JPH0625219B2 - Method for producing catalyst component for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a catalyst component for producing a polyolefin. More specifically, the present invention relates to a novel carrier for a supported Ziegler-Natta catalyst a. Magnesium alkoxide, aluminum halide, titanate ester,
Alcohol and optionally organic acid ester (I)
Or b. A magnesium alkoxide, an aluminum halide and an organic acid ester (I) are co-ground to form a complex compound, and the complex compound titanate ester and alcohol are heated and dissolved in an inert hydrocarbon solvent for each of the above a and b. The present invention relates to a method of using a solid product (I) precipitated by mixing and reacting a solution obtained with silicon halide and an organic acid ester.

However, in the present invention, the term “polyolefin” means a homopolymer of an α-olefin having 3 or more carbon atoms and 3 carbon atoms.
A copolymer of the above α-olefin and another α-olefin having 2 or more carbon atoms, in which the former component ratio in the copolymer is 50% by weight or more.

Conventionally, as the improvement direction of Ziegler-Natta type catalyst,
A catalyst which gives a polymer having high polymerization activity and high stereoregularity has been energetically pursued. However, in recent years, in addition to these performances, the performance that the particle shape of the obtained polymer is good has been required.

The inventors including the present inventors have already proposed a method for producing a polyolefin using a supported solid catalyst component which gives a polymer having high polymerization activity, high stereoregularity, and good particle shape. No. 189012 (hereinafter referred to as prior invention). The proposal is different from the present invention after the solid product (II) is obtained from the magnesium alkoxide in the same manner as in the present invention, and the solid product (II) is dried to such an extent that almost no liquid inert hydrocarbon remains. This is a method of producing a solid powder, further preliminarily polymerizing it to obtain a supported solid catalyst component, and producing a polyolefin using the supported solid catalyst component. However, after that, as a result of intensive studies aimed at simplifying the production process of the supported solid catalyst component, it was found that the step of drying the solid product (II) of the prior application invention and the step of carrying out the prepolymerization treatment can be omitted, The present invention has been completed.

As is clear from the above description, the present invention is to provide a method for producing a catalyst component having a polymerization performance equal to or higher than that of the catalyst component production method according to the prior application by a remarkably simple method. Another object is to provide a method for producing a novel polyolefin using this catalyst component.

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

(1) a. Magnesium alkoxide, general formula AlX
aluminum halide represented by _n R ¹ _3-n (wherein X is Cl or Br, R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, n is a number from 0 to 3), the general formula Ti
Orthotitanate represented by (OR ² ) ₄ and / or general formula Polytitanate represented by (here, R ² ,
R ³ , R ⁴ , R ⁵ and R ⁶ are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and m is a number of 2 to 20), saturated aliphatic Heating the alcohol or phenol and optionally the aliphatic or aromatic carboxylic acid ester (I) in an inert hydrocarbon solvent to dissolve, or b. A complex compound is obtained by co-milling magnesium alkoxide, the aluminum halide and the aliphatic or aromatic carboxylic acid ester (I), and the complex compound, the orthotitanic acid ester and / or the polytitanic acid ester and an aliphatic saturated alcohol. Alternatively, phenol is dissolved in an inert hydrocarbon solvent, and the solution thus obtained is treated with a silicon halide represented by the general formula SiX _n R ⁷ _4-n (where X is Cl or Br and R ⁷ is a carbon number). An alkyl group having 1 to 10, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, n
Is a number of 1 to 4) and an aliphatic or aromatic carboxylic acid ester (II) to precipitate a solid product (I), and the solid product (I) has the general formula TiX _q (OR ⁹ )
Titanium halide represented by _4-q (where X is C
l and R ⁹ are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and q is a number of 1 to 4) and / or vanadium tetrachloride, and The solid after the reaction is washed with a liquid inert hydrocarbon to obtain a solid product (II), and the solid product (II) is obtained in the state where at least 50% by weight of the liquid inert hydrocarbon coexists. A method for producing a catalyst component for producing a polyolefin, comprising:

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 was added a. Mixing with aluminum halide, titanic acid ester and alcohol and optionally organic acid ester in an inert hydrocarbon solvent and heating to dissolve; b. A magnesium alkoxide, an aluminum halide and an 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 represents an alkyl group having 1 to 15 carbon atoms, an aryl group, a cycloalkyl group having 3 to 15 carbon atoms, an aralkyl group, or the like. For example, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium diptoxide, magnesium dicyclohexoxide, magnesium dialoxide, magnesium diphenoxide and the like can be mentioned. The aluminum halide _AlX n ^R _{1 3} -
a compound represented by n, wherein X is Cl or B
r and R ¹ are alkyl groups having 1 to 10 carbon atoms, aryl groups or cycloalkyl groups having 3 to 10 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. As titanic acid ester, Ti
An orthotitanate represented by (OR ² ) ₄ and It is a polytitanate ester represented by. Where R
² , R ³ , R ⁴ , R ⁵ and R ⁶ are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and m is a number of 2 to 20. Specifically, titanate esters such as methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, n-butyl orthotitanate, i-amyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate. , Polymethyl titanate, ethyl polytitanate,
Polytitanate esters (2-20 mer) such as poly (n-propyl titanate), i-propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, phenyl polytitanate and cyclopentyl polytitanate are used. Can be used. As the alcohol, an aliphatic alcohol having 1 to 18 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, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethyl- In addition to monohydric alcohols such as 1-hexyl alcohol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, trimethylene glycol and glycerin can also be used. 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. Inert hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene,
Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane and chlorobenzene 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,
Carbon number 2-18 such as propyl acetate, butyl acetate, ethyl propionate, butyl propionate and ethyl butyrate
Or an aromatic carboxylic acid ester having 8 to 24 carbon atoms such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate.

As a method for specifically dissolving magnesium alkoxide, the method described above includes: a. Magnesium alkoxide, aluminum halide, titanic acid ester and alcohol are mixed and suspended in an inert hydrocarbon solvent in any order, and the suspension is heated and dissolved with stirring. ii Aluminum halide, titanate ester and alcohol are heated in an inert hydrocarbon solvent with stirring, and magnesium alkoxide is added to the solution to dissolve it, or
iii) A method in which magnesium alkoxide, titanic acid ester and alcohol are heated and dissolved in an inert hydrocarbon solvent and aluminum halide is added to the solution can be mentioned. 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 the magnesium alkoxide by the method of the above-mentioned b, the three compounds are first 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 thereof include a method in which an organic acid ester is added to a mixture of magnesium alkoxide and aluminum halide or a co-pulverized product and co-pulverized, 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. The same solvent as that used in the co-grinding described above can be used as the solvent in the solution reaction.

A complex compound composed of magnesium alkoxide, aluminum halide and organic acid ester can be obtained by powdering at room temperature, but it is easy to dissolve in hydrocarbon in the next step, that is, coexistence of titanic acid ester and alcohol. Therefore, the powder of the complex compound is preferably a fine powder having a large specific surface area as much as possible. The amount of aluminum halide used is 1 mol of magnesium alkoxide.
With respect to 0.001-0.7 mol, preferably 0.01
Is 0.5 mol, and the amount of the organic acid ester (I) used is 0.05 to 1 mol of magnesium alkoxide.
It is 0.5 mol.

The amount of organic acid ester (I) used with respect to aluminum halide is 0.1 to 50 mol, preferably 0.5 to 10 mol, of organic acid ester (I) per 1 mol of aluminum halide. When using a solvent for co-milling, the amount of the solvent used is the magnesium alkoxide used,
Total amount of aluminum halide and organic acid ester 1
0.05 to 100 ml of solvent, preferably 0.
1 to 50 ml. 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-milling is 0 to 150 ° C, preferably 20 to 100
The temperature and the temperature are 5 minutes to 100 hours, but the time varies depending on the means of pulverization. For example, in a pulverizing method capable of giving strong energy in a short time such as a vibration mill, it takes 5 minutes to 2 minutes.
Although it may be 0 hours, it takes 30 minutes to 100 hours in a pulverizing method such as a ball mill which does not give strong energy in a short time. 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 described above, 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 15
It is 0 ° 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. Therefore, it is preferable to filter out a small amount of insoluble matter that does not dissolve easily. 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 per 1 mol of magnesium alkoxide used to obtain magnesium alkoxide or complex compound.
l, preferably 0.5 to 2.0 mol, and when a polytitanate ester is used, the unit corresponding to the orthotitanate ester in the polytitanate ester molecule is converted to a mol unit and the mol is the same as the orthotitanate ester. Just decide the ratio. 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.

On the other hand, 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 be in an amorphous form, and the object of the present invention cannot be achieved. . Further, the titanic acid ester and the alcohol must be used in common, and the individual use of each of them cannot achieve the object of the present invention.

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

Next, the above solution is reacted with a silicon halide and an organic acid ester (II) to obtain a solid product ((I). The solid product (I) can be obtained by adding a solution containing magnesium alkoxide to an organic acid. After the ester is added and reacted, silicon halide is added to precipitate a solid, and the silicon halide is added and reacted together with the organic acid ester,
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 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 general formula SiX _n R ⁷ ₄ -n is used.
And / or compounds represented by the general formula SiX _n (OR ⁸ ) _4-n can be used. Here, X is Cl or Br, R ⁷ and R ⁸ are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 1 to 10 carbon atoms, and n is a number of 1 to 4. Specifically, SiX
As _{n R} 7 ⁴ _-n, silicon tetrachloride, silicon tetrabromide, three Echirukei containing trichloride, propyl silicon chloride, trichloride Buchirukei arsenide, terphenyl silicon trichloride, cyclohexyl silicon chloride, tribromide Echirukei element dichloride Jiechirukei arsenide, etc. can be used dichloride Jibuchirukei arsenide and chloride Toriechirukei ^{_{element, SiX n (oR 8) 4}} -n
Examples include silicon tetrabromide, ethoxysilicon trichloride, propoxysilicon trichloride, ptooxysilicon trichloride, phenoxysilicon trichloride, ethoxysilicon tribromide, diethoxysilicon dichloride, diptoxysilicon dichloride and triethoxysilicon chloride. Can be used. The above compounds may be used as a mixture of two or more. Among them, silicon tetrachloride is preferable. Organic acid ester (I
I) and the silicon halide may be used as they are or after being 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 the organic acid ester used is based on 1 mol of the magnesium alkoxide initially used,
It is 0.05 to 0.6 mol. This amount of organic acid ester may be used at one time, or may be used in several stages. The reaction temperature is 30 to 150 ° C, preferably 50 to 1
The reaction time is 30 ° C. and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours in each step. The total amount of the organic acid ester (I) and the organic acid ester (II) used is 0.1 to 0.7 mol, preferably 0.1 to 0.7 mol, based on 1 mol of the magnesium alkoxide used for producing the solid product (I).
It is 1 to 0.6 mol. The reaction condition of the homogeneous solution and the silicon halide is a temperature of 40 to 150 ° C., preferably 50 to 1
30 ° C., time 5 minutes to 10 hours, preferably 10 minutes to 5
It's time. The amount of silicon halide used is 0.1 to 50 mol per 1 mol of magnesium alkoxide used.
1, 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). As titanium halide, TiX _q (O
A compound represented by R ⁹ ) _4-n can be used. Here, X is Cl, R ⁹ is an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and q is a number of 1 to 4. Specifically, titanium tetrachloride, ethoxy titanium trichloride, propoxytan trichloride, butoxy titanium trichloride, octanoxy titanium trichloride, phenoxy titanium trichloride, cyclohexoxy titanium trichloride, diethoxy titanium dichloride, dichloride Examples thereof include diptoxytitanium, difuninokititanium dichloride, triethoxytitanium chloride and triphenoxytitanium 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, relative to l.

The reaction temperature of the solid product (I) with titanium halide or vanadium halide is 40 to 150 ° C, preferably 5
The temperature is 0 to 130 ° C., and the time is 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. Specifically, aliphatic hydrocarbons such as hexane, heptane, nonane, decane and kerosene can be mentioned. Solid product (II) is at least 5 during and after washing.
It is necessary that 0 wt% of the previously mentioned liquid deactivated hydrocarbon be present. 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 is present with respect to 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.

At least 50% by weight of solid product (II) after washing
It is important to store in the coexistence of the liquid inert hydrocarbon, and to provide for polymerization.

The solid product (II) can be used as a catalyst for polyolefin production by combining it with an organoaluminum compound as a solid catalyst component and optionally an organic acid ester. As the organic aluminum compound, a general formula Al
The compound represented by X _s R ¹⁰ ₃ -s may be used. Here, X is Cl, R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and s is a number of 0 to 2. Triethyl aluminum, tri-n-propyl aluminum, tri-
Examples thereof include i-butylaluminum, tricyclopentylaluminum, tricyclohexylaluminum, dimethylaluminium chloride, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride and ethylaluminum dichloride. 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, or triethylaluminum and tri-i-butyl. It is also preferable to use a mixture of three kinds of organoaluminum compounds such as aluminum and ethylaluminum sesquichloride. As the organic acid ester, the same compound as the above-mentioned organic acid ester (I) or (II) can be used. Among them, aromatic carboxylic acid esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate are preferable.

The combination method of the solid product (II), the organoaluminum compound and the organic acid ester is such that the solid product (II), the organoaluminum compound and the organic acid ester are independently fed 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 organic acid ester is fed to the polymerization vessel,
Etc., 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 one of the components 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., preferably −30 to + 30 ° C., the time is 5 minutes to 5 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 the organic acid ester used is 0.01 to 1 mol, preferably 0.05, relative to 1 mol of the organic aluminum compound.
~ 0.7 mol. When the mixed organoaluminum compound or mixed organic acid ester is used, the total mol number thereof may be 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 organic acid ester. Α with 3 or more carbon atoms
-As olefins, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,
4-methylpentene-1 and 3-methylpentene-1
Etc. can be used. 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, and 1,4-pentadiene, in addition to the α-olefin having 3 or more carbon atoms described above. The amount of the other α-olefin used is an amount contained in the copolymer in an amount of 30 mol% 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 40-2
The temperature is 00 ° C, preferably 50 to 150 ° C, and the polymerization pressure is atmospheric pressure to 100 kg / cm ³ (G), preferably 5 to 50 kg.
/ Cm ³ (G). The polymerization can be carried out in any of batch mode, semi-continuous mode and continuous mode.
Industrially, continuous 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 and storage of the solid catalyst components described above, the preparation of the catalyst, and the production of the polymer have to be carried out in an atmosphere of an inert gas such as nitrogen or helium, but in some cases they are also carried out in an atmosphere of monomers or under vacuum conditions. be able to.

The main effects of the present invention are as follows. First, the polymerization activity is extremely high, and there is no need to remove the residual catalyst in the polymer. It is extremely economical because a polymer purification step is unnecessary. Second, the stereoregularity of the polymer is extremely high. Isotactic index (hereinafter II
(Abbreviated as) indicates that this is high. 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 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. Further, industrially, the polymer can be easily transported and recovered, and the operation to supply it to the granulator and the processing can be facilitated, and the productivity is remarkably improved. Dust explosion due to fine powder can be suppressed, which is effective in preventing entrainment.

Further, the copolymerization also facilitates the production of the copolymer, since the deterioration of the polymer particle shape and the decrease in bulk specific gravity are small.

Another main effect of the present invention is that even if the step of drying the solid product (II) and the step of performing the prepolymerization treatment are omitted, the same effect as the invention of the prior application can be obtained, and the omission of these steps By this, the production of the solid product (II) can be carried out very easily.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.

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

(1) Melt flow rate (abbreviated as MFR) is ASTM
According to D1238 (L).

(2) Bulk specific gravity of polymer (abbreviated as BD) is ASTM
According to D1895.

(3) The shape of the solid product (I), the solid product (II) and the polymer particles are observed with an optical microscope. The polymers obtained in any of the examples had a shape close to a sphere.

(4) The particle size distribution of the polymer was determined according to JIS K0069 using a sieve according to JIS Z8801. The particle size distribution of the solid product (I) and the solid product (II) is L
It was determined by a Microtrac analyzer manufactured by eds & Northrup.

(5) The cumulative 50% by weight of the particle size distribution curve in the above particle size distribution is the average particle size, and the value obtained by dividing the cumulative 85% by particle size by the cumulative 15% by weight is the uniformity index. .

(6) The amount of fine polymer powder is the ratio of the amount of polymer having a particle size of less than 100 μm to the total amount.

(7) II (1) means liquid phase polymerization using an inert hydrocarbon In the case of liquid phase polymerization and gas phase polymerization using α-olefin as a solvent (8) II (2) is the case of liquid phase polymerization using an inert hydrocarbon In the case of liquid phase polymerization and gas phase polymerization using α-olefin as a solvent Example 1 (1) Preparation of supported solid catalyst component In a glass flask, purified decane 50 ml, magnesium diethoxide 5.7 g, and aluminum chloride 0.67.
g, n-butyl orthotitanate 17.1 g, 2-ethyl-1-hexanol 19.6 g and ethyl benzoate 1.5 g 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 further stirred at the same temperature for 1 hour. Then, 1.9 g of ethyl benzoate was added and the mixture was heated to 70 ° C. for 1 hour. After the reaction, the solid was washed with purified hexane to obtain a solid product (I).
The total amount of the solid product (I) was 1,2-dichloroethane 5
It was mixed with 50 ml of titanium tetrachloride diluted with 0 ml and reacted at 80 ° C. for 2 hours while stirring, 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 2
It was 1 μm and the uniformity index was 1.44. The composition analysis result of the solid product (II) obtained by drying at 25 ° C. under reduced pressure (10 ⁻³ mmHg) for 3 hours was Ti 3.24% by weight (hereinafter referred to as “%”), ethyl benzoate 10.7%, Butoxy group 1.6
% And a 2-ethylhexanoxy group was 2.2%.

(2) Production of Polyolefin In a stainless reactor equipped with a multi-stage stirrer having an internal volume of 3 and having been replaced with nitrogen, 1.5 mmol of triethylaluminum, 0.5 mmol of diethylaluminum chloride, and 0.5 mmol of methyl p-toluate solid product (II) After adding 4.0 × 10 ⁻³ mg atom of Ti atom and 300 ml 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 was discharged to obtain 220 g of powdery polypropylene. The results are shown in the table. This powdery polypropylene had an average particle size of 620 μm and was not easily ground.

Comparative Example 1 In the same manner as in Example 1, except that the solid product (II) was washed with purified hexane and then dried under reduced pressure (10 ⁻³ mmHg) at 25 ° C. for 3 hours to obtain a solid product (II) equivalent product. A supported solid catalyst component was prepared in the same manner as in Example 1, and polypropylene was produced using the solid product (II) equivalent.

Comparative Example 2 3 g of the solid product (II) equivalent obtained in Comparative Example 1
Was suspended in 200 ml of purified hexane containing 10 mmol of triethylaluminum cooled to 0 ° C., and the polymer yield was about 10 g-polymer / g-solid product (II) in suspension at the same temperature while stirring. Ethylene to 5
I breathed time. It was washed with purified hexane until triethylaluminum was not detected in the filtrate and dried at 25 ° C. under reduced pressure (10 ⁻³ mmHg) for 3 hours to obtain a solid product (II
I) got. Ti in the solid product (III) is 0.29%
Met. A polypropylene was produced in the same manner as in (2) of Example 1 except that the solid product (III) was used in place of the solid product (II) of (2) of Example 1.

Example 2 (1) Preparation of supported solid catalyst component In a stainless steel flask, 50 ml of purified nonane,
Magnesium diethoxide 5.7 g, ethyl aluminum dichloride 0.952 g, ethyl orthotitanate 1
7.2 g, 13.0 g of n-octanol and 1.63 g of ethyl p-anisate were mixed and stirred at 110 ° C.
It was heated for 3 hours to dissolve. The homogeneous solution was heated to 50 ° C., 58 g of ethyl silicon trichloride containing 1.98 g of ethyl p-anisate 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 purified. The solid product (I) was obtained by washing with hexane. The total amount of the solid product (I) was mixed with 100 g of ethoxytitanium trichloride diluted with 30 ml of toluene and stirred at 110 ° C. for 1 hour.
The mixture was reacted for a time, washed with purified heptane, and without drying, purified heptane was added to obtain a heptane suspension. Solid product (II) was present in suspension 1 in a proportion of 10 g.

The solid product (II) has a nearly spherical shape and an average particle size of 2
It was 2 μm and the uniformity index was 1.44. The composition analysis results of the solid product (II) obtained by drying under reduced pressure at 30 ° C. for 3 hours were a Ti content of 3.05% and an ethyl anisate content of 9.8%.

(2) Production of polyolefin In a nitrogen-substituted autoclave having an internal volume of 3.6, 6 mmol of triethylaluminum and 1.
5 mmol and solid product (II) in terms of Ti atom of 8.
After adding 0 × 10 ⁻³ mg atom, 500 ml of hydrogen was introduced together with 1 kg of liquid propylene, and polymerization was carried out at 70 ° C. for 1 hour. During that time, the total pressure was 32 kg / cm ² (G). Then, unreacted propylene was discharged to obtain 318 g of powdered polypropylene. The results are shown in the table. The powdery polypropylene had an average particle size of 490 μm and was hardly ground.

Comparative Example 3 Similar to Example 2 except that the solid product (II) was washed with purified heptane and then dried at 30 ° C. under reduced pressure for 3 hours to obtain a solid product (II) equivalent. Then, a supported solid catalyst component was prepared to produce polypropylene.

Comparative Example 4 3 ml of the solid product (II) equivalent obtained in Comparative Example 3 was cooled to 5 ° C. in the presence of a small amount of propylene, and 300 ml of purified hexane containing 5 mmol of triethylaluminum.
And the polymer yield was about 5 g-polymer / g-solid product (II) in suspension at the same temperature with stirring.
Was blown in for 3 hours. It was washed with purified hexane and dried at 30 ° C. under reduced pressure for 3 hours to obtain a solid product (III). Ti in the solid product (III)
Was 0.48%. Polypropylene was produced in the same manner as in (2) of Example 2 except that the solid product (II) in Example 2 (2) was used in place of the solid product (II).

Example 3 (1) Preparation of supported solid catalyst component In a glass flask, 50 ml of purified decane, 5.7 g of magnesium diethoxide, 0.424 g of diethylaluminum chloride, and n-butyl orthotitanate 17.
1 g and n-ethyl-1-hexanol 19.6 g were mixed and heated to 130 ° C. for 1.5 hours with stirring to obtain a uniform solution. The homogeneous solution was heated to 70 ° C., 1.8 g of ethyl benzoate 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,
It was stirred for another hour. Subsequently, 1.6 g of ethyl benzoate
Was added and the mixture was stirred for 1 hour, then the solid was separated and washed with purified hexane to obtain a solid product (I). Using this solid product (I), thereafter, a supported solid catalyst component was prepared in the same manner as in (1) of Example 1.

The solid product (II) has a nearly spherical shape and an average particle size of 1
9 μm, homogeneity index 1.46, dry solid product (II)
The Ti content therein was 3.45%.

(2) Production of Polyolefin Purified hexane 1 was put into an autoclave with an internal volume of 2 and purged with nitrogen, and 1.5 mmol of triethylaluminum and 0.5 mmol of ethylaluminum sesquichloride, p-
Ethyl anisate 0.5 mmol and solid product (II) were added with 4.0 × 10 ⁻³ mg atom in terms of Ti atom, and hydrogen 2
After adding 00 ml, the total pressure of propylene is 10 kg / cm ³
Polymerization was carried out at 70 ° C. for 1 hour while continuously introducing so as to give (G). Then, the hexane-insoluble matter was separated by filtration and dried to obtain 75.2 g of powdery polypropylene.
The results are shown in the table. This powdery polypropylene had an average particle size of 370 μm and was not easily ground.

Comparative Example 5 In Example 3, the solid product (II) was washed with purified hexane in the same manner as in Comparative Example 2 to obtain the solid product (III).
To obtain polypropylene.

Examples 4-6 In Example 1, n-butyl orthotitanate 17.1
23.9 g in place of g (Example 4), ethyl polytitanate (pentamer) 8.5 g in place of n-butyl orthotitanate (Example 5), or 2-ethyl- 1-Phenolic acid instead of hexanol
A supported solid catalyst component was prepared in the same manner as in Example 1 except that 8.9 g was used (Example 6) to produce polypropylene.

Example 7 In (2) of Example 3, 1- was used instead of propylene.
A propylene-butene copolymer was obtained in the same manner as in Example 3 (2) except that propylene containing 10 mol% of butene was used. The butene content in the copolymer was 3.8 mol%.

Examples 8-9 In (2) of Example 2, substituting 0.88 g of ethyl acetate first and then 0.97 g of ethyl acetate instead of ethyl p-anisate used in the two steps (Example 8), Or vanadium tetrachloride 96 instead of ethoxytitanium trichloride
(1) of Example 2 except that g was used (Example 9).
A supported solid catalyst component was prepared in the same manner as in, and polypropylene was produced in the same manner as in (3) of Example 3 except that these supported solid catalyst components were used in place of (2) of Example 3. .

Example 10 11.4 g of magnesium diethoxide and 1.4 g of aluminum chloride were placed in a vibration mill made of stainless steel having an internal volume of 100 ml.
34 g and 3.0 g of ethyl benzoate were sequentially added, and 10 stainless steel balls (13 mmφ5 and 10 mmφ)
5 pieces) were placed therein, and the mixture was sealed and co-pulverized 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, and purified decane 5
0 ml, n-butyl orthotitanate 17.1 g and 2-
Ethyl-1-hexanol (19.6 g) was added, and the mixture was heated to 130 ° C. for 2 hours with stirring to obtain a uniform solution. After making the solution homogeneous, a solid product (II) was prepared in the same manner as in (1) of Example 1, and polypropylene was produced in the same manner as in (2) of Example 1.

Example 11 The solid product (I) was reacted with titanium tetrachloride in dichloroethane in the same manner as in (1) of Example 1 and washed with purified hexane, and then hexane and the solid product (II) were mixed at the same weight ratio. In the existing suspension state, a polyolefin was produced in the same manner as in (2) of Example 1 using the solid product (II).

The above results are shown in the table.

[Brief description of drawings]

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

Claims (6)

[Claims] 1. A. Magnesium alkoxide, an aluminum halide represented by the general formula AlX _n R ¹ _3-n (where X is Cl or Br, and R ¹ has 1 to 1 carbon atoms).
An alkyl group of 0, an aryl group or a cycloalkyl group of 3 to 10 carbon atoms, n is a number of 0 to 3), an orthotitanate represented by the general formula Ti (OR ² ) ₄ 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 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and m is a number of 2 to 20), saturated aliphatic Heating the alcohol or phenol and optionally the aliphatic or aromatic carboxylic acid ester (I) in an inert hydrocarbon solvent to dissolve, or b. A complex compound is obtained by co-milling magnesium alkoxide, the aluminum halide and the aliphatic or aromatic carboxylic acid ester (I), and the complex compound, the orthotitanic acid ester and / or the polytitanic acid ester and an aliphatic saturated alcohol. Alternatively, phenol is dissolved in an inert hydrocarbon solvent, and the solution thus obtained is treated with a silicon halide represented by the general formula SiX _n R ⁷ _4-n (where X is Cl or Br and R ⁷ is a carbon number). An alkyl group having 1 to 10, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, n
Is a number of 1 to 4) and an aliphatic or aromatic carboxylic acid ester (II) to precipitate a solid product (I), and the solid product (I) has the general formula TiX _q (OR ⁹ )
Titanium halide represented by _4-q (where X is C
l and R ⁹ are an alkyl group having 1 to 10 carbon atoms, an aryl group or a cycloalkyl group having 3 to 10 carbon atoms, and q is a number of 1 to 4) and / or vanadium tetrachloride, and The solid after the reaction is washed with a liquid inert hydrocarbon to obtain a solid product (II), and the solid product (II) is obtained in the state where at least 50% by weight of the liquid inert hydrocarbon coexists. A method for producing a catalyst component for producing a polyolefin, comprising: 2. The aluminum halide is 0.01 to 0.5 mol per 1 mol of magnesium alkoxide.
1, 0.5 to 3.0 mol of the orthotitanate ester, 0.5 to 6.0 of saturated aliphatic alcohol or phenol
mol and aliphatic or aromatic carboxylic acid ester (I) 0.05 to 0.5 mol, and the magnesium alkoxide in an inert hydrocarbon solvent at 50 to 150 ° C.
The method according to claim (1), wherein heating is performed for 5 minutes to 5 hours for dissolution. 3. The aluminum halide is 0.01 to 0.5 mol per mol of magnesium alkoxide.
1 and 0.05 to 0.5 mol of the aliphatic or aromatic carboxylic acid ester (I) to obtain a complex compound, and 1 mol of the magnesium alkoxide, which is a constituent raw material of the complex compound, is used for the orthotitanic acid. Using 0.5 to 3.0 mol of ester and 0.5 to 6.0 mol of aliphatic saturated alcohol or phenol, 50 to 50 mol of the complex compound, the orthotitanate and the aliphatic saturated alcohol or phenol in an inert hydrocarbon solvent are used. Claim 1 (1) to dissolve by heating at 150 ° C for 5 minutes to 5 hours.
The method described in the section. 4. An inert hydrocarbon solution of a magnesium alkoxide obtained by dissolving the aluminum halide, the orthotitanate, an aliphatic saturated alcohol or phenol, and an aliphatic saturated or aromatic carboxylic acid ester (I). 1 to 20 mol of the silicon halide and 0.1 to 0.6 mol of the aliphatic or aromatic carboxylic acid ester (II) in 50 to 130 ° C. with respect to 1 mol of the magnesium alkoxide
The method according to claim (1), wherein the reaction is carried out for 10 minutes to 5 hours. 5. When precipitating a solid product (I) from a homogeneous solution, the solution is reacted with an aliphatic or aromatic carboxylic acid ester (II) and then reacted with silicon halide to precipitate a solid. Or an aliphatic or aromatic carboxylic acid ester (II) is reacted with silicon halide at the same time to precipitate a solid, or a silicon halide is reacted to precipitate a solid and then an aliphatic or aromatic carboxylic acid ester (II The method according to claim (1), wherein the method of reacting II) is used, or a method in which any two or more of the above are combined is used. 6. The solid product (I) contains 5 to 5 mol of the titanium halide and / or vanadium tetrachloride per mol of the magnesium alkoxide used for its preparation.
After reacting at 0 to 130 ° C. for 10 minutes to 2 hours, the reaction product is washed with an inert hydrocarbon solvent to give a solid product (II).
The method according to claim (1).