KR101281324B1 - Method for producing branched conjugated diene polymer - Google Patents

Abstract

In the polymerization machine, a polymerization step of continuously polymerizing or copolymerizing a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound with an alkali metal initiator in a hydrocarbon solvent to obtain a living polymer or a living copolymer, and a living polymer or a living copolymer The coupling reactor connected through a pipe provided at the outlet of the polymerizer to discharge, wherein the living room is provided in a coupling reactor in which opening-adjustment means is provided in the pipe for discharge from the coupling reactor connected to the coupling reactor. A coupling step of reacting a polyfunctional compound with a polymer or living copolymer to carry out a coupling reaction, and a step of desolventing the polymer, or a living copolymer, and the living polymer or living copolymer and the polyfunctional compound are prepared within 5 minutes after the polymerization step. Reaction and the polymerization by the opening control means. The pressure at the outlet minutes controlled to 0.5 to 2MPaG a method for manufacturing a ground-conjugated diene-based polymer.

Description

Method for producing branched conjugated diene polymer {METHOD FOR PRODUCING BRANCHED CONJUGATED DIENE POLYMER}

The present invention relates to a process for the preparation of branched conjugated diene-based polymers.

Conventionally, an alkali metal initiator is used to polymerize a conjugated diene compound in a hydrocarbon solvent or copolymerize a conjugated diene compound and a vinyl aromatic compound, and then react with a polyfunctional low molecular compound to carry out a coupling reaction to perform a branched polymer or branched air. The method of obtaining coalescing is proposed (for example, refer patent document 1).

Moreover, as a method of obtaining a branched copolymer, it is a method of performing superposition | polymerization continuously by at least 2 reaction zone, The technique which performs a coupling reaction by adding a polyfunctional low molecular compound to a 1st reaction zone ( For example, refer patent document 2).

Moreover, it is a method of performing superposition | polymerization continuously using two polymerizers, The technique which performs a coupling reaction by adding a polyfunctional low molecular compound in a 2nd polymerizer is disclosed (for example, refer patent document 3). ).

Moreover, after performing continuous superposition | polymerization using two polymerizers, the technique of adding a polyfunctional low molecular weight compound and performing a coupling reaction using a static mixer is disclosed (for example, refer patent document 4).

Japanese Patent Publication No. 49-36957 Japanese Patent Publication (Small) 54-6274 Japanese Patent Publication No. 61-255917 International Publication No. 2006/104215

However, the method of producing a branched conjugated diene polymer by continuously performing a coupling reaction subsequent to the continuous polymerization of the conjugated diene polymer is industrial because a slight change in the process greatly affects the quality of the final product. In order to stably produce a branched conjugated diene type polymer, it becomes an important subject.

Therefore, in the present invention, a branched conjugated diene polymer, that is, a branched conjugated diene polymer rubber or a branched random copolymer rubber of a conjugated diene compound and a vinyl aromatic compound can be industrially and efficiently provided. It is an object of the present invention to provide a method for producing the above-mentioned high quality polymer rubber or copolymer rubber.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors polymerizes a conjugated diene compound or a conjugated diene compound, and a vinyl aromatic compound continuously in a hydrocarbon solvent using an alkali metal initiator, and makes the polyfunctional compound react with the living polymer or living copolymer obtained. As a result of examining the manufacturing method of the branched conjugated diene polymer which performs a coupling reaction, the pressure of the outlet of the product taking out of the polymerization machine which performs the said superposition | polymerization, controlling the time until the coupling reaction after superposition | polymerization is performed. By controlling the above, it was found that the above object can be achieved, and the present invention has been completed.

That is, the present invention is as follows.

[1] a polymerization step in which a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound are continuously polymerized or copolymerized with an alkali metal initiator in a hydrocarbon solvent to obtain a living polymer or living copolymer;

A coupling reactor connected through a pipe provided at an outlet of the polymerizer for discharging the living polymer or living copolymer, wherein opening degree adjustment means is provided in a pipe for discharge connected to the coupling reactor. A coupling step of reacting the living polymer or living copolymer with a polyfunctional compound in a coupling reactor in which a coupling reaction is carried out,

Desolvent process,

After the said polymerization process, the said living polymer or a living copolymer and a polyfunctional compound are made to react within 5 minutes,

The manufacturing method of the branched conjugated diene type polymer which controls the pressure at the exit of the said polymerization machine to 0.5-2 MpaG by the said opening degree adjusting means.

[2] The branched conjugated diene-based polymer according to the above [1], wherein the coupling reactor has a rotary stirrer and is a tank reactor having a capacity of 0.5 to 50% of the capacity of the polymerizer. Manufacturing method.

[3] the polymerization reactor is a tank reactor having a stirrer,

In the said polymerization process, the manufacturing method of the branched conjugated diene type polymer as described in said [1] or [2] which randomly copolymerizes a conjugated diene and a vinyl aromatic in presence of a polar compound.

[4] a step of measuring the Mooney viscosity by sampling the living polymer or living copolymer between the coupling step and the coupling step;

[1] to [3], further comprising a step of sampling the branched conjugated diene polymer and measuring the Mooney viscosity when the residence time from the outlet of the polymerizer after the coupling step is less than 15 minutes. The manufacturing method of the branched conjugated diene type polymer in any one of them.

[5] The method for producing a branched conjugated diene polymer according to any one of [1] to [4], wherein one tank reactor having a stirrer is used as the polymerizer.

[6] The method for producing a branched conjugated diene polymer according to any one of [1] to [5], using a polyepoxy compound having a tertiary amino group in the molecule as the multifunctional compound.

[7] The polyfunctional compound is

A glycidylamino group-containing low molecular compound having two or more tertiary amino groups and three or more glycidyl groups bound to the amino group in the molecule, and a dimer or more oligomer component of the glycidylamino group-containing low molecular compound,

Production of the branched conjugated diene polymer according to any one of the above [1] to [6], wherein the low molecular weight compound is 75 to 95% by mass and the oligomer is 25 to 5% by mass based on the total amount of the polyfunctional compound. Way.

[8] The method for producing a branched conjugated diene polymer according to any one of [1] to [7], wherein a reaction ratio of the living polymer or the living copolymer and the multifunctional compound is 10 to 80 mass%.

[9] The branched conjugated diene polymer has a molecular weight distribution measured by gel permeation chromatography (GPC) of 1 peak and has a weight average molecular weight of 500,000 to 2 million in terms of polystyrene. The manufacturing method of the branched conjugated diene type polymer in any one of [8].

[10] The branched conjugated diene polymer is a copolymer of a conjugated diene compound and a vinyl aromatic compound, and a short chain of the vinyl aromatic compound by ozone decomposition is 40% or more relative to the total amount of the vinyl aromatic compound, The manufacturing method of the branched conjugated diene type polymer in any one of said [1]-[9] whose 8 or more chains are 5% or less.

According to the production method of the present invention, it is possible to stably and efficiently produce a high quality branched conjugated diene polymer.

That is, the branched conjugated diene-based polymer with little variation in viscosity and degree of branching, high conversion ratio and high degree of branching in a short residence time can be produced continuously with little gel generation and energy saving.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail.

In addition, this invention is not limited to the following description, It can variously deform and implement within the range of the summary.

[Method for producing branched conjugated diene polymer]

The manufacturing method of the branched conjugated diene polymer of this embodiment is

A polymerization step in which a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound are continuously polymerized or copolymerized with an alkali metal initiator in a hydrocarbon solvent to obtain a living polymer or a living copolymer,

A coupling reactor connected through a pipe provided at an outlet of the polymerizer for discharging the living polymer or living copolymer, the coupling reactor having an opening control means installed in a discharge pipe connected to the coupling reactor; A coupling step of reacting the living polymer or living copolymer with a polyfunctional compound to perform a coupling reaction,

It has a process of desolventing.

Further, after the polymerization step, the living polymer or living copolymer and the polyfunctional compound are allowed to react within 5 minutes,

The opening degree adjusting means controls the pressure at the outlet of the polymerization reactor to 0.5 to 2 MPaG.

(Manufacturer which performs the manufacturing method of a branched conjugated diene type polymer)

First, the manufacturing apparatus (henceforth simply a manufacturing apparatus) which implements the manufacturing method of the branched conjugated diene type polymer of this embodiment is demonstrated.

The manufacturing apparatus is equipped with a polymerizer and a coupling reactor.

<Polymerizer>

As a polymerizer, the tank reactor which has a stirrer is preferable, and a vertical type | mold polymerizer is more preferable from a viewpoint of easy start and stop.

The vertical type refers to a structure provided so that the central axis of the tank reactor becomes vertical.

In the polymerization process mentioned later, especially in the polymerization process of random-copolymerizing a conjugated diene and a vinyl aromatic, it is preferable to use a molding reactor for copolymerization with high randomness. As the method for evaluating randomness, a method by ozone decomposition is used.

Although the polymerizer is a structure which uses one tank reactor which has a stirrer, and the structure which connects several polymerizers in series, The structure which uses one group of polymerizers is preferable because a living rate becomes high.

Coupling Reactor

The coupling reactor is connected via a pipe provided at the outlet of the polymerizer for discharging the polymer obtained in the polymerizer described above.

Moreover, the opening degree adjustment means is provided in the piping for discharge | emission from the coupling reactor connected to the said coupling reactor.

By adjusting this opening degree adjustment function, the pressure at the exit of the polymerization reactor can be controlled.

In a coupling reactor, a polyfunctional compound is mixed with the solution of the living polymer or living copolymer obtained by the polymerization reaction in the said polymerization machine, and it performs coupling reaction as mentioned later.

The coupling reactor is equipped with a rotary stirrer and is preferably a tank reactor having a capacity of 0.5 to 50% of the capacity of the polymerizer, and is preferably a tank reactor having a capacity of 1 to 20%.

If it is a model reactor, the advantage that the problem of being blocked by the gel produced | generated by the polymerization machine is unlikely to generate | occur | produce.

Moreover, a coupling reaction can be performed stably with respect to the fluctuation | variation of the flow volume of a polymer and a polyfunctional compound. Moreover, if it is the volume of the said range, a more stable coupling reaction can be performed.

If the volume of the coupling reactor is excessive, the residence time becomes long, and the variation range such as viscosity and branching degree of the branched polymer after coupling becomes large, making it difficult to control. In addition, as a volume, it is a volume of a liquid phase, and when a gaseous phase exists and a stirrer or other apparatus exists, the part is not included.

Moreover, as for a coupling reactor, it is preferable that relationship d / D of internal diameter D (m) and blade diameter d (m) of a stirrer is 0.5 or more, and it is more preferable that d / D is 0.6 or more.

When the inner diameter and the blade diameter of the stirrer satisfy the above relationship, there is little variation in the viscosity and branching degree of the coupling polymer produced even at a relatively small capacity, thereby enabling a stable coupling reaction.

In addition, it is preferable that the product nd of the rotation speed n (s- ¹ ) and the blade diameter d (m) of the rotary stirrer of a coupling reactor is 0.1 or more, and the economical range is more preferable in the range of 0.2-5.

In this case, the variation of the viscosity and the branching degree of the produced polymer is less, and the volume of the coupling reactor can be made smaller.

(Polymerization step)

In the above-described polymerizer, a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound are continuously polymerized or copolymerized with an alkali metal-based initiator in a hydrocarbon solvent to obtain a living polymer or a living copolymer.

First, the material used in a superposition | polymerization process is demonstrated, and a concrete superposition | polymerization process is demonstrated subsequently.

<Conjugated Diene Compound>

Although it is not limited to the following as a conjugated diene compound, For example, 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, 1, 3- pentadiene, 3-methyl- 1, 3- penta Dienes, 1,3-heptadiene, 1,3-hexadiene and the like. In particular, 1, 3- butadiene and isoprene are preferable.

These may be used independently and may combine 2 or more types.

<Vinyl aromatic compound>

Although it is not limited to the following as an aromatic vinyl compound, For example, styrene, p-methylstyrene, (alpha) -methylstyrene, vinyl ethylbenzene, vinyl xylene, vinyl naphthalene, diphenylethylene, etc. are mentioned. In particular, styrene is preferable.

These may be used independently and may combine 2 or more types.

<Hydrocarbon solvent>

Saturated hydrocarbons, aromatic hydrocarbons, etc. are used as a hydrocarbon solvent, For example, Aliphatic hydrocarbons, such as butane, a pentane, hexane, a pentane, heptane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, and xylene, and hydrocarbons including mixtures thereof.

The conjugated diene compound, the aromatic vinyl compound, and the hydrocarbon solvent described above have high concentrations of activity by removing impurities, water, arenes, acetylenes, and carbonyls, respectively, alone or before the respective mixtures are subjected to a polymerization reaction described later. A polymer having a terminal can be obtained, and further a high modification rate can be achieved.

As the amount of these impurities, it is preferable that the water per mass of the total monomers provided to the polymerization reaction is less than 20 ppm, and the arenes and acetylenes are less than 200 ppm.

However, some amount of chain transfer agent, for example, arenes, specifically 1,2-butadiene, propadiene, may be present in the range of less than 200 ppm to prevent gel formation in the polymerization.

<Alkali metal initiator>

As an alkali metal type initiator, all the alkali metal compounds which have a function of a polymerization start can be used.

In particular, an organolithium compound is preferable.

As the organolithium compound, a low molecular weight, an organolithium compound of a solubilized oligomer, one having lithium alone in one molecule, a plurality of lithium in one molecule, and a carbon-lithium bond in the bonding mode of the organic group and lithium Including, including nitrogen-lithium bonds, containing tin-lithium bonds, and the like.

As an organolithium which is the said alkali metal type initiator, the specific example of the compound containing a mono organolithium compound, a polyfunctional organolithium compound, and a nitrogen-lithium bond is illustrated below.

Although it is not limited to the following as a mono organolithium compound, For example, n-butyllithium, sec-butyllithium, tert- butyllithium, n-hexyl lithium, benzyl lithium, phenyl lithium, stilben lithium, etc. are mentioned.

Although it is not limited to the following as a polyfunctional organolithium compound, For example, 1, 4- dirithio butane, the reactant of sec-butyllithium and diisopropenylbenzene, 1, 3, 5- tririthio benzene, n- And a reaction product of butyllithium with 1,3-butadiene and divinylbenzene, and a reaction product of n-butyllithium and polyacetylene compound.

In addition, as a compound containing a nitrogen-lithium bond, it is not limited to the following, For example, dimethylamino lithium, dihexyl amino lithium, diisopropyl amino lithium, hexamethylene imino lithium, etc. are mentioned.

Furthermore, the organoalkali metal compound disclosed in US Patent 5,708,092 specification, UK Patent 2,241,239 specification, US Patent 5,527,753 specification, etc. can also be used.

As the organolithium compound, n-butyllithium and sec-butyllithium are more preferable.

These organolithium compounds may be used independently and may use 2 or more types together.

As an organoalkali metal compound other than an organolithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound, an organic cesium compound, etc. are mentioned.

Examples of the organic alkali metal compound other than the organolithium compound include, but are not limited to, sodium naphthalene and potassium naphthalene, and lithium, sodium, potassium alkoxides, sulfonates, carbonates, amides, and the like are used.

Alkali metal-type initiator can also be used together with another organometallic compound.

As another organometallic compound, an organic magnesium compound, an organoaluminum compound, etc. are mentioned, for example, Dibutyl magnesium, triethyl aluminum, etc. are mentioned specifically ,.

<Polar Compound>

By using a polar compound together with the alkali metal-based initiator mentioned above, superposition | polymerization initiation rate can be raised, the microstructure of the conjugated diene unit in a polymer can be controlled, and the monomer reactivity ratio in copolymerization can be controlled.

Although it is not limited to the following as a polar compound, For example, an ether compound, a tertiary amine compound, a metal alkoxide compound, a phosphine compound, an organic sulfonic acid metal compound, etc. are used.

The polar compound has an effective randomization effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound described later, and can be used as an agent for adjusting the distribution of the aromatic vinyl compound and for adjusting the amount of styrene blocks.

For example, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2 Ethers such as oxolanyl) propane and the like; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidin and the like; Alkali metal alkoxide compounds such as potassium-t-amylate, potassium-t-butyrate, sodium-t-butyrate, sodium-t-amylate and the like; Phosphine compounds such as triphenylphosphine and the like; Alkyl or aryl sulfonic acid compounds, such as potassium dodecyl benzene sulfonate and sodium dodecyl benzene sulfonate, etc. are mentioned.

These polar compounds may be used alone or in combination of two or more thereof.

Although the usage-amount of a polar compound can be suitably selected according to the objective and the grade of effect, Usually, it is 0.01-100 mol with respect to 1 mol of alkali metal type initiators mentioned above.

In addition to adjusting the copolymerization reactivity ratio, such a polar compound may be appropriately used in accordance with the desired amount of vinyl bonds as a microstructural regulator of the polymer diene moiety.

As a polar compound, the ether group containing hydrocarbon compound which has a 2 or more ether group in a molecule | numerator, at least 1 of them forms a ring is preferable.

By using these, the effect that a monomer conversion rate is high, there is little deactivation, and the living polymer rate of a copolymer becomes high can be acquired.

As an ether group containing hydrocarbon compound which has two or more ether groups in a molecule | numerator, and at least one of them forms a ring, for example, alkyl of 2, 2-bis (2-oxolanyl) propane and tetrahydropyranylmethanol Ether and the like, and preferably 2,2-bis (2-oxolanyl) propane.

<Polymerization process>

By using the alkali metal initiator as described above, a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound are continuously polymerized or copolymerized in the hydrocarbon solvent to obtain a living polymer or a copolymer.

5-30 mass% is preferable, and, as for the monomer concentration in a polymerization solution, 10-20 mass% is more preferable.

In this polymerization step, it is necessary to continuously provide necessary raw materials such as monomers, hydrocarbon solvents, alkali metal initiators, etc. from one or more predetermined nozzles provided in the polymerization reactor, and correspond to the outlet of the polymerization reactor for discharging the polymer solution after polymerization of the contents. It extracts continuously from the predetermined nozzle different from the said nozzle.

It is preferable to perform a superposition | polymerization process as the temperature of the exit of a polymerization machine as 70 degreeC-110 degreeC, 90-110 degreeC is more preferable, and 95 degreeC-107 degreeC is still more preferable.

By making polymerization temperature 110 degrees C or less, a living rate becomes high and a high coupling yield is obtained.

On the other hand, high conversion ratio is obtained by making polymerization temperature 70 degreeC or more.

The higher the conversion ratio of the monomer at the outlet of the polymerization reactor, the better, but it is preferably 95% or more, more preferably 98% or more, and still more preferably 99% or more.

In addition, the conversion rate is influenced by the exit temperature of the polymerization reactor, the temperature distribution in the polymerization reactor, the stirring state, the amount of the initiator, the type and amount of the polar compound, and the average residence time, and the conversion rate is increased at the same time to increase the living ratio. It is preferable. When the conversion ratio is sufficiently high as described above, the shorter the average residence time in the polymerization reactor, the higher the living ratio of the polymer obtained, and the higher the coupling yield in the coupling step described later.

The average residence time in the polymerizer is preferably within 40 minutes. More preferably, it is within 35 minutes, and when it is too short, since conversion rate falls, 15 minutes or more are preferable.

(Coupling process)

A coupling process is a process of making a coupling reaction by making a polyfunctional compound react with the said living polymer or living copolymer obtained in the said superposition | polymerization process.

First, it uses about the material used in a coupling process, and then a concrete coupling process is demonstrated.

<Multifunctional compound>

As a polyfunctional compound, the compound which has two or more functional groups in a molecule | numerator which react with a living polymer or a living copolymer to form a bond is used.

The polyfunctional compound is a polyfunctional compound having at least three branches by a coupling reaction, having at least three or more identical or different functional groups in one molecule, and having four to eight branches.

Moreover, as a result of the coupling reaction, it may be a thing to introduce heterogeneous functional groups into the terminal of a polymer or a copolymer.

As for the usage-amount of a polyfunctional compound, 0.05-5 equivalent is preferable as a functional group of a polyfunctional compound with respect to 1 mol of alkali metal type initiators mentioned above, More preferably, it is 0.1-2 equivalent.

As a functional group which reacts with a living polymer or a living copolymer, and forms a bond, For example, a halogen group, a carbonyl group, a carboxylic ester group, a carboxylic acid amide group, a carboxylic acid halogenide group, a thiocarbonyl group, a thiocarboxyl Acid ester groups, thiocarboxylic acid amide groups, thiocarboxylic acid halogenide groups, isocyanate groups, thioisocyanate groups, epoxy groups, thioepoxy groups, alkoxysilyl groups, and functional double bonds include vinyl groups and imino groups. Can be.

Moreover, it is preferable to use the thing which does not bind with a living terminal in the molecule | numerator of a polyfunctional compound, but has compatibility with a filler, or has a functional group which has binding reactivity.

Such functional groups include tertiary amino groups, primary or secondary amino groups protected with silicon compounds, and the like.

Preferable examples of the polyfunctional compound include silicon tetrahalide, bis (trihalogenated silyl) alkane, tin tetrahalide, tetraalkoxysilicon, trialkoxyalkylsilicon, hexaalkoxydisilane, bis (trialkoxysilyl) alkane, bis (trialkoxysilylalkyl ) Alkylamine, bis (trialkoxysilylalkyl) trialkylsilylamine, tris (trialkoxysilylalkyl) amine, 1,4-bis (trialkoxysilylalkyl) piperazine, 1,3-bis (trialkoxysilylalkyl) Imidazolidine, 1,3-bis (trialkoxysilylalkyl) hexahydropyrimidine, 1,1-dialkoxy-2 (trialkoxysilylalkyl) -1-sila-2-azacyclopentane, 1,1- Dialkoxy-2 (trialkoxysilylalkyl) -1-sila-2-azacyclohexane, 1,1-diakoxy-2 (trialkoxysilylalkyl) -1-sila-2-azacycloheptane, dicarboxylic acid Diester, tricarboxylic acid triester, carbonic acid diester, compound having three or more glycidyl ether groups, article The compound which has 3 or more of lycidyl amino groups, the compound which has 2 or more of diglycidyl amino groups, etc. are mentioned.

Specifically, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, tin tetrachloride, 1,2-bis (trichlorosilyl) ethane, tetramethoxysilicone, tetraethoxysilicon, trimethoxymethylsilicon, hexaethoxy Sidisilane, 1,2-bis (trimethoxysilyl) ethane, 1,1-bis (trimethoxysilyl) ethane, bis (3-triethoxysilylpropyl) methylamine, bis (2-trimethoxysilyl Ethyl) propylamine, bis (3-trimethoxysilylpropyl) trimethylsilylamine, tris (trimethoxysilylmethyl) amine, tris (3-triethoxysilylpropyl) amine, 1,4-bis [3- ( Trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, 1,3-bis [3- (trimethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (Triethoxysilyl) propyl] hexahydropyrimidine, 1,3- ratio [3- (tributoxysilyl) propyl] -1,2,3,4-tetrahydropyrimidine, 1,1-dimethoxy-2 (3-trimethoxysilylpropyl) -1-sila-2-aza Cyclopentane, 1,1-diethoxy-2- (3-triethoxysilylpropyl) -1-sila-2-azacyclopentane, 1,1-dimethoxy-2- (3-dimethoxymethylsilylpropyl) -1-sila-2-azacyclopentane, 1,1-dimethoxy-2 (4-trimethoxysilylbutyl) -1-sila-2-azacyclohexane, 1,1-dimethoxy-2 (5- Trimethoxysilylpentyl) -1-sila-2-azacycloheptane, dimethyl adipic acid, trimethyl trimellitic acid, triethyl trimethyl, dimethyl carbonate, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether , Tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidylmethaxylenediamine, tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-4 -(4-glycidyl-1-piperazinyl) aniline, N, N-diglycidyl-4-glycidyloxyaniline Can.

As a more preferable example of a polyfunctional compound, the polyepoxy compound which has a tertiary amino group in a molecule | numerator can be mentioned. If the epoxy group is three or more, a branched polymer is obtained.

In this case, the branched polymer obtained without generating a by-product will be excellent in the performance as a rubber.

Specifically, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidylmethaxylenediamine, tetraglycidyl-4,4'-diaminodiphenylmethane, N, N- diglycidyl 4- (4-glycidyl-1-piperazinyl) aniline and N, N- diglycidyl-4-glycidyloxyaniline are mentioned.

As a more preferable example of a polyfunctional compound, the glycidylamino group containing low molecular compound which has two or more tertiary amino groups and three or more glycidyl groups couple | bonded with the said amino group, and the dimer of the said glycidylamino group containing low molecular compound The polyfunctional compound containing the above oligomer component and containing 75-95 mass% of said low molecular weight compounds and 25-5 mass% of the said oligomers with respect to whole quantity of a polyfunctional compound is mentioned.

Specifically, the mixture containing tetraglycidyl-1, 3-bisaminomethyl cyclohexane and its oligomer component is mentioned.

By using the above polyfunctional compound, the branched conjugated diene compound has better physical properties as a rubber.

Coupling Process

In this coupling process, a polyfunctional compound is mixed and reacted with the living polymer or living copolymer solution discharged | emitted from the polymerizer exit.

At this time, the above-mentioned polymerizer and the coupling reactor are connected in series by piping provided at the outlet of the polymerizer, and after discharged from the outlet of the polymerizer to the living polymer or living copolymer solution discharged from the polymerizer outlet. It is necessary to react by mixing the multifunctional compound within 5 minutes with an average residence time. The average residence time is preferably within 3 minutes, more preferably within 2 minutes.

In the present embodiment, the opening degree adjusting means capable of controlling the pressure at the outlet of the polymerizer is provided in the pipe for discharge connected to the coupling reactor as described above, whereby the outlet of the polymerizer is thereby provided. The pressure at is controlled to 0.5 to 2 MPaG.

Preferable pressure may be a pressure that does not vaporize because it is sufficiently higher than the vapor pressure in the polymerization reactor, preferably in the range of 0.6 to 1.5 MPaG, and more preferably in the range of 0.7 to 1.2 MPaG. In addition, the range in which the pressure fluctuates with respect to the set value is preferably within ± 0.2 MPa, more preferably within ± 0.1 MPa, and smaller is more preferable.

As the opening degree adjusting means, an automatic or manual pressure control valve, an orifice plate, or the like can be applied. In particular, automatic pressure control valves are preferred. When using an automatic pressure control valve, when the opening degree of a control valve changes large, it is preferable to use a manual pressure control valve together with an automatic pressure control valve.

The control of the pressure at the outlet of the polymerization reactor is carried out over the entire process of producing the target branched conjugated diene polymer through the above-described polymerization step and the coupling step.

Thus, the viscosity and the powder of the branched conjugated diene polymer produced by controlling the pressure at the exit of the polymerization reactor by specifying the installation position of the opening degree adjusting means in the piping for discharge from the coupling reactor connected to the coupling reactor. There is little variation in map, and stable production is possible.

The installation position of the opening adjustment means is a pipe for discharge that reaches and connects downstream of the coupling reactor, and may be anywhere as far as the next step.

In the piping for discharge connected to a coupling reactor, the mixer which mixes an additive, extender oil, etc. may be provided.

In the method for producing a branched conjugated diene-based polymer of the present embodiment, in order to prevent sudden pressure drop due to the operation of the opening control means and vaporization of the solvent resulting therefrom, and to maintain a uniform state in concentration and flow rate. The polymerization apparatus in which the opening degree adjusting means is provided downstream of the coupling reactor is used.

By controlling the pressure at the outlet of the polymerization reactor to 0.5 to 2 MPaG, a sufficient conversion ratio can be ensured, and since it can be carried out by a relatively simple facility, it is also economically preferable.

In addition, it is necessary to substantially set the pressure at the outlet of the polymerizer to this range, and the installation place of the pressure detector for automatically controlling the pressure is not limited to the outlet of the polymerizer. May be any of piping and a coupling reactor, and may be upstream than the opening degree adjusting means.

In addition, it is also possible to provide opening degree adjustment means in the outlet piping of the polymerization reactor and the outlet piping of the coupling reactor, respectively. Also in this case, it is preferable to control the outlet pressure of the polymerization reactor mainly by the opening degree adjusting means of the outlet pipe of the coupling reactor, and the opening pipe adjustment means installed in the outlet pipe of the polymerization reactor to the outlet piping of the coupling reactor. It is also possible to assist the pressure control by the opening degree adjustment means provided.

As described above, by completing the polymerization process and the coupling process for a short time at a relatively high temperature, there is little variation in viscosity and degree of branching, and a branched conjugated diene polymer having a high conversion ratio and any branching degree in a short residence time is obtained. Energy production can be carried out continuously while reducing the gel production.

[Viscosity Management Process]

In the manufacturing method of the branched conjugated diene type polymer of this embodiment, the process of sampling the said living polymer or a living copolymer and measuring a Mooney viscosity between the above-mentioned polymerization process and the above-mentioned coupling process, and coupling It is preferable to further have the process of sampling a branched conjugated diene type polymer and measuring a Mooney viscosity when the residence time from the exit of the said polymerization machine is less than 15 minutes after a process.

Thereby, the viscosity and branching of the branched conjugated diene polymer can be stabilized. As for the residence time from the exit of the said polymerizer to sampling, less than 10 minutes are more preferable.

Mooney viscosity is 2 minutes per minute after preheating at arbitrary temperature in the range of 100 degreeC-130 degreeC normally for 1 minute using a Mooney viscometer using the Mooney viscometer as follows. It rotates and the viscosity after 4 minutes is measured.

Specifically, the Mooney viscosity of the living polymer or living copolymer in the precoupling stage is measured and managed from a predetermined sampling nozzle at the stage before the outlet of the polymerizer or the polyfunctional compound is added, and the outlet of the coupling reactor or the After that, it is preferable to measure and manage the Mooney viscosity of the branched conjugated diene polymer obtained after the coupling process from a predetermined sampling nozzle at the position where the residence time from the polymerization reactor outlet is less than 15 minutes.

The sampling nozzle is provided with a branch pipe in a predetermined pipe or the like, a container having a capacity required for sampling, and a predetermined partition valve before and after, and a pipe for introducing an inert gas into the container as necessary. It is preferable to set it as one structure.

The residence time is calculated based on the volume of the liquid phase passing through the equipment.

If there is a gas phase, the stirrer and other devices are not included.

Before and after the coupling process, the Mooney viscosity of the living polymer or living copolymer is measured and managed, and the residence time from the polymerizer outlet can be relatively short, thereby quickly detecting variations in the product during the process. It can respond, and finally stabilizes the viscosity and branching degree of the branched conjugated diene type polymer made into the objective.

In this embodiment, it is preferable that the living polymer or living copolymer before a coupling process has a Mooney viscosity (ML-I) of 110 degreeC in the range of 50-100, and the branched conjugated diene type polymer or air after a coupling process is airborne. It is preferable that coalescence has the Mooney viscosity (ML-C) of 110 degreeC in the range of 100-150.

Moreover, it is preferable that said (ML-C) is 1.2 to 3 times the range of said (ML-I).

As a management width | variety of Mooney viscosity before a coupling process, it is preferable to set it as +/- 10 with respect to a target value, and it is more preferable to set it as +/- 5 within.

In addition, it is preferable to make the management width | variety of the Mooney viscosity after a coupling process into less than +/- 15 with respect to a target value, and it is more preferable to set it within +/- 8.

Moreover, it is preferable to manage the width | variety of the Mooney viscosity before a coupling process in the numerical range narrower than the width | variety of the Mooney viscosity after a coupling process.

As a method of managing in these numerical ranges, for example, the amount of the initiator is increased and controlled so that the Mooney viscosity before coupling falls into the management width, and the amount of the polyfunctional compound is increased and managed so that the Mooney viscosity after coupling falls within the management width. do.

By managing in this way, the viscosity, molecular weight and branching degree of the branched conjugated diene type polymer made into the objective can be optimized, and stable quality can also be ensured also about the processability of rubber and the performance of a vulcanized rubber.

[Quality Control Process]

In the manufacturing method of the branched conjugated diene polymer of this embodiment, after the coupling process mentioned above, the branched conjugated diene polymer which passed through the said opening degree control means provided in the piping for discharge of a coupling reactor (in air) The solution of the coalescence) is preferably stored in a storage tank and subjected to a quality control step of controlling quality.

The storage tank is preferably maintained at a pressure of about 0.05 to 0.3 MPaG.

In addition, a stopper, a neutralizing agent, an antioxidant, or a process oil may be further added, if necessary, before storage in the storage tank, in the storage tank, or before the desolvent process from the storage tank. In the quality control process, a Mooney viscosity, branching degree, additive amount, and a composition ratio in the case of a copolymer are measured as an inspection.

Desolvent Process

After the quality control process, the branched conjugated diene-based polymer (copolymer) solution or the dielectric branched conjugated diene-based polymer (copolymer) solution is sent to a predetermined finisher by a predetermined pump or the like to remove the solvent. Do it.

Thereby, the branched conjugated diene type polymer made into the objective is obtained.

As a method of desolventing and obtaining a branched conjugated diene type polymer, a conventionally well-known method is applicable.

For example, the solvent is separated by steam stripping or the like, followed by filtration, further dehydration and drying treatment to obtain it, concentrating in a flushing tank, and devolatilizing in a vent extruder or the like, drum dryer or the like. Direct devolatilization may be applied.

[Branched conjugated diene polymer]

By passing through each process mentioned above, the target branched conjugated diene type polymer is obtained.

Hereinafter, the characteristic of the branched conjugated diene type polymer obtained by implementing the manufacturing method of this embodiment is demonstrated.

(Reaction rate with polyfunctional compound)

It is preferable that the branched conjugated diene type polymer obtained by the manufacturing method of this embodiment is 10-80 mass% of reaction ratio with the polyfunctional compound mentioned above.

When the reaction ratio with the polyfunctional compound is within the above range, it becomes an appropriate branching, and the workability is good, and when the vulcanized rubber is used, excellent physical properties are obtained.

(Molecular weight distribution)

The branched conjugated diene-based polymer obtained by the production method of the present embodiment has a molecular weight distribution of 1 acid, that is, 1 peak by gel permeation chromatography (GPC), and has a weight average molecular weight of 50 in terms of molecular weight in terms of polystyrene. It is preferable that it is 10,000-2 million.

If a weight average molecular weight is the said numerical range, workability will become favorable and the outstanding physical property will be obtained when it is set as a vulcanized rubber.

It is preferable that it is 1.7-3.0 as Mw (weight average molecular weight) / Mn (number average molecular weight), and, as for molecular weight distribution by GPC, it is preferable that it is 1.8-2.8.

If molecular weight distribution is the said range, workability will become favorable and the outstanding physical property will be obtained when it is set as a vulcanized rubber.

(Preferred Form of Branched Conjugated Diene-Based Polymer)

The branched conjugated diene type polymer obtained by the manufacturing method of this embodiment superposes | polymerizes or copolymerizes a conjugated diene compound, a conjugated diene compound, and a vinyl aromatic compound, respectively.

For example, polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-isoprene copolymer is preferable, and it is more preferable that it is a styrene-butadiene copolymer.

When the branched conjugated diene polymer is a branched random copolymer of the conjugated diene compound and the vinyl aromatic compound, the mass ratio of the conjugated diene compound in the branched random copolymer is 50 to 80 mass%, and the mass ratio of the vinyl aromatic compound is 50 It is preferable that it is-20 mass%.

Moreover, it is preferable that the vinyl structure of the conjugated diene part of the said copolymer is 30-65 mol%.

If it is the said range, when a vulcanized rubber is manufactured using a branched conjugated diene type polymer (copolymer) as mentioned later, and it is used as a rubber | gum for the tread of a passenger car tire, the balance of wet skid resistance and fuel efficiency is favorable. do.

When the branched conjugated diene-based polymer obtained by the production method of the present embodiment is a branched random copolymer of a conjugated diene compound and a vinyl aromatic compound, one having a small or no component having a chain length of aromatic vinyl of 30 or more desirable.

Specifically, when the branched conjugated diene polymer obtained by the production method of the present embodiment is a butadiene-styrene copolymer, the method of Kolthoff (IMKOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946) When the branched conjugated diene-based polymer is decomposed by the method described in the above) and measured by a known method for analyzing the amount of polystyrene (the amount of block styrene) insoluble in methanol, the amount of the block styrene relative to the total amount of the branched conjugated diene-based polymer is measured. It is preferable that it is 5 mass% or less, and it is more preferable that it is 3 mass% or less.

More specifically, when the branched conjugated diene-based polymer obtained by the production method of the present embodiment is decomposed by the method of ozone decomposition and the styrene chain distribution is analyzed by GPC, the isolated styrene, that is, the chain of styrene units It is preferable that styrene (short chain of styrene) of 1 is 40 mass% or more with respect to the total amount of bound styrene, and long-chain block styrene, ie, styrene whose chain of a styrene unit is 8 or more, is 5 mass% or less with respect to the total amount of bound styrene.

In addition, it is not limited to styrene, It is preferable that it is the said numerical range in common about the vinyl aromatic compound which comprises a branched conjugated diene type polymer.

By setting it as the said numerical range, vulcanized rubber using a branched conjugated diene type polymer aims at reducing kinetic performance, for example, the heat generation at the time of deformation and recovery of a rubber | gum.

[Genetic polymer]

The branched conjugated diene polymer obtained by the manufacturing method of this embodiment can also be made into a dielectric polymer by adding process oil as needed before the above-mentioned desolvent process.

As said process oil, aromatic oil, naphthenic oil, paraffin oil, and the aromatic replacement oil whose polycyclic aromatic component by IP346 method is 3 mass% or less are preferable, for example.

In particular, it is preferable to use an aromatic substitute oil having a polycyclic aromatic component of 3% by mass or less from the viewpoint of environmental safety, oil bleeding prevention, and wet grip characteristics.

Examples of the aromatic replacement oils include RAE, in addition to TDAE, MES, and the like described in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999).

Although the usage-amount of extender oil is arbitrary, it is 10-60 mass parts normally with respect to 100 mass parts of branched conjugated diene type polymers. Generally, 20 to 37.5 parts by mass is preferable.

[Branched conjugated diene-based polymer composition]

The vulcanized rubber composition of the branched conjugated diene polymer is obtained by adding and mixing a predetermined material to the branched conjugated diene polymer obtained as described above.

Branched conjugated diene polymers are generally processed by methods commonly used in the rubber industry and used as rubber products.

The vulcanized rubber composition using the branched conjugated diene-based polymer is blended with a predetermined other rubber material as necessary to the branched conjugated diene-based polymer to blend a filler, and a silane coupling agent, a softener for rubber, a vulcanizing agent, and a vulcanizing agent. It is obtained by adding and processing an adjuvant and other additives.

Specifically, a kneader with temperature control is used to knead the branched conjugated diene polymer by adding other rubber materials, fillers (silica and / or carbon black), silane coupling agents, rubber softeners, anti-aging agents and the like as necessary. To obtain a rubber compound. In that case, it is performed in 1 step | paragraph or in multistage. In order to improve the dispersion of the filler, kneading is preferably performed in multiple stages. After cooling the obtained rubber compound, it is kneaded by adding a vulcanizing agent, a vulcanizing aid and the like. By molding and vulcanizing this, a vulcanized rubber composition using the branched conjugated diene polymer of interest is obtained.

As the other rubber material, natural rubber and synthetic rubber can be applied. Examples of the synthetic rubber include low cis polybutadiene, high cis polybutadiene, VCR (vinyl cis butadiene rubber), SBR (styrene butadiene rubber), isoprene rubber, butyl rubber, EPDM (ethylene propylene propylene diene rubber) and the like. Can be mentioned.

Examples of the filler include inorganic fibrous materials such as carbon black, precipitated silica, fumed silica, clay, talc, miker, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber.

In particular, carbon black and precipitated silica are preferably used.

The said silane coupling agent is a compound which has the function which makes the interaction of the above-mentioned rubber component and a silica type inorganic filler close, and has affinity or binding group with respect to each of a rubber component and a silica type inorganic filler.

Generally as a silane coupling agent, the compound which has a sulfur bond part, an alkoxy silyl group, and a silanol group part in 1 molecule is used.

The silane coupling agent is not limited to the followings, but is, for example, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide And bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide.

As the rubber softener, mineral oil or a liquid or low molecular weight synthetic or vegetable softener is preferably used.

As the vulcanizing agent, radical initiators, sulfur, sulfur compounds and the like can be used.

Zinc oxide, stearic acid, etc. can be used as said vulcanization adjuvant.

Other additives include vulcanization accelerators, anti-aging agents, waxes, conductive agents, colorants and the like.

<Examples>

Hereinafter, although a specific Example and a comparative example are given and demonstrated, this invention is not limited to these.

First, the measuring method and the evaluation method of the physical property applied to the Example and the comparative example are shown below.

[(1) styrene bound]

The sample for measurement was made into the chloroform solution, the absorption amount of the ultraviolet-ray (UV) of wavelength 254nm by the phenyl group of styrene was measured using UV-2450 by Shimadzu Corporation, and the amount of bound styrene (mass%) was measured.

[(2) styrene chain]

According to Korthoff's method, the osmic acid decomposition product of the sample for measurement was obtained, and the insoluble polystyrene equivalent to block polystyrene was precipitated in methanol using this.

This amount of insoluble polystyrene was quantified, and the amount of block styrene was calculated as mass% per polymer.

In addition, the content of styrene short chains having one styrene unit and styrene long chains having eight or more styrene units in succession was determined by using a method such as Tanaka et al. (Polymer, 22, 1721 (1981)) to convert styrene-butadiene copolymer rubber to ozone. After digestion, the result was analyzed by gel permeation chromatography (GPC).

[(3) Microstructure of Butadiene Part (Amount of 1,2-Vinyl Bond)]

The sample for measurement was made into the carbon disulfide solution, and it measured in the range of 600-1000 cm <^-1> of infrared spectrums by Nippon Bunko Co., Ltd. product: FT-IR230 using the solution cell, and absorbed by the absorbance in a predetermined wave number. The microstructure of the butadiene moiety (amount of 1,2-vinyl bond) was obtained according to the calculation method of the ton method.

[(4) Mooney Viscosity]

Preheating was performed for 1 minute using the L-type rotor according to JISK6300-1, and the viscosity after 4 minutes was measured.

In addition, about measurement temperature, it described with numerical data in the description of [Example 1], [Comparative Example 1], and [Comparative Example 2] mentioned later.

[(5) Average Molecular Weight and Molecular Weight Distribution]

Chromatograms were measured by gel permeation chromatography (GPC) using three columns of polystyrene gels as fillers, and each was determined according to the conventional method from the relationship between the retention capacity and the molecular weight obtained by a calibration curve using standard polystyrene. The frequency with respect to the total peak area for every molecular weight range was computed, and number average molecular weight, weight average molecular weight, and molecular weight distribution were calculated.

Tetrahydrofuran (THF) was used as the eluent.

The column is a guard column; Toso TSKguardcolumn HHR-H, column; Toso TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR, oven temperature: 40 ° C., THF flow rate 1.0 mL / min, dosing agent: HLC-8020, detector; RI was used.

The sample for measurement was measured by injecting 200 microliters using what melt | dissolved 20 mg in 20 mL of THF.

[(6) Coupling Reaction Rate]

(5) using a sample solution containing a sample and a low molecular weight internal standard polystyrene molecular weight 5000 (polystyrene is not adsorbed) by applying a modified component adsorbed on a GPC column with a silica-based gel filler. GPC (Dozer: HLC-8020) of polystyrene gel (TOSK), silica column (Guard column; DIOL 4.6 x 12.5 mm 5 micron, column; Zorbax PSM-1000S, PSM-300S, PSM- Chromatograms on both sides of 60PC, Oven Temperature: 40 ° C, 0.5 mL / min THF flow rate (DoStor: CCP8020 Series build-up GPC system; AS-8020, SD-8022, CCPS, CO-8020, RI-8021) Based on the internal standard polystyrene peak, the adsorption amount on the silica column was measured from these differences to determine the coupling reaction rate.

As a sample for measurement, 200 microliters of 20 mg of objects to be measured were dissolved together with 5 mg of standard polystyrene in 20 mL of THF, and the measurement was carried out.

As a specific procedure, the total area of the peak of the chromatogram using the polystyrene column was 100, the sample peak area was P1, the peak area of the standard polystyrene was P2, and the whole of the peak area of the chromatogram using the silica column was The sample peak area was P3 and the peak area of the standard polystyrene was P4, and each was determined to be 100, and the coupling reaction rate was calculated by the following equation.

Coupling Reaction Rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100

[(7) Quantification of Low Molecular Compound and Oligomer Component of Multifunctional Compound Used in Coupling Reaction]

Doso TSKgel G3000HXL, G2000HXL, and G1000HXL were used as the GPC column, THF was used as the eluent, and the tolerant HLC-8220GPC apparatus was used.

The detector used RI and oven temperature as 40 degreeC, the eluate flow volume was 1.0 mL / min, and it used 200 mg of 1.0 mg / mL THF solutions as a sample for a measurement, and 200 microliters of this injected GPC measurement.

In addition, the molecular weight was corrected with standard polystyrene.

Thereby "the glycidylamino group containing low molecular compound which has 2 or more of tertiary amino groups and 3 or more glycidyl groups couple | bonded with the said amino group", and "the oligomer component of the dimer or more of the said glycidylamino group containing low molecular compound" Content in the polyfunctional compound of was obtained.

[(8) conversion rate]

About 20 mL of the polymer solution obtained from the polymerizer exit was injected into the 100 mL bottle which sealed 0.50 mL of n-propylbenzene and about 20 mL of toluene as an internal standard, and produced the sample.

The sample was measured by gas chromatography equipped with a packed column loaded with Apizone grease, and the residual monomer content in the polymer solution was obtained from the calibration curves of the butadiene monomer and the styrene monomer obtained in advance, and the conversion ratio of the butadiene monomer and the styrene monomer was determined. Obtained.

[(9) Mooney Stress Relief (MSR)]

The Mooney viscosity and Mooney relaxation rate were measured using 1201 degreeC by the method of ISO289-1 and ISO289-4 (2003) using Ueshima Seisakusho VR1132 as a Mooney viscosity meter.

First, it heated for 1 minute at 120 degreeC, the rotor was rotated at 2 rpm after that, the torque after 4 minutes was measured, and it was set as Mooney viscosity (ML1 _{+ 4} ). After that, the rotation of the rotor was immediately stopped, and the torque T every 0.1 second of 1.6 to 5 seconds after the stop was recorded in the Mooney unit, and the straight line when the torque and the time t (seconds) were plotted in both numbers. The slope was calculated | required and its absolute value was made into Mooney relaxation rate (MSR).

When the Mooney viscosity is the same, the more Mooney, the Mooney relaxation rate (MSR) becomes smaller, so that the Mooney viscosity can be used as an index.

Example 1

It is 10 liters in internal size, and ratio of inside height and diameter (L / D) is 4, and it is a vertical type which has an inlet at the bottom and an outlet at the top, and has a stirrer and a jacket for temperature adjustment. One polymerizer was used.

The static mixer immediately before entering the polymerizer at 27.3 g / min for 1,3-butadiene, 12.9 g / min for styrene, 182.9 g / min for hexane, and 0.006 g / min for n-butyllithium, in which impurities such as moisture are removed in advance. After mixing, the mixture was continuously fed to the bottom of the polymerizer at the above rate, and 2,2-bis (2-oxolanyl) propane as a polar substance was added at a rate of 0.0402 g / min and n-butyl as a polymerization initiator. Lithium was supplied to the bottom of the polymerizer at a rate of 0.0133 g / min, and the polymerization reaction was continuously performed so that the internal temperature of the polymerizer outlet was 105 ° C. At this time, the average residence time in the polymerization vessel was 30 minutes.

In addition, 1,3-butadiene used contained 70 ppm of 1,2-butadiene.

After the polymerization reaction was carried out as described above, the living polymer solution was continuously discharged from the pipe bonded to the polymerizer.

Moreover, the nozzle for sampling was installed in the middle of piping.

The piping was led to the bottom of the coupling reactor to carry out the subsequent steps, and the polyfunctional compound was supplied from the piping in front of the coupling reactor.

The residence time of the living polymer solution from the polymerizer outlet to the coupling reactor was 1 minute.

Tetraglycidyl-1,3-bisaminomethylcyclohexane and a dimer or more oligomer component thereof as a polyfunctional compound, and with respect to the total amount of the polyfunctional compound, said tetraglycidyl-1,3-bisaminomethyl The mixture containing 90 mass% of cyclohexane and 10 mass% of the said oligomers was used.

The mixture was prepared in 1000-fold dilution with cyclohexane and the polyfunctional compound was fed at a rate of 0.0095 g / min, ie, 1000-fold dilution at 9.5 g / min, for coupling in the coupling reactor. The reaction was carried out.

The coupling reactor was 1.5 liters in volume and 15% of the volume of the polymerizer.

The average residence time in the coupling reactor was 4.3 minutes.

The coupling reactor was cylindrical and the one provided with the stirring blade was used. The inner diameter D of the coupling reactor was 0.104 m, the diameter d of the stirring blade was 0.083 m, and the ratio d / D of the diameter of the stirring blade to the inner diameter was 0.8.

The rotation speed n of the stirrer was 10 s ⁻¹ , and the product nd of the rotation speed and the blade diameter was 0.83.

The coupling reactor was kept warm by steam traces, and the internal temperature was 95 ° C.

An automatic pressure control valve was installed in the piping for discharging from the coupling reactor as an opening degree control means.

The pressure at the top end of the polymerization reactor described above was detected, and the opening degree adjusting means was controlled so that the pressure was 0.9 MPaG.

Pipe for discharge from the coupling reactor was introduced into a storage tank having a stirrer of a capacity of 100 liters.

The nozzle for sampling was provided downstream of the said automatic pressure control valve.

The residence time from the exit of the above-mentioned polymerization reactor to the nozzle for sampling was 6.5 minutes, and the residence time until immediately before entering the storage tank was 7 minutes.

Antioxidant and extender oil were added continuously before entering a storage tank.

As the antioxidant, 0.5 parts by mass of BHT (dibutylhydroxytoluene) is added per 100 parts by mass of the polymer obtained after the above coupling reaction, that is, the polymer removed from the polymer solution, and S-RAE oil (Japan Energy Co., Ltd.) 37.5 mass parts of NC-140) was added per 100 mass parts of said polymers.

In addition, piping from the polymerization reactor outlet to the storage tank was sufficiently insulated.

The pressure of the storage tank was 0.2 MPa.

The polymer solution in the storage tank was sent to the finisher and desolvated to recover the polymer.

A drum dryer was used as a finisher.

In the state where the polymerization reaction in the above-described polymerization reactor has been normalized, contact with air occurs in a mixed solution of about 1 mL of methanol and about 30 mL of cyclohexane from the polymer solution from the sampling nozzle installed in the pipe for discharging from the polymerization reactor. Extraction was carried out in small portions with caution, so as not to be prevented. After the addition of antioxidant (BHT) to 0.2 g per 100 g of the polymer, the solvent was removed by a drum dryer to obtain a sample for Mooney viscosity measurement.

The sample further passed 10 passes on a 6 inch roll set at 110 ° C.

The amount of n-butyllithium which is a polymerization initiator used in the said polymerization reaction was increased and decreased so that the Mooney viscosity (ML-I) of 110 degreeC of a sample and the fluctuation range might be 70 +/- 3.

Specifically, when the Mooney viscosity was near the upper limit, the amount of n-butyllithium was increased by 1%. On the contrary, when the Mooney viscosity was near the lower limit, the amount of n-butyllithium was decreased by 1%.

Moreover, butadiene reached 99.5% and styrene reached 98.5% in the polymerization conversion ratio in the place which exited the polymerization machine.

The polymer solution sampled from the sampling nozzle installed in the pipe for discharging from the above-mentioned coupling reactor was extracted in small amounts with sufficient care to avoid contact with air in a mixed solution of about 1 mL of methanol and about 30 mL of cyclohexane. After adding antioxidant (BHT) so that it might become 0.2 g per 100 g of polymers, the solvent was removed with the drum dryer and the sample of Mooney viscosity measurement was obtained.

The Mooney viscosity (ML-C) of 110 degreeC of the branched conjugated diene type polymer after this coupling reaction, and its fluctuation range were 135 +/- 3.

The molecular weight distribution of the branched conjugated diene polymer by GPC was 1 peak, the weight average molecular weight (Mw-C) was 830,000, and the ratio (Mw-C / Mn-C) of the weight average molecular weight and the number average molecular weight was 2.5. .

In addition, the amount of bonded styrene was 32 mass%, and the amount of 1,2-bond in a butadiene coupling unit was 38 mol%.

As for the styrene chain, the block styrene amount by Korthoff's method is 0% by mass, the styrene short chain by ozone decomposition is 47% by mass relative to the total styrene amount, and the content of styrene long chains in which 8 or more styrene units is 1 is continuous. It was mass%.

The coupling reaction rate, that is, the proportion of the branched conjugated diene polymer adsorbed on the silica column was 45% by mass.

Mooney viscosity and Mooney relaxation rate (MSR) were measured by the method of ISO289-4: 2003, Mooney viscosity ML1 + 4 at 120 degreeC was 125, and MSR was 0.351.

Furthermore, after adding 37.5 mass parts of S-RAE oils (NC-140 by Japan Energy Co., Ltd.) to 100 mass parts of branched conjugated diene polymers to this branched conjugated diene polymer solution, a solvent is removed and dielectric powder is removed. A ground conjugated diene polymer (sample PA) was obtained.

In addition, it was confirmed that no formation of gel was observed in the obtained branched conjugated diene-based polymer or in the equipment.

Comparative Example 1

The automatic pressure control valve was not installed in the "pipe for discharge from the coupling reactor", but was installed in the pipe for discharge from the polymerization reactor.

Other conditions were performed similarly to Example 1.

The copolymer before the coupling reaction had a Mooney viscosity (ML-I) of 110 ° C. and its variation range of 70 ± 3, and a Mooney viscosity of 110 ° C. of the branched conjugated diene polymer after the coupling reaction. C) and its variation range was 128 ± 9.

Moreover, the weight average molecular weight (Mw-C) of the branched conjugated diene type polymer after a coupling reaction was 790,000, and ratio (Mw-C / Mn-C) of a weight average molecular weight and a number average molecular weight was 2.7.

In addition, the amount of bonded styrene was 32 mass%, and the amount of 1,2-bond in a butadiene coupling unit was 38 mol%.

The coupling reaction rate, that is, the proportion of the branched conjugated diene polymer adsorbed on the silica column was 40 mass%.

Mooney viscosity and Mooney relaxation rate (MSR) were similarly measured, and Mooney viscosity ML1 + 4 at 120 degreeC was 117, and MSR was 0.422.

Further dielectric was obtained to obtain a dielectric branched conjugated diene polymer (sample PB).

Slight gel formation was observed in the obtained branched conjugated diene-based polymer and storage tank.

Comparative Example 2

13.65 g / min butadiene, 6.45 g / min styrene, 91.45 g / min hexane and 0.003 g / min n-butyllithium were mixed in a static mixer immediately before entering the polymerizer, Continuously at a rate of 0.0201 g / min for 2,2-bis (2-oxolanyl) propane as a polar substance and n-butyllithium for 0.00665 g / min as a polymerization initiator to the bottom of the polymerizer. It supplied, and performed polymerization reaction so that internal temperature of the exit of a polymerization reactor might be 105 degreeC.

At this time, the average residence time in the polymerization vessel was 60 minutes.

The living polymer solution was continuously discharged from the polymerizer section, and a nozzle for sampling was installed in the middle of the piping for discharge of the polymerizer section.

The piping was led to the bottom of the coupling reactor in which the coupling reaction was carried out in a subsequent step, and the polyfunctional compound was fed from the piping in front of the coupling reactor.

The length of the pipe from the exit of the polymerization reactor to the front of the coupling reactor was three times as long as the apparatus used in Example 1.

The residence time from the polymerizer outlet to the coupling reactor was 6 minutes.

Tetraglycidyl-1,3-bisaminomethylcyclohexane and a dimer or more oligomer component as a polyfunctional compound, with respect to the total amount of the polyfunctional compound, said tetraglycidyl-1,3-bisaminomethyl The mixture containing 90 mass% of cyclohexane and 10 mass% of the said oligomers was used.

This mixture was made into a 1000-fold dilution with cyclohexane, and the coupling reaction was carried out by supplying a polyfunctional compound at a rate of 0.00475 g / min, that is, a 1000-fold dilution solution at a rate of 4.75 g / min.

The average residence time in the coupling reactor was 8.3 minutes.

The piping for discharge | emission from a coupling reactor was provided with the automatic pressure control valve as an opening degree adjustment means.

The pressure at the top exit of the polymerization reactor described above was detected, and the opening degree adjusting means was controlled so that the pressure was 0.9 MPaG.

The average residence time from the polymerizer outlet to the sampling nozzle after the coupling reaction was 18 minutes.

The living copolymer before the coupling reaction has a Mooney viscosity (ML-I) of 110 ° C. and its fluctuation range of 70 ± 7, and a Mooney viscosity (ML-C) of 110 ° C. of the branched conjugated diene polymer after this coupling, and The variation range was 123 ± 9.

In addition, the weight average molecular weight (Mw-C) of the branched conjugated diene type polymer after a coupling reaction was 750,000, and ratio (Mw-C / Mn-C) of a weight average molecular weight and a number average molecular weight was 2.8.

In addition, the amount of bonded styrene was 32 mass%, and the amount of 1,2-bond in a butadiene coupling unit was 38 mol%.

The coupling reaction rate, that is, the proportion of the branched conjugated diene polymer adsorbed on the silica column was 35% by mass.

Mooney viscosity and Mooney relaxation rate (MSR) were measured similarly, Mooney viscosity ML1 + 4 at 120 degreeC was 113, and MSR was 0.473.

Further dielectric was obtained to obtain a dielectric branched conjugated diene polymer (sample PC). Slight gel formation was observed in the obtained branched conjugated diene-based polymer and polymerizer.

In Example 1, the fluctuation | variation of the Mooney viscosity of the obtained branched conjugated diene type polymer was small, and the coupling reaction rate was also high.

In Comparative Example 1, the Mooney viscosity of the branched conjugated diene-based polymer obtained is lowered because the position of the automatic pressure control valve is provided in the piping for discharging from the polymerization reactor, not in the piping for discharging the coupling reactor. In addition, the variation in Mooney viscosity was large, and the coupling reaction rate and branching also decreased.

In Comparative Example 2, since the residence time from the exit of the polymerizer to the addition of the polyfunctional compound deviates from the present invention, the Mooney viscosity of the obtained branched conjugated diene-based polymer is lowered, and the Mooney viscosity is also large. Coupling reaction rate and branching also fell.

A rubber composition was prepared according to the formulation shown in Table 1 below, using (sample PA) to (sample PC) prepared as described above, that is, a dielectric branched conjugated diene polymer as a raw material rubber.

It shows below about the raw material shown in the said Table 1.

(1) Silica ultra quality VN3: product made by Evonik Degussa Japan

(2) Sea KH: made in cabot Japan Kabuki Kaisha, show black N339

(3) Si75: product made by Evonik Degusa Japan

(4) Sunrust N (WAX): Ouchi Shinko Kagaku high school Kabushiki Kaisha

(5) Anti-aging 810NA: Shin-Ouchi Shinko Kagaku Kogyo Co., Ltd., green 810-NA

(6) Vulcanization accelerator CZ: Nochseller CZ-G made by Ouchi Shinko Kagaku Kogyo Co., Ltd.

(7) Vulcanization accelerator D: Nochseller D made by Ouchi Shinko Kagaku Kogyo Co., Ltd.

[Method for producing rubber composition]

Raw material rubber, fillers (silica and carbon black), organic silane coupler under conditions of 65% filling rate and rotor speed 50/57 rpm as kneading in the first stage using a sealed kneader equipped with a temperature control device (capacity 0.3 liter) The ring agent, oil, zinc oxide and stearic acid were kneaded.

At this time, the temperature of the closed kneader was controlled, and the discharge temperature (compound) was obtained at 155 to 165 ° C to obtain a crude rubber compound.

The crude rubber compound obtained above was then cooled to room temperature as kneading in the second stage, and then kneaded again to add an anti-aging agent and improve the dispersion of silica to obtain a rubber compound. Also in this case, discharge temperature (blend) was adjusted to 155-160 degreeC by the temperature control of a kneader.

After cooling, the sulfur and the vulcanization accelerator were kneaded by an open roll set at 70 ° C. as kneading in the third stage.

This was molded and vulcanized at 160 ° C. for a predetermined time to obtain a target vulcanized rubber composition.

Physical properties of the rubber compound and the vulcanized rubber composition were measured by the following methods, and the measurement results are shown in Table 2 below.

[Measurement Method of Physical Properties of Rubber Compound and Vulcanized Rubber Composition]

<(1) Bonding rubber (mass%)>

About 0.2 g of the rubber compound after completion of the kneading step of the second stage described above was cut into a rectangle having a side of about 1 mm, and placed in a Harris box (100 mesh gold mesh) to measure the weight.

Then, it was immersed in toluene for 24 hours, and it dried and measured the weight after that.

The amount of rubber bound to the filler was calculated from the amount of the non-hazardous component and the ratio of the rubber bound to the filler relative to the amount of rubber in the original rubber blend was determined.

<(2) rubber compound Mooney viscosity>

The Mooney viscosity of the rubber compound after completion of the kneading step of the second stage described above was preheated at 130 ° C. for 1 minute using an L-type rotor according to JIS K6300-1 using a Mooney viscometer, and then rotated every two revolutions per minute. 4 The viscosity after minutes was measured.

When the Mooney viscosity was a small value, it was judged that the energy consumption was small at the time of kneading and the workability was good.

<(3) Hardness of Vulcanized Rubber Composition>

According to JIS K6253, the durometer type A hardness was measured using the static pressure load machine "CL-150L type" for the digital rubber hardness tester "DD2-A type" by Toshiki Kaiki Co., Ltd.

<(4) Tensile Test on Vulcanized Rubber Composition>

Tensile stress (100% Mo) at 100% elongation of the test piece (MPa), tensile stress (300% Mo) at 300% elongation using the dumbbell-shaped No. 3 type by the tensile test method of JIS K6251 (unit: MPa), tensile strength (unit: MPa), and breaking elongation (unit:%) were measured.

It was judged that the higher the tensile strength and the breaking elongation, the better.

<(5) Resilience (%) of vulcanized rubber composition>

The rebound elasticity in 0 degreeC and 50 degreeC was measured by the Lupeke-type repulsion elasticity test method of JISK6255.

The rebound elasticity of 0 ° C. was used as an index of wet skid resistance, ie, grip performance, and was determined to be better as the lower.

The rebound elasticity of 50 ° C. was used as an index of low rolling resistance of the tire, and the higher was judged to be good.

<(6) Exothermicity (° C) of the Vulcanized Rubber Composition>

A Goodrich flexometer was used to express the difference between the rotational speed 1800 rpm, the stroke 0.225 inch, the load 55 pounds, the measurement start temperature of 50 ° C., and the temperature after 20 minutes and the start temperature.

It was judged that the smaller the value was, the better the exothermicity was.

<(7) Measurement of Viscoelastic Properties of Vulcanized Rubber Composition>

Tan δ was measured by using an Ares viscoelastic tester manufactured by Leometrics Scientific Co., Ltd., at a frequency of 10 Hz and at each measurement temperature (0 ° C. and 50 ° C.) by a torsion method.

The higher tanδ (loss tangent) measured at low temperature (0 ° C) and distortion 1%, the better wet skid resistance, ie grip performance, and tanδ (loss tangent measured at high temperature (50 ° C), distortion 3%). The lower the), the lower the hysteresis loss, and the lower the rolling resistance of the tire, that is, the lower fuel economy.

<(8) Wear Resistance (Index) of Vulcanized Rubber Composition>

Abrasion resistance was measured by test method A, load 44.1 N, and 3000 revolutions of wear according to JIS K6264-2 using a Yasuda Sekisaki Akron rubber wear tester.

Example 1 was represented by the index made into 100.

The higher the index, the less the wear and the better.

As is clear from Example 1 and Comparative Examples 1 and 2 of Table 2, the rubber compound using the branched conjugated diene-based polymer produced by the production method of the present embodiment has a high amount of bonding rubber, and the vulcanized rubber composition has a high temperature. High rebound elasticity and low high temperature tan δ (loss tangent) resulted in low hysteresis loss and excellent low rolling resistance, that is, low fuel consumption of the tire.

Moreover, the balance between low fuel consumption and wet skid resistance (low temperature tan δ) was also excellent, and also less heat was generated, and abrasion resistance was also good.

In the comparative example 1, since the position of an automatic pressure control valve is provided in the piping for discharge from a polymerization reactor instead of the piping for discharge of a coupling reactor, the Mooney viscosity of the obtained copolymer falls and Mooney viscosity Was also large, and the coupling reaction rate also decreased.

As a result, the amount of bonded rubber is low, the high rebound elasticity is low, and the high temperature tan δ is high, so that the hysteresis loss is large, and the tire has low rolling resistance, that is, low fuel consumption.

In addition, the balance between low fuel consumption and wet skid resistance (low temperature tan δ) was also lowered, and further, heat generation was high and wear resistance was also poor.

In Comparative Example 2, since the residence time from the exit of the polymerizer to the addition of the polyfunctional compound deviates from the present invention, the Mooney viscosity of the obtained branched conjugated diene-based polymer is lowered, and the Mooney viscosity is large. Coupling reaction rate also fell.

As a result, the amount of bonding rubber is low, the breaking strength is low, the high rebound elasticity is low, and the high temperature tan δ is high, so that the hysteresis loss is large, and the tire has low rolling resistance, that is, low fuel consumption. In addition, the balance between low fuel consumption and wet skid resistance (tan at low temperature) was also lowered, and further, heat generation was high and wear resistance was also poor.

This application is based on Japanese Patent Application No. 2009-116541 for which it applied to Japan Patent Office on May 13, 2009, The content is taken in here as a reference.

The manufacturing method of the branched conjugated diene type polymer of this invention has industrial possibility as a manufacturing technique of the branched conjugated diene type polymer which comprises rubber composition suitable for rubber | gum for rubber, dustproof rubber, and shoes.

Claims (11)

A polymerization step in which a conjugated diene compound or a conjugated diene compound and a vinyl aromatic compound are continuously polymerized or copolymerized with an alkali metal initiator in a hydrocarbon solvent to obtain a living polymer or a living copolymer,
A coupling reactor connected through a pipe provided at an outlet of the polymerizer for discharging the living polymer or living copolymer, wherein opening degree adjustment means is provided in a pipe for discharge connected to the coupling reactor. A coupling step of reacting the living polymer or living copolymer with a polyfunctional compound in a coupling reactor in which a coupling reaction is carried out,
Desolvent process,
After the said polymerization process, the said living polymer or a living copolymer and a polyfunctional compound are made to react within 5 minutes,
The manufacturing method of the branched conjugated diene type polymer which controls by the said opening degree control means the pressure at the exit of the said polymerization machine to 0.5-2 Mpa. The method for producing a branched conjugated diene polymer according to claim 1, wherein the coupling reactor is a tank reactor having a rotary stirrer and having a capacity of 0.5 to 50% of the capacity of the polymerizer. The said polymerizer is a shaping | molding reactor provided with a stirrer,
In the said polymerization process, the manufacturing method of the branched conjugated diene type polymer which randomly copolymerizes a conjugated diene and a vinyl aromatic in presence of a polar compound. The process according to claim 1 or 2, wherein the Mooney viscosity is measured by sampling the living polymer or living copolymer between the coupling step and the coupling step in the polymerization step;
A method for producing a branched conjugated diene-based polymer, further comprising a step of sampling the branched conjugated diene-based polymer and measuring the Mooney viscosity when the residence time from the outlet of the polymerizer after the coupling step is less than 15 minutes. . The manufacturing method of the branched conjugated diene type polymer of Claim 1 or 2 which uses one shaping | molding reactor provided with a stirrer as said polymerizer. The method for producing a branched conjugated diene polymer according to claim 1 or 2, wherein a polyepoxy compound having a tertiary amino group in a molecule is used as the multifunctional compound. The glycidylamino group-containing low molecular compound according to claim 1 or 2, wherein the multifunctional compound has two or more tertiary amino groups and three or more glycidyl groups bonded to the amino group in the molecule, and the glycidyl group. It contains the oligomer component of the dimer or more of a di-amino group containing low molecular weight compound,
The method for producing a branched conjugated diene polymer, wherein the low molecular weight compound is 75 to 95% by mass and the oligomer is 25 to 5% by mass based on the total amount of the polyfunctional compound. The manufacturing method of the branched conjugated diene polymer of Claim 1 or 2 whose reaction ratio of the said living polymer or the said living copolymer and the said polyfunctional compound is 10-80 mass%. The branched conjugated diene-based polymer according to claim 1 or 2, wherein the branched conjugated diene-based polymer has a molecular weight distribution measured by gel permeation chromatography (GPC) and has a weight average molecular weight of 500,000 to 200 in terms of molecular weight in terms of polystyrene. The manufacturing method of branched conjugated diene type polymer. The branched conjugated diene polymer according to claim 1 or 2 is a copolymer of a conjugated diene compound and a vinyl aromatic compound,
The short chain of a vinyl aromatic compound by ozone decomposition method is 40 mass% or more with respect to the said vinyl aromatic compound whole quantity, and the 8 or more chain of a vinyl aromatic compound is 5 mass% or less, The manufacturing method of the branched conjugated diene type polymer. The branched conjugated diene polymer according to claim 1 or 2,
The coupling reaction ratio of the said living polymer or the said living copolymer and the said polyfunctional compound is 10-80 mass%,
A method for producing a branched conjugated diene polymer, wherein the molecular weight distribution measured by gel permeation chromatography (GPC) is 1 peak and the weight average molecular weight is 500,000 to 2 million in terms of molecular weight in terms of polystyrene.