JPH11286508A - Production of butadiene polymer and conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a butadiene polymer that has a high content of living chains, high cis-bond content, large molecular weight, narrow molecular weight distribution, extremely low content of branching structure, and to provide a production process for a conjugated diene polymer that can progress the living polymerization with high activity. SOLUTION: Relating to butadiene homopolymer, or copolymers of butadiene with copolymerizable monomers, cis linkage units amount to >=50% in the whole butadiene units, the number-average molecular weight (Mn) is 1,000-10,000,000 and the living chains bearing transition metal in group IV on the molecular chain terminals are contained in an amount of >=80% in the whole molecular chains. The objective diene polymer is prepared by polymerizing a conjugated diene monomer or a mixture thereof with other copolymerizable monomers at a temperature lower than 20 deg.C in the presence of a catalyst comprising (A) an organometallic compound of a transition metal in group VI in the periodic table bearing a cyclopentadienyl skeleton and (B) a cocatalyst selected from an organoaluminum oxy compound (a), or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a butadiene polymer having a large number of cis bonds and a high living chain content, and a method for producing a conjugated diene polymer using a specific metallocene catalyst.

[0002]

2. Description of the Related Art Metallocene catalysts are generally highly active, so that their production efficiency is high in the field of polymerization,
There are also features such as excellent control of the tacticity of the polymer,
The use of rubber in the production of rubber is also being considered.

Also in the case of butadiene rubber, a catalyst for conjugated diene polymerization comprising a combination of a transition metal compound belonging to Group IV of the periodic table represented by the following general formula 1 and aluminoxane, which is excellent in controlling the stereoregularity of the polymer, is used. It has been proposed (JP-A-9-77818, etc.). It is disclosed that polymerization of butadiene with this catalyst resulted in a polymer having a cis bond content of 96%. However, the molecular weight of the polymer, molecular weight distribution, regulation of the branched structure, and,
No living property of the polymerization is described. General formula 1:

[0004]

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Wherein M is a transition metal of Group IV of the periodic table,
X represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, Y ′
Is a hydrocarbon group having 1 to 20 carbon atoms and may itself form a ring with a cyclopentadienyl group, and Z is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Note that the structure in which a circle is drawn in the pentagon in the general formula 1 represents a cyclopentadiene ring structure (hereinafter the same).

The periodic table I of the periodic table represented by the following structural formula
A metallocene catalyst comprising a Group V transition metal compound is used in Mac
romol. Chem. , Macromol. S
ymp. 1997, Vol. 118, pages 55-60. However, no example was known in which this was used for the polymerization of a conjugated diene monomer. MeO (CO) CH ₂ CpTiCl ₃ (In the formula, Cp represents a cyclopentadiene ring structure; the same applies to the following.)

In recent years, the periodic table I of the above-mentioned structural formula
Application of metallocene catalysts composed of group V transition metal compounds to butadiene polymerization has been announced (Preliminary Proceedings of the 1st S & T Symposium on Creation of Highly Functional Materials for Industrial Science and Technology, 1
December 10, 997, p. 77). This polymerization is highly active, 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 living property and the branched structure of the butadiene polymer have not been known.

High cis-content butadiene polymers having a high molecular weight and a cis-bond content of 90% or more, which are polymerized using typical co-polymerization catalysts of the Co, Ni, Ti and Nd systems, are known. . However, the living property of polymerization is not known for Co-based, Ni-based, and Ti-based catalysts. In Nd-based catalyst polymerization, a polymerization reaction having relatively living properties is considered to proceed, but the content of living chains is unclear. From the description of WO 95/04090, the maximum value of the living chain content is estimated to be 75%. Further, the polymers obtained with these catalyst systems have many branched structures, and even the Nd-based polymer having the least branched structure has its root mean square radius (RMSR, nm) and absolute molecular weight (M
W, g / mol) is log (RMSR) = 0.638 x log (MW)-
2.01 is satisfied, and the number of branched structures is relatively large.

On the other hand, when an organolithium catalyst is used, living polymerization of a conjugated diene monomer proceeds, and a butadiene polymer having a high molecular weight, a narrow molecular weight distribution and substantially no branched structure can be obtained. The content remains below 40%.

As described above, in the prior art, living polymerization of a conjugated diene monomer is performed stereospecifically (high cis-regulated) with high activity, and it has a high molecular weight, a narrow molecular weight distribution and substantially no branched structure. In addition, a polymer having a high cis bond content could not be obtained.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a butadiene polymer having a high living chain content and a high 1,4-cis content and having substantially no branched structure, and to control the temperature during polymerization. It is an object of the present invention to provide a method for producing a conjugated diene-based polymer by which a polymer having a high living property is obtained.

[0012]

Thus, according to the present invention, there is provided a homopolymer of butadiene or a copolymer of butadiene and a monomer copolymerizable therewith, wherein all butadiene-derived cis-bonds are present. The unit derived from butadiene is 50% or more, and the number average molecular weight (Mn) is 1,000.
Provided is a butadiene-based polymer characterized by containing 80% or more of a living chain having a transition metal of Group IV of the periodic table at a molecular terminal in a total molecular chain of at least 10,000,000.

According to the present invention, (A) a transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound (a), and the transition metal compound (A) An ionic compound (b) capable of producing a cationic transition metal compound by reacting with a cation, a Lewis acid compound (c) capable of producing a cationic transition metal compound by reacting with the transition metal compound (A), I to I
In the presence of a catalyst comprising at least one cocatalyst selected from organometallic compounds (d) of Group II main element metals,
There is provided a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene monomer or a conjugated diene monomer and a monomer copolymerizable therewith at a temperature of 20 ° C. or lower.

[0014]

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, (b) an ionic compound capable of forming a cationic transition metal compound by reacting with the transition metal compound (A), and (c) reacting with the transition metal compound (A). A Lewis acid compound capable of producing a cationic transition metal compound by heating, and (d) Periodic Tables I to I
A catalyst obtained from at least one cocatalyst selected from organometallic compounds 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), is as follows:
Preferred is a transition metal compound belonging to Group IV of the periodic table represented by the following general formula 2. General formula 2:

[0016]

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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, May be different, and any one of X may be bonded to the cyclopentadienyl group with or without a crosslinking group to form a cyclic structure, and p is 2 or 3, Q is an organic group, which may combine with a cyclopentadienine ring structure to form a cyclic structure, and when Q is two or more, they may be different from each other; Is an integer. )

That is, the transition metal compound represented by the general formula 2 has only one cyclopentadienyl group or
It is a so-called half metallocene compound or a geometrically constrained catalyst having a plurality of fused cyclic substituents such as an indenyl group and a fluorenyl group as ligands.

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.

X represents a halogen atom such as a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I), and preferably a 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 which may be substituted with a hydrocarbon group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms such as dimethylamino, diethylamino, diisopropylamino, dibutylamino and di-t-butylamino. And a dialkylamino group. p is 2 or 3, and preferably 3.

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 cis content. When m is 2 or more, Q may be the same or different. Specific examples of the organic group include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, cyclohexyl, and adamantyl;
Examples thereof include an aryl group having 6 to 20 carbon atoms such as phenyl and an aralkyl group having 7 to 30 carbon atoms such as benzyl and triphenylmethyl. The organic group Q bonded to the cyclopentadiene ring structure may form a polycyclic group such as an indenyl group and a fluorenyl group together with the cyclopentadiene ring structure.

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 cis content of the polymer,
A bulky hydrocarbon group having 3 to 30 carbon atoms such as a trimethylsilyl group, a t-butyl group, and a triphenylmethyl group, or an organic group having at least one Lewis basic atomic group 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: cyclopentadienyl group having three substituents, indenyl group having two substituents on the cyclopentadiene ring, or (substituted) fluorenyl having one substituent on the cyclopentadiene ring Means a group. m = 4: a cyclopentadienyl group having four substituents or an (substituted) indenyl group having three substituents on a cyclopentadiene ring. m =
5: Refers to a cyclopentadienyl group having five substituents.

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 4 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.

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, specific examples include
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) Trisubstituted cyclopentadienyltitanium tri (or di) chloride, for example,
(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) Penta-substituted cyclopentadienyl titanium tri (or di) chloride, specifically, pentamethylcyclopentadienyl titanium tri (di) chloride, pentaphenylcyclopentadienyl titanium 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) inde 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 having three substituents on the cyclopentadiene ring tri (or di) chloride, specifically, (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, for example, (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 with 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 a fluorine atom, a bromine atom and an iodine atom. (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. (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 their corresponding (13) to (1)
The compound having the structure of 8) is more preferable, the compound of the structure of (2) and the corresponding structure of (13) to (17) is further preferable, and the compound of the structure of (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, 118, 55-60
On the basis of the description on the page, MeOCH ₂ CH ₂ CpTi
In the case of Cl ₃ , see Transition Met. Ch
em. , 1990, Vol. 15, p. 483.

Among them, (A ') Periodic Table IV having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from a carbonyl group, a sulfonyl group, an ether group and a thioether group. Group transition metal compounds are preferred. Group IV transition metal compound of the Periodic Table having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from the carbonyl group, sulfonyl group, ether group and thioether group as the component (A ') Is preferably the following general formula 3,
Alternatively, a transition metal compound of Group IV of the periodic table represented by the general formula 4 is preferable, and a transition metal compound of a group IV of the periodic table represented by the following general formula 3 is more preferable. General formula 3:

[0048]

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Wherein M is a transition metal of Group IV of the periodic table,
X ¹ , X ² , and X ³ represent a hydrogen atom, a halogen, and a C 1 to C 1
Y is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms, and itself forms a ring with a cyclopentadienyl group. Z ¹ and Z ² are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, A is an oxygen atom or a sulfur atom, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, A hydrocarbon oxy group of 1 to 12 or a hydrocarbon thio group of 1 to 12 carbon atoms, and n is an integer of 0 to 5. General formula 4:

[0050]

Embedded image

(Wherein M is a transition metal of Periodic Table IV, X
¹ , X ² and X ³ represent a hydrogen atom, a halogen, and a C 1 to C 12
Is a hydrocarbon group of 1 to 12 carbon atoms, and Y is a hydrogen atom or a hydrocarbon group of 1 to 20 carbon atoms, which itself forms a ring with a cyclopentadienyl group. Z ¹ and Z ² are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, A is an oxygen atom or a sulfur atom, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and n is 0 to It is an integer of 5. )

The transition metal compound represented by the general formula 3 or 4 is more preferably a cyclopentadienyl group having only one substituent such as a cyclopentadienyl group, an alkyl, an aryl or a cycloalkyl group. Or a so-called metallocene compound having a plurality of fused cyclic substituents as ligands, and the cyclopentadienyl group of the ligands has> C = O structure,> C = S structure, -C-O- C
And at least one atomic group selected from the group consisting of a structure and a -CSC- structure in the substituent. Also,
The transition metal of Group IV of the periodic table (M in the formula) is preferably Ti, Zr or Hf, more preferably Ti. X
¹ , X ² , and X ³ are each a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom; and the hydrocarbon group is an alkyl group such as methyl or neopentyl; an aralkyl group such as benzyl; Examples of the oxy group include an alkoxy group such as methoxy, ethoxy, and isopropoxy, and an aralkyloxy group such as a benzyloxy group. As the hydrocarbon oxy group, an alkoxy group is preferable. Y is, for example, a hydrogen atom, and
Methyl, ethyl, propyl, isopropyl, butyl, t
Examples thereof include an alkyl group such as -butyl, an anilyl group such as phenyl, an aralkyl group such as benzyl, and a hydrocarbon group containing a silicon atom such as a trimethylsilyl group. Y bonded to the cyclopentadiene ring may form a polycyclic group such as an indenyl group and a fluorenyl group together with the cyclopentadiene ring.

As Z ¹ and Z ² , for example, a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, t-
Alkyl groups such as butyl, aryl groups such as phenyl,
And aralkyl groups such as benzyl. R ¹ is, for example, a hydrogen atom, and examples of the hydrocarbon group include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; an aryl group such as phenyl; an aralkyl group such as benzyl; Methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy and other alkoxy groups, phenyloxy groups and other aryloxy groups, benzyloxy groups and other aralkyloxy groups, and hydrocarbon thio groups as methylthio, ethylthio and propylthio , Isopropylthio,
Examples thereof include an alkylthio group such as butylthio and t-butylthio, an arylthio group such as a phenylthio group, and an aralkylthio group such as a benzylthio group. As R ¹ , a hydrocarbon oxy group is preferable, and among them, an alkoxy group is particularly preferable. Examples of R ² include hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. n is preferably 1 or 2.

As a specific example of the transition metal compound of Group IV of the periodic table (A), MeO (CO) C represented by the general formula 3 is used.
H ₂ CpTiCl ₃ , MeO (CO) CH (Me) CpT
iCl ₃ , {3- [MeO (CO) CH ₂ ]} (1-M
e) CpTiCl ₃ , MeOCH ₂ C represented by the general formula 4
H ₂ CpTiCl _{3 and the} like (Me in the formula represents a methyl group, and Cp represents a cyclopentadienyl structure).

The method for preparing the Group IV transition metal compound (A) in the periodic table is not particularly limited. For example, MeO (CO)
In the case of CH ₂ CpTiCl ₃ , Macromol. Sy
mp. In the case of MeOCH ₂ CH ₂ CpTiCl ₃ , in accordance with the description in Transition Met., 1997, Vol. 118, pages 55-60. Chem. , 1
It may be prepared according to the description in Vol. 15, pp. 483, 990.

Of 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 5: Or it is a cyclic polymer and is a so-called aluminoxane. Formula ^{5: (-Al (R 5)} O-) n (R 1 is a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof, include methyl, ethyl, propyl, alkyl groups such as isobutyl R ⁵ may be substituted with a halogen atom and / or an R ⁶ O group, and R ⁶ 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.

Examples of non-coordinating anions include tetra (phenyl) borate and 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.

As specific examples of the carbonium cation,
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 selected and arbitrarily selected from the above-mentioned non-coordinating anions can be used.

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

Among the cocatalysts (B), specific examples of the Lewis acid compound (c) which can react with the transition metal compound (A) to form a cationic transition metal compound include tris (pentafluorophenyl) boron, Tris (monofluorophenyl) boron, tris (difluorophenyl) boron, and triphenylboron are exemplified.

Among the cocatalysts (B), of the 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 (c)
(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).

The cocatalyst (B) comprises (A ′) a carbonyl group,
When using a Group IV transition metal compound having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from a sulfonyl group, an ether group, and a thioether group, an aluminoxane (a ′);
Alternatively, it is particularly preferable to comprise an ionic compound (b ′) capable of producing a cationic transition metal compound by reacting with the transition metal compound (A ′).

The aluminoxane (a ') is as described above.

Examples of the ionic compound (b ′) capable of forming a cationic transition metal compound by reacting with the transition metal compound (A ′) include an anion of tetrakis (pentafluorophenyl) borate and (CH ₃ ) ₂ N ( C
Amine cations having active protons such as ₆ H ₅ ) H ⁺ , trisubstituted carbonium cations such as (C ₆ H ₅ ) ₃ C ⁺ , carborane cations, metal carborane cations,
An ionic compound with a ferrocenium cation having a transition metal can be used.

In the present invention, a conjugated diene monomer may be further used in combination with a metal hydride compound, an organometallic compound of a main element metal of Groups I to III of the periodic table, an organometallic halogen compound, or a hydrogenated organometallic compound. The body may be polymerized. When a compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (A) is used as the component (B), it is preferable to use an organometallic compound of a main element metal of Group III of the periodic table in combination. . As the metal hydride compound, for example, NaH, LiH, CaH ₂ , LiAlH ₄ ,
NaBH _{4 and the} like. Examples of the organometallic compound of the main element metal include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. 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 transition metal compound (A)
And / or the cocatalyst (B) can be used by being supported on a carrier. Examples of the carrier include an inorganic compound and an organic polymer compound. The inorganic compound is preferably an inorganic oxide, an inorganic chloride, an inorganic hydroxide, or the like, and may contain a small amount of a carbonate or a sulfate. Preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia and calcia, and inorganic chlorides such as magnesium chloride. These inorganic compounds are
Average particle size is 5-150 μm, specific surface area is 2-800 m
² / g of porous fine particles are preferable, for example, 100 to 80.
It can be used after heat treatment at 0 ° C. 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 an α-olefin homopolymer having a functional group obtained by chemically modifying a polymer having units such as ethylene, propylene, and butene, and α.
Olefin copolymers, polymers having units of acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and the like, and chemically modified products thereof. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used. By supporting the transition metal compound (A) and / or the cocatalyst (B), it is possible to prevent contamination of the catalyst due to adhesion to the polymerization reactor.

(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.

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, and (meth) acrylates such as methyl methacrylate.

(Method for Producing Conjugated Diene Polymer) In the present invention, a method for polymerizing a conjugated diene monomer or a conjugated diene monomer and a monomer copolymerizable therewith is not particularly limited. A transition metal compound (A);
An organoaluminum oxy compound (a), an ionic compound (b) capable of reacting with the transition metal compound (A) to form a cationic transition metal compound, and a cationic transition metal compound reacting with the transition metal compound (A) The following method using a Lewis acid compound (c) capable of producing a compound and at least one cocatalyst (B) selected from organometallic compounds (d) of the main element metals of Groups I to III of the periodic table. (I)
To (VI) are applicable.

(I) After the components (A) and (B) have been brought into contact in advance, polymerization is carried out by bringing the components into contact with a monomer. (II) After the component (A) and the monomer are brought into contact in advance, the polymerization is carried out by further bringing the component (B) into contact. (III) After the component (B) and the monomer are brought into contact in advance, the polymerization is carried out by further bringing the component (A) into contact. (IV) The components (A) and (B) are mixed, brought into contact with a carrier, the generated supported catalyst is separated, and the supported catalyst is brought into contact with a monomer to carry out polymerization. (V) After the component (A) is brought into contact with the carrier, (B)
The catalyst is brought into contact with the components, the formed supported catalyst is separated, and the supported catalyst is brought into contact with the monomer to carry out polymerization. (VI) After the component (B) is brought into contact with the carrier, the component (A) is further brought into contact with the component, and the produced supported catalyst is separated.
The polymerization is carried out by bringing the supported catalyst into contact with the monomer.

In the methods (I) to (VI), the transition metal compound (A) is used because the efficiency of the initiator and the polymerization activity are improved and the molecular weight distribution of the obtained polymer can be further narrowed. An organoaluminum oxy compound (a), an ionic compound (b) capable of reacting with the transition metal compound (A) to form a cationic transition metal compound, and a cationic transition metal compound reacting with the transition metal compound (A) Acid compound (c) capable of producing a compound of formula (I), and Periodic Tables I to III
After pre-contact (aging) with at least one cocatalyst (B) selected from organometallic compounds (d) of main group element metals, and further contacting with a monomer, (I)
The methods (IV) to (VI) are preferred, and the method (I) is particularly preferred. According to this method, the weight average molecular weight (M
w) and the number average molecular weight (Mn).
A w / Mn) of 1.6 or less can be easily obtained.

The contact temperature of component (A) with component (B) (T,
° C) is preferably from -100 to + 80 ° C, and from -80 to +70.
C is particularly preferred. The contact time (t, min), that is, the time from contact to the start of polymerization preferably satisfies 0.017 <t <6000exp (-0.0921T), and 0.083 <t <4000exp (-0.0921T). It is more preferable to satisfy. At a high temperature exceeding 80 ° C., the desired aging effect cannot be obtained, and at a low temperature below -100 ° C., there is a disadvantage 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. An aging time of less than 0.017 minutes, ie, about 1 second or less, makes practical operation difficult.

The component (A) and the component (B) can be used in the state 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 chloroform, methylene chloride, dichloroethane, chlorobenzene, etc. It is a halogenated hydrocarbon solvent. Preferred solvents are aromatic hydrocarbons such as toluene and benzene. Further, two or more kinds of solvents may be used as a mixture.

The amount of the catalyst used is usually 100 to 0.01 mmol of the transition metal compound (A) per 1 mol of the monomer,
Preferably from 10 to 0.1 mmol, more preferably from 5 to
It is in the range of 0.2 mmol. As described below, the polymerization reaction of the present invention in which a specific polymerization temperature is applied is a so-called living polymerization system. Therefore, the molecular weight of the resulting polymer can be regulated by the ratio of the transition metal compound to the monomer. The transition metal compound (A) per mole of the monomer which is particularly preferable for obtaining a polymer preferable as a rubber material
Is between 5 and 0.2 mmol. Also, with this amount of catalyst used, a polymer having a particularly narrow molecular weight distribution is obtained. Specifically, a polymer having Mw / Mn of 1.6 or less can be easily obtained.

The cocatalysts (a), (b), (c) and (d) may be used alone or in combination. When each is used alone, an organic aluminum oxy compound (a) such as aluminoxane may be used. / The transition metal compound (A) has a molar ratio of usually 10 to 10,000, preferably 100 to 5,000,
More preferably, it is 200 to 3,000. The molar ratio of the ionic compound (b) / the transition metal compound (A) is usually 0.01 to 100, preferably 0.1 to 10. The molar ratio of Lewis acidic compound (c) / transition metal compound (A) is usually 0.01 to 100, preferably 0.1 to 10. When an organometallic compound is used, the molar ratio of the organometallic compound (d) / the transition metal compound (A) is usually 0.1.
It is 1 to 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 polymerization temperature is -100 to 20 ° C, preferably -80 to 15 ° C, more preferably -60 ° C to 10 ° C. The temperature is preferably lower from the viewpoint of promoting the living polymerization to produce a polymer having a small number of branched structures, and increasing the rate of the initiation reaction for the growth reaction to produce a polymer having a narrow molecular weight distribution. On the other hand, it is not preferable to use an extremely low temperature in terms of manufacturing cost.

The polymerization time is 1 second to 360 minutes, and the polymerization pressure is normal pressure to 30 kg / cm ² . 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 performed by adding a polar compound such as an ether such as ethyl ether, diglyme, tetrahydrofuran, or dioxane, or an amine such as triethylamine or tetramethylethylenediamine.

For controlling the molecular weight of the polymer, a chain transfer agent may be added. As the chain transfer agent, those generally used in the polymerization reaction of cis-1,4-polybutadiene rubber are used. In particular, allenes such as 1,2-butadiene, cyclic dienes such as cyclooctadiene,
And, hydrogen is preferably used.

The termination of the polymerization reaction is usually carried out by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached. As the polymerization terminator, for example, alcohols such as methanol, ethanol, propanol, butanol, and isobutanol are used, and they may contain an acid such as hydrochloric acid. After termination of the polymerization reaction, the method of recovering the polymer is not particularly limited, for example,
A steam stripping method, precipitation with a poor solvent, or the like may be used.

(Butadiene-based polymer) According to the method for producing a conjugated diene polymer of the present invention, not only can the polymer be produced efficiently due to its high activity, but also the living polymerization can be advanced. Among the conjugated diene polymers obtained by the production method, butadiene homopolymer, or
A copolymer of butadiene and a monomer copolymerizable therewith, wherein all butadiene-derived units have at least 50% of cis-bonded butadiene-derived units, and have a group IV transition in the periodic table at the molecular terminal. It is characterized by containing 80% or more of a living chain having a metal in the whole molecular chain, preferably having a number average molecular weight (Mn) of 1,000 to 10,000.
000 butadiene-based polymer is a novel polymer.

In general, the evaluation of living polymerizability is as follows.
a) the molecular weight distribution of the resulting polymer is extremely narrow (close to monodisperse); b) the number average molecular weight increases proportionately with increasing polymer yield, and the molecular weight distribution does not widen; A) the number average molecular weight (Mn) of the polymer can be regulated by the monomer / catalyst ratio, d) post-polymerization (two-stage polymerization) is possible, and e) terminal functionalization is possible. Will be

The living chain content can be estimated by any of the evaluation criteria a) to e) above, but d) or e) can be accurately evaluated. In d), basically, in the GPC curve of the polymer obtained by the two-stage polymerization,
The living chain content can be determined from the mole fraction of the molecule forming the peak of the polymer having a higher molecular weight than the polymer obtained by the one-stage polymerization. For example, if the living chain content is 8
If it is 0% or more, the mole fraction of the polymer obtained by the single-stage polymerization will be less than 20%, and the mole fraction of the molecule forming the peak of the polymer having a higher molecular weight will be 80% or more. However, when a by-product is formed, a polymer having a lower molecular weight than the polymer obtained by the single-stage polymerization is present, so that the living chain content is lower than the actual value depending on the amount.

In e), the living polymer is terminal-modified, and the living chain content can be determined from the terminal modification ratio of the polymer. If the terminal modification rate is 80% or more, the living chain content is 80% or more. The terminal modification ratio can be determined by measuring the number average molecular weight and the terminal modifying group concentration of the polymer. The method varies depending on the type of the terminal modifier. For example, in the case where the living polymer of butadiene is modified with carbon monoxide, the number average molecular weight is measured by GPC, and the terminal is determined by infrared absorption spectrum. What is necessary is just to measure the carbonyl group concentration.

The novel living butadiene-based polymer has 50 repeating units derived from 1,3-butadiene.
% Or more, preferably 70% or more, more preferably 80%
The above, particularly preferably 90% or more of the copolymer or 1,
Homopolymers of 3-butadiene, most preferred are homopolymers of 1,3-butadiene. 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.

The living butadiene polymer of the present invention comprises
The cis bond in all the repeating units derived from 1,3-butadiene is 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 living butadiene polymer of the present invention has a number average molecular weight (Mn) of 1,000 to 10,000,000,
0, preferably 5,000 to 5,000,000, more preferably 10,000 to 2,000,000, and particularly preferably 20,000 to 1,000,000. 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 molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of the living butadiene polymer of the present invention is not particularly limited, but is preferably 1.9 or less. Preferably it is 1.6 or less, more preferably 1.4 or less. If the molecular weight distribution is too wide, there arises a problem that when crosslinked, the properties of the crosslinked product such as abrasion resistance decrease.

The branched structure of the polymer was determined by GPC-multi-angle light scattering (MALLS), and the root mean square radius (RMSR, nm) and absolute molecular weight (MW, g / mol)
(Measurement is performed at 40 ± 2 ° C. using tetrahydrofuran (THF) as an eluent). The term “branched structure” as used herein refers to a structure generated by an elementary reaction (such as a transfer reaction) other than a normal addition reaction of a monomer, and is not a side chain vinyl group derived from a 1,2 bond. The branched structure of the living butadiene polymer of the present invention is not particularly limited, but preferably satisfies Formula 1. Equation 1: log (RMSR)> a × log (MW) −b where the coefficient a is 0.638 and the coefficient b is 2.01
It is.

Since the polymer of the present invention is produced by a living polymerization reaction, it is a high cis structure butadiene polymer having substantially no branched structure, and is a completely novel polymer.

The living butadiene polymer of the present invention is contacted with a reagent having an active hydrogen such as alcohol or a reagent having a suitable reactivity such as carbon monoxide.
It can be a so-called dead polymer having no transition metal of Group VI of the periodic table at a molecular terminal. The dead butadiene-based polymer includes a novel polymer having the following structure.

For example, a butadiene homopolymer, or
A copolymer of butadiene and a monomer copolymerizable therewith, wherein butadiene units having cis bonds in all units derived from butadiene are 50% or more, and have a weight average molecular weight (Mw) and a weight average molecular weight (Mw). Mw) and the ratio (Mw / Mn) of the number average molecular weight (Mn) to the following formula γ: Formula γ: log (Mw / Mn) <A × log (Mw) −
B is a novel polymer. Here, it is preferable that A = 0.162 and B = 0.682 be satisfied.
0.161 is more preferably satisfied, and A = 0.
160 is more preferable, and A = 0.1
It is particularly preferable that 59 be satisfied. Equation γ is
It is preferable that B = 0.684 is satisfied, and B = 0.84.
687 is more preferable, and B = 0.69
It is particularly preferable that 0 is satisfied.

Further, for example, a butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable with butadiene, wherein 50% of units derived from cis-bonded butadiene in all units derived from butadiene are present. As described above, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) is 1.6 or less and Mn is 1,000 to 10,000.
Living and dead butadiene polymers having a molecular weight of 0000 are also novel polymers having a structure.

A butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable with butadiene, wherein at least 50% of cis-bonded butadiene-derived units are present in all butadiene-derived units, and Mn is 1,000-1
Living and dead butadiene-based polymers having a molecular weight of 0,000,000 and satisfying the following formula 1 ′ are novel polymers having a structure. Formula 1 ′: log (RMSR)> a × log (MW) −
b where coefficient a is 0.638 and coefficient b is 2.01
Less, preferably 2.00 or less, more preferably 1.9.
9 or less. This polymer is a high cis structure butadiene polymer having substantially no branched structure.

The living polymer having a small number of branched structures according to the present invention is a homopolymer of butadiene or a copolymer of butadiene and a monomer copolymerizable therewith when brought into contact with a suitable reactive reagent. Inducing all butadiene-derived units into a dead-butadiene-based polymer in which at least 50% of butadiene-derived units are cis-bonded and a molecular chain having a functional group at a molecular terminal is at least 80% in all the molecular chains. be able to.

The living polymer having a small branched structure of the present invention is contacted with a suitable polyfunctional reagent to give a butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable therewith. Wherein cis-bonded butadiene-derived units are 50% of all butadiene-derived units.
% Of a branched butadiene-based polymer having a star-shaped molecular form.

Further, the living polymer having a small number of branched structures of the present invention is a homopolymer of butadiene or a copolymer of butadiene and a monomer copolymerizable therewith when brought into contact with an appropriate different monomer. In the total units derived from butadiene, the units derived from cis-bonded butadiene are 5 units.
Butadiene-based blocks that are 0% or more can be derived into living and dead block copolymers as one component.

[0105]

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

(Transition Metal Compound Production Example 1) (2-Methoxycarbonylmethyl) cyclopentadienyltrichlorotitanium [MeO (CO) CH ₂ CpTiC
l ₃ ] Synthesis of trimethylsilylcyclopentadienyl sodium (3
2 g, 200 mmol) in 400 ml of tetrahydrofuran (hereinafter referred to as THF) solution under argon atmosphere.
At 8 ° C., methyl bromoacetate (30.6 g, 200 m
mol) of a 100 ml THF solution 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 formed solid was separated by filtration and then subjected to vacuum distillation (65-66 ° C./3 mmHg) to obtain about 30 g (yield 70%) of (2-methoxycarbonylmethyl) trimethylsilylcyclopentadiene [ TMSCp
CH ₂ COOMe] was obtained. The structure of the product is ¹ H-NMR
Confirmed from.

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 precipitated. It was confirmed by ¹ H-NMR that the product was (2-methoxycarbonylmethyl) cyclopentadienyltrichlorotitanium.

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

(Transition Metal Compound Production Example 2) Synthesis of (2-methoxyethyl) cyclopentadienyltrichlorotitanium [MeOCH ₂ CH ₂ CpTiCl ₃ ] sodium trimethylsilylcyclopentadienyl 32
g (200 mmol) in 400 ml THF solution at −78 ° C. under argon atmosphere.
8.9 g (200 mmol) of a 100 ml THF solution was slowly added dropwise. After completion of the dropwise addition, the mixture was heated and refluxed overnight.
Thereafter, THF was distilled off under reduced pressure, and the generated solid was separated by filtration. Then, about 33% was obtained by vacuum distillation (80 ° C., 1 mmHg).
g (85%) of (2-methoxyethyl) trimethylsilylcyclopentadiene [TMSCpCH ₂ CH ₂ OMe]
I got 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), 3.61 (m, 2H), 3.40
(S, 3H), 3.02 (m, 2H), 0.22 (s,
9H)

The obtained TMSCpCH ₂ CH ₂ OMe
O. 0.25 ml (2.2 mmol) of titanium tetrachloride was added to 50 g (2.5 mmol) of a 20 ml dry methylene chloride solution at −78 ° C. under an argon atmosphere, and stirring was continued at room temperature for 3 hours. Then, the reaction solution was cooled to -78 ° C to obtain 0.43 g (yield: 70%) of precipitated orange crystals. The product is (2-methoxyethyl) cyclopentadienyltrichlorotitanium [MeOCH ₂ CH ₂ CpTiCl
₃ ] was confirmed from ¹ H-NMR.

¹ H-NMR (ppm, TMS, CDC
l ₃ ): 6.91 (s, 4H), 3.70 (t, 2
H), 3.37 (s, 3H), 3.10 (t, 2H)

(Transition Metal Compound Production Example 3) Synthesis of Trimethylsilylcyclopentadienyltrichlorotitanium [Me ₃ SiCpTiCl ₃ ] Bis (trimethylsilyl) cyclopentadiene is described in J. Am.
C. S. It was synthesized according to the description of Dalton, 1980, p. 1156, and purified by distillation under reduced pressure. Bis (trimethylsilyl) cyclopentadiene 2.1 g (10 m
mol) in 100 ml of dry n-hexane solution at −78 ° C. under argon atmosphere at 1.1 ml of titanium tetrachloride (10 ml).
(mmol) was added dropwise and stirred for 4 hours. After evaporating the solvent, 2.1 g (yield 70%) of yellow crystals were obtained by sublimation. ¹ H-NMR that the product is Me ₃ SiCpTiCl ₃
Confirmed from. ¹ H-NMR (ppm, TMS, CDCl ₃ ): 6.85
(T, 2H), 6.66 (t, 2H), 0.10 (s,
9H)

Example 1 A 300 ml pressure-resistant glass flask equipped with a stirrer was used as a polymerization machine, and a polymerization reaction was carried out under an argon atmosphere. 86.6 g of toluene
And a toluene solution of 75.0 mmol of methylaluminoxane (manufactured by Tosoh Akzo) were charged, and the temperature was kept at 25 ° C. Here, (2-methoxycarbonylmethyl) cyclopentadienyltrichlorotitanium (MeO (CO) CH ₂
CpTiCl ₃ , hereinafter abbreviated as TiES) 0.075 mm
After aging at 25 ° C for 5 minutes, the mixture was rapidly cooled to a constant temperature of -25 ° C. 2.35 g of butadiene was charged to start the first-stage polymerization reaction,
Stirred at 5 ° C. Eight minutes later, 10 g of the polymerization solution was sampled and subjected to the measurement of the conversion and the GPC measurement. Ten minutes after the start of the one-stage polymerization, 6.13 g of butadiene was added, and -25 was added.
The second-stage polymerization reaction was performed at 100 ° C. for 100 minutes. The polymerization reaction was stopped by adding an acidic methanol solution, and the polymerization solution was poured into a large amount of acidic methanol to precipitate a polymer. The operation of dissolving the polymer in toluene, centrifuging the solution to remove ash, and reprecipitating in acidic methanol was repeated twice. The obtained polymer was dried and weighed to determine the polymer yield.

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-bond to 1,2-bond in the polymer was determined, and ¹³ C-NMR (cis 28 ppm, trans
The ratio of cis to trans was determined from 33 ppm) to determine the microstructure of the polymer.

For GPC analysis, two columns of Tosoh GMH or G-7000 and G-5 were used as columns.
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) using the 000 connected.

The results were as follows. One-step polymerization: polymer yield; 100%, Mn;
Mw / Mn; 1.43, two-stage polymerization: polymer yield; 100
%, Mn; 463,000, Mw / Mn; 1.09, cis; 93%, trans; 2%, 1, 2; 5%.

FIG. 1 shows a GPC elution curve. In the GPC curve of the polymer obtained by the two-stage polymerization, the peak of the polymer formed by the one-stage polymerization completely disappears.

As described above, in this example, butadiene undergoes living polymerization at a very high rate (high activity), and has a living chain content of 100%, a high cis content, a large molecular weight, and a very narrow molecular weight distribution. It can be seen that is obtained.

Example 2 Methylaluminoxane 24.
TiES 0.0244mm in 4mmol toluene solution
ol of toluene solution was dropped and aged at 25 ° C. for 5 minutes. Under a nitrogen atmosphere, 52.4 g of toluene and 5.5 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 3 minutes. Thereafter, the polymerization reaction was stopped with a small amount of acidic methanol solution, and then the polymerization solution was poured into a large amount of acidic methanol, and the precipitated white solid was collected by filtration and dried,
A butadiene polymer was obtained. The polymer yield was 100%. Table 1 shows the results.

The "polymerization activity" expressed as the polymer yield per 1 mmol of the transition metal in the transition metal compound in the transition metal compound used in the polymerization reaction was 4700 g / mmol-.
M · h.

For the GPC-MALLS measurement, a column in which G-7000 and G-5000 manufactured by Tosoh Corporation were connected as a column, tetrahydrofuran (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. The coefficients of Equation 1 are a = 0.655, b = 2.08
Met. Where RMSR (100) and RMSR
(50) is the RM corresponding to a molecular weight of 1,000,000 and 500,000
This is the value of SR.

(Comparative Examples 1 and 2) For comparison, commercially available Nd
Catalyst butadiene polymer (Neocis 60, manufactured by Enikem)
And Co catalyst butadiene polymer (Nippon Zeon, N
ipol BR1220) was analyzed in the same manner as in Example 2. The results are shown in Table 1.

[0125]

[Table 1]

Table 1 shows that the production method of the present invention is highly active, and the resulting butadiene-based polymer has a high cis content, a large molecular weight, a narrow molecular weight distribution, and a low branched structure.

(Examples 3 to 10 and Comparative Example 3) Example 2 was prepared using TiES as a transition metal compound under the conditions shown in Table 2.
Polymerization and analysis were performed in the same manner as described above. The results are shown in Table 2. At a polymerization temperature of -25 ° C and 0 ° C, the number average molecular weight increases with an increase in yield, and a narrow molecular weight distribution is maintained. Also, the number average molecular weight is regulated by the monomer / catalyst ratio. Further, in Examples 3, 5 and 6, almost monodispersed high cis butadiene polymers were obtained. From these facts, Example 2 and Examples 3 to 10
Was found to have a living chain content of 80% or more.

[0128]

[Table 2]

(Examples 11 to 16, Comparative Examples 4 to 6) (2-methoxyethyl) cyclopentadienyltrichlorotitanium (MeOCH ₂ CH ₂ CpTi) as a transition metal compound
Polymerization and analysis were performed in the same manner as in Example 2 using Cl ₃ (hereinafter abbreviated as TiET) under the conditions shown in Table 3. The results are shown in Table 3. At a polymerization temperature of -25 ° C and 0 ° C, the number average molecular weight increases with an increase in yield, whereas at 25 ° C, the number average molecular weight does not increase. From these, it was found that living polymerization was progressing in Examples 11 to 16.

[0130]

[Table 3]

(Examples 17, 18 and Comparative Example 7) Polymerization and analysis were carried out in the same manner as in Example 2 by using trimethylsilylcyclopentadienyltrichlorotitanium (hereinafter abbreviated as TiTMS) as a transition metal compound. Table 4 shows the conditions and results. At a polymerization temperature of −25 ° C., a polymer having a molecular weight distribution close to monodispersion is obtained, whereas at 25 ° C., a polymer having a somewhat wider molecular weight distribution is obtained. From this, it was found that living polymerization was progressing in Examples 17 and 18.

[0132]

[Table 4]

(Examples 19 and 20) Examples using TiTMS as a transition metal compound, triphenylcarbonium tetra (pentafluorophenyl) borate as a catalyst component (B), and triisobutylaluminum (TIBA) as a third catalyst component. Polymerization and analysis were carried out in the same manner as in 17. Table 5 shows the conditions and results. Polymerization temperature -4
At 0 ° C., Mn increases as the yield increases, and the molecular weight distribution of the resulting polymer is close to monodisperse. From this, it was found that living polymerization proceeded in Examples 19 and 20.

[0134]

[Table 5]

Examples 21 and 22 Cyclopentadienyltrichlorotitanium (hereinafter referred to as CpT) was used as a transition metal compound.
Polymerization and analysis were performed in the same manner as in Example 2 using iCl ₃ ). CpTiCl ₃ used was purified by recrystallization in a methylene chloride solvent at −35 ° C. Table 6 shows the polymerization conditions and the results. At a polymerization temperature of −25 ° C., a polymer having a molecular weight distribution close to monodispersion is obtained. From this, it was found that living polymerization proceeded in Examples 21 and 22.

[0136]

[Table 6]

(Examples 23 to 25, Comparative Example 8) CpTiCl ₃ as a transition metal compound, triphenylcarbonium tetra (pentafluorophenyl) borate as a catalyst component (B), and triisobutylaluminum as a third catalyst component ( Using TIBA), polymerization and analysis were carried out in the same manner as in Example 21. Table 7 shows the conditions and results.
At a polymerization temperature of −25 ° C., Mn increases with an increase in yield,
The molecular weight distribution of the resulting polymer is close to monodisperse. Meanwhile, 2
The molecular weight distribution of the polymer obtained by polymerization at 5 ° C. is multimodal. From this, it was found that living polymerization was proceeding in Examples 23 to 25.

[0138]

[Table 7]

[0139]

According to the method for producing a conjugated diene polymer of the present invention, a living polymerization reaction is advanced with high activity. The butadiene-based polymer obtained by using this production method is characterized by having a high living chain content, a large number of cis bonds, a large molecular weight, a narrow molecular weight distribution, and a very low branched structure content. The butadiene-based polymer of the present invention,

[Brief description of the drawings]

FIG. 1 is an elution curve of gel permeation chromatography.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasuzou Suzuki 2-805-808, Azuma, Tsukuba, Ibaraki Prefecture (72) Inventor Tetsu Miyazawa 4-403-103, Matsushiro 4-chome, Tsukuba, Ibaraki Prefecture (72) Inventor Sat Kenji Hara 2-806-703 Azuma, Tsukuba-shi, Ibaraki Pref. (72) Inventor Masahide Murata 2-15-504, Suido 2-chome, Bunkyo-ku, Tokyo (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa, Tsukuba-shi, Ibaraki Pref. (72) Inventor Masanao Kawabe 2-6-1203 Takezono, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Yoshifumi Fukui 4-63-507, Ninomiya 4-chome, Tsukuba-shi, Ibaraki Prefecture (72) Jin Jiju, Ishikawa Prefecture 3-14-4 Hiromi Heights, Kanazawa 201 (72) Inventor Hideaki Hagiwara 2-6-14 Sakurai Heights 2-6-14, Akubo, Tsukuba, Ibaraki Pref. (72) Toshio Kase 5-Chome, Matsushiro, Tsukuba, Ibaraki Issue

Claims (3)

[Claims] 1. A butadiene homopolymer or a copolymer of butadiene and a monomer copolymerizable with butadiene, wherein at least 50% of units derived from cis-bonded butadiene are present in all units derived from butadiene. Has a number average molecular weight (Mn) of 1,000 to 10,000,000,
A butadiene-based polymer characterized by containing 80% or more of living chains having a transition metal of Group IV of the periodic table at the molecular terminal in all molecular chains. 2. A cationic transition metal compound which reacts with a transition metal compound (A) belonging to Group IV of the periodic table having a cyclopentadienyl skeleton, an organoaluminum oxy compound (a), and the transition metal compound (A). (B), a Lewis acid compound (c) capable of reacting with the transition metal compound (A) to form a cationic transition metal compound, and an organic metal of a main element metal of Groups I to III of the periodic table. In the presence of a catalyst comprising at least one cocatalyst (B) selected from the metal compounds (d), a conjugated diene monomer, or a conjugated diene monomer and a monomer copolymerizable therewith can be used. A method for producing a conjugated diene-based polymer, wherein the polymerization is carried out at a temperature of not more than ℃. 3. The (A) transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton comprises a carbonyl group,
The conjugated diene polymer according to claim 2, which is a transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from a sulfonyl group, an ether group, and a thioether group. Manufacturing method.