JPH10218934A - Butadiene polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To polymerize butadiene at a high activity by specifying the most stable structure (S, r) of a butadiene polymn. catalyst comprising a boron compd. and a metallocene-type complex of a group-V transition metal compd. SOLUTION: The relations: S (the void area at the position 3Åapart from the central transition metal element, Å<2> )>=1.5 and r (the distance from the central transition metal element to a boron element, Å)<=10 are caused to be satisfied. The polymn. catalyst is prepd. by bringing a group-V transition metal compd. into contact with an ionic compd. of a noncoordinating borate anion and a cation. The polymn. is conducted by using a metallocene-type complex of a group-V transition metal compd. (e.g. cyclopentadienylvanadium trichloride), by using a boron compd. [e.g. triphenylcarbonium tetrakis(pentafluorophenyl)borate], in a nitrogen-purged autoclave, by using toluene and 1,3-butadiene as the solvent, and by adding triisobutylaluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metallocene complex of a transition metal compound of Group V of the Periodic Table and a novel catalyst for the polymerization of butadiene comprising (B) a boron compound.

[0002]

2. Description of the Related Art As a polymerization catalyst using a metallocene compound of a vanadium (V) group V transition metal, for example,
Polymer vol. 37 (2) p. 363 (1996) contains (substituted C ₅ H
₅ ) Polybutadiene containing 10 to 20% of 1,2-structure in a high cis structure using a catalyst comprising a vanadium (III) compound such as VCl ₂ or (substituted C ₅ H ₅ ) ₂ VCl and methylalumoxane. Has been reported, but the polymerization activity is low.

Also, Organometallics, 1995, 14, 746,
J. Am. Chem. Soc., 1995, 117, 12793, etc., have attempted to evaluate the activity of metallocene catalyst compounds for polybutadiene polymerization based on the chemical structures of metallocene catalysts and monomers using molecular orbital methods. It has been reported. However, these catalyst systems have not been evaluated for their effect on activity depending on the type of cocatalyst.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a metallocene type polymerization catalyst belonging to Group V of the periodic table, which is capable of polymerizing butadiene with high activity.

[0005]

The present invention relates to a catalyst for butadiene polymerization comprising (A) a metallocene complex of a transition metal compound of Group V of the periodic table, and (B) a boron compound. The most stable structure is given by the following formulas (1) and (2)
A catalyst for butadiene polymerization characterized by satisfying the following relationship: S ≧ 1.5 (1) r ≦ 10 (2) (where, S (Å ² ) indicates a void area at a position 3 ° from the central transition metal element in the most stable structure of the catalyst, and r
(Å) shows the distance between the central transition metal element and the boron element in the most stable structure of the catalyst. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (A) The periodic table of the present invention
A metallocene complex of a group V transition metal compound, and (B) the most stable structure of a butadiene polymerization catalyst comprising a boron compound, a void area S (Å ² ) at a position 3Å from the central transition metal element in the most stable structure, And the distance r between the central transition metal element and the boron element in the most stable structure
(Å) can be calculated by a computer including the following components. However, the above-mentioned void area S is a position of 3 ° along the path of entry of the monomer from the central transition metal element, and has a diameter of 3 °.
Draw a circle of Å, and the circle is the remaining area of each atom in the most stable structure excluding the van der Waals volume.

That is, (a) an input device for inputting the structures of the metallocene complex and the boron compound, and (b) the most stable structure formed from the structures of the metallocene complex and the boron compound input to the above input device. A first arithmetic unit for calculation, (c) at a position 3 ° from the central transition metal element formed between the elements along the entry path of the butadiene monomer based on the most stable structure obtained by the first arithmetic unit. A second computing device for calculating the void area S, (d) a third computing device for calculating the distance r between the central transition metal element and the boron element using the most stable structure obtained by the first computing device (E) the most stable structure obtained by the first arithmetic unit, the void area S obtained by the second arithmetic unit, and the distance between the central transition metal element and the boron element obtained by the third arithmetic unit a storage device for storing r Beauty (f) can be calculated by the computing device including a display device.

The above-described computing device will be described with reference to FIG. FIG. 1 is a block diagram illustrating an example of a configuration of a computing device. This is an example of a computing device including an input device 1, a first computing device 11, a second computing device 12, a third computing device 13, a storage device 2, and a display device 3.

As the input device 1, in addition to a keyboard, a graphic input device such as a light pen or an image reader, a punch card reader, or the like can be used. Two or more of these devices can be used in combination.

As the arithmetic units 11 to 13, so-called personal computers can be used as CPUs. Further, a minicomputer, a supercomputer, or the like can be used as needed.

As the storage device 2, a floppy disk, hard disk, tape, or the like can be used.

As the display device 3, a cathode ray tube, a liquid crystal display, various printers, plotters and the like are suitably used. These may be used in combination.

The operation of each component of the above-described computing device will be described in detail below.

The input device is a device for inputting the chemical structures of the metallocene complex and the boron compound. The chemical structure may be input as graphic information, and may constitute each chemical structure, such as a methylene group, methyl group, substituted methylene group, alkyl group, phenylene group, phenyl group, or amide bond or ester bond. A number may be assigned to each of the atomic groups, and input may be made by a combination of the numbers. Alternatively, spatial coordinates in an existing database may be input.

The first arithmetic unit 11 calculates the most stable structure of a catalyst comprising a metallocene complex and a boron compound. As a technique used in this case, a molecular mechanics method, a semi-empirical molecular orbital method, an ab initio molecular orbital method, or the like is used. Among them, the molecular mechanics method is suitably used.

In the second arithmetic unit 12, based on the most stable structure of the catalyst determined by the arithmetic unit 11, a position 3 ° away from the central transition metal element formed between the elements along the entry path of the butadiene monomer. Calculate the void area S.

The third arithmetic unit 13 calculates the distance r between the central transition metal element and the boron element based on the most stable structure of the catalyst obtained by the arithmetic unit 11.

The components of the butadiene polymerization catalyst of the present invention are described below.

The catalyst for butadiene polymerization formed from (A) a metallocene complex of a transition metal compound belonging to Group V of the periodic table and (B) a boron compound are represented by the following general formula: (a) a general formula R _n M (O) _m X _p · L _a (wherein, M represents a periodic table group V transition metal, R represents a cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group or substituted fluorenyl group O represents oxygen, X represents hydrogen,
A halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or an amide group, L represents a Lewis basic compound,
(N, m, p) is (n = 1, m = 1, p = 2), (n
= 1, m = 0, p = 3), (n = 2, m = 0, p =
1), a number selected from the combination of (n = 1, m = 0, p = 2), and a is 0, 1, or 2. ), And a (b) ionic compound component of a non-coordinating borate anion and a cation.

The general formula R _n M in the above component (a)
In (O) _{m Xp} · La, M is _a transition metal belonging to Group V of the periodic table. Specifically, vanadium (V), niobium (N
b) or a transition metal of Group Va in the periodic table such as tantalum (Ta), and preferably vanadium.

In the general formula R _n M (O) _m X _p · La, 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, isopropyl, 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 pentamethylcyclopentadienyl group, and a vinylcyclopentadienyl group. Among them, R is preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an indenyl group, or the like.

[0024] In the general formula _{R n M (O) m X} p · L a, X represents hydrogen, halogen, hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group or an amide group. Specific examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom is preferable.

Specific examples of the hydrocarbon substituent having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl,
Examples thereof include linear or branched aliphatic hydrocarbon groups such as butyl, t-butyl, neopentyl, hexyl, and octyl, and aromatic hydrocarbon groups such as phenyl, tolyl, naphthyl, and benzyl. Furthermore, hydrocarbon groups containing a silicon atom such as trimethylsilylmethyl and bistrimethylsilylmethyl are also included. Among them, methyl, benzyl, trimethylsilylmethyl and the like are preferable.

Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, propoxy, butoxy, t-
Butoxy and the like. Further, amyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, thiomethoxy and the like may be used. Among them, methoxy, t-butoxy and the like are preferable. Phenoxy is also used.

Specific examples of the amide group include dimethylamide, diethylamide, diisopropylamide and the like. Among them, dimethylamide, diethylamide and the like are preferable.

[0028] In the general formula _{R n M (O) m X} p · L a, L is a Lewis basic compound, a Lewis basic common inorganic that can be coordinated to a metal with a pair electron, is an organic compound. Among them, compounds having no active hydrogen are particularly preferred. Specific examples include ethers, esters, ketones, amines, phosphines, and silyloxy compounds.

The general formula of the present invention: R _n M (O) _m X _p · L
_a is RMX ₃ , RM (O) X ₂ , R ₂ MX · L
_a, such as the RMX ₂ · L _a, and the like. M is vanadium _{RVX 3, RV (O) X} 2, R 2 VX · L a, R
Bananjiumu compounds such as VX ₂ · L _a is preferable.

Specific compounds of RMX ₃ include cyclopentadienyl vanadium trichloride, methylcyclopentadienyl vanadium trichloride, pentamethylcyclopentadienyl vanadium trichloride and the like.

Specific compounds of M (O) X ₂ include the following compounds. Cyclopentadienyloxovanadium dichloride, substituted cyclopentadienyloxovanadium dichloride, for example, methylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl) oxovanadium dichloride and the like can be mentioned.

[0032] Examples of specific compounds of the RMX ₂ · L _a is,
The following compounds are mentioned. Cyclopentadienyl vanadium dichloridebistriethylphosphine complex,
Cyclopentadienyl vanadium dichloride bistrimethylphosphine complex, (cyclopentadienyl)
And phosphine complexes such as (bisdi-iso-propylamide) vanadium trimethylphosphine complex and monomethylcyclopentadienyl vanadium dichloride bistriethylphosphine complex.

[0033] Specific compounds of R ₂ MX · L _a is
The following compounds are mentioned. Dicyclopentadienyl vanadium chloride, bis (methylcyclopentadienyl) vanadium chloride, bis (1,3-dimethylcyclopentadienyl) vanadium chloride, bis (1-methyl-3-butylcyclopentadienyl) vanadium chloride , Bis (pentamethylcyclopentadienyl) vanadium chloride, bis (trimethylsilylcyclopentadienyl) vanadium chloride and the like.

The non-coordinating borate anion in the component (b) of the ionic compound of a non-coordinating borate anion and a cation includes, for example, tetra (phenyl) borate, tetrakis (monofluorophenyl) borate,
Tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) Borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarboundecaborate. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include a trisubstituted carbonium cation such as a triphenylcarbonium cation and a trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include a tri (methylphenyl) 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-diethylanilinium cation, N, N-2,4,6 -
Examples thereof include N, N-dialkylanilinium cations such as pentamethylanilinium cation, dialkylammonium cations such as di (i-propyl) ammonium cation and dicyclohexylammonium cation.

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

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 (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferred.

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

Here, the conjugated diene compound monomer to be polymerized may be a whole or a part. In the case of some of the monomers, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution.

As the conjugated diene compound monomer, 1,3-
Butadiene, isoprene, 1,3-pentadiene, 2-ethyl
Examples thereof include -1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2,4-hexadiene.

These monomer components may be used alone or in combination of two or more.

In addition to conjugated dienes, ethylene, propylene, butene-1, butene-2, isobutene, pentene-
Acyclic monoolefins such as 1,4-methylpentene-1, hexene-1, and octene-1, cyclopentene, cyclohexene, and cyclic monoolefins such as norbornene, and / or aromatic vinyl compounds such as styrene and α-methylstyrene; Non-conjugated diolefins such as dicyclopentadiene, 5-ethylidene-2-norbornene and 1,5-hexadiene may be contained in small amounts.

The polymerization method is not particularly limited.
Solution polymerization or the like can be applied. Examples of the solvent in the solution polymerization include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as n-hexane, butane, heptane, and pentane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; -Butene, cis-2-butene, trans-2-
Examples thereof include hydrocarbon solvents such as olefin hydrocarbons such as butene, mineral spirit, solvent naphtha, and kerosene, and halogenated hydrocarbon solvents such as methylene chloride. Alternatively, the polymerization may be performed by bulk polymerization using 1,3-butadiene itself as a polymerization solvent.

Among them, toluene, cyclohexane, a mixture of cis-2-butene and trans-2-butene and the like are preferably used. Bulk polymerization and polymerization using a hydrocarbon solvent having a low boiling point have an advantage that large energy is not required for solvent recovery.

The polymerization temperature is preferably in the range of -100 to 150 ° C, more preferably in the range of -100 to 100 ° C, and more preferably in the range of -50 to 100 ° C.
Is even more preferable, and a range of -50 to 60 ° C is particularly preferable. The polymerization time is preferably in the range of 10 minutes to 12 hours,
30 minutes to 6 hours are particularly preferred.

After the polymerization has been 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.

The microstructure was determined by infrared absorption spectrum analysis. Cis-1,4-structure 740cm ^-1 , trans-1,4
-Structure Microstructure was calculated from the absorption intensity ratio of 967 cm ^-1 and 1,2-structure (vinyl) 911 cm ^-1 .

The molecular weight distribution was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.

[0050]

【Example】

(Example 1) The inside of a 1.5 L autoclave was replaced with nitrogen, and 168 mL of toluene and 32 mL of 1,3-butadiene were charged. Next, 200 μmol of triisobutylaluminum as the component (c), 1.8 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) as the component (b) and cyclohexane as the component (a) Pentadienyl vanadium trichloride (CpVCl ₃ ) 1.
2 μmol was added, and polymerization was performed at a polymerization temperature of 30 ° C. for 60 minutes.
Table 1 shows the polymerization results.

For the butadiene polymerization catalyst composed of the above components, the most stable structure of the catalyst was calculated by the above-mentioned calculator (using the molecular mechanics method in the arithmetic unit 11), and based on the most stable structure, the butadiene monomer The void area S at a position 3 ° from the central transition metal element formed between the elements along the ingress route and the distance r between the central transition metal element and the boron element were calculated. Table 2 shows the calculation results of S and r.

Example 2 In Example 1, 5 μmol of pentamethylcyclopentadienyl vanadium trichloride (Me ₅ CpVCl ₃ ) was used as the component (a), and triphenylcarbonium tetrakis (pentafluorophenyl) borate was used as the component (b). (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 7.5 μmol, and the same procedure as in Example 1 was carried out except for using 500 μmol of triisobutylaluminum as the component (c). Table 1 shows the polymerization results, and Table 2 shows the calculation results of S and r.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

According to the present invention, there is provided a polymerization catalyst of a group V metallocene type which can polymerize butadiene with high activity.

[Brief description of the drawings]

FIG. 1 is a block diagram illustrating an example of a configuration of a computing device according to the present invention.

Claims (1)

[Claims] 1. A butadiene polymerization catalyst comprising (A) a metallocene complex of a transition metal compound of Group V of the periodic table and (B) a boron compound, wherein the most stable structure of the catalyst is represented by the following formula (1). ) And (2). S ≧ 1.5 (1) r ≦ 10 (2) (where, S (Å ² ) indicates a void area at a position 3 ° from the central transition metal element in the most stable structure of the catalyst, and r
(Å) shows the distance between the central transition metal element and the boron element in the most stable structure of the catalyst. )