JPH09194526A - Conjugated diene polymerization catalyst - Google Patents

Abstract

(57) [Summary] [Structure] A group V transition metal compound of a specific periodic table and an ionic compound capable of reacting with an organoaluminum oxy compound or the transition metal compound in place of it to form a cationic transition metal compound. A conjugated diene polymerization catalyst composed of a combination. [Effect] To provide a novel catalyst system for producing a polymer in which a conjugated diene has a controlled microstructure, which has a high polymerization activity,
The molecular weight distribution is narrow, and the composition distribution is narrow in copolymerization. Therefore, a polymer having excellent mechanical properties can be obtained from this catalyst system.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for polymerizing a conjugated diene.

[0002]

2. Description of the Related Art In recent years, metallocene types such as Ti, Zr and Hf, which are highly active as olefin polymerization catalysts, have narrow molecular weight distributions of formed polymers and narrow composition distributions in copolymerization, and are capable of obtaining olefin polymers having excellent physical properties. A catalyst system comprising a combination of a complex and an organic aluminum oxy compound such as methylalumoxane has attracted attention. These are Macromle
cular Science, 1994, C34, No3, p. 439, Progress Pol
ymer Science, 1995, 20, 309 pages, 459 pages, Journal
Organometallic Chemistry, 1995, Volume 497, No 1-2. As the metallocene metal used as an olefin polymerization catalyst, Group IVB elements of the Periodic Table are the most well known. Others, Catalyst, 1994, Vol. 36, 8
No., p.572, Journal of Polymer Science, 1994, 51, No. 10, 637
As described on the page, many elements of Group VB of the periodic table such as Ta and Nb, Sc, and lanthanoid elements have been reported recently.

By the way, Ti, V, Co, N as a coordination anionic polymerization catalyst for conjugated dienes such as butadiene and isoprene
Transition metal compounds such as i and Nd are well known. For V 2 compounds, for example, the VCl ₃ / AlEt ₃ system is known to be able to control the structure of polymers. A catalyst system has also been developed in which the cocatalyst is methylalumoxane, and the polymer structure depends on the transition metal (Polymer Communication, 1991, 32
(No. 17, p. 514). Transformer 1 from V (acac) ₃ / MAO system
4 Polybutadiene having a predominant structure is obtained.

Cyclopentadienyltitanium trichloride [(η ⁵ C ₅ H ₅ ) TiCl ₃ ] is described in detail with respect to the polymerization of conjugated dienes with metallocenes of Group IV transition metals, which are attracting attention as high-performance olefin polymerization catalysts. Researched, Porri
Have reported the research results (Macromolecular Sy
mposia, 1995, 89 pages, 383). However, the polymerization activity of the conjugated diene in this system is not yet sufficient. The polymer structure is greatly affected by the type of diene as a monomer and the polymerization temperature.In the case of polybutadiene, the cis structure is the main, and in 1,3-pentadiene, cis and 1,2
Structures are included in approximately equal amounts. Furthermore, when the polymerization temperature is as low as -30 ° C or lower, most of the structures are 1,2. Also Ka
Minsky et al. Copolymerization of ethylene and butadiene with a combination of bis (cyclopentadienyl) zirconium dichloride [(η ⁵ C ₅ H ₅ ) ₂ ZrCl ₂ ] and methylalumoxane, a metallocene catalyst with a very high olefin polymerization activity. (Macromolecular Symposia, 1986, Section 4, 103
P.). There is no mention of the comonomer composition of the polymer and the activity is very low.

The compound of V, which is an element of Group VB of the periodic table, is a butadiene polymerization catalyst as described above.
As a new catalyst system, JP-A-6-73128 has an imidoaryl ligand which is a catalyst for an amorphous copolymer of ethylene, including a copolymer of ethylene and a diene [V
_{Cl 3 N (2,6, di (} isoC 3 H 7) C 6 H 3) the combination of] the trialkyl aluminum is disclosed. This publication is unclear because it does not describe polymerization of conjugated dienes as dienes. Further V
Copolymerization catalysts of olefins and dienes consisting of combinations of metallocenes and organoaluminum oxy compounds are disclosed in JP-A-64-66216, JP-A-63-501962, and ethylene and butadiene having a cyclopentane structure in the polymer main chain. The copolymer with is disclosed in Japanese Patent Publication No. 1-501633.
In all of these publications, bis (cyclopentadienyl) vanadium dichloride [(η ⁵ C ₅ H ₅ ) ₂ VCl ₂ ] is the only V metallocene listed as a specific example. There is no description.

Recently, a metallocene catalyst of Group IVB of the periodic table
Of the ionizing agent as a cocatalyst used in the system
A catalyst system in combination with a Group VB metallocene was proposed.
(Special table No. 7-509016). This publication contains polyanio
Having imide as an auxiliary ligand [(η^FiveC_FiveH_Five) VCl_TwoN (p-
CH_Three-C₆H_Four)], With a carbolide (η^FiveC_Five(CH_Three)_Five) (C _TwoB
₉H₁₁) Ta (CH_Three)_TwoAre listed. However, eventually
There is no description of polymerization or copolymerization of conjugated dienes, and central transition
Limited to complexes where the metal is in the highest oxidation state.

[0007]

It is an object of the present invention to provide a new catalyst system for the production of polymers with controlled microstructure of conjugated dienes.

[0008]

The present invention relates to a group V transition metal compound of the periodic table represented by formula (1) or formula (2),
The present invention relates to a catalyst for conjugated diene polymerization, which comprises a combination with an organoaluminum oxy compound or an ionic compound capable of reacting with the transition metal compound in place of it to form a cationic transition metal compound.

LMX ₂ (NR) (1) MX ₃ (NR) (2) (In the formula, M is a Group V transition metal, X is hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom. To hydrocarbon oxy group having 1 to 20 carbon atoms, hydrocarbon amino group having 1 to 20 carbon atoms, L is cyclopentadienyl group, indenyl group, fluorenyl group, or some of these hydrogen atoms has 1 to 20 carbon atoms (A group substituted with a group, a part of X and L bonded by a hydrocarbon group or a silyl hydrocarbon group, NR is an imide group, and R is a hydrocarbon group having 1 to 20 carbon atoms.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal of Group V of the periodic table represented by the formula (1) or (2) of the present invention is V, Ta, or Nb.
And the preferred metal is V 2. X is hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, or a hydrocarbon amino group having 1 to 20 carbon atoms. Specific examples of halogen include chlorine, bromine, and carbon. Examples of the hydrogen group include methyl group, benzyl group, neopentyl, hydrocarbon oxy group such as methoxy, ethoxy and isopropoxy, and amino group such as dimethylamino group, diethylamino group, diisopropylamino group and dioctylamino group.

L is a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a hydrogen atom thereof partially substituted with a hydrocarbon group having 1 to 20 carbon atoms, the substituent being a methyl group, Ethyl group, propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group,
Examples include a hydrocarbon group containing a silicon atom, such as a t-butyl group, a hexyl group, a phenyl group, a benzyl group, and a trimethylsilyl group. Furthermore, when the cyclopentadienyl ring is X
And those partially bonded to each other by a cross-linking group such as a Me ₂ Si group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group and a substituted ethylene group.

NR is an imide group, R is a hydrocarbon group having 1 to 25 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a sec-butyl group,
iso-butyl group, t-butyl group, hexyl group, octyl group,
Neopentyl group, phenyl group, benzyl group, methylphenylmethyl group, dimethylphenylmethyl group, naphthyl group, 2,6-dimethylphenyl group, 2,6-iso-propyl group, 3,
4-dimethylphenyl group and the like can be mentioned.

Cyclopentadienyl vanadium (methylimide) is a specific example of the Group V transition metal compound of the periodic table represented by the general formula of the formula (1) or (2) of the present invention.
Dichloride, cyclopentadienyl vanadium (phenylimide) dichloride, cyclopentadienyl vanadium (2,6-dimethylphenylimide) dichloride,
Cyclopentadienyl vanadium (2,6-diiso-propylphenylimide) dichloride, (methylcyclopentadienyl) vanadium (phenylimide) dichloride, (1,3-dimethylcyclopentadienyl) vanadium (phenylimide) dichloride , (1-methyl-3-butylcyclopentadienyl) vanadium (phenylimido) dichloride, (pentamethylcyclopentadienyl) vanadium (phenylimido) dichloride, indenylvanadium (phenylimido) dichloride, 2-
Methylindenyl vanadium (phenylimide) dichloride, fluorenyl vanadium (phenylimide) dichloride, dimethylsilyl (cyclopentadienyl)
(t-Butylamino) vanadium (phenylimide) chloride, dimethylsilyl (pentamethylcyclopentadienyl) (t-butylamino) vanadium (phenylimide) chloride, cyclopentadienyl vanadium (phenylimide) dimethoxide, cyclopentadiene Enilvanadium (phenylimide) diiso-propoxide,
Cyclopentadienyl vanadium (phenylimide) (i
so- propoxy) chloride, (cyclopentadienyl) (bisdiethylamino) vanadium (phenylimide), (cyclopentadienyl) (bisdiiso-propylamino) vanadium (phenylimide), vanadium (methylimide) trichloride, vanadium ( Phenylimide) trichloride, vanadium (phenylimide) trimethoxide, vanadium (phenylimide)
Dimethoxy chloride, vanadium (phenylimide)
Methoxy dichloride can be mentioned.

In the present invention, an olefin is combined with a group V transition metal compound represented by the formula (1) and an alumoxane or / and an ionic compound capable of reacting with the transition metal compound to form a cationic complex. Can be polymerized. Alumoxane in the present invention is a general formula (-Al
(R) O-) _m is a linear or cyclic polymer represented by (R is a hydrocarbon group having 1 to 10 carbon atoms, and some of which are partially substituted with a halogen atom and / or RO group. M is a degree of polymerization and is 5 or more, preferably 10 or more) is an organoaluminum oxy compound. Examples of R 1 include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable.

The ionic compound capable of reacting with a transition metal compound to form a cationic complex is a bulky, non-coordinating tetrakis (penta), which is well known as an anion in a transition metal group of Group IV metallocene catalyst system. Fluorophenyl)
Borates, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetraphenylborate, and aluminates thereof can be mentioned. On the other hand, examples of the cation include N, N- having an active proton such as (alkyl) ₂ N (C ₆ H ₅ ) H ^+.
Dialkylanilinium cation, trialkylammonium cation, triallylphosphonium cation, (C
₆ H ₅ ) ₃ C ⁺ trisubstituted carbonium cations, oxonium cations, sulfonium cations, carborane cations, metal carborane cations, ferrocenium cations having a transition metal, further main element metal, transition metal cations and Examples thereof include cations in which ethers, amines and the like are coordinated.

In the present invention, in addition, a metal hydride compound, an organometallic compound of a main element metal of Group I to III of the periodic table, an organometallic halogen compound, and a hydrogenated organometallic compound can be used in combination in the polymerization. . Examples of the metal hydride compound include NaH, LiH, CaH ₂ , LiAlH ₄ , and NaBH _4.
As the main element metal organometallic compound, for example, methyl lithium, butyl lithium, phenyl lithium, dibutyl magnesium, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum,
Examples of the organometallic halogen compound include ethyl magnesium chloride, butyl magnesium chloride,
Dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride,
Examples of ethyl aluminum dichloride and hydrogenated organometallic compounds include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In the present invention, a transition metal compound and / or
Alternatively, an ionic compound can be used by being supported on an inorganic compound or an organic polymer compound. JP 61-31404
No. 61, No. 61-276805, No. 61-108610, No. 61-296008
No. 63-501368, Japanese Unexamined Patent Publication No. 1-207303, Special Table 1-
No. 503715, No. 2-503687, JP-A No. 2-170805, Special Table No. 3-
No. 502210, and JP-A-3-234710 each describe a method of supporting a transition metal compound, or a transition metal compound and an organoaluminum oxy compound and / or an organoaluminum compound on a porous inorganic compound, Can be adopted.

As the inorganic compound as the carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be adopted. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia. These inorganic oxides have an average particle size of 5 to 15
Porous fine particles having a particle size of 0 μm and a specific surface area of 2 to 800 m ² / g are preferable, and can be used after being heat-treated at, for example, 100 to 800 ° C.

The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in its side chain. As specific examples, ethylene, propylene, α-olefin homopolymer having the functional group by chemical modification such as polybutene, α-olefin copolymer, acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, homopolymer such as divinylbenzene, Copolymers and their chemically modified products can be mentioned. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used. By carrying a transition metal compound and / or an ionic compound,
It is possible to prevent the catalyst from adhering to the polymerization reactor.

In the present invention, although not particularly limited,
With the above catalyst system, the conjugated diene can be polymerized by the following method. However, in the present invention, the polymerization of the conjugated diene also includes binary or terpolymerization with a small amount of a different olefin, conjugated diene, or non-conjugated diene.

Hydrocarbon or halogenated hydrocarbon solution [N] or slurry [M] of transition metal compound and aluminoxane and / or ionic compound hydrocarbon or halogenated hydrocarbon solution or slurry [I] are contacted in advance. After that, the conjugated diene is polymerized. [M] is contacted with the monomer in advance, and then [I] is contacted to carry out polymerization. [I] is contacted with the monomer in advance, and then [M] is contacted to carry out polymerization. After mixing a solution [N] of a hydrocarbon or a halogenated hydrocarbon of a transition metal compound and a solution [P] of a hydrocarbon or a halogenated hydrocarbon of an aluminoxane or / and an ionic compound, contact with a carrier and separate the carrier. Then, the monomers are brought into contact with each other to carry out polymerization. After the [N] and the carrier are brought into contact with each other, the [P] is brought into contact therewith, and the carrier is separated to polymerize the conjugated diene. After the [P] and the carrier are brought into contact with each other, the [N] is brought into contact therewith, and the carrier is separated to polymerize the conjugated diene.

As the hydrocarbon solvent for dissolving and slurrying each component, for example, an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, and a halogenated hydrocarbon solvent. Examples thereof include chloroform, methylene chloride, dichloroethane, chlorobenzene and the like.

In the above, the contact of each component is usually 0 to
Perform at 100 ° C for 10 to 180 minutes. The amount of each component used is such that the aluminoxane / transition metal compound molar ratio is usually 10 to 10,000, preferably 50 to 3000, and the ionic compound / transition metal compound molar ratio is usually 0.01 to 100, preferably 0.1 to 10. is there. Further, when the organometallic compound is shared, the molar ratio of the organometallic compound / transition metal compound is usually from 0.1 to 10,000.
, Preferably 1 to 1000. The molecular weight of the polymer can be controlled by hydrogenation, polymerization temperature, and catalyst concentration.

The polymerization according to the present invention can be carried out by a flow method using a supported catalyst, a stirring gas phase method, a slurry method in an inert hydrocarbon solvent, or a solution method in an inert hydrocarbon solvent. Can also be adopted. The polymerization conditions are usually a temperature of 5
It is carried out at a temperature of ~ 110 ° C, a time of 10 to 360 minutes, and a normal pressure of ~ 50 kg / cm ² .

Specific examples of the conjugated diene in the present invention include:
Butadiene, isoprene, 2,3-dimethylbutadiene, 1,
Examples thereof include 3-pentadiene, 2-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Specific examples of the olefin that can be used in the copolymerization with the conjugated diene in the present invention include ethylene, propylene and butene.
-1,4-methylpentene-1, hexene-1, octene-1, norbornene, cyclopentene, trimethylvinylsilane, non-conjugated diene such as dicyclopentadiene, 5-ethylidene-2-norbornene, or 1,5-hexadiene be able to.

[0026]

EXAMPLES In the examples, "polymerization activity" is the polymer yield (kg) per 1 mmol of transition metal of the transition metal compound catalyst used in the polymerization reaction. 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.

The microstructure was determined by infrared absorption spectrum analysis. Cis 740 cm ^-1 , transformer 980 cm ^-1 , vinyl
The microstructure was calculated from the absorption intensity ratio at 910 cm ^-1 .

Example 1 [Preparation of Transition Metal Compound A] Journal American Chemica
Vanadium (phenylimido) trichloride: VCl ₃ (NC ₆ H ₅ ) was prepared according to the synthetic method described in Society, 1987, Vol. 109, page 7408.

[Butadiene Polymerization] 10 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) was added as a toluene solution to 200 ml of toluene, and the solution was kept at 20 ° C. butadiene
100 ml was added, 10 μmol of the above transition metal compound (A) was added as a toluene solution, and polymerization was carried out for 1 hour. HC
Polymerization was stopped with a 1-containing ethanol solution, followed by filtration and drying to obtain a white butadiene polymer in a yield of 1.4 (kg / mmol.Mh). Micro structure is cis 45.8%, transformer 23.5%, vinyl
It was 30.7%.

Example 2 [Preparation of Transition Metal Compound B] Journal American Chemica
Cyclopentadienyl vanadium (phenylimido) dichloride: (C ₅ H ₅ ) VCl ₃ (NC ₆ H ₅ ) was prepared according to the synthetic method described in Society, 1987, Vol. 109, page 7408.

[Butadiene polymerization] To 200 ml of toluene, 10 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) was added as a toluene solution, and the solution was kept at 20 ° C. butadiene
100 ml was added, and 10 μmol of the above transition metal compound (B) was added as a toluene solution to carry out polymerization for 1 hour. HCl
Polymerization was stopped with the contained ethanol solution, filtered and dried to obtain a white butadiene polymer in a yield of 3.1 (kg / mmol.Mh). Micro structure is cis 87.6%, trans 4.0%, vinyl 8.
It was 4%.

Example 3 [Butadiene polymerization] To 200 ml of toluene, 2 mmol of triisobutylaluminum was added as a toluene solution, and the solution was added.
Keep at 20 ° C. After adding 100 ml of butadiene, (CH ₃ ) ₂ NH
20 μmol of (C ₆ H ₅ ) B (C ₆ F ₅ ) ₄ and the above transition metal compound (B)
10 μmol was added as a toluene solution and polymerization was carried out for 1 hour. Polymerization was stopped with an ethanol solution containing HCl, filtered, and dried to give 4.5 (kg / mmol.M.
Obtained in the yield of h). Micro structure is cis 88.4%, transformer 3.
They were 9% and 7.7% vinyl.

Comparative Example 1 To 200 ml of toluene, 10 mmol of methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) was added as a toluene solution, and the solution was added to 20 ml.
Keep at ° C. Add 100 ml of butadiene and dicyclopentadienyl vanadium dichloride: ((C ₅ H ₅ ) ₂ VCl ₂ ) 10 μmol
Was added as a toluene solution and polymerization was carried out for 1 hour.
Polymerization was stopped with an ethanol solution containing HCl, filtered and dried to obtain a white butadiene polymer in a yield of 0.13 (kg / mmol.Mh).

[0034]

INDUSTRIAL APPLICABILITY The present invention provides a novel catalyst system for producing a polymer having a controlled conjugated diene microstructure, which has a high polymerization activity, a narrow molecular weight distribution, and a narrow composition distribution in copolymerization. Therefore, a polymer having excellent mechanical properties can be obtained from this catalyst system.

Claims (1)

[Claims] 1. A cationic transition metal compound is produced by reacting a group V transition metal compound of the periodic table represented by formula (1) or formula (2) with an organoaluminum oxy compound or the transition metal compound in place of it. A catalyst for conjugated diene polymerization, which comprises a combination with a possible ionic compound. LMX ₂ (NR) (1) MX ₃ (NR) (2) (In the formula, M is a Group V transition metal, X is hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. Hydrocarbon oxy group, hydrocarbon amino group having 1 to 20 carbon atoms, L is cyclopentadienyl group, indenyl group, fluorenyl group, or some of hydrogen atoms thereof are substituted with hydrocarbon group having 1 to 20 carbon atoms Those having a part of X and L bonded by a hydrocarbon group or a silyl hydrocarbon group, NR is an imide group, and R is a hydrocarbon group having 1 to 20 carbon atoms.)