JPH08143617A - Production of polymerization catalyst and polyolefin - Google Patents

Abstract

PURPOSE: To obtain a polymerization catalyst preventing attachment of an olefin polymer onto a polymerization reactor and providing a polyolefin without removing of boron in the polymer by including a specific B-containing (co)polymer and a specific metallocene compound as principal components. CONSTITUTION: This catalyst contains (A) a B-containing (co)polymer containing a constitution unit expressed by formula I (R<1> -R<6> are each H or a 1-10C hydrocarbon, etc.; Y is a 1-10C alkylene, phenylene or silylene; (j) is 0 or 1; X<+> is a monovalent cation such as carbonium or anilinium) [a constitution unit expressed by formula II is especially preferable (R<14> -R<17> are each H or a halogen; X<+> is triphenylcarbonium, N,N-dimethylanilinium or trimethylammonium)] and (B) a metallocene compound wherein the central metal is a IV group element in the periodic table in a weight ratio of the components A:B=(1:1) to (1:0.001). Suitable example of the component B is different depending on the resin, for instance, to produce a PE, bis(cyclopentaphenyl)titanium dichloride, etc., and to produce an isotactic PP, ethylene bis(1-indenyl)zirconium dichloride, etc., are exemplified.

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 polyolefin, and more particularly to a method for producing a polyolefin using a metallocene catalyst.

[0002]

2. Description of the Related Art Group 4 element (T
It is well known that a metallocene compound having i, Zr, Hf) as a central metal has an olefin polymerization action,
The metallocene compound alone does not cause a polymerization reaction, and it has a polymerization activity only when it is combined with the following cocatalyst.

It has been reported that an organic aluminum halide compound (for example, Et ₂ AlCl) causes ethylene polymerization when combined with the above metallocene compound in a toluene solvent (Adv. Organometal).
lic Chemistry, Vol. 18, p130
(1980)), but the activity is extremely low.

It is also known that aluminoxanes, especially methylaluminoxane, also serve as a cocatalyst for metallocene compounds (Adv. Organometalli).
cChemistry Vol. 18 , p99 (198
0)) requires a large excess amount with respect to the metallocene compound, so that the activity per cocatalyst is extremely low. It has been studied to support this methylaluminoxane on a carrier (Japanese Patent Publication No. 6-39496, JP-A-61-10861).
0). However, this method has the disadvantage that methylaluminoxane is partially released from the carrier during the polymerization. Therefore, it is hard to say that methylaluminoxane is completely immobilized. Further, an attempt has been made to immobilize methylaluminoxane itself by treating it with a small amount of water to make it insoluble (JP-A-2-167302), but there is a problem that the activity per methylaluminoxane is further reduced.

In recent years, it has been found that a boron compound acts as a cocatalyst for a metallocene compound to cause ethylene polymerization.
Ordan et al. (J. Am.
Chem. Soc. , 109, p4111 (198
7)). The boron compound (tetraphenylborate) used by Jordan et al. Is more efficient than aluminoxanes because the ratio of the amount used to metallocene is close to 1, but its activity is low because hydrogen on the phenyl group is coordinating.

Since tetrakis (pentafluorophenyl) borate is a non-coordinating anion having no coordinating hydrogen in the molecule, it is known to have higher activity than the above tetraphenylborate (special feature). Kaihei 3-20
7703, 207704). Attempts have been made to immobilize this tetrakis (pentafluorophenyl) borate on a carrier to form a solid catalyst (JP-A-5-15592).
9, JP-A-3-234709), since it is originally non-coordinating, it is not sufficiently immobilized and is easily detached from the carrier. Further, since these boron compounds are toxic, they may flow out from the product polymer to the outside, resulting in poor hygiene.

If the cocatalyst component is not sufficiently immobilized, whether it is an aluminoxane type or a boron type, when a metallocene catalyst is applied to a continuous polymerization process for olefin polymerization (slurry process, gas phase process), the polymer Cause adhesion to the reactor. Therefore, there is a demand for a completely immobilized cocatalyst.

[0008]

PROBLEM TO BE SOLVED BY THE INVENTION The present invention provides a catalyst capable of preventing the adhesion of an olefin polymer to a polymerization reactor, and a polyolefin having excellent hygiene in which a boron compound is not released from the olefin polymer. .

[0009]

As a result of intensive studies to solve the above problems, the present inventors have synthesized a boron-containing compound having a carbon-carbon double bond incorporated in the molecule, and We succeeded in synthesizing a new boron-containing polymer by homopolymerization as a monomer or copolymerization with a suitable comonomer. Surprisingly, when this boron-containing polymer was used in combination with a metallocene compound for an olefin polymerization catalyst, it was found that, in a gas phase process or a slurry process, the polymer was not attached to the reactor at all, and the activity was not lost. The present invention has been completed by finding a method for producing a polyolefin in which boron in a polymer is not separated.

The boron-containing polymer (a) is a (co) polymer containing the structural unit represented by the general formula (1).

Embedded image In the formula (1), B means a boron atom and C means a carbon atom. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, silicon-containing hydrocarbon groups, or halogen-containing carbon atoms such as fluorine, chlorine, and bromine. It means a hydrogen group and may be the same or different. Y is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a silylene group. j is 0 or 1. X ⁺ represents a monovalent cation and means carbonium, anilinium, ammonium, ferrocenium, phosphonium, sodium, potassium, lithium and the like.

A more preferred structural unit structure is represented by the formula (2)
It is shown in.

Embedded image In the formula (2), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ mean a hydrogen atom or a halogen atom. R ¹¹ , R ¹² , and R ¹³ mean a hydrocarbon group having 1 to 10 carbon atoms or a halogen-containing hydrocarbon group. X + represents a monovalent cation and is preferably triphenylcarbonium, N, N-dimethylanilinium or trimethylammonium.

A more preferred structure of the structural unit is shown in formula (3).

[Chemical 4] In the formula (3), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen atoms or halogen atoms. X ⁺ means a monovalent cation, preferably triphenylcarbonium, N, N-dimethylanilinium or trimethylammonium.

The boron-containing polymer (a) contains the structural unit represented by the formula (1) in the polymer chain in an amount of 0.1 to 100% by weight, preferably 50 to 100% by weight. In addition to the structural unit represented by the formula (1), examples of the structural unit capable of existing in the polymer include the structural unit represented by the formula (4). Two or more kinds of these structural units may be present in the polymer.
The arrangement of these constituent units may be random, statistical, or block-like, and has stereoregularity such as isotactic, syndiotactic, atactic, and heterotactic. Good.

Embedded image Here, R ¹⁸ means a hydrocarbon group such as a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylsilyl group, or the like. Specifically, methyl group, ethyl group, 1-propyl group, 1-butyl group, phenyl group, p-methylphenyl group, vinyl group, ethenyl group, vinylmethyl group, p-vinylphenyl group, m-vinylphenyl group. A group etc. can be illustrated.

The structure and composition of the constituent units of the polymer are
It can be determined by measuring ¹ H-NMR, ¹³ C-NMR and ¹⁹ F-NMR.

As an example of the boron-containing polymer of the present invention, trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate is used as a boron-containing monomer and is represented by the general formula (5) obtained as a result of copolymerization with styrene. The calculation of the composition ratio can be illustrated by taking a polymer as an example, but the boron-containing polymer of the present invention is not limited thereto.

[Chemical 6]

Specific calculation method of monomer composition: A sample of NMR was prepared by dissolving 100 mg of the polymer of the present invention in dimethyl sulfoxide-d ₆ . ¹ H-N of this
An actual example of a signal obtained by measuring MR with TMS as a reference is shown in FIG. Δ derived from a boron-containing monomer and assigned to the methyl proton of trimethylammonium
The peak integrated value X of = 1.96 ppm is calculated. Further, δ = 5.2 to 6 derived from aromatic protons in the same spectrum.
The integrated value Y of the signal in the range of 5 ppm is obtained. From these values, m / n is calculated using the following formula. m / n = 1 / ((9X / 5Y) -0.8))

In addition to the method of calculating m / n using NMR, it is also possible to carry out elemental analysis of the polymer (carbon, hydrogen) and estimate it from the composition formula of each of the constituent monomers. The presence of the boron-containing monomer as a repeating unit constituting the polymer in the (co) polymer means that the (co) polymer purified by reprecipitation (described in the preceding paragraph) was measured by ¹⁹ F-NMR (C ₆ F). ₆ = -162.2 ppm in DMSO
-D ₆ standard). An example of the obtained spectrum is shown in FIG. δ = 128.1 (s, 2
F, o-F),-165.3 (s, 2F, m-F),-
161.5 (s, 1F, p-F), it can be seen that the way the signal splits is different from that measured with the boron-containing monomer alone. A spectrum of trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate is shown in FIG. 3 as a typical example of the boron-containing monomer. The attribution of each signal in this case is
_{(C 6 F 6 = -162.2ppm in} DMSO-d
₆ criteria) δ = 128.3 (d, 2F, o-F), -16
4.9 (t, 2F, m-F), -161.6 (t, 1
F, p-F). Here, the value of m / n is not particularly limited and may be 0, but is preferably 0.0001 to
The range is 100.

The weight average molecular weight (M
w) is 1,000 to 5,000,000, preferably 1,000 to 20,000. The molecular weight of the (co) polymer of the present invention is calculated as a polystyrene-equivalent molecular weight by gel permeation chromatography using universal calibration. The solvent used for the measurement was trichlorobenzene and the column temperature was 120.
RI was measured as a detector under conditions of 1 cc / min at a temperature of ℃. A suitable column is Showa Denko (AT-806MS).

Specific examples of the boron-containing polymer (a) can be shown as follows, but the invention is not limited thereto. For example, poly (N, N-dimethylanilinium tris (pentafluorophenyl) vinyl borate), poly (N, N-dimethylanilinium tris (pentafluorophenyl) vinylphenyl borate)
co-styrene), poly (N, N-dimethylanilinium allyltris (pentafluorophenyl) borate), poly (N, N-dimethylanilinium allyltris (pentafluorophenyl) borate-co-styrene), poly (N, N). -Dimethylanilinium tris (pentafluorophenyl) -4-vinylphenylborate), poly (N, N-dimethylanilinium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene), poly (N, N) -Diethylanilinium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene-co-divinylbenzene), poly (N, N-dimethylanilinium)
Tris (pentafluorophenyl) -4-vinylphenylborate-co-butadiene), poly (N, N-dimethylanilinium tris (pentafluorophenyl)
-4-vinylphenyl borate-co-isoprene),
Poly (methyldiphenylammonium tris (pentafluorophenyl) vinylborate), poly (methyldiphenylammonium tris (pentafluorophenyl) vinylphenylborate-co-styrene), poly (trimethylammonium allyltris (pentafluorophenyl) borate), poly ( Trimethylammonium allyl tris (pentafluorophenyl) borate-co-styrene), poly (trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate), poly (trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate) co-styrene), poly (trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate-co-su Ethylene-co-divinylbenzene), poly (triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate), poly (triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene ), Poly (triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene-co-divinylbenzene), poly (triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate-
co-hexene), poly (triphenylcarbonium)
Tris (pentafluorophenyl) vinylphenylborate), poly (triphenylcarbonium tris (pentafluorophenyl) vinylphenylborate-co
-Styrene), poly (triphenylcarbonium tris (pentafluorophenyl) vinylphenylborate-co-styrene-co-divinylbenzene), poly (triphenylcarbonium allyltris (pentafluorophenyl) borate), poly (triphenylcarbonitrile) Allyl tris (pentafluorophenyl) borate-co-styrene), poly (triphenylcarbonium allyl tris (pentafluorophenyl) borate-co-styrene-co-divinylbenzene), poly (ferrocenium tris (pentafluorophenyl) -4- Vinylphenyl borate), poly (ferrocenium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene), poly (ferrocenium tris (pentafluoro) (Rophenyl) -4-vinylphenyl borate-co-styrene-co-divinylbenzene).

The boron-containing polymer (a) according to the present invention may be combined with a carbon-carbon double bond-containing boron compound, a catalyst and optionally a suitable comonomer in a suitable solvent.
It can be obtained by homopolymerization or copolymerization at a temperature in the range of 100 to 200 ° C, preferably 30 to 100 ° C. Suitable solvents include n-hexane, n-pentane, n-heptane, n-octane, benzene, toluene, dichloromethane, 1,2-dichloroethane, chloroform, tetrachloroethane, bromobenzene, diethyl ether, tetrahydrofuran, 1,2- Examples thereof include dimethoxyethane, 1,4-dioxane, acetone, methylethyl, methanol, ethanol, t-butanol, isopropanol, acetonitrile and N, N-dimethylformamide. Preferred are acetonitrile, toluene and acetone.

As the catalyst, azobisisobutyronitrile, benzoyl peroxide, hydrogen peroxide, boron trifluoride
Diethyl ether complex, concentrated sulfuric acid, iodine, tin tetrachloride,
Perchloric acid, sodium, potassium, lithium, n-butyllithium, liquid ammonia can be mentioned. Further, a Ziegler-based catalyst or a metallocene catalyst can also be used. Preferred are azobisisobutyronitrile and benzoyl peroxide.

The boron compound having a carbon-carbon double bond incorporated in the molecule is represented by the general formula (6).

[Chemical 7] In formula (2), B means a boron atom and C means a carbon atom. R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group, or a halogen-containing carbon atom such as fluorine, chlorine, or bromine. It means a hydrogen group and may be the same or different. Y is an alkylene group having 0 to 10 carbon atoms, a phenylene group, or a silylene group. k is 0 or 1. X ⁺ means a monovalent cationic compound and means a cation such as carbonium, anilinium, ammonium, ferrocenium, phosphonium, sodium, lithium or potassium.

The structure of the boron compound of the present invention represented by the general formula (6) will be described in more detail. R ¹⁹ , R ²⁰ , R
²¹ is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably hydrogen. R ²² , R ²³ and R ²⁴ are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms or halogenated hydrocarbons, preferably phenyl group, pentafluorophenyl group, 2,4,6-trifluoromethylphenyl. Group, a 3,5-bistrifluoromethylphenyl group, and more preferably a pentafluorophenyl group. Y is an alkylene group having 1 to 6 carbon atoms, preferably a methylene group, ethylene group, propylene group, butylene group, p-phenylene group, m-phenylene group, o-phenylene group, and more preferably It is a p-phenylene group. k is 0 or 1. X ⁺ means a monovalent cation and means a cation such as carbonium anilinium, ammonium, ferrocenium, sodium, lithium and potassium, preferably a carbocation such as triphenylcarbonium, trimethylammonium and triethylammonium. , Tripropylammonium, N, N-dimethylanilinium, trialkylammonium such as triphenylammonium, ferrocenium, dimethylferrocenium. More preferably,
Trimethyl ammonium, triphenyl carbonium,
It is N, N-dimethylanilinium.

Specific boron compounds of the present invention can be exemplified as follows, but the invention is not limited thereto. For example, triphenyl carbonium tris (pentafluorophenyl) vinyl borate, triphenyl carbonium allyl tris (pentafluorophenyl) borate triphenyl carbonium tris (pentafluorophenyl) -2-vinylphenyl borate,
Triphenyl carbonium tris (pentafluorophenyl) -3-vinylphenyl borate, triphenyl carbonium tris (pentafluorophenyl) -4-
Vinylphenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) vinyl borate, N, N-diethylanilinium allyl tris (pentafluorophenyl) borate, N, N-dimethylanilinium tris (pentafluorophenyl) -4 −
Vinylphenyl borate, trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate, N, N-dimethylanilinium 4-allylphenyltris (pentafluorophenyl) borate,
N, N-dimethylanilinium triphenylvinylborate, N, N-dimethylanilinium bis (pentafluorophenyl) bis (4-vinylphenyl) borate, N, N-dimethylanilinium pentafluorophenyltris (4-vinylphenyl) ) Borate and sodium tris (pentafluorophenyl) vinyl borate can be exemplified.

In the synthesis of the boron-containing polymer (a), it is possible to copolymerize with a comonomer, but in this case, ethylene, propylene, 1-butene,
Examples include 1-pentene, 1-hexene, styrene, 4-methylstyrene, butadiene, 1,5-hexadiene, isoprene, 1,4-divinylbenzene, 1,3-divinylbenzene, and 1,2-divinylbenzene. it can. Preferred are styrene and 1,4-divinylbenzene.

The obtained boron-containing polymer can be purified by the reprecipitation method. Specifically, 3 g of the boron-containing polymer of the present invention is dissolved in 30 ml of acetone at room temperature, and then this is put into a large amount of hexane and reprecipitated. By repeating this operation, the unreacted monomer, which is the main impurity contained in the (co) polymer, can be removed.

The metallocene compound (b) used in the present invention is represented by the general formula (7). ^{_{[(Η 5 -C 5 R 24}} h) p R 26 s (η 5 -C 5 R 25 i)] MeQ 3-p and ^{[(R 24 N) R 26} s (η 5 -C 5 R 24 h) ] MeQ '---- (7) In formula (7), Me is group 3, 4 and 5 in the periodic table (inorganic chemical nomenclature 1990 rule), yttrium, scandium, lanthanide series element, It is selected from titanium, zirconium, hafnium, vanadium, niobium and tantalum. (Η ₅ −C ₅ R ²⁴ _h ), (η ₅ −C ₅ R ²⁵
_i ) is cyclopentadienyl or substituted cyclopentadienyl, and when h is 2 or more, R ²⁴ may be the same or different, and hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group , An aryl group, an alkylaryl group, an arylalkyl group, an alkylsilyl group, a silylalkyl group, or two adjacent carbon atoms may combine to form a ring. When i is a number of 2 or more, R ^{25 s} may be the same or different and each is hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group,
It may be an alkylaryl group, an arylalkyl group, an alkylsilyl group, a silylalkyl group, or two adjacent carbon atoms may combine to form a ring. R ²⁶ is an alkylene group having 1 to 4 carbon atoms, a dialkylgermylene group or an alkylsilylene group, and has a (η ₅ -C ₅ R ²⁴ _h ) ring and a (η ₅ -C ₅ R ²⁵ _i ) ring, or ( η ₅ −C ₅ R
²⁴ _h ) has the role of connecting the ring and (R ²⁴ N). Q is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. s means an integer of 0 or 1, p is 0 or 1, s is 0 when p is 0, h and i are 4 when s is 1, and 5 when s is 0.

The metallocene compound used preferably differs depending on the resin to be produced. For the production of polyethylene and ethylene-based copolymers, bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (n-butyl) Cyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) hafnium dimethyl, ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis Preference is given to (1-indenyl) zirconium dichloride, dimethylsilylenebis (1-indenyl) zirconium dimethyl, dimethylsilylenebis (benzoindenyl) zirconium dichloride. There.

For the production of isotactic polypropylene, ethylene bis (1-indenyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis (1-indenyl) zirconium dichloride are used. ,
Dimethyl silylene bis (1-indenyl) zirconium dimethyl, dimethyl silylene bis (benzoindenyl)
Zirconium dichloride, dimethyl silylene bis (2-
Methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl)
Zirconium dichloride, dimethyl silylene bis (2-
Methyl-4-isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, isopropylidene (3-t-butylcyclopentadienyl) (3
-T-butylindenyl) titanium dichloride, isopropylidene (3-t-butylcyclopentadienyl)
(3-t-Butylindenyl) zirconium dichloride and dimethylsilylene (3-t-butylcyclopentadienyl) fluorenylzirconium dichloride are preferable. Further, two or more kinds of the metallocene compounds shown here may be mixed and used.

Isopropylidene (cyclopentadienyl) fluorenyl zirconium dichloride is preferred for the production of syndiotactic polypropylene and cyclopentadienyl titanium trichloride is preferred for the production of syndiotactic polystyrene.

Although the above (a) and (b) are the main constituent components of the catalyst of the present invention, a carrier (c) and an organoaluminum compound (d) can be used in addition to this component. As the carrier component (c), alumina, silica,
Examples include magnesium chloride, calcium carbonate, polyethylene, polypropylene, polystyrene and the like. It is preferable that the carrier has a narrow particle size distribution.

As the organoaluminum compound (d),
Examples include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri (n-butyl) aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, diisobutyl aluminum chloride.
Regarding the catalyst components (a), (b) and (c), (d) shown in the present invention, the method of using these catalyst components is as follows: polymerization pre-contact method, pre-contact concentration, addition method to reactor, addition order Although not limited thereto, preferred methods can be exemplified.

Method for using catalyst component (A); Catalyst component (a)
And (b) are contacted in advance in an aromatic hydrocarbon, the solvent is removed, a poor solvent is added to form a slurry, and the slurry is introduced into the reactor. At this time, toluene is preferable as the aromatic solvent and n-hexane is preferable as the poor solvent. Further, the use ratio of (a) and (b) is a weight ratio of (a) :( b) = 1: 1 to
It is preferably used in the range of 1: 0.001.

Method for using catalyst component (B); catalyst component (a)
And (b) are pre-contacted in an aromatic hydrocarbon, the solvent is removed, a poor solvent is added to form a slurry, and the slurry is introduced into a reactor in which the organic aluminum (d) is present.
At this time, the amount of (d) used is (b) :( d) =
It is preferably used in the range of 1: 1 to 1: 1000.

Method for using catalyst component (C); catalyst component (b)
And (d) are pre-contacted with each other, then this is mixed with (a), and the following is the same operation as in (A), in which the catalyst is made into a slurry and then introduced into the reactor. The molar ratio of the components (b) and (d) at the time of pre-contact is preferably (b) :( d) = 1: 2 to 1:50.

Method for using catalyst component (D): A catalyst slurry was prepared from the components (b), (d) and (a) by the same method as the method (C), and then the reaction was carried out in the presence of the component (d). How to introduce into the vessel.

Prepolymerized olefins using the catalysts obtained from the above components (a) to (d) may be used as the catalyst. Examples of the olefin prepolymerized at this time include ethylene, propylene, and styrene.

Olefin monomers polymerizable with the catalyst of the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, butadiene, 1,5-hexadiene, 1,9. -Decadien, styrene, divinylbenzene, methylstyrene, chlorostyrene and the like can be exemplified. It is also possible to copolymerize using a mixture of these monomers in an arbitrary ratio. When polymerizing a polyolefin using the catalyst of the present invention, it is possible to use hydrogen as a chain transfer agent (molecular weight modifier).

The catalyst produced by using the catalyst components (a) and (b) (optionally adding (c) and (d)) can be used in a slurry process or a gas phase process. For example, in the slurry process, propane, butane, isobutane, pentane, as a solvent used for the polymerization,
Hydrocarbons such as isopentane, hexane and cyclohexane can be used. Butane and isobutane are preferred. The organoaluminum compound (d) may be used in these solvents, and in this case, the amount of the organoaluminum is preferably 1 to 5 mmol. When ethylene is used as a monomer, the ethylene partial pressure is 0.1 to 20.
The range of kg / cm ² is preferred. Polymerization temperature is 50 to 90
C. is preferable, and more preferably 60 to 80.degree.

In the gas phase process, organoaluminum (d) may be used in the gas phase, in which case the concentration of organoaluminum in the reaction system is from 50 to 500 ppm, preferably 1
It is 50 to 400 ppm. When ethylene is used as a monomer, the ethylene partial pressure is 0.1 to 20 kg / cm
A range of ² is preferred. The polymerization temperature is preferably 50 to 90 ° C, more preferably 60 to 80 ° C.

[0041]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The synthesis operation was performed under a nitrogen atmosphere as needed. The instruments used for the analysis were nuclear magnetic resonance spectrum (EX-400 manufactured by JEOL Ltd.), GPC (Water).
s-150C), elemental analyzer (Heraens CH)
N-O-RAPID).

Example 1 [Synthesis of poly (trimethylammonium tris (pentafluorophenyl) -4-vinylborate-co-styrene) (9:91 mol%)] Trimethylammonium tris (pentafluorophenyl) -in a 20 ml glass ampoule. 4-Vinyl borate (1.35 g; 2.
0 mmol), purified styrene (2.29 ml; 20 mm)
ol), azobisisobutyronitrile (0.109 g)
Then, acetonitrile (3.4 ml) was charged, and after sufficiently degassing, the tube was sealed and heated at 80 ° C. for 20 hours with stirring. After completion of the reaction, the content of the ampoule was dissolved in acetone, reprecipitated with hexane and dried under reduced pressure to obtain a white solid. This solid was found to be poly (trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene) from ¹ H- and ¹⁹ F-NMR spectra.
It turned out to be. The comonomer composition ratio was determined from elemental analysis values and ¹ H-NMR integrated values. Both values were in agreement. The molecular weight and elemental analysis values are shown below. <Yield> 1.18 g (34%) <Molecular weight>Mn; 3700 Mw; 6700 <Elemental analysis value> C (%) H (%) N (%) <Calculated value> 76.26 5.70 0.82 < Measured value> 76.94 6.05 1.13

Examples 2 to 10 Trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate (1) or triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate (2) as the monomer (A) A boron-containing polymer was synthesized in the same manner as in Example 1, except that styrene was used as the monomer (B) and the composition of the charged monomers was changed. Table 1 shows the reaction conditions and yields, and Table 2 shows the monomer composition ratio (m / n molar ratio) and molecular weight of the product.

Comparative Example 1 The same operation as in Example 1 was carried out except that trimethylammonium tetrakis (pentafluorophenyl) borate was used instead of trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate in Example 1. Radical copolymerization with styrene was performed. As a result of analyzing the obtained polymer, it was a simple polystyrene and contained no borate.

Example 11 [Preparation of solid catalyst] Cp ₂ ZrCl ₂ (0.277 g)
Triisobutylaluminum (TIB
2.0 ml of a toluene solution (0.5 mol / l) of A)
In addition, a Cp ₂ ZrCl ₂ / TIBA mixed toluene solution (0.0316 mmol / ml) was prepared. Example 1
Poly (trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate-co-styrene) synthesized in (9:91 mol%) (0.103
g) was dissolved in 10 ml of toluene. The number of moles of borate contained in this copolymer can be calculated from the monomer composition ratio and was 60 μmol. 1.72 ml (5) of the Cp ₂ ZrCl ₂ / TIBA mixed toluene solution (0.0316 mmol / ml) previously prepared was added to this solution.
4.4 μmol) was added. After stirring at room temperature for 1 hour as it was, toluene was distilled off under reduced pressure to obtain a white solid.
This solid was thoroughly washed with n-hexane and dried under reduced pressure to prepare a solid catalyst (0.115 g).

Example 12 Instead of poly (trimethylammonium tris (pentafluorophenyl) -4-vinylborate (9:91 mol%) in Example 11, the boron-containing polymer synthesized in Example 2 (17:83 mol%) ) (0.053
1 g) (number of moles of borate; 44 μmol), Cp ₂ Z
rCl ₂ / TIBA mixed toluene solution (0.0316 m
mol / ml) was 1.28 ml (40.4 μmol), but the solid catalyst (0.
0616g) was prepared.

Example 13 Instead of poly (trimethylammonium tris (pentafluorophenyl) -4-vinylborate (9:91 mol%) in Example 11, the boron-containing polymer synthesized in Example 3 (5:95 mol%) ) (0.126
g) (number of moles of borate; 47.5 μmol), Cp ₂
ZrCl ₂ / TIBA mixed toluene solution (0.0316
mmol / ml) to 1.31 ml (41.5 μmol)
A solid catalyst (0.135 g) was prepared in the same manner as in Example 11 except that the solid catalyst was used.

Example 14 Instead of Cp ₂ ZrCl _{2 in} Example 11, Me ₂ Si
[Ind] ₂ ZrCl ₂ (0.0180 g; 40.0 μ)
mol), poly (trimethylammonium tris (pentafluorophenyl) borate-co-styrene)
A solid catalyst (0.0915 g) was prepared in the same manner as in Example 11 except that (9:91 mol%) (0.076 g) (mol number of borate; 44 μmol) was used.

[Production of high-density polyethylene, linear low-density polyethylene and polypropylene using the above solid catalyst] Example 15 [Production of high-density polyethylene] TIBA (4.0 mmol) and isobutane (800 m in a 1.5 l autoclave)
1) was charged, the temperature was raised to 70 ° C., and the total amount of the solid catalyst (0.115 g) prepared in Example 11 was made into n-hexane slurry and introduced from a catalyst adder. Then ethylene 10
When kg / cm ² was supplied and polymerization was performed for 30 minutes,
120 g of polymer was obtained. Further, at this time, no adhesion of polymer to the reactor was observed.

Example 16 Polymerization of ethylene was carried out in the same manner as in Example 15 except that the solid catalyst (0.0616 g) prepared in Example 12 was used as the catalyst in Example 15, resulting in 55 g of polymer. was gotten. Further, at this time, no adhesion of polymer to the reactor was observed.

Example 17 Polymerization of ethylene was carried out in the same manner as in Example 15 except that the solid catalyst (0.135 g) prepared in Example 13 was used as the catalyst in Example 15, resulting in 28 g of polymer. was gotten. Further, at this time, no adhesion of polymer to the reactor was observed.

Comparative Example 2 Cp ₂ Zr was used as a catalyst instead of the solid catalyst in Example 15.
Cl ₂ (0.292 mg; 1.0 μmol), TIBA
(1.5 mmol), “C ₆ H ₅ NHMe ₂ ] [B (C
A mixed toluene solution of ₆ F ₅ ) ₄ ] (1.202 mg; 1.5 μmol) was charged in a catalyst adder, and ethylene was polymerized in the same manner as in Example 15 to obtain 100 g of a polymer. . In this polymerization, the polymer was remarkably attached to the reactor.

Example 18 [Production of linear low density polyethylene] TIBA (4.0 mmol) and isobutane (80
0 ml) and 1-hexene (15 g) were charged, the temperature was raised to 70 ° C., and the total amount of the solid catalyst (0.115 g) prepared in exactly the same manner as in Example 11 was made into n-hexane slurry, which was then added from the catalyst adder. Introduced. Then 10 kg of ethylene
/ Cm ² was supplied and polymerization was carried out for 30 minutes.
0 g of polymer was obtained. Further, at this time, no adhesion of polymer to the reactor was observed.

Example 19 [Production of polypropylene] T was added to a 1.5 l autoclave.
IBA (4.0 mmol), propylene (8.0 mo
1) was charged and the temperature was raised to 50 ° C., and then the total amount of the solid catalyst prepared in Example 14 (0.0915 g) was introduced as an n-hexane slurry by using a catalyst adder and polymerized for 30 minutes. Was obtained. At this time, no adhesion of polymer to the reactor was observed.

Comparative Example 3 In Example 15, instead of the solid catalyst, Me ₂ Si [Ind] was used.
₂ ZrCl ₂ (0.449 mg; 1.0 μmol), T
IBA (1.5mmol), "C ₆ H ₅ NHMe2]
[B (C ₆ F ₅ ) ₄ ] (1.202 mg; 1.5 μmo
When propylene was polymerized in the same manner as in Example 15 except that the mixed toluene solution of l) was used, 80 g of a polymer was obtained. In this polymerization, the polymer was strongly attached to the reactor.

Example 20 The high-density polyethylene containing the boron-containing polymer obtained in Example 15 was extracted with cyclohexane for 8 hours, and the trace amount of the extract recovered from the extraction solvent was subjected to elemental analysis. Was not detected at all.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

By using the catalyst of the present invention for olefin polymerization, it is possible to prevent the olefin polymer from adhering to the polymerization reactor. In addition, a polyolefin having excellent hygiene and free of a boron compound from the olefin polymer can be obtained.

[Brief description of drawings]

FIG. 1 is an example of a ¹ H-NMR spectrum diagram of a boron-containing polymer of the present invention.

FIG. 2 is an example of a ¹⁹ F-NMR spectrum diagram of the boron-containing polymer of the present invention.

FIG. 3 ¹⁹ F-NM of boron-containing compound monomer of the present invention
It is an example of an R spectrum diagram.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (2)

[Claims] 1. A boron-containing polymer (a) containing a structural unit represented by the general formula (1): [B means a boron atom and C means a carbon atom. R ¹ , R
² , R ³ , R ⁴ , R ⁵ , and R ⁶ represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group, or a halogen-containing hydrocarbon group such as fluorine, chlorine, or bromine. However, they may be the same as or different from each other. Y is an alkylene group having 1 to 10 carbon atoms, a phenylene group, or
It is a silylene group. j is 0 or 1. X ⁺ represents a monovalent cation and means carbonium, anilinium, ammonium, ferrocenium, phosphonium, sodium, potassium, lithium and the like. ] And a metallocene compound (b) whose central metal is an element of Group 4 of the Periodic Table (according to the 1990 rules of inorganic chemistry). 2. A method for producing a polyolefin, which comprises using the polymerization catalyst according to claim 1.