JP2002302512A - Polybutadiene and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polybutadiene which has a microstructure that comprises a high cis structure moderately containing 1,2-structures and scarcely contains trans-structures, and has improved characteristics such as improved cold flow. SOLUTION: This modified polybutadiene is obtained by modifying raw material polybutadiene having the following characteristics in the presence of a transition metal catalyst. The characteristic of the raw material polybutadiene: a ratio (Tcp/ML1+4 ) of a 5% toluene solution viscosity (Tcp) measured at 25 deg.C to Mooney viscosity (ML1+4 ) at 100 deg.C is >=2.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polybutadiene having a controlled microstructure and a controlled linearity, and a method for producing the same.

[0002]

2. Description of the Related Art Polybutadiene has a so-called microstructure in which a bonding portion (1,4-structure) formed by polymerization at the 1,4-position and a 1,2-structure.
And a bonding portion (1,2-structure) formed by polymerization at the position coexist in the molecular chain. The 1,4-structure is further divided into two types, a cis structure and a trans structure. On the other hand, the 1,2-structure takes a structure having a vinyl group as a side chain.

[0003] It is known that polybutadienes having different microstructures are produced by a polymerization catalyst, and are used for various purposes depending on their properties. In particular, polybutadiene having high molecular linearity (linearity) has excellent characteristics in abrasion resistance, heat resistance, and rebound resilience. As an index of linearity, 25
5% toluene solution viscosity (Tcp) measured at 100 ° C. and 100
Tcp, which is the ratio to the Mooney viscosity (ML _{1 + 4} )
/ ML _{1 + 4} is used. Tcp indicates the degree of entanglement of molecules in a concentrated solution, and the larger Tcp / ML _{1 + 4} , the smaller the degree of branching and the greater the linearity.

As disclosed in Japanese Patent Application Laid-Open No. 9-291108 and the like, a high catalyst is produced by a metallocene-type complex of a vanadium metal compound and a polymerization catalyst comprising an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. It is possible to produce a polybutadiene having a microstructure with a suitable structure including a 1,2-structure and a small trans structure and a high molecular linearity.
It has been found by the applicant. Since this polybutadiene has excellent properties, application to impact-resistant polystyrene resins, tires, and the like has been studied. However, since it shows a relatively high cold flow, there are cases where improvement is required during storage and transportation.

On the other hand, a method for producing a conjugated diene having a branched structure is disclosed in Japanese Patent Application Laid-Open No. 5-52406. The publication discloses that a conjugated diene is polymerized in the presence of a composite catalyst comprising an organic compound of a rare earth element, an organometallic aluminum compound, and a halogen-containing Lewis acid, and then an ester compound of a carboxylic acid and an alcohol or a phenol. It discloses that a selected coupling agent is added to produce a diene polymer having a branched structure. JP-A-8-208751 discloses that by treating a diene rubber polymerized with a neodymium catalyst with a sulfur chloride-based compound, the cold flow is improved and the inherent odor of the rubber is also improved. .

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a polybutadiene having a microstructure containing a 1,2-structure appropriately in a high cis structure and having a small number of trans structures, and having improved properties such as cold flow, and a method for producing the same. Is provided.

That is, the present invention provides a modified polybutadiene obtained by modifying a starting polybutadiene having the following characteristics in the presence of a transition metal catalyst. Characteristics of raw polybutadiene: 25 5% toluene solution viscosity measured at ° C. (Tcp) and the arm at 100 ° C. - D - the ratio of the viscosity _{(ML 1 + 4) (Tcp} / ML 1 + 4) is 2.
5 or more.

Further, the present invention provides the following method as a method for producing the above-mentioned modified polybutadiene of the present invention. Using a catalyst comprising (A) a metallocene complex of a transition metal compound, and (B) an ionic compound of a non-coordinating anion and a cation and / or an alumoxane at 25 ° C.
5% toluene solution viscosity (Tcp) measured at 100 ° C
And the ratio to the Mooney viscosity (ML _{1 + 4} ) (Tcp / ML)
_{(1 + 4} ) a method for producing a modified polybutadiene, comprising producing a raw material polybutadiene having a value of 2.5 or more, and further adding a transition metal catalyst for modification. "(A) metallocene complex of transition metal compound, (B)
An ionic compound of a non-coordinating anion and a cation,
5% measured at 25 ° C. using a catalyst comprising (C) an organometallic compound of a Group 1 to 3 element of the periodic table and (D) water.
After producing a raw material polybutadiene having a ratio (Tcp / ML _{1 + 4} ) of the toluene solution viscosity (Tcp) to the Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of 2.5 or more, the transition metal A method for producing a modified polybutadiene, comprising modifying the composition by adding a catalyst. "

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polybutadiene of the present invention and a method for producing the same will be described in detail. The raw material polybutadiene used for the reaction in the present invention has a 1,2-structure content of 4 to 30%, preferably 5 to 25%, more preferably 7 to 25%.
-15%, cis-1,4-structure content is 65-95%,
Preferably 70-95%, more preferably 70-92%
%, The trans-1,4-structure content is 5% or less, preferably 4.5% or less, more preferably 0.5 to 4%.

If the microstructure is outside the above range, the reactivity of the polymer (such as graft reaction and cross-linking reactivity) is not appropriate, and the rubber-like properties when used as an additive or the like are deteriorated. It unfavorably affects the balance and appearance.

The raw material polybutadiene used in the present invention has a viscosity of toluene solution (Tcp) of the polybutadiene and the Mooney at 100 ° C.
The ratio (Tcp / ML _{1 + 4} ) to the viscosity (ML _{1 + 4} ) is 2.5 or more, and preferably 3 to 5.

The toluene solution viscosity (Tcp) of the raw material polybutadiene in the present invention is preferably from 25 to 600, particularly preferably from 60 to 300.

The polybutadiene used as a raw material in the present invention has a Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of 10
To 200 are preferable, and 25 to 100 are particularly preferable.

The molecular weight of the raw material polybutadiene in the present invention is preferably from 0.1 to 10, particularly preferably from 1 to 3, as the intrinsic viscosity [η] measured at 30 ° C. in toluene.

The molecular weight of the raw material polybutadiene in the present invention is preferably in the following range as the molecular weight in terms of polystyrene. Number average molecular weight (Mn): 0.2 × 10 ⁵ to 10 × 1
0 ⁵ , more preferably 0.5 × 10 ^{5 to} 5 × 10 ⁵ weight average molecular weight (Mw): 0.5 × 10 ^{5 to} 20 × 10 ^5
5 , more preferably 1 × 10 ⁵ to 10 × 10 ⁵ The molecular weight distribution (Mw / Mn) of the raw material polybutadiene in the present invention is preferably 1.5 or more, more preferably 1.6 to 10, and still more preferably. Is 1.8 to 5.

The raw material polybutadiene in the present invention is:
For example, it can be produced by polymerizing butadiene using (A) a metallocene complex of a transition metal compound and (B) a catalyst comprising an ionic compound of a non-coordinating anion and a cation and / or alumoxane.

Alternatively, the raw material polybutadiene in the present invention may be (A) a metallocene complex of a transition metal compound,
(B) an ionic compound of a non-coordinating anion and a cation, (C) an organometallic compound of an element of Groups 1 to 3 of the periodic table,
And (D) butadiene using a catalyst consisting of water.

Examples of the metallocene complex of the transition metal compound of the component (A) include metallocene complexes of transition metal compounds of Groups 4 to 8 of the periodic table.

For example, a metallocene complex of a transition metal compound of Group 4 of the periodic table such as titanium or zirconium (for example, CpTiCl ₃ ) or a metallocene type of a transition metal compound of Group 5 of the periodic table such as vanadium, niobium or tantalum. Complexes, metallocene-type complexes of transition metal compounds of Group 6 such as chromium, and metallocene-type complexes of transition metal compounds of Group 8 such as cobalt and nickel.

Among them, a metallocene complex of a transition metal compound of Group 5 of the periodic table is preferably used.

The metallocene complex of the transition metal compound of Group V of the periodic table includes (1) RM · La (2) R _n MX _2-n · La (3) R _n MX _3-n · La ( 4) RMX ₃ .La (5) RM (O) X ₂ .La (6) R _n MX _3-n (NR ′) and the like.
Is 1 or 2, a is 0, 1 or 2.)

Among them, RM La, RMX ₃ La, R
M (O) X ₂ · La is preferred.

M is a transition metal compound of Group 5 of the periodic table, specifically, vanadium (V), niobium (Nb), or tantalum (Ta), and a preferred metal is vanadium.

R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group.

As the substituent in the substituted cyclopentadienyl group, the substituted indenyl group or the substituted fluorenyl group, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, hexyl And the like, a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, an aromatic hydrocarbon group such as phenyl, tolyl, naphthyl and benzyl, and a silicon-containing hydrocarbon group such as trimethylsilyl. Further, those in which a cyclopentadienyl ring is bonded to a part of X by a crosslinking group such as dimethylsilyl, dimethylmethylene, methylphenylmethylene, diphenylmethylene, ethylene, and substituted ethylene are also included.

X is hydrogen, halogen, C 1-20
Represents a hydrocarbon group, an alkoxy group, or an amino group. X
May be the same or different from each other.

Specific examples of the halogen include a fluorine atom,
Examples include a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include linear or branched aliphatic hydrocarbon groups such as methyl, ethyl and propyl, phenyl,
And aromatic hydrocarbon groups such as tolyl, naphthyl and benzyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included. Among them, methyl, benzyl, trimethylsilylmethyl and the like are preferable.

Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy and the like. Further, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, methylthio and the like may be used.

Specific examples of the amino group include dimethylamino, diethylamino, diisopropylamino, bistrimethylsilylamino and the like.

Among the above, X represents hydrogen, fluorine atom, chlorine atom, bromine atom, methyl, ethyl, butyl,
Preferred are methoxy, ethoxy, dimethylamino, diethylamino, bistrimethylsilylamino and the like.

L is a Lewis base, which is a general Lewis basic inorganic or organic compound capable of coordinating to a metal. Among them, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, silyloxy compounds, olefins, dienes,
Aromatic compounds, alkynes and the like can be mentioned.

NR 'is an imide group, and R' is a hydrocarbon substituent having 1 to 25 carbon atoms. Specific examples of R ′ include methyl, ethyl, propyl, i-propyl, n-
Butyl, i-butyl, sec-butyl, t-butyl, hexyl, octyl, neopentyl and other linear aliphatic or branched aliphatic hydrocarbon groups, phenyl, tolyl, naphthyl, benzyl, 1-phenylethyl , 2-
Phenyl-2-propyl, 2,6-dimethylphenyl,
And aromatic hydrocarbon groups such as 3,4-dimethylphenyl. Further, a hydrocarbon group containing a silicon atom such as trimethylsilyl is also included.

Of these metallocene complexes of transition metal compounds of Group V of the periodic table, vanadium compounds wherein M is vanadium are particularly preferred. For example, RV · La, R
VX ・ La, R ₂ V ・ La, RVX ₂・ La, R ₂ VX
• La, RVX ₃ • La, RV (O) X ₂ • La, etc. are preferred. In particular, RV ・ La, RVX ₃・ L
a, RV (O) X ₂ · La is preferred.

The following compounds (i) to (xvi) are specific examples of the compound represented by RMX ₃ · La.

(I) Cyclopentadienyl vanadium trichloride. Monosubstituted cyclopentadienyl vanadium trichloride, for example, methylcyclopentadienyl vanadium trichloride, ethylcyclopentadienyl vanadium trichloride, propylcyclopentadienyl vanadium trichloride, isopropylcyclopentadienyl vanadium trichloride and the like. Can be

(Ii) 1,2-disubstituted cyclopentadienyl vanadium trichloride, such as (1,2-disubstituted)
Dimethylcyclopentadienyl) vanadium trichloride.

(Ii) 1,3-disubstituted cyclopentadienyl vanadium trichloride such as (1,3
-Dimethylcyclopentadienyl) vanadium trichloride and the like.

(Iii) 1,2,3-trisubstituted cyclopentadienyl vanadium trichloride, for example,
(1,2,3-trimethylcyclopentadienyl) vanadium trichloride and the like.

(Iv) 1,2,4-trisubstituted cyclopentadienyl vanadium trichloride, for example
(1,2,4-trimethylcyclopentadienyl) vanadium trichloride and the like.

(V) Tetra-substituted cyclopentadienyl vanadium trichloride, for example, (1,2,3,4
-Tetramethylcyclopentadienyl) vanadium trichloride.

(Vi) Penta-substituted cyclopentadienyl vanadium trichloride, such as (pentamethylcyclopentadienyl) vanadium trichloride.

(Vii) indenyl vanadium trichloride. (Viii) Substituted indenyl vanadium trichloride, such as (2-methylindenyl) vanadium trichloride.

(Ix) Monoalkoxides, dialkoxides, trialkoxides and the like in which the chlorine atom of the compounds (i) to (viii) is substituted with an alkoxy group. For example, cyclopentadienyl vanadium tri-t-
Butoxide, cyclopentadienyl vanadium tri-i
-Propoxide, cyclopentadienyl vanadium dimethoxy chloride and the like.

(X) Methyl forms in which the chlorine atom in (i) to (ix) is substituted with a methyl group.

(Xi) R and X bonded by a hydrocarbon group or a silyl group. For example, (t-
Butylamido) dimethyl (eta ⁵ - such as cyclopentadienyl) silane vanadium dichloride and the like.

(Xii) Methyl forms wherein the chlorine atom of (xi) is substituted with a methyl group.

(Xiii) Monoalkoxy and dialkoxy compounds in which the chlorine atom of (xi) is substituted with an alkoxy group.

(Xiv) Compounds obtained by substituting the monochloro compound of (xiii) with a methyl group.

(Xv) Amides wherein the chlorine atom of (i) to (viii) is substituted by an amide group. For example, cyclopentadienyl tris (diethylamide) vanadium, cyclopentadienyl tris (i-propylamido) vanadium and the like can be mentioned.

(Xvi) A methyl compound in which the chlorine atom of (xv) is substituted with a methyl group.

Specific compounds represented by the above RM (O) X ₂ include the following (a) to (d). (A) Cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl) oxovanadium dichloride and the like. A methyl compound in which a chlorine atom of each of the above compounds is substituted with a methyl group is also included.

(B) R and X may be bonded by a hydrocarbon group or a silyl group. For example, (t-butylamido) dimethyl (eta ⁵ - cyclopentadienyl) silane oxovanadium chloride amide chloride of like, or the like methyl derivatives obtained by substituting the chlorine atoms in these compounds with a methyl group.

(C) Cyclopentadienyloxovanadium dimethoxide, cyclopentadienyloxovanadium dii-propoxide and the like. A methyl compound in which a chlorine atom of each of the above compounds is substituted with a methyl group is also included.

(D) (cyclopentadienyl) bis (diethylamido) oxovanadium and the like.

In the component (B), the non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation includes, for example, tetra (phenyl) borate,
Tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate and the like. Can be

On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl 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)
Examples thereof include a carbonium cation and a tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include:
Trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation, N, N-dimethylanilinium cation;
Examples thereof include N, N-dialkylanilinium cations such as N-diethylanilinium cation and dialkylammonium cations such as di (i-propyl) ammonium cation.

Specific examples of the phosphonium cation include:
Triaryl phosphonium cations such as triphenyl phosphonium cation can be mentioned.

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

Among them, ionic compounds include triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) )
And 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred. The ionic compounds may be used alone or in combination of two or more.

Alumoxane may be used as the component (B). The alumoxane is obtained by contacting an organoaluminum compound with a condensing agent, and includes a chain aluminoxane represented by the general formula (-Al (R ') O) n or a cyclic aluminoxane. (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more.) . R ′ is methyl, ethyl,
A propyl and isobutyl group are exemplified, and a methyl group is preferred. Examples of the organoaluminum compound used as a raw material of the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

Alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

Examples of the condensing agent include water, which is a typical one, and any other condensing agent capable of condensing the trialkylaluminum, such as adsorbed water of inorganic substances and diol. .

The conjugated diene may be polymerized by combining the components (A) and (B) with an organometallic compound of a Group 1 to 3 element of the periodic table as the component (C).
The addition of the component (C) has the effect of increasing the polymerization activity. Examples of the organometallic compounds of Group 1 to 3 elements of the periodic table include organoaluminum compounds, organolithium compounds, organomagnesium compounds, organozinc compounds, and organoboron compounds.

Specific compounds include methyllithium, butyllithium, phenyllithium, bistrimethylsilylmethyllithium, dibutylmagnesium, dihexylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, boron trifluoride, triphenylboron And the like.

Further, ethyl magnesium chloride,
Dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride,
Also included are organometallic halogen compounds such as ethylaluminum dichloride, and hydrogenated organometallic compounds such as diethylaluminum hydride and sesquiethylaluminum hydride. Further, two or more kinds of organometallic compounds can be used in combination.

As a combination of the above catalyst components, (A)
RMX ₃ such as cyclopentadienyl vanadium trichloride (CpVCl ₃ ) or cyclopentadienyl oxovanadium dichloride (Cp
V (O) Cl ₂ ), RM (O) X ₂ , triphenylcarbenium tetrakis (pentafluorophenyl) borate as the component (B), and trialkylaluminum such as triethylaluminum as the component (C). It is preferably used.

When an ionic compound is used as the component (B), the above alumoxane may be used in combination as the component (C).

The mixing ratio of each catalyst component varies depending on various conditions and combinations. The molar ratio (B) / (A) of the metallocene complex of the component (A) and the alumoxane of the component (B) is as follows.
Preferably from 1 to 100,000, more preferably from 10 to 1
0000.

The molar ratio (B) / (A) of the metallocene complex of the component (A) to the ionic compound of the component (B) is preferably from 0.1 to 10, more preferably from 0.5 to 5. is there.

The molar ratio (C) / (A) of the metallocene complex of the component (A) to the organometallic compound of the component (C) is preferably from 0.1 to 10,000, more preferably from 10 to 10.
00.

In the present invention, the catalyst system
Further, it is preferable to add water as the component (D).
The molar ratio (C) / (D) between the organometallic compound of the component (C) and water of the component (D) is preferably from 0.66 to 5,
More preferably, it is 0.7 to 1.5.

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

At the time of polymerization, hydrogen can be allowed to coexist if necessary.

The amount of hydrogen is preferably 500 mmol or less per 1 mol of butadiene, or 20 ° C.
It is 12 L or less at 1 atm, more preferably 50 mmol or less, or 1.2 L or less at 20 ° C. and 1 atm.

The butadiene monomer to be polymerized in this step (before modification by adding a transition metal catalyst) is
It may be the whole amount or a part. When the butadiene monomer to be polymerized in this stage is a part of the monomer, the mixture of the above catalyst components can be mixed with the remaining butadiene monomer or the remaining butadiene monomer solution. The remaining butadiene monomer or the remaining butadiene monomer solution is additionally added after the polymerization reaction and before or after the addition of a transition metal catalyst described later.

In addition to butadiene monomer, isoprene,
Conjugated dienes such as 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, ethylene, propylene, butene-
Acyclic monoolefins such as 1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1, octene-1, cyclopentene, cyclohexene,
Contains a small amount of a cyclic monoolefin such as norbornene, and / or an aromatic vinyl compound such as styrene or α-methylstyrene, a non-conjugated diolefin such as dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,5-hexadiene. You may go out.

The polymerization method is not particularly limited.
Alternatively, bulk polymerization using 1,3-butadiene itself as a polymerization solvent can be applied. As the polymerization solvent, toluene, benzene, aromatic hydrocarbons such as xylene, n
-Aliphatic hydrocarbons such as hexane, butane, heptane and pentane, cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane, olefinic hydrocarbons such as 1-butene and 2-butene, mineral spirits, solvent naphtha and kerosene. Examples thereof include hydrocarbon solvents and halogenated hydrocarbon solvents such as methylene chloride.

In the present invention, it is preferable to carry out prepolymerization at a predetermined temperature using the above-mentioned catalyst. The prepolymerization can be performed by a gas phase method, a solution method, a slurry method, a bulk method, or the like. The solid or solution obtained in the prepolymerization may be separated and then used for the main polymerization, or the main polymerization may be carried out without separation.

The polymerization temperature is preferably in the range of -100 to 200 ° C, particularly preferably in the range of -50 to 120 ° C. The polymerization time is preferably in the range of 2 minutes to 12 hours, particularly preferably in the range of 5 minutes to 6 hours.

After the polymerization reaction reaches a predetermined polymerization rate, a transition metal catalyst is added and reacted to modify the polymer chain.

The transition metal catalyst in the present invention is preferably a system comprising a transition metal compound, organoaluminum and water.

The transition metal compounds in the transition metal catalyst include titanium compounds, zirconium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, ruthenium compounds, cobalt compounds, nickel compounds, palladium compounds, copper compounds, silver compounds, zinc compounds, and the like. And the like. Among them, a cobalt compound is particularly preferred.

As the cobalt compound, a salt or complex of cobalt is preferably used. Particularly preferred are cobalt salts such as cobalt chloride, cobalt bromide, cobalt nitrate, cobalt octylate, cobalt naphthenate, cobalt versatate, cobalt acetate, cobalt malonate, and bisacetylacetonate and trisacetylacetonate of cobalt. And organic base complexes such as triarylphosphine complex, trialkylphosphine complex, pyridine complex and picoline complex of cobalt acetoacetate and cobalt halide, and ethyl alcohol complex.

Among them, preferred are cobalt octylate, cobalt naphthenate, cobalt versatate, cobalt bisacetylacetonate and trisacetylacetonate.

Examples of the organoaluminum in the transition metal catalyst include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, dimethylaluminum chloride, dimethylaluminum bromide and diethylaluminum chloride. , Diethyl aluminum bromide, diethyl aluminum iodide, dibutyl aluminum chloride, dibutyl aluminum bromide, dialkyl aluminum halide such as dibutyl aluminum iodide, methyl aluminum sesquichloride, methyl aluminum sesquibromide, ethyl aluminum sesquichloride,
Examples thereof include monoalkylaluminum halides such as alkylaluminum sesquibromide such as ethylaluminum sesquibromide, methylaluminum dichloride, methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum dibromide, butylaluminum dichloride, and butylaluminum dibromide. These may be used alone, or a plurality of them may be selected and used as a mixture. Among them, diethyl aluminum chloride is preferably used.

In the transition metal catalyst of the present invention, the amount of the cobalt compound to be added may be in any range depending on the desired degree of branching. Preferably, the amount of the transition metal compound per 1 mol of butadiene present during the modification reaction is X 10 ^-7 to 1 x 10 ^-3 mol, particularly preferably 5
X 10 ^-7 to 1 X 10 ^-4 mol.

[0090] The amount of the organic aluminum by the desired degree of branching, a catalytic amount of any range also can be used, preferably butadiene per mole present during the modification reaction, the organoaluminum 1 × 10 ^-5 ~5 × 10 ^{- It is 2} mol, particularly preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol.

The amount of water added can be in any range depending on the desired degree of branching, but is preferably 1.5 mol or less, particularly preferably 1 mol or less, per 1 mol of the organoaluminum compound.

After the polymerization is carried out for a predetermined period of time, after terminating the polymerization by injecting a terminating agent such as alcohol, the pressure inside the polymerization tank is released as required, and post-treatments such as washing and drying steps are performed.

The modified polybutadiene obtained in the present invention is
5% toluene solution viscosity (Tcp) measured at 25 ° C. and 1
Ratio to Mooney viscosity (ML _{1 + 4} ) at 00 ° C. (Tcp
/ ML _{1 + 4} ) is preferably 3 or less, more preferably 0.
9 to 3, particularly preferably 1.2 to 2.5.

The modified polybutadiene obtained in the present invention has a 5% toluene solution viscosity (Tc
p) is preferably from 30 to 300, more preferably from 45 to 200.

The modified polybutadiene obtained in the present invention has a Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of preferably 10 to 200, more preferably 25 to 100.

The modified polybutadiene obtained by the present invention has a cold flow rate (CF) of 20 mg / mi.
It is preferably less than n, particularly preferably less than 15 mg / min.

[0097]

The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples. The microstructure, intrinsic viscosity ([η]), toluene solution viscosity (Tcp), Mooney viscosity (ML _{1 + 4} ,
100 ° C.) and the method of measuring the cold flow rate (CF) are as follows.

The microstructure was determined by infrared absorption spectrum analysis. Cis 740 cm ^-1 , transformer 967 cm
^The microstructure was calculated from the absorption intensity ratio between ^-1 and 910 cm ^-1 of vinyl.

The intrinsic viscosity ([η]) was measured at 30 ° C. using a toluene solution.

The viscosity of the toluene solution (Tcp) was determined by dissolving 2.28 g of the polymer in 50 ml of toluene and using a standard solution for calibration of a viscometer (JIS Z 8809) as a standard solution. Using 400
It was measured at 25 ° C.

Mooney viscosity (ML _{1 + 4} , 100 ° C.)
It measured based on JISK6300.

The cold flow rate (CF) is obtained by keeping the obtained polymer at 50 ° C., sucking it in a glass tube having an inner diameter of 6.4 mm with a differential pressure of 180 mmHg for 10 minutes, and measuring the weight of the sucked polymer. It was determined as the amount of polymer aspirated per minute.

Synthesis Example 1 (Production of Raw Polybutadiene) The inside of a 1.7 L autoclave was purged with nitrogen.
260 ml of cyclohexane and 140 ml of butadiene are charged and stirred. Then, 6 μl of water was added and stirring was continued for 30 minutes. 90 ml of hydrogen at 20 ° C. and 1 atm were weighed and injected with an integrating mass flow meter, then 0.36 ml of a 1 mol / L toluene solution of triethylaluminum (TEA) was added, and the mixture was stirred for 3 minutes. Enilvanadium trichloride (CpVCl ₃ )
0.4 ml of a 5 mmol / L toluene solution, triphenylcarbenium tetrakis (pentafluorophenyl)
2.5 mmol of borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
/ L of a toluene solution of 1.2 ml in this order, and a polymerization temperature of 4
Polymerization was carried out at 0 ° C. for 30 minutes. After the reaction, 2,6-di-t
After injecting ethanol containing -butyl-p-cresol to terminate the reaction, the solvent was evaporated and dried to obtain 40 g of polybutadiene. The obtained polymer was regarded as a raw material polybutadiene of Examples 1 to 7 and Comparative Examples 1 and 2 below. Table 2 (Synthesis Example 1) shows the physical properties of the raw material polybutadiene.

Example 1 (Production of Modified Polybutadiene) In the same manner as in Synthesis Example 1, polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes, and then 4.2 ml of toluene containing 300 mg / L of water and diethylaluminum chloride. (DE
AC) 4 ml of a 1 mol / L toluene solution and 2 ml of a 5 mmol / L cobalt octylate (Co (Oct) ₂ ) toluene solution were added and reacted at 40 ° C. for 10 minutes. After the reaction, ethanol containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and then the solvent was evaporated and dried to obtain a modified polybutadiene. Tables 1 and 2 show the polymerization results.

Example 2 (Production of Modified Polybutadiene) The same operation as in Example 1 was performed except that the amount of hydrated toluene (300 mg / L) added after the polymerization was changed to 8.4 ml.
Tables 1 and 2 show the polymerization results.

Example 3 (Production of Modified Polybutadiene) The same operation as in Example 1 was carried out except that 5 μl of water was added instead of hydrous toluene (300 mg / L) added after polymerization. Tables 1 and 2 show the polymerization results.

Example 4 (Production of Modified Polybutadiene) The same operation as in Example 1 was performed except that 10 μl of water was added instead of water-containing toluene (300 mg / L) added after polymerization. Tables 1 and 2 show the polymerization results.

Example 5 (Production of Modified Polybutadiene) The same operation as in Example 2 was performed except that the reaction time after the polymerization was changed to 5 minutes. Tables 1 and 2 show the polymerization results.

Example 6 (Production of Modified Polybutadiene) The same operation as in Example 3 was performed except that the reaction time after the polymerization was changed to 5 minutes. Tables 1 and 2 show the polymerization results.

Example 7 (Production of Modified Polybutadiene) The same operation as in Example 3 was performed except that the reaction time after the polymerization was changed to 15 minutes. Tables 1 and 2 show the polymerization results.

Comparative Example 1 (Production of Polybutadiene) In the same manner as in Synthesis Example 1, polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes, and stirring was continued for 10 minutes without adding anything (ie, Except that polymerization was carried out for 40 minutes), the same operation as in Example 1 was performed. Tables 1 and 2 show the polymerization results.

Comparative Example 2 (Production of polybutadiene) The same operation as in Example 1 was carried out except that cobalt octylate was not added after the polymerization. Tables 1 and 2 show the polymerization results.

Synthesis Example 2 (Production of Raw Polybutadiene) The inside of a 1.7 L autoclave was purged with nitrogen.
260 ml of cyclohexane and 140 ml of butadiene are charged and stirred. Then, 6 μl of water was added and stirring was continued for 30 minutes. At 25 ° C., 95 ml of hydrogen at a pressure of 1 atm were weighed and injected by an integrating mass flow meter, then 0.36 ml of a 1 mol / L toluene solution of triethylaluminum (TEA) was added, and the mixture was stirred for 3 minutes. Enilvanadium trichloride (CpVCl ₃ )
0.42 ml of a 5 mmol / L toluene solution, 2.5 mm of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
ol / L of a 1.25 ml toluene solution was added in this order, and polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes. After the reaction, 2,6-
After injecting ethanol containing di-t-butyl-p-cresol to stop the reaction, the solvent was evaporated and dried to obtain 41 g of polybutadiene. Table 4 (Synthesis Example 2) shows the physical properties of the raw material polybutadiene. The obtained polymer was regarded as the starting polybutadiene of Examples 8 to 11 and Comparative Example 3 below.

Example 8 (Production of Modified Polybutadiene) In the same manner as in Synthesis Example 2, polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes, and then 8.4 ml of toluene containing 300 mg / L of water and diethylaluminum chloride. (DE
AC) 2 ml of a 1 mol / L toluene solution and 1 ml of a 5 mmol / L cobalt octylate (Co (Oct) ₂ ) toluene solution were added and reacted at 40 ° C. for 5 minutes. After the reaction, ethanol containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and then the solvent was evaporated and dried to obtain a modified polybutadiene. Table 3,
4 shows the polymerization results.

Example 9 (Production of Modified Polybutadiene) The same operation as in Example 8 was performed except that 5 μl of water was added instead of water-containing toluene (300 mg / L) added after polymerization. Tables 3 and 4 show the polymerization results.

Example 10 (Production of Modified Polybutadiene) The same operation as in Example 8 was carried out except that 8 μl of water was added instead of water-containing toluene (300 mg / L) added after the polymerization. Tables 3 and 4 show the polymerization results.

Example 11 (Production of modified polybutadiene) 1 mol of diethylaluminum chloride (DEAC)
The same operation as in Example 9 was performed except that the addition amount of the toluene solution of 1 mmol / L and the addition amount of the toluene solution of 5 mmol / L of cobalt octylate (Co (Oct) ₂ ) were 0.5 ml. Tables 3 and 4 show the polymerization results.

Comparative Example 3 (Production of Polybutadiene) After conducting polymerization at a polymerization temperature of 40 ° C. for 30 minutes in the same operation as in Synthesis Example 2, stirring was continued for 5 minutes without adding anything (ie, (The polymerization was carried out for 35 minutes.) Tables 3 and 4 show the polymerization results.

Synthesis Example 3 (Production of Raw Material Polybutadiene) The inside of a 1.7 L autoclave was purged with nitrogen.
260 ml of cyclohexane and 140 ml of butadiene are charged and stirred. Then, 5 μl of water was added and stirring was continued for 30 minutes. 100 ml of hydrogen at 20 ° C. and 1 atm were weighed and injected by an integrating mass flow meter, then 0.36 ml of a 1 mol / L toluene solution of triethylaluminum (TEA) was added, and the mixture was stirred for 3 minutes. Enilvanadium trichloride (CpVC
l ₃ ) 0.5 ml of a 5 mmol / L toluene solution, 2.5 m of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
1.5 ml of a toluene solution of mol / L was added in this order, and polymerization was performed at a polymerization temperature of 40 ° C. for 30 minutes. After the reaction, 2,6-
After injecting ethanol containing di-t-butyl-p-cresol to stop the reaction, the solvent was evaporated and dried to obtain 40 g of polybutadiene. Table 6 (Synthesis Example 3) shows the physical properties of the raw material polybutadiene. The obtained polymer was regarded as a starting polybutadiene of Examples 12 to 16 below.

Example 12 (Production of Modified Polybutadiene) Polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes in the same manner as in Synthesis Example 3, except that the amount of hydrogen added was changed to 20 ° C. and 115 ml in terms of 1 atm. Further, 10 ml of toluene containing 300 mg / L of water, diethylaluminum chloride (D
EAC) 0.2 ml of a 1 mol / L toluene solution and 0.5 ml of a 5 mmol / L cobalt octylate (Co (Oct) ₂ ) toluene solution were added, and the mixture was reacted at 40 ° C. for 15 minutes. After the reaction, ethanol containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and then the solvent was evaporated and dried to obtain a modified polybutadiene. Tables 5 and 6 show the polymerization results.

Example 13 (Production of Modified Polybutadiene) The hydrogenation amount was adjusted to 130 ml at 20 ° C. and 1 atm. After polymerization, water 7 was used instead of water-containing toluene (300 mg / L).
The same operation as in Example 12 was performed except that μl was added and the amount of the 1 mol / L toluene solution of DEAC added was 0.5 ml. Tables 5 and 6 show the polymerization results.

Example 14 (Production of Modified Polybutadiene) The inside of a 1.7 L autoclave was purged with nitrogen.
260 ml of cyclohexane and 140 ml of butadiene are charged and stirred. Then, 5 μl of water was added and stirring was continued for 30 minutes. At 20 ° C., 1 ml of hydrogen was measured and injected with an integrating mass flow meter at a pressure of 1 atm. Then, 0.36 ml of a 1 mol / L toluene solution of triethylaluminum (TEA) was added, and the mixture was stirred for 3 minutes. Enilvanadium trichloride (CpVC
l ₃ ) 0.5 ml of a 5 mmol / L toluene solution, 2.5 m of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
1.5 ml of a toluene solution of mol / L was added in this order, and polymerization was performed at a polymerization temperature of 40 ° C. for 30 minutes. In addition, 30
4.8 ml of toluene containing 0 mg / L, 0.1 ml of a 1 mol / L solution of diethylaluminum chloride (DEAC) in toluene, and cobalt octylate (Co (Oc
t) ₂ ) 0.5 ml of a 5 mmol / L toluene solution was added and reacted at 40 ° C. for 30 minutes. After the reaction, ethanol containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and then the solvent was evaporated and dried to obtain a modified polybutadiene. Tables 5 and 6 show the polymerization results.

Example 15 (Production of Modified Polybutadiene) The hydrogenation amount was set to 140 ml in terms of 20 ° C. and 1 atm. After polymerization, water 5 was used instead of water-containing toluene (300 mg / L).
The same operation as in Example 14 was performed except that μl was added and the addition amount of a 1 mol / L toluene solution of DEAC was 0.3 ml. Tables 5 and 6 show the polymerization results.

Example 16 (Production of Modified Polybutadiene) The amount of water added after the polymerization was adjusted to 8 μl, and 1 m of DEAC was added.
The same operation as in Example 15 was performed except that the amount of the ol / L toluene solution added was 0.5 ml. Tables 5 and 6 show the polymerization results.

Synthesis Example 4 (Production of Raw Polybutadiene) The inside of a 1.7 L autoclave was purged with nitrogen.
260 ml of cyclohexane and 140 ml of butadiene are charged and stirred. Then, 5.4 μl of water was added and 30
Stirring was continued for minutes. 100 ml of hydrogen at 20 ° C. and 1 atm were weighed and injected by an integrating mass flow meter, then 0.36 ml of a 1 mol / L toluene solution of triethylaluminum (TEA) was added, and the mixture was stirred for 3 minutes. Enilvanadium trichloride (CpV
0.5 ml of a toluene solution containing 5 mmol / L of Cl ₃ ) and 2.5 of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ )
1.5 ml of a toluene solution of mmol / L was added in this order, and polymerization was performed at a polymerization temperature of 40 ° C. for 30 minutes. After the reaction,
After injecting ethanol containing -di-t-butyl-p-cresol to terminate the reaction, the solvent was evaporated and dried to obtain 42 g of polybutadiene. Table 8 (Synthesis Example 4) shows the physical properties of the raw material polybutadiene. The obtained polymer was regarded as a starting polybutadiene of Examples 17 to 22 below.

Example 17 (Production of Modified Polybutadiene) Polymerization was carried out at a polymerization temperature of 40 ° C. for 30 minutes in the same manner as in Synthesis Example 4 except that the amount of hydrogenation was changed to 20 ° C. and 110 ml in terms of 1 atm. Further, 6 μl of water, 1.0 ml of a 1 mol / L solution of diethylaluminum chloride (DEAC) in toluene, and cobalt octylate (Co (Oct)) were added.
₂ ) 0.5 ml of a 5 mmol / L toluene solution was added and reacted at 40 ° C. for 15 minutes. After the reaction, 2,6-di-t
After stopping the reaction by injecting ethanol containing -butyl-p-cresol, the solvent was evaporated and dried,
A modified polybutadiene was obtained. Tables 7 and 8 show the polymerization results.

Example 18 (Production of modified polybutadiene) The same operation as in Example 17 was carried out except that the amount of hydrogenation was 125 ml in terms of 20 ° C. and 1 atm, and 31 g (50 ml) of 1,3-butadiene was added after polymerization. went. Tables 7 and 8 show the polymerization results.

Example 19 (Production of Modified Polybutadiene) The same operation as in Example 17 was carried out except that the amount of hydrogenation was 130 ml in terms of 20 ° C. and 1 atm, and 62 g (100 ml) of 1,3-butadiene was added after polymerization. went. Tables 7, 8
Shows the polymerization results.

Example 20 (Production of Modified Polybutadiene) The amount of hydrogen added was set to 100 ml at 20 ° C. and 1 atm.
After the polymerization, 4.2 ml of toluene containing 300 mg / L of water,
1 mol of diethyl aluminum chloride (DEAC)
/ L toluene solution 0.1 ml, cobalt octylate
(Co (Oct) _Two) 5 mmol / L toluene solution
The same operation as in Example 17 was performed except that 0.5 ml was added.
Was. Tables 7 and 8 show the polymerization results.

Example 21 (Production of Modified Polybutadiene) The same operation as in Example 20 was carried out except that the amount of hydrogenation was changed to 20 ° C. and 105 ml in terms of 1 atm, and after polymerization, 31 g (50 ml) of 1,3-butadiene was added. went. Tables 7 and 8 show the polymerization results.

Example 22 (Production of Modified Polybutadiene) The same operation as in Example 20 was carried out except that the amount of hydrogenation was changed to 20 ° C., 105 ml in terms of one atmosphere, and after polymerization, 62 g (100 ml) of 1,3-butadiene was added. went. Tables 7, 8
Shows the results of polymerization.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

[Table 7]

[0139]

[Table 8]

As is clear from the above examples, according to the present invention, polybutadiene having a high cis structure, a microstructure containing a 1,2-structure and a small number of trans structures, and having a high molecular linearity was obtained. It is possible to obtain a polybutadiene having improved cold flow characteristics by reducing linearity without changing the structure.

[0141]

The modified polybutadiene of the present invention has a microstructure containing a 1,2-structure with a moderately high cis structure and a small number of trans structures, and has improved properties such as cold flow. Further, according to the method for producing polybutadiene of the present invention, the above-mentioned modified polybutadiene of the present invention can be obtained.

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Claims (12)

[Claims] 1. A modified polybutadiene obtained by modifying a raw material polybutadiene having the following characteristics in the presence of a transition metal catalyst. Characteristics of raw polybutadiene:
5% toluene solution viscosity (Tcp) measured at 25 ° C. and 1
Ratio to Mooney viscosity (ML _{1 + 4} ) at 00 ° C. (Tcp
/ ML _{1 + 4} ) is 2.5 or more. 2. A raw material polybutadiene produced using a catalyst comprising (A) a metallocene complex of a transition metal compound, and (B) an ionic compound of a non-coordinating anion and a cation and / or an alumoxane. Claim 1.
3. The modified polybutadiene according to item 1. 3. The raw material polybutadiene comprises (A) a metallocene complex of a transition metal compound, (B) an ionic compound of a non-coordinating anion and a cation, and (C) a first to third periodic table.
2. The modified polybutadiene according to claim 1, which is produced using a catalyst comprising an organometallic compound of a group III element and (D) water. 4. The modified polybutadiene according to claim 1, wherein the transition metal catalyst comprises (1) a cobalt compound, (2) an organoaluminum, and (3) water. 5. The modified polybutadiene having a ratio (Tcp / ML _{1 + 4} ) of 5% toluene solution viscosity (Tcp) measured at 25 ° C. to Mooney viscosity (ML _{1 + 4} ) at 100 ° C. of 3
The modified polybutadiene according to claim 1, which is: 6. The modified polybutadiene according to claim 1, wherein the modified polybutadiene has a cold flow rate (CF) of less than 20 mg / min. 7. 5% measured at 25 ° C. using (A) a metallocene complex of a transition metal compound and (B) a catalyst comprising an ionic compound of a non-coordinating anion and a cation and / or an alumoxane. Viscosity of toluene solution (Tcp)
And the ratio (T ₁ ) of the Mooney viscosity (ML _{1 + 4} ) at 100 ° C.
A method for producing a modified polybutadiene, comprising producing a raw material polybutadiene having a cp / ML _{1 + 4 (} cp / ML _{1 + 4} ) of 2.5 or more, and further modifying it by adding a transition metal catalyst. 8. The method for producing a modified polybutadiene according to claim 7, wherein a butadiene monomer is additionally added before or after adding the transition metal catalyst. 9. The method for producing a modified polybutadiene according to claim 7, wherein the transition metal catalyst comprises (1) a cobalt compound, (2) an organoaluminum, and (3) water. 10. (A) a metallocene complex of a transition metal compound, (B) an ionic compound of a non-coordinating anion and a cation, (C) an organometallic compound of a Group 1 to 3 element of the periodic table, and (D) Using a catalyst consisting of water, the ratio of the 5% toluene solution viscosity (Tcp) measured at 25 ° C. to the Mooney viscosity (ML _{1 + 4} ) at 100 ° C. (Tcp / ML _{1 + 4} ) A method for producing a modified polybutadiene, which comprises producing a raw material polybutadiene having an average molecular weight of 2.5 or more, and further adding a transition metal catalyst for modification. 11. The method for producing a modified polybutadiene according to claim 10, wherein a butadiene monomer is additionally added before or after adding the transition metal catalyst. 12. The method for producing a modified polybutadiene according to claim 10, wherein the transition metal catalyst comprises (1) a cobalt compound, (2) organoaluminum, and (3) water.