JP2000086727A - Coupling type butadiene-based polymer, and production of coupling type conjugated diene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coupling type butadiene-based polymer having a high 1,4-cis content and a narrow molecular weight distribution and to provide a method for efficiently producing the polymer. SOLUTION: This coupling type polymer comprises (I) 0-90 pts.wt. of a butadiene-based polymer having >=50% cis-bond unit in a butadiene unit and 1,000-10,000,000 number-average molecular weight (Mn) and (II) 100-10 pts.wt. of a polymer composed of at least two molecules of the polymers (I) bonded through a coupling agent. A method for producing the coupling type butadiene- based polymer comprises polymerizing a conjugated diene monomer in the presence of a catalyst obtained by bringing a cyclopentadienyl skeleton- containing transition metal compound of the group IV of the periodic table into contact with a cocatalyst under conditions satisfying the following two equations -100<T<80 and 0.017<t<6000 exp(-0.0921 T) ((t) is a contact time (minute); and T is a contact temperature ( deg.C)).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coupling type butadiene polymer having many cis bonds and a method for efficiently producing a coupling type conjugated diene polymer using a specific metallocene catalyst.

[0002]

2. Description of the Related Art Metallocene catalysts are generally highly active, so that they have high polymer production efficiency and are superior in controlling the stereoregularity of the polymer. Are being considered.

[0003] Makromol. Chem. Rapi
d. Commun. 1990, 11, 519,
J. Organomet. Chem. , 451, 67, Macromol. Symp. , 1
995, Vol. 89, p. 383, Macromol. R
rapid Commun. , 1996, Vol. 17, 7
On page 81, butadiene polymerization using cyclopentadienyltitanium trichloride / methylaluminoxane as a catalyst is reported. This polymerization proceeds with high activity, and a polymer having about 80% of cis-bonded units is generated. However, a gel polymer is generated, and the molecular weight of the polymer,
Molecular weight distribution, regulation of branched structure, living property of polymerization, and generation of high molecular weight components by reaction of active molecular terminals with reactive reagents (hereinafter, referred to as "coupling agent") (hereinafter, referred to as "coupling") ) Is not described. The above Makromol. Chem. Rapid.
Commun. 1990, vol. 11, p. 519, butadiene is polymerized by a method in which cyclopentadienyltitanium trichloride and methylaluminoxane are brought into contact in advance, but the conditions and effects are not described.

JP-A-8-113610 discloses a catalyst composed of cyclopentadienyltitanium trichloride / methylaluminoxane / triethylaluminum. By using this catalyst, a butadiene polymer having a Mw / Mn of 1.93 is obtained. Although coalescence has been obtained, there is no description on regulation of the branched structure, living property of polymerization, and coupling.

Japanese Patent Application Laid-Open No. 9-77818 discloses a transition metal compound of Group IV of the periodic table represented by the following general formula 1 which is highly active and has excellent control of tacticity of a polymer, and an aluminoxane. There has been proposed a conjugated diene polymerization catalyst comprising a combination of the above. It is disclosed that the polymerization of butadiene by this catalyst proceeded with high activity, and a polymer having 96% of cis-bonded units was obtained. However, it does not describe the molecular weight, molecular weight distribution, regulation of the branched structure, living property of polymerization, and coupling of the polymer. General formula 1:

[0006]

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Wherein M is a transition metal of Group IV of the periodic table,
X is a hydrogen atom, a halogen, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon oxy group having 1 to 12 carbon atoms, and Y 'is a hydrocarbon group having 1 to 20 carbon atoms, which itself has a cyclopentadiene ring structure. And may form a ring by bonding
Z is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. The structure in which the circle is drawn in the pentagon in the general formula 1 is
Represents a cyclopentadiene ring structure. Hereinafter, the same applies to general formula 2).

Further, a metallocene catalyst comprising a transition metal compound belonging to Group IV of the periodic table represented by the following structural formula 1 is represented by Ma
cromol. Chem. , Macromol. Sym
p. 1997, Vol. 118, pages 55-60. However, no example was known in which this was used for the polymerization of a conjugated diene monomer. Structural formula 1: MeO (CO) CH ₂ CpTiCl ₃ (In the formula, Cp represents a cyclopentadienyl group. The same applies to the following.)

Recently, application of a metallocene catalyst comprising a transition metal compound belonging to Group IV of the periodic table represented by the above structural formula 1 to the polymerization of butadiene has been announced (the first scientific and technological research and development of the first highly functional material). Proceedings of Creation Technology Symposium,
December 10, 1997, p. 77). The polymerization proceeds with high activity, the resulting polybutadiene has a high 1,4-cis bond content, and the molecular weight distribution is somewhat narrower than conventional high cis butadiene polymers. However, the regulation of the branched structure of the polymer, the living property of polymerization, and the coupling are not known.

High molecular weight polymerized using typical Co-, Ni-, Ti- and Nd-based coordination polymerization catalysts,
Butadiene polymers having a high cis-bond content of 90% or more of cis-bonded units are known. However, the molecular weight distribution of butadiene polymers obtained with these catalyst systems is broad. In addition, this butadiene polymer has many branched structures, and even a Nd-based polymer having the least branched structure has its root mean square radius (RMSR, nm) and absolute molecular weight (MW, g / mo).
The relationship of 1) is log (RMSR) = 0.638 x log (MW)-
2.01. Further, regarding the living property and coupling of polymerization, Co-based, Ni-based
Is not known for titanium-based and Ti-based catalysts. In Nd-based catalyst polymerization, a polymerization reaction having relatively living properties is said to proceed, but the content of living chains is unknown, and W
From the description of O 95/04090, the maximum value of the living chain content is estimated to be 75%. However, the polymer not only has many branched structures as described above, but also has a wide molecular weight distribution of at least 3.1.

A method for producing a conjugated diene polymer by carrying out a coupling reaction after polymerization using an Nd catalyst is also known (JP-A-63-178102, JP-A-63-297403, JP-A-63-30510
No. 1). However, in this case, the molecular weight distribution of the polymer before the coupling reaction is estimated to be approximately 3 or more from the disclosed GPC elution curve. In addition, it has a large number of branched structures, and it is not known how much coupling is present.

On the other hand, when an organolithium catalyst is used, living polymerization of butadiene proceeds, and a coupling type butadiene polymer having a high molecular weight, a narrow molecular weight distribution and substantially no branched structure can be obtained. Only 40% or less of cis-bonded units are present.

As described above, in the prior art, butadiene is subjected to a coupling reaction by living-polymerizing butadiene with high stereoactivity (high cis regulation) at a high activity. A polymer was not obtained.

[0014]

SUMMARY OF THE INVENTION The object of the present invention is to
A coupling type butadiene polymer having a high 4-cis bond content and a small molecular weight distribution, and a conjugated diene monomer polymerized using a specific metallocene catalyst, and then contacted with a coupling agent to form a coupling type butadiene. An object of the present invention is to provide a method for producing a conjugated diene polymer from which a polymer can be obtained efficiently.

[0015]

According to the present invention,
(I) a butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable therewith, wherein the cis-bonded unit in the butadiene unit is 50% or more;
Number average molecular weight (Mn) of 1,000 to 10,000,000
A cup comprising: 0 to 90 parts by weight of a polymer which is 00, and (II) 100 to 10 parts by weight of a polymer in which at least two molecules of the polymer (I) are bonded via a coupling agent. A ring-type butadiene-based polymer is provided.

According to the present invention, (A) a transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton, (B) (a) an organoaluminum oxy compound, and (b) the transition metal An ionic compound capable of producing a cationic transition metal compound by reacting with the compound (A),
(C) a Lewis acid compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (A), and (d) an organometallic compound of a main element metal of Groups I to III of the periodic table. A conjugated diene monomer, or a conjugated diene monomer and a monomer copolymerizable therewith in the presence of a catalyst obtained by contacting a kind of co-catalyst under the conditions satisfying the following formula α and the following formula β: After polymerizing
Provided is a method for producing a coupling type conjugated diene-based polymer, which comprises contacting a coupling agent capable of reacting with a living polymer having a Group IV transition metal at the molecular end of the periodic table with the polymer. . Formula α: −100 <T <80 Formula β: 0.017 <t <6000exp (−0.0921T) Here, t is a contact time (minute), and T is a contact temperature (° C.).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION (Polymerization Catalyst) The catalyst for conjugated diene polymerization used in the present invention comprises (A) a transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton;
(B) (a) an organoaluminum oxy compound (a), an ionic compound (b) capable of forming a cationic transition metal compound by reacting with the transition metal compound (A), and reacting with the transition metal compound (A) Acid compound (c) capable of forming a cationic transition metal compound by heating, and Periodic Tables II to I
The catalyst is obtained from at least one cocatalyst selected from organometallic compounds (d) of Group II main element metals.

The transition metal compound of Group IV of the periodic table having a cyclopentadienyl skeleton, which is the component (A),
Preferred is a transition metal compound belonging to Group IV of the periodic table represented by the following general formula 2. General formula 2:

[0019]

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Wherein M is a transition metal of Group IV of the periodic table,
X is a hydrogen atom, a halogen, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, or an amino group which may be substituted with a hydrocarbon group having 1 to 12 carbon atoms, And any one of X may be bonded to the cyclopentadienyl group with or without a cross-linking group to form a cyclic structure, and p is 2 or 3. , Q are organic groups, which may themselves form a ring with a cyclopentadienyl group, and when Q is two or more, they may be different from each other; m is an integer of 0 to 5; It is. )

That is, the transition metal compound represented by the general formula 2 has a so-called ligand having one of a plurality of fused cyclic substituents such as a cyclopentadienyl group or an indenyl group or a fluorenyl group as a ligand. Half metallocene compounds or geometrically constrained catalysts.

The transition metal of Group IV of the periodic table (M in the formula) is preferably titanium (Ti), zirconium (Z
r) or hafnium (Hf), more preferably Ti.

As X, halogen includes fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I), preferably chlorine atom. Examples of the hydrocarbon group include methyl and neopentyl having 1 to 1 carbon atoms.
And an aralkyl group having 7 to 12 carbon atoms such as 12 alkyl groups and benzyl. Examples of the hydrocarbonoxy group include methoxy, ethoxy, isopropoxy and the like having 1 to 1 carbon atoms.
7 to 7 carbon atoms such as an alkoxy group and a benzyloxy group
And 12 aralkyloxy groups. Examples of the amino group that may be substituted with a hydrocarbon group include a dialkylamino group having an alkyl group having 1 to 12 carbon atoms such as dimethylamino, diethylamino, diisopropylamino, dibutylamino, and di-t-butylamino. . p is 2 or 3, and preferably 3.

Any one of X and the cyclopentadienyl group may be directly bonded with or without a bridging group. In this case, the transition metal compound (A) has a so-called metallocycle structure. It becomes a geometrically constrained catalyst. Examples of the cross-linking group include a hydrocarbon group having 1 to 24 carbon atoms, and a silylene group containing a hydrocarbon group having 1 to 24 carbon atoms. Specific examples thereof include methylsilylene, dimethylsilylene, methylphenylsilylene, diphenylsilylene, dibenzylsilylene, tetramethyldisilylene, dimethylmethylene, diphenylmethylene, and the like. A preferred crosslinking group is dimethylsilylene.

Q is an organic group, and m representing the number thereof is 0
M is preferably 1 or more from the viewpoint of increasing the ratio of cis-bonded units. When m is 2 or more, Q may be the same or different. Specific examples of the organic group include those having 1 to 2 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, cyclohexyl, and adamantyl.
An alkyl group having 0, an aryl group having 6 to 20 carbon atoms such as phenyl, and a carbon atom having 7 carbon atoms such as benzyl and triphenylmethyl;
To 30 aralkyl groups. The organic group Q bonded to the cyclopentadiene ring may form a polycyclic group such as an indenyl group and a fluorenyl group together with the cyclopentadiene ring.

Other organic groups Q include a hydrocarbon group containing a silicon atom such as a trimethylsilyl group, a hydrocarbon group containing a tin atom such as a trimethylstannyl group, and a germanium atom such as a trimethylgermyl group. In addition to hydrocarbon groups, hetero groups such as ether groups, thioether groups, carbonyl groups, sulfonyl groups, ester groups, thioester groups, tertiary amino groups, secondary amino groups, primary amino groups, amide groups, phosphino groups, and phosphinyl groups Organic groups having one or more atomic groups having atoms are also included.

As the organic group Q, from the viewpoint of increasing the polymerization activity and further increasing the ratio of cis-bonded units of the polymer, a bulky carbon atom such as a trimethylsilyl group, a t-butyl group or a triphenylmethyl group is used. An organic group having 3 to 30 hydrocarbon groups or one or more Lewis basic atomic groups having a hetero atom is more preferable.

The relationship between the value of m representing the number of organic groups Q and the structure of the ligand is as follows. m = 0: means a cyclopentadienyl group having no substituent. m = 1: a cyclopentadienyl group having one substituent or an (substituted) indenyl group having no substituent on the cyclopentadiene ring. m = 2: cyclopentadienyl group having two substituents, (substituted) indenyl group having one substituent on the cyclopentadiene ring, or (substituted) fluorenyl having no substituent on the cyclopentadiene ring Means a group. m = 3: a cyclopentadienyl group having three substituents, a (substituted) indenyl group having two substituents on a cyclopentadiene ring,
Alternatively, it means a (substituted) fluorenyl group having one substituent on a cyclopentadiene ring. m = 4: a cyclopentadienyl group having four substituents or an (substituted) indenyl group having three substituents on a cyclopentadiene ring. m = 5: means a cyclopentadienyl group having five substituents.

Specific examples of the Group IV transition metal compound (A) in the periodic table include the following (1) to (18).

(1) unsubstituted cyclopentadienyl titanium tri (or di) chloride,

(2) Monosubstituted cyclopentadienyltitanium tri (or di) chloride, for example,
Methylcyclopentadienyltitanium tri (di) chloride, trimethylsilylcyclopentadienyltitanium tri (di) chloride, t-butylcyclopentadienyltitanium tri (di) chloride, triphenylmethylcyclopentadienyltitanium tri (di) chloride Chloride, adamantylcyclopentadienyltitanium tri (di) chloride, (2-methoxyethyl) cyclopentadienyltitanium tri (di) chloride (Me
OCH ₂ CH ₂ CpTiCl _p ; p = 3 or 2), [2
-(T-butoxy) ethyl] cyclopentadienyltitanium tri (di) chloride (t-BuOCH ₂ CH ₂ C
pTiCl _{p; p} = 3 or 2), phenoxyethyl cyclopentadienyl titanium tri (di) chloride _{(PhOCH 2 CH 2 CpTiCl p;} p = 3 or 2), 2- (2-methoxyethoxy) ethyl cyclopentadienyl Titanium tri (di) chloride (MeOC
H ₂ CH ₂ OCH ₂ CH ₂ CpTiCl _p ; p = 3 or 2), methoxycarbonylmethylcyclopentadienyltitanium trichloride (MeO (CO) CH ₂ Cp
TiCl _{p; p} = 3 or 2), t-butoxycarbonyl methyl cyclopentadienyl titanium tri (di) chloride (t-BuO (CO) CH 2 CpTiCl p; p
= 3 or 2), phenoxycarbonylmethylcyclopentadienyltitanium tri (di) chloride (PhO
(CO) CH ₂ CpTiCl _p ; p = 3 or 2), 2-
(N, N-dimethylamino) ethylcyclopentadienyltitanium tri (di) chloride (Me ₂ NCH ₂ CH
₂ CpTiCl _p ; p = 3 or 2), 2- (N, N-diethylamino) ethylcyclopentadienyltitanium tri (di) chloride (Et ₂ NCH ₂ CH ₂ CpTiC)
l _p ; p = 3 or 2), 2- (N, N-di-i-propylamino) ethylcyclopentadienyltitanium tri (di) chloride (i-Pr ₂ NCH ₂ CH ₂ CpTi
Cl _p ; p = 3 or 2), etc.

(3) Disubstituted cyclopentadienyltitanium tri (or di) chloride, specifically,
(1-methyl) (2-trimethylsilyl) cyclopentadienyltitanium tri (di) chloride, (1-t-
Butyl) [3- (2-methoxyethyl)] cyclopentadienyltitanium tri (di) chloride, (1-trimethylsilyl) (3-methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) chloride,
{3- [2- (N, N-diethylamino) ethyl]}
(1-phenyl) cyclopentadienyltitanium tri (di) chloride and the like,

(4) Tri-substituted cyclopentadienyltitanium tri (or di) chloride, specifically,
(1,2-dimethyl) (4-trimethylsilyl) cyclopentadienyltitanium tri (di) chloride,
(1,2-dimethyl) [4- (2-methoxyethyl)]
Cyclopentadienyltitanium tri (di) chloride, (1,2-dimethyl) (4-methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) chloride, (1,2-dimethyl) {4- [2- ( N, N-
Diethylamino) ethyl] cyclopentadienyltitanium tri (di) chloride, etc.

(5) Tetra-substituted cyclopentadienyltitanium tri (or di) chloride, such as (1,2,3-trimethyl) (4-trimethylsilyl) cyclopentadienyltitanium tri (di) chloride, (1,2,4-trimethyl) [3- (2-methoxyethyl)] cyclopentadienyltitanium tri (di) chloride, (1,2,3-trimethyl) (4-
(Methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) chloride, (1,2,3-trimethyl) {4- [2- (N, N-diethylamino) ethyl]} cyclopentadienyltitanium tri (di) chloride Such,

(6) Pentasubstituted cyclopentadienyltitanium tri (or di) chloride, for example, pentamethylcyclopentadienyltitanium tri (di) chloride, pentaphenylcyclopentadienyltitanium tri (di) chloride , (Tetramethyl)
(Trimethylsilyl) cyclopentadienyltitanium tri (di) chloride, (tetramethyl) (2-methoxyethyl) cyclopentadienyltitanium tri (di)
Chloride, (tetramethyl) (methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) chloride, (tetramethyl) [2- (N, N-diethylamino) ethyl] cyclopentadienyltitanium tri (di) chloride, etc.

(7) (Substituted) indenyl titanium tri (or di) chloride having no substituent on the cyclopentadiene ring, for example, indenyl titanium tri (di) chloride, (4-methyl) indene Nil titanium tri (di) chloride, etc.

(8) (Substituted) indenyl titanium tri (or di) chloride having one substituent on the cyclopentadiene ring, specifically, (1-trimethylsilyl) indenyl titanium tri (di) chloride;
[1- (2-methoxyethyl)] indenyl titanium tri (di) chloride, (2-methoxycarbonylmethyl) indenyl titanium tri (di) chloride, {1
-[2- (N, N-diethylamino) ethyl]} indenyltitanium tri (di) chloride, (4-methyl)
(1-trimethylsilyl) indenyl titanium tri (di) chloride and the like,

(9) (Substituted) indenyl titanium tri (or di) chloride having two substituents on the cyclopentadiene ring, specifically, (1-trimethylsilyl) (3-methyl) indenyl titanium tri ( Di)
Chloride, [1- (2-methoxyethyl)] (3-methyl) indenyltitanium tri (di) chloride,
(2-methoxycarbonylmethyl) (3-methyl) indenyltitanium tri (di) chloride, {1- [2-
(N, N-diethylamino) ethyl] {(3-methyl)
Indenyl titanium tri (di) chloride, (3,4
-Dimethyl) (1-trimethylsilyl) indenyltitanium tri (di) chloride,

(10) (Substituted) indenyl titanium tri (or di) chloride having three substituents on the cyclopentadiene ring, for example, (1-trimethylsilyl) (2,3-dimethyl) indenyl titanium Tri (di) chloride, [1- (2-methoxyethyl)]
(2,3-dimethyl) indenyl titanium tri (di)
Chloride, (2-methoxycarbonylmethyl) (1,
3-dimethyl) indenyltitanium tri (di) chloride, {1- [2- (N, N-diethylamino) ethyl]} (2,3-dimethyl) indenyltitanium tri (di) chloride, (2,3 4-trimethyl) (1-
Trimethylsilyl) indenyl titanium tri (di) chloride,

(11) (Substituted) fluorenyltitanium tri (or di) chloride having no substituent on the cyclopentadiene ring, for example, fluorenyltitanium tri (di) chloride, 2-methylfluoride Olenyl titanium tri (di) chloride, etc.

(12) (Substituted) fluorenyltitanium tri (or di) chloride having one substituent on the cyclopentadiene ring, specifically, (9-trimethylsilyl) fluorenyltitanium tri (di) chloride , [9- (2-methoxyethyl)] fluorenyltitanium tri (di) chloride, (9-methoxycarbonylmethyl) fluorenyltitanium tri (di) chloride, {9- [2- (N, N-diethylamino) ) Ethyl]｝ fluorenyltitanium tri (di) chloride,
(1-methyl) (9-trimethylsilyl) indenyl titanium tri (di) chloride,

(13) Compounds having a structure in which Ti, which is the central metal of the compounds of (1) to (12), is substituted by Zr or Hf, for example, cyclopentadienyl zirconium tri (di) chloride, ( Trimethylsilyl) cyclopentadienylzirconium tri (di) chloride,
(2-methoxyethyl) indenyl hafnium tri (di) chloride, (methoxycarbonylmethyl) fluorenylzirconium tri (di) chloride, [2-
(N, N-diethylamino) ethyl] cyclopentadienylzirconium tri (di) chloride, etc.

(14) Compounds having a structure in which all or part of the chlorine atoms bonded to the central metal of the compounds of (1) to (13) are substituted with fluorine, bromine and iodine atoms. (Trimethylsilyl) cyclopentadienyltitanium tri (di) fluoride, (2-methoxyethyl) cyclopentadienyltitanium tri (di)
Bromide, (methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) iodide, [2-
(N, N-diethylamino) ethyl] cyclopentadienyltitanium tri (di) iodide,

(15) A compound having a structure in which all or a part of the halogen atoms bonded to the central metal of the compounds of (1) to (14) are substituted with a hydrocarbon group, for example, (trimethylsilyl) cyclopentane Dienyl titanium tri (di) methyl, (2-methoxyethyl) cyclopentadienyl titanium tri (di) benzyl, (methoxycarbonylmethyl) cyclopentadienyl titanium tri (di) methyl, [2- (N, N- Diethylamino) ethyl] cyclopentadienyltitanium tri (di) methyl,

(16) A compound having a structure in which all or a part of a halogen atom or a hydrocarbon group bonded to a central metal of the compound of (1) to (15) is substituted with a hydrocarbonoxy group, specific examples thereof include: (Trimethylsilyl) cyclopentadienyltitanium tri (di) methoxide, (2-methoxyethyl) cyclopentadienyltitanium tri (di) butoxide, (methoxycarbonylmethyl) cyclopentadienyltitanium tri (di) ethoxide,
[2- (N, N-diethylamino) ethyl] cyclopentadienyltitanium tri (di) butoxide, etc.

(17) Compounds having a structure in which all or part of the halogen atom, hydrocarbon group or hydrocarbonoxy group bonded to the central metal of the compounds of (1) to (16) is substituted with an amide group, specific examples Include (trimethylsilyl) cyclopentadienyltitanium tris (bis) dimethylamide, (2-methoxyethyl) cyclopentadienyltitanium tris (bis) diethylamide, (methoxycarbonylmethyl) cyclopentadienyltitanium tris (bis) diamide Propylamide, [2- (N, N-diethylamino) ethyl] cyclopentadienyltitanium tris (bis) dioctylamide,

(18) X of the compound of (14) to (17)
And a compound having a structure in which any one of the above and an organic group Q are directly bonded without or through a cross-linking group (for example, dimethylsilylene) to form a cyclic structure.
[T-butyl (dimethyl-cyclopentadienylsilyl) amide] di (mono) chlorotitanium, [t-butyl (dimethyl-cyclopentadienylsilyl) amide]
Di (mono) methyl titanium, [t-butyl (dimethyl-cyclopentadienylsilyl) amide] di (mono) methyl zirconium, [t-butyl (dimethyl-fluorenylsilyl) amide] di (mono) methyl titanium , And the like.

Of these, (1), (2), (7),
(8), (11), (12) and the corresponding compounds having the structures of (13) to (18) are preferable,
(1), (2) and corresponding (13) to
The compound having the structure (18) is more preferable, the compound having the structure (2) and the corresponding compound having the structure (13) to (17) is further preferable, and the compound having the structure (2) is particularly preferable.

The method for preparing the transition metal compound of Group IV of the periodic table represented by the general formula 2 is not particularly limited. For example, M
Macrom for eO (CO) CH ₂ CpTiCl ₃
ol. Symp. 1997, Vol. 118, 55-6
On the basis of the description on page 0, the MeOCH ₂ CH ₂ CpT
In the case of iCl ₃ , see Transition Met. Ch
em. , 1990, vol. 15, p. 483.

Among the cocatalysts (B) used in combination with the Group IV transition metal compound (A) of the periodic table, the organoaluminum oxy compound (a) is preferably a straight chain compound represented by the following general formula 3. Or it is a cyclic polymer and is a so-called aluminoxane. General formula 3: (—Al (R ¹ ) O—) n (R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, and isobutyl. R ¹ may be substituted with a halogen atom and / or an R ² O group, and R ² is a hydrocarbon group having 1 to 10 carbon atoms. Is methyl, ethyl,
Examples include an alkyl group such as propyl and isobutyl, and among them, a methyl group is preferable. n is a degree of polymerization, 5 or more;
Preferably it is 10 or more, preferably 100 or less, more preferably 50 or less. )

Among the cocatalysts (B), the ionic compound (b) capable of forming a cationic transition metal compound by reacting with the transition metal compound (A) includes an ionic compound of a non-coordinating anion and a cation. Is mentioned.

The non-coordinating anion includes, for example, tetra (phenyl) borate, tetra (fluorophenyl)
Borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra ( Xyl) borate,
Triphenylpentafluorophenyl borate, tris (pentafluorophenyl) phenyl 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:
Examples include trisubstituted carbonium cations such as triphenylcarbonium cation and trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include tri (methylphenyl)
A carbonium cation and a tri (dimethylphenyl) carbonium cation.

Specific examples of the oxonium cation include:
Alkyloxonium cations such as hydroxonium cation OH ₃ ⁺ and methyloxonium cation CH ₃ OH ₂ ⁺ ; dimethyloxonium cation (CH ₃ ) ₂ OH ⁺
And trialkyloxonium cations such as trimethyloxonium cation (CH ₃ ) ₃ O ⁺ 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, tributylammonium cation, N, N-diethylanilinium cation, and N such as N, N-2,4,6-pentamethylanilinium cation , N-dialkylanilinium cations, di (i-propyl) ammonium cations, dicycloammonium cations and the like.

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

As the ionic compound, a non-coordinating anion and a cation which are arbitrarily selected and combined can be used.

Of the above, triphenylcarbonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl)
Ionic compounds such as borate and 1,1′-dimethylferrocenium tetra (pentafluorophenyl) borate can be more preferably used.

Specific examples of the Lewis acid compound (c) which can form a cationic transition metal compound by reacting with the transition metal compound (A) among the cocatalyst (B) include tris (pentafluorophenyl) boron, Tris (monofluorophenyl) boron, tris (difluorophenyl) boron, and triphenylboron are exemplified.

Among the cocatalysts (B), Periodic Tables I to II
The organometallic compound (d) of a Group I main element metal includes not only an organometallic compound in a narrow sense but also an organometallic halogen compound and a hydrogenated organometallic compound of a Group I to III main element metal of the periodic table. Examples of the organometallic compound include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and the like, with trialkylaluminum being preferred. Examples of the organometallic halogen compound include ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride. Examples of the hydrogenated organometallic compound include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In the present invention, the above-mentioned (a) to (a)
(D) may be used alone or in combination.
Preferred promoters are (a) alone, (c) alone, (a) and (d), (b) and (d), and (c) and (d).

In the present invention, the transition metal compound (A)
And / or the cocatalyst (B) can be used by being supported on the same carrier. Examples of the carrier include an inorganic compound and an organic polymer compound. As the inorganic compound, inorganic oxides, inorganic chlorides, inorganic hydroxides and the like are preferable,
It may contain a small amount of carbonate or sulfate. Preferred specific examples include inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia, and inorganic chlorides such as magnesium chloride.
These inorganic compounds have an average particle size of 5 to 150 μm,
Porous fine particles having a specific surface area of ² to 800 m ² / g are preferred. For example, heat treatment can be performed at 100 to 800 ° C. to support the transition metal compound (A) and / or the cocatalyst (B). The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring, or a functional group such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom in a side chain. Specific examples of the organic polymer compound include α-olefin homopolymer, α-olefin copolymer, and acrylic acid having a functional group obtained by chemically modifying a polymer having units such as ethylene, propylene, and butene. And polymers having units of methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and the like, and chemically modified products thereof. These organic polymer compounds are used in the form of spherical fine particles having an average particle diameter of 5 to 250 μm. By supporting the transition metal compound and / or the ionic compound, contamination due to adhesion of the catalyst to the polymerization reactor can be prevented.

(Monomer) The conjugated diene monomer used in the present invention includes 1,3-butadiene and 2-methyl-1,3
-Butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like. Among the conjugated dienes, 1,3-butadiene and 2-methyl-1,3
-Butadiene is preferred, and 1,3-butadiene is more preferred. These conjugated diene monomers can be used alone or in combination of two or more, but it is particularly preferable to use 1,3-butadiene alone. When two or more kinds are used in combination, the chain distribution may be random or block.

The monomers copolymerizable with the conjugated diene monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene and p-methylstyrene. tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p
-Chlorostyrene, p-bromostyrene, 2-methyl-
1,4-dichlorostyrene, 2,4-dibromostyrene, aromatic vinyl such as vinylnaphthalene, ethylene,
Olefins such as propylene and 1-butene; cyclic olefins such as cyclopentene and 2-norbornene;
-Hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2
Non-conjugated dienes such as norbornene, (meth) acrylates such as methyl methacrylate, (meth) acrylonitrile, (meth) acrylamide and the like. These copolymerizable monomers may be distributed randomly or in blocks in the polymer.

(Production Method of Coupling-Type Conjugated Diene Polymer) In the present invention, the conjugated diene monomer is added in the presence of a catalyst in which the transition metal compound (A) and the cocatalyst (B) have been contacted (aged) in advance. A monomer or a conjugated diene monomer and a monomer copolymerizable therewith are polymerized. Specifically, aging and polymerization may be performed by the following methods (i) to (iv), and the method (i) is particularly preferable.

(I) The components (A) and (B) are brought into contact with each other in advance, and then contacted with a monomer to carry out polymerization. (Ii) After bringing the component (A) and the component (B) into contact with each other and further bringing the component into contact with a carrier, the produced supported catalyst is separated, and the supported catalyst is brought into contact with a monomer to carry out polymerization. (Iii) After the component (A) is brought into contact with the carrier, the component (B) is further brought into contact with the carrier, and the produced supported catalyst is separated.
The polymerization is carried out by bringing the supported catalyst into contact with the monomer. (Iv) After bringing the component (B) into contact with the carrier, the component (A) is further brought into contact with the component, and the generated supported catalyst is separated.
The polymerization is carried out by bringing the supported catalyst into contact with the monomer.

By performing aging, polymerization activity and initiator efficiency are improved. As will be described further below, the polymerization reaction of the present invention applying a specific polymerization temperature is a so-called living polymerization system. Therefore, a polymer having a desired molecular weight can be obtained by a synergistic effect with increasing the initiator efficiency by aging. As a result, the coupling reaction can be promptly performed, and the content of the coupled polymer (II) can be increased. Further, the molecular weight distribution of the uncoupled polymer (I) can be further narrowed, and specifically, the molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Is less than 1.5, butadiene-based polymer is easily obtained.

The contact temperature of component (A) with component (B) (T,
° C) must be in the range of -100 to + 80 ° C,-
A range from 80 to + 70 ° C is preferred. Contact time (t, min)
That is, the time from contact to the start of polymerization must satisfy 0.017 <t <6000exp (-0.0921T), and preferably satisfies 0.083 <t <4000exp (-0.0921T). If the contact temperature is too high, the desired aging effect cannot be obtained, and if it is too low, it is disadvantageous in economy. At low temperatures, there is no problem if stored for a long time in contact, but when the temperature is high, the polymerization activity tends to be deactivated, and when the contact time is long, polymerization is difficult. 0.017
An aging time of less than a minute, ie, less than about 1 second, is difficult to operate realistically.

The components (A) and (B) can be used in the form of either a solution or a slurry, respectively, but are preferably in the form of a solution in order to obtain a higher polymerization activity. The solvent used for preparing the solution or slurry is a hydrocarbon solvent such as butane, pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, or a solvent such as chloroform, methylene chloride, dichloroethane, or chlorobenzene. It is a halogenated hydrocarbon solvent, and two or more solvents may be used as a mixture. Preferred solvents are aromatic hydrocarbons such as toluene and benzene.

The amount of the catalyst used depends on the intended use of the obtained coupling polymer, but is usually 100 to 0.01 mmol, preferably 10 to 0.01 mmol of the transition metal compound (A) per 1 mol of the monomer. 0.1 mmol, more preferably in the range of 5 to 0.2 mmol. As described below,
The polymerization reaction of the present invention applying a specific polymerization temperature is a so-called living polymerization system. Therefore, the molecular weight of the produced polymer (I) can be regulated by the ratio of the transition metal compound to the monomer. When a coupling type polymer which is preferable as a rubber material is obtained, the amount of the transition metal compound (A) is preferably set to the above-mentioned amount. In addition, when the amount of the catalyst is used, a polymer (I) having a particularly narrow molecular weight distribution can be obtained, and specifically, a polymer having Mw / Mn of less than 1.5 can be easily obtained.

Co-catalysts (a), (b), (c), (d)
May be used alone or in combination of two or more as described above, but when used alone, the molar ratio of the organoaluminum oxy compound (a) / transition metal compound (A) is usually 1
0 to 10,000, preferably 100 to 5,000, more preferably 200 to 3,000, and the molar ratio of ionic compound (b) / transition metal compound (A) is usually 0.01.
-100, preferably 0.1-10, and the molar ratio of Lewis acidic compound (c) / transition metal compound (A) is also usually 0.01.
To 100, preferably 0.1 to 10, and the organometallic compound (d) / transition metal compound (A) molar ratio is usually 0.1 to 100.
It is 10,000, preferably 1 to 1,000.

In the production method of the present invention, the conjugated diene monomer or the conjugated diene monomer and a monomer copolymerizable therewith can be polymerized by a solution polymerization method in an inert solvent,
In addition to a slurry polymerization method and a bulk polymerization method using a monomer as a diluent, a gas phase polymerization method in a gas phase stirring tank or a gas phase fluidized bed can be employed. Among these methods, the solution polymerization method is preferable in terms of maintaining living polymerizability and producing a polymer having a narrow molecular weight distribution.

The inert solvent used is the same as described above, and two or more solvents may be used as a mixture.

Further, a polymerization reaction may be carried out by adding polar compounds such as ethers such as ethyl ether, diglyme, tetrahydrofuran and dioxane, and amines such as triethylamine and tetramethylethylenediamine.

The polymerization temperature is not particularly limited, but is usually -1.
00 to + 100 ° C, preferably -80 to + 60 ° C, more preferably -70 ° C to + 40 ° C, particularly preferably -6.
0 to + 20 ° C. From the viewpoint of producing an uncoupled polymer (I) having a narrow molecular weight distribution by increasing the rate of the initiation reaction with respect to the growth reaction, and a polymer (I) in which living polymerization proceeds and a polymer (I) having a small number of branched structures is bonded.
From the viewpoint of producing I), the temperature is preferably lower. On the other hand, it is not preferable to use an extremely low temperature in terms of manufacturing cost.

The polymerization time is usually 1 second to 360 minutes, and the polymerization pressure is normal pressure to 30 kg / cm ² .

In the method for producing a coupling type conjugated diene polymer of the present invention, when the polymerization reaction reaches a predetermined polymerization conversion, a living polymer having a transition metal of Group IV of the periodic table at a molecular terminal is obtained. A coupling agent capable of reacting with the coalescence is added to the polymerization system and brought into contact with the living polymer.
In the present invention, the polymer (I) having a plurality of molecules reacted with the reactive reagent to be bound as one molecule is the polymer (II), and such a reactive reagent is coupled. Agents.

The coupling reaction mode includes a type in which a living polymer (I) having a plurality of molecules is brought into contact with one molecule of a coupling agent to form a directly coupled polymer (II) (ie, a coupling agent). When a polyfunctional reagent, for example, tin tetrachloride is used, a single-molecule living polymer (I) and a single-molecule coupling agent are contacted to form a terminal-modified polymer, followed by a post-treatment. (For example, when N-methylpyrrolidone is used as a coupling agent), or when both the former and the latter coexist. It is possible.

Living Polymer (I) in Coupling Agent
It is preferable that the number of reaction sites with is plural, but if the latter action can proceed, one may be used.

Examples of the coupling agent include typical oxygen molecules, carbon monoxide, carbon dioxide, carbon disulfide, carbonyl sulfide, sulfur dioxide and the like, halogen molecules such as chlorine, bromine and iodine; vinylbenzyl chloride, Organic halides such as methylene bromide; epoxy compounds (eg, 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′-tetraglycidyldiaminodiphenylmethane, etc.), thiirane compounds (eg, thiirane, methylthiirane, phenylthiirane), and ethyleneimine derivatives (eg, ethyleneimine, propyleneimine, N-phenylethyleneimine, N- Hetero three-membered ring compounds such as (β-cyanoethyl) ethyleneimine and 2,5-bis (1-aziridinyl) -p-benzoquinone;

For example, 2,5-hexanedione and N-substituted aminoketones (for example, 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, 1,3-
Bis (diphenylamino) -2-propanone, 1,7-
Bis (methylethylamino) -4-heptanone, 4-dimethylaminobenzophenone, 4-di-t-butylaminobenzophenone, 4-diphenylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'- Bis (diethylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone, etc.), N-substituted aminothioketones (for example, N-
Ketone compounds such as those corresponding to examples of substituted amino ketones);

Pentandial, N-substituted benzaldehydes (for example, 4-dimethylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-
Aldehyde compounds such as divinylaminobenzaldehyde) and N-substituted benzthioaldehydes (for example, those corresponding to the examples of N-substituted benzaldehyde); ethyl (thio) ketene, butyl (thio) ketene, phenyl (thio) ketene , A compound having a ketene structure such as toluyl (thio) ketene or a thioketene structure; a compound having an ester structure or a lactone structure such as ethyl acetate, fatty acid glycerol ester, glycerol triacetate, glycerol tributyrate, and γ-butyrolactone; Compounds having an acid halide structure such as benzoic acid chloride, phthalic acid chloride, maleic acid chloride and trimesoyl chloride; carbodiimide structures such as N, N'-diphenylcarbodiimide and N, N'-diethylcarbodiimide A compound having the structure:

Pyridine compounds having a halogen on a carbon atom adjacent to a nitrogen atom (2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5-tripyridine Bromoimidazole, 3,6-dichloro-4-methylpyridazine, 3,
4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino-4,6-dichloropyrimidine, 6-chloro-2, 4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6
-Methylpyrimidine, 4,6-dichloro-2- (methylthio) pyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6 -Dichloropyrazine,
2,4-bis (methylthio) -6-chloro-1,3,5
-Triazine, 2,4,6-trichloro-1,3,5-
Triazine, 2-bromo-5-nitrothiazole, 2-
Chlorobenzothiazole, 2-chlorobenzoxazole, etc., pyridyl-substituted ketones (eg, methyl-2-
Pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone, propyl-3-pyridyl ketone, 2-benzoylpyridine, and the like; and vinylpyridines (for example, 2-vinylpyridine) , A compound having a pyridine unit such as 4-vinylpyridine;

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, picolinamide, N, N-dimethylisonicotinamide, succinamide, phthalamide, N, N,
N ', N'-tetramethylphthalamide, oxamide, N, N, N', N'-tetramethyloxamide, 2
-Furancarboxylic acid amide, N, N-dimethyl-2-furancarboxylic acid amide, quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid amide, and N-substituted lactams (for example, N-methyl-
β-propiolactam, N-phenyl-β-propiolactam, N-methyl-2-pyrrolidone, N-phenyl-
2-pyrrolidone, Nt-butyl-2-pyrrolidone, N
-Phenyl-5-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-phenyl-2-piperidone, N
Compounds having an amide structure such as -methyl-ε-caprolactam), N-substituted thiolactams (for example, those corresponding to examples of N-substituted lactams);

Urea, polymethylene urea, N-substituted cyclic ureas (for example, 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone,
1-dipropyl-2-imidazolidinone, 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-imidazolidinone, etc.), N-substituted cyclic thioureas (for example,
Compounds having a urea structure or a thiourea structure such as those corresponding to examples of N-substituted cyclic ureas; succinimide, N-methylsuccinimide, maleimide, N-methylmaleimide, phthalimide, N-methylphthalimide,
Compounds having an imide structure such as polyimide; compounds having a carbamic acid structure such as methyl carbamate, methyl N, N-diethylcarbamate, isocyanuric acid, N, N ′, N′-trimethylisocyanuric acid, and having an isocyanuric acid structure Compounds, compounds having a derivative structure thereof, and corresponding thiocarbonyl-containing compounds; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,3,5-benzene triisocyanate Isocyanate, polymeric type diphenylmethane diisocyanate,
Compounds having an isocyanate structure or a thioisocyanate structure such as isophorone diisocyanate, hexamethylene diisocyanate, 2,4-tolylene dithioisocyanate, hexamethylene dithioisocyanate;

Silicon compounds having a halogen atom or an alkoxy group (eg, hexachlorodisilane, bis (trichlorosilyl) ethane, silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride, silicon tetraiodide, tetramethoxysilane, tetraethoxy Silane, trichloromethylsilane, ethyltrichlorosilane, n-butyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-
Aminopropyltriethoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methyldichlorosilane, methylphenyldichlorosilane, dimethyldiethoxysilane, diphenyldimethoxysilane, etc.), as well as germanium compounds (for example, germanium tetrachloride,
Germanium tetrabromide, germanium tetraiodide, germanium tetraethoxide, ethyl germanium trichloride, germanium diiodide, dimethylgermanium dichloride, diethylgermanium dichloride, etc., and tin compounds (for example, bis (trichlorostannyl) ethane, Tin chloride, tin tetrabromide, tin tetraiodide, tin tetrafluoride, tetra-t-butoxytin, methyltin trichloride, phenyltin trichloride, n-butyltin trichloride, tin dichloride, tin dibromide, Tin iodide,
Tin difluoride, dimethyltin dichloride, di-n-butyltin dichloride, di-t-butyltin dichloride, diphenyltin dichloride, divinyltin dichloride, diethoxytin, etc., as well as phosphorus compounds (phosphorus pentachloride, phosphorus pentabromide, pentafluoride) Phosphorus, 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, etc.).

In order to obtain a coupling type polymer which is preferable as a rubber material, a compound having a ketone structure, a compound having an ester structure or a lactone structure, a compound having an amide structure, a compound having an isocyanate structure or a thioisocyanate structure Preferably, silicon having a halogen atom or an alkoxy group, also germanium, tin, also a phosphorus compound and the like, N-substituted lactams, corresponding N-substituted thiolactams, a tin compound having a halogen atom or an alkoxy group is more preferable, Tin compounds having a halogen atom are more preferred, and tin tetrachloride is particularly preferred.

The amount of the coupling agent to be used is generally 0.01 to 1,000 per mol of the transition metal compound (A).
The range is 0 mol, preferably 0.05 to 100 mol, and more preferably 0.1 to 10 mol.

The coupling agent usually has a polymerization conversion of 10
%. In addition, as the polymerization proceeds, the polymerization rate decreases, the living terminal is likely to be deactivated, and the content of the coupling component may decrease. Therefore, if the polymerization conversion rate exceeds 10%, it should be added promptly. Is preferred.

The coupling reaction temperature is not particularly limited, but is usually -100 to + 100 ° C, preferably -80 to 6 ° C.
0 ° C, more preferably -70 ° C to + 40 ° C, particularly preferably -60 to + 20 ° C. The coupling reaction time is usually 1 minute to 300 minutes.

The termination of the coupling reaction is usually carried out by adding a reaction terminator to the reaction system when a predetermined coupling ratio is reached. As a reaction terminator,
For example, alcohols such as methanol, ethanol, propanol, butanol, and isobutanol are used, and they may contain an acid such as hydrochloric acid.

The coupling type polymer is obtained as a composition containing an uncoupled polymer and a coupled polymer. The coupled polymer having a different number of bonded conjugated diene-based polymers is obtained. May be contained. These can be used after purification, if necessary, due to differences in molecular weight or the like. However, they are usually used as coupling polymers without purification.

In order to prevent the Mooney viscosity of the coupling polymer from changing unnecessarily during storage, a Mooney viscosity stabilizer can be added. Specific examples of Mooney viscosity stabilizers 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,
Ethyleneimine, cyclohexenimine, pyrrolidine,
Piperidine, morpholine, thiomorpholine, pyridine,
Organic amino compounds such as pyrrole, pyrimidine, triazine, indole, quinoline, and purine are exemplified.

The amount of the Mooney viscosity stabilizer is not particularly limited, but is preferably 0.1 to 40 mol, more preferably 0.5 to 20 mol, as an amino group per 1 mol of the functional group of the coupling agent. ~ 15 mol is particularly preferred. If the addition amount is too small, the Mooney viscosity may change due to storage or the like, which may make it unsuitable for use.If it is too large, bleeding may occur, or the crosslinking speed may become too high to control when used after crosslinking. is there.

An antioxidant can be added at any stage from immediately after the completion of the coupling reaction to the drying step of the coupling polymer. Examples of the anti-aging agent include a phenol stabilizer, a sulfur stabilizer, a phosphorus stabilizer, and an amine stabilizer.

The phenolic stabilizer is disclosed in JP-A-4-252.
243, for example, such as 2,6-di-tert-butyl-4-methylphenol,
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-
Examples include di-methylphenol.

Examples of the sulfur-based stabilizer include dilauryl thiodipropionate, distearyl thiodipropionate, aminothioglycolate, 1,1'-thiobis (2-naphthol), ditridecylthiodipropionate, Distearyl-β, β′-thiodipropionate and the like are exemplified.

Phosphorus stabilizers are also known and include, for example, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), and tris (2,4-di-tert-butylphenyl). Phosphite is exemplified.

Examples of the amine-based stabilizer include phenyl-α-naphthylamine, phenyl-β-naphthylamine, aldol-α-naphthylamine, p-isopropoxydiphenylamine, p- (p-toluenesulfonylamide) diphenylamine and bis (phenyl). Isopropylidene) -4,4′-diphenylamine, N, N′-diphenylethylenediamine, N, N′-diphenylpropylenediamine, octylated diphenylamine,
N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine and the like are exemplified.

The amount of the antioxidant to be added is usually 0.01 to 5.0 parts by weight per 100 parts by weight of the coupling type polymer.
Preferably it is 0.05 to 2.5 parts by weight. If the amount of the antioxidant is too small, the heat resistance is poor and the effect of adding the antioxidant is too small. If the amount of the antioxidant is too large, the thermal discoloration of the rubbery polymer becomes too poor. These antioxidants can be used alone or as a mixture of two or more antioxidants.

After stopping the coupling reaction, the method for recovering the coupling polymer is not particularly limited, and for example, a steam stripping method, precipitation with a poor solvent, or the like may be used.

(Coupling-Type Butadiene-Based Polymer) Among the coupling-type conjugated diene polymers obtained by the production method of the present invention, (I) butadiene homopolymer or butadiene and a monomer copolymerizable therewith Wherein the cis-bonded unit in the butadiene unit is 50% or more, and the number average molecular weight (Mn) is 1,000.
0 to 90 parts by weight of a polymer having a weight of 10,000,000
And (II) a polymer 100 to which at least two molecules of the polymer (I) are bonded via a polyfunctional reagent;
The coupling type butadiene-based polymer characterized by being composed of 10 parts by weight is a novel polymer.

The novel coupling type butadiene-based polymer has a repeating unit derived from 1,3-butadiene of 50% or more, preferably 70% or more, more preferably 8% or more.
0% or more, particularly preferably 90% or more of a copolymer or a 1,3-butadiene homopolymer, and most preferably a 1,3-butadiene homopolymer. If the number of repeating units derived from butadiene is too small, preferable properties of the butadiene-based polymer of the present invention based on the large number of cis bonds are impaired.

In the coupling type butadiene polymer of the present invention, cis-bonded units in units derived from 1,3-butadiene are 50% or more, preferably 80% or more, more preferably 90% or more. If the cis bond is too small, problems such as a decrease in tensile strength occur, and the rubber loses its desirable properties. Here, the cis bond is a 1,4-cis bond.

The GPC (gel permeation) of the component (I) in the coupling type butadiene polymer of the present invention.
The number average molecular weight (Mn) in terms of polybutadiene measured by chromatography is 1,000 to 10,000,
5,000, preferably 5,000 to 5,000,000.
00, more preferably 10,000 to 1,000,000
0, particularly preferably 20,000 to 500,000. If the molecular weight is too small, the physical properties as a polymer such as low mechanical strength become insufficient, and conversely, if the molecular weight is too large, molding becomes difficult.

The GPC (gel permeation) of the component (I) in the coupling type butadiene polymer of the present invention.
The molecular weight distribution (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polybutadiene measured by chromatography), is preferably less than 3.0, more preferably less than 2.0. Preferably, and more preferably, less than 1.5. If the molecular weight distribution is too wide,
When crosslinked, there arises a problem that physical properties of the crosslinked product such as abrasion resistance are reduced. The component (I) in the coupling type butadiene polymer of the present invention has a weight average molecular weight (M
w), weight average molecular weight (Mw) and number average molecular weight (M
n) between the ratio (Mw / Mn) of the formulas: γ: log (Mw / Mn) <A × log (Mw) −
B is preferably satisfied when A = 0.162 and B = 0.682, more preferably the expression γ holds even when A = 0.161, and further preferably holds even when A = 0.160. It is particularly preferable that A is equal to 0.159. The expression γ is preferably satisfied even when B = 0.684, more preferably satisfied even when B = 0.687, and particularly preferably satisfied even when B = 0.690.

In the coupling type butadiene polymer of the present invention, the polymer (I) preferably does not substantially have a branched structure. The branched structure of the polymer (I) is GPC
-Root mean square radius (RMSR, nm) and absolute molecular weight (M) determined by multi-angle light scattering (MALLS) measurement
W, g / mol) (measurement is performed at 40 ± 2 ° C. using tetrahydrofuran (hereinafter referred to as “THF”) as an eluent). The term "branched structure" as used herein refers to a structure formed by an elementary reaction (such as a transfer reaction) other than the normal addition reaction of monomers. Therefore, 1,
It is not a side chain vinyl group derived from two bonds,
It is not a long-chain branch generated by a coupling reaction. The branched structure of the component (I) in the coupling type butadiene polymer of the present invention preferably satisfies the following formula δ. Equation δ: log (RMSR)> a × log (MW) −b where the coefficient a is 0.638 and the coefficient b is 2.01
It is. The coefficient b is preferably 2.00 or less, more preferably 1.99 or less. The polymer that satisfies the formula δ is a butadiene-based polymer having a large cis-bond content and having substantially no branched structure since it is produced by a living polymerization reaction.

The coupling type butadiene-based polymer of the present invention includes the polymer (II) in which at least two molecules of the polymer (I) are bonded via a coupling agent. The content (coupling ratio) of the polymer (II) in the coupling type butadiene polymer is 10% or more, preferably 20%.
Or more, more preferably 30% or more. The upper limit of the content of the polymer (II) is not particularly limited,
Values can be up to 100%. If the coupling ratio is too low, the effect of the coupling, such as improvement in dimensional stability at room temperature, will be insufficient. Coupling rate (%)
Can be determined from the peak area of the polymer (I) and the peak area of the polymer (II) in the GPC curve. The peak area of the polymer (I) cannot be substantially distinguished by GPC. The polymer (I) may include a polymer to which a coupling agent is bonded. Normal,
There is no substantial difference in molecular weight between those with and without the coupling agent.

The molecular weight of the polymer (II) in the coupling type butadiene polymer of the present invention is at least twice, preferably at least three times, the molecular weight of the polymer (I).

The molecular form of the polymer (II) in the coupling type butadiene polymer of the present invention is linear when the polymer (I) is bonded to two molecules, but is preferably a polymer (I). I) is a star shape generated when three or more molecules are bonded.

The chemical structure of the coupling site of the polymer (II) in the coupling type butadiene polymer of the present invention is not particularly limited, but preferably has a tin-butadienyl bond.

[0113]

EXAMPLES The present invention will be specifically described below with reference to examples.

(Transition Metal Compound Production Example 1) Synthesis of (2-methoxycarbonylmethyl) cyclopentadienyltrichlorotitanium Trimethylsilylcyclopentadienyl sodium (3
Methyl bromoacetate (3 g, 200 mmol) in 400 ml THF solution at −78 ° C. under argon atmosphere.
(0.6 g, 200 mmol) in 100 ml of THF was slowly added dropwise. After completion of the dropwise addition, stirring was further continued at -78 ° C overnight. Thereafter, THF was distilled off under reduced pressure, and the generated solid was filtered off, followed by vacuum distillation (65-66 ° C./3 m
mHg) to obtain about 30 g (yield 70%) of (2-methoxycarbonylmethyl) trimethylsilylcyclopentadiene [TMSCpCH ₂ COOMe]. The structure of the product was confirmed by ¹ H-NMR.

¹ H-NMR (ppm, TMS, CDC
l ₃₎ 6.55-6.20 (m, hydrogen bonded to carbon constituting double bond in cyclopentadiene ring), 3.5
-3.35 (m, hydrogen bonded to carbon constituting a single bond in the cyclopentadiene ring), 3.15-2.98
(M, hydrogen bonded to carbon constituting a single bond in the cyclopentadiene ring), 3.69 (s, 2H), 3.67
(S, 3H), -0.22 (s, 9H)

4.2 g of (2-methoxycarbonylmethyl) trimethylsilylcyclopentadiene (20 mm
3.8 g (20 mmol) of titanium tetrachloride was added to 100 ml of a dry methylene chloride solution of 1) at 0 ° C. under an argon atmosphere, and stirring was continued at room temperature for 3 hours. Reaction solution at -30 ° C
Then, orange crystals (4.0 g, yield 70%) were obtained. The product is (2-methoxycarbonylmethyl) cyclopentadienyltrichlorotitanium [MeO (CO) C
H ₂ CpTiCl ₃ , hereinafter abbreviated as “TiES”] was confirmed by ¹ H-NMR.

¹ H-NMR (ppm, TMS, CDC
l ₃ ) 7.05 (s, 4H), 3.92 (s, 2H),
3.76 (s, 3H)

Comparative Example 1 In a sealed pressure-resistant glass ampoule having an inner volume of 150 ml, under a nitrogen atmosphere, 49 g of toluene and 1.0 g of butadiene were charged to a constant temperature of 50 ° C., and n-BuLi 0.02 mmol
l of hexane solution was added and polymerized at 50 ° C. for 60 minutes. 0.0014 mmol of tin tetrachloride was added to this polymerization solution.
Was added and reacted at 50 ° C. for 60 minutes. Quenching was performed by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol containing an antioxidant to precipitate a polymer. The obtained polymer was dried and weighed to determine the polymer yield. The polymer was analyzed by the following method.
The results are shown in Table 1.

The microstructure of the polymer was determined by NMR analysis. That is, ¹ H-NMR analysis (1,4-bond
5.4-5.6 ppm, 1,2-bond 5.0-5.1
ppm), the ratio of 1,4-bonds to 1,2-bonds in the polymer was determined, and the ratio of cis to trans was determined from ¹³ C-NMR analysis (cis 28 ppm, trans 33 ppm) to determine the microstructure of the polymer. Were determined.

For GPC analysis, THF was used as an eluent,
A column in which two GMHs manufactured by Tosoh Corporation or a column in which G-5000 and G-4000 are connected is used as a column, and an ultraviolet absorption detector (UV, detection wavelength: 310 n) is used as a detector.
m) and a differential refractive index detector (RI). The number average molecular weight and the molecular weight distribution were determined based on a calibration curve prepared using a standard polybutadiene sample (manufactured by Polymer Laboratories).

Example 1 A toluene solution of 0.033 mmol of TiES was dropped into a toluene solution of 33.3 mmol of methylaluminoxane, and the solution was aged at 25 ° C. for 5 minutes. Under a nitrogen atmosphere, 49 g of toluene and 1.0 g of butadiene were charged into a sealed pressure-resistant glass ampoule having an inner volume of 150 ml, and cooled to -25 ° C. The aged catalyst was added to the ampoule and polymerized at -25 ° C for 5 minutes. After sampling a small amount of the polymerization solution for GPC measurement, a toluene solution of 0.013 mmol of tin tetrachloride was added to the polymerization solution, and the mixture was allowed to react for 60 minutes while naturally warming to room temperature. Quenching was performed by adding a small amount of methanol, and the polymerization solution was poured into a large amount of acidic methanol containing an antioxidant to precipitate a polymer. The polymer was dissolved in toluene, the solution was centrifuged to remove ash, and then reprecipitated in acidic methanol. The obtained polymer was dried and weighed to determine the polymer yield. Table 1 shows values obtained by the same analysis as in Comparative Example 1. It can be seen that the ratio of cis-bonded units in the resulting butadiene polymer is high, the molecular weight distribution of component (I) is narrow, and the coupling ratio is 36%. Also, such polymers have been obtained very efficiently.

Example 2 50 mmol of methylaluminoxane and 0.1% of TiES were used.
05 mmol, ethyl acetate 0.0 as a coupling agent
Polymerization and analysis were carried out in the same manner as in Example 1 except that 4 mmol was used. Table 1 shows the results.

Reference Examples 1, 2 and 3 High-molecular-weight butadiene polymer samples were prepared under the conditions shown in Table 2 (Reference Example 1). Along with the obtained sample, commercially available N
d-catalyzed butadiene polymer (Neocis 6 manufactured by Enikem Corporation)
0) and a Co-catalyzed butadiene polymer (Nipol BR1220 manufactured by Zeon Corporation) were subjected to the following GPC-MALLS measurement in order to know the branched structure.

As columns, G-7000 manufactured by Tosoh Corporation and G
-5000, THF as an eluent,
The measurement was performed at 40 ± 2 ° C. using DAWN-F manufactured by Wyatt Technology as a multi-angle light scattering detector, and the root mean square radius (RMSR, nm) and absolute molecular weight (MW, g / m) were measured.
ol) was determined in the molecular weight region where the measured value was significant. In the polymer of Reference Example 1, the coefficient of the formula δ is a =
0.655, b = 2.08. Where RMSR
(100) and RMSR (50) are the RMSR values corresponding to the molecular weights of 1,000,000 and 500,000. Therefore, T
It can be said that the butadiene polymer obtained by the iES catalyst contains substantially no branch.

It can be easily analogized that the component (I) in the polymers of Examples 1 and 2 does not substantially contain a branched structure.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

The coupling type polymer of the present invention comprises 1,
It has the property that the ratio of 4-cis bonded units is high.

This coupling type polymer is excellent in processability and reinforcing properties as rubber.

(Preferred Embodiment) The coupling type butadiene polymer of the present invention, that is, "(I) a butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable therewith, wherein the cis-bonded unit in the butadiene unit Is 50% or more, and the number average molecular weight (Mn) is 1,000 to 10,000.
0 to 90 parts by weight of a polymer which is 00,000;
(II) a preferred embodiment of the "coupling-type butadiene-based polymer" characterized by comprising 100 to 10 parts by weight of a polymer in which at least two molecules of the polymer (I) are bonded via a polyfunctional reagent. The summary is as follows.

(1) The coupling type butadiene-based polymer has a homopolymer of 1,3-butadiene or a repeating unit derived from 1,3-butadiene of 50% or more, preferably 70% or more, more preferably 80% or more. % Or more, particularly preferably 90% or more, and most preferably,
It is a homopolymer of 1,3-butadiene. (2) Coupling type butadiene-based polymer
50% or more of cis-bonded units in the 3-butadiene unit;
It is preferably at least 80%, more preferably at least 90%. (3) The number average molecular weight (Mn) of the component (I) in the coupling type butadiene polymer is from 1,000 to 10,000.
00,000, preferably 5,000-5,000.
0000, more preferably 10,000 to 1,000.
0000, particularly preferably 20,000 to 500,0.
00. (4) Weight average molecular weight (Mw) and number average molecular weight (M) of component (I) in the coupling type butadiene polymer
The ratio (Mw / Mn) of n) is preferably less than 3.0, more preferably less than 2.0, even more preferably less than 1.5.

(5) The component (I) in the coupling type butadiene polymer is composed of a weight average molecular weight (Mw) and a ratio (Mw / Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Mn), it is preferable that the following formula γ: logarithm γ: log (Mw / Mn) <A × log (Mw) −B holds when A = 0.162 and B = 0.682, and the formula γ is It is more preferable that A = 0.161 is satisfied, it is more preferable that A = 0.160, and it is particularly preferable that A = 0.159 is also satisfied. The expression γ is preferably satisfied even when B = 0.684, more preferably satisfied even when B = 0.687, and particularly preferably satisfied even when B = 0.690. (6) Component (I) in the coupling type butadiene-based polymer has substantially no branched structure, and has a root mean square radius (RMSR, nm) determined by GPC-multi-angle light scattering (MALLS) measurement. And absolute molecular weight (MW, g / m
ol), the following formula δ is preferably satisfied. Equation δ: log (RMSR)> a × log (MW) −b where the coefficient a is 0.638 and the coefficient b is 2.01
It is. The coefficient b is preferably 2.00 or less, more preferably 1.99 or less.

(7) Component (I) in the coupling type polymer
I) is a polymer having a linear form in which two molecules of the component (I) are bonded or a polymer having a star shape in which three or more molecules of the component (I) are bonded, and more preferably the latter star. It is a polymer having a mold shape. (8) Component (I) in the coupling type butadiene polymer
The content of I) is 10 to 100%, preferably 20 to 10%.
0%, more preferably 30 to 100%.

II. A process for producing the terminal-modified conjugated diene polymer of the present invention, namely, (A) a transition metal compound belonging to Group IV of the Periodic Table having a cyclopentadienyl skeleton, and (B) (a) Organic aluminum oxy compounds,
(B) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (A), and (c) a Lewis acid capable of producing a cationic transition metal compound by reacting with the transition metal compound (A). A catalyst obtained by contacting the compound with (d) at least one cocatalyst selected from organometallic compounds of the main element metals of Groups I to III of the periodic table under conditions satisfying the following formulas α and β: In the presence, a conjugated diene monomer or a conjugated diene monomer and a monomer copolymerizable therewith are polymerized.
A method for producing a coupling-type conjugated diene-based polymer, which comprises contacting a polyfunctional reagent capable of reacting with a living polymer having a group transition metal at a molecular terminal with the polymer. Formula α: −100 <T <80 Formula β: 0.017 <t <6000exp (−0.0921T) where t is a contact time (minute) and T is a contact temperature (° C.) ”. Is summarized as follows.

(9) The transition metal compound of Group IV of the periodic table having a cyclopentadienyl skeleton, which is the component (A),
Preferred is a transition metal compound belonging to Group IV of the periodic table represented by the general formula 2.

(10) In the general formula 2, in the periodic table I
The Group V transition metal (M in the formula) is preferably titanium (T
i), zirconium (Zr) or hafnium (H
f), more preferably Ti. (11) In the general formula 2, as X, a halogen is preferably a chlorine atom, the hydrocarbon group is an alkyl group having 1 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and the hydrocarbonoxy group is a carbon atom. An amino group which is an alkoxy group having 1 to 12 or an aralkyloxy group having 7 to 12 carbon atoms and which may be substituted with a hydrocarbon group has 1 to 12 carbon atoms.
It is a dialkylamino group having 12 alkyl groups. (12) In the general formula 2, p is 2 or 3, and preferably 3. (13) In the general formula 2, m representing the number of organic groups Q is an integer of 0 to 5, preferably m is 1 or more.
Is selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. The organic group Q bonded to the cyclopentadiene ring is Further, the organic group Q may be a hydrocarbon group containing a silicon atom, a hydrocarbon group containing a tin atom, a hydrocarbon group containing a germanium atom, an ether group, or a thioether group. Organic groups having at least one atomic group having a hetero atom such as carbonyl group, sulfonyl group, ester group, thioester group, tertiary amino group, secondary amino group, primary amino group, amide group, phosphino group, phosphini group You may choose from.

(14) In the general formula 2, the organic group Q is
It is a bulky hydrocarbon group having 3 to 30 carbon atoms or an organic group having at least one Lewis basic atomic group having a hetero atom. (15) Among the cocatalysts (B) used in combination with the Group IV transition metal compound (A) of the periodic table, the organoaluminum oxy compound (a) is preferably a straight-chain or aluminum compound represented by the following general formula 3. It is a cyclic polymer. Formula ^{3: (-Al (R 1)} O-) n (R 1 is a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group, R ¹ is a halogen atom and / or R ² O
R ² may have 1 to 1 carbon atoms.
10 hydrocarbon groups, and n is 5 or more, more preferably 10 or more, preferably 100 or less, more preferably 50 or more.
It is as follows. (16) Among the cocatalysts (B), the ionic compound (b) which can form a cationic transition metal compound by reacting with the transition metal compound (A) is a non-coordinating anion, a carbonium cation, or an oxo compound. It is an ionic compound with a cation selected from among a ammonium cation, an ammonium cation, a phosphonium cation, and a ferrocenium cation having a transition metal.

(17) Among the cocatalysts (B), Lewis acid compounds (c) capable of forming a cationic transition metal compound by reacting with the transition metal compound (A) include tris (pentafluorophenyl) boron and tris It is selected from (monofluorophenyl) boron, tris (difluorophenyl) boron and triphenylboron. (18) Among the co-catalysts (B), the organometallic compound (d) of a main element metal of Groups I to III of the periodic table is not only an organic metal compound in a narrow sense, but also a main element of Groups I to III of the periodic table. The metal is selected from organometallic halogen compounds and hydrogenated organometallic compounds. (19) Preferred cocatalysts (B) are (a) alone, (c) alone, (a) and (d), (b) and (d) or combinations of (c) and (d). (20) The conjugated diene monomer is 1,3-butadiene, 2
-Methyl-1,3-butadiene, 2,3-dimethyl-
It is selected from 1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, preferably 1,3-butadiene or 2-
Methyl-1,3-butadiene, and more preferably 1,3-butadiene.

(21) According to any one of the following methods (i) to (iv), the transition metal compound (A) and the co-catalyst (B)
And a conjugated diene monomer or a conjugated diene monomer and a monomer copolymerizable therewith are polymerized in the presence of a catalyst which has been brought into contact (aged) in advance. (I) After contacting the component (A) and the component (B) in advance,
Further, the polymerization is carried out by contacting with a monomer. (Ii) After bringing the component (A) and the component (B) into contact with each other and further bringing the component into contact with a carrier, the produced supported catalyst is separated, and the supported catalyst is brought into contact with a monomer to carry out polymerization. (Iii) After the component (A) is brought into contact with the carrier, the component (B) is further brought into contact with the carrier, and the produced supported catalyst is separated.
The polymerization is carried out by bringing the supported catalyst into contact with the monomer. (Iv) After bringing the component (B) into contact with the carrier, the component (A) is further brought into contact with the component, and the generated supported catalyst is separated.
The polymerization is carried out by bringing the supported catalyst into contact with the monomer. (22) Contact temperature (T, ° C) between component (A) and component (B)
Is in the range of −100 to + 80 ° C., preferably −80 to + 80 ° C.
70 ° C. and the contact time (t, min) is 0.017
<T <6000exp (-0.0921T),
Preferably, 0.083 <t <4000exp (-0.0
921T). (23) The catalyst is used in an amount of 100 to 0.01 mmol, preferably 10 to 0.1 mmol, more preferably 5 to 0.1 mmol of the transition metal compound (A) per 1 mol of the monomer.
In the range of 2 mmol.

(24) The molar ratio of the organoaluminum oxy compound (a) / transition metal compound (A) is usually 10 to 1
000, preferably 100 to 5,000, more preferably 200 to 3,000, and the molar ratio of ionic compound (b) / transition metal compound (A) is usually 0.0
The molar ratio of the Lewis acidic compound cocatalyst (c) / the transition metal compound (A) is usually from 0.01 to 100, preferably from 0.1 to 10. The molar ratio of the organometallic compound (d) / transition metal compound (A) is usually from 0.1 to 10,000, preferably from 1 to 10,000.
1,000. (25) Polymerization is performed by a solution polymerization method. (26) a polymerization temperature of -100 to + 100 ° C, preferably -80 to + 60 ° C, more preferably -70 to + 40 ° C;
More preferably, it is −60 to + 20 ° C. (27) The polymerization time is from 1 second to 360 minutes. (28) The polymerization pressure is from normal pressure to 30 kg / cm ² .

(29) After the polymerization conversion reaches 10%, a polyfunctional reagent capable of reacting with a living polymer having a transition metal of Group IV of the periodic table at a molecular terminal (that is, a “coupling agent”) Is added to the polymerization system and brought into contact with the living polymer. (30) The coupling agent is an oxygen molecule, carbon monoxide, carbon dioxide, carbon disulfide, carbonyl sulfide, sulfur dioxide,
A halogen molecule, a hetero three-membered ring compound, a ketone compound, a hetero three-membered ring structure compound, a compound having a ketone structure, an aldehyde compound, a compound having a ketene structure or a thioketene structure, a compound having an ester structure or a lactone structure, and an acid halide structure. Compounds having a carbodiimide structure, compounds having an amide structure, compounds having a urea structure or a thiourea structure, compounds having an imide structure, compounds having a carbamic acid structure, compounds having an isocyanuric acid structure, and derivatives thereof. Or a thiocarbonyl-containing compound corresponding thereto, a compound having an isocyanate structure or a thiocyanate structure, a silicon compound having a halogen atom or an alkoxy group, a germanium compound, and a tin compound And include those that are likewise selected from the phosphorus compounds.

(31) The amount of the coupling agent to be used is generally 0.1 to 1,000, per mole of the transition metal compound (A).
The range is 0 mol, preferably 0.05 to 100 mol, and more preferably 0.1 to 10 mol. (32) The coupling reaction temperature is usually -100 to +1
00 ° C, preferably -80 to 60 ° C, more preferably -70 to + 40 ° C, particularly preferably -60 to + 20 ° C, and the coupling reaction time is 1 minute to 300 minutes.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Michihiko Asai 3-711 Namiki, Tsukuba City, Ibaraki Prefecture (72) Yasumi Suzuki 2-805, Azuma Azuma, Tsukuba City, Ibaraki Prefecture (72) Inventor Tetsu Miyazawa Ibaraki Prefecture 4-403-103 Matsushiro, Tsukuba-shi (72) Inventor Kenji Tsuchihara 2-806-703, Azuma, Azuma, Tsukuba-shi, Ibaraki (72) Inventor Masahide Murata 3-15-504 2-72, Suido 2-chome, Bunkyo-ku, Tokyo (72) ) Inventor Hiroyuki Ozaki 4-6-202 Onogawa, Tsukuba City, Ibaraki Prefecture (72) Inventor Masanao Kawabe 2-6-1203, Takezono 2-chome, Tsukuba City, Ibaraki Prefecture (72) Inventor Yoshifumi Fukui Ninomiya 4-chome, Tsukuba City, Ibaraki Prefecture No. 6-3-507 (72) Inventor Jin Jiju 3-14-4 Hiromi Heights, Kanazawa City, Ishikawa Prefecture 201 (72) Inventor Hideaki Hagiwara 2-6-14, Akubo, Tsukuba City, Ibaraki Prefecture Sakurai Heights 203 (72) ) Inventor Toshio Kase 5-2-2 Matsushiro, Tsukuba-shi, Ibaraki F-term (reference) 4J100 AA02Q AA03Q AA04Q AB00Q AB02Q AB03Q AB04Q AB08Q AB09Q AL03Q AM02Q AM15Q AR04Q AR11Q AR22Q AS01P AS02P CA03P AS01 AS01P ASCA FA10 FA27 FA28 HA35 HB01 HB04 HB05 HB35 HB50 HB57 HC04 HC10 HC25 HC28 HC33 HC38 HC39 HC42 HC47 HC50 HC51 HC57 HC59 HC63 HC69 HC72 HC75 HC77 HC78 HC80 HC83 HC85 HD07 HD08

Claims (2)

[Claims] (I) a butadiene homopolymer or
A copolymer of butadiene and a monomer copolymerizable therewith, wherein the number of cis-bonded units in the butadiene unit is 50.
% Or more and a number average molecular weight (Mn) of 1,000 to 1
0 to 90 parts by weight of a polymer, which is 0,000,000, and (II) 100 to 10 parts by weight of a polymer in which at least two molecules of the polymer (I) are bonded via a coupling agent. Characterized coupling type butadiene polymer. 2. A transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton, and (B)
(A) an organoaluminum oxy compound, (b) an ionic compound capable of forming a cationic transition metal compound by reacting with the transition metal compound (A), and (c) a cationic compound reacting with the transition metal compound (A). A Lewis acid compound capable of forming a transition metal compound, and (d) Periodic Tables I to III
A conjugated diene monomer, or conjugated, in the presence of a catalyst obtained by contacting at least one cocatalyst selected from an organometallic compound of a main group metal with a condition satisfying the following formula α and the following formula β: After polymerizing a diene monomer and a monomer copolymerizable therewith, a coupling agent capable of reacting with a living polymer having a transition metal of Group IV of the periodic table at a molecular terminal is brought into contact with the polymer. A method for producing a coupling-type conjugated diene-based polymer, characterized in that: Formula α: −100 <T <80 Formula β: 0.017 <t <6000exp (−0.0921T) Here, t is a contact time (minute), and T is a contact temperature (° C.).