JP3529921B2 - Solid catalyst for olefin polymerization and prepolymerization catalyst for olefin polymerization - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst for olefin polymerization and a prepolymerization catalyst for olefin polymerization, and more specifically, a solid catalyst for olefin polymerization which has excellent fluidity and can be stably polymerized for a long period of time. And a prepolymerization catalyst for olefin polymerization.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polyethylene, polypropylene,
Ethylene / α-olefin copolymer, propylene / α-
An olefin polymer such as an olefin copolymer is obtained by (co) polymerizing an olefin in the presence of a solid catalyst containing a metallocene compound of a Group IVB metal such as zirconium and a metallocene solid catalyst composed of an organoaluminum component. Is manufactured by.

When an olefin is vapor-phase polymerized in the presence of a metallocene-based solid catalyst as described above using a fluidized bed reactor, polymer lumps, sheets, etc. are generated in the fluidized bed, and polymer particles are formed. In some cases, the fluidity was lowered and the mixed state in the fluidized bed became non-uniform, making it impossible to perform continuous operation stably over a long period of time.

Further, when slurry polymerization is carried out in the presence of the above-mentioned metallocene type solid catalyst, polymer lumps, sheet-like substances and the like are generated in the polymerization vessel, and the polymer adheres to the stirring blade to stabilize for a long period of time. There were times when it became impossible to operate continuously.

Further, the solid catalyst as described above often has low fluidity, and it may be difficult to supply it to the polymerization reactor. When a solid catalyst is loaded with a surfactant, such a problem is improved to some extent, but there is a problem that the polymerization activity is lowered.

The inventors of the present invention have conducted studies in view of the above-mentioned prior art, and as a result, the solid catalyst carrying a specific surfactant reduces the above problems and does not lower the polymerization activity. This has led to the completion of the present invention.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior arts, and is a solid catalyst for olefin polymerization and a preliminary catalyst for olefin polymerization, which has excellent fluidity and does not easily generate a heat spot during polymerization. The purpose is to provide a polymerization catalyst.

[0008]

SUMMARY OF THE INVENTION A solid catalyst for olefin polymerization according to the present invention comprises (A) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and (B) an organoaluminum oxy compound. (C) Polyoxyethylene alkyl ether compound
Is characterized by comprising a polyoxypropylene alkyl ether compound and (D) a particulate carrier.

The olefin polymerization prepolymerization catalyst according to the present invention comprises: (A) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton; (B) an organoaluminum oxy compound; C) Polyoxyethylene alkyl ether or poly
It is characterized by comprising an oxypropylene alkyl ether , (D) a particulate carrier, and (E) an olefin polymer produced by prepolymerization.

[0010]

The solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention have excellent fluidity,
A heat spot during the polymerization is unlikely to occur, and it is possible to prevent the occurrence of sheeting and polymer lumps, and to stably polymerize the olefin for a long term. Further, it has the same polymerization activity as a solid catalyst or a prepolymerization catalyst having the same composition except that it does not contain a nonionic surfactant.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention will be specifically described below.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers not only to homopolymers. In some cases, it is used in the sense of including a copolymer.

The solid catalyst for olefin polymerization according to the present invention comprises (A) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, (B) an organoaluminum oxy compound, and (C) ) Polyoxyethylene alkyl ether or poly
It is formed from oxypropylene alkyl ether and (D) a particulate carrier.

The olefin polymerization prepolymerization catalyst according to the present invention comprises: (A) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton; (B) an organoaluminum oxy compound; C) Polyoxyethylene alkyl ether or poly
It is formed from oxypropylene alkyl ether , (D) a particulate carrier, and (E) an olefin polymer produced by prepolymerization.

First, the respective components forming the solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention will be described below. (A) Transition metal compound (A) Group 4 of the periodic table having a cyclopentadienyl skeleton Examples of the transition metal compound include compounds represented by the following general formula (I).

ML _X (I) In the formula, M is 1 selected from transition metal atoms of Group 4 of the periodic table.
It represents a transition metal atom of the species, preferably zirconium, titanium or hafnium.

X is the valence of the transition metal and represents the number of L. L represents a ligand or a group which coordinates to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a hydrocarbon group of 1 to 12 carbon atoms, an alkoxycarbonyl group, an aryloxy group, trialkylsilyl group, SO ₃ R (wherein, R good number of carbon atoms which may have a substituent such as a halogen Is 1 to 8 hydrocarbon groups), a halogen atom, and one kind of group or atom selected from the group consisting of hydrogen atoms.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, alkyl-substituted cyclopentadienyl group, indenyl group, alkyl-substituted indenyl group, 4,5,6,7-tetrahydroindenyl group. Examples thereof include a group and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the general formula (I) contains two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons among them are: It may be bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group or the like.

A compound having two ligands having a cyclopentadienyl skeleton is preferably used as the transition metal compound (A), and two ligands having a cyclopentadienyl skeleton in which M is zirconium are used. The compound having is more preferably used.

[0022] (B) specifically organoaluminum oxy compound (B) an organoaluminum oxy-compound, conventionally known aluminoxane and JP 2-786
Examples thereof include benzene-insoluble organoaluminum oxy compounds as exemplified in JP-A-87.

(C) Nonionic Surfactant As the nonionic surfactant (C),-(CH ₂ CH _2
2 O) _n H or-{CH ₂ CH (CH ₃ ) O} _n H
(However, n is 2 to 30) are exemplified, and specific examples thereof include the following compounds.

The general formula C _m H _{2m + 1} O (CH ₂ CH ₂ O)
polyoxyethylene alkyl ether represented by _n H, a general formula C _m H _{2m + 1} O {CH ₂ CH (CH ₃ ) O} _n
A polyoxypropylene alkyl ether represented by H, a general formula C _m H _{2m + 1} C ₆ H ₄ O (CH ₂ CH ₂ O)
polyoxyethylene alkyl phenyl ether represented by _n H, a general formula C _m H _{2m + 1} C ₆ H ₄ O {CH ₂ CH
A polyoxypropylene alkylphenyl ether represented by (CH ₃ ) O} _n H, a general formula (C _m H _{2m + 1} ) ₂
Polyoxyethylene sec-alkyl ether represented by CHO (CH ₂ CH ₂ O) _n H, a general formula (C
_m H _{2m + 1} ) ₂ CHO {CH ₂ CH (CH ₃ ) O} _n H
A polyoxypropylene sec-alkyl ether represented by the general formula (C _m H _{2m + 1} ) ₃ CO (CH ₂ CH ₂ O)
polyoxyethylene tert-alkyl ether represented by _n H, a general formula (C _m H _{2m + 1} ) ₃ CO {CH ₂ CH (C
H ₃ ) O} _n H polyoxypropylene ter
t-alkyl ether.

M representing the number of carbon atoms of the alkyl group represented by (C _m H _{2m + 1} ) in the above general formula is in the range of 1 to 30, preferably 6 to 20, and more preferably 8 to 18. Is desirable. In addition, n indicating the number of repeating units of the oxyethylene unit represented by (CH ₂ CH ₂ O), and {C
It is desirable that n, which represents the number of repeating units of the oxypropylene unit represented by H ₂ CH (CH ₃ ) O}, is in the range of 2 to 30, preferably 3 to 20, and more preferably 4 to 10.

Among the ether compounds represented by the above general formula, polyoxyethylene lauryl ether,
Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl ether, polyoxyethylene nonylphenyl ether,
Polyoxyethylene sec-lauryl ether and the like are preferable, and among these compounds, a compound having 4 to 10 repeating units of oxyethylene units is particularly preferable.

(D) Fine particle carrier (D) The fine particle carrier is specifically SiO ₂ , Al.
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , Ca
O, ZnO, BaO, ThO _2, etc., or a mixture containing them, for example, SiO ₂ —MgO, SiO ₂ —Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
An inorganic carrier such as Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO,
Alternatively, an organic carrier such as polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, or styrene-divinylbenzene copolymer can be used.

It is desirable that the fine particle carrier (D) has an average particle size of 1 to 300 μm, preferably 10 to 200 μm. (F) Organoaluminum compound The solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention include the transition metal compound (A),
Although it contains (B) an organoaluminum oxy compound, (C) a particulate carrier, and (D) a nonionic surfactant as essential components, it may contain (F) an organoaluminum compound if necessary. Good.

As such an organoaluminum compound (F), for example, an organoaluminum compound represented by the following general formula (II) can be exemplified. R ^a _n AlX _3-n ... (II) (In the formula, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, and X
Represents a halogen atom or a hydrogen atom, and n is 1 to 3. ) Specific examples of the (F) organoaluminum compound include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and the like.

Further, as the organoaluminum compound (F), a compound represented by the following general formula (III) can also be used. R ^a _n AlY _{3 −n} (III) (wherein R ^a is the same as the above formula (II), and Y is —OR.
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂
Group, —SiR ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, Isobutyl group,
A cyclohexyl group, a phenyl group and the like are shown, R ^e is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ^f and R ^g are a methyl group, an ethyl group and the like. ) Solid Catalyst for Olefin Polymerization The solid catalyst for olefin polymerization according to the present invention has the above-mentioned (A).
It is formed from a transition metal compound, the (B) organoaluminum oxy compound, the (C) nonionic surfactant, and the (D) particulate carrier. FIG. 1 shows a process for preparing a solid catalyst for olefin polymerization.

Such a solid catalyst for olefin polymerization is
It can be prepared by mixing and contacting (A) a transition metal compound, (B) an organoaluminum oxy compound, (C) a nonionic surfactant, and (D) a fine particle carrier.

The order of contacting each component is selected arbitrarily, but preferably, the (A) transition metal compound, (B) organoaluminum oxy compound, and (D) particulate carrier are placed in an inert hydrocarbon solvent or It is selected that mixed contact is carried out in an olefin medium to prepare a solid catalyst component, and then the solid catalyst component and the (C) nonionic surfactant are mixed and contacted. When the solid catalyst component is prepared, (F) an organoaluminum compound may be further added.

Specific examples of the inert hydrocarbon solvent used for preparing the solid catalyst component include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane and cyclohexane. Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

In preparing the solid catalyst component, (A)
The transition metal compound (calculated as a transition metal atom) is usually used in an amount of 0.001 to 1.0 mmol, preferably 0.005 to 0.5 mmol, per 1 g of the particulate carrier (D),
(B) The organoaluminum oxy compound is usually 0.1 to
It is used in an amount of 100 mmol, preferably 0.5 to 20 mmol. When (F) an organoaluminum compound is used, it is usually 0.001 per 1 g of the fine particle carrier (D).
It is used in an amount of ~ 1000 mmol, preferably 2-500 mmol.

The temperature for mixing and contacting the above components is
Usually, it is -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 6 minutes.
00 minutes.

When the solid catalyst component and the nonionic surfactant (C) are mixed and contacted with each other, the nonionic surfactant (C) is added in an amount of 0.1 to 100 parts by weight of the solid catalyst component.
It is used in an amount of 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

The mixed contact of the solid catalyst component and the nonionic surfactant (C) can be carried out in an inert hydrocarbon solvent, and as the inert hydrocarbon solvent, those similar to the above can be mentioned. .

When the solid catalyst component and the nonionic surfactant (C) are mixed and contacted in an inert hydrocarbon solvent,
The solid catalyst for olefin polymerization is obtained as a suspension of a hydrocarbon solvent. In this case, it is preferable to remove the solvent and dry the obtained solid catalyst for olefin polymerization before using it for polymerization. Desirably, the drying is carried out in an inert gas atmosphere, preferably under a nitrogen stream, at a temperature of 0 to 60 ° C., preferably 20 to 40 ° C. for 1 to 50 hours, preferably 1 to 20 hours.

For the olefin polymerization thus obtained
The solid catalyst is (D) particulate carrier per 1 g, and (A) transition
The transfer metal compound is approximately 5 × 10 in terms of transition metal atoms.^-6-10
^-3Mol, preferably 10^-Five~ 3 x 10^-FourCarried in molar amounts
(B) organoaluminum oxy compound
About 10 in terms of um atoms^-3-10^-1Mol, preferably 2x
10^-3~ 5 x 10^-2(C) non-iod supported in a molar amount.
10 surfactants ^-6-10^-3Mol, preferably 5x
10^-Five~ 5 x 10^-FourDesired to be supported in a molar amount
Good

Since the solid catalyst for olefin polymerization of the present invention has excellent fluidity, it is easy to handle and easy to supply to the polymerization vessel. In addition, heat spots are less likely to occur during polymerization, sheeting and polymer lump formation can be prevented, and olefins can be stably polymerized over a long period of time. Furthermore, it has the same polymerization activity as a solid catalyst having the same composition except that it does not contain a nonionic surfactant.

Prepolymerization Catalyst for Olefin Polymerization The prepolymerization catalyst for olefin polymerization comprises (A) a transition metal compound, (B) an organoaluminum oxy compound, (C) a nonionic surfactant, and ( It is formed from D) a fine particle carrier and (E) an olefin polymer produced by prepolymerization. FIG. 2 shows a process for preparing a prepolymerized catalyst for olefin polymerization.

As a method for preparing such a prepolymerization catalyst for olefin polymerization, for example, (1) (A) transition metal compound, (B) organoaluminum oxy compound,
In the presence of (C) a nonionic surfactant, a small amount of olefin is prepolymerized to a solid catalyst component obtained by mixing and contacting (D) a particulate carrier in an inert hydrocarbon solvent or in an olefin medium. Method, (2) (A) transition metal compound, (B) organoaluminum oxy compound,
(D) A prepolymerized catalyst component is prepared by prepolymerizing a small amount of olefin with a solid catalyst component obtained by mixing and contacting with a fine particle carrier in an inert hydrocarbon solvent or in an olefin medium, and the prepolymerization is carried out. There is a method in which the catalyst component and the nonionic surfactant (C) are mixed and brought into contact with each other.

The organoaluminum compound (F) can be used during preparation of the solid catalyst component and / or during prepolymerization. Examples of the inert hydrocarbon solvent used for preparing the prepolymerized catalyst for olefin polymerization include the same inert hydrocarbon solvents used for preparing the solid catalyst component.

In preparing the prepolymerization catalyst for olefin polymerization, (A) transition metal compound (transition metal atom conversion)
Is usually 0.001 to 1 g of (D) fine particle carrier.
It is used in an amount of 1.0 mmol, preferably 0.005 to 0.5 mmol, and (B) the organoaluminum oxy compound is usually 0.1 to 100 mmol, preferably 0.5.
Used in an amount of ~ 20 mmol. When the (F) organoaluminum compound is used, it is generally used in an amount of 0.001 to 1000 mmol, preferably 0.01 to 500 mmol, per 1 g of the fine particle carrier (D).

In the method (1), the nonionic surfactant (C) is added to 100 parts by weight of the solid catalyst component.
0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight,
It is more preferably used in an amount of 0.4 to 5 parts by weight, and in the method (2), 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, relative to 100 parts by weight of the prepolymerization catalyst component. Parts, more preferably 0.4 to 3 parts by weight.

The olefin polymerization prepolymerization catalyst is obtained as a suspension of a hydrocarbon solvent. In the present invention, the solvent is removed and the obtained olefin polymerization prepolymerization catalyst is dried and then used for polymerization. preferable. Desirably, the drying is performed in an inert gas atmosphere, preferably under a nitrogen stream, at a temperature of 0 to 100 ° C., preferably 20 to 60 ° C. for 1 to 50 hours, preferably 1 to 20 hours.

The prepolymerization catalyst for olefin polymerization obtained as described above is (D) per 1 g of the particulate support,
(A) The transition metal compound is approximately 5 × 10 in terms of transition metal atoms.
^-6 to 10 ^-3 mol, preferably 10 ^{-5 to} 3 × 10 ^-4 mol, and (B) the organoaluminum oxy compound is converted to an aluminum atom content of about 10 ^-3 to 10 ^-1 mol, preferably Supported in an amount of 2 × 10 ^{−3 to} 5 × 10 ⁻² mol,
(C) The nonionic surfactant is supported in an amount of 10 ⁻⁶ to 10 ⁻³ mol, preferably 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol,
It is desirable that the olefin polymer (E) produced by the preliminary polymerization is supported in an amount of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g.

The prepolymerization catalyst for olefin polymerization of the present invention is excellent in fluidity and therefore easy to handle and easy to supply to the polymerization vessel. In addition, heat spots are less likely to occur during polymerization, sheeting and polymer lump formation can be prevented, and olefins can be stably polymerized over a long period of time. Further, it has the same polymerization activity as the prepolymerization catalyst having the same composition except that it does not contain a nonionic surfactant.

Polymerization Olefin polymerization using the solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention is carried out by slurry polymerization or gas phase polymerization. In the polymerization, (D) the organoaluminum oxy compound (C) and / or (F) the organoaluminum compound which is not supported on the particulate carrier can be further used.

The polymerization temperature of the olefin is usually -50 to 100 ° C., preferably 0 when carrying out the slurry polymerization.
It is desirable to be in the range of 90 ° C. When carrying out gas phase polymerization, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. The polymerization pressure is usually from atmospheric pressure to 100 kg / cm ² , preferably from atmospheric pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch-wise, semi-continuous and continuous processes. It can be carried out.

The olefins which can be polymerized by the solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention include α-α having 2 to 20 carbon atoms.
Olefins such as ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; carbon number 3-20 Cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5, Examples thereof include 8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

By supporting a nonionic surfactant on the solid catalyst component and the prepolymerization catalyst component, the polymerization activity on the solid catalyst surface and the prepolymerization catalyst surface is suppressed to some extent, but the activity on the catalyst surface is suppressed. Since the monomer easily enters the active sites inside the catalyst and the amount of polymerization at the active sites inside the catalyst is improved, the polymerization activity of the entire catalyst (g-
Polymer / mmol-transition metal atom / hr) does not decrease.

[0053]

INDUSTRIAL APPLICABILITY The solid catalyst for olefin polymerization and the prepolymerization catalyst for olefin polymerization according to the present invention are excellent in fluidity, can prevent the generation of heat spots during polymerization, and further contain a nonionic surfactant. It has the same polymerization activity as the catalyst that does not contain it.

[0054]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0055]

Example 1 Preparation of Solid Catalyst 154 of 10 kg of silica dried at 250 ° C. for 10 hours
After suspending in 1 liter of toluene, it was cooled to 0 ° C.
Then, to this suspension, 50.5 liters of a methylaminoxane toluene solution (Al = 1.52 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system is 0 to
It was kept in the range of 5 ° C. Continue to react at 0 ℃ for 30 minutes,
Then, the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was performed at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make the total volume 160 liters.

22.0 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.7 mmol / liter) was added to the suspension thus obtained. The mixture was added dropwise at 80 ° C over 30 minutes, and further reacted at 80 ° C for 2 hours. Then, the supernatant was removed, and the solid catalyst component was washed twice with hexane to obtain a solid catalyst component containing 3.2 mg of zirconium per 1 g of the solid catalyst component.

The solid catalyst component thus obtained was 1600 g (400
g / L-hexane) with Emulgen 108 ^™ (Kao, polyethylene oxide lauryl ether) 14
g, and dried at room temperature under a nitrogen stream for 48 hours.

Polymerization Using a continuous fluidized bed gas phase polymerization apparatus, the total pressure is 20 kg / cm.
Copolymerization of ethylene and 1-hexene was carried out at ^2- G, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.7 m / sec.

The solid catalyst component prepared above was 1.7 g /
hr and triisobutylaluminum 5 mmol /
It was continuously fed at a rate of hr, and ethylene, 1-hexene, hydrogen and nitrogen were continuously fed in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene =
0.025, hydrogen / ethylene = 4.6 × 10 ⁻⁴ , ethylene concentration = 70%). The obtained ethylene / 1-hexene copolymer has a yield of 6.4 kg / hr and a density of 0.9.
20 g / cm ³ , MFR 4.1 g / 10 min, bulk specific gravity 0.42 g / cm ³ , average polymer particle size 920 μm, 100 μm or less fine polymer amount 0.0 % By weight.

After continuous operation for one day, the inner wall of the polymerization apparatus and the dispersion plate were inspected, and no adhering polymer was found.

[0061]

Example 2Preparation of prepolymerization catalyst In a 350 liter reactor that had been thoroughly purged with nitrogen, the
Charge 7.0 kg of the solid catalyst component prepared in 1 and hexane.
To a total volume of 285 liters. Up to 10 ℃ in the system
After cooling, ethylene is 8 Nm³5 minutes at a flow rate of / hr
Blow into hexane. During this time, the temperature in the system is 10
Hold at -15 ° C. After that, stop supplying ethylene
2.4 mol of triisobutylaluminum and 1-
1.2 kg of hexane was charged. The system was closed system
Later, 8 Nm³Re-start the supply of ethylene at a flow rate of / hr
did. After 15 minutes, change the flow rate of ethylene to 2 Nm.³/ Hr down
The pressure inside the system at 0.8 kg / cm²-G. During this time
Moreover, the temperature in the system rose to 35 ° C. Then in the system
Ethylene 4Nm while adjusting the temperature to 32 ~ 35 ℃
³It was supplied at a flow rate of / hr for 3.5 hours. During this time,
Pressure is 0.7-0.8 kg / cm²-Held by G
It was Then, the system was replaced with nitrogen, and the supernatant
The liquid was removed and washed twice with hexane. In this way
3 g of polymer is prepolymerized per 1 g of solid catalyst component
A prepolymerized catalyst (a) was obtained. This prepolymerized polymer
Has an intrinsic viscosity [η] of 2.1 dl / g and 1-hexene
The content of nitrogen was 4.8% by weight.

2000 g of the obtained prepolymerized catalyst (a)
(500 g / l-hexane) to Emulgen 108
20 g of ^TM (manufactured by Kao) was added, and the mixture was kept at room temperature under nitrogen flow for 48
After drying for an hour, a prepolymerized catalyst (b) was obtained.

Polymerization Using a continuous fluidized bed gas phase polymerization apparatus, total pressure 20 kg / cm
Copolymerization of ethylene and 1-hexene was carried out at ^2- G, a polymerization temperature of 90 ° C., and a gas linear velocity of 0.7 m / sec.

The prepolymerized catalyst (b) prepared above was used for 8.
Polymerization was initiated while continuously supplying 4 g / hr and triisobutylaluminum at a rate of 5 mmol / hr. Ethylene, 1-hexene, hydrogen, and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.024, hydrogen / ethylene = 4.5 × 10). ^-4 , ethylene concentration = 71%). The yield of the obtained ethylene / 1-hexene copolymer was 6.1 k.
g / hr and the density is 0.922 g / cm ³ ,
MFR is 3.6 g / 10 minutes and bulk specific gravity is 0.39 g /
cm ³ , the average particle size of the polymer was 750 μm, and the amount of finely divided polymer of 100 μm or less was 0.0% by weight.

After the continuous operation for 2 days, the inner wall of the polymerization apparatus and the dispersion plate were inspected and no adhering polymer was found.

[0066]

COMPARATIVE EXAMPLE 1 Polymerization Example 2 was repeated except that the prepolymerized catalyst (b) was replaced with the prepolymerized catalyst (a) prepared in Example 2 to prepare ethylene and 1-hexene. However, a sheet-shaped polymer was formed on the wall surface of the polymerization before reaching the specified polymerization amount, and continuous polymerization was impossible.

[0067]

Example 3 Preparation of Prepolymerized Catalyst 2000 g (5) of the prepolymerized catalyst (a) obtained in Example 2
Emulgen 108 in (00 g / liter-hexane)
Add 100 g of ^TM (manufactured by Kao), and under nitrogen flow at room temperature 4
After drying for 8 hours, a prepolymerized catalyst (c) was obtained.

Polymerization 1 liter of hexane was charged into a stainless steel autoclave having an internal volume of 2 liter which had been sufficiently replaced with nitrogen, and the system was replaced with ethylene. Then, 40 ml of 1-hexene, 0.75 mmol of triisobutylaluminum and 0.6 g of the prepolymerized catalyst (c) prepared above were charged, and the temperature in the system was raised to 70 ° C. Then, the polymerization was started by introducing ethylene. Then, while continuously feeding ethylene, polymerization was carried out for 1.5 hours under the polymerization conditions of 8 kg / cm ² -G and 80 ° C. The polymer was recovered by filtration and dried under reduced pressure at 80 ° C. overnight to give a melt flow rate of 0.13 g / 10 minutes and a density of 0.9.
Was 26 g / cm ^3, a bulk specific gravity of 0.41 g / cm ^3, average particle size was obtained ethylene-1-hexene copolymer 320g is 650 .mu.m.

At this time, no adhesion of the polymer to the wall of the polymerization vessel or the stirring blade was observed.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing a solid catalyst for olefin polymerization according to the present invention.

FIG. 2 is an explanatory view showing a process for preparing a prepolymerization catalyst for olefin polymerization according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Kichi ▼ Next Ken 1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries, Ltd. (72) Hiroshi Nishi Kawa, Kuga, Yamaguchi Prefecture 6-1-2, Waki, Waki-gun, Mitsui Petrochemical Industry Co., Ltd. (56) Reference JP-A-8-208717 (JP, A) Special table 10-507471 (JP, A) Special table 10- 501729 (JP, A) Special Table 2001-505228 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (2)

(57) [Claims] 1. (A) having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, (C) a polyoxyethylene alkyl ether compound,
Is a solid catalyst for olefin polymerization, which comprises a polyoxypropylene alkyl ether compound and (D) a particulate carrier. 2. (A) having a cyclopentadienyl skeleton
A transition metal compound of Group 4 of the periodic table , (B) an organoaluminum oxy compound, (C) a polyoxyethylene alkyl ether compound,
Is a polyoxypropylene alkyl ether compound , (D) a particulate carrier, and (E) an olefin polymer produced by prepolymerization, which is a prepolymerization catalyst for olefin polymerization.