JP2019014656A - Purine derivative compounds and purine derivative compound-modified conjugated diene polymers - Google Patents

Abstract

To provide a novel purine derivative compound that is useful as a tire modifier added for achieving both tire physical properties such as fuel economy and production cost, and a modified conjugated diene polymer obtained by the reaction with the purine derivative compound.SOLUTION: The present invention provides a purine derivative compound represented by a formula (1), and a modified conjugated diene polymer obtained by the reaction with the purine derivative compound. [R-Rindependently represent a C1-16 substituent excluding H].SELECTED DRAWING: None

Description

  The present invention relates to a novel purine derivative compound and a method for producing the same.

  As one embodiment, the present invention provides a modified conjugated diene polymer modified with the above purine derivative compound and a method for producing the same.

  Conventionally, as rubber for automobile tires, a rubber composition containing polybutadiene rubber (BR) or styrene-butadiene rubber (SBR) as a main component and blended with natural rubber or the like has been used. In recent years, a material for tires that can simultaneously improve various physical properties such as low fuel consumption, wet skid performance, and wear resistance has been demanded due to a social demand for reduction in fuel consumption of automobiles.

Many proposals have been made for the polymerization catalysts for conjugated dienes such as 1,3-butadiene, some of which have been industrialized. For example, the production method of a low cis type conjugated diene polymer is an alkali metal compound, and the production method of a high cis type conjugated diene polymer is a compound such as titanium, cobalt, nickel or neodymium (generally called a coordination polymerization catalyst). Are often used.

By using a specific polymerization catalyst, a modified conjugated diene polymer can be obtained by reacting a compound having a reactive functional group (modifier) with an active polymerization terminal at the end of the polymerization step of the conjugated diene polymer. . Examples of the polymerization catalyst system capable of synthesizing such a modified conjugated diene polymer include an alkali metal compound catalyst and a coordination polymerization catalyst comprising a rare earth element.

By using the method for producing a modified conjugated diene polymer described above, a modified conjugated diene polymer in which a functional group that enhances the affinity with the filler particles is introduced at the molecular chain terminal of the conjugated diene polymer can be produced. The modified conjugated diene polymer thus obtained can be suitably used as a useful tire material for improving various physical properties such as low fuel consumption.

  Various modifiers to be introduced into the molecular chain terminal of the conjugated diene polymer are known. For example, Patent Documents 1 to 6 disclose polybutadiene or diene rubber having an active polymerization terminal as nitroamino. Disclosed is a method for producing a modified conjugated diene polymer by reacting with a compound, a nitro compound, a nitroalkyl compound, an amine compound, an imide compound, a quinone compound, a thiazole compound, a sulfenamide compound, or the like. Yes. However, no examples have been reported using purine derivatives or compounds obtained by chemically modifying them, which can be obtained relatively inexpensively as modifiers.

  Regarding a chemically modified purine derivative compound and a production method thereof, Patent Document 7 discloses that 1,3-dimethyl-7H-purine-2,6-dione [common name: theophylline] is chemically modified and 1,3-dimethyl- A method for producing 7- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione [common name: 7- (4-pyridylmethyl) theophylline] is disclosed. However, 2,6-dihydroxy-3,7-dimethylpurine [common name: theobromine], which is a regioisomer, was chemically modified to give 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7- A method for producing dihydro-1H-purine-2,6-dione [common name: 1- (4-pyridylmethyl) theobromine] has not been reported. In Patent Document 7, 1,3-dimethyl-7H-purine-2,6-dione [common name: theophylline] is chemically modified to give 1,3-dimethyl-7- (pyridin-4-ylmethyl)- A method for producing 3,7-dihydro-1H-purine-2,6-dione [common name: 7- (4-pyridylmethyl) theophylline] is disclosed. However, a 4-((diethylamino) methyl) benzyl group was introduced and 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6- A method for producing dione [common name: 7- (4-((diethylamino) methyl) benzyl) theophylline] has not been reported.

JP-A-63-139902 JP-A 63-278946 JP 63-278947 A JP 2001-139633 A JP 2001-139634 A JP 2002-30110 A U.S. Pat.No. 3,015,658

It is necessary to develop a new modifier and a modified conjugated diene polymer in order to balance various tire physical properties such as low fuel consumption and production costs. Another object of the present invention is to provide a novel purine derivative compound and a method for producing the compound capable of suppressing side reactions.

  As a result of intensive studies to achieve the above object, the present inventor has developed a novel purine derivative compound and a method for producing the compound capable of suppressing side reactions by adopting a series of steps shown below. It came to invent. Another embodiment of the present invention provides a modified conjugated diene polymer modified with the above purine derivative compound and a method for producing the same, a step of polymerizing the conjugated diene with a polymerization catalyst, and the resulting conjugated diene. Reacting the polymer with the purine derivative compound.

  According to the present invention, a compound represented by the following general formula (1) and a production method thereof can be provided.

In the formula, R ¹ , R ² and R ³ each independently represent a substituent having 1 to 16 carbon atoms excluding a hydrogen atom, N represents a nitrogen atom, and O represents an oxygen atom.

According to one embodiment of the present invention, a modified conjugated diene polymer modified with the compound represented by the general formula (1) described in the previous section can be provided.

  The present invention provides a novel purine derivative compound and a method for producing the same. Further, the purine derivative compound of the present invention can be suitably used as a modifier for a conjugated diene polymer, and the rubber composition containing the obtained purine derivative compound-modified conjugated diene polymer has low fuel consumption and wear resistance. Excellent tire physical properties such as

It is the result of having analyzed by the gas chromatography method about the crude product of the compound synthesize | combined in Example 1. FIG. It is the result of having analyzed by the gas chromatography method about the crude product of the compound synthesize | combined in the comparative example 1. FIG. It is the result of having analyzed by the gas chromatography method about the crude product of the compound synthesize | combined in Example 2. FIG. It is the result of having analyzed by the gas chromatography method about the crude product of the compound synthesize | combined in the comparative example 2. FIG. It is the result of having analyzed by the electron ionization mass spectrometry about the compound synthesize | combined in Example 1. FIG. It is the spectrum chart obtained by analyzing using the < ¹ > H-NMR method about the same compound synthesize | combined in Example 1, and assignment of each signal. It is the result of having analyzed by the electron ionization mass spectrometry about the compound synthesize | combined in Example 2. FIG. It is the spectrum chart obtained by analyzing using the < ¹ > H-NMR method about the same compound synthesize | combined in Example 2, and attribution of each signal.

[Purine derivative compounds]
The present invention relates to a compound represented by the following general formula (1) and a method for producing the same.

In the formula, R ¹ , R ² and R ³ each independently represent a substituent having 1 to 16 carbon atoms excluding a hydrogen atom, N represents a nitrogen atom, and O represents an oxygen atom.

In one or more embodiments, the substituents represented by R ¹ , R ² , and R ³ in the general formula described in the preceding paragraph are not limited, but are aliphatic groups, heteroaliphatic groups, or aromatic groups. Group or heteroaromatic group. These substituents can contain 1 to 16 carbon atoms. These substituents are not limited, but may contain one or more heteroatoms such as a boron atom, a nitrogen atom, an oxygen atom, a fluorine atom, a silicon atom, a phosphorus atom, a sulfur atom, and a chlorine atom. Good. In this specification, in order to simplify the description, a purine derivative subjected to chemical modification that introduces a substituent by a chemical reaction may be referred to as a modified purine derivative.

  Specific examples of the aliphatic group described in the preceding paragraph include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, isopropyl group, s-butyl group, t -Alkyl groups such as butyl group, neopentyl group, 2-ethylhexyl group, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group , Alkenyl groups such as cyclohexenyl group, and the like. Specific examples of the heteroaliphatic group described in the preceding paragraph include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, s-butoxy group, and n-pentyloxy. Group, i-pentyloxy group, n-hexyloxy group, n-octyloxy group, methoxymethoxy group, ethoxyethoxy group, 3- (i-propyloxy) propyloxy group, alkoxy group such as 1,3-dioxo group Acyl groups such as acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, heptanoyl group; hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group; methoxycarbonyl group, ethoxy Carbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group alkoxycarbonyl groups such as n-butoxycarbonyl group, t-butoxycarbonyl group, s-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group; methylamino group, ethylamino group, n-propylamino group , Alkylamino groups such as n-butylamino group; dialkylamino groups such as dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group; methoxycarbonylmethyl group, ethoxycarbonylmethyl group, alkoxycarbonylalkyl groups such as n-propoxycarbonylmethyl group, isopropoxycarbonylethyl group, phenoxycarbonyl group; methylthio group, ethylthio group, n-propylthio group, t-butylthio group, s-butylthio group, n-pentylthio group, n -Heki Alkylthio group such as ruthio group; methylsulfonyl group, trifluoromethylsulfonyl group, ethylsulfonyl group, pentafluoroethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, t-butylsulfonyl group, s Alkylsulfonyl groups such as -butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group; methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, isopropylcarbonylamino group, n-butylcarbonylamino group , T-butylcarbonylamino group, s-butylcarbonylamino group, alkylcarbonylamino group such as n-pentylcarbonylamino group, and the like. Examples of the aromatic group described in the preceding paragraph include a monocyclic or polycyclic aromatic group. Specifically, a phenyl group, a 4-methylphenyl group, a 4-t-butylphenyl group, a biphenyl group, 4 -Aryl group such as trifluoromethylphenyl group, 4-methoxyphenyl group, 4-chlorophenyl group, 4-fluorophenyl group, naphthalen-1-yl group, naphthalen-2-yl group, and the like. Examples of the heteroaromatic group described in the preceding paragraph include a monocyclic or polycyclic heteroaromatic group, and specifically include a pyridyl group, a pyridylmethyl group, a dimethylaminophenyl group, a diethylaminophenyl group, and dimethylaminomethyl. Phenyl group, diethylaminomethylphenyl group, dimethylaminomethylbenzyl group, diethylaminomethylbenzyl group, thienyl group, pyrrolyl group, pyrazinyl group, bipyridyl group, indolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl Carbazolyl group, benzo [a] carbazolyl group, benzo [b] carbazolyl group, benzo [c] carbazolyl group, phenazinyl group, phenoxazinyl group, phenothiazinyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, etc. Benzofuranyl group, oxazolyl group, oxadiazolyl group, indolo [3,2,1-kl] phenoxazinyl group, indolo [3,2,1-jk] carbazolyl group, and the like.

  The modified purine derivative can be obtained by reacting a modified purine derivative and a compound having a substituent introduced by modification and an appropriate leaving group in a solvent. Although it is not necessary to add an additive in particular, an additive may be added as necessary, and a step of adding such an additive to the reaction system may be further included. Moreover, in order to suppress a side reaction, the process of adding a suitable acidic compound after completion | finish of reaction is included.

  As the modified purine derivative, a raw material compound in which a hydrogen atom is bonded to a nitrogen atom located at the 1-position, 3-position and / or 7-position of the purine skeleton by a covalent bond can be used. Such compounds include 2,6-dihydroxy-3,7-dimethylpurine [common name: theobromine], 1,7-dimethylxanthine [common name: paraxanthine], 1,3-dimethyl-7H-purine- 2,6-dione [common name: theophylline], 3,7-dihydro-1H-purine-2,6-dione [common name: xanthine], and the like.

  In the compound having a substituent introduced by the modification and an appropriate leaving group, examples of the suitable leaving group include a chloro group, a bromo group, an iodo group, a mesyl group, a trifuryl group, and a tosyl group. Moreover, the protonated salt can also be used for the compound which has a substituent introduced by modification, and a suitable leaving group. Examples of protonated salts include hydrochloride, hydrobromide, hydroiodide, sulfate and the like.

  As said solvent, the conventional solvent which does not exert reaction inhibition can be used. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetonitrile, propionitrile, nitromethane, dibutyl ether, 1,2-dimethoxyethane, 1,2-diethoxy Ethane, di-2-methoxyethyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 1,4-dioxane, acetone, ethyl methyl ketone, diethyl ketone, methyl isobutyl ketone, benzene , Toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, nitrobenzene, pentane, hexane, heptane, cyclohexane, methylcyclohexane, Le cyclohexane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, water and the like. Among these, an aprotic polar solvent is preferable, and N, N-dimethylformamide is more preferable. These solvents may be used singly or in combination of two or more.

  As said additive, a basic substance and / or a phase transfer catalyst are mentioned, for example. Examples of the basic substance include alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate, alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, and alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate. Metal bicarbonate, alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, alkaline earth metal hydroxide such as magnesium hydroxide, calcium hydroxide, sodium methoxide, sodium ethoxide, sodium Alkali metal alkoxides such as isopropoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, lithium methoxide, lithium isopropoxide, lithium t-butoxide, magnesi Mumetokishido, alkaline earth metal alkoxides such as magnesium ethoxide, sodium hydride, and metal hydride such as calcium hydride. Of these, alkali metal carbonates are preferred, and potassium carbonate is more preferred. Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, crown ethers, and the like. These additives may be used alone or in combination of two or more.

  The reaction temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 40 to 100 ° C.

The reaction time is preferably in the range of 1 minute to 100 hours, more preferably 30 minutes to 5 hours.

By performing a step of adding an appropriate acidic compound after completion of the reaction, side reactions can be suppressed. As the acidic compound, any acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, sulfuric acid, tosylic acid, trifluoroacetic acid, and acetic acid can be used.

The modified purine derivative obtained by the present invention can be converted to a protonated salt by reacting with an acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and the like.

The modified purine derivative obtained by the present invention can be purified by methods such as extraction, washing, chromatography, crystallization, recrystallization and the like. However, these purification methods are not particularly limited.

The present invention relates to 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione and a method for producing the same.

  The above 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione is suitable as 2,6-dihydroxy-3,7-dimethylpurine. It can be obtained by reacting a 4-pyridylmethyl compound having a leaving group in a solvent. Although it is not necessary to add an additive in particular, an additive may be added as necessary, and a step of adding such an additive to the reaction system may be further included. Moreover, in order to suppress a side reaction, the process of adding a suitable acidic compound after completion | finish of reaction is included. The other description regarding the manufacturing method is the same as the above description.

  Examples of the 4-pyridylmethyl compound having an appropriate leaving group include 4- (chloromethyl) pyridine, 4- (bromomethyl) pyridine, 4- (iodomethyl) pyridine, 4- (mesylmethyl) pyridine, 4- (Trifurylmethyl) pyridine, 4- (tosylmethyl) pyridine, and the like can be used. Moreover, the protonated salt can also be used for the 4-pyridylmethyl compound which has a suitable leaving group. Examples of protonated salts include hydrochloride, hydrobromide, hydroiodide, sulfate and the like.

The present invention relates to 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione and a method for producing the same.

  The above 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione is 1,3-dimethyl-7H-purine-2. , 6-dione and a 4-((diethylamino) methyl) benzyl compound having an appropriate leaving group can be obtained in a solvent. Although it is not necessary to add an additive in particular, an additive may be added as necessary, and a step of adding such an additive to the reaction system may be further included. Moreover, in order to suppress a side reaction, the process of adding a suitable acidic compound after completion | finish of reaction is included. The other description regarding a manufacturing method is the same as that of the said description.

Examples of the 4-((diethylamino) methyl) benzyl compound having an appropriate leaving group include 4-((diethylamino) methyl) benzyl chloride, 4-((diethylamino) methyl) benzyl bromide, 4-(( Diethylamino) methyl) benzyl iodide, 4-((diethylamino) methyl) benzyl mesylate, 4-((diethylamino) methyl) benzyl triflate, 4-((diethylamino) methyl) benzyl tosylate, etc. can be used. . A protonated salt can also be used for a 4-((diethylamino) methyl) benzyl compound having an appropriate leaving group. Examples of protonated salts include hydrochloride, hydrobromide, hydroiodide, sulfate and the like.

[About Purine Derivative Compound Modified Conjugated Diene Polymer]
The present invention is a method for producing a modified conjugated diene polymer, which comprises (I) a step of polymerizing a conjugated diene with a coordination polymerization catalyst, and (II) the obtained conjugated diene polymer as a purine derivative of the present invention. And a modified conjugated diene polymer obtained by the method.

  The present invention is a method for producing a modified conjugated diene polymer, wherein the coordination polymerization catalyst (A) is a rare earth metal compound and (B) an element selected from Groups 2, 12, and 13 of the periodic table. A process comprising polymerizing a conjugated diene using the organometallic compound of (II), and (II) a step of reacting the obtained conjugated diene polymer with the purine derivative of the present invention, and a modified conjugated diene obtained by the method It relates to a polymer.

  The present invention is a method for producing a modified conjugated diene polymer, which comprises (I) a step of polymerizing a conjugated diene with (C) an alkali metal compound, and (II) the obtained conjugated diene polymer as a purine of the present invention. And a modified conjugated diene polymer obtained by the method.

  In one or more embodiments, by using a specific polymerization catalyst, a compound having a reactive functional group (modifier) is reacted with an active polymerization terminal at the end of the polymerization step of the conjugated diene polymer, thereby modifying the modified conjugate. A diene polymer can be obtained. Examples of the polymerization catalyst system that can synthesize such a modified conjugated diene polymer include a coordination polymerization catalyst composed of an alkali metal compound catalyst or a rare earth metal compound. Hereinafter, in order to simplify the explanation, a coordination polymerization consisting of several specific types of alkali metal compound catalysts and rare earth metal compounds will be described as an example. It would be possible to select a polymerization catalyst for the conjugated diene polymer to which the reaction is applicable.

  The rare earth metal compound which is component (A) constituting the coordination polymerization catalyst system is not particularly limited, and is a diketone type rare earth metal complex, a ketimine type rare earth metal complex, a diimine type rare earth metal complex, a rare earth metal alkoxide, a rare earth metal. Examples thereof include carboxylates and rare earth metal phosphates. Rare earth metal compounds are preferred in that a high cis type conjugated diene polymer having a 1,4-cis structure is obtained more than an alkali metal compound polymerization catalyst. As the rare earth metal, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and the like are preferably used.

  The rare earth metal compound which is the component (A) constituting the above coordination polymerization catalyst system may be used alone or in combination of two or more.

  There is no particular limitation on the order of addition of each component constituting the coordination polymerization catalyst system.

  In the present invention, each coordination polymerization catalyst component can be supported on an inorganic compound or an organic polymer compound.

  The kind of the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is not particularly limited, but preferably a diketone type rare earth metal complex represented by the following general formula (2) is used. Can be used.

In the formula, R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, O represents an oxygen atom, and M represents a rare earth metal atom.

Specific examples of the substituent having 1 to 12 carbon atoms in R ^{4 to} R ⁶ of the general formula (2) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, Isobutyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and other saturated hydrocarbon groups; vinyl group, 1-propenyl group, allyl group and other unsaturated hydrocarbon groups, cyclohexyl group, Alicyclic hydrocarbon groups such as methylcyclohexyl group and ethylcyclohexyl group; aromatic hydrocarbon groups such as phenyl group, benzyl group, toluyl group, and phenethyl group It is. Furthermore, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at an arbitrary position are also included. Among them, a saturated hydrocarbon group having 1 to 12 carbon atoms is preferable, and a saturated hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

In R ^{4 to} R ⁶ of the general formula (2), R ⁵ is preferably hydrogen or a substituent having 1 to 12 carbon atoms, and R ⁴ and R ⁶ are preferably a substituent having 1 to 12 carbon atoms. In particular, R ⁵ is preferably hydrogen or a substituent having 1 to 6 carbon atoms, and R ⁴ and R ⁶ are preferably substituents having 1 to ⁶ carbon atoms.

In R ^{4 to} R ⁶ of the general formula (2), R ⁵ is preferably hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, and R ⁴ and R ⁶ are preferably saturated hydrocarbon groups having 1 to 12 carbon atoms. In particular, R ⁵ is preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ and R ⁶ are preferably saturated hydrocarbon groups having 1 to ⁶ carbon atoms.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, a scandium compound may be tris (2,2,6,6-tetramethyl-3,5 -Heptanedionate) scandium, Tris (2,2,6-trimethyl-3,5-heptanedionate) scandium, Tris (2,6-dimethyl-3,5-heptanedionate) scandium, Tris (3,5-heptanedionate) scandium, Tris (2,4-pentanedionato) scandium, tris (2,4-hexanedionato) scandium, tris (1,5-dicyclopentyl-2,4-pentandionato) scandium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) scandium and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) scandium and tris (2,6-dimethyl-3,5-heptaneedionato) scandium are preferable.

  When the rare earth metal compound which is the component (A) constituting the above coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of an yttrium compound, tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) yttrium, tris (2,2,6-trimethyl-3,5-heptanedionato) yttrium, tris (2,6-dimethyl-3,5-heptanedionato) yttrium, tris (3,5-heptanedionato) yttrium, tris (2,4-pentanedionato) yttrium, tris (2,4-hexanedionato) yttrium, tris (1,5-dicyclopentyl-2,4-pentandionato) yttrium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) yttrium and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) yttrium and tris (2,6-dimethyl-3,5-heptaneedionato) yttrium are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of a lanthanum compound, tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) lanthanum, Tris (2,2,6-trimethyl-3,5-heptanedionato) lanthanum, Tris (2,6-dimethyl-3,5-heptanedionato) lanthanum, Tris (3,5-heptanedionato) lanthanum, Tris (2,4-pentanedionato) lanthanum, tris (2,4-hexanedionato) lanthanum, tris (1,5-dicyclopentyl-2,4-pentanedionato) lanthanum, tris (1,5-dicyclohexyl- 2,4-pentanedionato) lanthanum and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) lanthanum and tris (2,6-dimethyl-3,5-heptanedionate) lanthanum are preferable.

  When the rare earth metal compound which is the component (A) constituting the above coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of a cerium compound, tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) cerium, tris (2,2,6-trimethyl-3,5-heptanedionato) cerium, tris (2,6-dimethyl-3,5-heptanedionato) cerium, tris (3,5-heptanedionato) cerium, tris (2,4-pentanedionato) cerium, tris (2,4-hexanedionato) cerium, tris (1,5-dicyclopentyl-2,4-pentandionato) cerium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) cerium and the like. Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) cerium and tris (2,6-dimethyl-3,5-heptaneedionato) cerium are used.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of a praseodymium compound, tris (2,2,6,6-tetramethyl-3,5 -Heptaneedionato) praseodymium, Tris (2,2,6-trimethyl-3,5-heptaneedionato) praseodymium, Tris (2,6-dimethyl-3,5-heptaneedionato) praseodymium, Tris (3,5-heptaneedionato) praseodymium, Tris (2,4-pentanedionato) praseodymium, tris (2,4-hexanedionato) praseodymium, tris (1,5-dicyclopentyl-2,4-pentanedionato) praseodymium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) praseodymium and the like. Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) praseodymium and tris (2,6-dimethyl-3,5-heptanedionato) praseodymium are used.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, a neodymium compound is tris (2,2,6,6-tetramethyl-3,5 -Heptaneedionato) neodymium, tris (2,2,6-trimethyl-3,5-heptaneedionato) neodymium, tris (2,6-dimethyl-3,5-heptaneedionato) neodymium, tris (3,5-heptaneedionato) neodymium, tris (2,4-pentanedionato) neodymium, tris (2,4-hexanedionato) neodymium, tris (1,5-dicyclopentyl-2,4-pentandionato) neodymium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) neodymium and the like. Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) neodymium and tris (2,6-dimethyl-3,5-heptaneedionato) neodymium are used.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, a gadolinium compound is tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) gadolinium, tris (2,2,6-trimethyl-3,5-heptanedionato) gadolinium, tris (2,6-dimethyl-3,5-heptanedionato) gadolinium, tris (3,5-heptanedionato) gadolinium, tris (2,4-pentanedionato) gadolinium, tris (2,4-hexanedionato) gadolinium, tris (1,5-dicyclopentyl-2,4-pentandionato) gadolinium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) gadolinium and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium and tris (2,6-dimethyl-3,5-heptanedionato) gadolinium are preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, a terbium compound is tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) terbium, Tris (2,2,6-trimethyl-3,5-heptaneedionato) terbium, Tris (2,6-dimethyl-3,5-heptaneedionato) terbium, Tris (3,5-heptandedionato) terbium, Tris (2,4-pentanedionato) terbium, tris (2,4-hexanedionato) terbium, tris (1,5-dicyclopentyl-2,4-pentandionato) terbium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) terbium and the like. Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) terbium and tris (2,6-dimethyl-3,5-heptanedionato) terbium are used.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of a dysprosium compound, tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) dysprosium, Tris (2,2,6-trimethyl-3,5-heptaneedionato) dysprosium, Tris (2,6-dimethyl-3,5-heptaneedionato) dysprosium, Tris (3,5-heptaneedionato) dysprosium, Tris (2,4-pentanedionato) dysprosium, tris (2,4-hexanedionato) dysprosium, tris (1,5-dicyclopentyl-2,4-pentanedionato) dysprosium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) dysprosium and the likeAmong them, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) dysprosium and tris (2,6-dimethyl-3,5-heptanedionato) dysprosium are used.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, in the case of a holmium compound, tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) holmium, Tris (2,2,6-trimethyl-3,5-heptanedionato) holmium, Tris (2,6-dimethyl-3,5-heptanedionato) holmium, Tris (3,5-heptanedionato) holmium, Tris (2,4-pentanedionato) holmium, tris (2,4-hexanedionato) holmium, tris (1,5-dicyclopentyl-2,4-pentandionato) holmium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) holmium and the like. Among these, preferably, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) holmium and tris (2,6-dimethyl-3,5-heptanedionato) holmium are used.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, an erbium compound is tris (2,2,6,6-tetramethyl-3,5 -Heptanedionato) erbium, Tris (2,2,6-trimethyl-3,5-heptanedionato) erbium, Tris (2,6-dimethyl-3,5-heptanedionato) erbium, Tris (3,5-heptanedionato) erbium, Tris (2,4-pentanedionato) erbium, tris (2,4-hexanedionato) erbium, tris (1,5-dicyclopentyl-2,4-pentandionato) erbium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) erbium and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) erbium and tris (2,6-dimethyl-3,5-heptanedionato) erbium are preferable.

  When the rare earth metal compound as the component (A) constituting the coordination polymerization catalyst system is a diketone type rare earth metal complex, for example, a thulium compound is tris (2,2,6,6-tetramethyl-3,5 -Heptanedionate) thulium, tris (2,2,6-trimethyl-3,5-heptanedionate) thulium, tris (2,6-dimethyl-3,5-heptanedionate) thulium, tris (3,5-heptanedionate) thulium, tris (2,4-pentanedionato) thulium, tris (2,4-hexanedionato) thulium, tris (1,5-dicyclopentyl-2,4-pentandionato) thulium, tris (1,5-dicyclohexyl- 2,4-pentanedionato) thulium and the like. Of these, tris (2,2,6,6-tetramethyl-3,5-heptanedionato) thulium and tris (2,6-dimethyl-3,5-heptaneedionato) thulium are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, for scandium compounds, trimethoxy scandium, triethoxy scandium, tri n-propoxy scandium, triisopropoxy scandium, Examples include tributoxy scandium, tripentoxy scandium, trihexyloxy scandium, and the like. Among these, triisopropoxy scandium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of an yttrium compound, trimethoxy yttrium, triethoxy yttrium, tri n-propoxy yttrium, triisopropoxy yttrium, Tributoxy yttrium, tripentoxy yttrium, trihexyloxy yttrium, and the like. Among them, triisopropoxy yttrium is preferable.

  When the rare earth metal compound as the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a lanthanum compound, trimethoxy lanthanum, triethoxy lanthanum, tri n-propoxy lanthanum, triisopropoxy lanthanum, Examples include tributoxylantan, tripentoxylantan, trihexyloxylantan, and the like. Among these, triisopropoxylantan is preferable.

  When the rare earth metal compound as the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a cerium compound, trimethoxycerium, triethoxycerium, tri-n-propoxycerium, triisopropoxycerium, Tributoxycerium, tripentoxycerium, trihexyloxycerium, and the like. Among these, triisopropoxycerium is preferable.

  When the rare earth metal compound that is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a praseodymium compound, trimethoxy praseodymium, triethoxy praseodymium, tri n-propoxy praseodymium, triisopropoxy praseodymium, Tributoxy praseodymium, tripentoxy praseodymium, trihexyloxy praseodymium, etc. are mentioned. Among these, triisopropoxy praseodymium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a neodymium compound, trimethoxy neodymium, triethoxy neodymium, tri n-propoxy neodymium, triisopropoxy neodymium, Tributoxyneodymium, tripentoxyneodymium, trihexyloxyneodymium, and the like. Among these, triisopropoxyneodymium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a gadolinium compound, trimethoxy gadolinium, triethoxy gadolinium, tri n-propoxy gadolinium, triisopropoxy gadolinium, Tributoxy gadolinium, tripentoxy gadolinium, trihexyloxy gadolinium, etc. are mentioned. Among them, triisopropoxy gadolinium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a terbium compound, trimethoxyterbium, triethoxyterbium, tri-n-propoxyterbium, triisopropoxyterbium, Tributoxyterbium, tripentoxyterbium, trihexyloxyterbium and the like can be mentioned. Among them, triisopropoxyterbium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a dysprosium compound, trimethoxy dysprosium, triethoxy dysprosium, tri n-propoxy dysprosium, triisopropoxy dysprosium, Tributoxy dysprosium, tripentoxy dysprosium, trihexyloxy dysprosium and the like can be mentioned. Among them, triisopropoxy dysprosium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of a holmium compound, trimethoxyformium, triethoxyholmium, tri-n-propoxyformium, triisopropoxyformium, Examples thereof include tributoxyholmium, tripentoxyholmium, trihexyloxyholmium, and the like. Among them, triisopropoxyformium is preferable.

  When the rare earth metal compound that is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, in the case of an erbium compound, trimethoxy erbium, triethoxy erbium, tri n-propoxy erbium, triisopropoxy erbium, Tributoxy erbium, tripentoxy erbium, trihexyloxy erbium, etc. are mentioned. Among these, triisopropoxy erbium is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal alkoxide, for example, for thulium compounds, trimethoxy thulium, triethoxy thulium, tri n-propoxy thulium, triisopropoxy thulium, Examples include tributoxy thulium, tripentoxy thulium, trihexyloxy thulium, and the like. Among these, triisopropoxyttrium is preferable.

  When the rare earth metal compound that is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, scandium 2-ethylhexanoate, scandium versatic acid, scandium naphthenate, scandium stearate, Scandium oleate, scandium benzoate, scandium picolinate, scandium formate, scandium acetate, scandium acrylate, scandium methacrylate, scandium valerate, scandium gluconate, scandium citrate, scandium fumarate, scandium lactate, scandium maleate, shu Scandium acid, and the like. Of these, scandium 2-ethylhexanoate and scandium versatate are preferable.

  When the rare earth metal compound as the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, yttrium 2-ethylhexanoate, yttrium versatic acid, yttrium naphthenate, yttrium stearate, Yttrium oleate, yttrium benzoate, yttrium picolinate, yttrium formate, yttrium acetate, yttrium acrylate, yttrium methacrylate, yttrium valerate, yttrium gluconate, yttrium citrate, yttrium fumarate, yttrium lactate, yttrium maleate, sulphur And yttrium acid. Of these, yttrium 2-ethylhexanoate and yttrium versatic acid are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, lanthanum 2-ethylhexanoate, lanthanum versatic acid, lanthanum naphthenate, lanthanum stearate, Lanthanum oleate, Lanthanum benzoate, Lanthanum picolinate, Lanthanum formate, Lanthanum acetate, Lanthanum acrylic acid, Lanthanum methacrylate, Lanthanum valerate, Lanthanum gluconate, Lanthanum citrate, Lanthanum fumarate, Lanthanum lactate, Lanthanum maleate, Shu And lanthanum acid. Of these, lanthanum 2-ethylhexanoate and lanthanum versatate are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, cerium 2-ethylhexanoate, cerium versatate, cerium naphthenate, cerium stearate, Cerium oleate, cerium benzoate, cerium picolinate, cerium formate, cerium acetate, cerium acrylate, cerium methacrylate, cerium valerate, cerium gluconate, cerium citrate, cerium fumarate, cerium lactate, cerium maleate, sulphur And cerium acid. Of these, cerium 2-ethylhexanoate and cerium versatate are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, praseodymium 2-ethylhexanoate, praseodymium versatate, praseodymium naphthenate, praseodymium stearate, Praseodymium oleate, praseodymium benzoate, praseodymium picolinate, praseodymium formate, praseodymium acetate, praseodymium acrylate, praseodymium methacrylate, praseodymium valerate, praseodymium citrate, praseodymium fumarate, praseodymium fumarate, praseodymium lactate, maleate And praseodymium acid. Among these, Preferably, praseodymium 2-ethylhexanoate and praseodymium versatate are mentioned.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, neodymium 2-ethylhexanoate, neodymium versatate, neodymium naphthenate, neodymium stearate, Neodymium oleate, neodymium benzoate, neodymium picolinate, neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, shu And neodymium acid. Of these, neodymium 2-ethylhexanoate and neodymium versatate are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, gadolinium 2-ethylhexanoate, gadolinium versatic acid, gadolinium naphthenate, gadolinium stearate, Gadolinium oleate, gadolinium benzoate, gadolinium picolinate, gadolinium formate, gadolinium acetate, gadolinium acrylate, gadolinium methacrylate, gadolinium valerate, gadolinium gluconate, gadolinium citrate, gadolinium fumarate, gadolinium lactate, gadolinium maleate, sulphur And gadolinium acid. Among these, Preferably, gadolinium 2-ethylhexanoate and gadolinium versatic acid are mentioned.

  When the rare earth metal compound that is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, terbium 2-ethylhexanoate, terbium versatate, terbium naphthenate, terbium stearate, Terbium oleate, Terbium benzoate, Terbium picolinate, Terbium formate, Terbium acetate, Terbium acrylate, Terbium methacrylate, Terbium valerate, Terbium gluconate, Terbium citrate, Terbium fumarate, Terbium lactate, Terbium maleate, Shu And terbium acid. Of these, terbium 2-ethylhexanoate and terbium versatate are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, dysprosium 2-ethylhexanoate, dysprosium versatate, dysprosium naphthenate, dysprosium stearate, Dysprosium oleate, dysprosium benzoate, dysprosium picolinate, dysprosium formate, dysprosium acetate, dysprosium acrylate, dysprosium methacrylate, dysprosium valerate, dysprosium gluconate, dysprosium citrate, dysprosium dysprosium lactate, And dysprosium acid. Of these, dysprosium 2-ethylhexanoate and dysprosium versatate are preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, holmium 2-ethylhexanoate, holmium versatate, holmium naphthenate, holmium stearate, Holium Oleate, Holmium Benzoate, Holmium Picolinate, Holmium Formate, Holmium Acetate, Holmium Acrylate, Holmium Methacrylate, Holmium Valerate, Holmium Gluconate, Holmium Citrate, Holmium Fumarate, Holmium Lactate, Holmium Maleate, Shu And holmium acid. Among these, Preferably, 2-ethyl hexanoic acid holmium and versatic acid holmium are mentioned.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, erbium 2-ethylhexanoate, erbium versatic acid, erbium naphthenate, erbium stearate, Erbium oleate, Erbium benzoate, Erbium picolinate, Erbium formate, Erbium acetate, Erbium acrylate, Erbium methacrylate, Erbium valerate, Erbium gluconate, Erbium citrate, Erbium fumarate, Erbium lactate, Erbium maleate, Shu And erbium acid. Of these, erbium 2-ethylhexanoate and erbium versatate are preferable.

  When the rare earth metal compound as the component (A) constituting the coordination polymerization catalyst system is a rare earth metal carboxylate, for example, 2-ethylhexanoate thulium, versatic thulium, naphthenate thulium, thulium stearate, Thulium oleate, thulium benzoate, thulium picolinate, thulium formate, thulium acetate, thulium acrylate, thulium methacrylate, thulium valerate, thulium gluconate, thulium citrate, thulium fumarate, thulium lactate, thulium maleate, sulphur And thulium acid. Among these, preferably, thulium 2-ethylhexanoate and thulium versatic acid are used.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, scandium di (2-ethylhexyl) phosphate, scandium dibutyl phosphate, scandium dipentyl Phosphate, scandium dihexyl phosphate, scandium diheptyl phosphate, scandium dioctyl phosphate, scandium di (1-methylheptyl) phosphate, scandium didecyl phosphate, scandium didodecyl phosphate, scandium Dioctadecyl phosphate, scandium dioleyl phosphate, scandium diphenyl phosphate, scandium di (p-nonylphenyl) phosphate, scandium butyl (2-ethylhexyl) phosphate, scandium (1-methylheptyl) ( 2-ethylhexyl) Salt, scandium (2-ethylhexyl) (p-nonylphenyl) phosphate, and the like. Among these, scandium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, yttrium di (2-ethylhexyl) phosphate, yttrium dibutyl phosphate, yttrium dipentyl Phosphate, yttrium dihexyl phosphate, yttrium diheptyl phosphate, yttrium dioctyl phosphate, yttrium di (1-methylheptyl) phosphate, yttrium didecyl phosphate, yttrium didodecyl phosphate, yttrium Dioctadecyl phosphate, yttrium dioleyl phosphate, yttrium diphenyl phosphate, yttrium di (p-nonylphenyl) phosphate, yttrium butyl (2-ethylhexyl) phosphate, yttrium (1-methylheptyl) ( 2-ethylhexyl) Salt, yttrium (2-ethylhexyl) (p-nonylphenyl) phosphate, and the like. Among them, preferably, yttrium di (2-ethylhexyl) phosphate is used.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, lanthanum di (2-ethylhexyl) phosphate, lanthanum dibutyl phosphate, lanthanum dipentyl phosphorus Acid salt, lanthanum dihexyl phosphate, lanthanum diheptyl phosphate, lanthanum dioctyl phosphate, lanthanum di (1-methylheptyl) phosphate, lanthanum didecyl phosphate, lanthanum dododecyl phosphate, lanthanum dioctadecyl Phosphate, lanthanum dioleyl phosphate, lanthanum diphenyl phosphate, lanthanum di (p-nonylphenyl) phosphate, lanthanum butyl (2-ethylhexyl) phosphate, lanthanum (1-methylheptyl) (2-ethylhexyl) ) Phosphate, lanthanum (2-ethylhexyl) (p-nonylphenyl) Down salt, and the like. Among these, lanthanum di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, cerium di (2-ethylhexyl) phosphate, cerium dibutyl phosphate, cerium dipentyl phosphorus Acid salt, cerium dihexyl phosphate, cerium diheptyl phosphate, cerium dioctyl phosphate, cerium di (1-methylheptyl) phosphate, cerium didecyl phosphate, cerium didodecyl phosphate, cerium dioctadecyl Phosphate, cerium dioleyl phosphate, cerium diphenyl phosphate, cerium di (p-nonylphenyl) phosphate, cerium butyl (2-ethylhexyl) phosphate, cerium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, cerium (2-ethylhexyl) (p-nonylphenyl) Down salt, and the like. Of these, cerium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, praseodymium di (2-ethylhexyl) phosphate, praseodymium dibutyl phosphate, praseodymium dipentyl Phosphate, praseodymium dihexyl phosphate, praseodymium diheptyl phosphate, praseodymium dioctyl phosphate, praseodymium di (1-methylheptyl) phosphate, praseodymium didecyl phosphate, praseodymium didodecyl phosphate, praseodymium Dioctadecyl phosphate, praseodymium dioleyl phosphate, praseodymium diphenyl phosphate, praseodymium di (p-nonylphenyl) phosphate, praseodymium butyl (2-ethylhexyl) phosphate, praseodymium (1-methylheptyl) ( 2-ethylhexyl) Salt, praseodymium (2-ethylhexyl) (p-nonylphenyl) phosphate, and the like. Among these, praseodymium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, neodymium di (2-ethylhexyl) phosphate, neodymium dibutyl phosphate, neodymium dipentyl phosphorus Acid salt, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium di (1-methylheptyl) phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl Phosphate, neodymium dioleyl phosphate, neodymium diphenyl phosphate, neodymium di (p-nonylphenyl) phosphate, neodymium butyl (2-ethylhexyl) phosphate, neodymium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, neodymium (2-ethylhexyl) (p-nonylphenyl) Down salt, and the like. Among these, neodymium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, gadolinium di (2-ethylhexyl) phosphate, gadolinium dibutyl phosphate, gadolinium dipentyl Phosphate, gadolinium dihexyl phosphate, gadolinium diheptyl phosphate, gadolinium dioctyl phosphate, gadolinium di (1-methylheptyl) phosphate, gadolinium didecyl phosphate, gadolinium didodecyl phosphate, gadolinium Dioctadecyl phosphate, gadolinium dioleyl phosphate, gadolinium diphenyl phosphate, gadolinium di (p-nonylphenyl) phosphate, gadolinium butyl (2-ethylhexyl) phosphate, gadolinium (1-methylheptyl) ( 2-ethylhexyl) Salt, gadolinium (2-ethylhexyl) (p-nonylphenyl) phosphate, and the like. Among these, Gadolinium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound which is the component (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, terbium di (2-ethylhexyl) phosphate, terbium dibutyl phosphate, terbium dipentyl phosphorus Acid salt, terbium dihexyl phosphate, terbium diheptyl phosphate, terbium dioctyl phosphate, terbium di (1-methylheptyl) phosphate, terbium didecyl phosphate, terbium didodecyl phosphate, terbium dioctadecyl Phosphate, terbium dioleyl phosphate, terbium diphenyl phosphate, terbium di (p-nonylphenyl) phosphate, terbium butyl (2-ethylhexyl) phosphate, terbium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, terbium (2-ethyl Hexyl) (p-nonylphenyl) phosphate, and the like. Among them, terbium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, dysprosium di (2-ethylhexyl) phosphate, dysprosium dibutyl phosphate, dysprosium dipentyl Phosphate, dysprosium dihexyl phosphate, dysprosium diheptyl phosphate, dysprosium dioctyl phosphate, dysprosium di (1-methylheptyl) phosphate, dysprosium didecyl phosphate, dysprosium didodecyl phosphate, dysprosium Dioctadecyl phosphate, dysprosium dioleyl phosphate, dysprosium diphenyl phosphate, dysprosium di (p-nonylphenyl) phosphate, dysprosium butyl (2-ethylhexyl) phosphate, dysprosium (1-methylhept Le) (2-ethylhexyl) phosphate, dysprosium (2-ethylhexyl) (p-nonylphenyl) phosphate, and the like. Among them, dysprosium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, holmium di (2-ethylhexyl) phosphate, holmium dibutyl phosphate, holmium dipentyl phosphorus Acid salt, holmium dihexyl phosphate, holmium diheptyl phosphate, holmium dioctyl phosphate, holmium di (1-methylheptyl) phosphate, holmium didecyl phosphate, holmium didodecyl phosphate, holmium dioctadecyl Phosphate, holmium dioleyl phosphate, holmium diphenyl phosphate, holmium di (p-nonylphenyl) phosphate, holmium butyl (2-ethylhexyl) phosphate, holmium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, holmium (2-ethyl Hexyl) (p-nonylphenyl) phosphate, and the like. Among these, holmium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, erbium di (2-ethylhexyl) phosphate, erbium dibutyl phosphate, erbium dipentyl phosphorus Acid salt, erbium dihexyl phosphate, erbium diheptyl phosphate, erbium dioctyl phosphate, erbium di (1-methylheptyl) phosphate, erbium didecyl phosphate, erbium didodecyl phosphate, erbium dioctadecyl Phosphate, erbium dioleyl phosphate, erbium diphenyl phosphate, erbium di (p-nonylphenyl) phosphate, erbium butyl (2-ethylhexyl) phosphate, erbium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, erbium (2-ethyl Hexyl) (p-nonylphenyl) phosphate, and the like. Of these, erbium di (2-ethylhexyl) phosphate is preferable.

  When the rare earth metal compound (A) constituting the coordination polymerization catalyst system is a rare earth metal phosphate, for example, thulium di (2-ethylhexyl) phosphate, thulium dibutyl phosphate, thulium dipentyl phosphorus Acid salt, thulium dihexyl phosphate, thulium diheptyl phosphate, thulium dioctyl phosphate, thulium di (1-methylheptyl) phosphate, thulium didecyl phosphate, thulium didodecyl phosphate, thulium dioctadecyl Phosphate, thulium dioleyl phosphate, thulium diphenyl phosphate, thulium di (p-nonylphenyl) phosphate, thulium butyl (2-ethylhexyl) phosphate, thulium (1-methylheptyl) (2-ethylhexyl) ) Phosphate, thulium (2-ethylhexyl) (p-nonylphenyl) Down salt, and the like. Of these, thulium di (2-ethylhexyl) phosphate is preferable.

  Examples of organometallic compounds of Group 2, 12 and 13 of the periodic table that are the component (B) constituting the coordination polymerization catalyst system include organic magnesium, organic zinc, and organic aluminum. . Among these compounds, dialkyl magnesium, alkyl magnesium chloride, alkyl magnesium bromide, dialkyl zinc, trialkyl aluminum, dialkyl aluminum chloride, dialkyl aluminum bromide, alkyl aluminum sesquichloride, alkyl aluminum sesquibromide, alkyl aluminum dichloride, dialkyl Such as aluminum hydride.

  Specific compounds include alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, butyl magnesium iodide, and hexyl magnesium iodide. Can be mentioned.

  Furthermore, dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethylbutyl magnesium, ethylhexyl magnesium and the like can be mentioned.

  Further, trialkyl zinc such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, didecyl zinc and the like can be mentioned.

  Furthermore, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like can be mentioned.

  Furthermore, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride, and hydrogenated organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydride. Can be mentioned.

  Alumoxane may be used as the component (B) constituting the coordination polymerization catalyst system. The alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and includes a chain alumoxane represented by the general formula (—Al (R ′) O—) n or a cyclic alumoxane ( R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group, n is the degree of polymerization, and is 5 or more, preferably 10 or more). Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable. Examples of the organoaluminum compound used as a raw material for alumoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

  Among these, alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

  Moreover, as a condensing agent, water is typically used, but in addition to this, any agent that undergoes a condensation reaction with the above-described trialkylaluminum, for example, adsorbed water such as inorganic substances, diol, and the like can be used.

  The organometallic compounds of Group 2, 12 and 13 of the periodic table that are the component (B) constituting the above coordination polymerization catalyst system can be used alone or in combination of two or more. Is possible.

  As the molecular weight regulator of the conjugated diene polymer obtained in the above-mentioned coordination polymerization catalyst system, a compound selected from hydrogen, a metal hydride compound, and a hydrogenated organometallic compound can be used.

  Examples of the molecular weight regulator metal hydride compound in the coordination polymerization catalyst system described above include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, and silane. , Germane, lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride, and the like.

  Hydrogenated organometallic compounds as molecular weight regulators in the coordination polymerization catalyst system described above include methylborane, ethylborane, propylborane, butylborane, phenylborane and other alkylboranes, dimethylborane, diethylborane, dipropylborane, dibutylborane, diphenyl. Dialkylborane such as borane, methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, phenylaluminum dihydride, etc., alkylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, Dialkyl aluminum hydride, diphenyl aluminum hydride, etc. Silanes such as aluminum hydride, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane Class, methyl germane, ethyl germane, propyl germane, butyl germane, phenyl germane, dimethyl germane, diethyl germane, dipropyl germane, dibutyl germane, diphenyl germane, trimethyl germane, triethyl germane, tripropyl germane, tributyl germane, triphenyl germane, etc. And germane.

  Among these, diisobutylaluminum hydride and diethylaluminum hydride are preferable, and diisobutylaluminum hydride is particularly preferable.

  You may add the ionic compound which consists of a non-coordinating anion and a cation to the coordination polymerization catalyst system mentioned above. Non-coordinating anions include, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (penta Fluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarbaundecaborate, tetrafluoroborate, hexafluorophosphate, etc. .

  On the other hand, examples of the cation include a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation.

  Specific examples of the carbenium cation include tri-substituted carbenium cations such as a triphenyl carbenium cation and a tri-substituted phenyl carbenium cation. Specific examples of the tri-substituted phenyl carbenium cation include a tri (methylphenyl) carbenium cation and a tri (dimethylphenyl) carbenium cation.

  Specific examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like, N, N-dimethylanilinium cations, N N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and the like N, N-dialkylanilinium cation, di (isopropyl) ammonium cation, dicyclohexylammonium cation and other dialkylammonium cations Can be mentioned.

  Specific examples of phosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation, etc. Of the arylphosphonium cation.

  As the above ionic compounds, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

  Among them, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1 ′ -Dimethyl ferrocenium tetrakis (pentafluorophenyl) borate etc. are preferable. An ionic compound may be used independently and may be used in combination of 2 or more type.

In the step of producing the conjugated diene polymer, when the catalyst used is (C) an alkali metal compound, for example, methyllithium, n-butyllithium, s-butyllithium, t-butyllithium, etc. may be mentioned. . Among these, n-butyllithium is preferable. An alkali metal compound (C) may be used independently and may be used in combination of 2 or more type.

  Conjugated diene compound monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2, 4-hexadiene etc. are mentioned. Among them, a conjugated diene compound monomer mainly composed of 1,3-butadiene is preferable. These monomer components may be used alone or in combination of two or more.

  The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization), solution polymerization, or the like using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent can be applied. Solvents for solution polymerization include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, Examples thereof include olefinic hydrocarbons such as olefin compounds and cis-2-butene and trans-2-butene. As the solvent used for the polymerization, several different types of solvents can be mixed and used.

  Among these, benzene, toluene, cyclohexane, cis-2-butene, trans-2-butene and the like are preferably used.

  The polymerization temperature is preferably in the range of -30 to 150 ° C, more preferably in the range of 0 to 80 ° C, and particularly preferably in the range of 30 to 70 ° C. The polymerization time is preferably in the range of 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours, and more preferably 10 minutes to 1 hour.

  The organic solvent used for the modification reaction can be freely used as long as it does not react with the conjugated diene polymer. Usually, the same solvent as used in the production of the conjugated diene polymer is used. Specific examples thereof include aromatic hydrocarbon solvents such as benzene, chlorobenzene, o-dichlorobenzene, toluene and xylene, and carbon atoms of 5 to 10 such as n-heptane, n-hexane, n-pentane and n-octane. And aliphatic hydrocarbon solvents such as cyclohexane, cyclohexane, methylcyclohexane, tetralin and decalin.

  The temperature of the reaction solution for the modification reaction is preferably in the range of −30 to 100 ° C., particularly preferably in the range of 10 to 90 ° C. The time for the denaturation reaction is not particularly limited, but is preferably in the range of 1 minute to 5 hours, and more preferably in the range of 3 minutes to 1 hour. If the modification reaction time is too short, the reaction does not proceed sufficiently, and if the time is too long, the polymer tends to gel.

  The amount of the conjugated diene polymer in the modification reaction solution is usually in the range of 2 to 300 g, preferably 10 to 200 g, per liter of the modification reaction solution.

  The amount of the modifier used in the modification reaction is usually in the range of 0.01 to 150 mmol, preferably 0.1 to 100 mmol, more preferably 0.2 to 50 mmol, with respect to 100 g of the conjugated diene polymer. If the amount used is too small, the amount of modifying groups introduced into the modified conjugated diene polymer will be small, and a sufficient modification effect will not be obtained. If the amount used is too large, unreacted modifier remains in the modified conjugated diene polymer, and it is not preferred because it takes time to remove it.

  In carrying out the modification reaction, after adding a modifier after the polymerization reaction, a polymerization terminator is added, and the solvent and unreacted monomers remaining in the reaction product are removed by a steam stripping method, a vacuum drying method, Or a method of adding a modifier after adding a polymerization terminator. Depending on the type of the polymerization terminator, the activity of the site where the polymer reacts with the modifier may be reduced, so a method of adding the modifier before termination of the polymerization is preferred.

[Example]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

Example 1: Synthesis of 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione
In a 1 L three-necked flask, 7.1 g (40 mmol) of 2,6-dihydroxy-3,7-dimethylpurine, 10 g (40 mmol) of 4- (bromomethyl) pyridine hydrobromide, and 12 g (87 mmol) of potassium carbonate ), 800 mL of N, N-dimethylformamide was added and stirred using a magnetic stirrer. After reacting at 60 ° C. for 3 hours, 20 mL of hydrochloric acid (6 mol / L) was added at the end of the reaction. N, N-dimethylformamide was distilled off, followed by extraction with a chloroform / saturated aqueous sodium hydrogen carbonate solution to obtain the desired crude product. The result of gas chromatography analysis of the obtained crude product is shown in FIG. The target product content in the crude product was 98% or more.

Comparative Example 1: Synthesis of 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione
In Example 1, the target compound was synthesized in the same manner except that 20 mL of hydrochloric acid (6 mol / L) was not added at the end of the reaction. The gas chromatographic analysis result of the obtained crude product is shown in FIG. The target product content in the crude product was 3.3%.

Example 2: Synthesis of 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione
In a 500 mL three-necked flask, 2.8 g (16 mmol) of 1,3-dimethyl-7H-purine-2,6-dione and 5.5 g of 4-((diethylamino) methyl) benzyl bromide hydrobromide ( 16 mmol), 4.8 g (34 mmol) of potassium carbonate and 260 mL of N, N-dimethylformamide were added and stirred using a magnetic stirrer. After reacting at 80 ° C. for 6 hours, 20 mL of hydrochloric acid (6 mol / L) was added at the end of the reaction. N, N-dimethylformamide was distilled off, followed by extraction with a chloroform / saturated aqueous sodium hydrogen carbonate solution to obtain the desired crude product. The gas chromatography analysis result of the obtained crude product is shown in FIG. The target product content in the crude product was 98% or more.

[Comparative Example 2: Synthesis of 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione]
In Example 2, the synthesis reaction of the target compound was carried out in the same manner except that 20 mL of hydrochloric acid (6 mol / L) was not added at the end of the reaction. The result of gas chromatography analysis of the obtained crude product is shown in FIG. The target product content in the crude product was 22.7%.

  As can be seen by comparing Example 1 and Comparative Example 1, and Example 2 and Comparative Example 2, the selectivity and yield of the target compound in the chemical modification reaction of the modified purine derivative can be obtained by using the method of the present invention. The rate can be improved. In addition, since the target compound can be obtained with high purity, depending on the intended use, the purification step of the compound can be omitted, and the production process can be simplified.

[Purification, mass spectrometry and ¹ H-NMR analysis of synthesis of 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione]
For the compound synthesized in Example 1, the obtained crude product was purified by silica gel column chromatography, and 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine- 4.2 g of 2,6-dione was isolated. The results of analysis by electron ionization mass spectrometry are shown in FIG. It can be seen that the molecular ion peak (m / z: 271) of the target compound is clearly observed. Moreover, about the same compound synthesize | combined in Example 1 which performed the same refinement | purification, the spectrum chart obtained by analyzing using the < ¹ > H-NMR method and attribution of each signal are shown in FIG. The chemical shift and integral value of each signal is as follows; δ _ppm (395.75 MHz, CDCl ₃ ): 3.56 (3H, s), 3.97 (3H, s), 5.16 (2H, s), 7.30 (2H, d), 7.52 (1H, s), 8.51 (2H, d). From the results of mass spectrometry and ¹ H-NMR analysis, the compound synthesized in Example 1 was the desired 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine- Identified as 2,6-dione. The structural formula of the product is shown in chemical formula (3).

[Purification, mass spectrometry and ¹ H-NMR analysis of 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione]
For the compound synthesized in Example 2, the obtained crude product was purified by silica gel column chromatography to obtain 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro- 1.3 g of 1H-purine-2,6-dione was isolated. The results of analysis by electron ionization mass spectrometry are shown in FIG. It can be seen that the molecular ion peak (m / z: 355) of the compound is clearly observed. Moreover, about the same compound synthesize | combined in Example 2, the spectrum chart obtained by analyzing using the < ¹ > H-NMR method and attribution of each signal are shown in FIG. The chemical shift and integral value of each signal is as follows; δ _ppm (395.75 MHz, CDCl ₃ ): 1.00 (6H, t), 2.48 (4H, q), 2.90 (2H, s), 3.39 (3H, s), 3.56 (3H, s), 5.46 (2H, s), 7.24 (2H, d), 7.33 (2H, d), 7. 52 (1H, s). From the results of mass spectrometry and ¹ H-NMR analysis, the compound synthesized in Example 2 was the target 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro- It was identified as 1H-purine-2,6-dione. The structural formula of the product is shown in chemical formula (4).

[Synthetic rubber modifier use]
The purine derivative compound of the present invention can be used as, for example, a synthetic rubber modifier in one embodiment. The synthetic rubber in which the compound of the present invention is introduced into the molecule has an effect of improving various physical properties such as low fuel consumption and wear resistance in tire applications.

[Example 3: Synthesis of 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene (using a coordination polymerization catalyst)]
In a system using a coordination polymerization catalyst, polybutadiene in which the compound synthesized in Example 1 was introduced into the molecule was synthesized. The inside of the pressure-resistant autoclave was replaced with nitrogen, and 500 mL of 1,3-butadiene and 475 mL of cyclohexane were added. 3.4 mL of triethylaluminum / cyclohexane solution (2 mol / L), 6 mL of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) gadolinium / cyclohexane solution (5 mmol / L), triphenylcarbenium 15 mL of tetrakis (pentafluorophenyl) borate / toluene solution (4 mmol / L) was added, and polybutadiene was polymerized at 20 ° C. for 25 minutes. Next, the 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione / o-dichlorobenzene solution synthesized in Example 1 (50 mmol / L) 10 mL was added, and the reaction with the polymerization active terminal of polybutadiene, that is, modification treatment was performed. After denaturation treatment at 20 ° C. for 15 minutes, the reaction was quenched by adding 5 mL of an ethanol solution containing an anti-aging agent, and then 300 mL of ethanol was added and the polymer was recovered and dried, and 3,7-dimethyl-1 30.2 g of-(pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene was obtained. Table 1 shows the physical rubber properties of the resulting modified polybutadiene.

Example 4: Synthesis of 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene (coordination polymerization catalyst used) ]]
In a system using a coordination polymerization catalyst, polybutadiene in which the compound synthesized in Example 2 was introduced into the molecule was synthesized. 7- (4-((diethylamino) methyl) benzyl) was similarly used except that the compound synthesized in Example 2 was used in place of the compound synthesized in Example 1 as the modifying agent used in Example 3. 28.3 g of -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene was obtained. Table 1 shows the physical rubber properties of the resulting modified polybutadiene.

[Comparative Example 3: Synthesis of unmodified polybutadiene (using coordination polymerization catalyst)]
In order to clarify the improvement effect of various tire properties by the modification treatment, as a comparison, unmodified polybutadiene was also synthesized in a system using a coordination polymerization catalyst. The method for synthesizing unmodified polybutadiene is the same as the method for synthesizing polybutadiene described above except that it does not include a step of modifying using the purine derivative compound synthesized in Example 1 and Example 2. Table 1 shows the physical rubber properties of the resulting unmodified polybutadiene.

[Example 5: Synthesis of 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene (using alkali metal compound polymerization catalyst)]
In a system using an alkali metal compound polymerization catalyst, polybutadiene in which the compound synthesized in Example 1 was introduced into the molecule was synthesized. The inside of the pressure-resistant autoclave was replaced with nitrogen, and 60 mL of 1,3-butadiene and 540 mL of cyclohexane were added. 0.30 mL of n-butyllithium / hexane solution (1.6 mol / L) was added, and polybutadiene was polymerized at 80 ° C. for 15 minutes. Next, the 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione / o-dichlorobenzene solution synthesized in Example 1 (50 mmol / L) 10 mL was added, and the reaction with the polymerization active terminal of polybutadiene, that is, modification treatment was performed. After performing the modification treatment at 80 ° C. for 15 minutes, 5 mL of an ethanol solution containing an anti-aging agent is added to quench the reaction, and then 300 mL of ethanol is added to recover and dry the polymer to obtain 31.9 g of modified polybutadiene. It was. Table 1 shows the physical rubber properties of the resulting modified polybutadiene.

Example 6 Synthesis of 7- (4-((diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene (alkali metal compound polymerization catalyst use)]
In a system using an alkali metal compound polymerization catalyst, polybutadiene in which the compound synthesized in Example 2 was introduced into the molecule was synthesized. 7- (4-((diethylamino) methyl) benzyl) was similarly used except that the compound synthesized in Example 2 was used in place of the compound synthesized in Example 1 as the modifying agent used in Example 5. 28.3 g of -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione-modified polybutadiene was obtained. Table 1 shows the physical rubber properties of the resulting modified polybutadiene.

[Production and evaluation of physical properties of tire vulcanized rubber composition using polybutadiene modified with purine derivative compound of the present invention as a constituent material]
Preparation and physical property evaluation of a vulcanized rubber composition for a tire were carried out using polybutadiene in which the purine derivative compound synthesized in Example 1 and Example 2 was introduced into the molecule. For comparison, the same evaluation was performed for unmodified polybutadiene. Using a Banbury mixer, the polybutadiene synthesized in Example 3, Example 4 or Comparative Example 3 (50 parts by mass), natural rubber (50 parts by mass), carbon black (50 parts by mass), process oil (3 parts by mass) Part), zinc oxide (3 parts by mass), stearic acid (2 parts by mass) and anti-aging agent (2 parts by mass) are kneaded, and then, using an open roll, sulfur powder (1.5 parts by mass) Part) and vulcanization accelerator (1 part by mass) were added. The obtained compounded rubber composition was press vulcanized at 150 ° C. for 15 minutes to prepare a test piece for evaluation. Using the obtained vulcanized test piece, low fuel consumption and wear resistance were evaluated. For low fuel consumption evaluation, based on JIS-K6394, a dynamic viscoelasticity measuring device (manufactured by GABO, EPLEXOR 100N) is used, measured at a frequency of 16 Hz and a dynamic strain of 0.3%, and a loss at 60 ° C. The coefficient tan δ was used as an index of low fuel consumption. Tan δ at 60 ° C. is generally used as an index of low heat generation performance in a tire rubber composition. As tan δ is smaller, heat generation is less likely, that is, the tire has better fuel efficiency. Moreover, about abrasion resistance evaluation, based on JIS-K6264-2, the pico abrasion tester was used, the mass change before and behind abrasion of a test piece was measured, and it used as an index of abrasion resistance. Table 2 shows 3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione modified polybutadiene, 7- (4-((diethylamino) methyl) benzyl ) 1,3-Dimethyl-3,7-dihydro-1H-purine-2,6-dione modified polybutadiene and low mileage index and abrasion resistance index of vulcanized rubber composition prepared using unmodified polybutadiene Indicates. The index in the table was set to 100 when unmodified polybutadiene was used, and the value was increased as the characteristics were improved. This shows that the purine derivative compound of the present invention can be suitably used as a modifier for improving various physical properties such as low fuel consumption and wear resistance as a tire material.

Claims (12)

The compound represented by the following general formula (1).
[Wherein, R ¹ , R ² and R ³ each independently represent a substituent having 1 to 16 carbon atoms excluding a hydrogen atom, N represents a nitrogen atom, and O represents an oxygen atom. ]   The method for producing a compound according to claim 1, comprising a step of using a modified purine derivative and an organic compound having a leaving group as raw materials and adding an acidic compound to the reaction system.   3,7-dimethyl-1- (pyridin-4-ylmethyl) -3,7-dihydro-1H-purine-2,6-dione.   The method for producing a compound according to claim 3, comprising a step of using a modified purine derivative and an organic compound having a leaving group as raw materials and adding an acidic compound to the reaction system.   7- (4-((Diethylamino) methyl) benzyl) -1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione.   6. The method for producing a compound according to claim 5, comprising a step of using a modified purine derivative and an organic compound having a leaving group as raw materials, and adding an acidic compound to the reaction system.   A method for producing a modified conjugated diene polymer, comprising: (I) a step of polymerizing a conjugated diene with a coordination polymerization catalyst; and (II) the obtained conjugated diene polymer. And reacting with the compound according to 5.   A modified conjugated diene polymer obtained by the method according to claim 7.   8. The coordination polymerization catalyst according to claim 7, wherein the coordination polymerization catalyst is a catalyst obtained from (A) a rare earth metal compound, (B) an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table. A process for producing the modified conjugated diene polymer as described.   A modified conjugated diene polymer obtained by the method according to claim 9.   A method for producing a modified conjugated diene polymer, comprising: (I) a step of polymerizing a conjugated diene with an alkali metal compound; and (II) an obtained conjugated diene polymer. And reacting with the compound described in 1.   A modified conjugated diene polymer obtained by the method according to claim 11.