JPH0995503A - Method for changing catalyst in steady vapor phase polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which the influence, such as gel formation, of a residual catalyst can be eliminated quickly when the catalyst change from a transition metal catalyst having a property of forming a high-molecular-weight polyolefin to a transition metal catalyst having a property of forming a low- molecular-weight polyolefin in the vapor-phase polymerization during a steady operation is performed. SOLUTION: This method for changing catalysts in the steady vapor phase polymerization of an olefin comprises the steps of: polymerizing an olefin in a vapor phase in the presence of a transition metal catalyst (1) having a property of forming a high-molecular-weight polyolefin, deactivating the catalyst (1) remaining in the reaction system, packing polyolefin particles, as polymer seeds, having a property of being not polymerized by the catalyst (1) into the reaction system and starting the polymerization again after a transition metal catalyst (2) having a property of forming a low-molecular polyolefin is supplied.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method of operating a reactor for producing a polyolefin by a gas phase polymerization method. More specifically, the present invention relates to a method for switching a transition metal-based catalyst having a high molecular weight polyolefin-forming ability to a transition metal-based catalyst having a low molecular weight polyolefin-forming ability in a gas phase polymerization apparatus which is operating steadily.

[0002]

2. Description of the Related Art As a reactor used for gas phase polymerization of olefins, a fluidized bed type, a stirred bed type, or a combination type of both types is mainly used (for example, JP-B-47-13962 and JP-A-51-51). No. 8584, etc.). As a catalyst for producing a polyolefin by polymerizing an olefin in a gas phase, a Ziegler-Natta type transition metal catalyst is conventionally used. In recent years, a new catalyst composed of a zirconium compound and a modified organoaluminum compound (JP-A-58-19309) has been proposed, and a completely different new catalyst has also been proposed (JP-A-5-19).
4639 gazette, JP-A-5-132518). In this way, various transition metal-based polymerization catalysts have been proposed. Of course, in these catalysts, not only different catalysts but also catalysts of the same system, their polymerization behavior, particularly the same MFR, can be provided. In many cases, the polymerization conditions for the use differ considerably.

Here, in industrial production, the catalyst supplied in the same reactor is often switched to continue production in order to switch the products to be produced. However, when switching from a transition metal-based catalyst having a high molecular weight polyolefin-forming ability to a transition metal-based catalyst having a low molecular weight polyolefin-forming ability, there is a problem that the residual catalyst of the polymerization after the switching is affected after the switching. For example,
In the case of producing a film grade after switching, if a transition metal-based catalyst having the ability to form a high molecular weight polyolefin remains, it is likely to cause gel generation. If it is merely a replacement of the contents of the reactor, it is assumed that a normal transient response is shown, and if the accumulated production amount is 13 times or more of the residence amount in the polymerization reactor, the residual concentration of the initial contents is It is expected to fall below 5 ppm by weight. However, when polymerizing an olefin in a gas phase to produce a polyolefin, some fine particles circulate in a circulation system, and some of them adhere to the inner surface of a pipe or accumulate in a dead space, and some of them It is peeled off and supplied again into the polymerization tank. Therefore, removal of the residual catalyst is not easy.

Therefore, a method of deactivating the catalyst in advance when switching the catalyst and then switching the catalyst can be considered. The method for stopping the polymerization of transition metal catalysts that have the ability to produce high molecular weight polyolefins such as Ziegler catalysts is to supply a kill gas (terminating agent) such as carbon dioxide into the system or open the system to the atmosphere. And how to introduce. That is, for example, a Ziegler-based catalyst uses a terminating agent such as an oxygen-containing compound such as carbon monoxide, carbon dioxide, oxygen, or air to stop the polymerization urgently (for example, US Pat. No. 430).
6044, U.S. Pat. No. 4,326,048, JP-A-60
-72904, etc.). Also, if the system is not opened extensively, the introduced air will not reach the entire system. Usually, the partition is inserted between the upper and lower piping parts of the polymerization tank, and only the inside of the tank is opened to inspect the inside. Therefore, deactivation may not always be sufficient. In addition, when the polymerization is restarted after the reaction is stopped, if impurities such as a terminating agent are once supplied to the system, after purging with an inert gas such as nitrogen, the inside is preliminarily cleaned with alkylaluminum or the like. It is being processed. In addition to stopping the reaction by using a terminating agent, in the case of stopping the polymerization by releasing the inside, similarly, the inside is pretreated in advance with alkylaluminum or the like.

However, as described in the above-mentioned US Pat. No. 4,326,048, when alkylaluminum is re-supplied, the once deactivated catalyst may be restored and the polymerization activity may be exhibited again. Regarding the supply of alkylaluminum, it may be supplied continuously not only during the treatment before the polymerization but also during the continuous polymerization depending on the kind of the catalyst system including the Ziegler catalyst (for example, JP-A-7-258).
45 gazette). Since there is a possibility of resupply of alkylaluminum after deactivation in this way, simply by adopting a stopping method such as a method of supplying a stopping agent into the system or a method of opening the system and introducing air into the system, It is difficult to eliminate the effects of residual catalyst.

[0006]

[Problems to be Solved by the Invention] When switching from a transition metal-based catalyst having a high molecular weight polyolefin-forming ability to a transition metal-based catalyst having a low molecular weight polyolefin-forming ability, promptly eliminate the influence of residual catalyst such as gel formation. This is an object of the present invention.

[0007]

That is, the first aspect of the present invention
Relates to a catalyst switching method in steady-state gas phase polymerization of an olefin, characterized by comprising the following steps (1) to (4). (1) A step of constantly polymerizing an olefin in a gas phase with a transition metal catalyst [I] capable of forming a high molecular weight polyolefin, and (2) a step of deactivating the catalyst [I] present in the reaction system. , (3) a step of forming a gas phase polymerization bed using polyolefin particles having substantially no polymerization activity by the catalyst [I] as a seed polymer, (4) a transition metal catalyst [II] capable of forming a low molecular weight polyolefin. The step of restarting the polymerization by supplying the olefin to constantly carry out the gas phase polymerization of the olefin. A second aspect of the present invention is the polyolefin particle according to the first aspect of the present invention, which has substantially no polymerization activity by the catalyst [I] in the step (3), but has polymerization activity by the catalyst [II]. The present invention relates to a catalyst switching method in steady-state gas phase polymerization of olefin, which is used as a seed polymer. A third aspect of the present invention is the above-mentioned first aspect of the present invention, wherein the catalyst [I] is used.
Is composed of a solid catalyst component containing at least titanium and / or vanadium and magnesium, and an organoaluminum compound, and relates to a catalyst switching method in steady-state gas phase polymerization of an olefin. In a fourth aspect of the present invention, in the first aspect of the present invention, an organoaluminum compound is supplied after the deactivation in the step (2) or in the step (4). The present invention relates to a catalyst switching method in steady-state gas phase polymerization. A fifth aspect of the present invention is the steady-state vapor phase polymerization of olefin, which is the catalyst according to the first aspect of the present invention, wherein the catalyst [II] is obtained by bringing the following components (1) to (5) into contact with each other. The present invention relates to a catalyst switching method. (1) A compound containing a Group IVB metal of the periodic table, (2)
A compound containing any of metals I to III of the periodic table,
(3) an organic cyclic compound having two or more conjugated double bonds,
(4) A modified organoaluminum compound and / or a boron compound having an Al-O-Al bond, (5) an inorganic compound carrier and / or a particulate polymer carrier.

The present invention will be described in detail below. Step (1) In the present invention, the catalyst is switched from the transition metal catalyst [I] capable of forming high molecular weight polyolefin to the transition metal catalyst [II] capable of forming low molecular weight polyolefin. Here, the meaning of the transition metal catalyst [I] having the ability to form a high molecular weight polyolefin (hereinafter, may be simply referred to as the catalyst [I]) in the present specification means a transition metal catalyst for olefin vapor phase polymerization. And hydrogen /
Under the same polymerization conditions such as olefin molar ratio, a transition metal catalyst [I
I] means a catalyst that produces a higher molecular weight polyolefin. Similarly, a transition metal catalyst [II] (hereinafter, simply referred to as a catalyst [I
I]. ) Is a transition metal catalyst for olefin vapor phase polymerization and has a lower molecular weight than the transition metal catalyst [I] capable of producing high molecular weight polyolefin under the same polymerization conditions such as hydrogen / olefin molar ratio. Means a catalyst for producing a polyolefin. Therefore, high molecular weight and low molecular weight herein are merely relative. The present invention is preferably applied when there is a difference in the molecular weights of polyolefins produced to the extent that MFR values differ by 10 times or more, preferably 50 times or more. As long as the above conditions are met, the catalyst can be used with the catalyst [I] in the step (1) and the catalyst [II] in the step (4) without particular limitation.

However, the preferable catalyst [I] is, for example, a transition metal catalyst comprising a solid catalyst component containing at least titanium and / or vanadium and magnesium and an organometallic compound. As the solid catalyst component, a solid catalyst component containing titanium and magnesium, which is used in a Ziegler-based catalyst conventionally known as a catalyst for olefin polymerization, a solid catalyst component containing vanadium and magnesium or a solid containing titanium, vanadium and magnesium. A catalyst component or the like can be used.

Next, the catalyst composed of a solid catalyst component containing at least titanium and / or vanadium and magnesium and an organometallic compound will be described. For example, metal magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, etc., or a double salt, double oxide, carbonate, chloride or hydroxide containing magnesium and an element selected from silicon, aluminum and calcium. Etc., and inorganic solid compounds containing magnesium such as those obtained by treating or reacting these inorganic solid compounds with oxygen-containing compounds, sulfur-containing compounds, aromatic hydrocarbons, halogen-containing substances, titanium compounds and / or vanadium compounds. Examples thereof include those obtained by carrying a known method.

Examples of the oxygen-containing compound include water; polysiloxane; organic oxygen-containing compounds such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters and acid amides; metal alkoxides; inorganic compounds such as metal oxychlorides. An oxygen compound can be illustrated. Examples of the sulfur-containing compound include organic sulfur compounds such as thiol and thioether, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide and sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic or polycyclic aromatic hydrocarbons such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of the halogen-containing substance include chlorine, hydrogen chloride, metal chlorides and organic halides.

Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides,
Examples thereof include halogenated oxides. Of these, a tetravalent titanium compound and a trivalent titanium compound are preferable, and the tetravalent titanium compound is specifically represented by the general formula T
i (OR) _n X _4-n (wherein R represents a hydrocarbon residue such as an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms, X represents a halogen element, and n represents 0 ≦ n ≦ 4), and specifically titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxy. Titanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium,
Diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, tributoxymonochlorotitanium, tetrabutoxytitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichloro. Titanium, triphenoxy monochloro titanium, tetraphenoxy titanium, etc. can be mentioned. As a trivalent titanium compound, a general formula Ti (OR) _m X _4-m (where R is a carbon number of 1 to
20 represents a hydrocarbon residue such as an alkyl group, an aryl group or an aralkyl group, and X represents a halogen element. m is a number in the range of 0 <m <4) and is obtained by reducing tetravalent alkoxytitanium halide represented by the formula: hydrogen, aluminum, titanium or an organometallic compound of Group I to Group III metal of the periodic table. And a trivalent titanium compound that can be used.

Of the above titanium compounds, tetravalent titanium compounds are particularly preferable. Specific examples of these catalysts include, for example, MgO-RX-TiCl ₄ system (Japanese Examined Patent Publication 5).
1-3514 _{JP), Mg-SiCl 4 -ROH-} T
iCl ₄ system (Japanese Patent Publication No. 50-23864), MgC
_{l 2 -Al (OR) 3 -TiCl} 4 system (JP-B 51-15
No. 2, JP-B-52-15111), MgCl
_2- SiCl ₄ -ROH-TiCl ₄ system (JP-A-49-1)
No. 06581), Mg (OOCR) ₂ -Al (O
R) ₃ -TiCl ₄ system (Japanese Patent Publication No. 52-11710), Mg-POCl ₃ -TiCl ₄ system (Japanese Patent Publication No. 51-1)
53), MgCl ₂ —AlOCl—TiCl ₄ system (Japanese Patent Publication No. 54-15316), MgCl ₂ —Al
_{(OR) n - X 3-} n -Si (OR ') m X 4-m -TiCl
₄ system (JP-A-56-95909), MgCl ₂ -R
OH- siloxane _{-Ti (OR) m X 4-} m -TiCl 4 system (Japanese Patent Application No. 5-284095), MgCl ₂ -RO
H- In surfactant _{-Ti (OR) m X 4-} m -TiCl 4 based solid catalyst component (Japanese Patent Application No. 5-284096 Patent Publication), etc. (In the formula, R and R 'are organic residue, X Represents a halogen atom) and a combination of an organoaluminum compound is mentioned as a preferred example.

As the vanadium compound, a tetravalent vanadium compound such as vanadium tetrachloride, vanadium tetrabromide and vanadium tetraiodide, a vanadium compound such as vanadium oxytrichloride and orthoalkylvanadate,
Examples thereof include trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. The vanadium compound is used alone or in combination with the titanium compound.

Another example of the catalyst system is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound and / or a vanadium compound is used as a solid catalyst component, and an organoaluminum compound is combined therewith. Can be illustrated. As the organic magnesium compound, for example, a general formula RMgX,
A magnesium compound represented by R ₂ Mg, RMg (OR), or the like (wherein R represents an organic residue having 1 to 20 carbon atoms, X represents a halogen atom), an ether complex thereof, or an organomagnesium compound thereof. In addition, other organometallic compounds, such as organosodium, organolithium, organopotassium, organoboron, organocalcium, organozinc, and the like, which have been modified and added can be used. Specific examples of the catalyst system include, for example, RMgX-TiCl.
₄ system (Japanese Patent Publication No. 50-39470), RMgX-phenol-TiCl ₄ system (Japanese Patent Publication 54-12953), RMgX-halogenated phenol-TiCl ₄ system (Japanese Patent Publication 54-12954), RMgX- CO ₂
There may be mentioned a combination of a solid catalyst component such as —TiCl ₄ system (JP-A-57-73009) with an organoaluminum compound.

Another example of the catalyst system contains, as a solid catalyst component, an inorganic oxide such as SiO ₂ , Al ₂ O ₃ and SiO ₂ .Al ₂ O ₃ and the above titanium and / or vanadium and magnesium. A solid substance obtained by contacting with a solid catalyst component is used, and an organoaluminum compound in combination therewith can be exemplified.
As the inorganic oxide, the above-mentioned SiO ₂ , Al ₂ O ₃ and Si are used.
In addition to O ₂ · Al ₂ O _3, etc., CaO, B ₂ O ₃ , SnO _2, etc. can be mentioned, and a double oxide of these oxides can also be used. In order to bring these various inorganic oxides into contact with the solid catalyst containing titanium and / or vanadium and magnesium, known methods can be adopted. That is, in the presence or absence of an organic solvent such as an inert hydrocarbon, an alcohol, a phenol, an ether, a ketone, an ester, an amine, a nitrile, or a mixture thereof, at a temperature of 20 to 4
5 minutes usually at 00 ° C, preferably 50 to 300 ° C
You may react by the method of making it react for 20 hours.

As a concrete example of the above catalyst system, for example, SiO ₂ --ROH--MgCl ₂ --TiCl ₄ (JP-A-56)
-47407 discloses), SiO ₂ -ROR'-MgO-
AlCl ₃ —TiCl ₄ (JP-A-57-187305), SiO ₂ —MgCl ₂ —Al (OR) ₃ —TiCl ₄
-Si (OR ') ₄ (JP 58-21405 _{JP), SiO 2 -TiCl 4 -R n} AlCl 3-n -MgCl
_{2 -Al (OR ') n Cl} 3-n ( _{JP-A-3-35004), SiO 2 -TiCl 4 -R} n AlCl 3-n -Mg
_{Cl 2 -Al (OR ') n} Cl 3-n -Si (OR ") m
Cl _4-m (JP-A-3-64306), SiO ₂ -M
_{gCl 2 -Al (OR ') n} Cl 3-n -Ti (OR ") 4 -
R _n AlCl _3-n (JP-A-3-153707), S
_{iO 2 -MgCl 2 -Al (OR '} ) n Cl 3-n -Ti (O
_{R ") n Cl 4-n} -R n AlCl 3-n ( JP 3-1850
4 _{JP), SiO 2 -TiCl 4 -R n} AlCl 3-n -M
_{gCl 2 -Al (OR ') n} Cl 3-n -R "m Si (OR
^''' ) _N X _{4- (m + m)} (JP-A-4-261408),
_{SiO 2 -R n MgX 2-n} -Al (OR ') n Cl 3-n -T
_{i (OR ") n Cl 4} -n -R '''OH-R n AlX
_3-n (Japanese Patent Laid-Open No. 5-117316), SiO ₂ -M
_{gCl 2 -Al (OR ') n} Cl 3-n -Ti (OR ") n C
l _4-n -R ^''' OH-R _n AlCl _3-n (Japanese Patent Laid-Open No. 5-194
No. 634) (in the above formula, R, R ′, R ″, R
^"'' Indicates a hydrocarbon residue. ) Etc. in combination with an organoaluminum compound.

In these catalyst systems, a titanium compound and / or a vanadium compound can be used as an adduct with an organic carboxylic acid ester, and the above-mentioned inorganic solid compound containing magnesium is contact-treated with the organic carboxylic acid ester. It can be used later. Furthermore, an organoaluminum compound can also be used as an adduct with an organic carboxylic acid ester. Also, in all cases it is possible to use catalyst systems prepared in the presence of organic carboxylic acid esters. Examples of the organic carboxylic acid ester used here include various esters of aliphatic, alicyclic, and aromatic carboxylic acids, and aromatic carboxylic acid esters having 8 to 12 carbon atoms are preferably used.
Specific examples thereof include alkyl esters of benzoic acid, anisic acid, toluic acid such as methyl and ethyl. The solid catalyst component may be subjected to prepolymerization before being fed to the reaction system and used in the form of a so-called prepolymer coated with a polymer.

The organoaluminum compound which can be used in the present invention together with the solid catalyst component containing at least titanium and / or vanadium and magnesium as the solid catalyst component has at least one aluminum-carbon atom bond in the molecule. Refers to an organoaluminum compound. For example, (i) the general formula R _m Al
(OR ′) _n H _p X _q (wherein R and R ′ are hydrocarbon groups containing usually 1 to 15, preferably 1 to 4 carbon atoms, such as an alkyl group, an aryl group, an alkenyl group, and a cyclo group. An alkyl group, etc., and in the case of an alkyl group, methyl, ethyl, propyl, isopropyl, isobutyl, se
Examples thereof include c-butyl, tert-butyl, hexyl, octyl and the like. R and R'may be the same or different. X represents a halogen atom, and m, n, p, and q are 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ p <3, and 0 ≦ q <, respectively.
It is a number in the range of 3 and satisfying m + n + p + q = 3. ), An organoaluminum compound represented by
i) Group I metal and aluminum of the periodic table represented by the general formula MAlR ₄ (where M is a metal selected from Li, Na or K, and R is the same hydrocarbon group as described above). And complex alkyl compounds with and the like.

Examples of the organoaluminum compound belonging to the above (i) include, for example, the general formula R _m Al (OR ′) _3-m (wherein R and R ′ are the same hydrocarbon groups as described above. M is preferably 1.5 ≦ m ≦ 3), R _m AlX _3-m (wherein R is the same hydrocarbon group as described above, and m is preferably 0 <m <3). ), The general formula R _m AlH _3-m (wherein R is the same hydrocarbon group as described above, and m is preferably in the range of 2 ≦ m <3) and the general formula R _m Al (OR ′. ) _N X _q (wherein R and R ′ are the same hydrocarbon groups as described above. X represents a halogen atom, and m, n and q are preferably 0 <m ≦ 3, 0 ≦ n <3, (The number is within the range of 0 ≦ q <3 and satisfies m + n + q = 3.)
And the like can be exemplified.

Specific examples of the organoaluminum compound belonging to (i) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, Trialkylaluminums such as trioctylaluminum; Trialkenylaluminums; Dialkylaluminium alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and R _2.5 Partially alkoxylated alkylaluminum having an average composition such as Al (OR) _0.5 ; Dialkylaluminum halides such as aluminum chlorochloride, dibutylaluminum chloride and diethylaluminum bromide; partially halogenated alkylaluminums such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride, and alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride, partially hydrogenated alkyl aluminum; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, Partial such as ethyl aluminum ethoxy bromide And the like can be exemplified alkoxylated and halogenated alkylaluminum. Examples of the organoaluminum compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H ₁₅ ) _{4 and the} like. Further, as the organoaluminum compound similar to (i), an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can also be used. As such a compound, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
_{N (C 2 H 5) Al} (C 2 H 5) can be exemplified _2. Among these, trialkylaluminum is preferable.

The organoaluminum compound which can be used as the catalyst [I] together with the solid catalyst component containing at least titanium and / or vanadium and magnesium as the catalyst component is not particularly limited in the amount used during steady operation, but is usually a titanium compound. 0 to 1 mole.
The range of 05 to 1000 mol is preferable.

The olefin used in the polymerization in the step (1) usually has 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms.
Olefins, for example, α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1. These can be used for homopolymerization or copolymerization at an appropriate ratio. As the copolymerization, for example, ethylene /
Copolymerization of ethylene such as propylene, ethylene / butene-1, ethylene / pentene-1, ethylene / hexene-1, ethylene / 4-methylpentene-1 with an α-olefin having 3 to 12 carbon atoms, and ethylene and other Copolymerization with two or more kinds of α-olefins and the like. Further, copolymerization using a diene is also possible for the purpose of modifying the polyolefin. Examples of the diene used for this purpose include butadiene, 1,4-hexadiene, ethylidene norbornene,
Dicyclopentadiene etc. are illustrated. In addition, in the specification of the present application, the meaning of copolymerization is included in the polymerization. The olefin feed to the reaction system can be fed alone or preferably with a suitable inert carrier gas such as nitrogen. Thus, as the preferred catalyst in the catalyst [I], the steady operation of the olefin polymerization by the solid catalyst component containing at least titanium and / or vanadium and magnesium as the solid catalyst component is carried out according to a conventional method in which the olefin, the solid catalyst and the organoaluminum compound are The polymer particles are constantly introduced into the reaction system, while the polymer particles produced are withdrawn to constantly polymerize the polymer particles.

Step (2) As described above, the catalyst [I] is changed to the catalyst [I] from the steady operation.
Switching to steady operation by [I] will be described. First, the catalyst [I] existing in the entire system in the polymerization equipment is deactivated. Prior to this deactivation, the catalyst [I] supply was stopped while maintaining the polymerization conditions of the catalyst [I]. It is preferable to maintain the polymerization conditions other than the supply of the catalyst [I] until the reaction is sufficiently lowered. This is because by this operation, the amount of the catalyst [I] substantially existing in the system can be reduced and the amount of the gaseous deactivator supplied later can be reduced. If the amount of the supplied deactivating agent is small, the purging work can be simplified. In addition,
When it is necessary to stop the reaction urgently, the deactivating agent may be introduced into the reaction system to deactivate it without stopping the supply of the catalyst [I]. In such a case, the supply of the catalyst is stopped at the same time as or after the introduction of the deactivator. The same applies to the stop of olefin supply.

Specifically, the supply of the catalyst is stopped (when the organoaluminum compound is supplied, the supply rate of the organoaluminum compound is reduced in accordance with the production rate of the olefin), and the olefin accompanying the olefin consumption Is maintained to maintain the pressure in the polymerization system, and gas circulation is continued. The polymer in the system can be appropriately extracted. Although the cooling of the circulating gas is also appropriately maintained, the heat generation in the reactor decreases as the polymerization decreases. After the polymerization rate in the reaction system is sufficiently reduced, the olefin supply is also stopped,
Only the system gas is circulated. Usually, the time required for this stop is several hours to several days, although it depends on the nature of the catalyst, the internal volume of the system, and the like.

After the reaction is stopped, the catalyst [I] is deactivated. The deactivation of the catalyst [I] is performed so as to deactivate the catalyst present not only in the polymerization tank but also in the entire polymerization system including the gas circulation system. In the deactivating operation, a method of performing the deactivating operation while holding the polymer powder remaining in the polymerization tank,
There is a method in which residual polymer powder is discharged from the polymerization tank and then deactivated. Preferably, the residual polymer powder is discharged from the polymerization tank and then deactivated.

The deactivating operation in the present invention is carried out by introducing a gaseous deactivating agent into the system. As the deactivator, a deactivator suitable for the properties of the catalyst [I] can be adopted, but in any case, the deactivator is naturally deactivated under the polymerization conditions of the step [4] with the catalyst [II]. It is necessary to employ a deactivator, its amount and deactivation method that do not restore the polymerization activity of the catalyst. Therefore, it is preferable to confirm the deactivating agent, its amount and deactivating method in another experiment in advance and to adopt it. Generally in a transition metal catalyst for olefin polymerization, usually,
Air containing water vapor (such as the atmosphere), oxygen containing water vapor, and water vapor itself are preferable. It is not preferable to use a deactivator such that the activity of the catalyst [I] is regenerated by the organometallic compound, for example, an organoaluminum compound, which may be supplied when the steady operation is restarted in step (4) after the catalyst is switched. For example, in the case of a solid catalyst component containing at least titanium and / or vanadium and magnesium as the catalyst component as the catalyst [I] in step (1), dry air containing almost no water vapor, molecular oxygen, carbon dioxide and monoxide. When carbon or the like is used as a deactivator, the activity of the catalyst [I] is restored when the organoaluminum compound, for example, alkylaluminum is supplied again, which is not preferable. Incidentally, an organoaluminum compound,
For example, alkylaluminum or the like may be introduced into the reaction system as one component of the catalyst or one component of the cocatalyst in the step (4), or, as described later, after treatment after the deactivation (step (4)). It may be introduced into the reaction system as a pretreatment. The gaseous quenching agent can be supplied into the system together with an appropriate carrier gas, for example, a reactive gas such as olefin, or preferably a non-reactive carrier gas such as argon, helium, nitrogen, particularly preferably nitrogen. .

A specific deactivating method can be appropriately selected according to various situations as described below. For example, when the whole system is closed and inactivated, it is divided into a case in which the powder is held in the polymerization tank to inactivate it and a case in which the powder is discharged and then inactivated. In any case, it is important to completely deactivate the catalyst [I] by circulating a gas containing a deactivator through the whole system using a blower such as a blower. It is not necessary to pay particular attention to the supply position of the deactivator in the case of discharging the powder. In the case of deactivating by holding the powder in the polymerization tank, the injection position of the deactivator is preferably immediately after the polymerization reaction tank. This is because when the deactivator is supplied from the lower part of the polymerization tank, the deactivator may be adsorbed to the polymer powder held in the polymerization tank first, and may not spread to the entire system. In such a case, the catalyst [I] in the entire system may not be deactivated unless a large amount of the deactivating agent is introduced. Once a large amount of the quenching agent is introduced into the system, the purging process of the excess quenching agent becomes complicated, which is not preferable. In any case, it is preferable that the minimum amount of the quenching agent is introduced, but it is necessary to select a sufficient amount of quenching. When deactivating the catalyst [I] existing in the polymerization system by opening the system and introducing the atmosphere, valves such as manholes, handholes, and drains at each site in the system should be installed so that dead space does not exist in the system It is preferable to open it to release the system. It takes a very long time to deactivate the catalyst [I] in the system simply by spontaneous diffusion of the air into the system.
Therefore, it is preferable to force the gas flow using a blower or the like. Specifically, for example, a method of introducing air from one end of the divided pipe using a blower and discharging the air from the opposite end can be adopted.

After the deactivating operation, it is preferable to appropriately remove the excess deactivating agent introduced into the system. The quenching agent can be removed by discharging the quenching agent out of the system as much as possible. The deactivator can be discharged to the outside of the system by purging the polymerization reaction system with an inert gas and substituting the gaseous deactivator. Nitrogen is preferred as the inert gas. In this method, nitrogen may be continuously circulated in the system, or it may be pressurized with nitrogen and then discharged to the vent. The temperature is a polymerization temperature and is 10 to 110 ° C, preferably 40 to 100 ° C. When purging by nitrogen circulation, the pressure is 0 to 1 MPa.
G, preferably 0.3 to 0.6 MPa · G.

In addition, in order to remove the quenching agent, the quenching agent is discharged to the outside of the system, and an organoaluminum compound is used.
It can also be carried out by reacting this with a quenching agent to convert the function of the residual quenching agent into a harmless one. Even in this case, it is preferable that the organoaluminum compound is introduced after the excess gaseous deactivator supplied in advance is discharged out of the system as much as possible. It is not necessary to pay particular attention to the supply position of the organoaluminum compound when the powder is discharged and deactivated. on the other hand,
When the powder is retained and deactivated, the injection position of the organoaluminum compound is preferably immediately after the polymerization reaction tank as in the case of introducing the deactivator. This is because, when organoaluminum is supplied from the lower part of the polymerization tank, the organoaluminum compound is first adsorbed by the polymer powder held in the polymerization tank and does not spread to the entire system, and part of the deactivator is piped. This is because there is a possibility of staying in the dead space inside. It is desirable to supply the organoaluminum compound while circulating nitrogen in the polymerization reaction system in order to make the organoaluminum compound uniformly dispersed. The nitrogen circulation pressure is 0 to 1 MPa · G, preferably 0.3 to 0.6.
It is suitable to carry out at MPa · G. The temperature of the circulating gas at this time is the same as the polymerization temperature of the catalyst [I], and is, for example, 10 to 110 ° C, preferably 40 to 100 ° C.
It is.

As the organoaluminum compound introduced into the system after the above deactivation, the same organoaluminum compound that may be used as a co-catalyst in the step (1) can be used. That is, the organoaluminum compound used herein refers to an organoaluminum compound having at least one aluminum-carbon atom bond in the molecule. For example, (i) the general formula R _m Al (O
R ′) _n H _p X _q (wherein R and R ′ are hydrocarbon groups containing usually 1 to 15, preferably 1 to 4 carbon atoms,
For example, it is an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or the like, and examples of the alkyl group include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, hexyl, octyl and the like. R and R'may be the same or different. X
Represents a halogen atom, and m, n, p, and q are 0 <
It is a number in the range of m ≦ 3, 0 ≦ n <3, 0 ≦ p <3 and 0 ≦ q <3, and satisfying m + n + p + q = 3. ), An organic aluminum compound represented by the formula (ii), and (ii) a general formula MAlR ₄ (where M is a metal selected from Li, Na or K, and R is the same hydrocarbon group as described above). , A complex alkyl compound of a Group I metal with aluminum in the periodic table, and the like.

Examples of the organoaluminum compound belonging to the above (i) include, for example, the general formula R _m Al (OR ′) _3-m (wherein R and R ′ are the same hydrocarbon groups as described above. M is preferably 1.5 ≦ m ≦ 3), R _m AlX _3-m (wherein R is the same hydrocarbon group as described above, and m is preferably 0 <m <3). ), The general formula R _m AlH _3-m (wherein R is the same hydrocarbon group as above, and m is preferably in the range of 2 ≦ m <3) and the general formula R _m Al (OR ′. ) _N X _q (wherein R and R ′ are the same hydrocarbon groups as described above. X represents a halogen atom, and m, n and q are preferably 0 <m ≦ 3, 0 ≦ n <3, (The number is within the range of 0 ≦ q <3 and satisfies m + n + q = 3.)
And the like can be exemplified.

Specific examples of the organoaluminum compound belonging to (i) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, Trialkylaluminums such as trioctylaluminum; Trialkenylaluminums; Dialkylaluminium alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and R _2.5 Partially alkoxylated alkylaluminum having an average composition such as Al (OR) _0.5 ; Dialkylaluminum halides such as aluminum chlorochloride, dibutylaluminum chloride and diethylaluminum bromide; partially halogenated alkylaluminums such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride, and alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride, partially hydrogenated alkyl aluminum; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, Partial such as ethyl aluminum ethoxy bromide And the like can be exemplified alkoxylated and halogenated alkylaluminum. Examples of the organoaluminum compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H ₁₅ ) _{4 and the} like. Further, as the organoaluminum compound similar to (i), an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can also be used. As such a compound, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
_{N (C 2 H 5) Al} (C 2 H 5) can be exemplified _2. Among these, trialkylaluminum is preferable. The addition amount of the organoaluminum compound is not particularly limited, but is 0.0 with respect to the total amount of the added quenching agent.
It can be appropriately selected from the range of 1 to 100 mol times.

Step (3) In the gas phase polymerization reaction using a fluidized bed of olefin, etc.,
A fluidized bed reactor is filled with a resin powder called a seed polymer in advance to start fluidization, and then a polymerization reaction is started. If the seed polymer is not used, the supplied catalyst is difficult to disperse and no granular resin is produced, and therefore a fluidized bed is not formed.Therefore, the seed polymer is always used at the start of operation in the fluidized bed polymerization reactor. . After the deactivation according to the present invention, when restarting the operation with the catalyst [II], the polymer powder remaining in the tank is discharged to the outside of the system and a new seed polymer is filled, and the remaining polymer powder is used as the seed polymer as it is. There is a method to use. Either method can be adopted in the present invention. Preferably, when restarting the operation with the catalyst [II], a method of discharging the polymer powder remaining in the tank to the outside of the system and filling a new seed polymer is used.

In the present invention, the seed polymer to be filled in the polymerization tank prior to the polymerization with the catalyst [II] is the following catalyst [II]
It is essential that the seed polymer does not have the same activity as the catalyst [I] under the polymerization conditions for. That is, it is important that the seed polymer has no polymerization activity that produces a polyolefin having a higher molecular weight than the catalyst [II] under the same polymerization conditions. The seed polymer is originally a seed polymer having the same activity as that of the catalyst [I] under the polymerization conditions for the catalyst [II], or the polymerization activity under the polymerization conditions for the next catalyst [II] is As a result of being revived,
When the seed polymer has the same polymerization activity as the catalyst [I], it is not preferable. For example, when a polyolefin powder obtained by polymerizing with a transition metal-based catalyst as described below is used as the seed polymer, a polyolefin having a higher molecular weight than that of the catalyst [II] is produced under the same polymerization conditions. It is possible that they have different polymerization activities.

As long as the above conditions are satisfied, the particles can be used as a seed polymer without particular limitation as long as they are particles capable of forming a gas phase polymerization bed such as a fluidized bed or a stirred bed. Usually polyolefin particles are preferred. The polyolefin particles are not particularly limited, but for example, polymer particles obtained by using the catalyst [I] or polymer particles obtained by using the catalyst [II], and particles that retain activity for each polymer particle The polymer particles having no polymerization activity due to the deactivation treatment can be used as a seed polymer. However, among these, as described above, the catalyst [I
It is not possible to use particles that may have polymerization activity to produce higher molecular weight polyolefins than I]. Therefore, polymer particles obtained from catalyst [I] that retain the polymerization activity of catalyst [I] cannot be filled as a seed polymer, and even if they are deactivated It is also not possible to use particles of inactive polymer particles in which the polymerization function of the catalyst [I] may be restored in some way.

When polymer particles obtained by using the catalyst [II] are introduced, the polymer particles may be subjected to a deactivation treatment, or may be used as a seed polymer while having the polymerization activity as the catalyst [II]. Good. Preferably, the particles are obtained from the catalyst [II], and the catalyst [II] is not subjected to deactivation treatment.
The polymer particles retain the polymerization activity as. For example, the polyolefin particles produced during the polyolefin polymerization using the catalyst [II] can be stored separately in an appropriate inert atmosphere such as nitrogen and used.

The seed polymer used in the present invention is preferably particles having an average particle size of 500 to 1500 μm and a bulk density of 250 to 500 kg / m ³ . The smaller the amount of fine powder having a particle size of less than 300 μm, the better. The seed polymer may be packed in any amount as long as it can form a fluidized bed or a stirred bed and is not particularly limited.

Except when the polymer particles held in the polymerization tank are used as a seed polymer, an inert gas may be used for purging after filling the seed polymer in order to remove impurities such as oxygen entrained during the filling. preferable.
That is, the inside of the polymerization reaction system is purged using an inert gas to replace the entrained impurities with the inert gas. Nitrogen is preferred as the inert gas. As this purging method, nitrogen may be continuously circulated in the system, or a method of pressurizing with nitrogen, discharging it to a vent and reducing the pressure, and repeating this may be used. The temperature at the time of purging is the same as the polymerization temperature of the catalyst [II], and is, for example, 10 to 110 ° C, preferably 40 to 100 ° C. When purging is performed by circulating nitrogen or the like, the pressure is 0 to 1 MPa · G, preferably 0.3 to 0.6 MPa · G.

Step (4) When the catalyst [I] or the catalyst [II] is charged with polymer particles deactivated by the deactivator as the seed polymer, the residual deactivator acts as the catalyst [II]. May affect the Therefore, in such a case, the organoaluminum compound is used to react with the quenching agent to produce a harmless compound,
That is, it is preferable to use a compound that does not become a catalyst poison. Since the seed polymer is filled in the polymerization tank, the injection position of the organoaluminum compound is preferably immediately after the exit of the polymerization reaction tank. The organoaluminum compound itself is also a catalyst [I
Since it may affect the polymerization of [I], it is preferable that the supply amount be the minimum necessary for detoxifying the quenching agent. It is desirable to supply the organoaluminum compound while circulating nitrogen in the polymerization reaction system in order to make the organoaluminum compound uniformly dispersed. This nitrogen circulation has a pressure of 0 to 1 MPa · G, preferably 0.3 to 0.6 M
Pa / G. The temperature is the same as the polymerization temperature of the catalyst [II] and is, for example, 10 to 110 ° C, preferably 40 to 100 ° C.

Next, if necessary, an olefin or the like is supplied, the pressure is raised, and the catalyst [II] is supplied to start the polymerization by the catalyst [II]. To be achieved. The catalyst [II] is a transition metal catalyst for olefin vapor phase polymerization as described above, and is a transition metal catalyst having a high molecular weight polyolefin-forming ability under the same polymerization conditions such as hydrogen / olefin molar ratio. I], a catalyst that produces a lower molecular weight polyolefin is used. MFR value of 10
The present invention is preferably applied when the molecular weights of the polyolefins produced differ by a factor of 2 or more, preferably 50 or more.

The catalyst can be used without particular limitation as long as the above conditions are met. However, the preferred catalyst [I] is
A catalyst obtained by bringing the following components (1) to (5) into contact with each other. (1) A compound containing a Group IVB metal of the periodic table, (2)
A compound containing any of Group I to III metals of the periodic table,
(3) an organic cyclic compound having two or more conjugated double bonds,
(4) Modified organoaluminum compound and / or boron compound having Al-O-Al bond, (5) inorganic compound carrier and / or particulate polymer carrier More preferably, the following components (1) to (5) are mutually added: It is a catalyst obtained by contacting. (1) General formula Me ¹ (OR ¹ ) _p R ² _q X ¹ _4-pq (R ¹ , R
² is a hydrocarbon group, X ¹ is a halogen atom, Me ¹ is Ti, Z
r or Hf, p is 0 ≦ p ≦ 4, and q is 0 ≦ q ≦
4, p + q is 0 ≦ p + q ≦ 4), (2) the general formula Me ² (OR ³ ) _m R ⁴ _n X ² _3-mn (wherein R ³ and R ⁴ are hydrocarbons). Group, X ² is a hydrogen atom or a halogen atom, Me ² is a Group III metal of the periodic table, and m is 0 ≦ m ≦
3, n is 0 ≦ n ≦ 3, m + n is 0 ≦ m + n ≦ 3)
A compound represented by, (3) an organic cyclic compound having two or more conjugated double bonds, (4) a modified organoaluminum compound having an Al-O-Al bond and / or a boron compound, (5) an inorganic compound carrier and / Or particulate polymer carrier

Next, this catalyst will be described. The catalyst component (1) in the present invention is a compound containing a Group IVB metal of the periodic table, and preferably has the general formula Me ¹ (OR ¹ )
It is represented by _p R ² _q X ¹ _4-pq . In the formula, R ¹ and R ^{2 each} independently represent a hydrocarbon group, preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably 1 to 12 carbon atoms. This includes methyl, ethyl, propyl, butyl, pentyl,
Examples thereof include an alkyl group such as a hexyl group, an alkenyl group such as a vinyl group and an allyl group, an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a trityl group. These may have branches. Ingredient (1)
When has two or more R ¹ or R ² , the hydrocarbon residues can be the same or different. X ¹ is a halogen atom of fluorine, iodine, chlorine or bromine, Me ¹ is Zr, Ti or Hf, and preferably Zr. p is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, p +
q is 0 ≦ p + q ≦ 4, preferably 0 <p + q ≦ 4
It is.

Specific examples of the compound which can be used as the component (1) include tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium and tetratolyloxy. Zirconium, tetrabenzyloxyzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetrabutylzirconium, tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetrachlorozirconium, triethoxymonochloro Zirconium, diethoxydichlorodiene Conium, monoethoxytrichlorozirconium, triisopropoxymonochlorozirconium, diisopropoxydichlorozirconium, monoisopropoxytrichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, monobutoxytrichlorozirconium, triphenoxymonochlorozirconium, di Phenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tetrabenzyloxyzirconium, tribenzyloxymonochlorozirconium, dibenzyloxydichlorozirconium, monobenzyloxytric B zirconium, tetrabromo zirconium, etc. tetraiodothyronine zirconium and the like. Further, a compound in which zirconium in the above zirconium compound is replaced with titanium and hafnium can also be used. Among these, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium and tetrabenzylzirconium are preferable. Further, these compounds can be used as a mixture of two or more kinds.

Component (2) is a compound containing any of metals I to III of the Periodic Table, preferably the general formula Me ²
It is represented by (OR ³ ) _m R ⁴ _n X ² _3-mn . In the formula, Me ² represents a Group III metal of the periodic table, and includes boron, aluminum and the like. R ³ and R ⁴ individually represent a hydrocarbon residue,
It preferably has 1 to 24 carbon atoms, and more preferably 1 to 12 carbon atoms.
Is a hydrocarbon residue of a methyl group, an ethyl group,
Alkyl group such as propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group and tolyl group, benzyl group, trityl group And aralkyl groups such as. These may have branches. If component (2) has more than one R ³ or R ⁴ , the hydrocarbon residues can be the same or different. X ² represents a hydrogen atom or a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n ≦ 3, m + n
Is 0 ≦ m + n ≦ 3.

Specific examples of compounds usable as the component (2) include trimethylboron, triethylboron, tri-n-propylboron, triisopropylboron, tri-n-butylboron, tri-tert-butylboron and tripentylboron. , Trioctylboron, triphenylboron, tribenzylboron, trimethylaluminum, triethylaluminum, diethylaluminum hydride, diethylaluminum chloride, ethylaluminum dichloride, tripropyloaluminum, dipropylaluminum hydride, dipropylaluminum chloride, propylaluminum dichloride, tri Isopropyl aluminum, diisopropyl aluminum hydride, diisopropyl aluminum chloride, ethyl Aluminum sesquichloride, propyl aluminum sesquichloride, isopropyl aluminum dichloride, tributyl aluminum, dibutyl aluminum chloride, butyl aluminum sesqui chloride, butyl aluminum dichloride, triisobutyl aluminum, diisobutyl aluminum hydride, diisobutyl aluminum chloride, trihexyl aluminum, dihexyl aluminum chloride, hexyl Aluminum dichloride,
Tripentyl aluminum, tridecyl aluminum,
Dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, diisobutyl aluminum methoxide, diisobutyl aluminum ethoxide,
Examples thereof include diisobutylaluminum propoxide and diisobutylaluminum butoxide. Among them, trimethylaluminum, triethylaluminum, diethylaluminum chloride, tripropyroaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, tripentylaluminum, diisobutylaluminum hydride and tridecylaluminum are preferable.

As the component (3), an organic cyclic compound having two or more conjugated double bonds is used, and preferably a cyclic carbonized compound having 2 to 4 conjugated double bonds and a total carbon number of 4 to 24. Hydrogen compounds are desired. The cyclic hydrocarbon compound may be partially substituted with 1 to 6 hydrocarbon residues, and the hydrocarbon residue may contain a silicon atom. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

Therefore, specific examples of the organic cyclic compound usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene,
tert-butylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,
2,4-trimethylcyclopentadiene, 1-ethyl-
4,5-Dimethylcyclopentadiene, 2-methyl-5
-Tert-butylcyclopentadiene, pentamethylcyclopentadiene, indene, methylindene, 4,7-
Dimethylindene, 4,5,6,7-tetrahydroindene, cycloheptatriene, cyclooctatetraene, azulene, methylazulene, fluorene, methylfluorene, cyclopentadienylsilane, cyclopentadienylmethylsilane, cyclopentadiene Examples thereof include enyldimethylsilane, cyclopentadienyltrimethylsilane, indenylsilane, indenyltrimethylsilane and the like.

A compound in which any one of the above-mentioned compounds is bound via a silicon atom and an alkylene group can also be used as the component (3) of the present invention. Specific examples are dicyclopentadienylsilane, dicyclopentadienylmonomethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiphenylsilane, bis (3-methylcyclopentadienyl) silane,
Bis (3-methylcyclopentadienyl) dimethylsilane, bis (1,3-dimethylcyclopentadienyl) silane, bis (1,3-dimethylcyclopentadienyl)
Dimethylsilane, diindenylsilane, diindenyldimethylsilane, diindenyldiephenylsilane, bis (3-methylindenyl) silane, bisindenylethane, bis (4,5,6,7-tetrahydro-1) -Indenyl) ethane, 1,3-bisindenylpropane,
1,3-bis (4,5,6,7-tetrahydroindenyl) propane, 2,2-bisindenylpropane, isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropyl Examples thereof include cyclopentadienyl-1-fluorene.

Among them, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, tert-butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,
Indene, methylindene, 4,7-dimethylindene, diindenyldimethylsilane and bisindenylethane are preferred.

As the component (4), a modified organoaluminum compound having an Al--O--Al bond and / or a boron compound is used. The modified organoaluminum compound is preferably 1 to 100 in the molecule, particularly preferably 1 to
It contains 50 Al-O-Al bonds. The modified organoaluminum compound can be produced by a known method and is not particularly limited, but generally, it can be produced by reacting organoaluminum with water. This reaction is
Usually done in an inert hydrocarbon. As the inert hydrocarbon, pentane, hexane, heptane, cyclohexane,
Aliphatic hydrocarbons such as benzene, toluene, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but it is preferable to use aliphatic hydrocarbons or aromatic hydrocarbons.

The organoaluminum compound used for preparing the modified organoaluminum compound has the general formula R ¹ _n Al (O
R ² ) It is represented by _m X _3-mn . In the formula, R is a carbon number of 1 to 1.
8, preferably 1 to 12 alkyl groups, alkenyl groups,
A hydrocarbon group such as an aryl group and an aralkyl group, X represents a hydrogen atom or a halogen atom, and n represents an integer of 1 ≦ n ≦ 3. Although any compound represented by the above formula can be used, trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, etc., but a methyl group is particularly preferable. The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is 0.25 / 1.
˜1.5 / 1, especially 0.5 / 1 to 1.2 / 1 is preferable. The reaction temperature is usually -70 to 150 ° C, preferably -20 to 100 ° C. The reaction time is usually selected in the range of 5 minutes to 50 hours, preferably 10 minutes to 20 hours. As the water used in the reaction, in addition to ordinary water, water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can be used.

As the boron compound as the component (4), a compound having at least one boron-carbon bond is preferably used, and examples thereof include borate and borane compounds. The borate, the general formula ^{[L 1] + [BR 5} R 6 R 7 R 8] - a compound represented by are preferred. In the formula, L ¹ is a compound that can be a cation, and examples thereof include Bronsted acids such as ammonium, anilium and phosphonium, or carbocations, methyl cations, ethyl cations, propyl cations, butyl cations, tropinium cations, benzyl cations and trityl cations. Can be mentioned. R ⁵ is an aromatic or substituted aromatic hydrocarbon group containing ⁵ to 20, preferably 6 to 16 carbon atoms, and the substituent is preferably an alkyl group or a halogen atom. R ⁶ ,
R ⁷ and R ⁸ are an aromatic or substituted aromatic hydrocarbon group containing 5 to 20 carbon atoms, preferably 6 to 16 carbon atoms, a hydride group, a halide group, a hydrocarbyl group, and the substituent is an alkyl group or A halogen atom is preferable, and R ⁶ , R ⁷ and R ⁸ may be the same as or different from R ⁵ .

Specific examples of borate include tributylammonium tetra (o-fluorophenyl) borate, tributylammonium tetra (p-fluorophenyl) borate, tributylammonium tetra (m-).
Fluorophenyl) borate, tributylammonium tetra (3,5-difluorophenyl) borate, tributylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (o-fluorophenyl) borate, dimethylanilinium tetra (p
-Fluorophenyl) borate, dimethylanilinium tetra (m-fluorophenyl) borate, dimethylanilinium tetra (3,5-difluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trityl tetra (o-fluorophenyl) ) Borate, trityl tetra (p-fluorophenyl) borate, trityl tetra (m-fluorophenyl) borate, trityl tetra (3,5-difluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, tropinium tetra (o- Fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m-fluorophenyl) borate, tropinium tetra (3,5)
-Difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate and the like. Among these, tributylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate and tropinium tetra (pentafluorophenyl) borate are preferable.

As the borane compound, a compound represented by the general formula BR ⁹ R
^The compound represented by ¹⁰ R ¹¹ is preferable. In the formula, R ⁹ is the same as R ^{5 in} the general formula of the borate compound, and R ¹⁰ is R ⁶ and R
¹¹ is the same as R ⁷ . Also, R ¹⁰ and R ¹¹
May be the same as or different from R ⁹ . Specific examples of the borane compound include tri (o-fluorophenyl) borane, tri (p-fluorophenyl) borane, tri (m-fluorophenyl) borane, tri (3,5-difluorophenyl) borane, tri (penta). Fluorophenyl) borane and the like. Among these, tri (pentafluorophenyl) borane is preferable.

As the component (5), an inorganic carrier and /
Alternatively, a particulate polymer carrier is used. The inorganic carrier may be in any shape such as powder, granules, flakes, foil or fibrous as long as it retains its original shape in the step of preparing the catalyst of the present invention. Even in the shape of, the maximum length is usually 5 to 200
A range of μm, preferably 10 to 100 μm is suitable. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g and a pore volume of 0.05 to ³ cm ³ .

As the inorganic carrier of the present invention, a carbon material,
Metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used. Suitable metal oxides that can be used for the inorganic carrier include single oxides or multiple oxides of metals of Groups I to VIII of the Periodic Table, for example Si.
O ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , Z
rO ₂ , Fe ₂ O ₃ , SiO ₂ , Al ₂ O ₃ .MgO, Al ₂
O ₃ · CaO, Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ ·
MgO · SiO ₂ , Al ₂ O ₃ · CuO, Al ₂ O ₃ · Fe ₂
O ₃ , Al ₂ O ₃ .NiO, SiO ₂ .MgO, etc. may be mentioned. The above formula represented by oxides is not a molecular formula but represents only the composition. As the metal chloride, specifically, MgCl ₂ , CaCl _{2 and the} like are particularly suitable, and examples of the metal carbonate include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but metal oxides, silica, alumina and the like are particularly preferably used.

The polymerization reaction with the catalyst [II] is carried out substantially in the gas phase. The olefin used in the polymerization using the catalyst [II] is usually an olefin having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, such as ethylene, propylene and butene, as in the above-mentioned olefin polymerization using the catalyst [I].
Examples include α-olefins such as 1, pentene-1, hexene-1, and 4-methylpentene-1. These can be used for homopolymerization or copolymerization at an appropriate ratio. As the copolymerization, for example, ethylene / propylene, ethylene / butene-1, ethylene / pentene-1, ethylene / hexene-1, ethylene / 4-methylpentene-1, etc., and an α / olefin having 3 to 12 carbon atoms. Copolymerization of ethylene, and ethylene and two or more other α
-Copolymerization with olefins and the like. Further, copolymerization using a diene is also possible for the purpose of modifying the polyolefin. Examples of the diene used for this purpose include butadiene, 1,4-hexadiene, ethylidene norbornene,
Dicyclopentadiene etc. are illustrated. In addition, in the specification of the present application, the meaning of copolymerization is included in the polymerization. The olefin feed to the reaction system can be fed alone or preferably with a suitable inert carrier gas such as nitrogen.

As the olefin polymerization conditions, the temperature is 2
The temperature is 0 ° C to 300 ° C, preferably 40 to 200 ° C, and the pressure is atmospheric pressure to 7 MPa · G, preferably 0.2 MPa ·.
G to 6 MPa · G. The molecular weight can be adjusted by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it can also be performed by adding a trace amount of hydrogen into the polymerization system. Further, for fine adjustment of the density, an organoaluminum compound can be added as a copolymerizability modifier. During steady operation, olefins and solid catalyst components [I
[I] is constantly introduced into the reaction system, while the produced polymer particles are extracted. After forming a fluidized bed or a stirred bed using the particles satisfying the above conditions, the above treatment is appropriately performed, and then an olefin gas is introduced while circulating nitrogen, and the pressure is gradually increased. Then catalyst [II]
Are supplied together with an inert gas such as nitrogen into the reactor. The polymerization reaction starts with the supply of the catalyst [II], the amount of polyolefin produced gradually increases, and reaches the state of steady operation. After that, the olefin and the catalyst [II] are supplied to the respective predetermined supply amounts in the steady state, so that the polymerization reaction proceeds steadily.

An organoaluminum compound can be preferably added during the regular polymerization in the step (4). As this organoaluminum compound, the same organoaluminum compound that may be used as a co-catalyst in the step (1) can be used. That is, the organoaluminum compound used herein refers to an organoaluminum compound having at least one aluminum-carbon atom bond in the molecule. For example, (i) the general formula R _m Al (OR ′) _n H _p X _q (where:
R and R ′ are hydrocarbon groups usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, such as alkyl groups, aryl groups, alkenyl groups, cycloalkyl groups, etc. , Ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, hexyl, octyl and the like. R and R'may be the same or different. X represents a halogen atom,
m, n, p, and q are 0 <m ≦ 3, 0 ≦ n <3, 0, respectively.
≦ p <3 and 0 ≦ q <3, and m + n +
It is a number that satisfies p + q = 3. ), An organoaluminum compound represented by the formula (ii), a general formula MAlR ₄ (wherein
M is a metal selected from Li, Na or K, and R is the same hydrocarbon group as described above. ), A complex alkyl compound of a Group I metal of the periodic table and aluminum, and the like.

Examples of the organoaluminum compound belonging to the above (i) include, for example, the general formula R _m Al (OR ′) _3-m (wherein R and R ′ are the same hydrocarbon groups as described above. M is preferably 1.5 ≦ m ≦ 3), R _m AlX _3-m (wherein R is the same hydrocarbon group as described above, and m is preferably 0 <m <3). ), The general formula R _m AlH _3-m (wherein R is the same hydrocarbon group as above, and m is preferably in the range of 2 ≦ m <3) and the general formula R _m Al (OR ′. ) _N X _q (wherein R and R ′ are the same hydrocarbon groups as described above. X represents a halogen atom, and m, n and q are preferably 0 <m ≦ 3, 0 ≦ n <3, (The number is within the range of 0 ≦ q <3 and satisfies m + n + q = 3.)
And the like can be exemplified.

Specific examples of the organoaluminum compound belonging to (i) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, Trialkylaluminums such as trioctylaluminum; Trialkenylaluminums; Dialkylaluminium alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and R _2.5 Partially alkoxylated alkylaluminum having an average composition such as Al (OR) _0.5 ; Dialkylaluminum halides such as aluminum chlorochloride, dibutylaluminum chloride and diethylaluminum bromide; partially halogenated alkylaluminums such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride, and alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride, partially hydrogenated alkyl aluminum; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, Partial such as ethyl aluminum ethoxy bromide And the like can be exemplified alkoxylated and halogenated alkylaluminum. Examples of the organoaluminum compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H ₁₅ ) _{4 and the} like. Further, as the organoaluminum compound similar to (i), an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can also be used. As such a compound, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
_{N (C 2 H 5) Al} (C 2 H 5) can be exemplified _2. Among these, trialkylaluminum is preferable. The addition amount of the organoaluminum compound is not particularly limited, but is 0.01 to 10 relative to the compound containing a transition metal as the catalyst (II) used in the step (4).
It can be appropriately selected from the range of 100 molar times.

By the above method, even when the grade after the catalyst is switched is a film grade, the gel is less generated by the catalyst switching, and the catalyst can be switched smoothly and with less loss such as off-grade products. Become.

[0064]

BEST MODE FOR CARRYING OUT THE INVENTION

(1) a step of polymerizing an olefin in a gas phase with a transition metal catalyst [I] which produces a high molecular weight polyolefin,
(2) a step of deactivating the catalyst [I] present in the reaction system, (3) a step of filling polyolefin particles having no polymerization activity by the catalyst [I] as a seed polymer, and (4) a low molecular weight polyolefin. By using the step of supplying the transition metal catalyst [II] and restarting the polymerization, the catalyst can be rapidly switched without any trouble.

[0065]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. <Catalyst preparation example> 500 ml equipped with "Catalyst A" stirrer and reflux condenser
50g of SiO ₂ baked at 600 ℃ in a 3-necked flask
Add 160 ml of dehydrated hexane and titanium tetrachloride 2.
2 ml was added, and the mixture was reacted under reflux of hexane for 3 hours.
After cooling, 30 ml of a hexane solution of diethylaluminum chloride (1 mmol / cc) was added, the mixture was reacted again under reflux of hexane for 2 hours, and dried at 120 ° C. under reduced pressure to remove hexane. The obtained reaction product is referred to as component (I). Separately, 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide were placed in a stainless steel pot having an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch, and the mixture was placed at room temperature under a nitrogen atmosphere at room temperature. Ball milling was performed for 16 hours to obtain a reaction product. This is designated as component (II). 5.4 g of the above component (II) was added to dehydrated ethanol 160
It was dissolved in ml, and the whole amount of the solution was added to a three-necked flask containing the component (I), reacted for 3 hours under reflux of ethanol, and then dried under reduced pressure at 150 ° C. for 6 hours to obtain a solid catalyst component. It was The titanium content in 1 g of the obtained solid catalyst component was 15 mg.

"Catalyst B" under nitrogen with electromagnetic induction stirrer 3
60 ml of purified toluene was placed in a 00 ml eggplant-shaped flask, and then tetrapropoxy zirconium (Zr (OP
r) ₄ ) 0.65 g and indene 1.85 g were added, and the mixture was stirred at room temperature for 30 minutes, then the system was kept at 0 ° C. and triethylaluminum (AlEt ₃ ) 1.84 g was added dropwise over 30 minutes. After that, the system was returned to room temperature and further stirred for 24 hours. Next, a toluene solution of methylaluminoxane (manufactured by Witco, concentration: 1.3 mmol / ml) was added to this solution.
After adding 50 ml and reacting at room temperature for 1 hour, the mixture was left at room temperature for one day. This solution is called a solution. Next, after adding 50 g of silica (manufactured by Fuji Devison Chemical Co., Ltd., grade # 952, surface area 300 m ² / g) to a 500 ml three-necked flask equipped with a stirrer under nitrogen in advance at 600 ° C. for 5 hours, the a The whole amount of the solution was added and stirred at room temperature for 2 hours. Then, nitrogen blowing was carried out to remove the solvent to obtain a solid catalyst B having good fluidity.

"Catalyst C" under nitrogen with electromagnetic induction stirrer 3
60 ml of purified toluene was placed in a 00 ml eggplant-shaped flask, and then tetrapropoxy zirconium (Zr (OP
r) ₄ ) 0.65 g and cyclopentadiene 1.32 g were added, and the mixture was stirred at room temperature for 30 minutes, then the system was kept at 0 ° C. and triethylaluminum (AlEt ₃ ) 1.84 g was added dropwise over 30 minutes. After finishing, return the system to room temperature and carry out 2 more.
Stir for 4 hours. Next, to this solution, a toluene solution of methylaluminoxane (manufactured by Witco, concentration 1.3 mmol
/ Ml) was added, and the mixture was reacted at room temperature for 1 hour and then left at room temperature for one day. This solution is called a solution. Next, silica (Fuji Davisson Chemical Co., Ltd.) which was previously fired at 600 ° C. for 5 hours in a 500 ml three-necked flask equipped with a stirrer under nitrogen was used.
Co., Ltd., grade # 952, surface area 300 m ² / g) 5
After adding 0 g, the whole amount of the solution a was added, and the mixture was stirred at room temperature for 2 hours. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst C having good fluidity.

<Catalyst deactivation and confirmation experiment of deactivation amount> In a small-scale autoclave experiment, all of catalysts A, B and C were deactivated by bringing them into contact with a sufficient amount of water, resulting in olefin polymerization activity. Confirmed to be lost. Further, none of the catalysts A, B and C, which were once deactivated with water, recover their polymerization activity under the polymerization conditions corresponding to the step (4) in the following Examples and Comparative Examples. It was confirmed. That is, 1.5 m in a well-dried batch type polymerization reactor with an internal volume of 3 liters.
After supplying mol of triethylaluminum, total pressure is 6kg
Use a mixed gas of ethylene / butene-1 / hydrogen ratio (molar ratio, the same applies below) = 1 / 0.4 / 0.1 and nitrogen (0.5 kgf / cm2 · G) to achieve f / cm2 · G. Introduced, the temperature is 85
℃. Then, supply about 100 mg of catalyst "I", and
Polymerize for a period of time. After that, a predetermined amount of a deactivator is introduced and it is confirmed that the reaction is stopped. If necessary, change the specified amount and repeat. After stopping the reaction, the operation of pressurizing with nitrogen to 7 kgf / cm 2 · G and depressurizing was repeated 9 times to completely replace the gas in the reactor with nitrogen, and then the total pressure was 6 kgf / cm 2 · G.
Ethylene / butene-1 ratio = 1 / 0.0 so that G
The mixed gas of No. 8 and nitrogen (0.5 kgf / cm 2 · G) are introduced, and the temperature inside the reactor is set to 75 ° C. This is the condition under which the catalyst "II" exhibits polymerization activity. Thereafter, an operation of supplying 0.5 mmol of triethylaluminum and holding it for 1 hour as it is is repeated until the total supply amount of triethylaluminum becomes equal to the amount of the quenching agent already used. During this operation, it is confirmed whether the polymerization reaction recovers. From the above experiment, the amount of the deactivating agent necessary for the polymerization activity not to be recovered even when triethylaluminum is supplied is determined as a value per unit weight of the catalyst. The catalyst retention amount in the fluidized bed system was calculated from the average residence time of the fluidized bed reactor and the catalyst feed rate, and the required deactivating agent amount of 10
Double the amount of the quenching agent. Further, in each of the following Examples and Comparative Examples in which powder is deactivated while holding,
When the introduction of the quenching agent from the quenching agent introducing pipe 6 is completed,
A part of the polymer powder in the polymerization tank is collected under a nitrogen atmosphere, and the collected polymer powder is filled in the same batch type polymerization vessel as described above. Then, an appropriate amount of triethylaluminum is supplied under the polymerization conditions for the catalyst "II" in step (4), and it is confirmed that the polymerization reaction does not recover.
Although the case where water is used as the quenching agent has been described, the same can be done when other quenching agents are used.

<Gel Measurement Method> After the catalyst (II) used in the step (4) was supplied, the accumulated production amount was about 20 times the accumulated amount in the tank.
The polymer particles when the double amount is produced are collected, kneaded and extruded, and granulated. The granulated pellets are formed into a film having a thickness of 90 μm by a T die. The gel (fisheye) of the film formed in this manner was used as a number (50 μm to 17 present per 100 cm ² per unit area).
0 μm gel). Taking the upper limit of the gel level acceptance value generally accepted in the film industry as 1,
The amount of gel is evaluated by the relative value to this. Therefore, lower values indicate less gel films.

Example 1 A fluidized bed reactor having a diameter of 25 cm shown in FIG. 1 was used. The fluidized bed reactor 1 comprises an upper space area 2 and a fluidized bed area 3, and a gas dispersion plate 4 is provided at the bottom of the fluidized bed area 3. A flow rate of 8 through a gas fluidized bed reactor 1 in the system, a gas circulation pipe 11, a blower 12 and a cooler 13 using a blower 12.
It circulates at 8 Nm ³ / h and the temperature is adjusted to 85 by adjusting the circulating gas temperature.
C. was maintained. Ethylene and butene-1 are supplied from the olefin supply pipe 7, and ethylene / butene-1 in the gas phase is supplied.
/ Hydrogen ratio = 1 / 0.4 / 0.1, and nitrogen concentration 30m
Adjust the amount of each gas to be ol%, total pressure 19kg
It was kept at f / cm ² · G. In addition, hydrogen was supplied from the olefin supply pipe 7 together with the olefins. The catalyst [A] obtained in the catalyst preparation example was supplied with the catalyst supply pipe 8 at a supply rate of 1.0 g / h.
Supplied by Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.0 kg / h.
The properties are MFR 0.8dg / min, density 920kg /
m ³ and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylarnium as a cocatalyst was decreased in accordance with the decrease in the rate of polyethylene production. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kg in 20 minutes.
The temperature was lowered to f / cm ² · G, and at the same time, the temperature was lowered to 50 ° C. The flow rate of gas in the system is 16 Nm ³ / using the blower 12.
While discharging from the vent pipe at h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm ² · for 5 hours.
Hold on to G.

While the gas was being circulated in the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was carried out for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and an amount of gas corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas was circulated using a blower 12, and the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h, while nitrogen was introduced from the nitrogen supply pipe 10, and the pressure was maintained for 24 hours. Was maintained at 6 kgf / cm ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the polymerization reactor was filled with nitrogen gas at 5 kgf /
The pressure in the system was raised to cm ² · G, and the gas in the system was circulated using the blower 12 through the path consisting of the fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 at a flow rate of 88 Nm 3 / h, and the circulating gas The temperature was maintained at 75 ° C. by adjusting the temperature. Ethylene / butene-1 ratio in the gas phase = 1 / 0.08,
The amount of each gas was adjusted to be 30 mol% of nitrogen and the total pressure was maintained at 19 kgf / cm ² · G. Next, triethylaluminum was supplied at a rate of 5 g / h from an alkylaluminum supply pipe 5-6 for 6 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, 0.7 g / h of the catalyst [B] obtained in the above catalyst preparation example was added.
The catalyst was supplied through the catalyst supply pipe 8 at the rate of 1 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.0 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Its properties were MFR of 1.9 dg / min and density of 919 kg / m ³ , its appearance was transparent white, and it was uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 1> In Example 1, substantially the same operation was performed except that the quenching agent was not introduced. That is,
A blower 12 was used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of a gas fluidized bed reactor 1, a gas circulation pipe, a blower 12 and a cooler 13 in the system, and the temperature was kept at 85 ° C. by adjusting the circulating gas temperature. . The amount of each gas is adjusted so that the ethylene / butene-1 / hydrogen ratio in the gas phase is 1 / 0.4 / 0.1 and the nitrogen concentration is 30 mol%, and the total pressure is maintained at 19 kgf / cm ² · G. did. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe 8 at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. Ethylene-butene-exhausted through polymer particle exhaust valves 14 and 15
The production rate of one copolymer was 3.8 kg / h. Its properties are MFR 0.9dg / min, density 921kg / m ³
And the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Circulating gas was discharged from the vent pipe 9 and the pressure in the system was changed to 5 in 20 minutes.
It was lowered to kgf / cm ² · G, and at the same time, the temperature was lowered to 75 ° C. Flow of gas in the system using blower 12 is 16 Nm
While discharging from the vent pipe at ³ / h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 5 kgf / cm for 5 hours.
It was held at ² · G.

Then, as in Example 1, without introducing the quenching agent, the ethylene / butene-1 ratio in the gas phase = 1.
The amount of each gas was adjusted to be 0.08 / 0.08 and nitrogen of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Next, triethylaluminum was supplied at a rate of 50 mg / h from the alkylaluminum supply pipe 5-for 3 hours. Feed rate of triethylaluminum is 25 mg / h
After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the polymer production rate gradually increased, and after 24 hours, 3.1 kg /
reached h. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. The properties are MFR 2.0dg / min, density 9
It was 19 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 670 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Embodiment 2> Similar to that shown in FIG.
A fluidized bed reactor 1 with a diameter of 25 cm was used. Blower 1
2 using a gas fluidized bed reactor 1 and gas circulation pipe 1
1, the blower 12 and the cooler 13 are circulated at a flow rate of 88 Nm ³ / h, and the temperature of the circulating gas is adjusted to 85 ° C. Ethylene in gas phase / Butene-1 /
Hydrogen ratio = 1 / 0.4 / 0.1, and nitrogen concentration 30mo
Adjust the amount of each gas to be 1%, total pressure 19kgf /
It was held at cm ² · G. The catalyst [A] obtained in the catalyst preparation example was 1.
It was supplied through the catalyst supply pipe at a supply rate of 0 g / h. Also, 0.8 g of triethylaluminum as a co-catalyst
/ H as a hexane solution at a promoter supply pipe 5-
Supplied from. Polymer particle discharge valves 14 and 15
The production rate of the ethylene-butene-1 copolymer discharged through was 4.2 kg / h. Moreover, the property is M
The FR was 0.9 dg / min, the density was 920 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as a cocatalyst was decreased in accordance with the decrease in the rate of polyethylene production. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kg in 20 minutes.
The temperature was lowered to f / cm ² · G, and at the same time, the temperature was lowered to 50 ° C. The flow rate of gas in the system is 16 Nm ³ / using the blower 12.
While discharging from the vent pipe at h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm ² · for 5 hours.
Hold on G.

While the gas was being circulated by the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was performed for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and an amount of gas corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / m ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. Then, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Lower the pressure in the fluidized bed reactor to normal pressure,
Separately, the polymer particles obtained at a steady state using the catalyst [B] were stored in advance under a nitrogen atmosphere and had an average particle size of 65.
17 kg of 0 μm linear low density polyethylene was charged into the reactor as a seed polymer under a nitrogen atmosphere. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.0 kg / h after 24 hours. The operation continued smoothly as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.1 kg / h. Moreover, the property is MFR.
The appearance was 1.9 dg / min, the density was 921 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 670 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 2> In Example 2, except that the polymer produced by using the catalyst [A] and not subjected to the deactivation treatment was used as the seed polymer used when the operation was restarted. Almost the same operation was performed. That is, a blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system, and the temperature of the circulating gas is adjusted to 85 ° C. Held in. The amount of each gas is adjusted so that the ethylene / butene-1 / hydrogen ratio in the gas phase is 1 / 0.4 / 0.1 and the nitrogen concentration is 30 mol%, and the total pressure is maintained at 19 kgf / cm ² · G. did. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. Polymer particle discharge valve 1
Ethylene-butene-1 discharged through 4 and 15
The production rate of the copolymer was 4.1 kg / h. Also,
Its properties were MFR 1.0 dg / min, density 919 kg / m ³ , and its appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and thereafter the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. The circulating gas was discharged from the vent pipe 9 and the pressure in the system was changed to 6 in 20 minutes.
It was reduced to kgf / cm ² · G and at the same time the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm
While discharging from the vent pipe at ³ / h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 5 hours.
Hold at ² · G.

While the gas was being circulated in the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was carried out for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of pressurizing the system with nitrogen to 5 kgf / cm 2 · G and then releasing it to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. Then, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Lower the pressure in the fluidized bed reactor to normal pressure,
Separately, the polymer particles obtained at steady state using the catalyst [A] were stored in advance under a nitrogen atmosphere in an average particle size of 78.
16 kg of 0 μm linear low-density polyethylene was charged into the reactor as a seed polymer under a nitrogen atmosphere. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 3 times.

Then, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.1 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR.
The appearance was 2.0 dg / min, the density was 921 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Example 3> In Example 2, substantially the same operation was carried out except that the seed polymer used at the time of restart of operation was a polymer prepared by using the catalyst [B] and subjected to deactivation treatment. . That is, using a blower 12, a flow rate of 88 Nm is passed through a path formed by the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system.
^It was circulated at ³ / h, and the temperature was kept at 85 ° C by adjusting the temperature of the circulating gas. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1
The amount of each gas was adjusted to be /0.4/0.1 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 is 4
It was kg / h. In addition, its properties are MFR 1.0dg /
min, the density was 920 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. The circulating gas was discharged from the vent pipe 9 and the pressure in the system was changed to 6 in 20 minutes.
It was reduced to kgf / cm ² · G and at the same time the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm
While discharging from the vent pipe at ³ / h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 5 hours.
Hold at ² · G.

While the gas was being circulated in the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was carried out for 5 hours using wet nitrogen from the deactivator introducing pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was supplied at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. Then, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Lower the pressure in the fluidized bed reactor to normal pressure,
Separately, the polymer particles obtained by using the catalyst [B] in a stationary state were stored for 2 weeks in a paper bag whose upper part was not closed in advance. The linear low-density polyethylene having an average particle size of 650 μm (that is, lost by the atmosphere). 17 kg (activated) was charged into the reactor as a seed polymer. Nitrogen supply pipe 10
After further supplying nitrogen, the pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 6 times. Then, the temperature was raised to 90 ° C., the gas was circulated using a blower 12, and the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h, while nitrogen was introduced from the nitrogen supply pipe 10 on the other hand. The time pressure was maintained at 6 kgf / cm ² · G. next,
The blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.07 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR.
The particles were 2.1 dg / min, the density was 922 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Example 4> In Example 2, substantially the same operation was performed except that the seed polymer used at the time of restart of operation was produced by using the catalyst [A] and subjected to deactivation treatment. That is, a blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system, and the temperature of the circulating gas is adjusted to 85 ° C. Held in. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1/0.
The amount of each gas was adjusted to be 4 / 0.1 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 is 3.
It was 9 kg / h. Moreover, the property is MFR 0.9d.
The g / min and the density were 921 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. The circulating gas was discharged from the vent pipe 9 and the pressure in the system was changed to 6 in 20 minutes.
It was reduced to kgf / cm ² · G and at the same time the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm
While discharging from the vent pipe at ³ / h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 5 hours.
Hold at ² · G.

While the gas was being circulated in the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation test of deactivation amount" was performed for 5 hours by using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and an amount of gas corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. Then, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [A] were stored in advance in a paper bag whose upper part was not closed for 3 weeks. 16 kg of linear low-density polyethylene having an average particle size of 810 μm (that is, deactivated by air) was charged as a seed polymer into the reactor. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 6 times. Then raise the temperature to 90 ° C and blower 1
2 and circulates the gas in the system at a flow rate of 16 Nm ³ /
While discharging from the vent pipe at h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 24 hours.
Hold at ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.07 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
The appearance was 2.0 dg / min, the density was 922 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 640 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Embodiment 5> Similar to that shown in FIG.
A fluidized bed reactor 1 with a diameter of 25 cm was used. Blower 1
2 using a gas fluidized bed reactor 1 and gas circulation pipe 1
1, the blower 12 and the cooler 13 were circulated at a flow rate of 88 Nm ³ / h, and the temperature of the circulating gas was adjusted to maintain the temperature at 85 ° C. Ethylene / butene-1 in the gas phase
/ Hydrogen ratio = 1 / 0.4 / 0.1, and nitrogen concentration 30m
Adjust the amount of each gas to be ol%, total pressure 19kg
It was kept at f / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.0 kg / h. Its properties are MFR 1.0 dg / min and density 920 kg / m ³ ,
The appearance was white.

Next, in order to reduce the polymerization ability of the catalyst remaining in the system, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. The circulating gas was discharged from the vent pipe 9, the pressure in the system was lowered to 6 kgf / cm ² · G in 20 minutes, and at the same time, the temperature was lowered to 50 ° C. The flow rate of gas in the system is 16 using the blower 12.
While releasing Nm ³ / h from the vent pipe, nitrogen was introduced from the nitrogen supply pipe 10 on the other side, and the pressure was 6 kgf /
It was held at cm ² · G.

While the gas was being circulated by the blower 12, the amount of water determined by the above "catalyst deactivation and deactivation amount confirmation experiment" was used for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. The linear low density polyethylene having an average particle size of 650 μm, in which the pressure in the fluidized bed reactor was reduced to normal pressure and the polymer particles obtained at a steady state by using the catalyst [B] were stored in advance under a nitrogen atmosphere. 17 kg of the seed polymer was charged into the reactor under a nitrogen atmosphere. Nitrogen is supplied from the nitrogen supply pipe 10, and the pressure in the system is 5 kgf / cm.
After boosting up to ² · G, depressurized, it was repeated three times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.0 kg / h after 12 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR.
The appearance was 1.9 dg / min, the density was 916 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 660 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 3> In Example 5, substantially the same operation was performed except that the deactivating operation was not performed. That is, using the blower 12, the gas fluidized bed reactor 1 in the system,
The gas was circulated at a flow rate of 88 Nm ³ / h through a path composed of the gas circulation pipe 11, the blower 12 and the cooler 13, and the temperature was kept at 85 ° C. by adjusting the circulating gas temperature. The amount of each gas is adjusted so that the ethylene / butene-1 / hydrogen ratio in the gas phase is 1 / 0.4 / 0.1 and the nitrogen concentration is 30 mol%, and the total pressure is maintained at 19 kgf / cm ² · G. did. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.9 kg / h. Its properties are MFR 0.8dg / min, density 919kg / m ³
And the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and thereafter the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. The linear low density polyethylene having an average particle size of 650 μm, in which the pressure in the fluidized bed reactor was reduced to normal pressure and the polymer particles obtained at a steady state by using the catalyst [B] were stored in advance under a nitrogen atmosphere. 17 kg of the seed polymer was charged into the reactor under a nitrogen atmosphere. Nitrogen is supplied from the nitrogen supply pipe 10, and the pressure in the system is 5 kgf /
After increasing the pressure to cm ² · G, the pressure was released, and this was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.09 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was fed at a rate of 50 mg / h from the alkylaluminum feed pipe 5-for 3 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased to 24
After 3.0 hours, it reached 3.0 kg / h. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR.
The appearance was 1.8 dg / min, the density was 917 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 640 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 4> In Example 5, the catalyst [A] was used as the seed polymer when the operation was restarted.
Moreover, substantially the same operation was performed except that the powder having the catalyst [A] activity was used. That is, the blower 12
Using a gas fluidized bed reactor 1 and gas circulation piping 1
1, the blower 12 and the cooler 13 were circulated at a flow rate of 88 Nm ³ / h, and the temperature of the circulating gas was adjusted to maintain the temperature at 85 ° C. Ethylene / butene-1 in the gas phase
/ Hydrogen ratio = 1 / 0.4 / 0.1, and nitrogen concentration 30m
Adjust the amount of each gas to be ol%, total pressure 19kg
It was kept at f / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.1 kg / h. Its properties are MFR 1.0 dg / min and density 920 kg / m ³ ,
The appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is reduced to 6 kgf / cm ² · G in 20 minutes.
At the same time, the temperature was lowered to 50 ° C. Blower 12
While the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h by using, the nitrogen was introduced from the nitrogen supply pipe 10 on the other hand, and the pressure was kept at 6 kgf / cm ² · G for 5 hours.

While the gas was being circulated in the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was carried out for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was supplied at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to atmospheric pressure, and the polymer particles obtained at a steady state using the catalyst [A] were stored in advance under a nitrogen atmosphere with an average particle size of 780 μm. 16 kg of linear low-density polyethylene of Example 1 was used as a seed polymer and charged into a reactor under a nitrogen atmosphere. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm 2 · G, and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.09 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.1 kg / h after 24 hours. The operation continued smoothly as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.1 kg / h. Moreover, the property is MFR.
The appearance was 1.8 dg / min, the density was 917 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 660 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Example 6> In Example 5, substantially the same operation was performed except that the powder deactivated by the catalyst [B] was used as the seed polymer at the time of restarting the operation. That is, using the blower 12, the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system circulate at a flow rate of 88 Nm ³ / h,
The temperature was maintained at 85 ° C. by adjusting the circulating gas temperature. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1 / 0.4 / 0.
The amount of each gas was adjusted to be 1 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.9 kg / h. Further, its properties were MFR 1.1 dg / min, density 920 kg / m ³ , and white appearance.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is reduced to 6 kgf / cm ² · G in 20 minutes.
At the same time, the temperature was lowered to 50 ° C. Blower 12
While the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h by using, the nitrogen was introduced from the nitrogen supply pipe 10 on the other hand, and the pressure was kept at 6 kgf / cm ² · G for 5 hours.

While the gas was being circulated in the blower 12, the amount of water determined by the above "catalyst deactivation and confirmation experiment of deactivation amount" was performed for 5 hours using wet nitrogen from the deactivator introduction pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were separately stored for 2 weeks in an unclosed upper part. 17 kg of linear low density polyethylene with a diameter of 650 μm (ie deactivated by air) was charged to the reactor as seed polymer. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 6 times. Then, the temperature was raised to 90 ° C., the gas was circulated using the blower 12, and the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h, while nitrogen was introduced from the nitrogen supply pipe 10 on the other hand. Time pressure is 6kgf / cm ² · G
Held in. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.09 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
The appearance was 2.0 dg / min, the density was 918 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Example 7> In Example 5, the catalyst was prepared by using the catalyst [A] as the seed polymer at the time of restarting the operation.
And the same operation was performed except that the deactivated powder was used. That is, a blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system, and the temperature of the circulating gas is adjusted to 85 ° C. Held in. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1/0.
The amount of each gas was adjusted to be 4 / 0.1 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 is 4 k.
It was g / h. In addition, its properties are MFR 1.0dg / mi
The density was 920 kg / m ³ and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped. Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is reduced to 6 kgf / cm ² · G in 20 minutes.
At the same time, the temperature was lowered to 50 ° C. Blower 12
While the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h by using, the nitrogen was introduced from the nitrogen supply pipe 10 on the other hand, and the pressure was kept at 6 kgf / cm ² · G for 5 hours.

While the gas was being circulated by the blower 12, the amount of water determined by the above-mentioned "catalyst deactivation and confirmation experiment of deactivation amount" was carried out for 5 hours by using wet nitrogen from the deactivator introducing pipe 6. Was introduced, and a gas in an amount corresponding to the amount of wet nitrogen introduced was discharged from the vent pipe 9. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12 and the temperature was 90 ° C.
Alkyl aluminum supply pipe at a rate of g / h 5-
For 6 hours. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [A] were stored in a paper bag with the upper part closed for 3 weeks in advance. 16 kg of linear low-density polyethylene with a diameter of 810 μm (that is, deactivated by the atmosphere) was charged into the reactor as a seed polymer. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 6 times. Then raise the temperature to 90 ° C and blower 1
2 and circulates the gas in the system at a flow rate of 16 Nm ³ /
While discharging from the vent pipe at h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 24 hours.
Hold at ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.09 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
The appearance was 2.0 dg / min, the density was 918 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 640 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

Example 8-1 A fluidized bed reactor 1 having a diameter of 25 cm, similar to that shown in FIG. 1, was used. A blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of a gas fluidized bed reactor 1, a gas circulation pipe 11, a blower 12 and a cooler 13 in the system, and the temperature is kept at 85 ° C. by adjusting the circulating gas temperature. did. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1 / 0.4 / 0.1 and nitrogen concentration 3
Adjust the amount of each gas to 0 mol%, and total pressure 1
It was maintained at 9 kgf / cm ² · G. Catalyst [A] obtained in Catalyst Preparation Example
Was fed through the catalyst feed pipe at a feed rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.0 kg / h. Its properties are MFR 0.9dg / min and density 919kg / m ³ ,
The appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. After the blower 12 was stopped and the pressure was lowered to normal pressure, handholes, drain valves, etc. were opened at various points in the polymerization circulation system. Further, using a blower, air was introduced into the polymerization system for 12 hours. At this time, it was introduced so as to allow flow to the entire circulation piping system. The amount of water calculated from the amount of introduced air and the relative humidity of the air was larger than that in the case of Example 1. After 12 hours, various handholes, drain valves, etc. were closed, the pressure in the system was increased to 5 kgf / cm ² · G with nitrogen, and then the operation of releasing the pressure to normal pressure was repeated 5 times. Raise the temperature to 90 ° C and use the blower 12 to flow the gas in the system at a flow rate of 16 Nm ³ / h.
At the same time, nitrogen is introduced from the nitrogen supply pipe 10 while releasing the pressure from the vent pipe, and the pressure is 6 kgf / cm ² · for 24 hours.
Hold on G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was supplied at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. After the blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were separately stored in a nitrogen atmosphere in advance to have an average particle size of 650 μm. 17 kg of linear low-density polyethylene as a seed polymer was charged into the reactor under a nitrogen atmosphere. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm 2 · G and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 2.7 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
It was 2.1 dg / min, the density was 921 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

Example 8-2 The same fluidized bed reactor 1 having a diameter of 25 cm as that shown in FIG. 1 was used. A blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of a gas fluidized bed reactor 1, a gas circulation pipe 11, a blower 12 and a cooler 13 in the system, and the temperature is kept at 75 ° C. by adjusting the circulating gas temperature. did. The ethylene / butene-1 / hydrogen ratio in the gas phase is adjusted to 1 / 0.07 / 0.0007, and the nitrogen concentration is adjusted to 30 mol%, and the amount of each gas is adjusted, and the total pressure is maintained at 19 kgf / cm ² · G. did. The catalyst [C] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 0.7 g / h. In addition, triethyl aluminum 25m
It was supplied from the alkylaluminum supply pipe 5 at a rate of g / h. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
It was 2.0 dg / min, the density was 919 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability of the catalyst remaining in the system, the supply of the catalyst [C] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated in the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. After stopping the blower 12 and reducing the pressure to normal pressure, handholes, drain valves, etc. were opened at various points in the polymerization circulation system. Further, using a blower, air was introduced into the polymerization system for 12 hours. At this time, it was introduced so as to allow flow to the entire circulation piping system. The amount of water calculated from the amount of introduced air and the relative humidity of the air was larger than that in the case of Example 1. After 12 hours, various handholes, drain valves, etc. were closed, the pressure in the system was increased to 5 kgf / cm ² · G with nitrogen, and then the operation of releasing the pressure to normal pressure was repeated 5 times. Raise the temperature to 90 ° C and use the blower 12 to flow the gas in the system at a flow rate of 16 Nm ³ / h.
At the same time, nitrogen is introduced from the nitrogen supply pipe 10 while releasing the pressure from the vent pipe, and the pressure is 6 kgf / cm ² · for 24 hours.
Hold on G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. After the blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were separately stored in a nitrogen atmosphere in advance to have an average particle size of 650 μm. 17 kg of linear low-density polyethylene as a seed polymer was charged into the reactor under a nitrogen atmosphere. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR2.
The appearance was 2 dg / min, the density was 921 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 660 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 5-1> In Example 8-1,
Almost the same operation was performed except that the system was not deactivated in the atmosphere by using a blower. That is, blower 1
2 using a gas fluidized bed reactor 1 and gas circulation pipe 1
1, the blower 12 and the cooler 13 were circulated at a flow rate of 88 Nm ³ / h, and the temperature of the circulating gas was adjusted to maintain the temperature at 85 ° C. Ethylene / butene-1 in the gas phase
/ Hydrogen ratio = 1 / 0.4 / 0.1, and nitrogen concentration 30m
Adjust the amount of each gas to be ol%, total pressure 19kg
It was kept at f / cm ² · G. The catalyst [A] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 1.0 g / h. Further, triethylaluminum was supplied as a cocatalyst at a rate of 0.8 g / h as a hexane solution from a cocatalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.1 kg / h. Its properties are MFR 1.0 dg / min and density 920 kg / m ³ ,
The appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. The blower 12 was stopped, the upper and lower sides of the fluidized bed reactor 1 were blocked, the handhole of the fluidized bed reactor 1 was opened, and it was left to stand overnight. Subsequently, the handhole was closed, the block valves were opened above and below the fluidized bed reactor 1, the pressure in the system was increased to 5 kgf / cm ² · G with nitrogen, and then the operation of releasing to normal pressure was repeated 5 times. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was supplied at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. After the blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were separately stored in a nitrogen atmosphere in advance to have an average particle size of 650 μm. 17 kg of linear low-density polyethylene as a seed polymer was charged into the reactor under a nitrogen atmosphere. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.1 kg / h after 24 hours. The operation continued smoothly as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.1 kg / h. Moreover, the property is MFR2.
The appearance was 0 dg / min, the density was 920 kg / m ³ , the appearance was transparent white, and the particles were uniform particles having an average particle size of 680 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Comparative Example 5-2> In Example 8-2,
Almost the same operation was performed except that the system was not deactivated in the atmosphere by using a blower. That is, blower 1
2 using a gas fluidized bed reactor 1 and gas circulation pipe 1
It was circulated at a flow rate of 88 Nm ³ / h through a path consisting of 1, the blower 12 and the cooler 13, and the temperature was kept at 75 ° C. by adjusting the circulating gas temperature. Ethylene / butene-1 in the gas phase
/ Hydrogen ratio = 1 / 0.07 / 0.0007, and the amount of each gas was adjusted so that the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. The catalyst [C] obtained in the catalyst preparation example was supplied through the catalyst supply pipe at a supply rate of 0.7 g / h. Also, triethylaluminum 25 mg /
It was supplied from the alkylaluminum supply pipe 5 at a rate of h. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 is 2.
It was 9 kg / h. Also, its properties are MFR 2.0d.
The g / min and the density were 919 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [C] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. The blower 12 was stopped, the upper and lower sides of the fluidized bed reactor 1 were blocked, the handhole of the fluidized bed reactor 1 was opened, and it was left to stand overnight. Then, the handhole was closed, block valves were opened above and below the fluidized bed reactor 1, the pressure in the system was increased to 5 kgf / cm ² · G with nitrogen, and then the operation of releasing to normal pressure was repeated 5 times. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 at the other side, and the pressure was 6 kgf / cm ² for 24 hours.・ Hold with G. next,
The blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. After the blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were separately stored in a nitrogen atmosphere in advance to have an average particle size of 650 μm. 17 kg of linear low-density polyethylene as a seed polymer was charged into the reactor under a nitrogen atmosphere. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased, reaching 3.0 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR2.
The appearance was 0 dg / min, the density was 921 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 660 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

Comparative Example 6 Almost the same as in Example 8-1, except that a powder produced using the catalyst [A] and having catalytic activity was used as the seed polymer when the operation was restarted. The operation was performed. That is, using the blower 12, the gas fluidized bed reactor 1 in the system, the gas circulation pipe 11,
It was circulated at a flow rate of 88 Nm ³ / h through a route consisting of the blower 12 and the cooler 13, and the temperature was kept at 85 ° C. by adjusting the temperature of the circulating gas. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1 / 0.4 / 0.1 and nitrogen concentration 30 mol
Adjust the amount of each gas so that the total pressure is 19% f / cm.
It was held at ² · G. The catalyst [A] obtained in the catalyst preparation example was 1.0
It was supplied through the catalyst supply pipe at a supply rate of g / h. Also, 0.8 g of triethylaluminum as a co-catalyst
/ H as a hexane solution at a promoter supply pipe 5-
Supplied from. Polymer particle discharge valves 14 and 15
The production rate of the ethylene-butene-1 copolymer discharged through the reactor was 4.1 kg / h. Moreover, the property is M
The FR was 1.1 dg / min, the density was 921 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. After the blower 12 was stopped and the pressure was lowered to normal pressure, handholes and drains were opened in various places in the polymerization system.
Furthermore, the operation of pressurizing the system with nitrogen to 5 kgf / cm 2 · G and then releasing it to normal pressure was repeated 5 times. Raise the temperature to 90 ° C and use the blower 12 to flow the gas in the system at a flow rate of 16 Nm ³ /
While discharging from the vent pipe at h, nitrogen is introduced from the nitrogen supply pipe 10 on the other side, and the pressure is 6 kgf / cm for 24 hours.
Hold at ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was supplied at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. After the blower 12 was stopped, the pressure in the fluidized bed reactor was reduced to normal pressure, and the polymer particles obtained at a steady state using the catalyst [A] were separately stored in a nitrogen atmosphere in advance with an average particle diameter of 780 μm. 16 kg of linear low-density polyethylene of Example 1 was used as a seed polymer and charged into a reactor under a nitrogen atmosphere. Nitrogen was supplied from the nitrogen supply pipe 10, the pressure in the system was increased to 5 kgf / cm ² · G, and then depressurized, which was repeated 3 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. Then
Triethylaluminum was fed at a rate of 50 mg / h from an alkylaluminum feed pipe 5-3 for 3 hours. Then, the feed rate of triethylaluminum is 25 mg / h
The ethylene / butene-1 ratio in the gas phase = 1 /
The amount of each gas was adjusted to 0.07 and the nitrogen concentration of 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. At this point, the reaction was already confirmed. After 1 hour, the catalyst [B] obtained in the catalyst preparation example was supplied at a rate of 0.7 g / h through the catalyst supply pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued smoothly as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.1 kg / h. Moreover, the property is MFR.
The appearance was 1.9 dg / min, the density was 920 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 670 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

Example 9 In Example 8-1, substantially the same operation was carried out except that the powder produced by the catalyst [B] and having deactivated catalytic activity was used as the seed polymer at the time of restarting the operation. It was That is, the blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system, and the temperature is adjusted to 8 by controlling the circulating gas temperature.
It was kept at 5 ° C. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1 / 0.4 / 0.1, and nitrogen concentration 30 mol%
Adjust the amount of each gas so that the total pressure is 19kgf / cm ² ·
Hold on to G. 1.0 g of the catalyst [A] obtained in the catalyst preparation example
It was supplied through the catalyst supply pipe at a supply rate of / h. Also,
Triethylaluminum as a co-catalyst was supplied as a hexane solution at a rate of 0.8 g / h from a co-catalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 4.0 kg / h. Moreover, the property is MFR.
It was 1.0 dg / min, the density was 919 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and then the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
While venting from the vent pipe at the other side, nitrogen is introduced from the nitrogen supply pipe 10 at the other side, and the pressure is 6 kgf / cm ² · G for 5 hours.
Held in. After the blower 12 was stopped and the pressure was lowered to normal pressure, handholes, drain valves, etc. were opened at various points in the polymerization circulation system. Furthermore, the air was introduced into the polymerization system using a blower. At this time, it was introduced so as to allow flow to the entire circulation piping system. The amount of water calculated from the amount of introduced air and the relative humidity of the air was larger than that in the case of Example 1. 1
After 2 hours, various handholes, drain valves, etc. were closed, the system was pressurized to 5 kgf / cm ² · G with nitrogen, and then the operation of releasing the pressure to normal pressure was repeated 5 times. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while the nitrogen supply pipe 10
More nitrogen was introduced and the pressure was maintained at 6 kgf / cm ² · G for 24 hours. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced through the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [B] were stored in advance in a paper bag whose upper part was not closed for 2 weeks. Average particle size was 650μ
17 kg of m linear low density polyethylene (ie, deactivated by air) was charged to the reactor as the seed polymer. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 6 times. Then, the temperature was raised to 90 ° C., the gas was circulated using a blower 12, and the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h, while nitrogen was introduced from the nitrogen supply pipe 10 on the other hand. The time pressure was maintained at 6 kgf / cm ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.07 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 2.9 kg / h. Moreover, the property is MFR.
The appearance was 2.0 dg / min, the density was 922 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 640 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

<Example 10> In Example 8-1, substantially the same operation was performed except that the powder produced by the catalyst [A] and having the deactivated catalytic activity was used as the seed polymer at the time of restarting the operation. It was That is, the blower 12 is used to circulate at a flow rate of 88 Nm ³ / h through a path consisting of the gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12 and the cooler 13 in the system, and the temperature is adjusted to 8 by controlling the circulating gas temperature.
It was kept at 5 ° C. Ethylene / butene-1 / hydrogen ratio in the gas phase = 1 / 0.4 / 0.1, and nitrogen concentration 30 mol%
Adjust the amount of each gas so that the total pressure is 19kgf / cm ² ·
Hold on to G. 1.0 g of the catalyst [A] obtained in the catalyst preparation example
It was supplied through the catalyst supply pipe at a supply rate of / h. Also,
0.8 g / h of triethylaluminum as a co-catalyst
It was supplied as a hexane solution at a rate of from the co-catalyst supply pipe 5-. The production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.8 kg / h. Moreover, the property is MFR.
The density was 0.9 dg / min, the density was 920 kg / m ³ , and the appearance was white.

Next, in order to reduce the polymerization ability, the supply of the catalyst [A] was stopped, and thereafter the gas composition and the polymerization temperature were maintained for 48 hours. The feed rate of triethylaluminum as the cocatalyst was decreased in accordance with the decrease in the polyethylene production rate. After 48 hours, the readings of the differential pressure gauge above and below the fluidized bed hardly changed, and the substantial reaction stopped.

Then, while the gas was being circulated by the blower 12, the polymer particles in the fluidized bed reactor 1 were discharged through the polymer particle discharge valves 14 and 15. Circulating gas is discharged from the vent pipe 9 and the pressure in the system is 6 kgf / in 20 minutes.
It was lowered to cm ² · G, and at the same time, the temperature was lowered to 50 ° C. Flow of gas in the system using blower 12 is 16 Nm ³ / h
At the same time, the nitrogen is introduced from the nitrogen supply pipe 10 while releasing it from the vent pipe at a pressure of 6 kgf / cmN ² · G for 5 hours.
Held in. The blower 12 was stopped, and handholes, drain valves, etc. were opened at various places in the polymerization circulation system. Furthermore, the air was introduced into the polymerization system using a blower. At this time, it was introduced so as to allow flow to the entire circulation piping system. The amount of water calculated from the amount of introduced air and the relative humidity of the air was larger than that in the case of Example 1. After 12 hours, close various handholes, drain valves, etc., and fill the system with nitrogen at 5 kgf / cm.
After raised to ² · G, it was repeated 5 times an operation to release to normal pressure. The temperature was raised to 90 ° C., the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h using the blower 12, while nitrogen was introduced from the nitrogen supply pipe 10 on the other hand,
The pressure was maintained at 6 kgf / cm ² · G for 24 hours. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure.

Next, nitrogen was introduced from the nitrogen supply pipe 10, the pressure was maintained at 5 kgf / cm ² · G, the gas was circulated by the blower 12, the temperature was 90 ° C., and triethylaluminum was fed at a rate of 5 g / h. Alkyl aluminum supply pipe 5-
For 6 hours. The blower 12 was stopped, the pressure in the fluidized bed reactor was lowered to normal pressure, and the polymer particles obtained at a steady state using the catalyst [A] were stored in advance in a paper bag whose upper part was not closed for 3 weeks. Average particle size was 810μ
16 kg of m linear low density polyethylene (ie deactivated by air) was charged to the reactor as the seed polymer. Supply nitrogen from the nitrogen supply pipe 10,
The pressure in the system was increased to 5 kgf / cm ² · G and then depressurized, which was repeated 6 times. Then, the temperature was raised to 90 ° C., the gas was circulated using a blower 12, and the gas in the system was discharged from the vent pipe at a flow rate of 16 Nm ³ / h, while nitrogen was introduced from the nitrogen supply pipe 10 on the other hand. The time pressure was maintained at 6 kgf / cm ² · G. Next, the blower 12 was stopped, and the gas was vented from the gas vent pipe 9 until the pressure in the system reached normal pressure. Subsequently, the operation of increasing the pressure in the system to 5 kgf / cm ² · G with nitrogen and then releasing the pressure to normal pressure was repeated 5 times.

Next, the inside of the reactor was filled with nitrogen gas at 5 kgf / cm ² · G.
The gas fluidized bed reactor 1, the gas circulation pipe 11, the blower 12, and the cooler 1 in the system
It was circulated at a flow rate of 88 m ³ / h through the route consisting of 3 and was maintained at a temperature of 75 ° C. by adjusting the temperature of the circulating gas. The amount of each gas was adjusted so that the ethylene / butene-1 ratio in the gas phase was 1 / 0.07 and the nitrogen concentration was 30 mol%, and the total pressure was maintained at 19 kgf / cm ² · G. Then, triethylaluminum was added at a rate of 5 g / h to the alkylaluminum supply pipe 5
− Was supplied for 4 hours. The feed rate of triethylaluminum was reduced to 25 mg / h, and after 1 hour, the catalyst [B] obtained in the catalyst preparation example was fed at a rate of 0.7 g / h through the catalyst feed pipe 8 to start the polymerization reaction. After the initiation of the polymerization reaction, the rate of polymer formation gradually increased and reached 2.9 kg / h after 24 hours. The operation continued as it was, and the production rate of the ethylene-butene-1 copolymer discharged through the polymer particle discharge valves 14 and 15 was 3.0 kg / h. Moreover, the property is MFR2.
The appearance was 0 dg / min, the density was 922 kg / m ³ , the appearance was white with a transparent feeling, and the particles were uniform particles having an average particle size of 650 μm. With respect to the obtained copolymer particles, the results of measuring the gel (fish eye) of the film according to the above-mentioned "gel measuring method" are shown in Table 1.

[0155]

[Table 1]

[0156]

EFFECTS OF THE INVENTION By adopting the method of the present invention, it is possible to smoothly switch the catalyst, and even when the polyolefin after switching is a film grade, the generation of gel due to the catalyst switching is small and the catalyst is turned off. Little loss of grade products.

[Brief description of drawings]

FIG. 1 is an explanatory view of a gas phase fluidized bed polymerization apparatus.

[Explanation of symbols]

 1 Gas Phase Fluidized Bed Reactor 2 Upper Space Area 3 Fluidized Bed Area 4 Gas Dispersion Plate 5-Cocatalyst Supply Pipe 5-Alkyl Aluminum Supply Pipe 6 Deactivator Introduction Pipe 7 Olefin Supply Pipe 8 Catalyst Supply Pipe 9 Vent Pipe 10 Nitrogen Supply pipe 11 Gas circulation pipe 12 Blower 13 Cooler 14, 15 Polymer particle discharge valve

Claims (5)

[Claims] 1. A method for switching a catalyst in steady-state gas phase polymerization of an olefin, which comprises the following steps (1) to (4): (1) a transition metal-based catalyst capable of forming a high molecular weight polyolefin [1] I] steadily polymerizing the olefin in the gas phase, (2) deactivating the catalyst [I] present in the reaction system, (3) substantially polymerizing the catalyst [I] A step of forming a gas phase polymerization bed using polyolefin particles not included in the above as a seed polymer, (4) by supplying a transition metal catalyst [II] capable of forming a low molecular weight polyolefin to restart the polymerization and steadily produce olefins The process of vapor phase polymerization. 2. In the step (3), the catalyst [I] has substantially no polymerization activity, but the catalyst [I]
The method for switching catalysts in the steady-state gas phase polymerization of olefins according to claim 1, wherein polyolefin particles having a polymerization activity according to I] are used as a seed polymer. 3. The catalyst switching method for steady-state gas phase polymerization of olefins according to claim 1, wherein the catalyst [I] comprises a solid catalyst component containing at least titanium and / or vanadium and magnesium and an organoaluminum compound. 4. The catalyst switching method in the steady gas phase polymerization of an olefin according to claim 1, wherein an organoaluminum compound is supplied after the deactivation in the step (2) or in the step (4). 5. The catalyst [II] comprises the following components (1) to
A method for switching a catalyst in the steady-state gas phase polymerization of an olefin according to claim 1, which is a catalyst obtained by bringing (5) into contact with each other, (1) a compound containing a group IVB metal of the periodic table, (2) A compound containing any one of Group I to III metals of the periodic table, (3) an organic cyclic compound having two or more conjugated double bonds, (4) a modified organoaluminum compound having an Al-O-Al bond, and / Or a boron compound,
(5) An inorganic compound carrier and / or a particulate polymer carrier.