KR100347077B1 - Organosilicon compound, Ziegler-Natta catalyst containing the same and process for polymerization of olefins - Google Patents

Abstract

The present invention relates to organosilicon compounds of formula (1):

In the above formula,

R ¹ and R ² may be the same or different and each is an alkyl group having 1 to 3 carbon atoms,

R ³ and R ⁴ may be the same or different and each is an alkyl group or halogen atom having 1 to 3 carbon atoms,

m and n are 0 or the integer 1 or 2, respectively.

The organosilicon compounds of the present invention employ olefins as useful electron donor components of Ziegler-Natta catalysts for polymerization.

Description

Organic silicon compound, Ziegler-Natta catalyst containing the same and process for polymerization of olefins}

Prior to the present invention, many specific organosilicon compounds used as electron donors (external cell donors) as components of Ziegler-Natta catalysts or as electron donors (internal electron donors) contained in solid catalyst components of Ziegler-Natta catalysts It has been proposed to be used to prepare polymers with improved steric regularity or to promote catalytic activity in olefin polymerization using catalysts.

Various methods have been proposed in the process for producing organosilicon compounds of this kind. For example, US Pat. No. 4,977,291 discloses that a silicone compound containing an aromatic group as a starting compound is hydrated in the presence of a catalyst, such as a Raney nickel catalyst, to provide a silicone compound having at least one cycloalkyl group. Methods of making are described.

In U.S. Patent No. 4,958.041, a tetraalkoxysilane or a monoorganotrialkoxysilane and a Grignard reagent containing a structural formula [R ¹ MgCl] are reacted to form a general formula [R ¹ R ² Si (OR ³ ). _2] (wherein, R ¹ and R ² represents a C3-C10 alkyl group or cycloalkyl group, respectively, R ³ represents a carbon cows 1-5 alkyl group, R ¹ and R ² is an alkyl group of at least one of branched-chain A method for producing an organosilicon compound is shown.

JP-A-5-255350 describes cycloalkoxysilanes of the general formula (R'O) _x (R ') _y Si (OR) _4-xy which are used as electron donors of Ziegler-Natta catalysts for olefin polymerization. R is independently selected from an alkyl group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms, and R 'is a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and substituted groups thereof. Are independently selected from and x is 1, 2, 3, or 4, and y is 0, 1, or 2. The symbol "JP-A" as used herein denotes a Japanese patent application published without examination. JP-A-5-310757 describes t-butoxycyclopentyldiethoxysilane and a process for preparing the same as a novel silane compound.

On the other hand, examples of the conventional polymerization method using a Ziegler-Natta catalyst containing an organosilicon compound as one component of the catalyst include the methods described in this JP-A-57-63310 and JP-A-57-63311. In this method, a composite of a solid catalyst component (a) consisting of a magnesium compound, a titanium compound and an internal electron donor, an organoaluminum compound (b), and an organosilicon compound (c) having a Si-OC bond as an external electron donor A catalyst comprising is used to polymerize olefins having 3 or more carbon atoms. However, this method has not always been satisfactory for obtaining stereoregular polymers in high yields, so further developments have been required.

On the other hand, JP-A-63-3010 discloses a catalyst system for the polymerization of olefins and an olefin polymerization method using such a catalyst system, and the catalyst system described in the patent application is made of dialkoxy magnesium and aromatic dicarboxylic acid. A solid catalyst component (a), an organoaluminum compound (b), and an organosilicon compound (c) produced by contacting a diester, an aromatic hydrocarbon with a titanium halide and heating the powder product.

JP-A-1-315406 describes a catalyst system for olefin polymerization and an olefin polymerization method using such a catalyst system, wherein the catalyst system contacts titanium tetrachloride with a suspension of diethoxy magnesium in alkylbenzene. , A solid catalyst component (a), an organoaluminum compound (b), and an organosilicon prepared by adding phthalic acid dichlorinate to obtain a solid, and further contacting the resulting solid with titanium tetrachloride in the presence of alkylbenzene. Compound (c).

JP-A-2-84404 discloses a catalyst system for polymerizing olefins and a method for homo- or copolymerization of olefins using such a catalyst system, which is prepared by contacting a magnesium compound with a titanium compound, Solid titanium catalyst components (a), organoaluminum compounds (b), and cyclopentyl groups or derivatives thereof, cyclopentenyl groups or derivatives thereof, or cyclopentadienyl groups or derivatives thereof, which basically contain titanium and halogen It contains the organosilicon compound (c) containing.

Each of the known techniques as described above allows for the purpose of high catalytic activity to omit the removal of residual catalyst components such as chlorine and titanium from the resulting polymer (deashing step), and at the same time, It is possible to enhance the yield of the stereoregular polymer or to improve the persistence of the catalytic activity during the polymerization and to obtain a result of the excellent catalytic activity.

However, in recent years, compared to olefin polymers obtained by using an organoaluminum compound and, if desired, a conventional catalyst system comprising a titanium trichloride type catalyst component with an electron donor compound as a third component, a higher active catalyst component, It has been pointed out that olefin polymers obtained by polymerization using a catalyst system containing an organoaluminum compound and an organosilicon compound have a narrow molecular weight distribution. Polyolefins having a narrow molecular weight distribution have poor applicability due to poor moldability. When conventional catalysts are used to obtain polyolefins with a wide range of molecular weight distributions, on the one hand they generally reduce the yield of sterically very regular polymers with high melting points.

Various methods have been proposed to solve this problem. For example, multi-stage polymerization systems have been described which yield polyolefins with a broad molecular weight distribution. Nevertheless, the multi-stage polymerization system must repeat the minor and complex polymerization process and also involves recovering the chelating agent used for the polymerization, which is therefore poor in labor and cost.

According to a recent method, JP-A-3-7703 discloses two or more solid titanium catalyst components (a), organoaluminum compounds (b), and electron donors which basically contain magnesium, titanium, halogens and electron donors. A process for polymerizing olefins in the presence of a catalyst system comprising an organosilicon compound (c) is described. According to the process described above, polyolefins with a wide range of molecular weight distributions can be produced without the need for labor-intensive multi-stage polymerization operations. However, using two or more organosilicon compounds as electron donors for polymerization is still tedious and complex.

Summary of the Invention

It is an object of the present invention to provide novel organosilicon compounds which are very useful as catalyst components, in particular to provide catalysts for polymerizing olefins such as propylene or ethylene, with such catalysts having particularly high catalytic activity and very high yields. Polymers with a wide range of molecular weight distribution and high crystallinity can be obtained while maintaining stereoregularity.

Another object of the present invention is to provide a Ziegler-Natta catalyst for olefin polymerization comprising an organosilicon compound as an effective electron donor component.

It is another object of the present invention to provide a process for polymerizing olefins to produce polyolefins of high molecular weight distribution and high stereoregularity in high yield.

As a result of extensive research on the catalyst for olefin polymerization in order to solve the problems of the conventional method described above, the present inventors have found that novel organosilicones used as internal and / or external electron donors act as components of the catalyst for olefin polymerization. We have succeeded in developing the compounds and found that the organosilicon compounds are very effective. That is, the above object is achieved with an organosilicon compound of formula (1):

[Formula 1]

In the above formula,

R ¹ and R ² may be the same or different and each is an alkyl group having 1 to 3 carbon atoms,

R ³ and R ⁴ may be the same or different and each is an alkyl group having 1 to 3 carbon atoms or a halogen atom,

m and n are 0 or the integer 1 or 2, respectively.

[Brief Description of Drawings]

1 is a chart showing the results of MS analyzing cyclohexylcyclopentyldimethoxysilane.

2 is a chart showing the results of two-dimensional analysis of ¹ H-NMR / ¹³ C-NMR (COSY spectrum) for analyzing cyclohexylcyclopentyldimethoxysilane.

Fig. 3 is a chart showing the results of IR for analyzing cyclohexylcyclopentyldimethoxysilane.

The present invention relates to an organosilicon compound that can be used as a silane binder or a catalyst component for olefin polymerization, and to a Ziegler-Natta catalyst containing an organosilicon compound as an electron donor effective for the polymerization of olefins. These Ziegler-Natta catalysts yield high yields of olefin polymers with high stereoregularity and broad molecular weight distribution. The invention also relates to a process for polymerizing olefins in the presence of said catalyst.

Examples of alkyl groups of R ¹ and R ² in formula (1) include methyl, ethyl, n-propyl, and isopropyl. Of these, methyl and ethyl are preferred.

The organosilicon compound of the present invention is a cyclohexyl group ( ) Or derivatives thereof and cyclopentyl groups ( ) Or a derivative thereof is an asymmetric organosilicon compound bonded directly to a silicon atom.

Examples of asymmetric organosilicon compounds (ie cyclohexylcyclopentyldialkoxysilanes) include cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldi-n-propoxysilane, and cyclohexylcyclo Pentyldiisopropoxysilanes are included. Among them, cyclohexylcyclopentyldimethoxysilane and cyclohexylcyclopentyldiethoxysilane are preferred compounds for use as electron donors serving as components of the catalyst for olefin polymerization.

Various derivatives of these asymmetric organosilicon compounds are also included within the scope of formula (1). In particular, one or two substituents (R ³ ) such as methyl group, chlorine or bromine at the 3-, 4- or 5-position of the cyclohexyl group, and / or the 2-, 3- or 5-position of the cyclopentyl group Preference is given to organosilicon compounds having one or two substituents (R ⁴ ), such as methyl group, chlorine or bromine at. Two substituents may be at the same position of a cyclohexyl or cyclopentyl group. When m or n in formula (1) is 2, the plurality of substituents (R ³ ) and (R ⁴ ) may be the same or different.

Examples of specific derivatives of asymmetric organosilicon compounds include 3-methylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldipropoxysilane, 4-methylcyclohexyl Cyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldiethoxysilane, 4-methylcyclohexylcyclopentyldipropoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclo Pentyl diethoxysilane, 3,5-methylcyclohexylcyclopentyldipropoxysilane, 3,3-dimethylcyclohexylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexylcyclopentyldimethoxysilane, cyclohexyl-2- Methylcyclopentyldimethoxysilane, cyclohexyl-2-methylcyclopentyldiethoxysilane, cyclohexyl-2-methylcyclopentyldipropoxy Column, 3-methylcyclohexyl-2-methylcyclopentyldimethoxysilane, 3-methylcyclohexyl-2-methylcyclopentyldiethoxysilane, 3-methylcyclohexyl-2-methylcyclopentyldipropoxysilane, 4- Methylcyclohexyl-2-methylcyclopentyldimethoxysilane, 4-methylcyclohexyl-2-methylcyclopentyldiethoxysilane, 4-methylcyclohexyl-2-methylcyclopentyldipropoxysilane, 3,5-dimethyl Cyclohexyl-2-methylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl-2-methylcyclopentyldiethoxysilane, 3,5-dimethylcyclohexyl-2-methylcyclopentyldipropoxysilane, 3,3 -Dimethylcyclohexyl-2-methylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexyl-2-methylcyclopentyldimethoxysilane, cyclohexyl-3-methylcyclopentyldimethoxysilane, cyclohexyl-3-methylcyclo Pentyl diethoxysilane, cyclohexyl-3-methyl Cyclopentyldipropoxysilane, 3-3methylcyclohexyl-3-methylcyclopentyldimethoxysilane, 3-methylcyclohexyl-3-methylcyclopentyldiethoxysilane, 3-methylcyclohexyl-3-methylcyclopentyldipe Lopoxysilane, 4-methylcyclohexyl-3-methylcyclopentyldimethoxysilane, 4-methylcyclohexyl-3-methylcyclopentyldiethoxysilane, 4-methylcyclohexyl-3-methylcyclopentyldipropoxysilane, 3,5-dimethylcyclohexyl-3-methylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl-3-methylcyclopentyldiethoxysilane, 3,5-dimethylcyclohexyl-3-methylcyclopentyldipropoxy Silane, 3,3-dimethylcyclohexyl-3-methylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexyl-3-methylcyclopentyldimethoxysilane, cyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, Cyclohexyl-2,3-dimethylcyclopentyl Ethoxysilane, cyclohexyl-2,3-dimethylcyclopentyldipropoxysilane, 3-methylcyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, 3-methylcyclohexyl-2,3-dimethylcyclopentyldie Methoxysilane, 3-methylcyclohexyl-2,3-dimethylcyclopentyldipropoxysilane, 4-methylcyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, 4-methylcyclohexyl-2,3-dimethylcyclo Pentyl diethoxysilane, 4-methylcyclohexyl-2,3-dimethylcyclopentyldipropoxysilane, 3,5-dimethylcyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl- 2,3-dimethylcyclopentyldiethoxysilane, 3,5-dimethylcyclohexyl-2,3-dimethylcyclopentyldipropoxysilane, 3,3-dimethylcyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexyl-2,3-dimethylcyclopentyldimethoxysilane, cyclohex -2,5-dimethylcyclopentyldimethoxysilane, cyclohexyl-2,5-dimethylcyclopentyldiethoxysilane, cyclohexyl-2,5-dimethylcyclopentyldipropoxysilane, 3-methylcyclohexyl-2,5 -Dimethylcyclopentyldimethoxysilane, 3-methylcyclohexyl-2,5-dimethylcyclopentyldiethoxysilane, 3-methylcyclohexyl-2,5-dimethylcyclopentyldipropoxysilane, 4-methylcyclohexyl-2 , 5-dimethylcyclopentyldimethoxysilane, 4-methylcyclohexyl-2,5-dimethylcyclopentyldiethoxysilane, 4-methylcyclohexyl-2,5-dimethylcyclopentyldipropoxysilane, 3,5-dimethyl Cyclohexyl-2,5-dimethylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl-2,5-dimethylcyclopentyldiethoxysilane, 3,5-dimethylcyclohexyl-2,5-dimethylcyclopentyldiprop Foxysilane, 3,3-dimethylcyclohexyl-2,5-dimethylcyclopentyldimethoxy Column, 4,4-dimethylcyclohexyl-2,5-dimethylcyclopentyldimethoxysilane, cyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, cyclohexyl-2,2-dimethylcyclopentyldiethoxysilane, cyclo Hexyl-2,2-dimethylcyclopentyldipropoxysilane, 3-methylcyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, 3-methylcyclohexyl-2,2-dimethylcyclopentyldiethoxysilane, 3- Methylcyclohexyl-2,2-dimethylcyclopentyldipropoxysilane, 4-methylcyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, 4-methylcyclohexyl-2,2-dimethylcyclopentyldiethoxysilane, 4-methylcyclohexyl-2,2-dimethylcyclopentyldipropoxysilane, 3,5-dimethylcyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl-2,2-dimethyl Cyclopentyl diethoxysilane, 3,5-dimethylcyclohexyl-2,2-dimethylcyclo Tildipropoxysilane, 3,3-dimethylcyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexyl-2,2-dimethylcyclopentyldimethoxysilane, cyclohexyl-3, 3-dimethylcyclopentyldimethoxysilane, cyclohexyl-3,3-dimethylcyclopentyldiethoxysilane, cyclohexyl-3,3-dimethylcyclopentyldipropoxysilane, 3-methylcyclohexyl-3,3-dimethyl Cyclopentyldimethoxysilane, 3-methylcyclohexyl-3,3-dimethylcyclopentyldiethoxysilane, 3-methylcyclohexyl-3,3-dimethylcyclopentyldipropoxysilane, 4-methylcyclohexyl-3,3 -Dimethylcyclopentyldimethoxysilane, 4-methylcyclohexyl-3,3-dimethylcyclopentyldiethoxysilane, 4-methylcyclohexyl-3,3-dimethylcyclopentyldipropoxysilane, 3,5-dimethylcyclohexyl -3,3-dimethylcyclopentyldimethoxysilane, 3,5-dimethylcyclohex -3,3-dimethylcyclopentyldiethoxysilane 3,5-dimethylcyclohexyl-3,3-dimethylcyclopentyldipropoxysilane, 3,3-dimethylcyclohexyl-3,3-dimethylcyclopentyldimethoxysilane, 4,4-dimethylcyclohexyl-3,3-dimethylcyclopentyldimethoxysilane, 3-chlorocyclohexylcyclopentyldimethoxysilane, 4-chlorocyclohexylcyclopentyldimethoxysilane, 3,5-dichlorocyclohexylcyclo Pentyldimethoxysilane, cyclohexyl-2-chlorocyclopentyldimethoxysilane, cyclohexyl-3-cyclopentyldimethoxysilane, cyclohexyl-2,3-dichlorocyclopentyldimethoxysilane, cyclohexyl-2,5-dichloro Cyclopentyldimethoxysilane, 3-chlorocyclohexyl-2-chlorocyclopentyldimethoxysilane, 4-chlorocyclohexyl-3-chlorocyclo pentyldimethoxysilane, and 3,5-dichlorocyclohexyl-2,3-dichloro It is a cycle comprising a cyclopentyl dimethoxysilane.

Preferred of these asymmetric organosilicon compounds are cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3, 5-dimethylcyclohexylcyclopentyldimethoxysilane. These organosilicon compounds can be used individually or in combination of two or more thereof.

The organosilicon compounds of the invention are useful as (internal and / or external) electron donors of various catalysts for olefin polymerization. That is, the organosilicon compound can be used as an electron donor in homo- or copolymerization such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, or vinylcyclohexane. In particular, the organosilicon compound is suitable for use as an electron donor in catalysts for homopolymerization of ethylene or propylene or for copolymerization of ethylene and propylene, the optimal use of which is an electron donor of catalysts for homopolymerization of propylene or copolymerization of propylene and ethylene. It is used as.

Cyclohexylcyclopentyl dialkoxysilanes of the invention can be prepared in a variety of ways. One of the simplest methods is a monocycloalkyltrialkoxysilane (i.e. a monocyclohexyl- or monocyclopentyl-trialkoxysilane) to Grignard reagents (ie Grignard reagents with cyclopentyl or cyclohexyl groups, respectively) It is reacted with to obtain an organosilicon compound.

For example, cyclopentyl chloride (commercially available) is reacted with magnesium in the presence of a solvent, for example ether such as tetrahydrofuran, diethylether, or di-n-butylether, to cyclopentyl chloride Obtain a Nyaar reagent (cyclopentylmagnesium chloride). This reaction can be carried out at a temperature from room temperature to 60 ° C. Cyclopentyl Grignard reagent is then reacted with cyclohexyltrimethoxysilane to obtain cyclohexylcyclopentyldimethoxysilane; This reaction is carried out in the presence of an ether such as tetrahydrofuran, diethyl ether, or di-n-butyl ether as in the reaction described above, or an aliphatic hydrocarbon solvent such as hexane or heptane or an aromatic such as toluene, benzene, or xylene It may be carried out in the presence of a hydrocarbon solvent. The reaction can be carried out at a temperature of 50 ° C. to 200 ° C., preferably at a temperature of 100 ° C. to 200 ° C. or at a temperature of 100 ° C. to 200 ° C. while boiling or refluxing the solvent.

Monocycloalkyltrialkoxysilanes used in the reactions described above, for example cyclohexyltrimethoxysilane, may be commercially available products, but may be prepared by various known methods. In one method, preferred compounds can be prepared by reacting cyclohexyltrichlorosilane with methanol to alkoxylate the silane compound with hydrogen chloride. The cyclohexyltrichlorosilane used for the reaction may be a commercially available product, but can be easily prepared by hydrosilylation of cyclohexane with trichlorosilane (HSiCl ₃ ). Another method of preparing cyclohexyltrimethoxysilane involves hydrogenating a commercial product of phenyltrimethoxysilane in the presence of a catalyst, such as a Raney nickel catalyst.

The resulting cyclohexylcyclopentyldimethoxysilane can be analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR), ultraviolet absorption spectroscopy (IR), mass spectroscopy (MS) and the like. ¹³ C-MNR spectroscopy (in CDCl ₃ ) is a signal at δ = 50.7 due to the carbon atom of the methoxy group, a signal at δ = 24.5, 26.8, 26.9, and 27.8 due to the cyclohexyl group, and cyclopentyl Δ = 22.8, 26.7, and due to the group. Spectrum with signal at 27.4 is shown. IR spectroscopy showed spectra with peaks around 1,100 cm ⁻¹ due to Si-OC bonding.

When used as an electron donor acting as one component of the Ziegler-Natta catalyst for olefin polymerization, the compound of the present invention, i.e., cyclohexylcyclopentyl dialkoxysilane, maintains high performance with respect to catalytic activity and is known as a high performance catalyst. It is possible to obtain polyolefins with a wide range of molecular weight distribution and high crystallinity while obtaining a high-stereoregular polymer without lowering performance than conventional catalysts.

The Ziegler-Natta catalyst of the present invention is not particularly limited as long as the organosilicon compound of formula (1) is contained as an internal or external electron donor, and conventional components for the Ziegler-Natta catalyst can be used together with the organosilicon compound. have. In a preferred embodiment of the invention, the Ziegler-Natta catalyst comprises magnesium, titanium, electron donor compounds, and halogens and is a solid catalyst component (A) prepared by contacting a magnesium compound, a titanium halide compound, and an internal electron donor compound (A ), An organoaluminum compound (B), and an organosilicon compound (C) of the chemical chamber (1) as an external electron donor.

Magnesium compounds that can be used to prepare the solid catalyst component (A) include metallic magnesium, magnesium dihalide, dialkylmagnesium, alkylmagnesium halides, dialkoxymagnesium, diaryloxymagnesium, and alkoxymagnesium halides. Alkyl or alkoxy moieties of the magnesium compounds described above generally have 1 to 6 carbon atoms and preferably have 1 to 4 carbon atoms.

Specific examples of magnesium halides are magnesium dichloride, magnesium dibromide, magnesium diiodide, and magnesium difluoride.

Specific examples of dialkyl magnesium include dimethyl magnesium, diethyl magnesium, ethyl methyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, butyl methyl magnesium, and butyl ethyl magnesium. These dialkyl magnesiums can be obtained by reacting metallic magnesium with halogenated hydrocarbons or alcohols.

Specific examples of alkylmagnesium halides include ethylmagnesium chloride, propylmagnesium chloride, and butylmagnesium chloride. These alkylmagnesium halides can be obtained by reacting metallic magnesium with halogenated hydrocarbons or alcohols.

Specific examples of dialkoxy magnesium and diaryloxymagnesium include dimethoxymagnesium, diethoxy magnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium and butoxyethoxy Magnesium is included.

Specific examples of alkoxymagnesium halides are methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, and butoxymagnesium chloride.

Preferred compounds among these magnesium compounds are dialkoxymagnesium, and diethoxymagnesium and dipropoxymagnesium are particularly preferable. Magnesium compounds can be used independently or in combination of two or more.

Preferred dialkoxymagnesiums which can be used are one or more dialkoxymagnesium species having 1 to 3 carbon atoms in the alkoxy moiety, which are granular or powdered, and their particles may be irregular or spherical. In case of using spherical particles of diethoxy magnesium, the resulting powder polymer may be of better particle shape and may be produced with a narrower particle size distribution. As a result, the resulting polymer powder has improved processing characteristics, and the difficulty caused by the fine particles can be eliminated.

As referenced above, the spherical diethoxy magnesium particles need not be substantially spherical, ellipsoidal or ellipse-like particles may also be used. The term "spherical" described above may be defined as the ratio (L / w) of the major axis diameter (L) to the minor axis diameter (w) of 3 or less, preferably 1 to 2, more preferably 1 to 1.5.

The dialkoxy magnesium used has an average particle size of 1 to 200 mu m, more preferably 5 to 150 mu m.

In the case of spherical diethoxy magnesium, the average particle size is 1 to 100 mu m, preferably 5 to 50 mu m, and more preferably 10 to 400 mu m. Preference is given to using particles having a narrow size distribution together with a small amount of fine or coarse particles. More particularly, coarse particles containing less than 20%, preferably less than 10%, containing less than 5 μm of fine particles Preference is given to using particles containing 10% or less, preferably 5% or less. However, the particle size distribution corresponds to ln (D ₉₀ / D ₁₀ ) of 3 or less, preferably 2 or less. Here, D ₉₀ and D ₁₀ each represent a cumulative 90% diameter and a cumulative 10% diameter of the cumulative particle size distribution shown from the smaller diameter side.

The dialkoxy magnesiums mentioned above are not always required as starting materials for the preparation of the solid catalyst component (A). For example, the dialkoxy magnesium described above can be prepared in situ from metallic magnesium and alcohol in the presence of a catalyst, for example iodine, in the preparation of a solid catalyst component (A).

The titanium halide compound that can be used to prepare the solid catalyst component (A) is of the general formula Ti (OR ⁵ ) _n X _4-n (wherein R ⁵ is an alkyl group having 1 to 4 carbon atoms, X is a chlorine atom, bromine An atom or an iodine atom, n is one or more titanium halides and alkoxytitanium halides represented by zero or an integer of 1, 2, or 3).

Specific examples of titanium halides include titanium tetrahalides such as TiCl ₄ , TIBr ₄ and TiI ₄ . Specific examples of alkoxytitanium halides include Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃ H ₇ ) Cl ₃ , Ti (On-C4H ₉ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₃ Cl, and Ti (On-C ₄ H ₉ ) ₃ Cl. Preferred titanium halide compounds are titanium tetrahalides, with TiCl ₄ being particularly preferred. Titanium halide compounds can be used independently or in combination of two or more.

Electron donor compounds that can be used to prepare the solid catalyst component (A) are organic compounds containing oxygen or nitrogen. Such compounds include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing Si-O-C bonds.

Specific examples of the electron donor compound include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexyl alcohol, and dodecanol; Phenols such as phenol and cresol; Ethers such as dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, and diphenyl ether; Methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl Monocarboxylic acid esters such as benzoate, phenyl benzoate, methyl p-toluylate, ethyl p-toluylate, methyl aniseate, and ethyl aniseate; Diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate Dicarboxylic acid esters such as dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate; Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, and benzophenone; Acid halides such as phthalic acid dichloride and terephthalic acid dichloride; Aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, and benzaldehyde; Amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine; Amides such as acetamide and acylamide; Nitriles such as acetonitrile, benzonitrile, and tolunitrile; And isocyanates such as phenyl isocyanate and n-butyl isocyanate.

Specific examples of organosilicon compounds containing Si-OC bonds include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, and tri-n-butylmethoxysilane , Tri-isobutylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di -t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyl Dimethoxysilane, dicyclohexyl diethoxysilane, dicyclopentyldimethoxysilane, disa Clopentyl diethoxysilane, cyclohexyl methyl dimethoxy silane, cyclohexyl methyl diethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl isopropyl dimethoxy silane, cyclohexyl ether diethoxysilane, cyclopentyl ethyl dimethoxy silane, cyclo Pentylethyldiethoxysilane, cyclopentylisopropyldimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclopentylisobutyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane , Phenylmethyl diethoxy silane, phenyl ethyl dimethoxy silane, phenyl ethyl diethoxy silane, cyclohexyl dimethyl methoxy silane, cyclohexyl dimethyl ethoxy silane, cyclohexyl diethyl methoxy silane, cyclohexyl diethyl ethoxy silane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, cyclo Pentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, Cyclohexyl (n-prefill) diethoxysilane, cyclohexyl (n-butyl) diethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltri Methoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n -Butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethyl Hexyltrime Sisilran, 2-ethyl hexyl tree in the silane, phenyl trimethoxy silane, phenyltrimethoxysilane, and a silane.

Among these, the preferred electron donor compound is an ester, and phthalic acid diester is more preferable. The ester residue in the phthalic acid diester is a straight or branched chain alkyl group having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples of suitable phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propylphthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethylmethyl phthalate, methylisopropyl phthalate, ethyl- n-propyl phthalate, ethyl-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate , Bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butylisohexyl phthalate, n-butylisooctyl phthalate, n-pentyl Hexyl phthalate, n-pentylisohexyl phthalate, isopentylheptyl phthalate, n-pentylisooctyl phthalate, n-pentylisononyl phthalate, isopentyl-n-decyl phthalate Nitrate, n-pentyl undecyl phthalate, isopentylisohexyl phthalate, n-hexylisooctyl phthalate, n-hexylisononyl phthalate, n-hexyl-n-decyl phthalate, n-heptylisooctyl phthalate Sononyl phthalate, n-heptyl neodecyl phthalate, and isooctylisononyl phthalate. These phthalic acid esters can be used independently or in combination of two or more. Preferred mixtures of phthalic acid esters include diethyl phthalate and bis (2-ethylhexyl) phthalate; Di-n-butyl phthalate and bis (2-ethylhexyl) phthalate; Diisobutyl and bis (2-ethylhexyl) phthalate; And diethyl phthalate, bis (2-ethylhexyl) phthalate and di-n-butyl phthalate.

The solid catalyst component (A) can be prepared by contacting the above-described magnesium compound, titanium halide compound and electron donor compound with a method appropriately selected from conventional methods. Known methods for producing the solid catalyst component (A) include, for example, JP-A-63-308004, JP-A-63-314211, JP-A-64-6006, JP-A-64 -14210, JP-A-64-43506, JP-A-63-3010, and JP-A-62-158704.

A typical method of preparing the solid catalyst component (A) is described below.

(1) Magnesium softened is dissolved in tetraalkoxy titanium, and the solution is contacted with polysiloxane to obtain a solid component. The solid component is reacted with silicon tetrachloride, contacted with phthalic acid dichloride, and reacted with titanium tetrachloride to obtain a solid catalyst component (A). The resulting solid catalyst component is pretreated with an organoaluminum compound, an organosilicon compound and an olefin.

(2) Anhydrous magnesium chloride and 2-ethylhexyl alcohol are reacted to form a homogeneous solution and brought into contact with phthalic anhydride. The resulting solution is contacted with a diester of titanium tetrachloride and phthalic acid to obtain a solid component. The product is further reacted with titanium tetrachloride to produce solid catalyst component (A).

(3) Metallic magnesium, butyl chloride, and butyl ether are reacted to synthesize an organomagnesium compound. The organic magnesium compound is contacted with tetrabutoxytitanium and tetraethoxysilane to obtain a solid, followed by contact with a diester of phthalic acid (e.g., an alkyl ester having 1 to 10 carbon atoms), dibutyl ether, and titanium tetrachloride. The catalyst component (A) is prepared. The resulting solid catalyst component may be pretreated with an organoaluminum compound, an organosilicon compound and an olefin.

(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound is contacted with an alcohol such as butane or 2-ethylhexyl alcohol in the presence of a hydrocarbon solvent to obtain a homogeneous solution. The resulting solution is contacted with a silicon compound such as SiCl ₄ , HSiCl ₃ or polysiloxane to obtain a solid portion. The solid component is contacted with titanium tetrachloride and phthalic acid diester in the presence of an aromatic hydrocarbon solvent, and the reaction mixture is further contacted with titanium tetrachloride to obtain a solid catalyst component (A).

(5) Magnesium chloride, tetraalkoxytitanium, and aliphatic alcohols are contacted in the presence of an aliphatic hydrocarbon to form a uniform solution. Titanium tetrachloride is added to the solution, and the mixture is heated to precipitate a solid component. The solid component is contacted with a diester of phthalic acid and further reacted with titanium tetrachloride to prepare a solid catalyst component (A).

(6) Metallic magnesium powder, alkyl monohalide and iodine are contacted. The resulting reactants, tetraalkoxytitanium, acid halides, and aliphatic alcohols are contacted in the presence of aliphatic hydrocarbons to form a uniform solution. Titanium tetrachloride is added to the solution, and the mixture is heated to precipitate a solid component. The solid component is contacted with a diester of phthalic acid and further reacted with titanium tetrachloride to prepare a solid catalyst component (A).

(7) The diethoxy magnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent and the resulting suspension is contacted with titanium tetrachloride. The mixture is heated and then contacted with a diester of phthalic acid (eg, an alkyl ester having 1 to 10 carbon atoms) to obtain a solid component. The solid component is washed with alkylbenzene and then contacted with titanium tetrachloride in the presence of alkylbenzene to obtain a solid catalyst component (A). The resulting solid catalyst component can be heat treated in the presence of a hydrocarbon solvent.

(8) Dietary magnesium is suspended in alkylbenzene, and the resulting suspension is contacted with titanium tetrachloride and phthalic acid chloride to obtain a solid component. The solid component is washed with alkylbenzene and contacted again with titanium tetrachloride in the presence of alkylbenzene to obtain a solid catalyst component (A). The resulting solid catalyst component may be contacted with the titanium tetrachloride more than once more.

(9) Co-milling the silicon compound represented by diethoxy magnesium, calcium chloride, and Si (OR ⁶ ) ₄ , wherein R ⁶ is an alkyl group or an aryl group, suspends the resulting pulverized product in an aromatic hydrocarbon. The suspension is contacted with diesters of titanium tetrachloride and phthalic acid (eg, alkyl esters having 1 to 10 carbon atoms) and the product is further contacted with titanium tetrachloride to prepare a solid catalyst component (A).

(10) The diesters of diethoxy magnesium and phthalic acid are suspended in alkylbenzene, and the suspension is added to titanium tetrachloride to obtain a solid component. The solid component is washed with alkylbenzene and further contacted with titanium tetrachloride in the presence of alkylbenzene to obtain a solid catalyst component (A).

(11) Calcium halides and aliphatic magnesium, such as magnesium stearate, are contacted with diesters of titanium tetrachloride and phthalic acid (e.g. alkyl esters having 1 to 10 carbon atoms) and the product is further contacted with titanium tetrachloride to give a solid catalyst Component (A) is prepared.

(12) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent and the resulting suspension is contacted with titanium tetrachloride. The mixture is heated and then reacted by contact with a diester of phthalic acid (e.g., alkyl ester having 1 to 10 carbon atoms). The resulting solids are washed with alkylbenzene and then contacted with titanium tetrachloride in the presence of alkylbenzene. To obtain a solid catalyst component (A). At any stage of the process described above, the system can be contacted with aluminum chloride.

(13) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent and the resulting suspension is contacted with titanium tetrachloride. The mixture is heated and then contacted with diesters of two or more phthalic acids having different carbon numbers of alkyl residues (eg diethyl phthalate and bis (2-ethylhexyl) phthalate) to obtain a solid component. The resulting solid component is washed with alkylbenzene and contacted with titanium tetrachloride in the presence of alkylbenzene to obtain a solid catalyst component (A). In the above production step, when the solid component is contacted with titanium tetrachloride, it may be contacted again with at least two phthalic acid diesters having different carbon atoms in the alkyl residue. In addition, diesters of phthalic acid can be used with the electron donor compounds listed above that are not diesters of phthalic acid.

(14) Diesters of diethoxy magnesium, titanium tetrachloride, and phthalic acid are contacted in the presence of chlorbenzene, and then the reaction is contacted with titanium tetrachloride and phthalic acid dichloride. The product is further contacted with titanium tetrachloride to produce a solid catalyst component (A). The solid catalyst component produced may be further contacted with titanium tetrachloride. In addition, at any stage of the manufacturing method described above, the silicon compound may be contacted with the manufacturing system.

(15) Diethoxymagnesium, 2-ethylhexyl alcohol, and carbon dioxide are contacted in the presence of toluene to form a uniform solution. The solution is contacted with a diester of titanium tetrachloride and phthalic acid to obtain a solid component. The solid component is dissolved in tetrahydrofuran and the solid component is precipitated. The resulting solid line is contacted with titanium tetrachloride to produce a solid catalyst component. If desired, contact with titanium tetrachloride can be repeated. At any stage of the production process, a silicon compound, such as tetrabutoxysilane, may be contacted with the production system.

The amount of magnesium compound, titanium halide compound and pendulum donor compound used to prepare the solid catalyst component (A) varies depending on the preparation method, and generally cannot be specified. For example, the titanium halide compound is used in an amount of 0.5 to 100 mo1, preferably 1 to 10 mo1 per mol of the magnesium compound, and the electron donor compound is used in an amount of 0.01 to 3 mol, preferably 0.02 to 1 mol. The titanium content in the solid catalyst component (A) is not particularly limited and is generally 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the solid catalyst component (A).

The organoaluminum compound (B) which can be used in the present invention is of the general formula R ⁷ _y AlY _3-y , wherein R ⁷ is an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, chlorine, bromine, and iodine atoms, y is an integer of 1, 2, or 3).

Specific examples of the organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride. These organoaluminum compounds can be used independently or in combination of two or more. Preferred of these are triethylaluminum and triisobutylaluminum.

The organosilicon compound (C) preferably used in the present invention includes a compound of the general formula (1).

When certain organosilicon compounds (C) are used in combination with the solid catalyst component (A) and the organoaluminum compound (B), olefin polymers with remarkably high stereoregularity and broad molecular weight distribution can be obtained compared with conventional catalysts. It can be produced in high yield.

In the present invention, the olefin is homo- or copolymerized in the presence of a Ziegler-Natta catalyst comprising a solid catalyst component (A), an organoaluminum compound (B), and an organosilicon compound (C). The ratio of component (A), (B), and (C) used is not specifically limited unless the effect of this invention is reduced. In general, the organoaluminum compound (B) is used in an amount of 1 to 500 mo1, preferably 5 to 400 mo1 per mol of the titanium atom in the solid catalyst component (A), and the organosilicon compound (C) is an organoaluminum compound ( It is used in an amount of 0.0020 to 2 mol, preferably 0.0025 to 0.5 mol per mol of B).

Ziegler-Natta catalysts of the present invention can be prepared by contacting components (A), (B) and (C) described above. There is no particular limitation on the contact order of components (A), (B), and (C). In general, component (B) is contacted with component (C) and then contacted with component (A), or component (B) is contacted with component (A) and then with component (C).

Preferred mixing of components (A), (B) and (C) are shown in Table 1 below.

The polymerization reaction according to the invention can be carried out in the presence or absence of an organic solvent. The olefin monomer used for the polymerization may be gaseous or liquid. The polymerization is carried out under a pressure of 10 MPa or less, preferably 5 MPa or less at a temperature of 200 ° C or less, preferably 100 ° C or less. The reaction can be carried out in a continuous system or in a batch system and can be carried out in one or two or more steps.

Homo- or copolymerized olefins according to the invention are not particularly limited and generally have 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane Olefins. These olefins can be used independently or in combination of two or more. The effect of the present invention, which results in high steric regularity, broad molecular weight distribution, and high yield, can be explained by homopolymerization of polyethylene or copolymerization of propylene and ethylene.

In order to improve the catalytic activity and steric regularity and the particle properties of the resulting polymer, it is preferable to carry out pre-polymerization substantially before the polymerization. Pre-polymerized monomers include ethylene and propylene as well as other monomers such as styrene and vinylcyclohexane.

The catalyst of the present invention is used in an amount of about 0.005 to 0.5 mmol, preferably about 0.01 to 0.5 mmol, in terms of titanium atoms in the solid catalyst component per liter in the polymerization reaction.

According to the present invention, the resulting olefin polymer has a broader molecular weight distribution than those produced by conventional methods at least one largely in the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) of the olefin polymer, and is stericly regular. The yield of the polymer is also extremely high. That is, the method of the present invention not only has a wide range of molecular weight distributions (e.g., Mw / Mn is 6 or more) but also has high stereoregularity with extremely high yield.

The invention is described in more detail with reference to the examples in comparison with the comparison below. However, it should be understood that the present invention is not limited to these examples. All percentages are weight percentages unless otherwise specified.

Example 1

Preparation of Cyclohexylcyclopentyldimethoxysilane:

18.5 g (0.76 mo1) of magnesium shavings were placed in a two-neck flask equipped with a stirrer, thermometer, Dimroth condenser, and dropping funnel. Magnesium was dried under an argon stream and 20 ml of di-n-butyl ether were added. The reaction was cooled to room temperature and a small amount of 1,2-dibromoethane was added to activate magnesium. A solution prepared by dissolving 79.6 g (0.76 mol) of cyclophenyl chloride in 600 ml of di-n-butyl ether. Was added dropwise over 3.5 hours. At this time, the temperature rose to 50 ° C. Then 143.0 g (0.07 mol) of cyclohexyltrimethoxysilane were added at room temperature and the reaction was refluxed for 1 hour.

After the reaction was completed, 372 g (0.38 mo1) of 10% sulfuric acid aqueous solution, which had cooled the reaction mixture to room temperature, was added dropwise at a temperature below 40 ° C. The organic layer was washed with 300 ml of 1% aqueous sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate. The reagent was dried, filtered and vacuum distilled to yield 143.6 g of a fraction having a boiling point of 78 ° C. at 0.2 Torr. Yield 84,6%. The reaction was identified as cyclohexylcyclopentyldimethoxysilane by two-dimensional analysis of MS, ¹ H-NMR / ¹³ C-NMR, and IR. The results of MS, ¹ H-NMR / ¹³ C-NMR (COSY spectrum), and IR are shown in FIGS. 1, 2, and 3, respectively.

Analysis by MS, ¹ H-NMR / ¹³ C-NMR, and IR was performed under the following conditions.

MS: Device ... Finigan Mat (GC-MS)

¹ H-NMR / ¹³ C-NMR: Apparatus ... JEOL GSX270, Solvent ... CDC1 ₃ .

IR: device ... Perkin Elmer 1600 Series (FT-IR), KBr sand method.

Example 2

Preparation of solid catalyst component (A-1):

A 200 ml round flask equipped with a stirrer thoroughly washed with nitrogen was charged with 10 g of diethoxy magnesium and 80 ml of toluene to prepare a suspension. 20 ml of titanium tetrachloride was added to the suspension, 1.0 ml of diethyl phthalate was added when the mixture reached 62 ° C, and the temperature was increased again. 3.5 ml of dibutyl phthalate was added when the temperature reached 110 ° C. It was set as. Then, the reaction was stirred for 1.5 hours while maintaining the temperature of 112 ℃. After completion of the reaction, the mixture was washed twice with 90 ml of 100 ml toluene, and 20 ml of carbon tetrachloride and 80 ml of toluene were added. The mixture was heated to 100 ° C. and reacted for 2 hours with stirring. After the reaction was completed, the reaction mixture was washed 10 times with 40 ml of 100 ml n-heptane to obtain a solid catalyst component (A-1). As a result of measuring the titanium content in this solid catalyst component (A-1), it was 2.46 weight%,

Preparation and polymerization of catalyst systems:

The prepared solid catalyst of 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylcyclopentyldimethoxysilane, and 0.0066 mmol of titanium atom in a 2.0 liter-volume autoclave equipped with a stirrer and cleaned with nitrogen gas. Component (A-1) was charged to form a catalyst system for polymerization. Subsequently, 1.8 L of hydrogen gas and 1.4 L of liquefied propylene were charged to a pressure vessel and polymerized at 70 DEG C for 30 minutes. The properties of the resulting polymers are shown in Table 2. In Table 2, n-heptane-insoluble content, polymerization activity, total yield of crystalline polymer, and molecular weight distribution were obtained as follows.

n-heptane-insoluble content:

N-heptane was boiled for 6 hours to quantify the resulting polymer ((a) g) and insoluble polymer ((b) g).

Polymerization activity:

(a) / weight of solid catalyst component (g)

Yield of total crystalline polymer:

((b) / (a)) × 100 (%)

Molecular Weight Distribution:

Mw / Mn

Mw: weight average molecular weight

Mn: number average molecular weight

Example 3

Preparation of solid catalyst component (A-2):

A 200 ml-volume round flask thoroughly washed with nitrogen and equipped with a stirrer was charged with 20 ml of titanium tetrachloride and 30 ml of toluene to prepare a mixed solution. To this mixed solution, 10 g of spherical diethoxy magnesium particles (length / width-1,1 / 1; average particle size 30 μm; In (D ₉₀ / D ₁₀ ) = 1.23), 50 ml of toluene, and 3.6 ml of di A suspension of n-butyl phthalate was added and the mixture was heated to 90 ° C. and reacted for 1 hour with stirring. After the reaction was completed, the reaction mixture was washed twice with 90 ml of 100 ml toluene and 20 ml of titanium tetrachloride and 80 ml of toluene were added, the mixture was heated to 110 캜 and reacted for 2 hours with stirring. After the reaction was completed, the reaction mixture was washed 10 times with 40 ml of 100 ml n-heptane to obtain a solid catalyst component (A-2). The solid of solid catalyst component (A-2) separated by solid-liquid separation was found to contain 2.87% titanium.

Preparation and Polymerization of Catalytic Systems:

Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component (A-2) was used. The reaction results are shown in Table 2.

Example 4

Preparation of solid catalyst component (A-3):

A suspension was prepared by filling a 200 ml-volume round flask thoroughly washed with nitrogen and equipped with a stirrer with 10 g of diethoxy magnesium and 80 ml of toluene. 20 ml of titanium tetrachloride was added to this suspension, and the mixture was heated to 60 ° C to add 1.0 ml of diethyl phthalate. The mixture was heated to 110 ° C. and 2.5 ml of di-iso-octyl phthalate was added. The mixture was heated to 112 ° C. and reacted for 1.5 hours with stirring. After the reaction was completed, the reaction mixture was washed twice with 90 ml of 100 ml toluene and 20 ml of titanium tetrachloride and 80 ml of toluene were added. The mixture was heated to 100 ° C. and reacted at 100 ° C. for 2 hours with stirring. After the reaction was completed, the reaction mixture was washed 10 times with 100 ml n-heptane at 40 ° C. to obtain a solid catalyst component (A-3). The solid of solid catalyst component (A-3) separated by solid-liquid separation was found to contain 2.74% titanium.

Preparation and Polymerization of Catalytic Systems:

Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component (A-3) was used. The reaction results are shown in Table 2.

Example 5

Preparation of the catalyst component (A-4) of the tongue:

A suspension was prepared by filling a 200 ml-volume round flask thoroughly washed with nitrogen and equipped with a stirrer with 10 g of diethoxy magnesium and 80 ml of toluene. 20 ml of titanium tetrachloride was added to this suspension, and the mixture was heated to 62 DEG C and 1.0 ml of diethyl phthalate was added. The mixture was heated to 110 ° C. and 4.0 ml of di-iso-octyl phthalate was added. The mixture was heated to 112 ° C. and reacted for 1.5 hours with stirring. After the reaction was completed, the reaction mixture was washed twice with 90 ml of 100 ml toluene and 20 ml of titanium tetrachloride and 80 ml of toluene were added. The mixture was heated to 100 ° C. and reacted at 100 ° C. for 2 hours with stirring. After the reaction was completed, the reaction mixture was washed 10 times with 40 ml of 100 ml n-heptane to obtain a solid catalyst component (A-4). The solids of the solid catalyst component (A-4) separated by the solid-liquid separation method were found to contain 2.17% of titanium.

Preparation and Polymerization of Catalytic Systems:

Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component (A-4) was used. The reaction results are shown in Table 2.

Comparative Example 1

Propylene was polymerized in the same manner as in Example 2 except for replacing cyclohexylcyclopentyldimethoxysilane with phenyltriethoxysilane. The reaction results are shown in Table 2.

Comparative Example 2

Propylene was polymerized in the same manner as in Example 2 except for replacing cyclohexylcyclopentyldimethoxysilane with cyclohexylmethyldimethoxysilane. The reaction results are shown in Table 2.

Comparative Example 3

Propylene was polymerized in the same manner as in Example 2 except for replacing cyclohexylcyclopentyldimethoxysilane with dicyclopentyldimethoxysilane. The reaction results are shown in Table 2.

Example 6

Preparation of solid catalyst component (A-5):

A 200 ml-volume round flask thoroughly washed with nitrogen and equipped with a stirrer was charged with 7.14 g of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml of 2-ethylhexyl alcohol, and the resulting mixture was stirred at 130 ° C. for 2 hours. Heated to obtain a uniform solution. Subsequently, 1.67 g of phthalic anhydride was added, followed by stirring at 130 ° C. for 1 hour. The resulting uniform solution was cooled to room temperature and 200 ml of titanium tetrachloride cooled to −20 ° C. was added dropwise over 1 hour. After the reaction was completed, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, 5.03 ml of diisobutyl terephthalate was added, and the resulting solution was then stirred for 2 hours to continue reaction at 110 ° C. . The hot reaction mixture was filtered to give a solid which was then dispersed in 275 ml of titanium tetrachloride and allowed to stand at 110 ° C. for 2 hours. Thereafter, the solid was separated from the hot dispersion by filtration, and the solid was washed with decane and heptane at 110 ° C. to obtain a solid catalyst component (A-5). The solids of the solid catalyst component (A-5) separated by the solid-liquid separation method were found to contain 2.06% of titanium.

Preparation and Polymerization of Catalytic Systems:

Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component (A-5) was used. The reaction results are shown in Table 2.

Example 7

Preparation of solid catalyst component (A-6):

A 250 ml-volume round flask thoroughly washed with nitrogen and equipped with a stirrer was charged with a solution of 1.4 ml of titanium tetrachloride dissolved in 74 ml of chlorobenzene, followed by 3.6 ml of diisobutyl phthalate and 11.8 g of diethoxy magnesium Was added. To the resulting solution was added a solution of 94 ml titanium tetrachloride dissolved in 24 ml chlorobenzene. Addition and dissolution of these compounds were carried out at 20-25 ° C. The resulting mixture was heated at 110 ° C. for 1 hour with stirring and then filtered hot. The resulting solid was added to a solution of 94 ml titanium tetrachloride dissolved in 24 ml chlorobenzene to form a slurry at room temperature. The solution obtained by dissolving 0.9 g of phthaloyl dichloride in 74 ml of chlorobenzene was then added to the slurry at room temperature and then heated to 110 ° C. with stirring for 30 minutes. The resulting mixture was filtered while hot to give a solid.

A solution of 94 ml titanium tetrachloride dissolved in 24 ml chlorobenzene was added to the solid prepared above at room temperature to form a slurry. 74 ml of chlorobenzene was further added to the slurry at room temperature, and then heated at 110 ° C. for 30 minutes with stirring. The resulting mixture was filtered while hot to give a solid. The solids were obtained by repeating the above process using the resulting solids. The resulting solid was then washed 10 times with 100 ml heptane at 25 ° C. Thus, solid catalyst component (A-6) was obtained. The solids of the solid catalyst component (A-6) separated by the solid-liquid separation method were found to contain 2.63% titanium.

Preparation and Polymerization of Catalytic Systems:

Propylene was polymerized in the same manner as in Example 2 except that the solid catalyst component (A-6) was used. The reaction results are shown in Table 2.

Comparative Example 4

Propylene was polymerized in the same manner as in Example 6 except that cyclohexylcyclopentyldimethoxysilane was replaced with cyclohexylmethyldimethoxysilane. The reaction results are shown in Table 2.

Comparative Example 5

Propylene was polymerized in the same manner as in Example 7, except that cyclohexylcyclopentyldimethoxysilane was replaced with cyclohexylmethyldimethoxysilane. The reaction results are shown in Table 2.

Example 8

Preparation of solid catalyst components:

A 200-ml round bottom flask equipped with an agitator completely replaced with nitrogen gas was charged with 10 g of diethoxy magnesium and 80 ml of toluene. The charge was stirred to give a suspension. 20 ml of titanium tetrachloride was added to this suspension. The mixture was heated and when its temperature reached 62 ° C., 1.0 ml of diethyl phthalate was added. This mixture was then heated and when its temperature reached 110 ° C., 3.4 ml of dioctyl phthalate was added. The resulting mixture was heated to 112 ° C. and stirred at that temperature for 1.5 hours to proceed with reaction. After the reaction was completed, the reaction was washed twice with 100 ml of toluene heated at 90 ° C. To the washed reaction was added 20 ml of titanium tetrachloride and 80 ml of toluene. The mixture was heated to 100 ° C. and stirred for 2 hours to proceed with the reaction. After the reaction was completed, the reaction was washed 10 times with 100 ml of n-heptane warmed at 40 ° C. to obtain a solid catalyst component. The titanium content of the solid catalyst component was measured and found to be 2.46% by weight titanium.

Preparation of Polymerization Catalyst and Polymerization of Olefin:

A 2.0 liter pressure vessel equipped with a stirrer sufficiently filled with nitrogen gas inside was charged with 1.66 mmol of triethylaluminum, 0.13 mmol of cyclohexylcyclopentyldimethoxysilane, and a solid catalyst component of 0.0066 mmol in terms of titanium atoms. I was. Thus, a catalyst for polymerization was formed. Thereafter, 1.8 L of sucrose and 1.4 L of liquid propylene were charged to carry out the polymerization at 70 DEG C for 30 minutes. The yield of the whole crystalline polymer was 98.3%, and the melting point of the obtained polymer was 164.0 ° C. The reaction results are shown in Table 2.

As described above, when used as an electron donor serving as a component of the catalyst for olefin polymerization, the organosilicon compound of the present invention typically maintains the same or higher catalytic activity as known high-performance catalysts and has high steric dimensionality. While obtaining a regular polymer, polyolefins with a wide range of molecular weight distribution and high crystallinity are produced. Thus, the organosilicon compound enables the production of low cost polyolefins for general use with excellent rigidity and moldability. In addition, the organosilicon compound of the present invention may be useful as, for example, a silane binder, a resin modifier, or the like.

Further, the Ziegler-Natta catalyst for olefin polymerization according to the present invention is asymmetric organic containing a specific solid catalyst component (A), an organoaluminum compound (B), and a cyclohexyl group or derivative thereof and a cyclopentyl group or derivative thereof. Silicone compound (C) is included. Polymerization of olefins in the presence of the catalyst of the present invention yields olefin polymers with high stereoregularity and broad molecular weight distribution in high yield.

Although the present invention has been described in detail with reference to specific embodiments, those skilled in the art will recognize that the present invention may be variously changed and modified within the spirit and scope of the present invention.

Claims (12)

Organosilicon Compounds of Formula (1) In the above formula, R ¹ and R ² may be the same or different and each is an alkyl group having 1 to 3 carbon atoms, R ³ and R ⁴ may be the same or different and each is an alkyl group or halogen atom having 1 to 3 carbon atoms, m and n are 0 or the integer 1 or 2, respectively. The method of claim 1, wherein the organosilicon compound is cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldi-n-propoxysilane, or cyclohexylcyclopentyldiisopropoxysilane An organosilicon compound characterized by the above-mentioned. As a Ziegler-Natta catalyst for olefin polymerization, (A) a solid catalyst component containing magnesium, titanium, an electron donor compound and a halogen as essential components prepared by contacting a magnesium compound, a titanium halide compound, and an electron donor compound; (B) an organoaluminum compound; And (C) an organosilicon compound represented by the following general formula (1) as an electron donor; Ziegler-Natta catalyst for olefin polymerization, comprising: [Formula 1] In the above formula, R1 and R2 may be the same as or different from each other, and each is an alkyl group having 1 to 3 carbon atoms, R3 and R4 may be the same or different from each other and are each an alkyl group having 1 to 3 carbon atoms or a halogen atom, m and n are 0 or the integer 1 or 2, respectively. 4. The Ziegler-Natta catalyst for olefin polymerization according to claim 3, wherein the magnesium compound used to prepare the solid catalyst component (A) is dialkoxy magnesium. 4. The Ziegler-Natta catalyst for olefin polymerization according to claim 3, wherein the magnesium compound used to prepare the solid catalyst component (A) is diethoxy magnesium. 4. The Ziegler-Natta catalyst for olefin polymerization according to claim 3, wherein the magnesium compound used to prepare the solid catalyst component (A) is diethoxy magnesium in the form of spherical particles. 4. The titanium halide compound according to claim 3, wherein the titanium halide compound used to prepare the solid catalyst component (A) is of the general formula Ti (OR ⁵ ) _n X _4-n , wherein R ⁵ is an alkyl group having 1 to 4 carbon atoms, Is a chlorine, bromine, or iodine atom, and n is 0, or an integer of 1, 2 or 3), a Ziegler-Natta catalyst for olefin polymerization, characterized in that the titanium halide or alkoxytitanium halide. 4. The Ziegler-Natta catalyst for olefin polymerization according to claim 3, wherein the electron donor compound used to prepare the solid side-solving component (A) is a diester of phthalic acid whose ester moiety is an alkyl group having 1 to 10 carbon atoms. The organoaluminum compound (B) according to claim 3, wherein the organoaluminum compound (B) is of the general formula R ⁷ _y AlY _3-y , wherein R ⁷ is an alkyl group having 1 to 4 carbon atoms, Y is hydrogen, chlorine, bromine or iodine atom, y Is an integer 1, 2 or 3) Ziegler-Natta catalyst for olefin polymerization. The organosilicon compound (C) according to claim 3, wherein the organosilicon compound (C) is cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane And 3,5-dimethylcyclohexylcyclopentyldimethoxysilane; and a Ziegler-Natta catalyst for olefin polymerization, characterized in that at least one selected from the group consisting of 3,5-dimethylcyclohexylcyclopentyldimethoxysilane. As solid catalyst components (A), organoaluminum compounds (B) and electron donors which contain magnesium, titanium, electron donor compounds and halogens as essential components, prepared by contacting magnesium compounds, titanium halide compounds, and electron donor compounds A process for the polymerization of olefins, wherein the olefins are homo- or copolymerized in the presence of a catalyst for olefin polymerization comprising the organosilicon compound (C) of formula (1): In the above formula, R ¹ and R ² may be the same or different and each is an alkyl group having 1 to 3 carbon atoms, R ³ and R ⁴ may be the same or different and each is an alkyl group or halogen atom having 1 to 3 carbon atoms, m and n are 0 or the integer 1 or 2, respectively. 12. The process according to claim 11, wherein the olefin is propylene or a composite of propylene and ethylene.