JP2000239446A - Organic sulfide compound having quaternary salt structure, manufacture thereof and rubber composition containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tire showing excellent anti-abrasion, wet grip and low fuel consumption by mixing a rubber-carbon black agent comprising a specific organic sulfide compound with a diene rubber and carbon black. SOLUTION: An organic sulfide compound is represented by formula I or formula II (R1 and R2 are each an 1-3C alkyl group; R3-R5 are each an 1-20C alkyl group; X is alkylene or arylene group; Y is a gegen anion; and n is 2-6). The amount of the sulfide is 0.1-100 mmol per 100 g of a diene-based rubber. The preparation method of the sulfide is not limited to a specified one but it can be prepared by reacting a dihalogeno compound (example: dichlorobutane) with a dialkylaminopyridine (example: dimethylaminopyridine) or a trialkylamine (example: diemethy laurylamine) followed by reacting a sulfide (an example: Na2S4-6 or a mixture thereof). The reaction temperature is preferably 10-130 deg.C and the reaction time is preferably 1-15 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coupling agent for rubber and carbon black, a method for producing the same, and a rubber composition containing the same.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for fuel economy in automobiles, and since the characteristics of tires have a significant effect on fuel economy, tire rubber compositions having excellent fuel economy have been developed. It is strongly desired. On the other hand, from the viewpoint of running safety, the grip force on wet road surface, that is, “wet grip” is emphasized. However, in general, it is necessary to reduce the hysteresis loss in order to obtain a fuel-saving tire. However, since a small hysteresis loss means a small rolling resistance, the wet grip force is reduced. On the other hand, the improvement of the wet grip force increases the rolling resistance, and the hysteresis loss increases, resulting in poor fuel economy. As described above, the two have a conflicting relationship, and therefore, research and development of a rubber composition that satisfies both are proceeding.

As one of means for developing a rubber composition for tires having a low rolling resistance and a wet grip force, a chemical bond between rubber molecules and carbon black is strengthened to disperse carbon black in the rubber composition. It is necessary to develop a rubber / carbon black coupling agent that improves the properties. Conventionally, as a rubber / carbon black coupling agent, a nitroso compound (Kenneth W. Doaket al .; Rubber Chem. Technol.,
28, 895 (1995), Payne, ARet al .; J. Rubber Res. In
st.Malaya, 22, 275 (1969), Walker, LAet al; Rubber
Age, 90, 925 (1962), Patts, KTet al., Rubber Che
m. Technol., 47, 289 (1974), Daneil F. Graves; Rubber
Chem. Technol., 66, 61 (1993)) and dinitroamine compounds (Yamaguchi, T. et al .; Kautsch. Gummi. Kunstst, 4).
2 403 (1989)), but was not satisfactory.

It has been reported that aminobenzenesulfonyl azide is used as a coupling agent for rubber and carbon black (Gonzalez, L. et al .; Rubber).
Chem. Technol., 69, 266 (1996)). However, there are disadvantages in that sodium azide requiring careful handling is used as a raw material for synthesis and that the production process is complicated over many steps.

[0005] As represented by dinitroamine compounds and aminobenzenesulfonyl azides, most conventional coupling agents for rubber and carbon black are amino group-containing compounds. This function is achieved by utilizing the bond between the carbonyl group and the carboxyl group present in the compound. Recently, it has been reported that a sulfur compound containing a dialkylamino group is used as a coupling agent for rubber and carbon black (JP-A-9-27-9).
8942).

However, the bond between the amino group and the carbon black is not so strong, and the development of a new rubber / carbon black coupling agent having a functional group capable of a stronger bond with the carbon black has been developed. Is desired.

Recently, it has been reported that a polymer having a hydroxyl group surface-modified fine particle with a quaternary ammonium group is retained on the surface via the ammonium group (Taunton, HJ et al.). .; Macromolecules, 2
1, 333 (1988)). In particular, an iminium ion group, which is one of the quaternary ammonium groups, is effective as a functional group that firmly binds to the surface of carbon black, and is composed of polybutadiene and carbon black terminal-modified with an iminium ion group. It has been reported that rubber compositions have greatly improved rebound resilience compared to unmodified ones (Kitahara, S. et al .; Kobunnshi Ronbunnshu, 4
9, 921 (1992)). However, the process for producing the terminal-modified polymer is not simple and requires a new process, so that the process up to the production of the rubber composition becomes longer, and a decrease in production efficiency is inevitable.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel rubber / carbon black coupling agent which is suitable for use in tires having excellent wear resistance and wet grip properties and high fuel efficiency. It is to provide.
Another object of the present invention is to easily and efficiently produce a novel rubber / carbon black coupling agent suitable for use in tires having excellent wear resistance and wet grip properties and high fuel efficiency. It is to provide a method. Still another object of the present invention is to provide a rubber composition for a tire which is excellent in abrasion resistance and wet grip properties and has high fuel efficiency.

[0009]

According to the present invention, the following general formulas (1) and (2):

[0010]

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(Wherein R ¹ and R ^{2 each} independently have 1 to 1 carbon atoms)
R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, X is an alkylene group and / or an arylene group, Y is a counter anion,
n is an integer of 2 to 6), and a coupling agent for rubber and carbon black comprising at least one organic sulfide compound selected from the compounds represented by the following formula:

According to the present invention, the following general formula (3):

[0013]

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Wherein X is an alkylene group and / or an arylene group, and Z is at least one halogen atom selected from a chlorine atom, a bromine atom and an iodine atom.
And a dihalogeno compound represented by the following general formula (4) or (5):

[0015]

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(Wherein R ¹ and R ^{2 each} independently have 1 to 1 carbon atoms)
And R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms), and reacting with a corresponding dialkylaminopyridine or trialkylamine represented by the following general formula: (6) or (7):

[0017]

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(Wherein R ¹ and R ^{2 each} independently have 1 to 1 carbon atoms)
R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, X is an alkylene group and / or an arylene group, Y is a counter anion,
Z is at least one halogen atom selected from a chlorine atom, a bromine atom and an iodine atom), and then the compound represented by the following general formula (8):

[0019]

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Wherein M is a metal atom or ammonium, and n is an integer of 2 to 6 to produce a coupling agent for rubber and carbon black. A method is provided.

According to the present invention, carbon black and the following general formulas (9) and (10) are further added to the diene rubber.

[0022]

Embedded image

(Wherein R ¹ and R ^{2 each} independently have 1 to 1 carbon atoms)
R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, X is an alkylene group and / or an arylene group, Y is a counter anion,
n is an integer of 2 to 6), and a rubber composition is provided which contains at least one organic sulfide compound.

The organic sulfide compound represented by the general formula (9) and / or (10) is preferably blended in an amount of 0.1 to 100 mmol, more preferably 0.5 to 50 mmol, based on 100 g of the diene rubber. .

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The coupling agent for rubber and carbon black according to the present invention has the general formula (1) or (2).
And at least one organic sulfide compound among the compounds represented by

In the general formula (1), R ¹ and R ²
Is independently an alkyl group having 1 to 3 carbon atoms. Specific examples of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Above all, from the viewpoint of bonding with carbon black, it is preferable that R ¹ and R ² are methyl groups because steric hindrance is small and production is easy. In the general formula (2),
R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms. Specific examples of R ³ , R ⁴ and R ⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Heptyl, octyl, decyl, octadecyl and the like can be mentioned.

In the general formulas (1) and (2), X
Is a hydrocarbon group composed of a linear alkylene group and / or an arylene group, and may be composed of only a linear alkylene group. As the straight-chain alkylene group, a straight-chain alkylene group having 2 to 10 carbon atoms is preferable because it has good physical properties (fuel efficiency and flexibility) when compounded in the rubber composition. ~ 8 linear alkylene groups are more preferred. Specific examples include ethylene, propylene,
Hexamethylene and the like. Examples of the arylene group include an aromatic hydrocarbon group having 6 to 18 carbon atoms, such as a phenylene group, a naphthylene group, and a xylylene group.

In the general formula (1) or (2), n
Is not particularly limited as long as it is an integer of 2 to 6, but n is 4 to 6
Is preferred from the viewpoint of controlling the reactivity with the rubber component in the rubber composition and the amount of free sulfur (the rubber becomes hard if the amount of free sulfur is too large). n is particularly preferably 2 to 4.

In the general formula (1) or (2), Y
Is a counter anion, for example, a common anion as an anion of an ammonium salt compound, for example, Cl ⁻ , Br ⁻ , I
^-, PF ₆ ^- and BF ₄ ^- and the like.

The dialkylamino group-containing sulfur compound described in JP-A-9-278942 is unstable, and a salt compound obtained by reaction with an acid such as hydrochloric acid is used as a coupling agent for rubber and carbon black. The organic sulfide compounds represented by the general formulas (1) and (2) according to the present invention have a feature that they are stable, while they must be used.

The method for producing the coupling agent for rubber and carbon black of the present invention is not particularly limited. For example, a dihalogeno compound represented by the general formula (3) and a dialkyl compound represented by the general formula (4) are used. Reaction with aminopyridine or a trialkylamine represented by the general formula (5) gives a corresponding compound represented by the general formula (6) or (7), and then the compound and the compound represented by the general formula (8) By reacting with the sulfide represented by
A coupling agent for rubber and carbon black can be easily and efficiently produced.

Hereinafter, the method for producing the coupling agent for rubber and carbon black of the present invention will be described in more detail. In the dihalogeno compound represented by the general formula (3), in the general formula (3), Z is at least one halogen atom selected from a chlorine atom, a bromine atom and an iodine atom. A bromine atom is preferred from the viewpoint of economy, and a chlorine atom is preferred from the viewpoint of economy.

In the general formula (1) or (2), X
Is not particularly limited as long as it is a hydrocarbon group comprising a linear alkylene group and / or an arylene group, and may be constituted only by a linear alkylene group. X is preferably a linear alkylene group having 2 to 10 carbon atoms, and is preferably a linear alkylene group having 2 to 8 carbon atoms, from the viewpoint of physical properties (fuel saving and flexibility) when compounded in the rubber composition. The alkylene group is more preferable. As the arylene group, preferably, an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenylene group or a naphthylene group is used, and a phenyl group is preferable from the viewpoint of easy production. Is preferred.

Examples of the dihalogeno compound represented by the general formula (3) include dichloroethane, dibromoethane, diiodoethane, dichloropropane, dibromopropane, diiodopropane, dichlorobutane, dibromobutane, diiodobutane, dichloropentane, dibromopentane, and the like. Diiodopentane, dichlorohexane, dibromohexane, diiodohexane, dichloroheptane, dibromoheptane, diiodoheptane, dichlorooctane, dibromooctane, diiodooctane, chlorobenzyl chloride, chlorobenzyl bromide, bromobenzyl bromide and the like. Can be. Among them, the dihalogeno compound is particularly preferably dichlorobutane, dibromobutane, dibromopentane, dichlorohexane, dibromohexane or chlorobenzyl chloride.

The dialkyl compound represented by the general formula (4)
In minopyridine, R¹And R ^TwoIs independently 1 carbon
Represents an alkyl group of 1 to 3;¹And R^TwoAs a specific example of
Methyl, ethyl, n-propyl, iso-
And a propyl group. Above all, R¹as well as
R^TwoIs a methyl group, the resulting rubber car
Carbon black and carbon black coupling agent
Since steric hindrance between them is small, it is
New In addition, a methyl group is preferred because it is easy to produce.
No.

The trialkyl represented by the general formula (5)
In amines, R^Three, R^FourAnd R ^FiveIs independently 1 carbon
-20 represents an alkyl group.

The rubber / carbon black according to the method of the present invention
When manufacturing coupling agents for
Using a halogeno compound in a solvent or using a solvent
Without dialkylaminopyridines or tria
Reaction with alkylamines to give general formulas (6) and (7)
The corresponding compound shown is obtained. In addition, the general formula (6) and
And (7), Y is, for example, Cl^-, Br^-,
I^-, PF₆ ^-And BF_Four ^-Ammonium chloride
A general anion is shown as a counter anion of the product.

The solvent used in the above reaction is not particularly restricted but includes, for example, hydrocarbons such as hexane and pentane, aromatic hydrocarbons such as benzene, toluene and xylene, tetrahydrofuran, dioxane, dimethoxyethane and diethylene glycol dimethyl ether. And the like. Preferred solvents include hexane, toluene, xylene and the like, and the raw material dihalogeno compound itself can be used as the solvent.

The amount of the dihalogeno compound and the dialkylaminopyridine used in the above reaction is not particularly limited. However, when about 1 mol of the dialkylaminopyridine is used with respect to 1 mol of the dihalogeno compound, the compound is represented by the general formula (6). The compound to be obtained is preferable because it can be obtained in the highest yield without accompanying by-products. The same applies to the reaction between a dihalogeno compound and a trialkylamine. When about 1 mol of the trialkylamine is used per 1 mol of the dihalogeno compound, the compound represented by the general formula (7) is most recovered without by-products. It can be obtained efficiently.

In the reaction between the dihalogeno compound and the dialkylaminopyridines or trialkylamines, the reaction time and the reaction temperature are not particularly limited. The reaction temperature is preferably 10 to 130 ° C, more preferably 50 to 100 ° C, and the reaction time is preferably 1 to 1
5 hours, more preferably 3 to 10 hours.

The compound represented by the above general formula (6) or (7) obtained by such a reaction is formed as a powder as the reaction proceeds, and is easily isolated and purified by filtration and washing from the reaction solution. . The solvent used for washing is not particularly limited as long as it dissolves the dihalogeno compound and the dialkylaminopyridines or trialkylamines.Examples include hydrocarbons such as hexane and pentane, benzene, and toluene. ,
Solvents such as aromatic hydrocarbons such as xylene. Preferred are hexane, toluene and xylene.

The general formula (6) obtained by such a reaction
Alternatively, by reacting the compound represented by (7) with the sulfide represented by the general formula (8), the target organic sulfide compound represented by the general formula (1) or (2) can be obtained. it can.

In the sulfide represented by the general formula (8), M is a metal atom or ammonium, and specific preferred examples of the metal atom include lithium, sodium, potassium and osmium. Among them,
From the viewpoints of reactivity and economy, the metal atom is preferably sodium. In the general formula (8), n is 2
It is preferable that n is 3 to 6 because it is stable, easy to handle, and inexpensive.

Specific examples of the sulfide used in the present invention include Na ₂ S ₂ , Na ₂ S ₃ , Na ₂ S ₄ , Na
_{2 S 5, Na 2 S 6} , K 2 S 6, O S2 S metal sulfides such as _{6; (NH 4) 2 S} 4, (NH 4) 2 S 5, (NH 4)
Ammonium sulfide such as ₂ S _9, and the like.
These sulfides may be used alone or, if necessary, as a mixture of two or more. Among them, sulfide is Na
₂ S _4-6 or a mixture thereof is preferred.

The amount of the reaction between the compound represented by the general formula (6) or (7) and the sulfide is not particularly limited, but is based on 1 mol of the compound represented by the general formula (6) or (7). hand,
It is preferable to use 0.1 to 5 moles of sulfide since the number of polysulfide bonds can be controlled to a desired number. Examples of the solvent that can be used in this reaction include alcohols such as methanol, ethanol, propanol, and ethylene glycol; ethers such as diethyl ether, dipropyl ether, tetrahydrofuran, and dioxane; and organic solvents such as ketones such as acetone and methyl ethyl ketone. be able to. These solvents may be used alone or, if necessary, as a mixture of two or more.
Among them, the solvent is preferably methanol or ethanol.

Although water can be used as a solvent, when water is used, only salts from the reaction mixture are removed since salts, which are by-products produced by the reaction, dissolve in water. A process is required. On the other hand, when an organic solvent is used, a salt produced as a by-product does not dissolve and can be precipitated in the organic solvent. Therefore, it is preferable to use an organic solvent. In the reaction of the compound represented by the general formula (6) or (7) with the sulfide, the reaction time and the reaction temperature are not particularly limited, but the reaction time is preferably 0.5 to 12 hours, more preferably. Is 1 to 8 hours,
The reaction temperature is preferably from 20 to 80 ° C, more preferably from 20 to 60 ° C.

The rubber composition for a tire according to the present invention is a composition obtained by blending carbon black and an organic sulfide compound with a diene rubber.

The type of the diene rubber used in the rubber composition of the present invention is not particularly limited.
R), isoprene-based rubbers such as polyisoprene rubber (IR); and butadiene-based rubbers such as polybutadiene rubber (BR) and styrene-butadiene copolymer rubber (SBR) can be used. If necessary, it can be used as a mixture of two or more. Among them, those containing butadiene rubber as the diene rubber have a good balance of wet grip, various properties of the tire such as fuel efficiency and roll processability, extrusion processability, processability such as molding processability. preferable.

The rubber composition of the present invention has a general formula
At least one organic compound represented by (9) or (10);
A sulfide compound is blended. As described above, the general formula
In (9) and (10), R¹And R^TwoIs independently charcoal
It is an alkyl group having a prime number of 1 to 3. R ¹And R^TwoExamples of
As a methyl group, an ethyl group, an n-propyl group, is
An o-propyl group and the like can be mentioned. Above all, R¹
And R^TwoIs preferably a methyl group. Also R^Three, R
^FourAnd R^FiveIs independently an alkyl group having 1 to 20 carbon atoms.
You.

In the general formulas (9) and (10), X is a hydrocarbon group consisting of a linear alkylene group and / or an arylene group, and may be composed of only a linear alkylene group. As the straight-chain alkylene group, carbon
A linear alkylene group having from 10 to 10 is preferable because physical properties (fuel efficiency and flexibility) when blended in the rubber composition are good, and a linear alkylene group having 2 to 8 carbon atoms is more preferable. The preferred arylene group is an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenylene group and a naphthylene group, and a phenyl group is preferred because it is easy to produce. n is an integer of 2 to 6, and when n is 4 to 6, it is more preferable because the reactivity between the rubber and the organic sulfide compound and the amount of sulfur released by the reaction can be controlled. When n is small, the reactivity between the rubber and the organic sulfide compound is reduced, and when n is large, the rubber may be too hard.

The amount of the organic sulfide compound to be compounded in the rubber composition according to the present invention is appropriately selected, but preferably 0.1 to 100 mmol, more preferably 0 to 100 mmol of the organic sulfide compound per 100 g of the diene rubber. 0.5 to 50
The addition of mmol is preferred because the abrasion resistance and wet grip properties are further improved, and the fuel economy is further improved.

In the rubber composition of the present invention, if necessary,
Additives such as a vulcanizing agent, a vulcanization accelerator, a reinforcing agent, a filler, a softening agent, a processing aid, an antioxidant, etc., which are used in normal rubber compounding, can be appropriately compounded.

[0053]

EXAMPLES Hereinafter, the present invention will be further described based on specific examples, but the present invention is not limited to these examples.

Preparation Example 1 Preparation of compound of formula (11)

[0055]

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200 ml of toluene was placed in a 500 ml flask,
Chlorobenzyl chloride 31.9 g (198.1 mmo
l), dimethylaminopyridine 24.2 g (198.1 m
mol), and the mixture was reacted at 60 ° C. for 15 hours with stirring. After the reaction solution was cooled to 30 ° C. or lower, the precipitated powder was separated by filtration and washed with toluene to obtain 55.1 g (yield 98%) of the desired compound.

The obtained compound was dissolved in CDCl ₃ ,
¹ H-NMR was measured (s: singlet, d: doublet,
m: multiple line, brs: broad singlet). The results were as follows. ¹ H-NMR (270 MHz, δ, ppm) 3.3 (s, -N
_{(CH 3) 2, 6H)} , 5.8 (s, -CH 2 -, 2
H) 6.8 (d, 3,3 'of pyridinium group (Pym)
Proton, 2H), 7.4 (d, phenylene group (P
h) proton, 2H) 7.6 (d, Ph proton,
2H), 8.8 (d, the proton at the 2,2′-position of Pym;
2H)

Preparation Example 2 Preparation of compound of formula (12)

[0059]

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To a 500 ml flask, 50.0 g (322.4 mmol) of 1,6-dichlorohexane and 39.4 g (322.4 mmol) of dimethylaminopyridine were added, and the mixture was reacted at 80 ° C. for 15 hours with stirring. After the reaction solution was cooled to 30 ° C. or lower, the precipitated powder was separated by filtration and washed with hexane to obtain 78.5 g of the desired compound (yield 87%).

The obtained compound was dissolved in CDCl ₃ to give ¹
1 H-NMR was measured. The results were as follows.

[0062]

(Equation 1)

Production Example 3 Production of Compound of Formula (13)

[0064]

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In a 500 ml flask, 200 ml of toluene,
Chlorobenzyl chloride 25.0 g (155.3 mmo
l), 46.2 g (155.3 mmo) of dimethyllaurylamine
l) was added, and the mixture was reacted at 60 ° C. for 15 hours with stirring.
After the reaction solution was cooled to 30 ° C. or lower, the precipitated powder was separated by filtration and washed with hexane to obtain 65.6 g (yield: 92%) of the desired compound.

The obtained compound was dissolved in CDCl ₃ to give ¹
1 H-NMR was measured. The results were as follows.

[0067]

(Equation 2)

Production Example 4 Production of Compound of Formula (14)

[0069]

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100 ml of ethanol was placed in a 500 ml flask.
l, sodium sulfide (9 hydrate) 21.2 g (88.3m
mol) and 8.5 g (265.0 mmol) of sulfur, and reacted at 40 ° C. for 8 hours with stirring. After cooling the reaction solution to 30 ° C. or lower, 50 g of the compound obtained in Production Example 1 (1
76.6 mmol) and 150 ml of ethanol were added, and the mixture was further stirred at room temperature for 15 hours. After completion of the reaction, the precipitated salt was filtered to obtain an ethanol solution containing the intended organic sulfide compound (content: 18% by weight).

The obtained compound was dissolved in CD ₃ OD to obtain ¹
1 H-NMR was measured. The results were as follows. ¹ H-NMR (270 MHz, δ, ppm) 3.2 (s, -N
_{(CH 3) 2, 12H)} , 5.5 (s, -CH 2 -, 4
H) 7.0 (d, proton at the 3,3'-position of Pym, 4
H), 7.3 (d, Ph proton, 4H), 7.5
(D, Ph proton, 4H), 8.4 (d, Pym 2,2'-position proton, 4H)

Preparation Example 5 Preparation of Compound of Formula (15)

[0073]

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100 ml of ethanol was placed in a 500 ml flask.
l, sodium sulfide (9 hydrate) 21.7 g (90.2m
mol) and 8.68 g (270.6 mmol) of sulfur, and reacted at 40 ° C. for 8 hours with stirring. Reaction solution at 30 ° C
After cooling to the following, 50 g of the compound obtained in Production Example 2
(180.3 mmol) and 150 ml of ethanol were added, and the mixture was further stirred at room temperature for 15 hours. After completion of the reaction, the precipitated salt was filtered to obtain an ethanol solution containing the intended organic sulfide compound (content: 18% by weight).

The obtained organic sulfide compound was converted to CD ₃ O
It was dissolved in D and ¹ H-NMR was measured. The results were as follows.

[0076]

(Equation 3)

From the ¹ H-NMR measurement results, the obtained organic sulfide compound was found to be disulfide, trisulfide,
Consisting of a mixture of tetrasulfides, each ratio was 15:27:58 from the integral ratio of protons.

Production Example 6 Production of Compound of Formula (16)

[0079]

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Ethanol 200m in 500ml flask
l, 13.1 g of sodium sulfide (9-hydrate) (54.5 m
mol) and 5.24 g (163.5 mmol) of sulfur, and reacted at 40 ° C. for 8 hours with stirring. After cooling the reaction solution to 30 ° C. or less, 50 g of the compound obtained in Production Example 3
(109.0 mmol) dissolved in 150 ml of ethanol was added, and the mixture was further stirred at room temperature for 15 hours. After completion of the reaction, the deposited red-orange powder was filtered off and washed with water to obtain 39.8 g (yield: 75.0%) of the desired organic sulfide compound.

The obtained organic sulfide compound was converted to CDCl
₃ and ¹ H-NMR was measured. The results were as shown below.

[0082]

(Equation 4)

Standard Examples 1-2, Examples 1-4 and Comparative Examples
Rubber compositions having the compounding compositions (parts by weight) shown in Tables I and 2 were prepared, and the loss factor tan δ at 0 ° C. and 60 ° C. of each rubber composition was measured. Standard Examples 1 and 2 are standard examples corresponding to a control rubber composition containing no organic sulfide compound. Comparative Examples 1 and 2 are comparative examples corresponding to the control rubber composition when the content of the organic sulfide compound is small.

[0084]

[Table 1]

[0085]

[Table 2]

Evaluation The tan δ (0 ° C. and 60 ° C.) rubber composition containing an organic sulfide compound has a loss factor (tan δ) at 0 ° C. which is lower than that of the standard and comparative examples.
(0 ° C.)) and the loss factor (tan δ) at 60 ° C.
(60 ° C.)), indicating that the wet grip and the fuel economy are improved.

It can be seen that the rubber composition containing the abrasion-resistant organic sulfide compound has improved abrasion resistance as compared with the standard example and the comparative example.

[0088]

The rubber / carbon black coupling agent of the present invention comprising the organic sulfur compound represented by the general formulas (1) and (2) is a diene rubber and carbon black as the rubber / carbon black coupling agent. By blending in a tire, a tire having excellent wear resistance and wet grip properties and high fuel economy can be obtained. According to the present invention, the coupling agent for rubber and carbon black can be easily and efficiently produced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 323/35 C07C 323/35 C07D 213/38 C07D 213/38 (72) Inventor Fumi Yayanagi Hiratsuka-shi, Kanagawa No. 2-1 Yokohama Rubber Co., Ltd. Hiratsuka Factory F-term (reference) 4C055 AA04 AA18 BA01 CA01 DA52 DB01 DB02 EA01 FA13 FA31 FA37 4H006 AA02 AA03 AB48 AC52 AC63 TA04 TB14 4J002 AC011 AC031 AC061 AC081 DA036 EU047 EV047 EV047 EV047 AA02 CB16 CB21 CB26 CC06 EE44 EE48 FF18

Claims (4)

[Claims] 1. The following general formulas (1) and (2): (Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms.
X is an alkylene group and / or an arylene group, Y is a counter anion, and n is an integer of 2 to 6). Coupling agent for rubber and carbon black. 2. The following general formula (3): (Wherein X is an alkylene group and / or an arylene group, and Z is at least one halogen atom selected from a chlorine atom, a bromine atom and an iodine atom) and the following general formula (4) Or (5): (In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³ , R ⁴ and R ⁵ are each independently a C 1 to C 20 group.
Is reacted with a dialkylaminopyridine or a trialkylamine represented by the following general formula (6) or (7): (In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³ , R ⁴ and R ⁵ are each independently a C 1 to C 20 group.
X is an alkylene group and / or an arylene group; Y is a counter anion; and Z is at least one selected from a chlorine atom, a bromine atom and an iodine atom.
Are obtained, and then the compound represented by the following general formula (8): Wherein M is a metal atom or ammonium, and n is 2
2. The method for producing a coupling agent for rubber and carbon black according to claim 1, comprising reacting the sulfide with a sulfide represented by the following formula: 3. A diene rubber containing carbon black and the following general formulas (9) and (10): (Wherein R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms, and R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms.
X is an alkylene group and / or an arylene group, Y is a counter anion, and n is an integer of 2 to 6). The rubber composition which mix | blends. 4. The rubber composition according to claim 3, wherein the amount of the organic sulfide compound is 0.1 to 100 mmol per 100 g of the diene rubber.