JPS6247881B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst component for α-olefin polymerization, and more particularly to a supported titanium catalyst component capable of producing a polymer having high activity, high stereoregularity, and uniform particle size. Conventionally, using a Ziegler-Natsuta type catalyst,
When obtaining olefin polymers, especially polypropylene, the resulting polymer is not treated in any way.
Many attempts have been made to obtain catalysts that are highly active and exhibit high stereoregularity, with the ultimate goal of converting them into products as they are. In recent years, the development of supported catalysts in which titanium is supported on various supports, especially magnesium compounds, has been progressing with the aim of increasing the polymerization ability per unit titanium in the titanium component, which is useful as a catalyst component. Although results are being achieved, the ultimate catalyst has not yet been completed. On the other hand, attempts are being made to obtain catalysts that can control the particle size of the resulting polymer while maintaining these high activities and high stereoregularities. Generally, it is said that the shape of the polymer obtained using a Ziegler-Natsuta type catalyst is greatly influenced by the shape of the catalyst components used, and even in the case of supported catalysts, attempts are made to control the shape of the catalyst. Some have been done, but the number is not large. Regarding supported catalysts using magnesium compounds, particularly magnesium chloride, for example, there is a method in which molten magnesium chloride is spray-dried to obtain spherical particles, and titanium tetrachloride is supported in a suspended state on the particles (in particular, spherical particles are obtained by spray drying molten magnesium chloride). Publication No. 49-65999, same
52-38590) and a method of supporting titanium tetrachloride in a suspended state in classified powdered magnesium chloride (Japanese Patent Application Laid-Open No. 127185/1985). However, the catalyst obtained by the above method is mainly used for the production of polyethylene, and the resulting polymer is also spherical, but in the case of the production of polypropylene, it shows low stereoregularity; It mainly relates to a catalyst for polymerizing ethylene, and although the resulting polymer has good particle characteristics, the polymerization efficiency of the catalyst is not necessarily high. Apart from these preparation methods for magnesium chloride, Japanese Patent Application Laid-Open No. 146292/1984 discloses a method of producing a magnesium compound with controlled particle characteristics by reacting metallic magnesium and an organic halide or an organic magnesium compound with an ester of orthosilicic acid. A method is described in which a substance whose main component is magnesium halide, particularly magnesium chloride, is obtained by treating this with an electron-donating compound and/or a halogen compound, and titanium tetrachloride is supported on this substance. . However, in this method, the activity and stereoregularity of the catalyst are not high, and although the particle size distribution of the obtained polymer is considerably improved, the ester of orthosilicic acid, which is essential for this method, is a special compound and is difficult to obtain. This cannot be said to be an economically advantageous method. The present inventors showed high activity, high stereoregularity,
The purpose of this invention is to provide a catalyst component capable of producing free-flowing polyolefins, especially polypropylene, with a narrow particle size distribution and less fines.
The present invention was completed through intensive research. That is, the present invention provides (1) (a) metallic magnesium, (b) a halogenated hydrocarbon represented by the general formula RX [wherein R is an alkyl group, aryl group, or cycloalkyl group having 1 to 20 carbon atoms] ;X is a halogen atom. ] and (c) a compound of the general formula X′ _n C(OR′) _4-n [wherein X′ is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group, or a cycloalkyl group; R′ has 1 to 20 carbon atoms
m is 0, 1 or 2; ] A magnesium-containing solid obtained by contacting (2) a titanium compound and (3) an electron-donating compound. Each compound used in preparing the magnesium-containing solid in the present invention will be explained. Any type of magnesium metal may be used, but powdered and chipped types are particularly suitable.
Before use, these metallic magnesium are washed with an inert hydrocarbon, such as a saturated aliphatic, alicyclic or aromatic hydrocarbon having 6 to 8 carbon atoms, and then washed with an inert gas such as nitrogen. It is desirable to heat and dry in the presence of. In the halogenated hydrocarbon represented by the general formula RX, R has 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms.
X is preferably an alkyl group, an aryl group or a cycloalkyl group, and X is chlorine or bromine. Specific examples thereof include methyl, ethyl, isopropyl, n-butyl, n-octyl, and cyclohexyl chloride, as well as bromide, chlorobenzene, O-chlorotoluene, and the like. In place of the above-mentioned magnesium metal and halogenated hydrocarbon, a compound obtained by bringing these compounds into contact in advance can be used.
A typical example is the so-called Grignard reagent, and specific examples include ClMgCH ₃ ,
ClMgC ₂ H ₅ , ClMgC ₃ H ₇ , ClMgC ₄ H ₉ , ClMgi−
_{C4H9 , ClMgC6H13 , ClMgC8H17 , BrMgC2H5 ,
BrMgC4H9} , BrMgi _{- C4H9 , IMgC4H9 ,}
Examples include ClMgC ₆ H ₅ and BrMgC ₆ H ₅ . A compound _represented by _the general formula , an aryl group or a cycloalkyl group, R' is selected from an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group, and m is selected from 0, 1 or 2, respectively. Specific examples of compounds where m is 0, 1 and 2 are shown below. When m is 0, the compound C(OR') ₄ , that is, the orthocarbonate ester is orthomethyl carbonate [C
(OCH ₃ ) ₄ ], orthoethyl carbonate [C(OC ₂ H ₅ ) ₄ ],
Propyl orthocarbonate [C(OC ₃ H ₇ ) ₄ ], butyl orthocarbonate [C(OC ₄ H ₉ ) ₄ ], isobutyl orthocarbonate [C(O-i-C ₄ H ₉ ) ₄ ], hexyl orthocarbonate [ C(OC ₆ H ₁₃ ) ₄ ], ortho-octyl carbonate [C
_{( OC8H17} ) ₄ ] etc. The compound when m is 1, X′C(OR′) ₃ , that is, orthoacid ester and its substituted compound,
Methyl orthoformate [HC
(OCH ₃ ) ₃ ], ethyl orthoformate [HC
(OC ₂ H ₅ ) ₃ ], propyl orthoformate [HC
(OC ₃ H ₇ ) ₃ ], butyl orthoformate [HC
(OC ₄ H ₉ ) ₃ ], isobutyl orthoformate [HC(O-
i-C ₄ H ₉ ) ₃ ], hexyl orthoformate [HC
(OC ₆ H ₁₃ ) ₃ ], octyl orthoformate [HC
(OC ₈ H ₁₇ ) ₃ ], phenyl orthoformate [HC
(OC ₆ H ₅ ) ₃ ], etc. are methyl orthoacetate [CH ₃ C
(OCH ₃ ) ₃ ], ethyl orthoacetate [CH ₃ C
(OC ₂ H ₅ ) ₃ ], Methyl orthopropionate [CH ₃ CH ₂ C (OCH ₃ ) ₃ ], Ethyl orthopropionate [CH ₃ CH ₂ C (OC ₂ H ₅ ) ₃ ], Others, C ₆ H _11C
(OC ₂ H ₅ ) ₃ , C ₆ H ₅ C (OC ₂ H ₅ ) ₃ , C ₇ H ₈ C
(OC ₂ H ₅ ) ₃ , C ₈ H ₁₁ C(OC ₂ H ₅ ) ₃ , etc., is ethyl orthobromoacetate [CH ₂ BrC(OC ₂ H ₅ ) ₃ ] in which the hydrogen atom of the alkyl group is replaced with a halogen atom. , ethyl orthochloroacetate [CH ₂ ClC (OC ₂ H ₅ ) ₃ ], ethyl ortho α-bromopropionate [CH ₃ CHBrC
(OC ₂ H ₅ ) ₃ ], ethyl ortho-α-chloropropionate [CH ₃ CHClC (OC ₂ H ₅ ) ₃ ], etc., but methyl ortho-chloroformate [ClC
(OCH ₃ ) ₃ ], ethyl orthochloroformate [ClC
(OC ₂ H ₅ ) ₃ ], propyl orthochloroformate [ClC
(OC ₃ H ₇ ) ₃ ], isobutyl orthochloroformate [ClC
(O・i-C ₄ H ₉ ) ₃ ], octyl orthochloroformate [ClC(OC ₈ H ₁₇ ) ₃ ], phenyl orthochloroformate [ClC(OC ₆ H ₅ ) ₃ ], ethyl orthobromoformate [BrC(OC ₂ H ₅ ) ₃ ], among them, orthoformate esters in which X' is H, especially methyl orthoformate, ethyl orthoformate, butyl orthoformate, and orthoformate in which R' is an alkyl group having 1 to 8 carbon atoms. Preferred compounds include octyl acid. Compounds where m is 2 and compounds of X′ ₂ C(OR′) ₂ include ethylidene dimethyl ether [CH ₃ CH (OCH ₃ ) ₂ ], ethylidene diethyl ether [CH ₃ CH (OC ₂ H ₅ ) ₂ ]. , methylal [CH ₂
(OCH ₃ ) ₂ ], methylene diether [CH ₂
(OC ₂ H ₅ ) ₂ ], monochloroacetal [CH ₂ ClCH
(OC ₂ H ₅ ) ₂ ], dichloroacetal [CHCl ₂ CH
(OC ₂ H ₅ ) ₂ ], trichloroacetal [CCl ₃ CH
(OC ₂ H ₅ ) ₂ ], monobromoacetal [CH ₂ BrCH
(OC ₂ H ₅ ) ₂ ], monoiodoacetal [CH ₂ ICH
(OC ₂ H ₅ ) ₂ ], benzaldehyde diethyl acetal [C ₆ H ₅ CH(OC ₂ H ₅ ) ₂ ], and the like. Among the above compounds, orthoformate,
Particularly suitable are alkyl esters having 1 to 8 carbon atoms, such as methyl orthoformate, ethyl orthoformate, and butyl orthoformate. Next, a method for preparing the magnesium-containing solid according to the present invention will be explained. The magnesium-containing solid is obtained by contacting the alkoxy compound with metallic magnesium and a halogenated hydrocarbon. The method of contacting the alkoxy compound with metal magnesium and halogenated hydrocarbon is not particularly limited,
You can do it in any way you like. For example, the three may be brought into contact with each other at the same time, or by bringing metal magnesium into contact with a halogenated hydrocarbon in advance as described above,
The alkoxy compound may be brought into contact with the alkoxy compound after forming a so-called Grignard reagent, but it is particularly desirable to add a solution of a halogenated hydrocarbon to a suspension of metallic magnesium in a solution of the alkoxy compound. These contact reactions can be carried out in the presence of an inert hydrocarbon as described above for metallic magnesium. Further, for the purpose of promoting these reactions, iodine, alkyl iodide, or inorganic halides such as calcium chloride, copper chloride, manganese chloride, and hydrogen halide can be used. The contact reaction temperature is 40-250℃, preferably 60-120℃.
C. for 1 to 10 hours. The ratio of the alkoxy compound to magnesium metal is 1:1 of magnesium in metal magnesium.
It is desirable to use magnesium metal and the alkoxy compound such that the number of OR' groups in the alkoxy compound is one or more, particularly in the range from 3 to 5, per atom. That is, in _the case of _an alkoxy compound represented by
In the case of an alkoxy compound represented by (OR′) ₃ ,
A range of 1/3 gram mole or more, particularly 1 to 5/3 gram mole is desirable. Further, it is preferable to use the halogenated hydrocarbon in an amount of 1 to 2 gram moles per gram atom of magnesium. The solid produced by the reaction can be separated from the reaction system to prepare the magnesium-containing solid, but it may be washed with an inert hydrocarbon if necessary. Next, the magnesium-containing solid can be made into a catalyst component by contacting it with a titanium compound and an electron-donating compound. As the titanium compound used in preparing the catalyst component, titanium tetrahalide, particularly titanium tetrachloride, is preferred. Also, titanium halogen alcoholates, halogen phenolates, e.g.
Ti(O・n-C ₄ H ₉ ) ₂ Cl ₂ , TiOC ₂ H ₅ Cl ₃ , Ti
(O.C ₆ H ₅ ) ₂ Cl ₂ etc. can also be used. Electron-donating compounds used in preparing the catalyst component include carboxylic acids, carboxylic acid esters, alcohols, ethers, ketones,
Examples include amines, amides, nitrites, aldehydes, alcoholates, phosphorus, arsenic, and antimony compounds bonded to organic groups via carbon or oxygen, phosphoamides, thioethers, thioesters, and carbonate esters. Among these, carboxylic acid esters and carboxylic acids are preferably used. Carboxylic acid esters are esters formed by condensation of saturated or unsaturated aliphatic, cycloaliphatic and aromatic mono- or polycarboxylic acids with aliphatic, cycloaliphatic and aromatic mono- or polyols. More specifically, butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl isobutyrate, methyl methacrylate, diethyl maleate, diethyl tartrate, ethyl hexahydrobenzoate, ethyl benzoate, p- Ethyl methoxybenzoate, methyl p-methylbenzoate, ethyl p-tertiary butylbenzoate, dibutyl phthalate, diallyl phthalate, α-
Examples include, but are not limited to, ethyl naphthoate. Among these, alkyl esters of aromatic carboxylic acids, particularly alkyl esters of benzoic acid or nuclear substituted benzoic acids having 1 to 8 carbon atoms such as p-methylbenzoic acid and p-methoxybenzoic acid, are preferably used. The carboxylic acids include saturated or unsaturated aliphatic, alicyclic and aromatic mono- or polycarboxylic acids or their acid anhydrides, preferably aromatic carboxylic acids and their acid anhydrides. As a specific example,
Benzoic acid, p-methylbenzoic acid, p-methoxybenzoic acid, phthalic acid and their acid anhydrides, benzoic anhydride, p-methylbenzoic anhydride, p-anhydride
-methoxybenzoic acid, phthalic anhydride, etc. In addition, in the reaction with the magnesium-containing solid, carboxylic acid esters,
For example, it is also possible to use compounds which allow the in situ preparation of alkyl esters of aromatic carboxylic acids, such as benzoyl chloride. The methods of contacting the magnesium-containing solid, the titanium compound, and the electron-donating compound can be carried out in an appropriate combination. For example, those three types at the same time,
Alternatively, any two of them may be brought into contact with each other in advance and then brought into contact with the remaining one. The proportion of the above three substances used is 1 gram mol or less, particularly 0.1 to 0.1 to 1 mol, of the electron-donating compound per 1 gram atom of magnesium in the magnesium-containing solid.
It is desirable to use it in the range of 0.3 gmol.
Further, it is suitable to use 0.2 to 2 mol, preferably 0.5 to 1.5 mol, of the electron donating compound per 1 mol of the titanium compound. The above-mentioned magnesium-containing solid, titanium compound, and electron-donating compound are contact-treated simultaneously or individually under heating conditions, e.g.
It is desirable that the contact be carried out at a temperature of 200°C for 0.5 to 5 hours. When the magnesium-containing solid is brought into contact with the electron-donating compound, it is preferable to do so in the presence of the same inert hydrocarbon as described above for metallic magnesium. Furthermore, the above-mentioned contact treatment can be carried out in the presence of a halogen compound. Of course, it may exist in the case of individual processing as well as simultaneous processing. Examples of the halogen compound include silicon halides such as silicon tetrachloride, aluminum halides such as aluminum trichloride, dialkyl aluminum monochloride, alkyl aluminum dichloride, benzoyl chloride, boron trichloride, phosphorus trichloride, etc. The following organic halogen compounds and halogen-containing compounds of Group a elements of the synchronous table other than carbon can be mentioned. Flexible organohalogen compounds are mono- and polyhalogen-substituted saturated and unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons. More specifically, aliphatic compounds include methyl chloride, methyl bromide, methyl iodide,
Methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2- Dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene,
1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, chlorinated paraffin Among alicyclic compounds, chlorocyclopropane, tetrachlorocyclopentane, hexachloropentadiene, hexachlorocyclohexane,
Examples of aromatic compounds include chlorobenzene, bromobenzene, o-dichlorobenzene, p-cyclobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride, and the like. In addition to these halo-substituted hydrocarbons, halo-substituted oxygenated compounds such as hexachloroacetone, chloroacetate,
Something like trichloroacetic acid ester may be used. Examples of halogen-containing compounds of Group A elements of the periodic table other than carbon include halogen compounds of silicon, germanium, tin, and lead, their homologs, and other compounds. Typical silicon halogen- _containing compounds are represented by the general formula _Si n These are polyhalosilanes such as halodisilane, octahalotrisilane, decahalotetrasilane, dodecahalopentasilane, tetradecahalohexasilane, and docosahalodecasilane. In these polyhalopolysilanes, each halosilane atom may be the same or different. Among these, preferred compounds are tetrahalosilanes corresponding to m=1. Examples of tetrahalosilanes include tetrachlorosilane, tetrabromosilane,
Tetraiodosilane, trichlorobromosilane,
Examples include trichloroiodosilane, trichlorofluorosilane, dichlordibromosilane, dichlordiiodosilane, chlortribromosilane, chlortriiodosilane, and tribromoiodosilane, but tetrachlorosilane is easily available industrially. Most preferred. Furthermore, some of the halogens in the above halosilane homologous compounds are alkyl groups, aryl groups, aralkyl groups,
It may be substituted with one or more of vinyl groups, alkoxy groups, and acyl groups. A typical germanium halogen compound is represented by GeX _n (X represents a halogen, m represents an integer of 2 or 4), and specific examples include GeCl ₂ ,
Examples include GeBr ₂ , GeI ₂ , GeCl ₄ , GeBr ₄ and GeL ₄ , and among these, GeCl ₂ and GeCl ₄ are preferred. Some of the halogens in the halogermanium compound may be substituted with one or more of an alkyl group, an aryl group, an aralkyl group, a vinyl group, an alkoxy group, and an acyl group. Typical tin halide compounds are SnX _n
(X and m are the same as above), and specific examples include SnCl ₂ , SnBr ₂ , SnI ₂ , SnCl ₄ , SnBr ₄ , SnI ₄ ,
_SnCl3Br , _SnCl2Br2 , _{SnBr3Cl , SnBr2I2 ,}
Examples include SnCl ₂ I ₂ , but among these, SnCl ₂ ,
_SnCl4 is preferred. A portion of the halogens in the above halostin compound may be substituted with one or more of an alkyl group, an aryl group, an aralkyl group, a vinyl group, an alkoxy group, and an acyl group. A typical lead halide compound is PbX _n
(X and m are the same as above), and specific examples include PbCl ₂ , PbCl ₄ , PbBr ₂ , PbBr ₄ , PbI ₂ , and PbI ₄ , with PbCl ₂ and PbCl ₄ being preferred. Some of the halogens in the halo lead compound may be substituted with one or more of an alkyl group, an aryl group, an aralkyl group, a vinyl group, an alkoxy group, and an acyl group. Further, these various halogen compounds can be used alone or in combination of two or more. Through this contact treatment, the magnesium-containing solid becomes approximately magnesium dihalide, which becomes a catalyst component in which a titanium compound and an electron-donating compound are encapsulated using this as a carrier. The catalyst component obtained by the method of the present invention has a particle size of 3 to 30 microns (μ), of which 10 to
It has a particle size distribution in which more than 70% of the particles are 20μ. The catalyst component of the present invention may be further contacted with the halogen compounds listed above. Furthermore, the catalyst component obtained as described above may be contacted with a mixture of an organoaluminum compound and an electron-donating compound. The organoaluminum compound used together with the electron-donating compound has the general formula R _o AlX _3-o (where R is an alkyl group or an aryl group, X is a halogen atom,
Indicates an alkoxy group or a hydrogen atom, n is 1n
Any number in the range of 3. ), preferably having 1 to 18 carbon atoms, such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohydride. Particularly preferred is an alkyl aluminum compound having 2 to 6 carbon atoms, or a mixture or complex compound thereof. Specifically, examples of trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum, and examples of dialkylaluminum monohalide include dimethylaluminum chloride, diethylaluminum chloride, and diethylaluminum bromide. Examples of monoalkylaluminum dihalides include methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and alkylaluminum sesquihalides. Examples of dialkylaluminium sesquichloride include dimethylaluminum methoxide, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide, diisobutylaluminum ethoxide, and diisobutylaluminum phenoxide. Examples of the dialkyl aluminum hydride include dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, and the like. The electron-donating compound used together with these organoaluminum compounds can be appropriately selected from the compounds listed above. The catalyst component thus obtained can be used for the homopolymerization of α-olefins or for the homopolymerization of ethylene or other α-olefins by combining with organoaluminum compounds.
- In copolymerization with olefins, the resulting polymer exhibits high activity and stereoregularity, and the resulting polymer has a very narrow particle size distribution, as well as translucency not seen with conventional supported catalysts. It exhibits an outstanding effect of having unique particle characteristics. The organoaluminum compound used in combination with the catalyst component when polymerizing α-olefin is appropriately selected from the above-mentioned organoaluminum compounds, but among them, trialkylaluminum is particularly preferable, and examples thereof include triethylaluminum, triethylaluminum, and triethylaluminum. Isobutylaluminum is mentioned. Further, these trialkylaluminums can be used in combination with other organoaluminum compounds, and specific examples thereof include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or these. It is desirable that mixtures or complex compounds are industrially easily available and exhibit excellent effects. The amount of the organoaluminum compound to be used in the catalyst component is generally 1 to 2000 g mol, preferably 50 to 500 g mol, per 1 gram atom of titanium in the catalyst component. The organoaluminum compound is preferably used in combination with the above-mentioned electron-donating compound used in the preparation of the catalyst component. Desirable electron-donating compounds include carboxylic acid esters among the above-mentioned electron-donating compounds, and among them,
Esters of aromatic carboxylic acids, especially benzoic acid, p
C1-C8 alkyl esters of nuclear-substituted benzoic acids such as -methoxybenzoic acid or p-methylbenzoic acid are preferred. In this case, the ratio of the organoaluminum compound to the electron donating compound is selected in the range of 0.1 to 10, preferably 1 to 5 gram atoms of the organoaluminum compound as aluminum per mole of the electron donating compound. The catalyst consisting of the catalyst component and the organoaluminum compound (and electron-donating compound) obtained as described above is effective in polymerizing olefins, and is particularly effective for polymerizing α-olefins having 3 to 6 carbon atoms, such as propylene, It can be used for stereospecific polymerization of butene-1,4-methyl-pentene-1, hexene-1, etc., and copolymerization of the above α-olefins with each other and/or with ethylene. Copolymerization includes both random and block copolymerization. When ethylene is used as a comonomer, it is usually selected in an amount of up to 30% by weight, especially in the range of 1 to 15% by weight, based on the α-olefin. The conditions for carrying out the polymerization reaction using the catalyst system of the present invention are the same as those commonly used. The reaction may be carried out in either a gas phase or a liquid phase. In the liquid phase, the reaction may be carried out in an inert hydrocarbon or a liquid monomer. Suitable solvents that can be used when carrying out the polymerization in a solvent are selected from the inert hydrocarbons mentioned above. The polymerization temperature is generally -80° to 150°C, preferably 40°C to 100°C. The pressure may be, for example, 1 to 40 atmospheres. The molecular weight during polymerization can also be controlled by known methods in which hydrogen or other known molecular weight regulators are present. This polymerization process can be carried out continuously or batchwise. When α-olefin is polymerized using the catalyst component of the present invention, the polymerization activity and stereoregularity of the catalyst are both high, so that both the decatalyst step and the atactic polymer removal step are unnecessary. At least the load can be significantly reduced, and the obtained polymer has the outstanding effect of exhibiting a uniform particle size distribution within a narrow range, having a large particle size and less fine powder, and therefore being highly free-flowing. have. Moreover, the obtained polymer exhibits a unique property of being translucent, which is not seen in conventional supported catalysts. The process for polymerizing olefins using the catalyst components of this invention is of particular interest in the production of isotactic polypropylene, random copolymers of ethylene and propylene, and block copolymers of propylene and ethylene. Next, the present invention will be specifically explained using examples. However, the present invention is not limited only to the examples. Note that the percentages (%) shown in the examples are based on weight unless otherwise specified. Polymerization activity Kc is the amount of polymer produced per gram of catalyst (g),
Kt is the amount of polymer produced per 1g of Ti in the catalyst (Kg)
It is. Heptane insoluble content (hereinafter abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, is:
This is the residual amount after extraction with boiling n-heptane for 6 hours using an improved Soxhlet extractor. Melt flow rate (MFR) was measured according to ASTM-D1238. Bulk density was measured according to ASTM-D1895-69 Method A. The particle size distribution of the polymer is W.
Measurements were made using standard sieves from S. Tyler. In addition, the specific surface area (SA), pore volume (PV), and mean pore radius (MPR) of the magnesium-containing solid and the catalyst component are determined by SORPTO- manufactured by CARLO ERBA.
The measurement was performed using a MATIC1810 type device, and the particle size distribution of the catalyst component was measured using a light transmission particle size distribution analyzer SKN500 type device manufactured by Seishin Enterprises. Example 1 Preparation of magnesium-containing solid In a reaction vessel equipped with a reflux condenser, 12.8 g (0.53 mol) of metallic magnesium chips (purity 99.5%, average particle size 1.6 mm) and n - 250 ml of hexane was added, and after stirring at 68°C for 1 hour, metallic magnesium was taken out and dried under reduced pressure at 65°C to obtain preactivated metallic magnesium. Next, a suspension of 88 ml (0.53 mol) of ethyl orthoformate and 0.5 ml of a 10% iodine methyl iodide solution as an accelerator was added to this magnesium metal, kept at 55°C, and further added to 100 ml of n-hexane. n-
Initially, 5 ml of a solution containing 80 ml (0.8 mol) of butyl chloride was added dropwise, and after stirring for 50 minutes, the remaining solution was added dropwise over 80 minutes. The reaction was carried out at 70° C. for 4 hours with stirring to obtain a solid reaction product. This reaction product was mixed with 300ml each of n-hexane at 50°C.
The solution was washed six times with water and dried under reduced pressure at 60° C. for 1 hour to recover 55.6 g of magnesium-containing solid. This solid contained 22.5% magnesium and 34.0% chlorine. In addition, its specific surface area (SA) is 230m ² /g, pore volume (PV) is 0.15cc/g, and average pore radius (MP
R.) was 15 angstroms (Å). Preparation of catalyst component The obtained magnesium-containing solid was placed in a 300 ml reaction vessel equipped with a reflux condenser under a nitrogen gas atmosphere.
13.5g, n-hexane 200ml and benzoyl chloride
4.32 ml (41.5 mmol, 0.33 g mol per gram atom of magnesium in the magnesium-containing solid) was added to form a suspension, and after contact reaction at 70°C for 2 hours, the solid material was dissolved in n-hexane at 65°C.
Washed three times with 150 ml. Next, add 150ml of titanium tetrachloride and heat at 120℃ for 2 hours.
Time contact treatment. Thereafter, the solid material was heat separated at 120°C, washed 10 times with 150ml each of n-hexane at 65°C, and dried under reduced pressure at 50°C for 1 hour to obtain a catalyst component of the present invention having the following composition: I got g. (Ti2.3
%, Mg19.8%, Cl67.1%) Also, this catalyst component
SA is 347m ² /g, PV is 0.36cc/g, MPR is
The particle diameter was 21 Å, and the particle size distribution was as follows. 26 microns or more 0.1% by weight 20 microns or more 21.7 〃 10 microns or more 70.4 〃 5 microns or more 6.0 〃 Less than 5 microns 1.8 〃 Polymerization of propylene In a stainless steel (SUS32) autoclave with an internal volume of 1 equipped with a stirrer, in a nitrogen gas atmosphere Below, an n-heptane solution containing 76.4 mg of the catalyst component and 1 mole of triethylaluminum (hereinafter abbreviated as TEAL) in n-heptane is expressed as aluminum per gram atom of titanium in the catalyst component.
11.0 ml corresponding to 300 gram atoms and 0.46 ml ethyl p-methoxybenzoate corresponding to 0.29 gram moles per gram atom of aluminum in the TEAL.
The mixture was mixed and held for 5 minutes. Next, after pressurizing 0.6 of hydrogen gas and 0.8 of liquefied propylene as molecular weight control agents, the reaction system was heated to 68
Polymerization of propylene was carried out for 30 minutes while the temperature was raised to ℃. After the polymerization was completed, unreacted propylene was purged to obtain 221 g of white powdered polypropylene. That is, the polymerization activity Kc is 2900 and Kt is 126. In addition, HI is 95.5%, MFR3.2, the polymer is translucent, and its bulk density is 0.51g/
cm ³ and had the following particle size distribution. 840 microns or more 0.5% by weight 590 microns or more 21.4 〃 420 microns or more 47.8 〃 350 microns or more 20.1 〃 250 microns or more 8.0 〃 149 microns or more 2.0 〃 53 microns or more 0.2 〃 Less than 53 microns 0 〃 Examples 2, 3 In Example 1 When preparing the magnesium-containing solid, the same procedure as Example 1 was carried out, except that instead of dropping the n-hexane solution of n-butyl chloride and reacting at 70°C for 4 hours, the reaction was carried out at the temperature shown in Table 1. A magnesium-containing solid and a catalyst component having the composition and physical properties shown in Table 5 were prepared, and propylene was polymerized in the same manner as in Example 1 using the catalyst component, and the results are shown in Table 1.

[Table] Example 4 When preparing the magnesium-containing solid in Example 1, instead of using ethyl orthoformate in an equimolar amount relative to metallic magnesium, the following conditions were used:
A magnesium-containing solid and a catalyst component having the composition and physical properties shown in Table 5 were prepared in the same manner as in Example 1, and propylene was polymerized using the catalyst component in the same manner as in Example 1. As a result, Kc3100 was obtained. ,
Kt150, HI92.9%, MFR6.0, bulk density 0.50g/ ^cm3
It was hot. Examples 5 to 7 When preparing the magnesium-containing solid in Example 1, the composition shown in Table 5 was prepared in the same manner as in Example 1, except that the compound shown in Table 2 was used instead of ethyl orthoformate. A magnesium-containing solid having physical properties and a catalyst component were prepared, and using the catalyst component, propylene was polymerized in the same manner as in Example 1. The results are shown in Table 2.

[Table] Examples 8 to 10 The composition and physical properties shown in Table 5 were prepared in the same manner as in Example 1, except that the benzoyl chloride used in preparing the catalyst component in Example 1 was used in the amount shown in Table 3. Prepare a catalyst component having the following properties, polymerize propylene in the same manner as in Example 1 using the catalyst component,
The results are shown in Table 3.

[Table] Example 11 Preparation of magnesium-containing solid In a reaction vessel equipped with a reflux condenser, 0.5 mol of n-butylmagnesium chloride and 200 ml of toluene were added, the reaction solution was kept at 50°C, and 146 g of phenyl orthoformate was added. (0.3 mol) and toluene 100ml
Add the mixed solution dropwise over 50 minutes, then heat to 70℃ while stirring
The reaction was carried out for 4 hours to obtain a solid reaction product. This reaction product was treated in the same manner as in Example 1, and 60.1 g of magnesium-containing solid was recovered. This solid contained 21.3% magnesium and 30.9% chlorine. Moreover, its physical properties were as follows. SA240m ² /g, PV0.16cc/g, MPR13Å Preparation of catalyst components After treating the magnesium-containing solid with benzoyl chloride in Example 1, ethyl benzoate was used in an amount equivalent to 1 gram atom of magnesium in the magnesium-containing solid. Except for this, a contact treatment with titanium tetrachloride was performed in the same manner as in Example 1 to obtain a catalyst component. The composition and physical properties of the catalyst components were as follows. Titanium content 2.0%, SA315m ² /g, PV0.34
cc/g Polymerization of propylene Propylene was polymerized in the same manner as in Example 1. As a result, Kc2050, Kt103, HI89.5%,
It had an MFR of 4.0 and a bulk density of 0.46 g/cm ³ . Examples 12, 13 The composition shown in Table 5 was prepared in the same manner as in Example 11, except that the compound shown in Table 4 was used in place of the phenyl orthoformate used in preparing the magnesium-containing solid in Example 11. A magnesium-containing solid and a catalyst component having physical properties were prepared, and using the catalyst component, propylene was polymerized in the same manner as in Example 1, and the results are shown in Table 4.

【table】

[Table] Example 14 Preparation of catalyst components 4.6 g of the magnesium-containing solid obtained in Example 1, 120 ml of n-hexane, and 1.7 g of benzoic anhydride were placed in a 300 ml reaction vessel equipped with a reflux condenser under a nitrogen gas atmosphere. g (7.5 mmol, 0.2 g mol per gram atom of magnesium in the magnesium-containing solid) to form a suspension, and after reacting with stirring at 70°C for 2 hours, the solid material was dissolved in n-hexane at 65°C.
Washed three times with 150 ml. Next, add 150ml of titanium tetrachloride and heat at 120℃ for 2 hours.
Time contact treatment. After this, the solid substance was heated to 120℃.
It was washed 10 times with 150 ml each of n-hexane at 65°C, and dried under reduced pressure at 50°C for 1 hour to obtain 4.1g of the catalyst component of the present invention having the following composition (Ti2.5
%). Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 using 75.4 mg of the above catalyst component to obtain 245 g of polypropylene. That is, Kc is 3250 and Kt is 130. or,
HI is 93.5%, MFR is 4.4, bulk density is 0.50
g/ ^cm3 . Example 15 Preparation of catalyst component Magnesium-containing solid obtained in Example 1 10.9
g, n-hexane 130 ml and benzoic acid 3.9 g (31.9
The contact treatment was carried out in the same manner as in Example 14 to obtain a catalyst component (2.9% Ti). Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 using 59.7 mg of the above catalyst component to obtain 137 g of polypropylene. That is, Kc is 2300 and Kt is 79. Also, HI
was 93.5%, MFR was 4.0, and bulk density was 0.48 g/cm ³ . Example 16 Preparation of catalyst component Magnesium-containing solid obtained in Example 1 6.7
g, n-hexane 130 ml and ethyl benzoate 2.8 ml
(19.6 mmol, 0.33 gram mol per gram atom of magnesium in the magnesium-containing solid) was used for catalyst treatment in the same manner as in Example 14 to obtain a catalyst component (3.7% Ti). Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 using 81.6 mg of the above catalyst component to obtain 125 g of polypropylene. That is, Kc is 1530 and Kt is 41. Also, HI
was 92.1%, MFR was 5.5, and bulk density was 0.48 g/cm ³ .

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing the catalyst component of the present invention.

Claims (1)

[Scope of Claims] 1 (1) (a) Metallic magnesium; (b) A halogenated hydrocarbon represented by the general formula RX [However, in the formula, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cyclo Alkyl group; X is a halogen atom. ] and (c) Compound of the general formula X′ _n C(OR′) _4-n (however, in the formula, Group; R′ has 1 carbon number
~20 alkyl, aryl or cycloalkyl groups; m is 0, 1 or 2. ] A magnesium-containing solid obtained by contacting. A catalyst component for α-olefin polymerization formed by contacting (2) a titanium compound and (3) an electron-donating compound. 2 (a) Metallic magnesium, (b) halogenated hydrocarbon represented by the general formula RX, and (c) general formula X′ _n C
Catalyst component according to claim 1, which comprises using a magnesium-containing solid obtained by simultaneously contacting (OR') _4-n compounds. 3. After (a) metallic magnesium and (b) a halogenated hydrocarbon represented by the general formula RX are brought into contact in advance, (c)
Catalyst component according to claim 1, comprising the use of a magnesium-containing solid obtained by contacting with a compound of the general formula X' _n C(OR') _4-n . 4 The compound of general formula X′ _n C(OR′) _4-n is of formula HC
(OR″) ₃ [However, in the formula, R″ is an alkyl group having 1 to 8 carbon atoms. ] Claims 1 to 3 are
Catalyst component according to any of paragraphs.