JPH03294310A - Production of ethylene/alpha-olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject straight chain low density copolymer useful as a raw material for forming films by employing an olefin polymerization catalyst comprising a specific solid Ti catalyst component and an organic metal compound catalyst component. CONSTITUTION:Ethylene and an >=3C alpha-olefin are copolymerized in the presence of an olefin polymerization catalyst comprising (A) a solid Ti catalyst component containing Ti, Mg, a halogen and a compound having two or more ether bonds through plural atoms and (B) one of the groups I-III metals (e.g. triethyl- aluminum). The compound A is prepared preferably by bringing MgCl2, etc., as a Mg compound, TiCl4 as a Ti compound and 2,2-diisobutyl-1,3- dimethoxypropane, etc., as the ether bond-containing compound into contact with each other.

Description

Detailed Description of the Invention: 1. Invention 1. So-called linear low-density polyethylene, linear medium-density polyethylene or linear chain obtained by copolymerizing ethylene and a-olefin. The present invention relates to ethylene/a-olefin copolymers such as extremely low density polyethylene.

Linear low-density polyethylene (LLDPE), a copolymer of ethylene and a-olefin, has superior impact strength when formed into a film compared to high-pressure low-density polyethylene (LDPE). It is widely used as a thick material for film forming.

As a result of research aimed at producing such a copolymer of ethylene and a-olefin, the inventor discovered that two or more atoms exist between titanium, magnesium, and halogen. A solid titanium catalyst component containing a compound having an ether bond [! a], and an organometallic compound catalyst component [n] containing a metal from Group 1 to Group M of the periodic table; titanium; magnesium; halogen; and electron donor (a)C herein A solid titanium catalyst component [rb] containing an electron donor and (unless otherwise specified, does not include compounds having two or more ether bonds present through multiple atoms), A catalyst comprising an organometallic compound catalyst component [n] containing a Group 1 to Group M metal and a compound [m] having two or more ether bonds existing through a plurality of atoms.

The present invention has been made in view of the above-mentioned prior art. The object of the present invention is to provide a method for producing an ethylene/a-olefin copolymer.

达m The first ethylene/σ-olefin copolymer according to the present invention
[Ia] A solid titanium catalyst component containing titanium, magnesium, a halogen, and a compound having two or more ether bonds present through a plurality of atoms; Copolymerizing ethylene and at least one selected from a-olefins having 3 or more carbon atoms in the presence of an olefin polymerization catalyst containing an organometallic compound catalyst component containing a group 1 to group m metal. It is characterized by

The first ethylene/α-olefin copolymer according to the present invention
Depending on the manufacturing method of Copolymers can be produced.

The second ethylene/a-olefin copolymer according to the present invention
Production method 1 [rb] titanium, magnesium, halogen, electron donor (a) (however, electron donor (a) is a compound having two or more ether bonds existing through multiple atoms) a solid titanium catalyst component containing [n
Presence of an organometallic compound catalyst component containing a metal from group 1 to group m of the periodic table, and an olefin polymerization catalyst containing a compound having two or more ether bonds existing through multiple atoms Tm ethylene and
It is characterized by copolymerizing at least one selected from a-olefins having 3 or more carbon atoms.

Second ethylene/a-olefin copolymer according to the invention
Depending on the manufacturing method of &dai above solid titanium catalyst component [r
When a catalyst containing al, the organometallic compound catalyst component [nl, and a compound having two or more ether bonds [m] is used, an ethylene/a-olefin copolymer can be produced.

Below, the method for producing an ethylene/a-olefin copolymer according to the present invention will be specifically explained.

, a solid containing titanium, magnesium, a halogen, and a compound having two or more ether bonds existing through a plurality of atoms. titanium catalyst component [ra]
and a catalyst containing the organometallic compound catalyst component [nl (hereinafter sometimes referred to as the first catalyst).

In addition, in the second method for producing ethylene/a-olefin according to the present invention, iL is a solid titanium catalyst component [r
b], the organometallic compound catalyst component [nl, and the above compound [m] having two or more ether bonds (hereinafter sometimes referred to as the second catalyst) is used.

Such a first. The solid titanium catalyst component [■a] or [Ib] constituting the second catalyst uses a magnesium compound, a titanium compound, and the above-mentioned compound having two or more ether bonds or an electron donor (a), It is prepared by bringing these compounds into contact with each other.

A magnesium compound can be used in the preparation of the solid titanium catalyst components [Za] and [rb], and examples of the magnesium compound include a magnesium compound having IL reducing ability and a magnesium compound having no reducing ability. .

Here, as a magnesium compound with reducing ability,
For example, the formula R may be the same or different, and X is a halogen).

Examples of organomagnesium compounds having such reducing ability include IL dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diptylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium hydride. These magnesium compound writing methods may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, impropoxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides 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.

These non-reducing magnesium compounds +4 may be compounds derived from the above-mentioned magnesium compounds having reducing properties or compounds derived during the preparation of the catalyst component. An analogy when it comes to deriving a non-reducing magnesium compound from a reducing magnesium compound! When a reducing magnesium compound is brought into contact with a halogen-containing compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or a compound having an OH group or an active carbon-oxygen bond, good.

In addition, magnesium compounds include the above-mentioned magnesium compounds with reducing properties and magnesium compounds without reducing properties, complex compounds of the above-mentioned magnesium compounds with other metals, complex compounds, and mixtures with other metal compounds. It's okay. Saraban 2 It may be a mixture of two or more of the above compounds, and may be used in a liquid state or a solid state. If the compound is solid, alcohol, carboxylic acid, aldehyde etc.
Amine skin May be used after being liquefied using metal acid esters.

Among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Examples of liquid titanium compounds used in preparing the solid titanium catalyst components [ra] and [rb] contained in the catalysts used in the first and second methods of the present invention include, for example, common titanium compounds. Dog Ti (OR), x, -.

(R is a hydrocarbon group, X is a halogen atom, and 0
≦g≦4).

More specifically, T i CL, T t B rt, Ti1. Tetrahalogenated titanium Ti (OCHs) C13, Ti (○C2Hs) C13, Ti (On-CaHs) C13, Ti (QC2H,) Br,, Ti (O
1soC,H@ ) B r s and trihalogenated alkoxytitanium; T i (OCH3) 2C12, T i (OC2HS) 2C12, T i (O
n-CaHe) 2C12, T i (QC2H,)
Dihalogenated alkoxytitaniums such as 2Br2: T i (OCH3)sCl.

T i (OC2H,) 3Cl.

Ti (On-C4H*)sCL Ti (QC2H,), Br Ti(OCHs)4, Ti(OC2H3)a, Ti(On-CJHe)a Ti(Oiso-C4H*)4 Ti(0-2- Tetraalkoxytitanium such as Ti(OCHs)-1 Ti(OC2Hs)a, T1(On-CJ He)a, T1(Oiso-CaH*)a, Ti(0-2-ethylhexyl)4 Examples include monohalogenated alkoxytitanium such as.

Among these, +L titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

These titanium compounds may be used alone or in the form of a mixture. Alternatively, hydrocarbonized fish may be used diluted with halogenated hydrocarbon.

In the preparation of the solid titanium catalyst component [ral] contained in the first catalyst used in the present invention, in addition to the compounds described above, a compound having two or more ether bonds existing through a plurality of atoms is used. It will be done.

Further, the solid titanium catalyst component [rb]L contained in the catalyst used in the second method according to the present invention is an electron donor (a) other than the compound having two or more ether bonds.
It is prepared using

As a compound having two or more ether bonds used in the preparation of such a solid titanium catalyst component [ral], the atomic carbon existing between these ether bonds is
Keihata Sour milk Compounds containing sulfur, phosphorus, boron, or two or more selected from these can be mentioned, and among these, a relatively bulky substituent is bonded to the atom between the ether bonds, and two or more Preferably, the compound contains a plurality of carbon atoms in the atoms existing between the above ether bonds.

Such compounds having two or more ether bonds include, for example, the following dog (where n is an integer of 2≦n≦10, and RI
# R26 is carbon, aquatic acid, halogen, nitrous sulfur,
At least one selected from phosphorus, boron and silicon
It is a substituent having a species element, and any R1-R26, preferably R+4, R2n may jointly form a ring other than a benzene ring, and even if the main chain contains atoms other than carbon. good. ) can be mentioned.

Examples of the above compounds having two or more ether bonds include 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, and 2-(2-ethylhexyl)-1,3-dimethoxypropane.
Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-
1,3-dimethoxypropane, 2-phenyl-1,3-
Dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p -chlorophenyl)-1,3-dimethoxypropane 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane,
2-(2-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-t-butylphenyl)-1,3-dimethoxy Propane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2.2-dipropyl-1,3-dimethoxypropane, 2
．． 2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2
-Methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2- Phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2.2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2.2-bis(2- cyclohexylethyl)-1,3-
Dimethoxypropane, 2-methyl-2-inbutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane 2
．． 2-diphenyl-1,3-dimethoxypropane, 2.
2-Dibenzyl-1,3-dimethoxypropane 2.2-
Bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-jethoxypropane,
2.2-diisobutyl-1,3-dibutoxypropane,
2-inbutyl-2-isopropyl-1,3-dimethoxypropane, 2.2-di-S-butyl-1,3-dimethoxypropane, 2.2-di-t-butyl-1,3-dimethoxypropane, 2 .2-dineobenyl 1,3-dimethoxypropane, 2-isopropyl-2-isobenthyl 1,3-
Dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,
3-dimethoxypropane, 2.3-diphenyl-4-jethoxybutane, 2.3-
Dicyclohexyl-1,4-jethoxybutane, 2.2
-dibenzyl-1,4-jethoxybutane, 2,3-dicyclohexyl-1,4-jethoxybutane, 2.3-
Diisopropyl-1,4-jethoxybutane, 2.2-
Bis(p-methylphenyl)-1,4-dimethoxybutane, 2.3-bis(p-chlorophenyl)-1,4-jethoxybutane 2.3-bis(p-fluorophenyl)-1,4-dimethoxybutane, 2.4-diphenyl-1,5-dimethoxypentane, 2
．． 5-diphenyl-1,5-dimethoxyhexane, 2.
4-diisopropyl-1,5-dimethoxypentane, 2
．． 4-diisobutyl-1,5-dimethoxypentane, 2
．． 4-diisoamyl-1,5-dimethoxypentane, 3
-Methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1.3-diisoamyloxypropane, 1.2-diisobutoxypropane 1.2-diisobutoxyethane, 1.3-diisoamyloxyethane, 1.3- Diisoamyloxypropane 1,3-diisoneobenoxyethane, 1,3-dineobenyloxypropane, 2,2-tetramethylene-1
,3-dimethoxypropane2,2-pentamethylene-1
,3-dimethoxypropane2.2-hexamethylene-1
, 3-dimethoxypropane 1,2-bis(methoxymethyl)cyclohexane, 2,8-dioxaspiro[5,5
] undecane, 3.7-') t+sahishik t: 1 [3
,3,1]/t,3.7-thioxabicyclo[3,
3,O]octas3.3-diisobutyl-1,5-oxononane, 6,6-dibutyldioxyhbutane1.
1-dimethoxymethylcyclopentane 1.1-bis(dimethoxymethyl)cyclohexane, 1.1-bis(methoxymethyl)bicyclol:2.2.1]hebutane, 1.1-dimethoxymethylcyclopentane, 2-methyl -2~methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-jethoxypropane 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane2. 2-diisobutyl-1,3-dimethoxycyclohexane 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl -1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-dithoxymethyl-1,3-jethoxycyclohexane, 2-cyclohexyl-2-ditoxymethyl- 1,3-dimethoxycyclohexane, 2-isopropyl-2-ditoxymethyl-1,3-jethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-jethoxycyclohexane 2-isobutyl-2-ethoxymethyl-1 , 3-jetoxycyclohexane, 2-isobutyl-2-ditoxymethyl-1,3-dimethoxycyclohexane, tris(p-methoxyphenyl)phosphine, etc. Methylphenylbis(methoxymethyl)silane, diphenylbis(methoxymethyl)silane, methylcyclohexane Examples include hexylbis(methoxymethyl)silane, di-t-butylbis(methoxymethyl)silane, cyclohexyl-t-butylbis(methoxymethyl)silane, and i-propyl-t-butylbis(methoxymethyl)silane.

Among these, 1,3-diethers are preferred;
．． 2-diisobutyl-1,3-dimethoxyprono(n),
2-isopropyl-2-isobenthyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane are preferred %1' l.

In addition to the solid titanium catalyst component [1a] used in the preparation of the first catalyst and the above-mentioned magnesium compound, the compound having two or more ether bonds and the liquid titanium compound, a carrier compound and a reaction aid. It may also be prepared by contacting organic and inorganic compounds containing silicon, phosphorus, aluminum, etc., electron donors (a) described below, and the like.

Such carrier compounds include A120a, 5tOa
, B2O5, MgO, Cab, Tio□, ZnO1Z
Resins such as nO2, SnO2, Bad, The, and styrene-divinylbenzene copolymer are used. Among these, A 1203, Si02, and styrene-divinylbenzene copolymer are preferred.

Furthermore, the electron donor (a) does not necessarily need to be used as a starting material, and can also be generated during the process of preparing the solid titanium catalyst component [Ial.

The solid titanium catalyst component [xblL] contained in the catalyst used in the second method according to the present invention is prepared using an electron donor (a) other than the above-mentioned compound having two or more ether bonds. Examples of such electron donors (a) include organic acid esters, organic acid haranates, and organic acid anhydrides.
ethers, ketones, tertiary amines, phosphites,
Examples include phosphoric acid ester, monononic acid amide, carboxylic acid amide, nitrile, etc., and specifically, ketones having 3 to 15 carbon atoms such as acetone, methyl ethino ν, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone. Classes: Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl acetate, benzaldehyde, tolualdehyde, and nathaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, acetic acid Cyclohexyl, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, rest
m-methyl, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, strict amyl toluyl, ethyl ethyl benzoate, anisic acid Organic acid esters having 2 to 18 carbon atoms such as methyl, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anise Acid halides having 2 to 15 carbon atoms such as acid chloride.

2 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc.
~20 ethers; acetic acid N.

Acid amides such as N-dimethylamide, N-benzoic acid, N-diethylamide, N-toluic acid, and N-dimethylamide Tertiary amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, and tetramethylethylenediamine: acetonitrile, benzo Examples include nitriles such as nitrile and trinitrile, and among these, aromatic carboxylic acid esters are preferred. Two or more of these compounds can be used in combination.

In addition, particularly preferred examples of organic acid esters include polyvalent carboxylic acid esters, and examples of such polyvalent carboxylic acids include the following general rule R''-C-COOR+ R4-C-COOR2, (Tatari , R1 is a substituted or unsubstituted hydrocarbon group R2,
R81Ra is hydrogen or substituted or unsubstituted hydrocarbon f
, R3, R41L hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group, and Rs and R4
may be connected to each other, and the hydrocarbon group R14Rs
Substituent iL N, OSS when is substituted
For example, C-0-CSCOORSC
OOH, OH, SO, H.

Examples include compounds having a skeleton represented by (having a group such as -C-N-C-NH2).

Such polyhydric carboxylic acid esters (specifically diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl a-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, diallyl 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, diethyl phthalate, ethylisobutyl phthalate, di-phthalate -Propyl, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl phthalate Aromatic polycarboxylic acid esters such as butyl, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid. Preferred examples include esters.

In addition, as another example of polyhydric carboxylic acid ester, iL
Examples include esters of long-chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Among these compounds, monocarboxylic acid esters are preferably used, and polycarboxylic acid esters, particularly phthalic acid esters, are preferably used.

In addition, these electron donors (a) L do not necessarily need to be used as starting materials, and can be used as solid titanium catalyst components [■
b] It can also be generated during the preparation process.

In addition to the solid titanium catalyst component [r b] 14, the above-mentioned magnesium compound, the compound having two or more ether bonds, the liquid titanium compound, silica phosphorus, which is used as a carrier compound and reaction aid, etc. It may also be prepared by using organic and inorganic compounds containing aluminum and the like and bringing them into contact.

The solid titanium catalyst component according to the present invention [ralL includes a magnesium compound as described above, a liquid titanium compound, a compound having two or more ether bonds, and optionally a carrier compound, an electron donor (a), etc. Prepared by contacting with.

Solid titanium catalyst component [ra
There are no particular restrictions on the method for producing 1. Here, several examples of the method will be briefly described below.

(1) Method of contacting and reacting a magnesium compound, a compound having two or more ether bonds, and a titanium compound in any order 9. During this reaction, each component is combined with the compound having two or more ether bonds and/or a titanium compound. Alternatively, the electron donor (ω) may be pretreated with a reaction aid such as a halogen-containing silicon compound.

(2) A method in which a non-reducing liquid magnesium compound and a liquid titanium compound are reacted in the presence of the compound having two or more ether bonds to precipitate a solid magnesium-titanium complex. Further reacting the titanium compound with the reaction product obtained in (3) (2) and electron donor (a) and titanium. Method for further reacting the compounds (5) The solid material obtained by pulverizing the magnesium compound, the above-mentioned compound having two or more ether bonds, and the titanium compound is reacted with halogen, halogen compound, and aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, or the magnesium compound and the above-mentioned compound having two or more ether bonds, or the magnesium compound and the titanium compound. It may be ground in the presence of a grinding aid or the like. Furthermore, after pulverization, the material may be pretreated with a reaction aid and then treated with a halogen or the like. In addition,
Examples of reaction aids include +4 organic aluminum compounds and halogen-containing silicon compounds.

(6) Gum in which the compound obtained in (1) to (4) above is treated with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) Support compounding of metal oxides, etc. Contact with organomagnesium compounds and halogen-containing compounds (8) A method of contacting the reactant with the compound having two or more ether bonds and the titanium compound; (8) a magnesium salt of an organic acid;
A gum in which a magnesium compound such as alkoxymagnesium or allyloxymagnesium is brought into contact with the compound having two or more ether bonds, a titanium compound, and optionally a halogen-containing compound (9) A magnesium compound and an alkoxytitanium are brought into contact with at least A method of reacting a solution containing a titanium compound, the above-mentioned compound having two or more ether bonds, and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound (10) Magnesium compound in a liquid state without reducing properties and an organoaluminum compound to precipitate a solid magnesium-aluminum complex, and then
A method of reacting the compound having two or more ether bonds with a titanium compound. By such a method, the solid titanium catalyst component [Ia
] When producing magnesium compounds, one curry is required for the amount of liquid titanium compounds and compounds having two or more ether bonds. The titanium compound in liquid state is used in an amount of 140.01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol.
It is used in amounts of 0 mol, particularly preferably 1 mol to 200 mol.

The temperature at which these compounds are brought into contact is usually -70t
-200°C, preferably 10°C - 150°C.

The solid titanium catalyst component [I'a
]l& Contains titanium, magnesium, halogen, and the above-mentioned ether compound having two or more ether bonds.

In this solid titanium catalyst component [ra], halogen/titanium (atomic ratio) is 132 to 100, preferably 4 to
90, the compound having two or more ether bonds/titanium (molar ratio) I is 0.01 to 100, preferably 0.2 to 10, and the magnesium/titanium (atomic ratio) is 2 to 100. The number is preferably 4 to 50.

In addition, the solid titanium catalyst component [r b] contained in the second catalyst used in the present invention is a magnesium compound, a liquid titanium compound, an electron donor (a), and a carrier compound if necessary. It is prepared by bringing these into contact with each other.

There are no particular limitations on the method for preparing such a solid titanium catalyst component [Ib].Here, several examples of this method will be briefly described below.

(1) A block in which a magnesium compound, an electron donor (a), and a titanium compound are reacted in any order.This reaction IL is a block in which each component is combined with an electron donor (a) and/or an organoaluminum compound or a halogen-containing silicon. It may be pretreated with a reaction aid such as a compound. In this method, the above electron donor (a) is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
The reaction product obtained in step (3) and (2) is reacted with a liquid titanium compound in the presence of an electron donor (a) to precipitate a solid magnesium-titanium complex. (4) The reaction product obtained in (1) or (2) and the electron donor (a) and the titanium compound are further reacted. (5) The magnesium compound and the electron donor (a), A block obtained by treating a solid material obtained by pulverizing a titanium compound with either a halogen, a halogen compound, or an aromatic hydrocarbon. The process may include a step of pulverizing a complex compound consisting of a magnesium compound and a titanium compound. Further, after pulverization, the material may be pretreated with a reaction aid and then treated with a halogen or the like. Examples of reaction aids include organic aluminum compounds and halogen-containing silicon compounds.

(6) Treatment of the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon (7) Compounding a carrier such as a metal oxide Contact with an organomagnesium and a halogen-containing compound The reactants are brought into contact with the electron donor (a) and the titanium compound (8) A magnesium compound such as a magnesium salt of an organic acid, an alkoxymagnesium, or an aryloxymagnesium is brought into contact with the electron donor (a), the titanium compound and optionally (9) A molten rattan containing at least a magnesium compound and an alkoxy titanium is reacted with an electron donor (a) and a halogen-containing compound such as a halogen-containing silicon compound as necessary. Square block (10) A square block in which a non-reducing liquid magnesium compound and an organoaluminium compound are reacted to precipitate a solid magnesium-aluminum complex, and then an electron donor (a) and a titanium compound are reacted. By such a method, the solid titanium catalyst component [I
When producing B, the amount of magnesium compound used, liquid titanium compound and electron donor (a)
4 The type of paper Although it varies depending on the contact conditions, contact order, etc., the electron donor (a) per mol of magnesium
The titanium compound in liquid state is used in an amount of 01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol.
It is used in an amount of 0 mol.

Temperature at which these compounds are brought into contact +4 Usually -7
The temperature is 0°C to 200°C, preferably 10°C to 150°C.

The solid titanium catalyst component thus obtained [r b
] +1 titanium, magnesium and halogen,
It contains an electron donor (a).

In this solid titanium catalyst component 'Cr b], the halogen/titanium (atomic ratio) ratio is 2 to 100, preferably 4
~90, the electron donor (a)/titanium (molar ratio) is 0.01-100, preferably 0.2-1O, and the magnesium/titanium (atomic ratio) is 2-100, preferably 4 -50 is desirable.

The catalyst used in the first method according to the present invention includes the solid titanium catalyst component [ra] as described above and the organometallic compound catalyst component [nl].

FIG. 1 shows an explanatory diagram of the preparation process of the catalyst used in the first method according to the present invention.

As such an organometallic compound catalyst component [I[], for example, an organometallic compound of an organoaluminum compound, a complex alkylation of a group 1 metal and aluminum, or an organometallic compound of a group 1 metal can be used.

As such an organometallic compound catalyst component, for example, R@nAIX, -, (wherein R@ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, and n is 1≦n ≦3) can be exemplified.

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.Specifically, IL Methylbutylethyl & n-propylisopropyl group Isobutyl group Pentyl group Hexyl group Octyl group These include cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

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

trimethylaluminum, triethylaluminum,
Trialkylaluminium such as triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum, alkenylaluminum such as imprenylaluminum, dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethyl Dialkyl aluminum halides such as aluminum bromide, methylaluminum sesquichloride, ethylaraminiram sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride,
Alkylaluminium sesquihalides such as ethylaluminum sesquipromide.

Alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dichloride, etc.

Other examples of organoaluminum compounds include R-,
A I Y3-, (wherein Rs is the same as above, Y
10RbL O5z Rc3L 0AIR'
2&NR・25 -5iR'3 group or -NAIRh2 group, n is 1 to 2, Rg, Rb1 R-S Rd and Rh are methyl5, ethyl5, isopropyl, isobutyl, cyclohexyl, phenyl, etc. Yes, R is hydrobile methyl pentaethyl group
It is also possible to use a compound represented by an isopropyl group or a phenylpentatrimethylsilyl group, and Rt and R- are an ethyl group or the like.

As such an organoaluminum compound (specifically, the following compounds are used).

(i) R”MA l (OR”) ff n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutyl aluminum methoxide, etc., (ii) RenA l (O3iRcs)3-nEt
2Al (O5iMe*) (1so-B u)a A l (OS iMe,
) (iso-B u) a A l (OS iE
ts ) etc., (iii) R@, A I (OA
R', )s, Et2A I OA I Et2 (iso-Bu) 2A I OA l (
iso-Bu)2 etc., (iv) R@, AI (N
R.2) 2-nMe2AINEt.

Et2AINHMe Me2AINHEt Et2A　IN　(Me, Si).

(1so-B u)2A I N (Me, S
i) 2 etc., (v) R'', A I (SiR'3
)s-n(1so-B u)2A I SiMe,
etc., (vi) Ral, A I (NA I R
h,) 3-rly Me (iso-B u)2A I N A l (1so-
B u) 2 Nare t As the above-mentioned organoaluminum compound, R-,A
I, R.llA 1 (ORb)3-. 1R@
, , A l (OA I R'2) 3-7 can be exemplified as a suitable example.

As a complex alkylated product of Group 1 metal and aluminum, a compound represented by the following formula can be exemplified, specifically, LiAl
(C2Hs) a, L i A l (CvH+s
) a.

■As an organometallic compound of group metals General formula RIR2M
2 (However, 1.. Rk and R1 are hydrocarbon groups having 1 to 15 carbon atoms or halogens, and may be the same or different from each other. Except when both are halogens. M2 is Mg, Zn, or Cd. Exemplary compounds represented by IL are diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like.

Two or more of these compounds can also be used in combination.

In addition, in the solid titanium catalyst component [Xa] contained in the catalyst used in the first method of the present invention, in addition to such an organometallic compound catalyst component [n], two or more of the above two or more A compound having an ether bond and/or an electron donor (b) may be used, and as such an electron donor (b), the above electron donor (a) and an organosilicon represented by the following general formula may be used. Among these, it is preferable to use the organosilicon compound having two or more ether bonds.

R, S t (OR') a-n (wherein R and R' are hydrocarbon groups, and 0xn<4) As an organosilicon compound represented by the above general formula. Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyljethoxysilane, bisO
Tolyldimethoxysilane, bism-)lyldimethoxysilane, bisp-)lyldimethoxysilane, bisp-)
Lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyl Triethoxysilas Decyltrimethoxysilane, Decyltriethoxysilane, Phenyltrimethoxysilane, Archlorprobyltrimethoxysilane, Methyltriethoxysilane, Ethyltriethoxysilane, Vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2
- norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane,
Dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane: dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis (2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylethylmethoxysilane,
Dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-) Lyldimethoxysilane, p-)lylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, Cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used.

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

In addition, examples of the electron donor (b) that can be used in addition to these organosilicon compounds include nitrogen-containing compounds, other oxygen-containing compounds, phosphorus-containing compounds, and the like.

As such a nitrogen-containing compound, specifically, the following compounds can be used.

■ 2.6-substituted piperidines such as: 2.5-1ll substituted piperidines such as: N, N, N',
'N'-tetramethylmethylenecyamis N, N, N',
Substituted methylene diamines such as N'-tetraethylmethylene diamine: Substituted methylene diamines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

As the phosphorus-containing compound, specifically, phosphite esters as shown below can be used.

Phosphite esters such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethylphenyl phosphite, etc.

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

2.64-substituted tetrahydrobilanes such as l[:CH.

2.5-[substituted tetrahydropyrans such as

The catalyst used in the second method according to the present invention includes the solid titanium catalyst component [r b ] and the organometallic catalyst component [U] as described above, and two or more ethers present via a plurality of atoms. It contains a compound [m] having a bond.

FIG. 2 shows an explanatory diagram of the preparation process of the catalyst used in the second method according to the present invention.

As such organometallic compound catalyst component [[+],
For example, a catalyst component consisting of an organometallic compound similar to that used in preparing the catalyst used in the first method according to the present invention is used.

The compound [m] having two or more ether bonds as described above is a compound having two or more ether bonds similar to that used in the preparation of the first solid titanium catalyst component according to the present invention. used.

Further, the catalyst used in the second method according to the present invention may contain an electron donor other than the compound having two or more ether bonds, and as such an electron donor, +L, for example, according to the present invention. The electron donor (b) used in the preparation of the catalyst used in the first method can be used.

The first ethylene/a-olefin copolymer according to the present invention
The manufacturing method involves copolymerizing ethylene and at least one selected from α-olefins having 3 or more carbon atoms in the presence of the catalyst as described above.

The second ethylene/Q-olefin copolymer according to the present invention
The manufacturing method involves copolymerizing ethylene and at least one selected from a-olefins having 3 or more carbon atoms in the presence of the above-mentioned catalyst.

As such a-olefin having 3 or more carbon atoms, L
L For example, a-olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1
-hexadecene, 1-octadecene and 1-eicosene.

1 of such a-olefins, especially 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
1-octene and 1-decene are preferred, and the ethylene content in the ethylene/a-olefin copolymer obtained from the polymer fiber is 70% by weight or more, preferably 80 to 96% by weight, and the density is 0.88. -0.950 g/caF, particularly 0.89-0.94 g/cm''.

If in the first and second polymerization methods according to the present invention.

At least two or more of these olefins are used in combination, and in addition, styrene, aromatic vinyl compounds such as allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetra Cyclododecene, 2-methyl-1,4,5,13-dimethano-1
, 2,3,4,4a, 5.8.8a-Cyclic olefins such as octahydronaphthalene, 6-methyl 1°6-octadiene, 7-methyl-1,6-octadiene, 6-
Ethyl-1,6-octadiene, 6-brobyl-1.6
-octadiene, 6-butyl-1,6-octadiene,
6-methyl-1,6-nonadiene, 7-methyl-1,6
-nonadiene, 6-ethyl-1,6-nonadiene, 7-
Conjugated dienes such as dienes such as ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene, and butadiene; Compounds having polyunsaturated bonds such as non-conjugated dienes can also be used as polymerization materials.

It is preferable to prepolymerize the a-olefin in the catalyst in the first and second methods of the present invention.

This prepolymerization 14 0 per 1 g of catalyst for olefin polymerization
．． 1-1000g preferably 0.3. ~s o o g
.

Particular preference is given to prepolymerizing the a-olefin in amounts of 1 to 200 g.

In the prepolymerization, a catalyst can be used at a higher concentration than the catalyst concentration in the system in the main polymerization.

In the first and second polymerization methods according to the present invention, 11 solid titanium catalyst component [ra] or [I
Concentration of b] per liter of liquid medium, in terms of titanium atoms, is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably 0.1 to 50 mmol.
A range of 20 mmol is desirable.

Amount of organometallic compound catalyst component [[I] 1 pc. Solid titanium catalyst component [Xa] or [Ib] 0.1 to 1 per Ig
The amount of solid titanium catalyst component [r
The amount is generally about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol, per mol of titanium atom in [a] or [r b].

14 Prepolymerization by the first and second polymerization methods according to the present invention. If necessary, the above-mentioned compound having two or more ether bonds or the electron donor (b) can also be used.

At this time, these compound salts are extracted by the first method according to the present invention.
It is used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, and more preferably 1 to 10 moles, per mole of titanium atoms in the solid titanium catalyst component [Xa].

Moreover, in the second method according to the present invention, IL of these chemical compounds solid titanium catalyst component [! b] titanium atom 1 in
per mole, 0.1 to 50 mol, preferably 0.5 to 3
It is used in an amount of 0 mol, more preferably 1 to 10 mol.

Prepolymerization IL can be carried out under mild conditions by adding the olefin and the catalyst components described above to an inert hydrocarbon medium.

The inert hydrocarbon media used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, etc. dicyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons.

Examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. 1 of these inert hydrocarbon media! It is particularly preferable to use aliphatic hydrocarbons. When using an inert hydrocarbon medium in this way, the prepolymerization is preferably carried out batchwise. On the other hand, prepolymerization can be carried out using the olefin itself as a solvent, or it can be carried out substantially in the absence of a solvent. In this case 1
& Prepolymerization is preferably carried out continuously.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, and is preferably substituted ethylene or propylene.

Reaction temperature during prepolymerization 14 Usually about -20 to +10
It is desirable that the temperature is in the range of 0°C, preferably about -20 to +80°C, more preferably 0 to +40°C.

In addition, a molecular weight regulator such as hydrogen chloride can also be used in the prepolymerization. Such molecular weight regulator Jj3
Use in an amount such that the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135°C is about 0.2 dl/g or less, preferably about 0.5 to 10 di/g. is desirable.

Prepolymerized IL As above Solid titanium catalyst component [ral or [Ib] Approximately 0.1 to 1000 per Ig
It is desirable to carry out the process in such a way that about 0.3 to 200 g of polymer is produced, preferably about 0.3 to 200 g.

In the present invention, 1. Polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods.

When the main polymerization takes a reaction form of liquid phase polymerization, the above-mentioned inert hydrocarbons can be used as the reaction solvent, and an olefin that is liquid under the reaction conditions can also be used.

In the first and second polymerization methods of the present invention, the solid titanium catalyst component [■ a] or [r b] L polymerization volume 1
Usually about 0.001 to 0.5 per Ti atom
It is used in an amount of mmol, preferably about 0.005 to 0.1 mmol. In addition, organometallic compound [n ] +L
The amount of metal atoms used is usually about 1 to 2000 moles, preferably about 5 to 500 moles, per mole of titanium atoms in the prepolymerized catalyst component in the polymerization system.

Furthermore, in the second polymerization method according to the present invention, the compound having two or more ether bonds is usually about 0.001 mol to 10 mol, preferably 0.001 mol to 1 mol of the acid component metal atom. It is used in an amount of 0.01 to 2 moles.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted and a polymer with a high melt flow rate can be obtained.

In the present invention, the polymerization temperature of the olefin is usually about 2
0 to 200°C, preferably about 50 to 150°C, at a pressure of 1
Normal pressure ~100kg101'', preferably about 2~
It is set at 50 kg/cII2.

In the polymerization method of the present invention, the substitute polymerization can be carried out in any of the batchwise, semi-continuous, and continuous methods.

Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

When ethylene and a-olefin are polymerized using the above catalyst, the intrinsic viscosity [V] is 0. O1~50
An ethylene/a-olefin copolymer having a dl/g, preferably 0.1 to 10 dl/g can be obtained.

The ethylene/a-olefin copolymer material according to the present invention is not limited to use as a film, but can also be used for T-guy adult pigs, blown film adult pigs, hollow adult pig injection adult pigs, extrusion molding, etc. It can be processed into various molded products. It can also be made into various composite films by extrusion coating or coextrusion with other films, and is also used for applications such as steel pipe coating materials, electric wire coating materials, and foam molded products. some regret
Other thermoplastic resins such as high-density polyethylene, medium-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, combinations of low-crystalline or amorphous ethylene with propylene or 1-butene It can also be used by blending it with polyolefins such as propylene/1-butene copolymer.

The ethylene/a-olefin copolymer obtained in the above manner is blended with IL, heat-resistant stabilizer, weather-resistant stabilizer, antistatic, anti-blocking berth, glider, pigment, dye, inorganic or organic filler, etc. as required. You can also.

In addition to the above-mentioned components, the catalyst of the present invention may contain other components useful for olefin polymerization.

Ishiri A Ko J First ethylene/a-olefin copolymer according to the present invention
Production method +L A solid titanium catalyst component [I
a], and an organometallic compound catalyst component containing a metal from group 1 to m of the periodic table [nl], in the presence of an olefin polymerization catalyst containing ethylene and a-
It is copolymerized with at least one selected from olefins. Therefore, it depends on the method for producing the ethylene/α-olefin copolymer according to the present invention! An ethylene/a-olefin copolymer can be produced using a catalyst containing the solid titanium catalyst component [ral] and the organometallic compound catalyst component [nl].

The second ethylene/a-olefin copolymer according to the present invention
A solid titanium catalyst component containing titanium, magnesium, halogen, and an electron donor (a) [!
b], an organometallic compound catalyst component containing a metal from Group 1 to Group M of the periodic table [nl and a compound having two or more ether bonds existing through multiple atoms [[II]
A copolymer is produced by copolymerizing ethylene and an a-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst containing the following. Therefore, according to the second method for producing an ethylene/a-olefin copolymer according to the present invention, the solid titanium catalyst component [ral, the organometallic compound catalyst component [nl], and two or more ether bonds An ethylene/a-olefin copolymer can be produced using a catalyst containing a compound [I[l] having the following.

(The following is a blank space) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of solid titanium catalyst component [A]) 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130°C for 2 hours to form a homogeneous solution. 21.3 f of phthalic anhydride was added to this solution, and the mixture was stirred and mixed at 130° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, 75 ml of this homogeneous solution was dropped in its entirety over 1 hour into 200 ml of titanium tetrachloride maintained at -20°C. After the charging was completed, the temperature of this mixing branch was raised to 110"C over 4 hours, and when it reached 110°C, 5.22i of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid part was collected by hot filtration, and this solid part was poured into 275 ml of
After resuspending in titanium tetrachloride, it was again heated at 110°C for 2
The heating reaction was carried out for a period of time. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component [A] prepared by the above operations was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition.

The composition of the solid titanium catalyst component [A] thus obtained was 2.4% by weight of titanium, 60% by weight of chlorine, 19.0% by weight of magnesium, and 12% by weight of diisobutyl phthalate.
．． It was 4% by weight.

[Prepolymerization of solid titanium catalyst component [A]] 400 m
100 ml of purified hexane was placed in a four-glass reactor equipped with a stirrer under a nitrogen atmosphere. h ethylaluminum 10 mmol, 2-isopropyl-2-isopentyl-1,3-
After adding 1.0 mmol of dimethoxypropane and 1.0 mmol of the above solid titanium catalyst component [A] in terms of Ti atoms, propylene was added at a rate of 3.2 NN/hour at a temperature of 20° C. for 1 hour, and the reaction was continued. supplied to the vessel. When the supply of propylene is finished, the inside of the reactor is replaced with nitrogen, and a cleaning operation consisting of removing the supernatant liquid and adding purified hexane is carried out.
After circulating, the mixture was resuspended in purified hexane and the entire amount was transferred to a catalyst bottle.

[Ethylene polymerization] Add 150 g of sodium chloride as a dispersant to an autoclave with an internal volume of 2 g that has been sufficiently purged with nitrogen, and while heating to 90°C, reduce the pressure with a vacuum pump for 2 hours so that the internal pressure of the autoclave is 50 mmHg or less. I did it.

The temperature of the autoclave was then lowered to room temperature. After replacing the inside of the autoclave with ethylene, 0.75 mmol of triisobutylaluminum and 18 ml of hexene were added, and after sealing the system, the temperature was raised and 1.51 q of hydrogen was added at 60°C.
r/cd, and while further pressurizing with ethylene, the prepolymerized catalyst component was reduced to 0.0 in terms of titanium atoms.
0.05 mmol was added. During the polymerization, the temperature was maintained at 80° C. and the pressure was maintained at 8 kg/C-G by supplementing with ethylene gas. After addition of the titanium catalyst component, 132 ml of hexene was supplied using a pump for 1 hour. Polymerization was terminated 1 hour after the addition of the titanium catalyst.

After weighing, the autoclave contents were poured into approximately ] p of water. After stirring for about 5 minutes, almost all of the sodium chloride was dissolved in the water, and only the polymer floated on the water surface. After collecting this floating polymer and washing it thoroughly with methanol,
Drying was carried out under reduced pressure at 80'C overnight.

The polymerization results are shown in Table 1.

Example 2 [Preparation of solid titanium catalyst component [B] After replacing a high-speed stirrer (manufactured by Tokushu Kika Kogyo) with an internal volume of 2 g with dead N2, 700 ml of refined kerosene, 1210 g of commercially available Mgcji,
24.2g of ethanol and Emazol 320 (trade name)
Add 3 g of sorbitan distearate (manufactured by Kao Atlas ■), raise the temperature of the system while stirring, and raise the temperature to 8oorpI at 120°C.
The mixture was stirred for 30 minutes. Under high-speed stirring, using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a No. 21 glass flask (equipped with a stirrer) filled with refined kerosene II cooled to -10"C. The solid produced was filtered. The carrier was collected, thoroughly washed with hexane, and then discarded.

7.5 g of the carrier was placed in 150 ml of titanium tetrachloride at room temperature, and the system was heated to 40°C, and after adding 1.33 m of 2-isopropyl 2 isopentyl 1,3-dimethoxypropane, the system was heated to 100°C. After stirring and mixing at 100°C for 2 hours, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and stirred and mixed at 120°C for 2 hours. Furthermore, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid titanium catalyst component [B]. The components are 3.1% by weight of titanium, 58% by weight of chlorine, and 17% by weight of magnesium.
Weight %, 2-isopropyl-2-isopentyl L, S-
The dimethoxypropane content was 19.7% by weight.

[Prepolymerization of solid titanium catalyst component [B] 400ml
100 ml of purified hexane, 10 mmol of triethylaluminum, 1.0 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and the above solid titanium catalyst component [B ] was added to the reactor at a rate of 2.47 NN/hour at a temperature of 20° C. for 1 hour. When the supply of propylene is finished, the inside of the reactor is replaced with nitrogen, and a cleaning operation consisting of removing the supernatant liquid and adding purified hexane is carried out.
After circulating, the mixture was resuspended in purified hexane and the entire amount was transferred to a catalyst bottle.

[Ethylene polymerization] The same method as in Example 1 was used.

The polymerization results are shown in Table 1.

Surface polymerization results 4,

[Brief explanation of drawings]

1st Figure 2 is For olefin polymerization according to the present invention It is an explanatory view of a catalyst adjustment process.

Claims (1)

[Scope of Claims] 1) [I a] A solid titanium catalyst component containing titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms, and [II ] Ethylene and an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst characterized by containing an organometallic compound catalyst component containing a metal from Group I to Group III of the periodic table. A method for producing an ethylene/α-olefin copolymer, which comprises copolymerization. 2) The solid titanium catalyst component [Ia] is prepolymerized with at least one selected from α-olefins having 2 to 20 carbon atoms. A method for producing an ethylene/α-olefin copolymer. 3) Ethylene α according to claim 1, wherein the compound having two or more ether bonds is a compound having two or more ether bonds existing through a plurality of carbon atoms. - A method for producing an olefin copolymer. 4) The above compound having two or more ether bonds has the following formula, ▲mathematical formula, chemical formula, table, etc.▼ (However, in the formula, n is an integer of 2≦n≦10, and R^1
~R^2^6 is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon, and any R^1~R
^2^6 may jointly form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. The method for producing an ethylene/α-olefin copolymer according to item 3. 5) [I b] Titanium, magnesium, halogen, and electron donor (a) (however, electron donor (a) is a compound having two or more ether bonds that exist through multiple atoms) [II] an organometallic compound catalyst component containing a Group I to III metal of the periodic table; and [III] two or more metals present via multiple atoms. In the presence of an olefin polymerization catalyst containing a compound having an ether bond, ethylene and
A method for producing an ethylene/α-olefin copolymer, which comprises copolymerizing an α-olefin having 3 or more carbon atoms. 6) The solid titanium catalyst component [Ia] is prepolymerized with at least one selected from α-olefins having 2 to 20 carbon atoms. A method for producing an ethylene/α-olefin copolymer. 7) Ethylene α according to claim 5, wherein the compound having two or more ether bonds is a compound having two or more ether bonds existing via a plurality of carbon atoms. - A method for producing an olefin copolymer. 8) The above compound having two or more ether bonds has the following formula, ▲mathematical formula, chemical formula, table, etc.▼ (However, in the formula, n is an integer of 2≦n≦10, and R^1
~R^2^6 is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon, and any R^1~R
^2^6 may jointly form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. The method for producing an ethylene/α-olefin copolymer according to Item 7.