JPH07278115A - Imidazoline compound, its production, dispersant and oil composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a novel imidazoline compound high in fat solubility, excellent in compatibility with various kinds of organic solvents, large in dispersibility in a small addition amount, and useful as an excellent dispersant capable of dispersing various inorganic or organic substances. CONSTITUTION:An imidazolidine compound is expressed by the formula [R is an olefinic (co)polymer chain having an average mol.wt. of >=600; X1, X2 each is H, alkyl which may have a polar group], e.g. a compound of the formula wherein R is a polyisobutenyl group having an average mol. wt. of 1100; X1, X2 each is an aminoethyl group. The compound of the formula is obtained by subjecting a vicinal dicarboxylic acid compound having an olefinic (co)polymer chain having an average mol. wt. of $600 and an ethylene diamine compound to a dehydrative cyclization reaction. An oil-soluble dispersant containing the imidazolidine compound as a main component is obtained. The compound is especially useful as an ash-free type cleansing dispersant. The dispersant is added to lubricants, polymers, coatings, inks, etc., and is useful as a dispersant for magnetic materials, EMI-corresponding coatings, moldings, conductive materials, flame-resistant materials, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel imidazoline compound having a specific imidazoline ring structure and a method for producing the same, and further a dispersant containing these compounds as a main component and an oil composition containing the dispersant. Regarding things.

[0002]

2. Description of the Related Art Generally, in a gasoline engine or a diesel engine, fuel or lubricating oil is deteriorated by oxygen or heat, and becomes oil-insoluble acid or sludge to contaminate a metal surface. Therefore, in order to prevent such fouling in the engine, a detergent-dispersant for removing generated acid and dispersing and solubilizing sludge is added. As the detergent-dispersant, a metal type has been conventionally used, but in recent years, particulate emission in the engine combustion chamber has become a problem, and an ashless type has been replaced. As the ashless-type detergent dispersant, polyalkenyl succinimide compounds have been widely used, but the cleaning action of the acid produced is weak and poses a problem.

Generally, as a cleaning action, it is necessary to have both the function of neutralizing the produced acid and the function of solubilizing the neutralized substance in oil. However, in the conventional studies, for example, (1) the base number of a compound has been increased by lowering the molecular weight of the compound or introducing a large number of basic groups in order to enhance the ability to neutralize with an acid. Therefore, the cleaning action is not improved, and (2) on the contrary, when the base number of the compound is lowered and the compatibility with oil is increased, the acid generated cannot be neutralized, so that the acid is neutralized and solubilized in oil. It was difficult to balance.

On the other hand, an imidazoline compound having a polar group such as amide or ester has been disclosed as an additive for oil. However, these have insufficient compatibility with the lubricating oil and cannot be used as a detergent-dispersant. For example, Japanese Patent Laid-Open No. 2-
In 196889 and JP-A-2-269194, N-imidazolinoethylalkenyl succinic acid ester or amide compounds are disclosed as corrosion inhibitors for fuel oils. However, although these compounds have acid neutralizing activity, they are inferior in solubilizing ability and cannot obtain a sufficient cleaning action. Further, JP-A-64-36692 discloses a low molecular weight imidazoline-based alkyl ester or amide compound having the ability to improve the lubricity of a lubricating oil, but it has almost no clean dispersion performance.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have conducted extensive studies for the purpose of providing an ashless type dispersant having an excellent cleaning action. As a result, the average molecular weight of 600 or more in which a specific imidazoline ring structure is introduced is obtained. It was found that the compound has a high ability to neutralize an acid and a high ability to be solubilized and has a high detergent dispersion property, and has completed the present invention.

[0006]

Thus, according to the present invention, (1) the general formula (A)

[Chemical 2] (In the formula, R represents an olefin (co) polymer chain having an average molecular weight of 600 or more, and X ₁ and X ₂ each independently represent hydrogen or an alkyl group which may have a polar group.). An imidazoline compound, (2) a method for producing an imidazoline compound, which comprises subjecting an adjacent dicarboxylic acid compound having an olefin (co) polymer chain having an average molecular weight of 600 or more to an ethylenediamine compound in a dehydration cyclization reaction,
There is provided an oil composition comprising (3) a dispersant containing the imidazoline compound of the present invention as a main component and (4) the dispersant of the present invention.

The details will be described below.

The imidazoline compound of the present invention has the general formula (A)

[Chemical 3] Can be expressed as

R in the formula is not particularly limited to a polymerization method and the like as long as it is a chain obtained by polymerizing or copolymerizing an olefinic monomer and having an average molecular weight of 600 or more. The olefinic monomer is not particularly limited as long as it is a compound having a polymerizable vinyl group, but the carbon number is usually 20 or less, preferably 2 to 10, more preferably 2 to 6, and among them, Alpha-olefins are particularly preferred. Specific examples include ethylene, propylene, n-butene, isobutene, n-pentene, isopentene, n-hexene, and the like, with ethylene, propylene and isobutene being preferred. These may be used alone or as a mixture. Moreover, you may add nonconjugated diolefins as needed.

The average molecular weight of R is at least 600 or more, preferably in the range of 800 to 5000, more preferably 1000 to 4000. If the molecular weight is too small, the compatibility with the lubricating oil is poor and the cleaning action is poor, and if it is too large, it may be difficult to dissolve depending on the type of oil.

X ₁ and X ₂ in the formula each independently represent a hydrogen atom or an alkyl group which may have a polar group.
Examples of the polar group include hydroxyl group, amino group, imino group, thiol group, ether group, thioether group, ester group, amide group, imide group and the general formula-((CH
₂ ) _a NH) _b —H (wherein a is an integer of 1 to 10 and b is 2)
Indicates an integer of -10. ), A polyalkylene polyamino group and the like are preferable, and a hydroxyl group, an amino group, an imino group, a polyalkylene polyamino group and the like are preferable, and a hydroxyl group, an amino group and an imino group are more preferable. The alkyl group which may have a polar group may be branched, and the carbon number is not particularly limited, but is usually 30 or less, preferably 1 to 18, and more preferably 2 to 9. .

The method for producing the imidazoline compound of the present invention is not particularly limited, and examples thereof include a method in which an adjacent dicarboxylic acid compound having an olefinic (co) polymer chain and an ethylenediamine compound are subjected to a dehydration cyclization reaction.

The adjacent dicarboxylic acid compound used in the reaction is not particularly limited as long as it has adjacent dicarboxylic acid structures and an average molecular weight of 600 or more. For example, US Pat. No. 3,018,250 and US Pat. Three
No. 024195, an olefinic (co) polymer such as polybutenyl succinic acid or an ethylene-propylene copolymer is thermally reacted with maleic anhydride, or a halogenated olefinic (co) polymer and an anhydride are used. Examples thereof include dicarboxylic acids, half esters and diesters obtained by reacting with maleic acid and then reacting with equimolar or more water or alcohol. The monomer and molecular weight of the olefin (co) polymer are the same as those of the above olefin (co) polymer chain.

Examples of the ethylenediamine compound used in the reaction include those represented by the general formula H ₂ NCH ₂ CH ₂ NHX (wherein X represents a hydrogen atom or an alkyl group which may have a polar group). Can be mentioned. Here, as the polar group, hydroxyl group, amino group, imino group, thiol group, ether group, thioether group, ester group, amide group, imide group and ethylenediaminoethyl group, triethylenetetraminoethyl group, tetraethylenepentaaminoethyl group Group, a polyalkylenepolyaminoalkyl group such as pentaethylenehexaaminoethyl group, and the like, preferably a hydroxyl group, an amino group, an imino group, a polyalkylenepolyaminoalkyl group, and more preferably a hydroxyl group, an amino group, an imino group and the like. . The alkyl group which may have a polar group may be branched and has a carbon number of usually 30 or less, preferably 1 to 18,
More preferably, it is in the range of 2 to 9.

Specific examples of the ethylenediamine compound include diethylenetriamine, N-aminopropylethylenediamine, N-hydroxyethylenediamine, and N-hydroxypropylethylenediamine as compounds having a polar group, and N-hydroxypropylethylenediamine as a compound having no polar group. Ethylethylenediamine, N-propylethylenediamine, N-butylethylenediamine, N-hexylethylenediamine, N-octylethylenediamine,
Examples thereof include N-tetradecylethylenediamine and N-hexadecylethylenediamine, but the invention is not limited thereto.

The reaction conditions between the adjacent dicarboxylic acid compound and the ethylenediamine compound are appropriately selected depending on the kind of the dicarboxylic acid compound used. Usually, the molar ratio of the dicarboxylic acid compound and the ethylenediamine compound is 1: 2.
The reaction temperature is 100-250.
C., preferably 150 to 230.degree. C., and the degree of vacuum is 1 to mercury column.
The reaction time is 50 mmHg, preferably 10 to 30 mmHg, and the reaction time is 0.5 to 24 hours, preferably 3 to 8 hours.
The reaction system may contain no solvent or a diluent such as 100 or 150 neutral light oil as a solvent, and may further contain an azeotropic dehydration solvent such as toluene or xylene, if necessary. Further, as a catalyst, a metal of Group II or IV of the periodic table, and oxides, hydroxides, chlorides, carbonates and organic carboxylates thereof of 0.0001 to 0 are used per 1 mol of the dicarboxylic acid component. You may add in 1 mol range. The obtained product is isolated by removing the solvent and unreacted ethylenediamine compound by vacuum distillation or the like, if necessary.

The imidazoline compound of the present invention can be reacted with one or more post-treatment reactants usually selected from the group consisting of boric acid (boronic acid), boron oxide, boron halide and boron ester. This treatment can significantly improve the thermal stability of the compound of the present invention,
The reaction of such a post-treatment agent is described, for example, in US Pat.
4025, wherein about 1-3 wt% boron compound,
Preferably boron is added, and the reaction mixture is heated and stirred at about 135-165 ° C. for 1-5 hours, followed by, if desired, stripping and filtration.

The imidazoline compound of the present invention thus obtained can be used as an excellent dispersant. Since the imidazoline compound has high fat solubility, it has excellent compatibility with various organic media, has a large dispersing effect with a small amount of addition, and can disperse various inorganic or organic substances.

Specific examples of the inorganic substance to be dispersed include, for example, metal as an inorganic reinforcing agent, clay, carbon black, calcium carbonate, barium sulfate, silica, mica,
Glass and asbestos; Metal compounds such as zinc, magnesium, lead and aluminum as reactive inorganic materials; Titanium dioxide, iron oxide, zinc chromate etc. as inorganic pigments; Zinc oxide, magnesium oxide as inorganic filler, Antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, tosonite, calcium sulfate, ammonium sulfate, calcium sulfite, talc, mica, glass balloons, glass beads, glass Fiber, calcium silicate, montmorillonite, bentonite, graphite, carbon fiber, molybdenum sulfide, boron fiber, silicon carbide fiber, zinc borate, barium metaborate, zirconium titanate, etc .; It is but, not limited to this.

As the organic substance, thioindigo,
Examples thereof include, but are not limited to, dioxazine, anhalaquinone, phthalocyanine, quinacridone, perylene, and β-naphthol organic pigment.

As the organic medium, benzene, toluene,
Various solvents such as hexane, cyclohexane, methyl ethyl ketone, acetone, methyl acetate; mineral oil base oils for various lubricating oils, α-olefin base oils, etc .; aromatic or naphthene base process oils; dioctyl phthalate, dibutyl Plasticizers such as phthalates; waxes, kerosene, etc.
Examples thereof include polymers such as rubber and plastic; vehicles such as alkyd resin, melanin resin, acrylic resin, urethane resin, and polyether resin; and paints and printing inks, but are not limited to these examples.

Since the dispersant of the present invention has an excellent detergency against acidic substances, it is particularly useful as a detergent dispersant for oil.

Examples of the oil added as the detergent-dispersant include fuel oil and lubricating oil, with lubricating oil being preferred. Examples of the lubricating oil include natural oils such as liquid petroleum, paraffin-based, naphthene-based or paraffin-naphthene-mixed solvent-treated or acid-treated mineral oils, oils having a lubricating oil viscosity derived from coal or Teiwa; Polyisobutylene,
Polymerization or copolymerization olefin such as ethylene-propylene copolymer, α-olefin; hydrocarbon oil such as alkylbenzene, polyphenyl, alkylated diphenyl ether and alkylated diphenyl sulfide and its derivatives, analogs and homologs, and halo-substituted carbon Hydrogen oil; alkylene oxide polymers such as polyethylene oxide; synthetic lubricating oils such as esters of dicarboxylic acids and various alcohols. Also, automatic transmission fluids, conduction shaft lubricants, gear lubricants, metalworking lubricants, pressure fluids and other lubricating oils and grease compositions and the like will benefit from the addition of the compounds of the present invention.

The amount of the (cleaning) dispersant used in the present invention varies depending on the substance to be dispersed, the medium thereof, the molecular weight of the dispersant, etc., but it is usually at least 0.005 with respect to the medium.
%, Preferably 0.05 to 50% by weight, more preferably 0.5 to 20% by weight.

The dispersant of the present invention can be used in combination with various ordinary additives depending on the intended use. Such additives include metallic detergents, corrosion and antioxidants, pour point depressants, viscosity index improvers, colorants, defoamers,
Examples thereof include wear resistance additives and wear modifiers.

The oil composition containing the dispersant of the present invention can be used for various purposes. For example, crankcase lubricants for spark-added and compression-added internal combustion engines such as automobile and truck engines, two-cycle engines, aircraft piston engines, marine and railway diesel engines, and the like can be mentioned. It can also be used as a lubricant for gas engines, stationary power engines, turbines and the like.

[0027]

EFFECTS OF THE INVENTION By carrying out the present invention, the cleaning action, which has been a drawback of ashless detergent dispersants, can be greatly improved, and it is excellent not obtained by conventional polyalkenyl succinimide compounds. A dispersant having the above properties and an oil composition containing the dispersant are obtained. This dispersant is added to lubricating oils (as detergent dispersants), polymers, paints, inks, etc., to bond magnets and magnetic recording (toners, disks,
Tape), magnetic materials such as magnetic fluids; paints and molded products compatible with EMI; conductive materials such as conductive / electrostatic composite materials; flame-retardant materials such as electric wires and building materials; pigments, catalysts, reaction inhibitors, laminated heat dissipation plates It is suitable as a dispersant for antifriction materials, dyes, FRTP, and the like, and an oil composition containing this dispersant can be used for fuel oils, lubricants, and the like.

[0028]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 A 3 liter four-necked flask equipped with a stirrer, a thermometer, a sample extraction tube, a condenser and a pressure gauge was charged with polyisobutenylsuccinic acid (HV-100 manufactured by Nippon Petrochemical Co., Ltd.).
M; 1045 g of average molecular weight 1100, 258 g of diethylenetriamine (hereinafter referred to as DETA) and 500 g of xylene were charged. At this time, the molar ratio of DETA to polybutenyl succinic acid was 2.5.

Next, this is sealed and the pressure is 400 mmH.
g at a temperature of 150 ° C. for 3 hours, then the temperature of the reaction system was raised, and the reaction was performed at a pressure of 30 mmHg and a temperature of 200 ° C. for 8 hours. The acid value at this time is 0.8,
It was confirmed that almost no acid component remained. After cooling
Unreacted DETA was removed by vacuum distillation, and the infrared spectrum of the reaction product was measured. Primary amino group (3300 cm
^-1 N-H stretching vibration) and imidazoline ring (1660c
m- ¹ imine band absorption), and almost no specific absorption of unreacted components was confirmed, so that this dehydration cyclization reaction proceeded almost completely, and the target compound, an imidazoline ring, was generally used. It was judged that a compound in which R in the formula (A) was a polyisobutenyl group having an average molecular weight of 1100 and X ₁ and X ₂ were aminoethyl groups was obtained. When the composition of the reaction product was analyzed by liquid chromatography (GPC; reverse phase partition mode), the content of the compound was 94%. This reaction product was designated as Compound A.

Example 2 N-hydroxyethylenediamine 2 instead of DETA
Example 1 was repeated except that 19 g was used, and R in the general formula (A) having an imidazoline ring had an average molecular weight of 1100.
A compound B in which the polyisobutenyl group, X ₁ and X ₂ are hydroxyethyl groups was obtained.

Example 3 Instead of polyisobutenyl succinic acid, a maleic acid adduct of ethylene-propylene copolymer (manufactured by Mitsui Petrochemical Co., Ltd.)
Lucant A-6020; average molecular weight 3000) 116
7 g, R was the same as in Example 1 except that 73 g of N-ethylethylenediamine was used instead of DETA, and R of the general formula (A) having an imidazoline ring had an average molecular weight of 3000.
To obtain a compound C in which the ethylene-propylene copolymer chain of, and X ₁ and X ₂ are ethyl groups.

Comparative Example 1 440 g of polyisobutenyl succinic anhydride (HV-100M; average molecular weight 1100) was placed in a 2 liter reactor equipped with a stirrer, a Dean-Stark apparatus and a temperature controller.
And xylene 408g. Then, 145 g of 1- (2-hydroxyethyl) -2-heptadecenyl imidazoline diluted in 143 g of xylene under stirring at room temperature.
Was dropped in 30 minutes. Then, the mixture was refluxed for 3 hours while removing water of reaction by azeotropic distillation. The amount of water recovered was 2.2 ml. Xylene was removed to obtain compound D.

Comparative Example 2 1- (2-Aminoethyl) -2-instead of 1- (2-hydroxyethyl) -2-heptadecenylimidazoline
Compound E was obtained in the same manner as in Comparative Example 1 except that 145 g of heptadecenyl imidazoline was added.

Example 4 Compounds A to E and a commercially available polybutenyl succinimide dispersant (average molecular weight 2100; hereinafter referred to as comparative agent).
1% to 100 neutral oil, 100 g of this oil
While stirring in a 200 ml beaker at 25 ° C, concentrated sulfuric acid was added dropwise from a microburet, and the amount of concentrated sulfuric acid added until the cloudiness started was measured. In Table 1, the sulfuric acid solubilizing ability is shown by an index with the concentrated sulfuric acid titer of the comparative agent being 100.

Example 5 The degree of sludge formation was compared by an ISO method oil deterioration test. Compounds A to E and the comparative agent were added to 200 ml of 150 neutral oil at 1% and vigorously stirred at 160 ° C. for 48 hours in the presence of copper. Next, this oil was dropped on about 1 ml of filter paper, and the degree of sludge formation was observed. The results are shown in Table 1.

Example 6 Compounds A to E and a comparative agent were added to hydrorefined paraffinic mineral oil in an amount of 1% to obtain a clean dispersion performance according to JIS K25.
According to No. 14, the lacquer adhesion to the varnish stick was evaluated. The results are shown in Table 1.

[0038]

[Table 1]

It can be seen from Table 1 that the compounds of the present invention have a sufficiently high concentrated sulfuric acid solubilizing ability, almost no sludge formation is observed, and an excellent clean dispersion with a very low degree of lacquer adhesion, as compared with the comparative agent. It can be seen that it shows sex. On the other hand, the compounds D and E used as comparative examples are ester or amide compounds having the same molecular weight as the compound of the present invention and an imidazoline structure, but they have a cleaning and dispersing performance which is not so different from that of the comparative agent. Not shown.

The embodiments of the present invention will be described below. (1) General formula

[Chemical 4] (In the formula, R represents an olefin (co) polymer chain having an average molecular weight of 600 or more, and X ₁ and X ₂ each independently represent a hydrogen atom or an alkyl group which may have a polar group.). Imidazoline compound. (2) The imidazoline compound according to (1), wherein the olefinic (co) polymer is a lower olefin (co) polymer. (3) The imidazoline compound according to (2), wherein the lower olefin is at least one selected from ethylene, propylene and isobutene. (4) The imidazoline compound according to any one of (1) to (3), wherein the polar group is a hydroxyl group, an amino group, an imino group or a polyalkylenepolyamino group. (5) The imidazoline compound according to any one of (1) to (4), which has an average molecular weight of 800 to 5,000. (6) The dehydration cyclization reaction of an adjacent dicarboxylic acid compound having an olefinic (co) polymer chain having an average molecular weight of 600 or more with an ethylenediamine compound is carried out, and the dehydration cyclization reaction is carried out. Process for producing imidazoline compound. (7) The ethylenediamine compound has the general formula H ₂ NCH ₂ CH
₂ NHX (In the formula, X represents a hydrogen atom or an alkyl group which may have a polar group.) The production method according to (6). (8) An oil-soluble dispersant containing the imidazoline compound according to any one of (1) to (5) as a main component. (9) The dispersant according to (8), wherein the dispersant is a detergent dispersant. (10) An oil composition containing the dispersant according to (8) or (9). (11) The oil composition according to (10), wherein the oil is a lubricating oil. (12) The oil composition according to (10) or (11), which contains at least 0.005% by weight of a dispersant.

Claims (4)

[Claims] 1. A compound represented by the general formula (A): (In the formula, R represents an olefin (co) polymer chain having an average molecular weight of 600 or more, and X ₁ and X ₂ each independently represent a hydrogen atom or an alkyl group which may have a polar group.). Imidazoline compound. 2. The method for producing an imidazoline compound according to claim 1, wherein an adjacent dicarboxylic acid compound having an olefin (co) polymer chain having an average molecular weight of 600 or more is subjected to a cyclodehydration reaction with an ethylenediamine compound. 3. An oil-soluble dispersant containing the imidazoline compound according to claim 1 as a main component. 4. An oil composition containing the dispersant according to claim 3.