JPH066703B2 - Viscosity index improver and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a viscosity index improver and a method for producing the same.

[Prior Art, Problems to be Solved by the Invention] Conventionally, viscosity index improvers based on olefin polymers have been widely used in engine oils, taking advantage of their excellent thickening effect. As the viscosity index improver, a solution containing 10 to 20% of an olefin polymer and 90 to 80% of mineral oil is usually used as a commercial product. If the amount of the olefin polymer is increased more than this, the product viscosity becomes large and the handling property becomes problematic, so that it cannot be practically used. For this reason, there is a demand for the supply of an olefin polymer containing a high concentration and having a low viscosity. In response to this demand, a few methods have been proposed. For example, Japanese Unexamined Patent Publication (Kokai) No. 58-171417 discloses a high-concentration product in which a graft or block copolymer of an olefin copolymer and a (meth) acrylate is used as a dispersant in a solvent which hardly dissolves the olefin copolymer. Is disclosed. In addition, JP-A-58-17141
No. 8 discloses that a graft or block copolymer of a polymer composed of an olefin copolymer and a vinyl monomer other than (meth) acrylate is used as a dispersant in a solvent that hardly dissolves the olefin copolymer. It discloses that a concentrated product is obtained. However, these methods require a larger amount of (meth) acrylate to prepare a dispersant, and also when a styrene / isoprene block copolymer is used as an emulsifier, a large amount of dispersant (for example, It cannot be said to be efficient because it has to be used for more than 12%), and when a styrene-isoprene block copolymer is used as an emulsifier, it causes haze when dissolved in mineral oil. However, there may be a problem in practical use.

Further, regarding the production method, the granular olefin copolymer is added to a poor solvent containing a dispersant using a special high shear rate stirrer as described in JP-A Nos. 58-171417 and 58-171418 to emulsify. The method of doing is disclosed.
However, these methods require a special stirrer and are not general, and since the olefin copolymer in the form of granules needs to be used, the propylene content in the olefin copolymer is
Inevitably it will be 30% or less or 70% or more (4
If it is 0 to 60%, the olefin copolymer raw material is soft and difficult to be formed into a granular form). Also, when the olefin polymer is used after being degraded or modified in a solvent solution before emulsification, the obtained olefin polymer is obtained. Degradation or modified solvent solution
There is a problem that it cannot be used as it is.

[Means for Solving the Problems] As a result of intensive studies on the high concentration non-aqueous dispersion of an efficient and low-viscosity olefin polymer, the present inventors have found that
The present invention has been completed. That is, in the present invention, the component (1) is an olefin polymer, and the component (2) is a reaction product of A and B shown below,
A is a compound in which an ethylenically unsaturated dicarboxylic acid is added to an olefin polymer having a weight average molecular weight of 500 to 500,000, and B is one or more selected from the group consisting of an amino group, a ketimine group, a hydroxyl group and an isocyanate group. A compound having a group, wherein A and B are bound by at least one bond selected from an amide bond, an imide bond and an ester bond, and the component (3) is essentially an olefin polymer. The above is a viscosity index improver characterized by comprising a medium which does not dissolve or hardly dissolves, and a method for producing the same.

The olefin polymer of the component (1) used in the present invention is
Generally, it is a polymer of olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, and a copolymer of these olefins with styrene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, etc. and hydrogenation of these polymers. Things can also be used. Of course, various degraded products of these olefin polymers can also be used. Generally, ethylene and propylene copolymers are preferred because they are easily available.

Further, as the component (1), an olefin polymer modified product containing an atom such as nitrogen, oxygen or sulfur, for example, a basic nitrogen-containing olefin polymer is used in addition to the effect of improving the viscosity index, varnish or sludge generated during use. Is preferable because it can provide dispersibility for dispersing. Examples of the basic nitrogen-containing olefin polymer include those obtained by adding or graft-copolymerizing an acid component such as (anhydrous) maleic acid or (meth) acrylic acid to the olefin polymer, and imidizing or amidating with a polyamine. Can be mentioned. Furthermore, those obtained by oxidizing or hydroperoxidizing an olefin polymer and reacting it with polyamines,
Mannich condensation of formaldehyde and polyamines after oxidization of olefin polymer, vinyl monomer containing nitrogen etc. in olefin polymer (N-vinylpyrrolidone, N-vinylthiopyrrolidone, dialkylaminoethyl (meth) acrylate) , N-vinylimidazole, etc.)
Grafted, non-vinyl compounds containing nitrogen, etc. in olefin polymers (phenothiazines, imidazoles, thiazoles, benzothiazoles, triazoles, thiazolinedins, pyrimidines, pyridines, piperidines, pyrrolidinones) , Oxazoles, thiomorpholines) and the like.

Generally, the amount of the compounds containing oxygen, nitrogen and sulfur is 0.01 to 10 parts by weight, preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the olefin polymer.

The weight average molecular weight of the olefin polymer is usually 500.
It is preferably about 500,000 but about 30,000 to 300,000 in terms of viscosity index, thickening effect and shear stability.

The component (2) used in the present invention is used to obtain a high-concentration non-aqueous dispersion of an olefin copolymer,
Its function is to be a dispersant for olefin copolymers.

Weight average molecular weight 500 used to make the dispersant
~ 500,000 olefin polymers to which ethylenically unsaturated dicarboxylic acids are added (hereinafter abbreviated as compound A)
As the ethylenically unsaturated dicarboxylic acid, 1 mol of an olefin polymer having a weight average molecular weight of 500 to 500,000 is
The compound added 1 mol or more is mentioned.

Here, as the olefin polymer, ethylene, propylene, butadiene, isoprene, isobutylene, and the like,
Polymers obtained by homopolymerizing or copolymerizing, and if necessary, styrene, cyclopentadiene, dicyclopentadiene, norbornene and the like, and hydrogenated or degraded products of these polymers are mentioned.

Preferred of these olefin polymers are those whose composition is similar to the olefin composition of component (1) to be dispersed. The molecular weight of the olefin polymer is usually 500 to 500,000, preferably 1,000 to 100,000.

The ethylenically unsaturated dicarboxylic acids are used to introduce a carboxyl group into the olefin polymer. These compounds are compounds having an ethylene bond and a carboxyl group or an anhydride group thereof, or a polar group which can be converted into a carboxyl group by oxidation or hydrolysis. As examples, maleic acid, unsaturated dicarboxylic acids such as itaconic acid and fumaric acid, maleic acid dichloride, fumaric acid dichloride, maleic acid monobutyl ester, maleic acid monobutylamide, unsaturated dicarboxylic acid derivatives such as chloromaleic acid, Examples thereof include unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated dicarboxylic acid anhydride derivatives such as chloromaleic anhydride.

The adduct of these compounds of the olefin polymer can be produced in the presence or absence of a free radical initiator by the method described in various documents (for example, US Pat. No. 3236917).

Compound A is preferably 1 to 200 ethylenically unsaturated dicarboxylic acids per olefin polymer molecule.
More preferably, 5 to 50 are added.

In the present invention, addition does not mean polymerization. The ethylenically unsaturated dicarboxylic acid does not exist as a graft polymer with respect to the olefin polymer, and is, for example, one equivalent of 1 active hydrogen added to the olefin polymer. That is, the unsaturated dicarboxylic acids in the compound A do not substantially form a segment in which two or more molecules are themselves bonded.

Further, in order to prepare the component (2), 1 selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group and a ketimine group.
A compound having at least one group (hereinafter, abbreviated as compound B) is required, and this compound has at least one functional group in one molecule.

Examples of these compounds B include the following compounds.

A compound having an amino group; ammonia, ethylamine, butylamine, hexylamine, octylamine,
Aliphatic amines such as nonylamine, decylamine, tridecylamine, cetylamine, dimethylamine, diisopropylamine, diamylamine, ethylenediamine,
Pyriamines such as diethylenetriamine, triethylenetetramine, dialkylaminopropylamine and 1,4-diaminomethylcyclohexane, alkanolamines such as monoethanolamine and monopropanolamine, unsaturated aliphatic amines such as allylamine and diallylamine, sicto Alicyclic amines such as hexaneamine, aromatic amines such as aniline, toluidine, benzylamine, diphenylamine, naphthylamine, morpholine,
Heterocyclic amines such as imidazoline and N-aminoalkylpiperazine, amines from natural products such as beef tallow amine, coconut amine and the like, and the number of carbon atoms of these amines is 2 to
4 alkylene oxide adducts and the like.

A compound having a ketimine group; monoethanolamine,
Those obtained by ketiminating amines such as monopropanolamine and diethylenetriamine with ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and alkylene oxide adducts having 2 to 4 carbon atoms of these compounds.

Compounds having a hydroxyl group; saturated or unsaturated monovalents such as methyl alcohol, butyl alcohol, isoamyl alcohol, myristyl alcohol, melysyl alcohol, allyl alcohol, propargyl alcohol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, and furfuryl alcohol. Alcohols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,10-decanediol, dipropylene glycol, 3-methylpentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol , Diethanolamine, dipropanolamine, triethanolamine, trimethylolpropane, glycerin, pentaerythritol, etc. And C2-C4 alkylene oxide adducts of these hydroxyl group-containing compounds, and further C2-C4 alkylene oxides of mono- or dialkylphenols (where the alkyl group usually has 6-20 carbon atoms) Additions etc.

Or or above, an isocyanate compound (tolylene diisocyanate, diphenylmethane monoisocyanate, diphenylmethane diisocyanate, diphenylmethane triisocyanate, hexamethylene diisocyanate, lysine diisocyanate, dicyclohexylmethane monoisocyanate, dicyclohexylmethane diisocyanate, dicyclohexylmethane triisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. ) And their carbon numbers 2-4
Alkylene oxide adduct of.

One or more compounds selected from the above and / or isocyanate compounds and carboxylic acids (acetic acid, propionic acid, hexylic acid, octylic acid, capric acid, undecylic acid, myristic acid, eicoic acid, oleic acid, oxalic acid, amber Acid, adipic acid, azelaic acid,
Sebacic acid, phthalic acid, phthalic anhydride, terephthalic acid, etc.), and alkylene oxide adducts thereof having 2 to 4 carbon atoms.

Among these various compounds B, preferable compounds are compounds having an oxyalkylene group and / or ester group in the molecule in view of performance as a dispersant, and particularly preferable compounds are compounds having an oxyalkylene group as an essential component in the molecule. Is. Most preferred are the alkylene oxide adducts of the compounds.

In addition, the compound B basically has a similar structure to the below-described component (3) (a medium in which the component (1) is not substantially dissolved or hardly dissolved) and / or a solubility parameter close to each other. Ingredient (1) when having
Is preferred because it can be easily dispersed. For example, component (3)
In the case of a medium using an alkylene glycol solvent, the compound B is preferably an alkylene glycol or an ester thereof, and in the case of a medium using a phthalate ester solvent as the component (3). It is preferable that the compound B is a phthalate ester type.

Alternatively, even if they do not have a similar structure, the case where the difference in the solubility parameter between the compound B and the component (3) is small (usually 2 or less) is also preferable for the same reason.

The compound B is preferable when the solubility of the compound B itself in the lubricating oil is low because the component (1) can be easily dispersed. For example, a terminal aminated polypropylene glycol having a molecular weight of about 2500 which is a preferable example of the compound B, and a polyester obtained from phthalic acid and ethylene glycol (molecular weight 1
No. 500) does not dissolve transparently when blended in 1% by weight of lubricating oil.

The ratio of the compound A to the compound B varies depending on the compound A, the compound B, or the component (3) used, and cannot be generally described, but usually, the compound A / compound B = 20/80 to 80/20.
(Weight ratio), and preferably 40/60 to 70/30 from the viewpoint of ease of dispersion and that turbidity does not occur when the improver of the present invention is added to a lubricating oil.

Component (2) is one or more of these compounds A and compound B.
It is obtained by condensing and / or reacting with at least one of the above.
In this case, the bond between the compound A and the compound B is any one or more of an amide bond, an imide bond and an ester bond.

The present invention also includes a method in which the carboxyl group of the compound A is directly reacted with one or more kinds of alkylene oxide to prepare the component (2). Furthermore, the compound obtained by directly reacting one or more compounds having two or more functional groups in the molecule of the compound B with the carboxyl group or its anhydride group of the compound A is also included in the present invention. The present invention also includes a compound obtained by directly reacting with alkylene oxide.

The component (3) is a medium in which the olefin polymer is substantially or hardly dissolved, and more specifically, the solubility (20 ° C.) in the olefin polymer is usually 10% or less,
It is preferably 5% or less. The term "solubility" as used herein means that when an olefin polymer is dissolved alone, it gives a uniform and transparent state, and when it becomes cloudy or undergoes phase separation, it is assumed that it was not dissolved.

Examples of media having such solubility include ester-based media,
Examples thereof include phosphoric acid ester type, alcohol having 6 or more carbon atoms, and alkylene oxide adduct type having 2 to 4 carbon atoms.

Also, mineral oil alone does not substantially dissolve the olefin polymer, which is included in the present invention. In this example, the mineral oil is substantially dissolved with oxygen and / or oxygen- and nitrogen-containing compounds. It also includes those modified (mineral oil modified) so as not to dissolve or hardly dissolve.

Examples of the ester type include monocarboxylic acids (acetic acid, propionic acid, hexylic acid, octylic acid, capric acid, undecylic acid, myristylic acid, etc.) and dicarboxylic acids (succinic acid, adipic acid, azelaic acid, fumaric acid, maleic acid). Acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc.), a compound containing a carboxyl group such as tricarboxylic acid (benzene tricarboxylic acid, etc.),
Monohydric alcohol (methanol, butanol, hexyl alcohol, cyclohexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, myristyl alcohol, melysyl alcohol, etc.)
And polyols (glycols such as ethylene glycol, triethylene glycol, tetraethene glycol, propylene glycol, dipropylene glycol, hexamethylene glycol and decamethylene glycol,
Glycerin, trimethylolpropane, pentaerythritol, etc.), alkylene oxide adducts of carbons 2 to 4 of these monohydric alcohols and polyols (the addition mole number of alkylene oxide is usually 0 to 50, preferably 1 to 35), etc. Is an ester compound.

Of these various ester-based compounds, preferred are diesters of dicarboxylic acids and monohydric alcohols, and di-, tri-, and tetra-esters of monocarboxylic acids with polyols, with succinic acid being particularly preferred. Diester compounds of adipic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and monohydric alcohols having 1 to 10 carbon atoms, or the above glycols and 1 to 1 carbon atoms
It is a diester compound with a monocarboxylic acid having 10.

As an example of the phosphate ester type, a triester of an alcohol having 4 to 10 carbon atoms is preferable.

Examples of the alcohol having 6 or more carbon atoms include 2-ethylhexyl alcohol, octyl alcohol, isooctyl alcohol, monohydric alcohols such as oxo alcohol having 6 to 10 carbon atoms, hexamethylene glycol, decamethylene glycol and pentaerythritol. Examples thereof include polyhydric alcohols.

Examples of the alkylene oxide adduct system include active hydrogen-containing compounds such as monofunctional or polyfunctional hydroxyl groups, amino groups, amide groups, and carboxyl groups and active hydrogen-containing heterocyclic compounds, and alkylene oxides having 2 to 4 carbon atoms. Compounds to which a class is added are included. Examples of the compound having a hydroxyl group include the above monohydric alcohols and polyols. Examples of the compound having a carboxyl group include the above-mentioned mono- or polycarboxylic acids. In addition, compounds having both a carboxyl group and a hydroxyl group in the molecule, such as citric acid, gluconic acid and the like are also included. Further, as the compound having an amino group, the compound having the amino group is used, and as the compound having an amide group, acetic acid amide, propionic acid amide, octyl acid amide, oleic acid amide, stearic acid amide,
Examples include propionic acid monomethylamide. Examples of active hydrogen-containing heterocyclic compounds include morpholine.

The number of moles of alkylene oxide added varies depending on the type of active hydrogen-containing compound to be added, but is usually 1 to 50, preferably 1 to 35. If the number of added moles becomes large, the solubility in mineral oil will decrease, and the final adjusted lubricating oil will produce scumming, making it difficult to use. Among these various alkylene oxide adducts, preferred is the general formula R-O- (AO) n-H (wherein R is an alkyl group or cycloalkyl group having 8 or less carbon atoms, n is a number of 1 to 35, A
Is a compound represented by an alkylene group having 2 to 3 carbon atoms).

The modified mineral oil can be synthesized, for example, by the same method as that for introducing a functional group into an olefin polymer.

Of these various components (3), dicarboxylic acid diester type and alkylene oxide adduct type are preferable.

Further, as the component (3), those containing mineral oil in these compounds can be used. In this case, the amount of the mineral oil is not particularly limited, but the solubility in the component (1) increases as the amount of the mineral oil increases. To maintain the solubility of 10% or less in the component (1), the amount of mineral oil in the medium of the component (3) is generally 85% or less.

Based on the weight of the improver of the present invention, the content of component (1) is usually 10-70%, preferably 20-60%, the content of component (2) is usually 0.5-20%, preferably 1-10.
%, The content of component (3) is usually 90 to 25%, preferably 70 to 30%.

In order to produce the improver of the present invention, the component (2) is previously synthesized. The production method of the component (2) depends on the kinds of the compound A and the compound B, but an ordinary method may be used. In this production, a solvent may be used to reduce the viscosity of the reaction system. This solvent may be the component (3) in the present invention, or (reduced pressure)
As long as it can be distilled off, a good solvent for olefin polymers (hexane, heptane, toluene, xylene, low boiling point synthetic hydrocarbons, etc.) may be used, or a mixture thereof.

After the component (2) thus produced is mixed and dissolved with the component (3), the solvent solution of the component (1) is distilled under reduced pressure to dilute the solvent used under the conditions of the components (1), ( It is preferable to add the solvent used for the dissolution of 2) while distilling off and to emulsify or disperse the olefin polymer, because a stable dispersion can be obtained even if the amount of the component (2) is small.

Of course, a method in which the component (2) is mixed and dissolved in a solvent solution of the component (1) and the component (1) is emulsified or dispersed in the component (3) in the presence of the component (2) by the same method is also preferable.

The solvent used to dissolve the component (1) is not particularly limited, and examples thereof include hexane, heptane, toluene, xylene, and low boiling point synthetic hydrocarbons. Regarding the addition condition, it is necessary that the solvent can be removed. The temperature is usually 50 to 200 ° C. If it is too high, the olefin polymer is decomposed, and the molecular chain of the component (1) is elongated, which makes it difficult to emulsify or disperse. Although the time varies depending on the temperature and pressure, it is usually 2 to 10 hours. If the addition rate is too fast, the distillation of the solvent will not catch up and the olefin polymer will not be emulsified or dispersed well. become.

The improver of the present invention may contain a pour point depressant for lubricating oil as the component (4). This is because the pour point depressing function is not sufficient with the components (1), (2) and (3) alone depending on the type of mineral oil used when producing the final engine oil, etc. This is because it may be necessary to add a depressant. Typical examples of such pour point depressants are poly (meth) acrylate-based compounds and chlorinated paraffin-naphthalene condensates. These are widely and generally commercially available. For example, as a poly (meth) acrylate-based compound,
The series is commercially available from Sanyo Kasei, the Plexol series from Japan Acrylic, and the chlorinated paraffin and naphthalene condensate series are available from Toho Chemical as the Leblanc series. Preferred are those based on poly (meth) acrylate. The content of the component (4) is usually 0 to 30%, preferably 5 to 20% based on the weight of the improver.
%.

Other optional components (detergent-dispersant, antioxidant, friction-reducing agent, etc.) can be added to the improver of the present invention, if necessary.

Component (4) is generally added after the dispersion has been prepared from components (1), (2) and (3).

The improver of the present invention is usually used by adding 1 to 20% by weight to a lubricating oil. For example, when the viscosity index improving action, the thickening action, and the component (1) is an olefin polymer modified product. , A cleaning and dispersing action, and when the component (4) is contained, it exerts a pour point depressing action.

Further, the improver of the present invention can be used as a composition of fuel oil, grease or the like, in addition to the lubricating oil, if necessary.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by weight, respectively.

Example 1 A 4-neck reactor equipped with a high-viscosity stirrer, a temperature detector, a condenser and a raw material inlet was used, and an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000) was added.
0, propylene content 50%, maleic anhydride content; 2
%) 40% xylene solution of 250 parts and aminated polyether (molecular weight: 2030, hydroxyl group of ketiminized monoethanolamine with methyl isobutyl ketone,
After adding 34 moles of propylene oxide, hydrolyzed 41.4 parts was charged, and under reflux (138-150).
(° C) While removing generated water out of the system, the reaction is carried out until the acid value becomes 0.04 or less (usually 2 hours) to obtain a 48.5% solution of the component (2).

Charge 24.7 parts of a 48.2% solution of component (2) thus obtained and 228 parts of a 4 mol adduct of n-butanol propylene oxide of component (3) into the same reactor (equipped with a vacuum distillation apparatus instead of a condenser). 120 after dissolution
Xylene was distilled off under the conditions of 5 ° C or less and 5 mmHg or less, and the ethylene-propylene copolymer N-vinylimidazole modified product (molecular weight: 1000) of component (1) was distilled and kept at about 100 ° C.
00, propylene content; 50% ethylene propylene copolymer, obtained by reacting 20 molar equivalents of N-vinylimidazole in the presence of benzoyl peroxide in xylene) in a 40% xylene solution (600 parts). In 4 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the entire amount of the component (1) solution, stirring the mixture for another 30 minutes to give an ethylene propylene copolymer content of 50.0
% Of the milky white dispersion is obtained.

Viscosity: 1045 cps / 25 ° C. Example 2 Ethylene propylene copolymer maleic anhydride adduct (molecular weight: 12000) was added to a 4-neck reactor equipped with a high-viscosity stirrer, temperature detector, condenser and raw material inlet.
0, propylene content 50%, maleic anhydride content; 2
%) Of 40% xylene solution and ketiminated polyether (molecular weight: 2030, monoethanolamine ketiminated with methyl isobutyl ketone, with 34 moles of propylene oxide added to the hydroxyl group) 41.4
Part, and under reflux (138-150 ° C.), removing the generated water outside the system, reacting until the acid value becomes 0.04 or less (usually 2 hours) to obtain a 48.5% solution of component (2) .

24.7 parts of the obtained 48.5% solution of the component (2) and 228 parts of the dibutyl phthalate of the component (3) were charged into a similar reactor (equipped with a vacuum distillation apparatus instead of the condenser) and dissolved, and then at 120 ° C., 5 mmHg Under the following conditions
Xylene was distilled off, and the N-vinylpyrrolidone modified product of the ethylene-propylene copolymer of the component (1) kept at about 100 ° C (molecular weight; 100,000, propylene content;
N-vinylpyrrolidone 1 in 50% ethylene propylene copolymer in xylene in the presence of benzoyl peroxide
600 parts of a 40% xylene solution (obtained by reacting 5 molar equivalents) is gradually added from the solution in 4 hours. During the addition, xylene is distilled off according to the addition rate and the component (1)
Is dispersed in the component (3) accordingly. After adding the entire amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 50.0%.

Viscosity: 876 cps / 25 ° C. Example 3 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic acid content; 2%) 40% xylene solution 250 parts and methyl alcohol propylene oxide adduct (molecular weight: 1480) 60.4 parts were charged, and after homogenization, 0.02 parts of tetrabutyl titanate was added. In addition, under reflux (138-150 ° C), while removing the generated water to the outside of the system, until the acid value becomes 0.04 or less (usually 6
Time) to obtain a 51.7% solution of component (2).

249 parts of dioctyl phthalate of component (3) was charged into the same reactor (equipped with a vacuum distillation device instead of a condenser), and at about 120 ° C. under 5 mmHg, about 1
540 parts of 40% xylene solution of component (1) ethylene propylene copolymer oxidative degradation product (molecular weight; degradation of 250,000 to 120,000; propylene content; 50%) kept at 00 ° C. and 51.7 of component (2) A mixture with 29.3 parts of a% solvent solution is gradually added from the liquid in 6 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is accordingly dispersed in the component (3). After adding the whole amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a pale yellowish milky white dispersion having an ethylene-propylene copolymer content of 45.0%.

Viscosity: 945 cps / 25 ° C Example 4 A 4-neck reactor equipped with a high-viscosity stirrer, a temperature detector, a condenser and a raw material charging port was charged with ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 3
%) Of 40% xylene solution, an equivalent reaction product of an ethylene oxide adduct of morpholine (molecular weight: 970) and hexamethylene diisocyanate (molecular weight: 113
0) Charge 69.2 parts, and react at 90 to 120 ° C until the acid value becomes 0.06 or less (usually 5 hours) to prepare 5 parts of component (2).
A 2.7% solution is obtained.

31.9 parts of a 52.7% solution of component (2) obtained and 4 mol of n-butanol ethylene oxide adduct of component (3)
A mixture of 200.9 parts and mineral oil 22.3 parts was charged into a similar reactor (equipped with a vacuum distillation device instead of a condenser) and dissolved, and then xylene was distilled off under the conditions of 120 ° C and 5 mmHg or less. Component (1) ethylene propylene copolymer dimethylaminoethyl methacrylate modified product (molecular weight: 120,000, propylene content: 50%) maintained at 100 ° C. in ethylene propylene copolymer in xylene in the presence of benzoyl peroxide in dimethylaminoethyl. A solution of 600 parts of 40% xylene solution (obtained by reacting 15 molar equivalents of methacrylate) is gradually added to the solution.
Add in time. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the entire amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 50.0%.

Viscosity: 1233 cps / 25 ° C Example 5 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 1.5
%) 40% xylene solution, polytetramethylene glycol (molecular weight: 510), and polyester obtained from phthalic anhydride (charge equivalent ratio: 3/2, molecular weight: 1)
800) 55.1 parts were charged, and after homogenization, 0.02 part of tetrabutyl titanate was added and refluxed (138-150).
℃), while removing the generated water outside the system, react until the acid value becomes 0.03 or less (usually 6 hours) to give 50.8% of component (2)
Get a solution.

47.2 parts of the obtained 50.8% solution of the component (2) and 216 parts of the tributyl phosphate of the component (3) were charged into a similar reactor (one equipped with a vacuum distillation apparatus instead of the condenser) and dissolved, and then at 120 ° C. Under a condition of 5 mmHg or less, xylene was distilled off, and the ethylene propylene copolymer dimethylaminoethyl methacrylate modification product (molecular weight: 120,000, propylene content: 50% ethylene propylene copolymer) of component (1) kept at about 100 ° C. was distilled off. A polymer obtained by reacting 15 molar equivalents of dimethylaminoethyl methacrylate in the presence of benzoyl peroxide in xylene) was added to 600 parts of a 40% xylene solution to gradually add 5 parts from the solution.
Add in time. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the entire amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 50.0%.

Viscosity: 903 cps / 25 ° C Example 6 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 2
%) 40% xylene solution (250 parts) and 51.4 parts of polyester (charge equivalent ratio: 5/4, molecular weight; 1260) obtained from triethylene glycol and adipic acid, and homogenized, and then added 0.02 part of tetrabutyl titanate. While refluxing (138 to 150 ° C.), the produced water is removed to the outside of the system and reacted until the acid value becomes 0.03 or less (usually 6 hours) to obtain a 50.1% solution of the component (2).

33.1 parts of the obtained 50.8% solution of the component (2) and 223.2 parts of the triethylene glycol dibutyrate of the component (3) were charged into a similar reactor (equipped with a vacuum distillation apparatus instead of the condenser) and dissolved. Xylene was distilled off under the conditions of ℃, 5 mmHg or less, and the component (1) ethylene propylene copolymer diethylaminoethyl methacrylate modified product (molecular weight: 1200
00, propylene content; 50% ethylene propylene copolymer, obtained by reacting 15 molar equivalents of dimethylaminoethyl methacrylate in the presence of benzoyl peroxide in xylene), and gradually adding 600 parts of a 40% xylene solution of 40%. Over 5 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the entire amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 50.0%.

Viscosity: 1230 cps / 25 ° C Example 7 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 2
%) Of 40% xylene solution, and 39.6 parts of polyester obtained from 1,8-octanediol and phthalic anhydride (equivalent ratio: 4/3, molecular weight: 970), homogenized, and then tetrabutyl titanate. Add 0.02 part under reflux (138-150 ° C) and remove the generated water to the outside of the system while reacting until the acid value becomes 0.03 or less (usually 6 hours) to give a 48.1% solution of component (2). obtain.

51.9 parts of the obtained 48.1% solution of the component (2) and 263 parts of the dioctyl phthalate of the component (3) were charged into a similar reactor (equipped with a vacuum distillation apparatus instead of the condenser), dissolved, and then heated at 120 ° C., 5 mmHg. Under the following conditions
Component (1) ethylene propylene copolymer dimethylaminoethyl methacrylate modified product (molecular weight; 120,000, propylene content; 50% of ethylene propylene copolymer) in which xylene was distilled off and kept at about 100 ° C. Then, 480 parts of a 40% xylene solution of a solution obtained by reacting 15 molar equivalents of dimethylaminoethyl methacrylate in the presence of benzoyl peroxide) is gradually added from the solution in 5 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the whole amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 40.0%.

Viscosity: 865 cps / 25 ° C. Example 8 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 3
%) 40 parts of 40% xylene solution and 64.9 parts of an equivalent reaction product (molecular weight: 1060) of polypropylene glycol (molecular weight: 840) and isophorone diisocyanate are charged at 90 to 120 ° C. until the acid value becomes 0.06 or less ( The reaction is usually performed for 6 hours to obtain a 52.4% solution of the component (2).

42.5 parts of the obtained 50.8% solution of the component (2) and 237.3 parts of the hexyl alcohol propylene oxide 8 mol adduct of the component (3) were charged and dissolved in a similar reactor (one equipped with a vacuum distillation apparatus instead of the condenser). After 12
Under conditions of 0 ° C. and 5 mmHg or less, xylene was distilled off and the temperature was kept at about 100 ° C. Component (1) ethylene-propylene copolymer (molecular weight; 100,000, propylene content; 50)
%) 40% xylene solution 540 parts gradually from the liquid 5
Add in time. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the whole amount of the solution of the component (1), the mixture is further stirred for 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 45.0%.

Viscosity: 1302 cps / 25 ° C. Example 9 Ethylene propylene copolymer fumaric acid adduct (molecular weight: 100,000, propylene content; 250 parts of 40% xylene solution of 60%, fumaric acid content; 3%) and ketiminized polyether (molecular weight: 1700, monopropanolamine ketiminized with methyl isobutyl ketone) with 35 moles of ethylene oxide added to the hydroxyl groups ) Prepare 52.0 copies, 1
At 30 to 140 ° C., while removing the produced methyl isobutyl ketone outside the system, the reaction is continued until the acid value becomes 0.06 or less (usually 2 hours) to obtain a 49.8% solution of the component (2).

200.2 parts of dibutyl phthalate of component (3) was charged in the same reactor (equipped with a vacuum distillation device instead of a condenser), and at about 10 ° C. under 5 mmHg, about 10
A mixture of 660 parts of a 40% xylene solution of the component (1) ethylene-propylene copolymer (molecular weight: 100,000, propylene content: 50%) kept at 0 ° C. and 31.8 parts of a 49.8% solvent solution of the component (2) was prepared. It is gradually added from the liquid in 6 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is accordingly dispersed in the component (3). After adding the whole amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improver of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 55.0%.

Viscosity: 1183 cps / 25 ° C. Example 10 A 4-neck reactor equipped with a stirrer for high viscosity, a temperature detector, a condenser and a raw material charging port was charged with an ethylene propylene copolymer maleic anhydride adduct (molecular weight: 10,000).
0, propylene content 50%, maleic anhydride content; 2
%) 40% xylene solution (250 parts) and morpholine propylene oxide adduct (molecular weight: 1250) (51.0 parts) were charged and homogenized, and then tetrabutyl titanate (0.02 part) was added to the mixture under reflux (138 to 150 ° C.) to generate. While removing water to the outside of the system, the reaction is carried out at 90 to 120 ° C. until the acid value becomes 0.04 or less (usually 6 hours) to obtain 50.0% of the component (2).
% Solution is obtained.

Charge 38.4 parts of the obtained 50.0% solution of component (2) and 220.8 parts of n-butanol propylene oxide 4 mol adduct of component (3) into the same reactor (equipped with a vacuum distillation apparatus instead of a condenser). 120 after dissolution
The xyle is distilled off under conditions of ℃, 5 mmHg or less, and about 1
Component (1) ethylene-propylene copolymer kept at 00 ° C (molecular weight: 100,000, propylene content: 50%)
600 parts of a 40% xylene solution of is gradually added from the solution in 4 hours. During the addition, xylene is distilled off according to the addition rate, and the component (1) is dispersed in the component (3) accordingly. After adding the entire amount of the solution of the component (1), the mixture is stirred for another 30 minutes to obtain the improving agent of the present invention which is a milky white dispersion having an ethylene-propylene copolymer content of 50.0%.

Viscosity: 1158 cps / 25 ° C Example 11 Content of ethylene-propylene copolymer obtained in Example 1 5
12 parts of polymethacrylate-based pour point depressant (Acluve 138 manufactured by Sanyo Kasei Co., Ltd.) was added to 100 parts of the improver of the present invention which was a 0.0% milky white dispersion,
The improver of the present invention, which is a pale yellowish-white dispersion, is obtained.

Viscosity: 1205 cps / 25 ° C [Effect of the invention] The improver of the present invention has a small amount of dispersant (for example, 5% or less).
In that case, it is efficient because it sufficiently exerts the effect, and has the effect of being a high-concentration non-aqueous dispersion of an olefin polymer having a low viscosity.

Further, in the production method of the present invention, since an ordinary stirring device can be used and it is not necessary to granulate the olefin polymer, there is no restriction on the propylene content, and the olefin polymer is degraded in a solvent solution before emulsification. Alternatively, when it is used after being modified, there is an advantage that the obtained olefin polymer degrading or modified solvent solution can be used as it is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C10M 159/12 (C10M 157/00 143: 00 145: 18 149: 12) (C10M 161/00 143 : 00 133: 56 129: 95) (C10M 165/00 143: 00 159: 12) (C10M 159/12 129: 93 133: 06 133: 22 129: 06) C10N 20:04 30:02 50:10

Claims (17)

[Claims] 1. A component (1) is an olefin polymer, and a component (2) is a reaction product of A and B shown below,
A is a compound in which an ethylenically unsaturated dicarboxylic acid is added to an olefin polymer having a weight average molecular weight of 500 to 500,000, and B is one or more selected from the group consisting of an amino group, a ketimine group, a hydroxyl group and an isocyanate group. A compound having a group, wherein A and B are bound by at least one bond selected from an amide bond, an imide bond and an ester bond, and the component (3) is essentially an olefin polymer. A viscosity index improver comprising a medium which does not dissolve or hardly dissolves. 2. The component (2) B comprises at least one group selected from the group consisting of an amino group, a ketimine group, a hydroxyl group and an isocyanate group in the molecule, an oxyalkylene group and / or
The improving agent according to claim 1, which is a compound having an ester group. 3. The component (2), B, is a compound which essentially contains at least one group selected from the group consisting of an amino group, a ketimine group, a hydroxyl group and an isocyanate group and an oxyalkylene group in the molecule. Item 1. The improver according to Item 1 or 2. 4. The component (2), B, is an alkylene oxide adduct having 2 to 4 carbon atoms of a compound having an amino group and / or a ketimine group and / or a hydroxyl group.
The improver according to any one of 1. 5. The improver according to claim 1, wherein the component (1) is an ethylene-propylene copolymer. 6. The improver according to claim 1, wherein the component (1) is a basic nitrogen-containing olefin polymer. 7. The improver according to claim 1, wherein the improver contains the component (1) in an amount of 20 to 60% by weight. 8. The improver according to claim 1, wherein the olefin polymer portion of component A (2) is a polymer having an olefin composition similar to that of component (1). 9. The weight ratio of A and B of component (2) is 20:80.
80:20 The improver according to any one of claims 1 to 8. 10. Component (3) is an olefin polymer of 10
The improver according to any one of claims 1 to 9, which is a medium having a solubility of not more than wt%. 11. Component (3) is a medium containing one or more compounds selected from phosphoric ester compounds, ester compounds, alcohol compounds having 6 or more carbon atoms and alkylene oxide adduct compounds. Item 11. The improver according to any one of Items 1 to 10. 12. The component (3) is a medium containing a mineral oil modified by oxygen and / or a compound containing oxygen and nitrogen so that the olefin polymer is not substantially dissolved or hardly dissolved. The improver according to any one of 1 to 11. 13. Components 1 to 1 wherein component (3) comprises mineral oil.
2. The improver according to any one of 2. 14. Component (4)
The improving agent according to any one of claims 1 to 13, which contains a pour point depressant for a lubricating oil. 15. The improver according to claim 1, wherein the improver contains the component (4) in an amount of 0 to 30% by weight. 16. A solvent solution of component (1) is added to a solution consisting of component (2) and component (3) under distillation conditions of the solvent, while performing desolvation.
The viscosity index according to claim 1, wherein the component (1) is emulsified or dispersed in the component (3) in the presence of the component (2), and the component (4) is added if necessary. Manufacturing method of improver. 17. A solvent solution of component (1) and component (2) in component (3), under the distillation conditions of the solvent,
The component (1) is emulsified or dispersed in the component (3) in the presence of the component (2) by adding the component (4) while removing the solvent, and the component (4) is added if necessary. 16. The method for producing the viscosity index improver according to any one of 15 to 15.