JP2945067B2 - Method for producing propylene random copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a propylene-based random copolymer obtained by copolymerizing propylene with ethylene and / or an α-olefin having 4 or more carbon atoms.

TECHNICAL BACKGROUND OF THE INVENTION Polypropylene is widely used as a packaging film and the like because of its excellent physical properties. In addition, in this type of application, since heat sealability at a low temperature is required, usually, an ethylene / propylene random copolymer obtained by copolymerizing ethylene or the like at about 1 to 5% by weight is advantageously used.

Such an ethylene / propylene random copolymer has the advantage of being excellent in transparency and scratch resistance as compared with low-density polyethylene used for the same purpose, but still has poor heat sealability at low temperatures. ing. In order to improve heat sealability, there is a method of increasing the copolymerization amount of ethylene, but in this case, the production ratio of the solvent-soluble copolymer increases, and the yield of the desired copolymer decreases. There is a disadvantage of doing so.

In order to solve such disadvantages, a titanium trichloride-based catalyst is used, and ethylene and α having 4 or more carbon atoms are added to propylene.
-A method of copolymerizing an olefin has been proposed (see JP-A-43-35487, JP-A-51-79195, and JP-A-52-16588).

In such a method, it can be said that the production ratio of the solvent-solubilizing polymer is reduced as compared with the case where the binary copolymerization of ethylene and propylene is performed, but is smaller than the case where the homopolymerization of propylene is performed. Then, there is a problem that the tendency is increased as the copolymerization amount of ethylene and / or α-olefin having 4 or more carbon atoms is increased.

Further, a catalyst formed from a specific solid titanium catalyst component, an organometallic compound catalyst component and an electron donor catalyst component is used for copolymerization of the propylene, ethylene and α-olefin having 4 or more carbon atoms, and Although a method of reducing coalescence has been proposed (Japanese Patent Application Laid-Open No. 54-26891), when the amount of ethylene used is increased to enhance the heat sealing property, a gel-like copolymer is formed and the slurry properties are reduced. As a result, there are problems that it is difficult to continue the polymerization and that a solid polymer cannot be obtained with a sufficiently high yield.

Further, in a conventional catalyst system comprising a solid titanium catalyst component, an organometallic compound catalyst component, and an electron donor catalyst component, even if the solid titanium catalyst component contains an electron donor, the organometallic compound catalyst component is not polymerized during polymerization. In addition, an electron donor catalyst component added together is indispensable, and if this electron donor catalyst component is not used, there is a problem that the soluble polymer of the obtained propylene-based random copolymer increases.

The present researchers conducted research to solve these problems and found that titanium, magnesium, halogen, and a compound having two or more ether bonds existing through multiple atoms A catalyst comprising a solid titanium catalyst component [Ia] containing: and an organometallic compound catalyst component [II] containing a Group I to Group III metal of the periodic table: and titanium, magnesium, halogen, A solid titanium catalyst component [I] including an electron donor (a) (wherein the electron donor (a) does not include a compound having two or more ether bonds existing through a plurality of atoms), A catalyst comprising an organometallic compound catalyst component [II] containing a metal of Groups I to III of the periodic table and a compound [III] having two or more ether bonds existing through a plurality of atoms: Look to achieve The present invention has been completed.

Object of the Invention The present invention has been made in view of such a situation, and propylene capable of producing a propylene-based random copolymer having a high heat sheet property, transparency, high blocking resistance, and a low solvent-soluble content. It is an object of the present invention to provide a method for producing a random copolymer.

SUMMARY OF THE INVENTION The first method for producing a propylene-based random 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): Selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing an organometallic compound catalyst component containing a Group I to Group III metal of the periodic table. Is characterized in that at least one kind of propylene is copolymerized with propylene.

According to the method for producing a propylene-based random copolymer according to the present invention, the solid titanium catalyst component [Ia] containing the compound having two or more ether bonds as described above as the electron donor and the organic metal Compound catalyst component [I
Since the catalyst formed from [I] is used, it is possible to produce a propylene-based random copolymer having high heat sealability, transparency and blocking resistance, and having a low hydrocarbon-soluble content, and In the case of, the electron donor (in the present specification, unless otherwise specified, the electron donor,
Without using the above compound having two or more ether bonds), a polymer having a low hydrocarbon-soluble content can be produced.

The first catalyst for olefin polymerization and the first olefin polymerization method according to the present invention may further comprise a compound having two or more ether bonds together with the organometallic compound catalyst component [II] or a specific compound, in addition to the above two components. By using a catalyst containing an electron donor, a polymer having a smaller amount of a solvent-soluble polymer can be obtained.

In the second method for producing a propylene-based random copolymer according to the present invention, [Ib] titanium, magnesium, halogen, an electron donor (a) (where the electron donor (a) is a Not containing a compound having two or more ether bonds present through atoms), and [II] an organometallic compound catalyst component containing a Group I to Group III metal of the periodic table, And [III] (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 the main chain may contain atoms other than carbon.) In the presence of an olefin polymerization catalyst containing a compound having two or more ether bonds represented by And propylene with at least one selected from the group consisting of α-olefins having 4 to 20 carbon atoms.

According to the second method for producing a propylene-based random copolymer according to the present invention, the solid titanium catalyst component [Ib] is used.
In addition, when the organometallic compound catalyst component [II] and the compound having two or more ether bonds are used, heat-sealability, transparency and blocking resistance are high, and propylene-based random copolymers having a low hydrocarbon-soluble content are used. Polymers can be produced.

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

In the first propylene-based random copolymer according to the present invention,
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 (Ia): And an organometallic compound catalyst component containing a Group I to Group III metal of the periodic table [I
I] (hereinafter sometimes referred to as the first catalyst)
Is used.

In the second method for producing a propylene-based random copolymer according to the present invention, titanium, magnesium, halogen, an electron donor (a) (where the electron donor (a) is
Excluding a compound having two or more ether bonds which are present via a plurality of atoms), and an organic metal containing a metal belonging to Group I to Group III of the Periodic Table. Compound catalyst component [II] 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 the main chain may contain an atom other than carbon.) A catalyst containing a compound [III] having two or more ether bonds represented by the following formula (hereinafter referred to as a second catalyst): May be written).

The solid titanium catalyst component [Ia] or [Ib] constituting such a first or second catalyst comprises a magnesium compound and a titanium compound, and a compound having two or more ether bonds or an electron donor. It is prepared by contacting these compounds with (a).

For the preparation of the solid titanium catalyst components [Ia] and [Ib] constituting the first and second catalysts used in the present invention, a magnesium compound can be used. And magnesium compounds having no reducing ability.

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. It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

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 components [Ia] and [Ib] constituting the first and second catalysts used in the present invention includes, for example, a general formula: Ti (OR _{GX4 -g} (R is a hydrocarbon group, X is a halogen atom,
.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 first catalyst used in the present invention, a compound having two or more ether bonds existing through a plurality of atoms in addition to the above-mentioned compound is used. Can be

The solid titanium catalyst component [Ib] contained in the second catalyst used in the present invention uses an electron donor (a) other than the compound having two or more ether bonds.

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, tolyl (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 [I
a] is an organic or inorganic material containing silicon, phosphorus, aluminum or the like used as a carrier compound and a reaction aid in addition to the magnesium compound, the titanium compound in a liquid state, and the compound having two or more ether bonds. It may be prepared by using a compound, 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 copolymer 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].

The solid titanium catalyst component [Ib] contained in the second catalyst used in the present invention is prepared using an electron donor (a) other than the compound having two or more ether bonds. Examples of such an electron donor (a) include organic acid esters, organic acid halides, organic acid anhydrides, ethers,
Ketones, aldehydes, tertiary amines, phosphites,
Examples thereof include a phosphoric ester, a phosphoric amide, a carboxylic amide, and a nitrile. Specific examples thereof include ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate,
Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone Organic acid esters having 2 to 18 carbon atoms such as, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; Chirueteru, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, ethers having 2 to 20 carbon atoms such as diphenylether; acetate N, N
Acid amides such as dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, trimethylamine, triethylamine, tributylamine,
Tertiary amines such as tribenzylamine and tetramethylethylenediamine; acetonitrile, benzonitrile,
Examples thereof include nitriles such as trinitrile, 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:

As such polycarboxylic acid esters, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate , Diethyl butylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethyldibutylmalonate, monooctylmaleate, dioctylmaleate, dibutylmaleate, dibutylbutylmaleate, diethylbutylbutylmaleate, diisopropylβ-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, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, Aromatic polycarboxylic esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic esters such as 3,4-furandicarboxylic acid. Preferred examples can be given.

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 carboxylic acid ester, particularly a polyvalent carboxylic acid ester,
Particularly, phthalic esters are preferably used.

These electron donors (a) need not necessarily be used as starting materials, and may be used as solid titanium catalyst components [I
b] It can also be produced during the preparation process. In addition, the solid titanium catalyst component [I b] includes, in addition to the magnesium compound, the liquid titanium compound and the electron donor (a), silicon, phosphorus, and aluminum used as a carrier compound and a reaction aid. And organic and inorganic compounds containing the same, and may be prepared by contacting them.

The solid titanium catalyst component [Ia] constituting the first 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, It is prepared by contacting a carrier compound, an electron donor (a) and the like, if necessary.

A solid titanium catalyst component using these compounds [I
Although a is not particularly limited, this method will be briefly described below with reference to several production methods.

(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 organic aluminum compound and a halogen-containing silicon compound.

(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 reducing property is reacted with an organoaluminum compound to deposit a solid magnesium-aluminum complex, and then the compound having two or more ether bonds and a titanium compound 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.

Further, the solid titanium catalyst component [Ib] constituting the catalyst used in the second method of the present invention comprises an electron donor (a)
, An organomagnesium compound, a titanium compound in a liquid state, and, if necessary, a carrier compound and an electron donor (a).
And the like.

The method for preparing such a solid titanium catalyst component [Ib] is not particularly limited, but the method will be briefly described below with several examples.

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

(2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor (a) 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, an electron donor (a), and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, a complex compound composed of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound.

(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 and a halogen-containing compound with an electron donor (a) and a titanium compound.

(8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor (a), 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, a titanium compound, an electron donor (a), and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound.

(10) A method in which a liquid magnesium compound having no reducibility is reacted with an organoaluminum compound to deposit a solid magnesium-aluminum composite, and then the electron donor (a) is reacted with a titanium compound. .

By such a method, the solid titanium catalyst component [I
The amount of the magnesium compound, the titanium compound in the liquid state, and the electron donor (a) used in the production of the compound b) varies depending on the type, contact conditions, contact order, and the like. Electron donor (a)
Is used in an amount of 0.01 mol to 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
b] contains titanium, magnesium and halogen, and an ether compound having two ether bonds existing through at least two carbon atoms.

In this solid titanium catalyst component [Ib], the halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90.
And the electron donor (a) / titanium (molar ratio) is 0.01 to
100, preferably 0.2 to 10, and the magnesium / titanium (atomic ratio) is desirably 2 to 100, preferably 4 to 50.

The catalyst used in the first method according to the present invention includes a solid titanium catalyst component [Ia] as described above and an organic metal containing a metal selected from Groups I to III of the periodic table. It contains a compound catalyst component [II].

As such organometallic compound catalyst component [II],
For example, an organic aluminum compound, a complex alkylated product of a Group I metal and aluminum, an organic metal compound of a Group II metal, and the like can be used.

As the organoaluminum compound, e.g., R ^a _n AlX
_3-n (wherein, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, 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,
Trialkyl aluminums such as triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and tri 2-ethylhexyl aluminum.

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 diisobucil 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 dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum 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 above-mentioned organoaluminum compound, R ^a ₃ Al, R
_{^{a n Al (OR b) 3}} -n, can be mentioned organoaluminum compounds represented by _{^{R a n Al (OAlR d 2}} ) 3-n Preferred examples.

The complex alkylated product of a Group I metal and aluminum is represented by the general formula M ¹ AlR ^j ₄ (where M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms). The compounds represented by the formulas can be exemplified. Specifically, LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like.

Group II metal organometallic compounds include compounds of the general formula R ₁ R ₂ M
₂ (provided that R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or halogen, which may be the same or different from each other, except that all are halogen. M ₂ is Mg, Zn,
Cd) can be exemplified, specifically,
Examples thereof include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, and butylmagnesium chloride.

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, together with such an organometallic compound catalyst component [II],
If necessary, the compound having two or more ether bonds and / or the electron donor (b) may be used. Examples of the electron donor (b) include the electron donors (a) and (b) described above. An organic silicon compound represented by the following general formula can be used, and 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, 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- Dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tri Cyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylethylmethoxy Sisilane, 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.

The catalyst used in the second method according to the present invention comprises a solid titanium catalyst component [Ib] and an organometallic compound catalyst component [II] as described above, and two or more ethers present through a plurality of atoms. An olefin polymerization catalyst containing a compound [III] having a bond is used.

As such organometallic compound catalyst component [II],
For example, a catalyst component composed of the same organometallic compound as used in the preparation of the first olefin polymerization catalyst according to the present invention is used.

As the compound [III] having two or more ether bonds as described above, the compound having two or more ether bonds similar to that used for preparing the first solid titanium catalyst component according to the present invention is used. Is used.

Further, the olefin polymerization catalyst used in the second method according to the present invention may contain, in addition to the compound having two or more ether bonds, an electron donor. For example, the electron donor (b) used for preparing the catalyst used in the first method according to the present invention.
Can be mentioned.

In the method for producing a propylene-based random copolymer according to the present invention, ethylene and an α-olefin having 4 or more carbon atoms are polymerized with propylene using the first catalyst or the second catalyst as described above. .

In the first and second methods for producing a propylene random copolymer according to the present invention, as the α-olefin having 4 or more carbon atoms, 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, 1-octene, 1-
Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

In the first and second polymerization methods according to the present invention, these α-olefins can be used alone or in combination. Further, aromatic vinyl compounds such as styrene and allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5 Cyclic olefins such as, 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 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-decadiene,
Compounds having polyunsaturation such as conjugated dienes and non-conjugated dienes such as dienes such as 6-methyl-1,6-undecadiene, isoprene and butadiene can also be used as the polymerization raw material.

In the first and second methods according to the present invention, it is preferable that the first catalyst and the second catalyst are preliminarily polymerized in advance, and the prepolymerization is performed in an amount of 0.1 to 1000 g per 1 g of the olefin polymerization catalyst.
It is preferably carried out by prepolymerizing the α-olefin in an amount of 0.3 to 500 g, particularly preferably 1 to 200 g.

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 first and second polymerization methods according to the present invention, the concentration of the solid titanium catalyst component [Ia] or [Ib] in the prepolymerization is usually about 0.001 to 1 in terms of titanium atoms per liter of the liquid medium. Desirably, it is in the range of 200 mmol, preferably about 0.01-50 mmol, particularly preferably 0.1-20 mmol.

The amount of the organometallic compound catalyst component [II] may be an amount such that a polymer of 0.1 to 1000 g, preferably 0.3 to 500 g per 1 g of the solid titanium catalyst component [Ia] or [Ib] is produced, The amount is usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component [Ia] or [Ib]. desirable.

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

In the second method according to the present invention, these compounds are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component [Ib]. Used in an amount of 1010 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 so that about 0.1 to 1000 g, preferably about 0.3 to 500 g, and particularly preferably 1 to 200 g of polymer is produced per 1 g of the solid titanium catalyst component [Ia] or [Ib]. It is desirable to carry out.

In the present invention, the 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.

When the main polymerization takes a reaction form of solution polymerization, the above-mentioned inert hydrocarbon or a liquid olefin under the reaction conditions can be used as a reaction solvent.

In the polymerization method of the present invention, the solid titanium catalyst component [Ia] or [Ib] is generally used in an amount of about 0.001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol, in terms of Ti atom per liter of polymerization volume. Used in millimolar amounts. The organometallic compound catalyst component [II] is such that the metal atom is usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. Used in appropriate amounts.

Further, in the second polymerization method according to the present invention, the compound having two or more ether bonds is usually used in an amount of about 0.001 mol to 10 mol per 1 mol of the metal atom of the component [II].
Preferably, it is used in an amount such that it becomes 0.01 mol to 2 mol.

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

In the present invention, the polymerization concentration of the olefin is usually about
At 20-200 ° C, preferably about 50-150 ° C, the pressure is usually
The pressure is set at normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . In the polymerization method of the present invention, the polymerization is a batch type,
It can be carried out by any of a semi-continuous method and a continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In the present invention, the first and second polymerization catalysts are:
In addition to the above components, other components useful for olefin polymerization can be contained.

The propylene-based random copolymer thus obtained is heat-sealable, heat-sealable, transparent,
Excellent blocking properties and low hydrocarbon solubles,
It is suitable for films, especially packaging films such as shrink films, for example, food packaging films. Of course, it is also suitable for applications such as hollow bottles.

Effect of the Invention The first method for producing a propylene-based random copolymer according to the present invention comprises: titanium, magnesium, a halogen,
A solid titanium catalyst component [Ia] containing a compound having two or more ether bonds existing through a plurality of atoms, and an organometallic compound catalyst component containing a Group I to Group III metal of the periodic table [ II], and propylene is copolymerized with at least one selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst.

According to the method for producing a propylene-based random copolymer according to the present invention, the solid titanium catalyst component [Ia] containing the compound having two or more ether bonds as described above as the electron donor and the organic metal Compound catalyst component [I
When the catalyst formed from I] is used, a propylene-based random copolymer having high heat sealability, transparency, and high blocking resistance, and having a low hydrocarbon soluble content can be produced, and at the time of polymerization. Further, even without using an electron donor (in the present specification, unless otherwise specified, the electron donor does not include the compound having two or more ether bonds), a polymer having a low hydrocarbon-soluble content can be used. Coalescence can be manufactured.

The first catalyst for olefin polymerization and the first olefin polymerization method according to the present invention may further comprise a compound having two or more ether bonds together with the organometallic compound catalyst component [II] or a specific compound, in addition to the two components. By using a catalyst containing an electron donor, a polymer having a lower soluble polymer content can be obtained.

In the second method for producing a propylene-based random copolymer according to the present invention, titanium, magnesium, halogen, an electron donor (a) (where the electron donor (a) is
A solid titanium catalyst component [Ia], the organometallic compound catalyst component [II], and the two or more ethers In the presence of an olefin polymerization catalyst containing a compound [III] having a bond, propylene is copolymerized with at least one selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms. I have.

According to the second method for producing a propylene-based random copolymer according to the present invention, the solid titanium catalyst component [Ib] is used.
In addition, when the organometallic compound catalyst component [II] and the compound having two or more ether bonds are used, heat-sealability, transparency and blocking resistance are high, and propylene-based random copolymers having a low hydrocarbon-soluble content are used. Polymers can be produced.

Hereinafter, the present invention will be described 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 and reacted at 130 ° C. for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added thereto, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After the thus obtained homogeneous solution was cooled to room temperature, 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the charging, the temperature of the mixture was raised to 10 ° C over 4 hours, and
Was reached, 4.79 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP) was added, and the mixture was kept under stirring at the same temperature for 2 hours.
After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [A] prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [A] thus obtained was 2.3% by weight of titanium, 63% by weight of chlorine, 22% by weight of magnesium and 9.8% by weight of IPAMP.

[Preliminary polymerization of solid titanium catalyst component [A]] Purified hexane (100 ml), triethylaluminum (10 mmol), 2-isopropyl-2-isopentyl-1,3 in a 400 ml four-necked glass reactor equipped with a stirrer under a nitrogen atmosphere. After adding 2 mmol of dimethoxypropane and 1.0 mmol of the solid titanium catalyst component [A] in terms of Ti atom, propylene was supplied to this reactor at a temperature of 20 ° C. at a rate of 3.3 N / hour for 1 hour. At the end of the supply of propylene, the inside of the reactor was replaced with nitrogen, and a washing operation was performed twice, comprising removing the supernatant and adding purified hexane. did.

[Polymerization] An autoclave having an internal volume of 2 was charged with 750 mL of purified hexane, and 0.75 mmol of triethylaluminum, 2-isopropyl-2-amine was added in a propylene atmosphere at 25 ° C.
0.075 mmol of isopentyl-1,3-dimethoxypropane and 0.015 mmol of the above prepolymerized product of the catalyst component [A] were added in terms of titanium atom. Then, after introducing 100 ml of hydrogen, the temperature was raised to 60 ° C., and a mixed gas of propylene-ethylene containing 7.3 mol% of ethylene was added to 1.5 ml.
The mixture was fed over a period of time to perform ethylene-propylene copolymerization. The pressure during the polymerization was kept at ² kg / cm ² G.

After the completion of the polymerization, the slurry containing the produced copolymer was charged into methanol to precipitate all the copolymer. After separation into a copolymer and a liquid phase by filtration, the copolymer is 80 ° C. under reduced pressure,
Drying was performed for 10 hours.

 Table 1 shows the physical properties of the obtained copolymer.

Example 2 The procedure of Example 1 was repeated, except that 0.075 mmol of 2-isopropyl-2-inpentyl-1,3-dimethoxypropane was not added during the polymerization.

 Table 1 shows the physical properties of the obtained copolymer.

Comparative Example 1 [Preparation of solid titanium catalyst component [B]] In preparation of solid titanium catalyst component [B] in Example 1, 2-isopropyl-2-isopentyl-1,3-
A Ti catalyst component [A] was prepared in the same manner as in Example 1, except that dimethoxypropane 4.79 ml was replaced with diisobutyl phthalate 5.22 ml.

[Preliminary Polymerization of Solid Titanium Catalyst Component [B]] In the prepolymerization of the solid titanium catalyst component [B] in Example 1, 2-isopropyl-2-isopentyl-1,
The procedure was performed in the same manner as in Example 1 except that 3-dimethoxypropane was replaced with cyclohexylmethyldimethoxysilane.

[Polymerization] In Example 1, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was changed to cyclohexylmethyldimethoxysilane, and ethylene in a propylene-ethylene mixed gas was changed from 7.3 mol% to 8.6 mol%. The procedure was performed in the same manner as in Example 1 except for the above.

 Table 1 shows the physical properties of the obtained copolymer.

[Brief description of the drawings]

FIG. 1 and FIG. 2 are explanatory diagrams of the preparation process of the olefin polymerization catalyst according to the present invention.

Continuation of front page (56) References JP-A-58-45209 (JP, A) JP-A-59-215304 (JP, A) JP-A-57-141410 (JP, A) JP-A-54-62288 (JP, A) , A) JP-A-1-146305 (JP, A) European Publication 362705 (EP, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (4)

(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): Selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing an organometallic compound catalyst component containing a Group I to Group III metal of the periodic table. A method for producing a propylene-based random copolymer, characterized by copolymerizing at least one kind of propylene with propylene. 2. The solid titanium catalyst component [Ia], wherein at least one selected from α-olefins having 2 to 20 carbon atoms is prepolymerized. The method for producing a propylene-based random copolymer described in the above section. [Ib] titanium, magnesium, halogen, an electron donor (a) (provided that the electron donor (a)
Does not include a compound having two or more ether bonds which are present through a plurality of atoms), and [II] an organic metal containing a Group I to Group III metal of the periodic table A compound catalyst component, and [III] 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 May be formed in the main chain, and an atom other than carbon may be contained in the main chain.) In the presence of an olefin polymerization catalyst containing a compound having two or more ether bonds represented by A method for producing a propylene-based random copolymer, characterized by copolymerizing at least one selected from the group consisting of α-olefins having 4 to 20 carbon atoms with propylene. 4. The solid titanium catalyst component [Ib], wherein at least one selected from α-olefins having 2 to 20 carbon atoms is prepolymerized. The method for producing a propylene-based random copolymer described in the above section.