JP6769261B2 - Method for Producing Modified Conjugated Diene Polymer, Rubber Composition, Modified Conjugated Diene Polymer - Google Patents

Description

The present invention relates to a modified conjugated diene polymer, a rubber composition, etc., in which a conjugated diene polymer using a polymerization catalyst composed of a rare earth metal compound or an alkali metal compound is modified with a quinazoline derivative.

Conventionally, as a rubber for an automobile tire, a rubber composition containing polybutadiene rubber (BR) or styrene-butadiene rubber (SBR) as a main component and a natural rubber or the like as a main component has been used.

In addition, conventionally, rubber compositions containing polybutadiene rubber (BR) or styrene-butadiene rubber (SBR) as the main component and other natural rubbers, etc., make the best use of their characteristics and are mainly used as tire materials and crawler type running. It is industrially produced and used as a crawler of an apparatus, an industrial rubber belt, and the like (Patent Documents 1 and 2).

In recent years, as a material for tires, both fuel efficiency and wear resistance have been required. That is, it is desired to develop a rubber material having a small rolling resistance (that is, a small tan δ in a high temperature region) and excellent wear resistance.

Japanese Unexamined Patent Publication No. 2007-23266 Japanese Unexamined Patent Publication No. 2004-346220 Japanese Patent Application Laid-Open No. 6-228221 Japanese Unexamined Patent Publication No. 2000-8617 JP-A-63-139902 Japanese Unexamined Patent Publication No. 63-278946 JP-A-63-278947 Japanese Unexamined Patent Publication No. 2001-139633 Japanese Unexamined Patent Publication No. 2001-139634 JP-A-2002-30110

For example, it is possible to improve fuel efficiency (that is, to reduce tan δ) by increasing the elastic modulus of polybutadiene rubber (BR), but there is a problem that various physical properties such as wear resistance deteriorate. ..

Many proposals have been made so far for polymerization catalysts of conjugated diene such as 1,3-butadiene and isoprene, and some of them have been industrialized. For example, as a method for producing a conjugated diene polymer having a high cis-1,4 structure, a combination of a compound such as titanium, cobalt, nickel or neodymium and organoaluminum is often used.

Polymerization of conjugated diene catalyzed by Group 3 elements of the Periodic Table is known, and various polymerization methods have been proposed so far. For example, Patent Document 3 discloses a carrier-supported solid catalyst for (co) polymerization of a conjugated diene in which at least one compound among metals having atomic numbers 57 to 71 or 92 is supported on a carrier.

As an example of modifying a high cisdiene rubber, Patent Document 4 states that cis-1,4-polybutadiene is produced using a titanium compound having a cyclopentadienyl skeleton as a catalyst, and then 4,4'-bis (diethylamino). ) A method of reacting and modifying benzophenone has been disclosed, but since the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is extremely small, less than 1.5, there is a problem in processability. There is.

Patent Documents 5 to 7 disclose a method for producing a modified diene-based rubber by reacting a diene-based rubber having an active alkali metal terminal with a nitroamino compound, a nitro compound, a nitroalkyl compound, or the like. However, those using a quinazoline derivative as a denaturing agent are not described.

Patent Documents 8 to 10 disclose a method of producing polybutadiene and then reacting it with an amine compound, an imide compound, a quinone compound, a thiazole compound, a sulfenamide compound, or the like to modify it. Those using a quinazoline derivative as a modifier are not described.

An object of the present invention is to provide a modifying agent for a quinazoline derivative, a modified conjugated diene polymer synthesized by a catalyst that is relatively easy to handle, a rubber composition containing them, and the like.

The present inventor has made the present invention as a result of diligent research to solve the above problems. That is, the present invention is as follows.

1. 1. Obtained from (A) rare earth metal compounds, (B) organic metal compounds of elements selected from Group 2, Group 12, and Group 13 of the Periodic Table, and (C) ionic compounds consisting of non-coordinating anions and cations. A modified conjugated diene polymer obtained by modifying a conjugated diene compound obtained by polymerizing a conjugated diene compound with a quinazoline derivative (D).

2. A modified conjugated diene polymer obtained by modifying a conjugated diene polymer obtained by polymerizing a conjugated diene compound using an alkali metal compound with a quinazoline derivative (D).

3. 3. (D) The modified conjugated diene polymer according to Item 1 or Item 2, wherein the quinazoline derivative is a quinazoline derivative having a carbonyl group.

4. A rubber composition containing the modified conjugated diene polymer according to any one of Items 1 to 3.

5. A tire using the rubber composition according to Item 4.

6. A rubber belt using the rubber composition according to Item 4.

7. Obtained from (A) rare earth metal compounds, (B) organic metal compounds of elements selected from Group 2, Group 12, and Group 13 of the Periodic Table, and (C) ionic compounds consisting of non-coordinating anions and cations. A step of polymerizing a conjugated diene compound using a catalyst to obtain a conjugated diene polymer,
A step of modifying the conjugated diene polymer with the (D) quinazoline derivative, and
A method for producing a modified conjugated diene polymer, which comprises.

8. (A) A step of polymerizing a conjugated diene compound using an alkali metal compound to obtain a conjugated diene polymer, and
A step of modifying the conjugated diene polymer with the (D) quinazoline derivative, and
A method for producing a modified conjugated diene polymer, which comprises.

9. (D) The method for producing a modified conjugated diene polymer according to Item 7 or Item 8, wherein the quinazoline derivative is a quinazoline derivative having a carbonyl group.

10. Obtained from (A) rare earth metal compounds, (B) organic metal compounds of elements selected from Group 2, Group 12, and Group 13 of the periodic table, and (C) ionic compounds consisting of non-coordinating anions and cations. A modified conjugated diene obtained by a step of polymerizing a conjugated diene compound using a catalyst to obtain a conjugated diene polymer and a step of modifying the conjugated diene polymer with a (D) quinazoline derivative. Polymer.

11. It is characterized by being obtained by (A) a step of polymerizing a conjugated diene compound using an alkali metal compound to obtain a conjugated diene polymer, and a step of modifying the conjugated diene polymer with (D) a quinazoline derivative. Modified conjugated diene polymer.

This makes it possible to provide a modified conjugated diene polymer using a quinazoline derivative modifier and a catalyst that is relatively easy to handle, a rubber composition containing them, and the like, and is excellent in wear resistance and fuel efficiency.

For determining the degree of modification of the modified conjugated diene polymer of the present invention, it is a graph showing the relationship between the value of UV / RI (1 / Mn) × 10 4. Here, UV represents a peak area value obtained from the UV absorbance obtained by GPC measurement of the polymer, and RI represents a peak area value obtained from the differential refractive index. Mn represents a number average molecular weight.

The present invention comprises (A) a rare earth metal compound, (B) an organic metal compound of an element selected from Group 2, Group 12, and Group 13 of the periodic table, and (C) an ionic compound consisting of a non-coordinating anion and a cation. It is characterized by being obtained by a step of polymerizing a conjugated diene compound using a catalyst obtained from the compound to obtain a conjugated diene polymer, and a step of modifying the conjugated diene polymer with a (D) quinazoline derivative. Regarding modified conjugated diene polymers.

The present invention was obtained by a step of (A) polymerizing a conjugated diene compound using an alkali metal compound to obtain a conjugated diene polymer, and a step of modifying the conjugated diene polymer with (D) a quinazoline derivative. The present invention relates to a modified conjugated diene polymer.

Examples of the modified conjugated diene polymer using the rare earth metal compound obtained in the present invention include cis-1,4-polybutadiene having a cis-1,4 structure of 94% or more, more preferably 95% or more. The [η] of the modified conjugated diene polymer can be preferably controlled to 0.1 to 10, more preferably 1 to 7, and particularly preferably 1.5 to 5.

The number average molecular weight (Mn) of the modified conjugated diene polymer obtained in the present invention is preferably 1,000,000 to 1,000,000, more preferably 30,000 to 700,000, and particularly preferably 50,000 to 550000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the modified conjugated diene polymer using the rare earth metal compound is preferably 1.5 to 10, more preferably 1. 5 to 7, particularly preferably 1.5 to 4. If Mw / Mn is small, workability may deteriorate.

The modified conjugated diene polymer of the present invention may be blended alone or blended with other synthetic or natural rubbers, oil-expanded with process oil if necessary, and then fillers such as carbon black, vulcanizers and additions. Vulcanized by adding a vulcanization accelerator and other ordinary compounding agents, and used for rubber applications that require mechanical properties, wear resistance and low fuel consumption of tires, hoses, belts, and other various industrial products. Ru. It can also be used as a modifier for plastic materials.

(About denaturation)
The modifier used in the present invention is (D) a quinazoline derivative (a compound having a quinazoline ring), and a quinazoline derivative having a carbonyl group such as a quinazolinone derivative or a quinazolindione derivative is preferable.
Specific examples of the quinazoline derivative having a carbonyl group include 2-quinazolinone, 4-quinazolinone, 6,7-dimethoxyquinazoline-4-one, 2,4 (1H, 3H) -quinazolinedione, 6,7-dimethoxy-2. , 4 (1H, 3H) -quinazolinone, metaqualon, etaqualone, chloroqualone, afloqualone and the like. One of these denaturants may be used alone, or two or more thereof may be used in combination.
In addition, many of these denaturants are easily available, which is industrially advantageous.

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

The temperature of the reaction solution for the denaturation reaction is preferably in the range of -30 to 100 ° C, particularly preferably in the range of 10 to 90 ° C. If the temperature is too low, the denaturation reaction proceeds slowly, and if the temperature is too high, the polymer tends to gel. The time of 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 denaturation reaction time is too short, the reaction will not proceed sufficiently, and if the denaturation reaction time is too long, the polymer will easily gel.

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

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 the modifying group introduced into the modified conjugated diene polymer will be small, and a sufficient modification effect cannot be obtained. If the amount used is too large, the unreacted modifier remains in the modified conjugated diene polymer, and it takes time to remove the unreacted modifier, which is not preferable.

When carrying out the denaturation reaction, a denaturant is added after the polymerization reaction, and then a polymerization inhibitor is added to remove the solvent and unreacted monomers remaining in the reaction product by steam stripping method, vacuum drying method, etc. A method of removing with the above method, or a method of adding a denaturing agent after adding a polymerization inhibitor, and the like can be mentioned. Depending on the type of 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 the polymerization terminator is preferred is preferable.

The degree of modification of the modified conjugated diene polymer of the present invention is calculated by a method using gel permeation chromatography (GPC) measurement. This will be described in detail with reference to FIG. 1 by taking modified polybutadiene as an example.

In FIG. 1, the vertical axis shows the ratio of the peak area value UV obtained from the UV absorbance of the polymer obtained by GPC measurement to the peak area value RI obtained from the differential refractometer (RI), and the UV / RI value. ..

The abscissa axis represents values of ^{(1 / Mn) × 10 4} , Mn is the number average molecular weight. In FIG. 1, Li-BR (unmodified) is a plot of UV / RI values of the polymer itself obtained by polymerizing 1,3-butadiene by living anionic polymerization using a Li-based catalyst for polymers having different number average molecular weights Mn. Can be approximated as a straight line. Further, in Li-BR (denaturation), the UV / RI value of the polymer modified by reacting the polymerization terminal with a predetermined modifier after polymerization by living anionic polymerization using a Li-based catalyst is set to a different number average molecular weight Mn. It is a plot of the polymer and can be approximated as a straight line.

In the case of living anionic polymerization, one molecule of polymer and one molecule of denaturant react quantitatively. For example, let A be the difference between the UV / RI value of Li-BR (denatured) and the UV / RI value of Li-BR (unmodified) at a certain number average molecular weight (Mn1). This indicates the amount of change in the UV / RI value when one molecule of the denaturant reacts with the single molecule chain having the number average molecular weight (Mn1), and corresponds to the degree of modification of 1.0. The degree of modification of the modified polybutadiene can be calculated based on this value.

In the same manner as for Li-BR, UV / RI values were calculated for the modified polybutadiene of the present invention having a certain number average molecular weight (Mn1) and the unmodified polybutadiene obtained by the same method used for the modification. Assuming that the difference is B, the degree of modification of the modified polybutadiene of the present invention can be expressed by the following formula.

The degree of modification of the modified polybutadiene of the present invention is not particularly limited, but is preferably 0.1 or more, and more preferably more than 0.1. If the degree of denaturation is less than 0.1, the effect of denaturation may not be sufficient. At a preferred degree of modification, the interaction between the polar functional groups of the modifier (amino group, carbonyl group, hydroxyl group, etc.) and the polar functional groups of the filler (filler) enhances the dispersibility of the filler in the rubber composition. be able to.

(About conjugated diene polymer)
The rare earth metal compound or alkali metal compound which is the component (A) of the catalyst system of the present invention is not particularly limited as long as it is soluble in a non-polar organic solvent, and is a diketone type rare earth metal complex or a ketoimin type rare earth metal complex. , Diimine type rare earth metal complex, rare earth metal alkoxide, rare earth metal carboxylate, rare earth metal phosphate, organic alkali metal compound and the like.
Further, the rare earth metal compound is preferable in that high cis polybutadiene having a larger 1,4-cis structure can be obtained than the alkali metal compound. As the rare earth metal, scandium, ittrium, lantern, praseodymium, neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and the like are preferably used.

Preferably, it is a diketone type rare earth metal complex represented by the following general formula (1).

However, R ¹ , R ² , and R ³ represent hydrogen 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 ^{1 to} R ³ of the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an 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 Saturated hydrocarbon groups such as groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, and dodecyl groups, unsaturated hydrocarbon groups such as vinyl groups, 1-propenyl groups, and allyl groups, cyclohexyl. Examples include an alicyclic hydrocarbon group such as a group, a methylcyclohexyl group and an ethylcyclohexyl group, and an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a toluyl group and a phenethyl group. Further, 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 arbitrary positions are also included. Of these, saturated hydrocarbon groups having 1 to 12 carbon atoms are preferable, and saturated hydrocarbon groups having 1 to 6 carbon atoms are particularly preferable.

In R ^{1 to} R ³ of the general formula (1), R ² is preferably hydrogen or a substituent having 1 to 12 carbon atoms, and R ¹ and R ³ are preferably a substituent having 1 to 12 carbon atoms. In particular, R ² is preferably hydrogen or a substituent having 1 to 6 carbon atoms, and R ¹ and R ³ are preferably a substituent having 1 to 6 carbon atoms.

In R ^{1 to} R ³ of the general formula (1), R ² is preferably hydrogen or a saturated hydrocarbon group having 1 to 12 carbon atoms, and R ¹ and R ³ are preferably saturated hydrocarbon groups having 1 to 12 carbon atoms. In particular, R ² is preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ³ are preferably saturated hydrocarbon groups having 1 to 6 carbon atoms.

When the component (A) of the catalytic system of the present invention 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-heptandionat) lanthanum, tris (2, 2,6-Trimethyl-3,5-Heptandionat) Lantern, Tris (2,6-Dimethyl-3,5-Heptandionato) Lantern, Tris (3,5-Heptandionato) Lantern, Tris (2,4-Pentandionato) Lanterns, Tris (2,4-hexanedionat) lanterns, Tris (1,5-dicyclopentyl-2,4-pentanedionat) lanterns, Tris (1,5-dicyclohexyl-2,4-pentanedionat) lanterns And so on. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) lantern and tris (2,6-dimethyl-3,5-heptandionat) lantern are preferred.

Among gadolinium compounds, gadolinium (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium, tris (2,2,6-trimethyl-3,5-heptandionat) gadolinium, tris (2,6-dimethyl) -3,5-Heptandionato) Gadolinium, Tris (3,5-Heptandionato) Gadolinium, Tris (2,4-Pentane Zionato) Gadolinium, Tris (2,4-Hexandionato) Gadolinium, Tris (1,5-di) Cyclopentyl-2,4-pentandionato) gadolinium, tris (1,5-dicyclohexyl-2,4-pentandionato) gadolinium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium and tris (2,6-dimethyl-3,5-heptandionat) gadolinium are preferred.

Among praseodymium compounds, praseodymium (2,2,6,6-tetramethyl-3,5-heptandionat) praseodymium, tris (2,2,6-trimethyl-3,5-heptandionat) praseodymium, tris (2,6-dimethyl) -3,5-Heptandionato) Praseodymium, Tris (3,5-Heptandionato) Praseodymium, Tris (2,4-Pentane Zionato) Praseodymium, Tris (2,4-Hexanedionat) Praseodymium, Tris (1,5-di) Cyclopentyl-2,4-pentandionato) praseodymium, tris (1,5-dicyclohexyl-2,4-pentandionato) praseodymium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) praseodymium and tris (2,6-dimethyl-3,5-heptandionat) praseodymium are preferred.

Among neodymium compounds, tris (2,2,6,6-tetramethyl-3,5-heptandionat) neodymium, tris (2,2,6-trimethyl-3,5-heptandionat) neodymium, tris (2,6-dimethyl) -3,5-Heptangionato) Neodymium, Tris (3,5-Heptangionato) Lantern, Tris (2,4-Pentane Zionato) Neodymium, Tris (2,4-Hexane Zionato) Neodymium, Tris (1,5-ji) Cyclopentyl-2,4-pentanedionato) neodymium, tris (1,5-dicyclohexyl-2,4-pentangionato) neodymium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) neodymium and tris (2,6-dimethyl-3,5-heptandionat) neodymium are preferred.

Among terbium compounds, terbium (2,2,6,6-tetramethyl-3,5-heptandionat) terbium, tris (2,2,6-trimethyl-3,5-heptandionat) terbium, tris (2,6-dimethyl) -3,5-Heptandionato terbium, Tris (3,5-Heptandionato) terbium, Tris (2,4-pentanionato) terbium, Tris (2,4-hexanezonato) terbium, Tris (1,5-di) Cyclopentyl-2,4-pentandionato) terbium, tris (1,5-dicyclohexyl-2,4-pentandionato) terbium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) terbium and tris (2,6-dimethyl-3,5-heptandionat) terbium are preferred.

Among dysprosium compounds, dysprosium (2,2,6,6-tetramethyl-3,5-heptandionat) dysprosium, tris (2,2,6-trimethyl-3,5-heptandionat) dysprosium, tris (2,6-dimethyl) -3,5-Heptandionato) Dysprosium, Tris (3,5-Heptandionato) Dysprosium, Tris (2,4-Pentane Zionato) Dysprosium, Tris (2,4-Hexane Zionato) Dysprosium, Tris (1,5-di) Cyclopentyl-2,4-pentanedionato) dysprosium, tris (1,5-dicyclohexyl-2,4-pentanedionato) dysprosium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) dysprosium and tris (2,6-dimethyl-3,5-heptandionat) dysprosium are preferred.

Among yttrium compounds, yttrium (2,2,6,6-tetramethyl-3,5-heptandionat) yttrium, tris (2,2,6-trimethyl-3,5-heptandionat) yttrium, tris (2,6-dimethyl) -3,5-Heptandionato) Yttrium, Tris (3,5-Heptandionato) Yttrium, Tris (2,4-Pentane Zionato) Dysprosium, Tris (2,4-Hexane Zionato) Yttrium, Tris (1,5-di) Cyclopentyl-2,4-pentandionato) yttrium, tris (1,5-dicyclohexyl-2,4-pentandionato) yttrium and the like can be mentioned. Of these, tris (2,2,6,6-tetramethyl-3,5-heptandionat) yttrium and tris (2,6-dimethyl-3,5-heptandionat) yttrium are preferred.

The (A) diketone type rare earth metal complex may be used alone or in combination of two or more.

When the component (A) of the catalyst system of the present invention is a rare earth metal alkoxide, for example, in the case of a lanthanum compound, trimethoxylanthanum, triethoxylanthanum, trin-propoxylanthanum, triisopropoxylanthanum, tributoxylanthanum, tripentoxylanthanum, Examples include trihexyloxylanthanum. Of these, triisopropoxylantan is preferred.

Examples of the gadolinium compound include trimethoxy gadolinium, triethoxy gadolinium, tri n-propoxy gadolinium, triisopropoxy gadolinium, tributoxy gadolinium, tripentoxy gadolinium, and trihexyloxy gadolinium. Of these, triisopropoxygadolinium is preferred.

Examples of praseodymium compounds include trimethoxypraseodymium, triethoxypraseodymium, trin-propoxypraseodymium, triisopropoxypraseodymium, tributoxypraseodymium, tripentoxypraseodymium, trihexyloxypraseodymium, and the like. Of these, triisopropoxypraseodymium is preferred.

Examples of neodymium compounds include trimethoxyneodymium, triethoxyneodymium, trin-propoxyneodymium, triisopropoxyneodymium, tributoxyneodymium, tripentoxyneodymium, and trihexyloxyneodymium. Of these, triisopropoxyneodymium is preferred.

Examples of the terbium compound include trimethoxyterbium, triethoxyterbium, trin-propoxyterbium, triisopropoxyterbium, tributoxyterbium, tripentoxyterbium, and trihexyloxyterbium. Of these, triisopropoxyterbium is preferred.

Examples of the dysprosium compound include trimethoxydysprosium, triethoxydisprosium, trin-propoxydysprosium, triisopropoxydysprosium, tributoxydysprosium, trypentoxydysprosium, and trihexyloxydysprosium. Of these, triisopropoxydysprosium is preferred.

Examples of the yttrium compound include trimethoxyyttrium, triethoxyittrium, trin-propoxyittrium, triisopropoxyittrium, tributoxyittrium, tripentoxyittrium, trihexyloxyyttrium and the like. Of these, triisopropoxyyttrium is preferable.

The rare earth metal alkoxide compound (A) may be used alone or in combination of two or more.

When the component (A) of the catalytic system of the present invention is a rare earth metal carboxylate, for example, 2-ethylhexanoate neodymium, versatic acid neodymium, naphthenate neodymium, stearate neodymium, oleateneodymium, benzoate neodymium, picolin Examples include neodymium acid, neodymium formic acid, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, and the like.

Of these, neodymium 2-ethylhexanoate and neodymium versatic acid are preferable. The rare earth metal carboxylate (A) may be used alone or in combination of two or more.

When the component (A) of the catalytic system of the present invention is a rare earth metal phosphate, for example, neodymdi (2-ethylhexyl) phosphate, neodymdibutyl phosphate, neodymdipentyl phosphate, neodymdihexyl phosphate, etc. Neodim diheptyl phosphate, neodym dioctyl phosphate, neodymdi (1-methylheptyl) phosphate, neodymdidecyl phosphate, neodymjidodecyl phosphate, neodymdioctadecyl phosphate, neodymiorail phosphate Salt, neodymdiphenyl phosphate, neodymdi (p-nonylphenyl) phosphate, neodymium butyl (2-ethylhexyl) phosphate, neodym (1-methylheptyl) (2-ethylhexyl) phosphate, neodym (2-ethylhexyl) Ethylhexyl) (p-nonylphenyl) phosphate, and the like.

Of these, neodimdi (2-ethylhexyl) phosphate is preferred. The rare earth metal phosphate (A) may be used alone or in combination of two or more.

When the component (A) of the catalyst system of the present invention is an organic alkali metal compound, examples thereof include methyllithium, n-butyllithium, sec-butyllithium, and t-butyllithium. Of these, n-butyllithium is preferable. The organic alkali metal compound (A) may be used alone or in combination of two or more.

As the organometallic compound of the Group 2, Group 12, and Group 13 elements of the periodic table, which is the component (B) of the catalyst system in the present invention, for example, organomagnesium, organozinc, organoaluminum, and the like are used. Of these compounds, preferred are dialkylmagnesium, alkylmagnesium chloride, alkylmagnesium bromide, dialkylzinc, trialkylaluminum, dialkylaluminum chloride, dialkylaluminum bromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, alkylaluminum dichloride, Dialkylaluminum hydride and the like.

Specific compounds include alkylmagnesium halides such as methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, octylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, butylmagnesium iodide, and hexylmagnesium iodide. Can be mentioned.

Further, dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium and ethylhexylmagnesium can be mentioned.

Further, trialkyl zinc such as dimethylzinc, diethylzinc, diisobutylzinc, dihexylzinc, dioctylzinc, and didecylzinc can be mentioned.

Further, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum can be mentioned.

In addition, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride, and hydrided organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydrides are also available. Can be mentioned.

Moreover, you may use almoxane as the component (B). Examples of the alumoxane are those obtained by contacting an organoaluminum compound with a condensing agent, and examples thereof include a chain alumoxane represented by the general formula (-Al (R') O-) n, and 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, which is 5 or more, preferably 10 or more). .. Examples of R'include methyl, ethyl, propyl and isobutyl groups, with methyl groups being preferred. Examples of the organoaluminum compound used as a raw material of alumoxane include trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, and a mixture thereof.

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

Further, as the condensing agent, water is a typical example, but in addition to this, any one in which the above-mentioned trialkylaluminum undergoes a condensation reaction, such as adsorbed water such as an inorganic substance or a diol, can be mentioned.

These organometallic compounds of Group 2, Group 12, and Group 13 elements of the Periodic Table can be used alone, but two or more of them can be used in combination.

Conjugated diene can be polymerized using the catalyst described above, and the obtained conjugated diene polymer has (1) hydrogen, (2) hydrogenated metal compound, and (3) hydrogenated organic metal as the molecular weight modifier. A compound selected from the compound can be used.

Examples of the (2) metal hydride compound of the molecular weight modifier in the present invention include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, and German. , Borane boron hydride, sodium hydride, lithium aluminum hydride, sodium hydride, and the like.

Further, as the (3) hydrogenated organic metal compound of the molecular weight modifier in the present invention, alkylborans such as methylboran, ethylboran, propylborane, butylboran and phenylboran, dimethylboran, diethylboran, dipropylboran, dibutylboran and diphenyl Dialkylboran such as borane, methylaluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, alkylaluminum dihydride such as phenylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, Dialkylaluminum hydride such as dibutylaluminum hydride, diphenylaluminum hydride, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane , Tributylsilane, silanes such as triphenylsilane, methylgerman, ethylgerman, propylgerman, butylgerman, phenylgerman, dimethylgerman, diethylgerman, dipropylgerman, dibutylgerman, diphenylgerman, trimethylgerman, triethylgerman, tri Germans such as propylgerman, tributylgerman, and triphenylgerman, and the like can be mentioned.

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

An ionic compound composed of a non-coordinating anion and a cation may be added to the catalyst system of the present invention as the component (C). This is necessary when the component (A) of the catalyst system of the present invention is a rare earth metal compound. Examples of non-coordinating anions include tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, and tetrakis (pentafluoro). Phenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (kisilyl) borate, triphenyl (pentafluorophenyl) borate, tris (penta) Fluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarbundecaborate, tetrafluoroborate, hexafluorophosphate and the like can be mentioned.

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

Specific examples of the carbocation cation include trisubstituted carbocation cations such as triphenylcarbenium cation and tri-substituted phenylcarbenium cation. Specific examples of the tri-substituted phenylcarbenium cation include tri (methylphenyl) carbenium cation and tri (dimethylphenyl) carbenium cation.

Specific examples of ammonium cations include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, N, N-dimethylanilinium cation, and N. , N-dialkylanilinium cations, N, N-2,4,6-pentamethylanilinium cations and other N, N-dialkylanilinium cations, di (isopropyl) ammonium cations, dicyclohexylammonium cations and other dialkylammonium cations Can be mentioned.

Specific examples of the phosphonium cation include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation and the like. Arylphosphonium cations can be mentioned.

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

Among them, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1'. -Dimethylpherosenium tetrakis (pentafluorophenyl) borate and the like are preferred. The ionic compound may be used alone, or two or more kinds may be used in combination.

The order of adding the catalyst components is not particularly limited.

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

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-Hexadien and the like can be mentioned. Of these, a conjugated diene compound monomer containing 1,3-butadiene as a main component 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) or solution polymerization using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent can be applied. Examples of the solvent in 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, and the above. Examples thereof include olefin compounds and olefin hydrocarbons such as cis-2-butene and trans-2-butene.

Of these, benzene, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is 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 even more preferably 10 minutes to 1 hour.

(Modified conjugated diene polymer composition)
The modified conjugated diene polymer composition of the present invention contains one or more kinds of modified conjugated diene polymers of the present invention, other than the modified conjugated diene polymer (α) of the present invention and (α). It is preferable to contain a diene polymer (β) and a rubber reinforcing agent (γ). The method for producing a modified conjugated diene polymer composition of the present invention is characterized by having a step of producing a modified conjugated diene polymer (α) by the above-mentioned method for producing a modified conjugated diene polymer of the present invention. is there.
Specifically, the modified conjugated diene polymer of the present invention may be blended alone or blended with other synthetic or natural rubbers, vulcanized with process oil if necessary, and then fillers such as carbon black. , Vulcanization agent, vulcanization accelerator, and other usual compounding agents are added to vulcanize, and the mechanical properties of tires, hoses, belts, crawler, and other various industrial products, wear resistance, fuel efficiency, etc. Can be used for rubber applications that require.

Further, the modified conjugated diene polymer of the present invention is used as a modifier for a plastic material, for example, impact-resistant polystyrene, that is, an impact-resistant polystyrene-based resin composition or a rubber-modified impact-resistant polystyrene-based resin composition. Can also be manufactured.

The mixing ratio of the modified conjugated diene polymer composition according to the present invention is preferably 90 to 5 parts by mass of the modified conjugated diene polymer (α) and 10 to 95 parts by mass of a diene polymer (β) other than (α). The rubber component (α) + (β) is 100 parts by mass, and the rubber reinforcing agent (γ) is 20 to 120 parts by mass.

As the diene-based polymer (β) other than (α) contained in the modified conjugated diene polymer composition, vulverable rubber is preferable, and specifically, natural rubber (NR) and ethylene propylene diene rubber (EPDM). , Diene rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), polyisoprene, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber, acrylonitrile-butadiene rubber, etc. Can be mentioned. Of these, NR and SBR are preferable. Further, in the case of SBR, solution-polymerized styrene-butadiene copolymer rubber (S-SBR) is particularly preferable, though not particularly limited. These rubbers may be used alone or in combination of two or more.

Examples of the rubber reinforcing agent (γ) used in the present invention include various inorganic reinforcing agents such as carbon black, silica, activated calcium carbonate, and ultrafine magnesium silicate. Of these, carbon black and silica are usually preferred. These rubber reinforcing agents may be used alone or in combination of two or more.

The carbon black preferably has a particle size of 90 nm or less and a dibutyl phthalate (DBP) oil absorption of 70 ml / 100 g or more, and examples thereof include FEF, FF, GPF, SAF, ISAF, SRF, and HAF.

Examples of silica include silicic acid-based fillers such as silicic acid anhydride, hydrous silicic acid, calcium silicate, and silicates such as aluminum silicate, in addition to silicon dioxide (represented by the general formula SiO ₂ ). Further, there are no particular restrictions on the aggregated state of silica such as dry silica, precipitation method silica, gel method silica, colloidal silica, and the production method such as wet method and dry method. These may be used alone or in combination of two or more. Wet silica having excellent wear resistance is preferable.

Further, a silane coupling agent can also be used as an additive. Silane coupling agent used as an additive, an organic silicon compound represented by the general formula ^{_{R 4 n SiR 5 4-n}} , R 4 is a vinyl group, an acyl group, an allyl group, allyloxy group, an amino group, an epoxy group, mercapto group, chloro group, alkyl group, phenyl group, hydrogen, a styryl group, a methacryl group, an acryl group, an organic group having 1 to 20 carbon atoms having a reactive group selected from the ureido group, R ⁵ is chlorine group , An alkoxy group, an acetoxy group, an isopropenoxy group, an amino group and the like, and n represents an integer of 1 to 3. The R ⁴ of the above silane coupling agent, those containing a vinyl group and / or a chloro group are preferable.

The amount of the silane coupling agent added is preferably 0.2 to 20 parts by mass, more preferably 3 to 15 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the filler such as silica. .. If it is less than the above range, it may cause scorch. Further, if it is more than the above range, it may cause deterioration of tensile characteristics and elongation.

The modified conjugated diene polymer composition according to the present invention can be obtained by kneading each of the above components using a commonly used Banbury, open roll, kneader, biaxial kneader or the like.

The modified conjugated diene polymer composition according to the present invention is usually used in the rubber industry such as a vulcanizing agent, a vulcanization aid, an antiaging agent, a filler, a process oil, zinc oxide, and stearic acid, if necessary. The compounding agent to be used may be kneaded.

As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide can be used. The vulcanizing agent is preferably blended in an amount of about 0.5 to 3 parts by mass with respect to 100 parts by mass of (α) + (β).

As the vulcanization aid, known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and the like can be used.

Examples of the antiaging agent include amine / ketone type, imidazole type, amine type, phenol type, sulfur type and phosphorus type.

Examples of the filler include inorganic fillers such as silica, calcium carbonate, basic magnesium carbonate, clay, lisage, and diatomaceous earth, and organic fillers such as carbon black, recycled rubber, and powdered rubber.

As the process oil, any of aromatic type, naphthenic type and paraffin type may be used.

The modified conjugated diene polymer composition obtained by the present invention is used for various rubber applications such as industrial products such as tires, anti-vibration rubbers, belts, hoses and seismic isolation rubbers, and footwear such as men's shoes, women's shoes and sports shoes. Can be used. In that case, it is preferable to blend the modified conjugated diene polymer of the present invention so as to contain 10% by weight or more. Further, the rubber-modified impact-resistant polystyrene-based resin composition can be used for various known molded products, but because of its excellent flame retardancy, impact resistance, and tensile strength, it is used in electrical / industrial applications, packaging materials, and housing. Suitable for related materials, materials for OA equipment, tools, daily necessities, etc. For example, it can be used in a wide range of applications such as housings for TVs, personal computers, air conditioners, exterior materials for office equipment such as copiers and quinazolinters, and food containers for frozen foods, lactic acid beverages, ice cream and the like.

(Rubber composition for tires and rubber composition for rubber belts)
The modified conjugated diene polymer composition of the present invention can be used as a rubber composition for tires and a rubber composition for rubber belts by adjusting the mixing ratios of (α) + (β) and the rubber reinforcing agent (γ), respectively. It can be preferably used.
The method for producing a tire of the present invention is a method for producing a tire containing a modified conjugated diene polymer, and includes a step of producing the modified conjugated diene polymer by the method for producing a modified conjugated diene polymer of the present invention described above. It is characterized by.
The rubber belt of the present invention uses the modified conjugated diene polymer composition of the present invention. The method for producing a rubber belt of the present invention is a method for producing a rubber belt containing a modified conjugated diene polymer, and includes a step of producing a modified conjugated diene polymer by the above-mentioned method for producing a modified conjugated diene polymer of the present invention. It is characterized by.

In the case of a rubber composition for tires, the rubber composition is a rubber component (α) + () composed of the modified conjugated diene polymer (α) of the present invention and a diene polymer (β) other than (α). It contains β) and a rubber reinforcing agent (γ), and preferably contains 30 to 80 parts by mass of the rubber reinforcing agent (γ) with respect to 100 parts by mass of the rubber component (α) + (β).

Further, in the case of a rubber composition for a rubber belt, the rubber composition is a rubber component (α) composed of the modified conjugated diene polymer (α) of the present invention and a diene polymer (β) other than (α). It contains + (β) and a rubber reinforcing agent (γ), and preferably contains 20 to 70 parts by mass of the rubber reinforcing agent (γ) with respect to 100 parts by mass of the rubber component (α) + (β). ..

The rubber composition for tires and the rubber composition for rubber belts according to the present invention contain a diene polymer (β) other than the modified conjugated diene polymer (α), and 90 to 5 parts by mass of the modified conjugated diene polymer (α). On the other hand, it is preferable to add 10 to 95 parts by mass of a diene polymer (β) other than the modified conjugated diene polymer (α).
The diene polymer (β) blended in the rubber composition for tires and the rubber composition for rubber belts according to the present invention is at least one of natural rubber, styrene-butadiene rubber (SBR), and polyisoprene. Is preferable.

Examples of the rubber reinforcing agent (γ) blended in the rubber composition for tires and the rubber composition for rubber belts according to the present invention include various carbon blacks, silica, activated calcium carbonate, ultrafine magnesium silicate, talc, mica and the like. Can be mentioned. Above all, it is preferable that at least one of carbon black and silica is used.

Examples based on the present invention will be specifically described below. The polymerization conditions, modification conditions and polymerization results are summarized in Table 1. The method for measuring physical properties is as follows.

Catalytic activity: The polymer yield (g) per 1 mmol of the central metal of the catalyst used in the polymerization reaction and 1 hour of the polymerization time. For example, when the catalyst is a lanthanum compound, the polymer yield (g) per 1 mmol of the lanthanum metal of the lanthanum compound used in the polymerization reaction and the polymerization time per hour.

(Evaluation of polybutadiene and modified polybutadiene)
Microstructure: Performed by infrared absorption spectrum analysis. The microstructure was calculated from the absorption intensity ratios of cis 734 cm ^-1 , transformer 967 cm ^-1 , and vinyl 910 cm ^-1 .

Number average molecular weight (Mn) and weight average molecular weight (Mw): Calibration performed by GPC (manufactured by Shimadzu Corporation) method using polystyrene as a standard substance and tetrahydrofuran as a solvent at a temperature of 40 ° C., and obtained from the obtained molecular weight distribution curve. The number average molecular weight and the weight average molecular weight were calculated by using a line.

Molecular weight distribution: Evaluated by Mw / Mn, which is a ratio of weight average molecular weight Mw and number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.

(Evaluation of composition)

Breaking strength: According to JIS K6252, Comparative Example B-1 shown in Table 4 was expressed as 100 as an exponential notation. The larger the index, the better.

Repulsion resilience: According to JIS K6255, repulsion resilience was measured at room temperature using a Dunlop tripsometer, and in Table 4, Comparative Example B-1 described was expressed as 100 as an exponential notation. The larger the index, the better.

Abrasion resistance (pico abrasion resistance): The pico abrasion resistance was measured according to the measurement method specified in JIS K6264-2, and in Table 4, Comparative Example B-1 described was expressed as 100 as an index. The larger the index, the better.

Fuel efficiency (tan δ (60 ° C.)): Using a viscoelasticity measuring device (GABO, EPLEXOR 100N), measure at a temperature range of −120 ° C. to 100 ° C., frequency of 16 Hz, dynamic strain of 0.3%, and 60 ° C. Tan δ in the above was used as an index of fuel efficiency. In Table 4, Comparative Example B-1 described is expressed as 100 as an exponential notation. The smaller the fuel consumption (tan δ), the better. The index in Table 4 is described so that the better the fuel efficiency, the larger the index.

(Example A-1)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 480 ml of a cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.6 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.0 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanthanum (La (dpm) ₃ ) was added, and then triphenyl. 10.0 ml of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerization at 20 ° C. for 20 minutes, 10.0 mL of an o-dichlorobenzene mixed solution (0.05 mol / L) of 6,7-dimethoxyquinazoline-4-one (DMQ) and triisobutylaluminum was added, and the mixture was added at the same temperature. A denaturation reaction was carried out for 10 minutes. Next, 5 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The degree of modification of the obtained modified polybutadiene was 0.84. Other polymerization results are shown in Table 1.

(Example A-2)
The experiment was carried out in the same manner as in Example A-1 except that the amount of triethylaluminum (TEAL) added in a cyclohexane solution (2 mol / L) was 3.0 ml and the polymerization time was 25 minutes. The polymerization results are shown in Table 1.

(Example A-3)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 530 ml of a cyclohexane solvent and 550 ml of butadiene was charged. Then 5.0 ml of a cyclohexane solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 4.4 ml of a toluene solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanthanum (La (dpm) ₃ ) was added, and then triphenyl. 11.0 ml of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerization at 20 ° C. for 20 minutes, 5.5 mL of an o-dichlorobenzene mixed solution (0.1 mol / L) of 6,7-dimethoxyquinazoline-2,4-dione (DMQDO) and triisobutylaluminum was added, and the same was added. The denaturation reaction was carried out at temperature for 10 minutes. Next, 5 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The polymerization results are shown in Table 1.

(Example A-4)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 240 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.5 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 2.0 ml of a cyclohexane solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) gadolinium (Gd (dpm) ₃ ) was added, and then triphenyl. 5.0 ml of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerization at 20 ° C. for 25 minutes, 5.0 mL of an o-dichlorobenzene mixed solution (0.05 mol / L) of 6,7-dimethoxyquinazoline-4-one (DMQ) and triisobutylaluminum was added, and at the same temperature. A denaturation reaction was carried out for 10 minutes. Next, 3 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The polymerization results are shown in Table 1.

(Reference example A-1)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 530 ml of a cyclohexane solvent and 550 ml of butadiene was charged. Then, 3.4 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.4 ml of a toluene solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanthanum (La (dpm) ₃ ) was added, and then triphenyl. 11.0 ml of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 20 minutes, 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturing agent to stop the polymerization reaction. Then, after releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Reference example A-2)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 480 ml of a cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.1 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 4.0 ml of a toluene solution (0.005 mol / L) of tris (2,2,6,6-tetramethyl-3,5-heptandionat) lanthanum (La (dpm) ₃ ) was added, and then triphenyl. 10.0 ml of a toluene solution (0.004 mol / L) of carbenium tetrakis (pentafluorophenyl) borate was added. After polymerizing at 20 ° C. for 25 minutes, 5 ml of an ethanol solution containing an antiaging agent was added without adding a denaturing agent to stop the polymerization reaction. Then, after releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

Since the modified polybutadiene of Examples A-1 to A-4 has a larger UV / RI value obtained by GPC analysis than the unmodified polybutadiene of Reference Examples A-1 to A-2, various modifiers bind to the polybutadiene. It is suggested that it is (denatured).

(Example B-1)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 450 ml of a cyclohexane solvent and 60 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.12 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerization at 80 ° C. for 15 minutes, 5.0 mL of an o-dichlorobenzene mixed solution (0.05 mol / L) of 6,7-dimethoxyquinazoline-4-one (DMQ) and triisobutylaluminum was added, and at the same temperature. A denaturation reaction was carried out for 10 minutes. Next, 5 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 70.3 g / L. Other polymerization results are shown in Table 2.

(Example B-2)
0.22 ml of n-butyllithium hexane solution (1.6 mol / L), o-dichlorobenzene mixed solution of 6,7-dimethoxyquinazoline-4-one (DMQ) and triisobutylaluminum (0.05 mol / L) Modified polybutadiene was synthesized in the same manner as in Example B-1 except that the volume was 7.5 mL. The yield was 71.9 g / L. Other polymerization results are shown in Table 2.

(Example B-3)
Hexane solution of n-butyllithium (1.6 mol / L) was made into 0.32 ml, and o-dichlorobenzene mixed solution of 6,7-dimethoxyquinazoline-4-one (DMQ) and triisobutylaluminum (0.05 mol / L). Modified polybutadiene was synthesized in the same manner as in Example B-1 except that the volume was 11.0 mL. The yield was 73.1 g / L. Other polymerization results are shown in Table 2.

(Example B-4)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 450 ml of a cyclohexane solvent and 60 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.14 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, the polymerization solution was cooled to 20 ° C. Then, 5.0 mL of an o-dichlorobenzene mixed solution (0.05 mol / L) of 6,7-dimethoxyquinazoline-2,4-dione (DMQDO) and triisobutylaluminum was added, and the denaturation reaction was carried out at the same temperature for 10 minutes. went. Next, 5 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover the modified polybutadiene. The recovered modified polybutadiene was then vacuum dried at 100 ° C. for 2 hours. The yield was 70.3 g / L. Other polymerization results are shown in Table 2.

(Example B-5)
A hexane solution of n-butyllithium (1.6 mol / L) in 0.32 ml, and an o-dichlorobenzene mixed solution of 6,7-dimethoxyquinazoline-2,4-dione (DMQDO) and triisobutylaluminum (0.05 mol / L) L) Modified polybutadiene was synthesized in the same manner as in Example B-4 except that the volume was 11.0 mL. The yield was 71.6 g / L. Other polymerization results are shown in Table 2.

(Comparative Example B-1)
The inside of the autoclave having an internal volume of 1.5 L was substituted with nitrogen, and a solution consisting of 450 ml of a cyclohexane solvent and 60 ml of butadiene was charged. Then, after raising the temperature to 80 ° C., 0.22 ml of a hexane solution (1.6 mol / L) of n-butyllithium was added. After polymerizing at 80 ° C. for 15 minutes, 5 ml of an ethanol solution containing an antiaging agent was added, the inside of the autoclave was released, and then ethanol was added to the polymerization solution to recover polybutadiene. The recovered modified polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The yield was 73.7 g / L. Other polymerization results are shown in Table 2.

(Comparative Example B-2)
Polybutadiene was synthesized in the same manner as in Comparative Example B-1 except that the amount of n-butyllithium hexane solution (1.6 mol / L) added was 0.30 ml. The yield was 74.2 g / L. Other polymerization results are shown in Table 2.

Since the modified polybutadiene of Examples B-1 to B-5 has a larger UV / RI value obtained by GPC analysis than the unmodified polybutadiene of Comparative Examples B-1 to B-2, various modifiers bind to the polybutadiene. It is suggested that it is (denatured).

(Example C-1)
Using modified polybutadiene synthesized according to Example A-1, natural rubber, carbon black (Diablack manufactured by Mitsubishi Chemical Co., Ltd.), zinc oxide, stearic acid, and antiaging agent (Sumitomo Chemical Co., Ltd.) were used in a plastomill according to the formulation shown in Table 3. Antigen 6C manufactured by Antigen Co., Ltd.) and oil (Viva Tec 400 manufactured by H & R Co., Ltd.) are added and kneaded, and then a vulcanization accelerator (Noxeller NS manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) and sulfur are added by roll. A compounded rubber was produced by carrying out the secondary compounding to be added. Further, this compounded rubber was molded according to the target physical properties, and the physical properties of the vulcanized product press-vulcanized at 150 ° C. were measured. Table 4 shows the results of measuring the physical properties of various formulations.

(Example C-2)
A compounded rubber was prepared in the same manner as in Example C-1 except that the modified polybutadiene synthesized according to Example A-2 was used instead of the modified polybutadiene synthesized according to Example A-2, and was molded and press vulcanized. The physical properties of the vulcanized product were measured. Table 4 shows the results of measuring the physical properties of various formulations.

(Example C-3)
A compounded rubber was prepared in the same manner as in Example C-1 except that the modified polybutadiene synthesized according to Example A-3 was used instead of the modified polybutadiene synthesized according to Example A-3, and was molded and press vulcanized. The physical properties of the vulcanized product were measured. Table 4 shows the results of measuring the physical properties of various formulations.

(Reference example C-1)
A compounded rubber was prepared in the same manner as in Example C-1 except that unmodified polybutadiene synthesized according to Reference Example A-1 was used instead of the modified polybutadiene synthesized according to Example A-1, and molded and press vulcanized. The physical properties of the vulcanized product were measured. Table 4 shows the results of measuring the physical properties of various formulations.

(Comparative Example C-1)
Formulated in the same manner as in Example C-1 except that JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation was used as the polybutadiene instead of the modified polybutadiene synthesized according to Example A-1. Rubber was prepared, molded, and press-vulcanized to measure the physical properties of the vulcanized product. Table 4 shows the results of measuring the physical properties of various formulations.

The formulation is shown in Table 3. The numerical values in Table 3 are parts by mass.

The numerical values in Table 4 are each item when each characteristic value of Comparative Example C-1 using JSR BR01 (polybutadiene polymerized using a Ni-based catalyst) manufactured by JSR Corporation is used as a reference (100). It is an index display for each. The larger the value, the better the characteristics.

As shown in Table 4, the compositions of Examples C-1 to C-3 using the modified polybutadienes obtained in Examples A-1 to A-3 are JSR BR01 (polybutadiene polymerized using a Ni-based catalyst). ) Is superior to the composition of Comparative Example C-1 in breaking strength, rebound resilience, abrasion resistance, and fuel efficiency (tan δ).

Further, as shown in Table 4, the composition of Examples C-1 to C-3 using the modified polybutadiene obtained in Examples A-1 to A-3 is Reference Example C-1 using unmodified polybutadiene. It is superior in breaking strength, rebound resilience, wear resistance, and fuel efficiency (tan δ) to the composition of.

Claims (9)

Obtained from (A) rare earth metal compounds, (B) organic metal compounds of elements selected from Group 2, Group 12, and Group 13 of the Periodic Table, and (C) ionic compounds consisting of non-coordinating anions and cations. A modified conjugated diene polymer obtained by modifying a conjugated diene compound obtained by polymerizing a conjugated diene compound with a quinazoline derivative (D). A modified conjugated diene polymer obtained by modifying a conjugated diene polymer obtained by polymerizing a conjugated diene compound using an alkali metal compound with a quinazoline derivative (D). (D) The modified conjugated diene polymer according to claim 1 or 2, wherein the quinazoline derivative is a quinazoline derivative having a carbonyl group. A rubber composition containing the modified conjugated diene polymer according to any one of claims 1 to 3. A tire using the rubber composition according to claim 4. A rubber belt using the rubber composition according to claim 4. Obtained from (A) rare earth metal compounds, (B) organic metal compounds of elements selected from Group 2, Group 12, and Group 13 of the Periodic Table, and (C) ionic compounds consisting of non-coordinating anions and cations. A step of polymerizing a conjugated diene compound using a catalyst to obtain a conjugated diene polymer,
A step of modifying the conjugated diene polymer with the (D) quinazoline derivative, and
A method for producing a modified conjugated diene polymer, which comprises. (A) A step of polymerizing a conjugated diene compound using an alkali metal compound to obtain a conjugated diene polymer, and
A step of modifying the conjugated diene polymer with the (D) quinazoline derivative, and
A method for producing a modified conjugated diene polymer, which comprises. (D) The method for producing a modified conjugated diene polymer according to claim 7 or 8, wherein the quinazoline derivative is a quinazoline derivative having a carbonyl group.