JPS5918402B2 - Manufacturing method for lubricating oil additives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a process for making compounds useful as lubricating oil additives.

Among the various additives added to lubricating oils, especially automotive lubricating oils, there are various surfactants.

Dispersants, especially ashless dispersants, are used to disperse carbon particles and other insoluble substances, such as decomposition products and fuel oxidation products, in the oil medium of the main constituent of lubricating oils. Insoluble substances are thus dispersed in the oil medium and can prevent the formation of deposits that degrade engine operation. As ashless dispersants used for the above purpose, certain Mannitz base derivatives obtained by reacting long-chain alkylphenols with aldehydes and polyalkylenes have been proposed.

These compounds are excellent dispersants and their inclusion imparts a certain degree of oxidation resistance to the lubricating oil. However, they generally have poor thermal stability;
Furthermore, when applied to diesel, the performance of the oil tends to decrease. The present invention describes the formula useful as a lubricating oil additive:
where each R1 is the same or different and is polybutyl, polyisobutyl or polypropyl having at least 30 carbon atoms, R2 is absent or of the formula: (wherein m is O or an integer, R1 is the same as above) ,5, /0R
5 and -C are the same as below), \. R
4 is hydrogen, methyl or a group represented by the formula: -Z{;] (wherein Z is sulfur or methylene, R1 is the same as above), each R5 is the same or different and is hydrogen, /0methyl or -CH2Cl -]2C\. Each group represented by /″
C is the same or different and means an amide group\,
-ru] Provides a method for producing a compound represented by the following.

In the compounds of the invention, the R1 group comprises at least 30,
Preferably it is a polyisobutyl or polypropyl group having 50 to 200 carbon atoms. These are derived from polyisobutylene or polypropylene with a molecular weight of 700 to 3000, preferably 900 to 2000, especially about 1000. The compound of formula [1] is obtained by reacting the polyisobutyl or polypropyl substituted phenol with a carbonyl substituted compound selected from the group consisting of glyoxylic acid, pyruvic acid and 2-oxoglutaric acid to form a bis(phenol substituted) carboxylic acid. This was added to N-aminoethylethanol, bis-aminopropylpiperazine, bis-hexamethylene triamine, dipropylene triamine, dimethylaminopropylamine, ethylene polyamine and IV-1-Product 1,) Nomomi 11 Mag) JL ?
It is produced by reacting with an amine selected from the group consisting of S7 reaction products to form the corresponding amide.

The starting bis(phenol-substituted) carboxylic acids or derivatives thereof used in the process of the invention are preferably the condensation products described in the Applicant's British Patent Specification No. 1,446,435.

The product described in GB 1446435 comprises (1) an alkyl-substituted monohydric phenol in which the alkyl substituent has at least 8 carbon atoms; and (2)
It is a condensation product with a carbonyl-substituted compound selected from glyoxalic acid, pyruvic acid, levulinic acid, 3-oxoglutaric acid, 2-oxoglutaric acid, and esters thereof. British Patent Specification No. 1,446,435 also describes the general formula: or in which each R1 is the same or different alkyl having at least 8 carbon atoms; R2 is none or less than 7,0;
m is O or an integer, R4, R5, Y and n are the same as below); W is none or a group represented by the formula (wherein p and q are the same or different and 0 or an integer, R4, R5, Y
and n is the same as below); each R4 is the same or different, or a group represented by the formula -Z-R6 (wherein Z is sulfur or two or more sulfur chains or none, R6 is alkyl, hydroxy-substituted aryl , aralkyl or alkylaryl group: each R5 is the same or different and is hydrogen, methyl or one (CH2)rl-C\; n is the same or different and is O or an integer from 1 to 2; each Y is the same or different and is hydroxy or is an alkoxy group] are also described.

In the above formula, when R3 is a group of formula [C], the groups represented by the formula may be arranged in any order.

For example, these may be randomly interspersed with each other,
It does not need to be arranged as a block. In the case of the above condensation product, the starting material alkyl-substituted phenol may have one or more other substituents on its aromatic ring corresponding to R4 in the compounds of the above formulas [A] and [B]. good.

If there are no substituents other than alkyl substituents, this corresponds to R4 being hydrogen. Preferably, the alkyl substituent is in the para position to R1 in formulas [A] and [B]. If other substituents are present, they are unsubstituted in at least one ortho position, at which position the phenol is fused with the carbonyl compound and the phenol residue is as shown in formulas [A] and [B]. is preferably substituted so that it can be bonded in the ortho position. group R4
Alternatively, in the case of a condensation product, the corresponding substituent may be absent or of the formula Z-R6, as described above.

In a preferred embodiment R4 is absent. That is,
In the case of R4 or a condensation product, it means that the corresponding substituent is hydrogen. Such compounds are derived from alkylphenols having no substituents other than alkyl substituents. In another embodiment, R4, or its corresponding substituent in the case of a condensation product, has the formula -ZR6, where Z is none or a chain of sulfur or 2 or more, preferably 2 to 4 sulfur atoms. In this embodiment, when Z is absent, R6 is a short-chain alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or has the formula -CHR7 (wherein R
7 is water or alkyl; R8 is an aryl or aralkyl group having at least one hydroxy substituent.

On the other hand, when Z is sulfur or two or more sulfur chains in this embodiment, R6 is preferably an aryl or alkylaryl group having a hydroxy substituent. The starting materials used in the production method of the present invention are R1 in formulas [A] and [B].
is polyisobutyl or polypropyl having at least 30 carbon atoms.
6435 or said condensation products in which R5 is hydrogen, methyl or -CH2CH2C<8.

These starting materials are reacted with an amine or mixture of amines as described above. The amino group present reacts with the /'' carboxyl group to form an amide group of -C1.

As mentioned above, the starting amines used in the production method of the present invention include N-aminoethylethanol, bis-aminopropylpiperazine, bis-hexamethylenetriamine, dipropylenetriamine, dimethylaminopropylamine,
selected from the group consisting of ethylene polyamines and reaction products of ethylene polyamines and dicyandiamide.

Examples of ethylene polyamines include ethylene diamine,
Mention may be made of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and higher polyethylenepolyamine mixtures. These ethylene polyamines are covered by British Patent No. 1068.
Reaction products reacted with dicyandiamide, such as those described in No. 235, can also be used. There are 3 useful higher polyamines
00-1000 or 50001 preferably 400-6
Particularly preferred are those having a molecular weight of 0.00 and obtained by polymerization of ethyleneimine.

Polymerization of ethyleneimide yields a mixture of polyalkylene polyamines having a wide range of molecular weights. They may be divided into molecular weight ranges useful in this invention. The amine is reacted with approximately equimolar amounts of bis(phenol-substituted) carboxylic acid or derivative thereof.

In this embodiment, when a preferred alkylene polyamine reactant or other amines initially containing two or more primary amino groups is used, the reaction product contains one or more residual primary amino groups. . Also, when using the preferred linear alkylene polyamines, the amine reacts with up to a two-fold molar ratio of bis(phenol-substituted) carboxylic acids or derivatives thereof. The resulting compounds of the present invention are useful as lubricating oil additives, and the compounds can also be further reacted with other reactants to give derivatives useful as lubricating oil additives. One or more residual amino groups react with a carboxylic acid to form an amine salt, amide, imide, imidazoline, or aldehyde, ketone, according to known methods. or mixtures thereof, or with mixtures of aldehydes and ketones to form Mannitz bases. Another alternative is to first react the amine with a suitable mole of carboxylic acid to form an imide, amide or amine salt with residual primary or secondary amino groups; Reacts with bis(phenol-substituted) carboxylic acids or their derivatives.

In another embodiment of the invention, the amine is a polyamine having one primary amino group, and it is a polyamine having an equimolar amount of bis(
Before or after reacting with the phenol-substituted) carboxylic acid or its derivative, it is reacted with an alkyl-substituted succinic acid or its anhydride in which the alkyl substituent has from 8 to 200 carbon atoms. Preferably, such substituent is the residue of a relatively low molecular weight olefin, such as isobutylene or propylene, or an oligomer of such an olefin. The method of the invention is easily carried out by heating the reactants together.

The preferred reaction temperature is 50-250°C, preferably 130°C.
The temperature is preferably 180 to 220°C, preferably 180 to 220°C. Inert solvents such as xylene, toluene or mineral oil may also be used. The reaction is conveniently carried out in a container open to the atmosphere. However, if desired, it may also be carried out under vacuum, low pressure or a stream of nitrogen. The reaction is usually completed in 1 to 6 hours, and most commonly in 2 to 4 hours. By adding the compound of the present invention, its derivative or a mixture thereof to the lubricating oil in a proportion of 0.3 to 15% by weight, preferably 1 to 6% by weight based on the total weight of the composition, the lubricating oil composition can be improved. can get.

Other lubricating oil additives may be added to such compositions and may also be in the form of additive concentrates, additive packages. The lubricating oil used may be any of the known synthetic ester oils such as dioctyl sebacate, but mineral oils having lubricating oil viscosities of known types are preferred. In such lubricating oil compositions, in particular, the polyisobutyl group has a molecular weight of 900 to 2.
000 is reacted with glyoxylic acid and the resulting intermediate is reacted with a polyethylene polyamine having an average of 4 to 6 amino groups (the molar ratio of the reactants is 1.0 to 2.0:1). :0.5 to 1.0) is preferably used. Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (a) Preparation of PIB phenol-glyoxylic acid intermediate Polyisobutylphenol 6929 (0.7 mol) prepared from polyisobutylene of molecular weight 1000 as described in Example 1 of British Patent Specification No. 1446435, glyoxylic acid A solution of monohydrate 64.49 (0.7 mol) and p-toluenesulfonic acid 59 dissolved in 500 me of toluene was mixed with Deen and Stark under a nitrogen atmosphere.
an and Stark) Heat at reflux temperature in a flask attached to a water separator until water evolution ceases (34 volumes of water collected).

The resulting solution was distilled to remove the solvent and a red viscous liquid 75
Get 09. Acid value = 40 KOH/9, saponification value -96
mw. 0(b) Preparation of diamide Product 3 of section (a) above
06.49 is mixed with 27.99% of tetraethylenepentamine and heated at 200° C. for 4 hours under nitrogen atmosphere.

After dilution with mineral oil 589, the product is filtered using filter aid. Acid value = 6Tf1fK0Y1/g (calculated value 0), total alkali value -52m7K0Yv9 (calculated value 60), nitrogen %
= 2.3 (calculated value 2.5) Example 2 Preparation of diamide without separation of intermediates Polyisobutylphenol 8909 (1.0 mol), glyoxylic acid monohydrate 929 (1.0 mol) and p- A solution of toluene sulfonic acid 79 in toluene 600r11e is heated at reflux temperature under a nitrogen atmosphere in a flask attached to a Dean and Stark water separator until water evolution ceases (41me of water is collected). ).

This solution is allowed to cool to several degrees centigrade, and then 94.59 (0.5 mol) of tetraethylenepentamine is added. After evaporation of the solvent, the mixture is heated at 200° C. for 4 hours under a nitrogen atmosphere. The product is diluted with mineral oil and filtered (yield 1
819, theoretical concentration 85%). Acid value = 12 Takumi KOdan/9
(calculated value 0), total alkali number -567n (VKOH/9
(calc. 65), Nitrogen % = 2.4 (calc. 2.7) Examples 3-11 By the general method of Example 2 above, many amides are prepared without separation of intermediates.

The general method is as follows. Polyisobutylphenol and glyoxylic acid monohydrate were dissolved in triene or xylene, p-toluenesulfonic acid (0.1% based on the weight of the reaction solution) was added and stirred, and the mixture was purified in a Dean and Stark separator under a nitrogen atmosphere. The water is collected and heated at reflux temperature until water evolution substantially ceases.

Cool the solution to 80-100°C and add tetraethylenepentamine (TEPA). The solvent is distilled off and the reaction is continued at 200° C. for 4 hours. The product is cooled, diluted with mineral oil and petroleum ether (boiling point 62-68°C) and filtered using deep filter aid. The petroleum ether is removed by vacuum distillation at a temperature below 170°C.

Yields are generally at least 90%. The remaining acid values are low, up to 7m7K0H/9. Furthermore, details of the preparation method are shown in Table 1 below. Thiobis Pl of Example 10
The B phenol starting material is prepared as follows: polyisobutylphenol (e.g., molecular weight 1000 PIB)
571.59 (0.5 mono(c) to sulfur 16.09 (0
．． 5 grams atom) and 4.09 grams of sodium hydroxide at 195° C. under a nitrogen atmosphere.

Hydrogen sulfide is generated and its amount decreases significantly after 20 hours. The reaction is then stopped and the product diluted with petroleum ether (boiling point 62-68°C). This solution was mixed with water-methanol (1:9) at 250 ml. Wash twice with Le and remove the solvent by vacuum distillation. Yield = 5639 (97%),
% Sulfur = 1.5 (calc. 1.4) The methylene-bis-PIB phenol starting material of Example 11 is prepared as follows: 102.6 g of polyisobutylphenol (e.g., 1000 PIB) (
0.1 mol), 40% formalin 4.19 (0.05 mol), 1 ml of concentrated hydrochloric acid and 60 me of toluene was stirred for 3.9 d in a Dean and Stark water separator.
Heat at reflux temperature until (calc. 4.1r11e) of water is collected (4 hours).

This solution was vacuum distilled at 13° C/20 m 7 tL and the product was filtered off. Yield = 82f! , hydroxyl value = 58.2 immediate KO
H/9 (calculated value 54.5) Examples 12 to 17 (reference example)
Many TEs were prepared by the methods described in Examples 3 to 11 (Table 1) above.
Polymers (monoamides) of PA are prepared.

These further react with other reactants to form succinimides, amides, Mannitz bases and Schiff bases. Details of these preparation methods are shown in Table 2 below. If alkenylsuccinic anhydride is used as the other reactant, it is added in the final step of amidation and the reaction is allowed to continue at 200° C. for an hour before diluting and filtering the product.

To prepare the amide/Mannitzig base mixture,
The amide was cooled, rediluted with toluene, alkylphenol added, and 40% formaldehyde (formalin) added.
Add the aqueous solution dropwise at 90-95°C.

This temperature is maintained for 1 hour, then the solution is heated to reflux temperature and the water is removed into a Dean and Stark separator.
After adding the diluent oil, the product is diluted and filtered as described above. Examples 18-25 Polyisobutylphenol (e.g., molecular weight 1000P
1B) 11439 (0.1 mol) was dissolved in glyoxylic acid 1 hydrate in 800 me of refluxing xylene in the presence of p-toluenesulfonic acid 2,0 f 1 until water collection in the Dean and Stark separators ceased (47 d collection). 92g (1.0
mol).

The solvent is then removed by vacuum distillation at a temperature below 17°C. The resulting intermediate is reacted with a number of different amines, as detailed in Table 3, by the following general method: The intermediate 1189 (0.1 mol) is reacted with a
In a flask without a condenser, stir with amine at 200° C. while distilling off the generated water.

The product was diluted with mineral oil to a concentration of 85% and purified with petroleum ether (
The solution is diluted at a boiling point of 62-68°C), filtered using a filter aid, and the solvent is removed by vacuum distillation at a temperature below 180°C. For more volatile amines, a slightly different method is used initially: (a) For dipropylene triamine (Example 19), the reactants are first heated at 170-180° C. for 0.5 h at 200° C. ℃ for 2 hours, then remove the condenser and heat to 20℃.
Heat under reflux for 2 hours.

(b) In the case of ethylenediamine (Example 20), the reactants are heated in 25 d of refluxing toluene for 0.5 h, the solvent is distilled off and the reaction is continued at 200° C. for 4 h.

(c) For dimethylaminopropylamine (Example 22), 100% excess was used and 3
react for an hour, distill off excess amine at below 21°C,
The reaction is continued for 4 hours at 200°C.

Example 26 Preparation of amine in oil solution PIB phenol (e.g. molecular weight 1300 PIB) 1
31.7f1 (0.1 mol), glyoxylic acid monohydrate 4.6 g (0.05 mol), p-toluenesulfonic acid 0
．． 16g and mineral oil 25g.

3 g of the mixture is stirred at 140° C. for 1.5 hours under nitrogen atmosphere.

The generated water is evaporated. The mixture is allowed to cool to 80°C, 9.59 (0.05 mol) of tetraethylenepentamine is added and the reaction is continued at 200°C for 4 hours. Finally, the product is filtered into petroleum ether. Nitrogen % = 1.7 (calculated value 1.9), TBN = 49m silver 0 days/Example 27 Polyisobutylphenol (e.g. molecular weight 1000PI
B) 267 g (0.25 mol) of glyoxylic acid monohydrate 239 (
0.25 mol) (12r11e collection).

47.39 (0.25 mol) of tetraethylenepentamine was added, toluene was distilled off, and the reaction was continued at 20°C for 4 hours to obtain a polymer (monoamide) of tetraethylenepentamine. 110 g (0.5 mol) of nonylphenol was mixed with 23 g (23 g) of glyoxylic acid in toluene in the same manner as above.
0.25 mol) and collect 12d of water. This toluene solution is added to the amide already formed, the toluene is distilled off, and the reaction is continued again at 200° C. for 4 hours. Add 79.89 g of mineral oil and filter the product into petroleum ether. Removal of solvent gives oil 3969. nitrogen%
=2.5 (calculated value 3.1), TBN=64m9K0H/
9, TAN=8m9K0dan/Example 28 (Reference example) PI
B phenol (e.g. molecular weight 1000 PIB) 243
．． 59 (0.22 mol) and nonylphenol 48.
49 (0.22 mol) was refluxed in toluene at 300 r.
11e until water generation stops (207rLe collection)
React with 40.59 (0.44 mol) of glyoxylic acid.

41.69 (0.22 mol) of tetraethylenepentamine are added, the toluene is distilled off and the reaction is continued at 200° C. for 4 hours.

The product is cooled, diluted with 61.69 g of mineral oil and filtered into petroleum ether solution. Yield = 353g, Nitrogen% -3.6
(calculated value 3.6), TBN=74m7K0H/9, TA
N=7 KOH/9 Example 29 Polypropylphenol (prepared by alkylating phenol with polypropylene having a molecular weight of 860 using boron trifluoride as a catalyst) in the same manner as in Example 1 above.
100.49 (0.04 mol) to glyoxylic acid 3.7
f! (React with 0.02 mono(c).

The resulting intermediate 506.9 (0.01 mol) was mixed with 0.73 g (0.005 mol) of triethylenetetraamine.
Heat at 00°C for 4 hours.

9.059 g of mineral oil is added, the product is filtered into petroleum ether solution and finally distilled under vacuum at 180°C. Nitrogen%=0.
4 (calculated value 0.5) Example 30 Using the general method of Example 1 above, polybutyl o-cresol (prepared by alkylating o-cresol with polybutene having a molecular weight of 1000 using boron trifluoride as a catalyst) 66.79 (0.05 mol) in 60ml of xylene solution
2.3 g (0.025 mol) of glyoxylic acid in e.g.

27.29 (0.01 mol) of this intermediate was combined with 1.169 (0.005 mol) of pentaethylenehexamine in 2
Stir at 00°C for 4 hours.

Add 4.959 g of diluted oil and filter the product into petroleum ether solution. Nitrogen% = 1.0 (calculated value 1.3), TBN
=20TI1fK0H/9 Example 31 Polybutylphenol, (e.g., molecular weight 1000PI
B) 194.39 (0.17 mol), 2-oxoglutaric acid 27.2f! (0.17 mol), oil factory (
boiling point 80-100'C) 14077!11 and water 30
ml of concentrated sulfuric acid while stirring and cooling 125! R.L.
Add e.

The mixture is stirred at room temperature for 6 days, further diluted with petroleum ether and washed three times with 200 d of water-methanol (1:9). Vacuum distillation at 160° C. gives acid 1489.

Saponification number=20.4WIK0H/9 The above acid 709 is heated with excess tetraethylenepentamine 109 at 200° C. for 4 hours.

The mixture was cooled, diluted oil 139 and petroleum ether 300 me were added, and the solution was dissolved in water-methanol (1:9
) Wash twice with 40r11e. Vacuum distillation produces product 8
Get 29. Nitrogen%=1.0, TBN=29WiK0H
/9 Example 32 (Reference Example) Product 100.09 (0.03 mol) of Example 26 above
with 8.5 g (0.03 mol) of isostearic acid.
Heat at 00°C for 4 hours.

Acid value decreases (5 KOH/9), TBN is 49-36
m(IKOH/9), the reaction is almost complete.

Example 33 Polyisobutylphenol (e.g. molecular weight 1000P
IB) 69.39 (0.07 mol), pyruvic acid 6.2
A solution of f1 (0.07 mono(ha)) and p-toluenesulfonic acid 19 dissolved in xylene is boiled under reflux conditions until the generation of water stops (3.2 me collection).

The solution is filtered and vacuum distilled to remove the solvent and yield the acid intermediate. This intermediate 23.49 (0,022 mono(c)
4.17g (0.022g) of tetraethylenepentamine
Heat with mono (c) at 200°C for 4 hours.

Add 4.769 g of diluted oil and filter the product into petroleum ether. Nitrogen%=2.3, TBN=72mvK0H/f
l Example 34 Similar to the method of Example 33 above, polybutylphenol (e.g., molecular weight 1000 PIB) 11
4.3 g (0.1 mol) of p-toluenesulfonic acid.
4.49 (0.05 mol) of pyruvate in the presence of 29.

Intermediates do not separate. Tetraethylenepentaamine4.
739 (0.025 mol) was added, the solvent was distilled off, the reaction was continued for 4 hours, the amine was diluted with 21.4 g of mineral oil,
Filter by conventional method.

Yield = 128f! , nitrogen %=1.1 (calculated value 1.1),
TBN=31m7K0H/9 Example 35 Polyisobutylphenol (e.g. molecular weight 650PIB) 87.5
9 (0.1 mol), glyoxylic acid monohydrate 4.69 (
0.05 mol) and p-toluenesulfonic acid 0.16
A solution of 9 in xylene 807ne is heated at reflux temperature until the evolution of water stops (1.9771e).

After cooling, tetraethylenepentamine 4.739 (0.
025 mol) is added, the xylene is distilled off and the mixture is heated at 200° C. for 4 hours under a nitrogen atmosphere.

The product is diluted with 16.69 g of mineral oil and filtered into petroleum ether solvent. Yield - 1049, Nitrogen % = 1.8 (calculated value 1.5) The suitability of the product of the present invention for use as an ashless dispersant in lubricating oils was determined by MS, Cl header AV-B engine test, panel coker test. and a spot test.

The C test was conducted using standard methods on two formulations containing the test additives.

Formulation A is a commercially available sulfonic acid metal detergent formulated to meet US Standard MIL-L46152 containing a viscosity index improver and an antioxidant/anti-wear additive.
W/30 mixture typically contains 4.5% ashless dispersant
was replaced with the same amount of the test additive.

The mixture has a sulfate ash content of 1%. Formulation B is similar to Formulation A above, but has a sulfate ash content of 0.5% and contains an ashless corrosion inhibitor.

After the test, the value was graded according to the condition of the engine according to the conventional method.

These grades are as follows. Except as noted,
The concentration of all additives tested was 4.5%.

Additive X is a useful commercially available ashless dispersant consisting of a boronated Mannitz base of polyisobutylphenol. Header AV-B engine tests were conducted according to conventional methods, and after testing, a value rating (maximum 10) was assigned according to the condition of the various parts of the test engine.

Carbon adhesion in the grooves of the test engine was also measured. Groove carbon and full value grade (up to 100)
The sample mixture used for the AV-B test contained commercially available useful sulfonate metal detergents, corrosion inhibitors and antioxidant/anti-wear additives, and was compliant with American Standard MI.
S formulated to comply with L-L-2104C
In the AE3O mixture, the 3.5% ashless dispersant normally contained was replaced with the same amount of the test additive, except as noted.

The panel coker test was run for 3.5 hours using the same sample mixture used in the AV-B test, using conventional equipment with minor modifications.

Instead of continuously splashing the oil, the oil was splashed for 15 seconds at 45 second intervals against an aluminum plate held at 600'F. The equipment was further modified to vent humid air through the oil sump and above the oil surface at a rate of 2.31/hour. For parts of the sump that are not normally immersed in oil, the value grade % according to the % cleanliness in the same way that engine pistons are graded after the Caterpillar 1-G test.
(100=completely clean). This test is believed to correlate well with the Caterpillar 1-G engine test.
The grades obtained are as follows: In the spot test, the test additive was mixed with mineral oil (V2, O = 3.5c
4% dissolved in S).

Carbon black (SpherOn9, e.g. Cal
1% of OtCarbOnCOy (average particle size 27 mμ) was added, and 10 g of the mixture was stirred for 1 hour using an ultrasonic generator in a 5 inch x 1 inch test tube. The test tube was then stored at 50° C. for 16 hours and allowed to cool. top of test tube 0
．． A drop of oil taken from a 5-inch tube was spotted onto chromatography paper using a thin glass rod. The spots were then developed for 24 hours and graded as follows.

A = Carbon is sufficiently dispersed B = Carbon is moderately dispersed c = carbon slightly dispersed D = Carbon does not disperse

Claims (1)

Claims: 1. (a) a substituted phenol having polybutyl, polyisobutyl or polypropyl substituents having at least 30 carbon atoms selected from the group consisting of glyoxylic acid, pyruvic acid and 2-oxoglutaric acid; with a carbonyl-substituted compound in a molar ratio of 1.0 to 2.0:1.0 at reflux temperature while distilling off water to form a bis(phenol-substituted) carboxylic acid, and then (b) This bis(phenol-substituted) carboxylic acid has a concentration of 50 to 250
0 C, an amine selected from the group consisting of N-aminoethylethanol, bis-aminopropylpiperazine, bis-hexamethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, ethylene polyamine and the reaction product of ethylene polyamine with dicyandiamide. A formula characterized by reacting with .5 to 1.0 mol: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, each R^1 is the same or different, and at least 3
Polyisobutyl or polypropyl with 0 carbon atoms, R^2 is absent or formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (where m is 0 or an integer, R^1 is the same as above) , R^5 and ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ is the same as below), R^4 is hydrogen, methyl, or the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z is sulfur or methylene, R^1 is the same as above), each R^5 is the same or different, hydrogen, methyl, or a ▲ mathematical formula, chemical formula, table, etc. A group represented by ▼, each ▲ mathematical formula , chemical formulas, tables, etc. ▼ means the same or different amide group] Method for producing the compound shown.