JPH059209A - Catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the title catalyst which can give an olefin polymer having high stereoregularity and a broad molecular weight distribution in high yields by mixing a solid catalyst comprising Ti, Mg and halogen with an organo- aluminum compound and a specified acetal compound. CONSTITUTION:A catalyst for the polymerization of an olefin comprising a solid catalyst component comprising titanium, magnesium and a halogen, an organoaluminum compound, and an acetal compound of the formula (wherein R<1> is a hydrocarbon group; R<2> to R<5> are hydrocarbon groups, halohydrocarbon groups or heteroatoms, and all or part of them may combine to form rings). This catalyst can be prepared, for example, by copulverizing a magnesium halide with a titanium halide and the electron-donating compound or by bringing them into contact with each other by dispersion or dissolution in a solvent. This catalyst can give economically an olefin polymer having very high rigidity.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst for producing a polyolefin having an extremely wide molecular weight distribution. More specifically, it relates to a supported Ziegler-type catalyst using an organosilicon compound having a special structure as an external donor, and polymerization of olefins.

[0002]

2. Description of the Prior Art The first factor that determines the moldability and rigidity of polyolefin polymers is the molecular weight distribution. Usually, as a means for broadening the molecular weight distribution, a method of controlling the molecular weight by the concentration of a molecular weight regulator (for example, hydrogen) or a so-called resin blend outside the polymerization system of a polymer having a high molecular weight and a polymer having a low molecular weight is used. There have been proposed methods for improving the physical properties of ethylene polymers, in particular, for ethylene polymers.

With respect to propylene-based polymers, it is possible to obtain polymers having a wide molecular weight produced by these methods, but these polymers do not have sufficiently satisfactory physical properties. It is considered that the reason for this is that the composition obtained by resin blending or the like does not have a sufficient mixed state of micro molecular chains. Conventionally, a propylene-based polymer obtained by using a titanium trichloride-type Ziegler-type catalyst has a wide molecular weight distribution (the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 7 to 12) and has high rigidity. It is known that a propylene-based polymer having the same can be obtained. However, since the titanium trichloride-type Ziegler-type catalyst has a low polymerization activity, it has a drawback that a large amount of catalyst components (especially halogen) remain in the obtained polymer and promote corrosion of the molding machine during polymer processing. ing. Therefore, in order to suppress the corrosive effect as much as possible, the step of removing the catalyst was indispensable.

On the other hand, in recent years, an electron donor (external donor) has been used as a co-catalyst for a supported Ziegler-type catalyst (see, for example, Japanese Patent Laid-Open Publication No.
4-94590, 55-36203, 57-633.
12, 62-11705), a catalyst satisfying high activity and high stereoregularity to the extent that the influence of halogen can be ignored even if the catalyst removal step is omitted has been developed. The breadth of the molecular weight distribution of the polymer obtained by the above is at most 4 to 6 in the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn),
The value of its rigidity was also insufficient. Therefore, it is required to develop a catalyst capable of producing a polymer having a wide molecular weight distribution while maintaining the properties of high activity and high stereoregularity.

Recently, two types of electron donors (external donors)
There is a proposal to broaden the molecular weight distribution by mixing (JP-A-2-70708, JP-A-3-7703). In such a method, at least one of them is added with an electron donor (external donor) that reduces stereoregularity, and thus sufficient stereoregularity cannot be obtained. Moreover, if the mixing ratio is not strictly controlled, the physical properties of the polymer produced during continuous use will be different. Further, a method using a silicon compound having a t-butoxy group has been proposed (JP-A-3-11900).
4). This method does not have a sufficient spread of the molecular weight distribution and the rigidity is insufficient.

[0006]

The use of an external donor as a co-catalyst for a supported Ziegler-type catalyst to make the molecular weight distribution of the polymer as wide as that of the polymer obtained by the titanium trichloride-type Ziegler-type catalyst is not possible. It was extremely difficult, and therefore the rigidity of the obtained polymer was unavoidable. It is an object of the present invention to solve this.

[0007]

Based on the above, the inventors of the present invention have earnestly studied the co-catalyst used for the supported Ziegler type catalyst, particularly the external donor, in order to obtain the olefin polymer which solves these problems. As a result, the catalyst used in the method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst is a solid catalyst component containing component (A) titanium, magnesium, and halogen as essential components. Component (B) organoaluminum compound, and component (C) general formula

[Chemical 2] (In the formula, R ¹ is a hydrocarbon group, R ^{2 to} R ⁵ are a hydrocarbon group or a halogenated hydrocarbon group, or a hetero atom. R ^{2 to} R ⁵
May be all or partly the same or all different. Further, R ^{2 to} R ⁵ may all or partially form a ring. The above problems can be solved by an olefin polymerization catalyst comprising an acetal compound represented by (4).

This effect can be obtained by using an acetal compound having a specific structure as a cocatalyst, especially as an external donor. It is known from the conventional knowledge that such an acetal compound has such an effect. That was unpredictable.

The present invention will be specifically described below. Examples of the magnesium compound used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxy magnesium such as ethoxy magnesium and isopropoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. And alkyl magnesium such as butylethyl magnesium can be exemplified. Further, it may be a mixture of two or more kinds of these compounds. Preferably, magnesium halide is used, or magnesium halide is formed during catalyst formation. More preferably, the halogen is chlorine. Examples of the titanium compound used in the present invention include titanium halides such as titanium tetrachloride and titanium trichloride; titanium alkoxides such as titanium butoxide and titanium ethoxide; and alkoxytitanium halides such as phenoxytitanium chloride. .. Also, a mixture of two or more of these compounds may be used. A tetravalent titanium compound containing halogen is preferable, and titanium tetrachloride is particularly preferable.

The halogen-containing compound used in the present invention is a halogen containing fluorine, chlorine, bromine, or iodine,
Chlorine is preferred, and the specific compounds actually exemplified are titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, phosphorus trichloride, phosphorus pentachloride. Phosphorus halides such as are typical examples, but depending on the preparation method, halogenated hydrocarbons, halogen molecules, hydrohalic acids (eg, HCl,
HBr, Hl, etc.) may also be used. These may be common to the titanium compound and the magnesium compound.

In preparing the solid catalyst component (A) used in the present invention, various electron donors (internal donors) may be added, or are preferable. As an electron donor,
Examples thereof include oxygen-containing compounds and nitrogen-containing compounds. More specifically, (a) methanol, ethanol, propanol, butanol, heptanol, hexanol, octanol, dodecanol, octadecyl alcohol, 2
-Ethyl-hexyl alcohol, benzyl alcohol,
It may have an alkyl group having 1 to 20 carbon atoms such as cumyl alcohol, diphenylmethanol and triphenylmethanol, and (b) phenol, cresol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol. C6 to C25 phenols, (C) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone and other C3 to C15 ketones, (d) acetaldehyde, propionaldehyde, tolualdehyde, naphthaldehyde and other carbons Aldehydes of the numbers 2 to 15.

(E) Methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl propionate, methyl n-butyrate, methyl isobutyrate, ethyl isobutyrate. , Isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl phenylacetate, methyl phenylbutyrate, propyl phenylacetate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoate Cyclohexyl acid, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
Organic acids having 2 to 20 carbon atoms such as diethyl phthalate, diisobutyl phthalate, diheptyl phthalate, dineopentyl phthalate, γ-butyrolactone, γ-parerolactone, coumarin, phthalide, diethyl carbonate, trimethyl orthoformate and ethyl orthoformate. Esters.

(F) Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, phenyl methoxyacetate,
Methyl ethoxyacetate, ethyl ethoxyacetate, butyl ethoxyacetate, phenyl ethoxyacetate, n-propoxyethyl acetate, i-propoxy-ethyl acetate, methyl n-butoxyacetate, ethyl i-butoxyacetate, n-hexyloxyacetate, sec- Hexyl oxyacetate octyl, 2
-Methyl methylcyclohexyloxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate,
N-octyl 3-ethoxypropionate, dodecyl 3-ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, ethyl 3- (i-propoxy) propionate, butyl 3- (i-propoxy) propionate, 3- ( n-propoxy) allyl propionate, 3-
Cyclohexyl (n-butoxy) propionate, ethyl 3-neopentyloxypropionate, butyl 3- (n-octyloxy) propionate, octyl 3- (2,6-dimethyldecyloxy) propionate, ethyl 4-ethoxyacetate, Cyclohexyl 4-ethoxybutyrate, 5-
(N-Propoxy) octyl valerate, ethyl 12-ethoxylaurate, ethyl 3- (1-indenoxy) propionate, methyl 3-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, 2- Ethyl methoxypropionate, n-butyl 2- (i-propoxy) butyrate, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate, 2
-Ethoxy, 2-phenyl butyl acetate, allyl 3-neopentyloxybutyrate, methyl 3-ethoxy, 3- (o-methylphenyl) propionate, 3-ethoxy, 2-
Ethyl (o-methylphenyl) propionate, 4-ethoxy, 2-methyl, ethyl 1-naphthylnonanoate, 2-
Methoxycyclopentanecarboxylic acid ethyl ester, 2
-Ethoxycyclohexanecarboxylic acid butyl ester,
3- (Ethoxymethyl) tetralin-2-acetic acid isopropyl ester, 8-butoxy, decalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, 2- (phenoxy) acetic acid methyl ester, 3- ( p-cresoxy) ethyl propionate, 4-
Methyl (2-naphthoxy) butyrate, Butyl 5-carbacryloxyvalerate, Methyl 2-phenoxypropionate, 3-
Ethyl (4-methylphenoxy) -2-phenylpropionate, 2-phenoxy, cyclohexanecarboxylic acid ethyl ester, thiophene-3-oxyacetate ethyl, 2
Alkoxy esters such as ethyl-(2-picolinoxymethyl) -cyclohexanecarboxylate and ethyl 3-furfuryloxypropionate.

(G) Methyl acetyl acetate, ethyl acetyl acetate, butyl acetyl acetate, methyl propionyl acetate, phenyl acetyl acetate, ethyl propionyl acetate,
Ethyl propionyl acetate, Phenyl propionyl acetate,
Butyl propionyl acetate, ethyl butyryl acetate, ethyl i-butanoyl acetate, ethyl pentanoyl acetate, methyl 3-acetylpropionate, ethyl 3-acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, 3-propionylpropionate Butyl acid, n-octyl 3-propionylpropionate, dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate, 3-
Ethyl (i-propionyl) propionate, 3- (i-
Butyl propionyl) propionate, allyl 3- (i-propionyl) propionate, cyclohexyl 3- (i-propionyl) propionate, ethyl 3-neopentanoylpropionate, butyl 3-n-laurylpropionate, 3- (2,2. 6-dimethylhexanoyl) methyl propionate, ethyl 4-propionyl butyrate, cyclohexyl 4-propionyl butyrate, octyl 5-butyryl valerate, ethyl 12-butyryl laurate, methyl 3-acetyl acrylate, methyl 2-acetyl acrylate,

Ethyl 3-benzoylpropionate, 3-
Methyl benzoylpropionate, ethyl 3-methylbenzoylpropionate, butyl 3-toluylbutyrate, ethyl o-benzoylbenzoate, ethyl m-benzoylbenzoate, ethyl p-benzoylbenzoate, butyl o-toluylbenzoate, o- Ethyl toluyl benzoate, ethyl m-toluyl benzoate, ethyl p-toluyl benzoate, o-
Ethyl (2,4,6 trimethylbenzoyl) benzoate,
Ethyl m- (2,4,6 trimethylbenzoyl) benzoate, ethyl p- (2,4,6 trimethylbenzoyl) benzoate, ethyl o-ethylbenzoylbenzoate, ethyl o-acetylbenzoate, o-propionylbenzoic acid Ketoesters such as ethyl, ethyl o-laurylbenzoate, ethyl o-cyclohexanoylbenzoate and ethyl o-dodecylbenzoate.

(H) Inorganic acid esters such as methyl borate, butyl titanate, butyl phosphate, diethyl phosphite and di (2-phenylphenyl) phosphorochloridate,
(I) ethers having 2 to 25 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran anisole, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, 2.2-dimethoxypropane, ) 2 to 2 carbon atoms such as acetic acid amide, benzoic acid amide, toluic acid amide
Acid amides of 0, (l) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthalic acid and other acid halides having 2 to 20 carbon atoms, (wo) acetic anhydride, phthalic anhydride Such as C2-C20 acid anhydrides, (wa) mono-methylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, etc. Amines, (f) acetonitrile, benzonitrile, trinitrile and other nitriles having 2 to 20 carbon atoms, (yo) ethylthioalcohol, butylthioalcohol, phenylthiol and other thiols having 2 to 20 carbon atoms, (t) Diethyl thioether, diphe Number 4 to 25 thioethers carbon, such as thioether, (Les) dimethyl sulfate, sulfates of from 20 C 2 -C such as diethyl sulfate,
(So) Phenylmethyl sulfone, diphenyl sulfone and other sulfonic acids having 2 to 20 carbon atoms, (tsu) phenyltrimethoxysilane, phenyltriethoxysilane,
Phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylmonoethoxysilane,
C2 to C24 such as triphenylmonomethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethyldianol, triphenylsilanol, diphenylsilanediol, lower alkyl silicate (especially ethyl silicate) Examples thereof include silicon-containing compounds. Two or more kinds of these electron donating compounds can be used. Among these, preferable are organic acid esters, alkoxyesters, ketoesters and the like.

The catalyst preparation method used in the present invention is not particularly limited, but the following examples can be mentioned. A method of obtaining a catalyst component by bringing magnesium halide, titanium halide and the above-mentioned electron donating compound into contact with each other by co-grinding or by dispersing or dissolving in a solvent. A method of preparing a complex of magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron donating compound), and contacting this with a complex of titanium halide or it and the above electron donating compound to obtain a catalyst component. .. A complex of magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron-donating compound) is prepared, and the above-mentioned electron-donating compound and titanium compound are successively contacted (the order may be changed). To obtain a catalyst component. A method for obtaining a catalyst component by contacting a magnesium compound (or a titanium compound further) with the electron-donating compound, and at the same time or at a subsequent stage contact with a titanium compound and / or a halogenation treatment to obtain a catalyst component (titanium at any stage). Including the use of compounds). The above-mentioned catalyst component may be produced by a method of supporting or impregnating it on a substance generally used as a catalyst carrier, for example, silica or alumina.

The quantitative relationship of each component in the component (A) is as follows:
It is optional as long as the effects of the present invention can be recognized, but the following ranges are generally preferred. The content of magnesium in the component (A) is 0.1 to 1 in terms of molar ratio to titanium.
It may be in the range of 000, preferably in the range of 2 to 200, and the content of halogen is 1 to 10 in a molar ratio with respect to titanium.
It may be in the range of 0, and when the electron-donating compound is used, the content thereof is in the range of 10 or less in terms of molar ratio to titanium,
It may be preferably in the range of 0.1 to 5.

The organoaluminum compound in the present invention is represented by the following general formulas (2) to (4). AlR ¹⁰ R ¹¹ R ¹²・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (2) R ¹³ R ¹⁴ Al-O-AlR ¹⁵ R ¹⁶・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (3)

[0020]

[Chemical 3]

[0021]

[Chemical 4]

In the formulas (2), (3) and (4), R ¹⁰ , R ¹¹ and R ¹² may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms, and R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms. R ¹⁷ is a hydrocarbon group having at most 12 carbon atoms, and n is an integer of 1 or more.

Typical of the organoaluminum compounds represented by the formula (2) are trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, diethylaluminum hydride and Alkyl aluminum hydride such as diisobutyl aluminum hydride and diethyl aluminum chloride,
Alkyl aluminum halides such as diethyl aluminum bromide and ethyl aluminum sesquichloride and ethyl aluminum sesquibromide. Further, among the organoaluminum compounds represented by the formula (3), typical ones include alkyl dialumoxane such as tetraethyl dialumoxane and tetrabutyl dialumoxane. Also, (4)
The formula represents an aluminoxane, which is a polymer of an aluminum compound. R ¹⁷ includes methyl, ethyl, propyl, butyl, benzyl and the like, preferably methyl and ethyl groups. n is preferably 1-10. Of these organoaluminum compounds, trialkylaluminum,
Alkyl aluminum hydrides and alkyl alumoxanes are preferred as they give particularly favorable results.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally 10 ^-4 mmol / l or more, preferably 10 ^-2 mmol / l or more. The molar ratio of titanium atom in the solid catalyst component is generally 0.5 or more, preferably 2 or more, and more preferably 10 or more. If the amount of organoaluminum used is too small, the polymerization activity will be significantly reduced. It should be noted that when the use of organoaluminum in the polymerization system is 20 mmol / l or more and the ratio with respect to titanium atoms is 1000 or more in molar ratio, it is not found that the catalyst performance is further improved even if these values are further increased. I can't.

The component (C) of the catalyst used in the present invention is
It is an acetal compound having a saturated or unsaturated 5-membered ring structure represented by the general formula (1).

[Chemical 5] In the formula, R ¹ is a hydrocarbon group, preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ¹ are chain-like ^one another. It may be bound by an aliphatic group. Specific examples thereof include methyl, ethyl, propyl group, ethylene chain and the like. Further, R ¹ does not have to be all the same, and they may be the same as or partially different from each other.

R ^{2 to} R ⁵ are a hydrocarbon group or a halogenated hydrocarbon group, a hydrogen atom or a hetero atom, and R ^{2 to} R ⁵ may be wholly or partially the same or all different. Further, R ^{2 to} R ⁵ may form a ring wholly or partially. Preferably, a hydrocarbon group having 1 to 20 carbon atoms, 1 to
20 halogenated hydrocarbon group, hydrogen atom or long period-hetero atom of 3B to 7B on the periodic table, more preferably hydrocarbon group having 1 to 15 carbon atoms, 1 to 10 halogenated hydrocarbon group, hydrogen Atom or long period type-second on the periodic table
It is a heteroatom of Group 3A to 7A in the fourth period. Specific examples include (a) hydrogen atom, (b) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, neopentyl, phenyl, 4-methylphenyl, 4-fluorophenyl, cyclohexyl, norbornane. , Hydrocarbon groups such as norbornene, (c) monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, methyl iodide, 2-fluoroethyl, 2,2 -Difluoroethyl,
2,2,2-trifluoroethyl, 1,2,2,2-tetrafluoroethyl, 1,1,2,2,2-perfluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2 , 2-trichloroethyl, 1,2,2,2-
Halogenated hydrocarbon groups such as tetrachloroethyl, 1,1,2,2,2-perchloroethyl, 2-bromoethyl, 1,2, -dibromoethyl, 2-ethyl iodide,
(D) Fluorine, chlorine, bromine and iodine atoms, (f) methoxy, ethoxy, propoxy, butoxy, t-butoxy, phenoxy and other alkoxy groups, (f) trimethylsilyl, triethylsilyl, trichlorosilyl, trimethylgermyl, triethylgel. Mill, trichlorogermyl group and other 4Bb group element groups, (to) cyano, isocyano, carboxy, amino, thiol groups, etc. (thi) 1H-indene, 9H-fluorene, 1H-cyclo [a] pentalene, 1H-benz [ f] A compound having an unsaturated 5-membered ring skeleton in the molecule such as indene and 1,4-methanobiphenylene, and a compound derived from them.

Specific examples of such compounds are shown below, but each compound may be a compound in which two or more molecules are fused (for example, Diels-Alder product). 5,5-dimethoxy-1,3-cyclopentadiene, 5,5-diethoxy-1,3-cyclopentadiene, 1,4-diethyl-2,3-dimethyl-5,5-dimethoxy-1,3-cyclopentadiene , 1,4-diethyl-2,3-dimethyl-5,5-diethoxy-1,3
-Cyclopentadiene, 2-t-butyl-5,5-dimethoxy-1,3-cyclopentadiene, 2-t-butyl-5,5-diethoxy-1,3-cyclopentadiene,
1,2,3,4-tetraphenyl-5,5-dimethoxy-1,3-cyclopentadiene, 1,2,3,4-tetraphenyl-5,5-diethoxy-1,3-cyclopentadiene, 1, 4-trimethylsilylyl-2,3-diphenyl-5,5-dimethoxy-1,3-cyclopentadiene, 2,3-trimethylsilyl-1,4-diphenyl-5,5-dimethoxy-1,3-cyclopentadiene,
1,2,3,4-tetrafluoro-5,5-diethoxy-1,3-cyclopentadiene, 1,2,3,4-tetrafluoro-5,5-diethoxy-1,3-cyclopentadiene, 1, 2,3,4-tetrachloro-5,5-dimethoxy-1,3-cyclopentadiene, 1,2,3
4-tetrachloro-5,5-diethoxy-1,3-cyclopentadiene, 1,2,3,4-tetrabromo-5,
5-dimethoxy-1,3-cyclopentadiene, 1,
2,3,4-tetrabromo-5,5-diethoxy-1,
3-cyclopentadiene, 1,2,3,4-tetrakis (trifluoromethyl) -5,5-dimethoxy-1,3
-Cyclopentadiene, 1,2,3,4-tetrakis (trifluoromethyl) -5,5-diethoxy-1,3
-Cyclopentadiene, 1,1-dimethoxy-1H-indene, 1,1-diethoxy-1H-indene, 2,3
-Diphenyl-1,1-dimethoxy-1H-indene,
2,3-diphenyl-1,1-diethoxy-1H-indene, 2,3,4,5,6,7-hexachloro-1,1
-Dimethoxy-1H-1 indene, 2,3,4,5,
6,7-hexachloro-1,1-diethoxy-1H-1
Indene, 9,9-dimethoxy-9H-fluorene,
9,9-diethoxy-9H-fluorene, 3-bromo-
9,9-dimethoxy-9H-fluorene, 3-bromo-
9,9-diethoxy-9H-fluorene, 2,3,4
5,6,7-hexahydrido-8,8-dimethoxy-1
H-cyclo [a] pentalene, 9,9-dimethoxy-
1,4-methanobiphenylene. The amount of component (C) used is
The molar ratio of component (C) / component (B) is 0.01 to 5, preferably 0.02 to 1.

Olefin The olefin used for polymerization is generally an olefin having at most 12 carbon atoms, and representative examples thereof include ethylene, propylene, butene-1,4-methylpentene-1, and hexene-. 1, octene-1 and the like. In carrying out the polymerization, these olefins may be homopolymerized, or two or more kinds of olefins may be copolymerized (for example, copolymerization of ethylene and propylene).

Polymerization Method and Its Conditions In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound or these and the acetal compound may be introduced individually into the polymerization vessel, but two or all of them may be introduced. May be premixed. The polymerization can be carried out either in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Further, in order to obtain a polymer having a practical melt flow, a molecular weight modifier (generally hydrogen) may coexist. The polymerization temperature is generally -10 ° C to 180 ° C, and practically 20 ° C.
It is above 130 ° C. In addition, the presence or absence of preliminary polymerization,
With respect to the form of the polymerization reactor, the method of controlling the polymerization, the method of post-treatment, etc., there is no limitation inherent in the present catalyst system, and all known methods can be applied.

[0030]

The present invention will be described in more detail with reference to the following examples. For the examples and comparative examples, the melt index at a load of 2.16 kg (that is, M
FI) and melt index at 10 kg load (ie, HLMFI) are JIS K-6758-1.
968 was measured. A larger value of HLMFI divided by MFI, that is, HLMFI / MFI, indicates that the molecular weight distribution is wider. The heptane index (that is, HR) is boiling n-heptane and represents the remaining amount in% after the obtained polymer is extracted for 6 hours. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (hereinafter referred to as “GPC”) using orthodichlorobenzene as a solvent at a temperature of 140 ° C. The initial flexural modulus (FM) was measured according to ASTM-D-790-66. In each of the examples, each of the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, silicon compound, etc.) used for the production and polymerization of the solid catalyst component was substantially free of water. In addition, the production and polymerization of the solid catalyst component were carried out under a nitrogen atmosphere in which substantially no water was present.

Example 1 (Preparation of solid Ti catalyst component (A)) 1.71 g of anhydrous magnesium chloride, 9 ml of decane and 8.4 ml of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution. 0.39 g of phthalic anhydride is added to this solution, and the mixture is stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then added dropwise to 72 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed liquid is raised to 110 ° C. over 4 hours, and when it reaches 110 ° C., 0.96 g of dibutyl phthalate is added, and the mixture is maintained at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 72 ml TiCl ₄ , and then the reaction was carried out again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, washed sufficiently with 110 ° C. decane and hexane until no free titanium compound was detected in the washing liquid, and then dried under reduced pressure.

(Polymerization) Into a 1.5 l stainless steel autoclave, 9.7 m of the solid component produced by the above method was added.
g, 9,9-dimethoxy-9H-fluorene 11.5m
g, 91 mg of triethylaluminum, and then 3
40 g propylene and 0.03 g hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. Result 14
6 g of polypropylene powder was obtained. The polypropylene powder had a heptane extraction residue (HR) of 92.9%. The ratio with the weight average molecular weight (Mw) and the number average molecular weight (Mn) by GPC was 12.6. MFI
Is 6.6 g / 10 minutes, HLMFI / MFI is 23.5, F
M = 17800 kg / cm ² .

Comparative Example 1, Examples 2 to 4 The catalyst was prepared and polymerized in the same manner as in Example 1 except that the type and amount of the catalyst component (C) used were changed as shown in Table 1. .. The results are shown in Table 1.

[0034]

[Table 1]

Example 5 (Preparation of solid Ti catalyst component (A)) 5 g of diethoxymagnesium, 1.42 g of ethyl 3-isobutoxy-2-phenylpropionate were placed in a 300 ml round bottom flask which was sufficiently dried under a nitrogen stream. 25 ml of methylene chloride was added. Stir at reflux for 1 hour, then add this suspension to room temperature at 200 ml T.
Pumped into iCl ₄ . The temperature was gradually raised to 110 ° C. and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the precipitated solid was filtered off and washed with 200 ml of n-decane at 110 ° C three times. 200 ml of TiCl ₄ was newly added and reacted at 120 ° C. for 2 hours. After the reaction was completed, the precipitated solid was separated by filtration, washed with 200 ml of n-decane at 110 ° C. three times, and washed with hexane at room temperature until no chlorine ion was detected in n-hexane.

(Polymerization) The solid component produced by the above method was placed in a 1.5-liter stainless steel autoclave for 5.8 m.
g, 1,2,3,4-tetrachloro-5,5-dimethoxy-1,3-cyclopentadiene (15.0 mg) and triethylaluminum (91 mg) were added, and then 340 g of propylene and 0.03 g of hydrogen were added. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. As a result, 164 g of polypropylene powder was obtained. The polypropylene powder had a heptane extraction residue (HR) of 96.9%. GP
Weight average molecular weight (Mw) and number average molecular weight (M
The ratio with n) was 15.0. MFI is 8.7g / 10
Min, HLMFI / MFI is 23.5, FM = 18400
It was kg / cm ² .

Comparative Example 2, Examples 6 to 8 A catalyst was prepared and polymerized in the same manner as in Example 5 except that the type and amount of the catalyst component (C) used were changed as shown in Table 2. .. The results are shown in Table 2.

[0038]

[Table 2]

Example 9 (Preparation of solid Ti catalyst component (A)) 1.71 g of anhydrous magnesium chloride, 9 ml of decane and 8.4 ml of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution. 0.39 g of phthalic anhydride is added to this solution, and the mixture is stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then added dropwise to 72 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and when it reached 110 ° C, 1.00 g of methyl 3-benzoylpropionate was added, and the mixture was stirred at the same temperature for 2 hours. Hold down. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and this solid portion was collected by 72 ml
After resuspending in iCl ₄ , heat reaction is performed again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, washed sufficiently with 110 ° C. decane and hexane until no free titanium compound was detected in the washing liquid, and then dried under reduced pressure.

(Polymerization) Into a stainless steel autoclave of 1.5 liters, the solid component produced by the above method was 9.7 m.
g, 1,2,3,4-tetrachloro-5,5-dimethoxy-1,3-cyclopentadiene (15.0 mg) and triethylaluminum (91 mg) were added, and then 340 g of propylene and 0.03 g of hydrogen were added. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. As a result, 146 g of polypropylene powder was obtained. The polypropylene powder had a heptane extraction residue (HR) of 97.2%. GP
Weight average molecular weight (Mw) and number average molecular weight (M
The ratio with n) was 13.8. MFI is 6.5g / 10
Min, HLMFI / MFI is 22.6, FM = 17,000
It was kg / cm ² .

Comparative Example 3, Examples 10 to 12 A catalyst was prepared and polymerized in the same manner as in Example 9 except that the type and amount of the catalyst component (C) used were changed as shown in Table 3. .. The results are shown in Table 3.

[0042]

[Table 3]

[0043]

As described above, according to the method of the present invention, an olefin polymer having high stereoregularity and an extremely broad molecular weight distribution can be obtained in a remarkably high yield. This allows the economical production of olefin polymers with extremely high rigidity.

[Brief description of drawings]

FIG. 1 is a flow chart for preparing a catalyst according to the present invention.

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[Procedure amendment]

[Submission date] July 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title of the invention Olefin polymerization catalyst

Claims (1)

Claim: What is claimed is: 1. A catalyst used in a method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, which contains component (A) titanium, magnesium and halogen as essential components. Solid catalyst component. Component (B) organoaluminum compound, and component (C) general formula: (In the formula, R ¹ is a hydrocarbon group, R ^{2 to} R ⁵ are a hydrocarbon group or a halogenated hydrocarbon group, or a hetero atom. R ^{2 to} R ⁵
May be all or partly the same or all different. Further, R ^{2 to} R ⁵ may all or partially form a ring. ) An olefin polymerization catalyst comprising an acetal compound represented by