KR102471052B1 - Isomer composition of myrcene derived compound and modified initiator comprising a functional group derived the same - Google Patents

Abstract

The present invention relates to an isomer composition of a myrcene derivative compound, a method for preparing the same, and a modified polymerization initiator prepared using the isomer composition and containing a functional group derived from the isomer composition.

Description

Isomer composition of myrcene derived compound and modified initiator comprising a functional group derived the same}

The present invention relates to an isomer composition of a myrcene derivative compound, a method for preparing the same, and a modified polymerization initiator prepared using the isomer composition and containing a functional group derived from the isomer composition.

In accordance with the recent demand for low fuel consumption for automobiles, conjugated diene-based polymers with low rolling resistance, excellent abrasion resistance and tensile properties, and control stability represented by wet road surface resistance are required as rubber materials for tires.

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

Natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known as rubber materials with low hysteresis loss, but these have a problem of low wet road surface 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) are produced by emulsion polymerization or solution polymerization and are 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 changed by coupling or modification. that it can be controlled. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, reduce the movement of the chain ends by linking or modifying the chain ends, and increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When such solution-polymerized SBR is used as a rubber material for tires, the glass transition temperature of rubber can be raised by increasing the vinyl content in the SBR, thereby controlling required physical properties of the tire, such as driving resistance and braking power, as well as increasing the glass transition temperature. Proper adjustment can reduce fuel consumption. The solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various denaturants. For example, U.S. Patent No. 4,397,994 suggests a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, are bonded using a binder such as a tin compound. did

On the other hand, solution polymerization SSBR is prepared using an anionic polymerization initiator, in which case an organolithium compound is mainly used as an anionic polymerization initiator. The organolithium compound is used as it is or modified with a functional group-containing compound capable of imparting a functional group to a polymer chain. For example, there is a method of preparing and using a modified polymerization initiator having a styrene-based structural unit, a conjugated diene-based structural unit, or an arylamine structural unit by reacting a styrene-based compound, a conjugated diene-based compound, or an arylamine compound with an organolithium compound. However, there are limitations in industrial use due to poor economic feasibility, and in particular, obtaining a modified polymerization initiator using a conjugated diene-based compound is difficult to manufacture because it is not easy to bond a functional group to a conjugated diene-based unit.

For example, JP3748277 describes an anionic polymerization initiator prepared by reacting an organolithium compound with an adduct in which nitrogen of a cyclic secondary amine is bonded to a conjugated diene carbon, but when prepared by the above reaction, cyclic secondary amine remains Therefore, it can act as a scavenger in the reaction, and the yield of the anionic polymerization initiator can be reduced. Therefore, filtration and purification after the reaction are required. Therefore, it is necessary to develop a modified polymerization initiator with excellent economic feasibility and good industrial applicability.

US 4397994 A JP 3748277 B2

The present invention has been made to solve the problems of the prior art, and is a novel material that can be used as a raw material for a modified polymerization initiator capable of providing a functional group to a polymer while being used in a polymerization reaction to easily initiate the reaction. An object of the present invention is to provide an isomeric composition of a myrcene derivative compound having a structure.

In addition, an object of the present invention is to provide a method for preparing the isomer composition.

In addition, an object of the present invention is to provide a modified polymerization initiator containing a functional group derived from the isomer composition.

In order to solve the above problems, the present invention is an isomer composition comprising two or more isomers of a myrcene derivative compound, wherein a compound represented by Formula 1 and a compound represented by Formula 2 are prepared in a ratio of 8:2 to 4:6. An isomer composition comprising in weight ratio is provided:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

A ₁ and A ₂ are each independently -NR _a R _b , -OR _c , or -SR _d ;

Wherein R _a to R _d are each independently a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms, unsubstituted or substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. , An alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 3 to 30 carbon atoms, wherein R _a and R _b are connected to each other to form an alkyl group having 1 to 30 carbon atoms or 5 unsubstituted carbon atoms It may form an aliphatic ring group of 20 to 20, an aromatic ring group of 5 to 20 carbon atoms, or a heterocyclic group of 3 to 20 carbon atoms.

In addition, the present invention includes a step of preparing an isomer composition comprising two or more isomers of a myrcene derivative compound by reacting a compound represented by the following Chemical Formula 3 with a compound represented by the following Chemical Formula 4, wherein the isomer composition is prepared as follows. Provided is a method for preparing an isomer composition comprising a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 8:2 to 4:6:

[Formula 3]

[Formula 4]

[Formula 1]

[Formula 2]

In Formulas 1 to 4,

A, A ₁ and A ₂ are each independently -NR _a R _b , -OR _c , or -SR _d ;

Wherein R _a to R _d are each independently a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms, unsubstituted or substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. , An alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 3 to 30 carbon atoms, wherein R _a and R _b are connected to each other to form an alkyl group having 1 to 30 carbon atoms or 5 unsubstituted carbon atoms to 20 aliphatic ring groups, C 5 to 20 aromatic ring groups, or C 3 to 20 heterocyclic groups;

X is Cl, Br or I.

In addition, the present invention provides a first compound comprising a compound-derived unit represented by Formula 1 and a compound-derived unit represented by Formula 5; and a second compound including a unit derived from a compound represented by Formula 2 and a unit derived from a compound represented by Formula 5, wherein the first compound and the second compound have a weight ratio of 8:2 to 4:6 A phosphorus modified polymerization initiator is provided:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

A ₁ and A ₂ are each independently -NR _a R _b , -OR _c , or -SR _d ;

Wherein R _a to R _d are each independently a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms, unsubstituted or substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. , An alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 3 to 30 carbon atoms, wherein R _a and R _b are connected to each other to form an alkyl group having 1 to 30 carbon atoms or 5 unsubstituted carbon atoms to 20 aliphatic ring groups, C 5 to 20 aromatic ring groups, or C 3 to 20 heterocyclic groups;

[Formula 5]

In Formula 5,

M is an alkali metal;

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

The isomer composition of the myrcene derivative compound according to the present invention can be used as a raw material for a polymerization initiator to form a modified polymerization initiator into which various functional groups are introduced, and the modified polymerization initiator initiates a polymerization reaction and simultaneously groups a functional group in a polymer chain. can be introduced.

Hereinafter, the present invention will be described in more detail to aid understanding of 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 ordinary or dictionary meanings, and the inventors use the concept of terms appropriately to describe their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.

The term 'substitution' used in the present invention may mean that the hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when the hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, the functional group, atomic group, Alternatively, one or two or more substituents may be present according to the number of hydrogen present in the compound, and when a plurality of substituents are present, each substituent may be identical to or different from each other.

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

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

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 mean an alkyl group containing one or two or more triple bonds.

The term 'cycloalkyl group' used in the present invention may include all saturated cyclic 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 a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded ( polycyclic aromatic hydrocarbon).

The terms 'derived unit' and 'derived functional group' used in the present invention may indicate a component or structure derived from a certain material or the material itself.

The present invention provides an isomer composition of a myrcene derivative compound that can be applied as a raw material for preparing a modified polymerization initiator.

The isomer composition according to an embodiment of the present invention is an isomer composition containing two or more isomers of a myrcene derivative compound, wherein a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2 are mixed at 8:2 to 4: It is characterized by including in a weight ratio of 6.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

A ₁ and A ₂ are each independently -NR _a R _b , -OR _c , or -SR _d ;

Wherein R _a to R _d are each independently a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms, unsubstituted or substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. , An alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 2 to 30 carbon atoms, or an aryl group having 3 to 30 carbon atoms, wherein R _a and R _b are connected to each other to form an alkyl group having 1 to 30 carbon atoms or 5 unsubstituted carbon atoms It may form an aliphatic ring group of 20 to 20, an aromatic ring group of 5 to 20 carbon atoms, or a heterocyclic group of 3 to 20 carbon atoms.

Specifically, in Formula 1, A ₁ and A ₂ are each independently -NR _a R _b , -OR _c , or -SR _d , wherein R _a to R _d are each independently N, O, It may be unsubstituted or substituted with a substituent containing at least one heteroatom selected from S, Si and F atoms, and in the case of unsubstituted, R _a to R _d are independently of each other an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 carbon atoms to 30 alkenyl group, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and when substituted with the above substituents, R _a to R _d are independently of each other It may be a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms, a heteroalkynyl group having 2 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms substituted with a substituent.

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

More specifically, in Formula 1, A ₁ and A ₂ may be each independently selected from substituents represented by Formulas 1a to 1c below.

[Formula 1a]

[Formula 1b]

[Formula 1c]

In 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 alkyl group having 2 to 10 carbon atoms, unsubstituted or substituted with a substituent containing one or more heteroatoms selected from N, O and S atoms. An alkenyl group having 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 3 to 10 carbon atoms, or R ₁ and R ₂ and R ₇ and R ₈ are bonded to each other to form 5 to 10 carbon atoms It forms an aliphatic ring group of 20 or an aromatic ring group of 5 to 20 carbon atoms,

R ₃ , R ₄ and R ₆ are each independently substituted with a substituent containing 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, or a heteroatom selected from N and O atoms, or An unsubstituted alkylene group having 1 to 10 carbon atoms,

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

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

More specifically, A ₁ and A ₂ may each independently be any one selected from substituents represented by Formulas a to j below.

[Formula a]

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

[Formula g]

[Formula h]

[Formula i]

[Formula j]

In general, when an isomer composition in which a plurality of isomers coexist is used for a polymerization reaction, an unintended reaction other than the desired reaction occurs together, resulting in a decrease in yield of the desired product or a decrease in physical properties. Therefore, in the case of an isomer composition, only one desired material is usually obtained through a specific separation and purification process and used.

However, the isomer composition of a myrcene derivative compound according to an embodiment of the present invention includes two or more isomers in a specific ratio, so that even if used directly as a raw material for a modified polymerization initiator without an additional purification step, the isomer composition prepared therefrom Since the modified polymerization initiator does not cause side reactions in polymerization, a polymer having excellent physical properties can be easily prepared. Thus, there is an economically superior advantage because additional equipment and work are not required. In addition, the isomer composition according to an embodiment of the present invention may have excellent storage stability by including two or more isomers in a specific ratio.

In addition, the present invention provides a method for preparing an isomer composition of the myrcene derivative compound that can be applied as a raw material for preparing a modified polymerization initiator.

In the method for preparing the isomer composition according to an embodiment of the present invention, a compound represented by the following Chemical Formula 3 and a compound represented by the following Chemical Formula 4 are reacted to prepare an isomer composition containing two or more isomers of a myrcene derivative compound. Step (Step A) is included, and the isomer composition is characterized in that it comprises a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 8:2 to 4:6.

[Formula 3]

[Formula 4]

[Formula 1]

[Formula 2]

In Formulas 1 to 4,

A is the same as the definition of A ₁ in Formula 1, A ₁ and A ₂ are as defined above, and X is Cl, Br or I.

Here, the compound represented by Chemical Formula 3 is one in which a reactive site is introduced into the molecular structure of β-myrcene, and may be prepared by a reaction between β-myrcene and a halogen-containing compound, such as a halogenation reaction.

The halogen-containing compound may be a material capable of reacting with β-myrcene to provide a reactive site in the molecular structure of β-myrcene to form a halogenated myrcene compound represented by Chemical Formula 3. The halogen-containing compound is not particularly limited, but may be, for example, a hypochlorite-based compound or hypochlorous acid (HClO), and the hypochlorite-based compound is, for example, calcium hypochlorite (Ca(OCl) ) ₂ ) or sodium hypochlorite (NaClO).

In addition, the β-myrcene and the halogen-containing compound may be reacted at a molar ratio of 1:0.8 to 1.2, specifically 1:0.8 to 1.0, and the β-myrcene and the halogen-containing compound are reacted at the above molar ratio. If so, the compound represented by Formula 3 can be easily prepared with a high conversion rate.

In addition, the reaction may be carried out in the presence of a reducing agent, and the halogenation reaction may be more easily achieved by the reducing agent.

The reducing agent is not particularly limited as long as it serves to facilitate the halogenation reaction, but may be, for example, carbon dioxide. Here, dry ice may be used as the carbon dioxide, and in this case, carbon dioxide may be provided while maintaining the reaction temperature of step 1 at a low temperature as described later.

In addition, the halogenation reaction may be performed in the presence of a polar solvent, wherein the polar solvent may be water. In addition, the reaction may be carried out under a temperature condition of 20 ℃ or less, specifically, a temperature condition of 5 ℃ to 15 ℃.

In addition, the reaction in step A may be carried out in the presence of a polar solvent and under a basic atmosphere, wherein the basic atmosphere may have a pH of 9 to 13 or a pH of 9 to 11. In addition, the basic atmosphere can be adjusted using an organic-inorganic base, and in this case, the organic-inorganic base is not particularly limited, but for example, potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), sodium hydroxide (NaOH) and It may be at least one selected from potassium hydroxide (KOH).

In addition, the reaction in step A may be performed at a high temperature of 80 ° C or higher, and specifically, the reaction in step A may be performed at a temperature of 80 ° C to 130 ° C for 12 hours to 24 hours. .

In addition, in step A, the compound represented by Formula 3 and the compound represented by Formula 4 may be reacted at a molar ratio of 1:0.1 to 20, specifically, 1:5 to 20.

According to an embodiment of the present invention, when the reaction in step A is carried out under the above conditions, for example, under a basic atmosphere at high temperature, the compound represented by Formula 1 and the compound represented by Formula 2 are mixed in a ratio of 8:2 to 4:6 An isomer composition comprising a weight ratio of can be easily prepared.

In addition, the reaction in step A may be carried out while stirring, wherein the stirring is appropriately controlled so that the compound represented by Formula 3 and the compound represented by Formula 4 can be easily mixed to achieve a reaction. It may be, for example, stirring at a speed of 800 rpm to 1200 rpm. If the reaction of step A is carried out while stirring, the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 can be easily mixed, and thus the reaction can be easily performed.

In addition, the present invention provides a modified polymerization initiator prepared using the isomer composition and containing a unit derived from the isomer composition.

The modified polymerization initiator according to an embodiment of the present invention may include a first compound including a compound-derived unit represented by Formula 1 and a compound-derived unit represented by Formula 5; and a second compound including a unit derived from a compound represented by Formula 2 and a unit derived from a compound represented by Formula 5, wherein the first compound and the second compound have a weight ratio of 8:2 to 4:6 to be characterized

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, A ₁ and A ₂ are as defined above,

[Formula 5]

In Formula 5,

M is an alkali metal;

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

The modified polymerization initiator according to an embodiment of the present invention is prepared from an isomer composition including a compound represented by Formula 1 and a compound represented by Formula 2, thereby combining a first compound including a unit derived from a compound represented by Formula 1 and a compound represented by Formula 2 A second compound including a unit derived from the compound represented by 2 may be simultaneously included.

Here, the first compound may specifically include one or more selected from compounds represented by Formulas 6-1 to 6-3 below.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

In Chemical Formulas 6-1 to 6-3, A ₁ is as defined in Chemical Formula 1, M is Na, K or Li, and R _e is hydrogen or an alkyl group having 1 to 10 carbon atoms.

In addition, the second compound may specifically include one or more selected from compounds represented by Chemical Formulas 7-1 to 7-3 below.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Chemical Formulas 7-1 to 7-3, A ₂ is as defined in Chemical Formula 2, M is Na, K or Li, and R _e is hydrogen or an alkyl group having 1 to 10 carbon atoms.

Meanwhile, the modified polymerization initiator according to an embodiment of the present invention may be prepared by reacting the isomer composition including the compound represented by Formula 1 and the compound represented by Formula 2 with the organometallic compound represented by Formula 5. have.

For example, the modified polymerization initiator is the isomer composition and the compound represented by Formula 5 are -20 ℃ to 100 ℃, or 0 ℃ to 90 ℃ temperature conditions of 1 bar to 10 bar, or 1 bar to 5 bar pressure conditions. In this case, the compound represented by Formula 5 is used in an amount of 0.01 to 5 mole ratio or 0.5 to 2 mole ratio relative to the total 1 mole of the compound represented by Formula 1 and the compound represented by Formula 2. it could be

In addition, the reaction may be carried out using a polar additive to control the reactivity, and examples of the polar additive include tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, and ethylene dimethyl. ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and It may be at least one selected from the group consisting of teramethylethylenediamine, and specifically, it may be triethylamine or tetramethylethylenediamine.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

manufacturing example

Chlorinated myrcene was prepared by adding β-myrcene, water, and calcium hypochlorite to methylene chloride in a reactor, adding dry ice, and reacting at 10° C. for 30 minutes. At this time, β-myrcene was used in a ratio of 0.4 mmol per 1 ml of methylene chloride, β-myrcene and calcium hypochlorite were used in a molar ratio of 1:0.825, and calcium hypochlorite and water were used in a volume ratio of 0.025:1.

Example 1

Chlorinated myrcene and morpholine prepared in Preparation Example were put into a reactor containing water and potassium carbonate and reacted at 100 ° C. for 20 hours at 1000 rpm with stirring, represented by the following Chemical Formula 1-1 and Chemical Formula 2-1 An isomeric composition comprising the compound was prepared. At this time, chlorinated myrcene and morpholine were used in a molar ratio of 1:3, and the compound represented by Chemical Formula 1-1 and the compound represented by Chemical Formula 2-1 in the prepared isomer composition had a weight ratio of 0.47:0.53.

[Formula 1-1]

[Formula 2-1]

On the other hand, it was confirmed that the above isomer composition was synthesized through molecular weight change, the molecular weight of β-myrcene as a starting material was 136 g/mol, and the molecular weight of chlorinated myrcene was 170 g/mol. The molecular weight of was 221 g/mol.

In addition, the ratio and molecular weight analysis of the compound represented by Formula 1-1 and the compound represented by Formula 2-1 in the isomer composition were measured by GC/Mass analysis. At this time, the column uses ZB-5MS (0.25 mm (ID) × 30 ml, 0.25 μm d.f. capillary), the gas flow rate (column (He)) is 1 ml / min, and the oven temperature is initially at 50 ° C. After 3 minutes, the temperature was raised to 320 °C at 10 °C/min and maintained for 15 minutes. The temperature of the injector was adjusted to 250 °C, the split ratio was 1/20, and the injection amount was adjusted to 0.2 μl.

Example 2

The chlorinated myrcene and pyrrolidine prepared in Preparation Example were placed in a reactor containing water and potassium carbonate and reacted at 80 ° C. for 20 hours at 1000 rpm with stirring to form the compound represented by the following formula 1-2 and formula 2-2 An isomeric composition comprising the compound represented by was prepared. At this time, chlorinated myrcene and pyrrolidine were used in a molar ratio of 1:5, and the compound represented by Chemical Formula 1-2 and the compound represented by Chemical Formula 2-2 in the prepared isomer composition had a weight ratio of 4:6.

[Formula 1-2]

[Formula 2-2]

On the other hand, it was confirmed that the above isomer composition was synthesized through molecular weight change, the molecular weight of β-myrcene as a starting material was 136 g/mol, and the molecular weight of chlorinated myrcene was 170 g/mol. The molecular weight of was 205 g/mol.

Here, molecular weight analysis and isomer ratio were analyzed in the same manner as in Example 1 above.

Example 3

The chlorinated myrcene and piperidine were put in a reactor containing water and potassium carbonate and reacted at 100° C. for 20 hours at 1000 rpm with stirring, and the compound represented by Formula 1-3 and the compound represented by Formula 2-3 An isomeric composition comprising was prepared. At this time, chlorinated myrcene and piperidine were used in a molar ratio of 1:5, and the compound represented by Chemical Formula 1-3 and the compound represented by Chemical Formula 2-3 in the prepared isomer composition had a weight ratio of 4:6.

[Formula 1-3]

[Formula 2-3]

On the other hand, it was confirmed that the above isomer composition was synthesized through molecular weight change, the molecular weight of β-myrcene as a starting material was 136 g/mol, and the molecular weight of chlorinated myrcene was 170 g/mol. The molecular weight of was 219 g/mol.

Here, molecular weight analysis and isomer ratio were analyzed in the same manner as in Example 1 above.

Example 4

Chlorinated myrcene and dimethylamine (using 50 wt% aqueous solution) prepared in Preparation Example were put in a reactor and reacted at 25° C. for 20 hours at 1000 rpm with stirring to obtain a compound represented by Formula 1-4 and Formula 2-4 An isomeric composition comprising the indicated compounds was prepared. At this time, chlorinated myrcene and dimethylamine were used in a molar ratio of 8:2, and the compound represented by Chemical Formulas 1-4 and 2-4 in the isomer composition had a weight ratio of 8:2.

[Formula 1-4]

[Formula 2-4]

On the other hand, it was confirmed that the above isomer composition was synthesized through molecular weight change, the molecular weight of β-myrcene as a starting material was 136 g/mol, and the molecular weight of chlorinated myrcene was 170 g/mol. The molecular weight of was 179 g/mol.

Here, molecular weight analysis and isomer ratio were analyzed in the same manner as in Example 1 above.

Example 5

15 ml of hexane, 1.1 ml (7.4 mmol) of tetramethylethyleneamine, and 1.5 ml (3.7 mmol) of 2.5M n-butyllithium were added to a vacuum-dried batch reactor, and mixed for 1 minute under nitrogen reflux. 0.82 g (3.7 mmol) of the isomer composition prepared in Example 1 was added and stirred at 50° C. for 5 minutes to prepare a modified polymerization initiator including a compound represented by Formula 6-1a and a compound represented by Formula 7-1a did

It was confirmed through molecular weight analysis that the prepared modified polymerization initiator was synthesized by a change in molecular weight between the isomer composition and the finally prepared modified polymerization initiator, the molecular weight of the isomer composition was 221 g/mol, and the molecular weight of the finally obtained modified polymerization initiator was 279 g/mol. At this time, the molecular weight of the modified polymerization initiator represents the molecular weight in which Li is substituted with H.

Specifically, molecular weight analysis was performed by GC/Mass analysis, using ZB-5MS (0.25 mm (ID) × 30 ml, 0.25 μm d.f. capillary) as a column, and gas flow rate (column (He)) Silver was 1 ml/min, the oven temperature was raised from 50 °C initially to 320 °C at 10 °C/min after 3 minutes and maintained for 15 minutes, the injector temperature was 250 °C, the split ratio was 1/20, and the injection amount was 0.2 μl. Adjusted and measured. In addition, the modified polymerization initiator was quenched to protonate the organolithium portion and then measured.

[Formula 6-1a]

[Formula 7-1a]

Example 6

15 ml of hexane, 1.1 ml (7.4 mmol) of tetramethylethyleneamine, and 1.5 ml (3.7 mmol) of 2.5M n-butyllithium were added to a vacuum-dried batch reactor, and mixed for 1 minute under nitrogen reflux. 0.76 g (3.7 mmol) of the isomer composition prepared in Example 2 was added and stirred at 50° C. for 5 minutes to prepare a modified polymerization initiator including a compound represented by Formula 6-1b and a compound represented by Formula 7-1b did

It was confirmed through molecular weight analysis that the prepared modified polymerization initiator was synthesized by a change in molecular weight between the isomer composition and the finally prepared modified polymerization initiator, the molecular weight of the isomer composition was 205 g/mol, and the molecular weight of the finally obtained modified polymerization initiator was 263 g/mol. At this time, the molecular weight of the modified polymerization initiator represents the molecular weight in which Li is substituted with H.

[Formula 6-1b]

[Formula 7-1b]

Example 7

15 ml of hexane, 1.1 ml (7.4 mmol) of tetramethylethyleneamine, and 1.5 ml (3.7 mmol) of 2.5M n-butyllithium were added to a vacuum-dried batch reactor, and mixed for 1 minute under nitrogen reflux. 0.81 g (3.7 mmol) of the isomer composition prepared in Example 3 was added and stirred at 50° C. for 5 minutes to prepare a modified polymerization initiator including a compound represented by Formula 6-1c and a compound represented by Formula 7-1c did

It was confirmed through molecular weight analysis that the prepared modified polymerization initiator was synthesized by a change in molecular weight between the isomer composition and the finally prepared modified polymerization initiator, the molecular weight of the isomer composition was 219 g/mol, and the molecular weight of the finally obtained modified polymerization initiator was 277 g/mol. At this time, the molecular weight of the modified polymerization initiator represents the molecular weight in which Li is substituted with H.

[Formula 6-1c]

[Formula 7-1c]

Example 8

15 ml of hexane, 1.1 ml (7.4 mmol) of tetramethylethyleneamine, and 1.5 ml (3.7 mmol) of 2.5M n-butyllithium were added to a vacuum-dried batch reactor, and mixed for 1 minute under nitrogen reflux. 0.66 g (3.7 mmol) of the isomer composition prepared in Example 4 was added and stirred at 50° C. for 5 minutes to prepare a modified polymerization initiator including a compound represented by Formula 6-1d and a compound represented by Formula 7-1d did

It was confirmed through molecular weight analysis that the prepared modified polymerization initiator was synthesized by a change in molecular weight between the isomer composition and the finally prepared modified polymerization initiator, the molecular weight of the isomer composition was 179 g/mol, and the molecular weight of the finally obtained modified polymerization initiator was 237 g/mol. At this time, the molecular weight of the modified polymerization initiator represents the molecular weight in which Li is substituted with H.

[Formula 6-1d]

[Formula 7-1d]

Claims (12)

An isomer composition containing two or more isomers of a myrcene derivative compound,
An isomer composition comprising a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 8:2 to 4:6:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
A ₁ and A ₂ are each independently -NR _a R _b , -SR _d or a substituent represented by Formula 1c below;
Wherein R _a , R _b and R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms. of an alkenyl group, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, wherein R _a and R _b are connected to each other to be substituted with an alkyl group having 1 to 30 carbon atoms or unsubstituted may form an aliphatic ring group having 5 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms,
[Formula 1c]

In Formula 1c,
R ₇ and R ₈ are each independently a substituent containing one or more heteroatoms selected from N, O and S atoms, or unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. An alkynyl group, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₇ and R ₈ are bonded to each other to form an aliphatic ring group having 5 to 20 carbon atoms or an aromatic ring group having 6 to 20 carbon atoms would,
R ₆ is 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, or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent containing a heteroatom selected from N and O atoms. It's Rengi,
X is one selected from N, O and S atoms, and when X is O or S, R ₈ does not exist.
The method of claim 1,
In Formula 1 and Formula 2, A ₁ and A ₂ are each independently a substituent represented by Formula 1a, a substituent represented by Formula 1b, or a substituent represented by Formula 1c. Isomer composition:
[Formula 1a]

[Formula 1b]

In Formula 1a and Formula 1b,
R ₁ , R ₂ and R ₅ are each independently a substituent containing at least one heteroatom selected from N, O, and S atoms, substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. An alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₁ and R ₂ are bonded to each other to form an aliphatic ring group having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms is to form the
R ₃ and R ₄ are each independently substituted or unsubstituted with a substituent containing 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, or N and O atoms; An alkylene group having 1 to 10 carbon atoms,
Z is one selected from N, O and S atoms, and when Z is O or S, R ₅ does not exist.
The method of claim 2,
In Formulas 1a to 1c,
Wherein R ₁ , R ₂ , R ₅ , R ₇ and R ₈ are each independently an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent containing at least one heteroatom selected from N, O and S atoms, or R ₁ and R ₂ and R ₇ and R ₈ are each bonded to each other to form an aliphatic ring group having 5 to 10 carbon atoms or an aromatic ring group having 5 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 member selected from N, O and S atoms, and when X is O or S, R ₈ does not exist, and when Z is O or S, R ₅ does not exist.
The method of claim 1,
In Formulas 1 and 2, A ₁ and A ₂ are each independently any one selected from substituents represented by Formulas a to j below:
[Formula a]

[Formula b]

[Formula c]

[Formula d]

[Formula e]

[Formula f]

[Formula g]

[Formula h]

[Formula i]

[Formula j]

.
A step of preparing an isomer composition containing two or more isomers of a myrcene derivative compound by reacting a compound represented by the following Chemical Formula 3 with a compound represented by the following Chemical Formula 4,
Method for preparing an isomer composition, wherein the isomer composition comprises a compound represented by Formula 1 and a compound represented by Formula 2 in a weight ratio of 8:2 to 4:6:
[Formula 3]

[Formula 4]

[Formula 1]

[Formula 2]

In Formulas 1 to 4,
A, A ₁ and A ₂ are each independently -NR _a R _b , -SR _d or a substituent represented by Formula 1c below;
Wherein R _a , R _b and R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms. of an alkenyl group, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, wherein R _a and R _b are connected to each other to be substituted with an alkyl group having 1 to 30 carbon atoms or unsubstituted may form an aliphatic ring group having 5 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms,
X' is Cl, Br or I;
[Formula 1c]

In Formula 1c,
R ₇ and R ₈ are each independently a substituent containing one or more heteroatoms selected from N, O and S atoms, or unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. An alkynyl group, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₇ and R ₈ are bonded to each other to form an aliphatic ring group having 5 to 20 carbon atoms or an aromatic ring group having 6 to 20 carbon atoms would,
R ₆ is 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, or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent containing a heteroatom selected from N and O atoms. It's Rengi,
X is one selected from N, O and S atoms, and when X is O or S, R ₈ does not exist.
The method of claim 5,
The method of preparing an isomer composition in which the compound represented by Formula 3 is prepared by reacting β-myrcene and a halogen-containing compound.
The method of claim 5,
A method for producing an isomer composition wherein the compound represented by Formula 3 and the compound represented by Formula 4 are reacted in a molar ratio of 1:0.1 to 20.
The method of claim 5,
The reaction is a method for producing an isomer composition that is carried out in the presence of a polar solvent in a basic atmosphere.
The method of claim 5,
The reaction is a method for producing an isomer composition that is carried out for 12 hours to 24 hours at a temperature condition of 80 ℃ to 130 ℃.
a first compound including a unit derived from a compound represented by Formula 1 and a unit derived from a compound represented by Formula 5; and
A second compound including a unit derived from a compound represented by Formula 2 and a unit derived from a compound represented by Formula 5,
A modified polymerization initiator wherein the first compound and the second compound have a weight ratio of 8:2 to 4:6:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
A ₁ and A ₂ are each independently -NR _a R _b , -SR _d or a substituent represented by Formula 1c below;
Wherein R _a , R _b and R _d are each independently an alkyl group having 1 to 30 carbon atoms, an alkyl group having 2 to 30 carbon atoms, unsubstituted or substituted with a substituent containing at least one heteroatom selected from N, O, S, Si and F atoms. of an alkenyl group, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, wherein R _a and R _b are connected to each other to be substituted with an alkyl group having 1 to 30 carbon atoms or unsubstituted may form an aliphatic ring group having 5 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms,
[Formula 1c]

In Formula 1c,
R ₇ and R ₈ are each independently a substituent containing one or more heteroatoms selected from N, O and S atoms, or unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. An alkynyl group, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₇ and R ₈ are bonded to each other to form an aliphatic ring group having 5 to 20 carbon atoms or an aromatic ring group having 6 to 20 carbon atoms would,
R ₆ is 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, or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent containing a heteroatom selected from N and O atoms. It's Rengi,
X is one selected from N, O and S atoms, and when X is O or S, R ₈ does not exist,
[Formula 5]

In Formula 5,
M is an alkali metal;
R _e is hydrogen, an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkynyl group of 2 to 30 carbon atoms, a cycloalkyl group of 5 to 30 carbon atoms, or an aryl group of 6 to 30 carbon atoms.
The method of claim 10,
A modified polymerization initiator wherein the first compound includes at least one selected from compounds represented by Formulas 6-1 to 6-3:
[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

In Formula 6-1 to Formula 6-3,
A ₁ is as defined in Formula 1 above,
M is Na, K or Li;
R _e is hydrogen or an alkyl group having 1 to 10 carbon atoms.
The method of claim 10,
A modified polymerization initiator wherein the second compound includes at least one selected from compounds represented by Formulas 7-1 to 7-3:
[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Formulas 7-1 to 7-3,
A ₂ is as defined in Formula 2 above;
M is Na, K or Li;
R _e is hydrogen or an alkyl group having 1 to 10 carbon atoms.