JP2959800B2 - Method for producing propylene-based block copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a propylene-based block copolymer.

Technical Background of the Invention Conventionally, in the presence of various stereospecific catalysts, a propylene crystalline polymer or a crystalline copolymer (hereinafter, sometimes referred to collectively as simply polypropylene) in the first stage ), And in the second and subsequent stages, in the presence of this crystalline polypropylene, propylene and another α-olefin are copolymerized to form a rubber-like polymer, thereby having excellent impact resistance at low temperatures. A method for producing a propylene-based block copolymer is known.

An object of the present invention is to provide a method for producing a propylene-based block copolymer using a specific catalyst which exhibits high catalytic activity and can obtain a propylene-based copolymer having excellent impact resistance. The purpose is.

SUMMARY OF THE INVENTION A method for producing a propylene-based block copolymer according to the present invention comprises: [Ia] titanium, magnesium, halogen, (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ together form a ring other than a benzene ring And a compound having two or more ether bonds represented by the following general formula (II): ] Propylene is polymerized or copolymerized in the presence of an olefin polymerization catalyst containing an organoaluminum compound catalyst component to produce a crystalline polymer, and at least two or more α-olefins are produced in the presence of the crystalline polymer. To produce a low-crystalline copolymer or an amorphous copolymer.

According to the method for producing a propylene-based block copolymer according to the present invention, a solid titanium catalyst component [Ia] containing a compound having two or more ether bonds as described above as an electron donor and the organic metal Compound catalyst component [I
Use of the catalyst formed from [I] enables efficient production of a propylene-based block copolymer having excellent impact resistance.

In addition to the above two components, it is also possible to use a catalyst containing the compound having two or more ether bonds or a specific electron donor together with the organometallic compound catalyst component [II].

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a propylene-based block copolymer according to the present invention will be specifically described.

In the method for producing a propylene-based block copolymer according to the present invention, a solid titanium catalyst component containing titanium, magnesium, a halogen, and a compound having two or more ether bonds existing through a plurality of atoms [ And a catalyst comprising an organoaluminum compound catalyst component [II].

The solid titanium catalyst component constituting such a catalyst [1
a] is prepared by using a magnesium compound and a titanium compound and the above-mentioned compound having two or more ether bonds or the electron donor (a), and bringing these compounds into contact with each other.

For the preparation of the solid titanium catalyst component [Ia] constituting the catalyst used in the present invention, a magnesium compound can be used. Examples of the organomagnesium compound include a magnesium compound having a reducing ability and a magnesium compound having a reducing ability. Magnesium compounds which are not used.

Here, as the magnesium compound having a reducing ability, for example, a compound represented by the formula X _n MgR _2-n (where n is 0 ≦ n <2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or When n is 0, two R's may be the same or different and X is a halogen, and X is a halogen).

Specific examples of the organomagnesium compound having such a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, Examples thereof include butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. 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; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

The magnesium compound is a complex compound, a complex compound of the above-mentioned magnesium compound and another metal, or a mixture of another metal compound, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property. You may. Further, a mixture of two or more of the above compounds may be used, and the compounds may be used in a liquid state or a solid state. When the compound is a solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters and the like.

Among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

The titanium compound in a liquid state used for the preparation of the solid titanium catalyst component [Ia] constituting the catalyst used in the present invention includes, for example, a general formula: Ti (OR) _g X _4-g (R is a hydrocarbon X is a halogen atom, and 0
.Ltoreq.g.ltoreq.4).
More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( dihalogenated alkoxy titanium such as _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 Br 2; Ti (OCH 3) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On- _{C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 Br; Ti (OCH 3) 4, Ti (OC 2 H 5) 4, Ti (On-C 4 H 9) 4 Ti (Oiso-C 4 H ₉ ) ₄ Ti (O-2-ethylhexyl) ₄ ; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (Oiso-C ₄ H ₉ ) ₄ , monohalogenated alkoxytitanium such as tetraalkoxytitanium such as ₄ , Ti (O-2-ethylhexyl) ₄ .

Of these, 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, it may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.

In the solid titanium catalyst component [Ia] contained in the catalyst used in the present invention, a compound having two or more ether engagements present through a plurality of atoms is used in addition to the above-mentioned compounds.

As the compound having two or more ether bonds used for preparing the solid titanium catalyst component [Ia] as described above, the atom existing between these ether bonds is carbon,
Examples thereof include silicon, oxygen, sulfur, phosphorus, boron, and a compound of two or more kinds selected from these. Among them, a relatively bulky substituent is bonded to an atom between ether bonds, and two Compounds in which a plurality of carbon atoms are contained in the atoms existing between the above ether bonds are preferable.

As such a compound having two or more ether bonds, the following formula: (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ , preferably R ¹
To R ²ⁿ may together form a ring other than a benzene ring, and an atom other than carbon may be contained in the main chain. ) Can be mentioned.

Examples of the compound having two or more ether bonds as described above include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, and 2-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- (diphenyl Methyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 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-dimethoxy Propane, 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-sik Hexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-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-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di- s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 , 3-Jim Kishipuropan, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,
3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3 -Dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis ( (p-chlorophenyl) -1,4-dimethoxybutane, 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-methoxymethyl Tetrahydrofuran, 3-methoxymethyl Dioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1 , 3-Dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3, 3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1 -Bis (methoxymethyl) bisic B [2,2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxy Propane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-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- Ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxyme Cyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl 1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane , Methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl)
Examples include silane and i-propyl-t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferred, and in particular, 2,2
-Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3 -Dimethoxypropane is preferred.

The solid titanium catalyst component [Ia] according to the present invention.
In addition to the magnesium compound, the titanium compound in the liquid state and the compound having two or more ether bonds, silicon and phosphorus used as a carrier compound and a reaction aid, organic and inorganic compounds including aluminum, It may be prepared by using an electron donor (a) described below or the like and bringing them into contact.

Such carrier compounds include Al ₂ O ₃ , SiO ₂ , B
Resins such as ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Among them, Al ₂ O ₃ , SiO ₂ and styrene
Dividylbenzene copolymers are preferred.

In addition, the electron donor (a) does not necessarily need to be used as a starting material, and can be generated in the process of preparing the solid titanium catalyst component [Ia].

Examples of the electron donor (a) other than the compound having two or more ether bonds include an organic acid ester, an organic acid halide, an organic acid anhydride, an ether, a ketone, an aldehyde,
Examples include tertiary amines, phosphites, phosphates, phosphoric amides, carboxylic amides, nitriles, and the like. Specific examples include carbon such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone. Number 3 ~
15 ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. Organic acid esters having 2 to 18 carbon atoms; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether and butyl ether C2 to C20 ethers such as amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide and toluic acid N, N-dimethylamide; Tertiary amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile and trinitrile can be exemplified, and among them, aromatic carboxylic acid esters are preferable. . These compounds can be used in combination of two or more.

Further, as the organic acid ester, a polycarboxylic acid ester can be mentioned as a particularly preferred example,
As such a polycarboxylic acid ester, the following general formula: (However, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of them is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other. Often, when the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a heteroatom such as N, O, S, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-N-C-, NH 2
And a skeleton represented by the following formula:

Such polycarboxylic acid esters include, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate , Diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate , Diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylates such as aliphatic polycarboxylates such as diethyl itaconate and dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate Acid esters, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, di-n-propyl phthalate,
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 butyl phthalate, Diphenyl phthalate, Diethyl naphthalene dicarboxylate, Dibutyl naphthalene dicarboxylate,
Preferable examples include aromatic polycarboxylic acid esters such as triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include long adipates such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters of chain dicarboxylic acids and the like can be mentioned. Among these compounds, it is preferable to use a sulfonate, particularly a polycarboxylic acid ester,
Particularly, phthalic esters are preferably used.

The solid titanium catalyst component [Ia] constituting the catalyst used in the present invention includes a magnesium compound as described above, a titanium compound in a liquid state, a compound having two or more ether bonds, and And a carrier compound, an electron donor (a) or the like.

A solid titanium catalyst component using these compounds [I
Although there is no particular limitation on the production method of a), the method will be briefly described below with several columns.

(1) A method of contacting and reacting a magnesium compound, the compound having two or more ether bonds, and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with a compound having two or more ether bonds and / or a reaction auxiliary such as an electron donor (a), an organoaluminum compound, or a halogen-containing silicon compound.

(2) A method in which a liquid magnesium compound having no reducing property is reacted with a liquid titanium compound in the presence of the compound having two or more ether bonds to precipitate a solid magnesium / titanium composite. .

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which the electron donor (a) and the titanium compound are further reacted.

(5) A method in which a solid obtained by pulverizing a magnesium compound, a compound having two or more ether bonds, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, or the magnesium compound and the compound having two or more ether bonds, or the step of pulverizing the magnesium compound and the titanium compound. It may be ground down. After the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. In addition,
Examples of the reaction assistant include an organoaluminum compound and a silicon-containing compound having a halogen.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, an organomagnesium compound, and a halogen-containing compound with the compound having two or more ether bonds and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or alloxymagnesium is brought into contact with the compound having two or more ether bonds and a titanium compound and / or a halogen-containing hydrocarbon.

(9) A method of reacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound, the compound having two or more ether bonds, and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound.

(10) A liquid magnesium compound having no reducibility is reacted with an organoaluminum compound to precipitate a solid magnesium-aluminum complex, and then the compound having two or more ether bonds and the titanium compound are removed. How to react.

By such a method, the solid titanium catalyst component [I
In the production of a), the amount of the magnesium compound, the titanium compound in a liquid state and the compound having two or more ether bonds to be used varies depending on the kind, contact conditions, contact order and the like. The compound having two or more ether bonds is 0.01 mol to
It is used in an amount of 5 mol, particularly preferably 0.1 mol to 1 mol, and the titanium compound in a liquid state is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol.

The temperature for contacting these compounds is usually -70 ° C.
To 200 ° C, preferably 10 ° C to 150 ° C.

The solid titanium catalyst component [I
a] contains titanium, magnesium, and halogen, and the above ether compound having two or more ether bonds.

In the solid titanium catalyst component [Ia], the halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90.
And the compound having two or more ether bonds /
Titanium (molar ratio) is 0.01-100, preferably 0.2-10, magnesium / titanium (atomic ratio) is 2-100,
Preferably, it is 4 to 50.

The catalyst used in the method according to the present invention contains the solid titanium catalyst component [Ia] and the organoaluminum compound catalyst component [II] as described above.

The organoaluminum compound can be used as the organoaluminum compound catalyst component [II], for example in R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or And n is 1 to 3).

In the above formula, ^Ra 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, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum,
Trialkylaluminums such as triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide.

Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminium sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum ^{_{compound, R a n AlY 3-n}} ( wherein R ^a is as defined above, Y is -OR ^b group, -OSiR ^c ₃ group,
-OAlR ^d ₂ group, -NR ^e ₂ group, a -SiR ^f ₃ group or -NAlR ^h ₂ group, n is ^{1~2, R g, R b,} R c, R d and R ^h are methyl Group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., ^Re is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g are methyl group. Or an ethyl group) can also be used.

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

(I) R ^a _n Al (OR ^b ) _3-n diethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc .; (ii) R ^a _n Al (OSiR ^c ₃ ) _3-n Et ₂ Al (OSiMe ₃₎ (such as _{iso-Bu) 2 Al (OSiMe} 3) (iso-Bu) 2 Al (OSiEt 3), (iii) R a n Al (OAR d 2) 3-n Et 2 AlOAlEt 2 (iso-Bu) such as _{2 AlOAl (iso-Bu) 2} , (iv) R a n Al (NR e 2) 3-n Me 2 AlNEt 2 Et 2 AlNHMe Me 2 AlNHEt Et 2 AlN (Me 3 Si) 2 (iso-Bu) 2 AlN (Me ₃ Si) ₂ etc., (v) R ^a _n Al (SiR ^f ₃ ) _3-n (iso-Bu) ₂ AlSiMe ₃ etc. As the organoaluminum compound as described above, ^Ra ₃ A
Preferred examples thereof include organoaluminum compounds represented by l, R ^a _n Al (OR ^b ) _3-n , and R ^a _n Al (OAlR ^d ₂ ) _3-n .

These compounds may be used in combination of two or more.

Further, in the catalyst used in the first method according to the present invention, such an organoaluminum compound catalyst component [II]
In addition, if necessary, the compound having two or more ether bonds and / or the electron donor (b) may be used. As such an electron donor (b), the above-mentioned electron donor (a ) And an organic silicon compound represented by the following general formula. Among them, a compound having two or more ether bonds and an organic silicon compound are particularly preferable.

R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxysilane. , T-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltriethyl Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, 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- Dicyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane , Tricyclopentylethoxysilane, dicyclopentylmethylethoxysilane, hexenyltrimethoxysilane, dicyclopentylethylmethoxy Silane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxy Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used. That. These organosilicon compounds can be used as a mixture of two or more kinds.

Examples of the electron donor (b) that can be used in addition to the organic silicon compound include a nitrogen-containing compound, another oxygen-containing compound, and a phosphorus-containing compound.

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

2,6-substituted piperidines such as: 2,5-substituted piperidines such as: N, N, N ', N'-tetramethylmethylenediamine, N, N,
Substituted methylenediamines such as N ', N'-tetraethylmethylenediamine: 1,3-dibenzylimidazolidine, 1,3-dibenzyl-
Substituted imidazolidines such as 2-phenylimidazolidine and the like.

As the phosphorus-containing compound, specifically, the following phosphites can be used.

Phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite;

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

2,6-substituted tetrahydropyrans such as: 2,5-substituted tetrahydropyrans.

In the method for producing a propylene-based block copolymer according to the present invention, block copolymerization is performed using the above-described catalyst.

In the method according to the present invention, the catalyst is preferably preliminarily polymerized, and the prepolymerization is carried out in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g per 1 g of the olefin polymerization catalyst. -By pre-polymerizing the olefin.

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

In the polymerization method according to the present invention, the concentration of the solid titanium catalyst component [Ia] in the preliminary polymerization is usually about 0.001 to 100 mmol, in terms of titanium atoms, per liter of the liquid medium.
Preferably about 0.01 to 50 mmol, particularly preferably 0.1 to 2
Desirably, the range is 0 mmol.

The amount of the organoaluminum compound catalyst component [II] is preferably 0.1 to 1000 g per 1 g of the solid titanium catalyst component [Ia].
It is sufficient that an amount of 0.3 to 500 g of polymer is generated,
Usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, per 1 mol of titanium atom in the solid titanium catalyst component [Ia],
Particularly preferably, the amount is 1 to 20 mol.

In the method according to the present invention, the above-mentioned compound having two or more ether bonds or an electron donor can be used. These compounds are contained in an amount of 0.1 to 1 mol of titanium atom in the solid titanium catalyst component [Ia]. ~ 50 mol, preferably
It is used in an amount of 0.5 to 30 mol, more preferably 1 to 10 mol.

The prepolymerization can be carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. As described above, when an inert hydrocarbon medium is used, the prepolymerization is preferably performed in a batch system. On the other hand, the olefin itself can be pre-polymerized in a solvent or can be pre-polymerized in a substantially solvent-free state. In this case, it is preferable to carry out the preliminary polymerization continuously.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, it is preferably propylene.

The reaction temperature during the prepolymerization is usually about -20 to + 100 ° C,
Preferably about -20 to + 80 ° C, more preferably 0 to +40
It is desirable to be in the range of ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer 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 more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is performed in an amount of about 0.1 to 1000 g, preferably about 0.3 to 500 g, per 1 g of the solid titanium catalyst component [Ia].
Particularly preferably, the reaction is carried out so as to produce 1 to 200 g of a polymer.

In the method for producing a propylene-based block copolymer according to the present invention, a plurality of stages of polymerization or copolymerization are performed, and these are selected from a crystalline polymer or copolymer production stage of propylene and an α-olefin. It can be classified into two or more non- or low-crystalline copolymer production stages.

In the present invention, the first-stage polymerization is a production stage of a crystalline polymer, and in such a first-stage polymerization, propylene homopolymerization or propylene and a small amount of at least one other α
-Highly stereoregular, highly crystalline polymers are produced by copolymerization with olefins.

Examples of such α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Pentene, 1-octene, 1-decene, 3-methyl-1
-Butene, 3-methyl-1-pentene and the like can be used.

In the present invention, the (co) polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Particularly preferred are a propylene solvent polymerization method and a gas phase polymerization method.

When the first-stage main polymerization takes a reaction form of solution polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, and an olefin liquid at the reaction temperature can be used.

In the present polymerization, the solid titanium catalyst component [Ia] or [I
b] is usually used in an amount of about 0.001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol, in terms of Ti atoms per liter of polymerization volume. The organoaluminum compound catalyst component [II] has a metal atom of usually about 1 to 2000 per mole of titanium atom in the prepolymerization catalyst component in the polymerization system.
Moles, preferably about 5-500 moles.

When hydrogen is used during the main polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a melt flow rate can be obtained.

In the present invention, the (co) polymerization temperature of propylene in the first stage polymerization is usually about 20 to 200 ° C, preferably about 5 to 200 ° C.
At 0 to 150 ° C., the pressure is usually set at normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² .

In order to obtain a rigid block copolymer, about 50 to about 95%, preferably 60 to about 90% by weight of the final product block copolymer composition is a crystalline copolymer of propylene. It is preferable to carry out the polymerization.

The step of producing the crystalline copolymer may be performed a plurality of times,
At this time, the polymerization conditions at each stage can be made different.

In the method according to the present invention, following the step of producing such a highly crystalline (co) polymer, at least two or more α-olefins are copolymerized in the presence of the obtained highly crystalline polymer. The step of producing the low crystalline or amorphous copolymer to be produced follows.

As the α-olefin used in the step of producing such a low-crystalline copolymer or amorphous copolymer, ethylene, propylene and α-olefins having 4 or more carbon atoms are used, and α-olefins having 4 or more carbon atoms are used. -As olefins,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-outadecene, 1-eicosene, and the like. be able to.

In the polymerization method according to the present invention, styrene, an aromatic vinyl compound such as allylbenze, an alicyclic vinyl compound such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, and 5-methyl-2-
Norbornene, tetracyclododecene, 2-methyl-1,
Cyclic olefins such as 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-otahydronaphthalene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene , 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-
1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-
Ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-
Compounds having polyunsaturation such as conjugated dienes and non-conjugated dienes such as dienes such as decadiene, 6-methyl-1,6-undecadiene, isoprene and butadiene can also be used as the polymerization raw material.

Polymerization using such α-orene fin can be performed under the same conditions as in the crystalline polymerization production step, or can be performed in a plurality of steps continuously, and the raw materials and conditions used in each step can be different. Particularly preferred is gas phase polymerization.

The copolymer produced in the step of producing such a non- or low-crystalline copolymer is preferably an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-pentene copolymer, an ethylene-hexene Copolymers, ethylene propylene butene copolymers, ethylene propylene pentene copolymers, ethylene propylene hexene copolymers and the like, such copolymers can be measured in decalin at 135 ℃ Intrinsic viscosity [η]
It is 0.5-20 dl / g, preferably 1-10 dl / g, particularly preferably 2-5 dl / g.

In the polymerization method of the present invention, the polymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system.

The propylene-based block copolymer thus obtained has an MFR (g / 10 min) of 0.01 to 1000, preferably 0.1 to 50.
0, more preferably 0.5 to 100, and 23 ° C-n-decane soluble part is 5 to 70% by weight, 8 to 55% by weight, 10 to 45% by weight.
A main monomer unit constituting the 23 ° C.-n-decane-soluble portion is 20 to 80% by weight, preferably 30 to 70% by weight,
Particularly preferably, it is 40 to 60% by weight.

Effect of the Invention The method for producing a propylene-based block copolymer according to the present invention is a solid titanium containing titanium, magnesium, a halogen, and a compound having two or more ether bonds existing through a plurality of atoms. Propylene is polymerized or copolymerized in the presence of an olefin polymerization catalyst containing the catalyst component [Ia] and the organoaluminum compound catalyst component [II] to produce a crystalline polymer, which is produced in the presence of the crystalline polymer. And copolymerizing at least two or more α-olefins to produce a low-crystalline copolymer or an amorphous copolymer.

According to the method for producing a propylene-based block copolymer according to the present invention, a propylene-based block copolymer excellent in rigidity and impact strength can be produced.

Further, the method according to the present invention can also be achieved by using, in addition to the above two components, a compound containing the above two or more ether bonds or a catalyst containing a specific electron donor together with the organometallic compound catalyst component [II]. .

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Measuring method The amount of the copolymer soluble in n-decane at 25 ° C was measured by the following method. That is, with stirrer 1
In a flask, 5 g of the copolymer sample, 0.3 g of 2,6-ditert
Add -butyl-4-methylphenol, 50 ml of n-decane and boil on a 130 ° C. oil bath. After dissolution, the mixture is allowed to cool naturally at room temperature for about 3 hours, and then cooled on a water bath at 25 ° C. for 8 hours or more. The n-decane solution containing the precipitated copolymer and the dissolved polymer was separated by filtration through a G-4 glass filter, and the solution was dried at 10 mmHg at 150 ° C. until a fixed amount was obtained. The amount of the soluble portion of the copolymer in water was calculated and determined as a percentage with respect to the weight of the sample copolymer.

Example 1 [Preparation of solid titanium catalyst component [A]] A high-speed stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.) having an internal volume of 2 was sufficiently used.
After replacing with N ₂ , 700 ml of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol, and ₃ g of Emazol 320 (trade name, sorbitan distearate, manufactured by Kao Atlas Co., Ltd.) were added. The mixture was stirred at 800 rpm for 30 minutes. Under high-speed stirring, the solution was transferred to a glass flask 2 (with a stirrer) into which purified kerosene 1 previously cooled to −10 ° C. was charged using a Teflon tube having an inner diameter of 5 mm. The resulting solid was collected by filtration and washed sufficiently with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the system was heated to 40 ° C.
After adding 1.33 ml of isopentyl-1,3-dimethoxypropane, the temperature was raised to 100 ° C. After stirring and mixing at 100 ° C. for 2 hours, a solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 120 ° C. for 2 hours. Further, a reaction solid was collected from the reaction product by filtration, and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The components are 3.1% by weight of titanium, 58% by weight of chlorine, 17% by weight of magnesium, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane 1 in terms of atom.
9.7% by weight.

[Preliminary polymerization] Preliminary polymerization was performed on the solid titanium catalyst component [A] as follows.

After 200 ml of purified hexane was charged into a 400 ml glass reactor purged with nitrogen, 0.66 mmol of triethylaluminum, 0.13 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and the solid titanium catalyst component [A ] Was charged in an amount of 0.066 mmol in terms of titanium atoms, and then propylene gas and ethylene gas were each charged to 3.04 mmol.
The mixture was fed at a rate of Nl / hr and 0.34 Nl / hr to the liquid phase of the polymerization vessel for 100 minutes while mixing. The temperature was kept at 20 ° C. ± 2 during the prepolymerization. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

As a result of the analysis, the solid catalyst component prepolymerized as described above contained about 1 g of the solid titanium catalyst component [A].
92 g of the polymer was preliminarily polymerized, while the amount of the polymer eluted in the solvent during the prepolymerization was determined by the Ti catalyst component [A].
It was equivalent to 6.2 g per g.

[Production of Copolymer] 0.5 kg of propylene and hydrogen
After adding N liter, the temperature was raised, and at 60 ° C, 1.8 mmol of triethylaluminum, 0.18 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 0.006 mmol of the prepolymerized catalyst component [A] in terms of titanium atom. Then, the homopolymerization of propylene was carried out while maintaining the temperature in the polymerization vessel at 70 ° C. 60 minutes after the temperature reached 70 ° C., the vent valve was opened, and propylene was purged until the pressure inside the polymerization reactor reached normal pressure.

After purging, copolymerization was subsequently carried out. That is, ethylene is 80 Nl / h, propylene is 120 Nl / h, and hydrogen is
The reactor was fed at a rate of 3.1 Nl / hour. The pressure inside the polymerization vessel
The vent opening of the polymerization vessel was adjusted to 10 kg / cm ² · G. The temperature during the copolymerization was kept at 70 ° C. The copolymerization time was 40 minutes, and after the elapse of the time, the gas in the polymerization vessel was purged to terminate the copolymerization.

The weight of the obtained copolymer was 325 g, and the MFR was 2.3 g /
After 10 minutes, the amount of decane-soluble components at 23 ° C. contained in the copolymer was 15.3% by weight.

Example 2 [Preparation of solid titanium catalyst component [B]] A high-speed stirrer (manufactured by Tokushu Kika Kogyo) having an internal volume of 2 was sufficiently used.
After replacing with N ₂ , 700 ml of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol, and ₃ g of Emazol 320 (trade name, sorbitan distearate, manufactured by Kao Atlas Co., Ltd.) were added. The mixture was stirred at 800 rpm for 30 minutes. Under high-speed stirring, the solution was transferred to a glass flask 2 (with a stirrer) into which purified kerosene 1 previously cooled to −10 ° C. was charged using a Teflon tube having an inner diameter of 5 mm. The resulting solid was collected by filtration and washed sufficiently with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the temperature of the system was raised to 40 ° C., and 1.33 ml of 2-isopropyl 2-isopentyl 1,3-dimethoxypropane was added, followed by 100 ° C. The temperature rose. 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 again stirred and mixed at 120 ° C. for 2 hours.
Further, 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, 17% by weight of magnesium, 2-isopropyl-2-isopentyl 1,3-dimethoxypropane 1 in terms of atom.
9.7% by weight.

[Preliminary polymerization] Preliminary polymerization was performed on the solid titanium catalyst component [B] as follows.

After charging 200 ml of purified hexane into a 400 ml glass-made reactor purged with nitrogen, 0.66 mmol of triethylaluminum, 0.13 mmol of 2-isopropyl 2-isopentyl 1,3-dimethoxypropane, and the solid titanium catalyst component [B] were added. After charging 0.066 mmol in terms of titanium atoms, propylene gas and ethylene gas were each charged at 3.04 Nl /
And at a rate of 0.34 Nl / h to the liquid phase of the polymerization vessel with mixing for 100 minutes. The temperature was kept at 20 ° C. ± 2 during the prepolymerization. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

As a result of the analysis, about 1 g of the solid titanium catalyst component [B] was added to the prepolymerized solid catalyst component as described above.
92 g of the polymer was preliminarily polymerized. On the other hand, the amount of the polymer eluted in the solvent during the prepolymerization was equivalent to 6.2 g per 1 g of the solid titanium catalyst component [B].

[Production of Copolymer] 0.5 kg of propylene and hydrogen
After adding N liter, the temperature was raised, and at 60 ° C., 1.8 mmol of triethylaluminum, 0.18 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and the prepolymerized solid titanium catalyst component [B] were converted to titanium atom. In conversion
0.006 mmol was added, and the temperature in the polymerization vessel was maintained at 70 ° C.
Homopolymerization of propylene was performed. Forty minutes after the temperature reached 70 ° C., the vent valve was opened, and propylene was purged until the pressure inside the polymerization reactor reached normal pressure.

After purging, copolymerization was subsequently carried out. That is, ethylene is 80 Nl / h, propylene is 120 Nl / h, and hydrogen is
The reactor was fed at a rate of 3.1 Nl / hour. The pressure inside the polymerization vessel
The vent opening of the polymerization vessel was adjusted to 10 kg / cm ² · G. The temperature during the copolymerization was kept at 70 ° C. The copolymerization time was 90 minutes, and after the lapse of the time, the gas in the polymerization vessel was purged to terminate the copolymerization.

The weight of the obtained copolymer is 363 g, and the MFR is 1.3 g / 10
In minutes, the amount of the decane-soluble component at 23 ° C. contained in the copolymer was 43% by weight.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a process for preparing an olefin polymerization catalyst according to the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-153709 (JP, A) JP-A-61-69823 (JP, A) JP-A-54-62288 (JP, A) JP-A-54-62 3183 (JP, A) European publication 362705 (EP, A2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 293/00-297/08 C08F 4/654

Claims (2)

(57) [Claims] [I] Titanium, magnesium, halogen and the following formula: (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ together form a ring other than a benzene ring And a compound having two or more ether bonds represented by the following general formula (II): ] Propylene is polymerized or copolymerized in the presence of an olefin polymerization catalyst containing an organoaluminum compound catalyst component to produce a crystalline polymer, and at least two or more α-olefins are produced in the presence of the crystalline polymer. And producing a low-crystalline copolymer or an amorphous copolymer by copolymerizing the propylene-based block copolymer. 2. The solid titanium catalyst component [Ia], wherein at least one selected from α-olefins having 2 to 20 carbon atoms is prepolymerized. 13. The method for producing a propylene-based block copolymer according to the above item.