98
0KOK OK OK HH12500,83
0,4620025,4201-decene 27
760 9.64 0KOK OK OK
OK OK 1250 0.79 0.4
5 200 30.2211-hexene
960 10.95 0KOK OK O
K SI, HSLH10000,840,46200
25,922 Propylene 375 7
．． 37 0KHOK OK OK OK
1250 0.82 Q, 52 200 21
．． 923 cyclododecene 36 1240 9.
09 0KOK SLHSI, HHSI, H1250
0,790,4520030,224 styrene
19 930 9.16 0KOK OK
SI,HHH7500,810,4620022,6
251-phenyl-2-edge 723 690 8.88 0KOK
SI, HSI, HHH7500,810,4720
025.0 The triglyceride used is lard oil.Embodiments of the present invention are listed below.

(1) 50 to 90 parts (by volume) of triglycerides and 50 to 90 parts (by volume) of triglycerides;
10 parts (by volume) of a co-sulfurized mixture with a hydrocarbon of the following structure containing from 2 to about 24 carbon atoms, where R1t R2s R3 is hydrogen or an alkyl group; The fatty acid moiety of the triglyceride (which is an aryl group, cycloalkyl group, or alkaryl group) mainly contains from 9 to 22 carbon atoms;
At least about 45 molar portions of the fatty acid moiety present in the triglyceride contain one ethylenically unsaturated carbon-carbon double bond, and the fatty acid moiety is a hydrocarbon other than the carboxyl group of the fatty acid moiety; The sulfurized mixture contains 7.5 to 11 parts by weight of active sulfur chemically bonded thereto, based on the above mixture, and the sulfur composition contains 25 parts by weight of active sulfur.

(2)) The composition according to (1) above, wherein the IJ glyceride is lard oil.

(3) The composition according to (2) above, wherein R4 is an alkyl group.

(4) The composition according to (2) above, wherein R1, R2, and R3 are hydrogen.

(5) 88-70 parts by volume of triglycerides and 12-30 parts by volume
The composition according to (1)K above, using parts by volume of hydrocarbons.

(6) The composition according to (5) above, wherein R' is an alkyl group.

(7) The composition according to (6) above, wherein R1, R2, and R3 are hydrogen.

(8)) The composition according to (7) above, wherein the IJ glyceride is lard oil.

(9) A composition comprising a major portion of mineral oil and a minor portion of the composition described in item 0).

(10) A composition comprising a major portion of mineral oil and a minor portion of the composition described in (8) above.

(U) A large amount of paraffin oil and 1 to 5 volumes of the above (1
A self-conducting fluid comprising the composition described in ).

(12) A self-conducting fluid comprising the composition described in (8) above, which is mostly paraffinic oil and has a volume ratio of 1 to 5.

(13) 50 to 90 parts by volume of triglycerides and 70 to 90 parts by volume of triglycerides;
10 parts by volume of a hydrocarbon containing from 2 to about 24 carbon atoms having the following structural formula: (R1, R2, R3 are hydrogen or an alkyl group; R4 is hydrogen, an alkyl group, an aryl group; (the fatty acid moiety of the triglyceride contains primarily 9 to 24 carbon atoms, and at least about 45 molar proportions of the fatty acid moieties present contain one ethylenically unsaturated The sulfurized mixture contains a carbon-carbon double bond, and the fatty acid moiety is carbon hydrogen except for the carboxyl group of the fatty acid moiety;
A composition comprising 25 parts by weight of sulfur in chemical combination therewith, wherein 5 to 18 parts by weight of the sulfur is part sulfur.

(14) The composition as described in 13 above, wherein R' is an alkyl group.

(15) )! 14 above, where the J glyceride is lard oil
The composition described in.

(16) 15 above, wherein R', R2, and R3 are hydrogen
The composition described in .

(17) 16 above, wherein 88 to 70 parts by volume of lard oil and 12 to 30 parts by volume of hydrocarbon are co-sulfurized in the mixture.
The composition described in .

(18) A composition consisting mostly of mineral oil and a small portion of the composition described in 13 above.

(19) A composition comprising a major portion of mineral oil and a minor portion of the composition described in 17 above.

(20) 7.5 to 11 weight fraction sulfur is used,
The heating process is from 365'F to 445'F (185°C to 229°C)
．． 4°C).

(21) 0.5-3 wt% phosphorus in the form of phosphorus sulfide is added to the co-sulfide mixture and the mixture is heated to 180-2
21. The method of claim 20, wherein the method is heated to 50°F (82.2°C to 121.1°C).

(22) 21 above, wherein the phosphorus sulfide used is phosphorus tritetrasulfide
The method described in.

(23) ) The above 2 in which the IJ glyceride is lard oil
The method described in 0.

(24) The method according to 23 above, wherein R4 is an alkyl group.

(25) 24 above, where R'', R2 and R3 are hydrogen
The method described in.

(26) The method according to 25 above, wherein 88 to 70 parts by volume of lard oil and 12 to 30 parts by volume of hydrocarbon are used.

(27) The temperature of the mixture is between about 250″F and about 330°F (
3. The method of claim 2, wherein elemental sulfur is added while the temperature is maintained between 121.1[deg.]C and 165.6[deg.]C.

(28)) The above 27 in which the IJ glyceride is lard oil.
The method described in.

(29) The method according to 28 above, wherein R' is an alkyl group.

(30) The method according to 29 above, wherein R'', R2, and R3 are hydrogen.

(31) The method according to 30 above, using 88 to 70 parts by volume of lard oil and 12 to 30 parts by volume of hydrocarbon.

(32) The amount of sulfur added is 16 to 25% by weight based on the triglyceride and hydrocarbon mixture, and the heating step is from about 330°F' to about 345"F (165,6°C to about 17%
3. The method according to claim 2, which is carried out at a temperature of 3.4°C.

(33) Adjust the temperature of the mixture to about 250°F to about 330°F (
33. The method according to 32 above, wherein elemental sulfur is added while maintaining the temperature at 121.1°C to 165.6°C.

(34) ) The above 33 in which the IJ glyceride is lard oil.
The method described in.

(35) The method according to 34 above, wherein the hydrocarbon is an olefin containing 12 to 24 carbon atoms.

Claims (1)

Claims: 150 to 90 parts (by volume) of lard oil and 50 to 10 parts (by volume) of the following structural formula containing from 3 to about 24 carbon atoms (wherein R1, R2, R3 are hydrogen or In the alkyl group, R
4 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an alkaryl group) with a hydrocarbon; the lard oil may contain up to 20 free fatty acids; Based on the above mixture 7
．． A lubricant additive composition comprising in chemical combination therewith an amount of sulfur corresponding to 5 to 25 parts by weight φ of sulfur or 7.5 to 25 parts by weight C12. Pork fat oil that may contain up to 220 portions of free fatty acids 50-9
0 parts (by volume) to 50 to 10 parts by volume of a hydrocarbon containing from 3 to about 24 carbon atoms and having the following structure (wherein R1, R2, R3 are hydrogen or alkyl groups, R
4 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an alkaryl group), 7.5 to 25% by weight of sulfur based on the above mixture is added, and the mixture is heated to about 330'F (165 , 6°C) to approximately 445'F (
125'F (51,7°C) to about 250°
A method for producing a lubricant additive composition comprising blowing gas at a humidity of F (121,1°C) for at least about 30 minutes. 3 Pork fat oil 50 which may contain up to 20% free fatty acid content
~90 parts (by volume) of 50 to 10 parts by volume of a hydrocarbon containing from 3 to about 24 carbon atoms and having the following structure, where R1, R2, R3 are hydrogen or an alkyl group, R
4 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an alkaryl group), and adding 7.5 to 25% by weight of 52C12 based on the above mixture,
Heat the mixture from about 80'F (82,2°C) to about 280°
F (137,8 °C) for 20 minutes to 10 hours, then from about 125'F (51,7 °C) to about 250 °C.
A method for producing a lubricant additive composition comprising blowing a gas at a temperature of F (121.1° C.) for at least about 30 minutes.