JPH0617402B2 - Method for manufacturing polyolefin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polyolefin. More specifically, it relates to a method for producing an odorless polyolefin using a novel supported solid catalyst component.

However, in the present invention, a polyolefin has 3 carbon atoms.
In addition to the homo- and copolymers of the above α-olefins,
A copolymer of an α-olefin having 3 or more carbon atoms and an α-olefin having 2 carbon atoms, in which the former is 50% by weight or more as a component ratio in the copolymer.

[Conventional technology]

Conventionally, it has been known that the stereoregularity of a polyolefin obtained by combining a supported solid catalyst component with an organoaluminum compound component and an aromatic carboxylic acid ester component is improved as a direction for improving a Ziegler-Natta type catalyst. . For example, JP-A-57-74307 and JP-A-
The technique of using aromatic carboxylic acid esters as one component of the catalyst to improve the stereoregularity of polyolefins, as in 58-32604, is known. However, in principle, when a polyolefin is produced in a solvent-free gas-phase polymerization process, the aromatic carboxylic acid ester, which is one component of the catalyst, is contained in the polyolefin. It is also well known that esters have a strong odor in the presence of a trace amount. Therefore, when an aromatic carboxylic acid ester is used as one component of a catalyst and a polyolefin is produced by a gas phase polymerization process, the polyolefin contains an aromatic carboxylic acid ester or a compound resulting from the change in the process. It produces a strong odor during storage and during the polyolefin granulation process. Production of polyolefin on an industrial scale is a problem because it causes environmental pollution.

Further, in JP-A-58-83006, a polyolefin formed by using a catalyst formed by combining a supported solid catalyst component with an organometallic compound component and an organosilicon compound component having a Si-OC or Si-NC bond is disclosed. A method of manufacturing is disclosed. In the prior application, it is essential that the supported solid catalyst component to be combined with the organosilicon compound component having a Si—OC bond contains a polyvalent carboxylic acid and / or an ester of a polyvalent hydroxy compound. However, it has not been known that the supported solid catalyst containing an aromatic carboxylic acid ester improves the stereoregularity of the obtained polyolefin even when it is combined with an organosilicon compound component having a Si—OC bond. The organosilicon compound having a Si—OC bond has a weak odor and has a property of relatively easily reacting with moisture in the atmosphere to be decomposed and converted into an odorless compound. Therefore, even if a small amount of the organosilicon compound having a Si—OC bond is contained in the polyolefin, the polyolefin has no odor.

[Outline of Invention]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned environmental pollution and poor workability due to strong odor, and as a result, found that a novel supported solid catalyst component containing an aromatic monocarboxylic acid ester was an organoaluminum compound component. And Si-OC
By combining with an organosilicon compound component having a bond, the polymerization activity is high enough to remove the residual catalyst in the polymer as an olefin polymerization catalyst, and this catalyst is highly stereoregular and odorless, and has a particle shape. The present invention has been completed by finding that it gives a good polyolefin.

As is clear from the above description, the object of the present invention is to provide a method for producing a polyolefin having high stereoregularity, odorless, and good particle shape, which does not require removal of residual catalyst in the polymer. That is.

The present invention has the following main configuration (1).

(1) a. Magnesium alkoxide, general formula AlX _n R
¹ _3-n (wherein X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 3) A) aluminum halide, titanic acid ester, saturated aliphatic alcohol and optionally aromatic carboxylic acid ester (I) dissolved by heating in an inert hydrocarbon solvent, or b. Magnesium alkoxide, the halogenated compound A complex compound is obtained by co-milling aluminum and aromatic carboxylic acid ester, and the complex compound, titanic acid ester and saturated aliphatic alcohol are heated and dissolved in an inert hydrocarbon solvent, and the solution thus obtained is added. General formula SiX _n R ⁷ _4-n (where X
Is Cl or Br, R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 1 to 4). And the aromatic carboxylic acid ester are mixed and reacted to precipitate a solid product (I), and the solid product (I) is mixed with Ti.
X ₄ (X is Cl) is reacted, and the solid after the reaction is washed with a liquid inert hydrocarbon to give a solid product (II), and the solid product (II) is at least 50% by weight thereof. Solid product (II) obtained in the coexistence of the liquid inert hydrocarbon of (2) is used as a solid catalyst component, and the solid catalyst component, the organoaluminum compound component, and Si-O
A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining an organosilicon compound component having a -C bond.

The configuration and effects of the present invention will be described in detail below.

First, a method for producing a supported solid catalyst component supporting a transition metal compound will be described.

First, magnesium alkoxide is mixed with a. Aluminum halide, titanic acid ester and alcohol and optionally organic acid ester in an inert hydrocarbon solvent and heated to dissolve, or b. Magnesium alkoxide,
The aluminum halide and the organic acid ester are co-ground to form a complex compound, and the complex compound is heated and dissolved in an inert hydrocarbon solvent in the coexistence of the titanate ester and alcohol. Magnesium alkoxide is a compound generally represented by Mg (OR ⁰ ) ₂ , where R ⁰ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 carbon atoms.
To 20 cycloalkyl groups or aralkyl groups. For example, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium diptoxide, magnesium dicyclohexide, magnesium dialoxide, magnesium diphenoxy and the like can be mentioned.

Halogen aluminum is a compound represented by AlX _n R ¹ _3-n , where X is Cl or Br, and R ¹ is a carbon number of 1 to 2.
An alkyl group of 0, an aryl group or a cycloalkyl group of 3 to 20 carbon atoms, and n is a number of 0 to 3. Examples thereof include aluminum trichloride, ethyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum chloride, dipropyl aluminum chloride, aluminum tribromide and ethyl aluminum dibromide.

Examples of the titanic acid ester include an orthotitanic acid ester represented by Ti (OR ² ) ₄ and It is a polytitanate ester represented by. here,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups having 1 to 20 carbon atoms,
It is an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is a number of 2 to 20. Specifically, orthotitanic acid such as methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, n-butyl orthotitanate, i-amyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate. Polytitanium such as ester, polymethyl titanate, ethyl polytitanate, polypropyl titanate, i-propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, phenyl polytitanate and cyclopentyl polytitanate. Acid esters (2-20 mer) can be used.

As the alcohol, an aliphatic alcohol having 1 to 20 carbon atoms and / or an aromatic alcohol having 6 to 24 carbon atoms can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-amyl alcohol,
In addition to monohydric alcohols such as n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethyl-1-hexyl alcohol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, trimethylene glycol and glycerin are also used. can do. Of these, aliphatic alcohols having 4 to 10 carbon atoms are preferable. Instead of these aliphatic alcohols or together with the aliphatic alcohols, phenols such as phenol or its derivatives can be used.

Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Halogenated hydrocarbons such as can be used. Of these, aliphatic hydrocarbons and halogenated aliphatic hydrocarbons are preferable.

Examples of the organic acid ester (the organic acid ester used at this stage is referred to as organic acid ester (I)) include ethyl acetate,
C2-C20 aliphatic carboxylic acid esters such as propyl acetate, butyl acetate, ethyl propionate, butyl propionate and ethyl butyrate, or ethyl benzoate,
It is an aromatic carboxylic acid ester having 8 to 24 carbon atoms such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate.

As a specific method for dissolving the magnesium alkoxide, in the above-mentioned method, Ia. Magnesium alkoxide, aluminum halide, titanic acid ester and alcohol are mixed and suspended in an inert hydrocarbon solvent in any addition order, The suspension is heated with stirring to dissolve ii. Aluminum halide, titanate and alcohol are heated with stirring in an inert hydrocarbon solvent and magnesium alkoxide is added to the solution to dissolve. Or ii
i Magnesium alkoxide in an inert hydrocarbon solvent,
The titanate ester and alcohol are heated and dissolved, and aluminum halide is added to the solution. In any method, the organic acid ester (I) can be added at any stage. The purpose of adding the organic acid ester is to make the dissolution of the magnesium alkoxide smooth and uniform and to improve the stereoregularity.

As the method of dissolving magnesium alkoxide by the method of Ib, first, the three components are reacted to form a complex compound by the following methods.

That is, magnesium alkoxide, aluminum halide and organic acid ester are simultaneously mixed and pulverized (hereinafter referred to as co-pulverization). The mixture or complex of aluminum halide and organic acid ester and magnesium alkoxide are co-ground. Aluminum halide is added to a mixture or complex of magnesium alkoxide and organic acid ester and co-milled. Alternatively,
Examples of the method include co-milling by adding an organic acid ester to a mixture of magnesium alkoxide and aluminum halide or a co-milled product, and any method can be adopted. Of these, or method is preferred. These reactions can be achieved by means of co-milling (described above). As a co-crushing means,
A vibration mill, a ball mill, a vibration ball mill, or the like is used. Magnesium alkoxides are believed to react with aluminum halides and organic acid esters to undergo complicated reactions. When co-milling, hexane, heptane,
Using aliphatic hydrocarbons such as nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, or halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, n-butane chloride and chlorobenzene. Good. When these solvents are used, they may be co-ground and then filtered off, or they may be used in the next reaction. It is known that aluminum halide and an organic acid ester and magnesium alkoxide and an organic acid ester form a complex, but the complex or the mixture may be used for co-milling. These complexes can be made by co-milling or reaction in solution. As the solvent at the time of such a solution reaction, the same solvent as that at the time of the co-milling described above can be used.

A complex compound composed of magnesium alkoxide, aluminum halide and organic acid ester is obtained as a powder at room temperature, but in the next step, that is, to facilitate dissolution in hydrocarbon in the coexistence of titanic acid ester and alcohol. In addition, the powder of the complex compound is preferably a fine powder having a specific surface area as large as possible. The amount of aluminum halide used is 1 mol of magnesium alkoxide.
To 0.001 to 0.7 mol, preferably 0.01 to 0.5 mol, and the amount of the organic acid ester (I) used is 0.05 to 0.5 mol per 1 mol of magnesium alkoxide.

The amount of the organic acid ester (I) used with respect to the aluminum halide is 0.1 to 50 mol, preferably 0.5 to 1 mol of the organic acid ester (I) per 1 mol of the aluminum halide.
It is 0 mol. When a solvent is used during co-pulverization, the amount of the solvent used is 0.05 to 100 m, preferably 0.1 to 50 m, based on 10 g of the total amount of magnesium alkoxide, aluminum halide and organic acid ester used. When a complex of aluminum halide and organic acid ester (I) or magnesium alkoxide and organic acid ester (I) is used, the complex may be formed within the above-mentioned molar ratio range.

The temperature of co-pulverization is 0 to 150 ° C., preferably 20 to 100 ° C., and the time is 5 minutes to 100 hours, but the time varies depending on the means of pulverization. For example, 5 minutes to 20 hours are required for a pulverizing method that can give strong energy in a short time such as a vibration mill, but 30 minutes to 100 hours are required for a pulverizing method that does not give strong energy in a short time such as a ball mill. And In the co-milling, since the magnesium alkoxide is a solid and the aluminum halide is also a solid in some cases, the specific surface area should be as uniform as possible and, as already mentioned, to facilitate the next operation. It is preferable to use fine powder having a large particle size.

The complex compound obtained as described above is dissolved in an inert hydrocarbon solvent in the coexistence of titanic acid ester and alcohol.

As a specific dissolution method, a complex compound, a titanic acid ester, an alcohol and an inert hydrocarbon are mixed and heated at the same time, and a complex compound, an alcohol and an inert hydrocarbon are mixed, and before or after heating. Add titanate ester and heat to dissolve. Complex compound, titanic acid ester, inert hydrocarbon are mixed, before heating or after heating, alcohol is added and dissolved, or titanic acid ester, alcohol and inert hydrocarbon are mixed, before heating or heating Examples thereof include adding a post-complex compound and heating it to dissolve it, and any dissolution method can be adopted. Among these, preferred. In either case, the solids in the mixture may be completely dissolved into a homogeneous solution,
A small amount of insoluble matter may remain. It is believed that this insoluble material is based on impurities contained in the starting material, such as magnesium alkoxide or aluminum halide. When a small amount of insoluble matter remains, it may adversely affect the particle shape of the solid catalyst, and it is preferable that the solid catalyst is completely dissolved into a uniform solution. Alternatively, such a small amount of insoluble matter may be filtered out to obtain a uniform solution.

Heating is required to dissolve the aforementioned mixture. The temperature is 40 to 170 ° C, preferably 50 to 150 ° C. The time is 5 minutes to 6 hours, preferably 10 minutes to 4 hours. When the organic acid ester contained in the complex compound is heated to a high temperature for a long time, it changes into a substance other than the organic acid ester and loses the ability to enhance stereoregularity. In some cases, it is necessary to take measures such as shortening the time. It is preferable that the temperature is as low as possible and the time is short, and therefore it is preferable to filter out a small amount of insoluble matter which is not easily dissolved. The amount of titanic acid ester used may be determined based on the amount of magnesium alkoxide used to obtain the magnesium alkoxide or complex compound. When orthotitanate is used as titanate, it is 0.1 to 3.0 mol, preferably 0.5 to 1 mol of magnesium alkoxide used to obtain the magnesium alkoxide or complex compound.
When the polytitanate ester is used, the unit corresponding to the orthotitanate ester in the polytitanate ester molecule may be converted to a mol unit and the molar ratio may be determined similarly to the orthotitanate ester. The amount of alcohol used is 0.1 to 6 mol, preferably 0.5 to 5 mol, per 1 mol of magnesium alkoxide used to obtain the magnesium alkoxide or complex compound.

The higher the amount of titanic acid ester and alcohol used with respect to the magnesium alkoxide, the more the solubility of the magnesium alkoxide or magnesium alkoxide complex in an inert hydrocarbon solvent increases, but an extremely large amount of silicon halide is used to resolidify. In addition to this, resolidification itself becomes difficult, and even if solidification is possible, controlling the particle shape is extremely difficult.

Conversely, if the amount of titanate ester and alcohol used is too small, the magnesium alkoxide or magnesium alkoxide complex will not be soluble in the inert hydrocarbon solvent, and the solid catalyst will become amorphous, and a spherical or near spherical particle-shaped polymer will be formed. Can't get Further, it is necessary to share the titanic acid ester and the alcohol, and the individual use of each cannot achieve the object of the present invention.

The amount of inert hydrocarbon used is 10 g of magnesium alkoxide or magnesium alkoxide complex compound.
It is 10 to 2000 m, preferably 50 to 1000 m. The composition of the compound dissolved and present in the solution is not clear.

Then, the above solution is reacted with silicon halide and organic acid ester (II) to obtain a solid product (I). The solid product (I) can be obtained by adding an organic acid ester to a solution containing magnesium alkoxide to cause a reaction, and then adding a silicon halide to precipitate a solid, and adding a silicon halide together with the organic acid ester. Let it react,
A solid is obtained by any method of precipitating a solid, precipitating a solid by adding silicon halide and then reacting by adding an organic acid ester, or a method of combining two or more thereof. The method of obtaining the solid product (I) by washing the obtained solid with an inert hydrocarbon solvent can be mentioned.

As the organic acid ester (II) used at this stage, the above-mentioned aliphatic carboxylic acid ester or aromatic carboxylic acid ester can be used.

As the silicon halide, a compound represented by the general formula SiX _n R ⁷ _4-n and / or the general formula SiX _n (OR ⁸ ) _4-n can be used. Here, X is Cl or Br, R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 1 to 4. Specifically, as SiX _n R ⁷ _4-n, silicon tetrachloride, silicon tetrabromide, three Echirukei containing trichloride, propyl silicon trichloride, Buchirukei containing chloride, terphenyl silicon trichloride, cyclohexyl silicon trichloride, odor Such as ethyl silicon chloride, diethyl silicon dichloride, dibutyl silicon dichloride and triethyl silicon chloride can be used.
X _n (OR ⁸ ) _4-n includes silicon tetrabromide, ethoxysilicon trichloride, propoxysilicon trichloride, butoxysilicon trichloride, phenoxysilicon trichloride, ethoxysilicon tribromide,
Diethoxy silicon dichloride, dibutoxy silicon dichloride, triethoxy silicon chloride and the like can be used. The above compounds may be used as a mixture of two or more. Among them, silicon tetrachloride is preferable. The organic acid ester (II) and the silicon halide may be used as they are or after they are diluted with a solvent. In that case, the same solvent as the above-mentioned inert hydrocarbon solvent can be used. The organic acid ester (II) is preferably reacted separately from the silicon halide or simultaneously with the silicon halide in a homogeneous solution. At this time, the silicon halide may be added to the uniform solution or the uniform solution may be added to the silicon halide. The amount of organic acid ester used is 1 mol of the magnesium alkoxide used first.
It is 0.05 to 0.6 mol for l. This amount of organic acid ester may be used at one time, or may be used in several stages. Reaction temperature is 30 to 150 ° C, preferably 50 to 130 ° C
And the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours for each step. The total amount of the organic acid ester (I) and the organic acid ester (II) used is the solid product (I)
0.1-0.7 mol, preferably 0.1-0.6 mol, per 1 mol of the magnesium alkoxide used for the production of The reaction condition between the homogeneous solution and the silicon halide is a temperature of 40 to 150.
C., preferably 50 to 130.degree. C., the time is 5 minutes to 10 hours, preferably 10 minutes to 5 hours. The amount of silicon halide used is 1 mol of the magnesium alkoxide used.
It is 0.1 to 50 mol, preferably 1 to 20 mol. A solid is deposited by reacting the silicon halide. The particle shape of the solid product (II) obtained in the next step is governed by the particle shape of the solid product (I). The reaction is extremely important.

After the organic acid ester and the silicon halide are reacted with the homogeneous solution to precipitate a solid as described above, the reaction mixture of the precipitation is continuously reacted in the next step, that is, with titanium halide and / or vanadium halide. The reaction can also be carried out. However, it is preferable to wash the deposited solid with the aforementioned inert hydrocarbon. This is because unreacted substances or by-products present in the reaction mixture after the precipitation may interfere with the subsequent reaction. After separating and washing the precipitated solid from the reaction mixture, a solid product (I) is obtained.

Next, the solid product (I) is reacted with titanium halide and / or vanadium halide to obtain the solid product (I
I). As the titanium halide, a compound represented by TiX _q (OR ⁹ ) _4-q can be used. Where X is
Cl and R ⁹ are alkyl groups having 1 to 20 carbon atoms, aryl groups or cycloalkyl groups having 3 to 20 carbon atoms, and q is a number of 1 to 4. Specifically, titanium tetrachloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, octanoxytitanium trichloride, phenoxytitanium trichloride, cyclohexoxytitanium trichloride, diethoxytitanium dichloride, dichloride Examples thereof include dibutoxy titanium, diphenoxy titanium dichloride, triethoxy titanium chloride, and triphenoxy titanium chloride. The above-mentioned titanium halides other than titanium tetrachloride can be produced by the reaction of titanium tetrachloride and orthotitanate, but a mixture of titanium tetrachloride and orthotitanate can also be used in this reaction. .

As the orthotitanate, the same orthotitanate as described above can be used.

Examples of vanadium halides include vanadium tetrachloride, vanadium oxytrichloride, and other vanadium derivatives having at least one chloro compound.
Again, a mixture or reactant of vanadium tetrachloride or vanadium oxytrichloride and orthotitanate can be used in this reaction. Of these halides, titanium tetrachloride is most preferred. The titanium halide and / or vanadium halide can be used as they are or diluted with a solvent. The solvent in that case may be the same as the above-mentioned inert hydrocarbon solvent. Solid product (I) and titanium halide and /
Alternatively, the reaction with vanadium halide is carried out by adding titanium halide and / or vanadium halide to a suspension of the solid product (I) in the previously mentioned inert hydrocarbon, or by adding titanium halide and / or halogen halide. The solid product (I) may be added and reacted in vanadium chloride. The amount of titanium halide or vanadium halide used is 1 mol of the magnesium alkoxide used.
It is 1 to 100 mol, preferably 3 to 50 mol with respect to l.

The reaction temperature of the solid product (I) with titanium halide or vanadium halide is 40 to 150 ° C, preferably 50 to 130.
The temperature and temperature are 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

After the reaction, it is washed by filtration or decantation,
Unreacted substances or by-products are removed. The solvent used for washing is a liquid inert hydrocarbon. Specific examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and kerosene. During and after washing, the solid product (II) is required to coexist with at least 50% by weight of the aforementioned liquid deactivated hydrocarbon. Particularly, the decantation method is preferable for the washing, and it is preferable that the liquid inert hydrocarbon coexists with the solid product (II) at least to the extent that the solid product (II) is immersed in the liquid inert hydrocarbon after the washing. . When less than 50% by weight of a liquid inert hydrocarbon coexists with the solid product (II), sufficient catalytic performance is not exhibited even if the liquid inert hydrocarbon is combined with an organoaluminum compound and then subjected to polymerization. That is, the polymer yield and bulk specific gravity are low,
The shape is inferior, the amount of fine powder is large, and the stereoregularity is low.

It is important that the solid product (II) after washing is stored in the coexistence of at least 50% by weight of the liquid inert hydrocarbon and subjected to polymerization.

The solid product (II) can be used as a catalyst for producing a polyolefin by combining it as a solid catalyst component with an organoaluminum compound component and an organosilicon compound component having a Si—OC bond. As the organoaluminum compound, it may be used a compound represented by the general formula AlX _s R ¹⁰ _3-s. Here, X is Cl, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and s is a number of 0 to 2. Triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl aluminum, tricyclopentyl aluminum, tricyclohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum chloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride, etc. Can be mentioned. Among them, triethylaluminum alone or a mixture of two kinds of organic aluminum compounds such as triethylaluminum and tri-i-butylaluminum, triethylaluminum and diethylaluminum chloride and triethylaluminum and ethylaluminum sesquichloride is preferable.

The organic silicon compound component has a general formula R ¹¹ _t Si (OR ¹² ).
A compound represented by _4-t can be used. Here, R ¹¹ and R ¹² are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and t
Is a number from 0 to 3.

Specifically, methyl silicate, ethyl silicate, butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methylethoxydimethoxysilane, methylphenoxydimethoxysilane, methylmethoxy. Ethoxyphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriphenoxysilane,
Ethyltribenzyloxysilane, ethylethoxydimethoxysilane, ethylmethoxydiethoxysilane, ethylphenoxydimethoxysilane, ethylmethoxyethoxyphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylphenoxy Dimethoxysilane, benzylmethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dichloropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, phenylmethoxyethoxyphenoxysilane, dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyldiphenoxysilane, dimethyldiben Rokishishiran, dimethyl methoxy silane, dimethyl-methoxyphenoxy silane,
Dimethylethoxyphenoxysilane, methylethyldimethoxysilane, methylethyldiphenoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiphenoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, phenylbenzyldimethoxysilane, methyl Cyclopropyldimethoxysilane, methylvinyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylbenzyloxysilane, triethylmethoxysilane, triethylethoxysilane, triethylphenoxysilane,
Triphenylmethoxysilane, tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, diethylmethylmethoxysilane, diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxy Examples thereof include silane and methylethylphenylphenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, methylethyldiethoxysilane, methylphenyldiethoxysilane, methylbenzyl Dimethoxysilane,
Dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane and trimethylethoxysilane are preferable.

The method for combining the solid product (II), the organoaluminum compound and the organosilicon compound is a method for independently supplying the solid product (II), the organoaluminum compound and the organosilicon compound to a polymerization vessel. The mixture and the solid product (II) are independently fed to the polymerization vessel, the mixture of the solid product (II), the organoaluminum compound and the organosilicon compound is fed to the polymerization vessel, and either method can be adopted. .

In some cases, or is preferred. When the three components are combined as described above, each component or any component may be dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane and kerosene before use. . The temperature in the case of mixing before feeding to the polymerization vessel as described above and is -50 to + 50 ° C,
It is preferably -30 to + 30 ° C, and the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is 10 to 1000 mol, preferably 50 to 500 mol, per 1 mol of titanium atom contained in the solid product (II) as the solid catalyst component. The amount of organosilicon compound used is 1 mol of organoaluminum compound
With respect to 0.01 to 2 mol, preferably 0.05 to 1 mol.
When a mixed organoaluminum compound or a mixed organosilicon compound is used, the total mol number of them should fall within the above range.

An α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms, using a catalyst obtained by combining the solid product (II) as a solid catalyst component, an organoaluminum compound and an organosilicon compound. As the α-olefin having 3 or more carbon atoms, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1 and 3-methylpentene-1 are used. be able to. Polymerization of these α-olefins includes not only homopolymerization but also copolymerization with one or two or more other α-olefins having 2 or more carbon atoms. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-butadiene and methyl-1,4-in addition to the α-olefin having 3 or more carbon atoms described above.
Hexadiene and the like can be mentioned. The amount of these other α-olefins used is the amount contained in the copolymer in an amount of 50% by weight or less. The polymerization can be carried out in the liquid phase or the gas phase. When the polymerization is carried out in the liquid phase, for example, an inert hydrocarbon solvent such as hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may also be used as the reaction medium. it can.

When carrying out the polymerization in the gas phase, in principle no reaction medium is used, but it is also possible to use either the catalyst or any of its components dissolved or suspended in the abovementioned inert hydrocarbons. The polymerization is carried out by bringing the catalyst into contact with the α-olefin in the polymerization vessel. Polymerization temperature is 40-200
℃, preferably 50 ~ 150 ℃, the polymerization pressure is atmospheric pressure ~ 1
It is 00 kg / cm ² G, preferably 5 to 50 kg / cm ² G. The polymerization can be carried out by any of a batch type, a semi-continuous type and a continuous type, but industrially a continuous type polymerization is preferred.

It is also possible to carry out the polymerization by multistage polymerization under different polymerization conditions. In order to control the molecular weight of the polymer, it is effective to add a molecular weight regulator such as hydrogen to the polymerization system.

The production or storage of the solid catalyst components described above, the preparation of the catalyst and the production of the polymer must be carried out in an atmosphere of an inert gas such as nitrogen or helium, but in some cases, also in a monomer atmosphere or in a vacuum condition. be able to.

The main effects of the present invention are as follows. First, the polymer obtained by the production method of the present invention is odorless, and at the time of granulation, the exhaust gas from the granulator vent part or the molten polymer at the granulator exit has almost no odor based on the organosilicon compound component. That is. This is economical because it facilitates handling of the polymer such as granulation and does not cause environmental pollution such as polluting the atmosphere.

Further, the catalyst obtained by combining the solid catalyst component of the present invention with the organoaluminum compound component and the organosilicon compound component has extremely high polymerization activity and does not require removal of residual catalyst in the polymer. It is extremely economical because a polymer purification step is unnecessary. In addition, the stereoregularity of the polymer is extremely high. This is shown by the high isotactic index (hereinafter abbreviated as II). It is extremely advantageous for polymer production by a gas phase polymerization method without using a solvent. Further, the particle shape of the obtained polymer is extremely good. That is, the shape of the polymer particles is a sphere or a shape close to a sphere, the particle size of the polymer can be controlled to a predetermined size, and the polymer particle size distribution can be controlled to be extremely narrow. Very small polymer or fines. As a result, it is possible to stably produce a polymer for a long period of time in a liquid phase polymerization method such as slurry polymerization or bulk polymerization or a gas phase polymerization method. In addition, industrial transportation and recovery of the polymer is easy, and it becomes easy to supply it to the granulator and operate it for processing and molding.
Productivity is greatly improved. Dust explosion due to fine powder can be suppressed, which is effective in preventing entrainment.
Further, even when the α-olefin is copolymerized in the method using the catalyst according to the present invention, the deterioration of the polymer particle shape and the decrease in bulk specific gravity are small, and the copolymer is easily manufactured.

In Examples and Comparative Examples, the definitions or measuring methods of various properties that define polymers are as follows.

(1) Melt flare rate (abbreviated as MER) is ASTM D1238 (L)
by.

(2) Bulk density of polymer (abbreviated as BD) is according to ASTM D1895.

(3) The presence or absence of odor was judged by a sensory test by 10 testers, and classified into 4 stages of A to D. A is odorless, 10
If all people judge that there is no odor, B is a little odor, and if 1 to 4 out of 10 people have odor, C
Is a case where 5 to 9 out of 10 persons have a smell, and D is a case where there is a strong smell, and all 10 persons have a smell.

(4) The shape of the solid product (I), the solid product (II) and the polymer particles are observed with an optical microscope.

(5) The particle size distribution of the polymer was determined using a sieve according to JIS Z 8801. The particle size distribution of the solid product (II) was determined by Micron Photosizer (manufactured by Seishin Enterprise Co., Ltd., SKC-2000 type). The cumulative 50% by weight of the particle size accumulation curve in the particle size distribution is the average particle size.

(6) II is the ratio of the extraction residue after extraction of the polymer with boiling n-hexane (69 ° C.) for 6 hours to the total amount before extraction.

(7) The fine powder amount of the polymer is a weight ratio of the total amount of the polymer having a particle diameter of less than 100 μm.

The present invention will be described below with reference to examples and comparative examples.

Example 1 (1) Preparation of solid catalyst component In a glass flask, purified decane 50m, magnesium diethoxide 5.7g, aluminum chloride 0.67g, n-butyl orthotitanate 17.1g, 2-ethyl-1-hexanol 19.6g. And 1.6 g of ethyl p-toluate were mixed and heated to 130 ° C. for 2 hours with stirring to dissolve them. The homogeneous solution was heated to 70 ° C., 51 g of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid, and the mixture was stirred at the same temperature for 1 hour. 2.1 g of ethyl p-toluate was added to 70 ° C. After reacting for a time, the solid was washed with purified hexane to obtain a solid product (I). The total amount of the solid product (I) is 1,2-
50m titanium tetrachloride diluted with 50m dichloroethane
The mixture was mixed with and reacted with stirring at 80 ° C. for 2 hours, washed with purified hexane, and without drying, purified hexane was added to obtain a hexane suspension. 50 g of solid product (II) was present in the suspension 1.

The above-mentioned operations and the same operations in the following Examples and Comparative Examples were all performed under a nitrogen atmosphere.

The solid product (II) has a nearly spherical shape and an average particle size of 21
The particle size distribution was very narrow. 25 ° C,
The composition analysis effect of the solid product (II) obtained by drying under reduced pressure (10 ^-3 mmHg) for 3 hours was as follows: Ti 3.3 wt% (hereinafter referred to as%), ethyl p-toluate 11.5%, butoxy group. It was 2.8% and 1.2% of 2-ethylhexanoxy group.

(2) Production of Polyolefin In a reactor made of stainless steel with a multi-stage stirrer and having an internal volume of 3 which was replaced by nitrogen, 2.0 mmol of triethylaluminum, 0.5 mmol of methylphenyldimethoxysilane and T of the solid product (II) were added.
After adding 6.5 × 10 ⁻³ mg atom of i atom and 800 m of hydrogen, polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 22 kg / cm ² (G). Then, unreacted propylene is discharged and powdered polypropylene
238 g was obtained. The results are shown in the table. This powdery polypropylene was difficult to grind.

(3) Odor sensory test Polypropylene immediately after polymerization had an unreacted propylene odor. Therefore, it was left in a nitrogen stream at 50 ° C. for 3 hours and then subjected to an odor sensory test. There was no propylene odor, and when 10 testers conducted a direct odor sensory test, all 10 judged that there was no odor (odor rank A). Henschel mixer (trade name) was prepared by adding 0.1% by weight of antioxidant and 0.1% by weight of lubricant to polypropylene after sensory test.
After thoroughly mixing in, using a single-screw granulator with a diameter of 20 mm and a vent in the center, granulated at 220 ° C,
Three ventilator exhaust gases judged that there was odor (odor rank B), and all of the molten polymer at the outlet of the granulator judged that there was no odor (odor rank A).

Comparative Example 1 Other than using the solid product (II) prepared in (1) of Example 1 as a solid catalyst component and using methyl p-toluate in place of the methylphenyldimethoxysilane of (2) of Example 1 A polyolefin was produced in the same manner as in Example 1 (2), and an odor sensory test was conducted in the same manner as in Example 1 (3). The results are shown in the table.

Example 2 (1) Preparation of solid catalyst component In a stainless steel flask, purified nonane 50 m,
5.7 g of magnesium diethoxide, 0.952 g of ethylaluminum dichloride, 17.2 g of ethyl orthotitanate, 13.0 g of n-octanol and 1.5 g of ethyl benzoate were mixed and heated at 110 ° C. for 3 hours with stirring to dissolve them. The homogeneous solution was heated to 50 ° C., 58 g of ethyl silicon trichloride containing 1.6 g of ethyl benzoate was added dropwise over 2.5 hours to deposit a solid, and the mixture was further stirred for 1 hour, and then the solid was washed with purified hexane to give a solid. The product (I) was obtained. The whole amount of the solid product (I) was mixed with 100 g of titanium tetrachloride diluted with 30 m of toluene and reacted at 110 ° C. for 1 hour while stirring,
It was washed with purified heptane and purified heptane was added without drying to give a heptane suspension. The solid product (II) was present in the suspension 1 in a proportion of 10 g.

The solid product (II) has a nearly spherical shape and an average particle size of 19
The particle size distribution was very narrow. 30 ° C,
The composition analysis result of the solid product (II) obtained by drying under reduced pressure for 3 hours shows that the Ti content is 2.9%, and ethyl benzoate is 8.3%.
Met.

(2) Production of polyolefin and odor sensory test The solid product (II) obtained in (1) of Example 2 was used in place of the solid product (II) in (2) of Example 1, and (2) of Example 1 except that diphenyldimethoxysilane was used instead of methylphenyldimethoxysilane.
A polyolefin was produced in the same manner as in (1), and the obtained polymer was used to carry out an odor sensory test in the same manner as in Example 1 (3). The polypropylene obtained by the production had a shape close to a sphere, its particle size distribution was narrow, and it was difficult to be ground. The results are shown in the table.

Comparative Example 2 Except that the solid product (II) prepared in Example 2 (1) was used as the solid catalyst component and methyl p-anisate was used in place of the diphenyldimethoxysilane of Example 2 (2). A polyolefin was produced in the same manner as in (2) of Example 2 and a odor sensory test was conducted. The results are shown in the table.

Example 3 In a glass flask, 50 m of purified decane, 5.7 g of magnesium diethoxide, 0.424 g of diethylaluminum chloride, 17.1 g of n-butyl orthotitanate and 19.6 g of n-ethyl-1-hexanol were mixed and stirred. 130 ° C
After heating for 1.5 hours, a homogeneous solution was obtained. 70 the homogeneous solution
The temperature was adjusted to 0 ° C., 2.2 g of ethyl p-anisate was added, and the mixture was stirred for 1 hour, then 51 g of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred for 1 hour. Subsequently, 1.9 g of ethyl p-anisate was added and stirred for 1 hour, then the solid was separated and washed with purified hexane to obtain a solid product (I). Thereafter, using this solid product (I), a solid catalyst component was prepared in the same manner as in (1) of Example 1.

A polyolefin was produced in the same manner as in Example 1 except that the solid catalyst component was used in place of the solid product (II) and phenyltriethoxysilane was used in place of methylphenyldimethoxysilane. A sensory test was conducted. The results are shown in the table.

Comparative Example 3 A polyolefin was produced in the same manner as in Example 3 except that methyl p-toluate was used instead of phenyltriethoxysilane, and an odor sensory test was conducted. The results are shown in the table.

Example 4 Magnesium diethoxide (11.4 g), aluminum chloride (1.34 g) and ethyl benzoate (3.0 g) were sequentially added to a stainless steel vibration mill having an internal volume of 100 m, and further 10 stainless steel balls (13 mmφ5 and 10 mmφ5). Put and seal
Co-pulverization was performed at 30 ° C. for 1 hour to obtain a fine powdery complex compound having a large specific surface area. 7.9 g of this complex compound was placed in a glass flask, 50 m of purified decane, 17.1 g of n-butyl orthotitanate and 19.6 g of 2-ethyl-1-hexanol were added, and the mixture was heated to 130 ° C for 2 hours while stirring to obtain a uniform solution. Got After making the solution homogeneous, a solid product (II) was prepared in the same manner as in (1) of Example 1, and 0.8 mmo was used in place of (2) of Example 1 instead of 0.05 mmol of methylphenyldimethoxysilane.
A polyolefin was produced in the same manner as in Example 1 except that 1 was used, and an odor sensory test was conducted. The results are shown in the table.

Example 5 In Example 1, 15 mol% of 1-butene was used instead of propylene.
A fixed catalyst component was prepared in the same manner as in Example 1 except that propylene containing was used to produce a polyolefin,
An odor sensory test was conducted. The butene content in the powdery propylene-butene copolymer was 5.7 mol%. The results are shown in the table.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) for explaining the method of the present invention.

Claims (9)

[Claims] 1. A magnesium alkoxide of the general formula Al
X _n R ¹ _3-n (where X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is 0 to 3). A halogenated aluminum halide, titanic acid ester, saturated aliphatic alcohol and optionally aromatic carboxylic acid ester (I) dissolved by heating in an inert hydrocarbon solvent, or b. Magnesium alkoxide, A complex compound is obtained by co-milling the aluminum halide and the aromatic carboxylic acid ester, and the complex compound, the titanic acid ester and the saturated aliphatic alcohol are heated and dissolved in an inert hydrocarbon solvent, and thus obtained. The solution of the general formula SiX _n R ⁷ _4-n (where X
Is Cl or Br, R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 1 to 4). And an aromatic carboxylic acid ester are mixed and reacted to precipitate a solid product (I), TiX ₄ (X is Cl) is reacted with the solid product (I), and the solid after the reaction is treated with a liquid inert carbon. A solid product (II) obtained by washing with hydrogen fluoride to obtain a solid product (II) in the presence of at least 50% by weight of the liquid inert hydrocarbon is a solid product (II). As a catalyst component, the solid catalyst component, an organoaluminum compound component, and Si-O
A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining an organosilicon compound component having a -C bond. 2. An orthotitanate represented by the general formula Ti (OR ² ) ₄ as a titanate and / or a general formula Polytitanate represented by (here, R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is 2
A method according to claim (1) using the number 20). 3. The method according to claim 1, wherein an aliphatic saturated alcohol having 1 to 20 carbon atoms is used. 4. The method according to claim 1, wherein an aromatic carboxylic acid ester having 8 to 24 carbon atoms is used. 5. Aluminum halide, 0.01 to 0.5 mol, orthotitanate ester and / or polytitanate ester (converted to orthotitanate ester) 0.5 to 3.0 mol, and saturated aliphatic alcohol 0.5 to 6.0 per mol of magnesium alkoxide. mol and aromatic carboxylic acid ester (I) 0.05-0.5 mol, the magnesium alkoxide in an inert hydrocarbon solvent at 50-150 ° C. for 5 minutes-5
The method according to claim (1), wherein the method is carried out by heating for dissolution. 6. A magnesium alkoxide, which is a constituent raw material of the complex compound, obtained by co-milling aluminum halide 0.01-0.5 mol and aromatic carboxylic acid ester 0.05-0.5 mol per 1 mol of magnesium alkoxide to form a complex compound. 0.5 to 3.0 mol of orthotitanium ester and / or polytitanate ester (converted to orthotitanate ester) per 1 mol, saturated aliphatic alcohol 0.5 to 6.
0 mol of said complex compound, orthotitanate and / or polytitanium ester and aliphatic saturated alcohol are dissolved in an inert hydrocarbon solvent by heating at 50 to 150 ° C. for 5 minutes to 5 hours to dissolve them. The method described in section (1). 7. A silicon halide having the general formula SiX _n R ⁷ _4-n
(Where X is Cl or Br, R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 1 to 4) The method according to claim (1). 8. An inactive hydrocarbon solution of magnesium alkoxide (hereinafter referred to as a homogeneous solution) dissolved with aluminum halide, titanic acid ester, saturated aliphatic alcohol and aromatic carboxylic acid ester to 1 mol of said magnesium alkoxide. And silicon halide 1-2
50 mol of 0 mol and 0.1-0.6 mol of aromatic carboxylic acid ester
Claim (1) in which the reaction is carried out at ~ 130 ° C for 10 minutes to 5 hours.
The method described in the section. 9. When precipitating a solid product (I) from a homogeneous solution, the solution is reacted with an aromatic carboxylic acid ester (II) and then reacted with silicon halide to precipitate a solid, or Aromatic carboxylic acid ester (II) is reacted with silicon halide at the same time to deposit a solid, or silicon halide is reacted to deposit a solid and then reacted with aromatic carboxylic acid ester (II), or The method according to claim (1), which uses a method in which any two or more of are combined. (10) The solid product (I) is reacted with 3 to 50 mol of titanium halide per 1 mol of magnesium alkoxide used in the production at 50 to 130 ° C. for 10 minutes to 2 hours, and then the reaction product is subjected to inert carbonization. Solid product (II) washed with hydrogen solvent
The method according to claim (1). (11) As an organosilicon compound having a Si—OC bond, a compound represented by the general formula R ¹¹ _t Si (OR ¹² ) _4-t (wherein R ¹¹ and R ¹² are an alkyl group having 1 to 20 carbon atoms, an aryl group, or An organosilicon compound having 3 to 20 carbon atoms and t being a number from 0 to 3) is used in an amount of 0.01 to 2 mol per 1 gram atom of Al of the organoaluminum compound component. The method described in. (12) The method according to claim (1), wherein the α-olefin is polymerized in a gas phase.