JPH07224115A - Catalyst for olefin polymerization, its production and polymerization of olefin using the same - Google Patents

Abstract

PURPOSE:To obtain the subject uniformly spherically granular catalyst, high in bulk density, narrow in granular size distribution, and capable of giving polymers of good fluidity, by treating under specified conditions resin powder having voids inside the granules in the presence of a liquid catalyst for olefin polymerization. CONSTITUTION:Resin powder such as of PE having voids inside the granules is subjected to repeated collision between a high-speed rotator and a stationary body placed in proximity thereto in the presence of a liquid catalyst for olefin polymerization such as an organoaluminum compound to encapsulate the resin powder 0.001-2ml/g in void volume inside the granules with the liquid catalyst, thus the aimed catalyst is obtained. It is preferable that an olefin is polymerized using this catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a novel catalyst component used for producing a polyolefin, a catalyst obtained by the process, and a process for olefin polymerization using the catalyst component. More specifically, the present invention relates to a solid catalyst suitable for producing a polyolefin having good particle properties such as a good shape, a high bulk density, a large average particle size, and a small amount of fine powder.

[0002]

2. Description of the Related Art The shape and particle size of a catalyst used in a medium- and low-pressure deashing process in the production of polyolefin are
It is an important factor along with its catalytic activity. In the gas phase polymerization process, which has been established as a large-scale production method in recent years, a gas phase fluidized bed has come to be used, and the scattering, shape, initial activity, etc. of the catalyst are closely related to the operability of the process.
Even in the slurry process, which is relatively easy to handle, the shape and specific gravity of the solid catalyst are important factors along with the catalytic activity. Conventional techniques for producing these solid catalyst components include a method of milling solid components, a precipitation method of depositing from a solution, a spray dry method of spraying a solution, a loading method of loading an inorganic substance or a resin powder, or a solid catalyst obtained. There has been proposed a method of obtaining a solid catalyst component by further preliminarily polymerizing. Among the above, in the supporting method using an inorganic substance or resin powder,
According to a general catalyst supporting method, for example, a method of impregnating a resin powder with a solution of a solid catalyst component and then drying this has been adopted. Further, when the catalyst itself is a liquid, in order to use the catalyst in a gas phase polymerization method, a method is proposed in which the catalyst is dissolved in a solvent that is very easily evaporated and is supplied to a flowing polymerization layer of polymer particles as seeds. ing.

However, when these catalyst components are used, a polymer having a high bulk density to some extent and a large average particle size can be obtained, but it is aimed at more stable drivability and is obtained by polymerization. Further improvement is required so that the powdered polymer can be directly supplied to the processing machine and the pelletizing step can be omitted. In particular,
In the supporting method using an inorganic substance or resin powder, even if the inorganic substance or resin powder is molded into a uniform spherical shape, the catalyst obtained by supporting the same does not always have a spherical shape. This also applies to the method of obtaining a solid catalyst component by prepolymerization. A method of further spheroidizing the catalyst once obtained is also difficult, but this is because the milling method itself is not suitable for obtaining uniform spherical particles. Properties such as the shape of the solid catalyst component for olefin polymerization influence the olefin polymerization, but a sufficient production method has not been proposed yet. Further, in the case of a liquid catalyst, it is not suitable for slurry polymerization or gas phase polymerization of an olefin by simply supporting it on a solid carrier, so that a liquid olefin polymerization catalyst is used for slurry polymerization or gas phase polymerization, particularly gas phase polymerization. It was difficult to apply. Further, it has been difficult to support a homogeneous catalyst on a carrier while maintaining the characteristic of being homogeneous.

[0004]

The present invention solves these drawbacks and further provides a polymer having a high bulk density, a narrow particle size distribution, a remarkably small fine particle portion and a good fluidity. An object is to provide a solid catalyst for olefin polymerization which can be obtained with activity.

[0005]

That is, the first aspect of the present invention
Is an olefin polymerization process in which a resin powder having voids inside the particles is repeatedly collided in the presence of a liquid catalyst for olefin polymerization, between a high-speed rotating body and a stationary body arranged close to the high-speed rotating body. The present invention relates to a method for producing a solid catalyst for olefin polymerization, which comprises obtaining a resin powder in which a liquid catalyst for use is enclosed. The second aspect of the present invention is that a resin powder having voids inside the particles is repeatedly used in the coexistence of a liquid catalyst for olefin polymerization between a high-speed rotating body and a stationary body arranged close to the high-speed rotating body. The present invention relates to a method for polymerizing an olefin, characterized in that a resin powder in which a liquid catalyst for olefin polymerization is enclosed by collision is used. A third aspect of the present invention relates to a solid catalyst for olefin polymerization, which is composed of resin powder having a void volume within the range of 0.001 to 2 ml / g in which the liquid catalyst for olefin polymerization is enclosed.

The method of the present invention will now be further described with reference to the drawings. FIG. 1 is a schematic process diagram of an apparatus for carrying out the method for producing a catalyst of the present invention. FIG. 2 shows a side surface inside the casing as seen from the line II-II in FIG. The apparatus of FIG. 1 has a casing 1 as a stationary body, and a disc 3 as a high-speed rotating body having a shock vane 2 rotating between the casing 1 and a narrow gap of 0.1 to 10 mm, for example, 3 mm.
And the surface of the shank is formed by a conical protrusion 4. The rotating body is rotated by a motor 5. The rotation speed of the disk 3 is adjusted so that the peripheral speed is in the range of 30 to 120 m / s. The inner wall of the casing has impact blades 2
An impact ring (not shown) may be attached to the position corresponding to the above to prevent abrasion due to colliding particles. When the rotating body rotates at high speed, a high-speed airflow is generated due to the fan effect of the impact blades 2 of the rotating body, and the high-speed airflow circulates inside and outside the casing via the circulation line 6. Resin powder as mother particles is supplied to the inside of the casing 1. This powder is supplied from the supply pot 7, and the obtained solid catalyst is collected by the product pot 8. In addition,
An inert gas for purging is supplied from an inert gas cylinder 9 in order to shield the catalyst from the air. The mother particles are charged from the supply pot 7 along the axis of the rotating body that rotates at high speed. At this time, the gas in the inert gas cylinder 9 is fed to the line 1
It is preferable to feed through 0. The charged powder collides with the conical projection 4 in the axial direction, jumps out in the radial direction, collides with the impact blades 2, and further collides with the inner wall of the casing. At this time, the high-speed airflow generated by the impact blades 2 circulates from the casing 1 through the circulation line 6 in the same stroke, and the mother particles repeatedly collide many times. During the circulation of the generated high-speed air flow, a small amount of the liquid catalyst for olefin polymerization is injected through a valve 11 with a syringe or the like. The liquid becomes a mist and enters the voids inside the mother particles while colliding with the mother particles in the high-speed air stream. The surface opening of the mother particles has a very small pore size close to closure due to the energy of collision with the casing or the like, and as a result, a solid catalyst in which the liquid is enclosed inside the resin particles can be obtained. Also, due to mechanical energy and surface heat energy due to friction,
The mother particles are spherical particles having a uniform surface and a small number of irregularities. The olefin polymerization solid catalyst thus obtained is transferred to the product pot 8 equipped with the filter 14 through the line 13 together with the ram valve 12 opened, and collected.

The resin used as the resin powder in the present invention is not particularly limited as long as it is a synthetic resin. A thermoplastic resin is preferable, and a polyolefin resin is more preferable. Most preferably, it is a polyolefin resin having the same physical and chemical properties as the polyolefin to be produced by polymerization. Specifically, ethylene, a homopolymer of propylene, a copolymer of ethylene and propylene, ethylene and 1-butene, 1-pentene, 1
-Hexene, copolymers with α-olefins such as 4-methyl-1-pentene, copolymers of propylene and ethylene,
Propylene and 1-butene, 1-hexene, 4-methyl-
Examples thereof include copolymers with α-olefins such as 1-pentene, polystyrene, and styrene-divinylbenzene copolymers.

The average particle size of the resin powder is 10 to 500 μm,
Preferably 20-300 μm, more preferably 30-
It is 200 μm. If the average particle size of the resin powder is smaller than 10 μm, the particle size of the polymer produced when subjected to polymerization will be small, and the fine particle portion of the polymer will be large, so that the object of the present application cannot be achieved. If it is larger than 500 μm, the particle size of the produced polymer is too large, the bulk density is lowered, and the fluidity is poor, so that the object of the present application cannot be achieved. The particle size distribution of the resin powder is not particularly limited, but in order to reduce the amount of fine powder of the obtained polymer, it is preferable that the amount of fine powder is small and the particle size distribution is narrow. Further, the shape of the resin powder is preferably spherical as much as possible in order to improve the fluidity of the catalyst powder after enclosing the liquid catalyst and to improve the shape of the polymer obtained.

The resin powder is heated and dried under reduced pressure before being supplied to the apparatus, or a small amount of the periodic table I
Water, oxygen and the like are preferably removed by a method such as a contact treatment with an organometallic compound of Group III to Group III. Preferable specific examples of the organometallic compound include organomagnesium compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, methylaluminoxane, n-butyllithium and Grignard compounds.

The resin powder used must have a large number of voids communicating with the surface inside. In order to measure the void volume inside such particles, first, put 10 g of sufficiently dried resin powder in a 50 ml Erlenmeyer flask,
Add toluene little by little and shake well. Initially, the resin powder flows, and when the Erlenmeyer flask is inverted, it runs off. However, when a certain amount of toluene is added, the resin powder does not drop even if the Erlenmeyer flask is inverted. The volume of toluene added up to this point is defined as the void volume inside the particles. The resin powder used in the present invention has a void volume of 0.001 to 2 ml / g, preferably 0.01 by the above measuring method.
Use ~ 1.8 ml / g. When the void volume in the resin powder is smaller than 0.001 ml / g, the amount of the liquid catalyst component that can be contained in the resin powder is remarkably small and the activity when subjected to polymerization is low, which is not preferable. Further, when the void volume in the resin powder is larger than 2 ml / g, the particle density of the resin powder itself becomes small, and when the liquid catalyst component is added to such a resin powder for gas phase polymerization, the liquid catalyst is polymerized. It is not preferable because it may cause problems such as easy scattering to the circulation system outside the reactor.

The liquid catalyst component is not particularly limited as long as it is a liquid catalyst for olefin polymerization containing a transition metal compound. The catalyst itself may be liquid, or may be a liquid catalyst of a solution dissolved in an appropriate solvent. Preferably, the one dissolved in a solvent is used. As a solvent,
Preferably used are hydrocarbon compounds, particularly aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene. As the transition metal compound, Group IV to Group VIII of the Periodic Table, preferably Group
Compounds of group IV to group VI can be used, and specific examples thereof include Ti, Zr, Hf, V, Cr and Mo. Examples of preferred specific liquid catalysts include Ti compounds such as ethyl vanadate (VO (OEt) ₃ ),
A soluble Ziegler catalyst composed of a V compound or a compound composed of Ti and V and an organometallic compound of Group I to Group III of the periodic table, for example, an organoaluminum compound, or a ligand having a cyclopentadiene structure is coordinated. And a complexed Zr and / or Hf compound, and a soluble metallocene catalyst comprising a reaction product of an organometallic compound of Group I to III of the periodic table or an organometallic compound such as alumoxane and water. . Next, the soluble metallocene catalyst will be described.

The soluble metallocene catalyst is a complex of at least one ligand having a cyclopentadiene structure coordinated with a transition metal compound of Group IVB, such as Zr or T.
It is characterized in that it contains a transition metal complex such as i and Hf, and the solvent is preferably a saturated hydrocarbon, particularly an aliphatic hydrocarbon such as hexane and heptane, an alicyclic hydrocarbon such as cyclohexane, or benzene, toluene, ethylbenzene. , A solution dissolved in an aromatic hydrocarbon such as xylene. More specifically, for example, it comprises a group IVB transition metal compound in which at least one ligand having a cyclopentadiene structure is coordinated to form a complex, and an organoaluminumoxy compound such as methylaluminoxane, A catalyst containing an organoaluminum compound as the case requires. Anions of Bronsted or Lewis acids such as boron compounds can also be used with or in place of organoaluminum oxy compounds such as methylaluminoxane.

Aluminoxane can be produced, for example, by the following known method. That is,
(1) A method of reacting an organic aluminum compound such as trialkylaluminum with a hydrocarbon solution of water-containing salts to recover a hydrocarbon solution, (2) an organic aluminum compound such as trialkylaluminum in an organic solvent. It is produced by a method of directly reacting with water, steam or the like to recover an organic solvent solution and (3) a method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide in an organic solvent. The thing by any of these methods can also be used.

Examples of the organoaluminum compound used for producing the aluminoxane include trialkylaluminums such as trimethylaluminum and triethylaluminum, tricycloalkylaluminums such as tricyclohexylaluminum, and dialkylaluminum halides such as dimethylaluminum chloride. To be done.

The Group IVB transition metal compound in which at least one ligand having a cyclopentadiene structure is coordinated to form a complex is specifically a transition metal such as Zr, Ti or Hf as a central metal. Which has at least one of its ligands having a cyclopentadiene structure. The ligand other than the ligand having a cyclopentadiene structure may be any ligand, for example, a hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom and the like.
Examples of the ligand having a cyclopentadiene structure include an alkyl-substituted cyclopentadienyl group such as a cyclopentadienyl group and a methylcyclopentadienyl group, a dicyclopentadienyl group, a methyldicyclopentadienyl group. Examples thereof include alkyl-substituted dicyclopentadienyl groups, indenyl groups, tetrahydroindenyl groups, fluorenyl groups, and the like. These may be substituted with a halogen atom, a trialkylsilyl group or the like.

Specific examples of the transition metal compound in which the Group IVB transition metal is Zr include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide and bis (cyclopentadienyl). ) Methyl zirconium monochloride, bis (cyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) zirconium dichloride and the like. In the present invention, a transition metal compound in which the zirconium metal of the zirconium compound is replaced with a titanium metal or a hafnium metal is also exemplified.

Examples of the organoaluminum compound used in combination as necessary include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum and the like.

The atomic ratio of the aluminum of the organoaluminum oxy compound to the transition metal of the Group IVB transition metal compound containing a ligand having a cyclopentadiene structure is usually 10 to 3000, preferably 20 to 2000. is there. The atomic ratio of the aluminum of the organoaluminum compound and the aluminum of the organoaluminum oxy compound, which are used in combination as needed, is usually in the range of 0.02 to 3, preferably 0.05 to 1.5.

Organoaluminumoxy compounds, Group IVB transition metal compounds containing a ligand having a cyclopentadiene structure, and organoaluminum compounds optionally used in combination are preferably saturated hydrocarbons, particularly hexane and heptane. Aliphatic hydrocarbons such as, cycloaliphatic hydrocarbons such as cyclohexane or benzene, toluene,
It is used as a liquid catalyst for olefin polymerization in the state of a solution dissolved in an aromatic hydrocarbon such as ethylbenzene or xylene. Although the catalyst of the present invention is supplied to the apparatus shown in FIG. 1 in the form of a solution with an organic solvent, it is important that it is a liquid even after being enclosed in the resin powder. Therefore, FIG.
It is preferable to employ a means such as cooling so that the solvent does not dry during the treatment by the apparatus of 1. The solid catalyst obtained by encapsulating these liquid catalysts in a resin powder by the method of the present invention can be used alone for olefin polymerization, and further contains an organometallic compound of Group I to Group III of the periodic table. It can also be added and used for the polymerization of olefins.

Next, the method for producing the solid catalyst of the present invention using the resin powder and the liquid catalyst component obtained as described above will be further described. The apparatus shown in FIG. 1 is disassembled in advance, each part, casing, etc. are washed with hexane and reassembled. Next, an inert gas is supplied from the inert gas cylinder 9 to sufficiently purge all lines. The resin powder is supplied to the supply pot 7 in the presence of an inert gas. 0.1 to 0.3 with the inert gas in the casing 1.
A slight pressure is applied to kg / cm ² G, the motor 5 is driven, and the disk 3 is rotated to circulate a high-speed air stream in the circulation line 6. Next, the valves 15 and 16 are opened to cause the mixed powder in the supply pot 7 to be co-flowed with the air stream and supplied to the casing 1.
The impact vanes 2 and the inner wall of the casing 1 are caused to collide. At this time, the powder particles collide with each other at the same time. The rotation speed of the disk 3 is set in the range of the peripheral speed of 30 to 120 m / s. It is necessary to take care that the resin powder used does not melt due to heat. After treating the resin powder for about 1 to 10 minutes, the liquid catalyst component for olefin polymerization is injected through the valve 11 using a syringe equipped with a purging device for preventing the inflow of air. The injection rate of the liquid catalyst component is not particularly limited, but a range of 0.1 to 3 ml / min is preferable.
The treatment time after injecting the liquid catalyst component is not particularly limited, but is 1 to 30 minutes, preferably 1 to 10 minutes. Then, the ram valve 12 is opened, and the resin powder containing the liquid catalyst component is collected together with the air flow in the product pot 8 sufficiently purged with the inert gas.

There are no particular restrictions on the material of the casing and the rotating body of the above apparatus, but it is desirable that the material be extremely wear-resistant and that the olefin polymerization catalyst is not deactivated. Similarly, the gas supplied to the apparatus for generating a high-speed air flow is also preferably an inert gas having very few impurities such as water, carbon monoxide, and carbon dioxide that deactivate the olefin polymerization catalyst, It is particularly preferable to use high-purity nitrogen gas.

The volume of the liquid catalyst component used is 0.1 to 1 times the total volume of the void volume, which is the product of the void volume (ml / g) of the resin powder particles and its usage amount (g), preferably 0.1. 5-0.
95 times. When the amount of the liquid catalyst component is remarkably small and less than 0.1 times the total volume of the void volume in the resin powder, the content of the liquid catalyst component is remarkably small and the activity when subjected to polymerization is low. When the volume of the liquid catalyst component is larger than the total volume of the void volume in the resin powder, the fluidity of the resin powder catalyst containing the liquid catalyst component is significantly deteriorated, and when the catalyst is recovered or supplied to the polymerization reactor. Etc. will cause trouble in handling the catalyst.

There are no particular restrictions on the temperature conditions of the above apparatus, but the operation is carried out at an ambient temperature lower than the melting point of the resin powder in order to prevent fusion of the resin powder due to heat generation mainly due to impact. Is desirable. This ambient temperature can be maintained by cooling the casing with cooling water or the like. It is preferable that not only the supply of each material to the apparatus of FIG. 1 but also the discharge of the obtained solid catalyst is performed under an inert gas, for example, a high-purity nitrogen atmosphere.

Polymerization of olefins using a catalyst obtained by impregnating a resin powder with the liquid catalyst component of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization. In particular, the catalyst of the present invention can be suitably used for slurry polymerization and gas phase polymerization. In the polymerization, an organometallic compound may be used in combination, but it may not be used. Specific preferred examples of the organometallic compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, methylaluminoxane and the like. All polymerization reactions are carried out in a state where oxygen, water, etc. are substantially cut off. In the case of slurry polymerization, it is carried out in the presence of an inert hydrocarbon such as hexane and heptane, and in the case of gas phase polymerization, it is carried out in the absence of a solvent.

The polymerization conditions of olefin are that the temperature is 20 to 1
The temperature is 20 ° C., preferably 50 to 100 ° C., and the pressure is atmospheric pressure to 70 kg / cm ² , preferably ² to 60 kg / cm ² . The molecular weight can be controlled to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it can be effectively performed by adding hydrogen to the polymerization system. Of course, there is no problem even if the catalyst of the present invention is used to carry out a two-step or multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature.

The method of the present invention can be applied to the polymerization of all olefins, but α-olefins having 2 to 12 carbon atoms are particularly preferable, for example, ethylene, propylene, 1-butene, 1-hexene, 4 Homopolymerization of α-olefins such as -methyl-1-pentene and ethylene and propylene, ethylene and 1-butene, ethylene and 1
-Hexene, ethylene and ethylene such as 4-methyl-1-pentene and the like, copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, copolymerization of propylene and 1-butene, and ethylene and two or more kinds of other α-. It is preferably used for copolymerization with olefins. Further, copolymerization with a diene for the purpose of modifying the polyolefin is also preferably carried out. Examples of the diene compound used at this time include butadiene,
1,4-hexadiene, ethylidene norbornene, dicyclopentadiene and the like can be mentioned. The comonomer content at the time of polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene with an α-olefin having 3 to 12 carbon atoms, in the ethylene / α-olefin copolymer, The α-olefin content of is 0 to 40 mol%, preferably 0 to 30 mol%.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples. <Example 1> (1) Production of solid catalyst High-density polyethylene powder (density of 0.
9643g / cm ³ , average particle size 80μm, MFR 8.8g / 10mi
n, void volume 0.04 ml / g) was used. 1 with stirrer
Put 100 g of the above powder in a liter flask,
300 ml of a 0.1 mmol / ml hexane solution of triethylaluminum was added, and the mixture was stirred at room temperature for 1 hour. Then, hexane was removed under heating and reduced pressure. On the other hand, as a liquid catalyst, a toluene solution of methylaminooxane (concentration 10 mm
bis (cyclopentadier) zirconium dichloride (0.6 g, 2 mmol) was added to 3 ml of ol / ml) and reacted at room temperature for 1 hour to prepare a catalyst component solution. The apparatus shown in FIG. 1 was disassembled in advance, each component, casing and the like were washed with hexane and then reassembled. It was confirmed that the oxygen concentration at each outlet to the atmosphere was within 1 ppm by using an oxygen analyzer, by supplying nitrogen gas from the nitrogen gas cylinder 9 to purge air and water in all lines. A 100 g sample of the high-density polyethylene resin powder was supplied from the flask to the supply pot 7 while purging with nitrogen in a plastic bag to prevent the resin from being exposed to air. The inside of the casing 1 is 0.1 kg / cm with the nitrogen gas from the nitrogen cylinder 9.
^By adjusting the pressure to ² G and driving the motor 5, the nitrogen gas in the casing 1 was circulated at high speed in the circulation line 6. The valves 15 and 16 were opened, and the resin particles in the supply pot 7 were put on the air flow to collide with the inner wall of the casing 1 and also to collide with each other. Two minutes after the resin powder was supplied and the treatment was started, the prepared liquid catalyst component was injected over 3 minutes from the valve 11 of FIG. 1 using a syringe equipped with a purging device for preventing the inflow of air. did. Three minutes after the injection, put a polybag for nitrogen purging on the filter 14 and the product pot 8 and open the ram valve 12 installed in the casing 1 while purging with nitrogen,
The resin powder inside was collected in the product pot 8 together with the air flow.
The recovered amount was about 82 g, which was a powder having good fluidity.

(2) Gas phase polymerization Using a stainless steel autoclave equipped with a stirrer as a gas phase polymerization apparatus, a circulation system including a blower, a flow rate controller and a dry cyclone is formed, and hot water is flown into a jacket of the autoclave. The temperature was adjusted by. 60
To the autoclave adjusted to ℃, 5 g / h of the above solid resin catalyst and a toluene solution of methylaluminoxane (1 mmol / ml) were fed at a rate of 30 mmol / h, and 1-butene / ethylene in the gas phase of the autoclave was supplied. Each gas was supplied while adjusting the molar ratio of to be 0.25, and while maintaining the total pressure at 8 kg / cm ² G, the gas in the system was circulated by a blower to intermittently withdraw the produced polymer for 10
A continuous polymerization of time was carried out. The catalyst efficiency was as high as 70,000 g-copolymer / g-Zr. The ethylene copolymer produced has a melt flow rate (MFR) of 5.05 g / 10 min.
(Based on ASTM D1238-65T), density 0.925
g / cm ^3, a bulk density of 0.46 g / cm ^3, was a round particulate matter having an average particle size of 360 .mu.m. No polymer was attached to the inner wall of the autoclave and the stirrer.

Example 2 (1) Production of Solid Catalyst The same polyethylene powder as in Example 1 was used as the resin powder. The liquid catalyst was prepared by the following method. First, 1.0 g of ethyl vanadate (VO (OEt) ₃ ) was added to 2 ml of heptane.
(5 mmol) was dissolved, 3.1 g (25 mmol) of ethyl aluminum sesquiclide was added dropwise thereto at room temperature, and the mixture was reacted at room temperature for 1 hour to prepare a catalyst component solution.
This was fed to the same equipment as in Example 1 and similarly 74 g
A solid resin catalyst having good fluidity was obtained. (2) Gas phase polymerization Using the same polymerization apparatus as in Example 1, gas phase polymerization was carried out. 6
Add the above solid resin catalyst to an autoclave adjusted to 0 ° C.
Feed at the rate of g / h, 1-butene in autoclave /
Each gas was supplied while adjusting the ethylene molar ratio to 0.45, and the gas in the system was circulated by a blower while maintaining the total pressure at 8 kg / cm ² G, while intermittently extracting the produced polymer. Continuous polymerization was carried out for 10 hours. The catalyst efficiency was as high as 70,000 g-copolymer / g-Zr. The produced ethylene copolymer has a melt flow rate (MF
R) 4.22g / 10min, a density 0.9223 g / cm ^3, a bulk density of 0.43 g / cm ^3, was a round particulate matter having an average particle size of 420 [mu] m. No polymer was attached to the inner wall of the autoclave and the stirrer.

[0030]

By using the method of the present invention, it is possible to produce a powder catalyst in which a liquid catalyst is contained in a resin powder and can be handled in the same manner as a solid catalyst.
Furthermore, when performing gas phase polymerization using this powder catalyst,
It can be supplied to a polymerization reactor in exactly the same manner as a solid catalyst supported on an inorganic carrier that is usually used, and by carrying out polymerization of an olefin in contact with a co-catalyst, particles having a uniform particle shape and a bulk density of A polymer powder having high fluidity and excellent flowability can be produced.

[Brief description of drawings]

FIG. 1 is a schematic process diagram of an apparatus used in the present invention.

FIG. 2 is a side view of the inside of the casing as seen from the line II-II in FIG.

[Explanation of symbols]

 1 Casing 2 Impact Blade 3 Disc 4 Conical Protrusion 5 Motor 6 Circulation Line 7 Supply Pot 8 Product Pot 9 Inert Gas Cylinder 12 Ram Valve 14 Filter

Claims (3)

[Claims] 1. The void volume inside the particles is 0.001-2 ml /
Solid catalyst for olefin polymerization, which is obtained by encapsulating a liquid catalyst for olefin polymerization in resin powder in the range of g. 2. A resin powder having voids inside the particles is repeatedly collided between a high-speed rotating body and a stationary body arranged in the vicinity thereof in the presence of a liquid catalyst for olefin polymerization. A method for producing a solid catalyst for olefin polymerization, which comprises obtaining a resin powder in which the liquid catalyst for olefin polymerization is enclosed. 3. A resin powder having voids inside a particle is repeatedly collided between a high-speed rotating body and a stationary body arranged in the vicinity thereof in the presence of a liquid catalyst for olefin polymerization. A method for polymerizing olefins, characterized in that the obtained resin powder in which the liquid catalyst for olefin polymerization is enclosed is used.