JPH0491103A - Production of ethylene-alpha-olefin copolymer - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject copolymer excellent in particle properties by suspending a solid catalyst component in a hydrocarbon solvent, feeding the resultant suspension to a vapor-phase polymerizer and copolymerizing ethylene with an alpha-olefin in the presence of a polymerization catalyst containing the solid catalyst component. CONSTITUTION:Ethylene is copolymerized with an alpha-olefin (e.g. propylene) in the presence of an olefin polymerization catalyst containing a solid catalyst component in the vapor phase. In the process, the solid catalyst component is suspended in a hydrocarbon solvent such as propane, n-butane or i-butane and the resultant suspension is fed to a vapor-phase polymerizer to copolymerize the ethylene with the alpha-olefin. Thereby, the objective copolymer, having 0.88-0.95g/cm<3> density of the copolymer measured according to the ASTM D 1505E and containing 2-25wt.% constituent units derived from the alpha-olefin is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene/α-olefin copolymer.
Ethylene/α-olefin copolymer with good particle properties can be obtained with good productivity.
The present invention relates to a method for producing an olefin copolymer.

Technical Background of the Invention Linear low-density polyethylene (LLDPE), which is a copolymer of ethylene and α-olefin, has superior impact strength when formed into a film compared to high-pressure low-density polyethylene (LDPE). Therefore, it is widely used as a raw material for film forming.

The above-mentioned ethylene/α-olefin copolymer is usually produced by a solution polymerization method or a suspension polymerization method in which ethylene and α-olefin are polymerized in the presence of a solid titanium catalyst component containing magnesium, titanium, and a halogen as essential components. It is produced by copolymerization.

By the way, it is known that when the above-mentioned polymerization is carried out by a gas phase polymerization method, a particulate copolymer can be obtained without requiring a drying step in the production process, and the production cost can be reduced. However, it has been difficult to determine the particle size of ethylene/α-olefin copolymer particles obtained by gas phase polymerization. That is, fine powder particles or coarse particles are likely to be generated. For example, when fine powder particles are generated, the generated particles tend to be mixed into the circulating gas during the manufacturing process and tend to adhere to the inside of the manufacturing line. moreover,
Particles may stick to each other, clogging the production line or clogging the blower or perforated plate. Furthermore, if large amounts of coarse particles are generated, the production line will be clogged.

Furthermore, if the particles adhere to each other and become large clumps, they can no longer flow and accumulate on the vessel wall or perforated plate, and if the clumps grow further, they can disturb the normal flow in the bed or clog the outlet. This will lead to termination of polymerization.

In addition, in conventional gas phase polymerization methods, the solid catalyst component may have poor fluidity, and in such cases, it is necessary to quantitatively and uniformly supply the catalyst in a dry state to the gas phase polymerization vessel. This was difficult, and the resulting copolymers could stick together, resulting in a decrease in the quality of the copolymer.

For this reason, conventionally, the solid catalyst component was supplied to the gas phase polymerization reactor after being dispersed in a solvent such as hexane, but it is also possible to suspend the solid catalyst component in hexane or the like and then supply it to the gas phase polymerization reactor. However, the particle properties of the resulting ethylene-based feedstock were not good, and the copolymer particles sometimes stuck together.

Therefore, it has been desired to develop a method for producing ethylene/α-olefin copolymers that can efficiently produce ethylene/α-olefin by gas phase polymerization with less generation of fine powder particles or coarse particles. Ta.

In view of the above-mentioned prior art, the present inventor conducted intensive research to obtain a copolymer with good particle properties, and found that the solid catalyst component was a low-carbon copolymer such as propane, n-butane, and l-butane. Suspended in a boiling point solvent, it is supplied to a gas phase polymerization vessel,
The present inventors have discovered that it is possible to efficiently produce an ethylene/α-olefin copolymer with excellent particle properties by main polymerizing ethylene and α-olefin in the gas phase, and have completed the present invention.

Purpose of the Invention The present invention has been made in view of the prior art as described above, and is an efficient method for producing ethylene/α-olefin copolymers with good particle properties and less generation of fine powders and coarse particles. The object of the present invention is to provide a method for producing an ethylene/α-olefin copolymer.

Summary of the Invention The method for producing an ethylene/α-olefin copolymer according to the present invention comprises copolymerizing ethylene and α-olefin in a gas phase in the presence of an olefin polymerization catalyst containing a solid catalyst component. In order to produce an ethylene/α-olefin copolymer that satisfies the following requirements, the above-mentioned solid catalyst component is suspended in a hydrocarbon solvent selected from propane, n-butane, and i-butane, and the mixture is heated in a gas phase polymerization vessel. It is characterized by supplying

(8) Density measured by ASTM D 1505E is 0.88-0.95 g/cor.

(B) The structural unit derived from α-olefin is 2
Detailed Description of the Invention The method for producing an ethylene/α-olefin copolymer according to the present invention will be specifically described below.

FIG. 1 shows an explanatory diagram of the manufacturing process of the ethylene/α-olefin copolymer according to the present invention.

The method for producing an ethylene/α-olefin copolymer according to the present invention involves copolymerizing ethylene and α-olefin in the gas phase in the presence of an olefin polymerization catalyst containing a solid catalyst component. - In producing the olefin copolymer, the solid catalyst component is suspended in a hydrocarbon solvent selected from propane, n-butane, and 1-butane, and then supplied to a gas phase polymerization vessel.

The solid catalyst component used in the present invention will be explained below.

As such a solid catalyst component, for example, a solid titanium catalyst component [A] or a solid transition metal catalyst component [B]
] and other solid catalyst components.

The solid titanium catalyst component [A] used in the present invention is obtained by contacting a titanium compound, a magnesium compound, and, if necessary, an electron donor.

As a titanium compound used for preparing such a solid titanium catalyst component [A], for example, a tetravalent titanium compound represented by the following formula can be mentioned.

T + (OR) tX <-t R is a hydrocarbon group, X is a halogen atom, 0≦g≦4 As such a compound, specifically, T r C] 4 ,
Tetrahalogenated titanium such as T IBr 4, T 114, Ti(○CH3)C13, T I(OC286)CI3, Ti(on-C4H9)CI3, Ti(○C2H6) B rs, Ti(0-1so) Trihalogenated alkoxytitanium with -C4H9)B rt, dihalogenation with Ti(OCH=)2C12, Ti(o C2H5)zCl□, Ti(On-C4H9)2C12, T'(OC2H5)2B r2 Dialkoxytitanium, T+(OCHl)3Cl, Ti(OC2H6)2Cl, Ti(On-C4HI)3C1, Monohalogenated trialkoxotitane with Ti(OC2Hs)3Br, Ti(OCH3)4, T Examples include tetraalkoxytitanium such as (○C2HE)4, T (on-C4H9)4, Ti(0-iso-C4Hi)t, and Ti(0-2-ethylhexyl)4.

In the above compounds, titanium is replaced by zirconium,
Mention may also be made of compounds substituted with hafnium, vanadium or chromium.

A magnesium compound is used to prepare the solid titanium catalyst component [A].

Examples of such magnesium compounds include magnesium compounds that have reducing ability and magnesium compounds that do not have reducing ability.

Here, as a magnesium compound having reducing ability,
For example, the formula % formula % (where n is 0≦n<2, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group, and when n is O, two R may be the same or different, and X is a halogen).

Specifically, organic magnesium compounds having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, octylbutylmagnesium, and ethylbutylmagnesium. Dialkylmagnesium compounds with magnesium, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include alkylmagnesium halides such as amylmagnesium chloride, alkylmagnesium alkoxides such as butyl ethoxymagnesium, ethyl butoxymagnesium, and octyl butoxymagnesium, and other butylmagnesium hydrides. These magnesium compounds may be used alone or may form a complex compound with an organometallic compound described below. Moreover, these magnesium compounds may be liquid or solid.

Further, specific examples of magnesium compounds that do not have reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, methoquinomagnesium chloride, nidoquinomagnesium chloride, isopropoquinomagnesium chloride, butoxy Alkoxymagnesium halites such as magnesium chloride, octoxymagnesium chloride, alkoxymagnesium halites such as phenoxymagnesium chloride, methylphenoxymagnesium chloride, ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n~octoxymagnesium,
Examples include alkoxymagnesiums such as 2-ethylhexoxymagnesium, allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylates such as magnesium laurate and magnesium stearate. Other magnesium metals and magnesium hydride can also be used.

These magnesium compounds without reducing ability may be compounds derived from the above-mentioned magnesium compounds having reducing ability, or compounds derived during the preparation of the catalyst component. In order to derive a magnesium compound that does not have a reducing ability from a magnesium compound that does have a reducing ability, for example, a magnesium compound that has a reducing ability can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. , a halogen-containing compound, or a compound having an OH group or an active carbon-oxygen bond.

In addition, in addition to the above-mentioned magnesium compounds with reducing ability and magnesium compounds without reducing ability, magnesium compounds include the above-mentioned magnesium compounds, such as aluminum, zinc, boron, helium, sodium,
It may be a complex compound or composite compound with other metals such as potassium, or a mixture with other metal compounds. Furthermore, it may be a mixture of two or more of the above compounds, and may be used in a liquid or solid state.

If the compound is solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters, and the like.

As the magnesium compound used for preparing the solid titanium catalyst component [A], many magnesium compounds other than those mentioned above can be used, but in the final solid titanium catalyst component [A], halogen-containing It is preferable to take the form of a magnesium compound. Therefore, when a halogen-free magnesium compound is used, a contact reaction with a halogen-containing compound is required during the preparation. Preferred are magnesium compounds without reducing ability, and particularly preferred are halogen-containing magnesium compounds.

When preparing the solid titanium catalyst component [A], an electron donor can be used if necessary.

Examples of such electron donors include oxygen-containing alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Mention may be made of electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates, and the like.

More specifically, methanol, ethanol, propatool, butanol,
Pentanol, hexanol, 2-ethylhexanol, octatool, dodecanol, octadenyl alcohol, oleyl alcohol, hensyl alcohol, phenylethyl alcohol, cumyl alcohol, isofurobil alcohol, isopropylpencyl alcohol, etc. with 1 to 1 carbon atoms 18 alcohols, halogen-containing alcohols with 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol, and trichlorohexanol, and lower alcohols such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol. Phenols with 6 to 20 carbon atoms that may have an alkyl group, ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, hensifhenone, and henzoquinone, acetaldehyde, propionaldehyde, octyl aldehyde, Aldehydes with 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde, and naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octinopeacetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate , methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, hensyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-
Organic acid esters with 2 to 18 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisyl chloride; methyl Ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc. with 2 carbon atoms
~20 ethers, acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethyl Examples include amines such as ethylenediamine, nitriles such as acetonitrile, hendinitrile, and trinitrile, and acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride. Two or more of these compounds can be used in combination.

Furthermore, particularly preferred examples of organic acid esters include polyvalent carboxylic acid esters, and examples of such polyvalent carboxylic acids include R'-C-COOR
2 R3-C-OCOR5 R'-C-OCOR' (R1 is a substituted or unsubstituted hydrocarbon group, R2
, R5, R@ are hydrogen or a substituted or unsubstituted hydrocarbon group, R3, R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R3 and R4 may be connected to each other, and the substituents when the hydrocarbon groups R1 to R6 are substituted include heteroatoms such as N, 0, and S, for example, C- ○-CSCOOR, C○OH, OH
,5O3H.

Examples include compounds having a skeleton represented by C-N-C-1N (having a group such as H2).

Specifically, such polyhydric carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate,
Diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl maleate dibutyl acid, diethyl butyl maleate, β
- Aliphatic polycarboxylic acid esters such as diisopropyl methylglutarate, sialyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconate, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate , aliphatic polycarboxylic acid esters such as diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, jetyl phthalate, ethyl isobutyl phthalate, and ethyl phthalate. -Propyl, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, n-heptyl phthalate, di-2 phthalate
-Ethyl hequinyl, di-n-dimethyl phthalate, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, etc. Preferred examples include aromatic polycarboxylic acid esters and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of polyhydric carboxylic acid esters include long chain diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebanate. Examples include esters of dicarboxylic acids. Among these compounds, it is preferable to use carboxylic esters, and it is particularly preferable to use polyhydric carboxylic esters, especially phthalic esters.

In addition to the above-mentioned compounds, compounds having two or more ether bonds existing through a plurality of atoms are also preferably used as electron donors.

These electron donors do not necessarily need to be used as starting materials, but can also be generated during the process of preparing the solid catalyst component.

Although there are no particular limitations on the method for preparing such a solid titanium catalyst component [A], several examples of the method will be briefly described below. Note that although an example using an electron donor is shown below, such an electron donor does not necessarily have to be used.

(1) A method in which a solution consisting of a magnesium compound, an electron donor, and a hydrocarbon solvent is subjected to a catalytic reaction to precipitate a solid, or after the solid is precipitated, a catalytic reaction is carried out with a titanium compound.

(2) A method in which a complex consisting of a magnesium compound and an electron donor is subjected to a catalytic reaction with a titanium compound.

(3) In the contact material of the inorganic carrier and the organomagnesium compound,
A method of catalytically reacting a halogen-containing compound and an electron donor, and then catalytically reacting a titanium compound.

(4) Obtaining an inorganic or organic support impregnated with the magnesium compound from a mixture of the inorganic or organic support and a solution containing the magnesium compound, electron donor and optionally further hydrocarbon solvent, and then contacting the titanium compound. Method.

(5) A method for obtaining an inorganic or organic carrier impregnated with a magnesium compound or a titanium compound from a mixture of a solution containing a magnesium compound, a titanium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier.

(6) A method in which a liquid organomagnesium compound is brought into contact with a halogen-containing titanium compound.

(7) A method of contacting a liquid organomagnesium compound with a halogen-containing compound and then contacting it with a titanium compound.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound.

(9) A method in which a complex consisting of an alkoxy group-containing magnesium compound and an electron donor is catalytically reacted with a titanium compound.

[10] A method in which a liquid magnesium compound without reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid magnesium-titanium complex.

ql) A method in which the reaction product obtained in α0) is further reacted with a titanium compound.

Q2 A method in which the reaction product obtained in (9) or αO) is further reacted with an electron donor and a titanium compound.

αe A method in which a solid material obtained by pulverizing a magnesium compound, an electron donor, and a titanium compound is treated with any one of a halogen, a halogen compound, and an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, a complex compound consisting of a magnesium compound and an electron donor, or a magnesium compound and a titanium compound. Alternatively, after pulverization, it may be pretreated with a reaction aid and then treated with a halogen. Examples of the reaction aid include organometallic compounds and halogen-containing silicon compounds.

04 A method of treating the compound obtained in α0) to 03 above with a halogen, a halogen compound, or an aromatic hydrocarbon.

(151 A method of contacting a contact reaction product with a metal oxide, an organomagnesium, and a halokene-containing compound with an electron donor and a titanium compound.

Oa A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

07) A method of reacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium, a titanium compound, an electron donor, and optionally a halogen-containing compound such as a halogen-containing silicon compound.

OaBy such a method, the solid titanium catalyst component [
When preparing [A], the amount of the titanium compound, magnesium compound, and electron donor added as necessary will vary depending on the type, contact conditions, contact order, etc. , the electron donor is preferably 0 to 5 mol, particularly preferably 0.
It is used in an amount of 1 mol to 1 mol, and the titanium compound is 0.0
1 mol to 1000 mol, particularly preferably 0.1 mol to 2
It is used in an amount of 0.00 mol.

The temperature at which these compounds are brought into contact is usually 70°C.
~200°C, preferably -30°C to 150°C.

In such a solid catalyst component, the halogen/titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the electron donor/titanium (molar ratio) is 0 to 100, preferably 0.2 to 90. 10, and the magnesium/titanium (
The atomic ratio) is preferably 2 to 100, preferably 4 to 50.

The solid titanium catalyst component [A] as described above may further contain an electron donor as necessary.

As such an electron donor, the electron donor used in preparing the solid titanium catalyst component [A] described above can be used, and furthermore, the organosilicon compound shown in the following - Arson can be used. can.

R,,Si(○R')4-.

(In the formula, R and R' are hydrocarbon groups, and 0<n<4
) Specifically, the organosilicon compounds represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxinelan, diphenyljethoxysilane, bis0tolyldimethoxysilane, bisml dildimethoxysolane, bisp-)lyldimethoxysilane, Bis p-tolyljethoxysilane, bisethyl phenyldimethoxysolane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyl Triethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane Silane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoquine silane, methyl triaryloxy (al
lyloxy) silane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2.3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxy Silane, dicyclopentyldimethoxysilane, his(2-methylcyclobentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethyl Methoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bispt=lyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethylnomethoxysilane, 2-norbornanetriethoxysilane, 2-norbornane Methyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, and the like are preferably used.

Two or more of these organosilicon compounds may be used in combination.

In addition, examples of electron donors that can be used in addition to these organosilicon compounds include nitrogen-containing compounds, other oxygen-containing compounds, and phosphorus-containing compounds.

Specifically, such nitrogen-containing compounds include 2.6-substituted piperidines, 2.5-substituted piperidines, N, N, N', N''-tetramethylmethylenediamine, N, N, N Examples include substituted methylene diamines such as ', N''-tetraethylmethylene diamine, and substituted methylene diamines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Specifically, the phosphorus-containing compounds include triethyl phosphite, tri-n-propyl phosphite, tri-isopropyl phosphite, tri-n-butyl phosphite, tri-isobutyl phosphite, diethyl-n
- Phosphite esters such as butyl phosphite and diethylphenyl phosphite can be mentioned.

Further, as the oxygen-containing compound, the following compounds can be used.

2.6-substituted tetrahydropyrans, 2.5-substituted tetrahydrobilanes.

Note that the solid titanium catalyst component [A] obtained as described above can also be supported on the following carrier compound.

Such carrier compounds include A1□03, SiO2
, B2O3, MgO, Cao, Tio2, Zn
Examples include resins such as O1Z n O2,5nOz, Bad, ThO and styrene divinylbenzene copolymers.

In the production method according to the present invention, a solid transition metal catalyst component [B] can be used as the solid catalyst component.

Such a solid transition metal catalyst component [B] can be obtained by bringing a transition metal compound and a carrier compound into contact. Examples of such transition metal compounds include compounds represented by the following formula.

M.L.

In the formula, M is a transition metal selected from the group consisting of T1, Zr, Hf, ■, and Cr, L is a ligand that coordinates to the transition metal, and at least two L are cycloalkagenyl skeletons. Ligands other than those having a cycloalkagenyl skeleton are hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, halogens, or hydrogen, and X is a transition metal. It is valence.

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a butylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, Examples include indenyl group and 4,5.6.7-tetrahydroindenyl group.

The ligand other than the ligand having a cycloalkagenyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkokene group, an aryloxy group, a halogen, or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl group includes nclopentyl group, cyclohexyl group, etc.; aryl group includes phenyl group, tolyl group, etc.; aralkyl group includes benzyl group, Examples include a neophyll group.

Examples of the alkoxy group include a methoxy group, ethoxy group, and butoxy group, and examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2kR3,R', R5,, M (wherein M is the above transition metal, R2 is a group having a cycloalkagenyl skeleton, R3, R4 and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group) , an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen, k is an integer of 1 or more, and k+1+m+n=4).

Preferably used transition metal compounds include the above formula % and at least two of R5, that is, R2 and R3, are groups having a cycloalkagenyl skeleton, and these two groups having a cycloalkagenyl skeleton are lower alkylene. For example, they are bonded via ethylene, propylene, etc., and R4 and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, an aryl group,
It is an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton of M or zirconium will be exemplified.

His(cyclopentagenyl)zirconium monochloride monohytride, Bis(cyclopentagenyl)zirconium moppromito monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl) neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis(indenyl) Zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dibromide, Bis(cyclopentagenyl)methylzirconium monochloride, Bis(cyclopentagenyl)ethylzirconium monochloride , Bis(cyclopentagenyl)cyclohexylzirconium monochloride, Bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium dichloride, Bis( t-Butylcyclopentagenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromite, bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium sipheninope His(cyclopentagenyl)zirconium dimethyl, Bis(cyclopentagenyl)zirconium methoxychloride, Bis(cyclopentagenyl)zirconium ethoxychloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium ethoxychloride ) Zirconium phenoxy chloride, Bis(fluorenyl) zirconium dichloride.

Furthermore, M includes at least two or more ligands having a cycloalkagenyl skeleton in which M is zirconium, and the at least two ligands having a cycloalkagenyl skeleton are bonded via a lower alkylene group. Specific examples of transition metal compounds are shown below.

Ethylenebis(indenyl)dimethylzirconium, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconium, Ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)methylzirconium mono Bromid, Ethylenebis(indenyl)zirconium dichloride, Ethylenebis(indenyl)zirconium dimethyldo, Ethylenebis(indenyl)zirconium methoxy monochloride, Ethylenebis(indenyl)zirconium ethoxymonochloride, Ethylenebis(indenyl)zirconiumphenoquine monochloride , Ethylenebis(cyclopentagenyl)zirconium dichloride, Propylenebis(cyclopentagenyl)norconium dichloride, Ethylenebis(t-butylcyclopentagenyl)zirconium monochloride, Ethylenebis(4,5,6,7- Telolahydro=1-indenyl)dimethylzirconium, Ethylenebis(4,5,6,7-telodihydro-l-indenyl)methylzirconium monochloride, Ethylenebis(4,5,6,7-telodihydro-1-indenyl)zirconium dichloride , ethylenebis(4,5,6,7-telodihydro-1-indenyl)zirconium dibromide, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, Ethylenebis(6-methyl-I-indenyl)zirconium dichloride, Ethylenebis(7-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, Ethylenebis(2,3-dimethyl) -1-indenyl) zirconium dichloride, ethylenebis(4,7-simethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-simethoxy-1-indenyl)
Zirconium dichloride.

Furthermore, in the above-mentioned zirconium compounds, compounds in which zirconium is replaced with titanium, hafnium, vanadium, or chromium can also be used.

These compounds may be used alone or in combination of two or more. Further, it may be used after being diluted with hydrocarbon or halogenated hydrocarbon.

Support compounds used for preparing the solid transition metal catalyst component [B] include Al2O3, SiO2, B2O3, MgO, CaO1T.
i O2, ZnO1Z n O2, 5n02, BaO
, Th○, and styrene-divinylbenzene copolymers.

Among these carrier compounds, SiO2 is preferably used.

The temperature at which these compounds are brought into contact is usually 20 to 8
0°C1 is preferably 0 to 50°C.

During the contact, a low boiling point solvent, which will be described later, may also be used.

Solid transition metal catalyst component thus obtained [B]
In, the carrier compound/transition metal (atomic ratio) is 20 to
It is desirable that the number is 2000, preferably 40 to 1000.

For the solid catalyst component used in the present invention, an electron donor, a reaction aid, etc. may be used in addition to the above-mentioned catalyst components, if necessary.

As such reaction aids, organic and inorganic compounds containing silicon, phosphorus, aluminum, etc. can be used.

The solid catalyst component as described above is used suspended in a low-boiling hydrocarbon solvent selected from propane, n-butane, and l-butane. The suspension method is not particularly limited, and can be carried out by boat fishing.

Such low boiling hydrocarbon solvents can be used alone or in combination.

In the suspension, the amount of the solid catalyst component is 1 to 300 g, preferably 2.5 to 300 g, per I kg of the low-boiling hydrocarbon solvent.
Use in an amount of 150 g.

The olefin polymerization catalyst used in the production method according to the present invention will be explained.

The olefin polymerization catalyst used in the present invention contains a solid catalyst component suspended in a low-boiling hydrocarbon solvent as described above, and may further contain an organometallic compound as shown below. .

In such an organometallic compound, the solid catalyst component is
In the case of the solid titanium catalyst component [A], the following organometallic compounds (a) can be used.

As such an organometallic compound (a), an organometallic compound of a metal from Group 1 to Group II of the periodic table is used, and specifically, for example, the following aluminum compounds are preferably used.

R″I, A1.X3-,.

In the formula, R. is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3.

In the above formula, R' is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. group, pentyl group,
These include hequinyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of such organometallic compounds include the following compounds.

trimethylaluminum, triethylaluminum, l
- Trialkyl aluminum such as lysobrobylaluminium, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkyl aluminum halides such as methylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and methylaluminum furomite.

Alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylalaminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquipromide.

Alkylaluminum halides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dichloride.

Alkyl aluminum hydride such as diethyl aluminum high 1 mirite and diisophthyl aluminum hydride.

Further, a compound represented by the following formula can also be used.

R".AIY3-1 In the formula, R" is the same as above, Y is 10Rb group, 03i
R'3 group, -0AIR'□ group, -NR'', group, -S i
R'3 group or -N A IRh2 group, R'n is 1 to 2, and Rb, RcSR' and R'' are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. Ro is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, and R' and R1 are methyl group, ethyl group, etc.

Specifically, the following compounds are used as such organometallic compounds.

(i) R', AI (○Rb), -.

Dimethylaluminum methoxide, ethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (ii) R'', A I (03!R'3)z-E
t2Δl(OS !Mei) (iso-B U)2A I(OS iMe3)(is
o-B 11) 2A I (○5iEL), (iii
) R".A I(OA IR'□)3-0E L
2A 10 A IE h (iso-B U) 2A 10 A 1 (iso-B
u) 2, (+v) R', A l(N R"
z)+-0Me2A IN E j2 E t 2 A I N HM e Me2A INHE t E t2AIN(Me2Si)2 (iso-Bu)2AIN(Me3Si)2, (v
) R' ”fiA l(S IR'3)3-n(
iso-B U)2A is iMe3 etc., (vi)
R'', Al(N A IRh2)3-”R' E t2A INA I E t2 e As the above organometallic compound, R'3Al, R'
,A I(ORb) ,-,,R',A I(OAI
Preferred examples include organometallic compounds represented by R'2)3-n.

■As complex alkylated products of group metals and aluminum,
-Arson% formula% (However, Ml is Ll, Na, and Ro is carbon number 1
-15 hydrocarbon groups) can be exemplified, and specifically, LiA
l(C2H5)4,L! Examples include Al(C7Hl5)4.

The above compounds can be used alone or in combination of two or more.

Among the above compounds, if you want to obtain an ethylene/α-olefin copolymer with a high melt tension, you can obtain a polymer with a high molecular weight by using a halogen-containing compound such as the one shown below. preferable.

dialkylaluminum halides, such as diethylaluminum chloride, ciprobylaluminium chloride, dibutylaluminum chloride, diethylaluminum bromide; alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide;
Partially halogenated alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc. Partially halogenated alkylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc. Alkoxylated and halogenated alkyl aluminum.

In the catalyst for reflexine polymerization as described above, the organometallic compound is contained in an amount of 2000 to 200% per mmol of titanium atom.
,000 g, preferably 5,000 to 100,000 g of polymer, and the amount is usually about 0.000 g per mole of titanium atoms in the solid titanium catalyst component [A].
Desirably amounts are from 1 to 300 mol, preferably from about 0.5 to 100 mol, particularly preferably from 1 to 50 mol.

In the catalyst for olefin polymerization according to the present invention, when a solid transition metal catalyst component [B] is used as the solid catalyst component, the organometallic compound is (b) as shown below.
Aluminoxane is preferably used.

Specific examples of such aluminoxane (b) include compounds represented by general formula [I] and general formula [I[].

- In arson [1] and [Ir], R is a methyl group,
It is a hydrocarbon group such as an ethyl group, a butyl group, or a butyl group, preferably a methyl group or an ethyl group, and particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 to 40.

The alkyl oxydialuminum unit and formula (
A mixed alkyloxyaluminum unit consisting of an alkyloxyaluminum unit represented by (OAI) [herein, R1 and R2 may represent the same hydrocarbon groups as R, and R1 and R2 represent different groups] It may be formed from. In that case, it is formed from mixed alkyloxyaluminum units containing methyloxine aluminum units (OA, 1) in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more of H3. Aluminoxane is preferred.

As a method for producing such aluminoxane, for example, the following method can be exemplified.

(1) Compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding trialkylaluminium to a suspension in a hydrocarbon medium and causing a reaction.

(2) A method in which water is directly applied to trialkylaluminum in a medium such as Hensen, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, method (1) is preferred. Note that the aluminoxane may contain a small amount of organic metal components other than aluminum.

In the present invention, a benzene-insoluble organoaluminumoxy compound proposed by the present applicant can also be used as the aluminoxane (b).

In the above catalyst for reflex polymerization, the amount of aluminoxane is 3,000 per mmol of the transition metal compound.
~200,000g, preferably 5,000-100,
The amount may be such as to produce 000 g of polymer, and is usually about 5 to 500 mol, preferably about 10 to 300 mol, per mol of transition metal atom in solid transition metal catalyst component [A].
It is desirable that the amount is mol, particularly preferably 20 to 200 mol.

In such a catalyst for reflex polymerization, the carrier compound/transition metal (atomic ratio) is 10 to +000, preferably 2.
It is desirable that the aluminoxane/transition metal (molar ratio) is 0 to 100, preferably 0.2 to 10.

The olefin polymerization catalyst containing the solid transition metal catalyst component [B] as described above may further contain a magnesium compound as described above.

During polymerization, the above-mentioned reflexine polymerization catalyst,
If necessary, an electron donor as described above may be added.

In the method for producing an ethylene/α-olefin copolymer according to the present invention, ethylene and α-olefin are polymerized in a gas phase using the above-mentioned olefin polymerization catalyst.

The α-olefin used in the present invention has 3 carbon atoms.
~27 α-olefins are preferred, such as propylene, 2-methylpropylene, 1-phthene, 1-hexene, 1-pentene, 4-methyl-1-hentene, 3-methyl-1-pentene, 1-octene, Examples include nonene-1, decene-1, undecene-1, dodecene-1, and the like. In addition to α-olefins, for example, polyenes can also be copolymerized. Examples of such polyenes include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.

During polymerization, the solid catalyst component as described above is supplied to a gas phase polymerizer in a suspended state in a low-boiling hydrocarbon solvent. When a low boiling point hydrocarbon solvent containing a solid catalyst component is supplied to a gas phase polymerization reactor, the low boiling point solvent contained in the suspension evaporates instantly, and the solid catalyst component is uniformly distributed in the reaction system in a dry state. distributed. When polymerization is carried out in the presence of such uniform catalyst particles, the polymerization is carried out stably, and ethylene/α-olefin copolymer particles having a uniform particle size can be obtained after the main polymerization.

Furthermore, low boiling point solvents such as propane, n-butane, and l-butane have large heat capacities, and when they vaporize, they also have the effect of removing polymerization heat.

The amount of olefin polymerization catalyst used in polymerization varies depending on the type of solid catalyst component used, but for example,
In the case of solid titanium catalyst component [A] as the solid catalyst component, the amount is 0.00001 to about 1 milli-T-L per polymerization reaction volume lβ, preferably about 0, in terms of titanium atoms in the solid catalyst component. Preferably, it is used in an amount of .001 to about 0.1 mmol.

In the case of the above catalyst, the olefin polymerization catalyst contains an organometallic compound in an amount of 1 to 1000 mol, preferably 3 to 500 mol, particularly preferably 5 to 100 mol, per 1 g atom of titanium in the solid catalyst component. It is suitable to use. Other compounds, such as electron donor components, may also be added, in which case the metal element 1 in the organometallic compound
The amount used is preferably 10 mol or less, preferably 1 mol or less, particularly preferably o, ooi to 0.1 mol per g atom.

In addition, as a solid catalyst component, a solid transition metal catalyst component [
When B] is used, it is preferably used in an amount of 10@-5 to 10 mmol, preferably 10@-5 to 1 mmole, per 11 polymerization reaction volumes, in terms of transition metal atoms in the solid catalyst component.

The olefin polymerization catalyst contains 1 to 1000 moles of aluminoxane, preferably 1 to 500 moles, particularly preferably 2 to 10 moles of aluminoxane per 1 g atom of the transition metal element in the solid catalyst component.
Preferably, it is used in an amount of 0 mol.

In the polymerization, 1.000 to 100.000 g per 1 g of the solid catalyst component as described above, preferably C3. ooooo
~50,000 g, more preferably 5,000-3
0.000 g of ethylene/α-olefin copolymer is produced by copolymerization.

The main polymerization is carried out in the gas phase, and at this time, the polymerization temperature is between 20 and 20°C.
It is carried out at 130°C, preferably 50 to 12o'C, more preferably 70 to 110°C. Polymerization pressure is 1-100g
/cm2, preferably 2 to 40 kg/cm2. Furthermore, an inert gas that forms a gaseous state within the polymerization system, such as methane, ethane, propane, butane, or nitrogen, may be supplied as appropriate.

Incidentally, during the polymerization, a molecular weight regulator such as hydrogen may be used.

Further, the main polymerization step can also be carried out in multiple stages of two or more stages.

Furthermore, prior to the above polymerization, preliminary polymerization may be performed.

Such prepolymerization can be carried out by suspension polymerization or solution polymerization.

The reaction temperature during prepolymerization is usually about -50 to +70°C,
Preferably about -20 to 60°C1, more preferably -1
It is desirable that the temperature is 0 to 50°C.

Incidentally, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. When it is desired to obtain an ethylene/α-olefin copolymer with a large melt tension in the main polymerization, the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135°C is
About 20dl! /g or more, preferably about 25-100cl
It is desirable to use it in an amount of 1/g, particularly preferably 30 to 60 Bg.

The prepolymerization is carried out in such a way that about 1 to 1000 g, preferably about 2 to 500 g, particularly preferably 2 to 300 g of ethylene-containing prepolymerized catalyst are produced of ethylene and the above-mentioned α-olefins per gram of solid catalyst component. That is desirable.

By producing a prepolymerization catalyst, in the main polymerization,
An ethylene/α-olefin copolymer having high melt tension is obtained.

Hereinafter, the ethylene/α-olefin copolymer obtained by the production method of the present invention will be specifically explained.

The ethylene/α-olefin copolymer obtained by the present invention is a random copolymer obtained by copolymerizing ethylene and α-olefin in the presence of the above-mentioned olefin polymerization catalyst. This ethylene/α-olefin copolymer may contain polyene or other copolymer in addition to ethylene and α-olefin as described above.

The ethylene/α-olefin copolymer obtained by the present invention has a density measured by ASTM D 1505E of 0.88 to 0.95 g/cm3, preferably 0.
．． 89-0.94 g/cm''.

The ethylene/α-olefin copolymer obtained by the present invention has 2 to 2 structural units derived from α-olefin.
5% by weight, preferably 4-23% by weight, particularly preferably 6-20% by weight, the structural units derived from ethylene being present in an amount of 75-98% by weight, preferably 77-96% by weight, particularly preferably Present in an amount of 80-94% by weight.

This ethylene/α-olefin copolymer is ASTM
Melt flow rate measured by D1238B (
MFR) is 0.01 to 100 g/10 minutes, preferably 0.05 to 50 g/10 minutes.

As mentioned above, this ethylene/α-olefin copolymer contains 10% by weight or less, preferably 5% by weight or less, particularly preferably 3% by weight or less of a structural unit derived from polyene or the like in addition to ethylene and α-olefin. weight%
It can be included in the following amounts:

The ethylene/α-olefin copolymer according to the present invention is obtained in the form of powder particles, and the average particle size is 200 to 3000 μm.
Preferably it is 500 to 1500 μm.

The ethylene/α-olefin copolymer obtained by the present invention is obtained in the form of particles with uniform particle sizes as described above, and has high melt tension, so it is particularly suitable as a packaging film. , not only for use as a film,
It can be processed into various molded products such as containers, daily necessities, pipes, tubes, etc. by T-die molding, blown film molding, blow molding, injection molding, extrusion molding, etc. It is also possible to make various composite films by extrusion coating or coextrusion molding with other films.
It is also used for steel pipe coatings, electric wire coatings, and foam molded products. Alternatively, other thermoplastic resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, polyj-butene, poly-4
- methyl-1-pentene, a low-crystalline or amorphous copolymer of ethylene and propylene or 1-butene,
It can also be used by blending it with a polyolefin such as a propylene/1-butene copolymer.

Furthermore, the ethylene/α-olefin copolymer obtained as described above may contain heat stabilizers, weather stabilizers, antistatic agents, antiblocking agents, lubricants, nucleating agents, pigments, dyes, inorganic or It is also possible to incorporate organic fillers and the like.

Effects of the Invention In the method for producing an ethylene/α-olefin copolymer according to the present invention, the catalyst component is supplied to the gas phase polymerizer in a state suspended in a low boiling point solvent as described above. The polymerization is carried out in the presence of a dry, uniformly dispersed catalyst.

Therefore, the obtained ethylene/α-olefin copolymer has good particle properties and high productivity.

In addition, in the present invention, ethylene, which has a large melt tension,
It is possible to produce an α-olefin copolymer, and when an ethylene/α-olefin copolymer with a high melt tension is formed into a film, a film of uniform thickness can be obtained, and it is also possible to form a thin film. It would be possible,
High-speed moldability is also improved.

[Examples] The present invention will be described below using specific examples, but the present invention is not limited to these examples.

Example 1 [Preparation of solid catalyst component] 119 g of commercially available anhydrous magnesium chloride, 579 d of 2-ethylhexyl alcohol, and 5.61 d of decane were mixed into 14
A heating reaction was carried out at 0°C for 3 hours to obtain a homogeneous solution containing magnesium chloride. Add 7 mL of propionic acid to this solution.
After adding 0i and carrying out a heating reaction at 70°C for 1 hour,
Cooled. While stirring this solution, a mixed solution consisting of triethylaluminum + 7W and decane 1.11 was added dropwise at 20'C over 30 minutes, and then heated to 80°C over 1 hour.
The temperature was raised to 80°C, and a heating reaction was carried out for 1 hour. Then 89 mj' of triethylaluminum and 560 m of decane
A mixed solution consisting of 1 was added dropwise for 30 minutes, and then 3
The reaction was carried out for 0 minutes. Thereafter, a mixed solution consisting of 189 ml of noethylaluminum chloride and 1,31 ml of decane was added dropwise over 30 minutes, and the reaction was carried out again at 80°C for 1 hour.

Next, the solid portion was separated by filtration to synthesize a solid component.

After resuspending the solid component thus obtained in 51 decane, 2-ethylhexoxytitanium trichloride was added to 18
After adding 8 mmol and carrying out a reaction at 80'C for 1 hour, the mixture was washed with decane to prepare a solid titanium catalyst component.

[Polymerization] The solid titanium catalyst component suspended in propane at a concentration of 1.5 mmol/β in terms of Ti atoms was introduced from tube 1 into a polymerization vessel having a diameter of 40 cmφ and a volume of 4001 as shown in FIG. Continuously supplied to the polymerization reactor at a rate of 0.20 mmol/h and tributylaluminum 1.6 mmol/h in terms of T1 atoms, and at the same time 14.0 kg of ethylene was supplied from tube 2.
/h and 1-hexene 4,5 Kg/h,
Further, hydrogen was supplied from tube 3 so that the H2/'ethylene molar ratio in the reactor was 0.20.

Polymerization conditions were a pressure of 18 kg/cdG and a polymerization temperature of 80°.
The C1 residence time was 4 hours, and the linear velocity of the circulating gas in the gas phase polymerizer was maintained at 50 cm/sec. The circulating gas from tube 4 passed through cooler B and was circulated through blower C to the polymerization reactor.

The copolymer was discharged from the system through pipe 5 at a rate of 8.3 kg/h.

The density of the obtained copolymer was 0.923 g/cTl, MF
R was 0g/10 minutes.

The proportion of particles that did not pass through a 14-mesh sieve, representing copolymer powder or aggregates of several tens or more, was hardly recognized as less than 1% by weight.

Moreover, the bulk specific gravity was as high as 0.40 g/car. In this state, the polymerization was terminated after confirming that the temperature in the fluidized bed, the temperature of the vessel wall in the polymerization zone, the flow rate of circulating gas, and the amount of discharged copolymer were kept extremely stable and constant for 7 days.

As a result of an open inspection of the polymerization vessel, almost no accumulation of copolymer powder was observed on the walls of the polymerization vessel.

The polymerization results are shown in Table 1.

Examples 2 to 4 As shown in Table 1, except that the type of prepolymerization catalyst suspension hydrocarbon solvent and the type of α-olefin during copolymerization were changed,
Polymerization was carried out in the same manner as in Example I. In each example, the polymerization was terminated after stable operation for 7 days was confirmed without any problems.

The polymerization results are shown in Table 1.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that hexane was used instead of propane as the suspension solvent for the polymerization catalyst.

Aggregates (particles that did not pass through an 80-mesh sieve) were found in the discharged copolymer powder from the early stage of polymerization, amounting to 7 to 12% by weight1, and the bulk specific gravity was as low as 0.29 g/cm'. . Approximately 20 hours after the start of polymerization, a phenomenon in which the vessel wall temperature repeatedly rises and falls begins to occur, and after 24 hours, I
Since the temperature rose to 00'C, the polymerization was stopped.

When the reactor was opened and inspected, plate-shaped copolymer powder aggregates measuring up to 40 cm square were found everywhere on the vessel walls and perforated plates, and it was confirmed that it was impossible to continue the polymerization.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the manufacturing process of an ethylene/α-olefin copolymer according to the present invention, and FIG. 2 is a schematic diagram of a gas phase polymerization vessel used in Examples. A...Polymerization reaction gas phase polymerization vessel B...Cooler C...Blower Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent attorney Shun Suzuki First diagram

Claims (1)

[Claims] (1) Copolymerizing ethylene and α-olefin in the gas phase in the presence of an olefin polymerization catalyst containing a solid catalyst component to produce an ethylene/α-olefin copolymer that satisfies the following requirements. For producing an ethylene/α-olefin copolymer, the solid catalyst component is suspended in a hydrocarbon solvent selected from propane, n-butane, and i-butane and then supplied to a gas phase polymerization vessel. Manufacturing method: (A) Density measured by ASTM D 1505E is 0.88 to 0.95 g/cm^3. (B) The structural unit derived from α-olefin is 2 to 2
Must be 5% by weight.