JP2005162809A - Aromatic vinyl-conjugated diene block copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic vinyl-conjugated diene block copolymer in which an aromatic vinyl-based polymer block having a syndiotactic configuration and having a large chain length is connected to a conjugated diene-based polymer block, and to provide a method for efficiently producing the block copolymer. <P>SOLUTION: This aromatic vinyl-conjugated diene block copolymer having an aromatic vinyl monomer polymer block (A) and a conjugated diene monomer polymer block (B) is characterized by having an aromatic vinyl monomer-originated monomer unit: conjugated diene monomer-originated unit ratio of 5:95 to 95:5, a number-average mol.wt. of 10,000 to 1,000,000, having at least one segment comprising ≥50 connected aromatic vinyl monomer molecules in the polymer block (A), and having a racemidiad ratio of ≥55% in the polymer block (A). A method for producing the aromatic vinyl-conjugated diene block copolymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aromatic vinyl / conjugated diene block copolymer having a long molecular chain, a narrow molecular weight distribution and high syndiotacticity, and a method for producing the aromatic vinyl / conjugated diene block copolymer.

  Conventionally, a styrene / butadiene block copolymer composed of a polystyrene polymer block (polystyrene segment) polymerized with styrene and a polybutadiene polymer block (polybutadiene segment) polymerized with butadiene, or a polyisoprene polymerized with a polystyrene segment and isoprene. Aromatic vinyl / conjugated diene block copolymers such as styrene / isoprene block copolymers composed of polymer blocks (polyisoprene segments) are industrially produced by living polymerization technology using alkali metal or alkaline earth metal catalysts. Have been produced.

  However, the polystyrene polymer block (polystyrene segment) in these aromatic vinyl / conjugated diene block copolymers has an atactic structure, and the polybutadiene polymer block (polybutadiene segment) has a cis bond content of less than 40%. There were few things. Therefore, these block copolymers have no crystallinity, are inferior in heat resistance and chemical resistance, have a problem that the tensile strength is lowered, and the properties preferable as an elastic material are lost.

  On the other hand, it is known that a conjugated diene monomer is polymerized with high activity by a transition metal catalyst such as cobalt, nickel, and titanium to give a conjugated diene polymer having a high cis bond content. However, in the polymerization method using these transition metal catalysts, the conjugated diene monomer cannot be subjected to living polymerization, and a block copolymer with an aromatic vinyl monomer cannot be synthesized.

In recent years, when a half titanocene-MAO catalyst system in which a half titanocene complex such as CpTiCl ₃ (Cp represents a cyclopentadienyl group) and methylaluminoxane (MAO) are used, butadiene polymerization proceeds rapidly. It has been reported that a polymer having a cis bond content of about 80% can be obtained (Non-Patent Documents 1 to 3, Patent Documents 1 and 2, etc.). However, since the gel-like polymer is produced by the methods described in these documents, it is impossible to regulate the molecular weight, molecular weight distribution, branch structure, and the like. Non-Patent Documents 1 to 3 and Patent Documents 1 and 2 do not describe living polymerization and block copolymerization using a half titanocene-MAO catalyst system.

  Non-Patent Document 4 and Patent Document 3 disclose a method for producing a block copolymer of an aromatic vinyl compound and a conjugated diene using a catalyst in which a metallocene complex of a rare earth metal compound and a borate promoter are combined. Has been. However, in the production methods described in these documents, a copolymer having a polystyrene polymer block (polystyrene segment) having high syndiotacticity cannot be produced.

  Non-Patent Documents 5 and 6, Patent Document 4 and the like include syndiotactic compounds under polymerization conditions of a butadiene partial pressure of 1.3 to 6.7 MPa and a polymerization temperature of 0 ° C. to 100 ° C. in the presence of a half titanocene-MAO catalyst system. It is disclosed that a styrene / butadiene block copolymer having a polystyrene polymer block having a structure (polystyrene segment) and a polybutadiene polymer block having a 1,4-cis bond (polybutadiene segment) can be obtained.

  However, the polymerization methods described in these documents have a low polymerization yield, a polystyrene segment chain obtained by polymerization is as short as 10 monomer structural units or less, and a polystyrene segment having an atactic structure is also mixed. It was. Therefore, the crystal melting point of the obtained copolymer is 205 to 230 ° C., which is lower than the crystal melting point of long-chain polystyrene having a syndiotactic structure.

  In addition, since the polymerization method described in this document is not living polymerization, a block copolymer such as a diblock type or a triblock type cannot be obtained, and it is difficult to control the molecular weight or molecular weight distribution. there were.

  Patent Document 5 discloses that a butadiene / styrene diblock copolymer is obtained by living polymerizing butadiene at −25 ° C. in the presence of a half titanocene-MAO catalyst system, and then adding styrene to the polymerization reaction system for polymerization. Is disclosed that can be synthesized. However, the method described in this document did not yield a polymer having a long polystyrene segment chain. Further, a multiblock type or radial block type copolymer could not be obtained.

Non-Patent Documents 7 and 8 and the like include Cp ^* TiMe ₃ / B (C ₆ F ₅ ) ₃ / Al (Oct) ₃ (Cp ^* represents a pentamethylcyclopentadienyl group, and Oct represents an n-octyl group. A method for synthesizing syndiotactic living polymers and block copolymers of styrenes using a catalyst system is disclosed. However, these documents do not disclose the synthesis of block copolymers of styrene and conjugated dienes.

Macromol. Chem. Rapid Commun. 1990, Vol. 11, p. 519. J. et al. Organomet. Chem. 1993, 451, 67. Macromol. Chem. Rapid Commun. 1996, Vol. 17, p. 781. Macromolecules, 2001, 34, 1539. Macromol. Chem. Phys. 2000, 201, 393 Macromolecules, 2002, 35, 9315. J. et al. Polym. Sci. Part A: Polym. Chem. 2001, 39, 3969. Macromol. Chem. Phys. 2002, 203, 24 Japanese Patent Laid-Open No. 8-113610 Japanese Patent Laid-Open No. 9-77818 JP 2001-288234 A JP 2000-186127 A JP 2000-154221 A

  The present invention has been made in view of the state of the prior art, and an aromatic vinyl / polymer block having a syndiotactic structure and a long chain length and a conjugated diene polymer block linked together. It is an object of the present invention to provide a conjugated diene block copolymer and a method for efficiently producing the block copolymer.

As a result of intensive studies to solve the above problems, the present inventors have found that an aromatic compound is present in the presence of a polymerization catalyst containing a reaction product of a half titanocene complex such as Cp ^* TiMe ₃ and a promoter such as an organoaluminum compound. After the vinyl monomer is living polymerized, the conjugated diene monomer is added with the aromatic vinyl monomer remaining in the reaction system, and the conjugated diene monomer is polymerized, thereby syndiotactic. It has been found that an aromatic vinyl / conjugated diene diblock copolymer comprising an aromatic vinyl polymer block having a tick structure and a conjugated diene polymer block having a high 1,4-cis bond content can be synthesized.

When the present inventors removed the conjugated diene monomer remaining in the system from the polymerization reaction product for obtaining the aromatic vinyl / conjugated diene-based diblock copolymer by a method such as purging, the aromatics again It has been found that the polymerization of the vinyl monomer proceeds and a triblock copolymer can be synthesized.
Further, the present inventors have found that a desired aromatic vinyl / conjugated diene multiblock copolymer can be synthesized by repeating the operation of adding and removing a conjugated diene monomer from the polymerization reaction product.
Furthermore, the present inventors have found that an aromatic vinyl / conjugated diene radial block copolymer can be synthesized by adding a coupling agent to the polymerization reaction product obtained from the aromatic vinyl / conjugated diene block copolymer. The present invention has been completed.

  Thus, according to the first aspect of the present invention, there is provided a block copolymer having a polymer block (A) of an aromatic vinyl monomer and a polymer block (B) of a conjugated diene monomer, which is aromatic. The ratio of the monomer unit (a) derived from the vinyl monomer and the monomer unit (b) derived from the conjugated diene monomer is the weight of the monomer unit (a) and the monomer unit (b). The ratio is 5:95 to 95: 5, the number average molecular weight (Mn) is 10,000 to 1,000,000, and the polymer block (A) has 50 or more aromatic vinyl monomers linked together. An aromatic vinyl / conjugated diene block copolymer having at least one segment and having a racemic dyad ratio of 55% or more in the polymer block (A) is provided.

  In the aromatic vinyl / conjugated diene block copolymer of the present invention, the 1,4-cis bond content in the polymer block (B) is preferably 50% or more.

The aromatic vinyl / conjugated diene block copolymer of the present invention is
(I) a diblock copolymer formed by bonding the polymer block (B) to the polymer block (A),
(ii) a multi-block copolymer formed by alternately bonding the polymer block (B) and the polymer block (A) to the polymer block (A), or
(iii) It is preferably a radial block copolymer obtained by bonding the polymer block (A) and the polymer block (B).

  According to the second of the present invention, the following formula (1) and / or formula (2)

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 aralkyl groups, C1-C20 alkylcarbonyloxy groups, C1-C20 alkoxy groups, C1-C20 alkylthio groups, C6-C20 aryloxy groups, C6-C20 An arylthio group, a cyclopentadienyl group which may have a substituent, an indenyl group which may have a substituent, or a fluorenyl group which may have a substituent.
M ¹ and M ² each independently represent a titanium atom, a zirconium atom, or a hafnium atom.
X ¹ and X ² each independently represent a halogen atom.
a, b and c each independently represent an integer of 0 to 4, and d and e each independently represents an integer of 0 to 3. Further, a + b + c ≦ 4 and d + e ≦ 3. )
A transition metal compound represented by:
An organoaluminum oxy compound; an ionic compound capable of reacting with the transition metal compound to produce a cationic transition metal compound; a Lewis acid compound capable of reacting with the transition metal compound to produce a cationic transition metal compound; Polymerizing an aromatic vinyl monomer in the presence of a polymerization catalyst containing a reaction product with at least one cocatalyst selected from the group consisting of organometallic compounds of group 2 or group 13 element metals;
And a step of polymerizing the conjugated diene monomer by adding a conjugated diene monomer to the reaction system in a state where the aromatic vinyl monomer remains in the reaction system. A method for producing a vinyl-conjugated diene block copolymer is provided.

The method for producing an aromatic vinyl / conjugated diene block copolymer of the present invention comprises a step of polymerizing an aromatic vinyl monomer in the presence of the polymerization catalyst,
In a state where the aromatic vinyl monomer remains in the reaction system, a step of adding a conjugated diene monomer to the reaction system to polymerize the conjugated diene monomer and a conjugated diene monomer remaining in the reaction system It is preferable to have a step of removing the body from the reaction system and polymerizing the aromatic vinyl monomer remaining in the reaction system.

  According to a third aspect of the present invention, an aromatic vinyl / conjugated diene block copolymer polymerization reaction product is obtained by the production method of the present invention, and then a coupling agent is added to the reaction product. A method for producing an aromatic vinyl / conjugated diene radial block copolymer is provided.

  The aromatic vinyl / conjugated diene block copolymer of the present invention has an aromatic vinyl polymer block (A) having a high syndiotacticity and a conjugated diene polymer block (B). Therefore, it is excellent in heat resistance, chemical resistance and tensile strength, and is useful as a reinforcing rubber material, a resin modifier, a compatibilizing agent, a thermoplastic elastomer and the like.

  According to the production method of the present invention, an aromatic vinyl / conjugated diene-based diene dimer polymer block having a syndiotactic structure with a high crystal melting point and having a long chain length and a conjugated diene polymer block linked together. A block copolymer, a multi-block copolymer, and a radial block copolymer can be easily and efficiently produced.

  Hereinafter, the present invention will be described in detail with respect to 1) an aromatic vinyl / conjugated diene block copolymer and 2) a method for producing an aromatic vinyl / conjugated diene block copolymer.

1) Aromatic vinyl / conjugated diene block copolymer The aromatic vinyl / conjugated diene block copolymer of the present invention comprises a polymer block (A) of an aromatic vinyl monomer and a polymer of a conjugated diene monomer. And at least a block (B).

(1) Aromatic vinyl monomer polymer block (A)
The polymer block (A) of the aromatic vinyl monomer is obtained by polymerizing the aromatic vinyl monomer, and has at least an aromatic vinyl-based segment in which 50 or more molecules of the aromatic vinyl monomer are connected. Have one.

  Examples of the aromatic vinyl monomer used for the polymer block (A) of the aromatic vinyl monomer include styrene which may have a substituent, vinyl naphthalene which may have a substituent, and the like. . These aromatic vinyl monomers can be used alone or in combination of two or more.

  Among these, in the present invention, styrene which may have a substituent is preferable because of high polymerization activity and easy availability.

Examples of styrene that may have a substituent include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, 4-tert-butylstyrene, and α-methyl. Styrene, α-methyl-4-methylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-bromostyrene, 2-methyl-1,4-dichlorostyrene, 2,4-dibromostyrene, 4 -Hydroxystyrene, 4-methoxystyrene, 4-tert-butoxystyrene and the like.
Among these, since an aromatic vinyl polymer block (A) having a high crystalline melting point is obtained, it is preferable to use styrene, 2-methylstyrene, 3-methylstyrene or 4-methylstyrene alone, and styrene alone Is particularly preferred.

The polymer block (A) of the aromatic vinyl monomer has at least one segment in which 50 or more aromatic vinyl monomers are connected.
The fact that the aromatic vinyl monomer has a segment in which 50 or more molecules are linked can be confirmed by isolating the polymer block (A) of the aromatic vinyl monomer and measuring the molecular weight thereof. Specifically, a part of the polymerization of the aromatic vinyl monomer is sampled, or the polymer block (B) of the conjugated diene monomer is decomposed by ozonolysis or metathesis decomposition of the generated block copolymer. By doing so, the polymer block (A) of the aromatic vinyl monomer can be isolated.
The polymer block (A) of the aromatic vinyl monomer has at least one segment having a number average molecular weight (Mn) of 5,200 to 1,000,000, preferably 10,000 to 500,000.

The polymer block (A) of the aromatic vinyl monomer is a crystalline polymer block having a high degree of syndiotactic structure (syndiotacticity) and a high crystal melting point. The syndiotactic structure refers to a structure in which side chains such as phenyl groups and substituted phenyl groups are alternately positioned in opposite directions with respect to a main chain in which the stereochemical structure is formed from a carbon-carbon bond. The syndiotacticity in the polymer can be quantified by, for example, ¹³ C-NMR measurement.

  In the aromatic vinyl / conjugated diene block copolymer of the present invention, the ratio of racemic dyad in the polymer block of the aromatic vinyl monomer is 55% or more, preferably 70% or more, more preferably 80% or more. Particularly preferably, it is 90% or more. A racemic dyad is a structural unit in which the side chain is located in the opposite direction to the main chain in two consecutive monomer units in a polymer block. Generally, the higher the ratio, the more syndiotacticity is. Can be said to be a high polymer.

  In the aromatic vinyl / conjugated diene block copolymer of the present invention, since the ratio of racemic dyad in the polymer block (A) of the aromatic vinyl monomer is 55% or more, the crystallinity is high and the heat resistance is high. Excellent in chemical and chemical resistance.

(2) Conjugated diene monomer polymer block (B)
The polymer block (B) of the conjugated diene monomer can be obtained by polymerizing the conjugated diene monomer.

  Examples of the conjugated diene monomer used in the polymer block (B) of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1,3- Examples include butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. These conjugated diene monomers can be used alone or in combination of two or more.

  Among these, in the present invention, 1,3-butadiene or 2-methyl-1 is used because of high polymerization activity and the ability to obtain a polymer block (B) having a high 1,4-cis bond content. 1,3-butadiene is preferably used alone, and 1,3-butadiene is particularly preferably used alone.

  In the aromatic vinyl / conjugated diene block copolymer of the present invention, the 1,4-cis bond content in the polymer block (B) of the conjugated diene monomer is preferably 50% or more, more preferably 60% or more. Especially preferably, it is 70% or more. The aromatic vinyl / conjugated diene block copolymer having a 1,4-cis bond content of 50% or more of the polymer block (B) of the conjugated diene monomer has excellent tensile strength and has characteristics as an elastic material. Excellent.

The 1,4-cis bond content in the polymer block (B) of the conjugated diene monomer can be determined from the measurement results of ¹ H-NMR and / or ¹³ C-NMR, for example.
The number average molecular weight (Mn) of the polymer block (B) of the conjugated diene monomer is usually 1,000 to 1,000,000, preferably 10,000 to 500,000.

  In the aromatic vinyl / conjugated diene block copolymer of the present invention, the monomer unit (a) derived from aromatic vinyl and the monomer unit (b) derived from conjugated diene monomer are monomer units. The weight ratio of (a) to the monomer unit (b) is 5:95 to 95: 5, preferably 10:90 to 90:10, more preferably 15:85 to 85:15. When the ratio of the monomer unit (a) to the monomer unit (b) is in such a range, the crystallinity is high, the heat resistance and the chemical resistance are excellent, and the tensile strength is high. An aromatic vinyl / conjugated diene block copolymer having the following structure is obtained.

  The number average molecular weight (Mn) of the aromatic vinyl / conjugated diene block copolymer of the present invention is usually 10,000 to 1,000,000, preferably 20,000 to 500,000. The molecular weight distribution (Mw / Mn), which is the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw), is preferably 2.5 or less, more preferably 2.0 or less.

  The form of the aromatic vinyl / conjugated diene block copolymer of the present invention is not particularly limited as long as it has a polymer block (A) and a polymer block (B) in the molecule.

  As the form of the aromatic vinyl / conjugated diene block copolymer of the present invention, the polymer block (A) is S, the polymer block (B) is D, and the coupling part between the segment and each block by the coupling agent is B. For example, the following may be mentioned.

(I) Diblock copolymer:
SD
(ii) Multiblock copolymer:
_{S- (D-S) n,} S- (D-S) n -D, S- (D-S) n -B- (S-D) n -S, S- (D-S) m -D -BD- (SD) _m -S
(iii) Radial block copolymer:
B [-(SD) _n- S] _l , B [-D- (SD) _m- S] _l
(In the above formula, n represents an integer of 1 or more, m represents an integer of 0 or more, and l represents an integer of 3 or more.)
Among these, from the viewpoint of ease of production, in the above formula, n is preferably 1, and m is preferably 0. Further, l is preferably 3 or 4, although it depends on the type of coupling agent described later.

    The aromatic vinyl / conjugated diene block copolymer of the present invention includes an aromatic vinyl polymer block (A) having a high syndiotacticity and a conjugated diene polymer block (B) having a high 1,4-cis bond content. Therefore, it is excellent in heat resistance, chemical resistance and tensile strength, and is useful as a reinforcing rubber material and a resin modifier.

  Among the aromatic vinyl / conjugated diene block copolymers of the present invention, the diblock copolymer is an impact modifier for aromatic vinyl polymers, aromatic vinyl polymers, and conjugated diene polymers. The multi-block copolymer and the radial block copolymer are useful as thermoplastic elastomers.

2) Method for Producing Aromatic Vinyl / Conjugated Diene Block Copolymer The method for producing an aromatic vinyl / conjugated diene block copolymer of the present invention polymerizes an aromatic vinyl monomer in the presence of a specific polymerization catalyst. And a second stage step of polymerizing the conjugated diene monomer with the aromatic vinyl monomer remaining. The method for producing an aromatic vinyl / conjugated diene block copolymer of the present invention is particularly suitable for producing the aromatic vinyl / conjugated diene block copolymer of the present invention.

  Examples of the aromatic vinyl monomer and the conjugated diene monomer used in the production method of the present invention include those listed as the monomers used in the block copolymer of the present invention.

(1) Polymerization catalyst In the present invention, the polymerization catalyst reacts with the transition metal compound represented by the formula (1) and / or the formula (2), the organoaluminum oxy compound, and the transition metal compound to be cationic. From the group consisting of an ionic compound capable of producing a transition metal compound, a Lewis acid compound capable of reacting with the transition metal compound to produce a cationic transition metal compound, and an organometallic compound of a Group 1, 2 or 13 element metal A material containing a reaction product with at least one selected cocatalyst is used.

(Transition metal compounds)
The transition metal compound used in the present invention is a transition metal compound represented by the formula (1) and / or (2).
In formulas (1) and (2), R ^{1 to} R ⁵ are each independently a hydrogen atom;
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, an alkyl group having 1 to 20 carbon atoms such as n-octyl group and n-decyl group; an aryl group having 6 to 20 carbon atoms such as phenyl group, 1-naphthyl group and 2-naphthyl group; tolyl group, xylyl group and mesityl Alkylaryl groups such as benzyl groups; aralkyl groups such as benzyl groups and phenethyl groups; acetoxy groups, propionyloxy groups, butylcarbonyloxy groups, pentylcarbonyloxy groups, hexylcarbonyloxy groups, octylcarbonyloxy groups, decylcarbonyloxy groups, hepta C1-C20 alkylcarbonyloxy group such as decylcarbonyloxy group; Si group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, amyloxy group, hexyloxy group, 2-ethylhexyloxy group and the like alkoxy group having 1 to 20 carbon atoms; methylthio group, ethylthio group, propylthio group Group, butylthio group, t-butylthio group, hexylthio group, octylthio group and other alkylthio groups having 1 to 20 carbon atoms; phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and other aryloxy groups having 6 to 20 carbon atoms Group; arylthio group having 6 to 20 carbon atoms such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group;

Cyclopentadienyl, methylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,3,4-tetramethylcyclopentadi Enyl group, trimethylsilylcyclopentadienyl group, 1,3-di (trimethylsilyl) cyclopentadienyl group, tertiary butylcyclopentadienyl group, 1,3-di (tertiary butyl) cyclopentadienyl group, penta Even if it has a substituent such as methylcyclopentadienyl group, 1,2,4-tri (trimethylsilyl) cyclopentadienyl group, 1,2,4-tri (tertiarybutyl) cyclopentadienyl group A good cyclopentadienyl group;
An indenyl group optionally having a substituent such as an indenyl group, a methyl indenyl group, a dimethyl indenyl group, a trimethyl indenyl group;
And a fluorenyl group which may have a substituent such as a fluorenyl group and a methylfluorenyl group.

  a, b and c each independently represent an integer of 0 to 4, and a + b + c ≦ 4. d and e each independently represent an integer of 0 to 3, and d + e ≦ 3.

M ¹ and M ² each independently represent one kind of transition metal atom selected from the group consisting of titanium (Ti), zirconium (Zr), and hafnium (Hf).
X ¹ and X ² each independently represent a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Among the transition metal compounds represented by the formula (1) or (2), in the present invention, a titanium compound is preferred because of its excellent polymerization catalyst activity, and a mono (cyclopentadienyl) represented by the following formula (3) ) Titanium compounds, mono (indenyl) titanium compounds or mono (fluorenyl) titanium compounds are more preferred.

In the formula, R ⁶ represents a cyclopentadienyl group which may have a substituent, an indenyl group which may have a substituent, or a fluorenyl group which may have a substituent. Specific examples of these groups are the same as those described above.

X, Y and Z are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an alkylthio group having 1 to 20 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a halogen atom.
Specific examples of these groups and halogen atoms include the same groups as those described above as examples of R ^{1 to} R ⁵ .

  Specific examples of the titanium compound represented by the formula (3) include cyclopentadienyl trimethyl titanium; cyclopentadienyl triethyl titanium; cyclopentadienyl tripropyl titanium; cyclopentadienyl tributyl titanium; 1,2-dimethylcyclopentadienyltrimethyltitanium; 1,2,4-trimethylcyclopentadienyltrimethyltitanium; 1,2,3,4-tetramethylcyclopentadienyltrimethyltitanium; pentamethylcyclo Pentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium;

  Pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; cyclopentadienylmethyltitanium dichloride; cyclopentadienylethyltitanium dichloride; pentamethylcyclopentadienylmethyltitanium dichloride; pentamethylcyclopentadi Cyclohexadienyl titanium titanium monochloride; cyclopentadienyl diethyl titanium monochloride; cyclopentadienyl titanium trimethoxide; cyclopentadienyl titanium triethoxide;

  Cyclopentadienyl titanium tripropoxide; cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide; pentamethylcyclopentadienyl titanium tripropoxide; Pentamethylcyclopentadienyl titanium tributoxide; pentamethylcyclopentadienyl titanium triphenoxide;

  Cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride; pentamethylcyclopentadienyl methoxy titanium dichloride; cyclopentadienyl tribenzyl Titanium; pentamethylcyclopentadienylmethyldiethoxytitanium; indenyltitanium trichloride; indenyltitanium trimethoxide; indenyltitanium triethoxide; indenyltribenzyltitanium; indenyltribenzyltitanium; pentamethylcyclopentadienyl Titanium trithiomethoxide; pentamethylcyclopentadienyl titanium trithiophenoxide and the like.

  In the present invention, a condensed titanium compound having a structure represented by the following formula (4) can also be used as the titanium compound.

In the formula, R ⁷ and R ⁸ each independently represent a halogen atom, an alkoxy group having 1 to 20 carbon atoms or an acyloxy group, and k represents an integer of 2 to 20. The alkoxy group having 1 to 20 carbon atoms include the same as those listed as specific examples of the R ¹ to R ^5.

Specific examples when the transition metal compound is a zirconium compound include tetrabenzylzirconium, zirconium tetraethoxide, zirconium tetrabutoxide, bisindenylzirconium dichloride, triisopropoxyzirconium chloride, zirconium benzyldichloride, tributoxyzirconium chloride, and the like. Is mentioned.
Specific examples of the hafnium compound include tetrabenzyl hafnium, hafnium tetraethoxide, hafnium tetrabutoxide, and the like.
These transition metal compounds may form complexes with esters, ethers and the like.

  Furthermore, in the present invention, as the transition metal compound, a transition metal compound having two ligands having conjugated π electrons, for example, a transition metal compound represented by the following formula (5) can also be used.

In the formula, M ¹ represents the same meaning as described above. R ⁹ and R ¹⁰ each independently represents a cyclopentadienyl group which may have a substituent, an indenyl group which may have a substituent, or a fluorenyl group which may have a substituent. Represent.

Specific examples of R ⁹ and R ¹⁰ are the same as those listed as specific examples of R ⁷ . R ⁹ and R ¹⁰ are each a hydrocarbon group having 1 to 5 carbon atoms such as an alkylidene group such as a methine group, an ethylidene group, a propylidene group or a dimethylcarbyl group; a dimethylsilyl group, a diethylsilyl group or a dibenzylsilyl group. Or an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms; or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium atoms;

R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or an alkylthio group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group, and 2-ethylhexyl group. Alkyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl groups and naphthyl groups; arylalkyl groups having 7 to 20 carbon atoms such as benzyl groups; and the like. Examples of the alkoxy group having 1 to 20 carbon atoms and the alkylthio group having 1 to 20 carbon atoms are the same as those listed as specific examples of R ^{1 to} R ⁵ .

  Specific examples of the transition metal compound represented by the formula (5) include biscyclopentadienyl titanium dimethyl, biscyclopentadienyl titanium diethyl, biscyclopentadienyl titanium dipropyl, and biscyclopentadienyl titanium dibutyl. Bis (methylcyclopentadienyl) titanium dimethyl, bis (tertiary butylcyclopentadienyl) titanium dimethyl, bis (1,3-dimethylcyclopentadienyl) titanium dimethyl, bis (1,3-ditertiary butylcyclo Pentadienyl) titanium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) titanium dimethyl, bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; biscyclopentadienyl titanium Dimethyl, bis (trimethylsilylcyclo Tantadienyl) titanium dimethyl, bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethyl, bis (1,2,4-tri ((trimethylsilyl) cyclopentadienyl) titanium dimethyl, bisindenyltitanium dimethyl, Bisfluorenyl titanium dimethyl, methylene biscyclopentadienyl titanium dimethyl, ethylidene biscyclopentadienyl titanium dimethyl, methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl, ethylidene bis (2, 3,4,5-tetramethylcyclopentadienyl) titanium dimethyl, dimethylsilyl bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl, methylene bisindenyl titanium dimethyl, ethylidene bisindenyl titanium The Cyl, dimethylsilylbisindenyltitanium dimethyl, methylenebisfluorenyltitanium dimethyl, ethylidenebisfluorenyltitanium dimethyl, dimethylsilylbisfluorenyltitanium dimethyl, methylene (tertiary butylcyclopentadienyl) (cyclopentadienyl) ) Titanium dimethyl, methylene (cyclopentadienyl) (indenyl) titanium dimethyl, ethylidene (cyclopentadienyl) (indenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethyl, methylene (cyclopentadienyl) ) (Fluorenyl) titanium dimethyl, ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethyl, dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethyl, methyl Len (indenyl) (fluorenyl) titanium dimethyl,

  Ethylidene (indenyl) (fluorenyl) titanium dimethyl, dimethylsilyl (indenyl) (fluorenyl) titanium dimethyl, biscyclopentadienyl titanium dibenzyl, bis (tertiary butylcyclopentadienyl) titanium dibenzyl, bis (methylcyclopentadi) Enyl) titanium dibenzyl, bis (1,3-dimethylcyclopentadienyl) titanium dibenzyl, bis (1,2,4-trimethylcyclopentadienyl) titanium dibenzyl, bis (1,2,3,4-) Tetramethylcyclopentadienyl) titanium dibenzyl, bispentamethylcyclopentadienyl titanium dibenzyl, bis (trimethylsilylcyclopentadienyl) titanium dibenzyl, bis (1,3-di- (trimethylsilyl) cyclopentadienyl) Titanium diben Bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dibenzyl, bisindenyltitanium dibenzyl, bisfluorenyltitanium dibenzyl, methylenebiscyclopentadienyltitanium dibenzyl, ethylidenebis Cyclopentadienyl titanium dibenzyl, methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl, ethylidene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl , Dimethylsilyl bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl, methylene bisindenyl titanium dibenzyl, ethylidene bisindenyl titanium dibenzyl, dimethylsilyl bisindenyl titanium dibenzyl, methylene Bisfluorenyl tita Dibenzyl, ethylidene bisfluorenyl titanium dibenzyl, dimethylsilyl bisfluorenyl titanium dibenzyl, methylene (cyclopentadienyl) (indenyl) titanium dibenzyl, ethylidene (cyclopentadienyl) (indenyl) titanium dibenzyl, dimethyl Silyl (cyclopentadienyl) (indenyl) titanium dibenzyl, methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl, ethylidene (cyclopentadienyl) (fluorenyl) titanium dibenzyl, dimethylsilyl (cyclopentadienyl) (Fluorenyl) titanium dibenzyl, methylene (indenyl) (fluorenyl) titanium dibenzyl, ethylidene (indenyl) (fluorenyl) titanium dibenzyl, dimethylsilyl (indenyl) (fluorenyl) ) Titanium dibenzyl,

  Biscyclopentadienyl titanium dimethoxide, biscyclopentadienyl titanium diethoxide, biscyclopentadienyl titanium dipropoxide, biscyclopentadienyl titanium dibutoxide, biscyclopentadienyl titanium diphenoxide, bis (methyl Cyclopentadienyl) titanium dimethoxide, bis (1,3-dimethylcyclopentadienyl) titanium dimethoxide, bis (1,2,4-trimethylcyclopentadienyl) titanium dimethoxide, bis (1,2,3 , 4-Tetramethylcyclopentadienyl) titanium dimethoxide, bispentamethylcyclopentadienyl titanium dimethoxide, bis (trimethylsilylcyclopentadienyl) titanium dimethoxide, bis (1,3-di (trimethylsilyl) cyclopentadi Enil) Tandimethoxide, bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dimethoxide, bisindenyl titanium dimethoxide, bisfluorenyl titanium dimethoxide, methylenebiscyclopentadienyl titanium dimethoxide, Ethylidene biscyclopentadienyl titanium dimethoxide, methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide, ethylidene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium Dimethoxide, dimethylsilylbis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide, methylenebisindenyltitanium dimethoxide; methylenebis (methylindenyl) titanium dimethoxide, ethylidenebisindenyltitanium di Toxide, dimethylsilyl bisindenyl titanium dimethoxide, methylene bisfluorenyl titanium dimethoxide, methylene bis (methylfluorenyl) titanium dimethoxide, ethylidene bisfluorenyl titanium dimethoxide, dimethylsilyl bisfluorenyl titanium dimethoxide, Methylene (cyclopentadienyl) (indenyl) titanium dimethoxide, ethylidene (cyclopentadienyl) (indenyl) titanium dimethoxide, dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethoxide,

  Ethylidene bisfluorenyl titanium dibenzyl, dimethylsilyl bisfluorenyl titanium dibenzyl, methylene (cyclopentadienyl) (indenyl) titanium dibenzyl, ethylidene (cyclopentadienyl) (indenyl) titanium dibenzyl; dimethylsilyl ( Cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl, ethylidene (cyclopentadienyl) (fluorenyl) titanium dibenzyl, dimethylsilyl (cyclopentadienyl) (fluorenyl) ) Titanium dibenzyl, methylene (indenyl) (fluorenyl) titanium dibenzyl, ethylidene (indenyl) (fluorenyl) titanium dibenzyl, dimethylsilyl (indenyl) (fluorenyl) titanium dibe Biscyclopentadienyl titanium dimethoxide, biscyclopentadienyl titanium diethoxide, biscyclopentadienyl titanium dipropoxide, biscyclopentadienyl titanium dibutoxide, biscyclopentadienyl titanium diphenoxide, bis (Methylcyclopentadienyl) titanium dimethoxide, bis (1,3-dimethylcyclopentadienyl) titanium dimethoxide, bis (1,2,4-trimethylcyclopentadienyl) titanium dimethoxide, bis (1,2 , 3,4-Taylamethylcyclopentadienyl) titanium dimethoxide, bispentamethylcyclopentadienyl titanium dimethoxide, bis (trimethylsilylcyclopentadienyl) titanium dimethoxide, bis (1,3-di (trimethylsilyl) cyclopentadi Nyl) titanium dimethoxide, bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dimethoxide, bisindenyl titanium dimethoxide, bisfluorenyl titanium dimethoxide, methylenebiscyclopentadienyl titanium dimethoxy Ethylidenebiscyclopentadienyl titanium dimethoxide, methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide, ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) ) Titanium dimethoxide, dimethylsilyl bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide, methylene bisindenyl titanium dimethoxide, methylene bis (methylindenyl) titanium dimethoxide; Luci Tandimethoxide, dimethylsilylbisindenyltitanium dimethoxide,

  Methylenebisfluorenyltitanium dimethoxide, methylenebis (methylfluorenyl) titanium dimethoxide, ethylidenebisfluorenyltitanium dimethoxide, dimethylsilylbisfluorenyltitanium dimethoxide, methylene (cyclopentadienyl) (indenyl) titanium Dimethoxide, ethylidene (cyclopentadienyl) (indenyl) titanium dimethoxide, dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethoxide, methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide, ethylidene (cyclopenta) Dienyl) (fluorenyl) titanium dimethoxide, dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethoxide, methylene (indenyl) (fluorenyl) titanium dimethoxy , Ethylidene (indenyl) (fluorenyl) titanium dimethoxide, dimethylsilyl (indenyl) (fluorenyl) titanium compounds such as titanium dimethoxide;

Zirconium compounds such as ethylidenebiscyclopentadienylzirconium dimethoxide, dimethylsilylbiscyclopentadienylzirconium dimethoxide;
And hafnium compounds such as ethylidenebiscyclopentadienyl hafnium dimethoxide and dimethylsilylbiscyclopentadienyl hafnium dimethoxide;
Among these, as a compound represented by Formula (5), a titanium compound is preferable.

  In the present invention, as the transition metal compound, 2,2′-thiobis (4-methyl-6-t-butylphenyl) titanium diisopropoxide; 2,2′-thiobis (4-methyl-6-t-) A bidentate coordination complex such as (butylphenyl) titanium dimethoxide can also be used.

(Cocatalyst)
In the present invention, as an auxiliary catalyst, an organoaluminum oxy compound, an ionic compound that can react with the transition metal compound to form a cationic transition metal compound, and a reaction with the transition metal compound can produce a cationic transition metal compound. At least one selected from the group consisting of a Lewis acid compound and an organometallic compound of a Group 1, 2 or 13 element metal of the periodic table is used.

  The organoaluminum oxy compound is preferably a linear or cyclic polymer represented by the following formula (6).

^{Wherein, R 13} represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹³ may be substituted with a halogen atom or a group represented by the formula: R ¹⁴ O (R ¹⁴ represents a hydrocarbon group having 1 to 10 carbon atoms).
Specific examples of R ¹³ and R ¹⁴ include alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable.
n represents the degree of polymerization, and is preferably 5 or more, more preferably 10 to 100, and particularly preferably 10 to 50. When the degree of polymerization n is less than 5, it is not preferable because the polymerization activity is lowered. On the other hand, when it exceeds 100, the polymerization activity is lowered, and problems such as difficulty in deashing are caused.

Examples of the ionic compound that can react with the transition metal compound to form a cationic transition metal compound include non-coordinating anions and cations.
Non-coordinating anions include tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) Examples thereof include borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xyyl) borate, triphenylpentafluorophenylborate, and tris (pentafluorophenyl) phenylborate.

  Of these, tetrakis (pentafluorophenyl) borate is particularly preferred. Specific examples thereof include triphenylcarbenium tetrakis (pentafluorophenyl) borate, 4,4 ′, 4 ″ -tri (methoxyphenyl) carbeniumtetrakis (pentafluorophenyl) borate, tri (toluyl) carbeniumtetrakis (penta Fluorophenyl) borate, 4,4 ′, 4 ″ -tri (chlorophenyl) carbenium tetrakis (pentafluorophenyl) borate, triphenylsilyltetrakis (pentafluorophenyl) borate, trimethoxysilyltetrakis (pentafluorophenyl) borate, tri (Thioisopropyl) silyltetrakis (pentafluorophenyl) borate, trimethylsilyltetrakis (pentafluorophenyl) borate, 4,4 ′, 4 ″ -tri (methoxyphenyl) silane Rutetorakisu (pentafluorophenyl) borate, tri (toluyl) silyl tetrakis (pentafluorophenyl) borate, 4,4 ', 4 "- tri (chlorophenyl) silyl tetrakis (pentafluorophenyl) borate and the like.

  Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, and a ferrocenium cation having a transition metal.

  Specific examples of the carbonium cation include triphenylcarbonium cation; trisubstituted phenylcarbonium cation such as tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation; It is done.

Specific examples of the oxonium cation include alkyloxonium cations such as hydroxonium cation OH ₃ ⁺ and methyloxonium cation CH ₃ OH ₂ ⁺ ; dialkyloxonium cations such as dimethyloxonium cation (CH ₃ ) ₂ OH ⁺ ; And trialkyloxonium cations such as trimethyloxonium cation (CH ₃ ) ₃ O ⁺ and triethyloxonium cation (C ₂ H ₅ ) ₃ O ⁺ ;

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-diethylanilinium cation, N, N-2,4,6- N, N-dialkylanilinium cations such as pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation; and the like.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  These ionic compounds can be used alone or in combination of two or more of the non-coordinating anions and cations exemplified above.

  Among these, as the ionic compound, triphenylcarbonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetra (pentafluoro) Phenyl) borate is particularly preferred.

  Specific examples of Lewis acid compounds that can react with the transition metal compound to form a cationic transition metal compound include tris (pentafluorophenyl) boron, tris (monofluorophenyl) boron, tris (difluorophenyl) boron, and triphenyl. Examples include boron.

  Specific examples of organometallic compounds of the periodic table 1, 2 or 13 element metal include: organolithium compounds such as methyllithium, butyllithium and phenyllithium; organomagnesium compounds such as dibutylmagnesium; trimethylaluminum, triethylaluminum and triisobutyl Organo aluminum compounds such as aluminum, trihexyl aluminum and trioctyl aluminum; Magnesium halogen compounds such as ethyl magnesium chloride and butyl magnesium chloride; Aluminum halogen compounds such as dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride and ethyl aluminum dichloride ; Diethylaluminum hydride, sesquiethylaluminum hydride, etc. Machine aluminum hydride; and the like.

In the present invention, a metal hydride compound can be used together with the organometallic compound of the periodic tables 1 and 2 and the group 13 element metal described above.
Examples of the metal hydride compound include lithium hydride, sodium hydride, calcium hydride, lithium aluminum hydride, sodium borohydride, and the like.

  In the present invention, as the cocatalyst, the organoaluminum oxy compound, an ionic compound capable of reacting with the transition metal compound to form a cationic transition metal compound, and reacting with the transition metal compound to produce a cationic transition metal compound. At least one selected from the group consisting of Lewis acid compounds and organometallic compounds of Group 1, 2 or 13 element metals of the periodic table may be used alone, or two or more may be used in combination.

  In the present invention, among these, an organoaluminum oxy compound alone, a Lewis acid compound that can react with the transition metal compound to form a cationic transition metal compound, an organoaluminum oxy compound, and the transition metal compound react with each other. An ionic compound capable of producing a cationic transition metal compound, or a Lewis acid compound capable of producing a cationic transition metal compound by reacting with the transition metal compound, and an organometallic compound of a periodic table Group 1, 2, or 13 element metal A combination with at least one selected from the group consisting of

  Particularly preferred for obtaining a polymer with a narrow molecular weight distribution is an ionic compound that can react with the transition metal compound to produce a cationic transition metal compound or a reaction with the transition metal compound to produce a cationic transition metal compound. And a combination of a Lewis acid compound that can be formed and at least one selected from the group consisting of organometallic compounds of Group 1, 2 or 13 element metals of the periodic table.

  The catalyst used for the production of the block copolymer of the present invention contains a reaction product of the above transition metal compound and a co-catalyst. A catalyst component may be added.

  The ratio of the transition metal compound and the cocatalyst used in the catalyst of the present invention varies depending on the type of compound and various polymerization conditions and is not uniquely defined, but is usually determined independently between the cocatalyst and the transition metal compound. The molar ratio is desirably within the following range.

  When an organoaluminum oxy compound is used as a cocatalyst, the molar ratio of aluminum / transition metal compound in the organoaluminum oxy compound is usually 1-1000,000, preferably 10-50,000, more preferably 100- 5,000.

When an ionic compound is used as a cocatalyst, the molar ratio of the ionic compound / transition metal compound is usually 0.01 to 100, preferably 0.1 to 10.
When a Lewis acid compound is used as a cocatalyst, the molar ratio of Lewis acid compound / transition metal compound is usually 0.01 to 100, preferably 0.1 to 10.
In addition, when using a Lewis' acid compound, it is preferable to use together the organometallic compound of periodic table 1, 2 and 13 group element metal.

When at least one selected from the group consisting of organometallic compounds of Group 1, 2 or 13 element metals of the periodic table is used as a cocatalyst, the molar ratio of organometallic compound / transition metal compound is usually 0.1-10. 1,000, preferably 1 to 1,000.
If the ratio of the transition metal compound and the cocatalyst is out of the above range, the polymerization activity is lowered, which is not preferable.

  The transition metal compound and the cocatalyst can be used in any state of a solution and a slurry, respectively, but in order to obtain higher polymerization activity, those in a solution state are preferable.

  Examples of the solvent used for preparing the solution or slurry include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane, and cyclohexane; mineral oil, benzene, toluene, xylene, and the like. And aromatic hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, chlorobenzene and the like. These solvents can be used alone or in combination of two or more. Among these, it is preferable to use an aromatic hydrocarbon solvent such as toluene or benzene.

  In the present invention, the transition metal compound represented by the formula (1) and / or the formula (2) can be used alone or supported on the support together with the promoter.

Examples of the carrier include inorganic compounds or organic polymer compounds.
Examples of the inorganic compound include inorganic oxides, inorganic chlorides, inorganic hydroxides, and the like, which may contain a small amount of carbonate or sulfate. Among these, inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia; inorganic chlorides such as magnesium chloride; are preferable.

The inorganic compound is preferably porous fine particles having an average particle size of 5 to 150 μm and a specific surface area of ² to 800 m ² / g, and can be used by heat treatment at 100 to 800 ° C.

  As the organic polymer compound, those having a functional group such as an aromatic ring, a substituted aromatic ring, a hydroxyl group, a carboxyl group, an ester group or a halogen atom in the side chain are preferable.

Specific examples of the organic polymer compound include an α-olefin homopolymer or α-olefin copolymer having a functional group obtained by chemically modifying a polymer having units such as ethylene, propylene, and butene; acrylic acid And polymers having units such as methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and the like. These organic polymer compounds are preferably spherical fine particles having an average particle diameter of 5 to 250 μm.
By carrying the transition metal compound and the cocatalyst as a simple substance, contamination due to adhesion of the catalyst to the polymerization reaction vessel can be prevented.

  The aromatic vinyl / conjugated diene block copolymer of the present invention comprises a first stage step of polymerizing an aromatic vinyl monomer in the presence of the polymerization catalyst described above, and the residual aromatic vinyl monomer. It can be produced by a second stage step of polymerizing a conjugated diene monomer.

(First stage process)
In the first step, the aromatic vinyl monomer is polymerized in the presence of the polymerization catalyst.
As a method for polymerizing the aromatic vinyl monomer, any of a bulk polymerization method, a solution polymerization method, and a suspension polymerization method can be used, and a bulk polymerization method or a solution polymerization method is preferable.
More specifically, the polymerization of the aromatic vinyl monomer is performed by (1) a method in which the transition metal compound and the cocatalyst are mixed in advance and then the aromatic vinyl monomer is added, and (2) the transition. A method of polymerizing by adding a promoter in the presence of a metal compound and an aromatic vinyl monomer, (3) a method of polymerizing by adding a transition metal compound in the presence of the promoter and an aromatic vinyl monomer, 4) After the transition metal compound, the cocatalyst and a small amount of aromatic vinyl monomer are mixed, the remaining aromatic vinyl monomer is added and polymerized.
Among these, the method (1) or (4) is preferable from the viewpoint of promptly starting the polymerization and improving the polymerization activity.

  Examples of the solvent used for polymerization include chain aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and mixed solvents composed of two or more of these. Among these, from the viewpoint of providing a monomer concentration of 0.5 to 100% by weight, alkanes having 4 to 26 carbon atoms, particularly branched alkanes, toluene, ethylbenzene, and mixtures thereof are preferable. Polymerization reaction by adding a small amount of polar compounds such as ethers such as anisole, diphenyl ether, ethyl ether, diglyme, tetrahydrofuran, dioxane; amines such as triethylamine, tetramethylethylenediamine, etc. within a range not impairing the effects of the present invention. May be performed.

The polymerization temperature of the aromatic vinyl monomer is in the range of −100 to + 250 ° C., preferably −50 to + 120 ° C., more preferably −30 to + 70 ° C.
The polymerization time of the aromatic vinyl monomer varies depending on the polymerization conditions such as temperature and solvent, but is usually 30 seconds to 36 hours, preferably 1 minute to 20 hours, more preferably 5 minutes to 10 hours.

  In the method for producing an aromatic vinyl / conjugated diene block copolymer of the present invention, the conjugated diene monomer is added to the polymerization reaction system with the aromatic vinyl monomer remaining in the first step. . The amount of the aromatic vinyl monomer that remains is theoretically sufficient if it is in excess of the transition metal compound, but it is difficult to leave a small amount of the aromatic vinyl monomer equivalent to the transition metal compound. Therefore, it is preferable to leave a large excess of the aromatic vinyl monomer as compared with the transition metal compound.

  The first step is completed by measuring the polymerization time and the polymer production amount of the aromatic vinyl monomer or the consumption amount of the aromatic vinyl monomer in advance under the same polymerization conditions, and using the measurement data based on the measurement data. You just have to decide. Alternatively, the polymerization conversion rate may be determined by sampling over time during the polymerization reaction.

(Second stage process)
In the second step, the conjugated diene monomer is added to the polymerization solution obtained in the first step and in which the aromatic vinyl monomer remains, and the conjugated diene monomer is polymerized.
Since the conjugated diene monomer has a very high polymerization reactivity with the catalyst used in the present invention compared to the aromatic vinyl monomer, the polymerization of the conjugated diene monomer has priority even in the presence of the aromatic vinyl polymer. The conjugated diene polymer block (B) is produced.

  In the present invention, random copolymerization may proceed depending on the types of the aromatic vinyl monomer and the conjugated diene monomer. Also in this case, since the polymerization reactivity of the conjugated diene monomer is high, a rubber-like conjugated diene polymer block having a high ratio of the conjugated diene monomer structural unit is generated. Therefore, the conjugated diene polymer block (B) of the present invention may include those obtained by random copolymerization of a small amount of an aromatic vinyl monomer.

  The polymerization conditions such as the polymerization temperature and polymerization time in the second stage step are the same as in the first stage step described above. In the second step, a solvent may be added as necessary, or the polymerization temperature may be changed.

After completion of the second step, a diblock copolymer can be produced by stopping the polymerization with the conjugated diene monomer remaining.
In order to stop the polymerization, a polymerization terminator may be added to the polymerization system. Examples of the polymerization terminator used include alcohols such as methanol, ethanol, propanol, butanol, and isopropanol. In addition, an alcohol containing an acid such as hydrochloric acid can also be used as a polymerization terminator.

  In the production method of the present invention, after completion of the second step, the conjugated diene monomer remaining in the polymerization system is removed without stopping the polymerization, and the operations in the first step and the second step are repeated. A multi-block copolymer can be produced.

  Since the conjugated diene monomer has a low boiling point, it is vaporized by flowing an inert gas such as nitrogen or argon in an open system, so that it can be easily removed out of the system. When the conjugated diene monomer is removed, the polymerization reaction of the aromatic vinyl monomer remaining in the polymerization system resumes. An aromatic vinyl monomer may be further added when removing the conjugated diene monomer.

  If the polymerization reaction is terminated after completion of the polymerization of the aromatic vinyl monomer, “aromatic vinyl polymer block (A) -conjugated diene polymer block (B) -aromatic vinyl polymer block (A)”. The triblock copolymer can be obtained.

  Further, in the same manner as described above, an operation of adding a conjugated diene monomer to polymerize the polymerization reaction system and removing the remaining conjugated diene monomer to polymerize the remaining aromatic vinyl monomer. By repeating this operation, a higher-order multiblock copolymer such as a tetrablock copolymer or a pentablock copolymer can be produced.

  In any case, after producing the desired multi-block copolymer, a polymerization terminator is added to the polymerization reaction system in the same manner as in the production of the diblock copolymer to terminate the polymerization. Can do.

  After producing an aromatic vinyl / conjugated diene diblock copolymer or an aromatic vinyl / conjugated diene multiblock copolymer, an aromatic vinyl can be added by adding a coupling agent to the polymerization reaction system without stopping the polymerization. A conjugated diene multiblock copolymer or an aromatic vinyl / conjugated diene radial block copolymer can be produced.

  A linear multi-block copolymer is obtained by adding a coupling agent and bonding the ends of two diblock copolymers and / or multi-block copolymers. Further, a star-type radial block copolymer can be obtained by bonding the ends of three or more diblock copolymers and / or multiblock copolymers.

When a coupling agent is added, a so-called coupling reaction proceeds.
This coupling reaction includes (i) a reaction in which a directly coupled polymer is produced by contacting a multi-molecule diblock polymer and / or multi-block polymer with one molecule of a coupling agent, (ii ) When one molecule of diblock polymer or multi-block polymer is contacted with one molecule of a coupling agent, a terminal-modified polymer is first formed, and then cupped during subsequent post-treatment (chemical reaction, heat treatment, etc.). It is either a reaction in which a ringed polymer is formed, or (iii) a combination of (i) and (ii) above.
In addition, although the reaction site | part of a coupling agent and a diblock polymer or a multiblock polymer may be one, it is preferable that it is plurality.

  Coupling agents used include oxygen molecules; carbon monoxide; carbon dioxide; carbon disulfide; carbonyl sulfide; sulfur dioxide; halogen molecules such as chlorine, bromine and iodine; organic halides such as vinylbenzyl chloride and trimethylene bromide; Is mentioned.

  In addition, hetero three-membered ring compounds; ketone compounds; aldehyde compounds; compounds having a ketene structure or thioketene structure; compounds having an ester structure or a lactone structure; compounds having an acid halide structure; compounds having a carbodiimide structure; A compound having an amide structure; a compound having a urea structure or a thiourea structure; a compound having an imide structure; a compound having a carbamic acid structure; a compound having an isocyanuric acid structure; a compound having a derivative structure thereof; Carbonyl-containing compounds; compounds having an isocyanate structure or thioisocyanate structure; silicon compounds, germanium compounds, tin compounds or phosphorus compounds having halogen atoms or alkoxy groups; halogenated hydrocarbons; It can be used in.

  Hetero 3-membered ring compounds include ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, epoxidized natural rubber, bisphenol A diglycidyl ether, glycerin triglycidyl ether, N, N, N ′, N′— Epoxy compounds such as tetraglycidyldiaminodiphenylmethane; thiirane compounds such as thiirane, methylthiirane, phenylthiirane; ethyleneimine, propyleneimine, N-phenylethyleneimine, N- (β-cyanoethyl) ethyleneimine, 2,5-bis (1 And ethyleneimine derivatives such as -aziridinyl) -p-benzoquinone.

  Examples of ketone compounds include 2,5-hexanedione; 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 N-substituted aminoketones such as' -bis (diphenylamino) benzophenone; N-substituted aminothioketones corresponding to the N-substituted aminoketones;

Examples of the aldehyde compound include pentane dial; N-substituted benzaldehydes such as 4-dimethylaminobenz (thio) aldehyde, 4-diphenylaminobenz (thio) aldehyde, 4-divinylaminobenz (thio) aldehyde, or N-substituted benz Examples include thioaldehydes.
Examples of the compound having a ketene structure or a thioketene structure include ethyl (thio) ketene, butyl (thio) ketene, phenyl (thio) ketene, toluyl (thio) ketene, and the like.

Examples of the compound having an ester structure or a lactone structure include ethyl acetate, fatty acid glycerol ester, glycerol triacetate, glycerol tributyrate, and γ-butyrolactone.
Examples of the compound having an acid halide structure include propionic acid chloride, benzoic acid chloride, phthalic acid chloride, maleic acid chloride, and trimesoyl chloride.
Specific examples of the compound having a carbodiimide structure include N, N′-diphenylcarbodiimide, N, N′-diethylcarbodiimide and the like.

  Examples of the compound having a pyridine unit include 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tribromoimidazole, and 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-tetrachloro Pyrimidine, 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- Pyridine compounds having a halogen on the carbon atom adjacent to the nitrogen atom, such as chlorobenzoxazole;

  Pyridyl-substituted ketones such as methyl-2-pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, propyl-3-pyridyl ketone, 2-benzoylpyridine; 2-vinylpyridine, Examples thereof include vinylpyridines such as 4-vinylpyridine.

  Examples of the compound having an amino structure include N, N-dimethylformamide, acetamide, N, N-diethylacetamide, aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide. N, N-ethylaminoacetamide, N, N-dimethyl-N′-ethylaminoacetamide, acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide, isonicotinamide, picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N, N ′, N′-tetramethylphthalic acid amide, oxamide, N, N, N ′, N′-tetramethyloxamide, 2-furancarboxylic acid amide, N, N-dimethyl-2-fur Carboxylic acid amide, quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid amide; 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 -N-substituted lactams such as methyl-ε-caprolactam; N-substituted thiolactams corresponding to the N-substituted lactams and the like.

  Examples of the compound having a urea structure or a thiourea structure include urea; polymethylene urea; 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,1-dipropyl-2-imidazo. Lidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3 -(2-methoxyethyl) -2-imidazolidinone, 1-methyl-3- (2-ethoxyethyl) -2-imidazolidinone, 1,3-di- (2-ethoxyethyl) -2-imidazolidi N-substituted cyclic ureas such as non; N-substituted cyclic thioureas (for example, those corresponding to the examples of N-substituted cyclic ureas) and the like.

Examples of the compound having an imide structure include succinimide, N-methylsuccinimide, maleimide, N-methylmaleimide, phthalimide, N-methylphthalimide, and polyimide.
As a compound having a carbamic acid structure, a compound having an isocyanuric acid structure, a compound having these derivative structures, and a thiocarbonyl-containing compound corresponding thereto, methyl carbamate, methyl N, N-diethylcarbamate, isocyanuric acid, N, N ′, N′-trimethylisocyanuric acid and the like can be mentioned.

  Examples of the compound having an isocyanate structure or a thioisocyanate structure include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,3,5-benzenetriisocyanate, polymeric type Diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene dithioisocyanate and the like.

  Examples of silicon compounds having a halogen atom or an alkoxy group include hexachlorodisilane, bis (trichlorosilyl) ethane, silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride, silicon tetraiodide, tetramethoxysilane, tetraethoxysilane, and trichloro. Methylsilane, ethyltrichlorosilane, n-butyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-aminopropyltriethoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methyldichlorosilane , Methylphenyldichlorosilane, dimethyldiethoxysilane, diphenyldimethoxysilane and the like.

  Germanium compounds having a halogen atom or an alkoxy group include germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium tetraethoxide, ethyl germanium trichloride, germanium diiodide, dimethylgermanium dichloride, diethylgermanium dichloride, etc. Can be mentioned.

  Examples of tin compounds having a halogen atom or an alkoxy group include bis (trichlorostannyl) ethane, tin tetrachloride, tin tetrabromide, tin tetraiodide, tin tetrafluoride, tetra-t-butoxytin, methyltin trichloride, Phenyltin trichloride, n-butyltin trichloride, tin dichloride, tin dibromide, tin diiodide, tin difluoride, dimethyltin dichloride, di-n-butyltin dichloride, di-t-butyltin dichloride, diphenyltin dichloride , Divinyltin dichloride, diethoxytin and the like.

  Examples of the phosphorus compound having a halogen atom or an alkoxy group include phosphorus pentachloride, phosphorus pentabromide, phosphorus pentafluoride, bis (dichlorophosphino) methane, 1,2-bis (dichlorophosphino) ethane, 1,2- Bis (dichlorophosphino) -1,2-dimethylhydrazine, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus trifluoride, thiophosphoryl chloride, methyldichlorophosphine, ethyldichlorophosphine, t-butyldichlorophosphine , Phenyldichlorophosphine, phenyldichlorophosphine oxide, dibromotriphenylphosphorane and the like.

  Examples of the halogenated hydrocarbon include p-di (chloromethyl) benzene, o-di (chloromethyl) benzene, m-di (chloromethyl) benzene, p-di (bromomethyl) benzene, o-di (bromomethyl) benzene, m-di (bromomethyl) benzene, p-di (chlorocarbonyl) benzene, o-di (chlorocarbonyl) benzene, m-di (chlorocarbonyl) benzene, 1,4-dichloro-2-butene, 1,4-dibromo -2-butene, 1,4-dichlorobutane, 1,4-dibromobutane and the like.

  The coupling agent may be selected according to the type of a polymer obtained by a coupling reaction obtained by a reaction with this coupling agent (hereinafter referred to as “coupling polymer”). For example, in order to obtain a radial block polymer preferable as a rubber material, a coupling agent includes a compound having a ketone structure; a compound having an ester structure or a lactone structure; a compound having an amide structure; an isocyanate structure or a thioisocyanate Compound having structure: Use of silicon compound, germanium compound, tin compound, phosphorus compound or halogenated hydrocarbon having halogen atom or alkoxy group is preferred, N-substituted lactams; corresponding N-substituted thiolactams; halogen atom Or it is more preferable to use a tin compound having an alkoxy group; a halogenated hydrocarbon.

  The amount of the coupling agent used is usually in the range of 0.01 to 1,000 mol, preferably 0.05 to 100 mol, more preferably 0.1 to 10 mol, per mol of the transition metal compound.

The temperature of the coupling reaction is not particularly limited, but is usually in the range of −100 ° C. to + 100 ° C., preferably −80 ° C. to + 60 ° C., more preferably −70 ° C. to + 40 ° C., particularly preferably −60 ° C. to + 20 ° C. is there.
The reaction time of the coupling reaction is usually 1 minute to 300 minutes.

The coupling reaction can be usually stopped by adding a reaction terminator to the reaction system when a predetermined coupling rate is reached.
As a reaction terminator to be used, alcohols such as methanol, ethanol, propanol, butanol, and isobutanol can be used. Alcohols may contain acids such as hydrochloric acid.

  The polymer obtained by the coupling reaction is usually obtained as a mixture containing an uncoupled polymer and a coupling polymer. Moreover, the mixture containing the multiple types of coupling type polymer produced by the different coupling reaction may be obtained. In such a case, it can be used after separation / purification as required depending on the difference in molecular weight, but it is usually used as it is as a coupling polymer without purification.

In the present invention, a Mooney viscosity stabilizer can be added in order to prevent the Mooney viscosity of the coupling type polymer from changing unnecessarily during storage.
Examples of Mooney viscosity stabilizers used include ethylamine, propylamine, butylamine, hexylamine, octadecylamine, aniline, naphthylamine, benzylamine, diphenylamine, triethylamine, dimethyloctadecylamine, m-phenylenediamine, p-phenylenediamine, N, N′-dimethyl-p-phenylenediamine, N, N′-dioctyl-p-phenylenediamine, N-propyl-N′-phenyl-p-phenylenediamine, N, N, N ′, N′-tetrabutylethylenediamine, Examples thereof include organic amino compounds such as ethyleneimine, cyclohexeneimine, pyrrolidine, piperidine, morpholine, thiomorpholine, pyridine, pyrrole, pyrimidine, triazine, indole, quinoline and purine.

  The amount of Mooney viscosity stabilizer added is not particularly limited, but is preferably 0.1 to 40 mol, more preferably 0.5 to 20 mol, and more preferably 1 to 15 mol in terms of amino group per mol of the functional group of the coupling agent to be used. Is particularly preferred. If the amount added is too small, the Mooney viscosity may change due to storage, etc., and may not be suitable for use.On the other hand, if it is too much, bleeding may occur and the crosslinking rate may become too fast to control when used. is there.

Moreover, in this invention, in order to improve the heat resistance of the copolymer obtained, you may add an anti-aging agent after completion | finish of a polymerization reaction.
Examples of the anti-aging agent to be used include phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, and amine-based stabilizers.

  As the phenol-based stabilizer, those known in JP-A-4-252243 can be used. For example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxyphenol 2,6-di-phenol-4-octadecyloxyphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxy-phenyl) propionate] -methane, 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (2 ′, 3'-di-hydroxypropylthiomethyl) -3,6-di-methylphenol, 2,4-bis (2'-acetyloxyethylthiomethyl) -3,6-di-methylphenol, and the like.

  Examples of the sulfur stabilizer include dilauryl thiodipropionate, distearyl thiodipropionate, aminothioglycolate, 1,1′-thiobis (2-naphthol), ditridecylthiodipropionate, distearyl- β, β′-thiodipropionate and the like can be mentioned.

  Examples of the phosphorus stabilizer include tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl phosphite), tris (2,4-di-tert-butylphenyl) phosphite and the like.

  Examples of the amine stabilizer include phenyl-α-naphthylamine, phenyl-β-naphthylamine, aldol-α-naphthylamine, p-isopropoxydiphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and bis (phenylisopropylidene). -4,4'-diphenylamine, N, N'-diphenylethylenediamine, N, N'-diphenylpropylenediamine, octylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl- Examples include p-phenylenediamine. These antioxidants can be used alone or in combination of two or more.

  The addition amount of the antioxidant is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the polymer. If the addition amount of the anti-aging agent is too small, the effect of adding the anti-aging agent cannot be obtained.

  The method for recovering the polymer after stopping the polymerization reaction is not particularly limited. For example, a steam stripping method, a precipitation method using a poor solvent, or the like can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to the following examples.

The molecular weight and molecular weight distribution were measured as polystyrene-equivalent molecular weights using high temperature gel permeation chromatography (HLC-8121GPC / HT, manufactured by Tosoh Corporation) under the following conditions.
Solvent: o-dichlorobenzene Flow rate: 1.0 ml / min
Column temperature: 140 ° C

NMR analysis was performed by measuring at 50 ° C. using a C ₂ D ₂ Cl ₄ solution using an EX400FT-NMR apparatus manufactured by JEOL.
The crystal melting point was measured using a differential scanning calorimeter (DSC-7) manufactured by PerkinElmer Co., Ltd. at a heating rate of 10 ° C./min.

Example 1 Synthesis of Syndiotactic Polystyrene (syn-PS) / cis-1,4-polybutadiene (cis-PB) Diblock Copolymer Under a nitrogen atmosphere, a sealed pressure-resistant glass ampoule having an internal volume of 300 ml was charged with toluene ( A total of 200 g) and a toluene solution (0.1 mmol) of Al (Oct) ₃ were introduced, and aging was performed at room temperature for 10 minutes.
Subsequently, a toluene solution (0.1 mmol) of pentamethylcyclopentadienyltitanium trimethyl (Cp ^* TiMe ₃ ) and a 0.1 wt.% B (C ₆ F ₅ ) ₃ isopar E (Isopar E) solution ( Tosoh Finechem Co., Ltd.) were sequentially added and aged at room temperature for 10 minutes.
After cooling the whole volume to −25 ° C., styrene monomer (ST) (1 g) was added to initiate polymerization. After polymerization for 2 hours, 15 g of the polymerization solution was sampled for analysis.
After setting the temperature of the polymerization system to −40 ° C., butadiene (BD) (4 g) was added as the second monomer. After polymerization for 4 hours, a small amount of hydrochloric acid methanol solution was added to stop the reaction.
The polymerization solution was poured into a large amount of hydrochloric acid-containing methanol containing an antioxidant to precipitate a polymer. The precipitate was collected by filtration, washed, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a copolymer 1. After the obtained copolymer 1 was fractionated into a soluble part and an insoluble part with respect to tetrahydrofuran (THF), various analyzes were performed.

  Addition amount (g) of styrene (ST) and butadiene (BD), polymerization temperature (° C.), polymerization time (h), polymerization conversion (%), polymer yield (%) with respect to the total amount of monomers used , Number average molecular weight (Mn), molecular weight distribution (Mw / Mn), ratio of racemic dyad of polystyrene polymer block (syn-PS (%)), ratio of cis bond of polybutadiene polymer block (cis-PB (%) )), Transbutadiene ratio of polybutadiene polymer block (tran-PB (%)), 1,2-bond ratio of polybutadiene polymer block (1,2-PB (%)), and crystal melting point (° C.) Is shown in Table 1.

The copolymer obtained in Example 1 is a block copolymer having a polymer block of styrene and a polymer block of butadiene, and is a monomer unit derived from styrene and a monomer unit derived from butadiene. The ratio was 49:51, and the number average molecular weight (Mn) was 238,000.
The proportion of racemic dyad in the polymer block of styrene was 95% or more.
The Mn of the styrene polymer block was 144,000, and the styrene chain length was 1,380.
The THF-soluble part contained a copolymer having a ratio of styrene-derived monomer units to butadiene-derived monomer units of 3:97.

Example 2 Synthesis of syn-PS / cis-PB block copolymer After producing a syn-PS / cis-PB block copolymer in the same manner as in Example 1, the polymerization solution was prepared without stopping the polymerization. A portion was sampled for analysis. Next, a toluene solution of 0.1 mmol of p-di (chloromethyl) benzene was added to carry out a coupling reaction for 30 minutes. The reaction was stopped in the same manner as in Example 1 to obtain a copolymer.
The molecular weight of the THF-insoluble part of the copolymer before and after the coupling reaction was measured. Before the coupling reaction, Mn = 214,000 and Mw / Mn = 1.8, whereas after the coupling reaction, Mn = 540,000 and Mw / Mn = 1.6. It was confirmed that the ring reaction proceeded.

Example 3 Synthesis of syn-PS / cis-PB / syn-PS triblock copolymer Polymerization of styrene was started in the same manner as in Example 1 except that the amount of styrene monomer (ST) was 1.8 g. did. After polymerization for 1 hour, 15 g of the polymerization solution was sampled for analysis.
Next, after cooling the polymerization system to −40 ° C., 4 g of butadiene (BD) was added to the polymerization solution. After polymerization for 6 hours, 15 g of the polymerization solution was sampled for analysis.
In order to proceed with the third stage copolymerization, a dry argon gas was introduced into the system to remove unreacted BD, the temperature of the polymerization system was set to -25 ° C, and the third stage copolymerization was carried out for 8 hours. Thereafter, a small amount of hydrochloric acid methanol solution was added to the polymerization solution to stop the reaction. The obtained polymerization solution was poured into a large amount of hydrochloric acid-containing methanol containing an antioxidant to precipitate a polymer. The precipitate was collected by filtration, washed, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a copolymer 2.

Addition amount (g) of styrene (ST) and butadiene (BD), polymerization temperature (° C.), polymerization time (h), polymerization conversion rate (%), number average molecular weight (Mn) in the first step to the third step ), Molecular weight distribution (Mw / Mn), polymer yield (%) with respect to the total amount of monomers used, ratio of racemic dyad in polystyrene polymer block (syn-PS (%)), polybutadiene polymer block Ratio of cis bond (cis-PB (%)) Ratio of trans bond of polybutadiene polymer block (tran-PB (%)), ratio of 1,2-bond of polybutadiene polymer block (1,2-PB (%) Table 2 shows the crystal melting point (° C.).
The THF-soluble part contained a copolymer having a ratio of styrene-derived monomer units to butadiene-derived monomer units of 2:98.

From Table 2, it is presumed that the triblock copolymer could be synthesized because Mn after each step increased.
The Mn of the styrene polymer block obtained in the first step and the third step was 144,000 and 53,000, respectively, and the styrene chain lengths were 1,380 and 510, respectively.
The ratio of the THF-insoluble part to the total amount of the copolymer obtained was 75%. Moreover, the ratio of the monomer unit derived from styrene and the monomer unit derived from butadiene in the THF-insoluble part was 80:20.

Proof that it is a triblock copolymer (metathesis decomposition of polybutadiene segment)
After adding the 0.1 g THF-insoluble part, 0.1 g of 1-octene and 2.0 g of o-dichlorobenzene to the 30 ml sealed pressure-resistant glass ampoule after the third step, the mixture was stirred at 140 ° C. in a nitrogen atmosphere, Dissolved.
Subsequently, a solution in which 1.0 mg of bis (tricyclohexylphosphine) benzylideneruthenium (IV) dichloride was dissolved in 2.0 g of o-dichlorobenzene was added as a metathesis decomposition catalyst and reacted for 1 hour.
After cooling, the reaction solution was poured into a large amount of hydrochloric acid-containing methanol containing an antioxidant to precipitate a polymer, filtered, washed, and dried at 60 ° C. under reduced pressure for 8 hours.
When the molecular weight of the obtained reaction product was measured, it was Mn = 19.4 × 10 ⁴ and Mw / Mn = 2.1. This value proved to be a triblock copolymer because it was in good agreement with the molecular weight and molecular weight distribution estimated when the butadiene block was partially decomposed.

Example 4 Synthesis of syn-PS / cis-PB / syn-PS / cis-PB / syn-PS pentablock copolymer ST and BD were polymerized in the same manner as in Example 2.
In order to proceed with the copolymerization in the third step, unreacted BD was removed with dry argon, and then the polymerization temperature was set to -25 ° C. After polymerization for 6 hours, 15 g of the polymerization solution was sampled for analysis. After 8 hours of polymerization, the polymerization temperature was lowered again to −40 ° C. as the fourth stage step, and butadiene (130 mmol) was added. After the polymerization for 6 hours, the third stage operation was repeated in order to proceed with the fifth stage copolymerization. After 8 hours of polymerization, a small amount of hydrochloric acid methanol solution was added to stop the reaction. The polymerization solution was poured into a large amount of hydrochloric acid-containing methanol containing an antioxidant to precipitate a polymer. The precipitate was collected by filtration, washed, and dried under reduced pressure at 60 ° C. for 8 hours to obtain a copolymer 3.

  Addition amount (g) of styrene (ST) and butadiene (BD) in the first step to the fifth step, polymerization temperature (° C.), polymerization time (h), polymerization conversion (%), number average molecular weight (Mn ), Molecular weight distribution (Mw / Mn), polymer yield (%) with respect to the total amount of monomers used, ratio of racemic dyad in polystyrene polymer block (syn-PS (%)), polybutadiene polymer block Ratio of cis bond (cis-PB (%)), ratio of trans bond of polybutadiene polymer block (tran-PB (%)), ratio of 1,2-bond of polybutadiene polymer block (1,2-PB ( %)) And the crystalline melting point (° C.) are shown in Table 3.

From Table 3, it is presumed that the pentablock copolymer could be synthesized from the increase in Mn after each step.
The Mn of the styrene block in the first, third, and fifth stage processes was 165,000, 57,000, and 9,000, respectively, and the styrene chain lengths were 1,590, 550, and 87, respectively. The ratio of the monomer unit derived from styrene and the monomer unit derived from butadiene was 68:32. The ratio of the THF-insoluble part to the total copolymer amount obtained was 55%.
The THF-soluble part contained a copolymer having a ratio of the monomer unit derived from styrene to the monomer unit derived from butadiene of 3:97.

Proof of pentablock copolymer (metathesis decomposition of polybutadiene segment)
When the metathesis decomposition of the polymer after the fifth step was performed in the same manner as in Example 3, the molecular weight of the obtained reaction product was Mn = 16.8 × 10 ⁴ and Mw / Mn = 1.7. .
Since this value agrees well with the molecular weight and molecular weight distribution estimated when the butadiene blocks in the second stage process and the fourth stage process are partially decomposed, it should be a pentablock copolymer. Proven.

Evaluation of the block copolymer as a compatibilizer The block copolymer (syn-PS-b-cis-PB) obtained in Example 1 and syn-PS and cis-PB synthesized with a CpTiCl ₃ -MAO catalyst were used. A blend sample (No. 1, 2) was synthesized by mixing in xylene at 120 ° C. for 1 hour.
The composition of the obtained sample was as follows.
(No. 1): syn-PS / cis-PB = 50: 50 (mol%)
(No. 2): syn-PS / cis-PB / syn-PS-b-cis-PB = 42.5: 42.5: 15 (mol%)

As a result of observing each obtained sample using SEM, the sample of which no syn-PS-b-cis-PB copolymer is added (No. 1) has a non-uniform surface morphology, and syn-PS And cis-PB were not compatible. On the other hand, the sample of (No. 2) to which the syn-PS-b-cis-PB copolymer was added had a uniform surface morphology, and syn-PS and cis-PB were compatibilized.
From this SEM photograph observation result, the syn-PS segment in the ST-BD block copolymer obtained in Example 1 is compatible with syn-PS, the cis-PB segment is compatible with cis-PB, and the syn- It has been found that the compatibility of the PS / cis-PB blend is improved.

Claims (8)

A block copolymer having a polymer block (A) of an aromatic vinyl monomer and a polymer block (B) of a conjugated diene monomer,
The ratio of the monomer unit (a) derived from the aromatic vinyl monomer and the monomer unit (b) derived from the conjugated diene monomer is such that the monomer unit (a) and the monomer unit (b) And a weight ratio of 5:95 to 95: 5,
The number average molecular weight (Mn) is 10,000 to 1,000,000,
The polymer block (A) of the aromatic vinyl monomer has at least one segment in which 50 or more molecules of the aromatic vinyl monomer are connected, and
An aromatic vinyl / conjugated diene block copolymer, wherein the ratio of racemic dyad in the polymer block (A) is 55% or more.   2. The aromatic vinyl / conjugated diene block copolymer according to claim 1, wherein the 1,4-cis bond content in the polymer block (B) is 50% or more.   3. The aromatic vinyl / conjugated diene block copolymer according to claim 1 or 2, wherein the aromatic vinyl / conjugated diene block copolymer is a diblock copolymer obtained by bonding the polymer block (B) to the polymer block (A).   The aromatic vinyl according to claim 1 or 2, wherein the aromatic vinyl is a multi-block copolymer formed by alternately bonding the polymer block (B) and the polymer block (A) to the polymer block (A). -Conjugated diene block copolymers.   The aromatic vinyl / conjugated diene block copolymer according to claim 1 or 2, which is a radial block copolymer obtained by bonding the polymer block (A) and the polymer block (B). Formula (1) and / or Formula (2) shown below

Wherein R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 aralkyl groups, C1-C20 alkylcarbonyloxy groups, C1-C20 alkoxy groups, C1-C20 alkylthio groups, C6-C20 aryloxy groups, C6-C20 An arylthio group, a cyclopentadienyl group which may have a substituent, an indenyl group which may have a substituent, or a fluorenyl group which may have a substituent.
M ¹ and M ² each independently represent a titanium atom, a zirconium atom, or a hafnium atom.
X ¹ and X ² each independently represent a halogen atom.
a, b and c each independently represent an integer of 0 to 4, and d and e each independently represents an integer of 0 to 3. Further, a + b + c ≦ 4 and d + e ≦ 3. )
A transition metal compound represented by:
An organoaluminum oxy compound; an ionic compound capable of reacting with the transition metal compound to produce a cationic transition metal compound; a Lewis acid compound capable of reacting with the transition metal compound to produce a cationic transition metal compound; Polymerizing an aromatic vinyl monomer in the presence of a polymerization catalyst containing a reaction product with at least one cocatalyst selected from the group consisting of organometallic compounds of group 2 or group 13 element metals;
And a step of polymerizing the conjugated diene monomer by adding a conjugated diene monomer to the reaction system in a state where the aromatic vinyl monomer remains in the reaction system. A method for producing a vinyl-conjugated diene block copolymer. Polymerizing an aromatic vinyl monomer in the presence of the polymerization catalyst;
In a state where the aromatic vinyl monomer remains in the reaction system, a step of adding a conjugated diene monomer to the reaction system to polymerize the conjugated diene monomer and a conjugated diene monomer remaining in the reaction system 7. A method for producing an aromatic vinyl / conjugated diene block copolymer according to claim 6, further comprising the step of polymerizing the aromatic vinyl monomer remaining in the reaction system by removing the body from the reaction system. An aromatic vinyl / conjugated conjugate comprising: a polymerization reaction product of an aromatic vinyl / conjugated diene block copolymer obtained by the method according to claim 6; and a coupling agent added to the polymerization reaction product. A method for producing a diene radial block copolymer.