JP2017082136A - Manufacturing method of polymer catalyst composition, manufacturing method of conjugated diene polymer and manufacturing method of modified conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polymer catalyst composition high in catalyst activity during polymerization and capable of enhancing the terminal modification rate of a polymer.SOLUTION: There is provided a manufacturing method of a polymer catalyst composition including a process (a) of reacting only a rare earth element compound represented by the following general formula (a-1):M-(AQ)(AQ)(AQ), where M is scandium, yttrium or lanthanoid element, AQ, AQand AQare functional groups which may be the same or different, A is nitrogen, oxygen or sulfur and has at least one M-A bond, ((A) component), at least one compound selected from a group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene and substituted or unsubstituted fluorene ((B) component) and an organic metal compound represented by the general formula (c-1) ((C) component) to obtain a reaction mixture.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a polymerization catalyst composition, a method for producing a conjugated diene polymer, and a method for producing a modified conjugated diene polymer.

  In general, it is important for rubber products such as tires to have durability such as high fracture resistance, wear resistance, crack growth resistance, etc. It is essential to use an excellent rubber component. As such a rubber component, natural rubber is known. However, since the price of natural rubber is soaring, there is a demand for the development of a synthetic rubber having properties equivalent to those of natural rubber that can be replaced by natural rubber.

  Examples of such synthetic rubber include conjugated diene polymers obtained by polymerizing conjugated dienes as monomers, such as polybutadiene and polyisoprene. In addition to the conjugated diene polymer, a modified conjugated diene polymer having a terminal modified with an arbitrary modifier during polymerization for the purpose of imparting desired performance such as heat resistance and weather resistance. Examples include coalescence.

  Here, in these conjugated diene polymers and modified conjugated diene polymers, it is considered that the higher the amount of cis-1,4 bonds in the unit derived from the conjugated diene, the higher the durability of the rubber product. (In fact, natural rubber has almost 100% cis-1,4 bond content). In view of this, various research and development have been conducted on polymers having a high cis-1,4 bond amount and catalysts used for the preparation thereof.

  For example, in Patent Document 1, a polymerization catalyst composition comprising at least one monomer selected from the group consisting of a conjugated diene monomer and a nonconjugated olefin in addition to a rare earth element-containing compound and at least one anion source. It has been reported that a conjugated diene polymer having a high amount of cis-1,4 bonds can be produced by using such a polymer material.

  Further, for example, in Patent Document 2, by using a catalyst obtained from an yttrium compound represented by a specific formula, an ionic compound composed of a non-coordinating anion and a cation, and an organometallic compound of a specific element, It is disclosed that a conjugated diene polymer having a high amount of cis-1,4 bonds can be produced.

JP 2013-194099 A JP 2011-105923 A

  However, when the present inventors examined, it turned out that the said conventional polymerization catalyst composition and catalyst have room for improvement from a viewpoint of the high catalyst activity.

  In addition, the conventional polymerization catalyst composition and catalyst described above have room for improvement in terms of the high terminal modification rate of the polymer when a modifying group is used in combination to introduce a modifying group to the terminal of the living polymer. I found out.

Accordingly, an object of the present invention is to provide a method for producing a polymerization catalyst composition that has high catalytic activity during polymerization and can increase the terminal modification rate of the polymer.
Another object of the present invention is to provide a method for producing a conjugated diene polymer that can polymerize a conjugated diene monomer with high catalytic activity.
Furthermore, an object of the present invention is to provide a method for producing a modified conjugated diene polymer, which can polymerize a conjugated diene monomer with high catalytic activity and obtain a modified conjugated diene polymer having a high terminal modification rate. There is also to provide.

The gist of the present invention for achieving the above object is as follows.
The method for producing the polymerization catalyst composition of the present invention comprises:
The following general formula (a-1):
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) (a-1)
[Wherein M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur; Yes; provided that it has at least one M-A bond] (hereinafter also referred to simply as “rare earth element compound”) (component (A)),
At least one compound selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene (component (B));
The following general formula (c-1):
YR ¹ _a R ² _b R ³ _c (c-1)
[In the formula, Y is a Group 1 of the Periodic Table, Group 2, a metal element selected from the group consisting of group 12 and group 13 elements of; R ¹ and R ² are 1 carbon atoms 10 hydrocarbon groups or hydrogen atoms, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms; provided that R ¹ , R ² and R ³ may be the same or different from each other; Further, when Y is a group 1 metal element of the periodic table, a is 1 and b and c are 0, and Y is a group 2 or group 12 metal element of the periodic table. In some cases, a and b are 1 and c is 0, and when Y is a group 13 metal element of the periodic table, a, b and c are 1.] Step (a) of obtaining a reaction mixture by reacting only with an organometallic compound (hereinafter, sometimes simply referred to as “organometallic compound”) (component (C))
It is characterized by including.
By this method, it is possible to prepare a polymerization catalyst composition that has high catalytic activity during polymerization and can increase the terminal modification rate of the polymer.

  The method for producing a polymerization catalyst composition of the present invention further includes a step (b) in which only the reaction mixture obtained in the step (a) is reacted with an aluminoxane compound (component (D)) to obtain a mixture. It is preferable. Thereby, since an aluminoxane compound functions as a co-catalyst, the catalyst activity at the time of superposition | polymerization can be improved more.

Moreover, the method for producing a polymerization catalyst composition of the present invention comprises a step (c) in which only the reaction mixture obtained in the step (b) is reacted with the halogen compound (component (E)) to obtain a reaction mixture. Furthermore, it is preferable to include.
As a result, when the conjugated diene monomer is polymerized, the amount of cis-1,4 bonds in the conjugated diene polymer can be increased, and the reaction of the aluminoxane compound that can function as a promoter is inhibited by the halogen compound. Can be suppressed.

  On the other hand, in the method for producing a polymerization catalyst composition of the present invention, the reaction mixture obtained in the step (a) is reacted only with the halogen compound (component (E)) to obtain a reaction mixture (d). It is also preferable to further contain. Thereby, when polymerizing a conjugated diene monomer, the amount of cis-1,4 bonds in the conjugated diene polymer can be increased.

  On the other hand, in the method for producing a polymerization catalyst composition of the present invention, the reaction mixture obtained in the step (d) is reacted with only the aluminoxane compound (component (D)) to obtain a reaction mixture (e ) May further be included. Thereby, catalyst activity can be improved.

  And the manufacturing method of the polymerization catalyst composition of this invention makes only the reaction mixture obtained by the said process (a), an aluminoxane compound ((D) component), and a halogen compound ((E) component) react, It is also preferable to further include the step (f) of obtaining a reaction mixture. Thereby, the controllability of polymerization can be improved.

In the method for producing a polymerization catalyst composition of the present invention, it is preferable that R ¹ , R ² and R ³ are not all the same in the general formula (c-1) from the viewpoint of enhancing the catalytic activity.

In the production method of the polymerization catalyst composition of the present invention, from the viewpoint of enhancing the effect of improving the catalytic activity, the aluminoxane compound (component (D)) is represented by the general formula (d-2):
_{- (Al (CH 3) x} (i-C 4 H 9) y O) m - ··· (d-2)
[Wherein x + y is 1; m is 5 or more] or a modified aluminoxane represented by the general formula (d-3):
_{- (Al (CH 3) 0.7} (i-C 4 H 9) 0.3 O) k - ··· (d-3)
A modified aluminoxane represented by the formula [wherein k is 5 or more] is preferable.

  The method for producing a conjugated diene polymer of the present invention is characterized by using a polymerization catalyst composition prepared by the method for producing a polymerization catalyst composition of the present invention. By this method, the conjugated diene monomer can be polymerized with high catalytic activity.

  In the method for producing a conjugated diene polymer of the present invention, 1,3-butadiene and / or isoprene are preferably used as monomers from the viewpoint of improving various performances of rubber products such as rubber compositions and tires.

  The method for producing a modified conjugated diene polymer of the present invention is characterized by using a polymerization catalyst composition prepared by the method for producing a polymerization catalyst composition of the present invention. By this method, a conjugated diene monomer can be polymerized with high catalytic activity, and a modified conjugated diene polymer having a high terminal modification rate can be obtained.

  In the method for producing a modified conjugated diene polymer of the present invention, 1,3-butadiene and / or isoprene are preferably used as monomers from the viewpoint of improving various performances of rubber products such as rubber compositions and tires. .

ADVANTAGE OF THE INVENTION According to this invention, the catalyst activity at the time of superposition | polymerization is high, and the manufacturing method of the polymerization catalyst composition which can raise the terminal modification rate of a polymer can be provided.
Moreover, according to this invention, the manufacturing method of the conjugated diene polymer which can superpose | polymerize a conjugated diene monomer with high catalyst activity can be provided.
Furthermore, according to the present invention, there is provided a method for producing a modified conjugated diene polymer, which can polymerize a conjugated diene monomer with high catalytic activity and obtain a modified conjugated diene polymer having a high terminal modification rate. Can be provided.

It is a figure which can be used in order to obtain | require the terminal modification rate of a polymer.

  Hereinafter, embodiments of the method for producing the polymerization catalyst composition of the present invention, the method for producing the conjugated diene polymer of the present invention, and the method for producing the modified conjugated diene polymer of the present invention will be described in detail.

(Method for producing polymerization catalyst composition)
The method for producing a polymerization catalyst composition according to an example of the present invention includes a rare earth element compound (component (A)), a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, and a substituted or unsubstituted fluorene. Only at least one selected compound (hereinafter sometimes referred to as “compound having a cyclopentadiene skeleton” in this specification) (component (B)) and an organometallic compound (component (C)) And a step (a) of obtaining a reaction mixture, and optionally a step of reacting the reaction mixture obtained in the step (a) with another compound to obtain a reaction mixture. .

The conventional polymerization catalyst composition or catalyst described above has room for improvement from the viewpoint of high catalytic activity, and thus the efficiency of the polymerization reaction. In addition, a modifier is used in combination with a modifying group at the end of the living polymer. In the case of introduction, there is room for improvement in terms of the high terminal modification rate of the polymer and, in turn, sufficient imparting of the desired performance to the polymer. Therefore, the present inventors have intensively studied and specified the rare earth element compound as the component (A) and the cyclopentadiene skeleton as the component (B) that can function as a conjugated ligand in the reaction system. A polymerization catalyst composition in which a reaction mixture obtained by reacting only a compound having an organic compound and a specified organometallic compound as component (C) that can function as an active species in the reaction system is effectively aged As a product, it has been found that the catalyst activity at the time of polymerization can be increased and the terminal modification rate of the polymer can be increased.
In the present specification, “only react” refers indirectly to mixing only the target component and an arbitrary solvent and holding at a constant temperature within a range of 0 to 100 ° C. for 30 minutes to 24 hours. .
Here, the reason why the above-described effect is achieved is not clear, but the influence of impurities in the subsequent process is minimized by sufficiently reacting the components (A), (B) and (C). It is presumed to be due to the action of being limited to the limit.

On the other hand, when the reaction is performed using, for example, an aluminoxane compound described later together with the components (A), (B), and (C), the compound acts as an impurity and the polymerization activity is reduced. It is believed that the desired polymerization catalyst composition cannot be obtained.
Moreover, when it reacts with the said (A) component, (B) component, and (C) component, for example using the halogen compound which is mentioned later, since the said compound acts as an impurity and superposition | polymerization activity falls. It is believed that the desired polymerization catalyst composition cannot be obtained.
Hereinafter, the steps that can be included in the method for producing a polymerization catalyst composition of an example of the present invention will be specifically described.

-Step (a)-
Step (a) is, as described above, at least one selected from the group consisting of rare earth element compounds (component (A)), substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene. In this step, only the seed compound (component (B)) is reacted with the organometallic compound (component (C)) represented by the general formula (c-1) to obtain a reaction mixture.

The holding temperature when only the component (A), the component (B), and the component (C) are reacted needs to be 0 ° C to 100 ° C, and preferably 15 ° C to 50 ° C. If the holding temperature is less than 0 ° C., sufficient reaction may not be performed and a desired reaction mixture may not be obtained. On the other hand, if the holding temperature exceeds 100 ° C., the catalyst activity may be deteriorated.
The retention time when only the component (A), the component (B), and the component (C) are reacted needs to be 30 minutes to 24 hours, and preferably 30 minutes to 12 hours. If the holding time is less than 30 minutes, a sufficient reaction may not be performed, and a desired reaction mixture may not be obtained. On the other hand, if the holding time is longer than 24 hours, the polymerization catalyst composition has a sufficient aging effect. May not be obtained.

-Step (b)-
In the method for producing a polymerization catalyst composition according to an example of the present invention, after the step (a), the reaction mixture obtained in the step (a) is reacted only with the aluminoxane compound (component (D)) to react. It is preferable to further include the step (b) of obtaining a mixture. Thereby, since an aluminoxane compound functions as a co-catalyst, the catalyst activity at the time of superposition | polymerization can be improved more.
It should be noted that step (b) cannot be performed when the method for producing a polymerization catalyst composition of an example of the present invention includes step (d) or step (f) described later.

The holding temperature when only the reaction mixture obtained in step (a) is reacted with the aluminoxane compound (component (D)) is preferably 0 ° C. to 50 ° C. from the viewpoint of further improving the catalytic activity during the polymerization. 15 to 30 ° C. is more preferable.
The retention time when only the reaction mixture obtained in step (a) is reacted with the aluminoxane compound (component (D)) is 30 minutes to 10 hours from the viewpoint of efficiently improving the catalytic activity during polymerization. Is preferable, and 30 minutes to 4 hours is more preferable.

-Step (c)-
When the production method of the polymerization catalyst composition of an example of the present invention includes the step (b), after the step (b), the reaction mixture obtained in the step (b) and the halogen compound (component (E)) It is preferable to further include a step (c) of reacting only with a) to obtain a reaction mixture. Thereby, the amount of cis-1,4 bonds of the conjugated diene polymer in the case of polymerizing the conjugated diene monomer can be increased. Moreover, by reacting the aluminoxane compound (component (D)) and then reacting with the halogen compound (component (E)), the possibility that the reaction of the aluminoxane compound that can function as a promoter is inhibited by the halogen compound is suppressed. can do.
It should be noted that step (c) cannot be performed when the method for producing a polymerization catalyst composition of an example of the present invention does not include step (b).

The holding temperature when only the reaction mixture obtained in the step (b) is reacted with the halogen compound (component (E)) is 0 from the viewpoint of increasing the amount of cis-1,4 bonds of the conjugated diene polymer. ° C to 50 ° C is preferable, and 15 ° C to 30 ° C is more preferable.
As a retention time when only the reaction mixture obtained in the step (b) is reacted with the halogen compound (component (E)), a viewpoint of efficiently increasing the amount of cis-1,4 bonds of the conjugated diene polymer. Therefore, 30 minutes to 10 hours are preferable, and 30 minutes to 2 hours are more preferable.

-Step (d)-
Moreover, in the manufacturing method of the polymerization catalyst composition of an example of this invention, it replaces with the process (b) mentioned above, and after the process (a), the reaction mixture obtained by the said process (a), and a halogen compound ( It is also preferable to further include a step (d) in which only the component (E) is reacted to obtain a reaction mixture. Thereby, the amount of cis-1,4 bonds of the conjugated diene polymer in the case of polymerizing the conjugated diene monomer can be increased.
It should be noted that step (d) cannot be performed when the method for producing a polymerization catalyst composition of an example of the present invention includes step (b) or step (f) described later.

The holding temperature when only the reaction mixture obtained in the step (a) is reacted with the halogen compound (component (E)) is 0 from the viewpoint of increasing the amount of cis-1,4 bonds in the conjugated diene polymer. ° C to 50 ° C is preferable, and 15 ° C to 30 ° C is more preferable.
The retention time when only the reaction mixture obtained in step (a) is reacted with the halogen compound (component (E)) is 30 from the viewpoint of increasing the amount of cis-1,4 bonds in the conjugated diene polymer. Minutes to 10 hours are preferable, and 30 minutes to 2 hours are more preferable.

-Step (e)-
When the production method of the polymerization catalyst composition of an example of the present invention includes the step (d), after the step (d), the reaction mixture obtained in the step (d) and the aluminoxane compound ((D) component) And (e) may be further included to obtain a reaction mixture. Thereby, catalyst activity can be improved.
It should be noted that step (e) cannot be performed when the method for producing a polymerization catalyst composition of an example of the present invention does not include step (d).

The holding temperature when only the reaction mixture obtained in the step (d) is reacted with the aluminoxane compound (component (D)) is preferably 0 ° C. to 50 ° C. from the viewpoint of further improving the catalytic activity during the polymerization. 15 to 30 ° C. is more preferable.
The retention time when reacting only the reaction mixture obtained in step (d) and the aluminoxane compound (component (D)) is 30 minutes to 10 hours from the viewpoint of efficiently improving the catalytic activity during polymerization. Is preferable, and 30 minutes to 2 hours is more preferable.

-Step (f)-
And in the manufacturing method of the polymerization catalyst composition of an example of this invention, it replaced with the process (b) mentioned above and the process (d) mentioned above, and obtained by the said process (a) after the process (a). It is also preferable to further include a step (f) in which only the reaction mixture is reacted with the aluminoxane compound (component (D)) and the halogen compound (component (E)) to obtain a reaction mixture. Thereby, the controllability of polymerization can be improved.
It should be noted that step (f) cannot be performed when the method for producing a polymerization catalyst composition of an example of the present invention includes step (b) or step (d).

As a holding temperature when only the reaction mixture obtained in the step (a) is reacted with the aluminoxane compound (component (D)) and the halogen compound (component (E)), the viewpoint of improving the catalytic activity at the time of polymerization. Therefore, 0 to 50 ° C is preferable, and 15 to 30 ° C is more preferable.
As a retention time when only the reaction mixture obtained in the step (a) is reacted with the aluminoxane compound (component (D)) and the halogen compound (component (E)), the viewpoint of improving the catalytic activity during polymerization. Therefore, 30 minutes to 10 hours are preferable, and 30 minutes to 2 hours are more preferable.

In each of the above steps, each component and an arbitrary solvent are usually added and mixed in a container such as an examiner, and it is visually confirmed that each component is dissolved, and then held at a predetermined temperature for a predetermined time (ie, And reacting only the added components). The mixing method is not particularly limited and may be appropriately selected depending on the purpose. Specifically, manual shaking of the container may be mentioned. Moreover, at the time of holding | maintenance for a predetermined time at predetermined temperature, it can be left still, without performing stirring etc.
When a solvent is used in each of the above steps, such a solvent is not particularly limited as long as it is inert, and may be any one, and examples thereof include n-hexane, cyclohexane, or a mixture thereof. Moreover, as such a solvent, it is preferable to use a solvent appropriately subjected to purification operations such as distillation, degassing, and freeze-drying.
The above steps are preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

  Next, components that can be blended in the polymerization catalyst composition of an example of the present invention will be specifically described.

-Rare earth element compound (component (A))-
The component (A) is represented by the following general formula (a-1):
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) (a-1)
[Wherein M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur; Yes; provided that it has at least one M-A bond]. Here, the lanthanoid elements are specifically lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. The component (A) has at least one M-A bond. The component (A) is a component that can improve the catalytic activity in the reaction system, shorten the reaction time, and increase the reaction temperature.
In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  As M, gadolinium is particularly preferable from the viewpoint of enhancing catalyst activity and reaction controllability.

When A is nitrogen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, NQ ¹ , NQ ² and NQ ³ ) include an amide group.
Examples of the amide group include aliphatic amide groups such as dimethylamide group, diethylamide group, and diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineobylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neobutenylphenylamide group, 2-isopropyl-6-neobutenylphenyl Examples include amide groups, arylamide groups such as 2,4,6-tert-butylphenylamide groups; bistrialkylsilylamide groups such as bistrimethylsilylamide groups. In particular, from the viewpoint of solubility in aliphatic hydrocarbons, bis A trimethylsilylamide group is preferred.
The said functional group may be used individually by 1 type, and may be used in combination of 2 or more type.

When A is oxygen, the rare earth element compound represented by the general formula (a-1) (that is, M- (OQ ¹ ) (OQ ² ) (OQ ³ )) is not particularly limited. Formula (I):
(RO) ₃ M (I)
A rare earth alcoholate represented by the following formula (I):
(R-CO ₂ ) ₃ M (II)
Rare earth carboxylates represented by the formula: Here, in each formula of the following compounds (I) to (II), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.

When A is sulfur, the rare earth element compound represented by the general formula (a-1) (that is, M- (SQ ¹ ) (SQ ² ) (SQ ³ )) is not particularly limited. Formula (III):
(RS) ₃ M (III)
A rare earth alkylthiolate represented by the following formula (IV):
(R-CS ₂ ) ₃ M (IV)
The compound represented by these is mentioned. Here, in each formula of the following compounds (III) to (IV), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.

-Compound having a cyclopentadiene skeleton (component (B))-
The component (B) is a compound having a cyclopentadiene skeleton, that is, at least one compound selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, substituted or unsubstituted fluorene.
In addition, the said (B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  In particular, the compound having a cyclopentadiene skeleton is preferably a substituted cyclopentadiene, a substituted indene or a substituted fluorene, and more preferably a substituted indene. Thereby, since the bulk height as a polymerization catalyst increases advantageously, reaction time can be shortened and reaction temperature can be made high. In addition, since the compound having a cyclopentadiene skeleton has many conjugated electrons, the catalytic activity in the reaction system can be further improved.

  Examples of the substituted cyclopentadiene include pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene, and the like.

  Examples of the substituted indene include 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, 3-benzyl-2-phenyl-1H-indene, and 1-benzyl. -1H-indene and the like are mentioned, and 3-benzyl-1H-indene and 1-benzyl-1H-indene are particularly preferable from the viewpoint of reducing the molecular weight distribution.

  Examples of the substituted fluorene include trimethylsilylfluorene and isopropylfluorene.

-Organometallic compound (component (C))-
The component (C) is represented by the general formula (c-1):
YR ¹ _a R ² _b R ³ _c (c-1)
[In the formula, Y is a Group 1 of the Periodic Table, Group 2, a metal element selected from the group consisting of group 12 and group 13 elements of; R ¹ and R ² are 1 carbon atoms 10 hydrocarbon groups or hydrogen atoms, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms; provided that R ¹ , R ² and R ³ may be the same or different from each other; When Y is a Group 1 metal element, a is 1 and b and c are 0. When Y is a Group 2 or Group 12 metal element, a and b are used. Is 1 and c is 0, and when Y is a Group 13 metal element, a, b, and c are 1].
Here, from the viewpoint of enhancing the catalytic activity, in the formula (c-1), it is preferable that all of R ¹ , R ² and R ³ are not the same.

Specifically, the component (C) is represented by the general formula (c-2):
AlR ⁴ _a R ⁵ _b R ⁶ _c (c-2)
[Wherein, R ⁴ and R ⁵ are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom; R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms; R ⁴ , R ⁵ and R ⁶ May be the same or different from each other].

Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, include isobutyl aluminum dihydride and the like, particularly, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, preferably diisobutylaluminum hydride, more particularly, diisobutylaluminum hydride are preferred.
The said organoaluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.

-Aluminoxane compound (component (D))-
(D) A component is a compound obtained by making an organoaluminum compound and a condensing agent contact.
By using the component (D), the catalytic activity in the polymerization reaction system can be further improved. Therefore, the reaction time can be shortened and the reaction temperature can be increased.

Here, as the organoaluminum compound used to obtain the component (D), for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and a mixture thereof can be mentioned. A mixture of aluminum and tributylaluminum is preferred.
Moreover, as a condensing agent used in order to obtain (D) component, water etc. are mentioned, for example.

As the component (D), for example, the general formula (d-1):
^{- (Al (R 7) O} ) n - ··· (d-1)
Wherein, R ⁷ is a hydrocarbon group having 1 to 10 carbon atoms; wherein a portion of the hydrocarbon group may be substituted by halogen and / or alkoxy group; R ⁷ is between the repeating units And may be the same or different; n is 5 or more].

The molecular structure of the aluminoxane may be linear or cyclic.
n is preferably 10 or more.
Examples of the hydrocarbon group for R ⁷ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is particularly preferable. The said hydrocarbon group may be used individually by 1 type, and may be used in combination of 2 or more type. The hydrocarbon group of R ^7, combination of methyl groups and isobutyl groups are preferred.

The aluminoxane preferably has high solubility in aliphatic hydrocarbons, and preferably has low solubility in aromatic hydrocarbons. For example, aluminoxane marketed as a hexane solution is preferable.
Here, examples of the aliphatic hydrocarbon include hexane and cyclohexane.

The component (D) is particularly represented by the general formula (d-2):
_{- (Al (CH 3) x} (i-C 4 H 9) y O) m - ··· (d-2)
[Wherein x + y is 1; m is 5 or more], may be a modified aluminoxane (hereinafter also referred to as “TMAO”). As TMAO, the product name: TMAO341 by Tosoh Fine Chemical Co., Ltd. is mentioned, for example.

Moreover, (D) component is general formula (d-3):
_{- (Al (CH 3) 0.7} (i-C 4 H 9) 0.3 O) k - ··· (d-3)
[Wherein k is 5 or more] may be a modified aluminoxane (hereinafter also referred to as “MMAO”). As MMAO, for example, product name: MMAO-3A manufactured by Tosoh Fine Chemical Co., Ltd. may be mentioned.

Further, the component (D) is particularly the general formula (d-4):
− [(CH ₃ ) AlO] _i − (d-4)
[Wherein i is 5 or more] may be a modified aluminoxane (hereinafter also referred to as “PMAO”). As PMAO, for example, product name: TMAO-211 manufactured by Tosoh Fine Chemical Co., Ltd. may be mentioned.

  The component (D) is preferably MMAO or TMAO among the MMAO, TMAO, and PMAO from the viewpoint of improving the effect of improving the catalyst activity, and in particular, from the viewpoint of further enhancing the effect of improving the catalyst activity. More preferably.

-Halogen compound (component (E))-
Component (E) is a halogen-containing compound that is a Lewis acid (hereinafter also referred to as “(E-1) component”), a complex compound of a metal halide and a Lewis base (hereinafter referred to as “(E-2) component”). And at least one compound selected from the group consisting of organic compounds containing active halogen (hereinafter also referred to as “component (E-3)”).

These compounds react with the component (A), that is, the rare earth element compound having at least one M-A bond, so that electrons are present at the cationic transition metal compound, the halogenated transition metal compound, and / or the transition metal center. A transition metal compound in an insufficient state is produced.
By using the component (E), the amount of cis-1,4 bonds in the conjugated diene polymer can be increased.

As the component (E-1), for example, an element of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 of the Periodic Table is included. Examples thereof include halogen-containing compounds, and aluminum halides or organometallic halides are particularly preferable.
Examples of halogen-containing compounds that are Lewis acids include titanium tetrachloride, tungsten hexachloride, tri (pentafluorophenyl) borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide. , Butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquichloride, aluminum G Examples include bromide, tri (pentafluorophenyl) aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride, etc., especially ethyl aluminum dichloride, ethyl aluminum dibromide, diethyl Aluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, and ethylaluminum sesquibromide are preferred.
As halogen, chlorine or bromine is preferable.
The halogen-containing compound that is the Lewis acid (component (E-1)) may be used alone or in combination of two or more.

Examples of the metal halide used for the component (E-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, Barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide , Manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. , Magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride, copper chloride are preferred, and more particularly, magnesium chloride. Zinc chloride, manganese chloride, copper chloride are preferable.
(E-2) As a Lewis base used for a component, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, and alcohol are preferable.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propio Nitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid Benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, olei Alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, etc. are mentioned, in particular, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol 1-decanol and lauryl alcohol are preferred.
The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
The complex compound ((E-2) component) of the metal halide and Lewis base may be used alone or in combination of two or more.

Examples of the component (E-3) include benzyl chloride.
The organic compound containing the active halogen (component (E-3)) may be used alone or in combination of two or more.

  Hereinafter, it describes about the mixture ratio between each component of the polymerization catalyst composition of an example.

  The molar ratio of the blending amount of the component (B) (compound having a cyclopentadiene skeleton) to the component (A) (rare earth element compound) is preferably more than 0 from the viewpoint of obtaining sufficient catalytic activity. More preferably, it is more preferably 1, or more, and from the viewpoint of suppressing a decrease in catalyst activity, it is preferably 3 or less, more preferably 2.5 or less. Particularly preferred is 2 or less.

  From the viewpoint of improving the catalytic activity in the reaction system, the molar ratio of component (C) (organometallic compound) to component (A) is preferably 1 or more, more preferably 5 or more, Further, from the viewpoint of suppressing a decrease in catalyst activity in the reaction system, it is preferably 50 or less, more preferably 30 or less, and specifically about 10 is preferable.

  From the viewpoint of improving the catalytic activity in the reaction system, the molar ratio of aluminum in component (D) (aluminoxane compound) to the rare earth element in component (A) is preferably 10 or more, and 100 or more. Further, from the viewpoint of suppressing a decrease in catalyst activity in the reaction system, it is preferably 1000 or less, and more preferably 800 or less.

The molar ratio of the amount of component (E) (halogen compound) to component (A) is preferably 0 or more, more preferably 0.5 or more, from the viewpoint of improving the catalytic activity. It is particularly preferably 0 or more, and it is preferably 20 or less, and more preferably 10 or less, from the viewpoint of maintaining the solubility of the component (E) and suppressing the decrease in catalyst activity.
Therefore, according to the said range, the effect which raises the amount of cis-1,4 bonds of a conjugated diene polymer can be made high.

(Method for producing conjugated diene polymer)
The method for producing a conjugated diene polymer according to an example of the present invention requires the use of a polymerization catalyst composition prepared by the method for producing a polymerization catalyst composition according to an example of the present invention. Specifically, the method for producing a conjugated diene polymer according to an example of the present invention includes:
Preparing a conjugated diene monomer, a monomer preparation step;
The rare earth element compound (component (A)) represented by the general formula (a-1), the compound having a cyclopentadiene skeleton (component (B)), and the organic represented by the general formula (c-1). A catalyst system preparatory step of preparing or preparing a metal compound (component (C)), optionally an aluminoxane compound (component (D)), and optionally a halogen compound (component (E));
A catalyst composition preparation step for preparing a polymerization catalyst composition through the step (a) and optionally a step appropriately selected from the above step (b) to step (f);
A polymerization reaction step of mixing the conjugated diene monomer and the polymerization catalyst composition to perform a polymerization reaction of the conjugated diene monomer;
including. In addition, a conjugated diene monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  According to this method, the polymerization reaction of the conjugated diene can be performed with high catalytic activity. Moreover, according to this method, since the amount of cis-1,4 bonds can be made extremely high, a conjugated diene polymer rich in elasticity can be provided, and as a rubber component when producing rubber products It can be used suitably.

(Method for producing modified conjugated diene polymer)
Moreover, the manufacturing method of the modified conjugated diene polymer of an example of this invention requires using the polymerization catalyst composition prepared with the manufacturing method of the polymerization catalyst composition of an example of this invention. Specifically, the method for producing a modified conjugated diene polymer as an example of the present invention includes:
Preparing a conjugated diene monomer, a monomer preparation step;
A catalyst composition preparation step as described above;
A polymerization reaction step of mixing the conjugated diene monomer and the polymerization catalyst composition to perform a polymerization reaction of the conjugated diene monomer;
And a modification step of introducing the modifying group into the terminal of the living polymer by introducing the modifying agent into the polymerization reaction system. In addition, a conjugated diene monomer may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, the polymerization reaction step and the modification step may be performed simultaneously or in duplicate.

  According to this method, the polymerization reaction of the conjugated diene can be performed with high catalytic activity. Moreover, according to this method, the amount of cis-1,4 bonds can be made extremely high, and the terminal modification rate can be increased. Therefore, it is possible to provide a conjugated diene polymer that is rich in elasticity and sufficiently has the desired performance derived from the modifier, and can be suitably used as a rubber component when producing rubber products.

-Conjugated diene monomer-
Examples of the conjugated diene monomer used in the method for producing a conjugated diene polymer of the present invention and the method for producing a modified conjugated diene polymer of the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2 , 3-dimethyl-1,3-butadiene, 1,3-hexadiene, and the like. In particular, from the viewpoint of improving various performances of rubber products such as rubber compositions and tires, 1,3-butadiene and / or It is preferable to use isoprene. These may be used alone or in combination of two or more. In particular, when isoprene and 1,3-butadiene are used as the conjugated diene monomer, the ratio of isoprene to 1,3-butadiene improves the catalytic activity in the reaction system and reduces the molecular weight distribution. Therefore, it is preferably 1 or more, more preferably 3 or more, and particularly preferably 7 or more.

-Modifier-
The modifier used in the method for producing a modified conjugated diene polymer of the present invention has a functional group capable of performing a substitution reaction or an addition reaction with the active organometallic moiety on the polymer having the active organometallic moiety. A functional group is imparted to the polymer by reacting a compound that does not contain an active proton that deactivates the active organometallic site, or increases the molecular weight due to coupling.
Typical modifiers include azacyclopropane group, ketone group, carboxyl group, thiocarboxyl group, carbonate, carboxylic acid anhydride, carboxylic acid metal salt, acid halide, urea group, thiourea group, amide group, thioamide Group, isocyanate group, thioisocyanate group, halogenated isocyano group, epoxy group, thioepoxy group, imine group, and MZ bond (where M is Sn, Si, Ge, P, Z is a halogen atom) And at least one functional group that does not contain active protons and onium salts that deactivate the active organometallic moiety.

  Specifically, the modifier is preferably at least one selected from the following compounds (a) to (j).

The compound (a) is a compound represented by the following general formula (V).

In the above formula, X ^{1 to} X ⁵ are a hydrogen atom, or a halogen atom, a carbonyl group, a thiocarbonyl group, an isocyanate group, a thioisocyanate group, an epoxy group, a thioepoxy group, a halogenated silyl group, a hydrocarbyloxysilyl group, and a sulfonyloxy group. A monovalent functional group containing at least one selected from the above and not containing active protons and onium salts. X ^{1 to} X ⁵ may be the same or different from each other, but at least one of them is not a hydrogen atom.
R ^{1 to} R ⁵ each independently represent a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, an arylene group having 6 to 18 carbon atoms, and an aralkylene group having 7 to 18 carbon atoms. Among these, an alkylene group having 1 to 18 carbon atoms, particularly an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be linear, branched or cyclic, but is particularly preferably linear. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group.
Or it may be bonded multiple aziridine ring via any of X ¹ to X ⁵ and R ¹ to R ^5.
Further, compound (a), the formula (V), it is preferable that not satisfy X ¹ = hydrogen atom and R ¹ = single bond simultaneously.

  Examples of the modifying agent represented by the general formula (V) include 1-acetylaziridine, 1-propionylaziridine, 1-butyrylaziridine, 1-isobutyrylaziridine, 1-valerylaziridine, and 1-isovalelide. Rylaziridine, 1-pivaloylaziridine, 1-acetyl-2-methylaziridine, 2-methyl-1-propionylaziridine, 1-butyryl-2-methylaziridine, 2-methyl-1-isobutyrylaziridine, 2- Methyl-1-valerylaziridine, 1-isovaleryl-2-methylaziridine, 2-methyl-1-pivaloylaziridine, ethyl 3- (1-aziridinyl) propionate, propyl 3- (1-aziridinyl) propionate, butyl 3 -(1-aziridinyl) propionate, ethylene glycol bis [3 -(1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) propionate], ethyl 3- (2-methyl-1-aziridinyl) propionate, propyl 3- (2-methyl-1-aziridinyl) Propionate, butyl 3- (2-methyl-1-aziridinyl) propionate, ethylene glycol bis [3- (2-methyl-1-aziridinyl) propionate], trimethylolpropane tris [3- (2-methyl-1-aziridinyl) Propionate], neopentyl glycol bis [3- (1-aziridinyl) propionate], neopentyl glycol bis [3- (2-methyl-1-aziridinyl) propionate], di (1-aziridinylcarbonyl) methane, 1, 2-di (1-azi Lysinylcarbonyl) ethane, 1,3-di (1-aziridinylcarbonyl) propane, 1,4-di (1-aziridinylcarbonyl) butane, 1,5-di (1-aziridinylcarbonyl) pentane , Di (2-methyl-1-aziridinylcarbonyl) methane, 1,2-di (2-methyl-1-aziridinylcarbonyl) ethane, 1,3-di (2-methyl-1-aziridinyl) Examples include, but are not limited to, carbonyl) propane, 1,4-di (2-methyl-1-aziridinylcarbonyl) butane, and the like.

Compound (b) is a halogenated organometallic compound or a halogenated metal compound represented by R ⁶ _n M′Z _4-n or M′Z ₄ or M′Z ₃ (wherein R ⁶ is The same or different hydrocarbon groups having 1 to 20 carbon atoms, M ′ is a tin atom, silicon atom, germanium atom or phosphorus atom, Z is a halogen atom, and n is 0 to an integer of 3).

In the above formula, when M ′ is a tin atom, examples of the compound (b) include triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin. Examples include dichloride, dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, tin tetrachloride and the like.
In the above formula, when M ′ is a silicon atom, examples of the compound (b) include triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyl. Examples include dichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyldichlorosilane, phenylchlorosilane, hexyltridichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and silicon tetrachloride.
In the above formula, when M ′ is a germanium atom, examples of the compound (b) include triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride, germanium tetrachloride and the like.
In the above formula, when M ′ is a phosphorus atom, examples of the compound (b) include phosphorus trichloride.

Further, as the compound (b), an organometallic compound containing an ester group represented by the following formula or a carbonyl group represented by the following formula in the molecule can also be used.
R ⁷ _n M ′ (— R ⁸ —COOR ⁹ ) _4-n
R ⁷ _n M ′ (— R ⁸ —COR ⁹ ) _4-n
(Wherein R ^{7 to} R ⁸ are the same or different and are hydrocarbon groups containing 1 to 20 carbon atoms, and R ⁹ is a hydrocarbon containing 1 to 20 carbon atoms. A carbonyl group or an ester group in the side chain, M ′ is a tin atom, a silicon atom, a germanium atom or a phosphorus atom, Z is a halogen atom, and n is an integer of 0 to 3 .)
In addition, you may use these compounds (b) together in arbitrary ratios.

Compound (c) is a heterocumulene compound, which is a denaturant having a Y═C═Y ′ bond in the molecule.
In the above formula, Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Y ′ is an oxygen atom, nitrogen atom or sulfur atom. Here, the compound (c) is a ketene compound when, for example, Y is a carbon atom and Y ′ is an oxygen atom, and when Y is a carbon atom and Y ′ is a sulfur atom. Is a thioketene compound, when Y is a nitrogen atom and Y ′ is an oxygen atom, is an isocyanate compound, and when Y is a nitrogen atom and Y ′ is a sulfur atom, An isocyanate compound, when Y and Y ′ are both nitrogen atoms, a carbodiimide compound; when both Y and Y ′ are oxygen atoms, carbon dioxide; and Y is an oxygen atom When Y ′ is a sulfur atom, it is carbonyl sulfide, and when Y and Y ′ are both sulfur atoms, it is carbon disulfide. However, the compound (c) is not limited to these combinations.

  Among these, examples of the ketene compound include ethyl ketene, butyl ketene, phenyl ketene, and toluyl ketene. Examples of the thioketene compound include ethylene thioketene, butyl thioketene, phenyl thioketene, toluyl thioketene, and the like. Examples of the isocyanate compound include phenyl isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane diisocyanate, hexamethylene diisocyanate and the like. Can be mentioned. Examples of the thioisocyanate compound include phenylthioisocyanate, 2,4-tolylene diisocyanate, hexamethylene dithioisocyanate, and the like. Examples of the carbodiimide compound include N, N′-diphenylcarbodiimide, N, N′-ethylcarbodiimide, and the like.

The compound (d) is a hetero three-membered ring compound having a bond represented by the following general formula (VI).

In the above formula, Y ′ is an oxygen atom or a sulfur atom.
Here, the compound (d) is, for example, an epoxy compound when Y ′ is an oxygen atom, and a thiirane compound when Y ′ is a sulfur atom. Here, examples of the epoxy compound include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, and epoxidized natural rubber. Examples of the thiirane compound include thiirane, methylthiirane, and phenylthiirane.

Compound (e) is a halogenated isocyano compound.
The halogenated isocyano compound has a> N═C—X bond (wherein X is a halogen atom).
Examples of the halogenated isocyano compound (e) include 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, 3,6-dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino- 4,6-dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4 , 5,6-tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6 Dichloropyrazine, 2,4-bis (methylthio) -6-chloro-1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitrothiazole, 2 -Chlorobenzothiazole, 2-chlorobenzoxazole and the like.

Compound (f) _{^{is, R 10 - (COOH) m}} , R 11 (COZ) m, R 12 - (COO-R 13), R 14 -OCOO-R 15, R 16 - (COOCO-R 17) m or A carboxylic acid, an acid halide, an ester compound, a carbonate compound, or an acid anhydride represented by the following general formula (VII).

In said formula, R < ¹⁰ > -R < ¹⁸ > is the same or different and is a hydrocarbon group containing a C1-C50 carbon atom, Z is a halogen atom, m is an integer of 1-5. is there.

Here, examples of the carboxylic acid in the compound (f) include acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyro Examples include merit acid, merit acid, polymethacrylic acid ester compound, or total hydrolyzate or partial hydrolyzate of polyacrylic acid compound.
Examples of the acid halide in the compound (f) include acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutanoic acid chloride, octanoic acid chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride, phthalic acid chloride, maleic acid. Examples include acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, and benzoyl fluoride.
Examples of the ester compound in the compound (f) include ethyl acetate, ethyl stearate, diethyl adipate, diethyl maleate, methyl benzoate, ethyl acrylate, ethyl methacrylate, diethyl phthalate, dimethyl terephthalate, Examples include tributyl merit acid, tetraoctyl pyromellitic acid, hexaethyl merit acid, phenyl acetate, polymethyl methacrylate, polyethyl acrylate, and polyisobutyl acrylate.
Examples of the carbonate ester compound in the compound (f) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate, diphenyl carbonate, and the like.
Examples of the acid anhydride in the compound (f) include acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptanoic anhydride, benzoic anhydride, and cinnamic anhydride. And intramolecular acid anhydrides such as succinic anhydride, methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, and styrene-maleic anhydride copolymers.

In addition, the compound mentioned as the compound (f) may contain an aprotic polar group such as an ether group or a tertiary amino group in the molecule as long as the object of the present invention is not impaired. Absent.
Furthermore, the compound (f) may contain a compound containing a free alcohol group or phenol group as an impurity.

Compound (g) is represented by _{^{R 19 k M "(OCOR 20}} ) 4-k, R 21 k M" (OCOR 22 -COOR 23) 4-k, or the following general formula (VIII), carboxylic It is a metal salt of an acid.

In the above formula, R ^{19 to} R ²⁵ are the same or different and are hydrocarbon groups containing a carbon atom having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, k Is an integer from 0 to 3.

R ¹⁹ _k M ″ (OCOR ²⁰ ) _4-k in the compound (g) includes, for example, triphenyltin laurate, triphenyltin-2-ethylhexate, triphenyltin naphthate, triphenyltin acetate, triphenyl Tin acrylate, tri-n-butyltin laurate, tri-n-butyltin-2-ethyl hexatate, tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin Laurate, tri-t-butyltin-2-ethylhexarate, tri-t-butyltin naphthate, tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethyl Hexatate, triisobutyltin Phthalate, triisobutyltin acetate, triisobutyltin acrylate, triisopropyltin laurate, triisopropyltin-2-ethylhexarate, triisopropyltin naphthate, triisopropyltin acetate, triisopropyltin acrylate, trihexyltin laurate, Trihexyltin-2-ethylhexamate, trihexyltin acetate, trihexyltin acrylate, trioctyltin laurate, trioctyltin-2-ethylhexaate, trioctyltin naphthate, trioctyltin acetate, trioctyltin Acrylate, tri-2-ethylhexyltin laurate, tri-2-ethylhexyltin-2-ethylhexarate, tri-2-ethylhexyltin naphthate, Tri-2-ethylhexyl tin acetate, tri-2-ethylhexyl tin acrylate, tristearyl tin laurate, tristearyl tin-2-ethyl hexatate, tristearyl tin naphthate, tristearyl tin acetate, tristearyl tin acrylate, tribenzyl Tin laurate, tribenzyltin-2-ethylhexarate, tribenzyltin naphthate, tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-2-ethylhexarate, diphenyltin distearate, diphenyltin dinaphthate Diphenyltin diacetate, diphenyltin diacrylate, di-n-butyltin dilaurate, di-n-butyltin di-2-ethylhexarate, -N-butyltin distearate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin diacrylate, di-t-butyltin dilaurate, di-t-butyltin di-2-ethylhexa Tate, di-t-butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di-t-butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin di-2-ethylhexarate, Diisobutyltin distearate, diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate, diisopropyltin-2-ethylhexarate, diisopropyltin distearate, diisopropyls Dinaphthate, diisopropyltin diacetate, diisopropyltin diacrylate, dihexyltin dilaurate, dihexyltin di-2-ethylhexarate, dihexyltin distearate, dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di- 2-ethylhexyltin dilaurate, di-2-ethylhexyltin-2-ethylhexarate, di-2-ethylhexyltin distearate, di-2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di- 2-ethylhexyl tin diacrylate, dioctyl tin dilaurate, dioctyl tin di-2-ethyl hexatate, dioctyl tin distearate, dioctyl tin dinaphthate, dioctyl tin di Acetate, dioctyltin diacrylate, distearyltin dilaurate, distearyltin di-2-ethylhexarate, distearyltin distearate, distearyltin dinaphthate, distearyltin diacetate, distearyltin diacrylate, di Benzyltin dilaurate, dibenzyltin di-2-ethylhexarate, dibenzyltin distearate, dibenzyltin dinaphthate, dibenzyltin diacetate, dibenzyltin diacrylate, phenyltin trilaurate, phenyltin tri-2- Ethyl hexatate, phenyl tin trinaphthate, phenyl tin triacetate, phenyl tin triacrylate, n-butyl tin trilaurate, n-butyl tin tri-2-ethyl hexatate, n-butyl Zutrinaphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2-ethylhexamate, t-butyltin trinaphthate, t-butyltin triacetate, t-butyltin triacrylate, isobutyl Tin trilaurate, isobutyltin tri-2-ethylhexarate, isobutyltin trinaphthate, isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri-2-ethylhexarate, isopropyltin trinaphthate Tate, isopropyl tin triacetate, isopropyl tin triacrylate, hexyl tin trilaurate, hexyl tin tri-2-ethylhexarate, hex Tin trinaphthate, hexyl tin triacetate, hexyl tin triacrylate, octyl tin trilaurate, octyl tin tri-2-ethyl hexatate, octyl tin trinaphthate, octyl tin triacetate, octyl tin triacrylate, 2-ethylhexyl tin tri Laurate, 2-ethylhexyltin tri-2-ethylhexarate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2-ethylhexyltin triacrylate, stearyltin trilaurate, stearyltin tri-2-ethylhexa Tate, stearyltin trinaphthate, stearyltin triacetate, stearyltin triacrylate, benzyltin trilaurate, benzyltin tri-2-ethylhex Examples include saturate, benzyltin trinaphthate, benzyltin triacetate, and benzyltin triacrylate.

R ²¹ _k M ″ (OCO—R ²² —COOR ²³ ) _4-k in the compound (g) is, for example, diphenyltin bismethylmalate, diphenyltin bis-2-ethylhexarate, diphenyltin bisoctylmalate, diphenyltin bis Octylmalate, diphenyltin bisbenzylmalate, di-n-butyltin bismethylmalate, di-n-butyltin bis-2-ethylhexarate, di-n-butyltin bisoctylmalate, di-n-butyltin bisbenzyl Malate, di-t-butyltin bismethylmalate, di-t-butyltin bis-2-ethylhexarate, di-t-butyltin bisoctylmalate, di-t-butyltin bisbenzylmalate, diisobutyltin bismethyl Malate, diisobutyltin bis-2-ethyl Xanthate, diisobutyltin bisoctylmalate, diisobutyltin bisbenzylmalate, diisopropyltin bismethylmalate, diisopropyltin bis-2-ethylhexarate, diisopropyltin bisoctylmalate, diisopropyltin bisbenzylmalate, dihexyltin bis Methylmalate, dihexyltin bis-2-ethylhexarate, dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin bis-2-ethyl Hexatate, di-2-ethylhexyltin bisoctylmalate, di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmalate, dioctyltin bis-2-ethyl Hexatate, dioctyltin bisoctyl malate, dioctyltin bisbenzyl malate, distearyltin bismethylmalate, distearyltin bis-2-ethylhexarate, distearyltin bisoctylmalate, distearyltin bisbenzylmalate Dibenzyltin bismethylmalate, dibenzyltin bis-2-ethylhexarate, dibenzyltin bisoctylmalate, dibenzyltin bisbenzylmalate, diphenyltin bismethylagitate, diphenyltin bis-2-ethylhexarate, Diphenyltin bisoctyl agitate, diphenyltin bisbenzyl agitate, di-n-butyltin bismethyl agitate, di-n-butyltin bis-2-ethylhexate, di-n-butyltin bisoctyl Ru-agitate, di-n-butyltin bisbenzyl agitate, di-t-butyltin bismethyl agitate, di-t-butyltin bis-2-ethyl hexatate, di-t-butyltin bisoctyl agitate, di-t-butyltin bisbenzyl agitate , Diisobutyltin bismethyl agitate, diisobutyltin bis-2-ethylhexaate, diisobutyltin bisoctyl agitate, diisobutyltin bisbenzyl agitate, diisopropyltin bismethylagitate, diisopropyltin bis-2-ethylhexate, diisopropyltin bisoctyl agitate , Diisopropyltin bisbenzyl agitate, dihexyltin bismethyl agitate, dihexyltin bis-2-ethylhexate, dihexyltin bismethy Agitate, dihexyltin bisbenzyl agitate, di-2-ethylhexyltin bismethyl agitate, di-2-ethylhexyltin bis-2-ethylhexate, di-2-ethylhexyltin bisoctyl agitate, di-2-ethylhexyltin bisben -Ethylhexyltin bisbenzyl agitate, dioctyltin bismethyl agitate, dioctyltin bis-2-ethylhexaate, dioctyltin bisoctyl agitate, dioctyltin bisbenzyl agitate, distearyltin bismethylagitate, distearyltin bis-2-ethyl Hexacetate, distearyl tin bisoctyl agitate, distearyl tin bisbenzyl agitate, dibenzyltin bismethyl agitate, dibenzyltin bis-2-ethyl Ruhekisateto, dibenzyl tin bis-octyl adipate Tate and dibenzyl tin bis benzyl azide Tate and the like.

  Examples of the compound represented by the formula (VIII) include diphenyltin maleate, di-n-butyltin maleate, di-t-butyltin maleate, diisobutyltin maleate, diisopropyltin maleate, dihexyltin maleate, Di-2-ethylhexyl tin malate, dioctyl tin malate, distearyl tin malate, dibenzyl tin malate, diphenyl tin agitate, di-n-butyl tin agitate, di-t-butyl tin agitate, diisobutyl tin agitate, diisopropyl tin agitate , Dihexyltin diacetate, di-2-ethylhexyltin agitate, dioctyltin agitate, distearyltin agitate, dibenzyltin agitate and the like.

  Compound (h) is an N-substituted aminoketone, N-substituted aminothioketone, N-substituted aminothioaldehyde, N-substituted aminothioaldehyde, or —C— (═M) —N <bond (M is an oxygen atom) in the molecule. Or a sulfur atom).

  Examples of the compound (h) include 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1,7-bis (methylethylamino) -4-heptanone, 4- Dimethylaminobenzophenone, 4-di-t-butylaminobenzophenone, 4-diphenylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( N-substituted aminoketones such as diphenylamino) benzophenone and corresponding N-aminothioketones; N-substituted aminoaldehydes such as 4-dimethylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-divinylaminobenzaldehyde, and the like N- A compound having —C— (═M) —N <bond (M represents an oxygen atom or a sulfur atom) in the molecule, for example, N-methyl-β-propiolactam, N-phenyl -Β-propiolactam, N-methyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-phenyl-5-methyl-2-pyrrolidone, N-methyl-2 -Piperidone, N-phenyl-2-piperidone, N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methyl-ω-caprolactam, N-phenyl-ω-caprolactam, N-methyl-ω-laur N-substituted lactams such as rilolactam and N-vinyl-ω-laurylactam, and the corresponding N-substituted thiolactams; 1,3-dimethylethyleneurea, 1,3 N-substituted cyclic ureas such as divinylethyleneurea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, and And corresponding N-substituted cyclic thioureas.

Compound (i) is a compound having an N≡C— bond.
Here, examples of the compound having an N≡C-bond include organic cyano compounds represented by the general formula R-CN, specifically, 2-cyanopyridine, 3-cyanopyridine, acrylonitrile and the like.

The compound (j) is a compound having a phosphate residue represented by the following general formula (IX).

In the general formula (IX), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and A monovalent hydrocarbon group selected from monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms or a hydrogen atom.
More specifically, for example, a phosphate residue represented by the following general formula (IX-2) can be mentioned.

  The above compounds (a) to (j) may be used alone or in combination of two or more, or used in combination with a modifier other than the compounds (a) to (j). You can also.

  The amount of the modifier used in the method for producing the modified conjugated diene polymer of the present invention varies depending on the desired terminal modification rate in the resulting modified conjugated diene polymer, but the molar amount relative to the amount of component (A) used. The ratio is preferably 0.1 to 100, and more preferably 1.0 to 50. By making the usage-amount of modifier | denaturant into the said range, modification | denaturation reaction advances more.

The reagents used in the above steps may be used without a solvent or with a solvent suitable for each reagent.
In each of the above steps, the reagent and the solvent are preferably those obtained by appropriately performing purification operations such as distillation, degassing, and lyophilization.
Moreover, it is preferable that each said process, especially a catalyst composition preparation process, a polymerization reaction process, and a modification | denaturation process are performed in inert gas atmosphere, such as nitrogen gas and argon gas.

  Here, the molar amount of the component (A) with respect to 100 g of the conjugated diene monomer is preferably 0.01 mmol or more, more preferably 0.03 mmol or more, from the viewpoint of sufficiently obtaining catalytic activity. Further, from the viewpoint of preventing the catalyst system from being excessive, it is preferably 0.5 mmol or less, and more preferably 0.05 mmol or less.

  The solvent is not particularly limited as long as it is inert in the polymerization reaction, and may be any one, and examples thereof include n-hexane, cyclohexane, or a mixture thereof. In addition, as a solvent, you may use the solvent used for preparation of the polymerization catalyst composition of an example of this invention as it is.

In the polymerization reaction step, a well-known method in the technical field such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. The reaction temperature is not particularly limited and can be, for example, −100 to 300 ° C., preferably 0 to 200 ° C., and more preferably 25 to 120 ° C. At high temperatures, the cis-1,4-selectivity may decrease, and at low temperatures, the reaction rate may decrease.
The reaction pressure is not particularly limited and can be, for example, normal pressure. At high pressure, the conjugated diene monomer may not be sufficiently taken into the polymerization reaction system, and at low pressure, the reaction rate may decrease.
The reaction time is not particularly limited and can be, for example, 0.5 to 3 hours.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Example at all.

<Manufacture of polymer>
A polymer was prepared according to the following.

Example 1
300 g of hexane solution containing 70 g of 1,3-butadiene was added to a 1000 mL pressure-resistant glass reactor sufficiently dried and purged with nitrogen.
On the other hand, in a glove box under a nitrogen atmosphere, trisbistrimethylsilylamidogadolinium [Gd (N (SiMe ₃ ) ₂ ) ₃ ] (component (A)) 200 μmol, 1-benzyl-1H-indene ((B ) Component) 400 μmol and 20 mmol of diisobutylaluminum hydride (component (C)) were added and mixed well, and then allowed to stand at 25 ° C. for 2 hours.
Thereafter, 80 ml of n-hexane and 120 mmol of MMAO (“MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.) (component (D)) were sufficiently mixed and then allowed to stand at 25 ° C. for 4 hours.
Thereafter, 400 μmol of diethylaluminum chloride (component (E)) was charged and mixed well, and then allowed to stand at 25 ° C. for 30 minutes to obtain a polymerization catalyst composition.
Next, the polymerization catalyst composition was taken out from the glove box, and an amount of the polymerization catalyst composition that was 14 μmol in terms of gadolinium was added to the glass reactor containing 1,3-butadiene. This reaction system was maintained at 50 ° C. for 150 minutes to conduct a polymerization reaction of 1,3-butadiene.
Thereafter, 20 mL of a modifying agent (“4,4′-bis (dimethylamino) benzophenone” manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the polymerization reaction system, and a denaturing reaction was performed for 1 hour.
Thereafter, 1 mL of an isopropanol solution containing 5% by mass of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to the polymerization reaction system to stop the polymerization reaction. Furthermore, the reaction product was separated by adding a large amount of isopropanol to a glass reactor, and further vacuum-dried at 60 ° C. to obtain a polymer A (yield: 60 g).

(Example 2)
In Example 1, polymer B was obtained in the same manner as in Example 1 except that 70 g of isoprene was used instead of 70 g of 1,3-butadiene (yield: 60 g).

(Example 3)
In Example 1, Polymer C was obtained in the same manner as in Example 1 except that triisobutylaluminum was used in place of diisobutylaluminum hydride as the component (C) (yield: 60 g).

Example 4
In Example 1, polymer D was used in the same manner as in Example 1 except that tetramethylcyclopentadiene (component (B)) was used instead of 1-benzyl-1H-indene (component (B)). (Yield: 59 g) was obtained.

(Example 5)
In Example 1, polymer E was obtained in the same manner as in Example 1 except that trimethylsilylfluorene (component (B)) was used instead of 1-benzyl-1H-indene (component (B)). (Yield: 59 g).

(Example 6)
In Example 1, Polymer F was obtained in the same manner as Example 1 except that TMAO (“TMAO341” manufactured by Tosoh Fine Chemical Co., Ltd.) was used as the component (D) instead of MMAO (yield: 60 g).

(Example 7)
In Example 1, as component (A), instead of trisbistrimethylsilylamido gadolinium [Gd (N (SiMe ₃ ) ₂ ) ₃ ], (RO) ₃ M [M is gadolinium, and R is a t-butyl group. The polymer G was obtained in the same manner as in Example 1 except that the rare earth alcoholate represented by (Gd (OtBt) ₃ , tris- (tert-butoxide) gadolinium) was used (yield: 58 g). ).

(Example 8)
In Example 1, as component (A), instead of trisbistrimethylsilylamido gadolinium [Gd (N (SiMe ₃ ) ₂ ) ₃ ], (RS) ₃ M [M is gadolinium, and R is a t-butyl group. The polymer H was obtained in the same manner as in Example 1 except that the rare earth alkylthiolate (Gd (StBt) ₃ , tris- (tert-butylthio) gadolinium) represented by 58g).

Example 9
In Example 1, Polymer I was obtained in the same manner as Example 1 except that both MMAO (component (D)) and diethylaluminum chloride (component (E)) were not mixed (yield: 50 g).

(Example 10)
A polymer J was obtained in the same manner as in Example 1 except that diethylaluminum chloride (component (E)) was not mixed in Example 1 (yield: 52 g).

(Example 11)
In Example 1, a polymer was obtained in the same manner as in Example 1 except that the step of “5 mmol of MMAO (component (D)) was sufficiently mixed and then allowed to stand at 25 ° C. for 4 hours” was omitted. K was obtained (yield: 50 g).

(Example 12)
In Example 1, 80 ml of n-hexane and 5 mmol of MMAO (“MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.) (component (D)) were sufficiently mixed, and then allowed to stand at 25 ° C. for 4 hours. A series of steps of “20 ml of aluminum chloride (component (E)) and sufficiently mixed and then allowed to stand at 25 ° C. for 30 minutes” was followed by “80 ml of n-hexane, 20 μmol of diethylaluminum chloride (component (E)). After thoroughly mixing, the mixture was allowed to stand at 25 ° C. for 4 hours. After that, 5 mmol of MMAO (“MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.) (component (D)) was added and mixed well, and then at 25 ° C. A polymer L was obtained in the same manner as in Example 1 except that a series of steps of “standing for 30 minutes” was performed (yield: 55 g).

(Example 13)
In Example 1, a polymer M was obtained in the same manner as in Example 1 except that the modification reaction was performed by adding a modifier (yield: 58 g).

(Example 14)
125 g of a hexane solution containing 30 g of 1,3-butadiene was added to a 1000 mL pressure-resistant glass reactor that had been sufficiently dried and purged with nitrogen.
On the other hand, in a glove box under a nitrogen atmosphere, trisbistrimethylsilylamidogadolinium [Gd (N (SiMe ₃ ) ₂ ) ₃ ] (component (A)) 72 μmol, 1-benzyl-1H-indene ((B Component) 144 μmol, diisobutylaluminum hydride (component (C)) 1.44 mmol, triisobutylaluminum (component (C)) 3.6 mmol were added and mixed well, and then allowed to stand at 25 ° C. for 12 hours.
Thereafter, 25 ml of n-hexane and 0.36 mmol of MMAO (“MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.) (component (D)) were sufficiently mixed and then allowed to stand at 25 ° C. for 4 hours.

Thereafter, 144 μmol of diethylaluminum chloride (component (E)) was added and mixed well, and then allowed to stand at 25 ° C. for 30 minutes to obtain a polymerization catalyst composition.
Next, the polymerization catalyst composition was taken out from the glove box, and an amount of the polymerization catalyst composition that was 15 μmol in terms of gadolinium was added to the glass reactor containing 1,3-butadiene. This reaction system was maintained at 50 ° C. for 60 minutes to carry out a polymerization reaction of 1,3-butadiene.
Thereafter, 2.2 mL of a modifying agent (“4,4′-bis (dimethylamino) benzophenone” manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the polymerization reaction system, and a denaturing reaction was performed for 1 hour.
Thereafter, 1 mL of an isopropanol solution containing 5% by mass of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to the polymerization reaction system to stop the polymerization reaction. Furthermore, the reaction product was separated by adding a large amount of isopropanol to a glass reactor, and further vacuum-dried at 60 ° C. to obtain a polymer N (yield: 60 g).

(Comparative Example 1)
In Example 1, component (A), component (B) and component (C) are first added and mixed and allowed to stand, then component (D) is mixed and allowed to stand, and then component (E) is mixed. -Instead of standing, (A) component, (B) component, (C) component, (D) component and (E) component were added together and mixed thoroughly, then at 25 ° C for 2 hours Except having stood still, it carried out similarly to Example 1, and obtained the polymer a (yield: 52g).

(Comparative Example 2)
In Example 1, component (A), component (B) and component (C) were first added and mixed for 2 hours, then component (D) was mixed for 4 hours, and then (E ) Instead of mixing and leaving the components for 30 minutes, first add (A) component, (B) component, (C) component and (D) component together, mix and leave for 2 hours, Next, a polymer b was obtained in the same manner as in Example 1 except that the component (E) was mixed and allowed to stand for 4 hours (yield: 52 g).

(Comparative Example 3)
In Comparative Example 2, a polymer c was obtained in the same manner as in Comparative Example 2 except that the mixing order of the component (D) and the component (E) was changed (yield: 52 g).

(Comparative Example 4)
In Example 1, the polymerization reaction was performed in the same manner as in Example 1 except that the timing of mixing the component (A) was changed simultaneously with the component (D) instead of the component (B) and the component (C). Went. However, the catalyst activity was low and a polymer could not be obtained.

(Comparative Example 5)
In Example 1, the mixing timing of the component (B) was changed at the same time as the component (D) instead of at the same time as the components (A) and (C). Combined d was obtained (yield: 55 g).

(Comparative Example 6)
In Example 1, the mixing timing of the component (C) was changed at the same time as the component (D) instead of the component (A) and the component (B). Combined e was obtained (yield: 51 g).

  The components and preparation procedures used in each example and comparative example are shown in Tables 1 and 2.

<Evaluation of catalyst activity during polymerization and analysis of polymer>
The following evaluation was performed for each of the examples and comparative examples. These results are also shown in Tables 1 and 2.

(Analysis of polymer number average molecular weight (Mn) and molecular weight distribution (Mw / Mn))
Gel permeation chromatography (GPC) (GPC device: manufactured by Tosoh Corporation, HLC-8220GPC; column: manufactured by Tosoh Corporation, TSKgel GMHXL-2; detector: differential refractometer (RI)) as a standard The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were calculated. The measurement temperature was 40 ° C. and the elution solvent was THF.

(Polymer terminal modification rate)
The terminal modification rate of the polymer will be described in detail with reference to FIG.
The vertical axis indicates the value of UV / RI obtained by gel permeation chromatography (GPC) measurement. UV indicates a peak area value obtained from the UV absorbance caused by the modifier that has reacted with the polymer, and RI indicates a peak area value obtained from the differential refractive index (RI) of the polymer itself.
The horizontal axis indicates a value of (1 / Mn) × 10 ³ , where Mn is the absolute molecular weight (number average molecular weight). In FIG. 1, LowCisBR is polymerized by anionic polymerization using a Li-based catalyst and modified with a modifier 4, 4′-bis (diethylaminobenzophenone) (DEAB), and has three types of UV having different number average molecular weights Mn. The value of / RI is plotted and can be approximated as a straight line. In the case of anionic polymerization, since it is 100% modified, it is represented by A as shown in the following formula, assuming that UV / RI of LowCisBR is 100%.
UV (Li-Br) / RI (Li-Br) = A
On the other hand, using a catalyst containing a lanthanum-based rare earth element (Nd) -containing compound that is coordination polymerization, high-cisBR modified with DEAB is plotted with five types of UV / RI values with different number average molecular weights Mn. Can be approximated as a straight line. In the case of coordination polymerization, there are portions that are not living during the polymerization, and it is difficult to modify 100%. The UV / RI of HighCisBR is represented by B as shown in the following formula.
UV (Nd-Br) / RI (Nd-Br) = B
The terminal modification rate can be defined as follows.
Terminal modification rate = B / A × 100 (%)
The terminal modification rate is calculated from the A value and B value obtained by using LowCisBR having the same absolute molecular weight (number average molecular weight) as HighCisBR.
Note that the UV / RI value obtained by subtracting the value of the unmodified line shown in FIG. 1 is used as the true value, assuming that the terminal modification rate of the unmodified polymer reacted with isopropanol is 0%. The A value and B value are shown in FIG.
The three straight lines shown in FIG. 1 can be used as a calibration curve. For example, if the absolute molecular weight Mn (number average) of HighCisBR is known, the terminal modification rate can be calculated.
As can be seen from FIG. 1, as the absolute molecular weight Mn (number average) increases, the terminal modification rate decreases and it becomes difficult to modify with a modifier.

  From the results of Tables 1 and 2, the rare earth element compound (component (A)) represented by formula (a-1), substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted Carrying out the step of reacting only at least one compound selected from the group consisting of fluorene (component (B)) and the organometallic compound represented by formula (c-1) (component (C)) According to the polymerization catalyst composition obtained in this way, it can be seen that a higher terminal modification rate is obtained as compared with the polymerization catalyst composition obtained without carrying out the above steps. Moreover, according to the polymerization catalyst composition obtained by implementing the said process, the polymer is obtained with the very little catalyst usage-amount. Therefore, it is clear that the polymerization catalyst composition produced by the production method of the polymerization catalyst composition of the present invention has high catalytic activity during polymerization and can increase the terminal modification rate of the polymer.

ADVANTAGE OF THE INVENTION According to this invention, the catalyst activity at the time of superposition | polymerization is high, and the manufacturing method of the polymerization catalyst composition which can raise the terminal modification rate of a polymer can be provided.
Moreover, according to this invention, the manufacturing method of the conjugated diene polymer which can superpose | polymerize a conjugated diene monomer with high catalyst activity can be provided.
Furthermore, according to the present invention, there is provided a method for producing a modified conjugated diene polymer, which can polymerize a conjugated diene monomer with high catalytic activity and obtain a modified conjugated diene polymer having a high terminal modification rate. Can be provided.

Claims (12)

The following general formula (a-1):
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) (a-1)
[Wherein M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur; And having at least one M-A bond], and a rare earth element compound (component (A)),
At least one compound selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene (component (B));
The following general formula (c-1):
YR ¹ _a R ² _b R ³ _c (c-1)
[In the formula, Y is a Group 1 of the Periodic Table, Group 2, a metal element selected from the group consisting of group 12 and group 13 elements of; R ¹ and R ² are 1 carbon atoms 10 hydrocarbon groups or hydrogen atoms, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms; provided that R ¹ , R ² and R ³ may be the same or different from each other; Further, when Y is a group 1 metal element of the periodic table, a is 1 and b and c are 0, and Y is a group 2 or group 12 metal element of the periodic table. In some cases, a and b are 1 and c is 0, and when Y is a group 13 metal element of the periodic table, a, b and c are 1.] Step (a) for obtaining a reaction mixture by reacting only with an organometallic compound (component (C))
A process for producing a polymerization catalyst composition, comprising: A step (b) of obtaining a mixture by reacting only the reaction mixture obtained in the step (a) with an aluminoxane compound (component (D));
The method for producing a polymerization catalyst composition according to claim 1, further comprising: Step (c) of obtaining a reaction mixture by reacting only the reaction mixture obtained in the step (b) with a halogen compound (component (E))
The manufacturing method of the polymerization catalyst composition of Claim 2 which further contains these. Step (d) in which the reaction mixture obtained in the step (a) is reacted only with the halogen compound (component (E)) to obtain a reaction mixture.
The method for producing a polymerization catalyst composition according to claim 1, further comprising: Step (e) of reacting only the reaction mixture obtained in the step (d) with an aluminoxane compound (component (D)) to obtain a reaction mixture
The method for producing a polymerization catalyst composition according to claim 4, further comprising: Step (f) of obtaining a reaction mixture by reacting only the reaction mixture obtained in the step (a) with an aluminoxane compound (component (D)) and a halogen compound (component (E)).
The method for producing a polymerization catalyst composition according to claim 1, further comprising: The method for producing a polymerization catalyst composition according to any one of claims 1 to 6, wherein in the general formula (c-1), not all of R ¹ , R ² and R ³ are the same. The aluminoxane compound (component (D)) is represented by the general formula (d-2):
_{- (Al (CH 3) x} (i-C 4 H 9) y O) m - ··· (d-2)
[Wherein x + y is 1; m is 5 or more] or a modified aluminoxane represented by the general formula (d-3):
_{- (Al (CH 3) 0.7} (i-C 4 H 9) 0.3 O) k - ··· (d-3)
The method for producing a polymerization catalyst composition according to claim 2, 3, 5, or 6, which is a modified aluminoxane represented by the formula: wherein k is 5 or more.   A method for producing a conjugated diene polymer, comprising using the polymerization catalyst composition prepared by the method for producing a polymerization catalyst composition according to claim 1.   A method for producing a modified conjugated diene polymer, comprising using the polymerization catalyst composition prepared by the method for producing a polymerization catalyst composition according to claim 1.   The method for producing a conjugated diene polymer according to claim 9, wherein 1,3-butadiene and / or isoprene is used as a monomer.   The method for producing a modified conjugated diene polymer according to claim 10, wherein 1,3-butadiene and / or isoprene is used as a monomer.

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