JP2003252927A - Modified polyolefin, method for producing the same and method for producing polyolefin-substituted dicarboxylic acid derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyolefin which is useful as an intermediate to the clearing dispersant for a lubricating oil; a method for producing the same; a method for producing a polyolefin-substituted dicarboxylic acid derivative in a high yield which is essentially free from a halogen atom such as chlorine bringing about a harmful substance by burning to discharge; and a dispersant for a lubricating oil obtained through producing a polyolefin- substituted succinimide using the polyolefin-substituted dicarboxylic acid derivative, wherein the dispersant has a low halogen content and is excellent in dispersion performance. <P>SOLUTION: The method comprises reacting (A) a polyolefin with (C) a radical polymerization initiator in the presence of the carboxylic acid salt of a specific transition metal (B) to produce the modified polyolefin which is abundantly reactive with an unsaturated dicarboxylic acid derivative. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polyolefin, a method for producing the same, a polyolefin-substituted dicarboxylic acid derivative using the modified polyolefin, a method for producing a polyolefin-substituted succinimide, and its use.

More specifically, it has at least one carbon-carbon double bond on average per molecule, and contains from 0.01 to 1.0 carboxyl groups on average per molecule. And a modified polyolefin.

It also relates to a method for producing a modified polyolefin, which comprises reacting (A) a polyolefin with (B) a radical initiator in the presence of a transition metal carboxylate.

Further, the present invention relates to a method for obtaining a polyolefin-substituted dicarboxylic acid derivative by adding an unsaturated dicarboxylic acid or a derivative thereof via the modified polyolefin, and further to a polyolefin-substituted dicarboxylic acid obtained by reacting an amine with the polyolefin-substituted dicarboxylic acid. The present invention relates to a method for producing succinimide and its use as a dispersant for lubricating oil.

[0005]

2. Description of the Related Art Polyolefin-substituted dicarboxylic acid derivatives are widely used in applications such as resin plasticizers, emulsification aids, rust preventives and fuel oil additives. In particular, an ashless dispersant added for the purpose of solubilizing and dispersing a sludge precursor generated during operation in a part of automobile engine oil or driving oil to prevent engine troubles due to sludge accumulation. Polyolefin-substituted dicarboxylic acid derivatives are often used as.

At present, as the ashless dispersant, polyisobutenyl succinimide which is a polyisobutenyl succinic acid derivative, polyisobutenyl succinic acid ester, polyalkylene polyamine obtained by the Mannich reaction and the like are used. There is. Of these, polyisobutenyl succinimide, which is excellent in performance and cost, is mainly used industrially. Polyisobutenyl succinimide can be obtained by further reacting polyisobutenyl succinic anhydride (hereinafter referred to as PIBSA) produced by the reaction of polyisobutylene and maleic anhydride with polyalkyleneamine and the like.

The above PIBSA is described in US Pat. No. 3,36.
It can be obtained by a thermal reaction of polyisobutylene and maleic anhydride as in the method described in No. 1,673. However, it has been pointed out that when ordinary polyisobutylene is used in this method, the reaction rate is extremely slow and the reaction efficiency is low.

As an effective method for improving the reaction rate and reaction efficiency, Japanese Examined Patent Publication No. 6-96610, US Pat. No. 3,172,892, US Pat. No. 3,912,764
Discloses a method of adding maleic anhydride to polyisobutylene in the presence of chlorine. According to such a method of reacting in the presence of chlorine, the reaction rate and the reaction efficiency are significantly improved at a low cost, and therefore, it is a method which is currently widely used industrially.

On the other hand, according to the method using chlorine as described above, an organic chlorinated product is produced as a by-product during the reaction. The chlorine content contained in the product may reach as high as 0.5 to 1%, and such by-product organic chlorinated product causes environmental problems such as generation of harmful product during combustion. It has been pointed out. Therefore, in recent years, the amount of chlorine contained in products tends to be limited, and various methods for reducing the chlorine content have been studied.

As a method for reducing the amount of by-produced organic chlorinated compound, for example, a method of treating PIBSA with an iodine source or a bromine source has been proposed as described in JP-A-7-268102. This method can also reduce the amount of chlorine to some extent, but it complicates the manufacturing process, and it is difficult to completely eliminate residual chlorine.

Japanese Patent Laid-Open No. 7-11275, Special Table 2000-
No. 515176 discloses a method of producing PIBSA thermally from polyisobutylene having a high vinylidene content, thereby essentially freeing an organic chloride. However, this method is effective only for highly reactive polyisobutylene having a high vinylidene content obtained by a special production method, and generally used polyisobutylene having a low vinylidene content is low in reactivity and thermal. In such a reaction, it is not possible to add a sufficient amount of maleic anhydride to exhibit the function, and it is difficult to say that it is a general-purpose method.

Further, as a method using a reaction by a thermal reaction, JP-A-2-99598 describes the use of an ethylene / α-olefin copolymer substituted with a monounsaturated (di) carboxylic acid. .

The product of such a thermal reaction does not contain a chlorine-containing by-product, but on the other hand, it is necessary to carry out the reaction under high temperature conditions in order to compensate for the low reactivity. A tar-like byproduct is generated due to the physical polymer. Such a tar-like byproduct needs to be removed by a filtration step after the reaction, but since the product has a high viscosity, there are problems such as difficulty in filtration. There have been many studies on the control of by-products, but no effective method has been found yet.

As described above, in the method for producing a dispersant for lubricating oil using polyisobutylene which has been conventionally suitably used, it is essentially free of an organic chlorinated compound and is efficiently polyolefin-substituted dicarboxylic acid. No method has been found for producing the derivative.

[0015]

DISCLOSURE OF THE INVENTION The present invention solves the above environmental problems, is essentially chlorine-free, and is a modification capable of highly efficiently adding an unsaturated dicarboxylic acid to a polyolefin. It is intended to provide a polyolefin and a method for producing the same. Further, by using the method of the present invention, essentially free of organic chlorinated compounds that can be harmful components during combustion, applications such as lubricating oil additives, fuel oil additives, plasticizers, emulsification aids, rust inhibitors, etc. It is an object of the present invention to provide a method for efficiently producing a polyolefin-substituted dicarboxylic acid derivative, which is useful for Further, it is an object of the present invention to provide a polyolefin-substituted succinimide produced by using this method and a lubricant dispersant containing the polyolefin-substituted succinimide as a main component.

[0016]

Means for Solving the Problems As a result of intensive studies to solve the above problems, (A) polyolefin is reacted with (C) radical initiator in the presence of (B) transition metal carboxylate. It was found that a modified polyolefin having a high reactivity with an unsaturated dicarboxylic acid derivative can be obtained. That is, (A) polyolefin is (B)
By reacting with a radical initiator (C) in the presence of a transition metal carboxylate, it has at least one or more carbon-carbon double bonds on average per molecule, and 0.1 to 1.0 -OC on average
A modified polyolefin having a carboxyl group represented by OR (R represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms) is obtained. It has been found that the modified polyolefin easily reacts with an unsaturated dicarboxylic acid to produce a highly efficient chlorine-free polyolefin-substituted dicarboxylic acid derivative. Further, it was found that the polyolefin-substituted succinimide obtained by reacting the polyolefin-substituted dicarboxylic acid derivative with an amine contains essentially no chlorine and can be used as a dispersant for lubricating oil having excellent dispersibility. .

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The modified polyolefin of the present invention, a method for producing the same, and a method for producing a polyolefin-substituted dicarboxylic acid derivative will be specifically described below.

Modified Polyolefin The modified polyolefin of the present invention has at least one carbon-carbon double bond on average per molecule, and has an average of 0.01 to 1.0 per molecule. -O
It contains a carboxyl group represented by COR (R represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms). The polyolefin used as the starting material in the present invention is generally a polymer of olefinic monomers having 2 to 20 carbon atoms, and such olefinic monomers include ethylene, propylene, 1-butene, isobutene, 1
-Hexene, 4-methyl-1-pentene, 3-methyl-
Examples thereof include 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-octadecene, 1-eicosene, and radical polymerization using a monomer such as the above as a radical initiator, and a Ziegler-Natta catalyst. It can be obtained by copolymerizing a single monomer or two or more kinds of monomers using a conventionally known method such as the coordination polymerization used and the cationic polymerization using a Lewis acid.

The above-mentioned polymers can be used as the polyolefin as the starting material of the present invention, but polyethylene, polypropylene, polybutene, polyisobutylene, ethylene / α-olefin copolymers are preferably used, and more preferably. Is polypropylene, polyisobutylene, or ethylene / α-olefin copolymer. As the ethylene / α-olefin copolymer, a copolymer of ethylene and at least one α-olefin having 3 to 20 carbon atoms is used, and an ethylene / propylene copolymer is particularly preferably used. In the above polymers, butadiene, isoprene, 1,3-pentadiene,
Conjugated dienes such as 1,3-hexadiene and non-conjugated diene components such as 1,4-pentadiene, 1,4-hexadiene and 1,5-hexadiene may be contained in an amount of about 0 to 5 mol%.

The molecular weight of the modified polyolefin of the present invention is not particularly limited, but the number average molecular weight (Mn) is preferably in the range of 300 to 100,000, more preferably 500 to 10,000. Such a number average molecular weight can be measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard substance.

The amount of carbon-carbon unsaturated bond contained in the modified polyolefin of the present invention is 1 on average per molecule.
The number is not less than 1.1, preferably not less than 1.1, more preferably not less than 1.2. The content of such a carbon-carbon unsaturated bond can be measured by a titration method, ¹³ C-NMR or the like.

The carboxyl group contained in the modified polyolefin of the present invention has the chemical formula [-O-C (= O)].
-R], R is hydrogen, and has 1 carbon atom.
To 30 aliphatic hydrocarbon groups or 6 to 3 carbon atoms
It is an aromatic hydrocarbon group of 0. Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, te.
a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as rt-butyl, neopentyl and n-hexyl; and having 2 to 30 carbon atoms such as vinyl, allyl and isopropenyl. , Preferably a linear or branched alkenyl group having 2 to 20; an alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl; cyclopropyl, cyclobutyl. , Cyclopentyl, cyclohexyl, adamantyl and the like have 3 to 30 carbon atoms, preferably 3 to 2 carbon atoms.
There may be mentioned 0 cyclic saturated hydrocarbon groups.

As the aromatic hydrocarbon group, phenyl, benzyl, naphthyl, biphenyl, terphenyl,
6 carbon atoms such as phenanthryl and anthracenyl
To 30, preferably 6 to 20 aryl groups; tolyl, i
so-propylphenyl, tert-butylphenyl,
Examples thereof include alkyl-substituted aryl groups such as dimethylphenyl and di-tert-butylphenyl.
Further, in the above hydrocarbon group, a hydrogen atom may be substituted with a halogen, and for example, a halogenated carbon atom having 3 to 30, preferably 3 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. A hydrogen group is mentioned. Of these, especially methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, phenyl, naphthyl, biphenyl and the like are preferable, and methyl group and phenyl group are particularly preferable.

The average content of the carboxyl group represented by [-O-C (= O) -R] contained in the modified polyolefin of the present invention per molecule is preferably 0.01 to.
1.0, more preferably 0.03 to 0.8,
More preferably, it is 0.05 to 0.5. The content of such a carboxyl group is measured by infrared spectroscopy, ¹³ C-NMR.
And the like.

Method for Producing Modified Polyolefin The method for producing a modified polyolefin of the present invention comprises reacting (A) a polyolefin with (C) a radical initiator in the presence of (B) a transition metal carboxylate.

As the polyolefin (A) in the present invention, various polyolefins described in the preceding paragraph can be used, and particularly polyethylene, polypropylene, polybutene,
Polyisobutylene and ethylene / α-olefin copolymer are preferably used.

In the transition metal carboxylate (B) of the present invention, the type of transition metal is not particularly limited,
Periodic table Group 7-11 transition metals are preferred, and such transition metals include Ti, Zr, V, Cr, Mo, W, Mn,
Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, A
Examples thereof include g and Au, and Cu is particularly preferably used. The valence of the transition metal is not particularly limited and is about 1-8, preferably about 1-6.

The carboxylic acid forming the carboxylic acid salt of the transition metal (B) is not particularly limited, but for example, acetic acid, propionic acid, pivalic acid, oxalic acid, malonic acid, lactic acid, malic acid, citric acid, Tartaric acid, benzoic acid,
Examples thereof include toluic acid, salicylic acid, phthalic acid and nicotinic acid, and particularly acetate and benzoate are preferably used.

The (B) transition metal carboxylate salt in the present invention may be used alone or in combination of two or more thereof, and the transition metal carboxylate salt as described above may be directly added at the initial stage of the reaction. Alternatively, it may be formed in the system during the reaction.

(B) A method of forming a carboxylic acid salt of a transition metal in the system during the reaction includes acyloxy radicals [.O-] by decomposing organic peroxides such as peroxyesters in the presence of various transition metal compounds. C (= O) -R]
And a method of reacting an acyloxy radical [.O-C (= O) -R] generated by reacting a carboxylic acid with a radical initiator having a hydrogen abstraction property. .

The various transition metal compounds used here are not particularly limited, but as described above, the transition metal compounds of Groups 7 to 11 of the Periodic Table are preferably used, and chlorides, bromides, iodides and the like of these transition metals are used. Halides; inorganic acid salts such as nitric acid, carbonic acid, boric acid, phosphoric acid; formic acid, acetic acid, propionic acid, pivalic acid, oxalic acid, malonic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, toluic acid, Organic acid salts such as salicylic acid, phthalic acid, nicotinic acid; metal oxo acid salts such as vanadic acid, stannic acid, antimonic acid, bismuth acid, molybdic acid, tungstic acid; oxides; hydroxides; methoxides, ethoxides, etc. Examples thereof include alkoxides; salts of phenols such as phenoxide; complexes of these metal compounds with a coordinating compound. The valence of the transition metal compound is not particularly limited,
It is about 1 to 8, preferably about 1 to 6.

Of these, copper compounds are preferably used, and particularly copper (I) oxide, copper (I) bromide, copper (I) acetate, etc. can be preferably used, and these can be used alone or in combination of two or more. Can be used in combination.

In the method of forming a carboxylate of a transition metal in the system by reacting the above transition metal compound with an acyloxy radical, examples of the organic peroxide that forms an acyloxy radical include tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyphenyl acetate, tert-butyl peroxyisobutyrate,
tert-butylperoxy-sec-octoate,
tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, t
Peroxyesters such as ert-butylperoxylaurate, tert-butylperoxyisophthalate, cumylperoxyneodecanoate; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, etc. Diacyl peroxide and the like can be exemplified, and preferably te
rt-Butyl peroxyacetate is used. These organic peroxides may be used alone or in combination of two or more.

In the method of forming a carboxylate of a transition metal by reacting the above transition metal compound with an acyloxy radical, an acyloxy radical is generated by reacting a carboxylic acid with a radical initiator having hydrogen abstraction. In this case, as the carboxylic acid,
For example, acetic acid, propionic acid, pivalic acid, oxalic acid,
Malonic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, toluic acid, salicylic acid, phthalic acid, nicotinic acid and the like can be exemplified, and acetic acid, benzoic acid and the like can be preferably used. These carboxylic acids may be used alone or in combination of two or more.

The radical initiator used in the case of producing an acyloxy radical by reacting a carboxylic acid with a hydrogen-abstracting radical initiator is not particularly limited as long as it is a hydrogen-abstracting initiator. However, organic peroxides and organic peresters are preferably used, for example, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperoxyacetate, ter
t-butyl peroxybenzoate, tert-butyl peroxyphenyl acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-
sec-octoate, tert-butylperoxypivalate, cumylperoxypivalate, di-tert
-Butyl peroxyisophthalate and the like can be exemplified, and di-tert-butyl peroxide is particularly preferably used. These organic peroxides can be used alone or in combination of two or more.

The amount of the (B) transition metal carboxylate used in the present invention is not particularly limited, but is preferably 0.0001 mol% to 120 mol%, particularly preferably 0.001 mol% to 100 mol%. Is.

There are no particular restrictions on the type of radical initiator (C) used in the method for producing a modified polyolefin of the present invention, and organic peroxides, inorganic peroxides, azo compounds,
Oxygen or the like can be used, and organic peroxide is preferably used. In particular, organic peroxides and organic peresters are preferably used, for example, benzoyl peroxide,
Dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl Peroxyacetate,
tert-butyl peroxybenzoate, tert-
Butyl peroxyphenyl acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-sec-octoate, tert-butyl peroxypivalate, cumyl peroxypivalate, di-t
Examples thereof include ert-butyl peroxyisophthalate, and these can be used alone or in combination of two or more kinds.

When a peroxy ester is used as a radical initiator, as described above, it is possible to simultaneously cause the hydrogen abstraction reaction of the polyolefin and the formation of the carboxylate salt of the transition metal compound which is the catalytically active component. The transition metal compound used in such a case does not need to be a carboxylic acid salt at the time of charging the reaction, and various transition metal compounds as described above can be used.

Such a peroxyester is t
tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butylperoxyphenylacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-sec-
Octoate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, t
ert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisophthalate, cumylperoxyneodecanoate and the like can be exemplified, and especially tert-butylperoxy. Acetate, te
rt-Butyl peroxybenzoate etc. can be used conveniently, and these can also be used individually or in combination of 2 or more types.

The amount of the radical initiator (C) used in the present invention is not particularly limited, but preferably 0.1 equivalent to
It is in the range of 5 equivalents, more preferably 0.5 equivalents to 3 equivalents, and particularly preferably 0.8 equivalents to 2 equivalents.

The reaction temperature in the method for producing the modified polyolefin of the present invention is not particularly limited, but is usually 25 ° C to 25 ° C.
0 ° C, preferably 50 ° C to 200 ° C, particularly preferably 8
It is in the range of 0 ° C to 180 ° C.

The reaction time in the method for producing the modified polyolefin of the present invention is not particularly limited, but is usually 0.5.
The time is from 20 hours to 20 hours, preferably from 1 hour to 10 hours, more preferably from 1 hour to 5 hours.

Method for Producing Polyolefin-Substituted Unsaturated Carboxylic Acid The method for producing a polyolefin-substituted dicarboxylic acid derivative of the present invention is a method of adding an unsaturated dicarboxylic acid or its derivative to a polyolefin, and at least (i) (A) a polyolefin. In the presence of (B) a transition metal carboxylate with a radical initiator (C), and (ii) adding unsaturated dicarboxylic acid to the product of step (i) and reacting.

The reaction [step (i)] of the first step in the present invention is a step of forming the modified polyolefin described above, and the details of this step are as described above. The second step reaction in the present invention is a step of adding an unsaturated dicarboxylic acid derivative to the product of step (i) to form a polyolefin-substituted dicarboxylic acid derivative.
The reaction can be carried out thermally, and the product of step (i) and the unsaturated dicarboxylic acid derivative are treated at 60 ° C to 250 ° C.
℃, preferably 80 to 220 ℃, more preferably 10
The reaction is carried out at a temperature of 0 ° C to 200 ° C. Usually, the reaction is carried out in the absence of a catalyst, but the reaction can also be carried out by adding a catalyst such as an organic peroxide or a Lewis acid.

The reaction time is usually 0.5 to 20 hours,
It is preferably 1 to 15 hours, more preferably 2 to 10 hours.

This reaction is usually carried out without a solvent, but it may be carried out in a suitable reaction solvent in some cases. Such reaction solvents include toluene, xylene, petroleum naphtha,
Mineral oil etc. can be illustrated.

Steps (i) and (ii) may be carried out continuously or may be carried out through a filtration step for removing the catalyst. When passing through the filtration step, it may be diluted with an organic solvent such as hexane, toluene, xylene, petroleum naphtha, mineral oil or the like for the purpose of reducing the viscosity. These diluents may be removed after filtration or may be left as a reaction solvent in the reaction of step (ii).

Examples of the unsaturated dicarboxylic acid derivative used in the polyolefin-substituted dicarboxylic acid derivative of the present invention include maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2,2].
1] Unsaturated dicarboxylic acids such as hept-2-ene-5,6-dicarboxylic acid; maleic anhydride, itaconic anhydride,
Unsaturated dicarboxylic acid anhydrides such as citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride; methyl maleate, diethyl fumarate, itaconic acid Dimethyl, diethyl citraconic acid, dimethyl tetrahydrophthalate,
Examples thereof include esters of unsaturated dicarboxylic acids such as dimethyl unsaturated dicarboxylic acid such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid,
Maleic anhydride is particularly preferably used.

The amount of the unsaturated dicarboxylic acid derivative used in step (ii) of the present invention is not particularly limited, but it is usually 1 to 5 equivalents, preferably 1.1 to 3 equivalents, relative to the modified polyolefin. More preferably 1.2
Is in the range of to 2 equivalents.

In the method for producing a polyolefin-substituted dicarboxylic acid derivative of the present invention, a volatile component distilling step for removing residual monomers and the like after the reaction of step (ii) and a filtration step for removing solids are carried out. In the case of filtration, it may be diluted with an organic solvent such as hexane, toluene, xylene, petroleum naphtha, mineral oil or the like for the purpose of reducing the viscosity during filtration. The reaction can also be carried out in a solvent using these diluents as a reaction solvent.

Method for producing polyolefin-substituted succinimide In the above-mentioned polyolefin-substituted dicarboxylic acid derivative,
When maleic anhydride is used as the unsaturated dicarboxylic acid derivative, it is further reacted with an amine, an alcohol, a reactive metal or a reactive metal compound by a known method described in US Pat. No. 4,234,435. can do. Amination, imidization, esterification, and metal chlorides of the thus obtained polyolefin-substituted dicarboxylic acid are halogen-free dispersants for lubricating oils, as well as resin plasticizers, emulsification aids, rust inhibitors, and fuels. It can be suitably used as an oil additive.

The polyolefin-substituted succinimide, which is often used as a dispersant for lubricating oils, is obtained by thermally reacting the polyolefin-substituted succinic acid obtained by the present invention with a polyamine. The polyamine is preferably an aliphatic, cycloaliphatic or heterocyclic polyamine having 3 to 25 carbon atoms.

Examples of the aliphatic polyamine used in the present invention include polyethyleneamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, as well as propylenediamine, trimethylenediamine, tripropylenetetramine and dimethylaminopropylamine. And so on.

Examples of cycloaliphatic polyamines include:
1,4-diaminocyclohexane and the like are preferably used.

Examples of the heterocyclic polyamine include tetrapyridine, dihydropyridine, piperidine,
Azetidine, pyrrole, piperazine, dihydroxypyridine, etc. can be illustrated.

The reaction of the polyolefin-substituted succinic anhydride with the above polyamine in the present invention is usually carried out under a high temperature condition of 100 ° C. or higher, preferably 120 ° C. to 300 ° C., more preferably 150 ° C. to 220 ° C. . The reaction time is usually 1 hour to 20 hours, preferably 2 hours to 1
5 hours.

During the above reaction, it is preferable to carry out while removing water generated during the reaction, and in that case, the reaction may be carried out under reduced pressure for the purpose of dehydration.

The polyolefin-substituted succinimide obtained by the above method can be preferably used as a dispersant for lubricating oil.

[0059]

EXAMPLES The present invention will now be described in detail with reference to Examples, but the scope of the present invention is not limited by the following.

The number average molecular weight (M
n) is an average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) using tetrahydrofuran (hereinafter THF) as a developing solvent. The average amount of carbon-carbon double bonds and carboxyl groups contained in one molecule of polyolefin was determined by ¹³ C-NMR analysis, and the number of C = C bond carbon atoms and C = O bond per 100 carbon atoms was determined. Calculated as carbon number,
Each was calculated by the following formula.

[Formula 1] [C = C unsaturated bond amount] = Mn / monomer unit constituting the polymer
Molecular weight * Number of carbon atoms contained in monomer unit * Per 100C
Unsaturated bond carbon number / 2/100

[Formula 2] [amount of carboxyl group] = Mn / content of monomer units constituting the polymer
Molecular weight * Number of carbon atoms contained in monomer unit * Cal per 100C
Bonyl carbon number / 100

The content of unreacted polyolefin in the polyolefin-substituted dicarboxylic acid derivative of the present invention was calculated by the following method.

The unreacted polyolefin component and the polar group-containing component were separated by column chromatography (filler: silica gel, Wakogel C-300) (developing solvent: hexane → THF) and calculated from the weight of each fraction by the following formula. .

[Equation 3] [Content of unreacted polyolefin] = hexane developing component weight / total
Weight (hexane developing component amount + THF developing component amount)

[Synthesis of Modified Polyolefin] Example A Polyisobutylene (number average molecular weight: Mn = 2,430,
Vinylidene content at the molecular end = 5%, chlorine content: 10 pp
m) 50 g (20.6 mmol) was placed in a 300 ml separable flask and the inside of the system was sufficiently purged with nitrogen, and then 0.674 g (4.70 mm) of copper (I) bromide [Cu ^I Br]
ol) was added and the mixture was heated to 140 ° C. with stirring. After the temperature was raised, 7.48 g (2% of tert-butyl peroxyacetate solution (manufactured by NOF CORPORATION: Perbutyl A 50% product))
8.3 mmol) was added dropwise over 1 hour. After completion of the dropping, the mixture was further reacted at 140 ° C. for 2 hours, cooled to room temperature, diluted 2-fold with hexane, and filtered through a 3 μm filter to remove solids, and then the solvent was distilled off 49 0.1 g of product was obtained. As a result of IR analysis, a carbonyl absorption band (1744 cm ⁻¹ ) due to an acetyl group was observed, and it was confirmed that an acetyl group was introduced into the product (FIG. 1). The other analysis results are shown in Table 1.

Example B The reaction was performed in the same manner as in Example A except that the reaction temperature was changed to 120 ° C. in Example A to obtain 49.3 g of a product. The analysis results of the product are shown in Table 1.

Example C In Example A, copper (I) bromide was replaced with copper (I) oxide [Cu ^I ₂
O] was reacted in the same manner as in Example A except that the amount was changed to 0.672 g (4.70 mmol) to obtain 49.5 g of a product. The analysis results of the product are shown in Table 1.

Example D The reaction was carried out in the same manner as in Example C except that the amount of copper (I) oxide [Cu ^I ₂ O] added in Example C was changed to 0.0336 g (0.23 mmol). Obtained 0.8 g of product. The analysis results of the product are shown in Table 1.

Example E Copper (I) bromide was added to copper (I) acetate [Cu ^I
(OCOCH ₃ )] 0.576 g (4.70 mmol)
Reaction was carried out in the same manner as in Example A, except that
8.9 g of product was obtained. The analysis results of the product are shown in Table 1.

Example F In Example A, copper (I) bromide was replaced with copper (II) acetate monohydrate [Cu ^II (OCOCH ₃ ) ₂ .H ₂ O] (5.62 g, 2).
8.1 mmol) and 2.06 g (14.1 mm) of tert-butyl peroxyacetate in di-tert-butyl peroxide (Nippon Yushi Co., Ltd .: Perbutyl D).
The reaction was performed in the same manner as in Example A except that the reaction temperature was changed to 150 ° C., and 49.0 g of a product was obtained. The analysis results of the product are shown in Table 1.

Example G In Example D, tert-butyl peroxyacetate was added to 4.14 g of di-tert-butyl peroxide.
(28.3 mmol), the reaction temperature was set to 150 ° C., and 1.41 g of acetic acid (manufactured by Wako Pure Chemical Industries: special grade) (23.
The reaction was performed in the same manner as in Example D except that 5 mmol) was added dropwise over 1 hour at the same time as di-tert-butyl peroxide to obtain 49.1 g of a product. The analysis results of the product are shown in Table 1.

Example H Acetic acid in Example G was replaced with 2.87 g (23.5 g) of benzoic acid.
mmol), and the reaction was carried out in the same manner as in Example G to obtain 48.7 g of a product. The analysis results of the product are shown in Table 1.

Comparative Example A The reaction was performed in the same manner as in Example A except that copper (I) bromide was not used in Example A. The analysis results of the product are shown in Table 1.

Comparative Example B The reaction was performed in the same manner as in Example G except that acetic acid was not used in Example G. Table 1 shows the product analysis results.
It was shown to.

[0076]

[Table 1]

* 1: Carboxylate is an acetate produced in the reaction system by the reaction of acetyl radical generated by decomposition of tert-butyl peroxyacetate with a copper compound * 2: Carboxylate is carboxylic acid and di- Carboxylic acid salt formed in the reaction system by reaction of acyloxy radical generated by reaction with tert-butyl peroxyde and copper oxide

[Synthesis of Polyolefin Substituted Succinic Anhydride] Example 1 30 g of modified polyisobutylene obtained in Example A
Was placed in a 300 ml separable flask and the inside of the system was sufficiently purged with nitrogen, then 4.21 g (42.9 mmol) of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to 200 ° C. with stirring. After reacting at 200 ° C. for 10 hours, volatile components such as residual maleic anhydride were distilled off under reduced pressure. Cool to room temperature, dilute twice with hexane, and
After removing the solid content by filtration using a μm filter, the solvent was distilled off to obtain 30.5 g of polyisobutylene-substituted succinic anhydride. As a result of the IR analysis, the carbonyl absorption band (1786 cm ^-1 , due to the succinic anhydride group,
1861 cm ⁻¹ ) was observed, confirming that polyisobutylene-substituted succinic anhydride was produced (FIG. 2). The other analysis results are shown in Table 2.

Example 2 The reaction was performed in the same manner as in Example 1 except that the modified polyisobutylene obtained in Example D was used to obtain 30.4 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Example 3 Using the modified polyisobutylene obtained according to Example D,
The amount of maleic anhydride added is 2.76 g (28.2 mmo
Reaction was performed in the same manner as in Example 1 except that the above was changed to 3).
0.6 g of polyisobutylene-substituted succinic anhydride was obtained.
The analysis results of the product are shown in Table 2.

Example 4 The reaction was performed in the same manner as in Example 1 except that the modified polyisobutylene obtained in Example E was used to obtain 30.1 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Example 5 The reaction was performed in the same manner as in Example 1 except that the modified polyisobutylene obtained in Example G was used to obtain 30.1 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Example 6 The reaction was performed in the same manner as in Example 1 except that the modified polyisobutylene obtained in Example H was used to obtain 29.9 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Example 7 After carrying out the reaction of Example E, the volatile matter was distilled off under reduced pressure without isolation of the modified polyolefin by filtration, and then 6.91 g (70.5 mmol) of maleic anhydride was added. I put it in. The temperature inside the reactor was raised to 180 ° C. and the reaction was carried out for 4 hours. After the reaction, dilute twice with hexane and add 3μ
The solid content was removed by filtration using an m filter, and then the solvent was distilled off to obtain 47.3 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Comparative Example 1 Unmodified polyisobutylene (number average molecular weight: Mn = 2
430, vinylidene content at the terminal of the molecule = 5%) and the reaction was carried out in the same manner as in Example 1 except that the reaction time was 20 hours, to obtain 28.5 g of polyisobutylene-substituted succinic anhydride. The analysis results of the product are shown in Table 2.

Comparative Example 2 Unmodified polyisobutylene (number average molecular weight: Mn = 2
430, vinylidene content at the molecular end = 5%) 3 g of 30 g
It was placed in a 00 ml separable flask and the inside of the system was sufficiently purged with nitrogen, and then heated to 160 ° C. with stirring.
After heating, 2.4 g (24.5 mmol) of maleic anhydride
And 0.48 g (3.3 mmol) of di-tert-butyl peroxide (manufactured by NOF CORPORATION: perbutyl D)
The radical grafting reaction was carried out by dropping over time. After reacting for an additional hour, volatile components such as residual maleic anhydride were distilled off under reduced pressure. After cooling to room temperature, the mixture was diluted twice with hexane and filtered through a 3 μm filter to remove solids, and then the solvent was distilled off to obtain 30.8 g of polyisobutylene-substituted succinic anhydride. The analysis results are shown in Table 2.

[0087]

[Table 2]

* 1: IR relative intensity ratio of carbonyl absorption band due to succinic anhydride group From the above results, the content of unmodified polyisobutylene by the method of the present invention is low, and the polyolefin-substituted succinic anhydride having a low chlorine content is highly efficient. It is clear that it is possible to produce derivatives. [Synthesis of polyolefin-substituted succinimide]

Example 8 20 g of the polyisobutylene-substituted succinic anhydride obtained in Example 1 was added to 100 ml with a Dean Stark attached.
After putting in a separable flask and thoroughly purging the inside of the system with nitrogen, the inside of the reactor was heated to 180 ° C. with stirring.
After the temperature was raised, 1.5 g (1.2 equivalents) of triethylenetetramine was added dropwise over 30 minutes, and the reaction was carried out at 180 ° C. for 5 hours while removing water. The total acid value of the polyisobutylene-substituted succinimide obtained after the reaction was 3.4 mgK.
OH / g, nitrogen content 2.3%, chlorine content 10ppm
It was below.

Example 9 1.5 g of a mixture of 1 part by weight of carbon black and 2 parts by weight of liquid paraffin, 1 g of the polyisobutylene-substituted succinimide obtained in Example 8 and 97.5 g of kerosene were mixed to obtain a 100 ml stopper. Put it in the attached glass cylinder,
The carbon black sedimentation situation is compared.
The dispersibility was evaluated by the dot method. The results are shown in Table 3.

Comparative Example 3 Dispersibility was evaluated in the same manner as in Example 9 except that 1 g of unmodified polyisobutylene was used instead of the polyisobutylene-substituted succinimide. The results are shown in Table 3.

[0092]

[Table 3]

From the results of this example, it is apparent that the polyolefin-substituted succinimide obtained according to the present invention has a low chlorine content and is useful as a dispersant for lubricating oil having excellent dispersibility.

[0094]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a modified polyolefin useful as a detergent-dispersant intermediate for lubricating oil and a method for producing the same. Further, according to the present invention, it is possible to provide a method for highly efficiently producing a polyolefin-substituted dicarboxylic acid derivative which does not essentially contain a halogen element such as chlorine, which causes emission of harmful substances during combustion. Furthermore, by producing a polyolefin-substituted succinimide using the polyolefin-substituted dicarboxylic acid derivative obtained by the method of the present invention, it is possible to provide a dispersant for lubricating oil having a low halogen content and excellent partial acidity.

[Brief description of drawings]

1 IR of the modified polyolefin product of Example A.
Chert (carbonyl absorption band due to acetyl group, 1
744 cm ^-1 )

FIG. 2 is an IR chart of the polyolefin-substituted succinic anhydride product of Example 1 (carbonyl absorption band due to succinic anhydride group, 1786 cm ⁻¹ , 1861 cm ⁻¹ ).

Continued front page    F term (reference) 4H104 BF03C JA01 LA02                 4J100 AA02P AA02Q AA03P AA03Q                       AA04P AA04Q AA06P AA06Q                       AA15Q AA16Q AA17Q AA18Q                       AA19Q AA21Q BA16H BA20H                       BA27H CA01 CA04 CA31                       DA01 DA28 HA01 HA45 HA57                       HA61 HA62 HB29 HC27 HC29                       HC30 HC36 HC46 HE17 JA15

Claims (21)

[Claims] 1. An average of at least one carbon-carbon double bond per molecule, and an average of 0.01 to 1.0 -OCOR (where R is A modified polyolefin, which contains a carboxyl group represented by a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms. 2. The (A) polyolefin before modification of the modified polyolefin containing a carboxyl group is polyethylene, polypropylene, polybutene,
A polyolefin selected from the group consisting of polyisobutylene and ethylene / α-olefin copolymers.
The modified polyolefin described in. 3. A number average molecular weight (Mn) of 500 to 1
The modified polyolefin according to claim 1 or 2, wherein the modified polyolefin is 10,000. 4. The modified polyolefin according to claim 1, wherein in the carboxyl group represented by —OCOR, R is a methyl group or a phenyl group. 5. A method for producing a modified polyolefin, which comprises reacting the (A) polyolefin with a (B) transition metal carboxylate in the presence of a (C) radical initiator. 6. The method for producing a modified polyolefin according to claim 5, wherein the transition metal carboxylate (B) is a transition metal carboxylate of Group 7 to 11 of the periodic table. 7. The method for producing a modified polyolefin according to claim 5, wherein the carboxylic acid salt of the transition metal (B) is a carboxylic acid salt of a copper compound. 8. (C) t-Butylperoxy in the presence of at least one copper compound selected from the group consisting of (A) polyolefin (B) copper acetate (I), copper bromide (I) and copper (I) oxide. A method for producing a modified polyolefin, which comprises reacting with acetate. 9. (A) polyolefin, (B) (B-
1) At least one carboxylic acid of (B-2) acetic acid or benzoic acid in the presence of at least one copper compound of copper (I) acetate (I) copper bromide and copper (I) oxide; C) A method for producing a modified polyolefin, which comprises reacting with a radical initiator. 10. The (A) polyolefin is polyethylene, polypropylene, polybutene, polyisobutylene,
A polyolefin selected from the group consisting of ethylene / α-olefin copolymers.
10. The method for producing a modified polyolefin according to any of 9. 11. The method for producing a modified polyolefin according to claim 5, wherein the number average molecular weight (Mn) is 500 to 10,000. 12. A method for adding an unsaturated dicarboxylic acid or a derivative thereof to (A) a polyolefin, which comprises: (I) (A) a polyolefin; and (B) a transition metal carboxylate in the presence of (C). A process for producing a polyolefin-substituted dicarboxylic acid derivative, which comprises the steps of reacting with a radical initiator and (ii) adding an unsaturated dicarboxylic acid to the product of step (i) and reacting it. 13. The polyolefin-substituted dicarbonate according to claim 12, wherein in step (i), the (B) transition metal carboxylate is a transition metal carboxylate of Group 7 to 11 of the periodic table. Method for producing acid derivative. 14. The method for producing a polyolefin-substituted dicarboxylic acid derivative according to claim 12 or 13, wherein in step (i), the (B) transition metal carboxylate is a copper compound carboxylate. Method. 15. A method for adding an unsaturated dicarboxylic acid or a derivative thereof to a polyolefin, which comprises: (B) copper acetate (I), copper (I) bromide, copper oxide; Reacting with (C) t-butylperoxyacetate in the presence of at least one copper compound of (I), and (ii) step (i)
A process for producing a polyolefin-substituted dicarboxylic acid derivative, which comprises the step of adding an unsaturated dicarboxylic acid to the product and reacting the product. 16. A method for adding an unsaturated dicarboxylic acid or a derivative thereof to a polyolefin, comprising at least (i) (A) polyolefin and (B) (B-
1) In the presence of at least one copper compound of copper (I) acetate, copper (I) bromide, and copper (I) oxide, (B-2) at least one carboxylic acid of acetic acid or benzoic acid;
(C) reacting with a radical initiator, and (ii)
A process for producing a polyolefin-substituted dicarboxylic acid derivative, which comprises the step of adding an unsaturated dicarboxylic acid to the product of step (i) and reacting it. 17. The method of claims 12-16, wherein the reaction of step (ii) is the reaction of the product of step (i) with maleic anhydride.
5. The method for producing a polyolefin-substituted maleic acid derivative according to any one of 1. 18. A polyolefin selected from the group consisting of polyethylene, polypropylene, polybutene, polyisobutylene and ethylene / α-olefin copolymers, wherein the polyolefin is a polyolefin.
A method for producing the polyolefin-substituted dicarboxylic acid derivative according to any one of 1. 19. The number-average molecular weight (Mn) is 500 to 10,000, and the molecular weight is 12 to 18.
A method for producing the polyolefin-substituted dicarboxylic acid derivative according to any one of 1. 20. A method for producing a polyolefin-substituted succinimide, which comprises reacting the polyolefin-substituted dicarboxylic acid derivative obtained by the method according to any one of claims 12 to 19 with an amine. 21. A dispersant for lubricating oil, comprising a polyolefin-substituted succinimide as a main component, which is obtained by the method of claim 20.