JPH11199625A - Production of conjugated diene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a conjugated diene polymer in high activity under a controlled condition using a new catalyst. SOLUTION: The characteristic of this method comprises using a catalyst obtained from (A) a titanium compound, (B) an ionic compound resulted from an incoordinated anion and cation, (C) an organic aluminum compound and (D) water (note that a molar ratio of C:D=(1:0.1) to (1:2)). The component A is a titanium compound shown by the formula; TiRX3 (R is a (substituted) cyclopentadienyl, (substituted) indenyl or (substituted) fluorenyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conjugated diene polymer using a polymerization catalyst comprising a titanium compound.

[0002]

2. Description of the Related Art Numerous proposals have been made on polymerization catalysts for conjugated dienes such as butadiene and isoprene, and polymers having various microstructures have been made possible, and some of them have been industrialized.

As a catalyst for polymerizing a conjugated diene using a titanium compound-based catalyst, for example, Macromol. Symm
p. , 89, 383 (1995) describe CpTiCl ₃
70-90% of cis-1,4 structure by MAO catalyst system
And a method for producing polybutadiene having a 1,2-structure of 10 to 20% has been reported. Also, Japanese Patent Application Laid-Open No. 9-28681
No. 0 discloses that (A) a compound represented by the general formula TiRX ₃ , wherein R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group; Hydrogen, halogen,
It represents a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group. ) Titanium compound,
A catalyst system comprising (B) an ionic compound of a non-coordinating anion and a cation and (C) an organoaluminum compound is disclosed. However, these catalyst systems have insufficient polymerization activity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a controlled conjugated diene polymer with high activity using a novel titanium compound-based polymerization catalyst.

[0005]

The present invention SUMMARY OF] is, (A) the general formula TiRX ₃ (wherein, R represents a cyclopentadienyl group,
X represents a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group. ), (B) an ionic compound of a non-coordinating anion and a cation, (C) an organoaluminum compound, and (D) water (provided that (C) :( D) = 1: 0.
1 to 2 (molar ratio). The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using a catalyst obtained from the above.

[0006] Further, the present invention relates to (A) the general formula TiRX
₃ (wherein R is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group,
X represents a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group. ), (B) an ionic compound of a non-coordinating anion and a cation, (C) an organoaluminum compound, and (D) water (provided that (C) :( D) = 1: 0. The present invention relates to a method for producing a conjugated diene polymer, which comprises polymerizing a conjugated diene compound using a catalyst comprising 1 to 2 (molar ratio).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the catalyst of the present invention is a titanium compound represented by the general formula TiRX ₃ . In the formula, R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group.

The substituent in the substituted cyclopentadienyl group, substituted indenyl group or substituted fluorenyl group includes methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl And a silicon atom-containing hydrocarbon group such as a group, a t-butyl group, a hexyl group, a phenyl group, a benzyl group, and a trimethylsilyl group. 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.

Specific examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, and a 1,3-di ( t-butyl) cyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,3,4-tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, 1-ethyl-2,3,4,5-tetramethylcyclo Pentadienyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl group, 1-trimethylsilyl-2 , 3,4,5-tetramethylcyclopentadienyl group, 1-
And a trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl group.

Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group,
2,4,5,6,7-hexamethylindenyl group and the like.

Specific examples of the substituted fluorenyl group include a methylfluorenyl group.

Of the above, R is preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an indenyl group, a 1,2,3-trimethylindenyl group, or the like.

X represents hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group.

[0014] Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrocarbon substituent having 1 to 20 carbon atoms include straight-chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl or branched aliphatic hydrocarbon groups. And aromatic hydrocarbon groups such as phenyl, 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.

[0016] Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy and the like. Further, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, thiomethoxy and the like may be used.

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

Specific examples of the amide group include diethylamide,
iso-propylamide, n-octylamide and the like.

Among the above, X is preferably a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, a dimethylamino group, a diethylamino group and the like.

In the present invention, specific compounds of TiRX ₃ include the following (1) to (18). (1) Cyclopentadienyl titanium trichloride.

(2) Monosubstituted cyclopentadienyl titanium trichloride, for example, methylcyclopentadienyl titanium trichloride, ethylcyclopentadienyl titanium trichloride, propylcyclopentadienyl titanium trichloride, isopropylcyclopentadienyl Titanium trichloride, t-butylcyclopentadienyl titanium trichloride, benzylcyclopentadienyl titanium trichloride, (1,1-dimethylpropyl) cyclopentadienyl titanium trichloride, (1,1-dimethylbenzyl) cyclopenta Dienyl titanium trichloride, (1-ethylpropyl) cyclopentadienyl titanium trichloride, (1-ethyl, 1-methylpropyl) cyclopentadienyl titanium trichloride, (diethylbenzyl) cyclopentadie Nyltitanium trichloride, (trimethylsilylcyclopentadienyl) titanium trichloride, (bis (trimethylsilyl) cyclopentadienyl) titanium trichloride and the like.

(3) 1,3-disubstituted cyclopentadienyl titanium trichloride, for example, (1,3-dimethylcyclopentadienyl) titanium trichloride, (1-methyl-3-ethylcyclopentadienyl) Titanium trichloride, (1-
Methyl-3-propylcyclopentadienyl) titanium trichloride, (1-methyl-3-bis (trimethylsilyl)
Silylcyclopentadienyl) titanium trichloride,
(1-methyl-3-phenylcyclopentadienyl) titanium trichloride, (1-methyl-3-tolylcyclopentadienyl) titanium trichloride, (1-methyl-3- (2,6-
(Dimethylphenyl) cyclopentadienyl) titanium trichloride, (1-methyl-3-butylcyclopentadienyl) titanium trichloride and the like.

(4) 1,2,3-trisubstituted cyclopentadienyl titanium trichloride, for example, (1,2,3-trimethylcyclopentadienyl) titanium trichloride, (1,2,3-triethylcyclo (Pentadienyl) titanium trichloride, (1,2,3-triphenylcyclopentadienyl) titanium trichloride and the like.

(5) 1,2,4-trisubstituted cyclopentadienyl titanium trichloride, for example, (1,2,4-trimethylcyclopentadienyl) titanium trichloride, (1,2,4-triethylcyclo (Pentadienyl) titanium trichloride, (1,2,4-triphenylcyclopentadienyl) titanium trichloride and the like.

(6) Tetra-substituted cyclopentadienyl titanium trichloride, for example, (1,2,3,4-tetramethylcyclopentadienyl) titanium trichloride, (1,2,3,4-
(Tetraphenylcyclopentadienyl) titanium trichloride and the like.

(7) Penta-substituted cyclopentadienyl titanium trichloride, for example, (pentamethylcyclopentadienyl) titanium trichloride, (1,2,3,4-tetramethyl-5-phenylcyclopentadienyl) Titanium trichloride, (1,2,3,4-tetraphenyl-5-methylcyclopentadienyl) titanium trichloride, (pentaphenylcyclopentadienyl) titanium trichloride and the like can be mentioned.

(8) Indenyl titanium trichloride.

(9) substituted indenyl titanium trichloride,
For example, (2-methylindenyl) titanium trichloride, (2-trimethylsilylindenyl) titanium trichloride and the like can be mentioned.

(10) Monoalkoxides and dialkoxides in which the chlorine atoms of the compounds of the above (1) to (9) are partially substituted with alkoxy groups. For example, cyclopentadienyl titanium t-butoxide dichloride, cyclopentadienyl titanium iso-propoxide dichloride, cyclopentadienyl titanium dimethoxy chloride, cyclopentadienyl titanium diiso-propoxycyclolide, cyclopentadienyl titanium Di-tert-butoxychloride, cyclopentadienyl titanium diphenoxycyclolide, cyclopentadienyl titanium iso-propoxy dichloride, cyclopentadienyl titanium ter-butoxy dichloride, cyclopentadienyl titanium phenoxy dichloride and the like can be mentioned.

(11) Methyl, dimethyl, and trimethyl forms in which the chlorine atom in the above (1) to (10) is substituted with a methyl group.

(12) Examples are those wherein R is bonded to X by a hydrocarbon group or a hydrocarbon silyl group. For example, (t-butylamido) dimethylsilyl (eta ⁵ - cyclopentadienyl) titanium dichloride, (t-butylamido) dimethylsilyl (trimethyl eta ⁵ - cyclopentadienyl) titanium dichloride, (t-butylamido) dimethylsilyl ( tetramethyl - eta ⁵ - such as cyclopentadienyl) titanium dichloride and the like.

(13) Methyl and dimethyl compounds obtained by substituting the chlorine atom of the above (12) with a methyl group are exemplified.

(14) Monoalkoxy and dialkoxy compounds in which the chlorine atom of the above (12) is substituted with an alkoxy group.

(15) Compounds obtained by substituting the monochloro compound of the above (14) with a methyl group.

(16) An amide in which the chlorine atom in the above (1) to (10) is substituted with an amide group. For example, (cyclopentadienyl) (tris-diethylamido) titanium, (cyclopentadienyl) (tris-iso-propylamido) titanium, (cyclopentadienyl) (tris-n-octylamido) titanium, (cyclopentadienyl) (Bisdiethylamide) titanium chloride, (cyclopentadienyl)
(Bis-iso-propylamide) titanium chloride, (cyclopentadienyl) (bis-n-octylamide) titanium chloride, (cyclopentadienyl) (diethylamide) titanium dichloride, (cyclopentadienyl)
(Iso-propylamido) titanium dichloride, (cyclopentadienyl) (n-octylamido) titanium dichloride and the like.

(17) Fluorenyl titanium trichloride, methyl fluorenyl titanium trichloride and the like. Further, a compound in which a chlorine atom is substituted by a methyl group, an alkoxy group, or an amide group is also exemplified.

Among them, cyclopentadienyl titanium trichloride, methylcyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, indenyl titanium trichloride, 1,2,3-trimethylindenyl titanium trichloride , Cyclopentadienyl titanium tri (methoxide), pentamethylcyclopentadienyl titanium tri (methoxide) and the like are preferably used.

The non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation of the component (B) of the catalyst system of the present invention is, for example, tetra (phenyl) borane.
, Tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, Tetrakis (tetrafluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] bore And tridecahydride-7,8-dicarboundecaborate.

On the other hand, examples of the cation include a carbenium 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 carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation and a tri-substituted phenyl carbenium cation. Specific examples of the tri-substituted phenylcarbenium cation include a tri (methylphenyl) carbenium cation and a tri (dimethylphenyl) carbenium 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, and N, N-dimethylanilinium. Cation, N, N-
Diethylanilinium cation, N, N-2,4,6-
Examples thereof include N, N-dialkylanilinium cations such as pentamethylanilinium cation, di (i-propyl) ammonium cation, and dialkylammonium cations such as dicyclohexylammonium cation.

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

As the ionic compound, a non-coordinating anion and a cation selected and arbitrarily selected from the above-mentioned non-coordinating anions can be preferably used.

Among the ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium Tetrakis (pentafluorophenyl) borate and the like are preferred. The ionic compounds may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound as the component (C) of the catalyst system of the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum. Aluminum can be mentioned.

Further, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organic aluminum halides such as sesquiethylaluminum chloride and ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride,
Organoaluminum hydride compounds such as sesquiethylaluminum hydride are also included. Two or more of these organoaluminum compounds can be used in combination.

The mixing ratio of each catalyst component varies depending on various conditions, but the molar ratio of component (A) to component (B) is preferably from 1: 0.1 to 10, more preferably from 1: 0.2. ~ 5.

The molar ratio of component (A) to component (C) is preferably from 1: 0.1 to 1000, more preferably from 1: 1 to 5
00.

The molar ratio of component (C) to component (D) is 1:
0.1 to 2, preferably 1: 0.1 to 1.5.

[0050] The order of addition of the catalyst components is not particularly limited.
For example, it can be performed in the following order. The component (D) is added to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent, the component (C) is added, and then the components (A) and (B) are added in an arbitrary order. After adding the components (D) and (C) to the conjugated diene compound monomer to be polymerized or a mixture of the monomer and the solvent,
The components (A) and (B) are added in any order.

Further, each component may be aged in advance and used. Above all, it is preferable to ripen the components (A) and (C).

As the aging conditions, the components (A) and (C) are mixed in an inert solvent in the presence of a conjugated diene. The aging temperature is from 0 to 100 ° C., preferably from 10 to 60 ° C., and the aging time is not particularly limited, but usually 0.5 minutes or more is sufficient, and it is stable for several days.

In the present invention, each catalyst component is an inorganic compound,
Alternatively, it can be used by being supported on an organic polymer compound.

The monomer that can be polymerized by using the catalyst in the present invention is not particularly limited, such as α-olefin, cyclic olefin, and conjugated diene, but conjugated diene compound monomers are particularly preferred.

As the conjugated diene compound monomer, 1,3-
Butadiene, isoprene, 1,3-pentadiene, 2-
Examples thereof include ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene. Among them,
Preferred is a conjugated diene compound monomer containing 1,3-butadiene as a main component. These monomer components may be used alone or in combination of two or more.

Here, the conjugated diene compound monomer to be polymerized may be the whole or a part of the monomer. In the case of some of the monomers, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution. In addition to conjugated dienes, acyclic monoolefins such as ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, 4-methylpentene-1, hexene-1, octene-1, cyclopentene, cyclohexene, norbornene And / or a small amount of 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. May be.

[0057] The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) using 1,3-butadiene itself as a polymerization solvent or solution polymerization can be applied. Solvents for solution polymerization include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; Olefinic hydrocarbons such as -butene, cis-2-butene, trans-2-butene,
Examples include hydrocarbon solvents such as mineral spirits, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride.

Among them, toluene, cyclohexane, a mixture of cis-2-butene and trans-2-butene, and the like are preferably used.

[0059] The polymerization temperature is preferably in the range of -100 to 100 ° C, particularly preferably in the range of -50 to 60 ° C. The polymerization time is preferably in the range of 10 minutes to 12 hours, particularly preferably 30 minutes to 6 hours.

After the polymerization is carried out for a predetermined time, the pressure inside the polymerization tank is released as required, and post-treatments such as washing and drying steps are performed.

[0061] By using the catalyst and the polymerization method of the present invention, the 1,2-structure content is 4 to 30%, preferably 5 to 30%.
25%, more preferably 5 to 20%, cis-1,4-structure content of 65 to 95%, preferably 70 to 95%, trans-1,4-structure content of 5% or less, preferably 4.5% % Or less of polybutadiene can be produced. These polybutadienes can be suitably used as impact modifiers for polystyrene.

[0062]

EXAMPLES In the examples, "polymerization activity" means the yield (g) of the polymer per 1 hour of the polymerization time per 1 mmol of titanium metal of the titanium compound used in the polymerization reaction.
The molecular weight distribution was determined using G using polystyrene as a standard.
Weight average molecular weight Mw and number average molecular weight M determined from PC
It was evaluated by the ratio Mw / Mn of n. Microstructure was performed by infrared absorption spectroscopy. Cis-1,4-structure 740 cm ^-1 , trans-1,4-structure 967c
The microstructure was calculated from the absorption intensity ratio of m ⁻¹ , 1,2-structure 910 cm ⁻¹ .

(Examples 1 to 14) The interior of an autoclave having an internal volume of 1.5 L was replaced with nitrogen, and 300 mL of toluene and 1.15 mol (62 g) of dehydrated butadiene were charged and stirred. Water (H ₂ O) shown in Table 1 was added and dissolved by stirring for 30 minutes. Next, triethylaluminum (TEA) was added as a component (C) in an amount shown in Table 1, and cyclopentadienyl titanium trichloride (CpT) was added as a component (A).
0.005 mmol of iCl ₃ ) and 0.0075 m of triphenylcarbenium tetra (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) as the component (B)
mol was added as a toluene solution, and polymerization was carried out at a polymerization temperature of 40 ° C. for 1 hour. After the polymerization, an antioxidant was added to release a part of unreacted 1,3-butadiene from the autoclave. The polymerization solution was poured into ethanol, and the polymer was precipitated, washed, filtered and dried. Tables 1, 2 and 3 show polymerization conditions and polymerization results.

[0064]

【table 1】

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

According to the present invention, a controlled conjugated diene polymer can be produced with high activity using a novel titanium compound-based polymerization catalyst.

Claims (2)

[Claims] (A) A compound represented by the general formula TiRX ₃ , wherein R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen. , A halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group), (B) an ionic compound of a non-coordinating anion and a cation, (C) Polymerizing a conjugated diene compound using an organoaluminum compound and a catalyst obtained from (D) water (provided that (C) :( D) = 1: 0.1 to 2 (molar ratio)). A method for producing a conjugated diene polymer, characterized in that: (A) A compound represented by the general formula TiRX ₃ , wherein R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and X represents hydrogen. , A halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an amino group or an amide group.) (B) an ionic compound of a non-coordinating anion and a cation; ) An organoaluminum compound, and (D) water (provided that (C) :( D) = 1: 0.1 to 2)
(Molar ratio). A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using a catalyst comprising