KR20190143216A - Method for preparing modified polymerization initiator by continuous reaction - Google Patents

Abstract

The present invention relates to a method for manufacturing a modified polymerization initiator through a continuous reaction in which side reactions are reduced and the modified polymerization initiator can be manufactured in a high yield. The method for manufacturing the modified polymerization initiator according to the present invention is performed by the continuous reaction, thereby being able to reduce the generation of unreacted materials during a lithiation reaction and being able to reduce the generation of by-products by reducing problems caused by an exothermic reaction of the lithiation reaction. Therefore, it is possible to increase a conversion rate and to manufacture the modified polymerization initiator of high purity in the high yield.

Description

Method for preparing modified polymerization initiator by continuous reaction

The present invention relates to a process for producing a modified polymerization initiator through a continuous reaction in which side reactions are reduced and a modified polymerization initiator can be produced in high yield.

Recently, in accordance with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low rolling resistance, excellent wear resistance and tensile characteristics, and adjustment stability represented by wet road resistance as a rubber material for tires.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a repulsive elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature or a small tan δ Goodrich heat generation is preferable.

As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet road resistance. Recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and can reduce the movement of the chain end by the binding or modification of the chain end and increase the bonding strength with the filler such as silica or carbon black. It is used a lot as a rubber material.

When such a solution polymerization SBR (hereinafter referred to as SSBR) is used as a rubber material for a tire, the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire properties such as running resistance and braking force. In addition, fuel consumption can be reduced by appropriately adjusting the glass transition temperature.

The SSBR is prepared using an anionic polymerization initiator, and the chain ends of the formed polymers are used by binding or modifying the chain ends of various polymers. In recent years, the development of the technique which modifies | modifies in a superposition | polymerization stage using the modified polymerization initiator, a modified monomer, etc. at the time of superposition | polymerization is performed.

For example, hexamethylene lithium initiators produced by the reaction of hexamethyleneimine (Hexamethyleneimine, HMI) and n-butyllithium (BuLi) are widely known as the modified polymerization initiator used in the preparation of SSBR. .

Scheme 1

However, in the case of the hexamethylene lithium initiator, the solubility in the solvent is low and precipitates over time, and although it can be used as a polymerization initiator, there is a problem in that the reactivity is poor compared to n-butyllithium. In addition, in order to compensate for the problem of the hexamethylene lithium initiator, a modified polymerization initiator is prepared by further reacting a conjugated diene compound such as isoprene or 1,3-butadiene to hexamethylene lithium synthesized in Scheme 1 as shown in Scheme 2 below. A method has been proposed.

Scheme 2

However, in the case of the modified polymerization initiator prepared as described above, although the solubility and reactivity are improved compared to the hexamethylene lithium initiator, there is still a problem that precipitation occurs and becomes inactivated over time.

On the other hand, in general, an anionic polymerization initiator such as a modified polymerization initiator is prepared through a batch process, or simultaneously produced an anionic polymerization initiator and SSBR in one batch reactor. In the former case, the prepared anionic polymerization initiator inevitably requires a storage step before it is used to manufacture SSBR, and there occurs a problem of losing activity by reacting with various scavengers such as moisture and air during the storage time. As a result, it may adversely affect the post-processing and may act as a factor of deteriorating the physical properties of the finally produced SSBR. In the latter case, the anion polymerization initiator production reaction and the SSBR polymerization reaction are performed in the same batch reactor to solve the problem of storage, but it is difficult to confirm whether the synthesis of the anion polymerization initiator is properly performed, and the physical properties of the finally prepared SSBR There is a problem that is worse than the case of adding a presynthesized anionic polymerization initiator. In addition, in a conventional batch process, raw materials are directly introduced and mixed by reaction to produce by-products or reverse reactions to generate unreacted products, resulting in lower yields.

Therefore, in recent years, a method of using a continuous reactor has been studied to solve the problem of the batch reactor.

For example, Korean Unexamined Patent Publication No. 10-2016-0092227 discloses a method of preparing an anionic polymerization initiator using a continuous reactor including a static mixer. In case of the above method, the concentration distribution and temperature distribution of the raw materials can be made uniform, and the lithiation reaction proceeds continuously, thereby reducing the storage problem and the yield reduction problem. However, the static mixer is used to solve the exothermic reaction problem of the lithiation reaction. There is a disadvantage in that the manufacturing cost is high because a special cooling device is not required.

KR 2016-0092227 A

The present invention has been made to solve the problems of the prior art, a modified polymerization initiator that can be used in the polymerization reaction can easily initiate the polymerization, while providing a filler affinity functional group to the polymer, by minimizing side reactions It is an object of the present invention to provide a method for producing a modified polymerization initiator that can be produced at a high conversion rate.

In order to solve the above problems, the present invention comprises the step of reacting a compound represented by the formula (1) and a compound represented by the formula (2), the reaction is a continuous reactor comprising a first channel and a second channel Before the reaction, the first reactant including the compound represented by Chemical Formula 1 is introduced into the continuous reactor through the first channel, and the second reactant including the compound represented by Chemical Formula 2 is the second channel. It provides a process for the preparation of the modified polymerization initiator is introduced into the continuous reactor via:

[Formula 1]

In Chemical Formula 1,

A is -NR _a R _b , -OR _c , or -SR _d ,

R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and carbon atoms A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms, a heteroalkynyl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms, wherein R _a to R _d is unsubstituted or substituted with a substituent including at least one heteroatom selected from N, O, S, Si, and F atoms, and R _a and R _b are each linked to be substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms. Ring aliphatic hydrocarbon ring groups having 5 to 20 carbon atoms, aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, or heterocyclic groups having 3 to 20 carbon atoms,

[Formula 2]

In Chemical Formula 2,

M is an alkali metal,

R _e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

The method for producing a modified polymerization initiator according to the present invention can be used for polymerization of a polymer to easily prepare a polymerization initiator capable of easily initiating polymerization and at the same time providing a filler affinity functional group to the polymer, as well as continuous By conducting through a continuous reaction using a reactor, it is possible to reduce the generation of unreacted materials during the lithiation reaction, and to reduce byproducts by reducing the problems caused by the exothermic reaction of the lithiation reaction with rapid defrosting, Accordingly, the conversion rate can be improved and a high purity modified polymerization initiator can be produced in high yield.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to the ordinary or dictionary meanings, and the inventors should properly explain the concept of terms in order to explain their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.

As used herein, the term 'substituted' may mean that the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent. When the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, the functional group, the atomic group, Alternatively, one, two or more substituents may be present depending on the number of hydrogens present in the compound, and when a plurality of substituents are present, the substituents may be the same as or different from each other.

The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl and sec-butyl. And branched alkyl groups such as tert-butyl and neo-pentyl may be included.

The term 'alkylene group' used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, butylene, and the like.

The term 'alkenyl group' used in the present invention may mean an alkyl group including one or two or more double bonds.

The term 'alkynyl group' used in the present invention may refer to an alkyl group including one or two or more triple bonds.

The term 'cycloalkyl group' used in the present invention may mean both cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

The term "aryl group" used in the present invention may mean a cyclic aromatic hydrocarbon, and also monocyclic aromatic hydrocarbon in which one ring is formed, or polycyclic aromatic hydrocarbon in which two or more rings are bonded ( polycyclic aromatic hydrocarbons) may include both.

The term 'heterocyclic group' used in the present invention may mean a monovalent aliphatic or aromatic cyclic hydrocarbon group including one or more heteroatoms.

As used herein, the terms 'derived unit' and 'derived functional group' may refer to components, structures, or the substance itself resulting from a substance.

The present invention provides a method for producing a modified polymerization initiator which can act as a polymerization initiator to initiate polymerization upon polymerization of a polymer, in particular a conjugated diene-based polymer, and at the same time act as a modifier to introduce functional groups into the polymer chain.

The method for preparing the modified polymerization initiator according to an embodiment of the present invention includes the step of reacting a compound represented by the following formula (1) and a compound represented by the formula (2), wherein the reaction comprises a first channel and a second channel The first reactant including the compound represented by Chemical Formula 1 before the reaction is introduced into the continuous reactor through the first channel, and the second reactant includes the compound represented by Chemical Formula 2 before the reaction. Is introduced into the continuous reactor through the second channel.

[Formula 1]

In Chemical Formula 1,

A is -NR _a R _b , -OR _c , or -SR _d ,

R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and carbon atoms A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms, a heteroalkynyl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms, wherein R _a to R _d is unsubstituted or substituted with a substituent including at least one heteroatom selected from N, O, S, Si, and F atoms, and R _a and R _b are each linked to be substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms. Ring aliphatic hydrocarbon ring groups having 5 to 20 carbon atoms, aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, or heterocyclic groups having 3 to 20 carbon atoms,

[Formula 2]

In Chemical Formula 2,

M is an alkali metal,

R _e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

Specifically, in Formula 1, A is -NR _a R _b , -OR _c , or -SR _d , R _a to R _d are independently of each other an alkyl group having 1 to 20 carbon atoms, alkenes having 2 to 20 carbon atoms Nyl group, C2-C20 alkynyl group, C3-C20 cycloalkyl group, C6-C20 aryl group, C1-C20 heteroalkyl group, C2-C20 heteroalkenyl group, C2-C20 heteroalky Or a heteroyl group having 2 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, wherein R _a to R _d each include one or more heteroatoms selected from N, O, S, Si, and F atoms. It may be substituted or unsubstituted with a substituent.

In addition, in the —NR _a R _b , R _a and R _b are connected to each other to be substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an aliphatic hydrocarbon ring group having 5 to 10 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or It may be to form a heterocyclic group having 3 to 10 carbon atoms, wherein the heterocyclic group wherein at least one of the carbon atoms forming the ring is substituted with a hetero atom, wherein the hetero atom is selected from N, O, S, Si and F atoms It may be one or more selected.

More specifically, in Chemical Formula 1, A may be selected from substituents represented by Chemical Formulas 1a to 1c.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In Formula 1a to Formula 1c,

R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are independently of each other an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon atoms Aryl groups of 6 to 10, heteroalkyl groups of 1 to 10 carbon atoms, heteroalkenyl groups of 2 to 10 carbon atoms, heteroalkynyl groups of 2 to 10 carbon atoms, heterocycloalkyl groups of 3 to 10 carbon atoms, or heteroaryl groups of 3 to 10 carbon atoms R ₁ and R ₂ and R ₇ and R ₈ may be bonded to each other to form an aliphatic hydrocarbon ring group having 5 to 20 carbon atoms or an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, wherein R ₁ , R ₂ , R ₅ , R ₇ and R ₈ may each be unsubstituted or substituted with a substituent including one or more heteroatoms selected from N, O and S atoms,

R ₃ , R ₄ and R ₆ are each independently a substituent containing a hetero atom selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an N and O atoms Substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,

X and Z are each independently selected from N, O and S atoms, and when X is O or S, R ₈ is not present, and when Z is O or S, R ₅ is not present.

Specifically in Formulas 1a to 1c, R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are independently substituted or unsubstituted with a substituent including one or more heteroatoms selected from N, O and S atoms. It may be an alkyl group having 1 to 10 carbon atoms or a heteroalkyl group having 1 to 10 carbon atoms, wherein R ₁ and R ₂ and R ₇ and R ₈ are each bonded to each other an aliphatic hydrocarbon ring group having 5 to 10 carbon atoms or 6 to 10 carbon atoms It may be to form an aromatic hydrocarbon ring group, R ₃ , R ₄ and R _{6 It} is an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms independently of each other, R ₅ is 1 to An alkyl group of 10, X and Z is one selected from N, O and S atoms, R ₈ does not exist when X is O or S, R ₅ may not be present when Z is O or S. have.

More specifically, the myrcene derivative compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-1 to Chemical Formula 1-11.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

In addition, in Formula 2, M is an alkali metal, R _e is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 carbon atoms. It may be an aryl group of 10 to 10, specifically M in formula 2 may be Na, K or Li, R _e may be hydrogen or an alkyl group having 1 to 10 carbon atoms.

On the other hand, the compound represented by the formula (1) according to an embodiment of the present invention may be prepared by reacting a functional group compound to myrcene (myrcene), for example represented by the following formula 4 in the presence of a polar organic solvent and a catalyst Reacting the halogenated myrcene with an acetylating agent to prepare an acetylated compound comprising a compound represented by Formula 5a and a compound represented by Formula 5b (step a); Hydrolyzing the acetylated compound to prepare a hydroxylated compound (step b); Reacting the hydroxylated compound with the leaving group-containing compound to prepare a leaving group-containing compound including the compound represented by Formula 6a and the compound represented by Formula 6b (step c); Reacting the leaving group-containing compound with a compound represented by Chemical Formula 7 (step d); And it may be prepared through a manufacturing method comprising the step of purifying (step e).

[Formula 4]

[Formula 5a]

[Formula 5b]

[Formula 6a]

[Formula 6b]

[Formula 7]

In Formula 4, Formula 5a, Formula 5b, Formula 6a, Formula 6b, and Formula 7, A is as defined above, L is a leaving group, and Y is Cl, Br or I.

The step a may be carried out by reacting the halogenated myrcene represented by the formula (4) with an acetylating agent in the presence of a polar organic solvent and a catalyst, wherein the halogenated myrcene, the catalyst and the acetylating agent are from 1: 0.1 to 5: 1 to At a molar ratio of 20, the reaction may be performed at a temperature of 30 ° C. to 100 ° C. for 10 minutes to 24 hours.

Here, the acetylated compound is an isomeric mixture comprising a compound represented by Formula 5a, which is an E / Z (Cis / Trans) isomer, and a compound represented by Formula 5b, by the reaction of Step a. A compound represented by the formula (5a) and a compound represented by the formula (5b) may be formed at the same time from the halogenated mircene compound represented.

In addition, the polar organic solvent may be a polar aprotic organic solvent or a polar proton organic solvent, and the polar aprotic organic solvent may be, for example, N, N-dimethylformamide and dimethyl sulfoxide. sulfoxide, DMSO) may be any one or more selected from the group consisting of, the polar protic organic solvent may be any one or more selected from the group consisting of acetic acid (acetic acid), n-butanol and n-propanol.

In addition, the catalyst may be any one or more selected from the group consisting of sodium iodide (NaI) and sodium bromide (NaBr).

In addition, the acetylating agent may be any one or more selected from the group consisting of sodium acetate (NaOAc), acetic acid (HOAc) and acetic anhydride (Ac ₂ O).

In addition, the halogenated myrcene represented by Formula 4 may be prepared by introducing a halogen group into the molecular structure of β-myrcene by reacting β-myrcene with a halogen-containing compound, wherein the halogen-containing compound is β-myrcene and The substance capable of reacting to form a halogenated myrcene may be, for example, calcium hypochlorite (Ca (OCl) ₂ ), sodium hypochlorite (NaClO), or hypochlorous acid (HClO). In addition, the β-myrcene and the halogen-containing compound is not particularly limited, but may be reacted in a molar ratio of 1: 0.8 to 1.2, or a molar ratio of 1: 0.8 to 1.0, in which case the halogenated myrcene represented by the formula (2) It can be easily produced at high conversion rates.

In this case, the reaction of the β-myrcene and the halogen-containing compound may be carried out in the presence of a reducing agent, wherein the reducing agent may be, for example, carbon dioxide to serve to facilitate the halogenation reaction.

Step b is a step for preparing a hydroxylated compound from the acetylated compound, can be carried out by hydrolyzing the acetylated compound, wherein the hydrolysis is prepared by preparing an aqueous solution of acetylated compound and adding a hydrolysis catalyst Can be done.

The acetylated compound aqueous solution may include an acetylated compound, alcohol and water, wherein the acetylated compound, alcohol and water in the aqueous solution may be appropriately adjusted to have an aqueous solution concentration suitable for the hydrolysis reaction, for example, acetylation. The compound, alcohol and water may have a molar ratio of 1:10 to 100: 5 to 50.

In addition, the hydrolysis catalyst catalyzes the hydrolysis of the acetylated compound, but is not particularly limited, for example, potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ) and lithium carbonate (Li ₂ CO ₃ ) It may be any one or more of. In this case, the hydrolysis catalyst may be used in 0.5 to 10 moles relative to 1 mole of the acetylated compound.

The step c is a step for preparing a leaving group-containing compound, can be carried out by reacting the hydroxylated compound and the leaving group-containing compound, specifically, the hydroxylated compound and the leaving group-containing compound is 1: 0.5 to It may be reacted at a molar ratio of 5.

In the above, the leaving group-containing compound is a leaving group corresponding to L in the compound represented by the formula 6a) and (6b react with hydroxy screen compounds, such as methane sulfonate group (CH ₃ SO ₃ ^{- -)} or a methyl sulfonate group ^{_{(C 7 H 7 SO 3 -}} ) of a material to provide an alkylsulfonate, such as, by reaction with the hydroxy Chemistry compound a substance which can provide a leaving group though not particularly limited, for example, chloride, methanesulfonyl (methanesulfonyl chloride ), p-toluenesulfonyl chloride, 2-propanesulfonyl chloride, trichloromethanesulfonyl chloride, cyclohexanesulfonyl chloride or cyclo Pentanesulfonyl chloride.

Step d is a step of preparing an isomeric composition comprising the compound represented by the formula (1) in which the functional group derived from the compound represented by the formula (7) is introduced, can be carried out by reacting the leaving group-containing compound and the compound represented by the formula (7) have. In this case, the leaving group-containing compound and the compound represented by the formula (7) may be reacted in a molar ratio of 1: 0.1 to 20, or 1: 0.1 to 10.

Step e is a step of purifying and obtaining a compound represented by Formula 1 from an isomer composition by purification, which may be performed through a conventional method in the art.

In one embodiment of the present invention, the reaction may be performed in a continuous reactor. In this case, the continuous reactor may represent a reactor that advances the reaction while continuously inputting the raw material used for the reaction.

Specifically, the reaction may be performed in a continuous reactor including a first channel and a second channel, the first reactant including the compound represented by the formula (1) before the reaction is continuous through the first channel The second reactant that is introduced into the reactor and includes the compound represented by Formula 2 may be introduced into the continuous reactor through the second channel. Here, the first channel and the second channel may respectively mean an input unit (or injection unit) for adjusting the input amount of each of the first reactant and the second reactant in the continuous reactor, in this case the first The input amount of the reactant and the second reactant may be adjusted independently of each other, and thus the input amount may be adjusted according to the reaction environment, thereby minimizing side reactions.

Further, the first reactant may be introduced into the continuous reactor at a rate of 1.0 g / min to 20.0 g / min through the first channel, and the second reactant may be 1.0 g / min to 20.0 g through the second channel. It may be introduced into the continuous reactor at a rate of / min. Specifically, the first reactant may be introduced into the continuous reactor at a rate of 1.0 g / min to 10.0 g / min through the first channel, and the second reactant may be 1.0 g / min through the second channel. It may be introduced into the continuous reactor at a rate of 10.0 g / min, it is possible to minimize side reactions by adjusting appropriately without a sudden change in the amount of the compound represented by the formula (1) and the compound represented by the formula (2) within this range.

In addition, during the reaction, the compound represented by Formula 1 and the compound represented by Formula 2 may be reacted in a molar ratio of 1: 0.5 to 1: 5, specifically, the compound represented by Formula 1 and represented by Formula 2 The compound may be reacted in a molar ratio of 1: 0.8 to 1: 1.5. When the compound represented by Formula 1 and the compound represented by Formula 2 are reacted at the molar ratio, side reactions may be reduced.

In addition, the preparation method according to an embodiment of the present invention is optionally modified by controlling the addition rate (flow rate) and the molar ratio of the first reactant and the second reactant as described above to selectively modify the polymerization initiator in the form of a polymer such as monomer or dimer. Can be prepared.

On the other hand, the first reactant may be a material having a fluidity so that the compound represented by the formula (1) is easily introduced into the continuous reactor to participate in the reaction, for example, the first reactant is the compound represented by the formula (1), Or it may be a solution containing a compound represented by the formula (1) and a reaction solvent.

In addition, the second reactant may be a material having fluidity such that the compound represented by Chemical Formula 2 may be easily introduced into the continuous reactor to participate in the reaction. For example, the second reactant may be the compound represented by Chemical Formula 2, or Or it may be a solution containing a compound represented by the formula (2) and a reaction solvent.

Here, when each of the first reactant and the second reactant is a solution, the concentration of the solution is not particularly limited, and the compound represented by Formula 1 and the compound represented by Formula 2 may be adjusted to have the aforementioned molar ratio.

In addition, the reaction solvent may be a hydrocarbon solvent that does not react with anions, such as linear hydrocarbon compounds such as pentane, hexane and octane; Derivatives thereof having a side branch; Cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; Aromatic hydrocarbon compounds such as benzene, toluene and xylene; And linear and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran. Specifically, the reaction solvent may be cyclohexane, hexane, tetrahydrofuran or diethyl ether.

On the other hand, the reaction according to an embodiment of the present invention can be carried out in the presence of a polar additive, if necessary, wherein the polar additive is included in the first reactant, or is included in the second reactant is introduced into the continuous reactor In detail, the polar additive may be included in the first reactant and introduced into the continuous reactor.

That is, the first reactant may include a polar additive, in which case the polar additive may be included in the first reactant in a molar ratio of 1.0 to 5.0 with respect to 1 mole of the compound represented by Formula 1, and this range Reactivity of the compound represented by the formula (1) and the compound represented by the formula (2) within the reaction can be easily adjusted to reduce the side reactions. The polar additive is not particularly limited, but tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene diethyl ether, diethyl glycol, dimethyl glycol, tertiary At least one selected from the group consisting of butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine May be

In addition, according to one embodiment of the present invention, the reaction may be carried out under a temperature range of 0 ℃ to 80 ℃, or 15 ℃ to 50 ℃ and pressure conditions of 0.5 bar to 10 bar, or 1 bar to 4 bar. In this range, the reaction rate is excellent, and there is an effect of minimizing side reactions.

The method for preparing the modified polymerization initiator according to the present invention is carried out in a continuous reaction using a continuous reactor, the mixing ratio of the reaction raw materials (for example, the compound represented by Formula 1 and the compound represented by Formula 2) during the lithiation reaction It is possible to reduce the generation of unreacted materials by increasing the temperature, and to reduce byproducts by reducing the problems caused by the exothermic reaction of the lithiation reaction with rapid defrosting. As a result, the conversion rate can be improved to stably produce a high purity modified polymerization initiator in high yield.

In addition, the present invention provides a modified polymerization initiator prepared through the above production method.

The modified polymerization initiator according to an embodiment of the present invention is characterized in that it comprises a compound derived unit represented by the formula (1) and a compound derived unit represented by the formula (2).

In addition, the modified polymerization initiator according to an embodiment of the present invention may be a monomer, wherein the modified polymerization initiator may be a monomer and an isomer thereof.

For example, the modified polymerization initiator may be one containing at least one selected from the group consisting of a compound represented by the following formula (3) and an isomer thereof.

[Formula 3]

In Formula 3, A is as defined in Formula 1, M is Na, K or Li, R _e is hydrogen or an alkyl group having 1 to 10 carbon atoms. In addition, in Chemical Formula 3, M may be bonded to an adjacent carbon by an ionic bond.

Meanwhile, the isomer of the compound represented by Formula 3 may include all of the structural isomers and stereoisomers of the compound represented by Formula 3, and for example, the compounds represented by Formulas 3-1 to 3-3. Can be.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In Formulas 3-1 to 3-3, A, M, and R _e are the same as defined in Formula 3.

In another embodiment of the present invention, the modified polymerization initiator may be at least one selected from dimers, trimers, and oligomers of the compound represented by Formula 3 and isomers thereof.

Here, the dimer may represent a form in which two compound-derived units represented by Formula 1 and one compound-derived unit represented by Formula 2 are combined per molecule, and the trimer is a compound-derived unit represented by Formula 1 It may represent a form in which three and one derived unit represented by the formula (2) is bonded, the oligomer may represent a form in which a plurality of compound derived units represented by the formula (1) and one derived unit represented by the formula (2) are combined. have.

In addition, the present invention provides a modified conjugated diene-based polymer comprising the functional group derived from the modified polymerization initiator.

The modified conjugated diene-based polymer according to an embodiment of the present invention may include a conjugated diene-based monomer-derived repeating unit, and may include a functional group derived from the modified polymerization initiator at at least one end thereof.

Herein, the conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed by the conjugated diene-based monomer upon polymerization, and the conjugated diene-based monomer may be, for example, 1,3-butadiene, 2,3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) It may be at least one selected from the group.

Meanwhile, the modified conjugated diene-based polymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the conjugated diene-based monomer-derived repeating unit, and the aromatic vinyl monomer-derived repeating unit may be an aromatic vinyl series The monomer may mean a repeating unit formed during polymerization, wherein the aromatic vinyl monomer may be, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methylstyrene, 4-propylstyrene, It may be at least one selected from the group consisting of 1-vinyl naphthalene, 4-cyclohexyl styrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited only to these.

Example 1

Two vacuum dried 2L stainless steel pressure vessels were prepared. 1740 g of hexane, 1.4 mol of a compound represented by Formula 1-5, and 1.4 mol of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 285 g of 2.5M n-butyllithium was added to 1845 g of hexane in a second pressure vessel to prepare a second reactant having 4 wt% of n-butyllithium solution (1.4 mol). With the pressure of each pressure vessel maintained at 5 bar, the mass flow meter was used to continuously feed the first reactant into the first channel at a rate of 1.0 g / min into the first channel and 1.0 second reactant into the second channel. Each was injected at an injection rate of g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 ℃, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula Was prepared. It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-5) and the final material obtained by GC / MS analysis, MS analysis result was m / z = 292 g / mol, starting material The molecular weight of the compound represented by Formula 1-5 was 234 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H.

Specifically, GC / MS analysis uses ZB-5MS (0.25 mm (ID) x 30 ml, 0.25 μm df capillary) as a column, the gas flow (He) is 1 ml / min, oven The temperature was increased to 320 ° C. at 10 ° C./min and maintained for 15 minutes after 3 minutes at the initial 50 ° C., and the injector temperature was adjusted to 250 ° C., split ratio 1/20, and the injection amount was 0.2 μl. In addition, the modified polymerization initiator was measured after protonation of the organolithium portion by quenching.

[Formula 1-5]

[Formula i]

Example 2

Two vacuum dried 2L stainless steel pressure vessels were prepared. 1740 g of hexane, 1.4 mol of a compound represented by Chemical Formula 1-7, and 1.4 mol of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 285 g of 2.5M n-butyllithium was added to 1845 g of hexane in a second pressure vessel to prepare a second reactant having 4 wt% of n-butyllithium solution (1.4 mol). With the pressure of each pressure vessel maintained at 5 bar, the mass flow meter was used to continuously feed the first reactant into the first channel at a rate of 1.0 g / min into the first channel and 1.0 second reactant into the second channel. Each was injected at an injection rate of g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 ℃, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula (ii) Was prepared. It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-7) and finally obtained through GC / MS analysis, MS analysis result was m / z = 295 g / mol, starting material The molecular weight of the compound represented by Formula 1-7 was 237 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-7]

[Formula ii]

Example 3

Two vacuum dried 2L stainless steel pressure vessels were prepared. 1740 g of hexane, 1.4 mol of a compound represented by Formula 1-6, and 1.4 mol of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 285 g of 2.5M n-butyllithium was added to 1845 g of hexane in a second pressure vessel to prepare a second reactant having 4 wt% of n-butyllithium solution (1.4 mol). With the pressure of each pressure vessel maintained at 5 bar, the mass flow meter was used to continuously feed the first reactant into the first channel at a rate of 1.0 g / min into the first channel and 1.0 second reactant into the second channel. Each was injected at an injection rate of g / min. Thereafter, the temperature of the continuous reactor is maintained at 25 ℃, the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator (backpressure regulator) to the modified polymerization initiator comprising a compound represented by the formula (iii) Was prepared. It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-6) and the finally obtained material by GC / MS analysis, MS analysis result was m / z = 279 g / mol, starting material The molecular weight of the compound represented by Formula 1-6 was 221 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-6]

[Formula iii]

Example 4

Two vacuum dried 2L stainless steel pressure vessels were prepared. 1740 g of hexane, 1.4 mol of a compound represented by Formula 1-1, and 1.4 mol of tetramethylethylenediamine were added to a first pressure vessel to prepare a first reactant. At the same time, 285 g of 2.5M n-butyllithium was added to 1845 g of hexane in a second pressure vessel to prepare a second reactant having 4 wt% of n-butyllithium solution (1.4 mol). With the pressure of each pressure vessel maintained at 5 bar, the mass flow meter was used to continuously feed the first reactant into the first channel at a rate of 1.0 g / min into the first channel and 1.0 second reactant into the second channel. Each was injected at an injection rate of g / min. Subsequently, the temperature of the continuous reactor is maintained at 25 ° C., and the internal pressure is reacted for 5 minutes while maintaining 2 bar using a backpressure regulator. The modified polymerization initiator including the compound represented by the following Formula iv Was prepared. It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-1) and the finally obtained material by GC / MS analysis, MS analysis result was m / z = 237 g / mol, starting material The molecular weight of the compound represented by Formula 1-6 was 179 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-1]

[Formula iv]

Example 5

In Example 1, a second reactant comprising n-butyllithium at 20.0 g / min in a second channel and a first reactant containing a compound represented by Formula 1-5 in a first channel in a continuous reactor A modified polymerization initiator was prepared in the same manner as in Example 1, except that the reaction was carried out at an injection rate of 20.0 g / min.

It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-5) and the finally obtained through GC / MS analysis, MS analysis result was m / z = 292 g / mol, starting material The molecular weight of the compound represented by Formula 1-5 was 234 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-5]

[Formula i]

Example 6

In Example 1, the first reactant containing the compound represented by Formula 1-5 in the first channel in a continuous reactor at 10.0 g / min, the second reactant comprising n-butyllithium in the second channel A modified polymerization initiator was prepared including the compound represented by the following Formula v, which is a dimeric structure, in the same manner as in Example 1 except that the reaction was carried out for 10 minutes by injecting at a rate of 5.0 g / min.

It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-5) and the final material obtained by GC / MS analysis, MS analysis result was m / z = 526 g / mol, starting material The molecular weight of the compound represented by Formula 1-5 was 234 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-5]

[Formula i]

[Formula v]

Comparative Example 1

After purging with nitrogen for some time and applying a vacuum, an inert reactor was prepared.

After adjusting the reactor internal temperature to 25 ℃, the internal pressure to 1 bar, 1740 g of n-hexane, 1.4 mol of tetramethylethylenediamine, 1.4 mol of 2.5M n-butyllithium (in n-hexane), the formula 1- 1.4 mol of the compound represented by 5 was sequentially added to the reactor and stirred for 5 minutes to prepare a modified polymerization initiator in which the compound represented by Formula (I) and the compound represented by Formula (V) were mixed. It was confirmed that the modified polymerization initiator was synthesized by the molecular weight change between the compound represented by the formula (1-5) and the final material obtained by GC / MS analysis, MS analysis results m / z = 292 g / mol and 526 g / mol The molecular weight of the compound represented by Chemical Formula 1-5 was 234 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-5]

[Formula i]

[Formula v]

Comparative Example 2

After purging with nitrogen for some time and applying a vacuum, an inert reactor was prepared.

After adjusting the temperature inside the reactor to 25 ℃, the internal pressure to 1 bar, 1740 g of n-hexane, 1.4 mol of tetramethylethylenediamine, 1.4 mol of 2.5M n-butyllithium (in n-hexane), the following formula 1- 1.4 mol of the compound represented by 7 was sequentially added to the reactor and stirred for 5 minutes to prepare a modified polymerization initiator in which the compound represented by Formula ii and the compound represented by Formula vi were mixed. The modified polymerization initiator was confirmed to be synthesized by the molecular weight change between the compound represented by the formula (1-7) and finally obtained through GC / MS analysis, MS analysis results m / z = 295 g / mol and 539 g / mol The molecular weight of the compound represented by Chemical Formula 1-7 was 237 g / mol. In this case, the GC / MS analysis of the modified polymerization initiator shows the result of replacing Li in the modified polymerization initiator with H. GC / MS analysis was performed in the same manner as in Example 1.

[Formula 1-7]

[Formula ii]

[Formula vi]

Experimental Example

The final conversion rate (yield) and the ratio of monomer and dimer in the modified polymerization initiator of Examples 1 to 6 and Comparative Examples 1 and 2 were compared and analyzed, and the results are shown in Table 1 below. . Herein, the conversion rate was determined based on the ratio of the substance corresponding to Chemical Formula 1 and the substance corresponding to Chemical Formula 1 in the final product, based on the substance corresponding to Chemical Formula 1.

division % Conversion Monomer ratio (mol%) Dimer ratio (mol%) Example 1 ≥95 100 0 Example 2 ≥90 100 0 Example 3 100 100 0 Example 4 100 100 0 Example 5 100 100 0 Example 6 ≥90 0 100 Comparative Example 1 ≤95 70 30 Comparative Example 2 ≤90 80 20

As shown in Table 1, it is confirmed that the production method of Examples 1 to 6 according to an embodiment of the present invention can be prepared in a high yield of the modified polymerization initiator of Comparative Example 1 and Comparative Example 2 It was.

In addition, in the case of Comparative Example 1 and Comparative Example 2, a modified polymerization initiator in the form of a mixture of monomers and dimers was prepared, whereas Examples 1 to 6 were confirmed to be made of a monomer or a dimer single material. Through the production method according to an embodiment of the present invention by performing a continuous reaction it was confirmed that by selectively adjusting the flow rate of the reactants introduced into the continuous reactor to a single material of the monomer or dimer according to the purpose.

Examples 7-12

Modified conjugated diene-based polymers containing functional groups derived from the modified polymerization initiator were prepared using the modified polymerization initiators prepared in Examples 1 to 6.

In a 20 L autoclave reactor, 21 g of styrene, 58 g of 1,3-butadiene and 581 g of n-hexane were added in the presence of each of the modified polymerization initiators prepared in Examples 1 to 6 to 80 at 50 ° C. The polymerization was carried out to a polymerization conversion rate of 99% while increasing the temperature to ℃. Subsequently, a small amount of 1,3-butadiene was added to cap the polymer end with butadiene, and 14 g of a solution in which 30 wt% of the antioxidant Wingstay K was dissolved in hexane was added thereto. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water to prepare a modified styrene-butadiene copolymer. Elemental analysis of each of the prepared copolymers confirmed that nitrogen atoms exist in the copolymer chain.

Claims (11)

To react the compound represented by the formula (1) and the compound represented by the formula (2),
The reaction is carried out in a continuous reactor comprising a first channel and a second channel,
Before the reaction, the first reactant comprising the compound represented by Formula 1 is introduced into the continuous reactor through the first channel, and the second reactant comprising the compound represented by Formula 2 is the continuous reactor through the second channel. Method for producing a modified polymerization initiator that is added to:
[Formula 1]

In Chemical Formula 1,
A is -NR _a R _b , -OR _c , or -SR _d ,
R _a to R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and carbon atoms A heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms, a heteroalkynyl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms, wherein R _a to R _d is unsubstituted or substituted with a substituent including one or more heteroatoms selected from among N, O, S, Si, and F atoms, and R _a and R _b are each linked to be substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms. Ring aliphatic hydrocarbon ring groups having 5 to 20 carbon atoms, aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, or heterocyclic groups having 3 to 20 carbon atoms,
[Formula 2]

In Chemical Formula 2,
M is an alkali metal,
R _e is hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
The method according to claim 1,
In Formula 1, A is a method for producing a modified polymerization initiator is selected from the substituents represented by Formula 1a to Formula 1c:
[Formula 1a]

[Formula 1b]

[Formula 1c]

In Chemical Formulas 1a to 1c,
R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon atoms Aryl groups of 6 to 10, heteroalkyl groups of 1 to 10 carbon atoms, heteroalkenyl groups of 2 to 10 carbon atoms, heteroalkynyl groups of 2 to 10 carbon atoms, heterocycloalkyl groups of 3 to 10 carbon atoms, or heteroaryl groups of 3 to 10 carbon atoms Wherein R ₁ and R ₂ and R ₇ and R ₈ may be bonded to each other to form an aliphatic hydrocarbon ring group having 5 to 20 carbon atoms or an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, wherein R ₁ and R ₂ , R ₅ , R ₇ and R ₈ are each unsubstituted or substituted with a substituent including one or more heteroatoms selected from N, O and S atoms,
R ₃ , R ₄ and R ₆ are each independently a substituent containing a heteroatom or a heteroatom selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and N and O atoms An alkylene group having 1 to 10 carbon atoms substituted or unsubstituted with
X and Z are each independently selected from N, O and S atoms, and when X is O or S, R ₈ is not present, and when Z is O or S, R ₅ is not present.
The method according to claim 2,
The R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms or unsubstituted or substituted with a substituent including one or more heteroatoms selected from N, O and S atoms. To a heteroalkyl group, wherein R ₁ and R ₂ and R ₇ and R ₈ may be bonded to each other to form an aliphatic hydrocarbon ring group having 5 to 10 carbon atoms or an aromatic hydrocarbon ring group having 6 to 10 carbon atoms,
R ₃ , R ₄ and R ₆ are each independently an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms,
R ₅ is an alkyl group having 1 to 10 carbon atoms,
X and Z are one kind selected from N, O and S atoms, and when X is O or S, R ₈ is not present, and when Z is O or S, R ₅ is not present. Way.
The method according to claim 1,
In Formula 2, R _e is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Method for producing a modified polymerization initiator.
The method according to claim 1,
Wherein the first reactant is introduced into the continuous reactor at a rate of 1.0 g / min to 20.0 g / min through the first channel.
The method according to claim 1,
Wherein the second reactant is introduced into the continuous reactor at a rate of 1.0 g / min to 20.0 g / min through the second channel.
The method according to claim 1,
The compound represented by Formula 1 and the compound represented by Formula 2 is a method for producing a modified polymerization initiator is reacted in a molar ratio of 1: 0.5 to 1: 5.
The method according to claim 1,
Wherein the reaction is carried out under a temperature range of 0 ° C. to 80 ° C. and a pressure of 0.5 bar to 10 bar.
The method according to claim 1,
Wherein the first reactant comprises a polar additive.
The method according to claim 9,
The polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene diethyl ether, diethyl glycol, dimethyl glycol, tert-butoxyethoxyethane, A modified polymerization initiator containing at least one selected from the group consisting of bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine. Manufacturing method.
The method according to claim 1,
Method for producing a modified polymerization initiator is a compound represented by Formula 1 is a compound represented by the formula 1-1 to formula 1-11:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]