JP2001026613A - Catalyst for olefin polymerization and olefin polymerizing process using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such a catalyst powder for olefin polymerization as having high fluidity and bulk density and also good adsorptivity and to provide a polymerizing process for an olefin polymer with the excellent particular properties of good adhesion and bulk density. SOLUTION: An olefin polymerization catalyst is obtained by a process comprising a preliminary polymerization which brings an olefin into contact with catalyst components containing component A: a transition metal compound and component B: fine particular carrier, and if necessary component C: an organic aluminum compound and/or component D: an organic aluminum oxycompound, a Lewis acid or an ionic compound convertible to a cation by reaction with the component A, and which is characterized in that a contacting temperature for the catalyst components with the olefin is made to change with time by means of the temperature up and/or the temperature down during the process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for olefin polymerization using the same. More specifically, the present invention relates to an olefin polymerization catalyst capable of polymerizing a polymer having excellent particle properties such as fluidity and adhesion with high polymerization activity, and a method for polymerizing an olefin using the catalyst.

[0002]

2. Description of the Related Art There have been many methods for producing an olefin polymer using a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a catalyst comprising a metallocene compound, a carrier, and an organoaluminum compound. Proposals have been made (JP-A-63-152600, JP-A-63-280703).
No., JP-A-2-84407, JP-A-3-234710, JP-A-4-870
No. 4, JP-A-4-11604, JP-A-5-140224, JP-A-5-15
No. 5930, JP-A-5-170823).

However, according to the methods proposed in these publications, the polymerization activity per solid catalyst component is not always sufficient, and the bulk density of the obtained olefin polymer is low, so that fine powders and the like are generated and particles are generated. The properties are not enough.

On the other hand, techniques which do not use organoaluminum compounds such as expensive alumoxane are represented by organic boron compounds such as Lewis acid represented by tris (pentafluorophenyl) borane and carboranetetrakis (pentafluorophenyl) borate. Catalysts using an anionic compound or the like, or using an organic boron compound and a trialkylaluminum in the coexistence have been proposed (Japanese Patent Laid-Open Nos. 1-501950, 1-502036, and JP-A-3-502036).
179055, JP-A-3-207703, JP-A-3-207704). In addition, a method of reducing the amount of alumoxane used by using alumoxane and a boron compound coexistently has been proposed (Japanese Patent Application Laid-Open No. 5-295021).

However, in the polymerization using these catalyst systems,
Because the primary particle system of the metallocene compound is extremely small,
In addition to the extremely small particle size of the produced polymer, it is difficult to handle the polymer, and fine polymer particles tend to adhere to the inner wall of the polymerization tank, making it difficult to stably produce a polymerization system. Also, a method of prepolymerizing an olefin using a clay, a clay mineral or an ion-exchangeable layered compound as a carrier has been proposed (JP-A-5-295022, JP-A 5-5-2022).
301917, JP-A-7-309906, JP-A-10-168109, JP-A-10-168111), although the polymerization activity is improved,
When the catalyst is handled as a powder, it is not always satisfactory in terms of fluidity and adhesion in a manufacturing apparatus.

An olefin polymer which has high flowability and bulk density and does not cause a problem of adhesion to a catalyst manufacturing apparatus or a polymerization reactor (has good adhesion), and has excellent particle properties. There has been a long-awaited demand for the development of a catalyst capable of producing methane.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to an olefin polymerization catalyst powder having high flowability and bulk density and good adhesion, and an olefin polymer having good adhesion and high bulk density and excellent particle properties. An object of the present invention is to provide a method for polymerization of coalescence.

[0008]

SUMMARY OF THE INVENTION The present invention has been found as a result of intensive studies to solve the problems of the prior art as described above.

That is, according to the present invention, a catalyst component containing the following components (A) and (B) and, if necessary, components (C) and / or (D) is brought into contact with an olefin to carry out prepolymerization. An olefin polymerization catalyst obtained by performing the pre-polymerization, wherein the preliminary polymerization includes a temperature control step of changing the contact temperature of the catalyst component and the olefin with time, providing an olefin polymerization catalyst. I do. Component (A): Group 4 to 6 transition metal compound having a conjugated five-membered ring ligand Component (B): fine particle carrier Component (C): organoaluminum compound Component (D): organoaluminum oxy compound, Lewis acid, and At least one compound selected from the group consisting of ionic compounds capable of converting component (A) into a cation by reacting with component (A)

The present invention also provides the olefin polymerization catalyst, wherein the temperature control step includes a step of raising the temperature from a low temperature stage to a high temperature stage and / or a step of lowering the temperature from a high temperature stage to a low temperature stage.

Further, the present invention provides the olefin polymerization catalyst, wherein the temperature control step comprises a step of raising a temperature from a low temperature stage to a high temperature stage. Further, the present invention provides the olefin polymerization catalyst, wherein the temperature control step comprises a temperature raising step from a low temperature stage to a high temperature stage and a temperature lowering step from a high temperature stage to a low temperature stage.

Further, the present invention provides the olefin polymerization catalyst, wherein a difference between a maximum temperature and a minimum temperature in the temperature control step is 1 to 150 ° C. Also, the present invention
The present invention provides the olefin polymerization catalyst, wherein the component (B) is an ion-exchange layered silicate.

[0013] The present invention also provides the catalyst for olefin polymerization, wherein the component (B) is an ion-exchangeable layered silicate treated in the presence of an acid and / or a salt. I do.

[0014] The present invention also provides the olefin polymerization catalyst, wherein the component (B) is an ion-exchanged layered silicate treated in the presence of an acid. Further, the present invention is characterized in that the component (C) is a compound represented by the following general formula (I),
The catalyst for olefin polymerization is provided.

[0015]

(AlR ⁴ _n X _3-n ) _m (I)

(In the formula (I), R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, a halogen, or an alkoxy group. N represents a number satisfying 0 <n ≦ 3; Represents an integer of 1 to 2.)

The present invention also provides a method for polymerizing olefins, comprising homopolymerizing or copolymerizing an olefin having 2 or more carbon atoms in the presence of any one of the above catalysts for olefin polymerization.

The present invention also provides a method for polymerizing olefins, comprising homopolymerizing or copolymerizing an olefin having 2 or more carbon atoms in the presence of any one of the above catalysts for olefin polymerization and an organoaluminum compound. I do.

The present invention is characterized in that in the olefin polymerization catalyst described above, the contact temperature between the olefin and the catalyst component is changed over time in two or more stages during the prepolymerization. This means that the prepolymerization rate is changed over time.

When performing the prepolymerization, even if the amount of the polymer per 1 g of the component (B) was the same, the prepolymerization rate was changed with time as compared with the case where the prepolymerization rate was constant. It is possible to control the morphology of the catalyst particles, not only to obtain a catalyst powder having high flowability and bulk density and good adhesion, but also to produce an olefin polymer having excellent particle properties. . The prepolymerization rate may be reduced or increased with time, or a combination thereof, as long as the improvement effect is recognized.

[0021]

Embodiments of the present invention will be described below. The olefin polymerization catalyst of the present invention is obtained by bringing a catalyst component containing the following components (A) and (B) into contact with an olefin to perform prepolymerization. In the description of the present invention, “including”, “consisting of”, and “combining” mean compounds and / or compounds other than the listed compounds or components as long as the effects of the present invention are not impaired. It means that components can be used in combination. The term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" is used to include not only homopolymers but also copolymers.

(1) Component (A) Component (A) used in the present invention has the following general formula (I):
It is a compound represented by (II) or (III).

[0023]

## STR3 ## _{(C 5 H 5-a R} 1 a) (C 5 H 5-b R 2 b) MXY ··· (I) Q (C 5 H 5-c R 1 c) (C 5 H 5 ^{_{-d R 2 d) MXY ··· (}} II) Q '(C 5 H 5-e R 3 e) ZMXY ··· (III)

Here, Q represents a binding group bridging two conjugated five-membered ring ligands. Q ′ represents a binding group that bridges the conjugated 5-membered ring ligand with the Z group. M represents a transition metal of Groups 4 to 6 of the periodic table. X and Y are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms,
An oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms. Z is oxygen,
Sulfur, alkoxy group having 1 to 20 carbon atoms, 1 to 4 carbon atoms
0 represents a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms.

R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a carbon group having 1 to 2 carbon atoms.
0 represents a halogen-containing hydrocarbon group, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. Examples of the hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group include methyl, ethyl, propyl,
Butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl,
Chloromethyl, chloroethyl and the like. Examples of the halogen group include fluorine, chlorine, bromine and iodine. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy groups. Examples of the aryloxy group include a phenoxy, methylphenoxy, and pentamethylphenoxy group. Examples of the silicon-containing hydrocarbon group include trimethylsilyl, triethylsilyl, and triphenylsilyl groups.
When a plurality of R ¹ , R ² and R ³ are present, they may be the same or different.

Also, two R ¹ , two R ² or two R ^{2
When 3} is present at adjacent carbon atoms of the cyclopentadienyl ring, they may be mutually bonded to form a C ₄ -C ₁₀ ring, and specifically, indenyl, tetrahydroindenyl, fluorenyl, It may form an otatahydrofluorenyl, azulenyl, hexahydroazulenyl group or the like.

A, b, c, d and e are each 0 ≦ a
≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 0 ≦ e ≦
An integer that satisfies 4. The bonding group Q bridging between the two conjugated five-membered ring ligands and the bonding group Q ′ bridging between the conjugated five-membered ring ligand and the Z group are specifically as follows: Things. That is, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group , Diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group,
A silicon-containing crosslinking group such as a disilylene group and a tetramethyldisilylene group; a germanium-containing crosslinking group; an alkylphosphine; an amine; Among these, an alkylene group, an alkylidene group and a silicon-containing cross-linking group are particularly preferably used.

M is a transition metal belonging to Group 4 to 6 of the periodic table, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten. Preferred are titanium, zirconium and hafnium, and particularly preferred are titanium and zirconium.

Z represents oxygen (-O-), sulfur (-S
-), An alkoxy group having 1 to 20, preferably 1 to 10 carbon atoms, a thioalkoxy group having 1 to 20, preferably 1 to 12 carbon atoms, silicon containing 1 to 40 carbon atoms, preferably 1 to 18 silicon atoms Hydrocarbon group, 1 to 40 carbon atoms, preferably 1 to 1
A nitrogen-containing hydrocarbon group of 8 and a phosphorus-containing hydrocarbon group having 1 to 40, preferably 1 to 18 carbon atoms, wherein a part of the Z group is bonded to a Q ′ group which is a bonding group. .

X and Y each represent hydrogen, a halogen group,
C1-20, preferably C1-10 hydrocarbon group, C1-20, preferably C1-10 alkoxy group, alkylamide group, C1-20, preferably 1-12
A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1
To 12 silicon-containing hydrocarbon groups. X and Y may be the same or different. Of these, a halogen group, a hydrocarbon group and an alkylamide group are preferred.

In the above general formula, (C ₅ H _5-a R
^{_{1 a), (C 5 H}} 5-b R 2 b), (C 5 H 5 -c R 1 c), (C 5 H
_5-d R ² _d), and (conjugated five-membered ring ligands represented by ^{_{C 5 H 5-e R 3}} e) may be the same or different from each other, respectively.

The component (A) of the present invention may be a mixture of the compounds represented by the general formulas (I), (II) and (III). Further, it can be used together with a known solid catalyst containing titanium trichloride as a main component or a carrier-supported catalyst containing magnesium, titanium and halogen as essential components.

(2) Component (B) Component (B) of the present catalyst is a fine particle carrier. The fine particle carrier may be either an organic compound or an inorganic compound. As the organic compound carrier, (1) carbon number 2
10 to 10 α-olefin polymers, for example, polyethylene,
(2) aromatic unsaturated hydrocarbon polymers such as polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-hexene-1 copolymer, propylene-divinylbenzene copolymer, for example, polystyrene, styrene-divinylbenzene Copolymers, and (3) a polar group-containing polymer,
For example, polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl chloride, polyamide, polyphenylene ether, polyethylene terephthalate, polycarbonate and the like are exemplified.

As the inorganic compound carrier, (1) inorganic oxide
Object, eg SiO₂, Al₂O₃, MgO, ZrO₂,
TiO₂, B₂O₃, CaO, ZnO, BaO, ThO
₂, SiO₂-MgO, SiO₂-Al₂O₃, SiO
₂-TiO₂, SiO₂-V₂O₅, SiO₂-CrO
₃, SiO₂-TiO₂-(2) inorganic halogen such as MgO
Compounds such as MgCl₂, AlCl₃, MnCl
₂(3) inorganic carbonates, sulfates, nitrates such as Na
₂(SO₄)₃, BaSO₄, KNO₃, Mg (N
O ₃)₂(4) oxides, such as Mg (OH)₂, Al
(OH)₃, Ca (OH) ₂(5) Inorganic silicate, for example
Clay, clay minerals, zeolites, diatomaceous earth, etc.
You. These inorganic silicates may be synthetic products,
Naturally occurring minerals may be used. Clay, clay mineral
Specific examples include allophane, such as allophane,
Kite, nacrite, kaolinite, anoxite, etc.
Kaolin, metahaloysite, halloysite, etc.
Leucite, chrysotile, lizardite, antigo
Serpentine tribes such as lights, montmorillonite, zaukonai
, Beidellite, nontronite, saponite, hex
Bars such as smectites such as trite and vermiculite
Miculite mineral, illite, sericite, chlorite, etc.
Mica mineral, attapulgite, sepiolite, paigol
Skeite, bentonite, Kibushi clay, Gairome clay, hin
Singelite, pyrophyllite, ryokudeite, etc.
Can be These may form a mixed layer.

As the inorganic compound carrier, (6)
Ion-exchangeable layered compounds other than silicates
it can. Such ion-exchange layered compounds include hexagonal
Close packing type, antimony type, CdCl₂Type, Cd
I₂Ionic crystalline compound having a layered crystal structure such as type
And the like. Ion exchange having such a crystal structure
Specific examples of the exchangeable layered compound include α-Zr (HAsO
₄)₂・ H₂O, α-Zr (HPO₄)₂, Α-Zr
(KPO₄)₂・ 3H₂O, α-Ti (HPO₄)₂,
α-Ti (HAsO₄)₂・ H₂O, α-Sn (HPO
₄)₂・ H₂O, γ-Zr (HPO₄)₂, Γ-Ti
(HPO₄)₂, Γ-Ti (NH₄PO₄) ₂・ H₂O
And crystalline acid salts of polyvalent metals.

These ion-exchange layered compounds may be used as they are, but may be subjected to an acid treatment with hydrochloric acid, nitric acid, sulfuric acid or the like.
And / or LiCl, NaCl, KCl, CaC
l ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , Ti (S
Those which have been subjected to salt treatment with O ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ or the like are preferable.

The component (B) may be subjected to shape control such as pulverization and granulation. In order to obtain an olefin polymer having excellent particle properties, granulation is preferably performed, and more preferably granulation is performed so as to have an average particle diameter of about 0.1 to 1000 μm.

When a compound having a radius of not less than 20 angstroms and a pore volume of less than 0.1 cc / g measured by a mercury intrusion method is used as component (B), high polymerization activity tends to be difficult to obtain. So, more than 0.1cc / g,
In particular, those having 0.3 to 5 cc / g are preferable. The spherical particles obtained as described above preferably have a compressive breaking strength of 0.2 MPa or more in order to suppress crushing and fine powder in the polymerization step. Particularly in the case of such a particle strength, a particle property improving effect is effectively exhibited.

The component (B) of the present invention is preferably an ion-exchange layered silicate, and more preferably an ion-exchange layered silicate treated in the presence of an acid and / or a salt. Preferred are ion-exchanged layered silicates that have been treated in the presence of an acid.

(3) Component (C) The catalyst component used in the present invention may contain component (C) and / or component (D) as necessary. Among them, the component (C) is an organoaluminum compound.
As the organoaluminum compound used as the component (C) in the present invention, a compound represented by the following general formula (I) is preferable.

[0041]

Embedded image (AlR ⁴ _n X _3-n ) _m (I)

In the above formula, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group or an amino group. n is from 1 to 3, m is from 1 to
It is an integer up to 2.

R ⁴ is preferably an alkyl group. X is preferably chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and an amino group having 1 to 8 carbon atoms when it is an amino group. Therefore,
Specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal decyl aluminum, diethyl aluminum chloride, diethyl aluminum sesquialuminum Chloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, preferred are m = 1, n = 3 trialkylaluminum and dialkylaluminum hydride. More preferably, R ⁴ is a trialkyl aluminum having 1 to 8 carbon atoms.

In the present invention, the compounds represented by the above formula (I) can be used alone, in combination of two or more or in combination. The use of the component (C) is possible not only at the time of preparing the catalyst but also at the time of polymerization.

(4) Component (D) The component (D) is at least selected from an organic aluminum oxy compound, a Lewis acid, and an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation. It is a kind of compound.

A representative example of the organic aluminum oxy compound is alumoxane. Alumoxanes are products obtained by the reaction of one trialkylaluminum or two trialkylaluminums with water. Specifically, methylalumoxane obtained from one type of trialkylaluminum, ethylalumoxane,
Butylalumoxane, isobutylalumoxane and the like, and methylethylalumoxane, methylbutylalumoxane obtained from two kinds of trialkylaluminum and water,
Methyl isobutylalumoxane and the like are exemplified. Also,
It is also possible to use a modified alumoxane by reacting two kinds of alumoxanes or one kind of alumoxane with another organoaluminum compound.

Preferred among these are those selected from the group consisting of methylalumoxane, isobutylalumoxane, hexaisobutylalumoxane, methylisobutylalumoxane, mixtures thereof, and mixtures of alumoxane and trialkylalumoxane. is there. Particularly preferred are methylalumoxane, methylisobutylalumoxane, or hexaisobutylalumoxane.

Another example of the organoaluminum oxy compound is a reaction product of an organoaluminum compound and an alkylboronic acid. Here, the alkylboronic acid is a compound represented by the general formula [R ⁵ B (OH) ₂ ], wherein R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or Shows a halogen-containing hydrocarbon group having 1 to 10 carbon atoms. More preferred examples of the reaction product include:
Examples of the reactant include one or more trialkylaluminums and the alkylboronic acid in a ratio of 10: 1 to 1: 1 (molar ratio). Specifically, (a) a 2: 1 reaction product of trimethylaluminum and methylboronic acid,
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid, (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid, (d) 2: 1 reaction of trimethylaluminum and ethylboronic acid And (e) a 2: 1 reaction product of triethylaluminum and butylboronic acid.

Certain Lewis acids can be regarded as "ionic compounds capable of converting component (A) into cations by reacting with component (A)". Therefore, a compound belonging to both the “Lewis acid” and the “ionic compound capable of converting the component (A) into a cation by reacting with the component (A)” belongs to either one.

Examples of the ionic compound capable of converting the component (A) into a cation by reacting with the component (A) include those represented by the following general formula (II).

[0051]

[K] ^{e +} [Z] ^e -... (II)

Here, K is an ionic cation component, for example, a carbonium cation, a tropylium cation, an aluminium cation, an oxonium cation,
Examples include a sulfonium cation and a phosphonium cation. In addition, cations of metals which are easily reduced by themselves, cations of organic metals, and the like can also be mentioned. Specific examples of these cations include (a) triphenylcarbenium, diphenylcarbenium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N
-Dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium , Pyrylium,
And (mouth) silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion and the like.

On the other hand, Z is an ionic anion component, which is a component (generally non-coordinating) which is a counter anion to component (A) or the converted cation species. Compound anions, organic aluminum compound anions, organic gallium compound anions, organic phosphorus compound anions, organic arsenic compound anions, organic antimony compound anions, and the like. In particular,
(A) tetraphenylboron, tetrakis (3,4,5
-Trifluorophenyl) boron, tetrakis @ 3,5
-Di (perfluoromethyl) phenyl) boron, tetrakis (perfluorophenyl) boron, (ii) tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis {3,5
-Di (perfluoromethyl) phenyl @ aluminum,
Tetrakis {3,5-di (t-butyl) phenyl} aluminum, tetrakis (perfluorophenyl) aluminum, (c) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3,5 -Di (perfluoromethyl) phenyl}
Gallium, tetrakis {3,5-di (t-butyl) phenyl} gallium, tetrakis (pendafluorophenyl) gallium, (2) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, (e) tetraphenyl arsenic, tetrakis ( Perfluorophenyl) arsenic,
(F) Tetraphenylantimony, tetrakis (perfluorophenyl) antimony, (tri) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.

Examples of the Lewis acid, particularly the Lewis acid capable of converting the component (A) into a cation, include various organic boron compounds and inorganic halogen compounds. In particular,
(A) Triphenylboron, tris (3,5-difluorophenyl) boron, tris (perfluorophenyl)
Organic boron compounds such as boron, (ii) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium chlorobromide,
There are metal halide compounds such as magnesium chloride iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide and magnesium bromide alkoxide.

(5) Preparation of Catalyst Component The catalyst component used in the present invention comprises the above components (A) and (B), and if necessary, the above components (C) or (D), or (C) and (C) It is prepared by contacting D). The components (C) and (D) are optional components, and may or may not be contained in the catalyst component. Further, only one of the component (C) and the component (D) may be contained, or both may be contained at the same time.

In preparing the catalyst component, the order of contact of component (A), component (B), component (C), and component (D) is not particularly limited. The contact may be performed in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, or xylene.

Regarding the amount of each catalyst component to be used, component (C) or (D) is used in an amount of 0.01 to 1 g per component (B).
10,000 mmol, preferably 0.1 to 100 mm
ol. The transition metal in the component (A) and the aluminum atom ratio in the component (C) or (D) have a ratio of 1: 0.0
1 to 1,000,000, preferably 1: 0.1 to 10
It is 0000. The component (A) is a component (B) 1
0.01 to 1000 μmol, preferably 0.1 g / g.
1 to 100 μmol. Component (A), component (B),
When contacting the components (C) and (D), the concentration of the component (A) is 0.01 to 100 μmol / ml, preferably 0.1 to 100 μmol / ml.
It is 1 to 10 μmol / ml. The concentration of the component (B) is from 0.01 to 100 g / ml, preferably from 0.01 to 10 g / ml.
g / ml. The concentration of the component (C) or (D) is 0.1 to 1000 μmol / ml, preferably 0.1 to 1000 μmol / ml.
100 μmol / ml.

The contact of each component is carried out between -50 ° C. and the boiling point of the solvent, particularly preferably between 0 ° C. and the boiling point of the solvent. The contact time is usually 1 minute to 48 hours, preferably
It is selected from about 1 minute to 12 hours.

(6) Prepolymerization The catalyst for olefin polymerization of the present invention comprises the above components (A) and (B) and, if necessary, the above components (C) or (D) or (C) and (D) And an olefin is brought into contact with the catalyst component obtained by pre-polymerization to carry out prepolymerization.

The preliminary polymerization is generally carried out in a slurry polymerization method in an inert solvent, a gas phase polymerization method using substantially no solvent,
A bulk polymerization method performed in a liquefied olefin can be used, but a slurry polymerization method and a bulk polymerization method are preferred.

In the prepolymerization using the catalyst component, the concentration of the component (A) is 0.01 to 100 μmol / ml, preferably 0.1 to 10 μmol / ml. The concentration of the component (B) is 0.01 to 100 g / ml, preferably 0.01 to 10 g / ml. The concentration of the component (C) or the component (D) is 0.1 to 1000 μmol / ml,
Preferably it is 0.1 to 100 μmol / ml.

The olefin used is ethylene,
Propylene, 1-butene, 1-hexene, 3-methyl-
Examples thereof include 1-butene, 4-methyl-1-pentene, vinylcycloalkane, styrene, divinylbenzene, derivatives thereof, and mixtures thereof.

The olefin may be introduced into the reactor in a specific amount before the prepolymerization, or may be fed sequentially, but it is preferable to feed the olefin sequentially.
When fed sequentially, the feed rate of olefin per hour is 0.001 per gram of component (B).
A range of １０００1000 g, preferably 0.1-100 g is suitable. More specifically, the feed of the olefin may be intermittently stopped during the prepolymerization, or the feed speed may be changed over time. At that time, hydrogen can be used in coexistence as necessary for adjusting the molecular weight, and it is also possible to coexist with an inert gas such as nitrogen for controlling the reaction.

The prepolymerization by contacting the catalyst component with an olefin is usually carried out at a temperature of -50 ° C to 100 ° C, preferably 0 ° C.
The reaction is performed in a temperature range of up to 90 ° C., but in the present invention,
The pre-polymerization step is characterized in that a temperature control step of changing the contact temperature (pre-polymerization temperature) between the catalyst component and the olefin with time during the pre-polymerization is included. The term "temperature change over time" as used herein may mean either a rise in temperature or a fall in temperature. Further, the temperature may be raised or lowered a plurality of times in the same pre-polymerization step. further,
The temperature rise and the temperature decrease may be combined in the same prepolymerization step. Preferably, the temperature is raised over time. In addition,
To raise or lower the temperature over time means active temperature control excluding a temperature increase due to heat generation during prepolymerization.

As a specific operation of the temperature change, (i)
A method in which a low-temperature step and a high-temperature step are provided one by one during the pre-polymerization step, and the temperature is raised or lowered once between both steps,
For example, at the start of prepolymerization, a method in which the prepolymerization is maintained at a low temperature stage (high temperature stage) for a certain period of time, then heated (or cooled) and maintained at a high temperature stage (or low temperature stage) for a certain period of time, followed by terminating the prepolymerization, A method of providing a plurality of low-temperature steps and / or high-temperature steps during the polymerization step (that is, a method of repeating the temperature increase and / or temperature decrease a plurality of times), for example, at the start of prepolymerization, maintaining the low-temperature step (or the high-temperature step) for a certain period of time Then, the temperature is raised (or lowered) and held at a high temperature stage (or a low temperature stage) for a certain period of time, and further lowered (or heated) and held at a low temperature stage (or a high temperature stage) for a certain period of time, followed by terminating the prepolymerization. Alternatively, at the beginning of the prepolymerization, the mixture is held at a low temperature stage (or high temperature stage) for a certain period of time, then heated (or cooled) and held for a certain period of time, and further heated (or heated) and held for a certain period of time. And a method in which to terminate the 備重 case,
(Iii) a method of continuously raising and / or lowering the temperature at a predetermined rate from the start of the pre-polymerization to the end of the pre-polymerization. In the operation of changing the temperature, the rate of temperature rise or fall is not particularly limited, but is 0.01 ° C. per minute.
The temperature is preferably in the range of -100 ° C, preferably 0.05-10 ° C.

In the above methods (i) and (ii), the low-temperature stage refers to a relatively low-temperature stage before or after a temperature rise among two successive stages having different temperatures. It refers to a relatively high temperature stage after the temperature rise.
Therefore, it is sufficient that the low-temperature stage and the high-temperature stage have a relative relationship to each other, and the temperature difference between the high-temperature stage and the low-temperature stage is 1-1.
The temperature is set to be 50 ° C., preferably 5 to 100 ° C. The preferred temperature ranges at each stage are not particularly limited because they are relative to each other. However, in the method (i) in which one low-temperature stage and one high-temperature stage are provided, respectively. The temperature in the low temperature stage is preferably -50 to 90C, more preferably about 0 to 60C, and the temperature in the high temperature step is preferably 0 to 100C, more preferably about 10 to 100C.
The holding time at the low temperature stage is 1 minute to 22 hours, more preferably about 30 minutes to 12 hours, and the holding time at the high temperature stage is 1 minute to 22 hours, more preferably about 30 to 12 hours. Is desirable.

In the above (ii), any number of low-temperature stages and / or high-temperature stages may be provided, and the number of low-temperature stages and the number of high-temperature stages may be the same or different.

In the above method (iii), the temperature may be continuously increased or decreased only, or the temperature may be continuously increased (or decreased) and then decreased (or increased). It may be repeated a plurality of times. The rate of heating or cooling may be kept constant or varied throughout the prepolymerization step.

The temperature change is such that the difference between the minimum temperature and the maximum temperature during prepolymerization is 1 ° C. to 150 ° C., preferably 5 ° C. to 15 ° C.
The temperature is preferably set to 0 ° C, more preferably 5 ° C to 60 ° C. The prepolymerization time is 2 minutes to 24 hours in total, and preferably about 30 minutes to 12 hours.

The operation of the temperature change is, more specifically,
(A) After maintaining at 10 ° C for 1 hour, raise the temperature to 60 ° C at 1 ° C / min and maintain for 1 hour. (B) After maintaining at 10 ° C for 1 hour, 20 ° C at 0.05 ° C / min. And maintained for 2 hours. (C) After maintaining at 60 ° C. for 1 hour, 1 ° C. /
Temperature to 10 ° C in 2 minutes and maintain for 2 hours.
After maintaining at 30 ° C. for 30 minutes, the temperature was raised to 30 ° C. at 1 ° C./min and maintained for 2 hours, and then continuously raised to 90 ° C. at 10 ° C./min and maintained for 1 hour. , The temperature is raised to 60 ° C. at 1 ° C./min, and after 30 minutes, the temperature is lowered to 30 ° C. at 1 ° C./min and maintained for 2 hours.

The prepolymerization in the present invention is carried out according to the above (A) to
0.1 g of the component (B) in the catalyst component containing the component (D) is used.
It is desirable to carry out the reaction so as to produce from 01 to 1000 g, preferably from 0.1 to 100 g, of the polymer. The catalyst thus obtained may be used as it is, or may be used after washing with an inert hydrocarbon solvent.

In the present invention, the component (C) may be newly combined as needed. That is, for example, in the preliminary polymerization step, the component (C) may be newly added. The amount of the component (C) used in this case is preferably in the range of 1: 0 to 10,000 based on the transition metal in the component (A) and the atom of aluminum in the component (C).

The olefin polymerization catalyst of the present invention thus obtained may be used after removing the solvent by drying. At that time, the reaction may be performed under reduced pressure or may be performed under a stream of an inert gas. Drying temperatures range from 0 to 100 ° C. Although the drying time is not particularly specified,
It can be done over a day.

(7) Olefin Polymerization In the present invention, an olefin having 2 or more carbon atoms can be homopolymerized or copolymerized in the presence of the above-mentioned olefin polymerization catalyst. As the olefin used for the polymerization, ethylene, propylene, 1-butene, 1-hexene,
Examples thereof include 3-methyl-1-butene, 4-methyl-1-pentene, vinylcycloalkane, styrene, divinylbenzene, and derivatives thereof. The polymerization may be homopolymerization or copolymerization. In the case of copolymerization, random copolymerization or block copolymerization may be used.

In the olefin polymerization method of the present invention, an organic aluminum compound is optionally combined with the olefin polymerization catalyst, and the olefin is homopolymerized or copolymerized in the presence of the olefin polymerization catalyst and the organic aluminum compound. It can also be polymerized. Such an organoaluminum compound can be appropriately selected from those listed as the component (C).

The polymerization reaction is carried out by solvent polymerization using a saturated hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or an aromatic hydrocarbon as a solvent,
It is carried out by a liquid phase solventless polymerization, a gas phase polymerization, and a melt polymerization substantially using no solvent. The solvent used for the solvent polymerization may be a saturated aliphatic or aromatic hydrocarbon alone or a mixture. Further, it is applied to continuous polymerization, semi-continuous polymerization, and batch polymerization. The polymerization temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited.
The range is 2000 kgf / cm ² . Further, hydrogen may be present as a molecular weight modifier in the polymerization system.

[0077]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples unless departing from the gist of the present invention. The following operations were all performed in an inert gas atmosphere. The solvent used in the complex synthesis, catalyst preparation and polymerization was dehydrated and purified using molecular sieve 4A, and deoxygenated by bubbling with purified nitrogen. In the examples, the melt flow index (expressed as MFR; unit is g / 10 min) was measured according to ASTM-D-1238.

(1) Evaluation of Bulk Density of Preliminary Polymerization Catalyst Bulk density was measured by flowing a solid catalyst component from a stainless steel funnel having an outlet hole diameter of 5 mm into a 10 cc container. Displayed with.

(2) Evaluation of Flowability of Prepolymerization Catalyst Flowability was 5 mmφ, 6.5 mmφ, 8 mmφ, 12 m
14 cc of the powder of the solid catalyst component was introduced into a stainless steel funnel having a cone angle of 30 ° having various outlet diameters of mφ, 16 mmφ, and 20 mmφ. The numbers are indicated by the minimum pore size at which outflow occurs.

(3) Evaluation of Aggregation of Polymer Particles The ratio of the weight (B) having a particle size of 1680 μm or more to the total weight of the polymer (A) is represented by percentage by weight. [1680
μm or more = (B) / (A) × 100]

Example 1 (1) Component (A) [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4-
Synthesis of (4-chlorophenyl) -4H-azulenyl {] zirconium] bromochlorobenzene (1.84 g, 9.59 mmol)
l) was dissolved in diethyl ether (10 mL) and hexane (10 mL).
tert-butyllithium in pentane solution (11.7 mL, 19.18 mmol, 1.6).
4N) was added dropwise at -78 ° C. 20 minutes at -70 ° C, -5
Stirred at 1.5 ° C. for 1.5 hours. To this solution was added 2-methylazulene (1.22 g, 8.63 mmol) and the mixture was added at -5 ° C for 1 hour.
After stirring for 0 minutes at room temperature for 1.5 hours, the purple color almost disappeared,
A white precipitate formed. After cooling to 0 ° C., tetrahydrofuran (10 mL) was added, and N-methylimidazole (15 μm) was added.
L) and dimethyldichlorosilane (0.52 mL, 4.3)
1 mmol), and the mixture was heated to room temperature and stirred at room temperature for 1.5 hours. Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
The obtained crude product was purified by silica gel column chromatography (hexane: hexane-dichloromethane = 1: 1) to give dimethylbis-1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -1, 4
-Dihydroazulene) (2.06 g, 85%).

The azulene (1.27 g) obtained above was dissolved in diethyl ether (15 mL), and hexane solution of normal butyl lithium (2.8 mL,
(1.6 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. The solvent was distilled off, and toluene (5 mL) and diethyl ether (0.12 mL) were added. Cooled to -78 ° C and purified by sublimation zirconium tetrachloride (530mg)
, And the mixture was gradually heated and stirred at room temperature for 4 hours. The resulting solution was subjected to frit filtration using Celite, and toluene (3
mL) on a frit. The filtrate was extracted with dichloromethane and concentrated under reduced pressure to give dichloro [1,1 '.
A racemic-meso mixture of -dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium (906 mg, including toluene) was obtained. The racemic-meso ratio was 6: 4.

(2) Purification of Complex The racemic-meso mixture (906 mg, including toluene) obtained above was suspended in dichloromethane (25 mL), and subjected to 40 spectral irradiation using a high-pressure mercury lamp (100 W). This solution was filtered using a frit, and the solvent was distilled off under reduced pressure. Toluene (7 mL) was added to the obtained solid, the mixture was allowed to stand, and the supernatant was removed. The same operation was performed with toluene (5 mL,
6 mL) and finally hexane (8 mL, 5 m
L). When dried under reduced pressure, a racemic body (275 mg) was obtained as a yellow powder. ¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.95 (s, 6
H, SiMe ₂ ), 2.13 (s, 6H, 2-Me), 4.83 (br s, 2H, 4-H),
5.70-5.90 (m, 8H), 6.05-6.11 (m, 2H), 6.73 (d, 2H), 7.
25-7.30 (m, 8H, arom) . Negative CI-MS 722 (M + C 36 H 32 35 Cl 4 Si 90 Zr).

(3) Production of Component (B) In a separable flask, 96% sulfuric acid (2500 g) was added to 3750 ml of pure water, and 1000 g of commercially available montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd.) was added at 60 ° C.
To form a slurry while stirring. This slurry was heated to 90 ° C. over 1 hour and reacted at 90 ° C. for 5 hours.
The reaction slurry was cooled to room temperature for 1.5 hours and washed with distilled water until the washing solution (filtrate) reached pH 3. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and further dried under reduced pressure at 200 ° C. for 6 hours to obtain 707.2 g of chemically treated smectite. The composition of this chemically treated montmorillonite was 5.21 wt% Al: 38.
9 wt%, Mg: 0.80 wt%, Fe: 1.60 wt
%, Na: <0.2 wt%, Al / Si = 0.1
39 [mol / mol].

(4) Synthesis of Catalyst In a glass reactor having an internal volume of 500 ml, 20.0 g of the chemically treated montmorillonite obtained in (2) was weighed, and 116.0 ml of heptane and 84.0 ml of a heptane solution of triethylaluminum (50 ml) were added. And the mixture was stirred at room temperature for 1 hour. Thereafter, the resultant was washed with heptane, and finally, the slurry amount was adjusted to 200.0 ml. Next, the previously prepared (r) -dichloro [1,
1'-dimethylsilylenebis {2-methyl-4- (4-
87.2 ml (300.37 μmol) of a toluene solution of chlorophenyl) -4H-azulenyl}] zirconium
And a solution of triisobutylaluminum in heptane 4.2
6 ml (3003.58 μmol) was added at room temperature.
Stirred for 0 minutes.

Then, (r) -dichloro [1,1 ′) was added to the montmorillonite treated with triethylaluminum.
A mixture of -dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium and triisobutylaluminum was added, and the mixture was further stirred at room temperature for 60 minutes. Next, heptane 209
The mixed slurry was added to a stirred autoclave having an internal volume of 1 liter into which ml was introduced, and stirred. When the temperature in the autoclave became stable at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes.
Subsequently, the temperature was raised to 50 ° C. at 1 ° C./min and maintained for 2 hours. Thereafter, the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave. The recovered catalyst slurry was allowed to stand, and the supernatant was extracted. 17.02 ml of a solution of triisobutylaluminum in heptane (1.
2.02 mmol) at room temperature, and the mixture was stirred at room temperature for 10 minutes, and dried under reduced pressure to recover 62.6 g of a solid catalyst component. The bulk density of this prepolymerized catalyst was 0.568 g / cc, and the flowability was 5 mmφ.

(5) Copolymerization of propylene-ethylene 2.86 ml of a heptane solution of triisobutylaluminum (40 ml) was placed in a 3-liter stirred autoclave.
0 mg) and 30.8 m of the prepolymerized catalyst obtained above.
g, liquefied propylene 750 g, ethylene 30 g and hydrogen 102 Nml were introduced.
The temperature was raised to 70 ° C., and the polymerization was carried out at 70 ° C. for 0.5 hour. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 198.1 g. The amount of the polymer produced per 1 g of the solid component per hour was 39620 g. The MFR of the polymer was 13.27 g / 10 min, and the bulk density was 0.40.
8 g / cc and an ethylene content of 3.87% by weight.
The ratio of particles having a size of 1680 μm or more is 5.68 wt%.
Met.

[0087]

Example 2 (1) Synthesis of Catalyst 20.0 g of the chemically treated montmorillonite obtained in Example 1 (2) was weighed into a glass reactor having an internal volume of 500 ml, and 116.0 ml of heptane and a heptane solution of triethylaluminum. 0 ml (50.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the resultant was washed with heptane, and finally, the slurry amount was adjusted to 200.0 ml. Next, (r)-synthesized in Example 1 (1) prepared in advance.
87.2 ml of a toluene solution of dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium (30 ml)
0.37 µmol) and 4.26 ml of triisobutylaluminum in heptane (3003.58 µmol)
Was added at room temperature and stirred for 60 minutes.

Then, (r) -dichloro [1,1 ′) was added to the montmorillonite treated with triethylaluminum.
A mixture of -dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium and triisobutylaluminum was added, and the mixture was further stirred at room temperature for 60 minutes. Next, heptane 209
The mixed slurry was added to a stirred autoclave having an internal volume of 1 liter into which ml was introduced, and stirred. When the temperature in the autoclave became stable at 20 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes.
Subsequently, the temperature was raised to 50 ° C. at 1 ° C./min and maintained for 2 hours. Thereafter, the remaining gas was purged, and the prepolymerized catalyst was recovered from the autoclave.

The recovered catalyst slurry was allowed to stand, and the supernatant was extracted. 17.02 ml (12.02 mmol) of a solution of triisobutylaluminum in heptane was added to the remaining solid component.
l) was added at room temperature, and the mixture was stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 66.1 g of a solid catalyst component. The bulk density of this prepolymerized catalyst was 0.530 g / cc. Also,
The flowability was 8 mmφ.

(2) Copolymerization of propylene-ethylene 2.86 ml of a heptane solution of triisobutylaluminum (40 ml) was placed in a 3 liter stirred autoclave.
0 mg) and 32.7 m of the prepolymerized catalyst obtained above.
g, liquefied propylene 750 g, ethylene 30 g and hydrogen 102 Nml were introduced.
The temperature was raised to 70 ° C., and the polymerization was carried out at 70 ° C. for 0.5 hour. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 196.0 g. The amount of polymer produced per 1 g of the solid component per hour was 39,200 g. The MFR of the polymer is 10.55 g / 10 min, and the bulk density is 0.45
9 g / cc and the ethylene content was 3.37% by weight.
The ratio of particles having a size of 1680 μm or more is 1.90 wt%.
Met.

[0091]

Comparative Example 1 (1) Synthesis of Catalyst 20.0 g of the chemically treated montmorillonite obtained in Example 1 (2) was weighed into a glass reactor having an internal volume of 500 ml, and 116.0 ml of heptane and a heptane solution of triethylaluminum. 0 ml (50.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the resultant was washed with heptane, and finally, the slurry amount was adjusted to 200.0 ml. Next, (r)-synthesized in Example 1 (1) prepared in advance.
87.2 ml of a toluene solution of dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium (30 ml)
0.37 µmol) and 4.26 ml of triisobutylaluminum in heptane (3003.58 µmol)
Was added at room temperature and stirred for 60 minutes.

Then, (r) -dichloro [1,1 ′) was added to the montmorillonite treated with triethylaluminum.
A mixture of -dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium and triisobutylaluminum was added, and the mixture was further stirred at room temperature for 60 minutes. Next, heptane 209
The mixed slurry was added to a stirred autoclave having an internal volume of 1 liter into which ml was introduced, and stirred. When the temperature in the autoclave became stable at 40 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes and maintained for 2 hours. Thereafter, the residual gas was purged, and the prepolymerized catalyst was recovered from the autoclave. The recovered catalyst slurry was allowed to stand, and the supernatant was extracted. The remaining solid component was added to a 17.0 solution of triisobutylaluminum in heptane.
2 ml (12.02 mmol) was added at room temperature, and the mixture was stirred at room temperature for 10 minutes and then dried under reduced pressure to obtain a solid catalyst component.
8 g were recovered. This prepolymerized catalyst had poor properties and was partially aggregated, but had a bulk density of 0.25 g / cc. The flowability did not flow even at 20 mmφ.

(2) Copolymerization of propylene-ethylene 2.86 ml of a heptane solution of triisobutylaluminum (40 ml) was placed in a 3-liter stirred autoclave.
0 mg) and 15.6 m of the prepolymerized catalyst obtained above.
g, liquefied propylene 750 g, ethylene 30 g and hydrogen 102 Nml were introduced.
The temperature was raised to 70 ° C., and the polymerization was carried out at 70 ° C. for 0.5 hour. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 103.4 g. The amount of polymer produced per 1 g of the solid component per hour was 20,670 g. The MFR of the polymer was 8.63 g / 10 min, and the ethylene content was 4.
00% by weight. The bulk density of the polymer could not be measured because the particles were partially aggregated. Also, 16
The ratio of particles having a size of 80 μm or more was 91.7% by weight.

[0094]

Comparative Example 2 (1) Synthesis of Catalyst Example-1 (2) in a glass reactor having an internal volume of 500 ml
20.0 g of the chemically treated montmorillonite obtained in the above was weighed, and 116.0 ml of heptane and 84.0 ml (50.0 mmol) of a heptane solution of triethylaluminum were added, followed by stirring at room temperature for 1 hour. Thereafter, the resultant was washed with heptane, and finally, the slurry amount was adjusted to 200.0 ml. Next, (r) synthesized in Example 1 (1) prepared in advance.
87.2 ml of toluene solution of -dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium (30
0.37 µmol) and 4.26 ml of triisobutylaluminum in heptane (3003.58 µmol)
Was added at room temperature and stirred for 60 minutes.

Next, (r) -dichloro [1,1 ′) was added to the montmorillonite treated with triethylaluminum.
A mixture of -dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium and triisobutylaluminum was added, and the mixture was further stirred at room temperature for 60 minutes. Next, heptane 209
The mixed slurry was added to a stirred autoclave having an internal volume of 1 liter into which ml was introduced, and stirred. When the temperature in the autoclave was stabilized at 60 ° C., propylene was fed at 476.2 mmol / hr for 120 minutes and maintained for 2 hours. Thereafter, the residual gas was purged, and the prepolymerized catalyst was recovered from the autoclave. The recovered catalyst slurry was allowed to stand, and the supernatant was extracted. The remaining solid component was added to a 17.0 solution of triisobutylaluminum in heptane.
2 ml (12.02 mmol) was added at room temperature, and the mixture was stirred at room temperature for 10 minutes, and then dried under reduced pressure to obtain a solid catalyst component.
66 g were recovered. The bulk density of this prepolymerized catalyst was 0.39
It was 8 g / cc. The flowability was 20 mmφ.

(2) Copolymerization of propylene-ethylene 2.86 ml of a heptane solution of triisobutylaluminum (40 ml) was placed in a 3-liter stirred autoclave.
0 mg) and 30.5 m of the prepolymerized catalyst obtained above.
g, liquefied propylene 750 g, ethylene 30 g and hydrogen 102 Nml were introduced.
The temperature was raised to 70 ° C., and the polymerization was carried out at 70 ° C. for 0.5 hour. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene-ethylene copolymer was 94.1 g. The amount of polymer produced per gram of solid component per hour was 18810 g. M of polymer
FR is 21.2 g / 10 min, ethylene content is 3.6
It was 0% by weight. The bulk density of the polymer could not be measured because the particles were partially aggregated. Also, 168
The ratio of particles having a size of 0 μm or more was 46.5 wt%.

[0097]

Example 3 (1) Component (A) [(r) -dichloro [1,1'-dimethylsilylenebis (2-methyl-4-
Synthesis of phenyl-4H-azulenyl)] zirconium] Synthesis was carried out according to the method described in JP-A-62-207232. 2.22 g of 2-methylazulene was dissolved in 30 ml of hexane, and 15.6 ml (1 equivalent) of a cyclohexane-diethyl ether solution of phenyllithium was added little by little at 0 ° C. After stirring this solution at room temperature for 1 hour, 30 ml of tetrahydrofuran cooled to −78 ° C.
Was added. 0.95 of dimethyldichlorosilane was added to this solution.
Then, the mixture was heated to room temperature, and further heated at 50 ° C. for 1.5 hours. Thereafter, an aqueous ammonium chloride solution was added,
After liquid separation, the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product is subjected to silica gel column chromatography (hexane / dichloromethane =
Purification by 5/1) gave 1.48 g of 1,1'-dimethylsilylenebis (2-methyl-4-phenyl-1,4-dihydroazulene).

768 mg of 1,1′-dimethylsilylenebis (2-methyl-4-phenyl-1,4-dihydroazulene) obtained above was dissolved in 15 ml of diethyl ether, and a hexane solution of normal butyllithium was added at −78 ° C. 1.98 ml (1.64 M) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 12 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure. 20 ml of toluene / diethyl ether (40/1) was added thereto, and 325 mg of zirconium tetrachloride was added at −60 ° C.
The temperature was gradually raised and the mixture was stirred at room temperature for 15 minutes. The obtained solution is concentrated under reduced pressure, and reprecipitated by adding hexane. Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4H) showing the following spectrum data is shown.
-Azulenyl)] a mixture of diastereomers of zirconium was obtained.

Diastereomer A: ¹ H-NMR (30
0 MHz, C ₆ D ₆ ) δ 0.51 (s, 6H, Si (CH ₃ ) ₂ ), 1.92 (s,
6H, CH ₃ ), 5.30 (br d, 2H), 5.75-5.95 (m, 6H), 6.13
(s, 2H), 6.68 (d, J = 14Hz, 2H), 7.05-7.20 (m, 2H, aro
m), 7.56 (d, J = 7 Hz, 4H) diastereomer B: ¹ H-NMR (300 MHz, C ₆
D ₆ ) δ0.44 (s, 3H, Si (CH ₃ )), 0.59 (s, 3H, Si (CH ₃ )),
1.84 (s, 6H, CH ₃ ), 5.38 (br d, 2H), 5.75-6.00 (m, 6
H), 6.13 (s, 2H), 6.78 (d, J = 14Hz, 2H), 7.05-7.20 (m,
2H, arom), 7.56 (d, J = 7Hz, 4H)

Mixture of diastereomers A and B 887 m
g was dissolved in 30 ml of methylene chloride and introduced into a pyrex glass reflector having a 100 W high-pressure mercury lamp. This solution was irradiated with light for 30 minutes under normal pressure while stirring (3.
After that, methylene chloride was distilled off under reduced pressure. The obtained yellow solid is washed with toluene, hexane and the like and then dried, and shows spectral data of diastereomer A. (r) -Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4H-) Azulenyl)] 437 mg of zirconium was obtained.

(2) Synthesis of Catalyst 2.4 g of MAO (supporting SiO ₂ ) manufactured by WITCO Co., Ltd. was placed in a glass reactor having an inner volume of 0.5 liter and equipped with a stirring blade.
(20.7 mmol-Al) was added and heptane 50 m
and stirred. 20.0 ml (63.7) of a (r) -dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl)] zirconium solution synthesized in (1) previously diluted in toluene.
μmol), 4.14 ml (3.03 mmol) of a solution of triisobutylaluminum in heptane was added, and then reacted at room temperature for 2 hours. Next, the slurry was added to a 1-liter stirring autoclave and stirred. When the temperature in the autoclave became stable at 20 ° C., propylene was fed at 57.1 mmol / hr for 120 minutes. Successively at 1 ° C / min at 40 ° C
, And the temperature was maintained for 2 hours. Thereafter, the residual gas was purged, and the prepolymerized catalyst was recovered from the autoclave.
After leaving the recovered catalyst slurry and extracting the supernatant,
After drying under reduced pressure, 7.4 g of a solid catalyst component was recovered. The bulk density of this prepolymerized catalyst was 0.450 g / cc, and the flowability was 8 mmφ.

(2) Polymerization of Propylene A 2.86 ml (40 ml) solution of triisobutylaluminum in heptane was stirred into a 3 liter stirring autoclave.
0 mg), 308 mg of the prepolymerized catalyst obtained above,
After introducing 750 g of liquefied propylene and 400 Nml of hydrogen, the temperature inside the autoclave was raised to 65 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 65 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene polymer was 180 g. 1g of solid component
The amount of polymer produced per hour was 1,800 g. The bulk density of the polymer was 0.45 g / cc, and no adhesion was observed in the autoclave.

[0103]

Comparative Example 3 (1) Catalyst Synthesis 2.4 g of MAO (supporting SiO ₂ ) manufactured by WITCO, Inc. was placed in a glass reactor having an inner volume of 0.5 liter and equipped with a stirring blade.
(20.7 mmol-Al) was added and heptane 50 m
(r) -Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl)] zirconium solution 20 synthesized in Example 3 (1), which was previously diluted with toluene. 2.0 ml (63.7 μmo
1) was added, followed by 4.14 ml (3.03 mmol) of a solution of triisobutylaluminum in heptane, followed by a reaction at room temperature for 2 hours. Next, the above slurry was added to a stirring type autoclave having an internal volume of 1 liter,
Stirred. When the temperature in the autoclave was stabilized at 40 ° C., propylene was added at 57.1 mmol / hr for 120 hours.
Feed for minutes. Subsequently, the temperature was maintained for 2 hours, after which the residual gas was purged, and the prepolymerized catalyst was recovered from the autoclave. The recovered catalyst slurry was allowed to stand, the supernatant was extracted, and then dried under reduced pressure to recover 7.2 g of a solid catalyst component. The bulk density of this prepolymerized catalyst is 0.36 g / cc.
And the flowability was 16 mmφ. In addition, some adhesion was observed on the inner wall of the autoclave.

(2) Polymerization of Propylene A 2.86 ml (40 ml) solution of heptane of triisobutylaluminum was added to a 3-liter stirred autoclave.
0 mg), 300 mg of the prepolymerized catalyst obtained above,
After introducing 750 g of liquefied propylene and 400 Nml of hydrogen, the temperature inside the autoclave was raised to 65 ° C, and polymerization was carried out for 1 hour while maintaining the temperature at 65 ° C. Thereafter, the unreacted residual gas was purged to stop the polymerization. As a result, the amount of the obtained propylene polymer was 134 g. 1g of solid component
The amount of polymer produced per hour was 1340 g. The bulk density of the polymer was 0.40 g / cc, and adhesion was observed on the inner wall of the autoclave.

[0105]

According to the present invention, it is possible to obtain an olefin polymerization catalyst powder having high flowability and bulk density and good adhesion. Such a catalyst can solve problems such as adhesion in a catalyst production apparatus, and adhesion or blockage in a catalyst supply step or a reactor in a polymer production process,
Thereby, the polymerization operation can be stably performed. Furthermore, by using such a catalyst, bulk polymerization,
When a heterogeneous polymerization method such as slurry polymerization or gas phase polymerization is adopted, an olefin polymer (having a homopolymer and a copolymer of two or more olefins) having no adhesion and a high bulk density and excellent in particle properties is obtained. ) Can be produced. In particular,
It is useful for polymerization in a system using a solvent for slurry polymerization or bulk polymerization.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating a method for producing a catalyst of the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoichi Maeda 1 Tohocho, Yokkaichi-shi, Mie Japan F-term in the Process Development Center of Polychem Corporation (reference) 4J028 AA01A AB01A AC01A AC08A AC10A AC26A AC28A AC31A AC37A AC39A AC41A AC42A AC44A BA01B BA02A BB01B BB02A BC12A BC13A BC15A BC16A BC19A BC24A BC25A CA14A CA15A CA16A CA19A CA25A CA26A CA27A CA28A CA29A CA30A CA44A CA49A CA54A CB08A CB09A CB94A DA01 DA02 DA02 DA02 EB04 EB04 EB09 AA03P AA04P AA08P AA16P AA17P AA20P AB02P AB16P CA01 CA04 DA16 DA43 FA10 FA28 FA43

Claims (11)

[Claims] 1. A catalyst component comprising the following components (A) and (B), and if necessary, component (C) and / or component (D), is brought into contact with an olefin to carry out prepolymerization. An olefin polymerization catalyst obtained, wherein the prepolymerization includes a temperature control step of changing a contact temperature between the catalyst component and the olefin with time. Component (A): Group 4 to 6 transition metal compound having a conjugated five-membered ring ligand Component (B): fine particle carrier Component (C): organoaluminum compound Component (D): organoaluminum oxy compound, Lewis acid, and At least one compound selected from the group consisting of ionic compounds capable of converting component (A) into a cation by reacting with component (A) 2. The catalyst for olefin polymerization according to claim 1, wherein the temperature control step includes a temperature raising step from a low temperature stage to a high temperature stage and / or a temperature lowering step from a high temperature stage to a low temperature stage. 3. The olefin polymerization catalyst according to claim 2, wherein the temperature control step comprises a step of raising the temperature from a low temperature stage to a high temperature stage. 4. The catalyst for olefin polymerization according to claim 2, wherein the temperature control step comprises a temperature raising step from a low temperature stage to a high temperature stage and a temperature lowering step from a high temperature stage to a low temperature stage. 5. The olefin polymerization catalyst according to claim 1, wherein a difference between a maximum temperature and a minimum temperature in the temperature control step is 1 to 150 ° C. 6. The olefin polymerization catalyst according to claim 1, wherein the component (B) is an ion-exchange layered silicate. 7. The component according to claim 1, wherein the component (B) is an ion-exchangeable layered silicate treated in the presence of an acid and / or a salt. Olefin polymerization catalyst. 8. The catalyst for olefin polymerization according to claim 1, wherein the component (B) is an ion-exchangeable layered silicate that has been treated in the presence of an acid. . 9. The olefin polymerization catalyst according to claim 1, wherein the component (C) is a compound represented by the following general formula (I). Embedded image (AlR ⁴ _n X _3-n ) _m (I) (In the formula (I), R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents hydrogen, halogen, or alkoxy. Represents a group, n
Represents a number satisfying 0 <n ≦ 3, and m represents an integer of 1 to 2. ) 10. A method for polymerizing olefins, comprising homopolymerizing or copolymerizing an olefin having 2 or more carbon atoms in the presence of the catalyst for olefin polymerization according to claim 1. Description: 11. Polymerization of olefins, wherein olefins having 2 or more carbon atoms are homopolymerized or copolymerized in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 9 and an organoaluminum compound. Method.