KR102041813B1 - Preparation Method of anionic polymerization initiator, device for anionic polymerization initiator and composite of anionic polymerization initiator produced by the method - Google Patents

Abstract

The present invention relates to a method for producing an anionic polymerization initiator, a production apparatus and an anionic polymerization initiator prepared therefrom, the method for producing an anionic polymerization initiator according to the present invention in a continuous reactor, a component represented by the formula (1); Organometallic compounds; And / or by reacting the conjugated diene compound in the form of a solution.

Description

Preparation Method of anionic polymerization initiator, device for anionic polymerization initiator and composite of anionic polymerization initiator produced by the method}

The present invention relates to a method for producing an anion polymerization initiator, a production apparatus thereof, and an anion polymerization initiator composition prepared therefrom.

As high-efficiency, eco-friendly, high-performance tire properties are required to reduce carbon dioxide emissions and improve fuel efficiency, tire material development that meets these needs has been actively made. In particular, unlike emulsion polymerization, styrene-butadiene rubber (hereinafter referred to as SSBR) obtained by solution polymerization is easily changed in structure, and the movement of the chain ends is reduced by the binding or modification of the chain ends and the binding force with carbon black is increased. It has been used as a rubber material for tire treads. In addition, as the silica filler is developed, low rolling resistance and high road braking force can be obtained at the same time, but for this, a technique of dispersing hydrophilic silica with hydrophobic SSBR is required.

Such methods include a method of wrapping silica particles themselves with a hydrophobic material, a method of using a coupling agent between silica and SSBR, and the like. Recently, a technology for introducing a part capable of reacting and bonding with silica or a part serving to help the SSBR polymer chain itself has been made by using a modification initiator, a modified monomer, a modifier, and the like during the SSBR anion polymerization. In particular, the modified initiator initiates anionic polymerization and at the same time serves to introduce a functional group at one end of the chain, thereby making it an essential material for producing such modified SSBR.

The hexamethylene lithium (HMI-Li) initiator among the anionic polymerization initiators used in the synthesis of SSBR is hexamethyleneimine (HMI) and n-butyl lithium (n-Butyllithium, BuLi, NBL) as shown in the following scheme. Is made in response.

Scheme 1

However, HMI-Li has a problem of low solubility in solvents and thus drops to precipitation over time, and can be used as an initiator but is less reactive than BuLi. In order to solve this disadvantage, conventionally, after passing through Scheme 1 as in Scheme 2, a polymerization initiator was prepared by further reacting a conjugated diene (R) such as isoprene (IP) or 1,3-butadiene (BD). . As the conjugated diene is further attached, the solubility in the organic solvent is increased, so that a stable reaction can be achieved, and the reactivity as an initiator is higher than that of HMI-Li, which is sufficient to initiate anionic polymerization.

Scheme 2

In Scheme 2 n is an integer from 1 to 100.

However, the denaturation initiator thus prepared is also unstable over time and falls into precipitation, or a very small amount of oxygen is combined with water to inactivate it. Therefore, the conventional process of preparing a polymerization initiator as described above and then introducing it into a polymerization reaction inevitably requires a storage step of the modification initiator, resulting in the aforementioned disadvantages. This may adversely affect the post-processing, which may cause deterioration of the final synthesized SSBR properties, making it difficult to maintain a certain quality.

In the prior art, an anionic polymerization initiator was prepared by a batch process, and then used for preparing a solution polymerization SSBR. Alternatively, the production of the anion polymerization initiator and the solution polymerization styrene-butadiene rubber in a batch reactor was simultaneously carried out in one pot.

In the former case, the storage step of the denatured initiator is inevitably required, and it loses activity by reacting with various scavengers such as moisture and air during the storage time of the anion of the synthesized initiator. This may adversely affect the post-processing, which may cause deterioration of the final synthesized SSBR properties, making it difficult to maintain a certain quality. In the latter case, the problem of storage could be solved as a step of causing the polymerization reaction to occur in the same batch reactor simultaneously with the initiator synthesis reaction. However, it is difficult to confirm whether the modified initiator synthesis is performed properly, and the physical properties are also lower than when adding the synthesized initiator. In addition, in all the existing batch processes, raw materials are directly introduced and mixed and reacted to produce by-products or reverse reactions to generate unreacted products, resulting in lower polymerization yields.

1. US Patent No. 5,625,017 2. US Patent No. 6,080,835

The present invention provides a method for producing an anion polymerization initiator, a production apparatus thereof and an anion polymerization initiator composition prepared therefrom.

The present invention to achieve the above object,

A component represented by Formula 1; And introducing an organometallic compound into a continuous reactor and reacting the same.

[Formula 1]

In Chemical Formula 1,

G ₁ and G ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 1,

Including when G ₁ and G ₂ are para isomers,

G ₁ is represented by the formula 1-a,

G ₂ is represented by the following Chemical Formula 1-b,

[Formula 1-a]

In Formula 1-a,

R ₁ , R ₂ and R ₃ independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms,

m is an integer from 0 to 20,

When m is 0, it represents a single bond,

[Formula 1-b]

In Formula 1-b,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond,

In the benzene structure of Formula 1, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ₁ and G ₂ are not bonded.

In addition, the present invention,

Mixer; And

A first inlet line and a second inlet line connected to the mixer,

The first inlet line supplies a component represented by Formula 1 according to claim 1, the second inlet line provides an apparatus for producing an anionic polymerization initiator, characterized in that to supply an organometallic compound.

In addition, the present invention,

It provides an anionic polymerization initiator composition comprising a component represented by the following formula (2):

[Formula 2]

In Chemical Formula 2,

G ′ ₁ and G ′ ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 2,

Including when G ' ₁ and G' ₂ are para isomers,

G ' ₁ is alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms Is substituted in the benzene ring,

G ' ₂ is represented by the following formula 2-a,

[Formula 2-a]

In Formula 2-a,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond,

In the benzene structure of Formula 2, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ′ ₁ and G ′ ₂ are not bonded.

According to the present invention, by preparing an anionic polymerization initiator including an isomer, it is possible to prevent the instability and inertness of the polymerization initiator and the deterioration of physical properties of the SSBR, to minimize by-products and unreacted materials, and to significantly improve the conversion rate. .

In addition, in the present invention, after synthesizing the polymerization initiator by a continuous polymerization reaction, it is possible to prepare the SSBR by simultaneously entering the SSBR raw material and the polymerization tank, thereby minimizing the problems such as deterioration of physical properties of the SSBR, It is possible to produce stable and consistent quality products.

In addition, the production method of the anionic polymerization initiator of the present invention has a shorter reaction time and a higher yield than a batch reactor, and thus, it is possible to economically reduce the production process time, such as can exhibit an excellent effect.

In addition, due to the high yield, it is possible not only to secure economical and stable quality for mass production, but also to significantly reduce the manufacturing process time.

1 is a schematic configuration diagram of an anion polymerization initiator production apparatus according to an embodiment of the present invention.
2 is a schematic configuration diagram of an anion polymerization initiator production apparatus according to another embodiment of the present invention.
3 shows the details of the microchannels and fluid flow within the microchannels in accordance with another embodiment of the present invention.
4 illustrates a separation configuration and coalescence configuration of the lower microchannel and the upper microchannel according to another embodiment of the present invention.
5 is a schematic configuration diagram of an anion polymerization initiator production apparatus according to another embodiment of the present invention.
6 is a gas chromatography (GC) graph of the anionic polymerization initiator composition according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The following detailed description is for illustratively illustrating the embodiments of the present invention, and therefore, even if there is a limiting expression, does not limit the scope of rights defined by the claims.

When preparing an anionic polymerization initiator in a batch reactor of the prior art, there was a problem that the synthesis yield is low and the initiator deactivation reaction by storage occurs.

The present inventors have found that the above-mentioned problems are solved through the manufacturing method according to the present invention, and have completed the present invention.

The present invention, a component represented by the formula (1); And introducing an organometallic compound into a continuous reactor and reacting the same.

[Formula 1]

In Chemical Formula 1,

G ₁ and G ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 1,

Including when G ₁ and G ₂ are para isomers,

G ₁ is represented by the formula 1-a,

G ₂ is represented by the following Chemical Formula 1-b,

[Formula 1-a]

In Formula 1-a,

R ₁ , R ₂ and R ₃ independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms,

m is an integer from 0 to 20,

When m is 0, it represents a single bond,

[Formula 1-b]

In Formula 1-b,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond,

In the benzene structure of Formula 1, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ₁ and G ₂ are not bonded.

In the present invention, an "alkyl group" is defined as a functional group derived from linear or branched saturated hydrocarbons.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 1 , 2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methyl-2-ethylpropyl group, 1-ethyl-2-methylpropyl Group, 1,1,2-trimethylpropyl group, 1-propylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like.

In the present invention, "alkenyl group" or "alkynyl group" means that one or more carbon-carbon double bonds or triple bonds are respectively included in the middle or terminal of the alkyl group as described above.

In one example, the component represented by Formula 1 may have a combined ratio of the ortho and meta isomers and the weight ratio of the para isomers may range from 1 to 4: 6 to 9.

Specifically, the component represented by Formula 1 may have a combined ratio of ortho and meta isomers and a weight ratio of para isomers in a range of 2 to 3: 7 to 9. By having the isomer weight ratio in the above range, the stability of the anionic polymerization initiator composition can be improved.

In one example, the component represented by Formula 1 may include the following Formula 3 to Formula 5:

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 3 and 5,

R ₁ , R ₂ and R ₃ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

R _a , R _b , R _c and R _d independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms,

m, n are independently an integer of 0 to 20,

When m or n is 0, it represents a single bond.

Specifically, the component represented by Formula 1 may include Formula 6 to Formula 8:

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 6 and 8,

R ₁ , R ₂ and R ₃ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

m, n are independently an integer of 0 to 20,

When m or n is 0, it represents a single bond.

More specifically, the component represented by Formula 1 may include a compound represented by Formula 9 to 11 below:

[Formula 9]

[Formula 10]

[Formula 11]

In Formula 9 and Formula 11,

R ₁₁ , R ₁₂ and R ₁₃ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

m is an integer from 0 to 20,

When m is 0, it represents a single bond.

In one example, the component represented by Formula 1 may include a compound of Formula 12 to 14:

[Formula 12]

[Formula 13]

[Formula 14]

In Chemical Formula 12 and Chemical Formula 14,

R ₁₁ and R ₁₂ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms.

For example, the component represented by Formula 1 may be 2-vinyl-N, N-dimethylbenzylamine, 3-vinyl-N, N-dimethylbenzylamine, or 4-vinyl-N, N-dimethylbenzylamine. .

The organometallic compound may include an organic component and a metal component, and in some cases, may further include a Br (bromine) element or a chlorine (Cl) element. Here, the organic component may be composed of an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and the like. Specifically, the organic component may be n-butyl group, n-pentyl group, s-butyl group or t-butyl group, and more specifically n-butyl group. In addition, the metal component may be an alkali metal or an alkaline earth metal. Specifically, it may be lithium, sodium, potassium, magnesium, rubidium, cesium, strontium, beryllium or calcium, more specifically lithium.

For example, the organometallic compound may include one or more selected from the group consisting of organic alkali metal compounds and organic alkaline earth metal compounds. Specifically, the alkali metal compound may be one or more selected from the group consisting of alkyl lithium, aryl lithium, alkenyl lithium, alkyl sodium, aryl sodium, alkenyl sodium, alkyl potassium, alkenyl potassium and aryl potassium, More specifically, n-butyl lithium (NBL) can be used. In addition, the alkaline earth metal compound may be an organic magnesium compound containing a Br (bromine) element or a chlorine (Cl) element, or an organic calcium compound or an organic strontium compound, more specifically methylmagnesium bromide (CH ₃ MgBr), ethyl Alkyl magnesium halides having 1 to 6 carbon atoms including magnesium bromide (CH ₃ CH ₂ MgBr), methylmagnesium chloride (CH ₃ MgCl), ethylmagnesium chloride (CH ₃ CH ₂ MgCl) and the like may be used.

In one example, a component represented by Formula 1; And an organometallic compound, each including a solvent, a solution including a component represented by Formula 1; And in the form of an organometallic compound solution.

As the solvent, a solvent which does not react with an anion may be used as the hydrocarbon compound, and specifically, linear hydrocarbon compounds such as pentane, hexane, heptane and octane; Derivatives thereof having double branches; Cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; Aromatic hydrocarbon compounds such as benzene, toluene and xylene; Linear and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran; Any one or more selected from among them can be used. Specifically, cyclohexane, hexane, tetrahydrofuran and diethyl ether, more specifically cyclohexane can be used.

Specifically, the concentration of the solution including the component represented by Formula 1 may be 0.1 to 50% by weight, the concentration of the organometallic compound solution may be 0.1 to 30% by weight, and the balance may be a solvent.

 In addition, a component represented by the formula (1); And the molar ratio of the organometallic compound may be 5: 1 to 1: 5, specifically 1: 1 to 1: 1.2. If the molar ratio of the organometallic compound is higher or lower than the above range, there may be a problem in that the production of the side reactants and the unreactants increases.

Specifically, the component represented by General formula (1); And a temperature for reacting the organometallic compound may be -80 to 100 ° C, and a reaction time may be 0.001 to 90 minutes. If the reaction temperature is too low, there may be a problem that the raw material is frozen, and if the reaction temperature is too high, there may be a problem that the initiator is pyrolyzed. If the reaction time is too short, there may be a problem that the reaction conversion rate is low, and if the reaction time is too long, there may be a problem that the production of side reactants increases.

In addition, a component represented by the formula (1); And before reacting the organometallic compound, it may include the step of further mixing a polar additive in a solution containing the component represented by the formula (1).

The polar additives include tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis ( 2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2 Bis (2-oxolanyl) propane, dipiperidinoethane, pyridine, quinuclidin, trimethylamine, triethylamine, tripropylamine, tetramethylethylenediamine, potassium-tert-butyrate, sodium-tert-butyrate, It may comprise one or more selected from sodium amylate and triphenylphosphine. Specifically, the polar additive may include tetrahydrofuran or tetramethylethylenediamine.

Method for producing an anionic polymerization initiator according to the present invention is a component represented by the formula (1); And supplying the conjugated diene compound to the continuous reactor after the step of reacting the organometallic compound to react.

In one example, the conjugated diene compound is 1,3-butadiene (BD), isoprene (IP), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3- Any one or more of pentadiene, 1,3-heptadiene, and 1,3-hexadiene can be used, and specifically, 1,3-butadiene or isoprene can be used. The conjugated diene compound may be reacted in the form of a conjugated diene compound solution including a solvent. As the solvent, any solvent that can be used usually may be used. Specifically, cyclohexane, hexane, tetrahydrofuran, diethyl ether and the like can be used, and more specifically, cyclohexane can be used.

Specifically, the concentration of the conjugated diene compound solution may be 1 to 100% by weight, and the balance may be a solvent.

In one example, a component represented by Formula 1; And the molar ratio of the conjugated diene compound may be 1: 1 to 1: 100, specifically 1: 2 to 1:10. When the molar ratio of the conjugated diene compound is higher than the above range, there may be a problem that the viscosity of the solution is increased, and when the molar ratio of the component represented by Formula 1 is lower than the above range, there may be a problem that the compound without the diene compound is increased.

Specifically, the temperature for reacting the conjugated diene compound may be 10 to 100 ℃, the reaction time may be 1 to 60 minutes. If the reaction temperature is too low, there may be a problem that the reaction initiation rate is slow, if the reaction temperature is too high there may be a problem that the initiator is thermally decomposed. In addition, when the reaction time is too short, there may be a problem that the reaction time is insufficient, if the reaction time is too long there may be a problem that the unnecessary process cost in the reaction is completed.

Specific examples of the step of reacting the conjugated diene compound according to the specific embodiment include: a component represented by Formula 1 discharged from the first mixer of the continuous reactor; The reactant and isoprene solution of the organometallic compound may be reacted by mixing in a second mixer. At this time, the solvent of the isoprene solution may be cyclohexane.

In the present invention, the fluids of the incoming raw materials are sequentially introduced into the first mixer and the second mixer to sequentially produce the first and second reactions, respectively, to prepare an anionic polymerization initiator. That is, since the production method of the present invention is stable and sequentially reacted, by-products and unreacted products are not generated unlike the conventional processes. In addition, it is possible to prepare an anionic polymerization initiator in a high yield. Therefore, according to one specific embodiment of the present invention, the conversion rate of the amine compound may be 95% or more.

In addition, after preparing an anionic polymerization initiator by the production method of the present invention, and put it directly into the solution-polymerized styrene-butadiene rubber (SSBR) synthesis by the on-demand method synthesis, solve the problem of storage stability of the conventional initiator In addition, anionic initiator reactivity may be improved to introduce an amine group such as a component represented by Formula 1 at the front-end of SSBR.

In addition, the present invention, a mixer; And a first inlet line and a second inlet line connected to the mixer,

The first inlet line supplies a component represented by Formula 1 according to claim 1, the second inlet line provides an apparatus for producing an anionic polymerization initiator, characterized in that to supply an organometallic compound.

Specifically, the mixer includes a first mixer and a second mixer connected in series, the first and second inlet lines connected to the first mixer; And a third inlet line connected to the second mixer, wherein the third inlet line may supply a conjugated diene compound.

More specifically, the mixer may have a structure in which the first mixer and the second mixer connected in series are repeated.

In one example, one or more of the first and second mixers may be a static mixer. In detail, the first mixer may be a first static mixer, and the second mixer may be a second static mixer.

The static mixers may each independently include one or more selected from the group consisting of a plate mixer, a Kenics mixer, and a Sulzer mixer. In addition, the static mixers may be connected in series.

In detail, a first inflow line may be provided at one end of the first static mixer, and a second inflow line may be provided in a horizontal or vertical direction with the first inflow line. In addition, a third inlet line may be connected to the second static mixer.

In addition, the manufacturing apparatus may further include a pressure control means for controlling the pressure inside. Isomer mixture, organometallic compound, and conjugated diene compound of the compound represented by Formula 1 injected into the manufacturing apparatus by the pressure control means may be mixed and reacted while flowing in the same direction.

In one example, at least one of the first and second mixers is a microreactor, which may include a plurality of microchannels that repeat branching and confluence. In the present invention, the micro reactor is composed of a channel having a size of 10 μm to 10 mm and has a mixing characteristic using a hydrodynamic structure. Among these, it is characterized by including a plurality of fine channels that repeats the branching and joining, but is not limited to this reactor.

Specifically, the first mixer may be a first micro reactor and the second mixer may be a second micro reactor.

In one example, either one of the first and second mixers may be a static mixer and the other may be a micro reactor. Specifically, the first mixer may be a static mixer and the second mixer may be a micro reactor. Alternatively, the first mixer may be a micro reactor and the second mixer may be a static mixer.

In one example, at least one of the first and second mixers may have a structure in which a static mixer and a micro reactor are sequentially connected. Specifically, the first mixer may include a first static mixer and a first micro reactor, and the second mixer may include a second static mixer and a second micro reactor. More specifically, the micro reactor may be connected to the front of the static mixer.

1 is a schematic configuration diagram of an anion polymerization initiator manufacturing apparatus according to an embodiment of the present invention, the apparatus comprises a first reaction zone (1), a first static mixer (2), a first inlet line (3), It may include a second inlet line (4), connecting pipe (5), secondary reaction zone (6), second static mixer (7), third inlet line (8), outlet (9).

2 is a schematic configuration diagram of an anion polymerization initiator manufacturing apparatus according to another embodiment of the present invention, the apparatus according to this embodiment may be largely composed of the first reaction zone 10 and the second reaction zone 20. have. The primary reaction zone 10 may comprise a first micro reactor 11 and the secondary reaction zone 20 may comprise a second micro reactor 21.

The first micro reactor 11 is a type of continuous reactor, and may include a first inlet line 12, a second inlet line 13, and a plurality of fine channels 14 and 15. The first inlet line 12 may be, for example, a component represented by Formula 1, and the second inlet line 13 may be, for example, an organometallic compound. Specifically, the component represented by Formula 1; And the organometallic compound may be supplied with a fluid, and may be supplied in gaseous or liquid form through a fluid connection. When supplied in liquid form, the component represented by Formula 1; And the organometallic compound may be fluidly supplied in the form of a solvent.

The microchannels 14 and 15 may be connected to or include the first inflow line 12 and the second inflow line 13. At least two microchannels 14 and 15 may be provided, and they may form a plurality of branching points (confluence points) 16 by repeating branching and merging. In the drawing, only two microchannels, that is, the upper microchannel 14 and the lower microchannel 15, are illustrated, but three or more microchannels are possible.

In the drawing, the plurality of microchannels 14 and 15 form a rhombus and periodically branch to form a regular pattern. However, the overall shape and the branching pattern of the plurality of microchannels 14 and 15 are not particularly limited. It can be changed according to, for example, circular, elliptical, spiral, polygonal, etc. is possible, and a mixed or irregular pattern of straight and curved sections is also possible.

The number of repetitions of branching and merging of the microchannels 14 and 15 is not particularly limited, and may be, for example, 5 to 1000 times, preferably 10 to 500 times, more preferably 50 to 200 times. If the number of repetitions of branching and confluence of the microchannels 14 and 15, that is, the number of branching points (confluence points) 16 is too small, the mixing effect may be lowered, and when too many, the production becomes difficult and the size of the mixer may be large. .

The size of the microchannels 14, 15 is not particularly limited and may be, for example, 10 to 10000 micrometers, preferably 50 to 5000 micrometers, more preferably 100 to 2000 micrometers. Herein, the size of the microchannels 14 and 15 may mean a diameter when the microchannels 14 and 15 are circular, and an average diameter when the microchannels 14 and 15 are not circular. The diameter of the microchannels 14 and 15 may be the same or different for each channel.

The first micro-reactor 11 may be manufactured by dividing, for example, by dividing and manufacturing the upper plate and the lower plate may be completed by joining the two plates. The first inflow line 12, the second inflow line 13, and the fine channels 14 and 15 may be configured to be disposed on the same plane, and the first inflow line 12 and the second inflow line ( 13), one or more of the microchannels 14, 15 may be arranged on another plane. In addition, the plurality of fine channels 14 and 15 may be arranged in a two-dimensional (planar) shape, or may have a three-dimensional arrangement such as a spiral. In addition, the plurality of fine channels 14 and 15 may be disposed in the horizontal direction so that each channel may be positioned at the same height. Alternatively, the plurality of fine channels 14 and 15 may be disposed in the vertical direction, and thus, the height of each channel may be different.

For example, the fluid flow in the microchannel mixer manufactured by dividing the upper plate and the lower plate is as follows. The A solution (organic metal compound) injected into the upper plate and the B solution (component represented by Chemical Formula 1) injected into the lower plate pass through the first branching point, and the upper part flows into the A solution, the lower part into the B solution, and branches. . That is, the left side of the top plate A solution and the left side of the bottom plate B solution may be divided into equal amounts by the left side passage, the right side of the top plate A solution and the right side of the bottom plate B solution. After branching, the flow on the left side can be directed only to the top plate, and the flow on the right side can be directed to flow only to the bottom plate. Thereafter, the fluid flowing to the upper plate and the fluid flowing to the lower plate are met at the second branch point, and the same way as described above may be repeated again and the method of meeting at the next branch point may be repeated. Conceptually speaking, if the flow of two layers of A / B is divided into two of A / B and A / B at the branching point, and then merged up and down, the flow of four layers of A / B / A / B can be made. Since the flow is divided by n powers of 2, the interface between A and B is dramatically increased, so the mixing effect can be maximized.

The second micro reactor 21 may be connected in series with the first micro reactor 11 via a connecting pipe 17, the third inlet line 22, the outlet 26, and the plurality of microchannels 23, 24. ) And a branching point (confluence point) 25 can be provided. The first reactant of the first micro-reactor 11 may be injected through the connecting pipe 17, the conjugated diene compound may be injected into the third inlet line 22, and the outlet 26 may be injected. Secondary reactants may be discharged. The second micro reactor 21 may be configured to be the same as or similar to the first micro reactor 11.

Figure 3 shows the detailed structure of the microchannel and the fluid flow in the microchannel according to another embodiment of the present invention, Figure 4 is a separate configuration and coalescing configuration of the lower microchannel and the upper microchannel according to another embodiment of the present invention It is shown.

The first micro reactor 11 may be configured to include an upper plate and a lower plate. The upper plate may be formed with an upper microchannel 14 having an open lower portion, and the lower plate may be formed with an upper microchannel 15 with an open upper portion, and the upper and lower microchannels 14 and 15 are combined to have a length. The flow path sealed in the direction can be formed. The flow path may have a rectangular cross section as shown in the figure, and may also be manufactured in a circle, oval or other polygon. The upper and lower microchannels 14, 15 may have respective inlet lines 12a, 13a and one common outlet 17a. The inflow lines 12a and 13a may be connected to the inflow lines 12 and 13, and may also form the inflow lines 12 and 13 as the inflow lines 12a and 13a extend outwardly of the upper and lower plates. The outlet 17a may be connected to the connecting pipe 17, and may also form the connecting pipe 17 while the outlet 17a itself extends to the outside of the upper and lower plates.

The upper microchannel 14 may have a plurality of branching points 16a and 16b disposed along the center, and branch into two branches of the left and right branching channels 14a and 14b at each branching point 16a and 16b. Each right branch channel 14b is blocked, and each left branch channel 14a is deflected toward the center and can continue to the next branch point 16b.

As such, the reason why one side of the branch channel is blocked and only the other side is continuously connected is to induce the fluid flow of the multilayer structure. If one side of the branch channel is not blocked, the two fluids may hardly be mixed or the mixing effect may be minimal.

Similarly, the lower microchannel 15 may have a plurality of branching points 16a, 16b disposed along the center, with two branches of the left and right branching channels 15a, 15b at each branching point 16a, 16b. Branching to each left branch channel 15a is blocked, and each right branching channel 15b is deflected toward the center and continues to the next branching point 16b.

Referring to FIG. 3, a first solution (indicated in red) selected from a solution containing a component represented by Formula 1 and an organometallic compound solution may be introduced into the inlet line 12a of the upper microchannel 14. The second solution (indicated in blue) may flow into the inflow line 13a of the lower microchannel 15.

Thereafter, the upper and lower microchannels 14 and 15 are coupled, for example, in the case of point A, two layers of the first solution layer in the upper microchannel 14 and the second solution layer in the lower microchannel 15. Flow into the flow.

By reaching the first branch point 16a, for example, at point B, the flow rate may increase as the channel width expands.

Then, after passing through the first branching point 16a, for example, in the case of point C, it may branch into a two-layer flow of the left branch channels 14a and 15a and a two-layer flow of the right branch channels 14b and 15b. . Up to this point a two-layer flow of about the same flow rate as point A in each channel can be maintained.

Then, as each branch channel 14b, 15a passes through the blocked point, for example in the case of point D, the left branch channel 14a of the upper microchannel 14 is connected and the left branch of the lower microchannel 15 Since channel 15a is blocked, the two-layer flow on the left flows only to the left branch channel 14a of the upper microchannel 14. On the contrary, since the right branch channel 14b of the upper microchannel 14 is blocked and the right branch channel 15b of the lower microchannel 15 is connected, the two-layer flow on the right is the right side of the lower microchannel 15. Only flow to branch channel 15b. At this time, since the fluid flows only in one microchannel, the flow rate of each channel at the point D is reduced to about half of the point C.

Then, at the second branching point 16b, for example, in the case of point E, the two-layer flow on the left side that flowed only upwards and the two-layer flow on the right side that flowed only downwards merged in the center to form a four-layer flow (first solution layer). / 2nd solution layer / 1st solution layer / 2nd solution layer) can be formed.

By repeating the above-described process it is possible to form a multi-layer flow in the n power of 2 at each branch point.

In short, the blue liquid in the lower plate and the red liquid in the upper plate flow, and after splitting left and right at the branch point, the flow on the right flows only to the lower plate and is led to the center, and the flow on the left flows only to the upper plate and to the center. . In other words, the flow that has been divided up and down is divided into left and right and then guided to the center and gathered up and down again, so that the flow divided into two is combined into a four-layer flow, and the flow divided into four is divided into two again at the next branch and at the center. The result is that the flow is divided by a power of 2 as the branching points are repeated, such as the eighth floor flow.

As such, when the fluid flow in the microchannel is branched from side to side, the two branched flows may be led to the center and merge up and down. When the flow of the fluid in the microchannel branches up and down, the two branched flows may be separated. Can be joined from side to side.

FIG. 5 is a schematic configuration diagram of an anion polymerization initiator manufacturing apparatus according to still another embodiment of the present invention, in which static mixers 19 and 28 are added to the apparatus of FIG. 2. The static mixers 19 and 28 may be connected in series with one or more mixers selected from the group consisting of a plate mixer, a Kenics mixer, and a Sulzer mixer.

In FIG. 5, the first reaction zone 10 may comprise a first micro reactor 11 and a first static mixer 19, and the second reaction zone 20 may comprise a second micro reactor 21 and a first reactor. 2 may include a static mixer 28. Each microreactor 11, 21 and static mixers 19, 28 can be connected in series via connecting tubes 17, 18, 27.

On the other hand, the manufacturing apparatus according to the present invention, each material injected into the continuous reactor is the first micro reactor 11 and the second micro reactor 21 in the case of Figure 2, the first micro reactor 11 in the case of Figure 5, Pressure to control the pressure inside the continuous reactor so as to flow side by side to the first static mixer 19, the second micro reactor 21 and the second static mixer 28, and to prevent the flow in the reverse direction. It may further comprise a control means.

That is, according to another embodiment of the present invention, the continuous process reactor may further include a pressure control means for controlling the pressure inside. The component, organometallic compound, and conjugated diene compound represented by the formula (1) injected into the manufacturing apparatus by the pressure control means may be mixed and reacted while flowing in the same direction (downstream direction) at a pressure above normal pressure.

The first inlet line according to the present invention is a component represented by the formula (1); And tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis (2-dimethyl Aminoethyl) ether, (dimethylaminoethyl) ethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis ( 2-oxolanyl) propane, dipiperidinoethane, pyridine, quinucdine, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, potassium-tert-butyrate, sodium-tert-butyrate, sodium amyl One or more polar additives selected from late, triphenylphosphine can be mixed and further fed.

In one example, a solution comprising a component represented by Formula 1; And a total flow rate of the organometallic compound solution may be 0.01 to 500 g / min. In addition, reactants (primary reactants) reacted with the component represented by the formula (1) and the organometallic compound; And the total flow rate of the conjugated diene compound solution may be 5 to 500 g / min, and the total reaction time may be 3 to 60 minutes.

In the apparatus for preparing an anionic polymerization initiator according to the present invention, the reaction temperature of the first mixer is -80 to 100 ° C, the reaction time is 0.001 to 90 minutes, the reaction temperature of the second mixer is 10 to 70 ° C, and the reaction time is It can be carried out in 1 to 60 minutes. If the reaction temperature is too low, there may be a problem that the reaction initiation rate is slow, if the reaction temperature is too high there may be a problem that the initiator is thermally decomposed. In addition, when the reaction time is too short, there may be a problem that the reaction conversion rate is low, and when the reaction time is too long, there may be a problem that the production of side reactants increases.

In addition, in the apparatus for preparing an anion polymerization initiator according to the present invention, the molar ratio of the component represented by Formula 1 injected into the first inlet line and the organometallic compound injected into the second inlet line may be 5: 1 to 1: 5. The molar ratio of the component represented by Formula 1 injected into the first inlet line and the conjugated diene compound injected into the third inlet line may be 1: 1 to 1: 100.

In the apparatus for producing an anionic polymerization initiator according to the present invention, the pressure inside the continuous reactor may be 1 to 30 bar.

In addition, the present invention provides an anionic polymerization initiator composition comprising a component represented by the following formula (2):

[Formula 2]

In Chemical Formula 2,

G ′ ₁ and G ′ ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 2,

Including when G ' ₁ and G' ₂ are para isomers,

G ' ₁ is alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms Is substituted in the benzene ring,

G ' ₂ is represented by the following formula 2-a,

[Formula 2-a]

In Formula 2-a,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond,

In the benzene structure of Formula 2, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ′ ₁ and G ′ ₂ are not bonded.

The anionic polymerization initiator composition of the present invention may have a long carbon chain in one nitrogen by having a structure of the formula (2).

Specifically, the component represented by the formula (2) may be in the range of 1 to 4: 6 to 9 weight ratio of the combined weight of the ortho and meta isomers and the para isomers. More specifically, the component represented by the formula (2) may be in the weight ratio of the combined weight of the ortho and meta isomers and para isomers may range from 2 to 3: 7 to 9, by having an isomer weight ratio as described above, Stability of the anionic polymerization initiator composition according to this can be improved.

When the anion polymerization initiator composition according to the present invention is stored for 20 hours or more at 0 ℃, the initiator purity may be 35 GC% to 60 GC%. Specifically, when the anionic polymerization initiator composition is stored for 20 hours or more at 0 ℃, the initiator purity may be 40 GC% to 55 GC% or 43 GC% to 50 GC%. Here, GC% means the ratio of the sum of three main polymerization initiators (polymerization initiators prepared from three isomers) peak GC Area to the GC Area of the entire composition excluding the solvent.

In one example, the anionic polymerization initiator according to the present invention may include at least one or more of the compounds of Formula 15 to Formula 17:

[Formula 15]

[Formula 16]

[Formula 17]

In Chemical Formula 15 to Chemical Formula 17,

G ′ ₁ is alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms. Substituted in the benzene ring disclosed in 17,

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

R _a , R _b , R _c and R _d independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond.

Specifically, the anionic polymerization initiator according to the present invention may include at least one compound of the compounds of Formulas 18 to 20:

[Formula 18]

[Formula 19]

[Formula 20]

In Chemical Formulas 18 to 20,

G ' ₁ is alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms, or alkyl magnesium chloride having 1 to 6 carbon atoms. Substituted in the benzene ring disclosed in

R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 0 to 20,

When n is 0, it represents a single bond.

More specifically, the anionic polymerization initiator may include Formula 21 and / or Formula 22:

[Formula 21]

[Formula 22]

In one example, the amine group substituted in the benzene structure disclosed in Formula 21 and Formula 22 may form an isomer of at least one of ortho, meta, and para based on the benzene structure.

The anionic polymerization initiator of the present invention may have a structure of any one of Formulas 21 to 22, and may have a long carbon chain in one nitrogen.

The anionic polymerization initiator may be prepared using the above-described manufacturing method.

It provides an anionic polymerization initiator prepared using the above-described manufacturing apparatus and production method. The anionic polymerization initiator may be a lithium amide system in which one end is modified with an amine. That is, the anionic polymerization initiator provided in the present invention may be an anionic polymerization initiator including a tertiary amine group, and may be a lithium amide based anionic polymerization initiator modified at the Han group end with an amine.

Meanwhile, in the prior art, an anionic polymerization initiator was prepared in a batch process and used to prepare a solution-polymerized styrene-butanediene rubber, or an anion polymerization initiator and a solution-polymerized styrene-butadiene rubber were simultaneously prepared in one batch in a batch reactor. In the former case, the storage step of the denatured initiator is inevitably required, and thus the deactivation of the synthesized initiator is made over time. This may adversely affect the post-processing, which may cause deterioration of the final synthesized SSBR properties, making it difficult to maintain a certain quality. In the latter case, the problem of storage can be solved as a step of causing the polymerization reaction to occur in the same batch reactor simultaneously with the initiator synthesis reaction. However, it is difficult to confirm whether the modified initiator synthesis is performed properly, and the physical properties are also lower than when adding the synthesized initiator.

In the present invention, by using a continuous reactor including any one or more of a static mixer and a micro-reactor, an anionic polymerization initiator is produced continuously during the transfer, it is possible to prevent side reactions to obtain a high yield.

In addition, after preparing an anionic polymerization initiator by the production method of the present invention, and put it directly into the solution-polymerized styrene-butadiene rubber (SSBR) synthesis by the on-demand method synthesis, solve the problem of storage stability of the conventional initiator In addition, anionic initiator reactivity may be improved to introduce tertiary amine groups into the front-end of SSBR.

Hereinafter, the present invention will be described in more detail based on examples, but the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

Three stainless steel pressure vessels vacuum dried were prepared. In the first pressure vessel, 161.7 g of hexane, 9.7 g of 2-vinyl-N, N-dimethylbenzylamine, 4.0 g of 3-vinyl-N, N-dimethylbenzylamine and 30.3 g of 4-vinyl-N, N-dimethylbenzylamine And 44.4 g of tetramethylethylenediamine was added thereto to prepare a vinyl-N, N-dimethylbenzylamine solution. Then, 75.7 g of 2.5M liquid n-butyllithium and 174.4 g of hexane were put into another pressure vessel to prepare an n-butyllithium solution.

The pressure in each pressure vessel was maintained at 4 bar. Using a mass flow meter, 3-vinyl-N, N-dimethylbenzylamine solution was injected into the first inlet line at 0.5 g / min, and n-butyllithium solution was injected into the second inlet line at 0.5 g / min. Each flow meets in a T union or Y type channel. At this time, the width of the tube or channel was 1/8 inch, the temperature was maintained at -30 ℃, and the internal pressure was maintained at 2 bar using the back pressure regulator. After the two raw materials were mixed, the residence time was adjusted to be 5 minutes. The molar ratio of n-butyllithium was 1.0 times and the molar ratio of tetramethyl ethylene diamine was about 1.4 times based on the total amount of isomers of vinyl-N, N-dimethylbenzylamine. The resulting initiator composition was inactivated by adding a small amount of ethanol for analysis.

Example 2

Except for the use of a mixture of 6.85 g of 2-vinyl-N, N-dimethylbenzylamine, 6.85 g of 3-vinyl-N, N-dimethylbenzylamine and 30.3 g of 4-vinyl-N, N-dimethylbenzylamine. An anionic polymerization initiator composition was prepared in the same manner as in Example 1.

Example 3

Except for the use of a mixture of 4.0 g of 2-vinyl-N, N-dimethylbenzylamine, 9.7 g of 3-vinyl-N, N-dimethylbenzylamine, and 30.3 g of 4-vinyl-N, N-dimethylbenzylamine An anionic polymerization initiator composition was prepared in the same manner as in Example 1.

 Comparative Example 1

100% 4-vinyl-N, N instead of using a mixture of 2-vinyl-N, N-dimethylbenzylamine, 3-vinyl-N, N-dimethylbenzylamine and 4-vinyl-N, N-dimethylbenzylamine Anionic polymerization initiator composition was prepared in the same manner as in Example 1 except that dimethylbenzylamine (p-DMVBA) was used.

 Experimental Example 1

In order to determine the composition ratio of the anionic polymerization initiator composition according to the present invention, gas chromatography analysis was carried out on Examples 1 to 3, and the results are shown in Table 1 below. The gram is shown in FIG. 6.

Referring to FIG. 6, peaks of tetramethylethylenediamine, which is an internal standard material, can be found in about 6 minutes, and 2-vinyl-N, N-dimethylbenzylamine, and 3-vinyl-N, N-dimethyl in 19 minutes. It is possible to identify the peaks of the initiators produced by the reaction of benzylamine and 4-vinyl-N, N-dimethylbenzylamine with n-butyllithium, respectively. In reality, Li (lithium) is replaced by hydrogen by ethanol. Specifically, the largest of the three peaks is an initiator produced by reaction of 4-vinyl-N, N-dimethylbenzylamine (p-DMVBA) with n-butyllithium, and the remaining two peaks are 2-vinyl-N , N-dimethylbenzylamine (o-DMVBA) and 3-vinyl-N, N-dimethylbenzylamine (m-DMVBA) are the peaks of the initiator produced by the reaction with n-butyllithium, the 4-vinyl-N, The length of the peak of the initiator produced from N-dimethylbenzylamine (p-DMVBA) and 2-vinyl-N, N-dimethylbenzylamine (o-DMVBA) and 3-vinyl-N, N-dimethylbenzylamine (m- The length ratio of the peaks of the initiator produced from DMVBA) is about 3 to 5 times. It can also be seen that the GC area ratio of the peaks of the initiators produced from tetramethylethylenediamine and 4-vinyl-N, N-dimethylbenzylamine (p-DMVBA) is about 1.2.

Experiment number Li molarity Peak GC area (%) TEMED Product Unknown One 3.5 30 69.6 0.4 2 3.5 35.5 62.9 1.6 3 3.5 40.5 56.7 2.8

Referring to Table 1, the amount of 2-vinyl-N, N-dimethylbenzylamine in the composition of 70% of the weight of the three isomers by the amount of 4-vinyl-N, N-dimethylbenzylamine is 3-vinyl-N, N -The higher the amount of dimethylbenzylamine, the more product is produced. Here, "Product" means an initiator formed by meeting n-butyllithium in all of o-, m-, and p-DMVBA. In addition, in Table 1, Li molar concentration means the concentration of the initiator.

Experimental Example 2

In order to evaluate the stability of the anionic polymerization initiator composition according to the present invention, a test was conducted over time for Example 1, and the results are shown in Table 2 below.

Elapsed time Storage temperature Comparative Example 1
(With 100% p-DMVBA raw material
Synthesized anionic polymerization initiator composition) Example 1
(22% o-DMVBA, 9% m-DMVBA, 69% p-DMVBA, anionic polymerization initiator composition synthesized from raw materials) 20 h 0 ℃ 23 GC% 47 GC%

Referring to Table 2, when the anion polymerization initiator composition of Comparative Example 1 is left at 0 ° C. for 20 hours, the ratio of the anion polymerization initiator in the anion polymerization initiator composition is 23 GC%, whereas the anion polymerization initiator composition of Example 1 is 0 ° C. If left for 20 hours at a ratio of the sum of the anionic polymerization initiator in the anionic polymerization initiator composition can be seen that 47 GC%. At this time, GC% means the ratio of the weight sum of three main polymerization initiators to the total composition weight.

From these results, it can be confirmed that the anionic polymerization initiator composition according to the present invention has high stability as compared to the anionic polymerization initiator composition containing only one type of isomer, including three types of isomers.

1, 10: first reaction zone
2, 19: first static mixer
3, 12: first inflow line
4, 13: 2nd inflow line
5, 17, 18, 27: connector
6, 20: secondary reaction zone
7, 28: second static mixer
8, 22: third inflow line
9, 26: outlet
11: first micro reactor
14, 23: upper microchannel
14a: left branch channel of upper microchannel
14b: right branch channel of upper microchannel
15, 24: lower microchannel
15a: Left branch channel of lower microchannel
15b: right branch channel of lower microchannel
16, 16a, 16b, 25: branch point (confluence point)
17a: fine channel outlet
21: second micro reactor

Claims (16)

A component represented by Formula 1; And injecting the organometallic compound into a continuous reactor for reacting.
Component represented by the formula (1), the weight ratio of the total weight of the ortho and meta isomers and para isomers is 1 to 4: 6 to 9 method for producing an anionic polymerization initiator:
[Formula 1]

In Chemical Formula 1,
G ₁ and G ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 1,
Including when G ₁ and G ₂ are para isomers,
G ₁ is represented by the formula 1-a,
G ₂ is represented by the following Chemical Formula 1-b,
[Formula 1-a]

In Formula 1-a,
R ₁ , R ₂ and R ₃ independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms,
m is an integer from 0 to 20,
When m is 0, it represents a single bond,
[Formula 1-b]

In Formula 1-b,
R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer from 0 to 20,
When n is 0, it represents a single bond,
In the benzene structure of Formula 1, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ₁ and G ₂ are not bonded. delete The method of claim 1,
The organometallic compound is a method for producing an anionic polymerization initiator comprising at least one member selected from the group consisting of organic alkali metal compounds and organic alkaline earth metal compounds. The method of claim 1,
A component represented by Formula 1; And supplying the conjugated diene compound to a continuous reactor after the step of reacting the organometallic compound to react. The method of claim 1,
A molar ratio of the component represented by the formula (1) and the organometallic compound is 5: 1 to 1: 5 method for producing an anionic polymerization initiator. The method of claim 4, wherein
A molar ratio of the component represented by the formula (1) and the conjugated diene compound is 1: 1 to 1: 100 method for producing an anionic polymerization initiator. The method of claim 1,
The continuous reactor includes a mixer; And a first inlet line and a second inlet line connected to the mixer,
The first inlet line supplies a component represented by Formula 1 according to claim 1, the second inlet line is a method for producing an anionic polymerization initiator, characterized in that for supplying an organometallic compound. The method of claim 7, wherein
The mixer comprises a first mixer and a second mixer connected in series,
First and second inlet lines connected to the first mixer; And a third inlet line connected to the second mixer,
The third inlet line is a method for producing an anionic polymerization initiator, characterized in that for supplying a conjugated diene compound. The method of claim 8,
At least one of the first and second mixers is a static mixer, characterized in that the production method of the anionic polymerization initiator. The method of claim 9,
The static mixer is a method for producing an anionic polymerization initiator, characterized in that each one or more selected from the group consisting of a plate mixer, a Kenics mixer and a Sulzer mixer independently. The method of claim 8,
At least one of the first and second mixers is a micro reactor,
The micro-reactor is a method of producing an anionic polymerization initiator, characterized in that it comprises a plurality of fine channels to repeat the branching and confluence. The method of claim 8,
At least one of the first and the second mixer is a method of producing an anionic polymerization initiator, characterized in that the static mixer and the micro reactor connected. The method of claim 8,
Reaction temperature of the first mixer is -80 ℃ to 100 ℃, reaction time is 0.001 to 90 minutes,
The reaction temperature of the second mixer is 10 ℃ to 100 ℃, the reaction time is 1 to 60 minutes, characterized in that the production method of the anionic polymerization initiator. To include a component represented by the formula (2),
The component represented by the formula (2) is an anionic polymerization initiator composition wherein the combined weight of the ortho and meta isomers and the weight ratio of the para isomers ranges from 1 to 4: 6 to 9.
[Formula 2]

In Chemical Formula 2,
G ′ ₁ and G ′ ₂ include two or more of ortho, meta, and para isomers based on the benzene structure disclosed in Formula 2,
Including when G ' ₁ and G' ₂ are para isomers,
G ' ₁ is alkyl lithium having 1 to 20 carbon atoms, alkyl sodium having 1 to 20 carbon atoms, alkyl potassium having 1 to 20 carbon atoms, alkyl magnesium bromide having 1 to 6 carbon atoms or alkyl magnesium chloride having 1 to 6 carbon atoms Is substituted in the benzene ring,
G ' ₂ is represented by the following formula 2-a,
[Formula 2-a]

In Formula 2-a,
R ₄ and R ₅ independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer from 0 to 20,
When n is 0, it represents a single bond,
In the benzene structure of Formula 2, hydrogen or an alkyl group having 1 to 6 carbon atoms is independently bonded to the carbon to which G ′ ₁ and G ′ ₂ are not bonded. delete The method of claim 14,
The anionic polymerization initiator composition is an anionic polymerization initiator composition, characterized in that the initiator purity is 35 to 60 GC% when stored at 0 ℃ for 20 hours or more.

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