JPH0617404B2 - Polyolefin manufacturing method - 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.

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, as a direction for improving Ziegler-Natta type catalysts, by combining a supported solid catalyst component with an organoaluminum compound component and an aromatic carboxylic acid ester component,
It is known that the stereoregularity of the obtained polyolefin is enhanced. For example, as disclosed in JP-A-57-74307 and JP-A-58-32604, a technique of using an aromatic carboxylic acid ester as a component of a catalyst for improving the stereoregularity of polyolefin 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 the catalyst and a polyolefin is produced by a gas phase polymerization process, the polyolefin contains the aromatic carboxylic acid ester or a compound resulting from the change in the process. It produces a strong odor during storage and during the granulation process of polyolefins. The production of such polyolefins on an industrial scale causes environmental pollution and is a problem. 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. At the beginning, it is essential that the supported solid catalyst component to be combined with the organosilicon compound component having a Si—OC bond contains an ester of a polyvalent carboxylic acid and / or a polyvalent hydroxy compound.
However, it has not yet been known that the stereoregularity of the obtained polyolefin is improved even when the supported solid catalyst containing an aromatic monocarboxylic acid ester 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.

[Object of the 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, a catalyst having high polymerization activity is provided, and it was found that this catalyst gives a polyolefin having a good stereoregular polymer particle shape and odorless, and completed the present invention. .

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. It is to be.

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

(1) magnesium alkoxide, titanate,
An aliphatic saturated alcohol having 1 to 20 carbon atoms and, if necessary, an aromatic carboxylic acid ester (I) are mixed and heated in an inert hydrocarbon solvent to be dissolved, and the solution thus obtained is subjected to 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 3 to 20 carbon atoms)
Which is a cycloalkyl group, wherein n is a number of 1 to 4) and a silicon halide and an aromatic carboxylic acid ester (I) are mixed and reacted to precipitate a solid product (I). TiX ₄ (where X is Cl or
Br) 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) contains at least 50% by weight of the liquid inert carbon. Using a solid product (II) obtained in the presence of hydrogen as a solid catalyst component, and using a catalyst obtained by combining the solid catalyst component with an organoaluminum compound component and an organosilicon compound component having a Si-OC bond. A method for producing a polyolefin, which comprises polymerizing an α-olefin.

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 titanic acid ester and an alcohol and optionally an organic acid ester in an inert hydrocarbon solvent and heated to dissolve. Magnesium alkoxide is a compound generally represented by Mg (OR ¹ ) ₂ , where R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group having 3 to 20 carbon atoms, an aralkyl group, or the like. For example, magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium dicyclohexoxide, magnesium dialoxide, magnesium diphenoxide and the like can be mentioned. 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 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 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. Ester, methyl polytitanate, polytitanate, polytitanate n-propyl, polytitanate i-propyl,
Polytitanate such as n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, phenyl polytitanate and cyclopentyl polytitanate can be used. Alcohol has 1 carbon
~ 20 aliphatic alcohols and / or 6 to 24 carbon atoms
Aromatic alcohols of 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-ethylhexyl alcohol. , Monohydric alcohols such as benzyl alcohol, ethylene glycol,
Polyhydric alcohols such as trimethylene glycol and glycerin can also be used. Among them, carbon number 4 to 1
An aliphatic alcohol of 0 is preferred. 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 are preferable.

Examples of the organic acid ester (I) or (II) include ethyl acetate, propyl acetate, butyl acetate, ethyl propionate,
2 to 2 carbon atoms such as butyl propionate and ethyl butyrate
It is an aliphatic carboxylic acid ester of 20 or an aromatic carboxylic acid ester of 8 to 24 carbon atoms such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl triylate, methyl anisate and ethyl anisate. The same applies to the aromatic carboxylic acid ester used during the polymerization of α-olefin.

Specifically, as a method of dissolving, magnesium alkoxide, titanic acid ester and alcohol are mixed and suspended in an inert hydrocarbon solvent in any addition order, and the suspension is heated and dissolved with stirring to dissolve. The titanate ester and alcohol are heated in an inert hydrocarbon solvent with stirring, and magnesium alkoxide is added to the solution and dissolved. Alternatively, the magnesium alkoxide is suspended in an inert hydrocarbon solvent while heating, and the titanate ester and alcohol are added to the suspension to dissolve the suspension. And the like. In any method, the organic acid ester can be added at any stage. The purpose of addition of the organic acid ester is to make the dissolution of the magnesium alkoxide smooth and uniform and to improve the stereoregularity, which is essential. Either method can be adopted, but the method is preferable because the operation is extremely simple. The solution after heating is completely dissolved into a uniform solution, but a small amount of insoluble matter may remain therein. Since a small amount of insoluble matter may adversely affect the particle shape of the solid catalyst, it is preferable that the solid catalyst is completely dissolved into a uniform solution. A small amount of insoluble matter may be removed by filtration to obtain a uniform solution. It is necessary to heat the suspension in order to dissolve it. Heating temperature is 4
The temperature is 0 to 200 ° C, preferably 50 to 150 ° C. The heating time is 5 minutes to 7 hours, preferably 10 minutes to 5 hours. The amount of titanate used is 0.1 mol for 1 mol of magnesium alkoxide orthotitanate.
˜5.0 mol, preferably 0.5 to 3.0 mol, and in the case of polytitanate, the amount used is the same as orthotitanate in terms of units corresponding to orthotitanate. The amount of alcohol used is magnesium alkoxide 1
It is 0.1 to 8.0 mol, preferably 0.5 to 6.0 mol, relative to mol. The larger the total amount of titanate ester and alcohol used relative to the magnesium alkoxide, the greater the solubility of the magnesium alkoxide in the inert hydrocarbon solvent,
In order to re-solidify the magnesium alkoxide in the obtained solution, an extremely large amount of silicon halide must be used, and the re-solidification itself becomes difficult, and it is extremely difficult to control the particle shape even when solidified. Becomes
On the other hand, if the total amount of the titanate ester and the alcohol used is too small, the magnesium alkoxide 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. The total amount of titanic acid ester and alcohol used is narrower than the range of the above total usable amount, and is 1.5 to 8.0 mol, preferably 2.5 to 0.6 mol, per 1 mol of magnesium alkoxide. The amount of the inert hydrocarbon solvent used is 0.1 to 5, preferably 0.3 to 3, with respect to 1 mol of the magnesium alkoxide. An organic acid ester is used if necessary. The organic acid ester used at this stage is referred to as organic acid ester (I). The amount of organic acid ester (I) used is 0.01-0.5 mol, preferably 0.05-0.5 mol, per 1 mol of magnesium alkoxide.
It is 0.4 mol.

Next, the above solution is reacted with a silicon halide and an organic acid ester to obtain a solid product (I). As a method for obtaining the solid product (I), a solution containing magnesium alkoxide is added to react with an organic acid ester and then reacted to add a silicon halide to precipitate a solid, by adding a silicon halide together with the organic acid ester. After solid is obtained by any method such as reaction and precipitation of solid, precipitation of solid by adding silicon halide and then reaction by addition of organic acid ester, or combination of two or more thereof, the solid is obtained. Can be washed with an inert hydrocarbon solvent to obtain a solid product (I).

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

Silicon halides include SiXl ▲ R ⁷ _4-1 ▼ and Xp (OR
⁸ ) Compounds represented by _4-l can be used. Here, X is Cl or Br, and R ⁷ and R ⁸ are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or 3 to 2 carbon atoms.
A cycloalkyl group of 0, and 1 and p are numbers from 1 to 4. Specifically, as SiXl ▲ R ⁷ _4-l ▼, silicon tetrachloride, silicon tetrabromide, ethyl trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, Ethyl silicon bromide, diethyl silicon dichloride, dibutyl silicon dichloride, triethyl silicon chloride and the like can be used alone or in admixture of two or more.

SiXp (OR ⁸ ) _4-p includes silicon tetrachloride, silicon tetrabromide,
Ethoxysilicon trichloride, propoxysilicon trichloride, butoxysilicon trichloride, phenoxysilicon trichloride, ethoxysilicon tribromide, diethoxysilicon dichloride, dibutoxysilicon dichloride, triethoxysilicon chloride, etc., alone or as a mixture of two or more. Can be used. Among them, silicon tetrachloride is preferable. The organic acid ester (II) 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 amount of the organic acid ester (II) used is 0.01 to 0.7 mol, preferably 0.0 to 1 mol of the magnesium alkoxide used.
It is 5 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 for reacting the organic acid ester (II) and the silicon halide with the above-mentioned solution containing magnesium alkoxide is 30 to 150 ° C., preferably 50 to 150 ° C., and the reaction time is 5 minutes to 5 for each step. The time is preferably 10 minutes to 2 hours. The total amount of the organic acid ester (I) and the organic acid ester (II) used is preferably 0.1 to 0.6 per 1 mol of the magnesium alkoxide used.

Even if only the organic acid ester (II) is added to the above-mentioned homogeneous solution and reacted, a solid does not precipitate, but if left in the reacted state for a long time, the organic acid ester (II) is a different compound. However, the function of controlling the stereoregularity of the finally obtained catalyst may deteriorate.

The amount of silicon halide used is 0.1 to 50 mol, preferably 1 to 50 mol, per 1 mol of magnesium alkoxide used.
It is 20 mol. A solid is deposited by adding silicon halide to the homogeneous solution and reacting it.

The particle shape of the solid product (II) described later is governed by the shape of the solid product (I). For the latter particle shape control,
It is determined by the reaction conditions of the homogeneous solution and the silicon halide. It is also possible to react the organic acid ester with the silicon halide to precipitate a solid, and subsequently subject this solid to a reaction of titanium halide and / or vanadium halide. However, it is preferable to wash the deposited solid once with the above-mentioned inert hydrocarbon solvent. This is because unreacted substances or by-products existing in the solution in which the solid is precipitated may interfere with the above reaction on the solid.

After the washing, a solid product (I) is obtained.

Next, the solid product (I) is reacted with titanium halide and / or vanadium halide to obtain a solid product (II). As the titanium halide, a compound represented by TiXq (OR ⁹ ) _4-q can be used. Where X is Cl,
R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group 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. Titanium halides other than titanium tetrachloride can be produced by the reaction of titanium tetrachloride with orthotitanate, but it is also possible to use a mixture of titanium tetrachloride and orthotitanate for this reaction. it can. As the orthotitanate, the same one as any of the above-mentioned orthotitanates 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. The reaction of the solid product (I) with titanium halide and / or vanadium halide gives the solid product (I)
Titanium halide and / or vanadium halide is added to the suspension in the inert hydrocarbon described above, or the solid product (I) is added to titanium halide and / or vanadium halide to carry out the reaction. You may let me. The amount of titanium halide or vanadium halide used is 1 to 100 mol, preferably 3 to 50 mol, based on 1 mol of the magnesium alkoxide used.

Reaction temperature of solid product (I) with titanium halide or vanadium halide 40-150 ° C, preferably 50-
130 ° C., time 5 minutes to 5 hours, preferably 10 minutes to 2
It's time. After the reaction, solids are separated by filtration or a decantation method, and then the solids are sufficiently washed with an inert solvent to remove unreacted substances or by-products. In the present invention, the particle shape of the solid product (II) at this stage needs to be good.

The solvent used for washing is a liquid inert hydrocarbon.
Specifically, hexane, heptane, octane, nonane,
Mention may be made of aliphatic hydrocarbons such as decane or kerosene. During and after washing, the solid product (II) is required to coexist with at least 50% by weight of the aforementioned liquid inert hydrocarbon. In particular, the decantation method is preferable for washing, and at least the solid product (I
It is preferable that the liquid inert hydrocarbon coexists with the solid product (II) at the position where I) is immersed in the liquid inert hydrocarbon. 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 it is subjected to subsequent 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. The solid product (II) after washing has at least 5
It is important to store it in the coexistence of 0% by weight of liquid inert hydrocarbon and to use it for polymerization.

The solid product (II) can be used as a catalyst for polyolefin production by combining it as a solid catalyst component with an organoaluminum compound and an organosilicon compound component having a Si—O—C bond. As the organoaluminum compound, a compound represented by the general formula AlX _s ▲ R ¹⁰ _3-s ▼ can be used. Where X is Cl and R ¹⁰ is 1 carbon
To 20 alkyl groups, aryl groups or 3 to 20 carbon atoms
Is a cycloalkyl group, and s is a number from 0 to 2. Specifically, 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 ethylaluminum dichloride and the like. 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 of R ¹¹ tSi (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 of 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, benzyltri Ethoxysilane, benzylphenoxydimethoxysilane, benzylmethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, phenylmethoxyethoxyphenoxysilane, cyclopropylmethoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiphenoxy Orchid, dimethyldibenziloxysilane, dimethylmethoxyethoxysilane, dimethylmethoxyphenoxysilane, dimethylethoxyphenoxysilane, methylethyldimethoxysilane, methylethyldiphenoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiphenoxysilane , Ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, phenylbenzyldimethoxysilane, methylcyclopropylzomethoxysilane,
Methylvinyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylbenzyloxysilane, triethylmethoxysilane, triethylethoxysilane, triethylphenoxysilane, triphenylmethoxysilane, tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethyl Phenylmethoxysilane, diethylmethylmethoxysilane, diethylmethylphenoxysilane,
Examples thereof include diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxysilane, and methylethylphenylphenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, Methylethyldiethoxysilane, methylphenyldiethoxysilane, methylbenzyldimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane and trimethylethoxysilane are preferable.

The solid product (II), the combination method of the organoaluminum compound and the organosilicon compound, the solid product (II), the organoaluminum compound and the organosilicon compound are independently fed to the polymerization vessel, The mixture and the solid product (II) are fed to the polymerization vessel independently, the mixture of the solid product (II), the organoaluminum compound and the organosilicon compound 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 component can be used by dissolving or suspending it in a liquid aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane and kerosene. . The temperature in the case of mixing before feeding to the polymerization vessel as in the above cases 1 and 2 is -50 to + 50 ° C, preferably -30 to + 30 ° C, and the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours. is there.

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

In the method of the present invention, a solid product (II) as a solid catalyst component, a catalyst obtained by combining an organoaluminum compound and an organosilicon compound, and an α having 3 or more carbon atoms are used.
Produce an α-olefin polymer using olefins. Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1 and 3
-Methylpentene-1 and the like 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. As the α-olefin having 2 or more carbon atoms, the α-olefin having 3 or more carbon atoms described above is used.
Other than olefins, mention may be made of ethylene, butadiene, isoprene, 1,4-pentadiene and methyl-1,4-hexaciene. Their other α-
The olefin is used in an amount of 50% by weight or less in the copolymer. 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
To 200 ° 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 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 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 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 indicated by a 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 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, industrially the polymer can be easily transported and recovered, the supply to the granulator and the processing operation can be facilitated, and the productivity is remarkably improved. Dust explosion due to fine powder can be suppressed, which is effective in preventing entrainment.

Also, copolymerization does not cause deterioration of polymer particle shape and decrease in bulk specific gravity, and the copolymer can be easily produced.

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 density of polymer (abbreviated as BD) is ASTM D
1895.

(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, 1
If 0 people all have no odor, B has a little odor, and 1 out of 10 people has odor, C
Is a case where 5 to 9 out of 10 people have a smell, and D is a case where there is a strong smell, and all 10 people are a case where there is 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 by using a sieve according to JIS Z8801. In addition, the particle size distribution of the solid product (II) is micron photo sizer (manufactured by Seishin Enterprise Co., Ltd., SKC-20
00 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 n-hexane (69 ° C.) that boils the polymer.
Is the ratio of the extraction residue after extraction for 6 hours to the total amount before extraction.

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

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

Example 1 (1) Preparation of solid catalyst component In a glass flask, 50 m of purified decane, 5.7 g of magnesium diethoxy, n-butyl orthotitanate 1
7.1 g, 2-ethyl-1-hexanol 19.6 g and p
-Mix 1.6 g ethyl toluate and mix with stirring 13
It was dissolved by heating at 0 ° C. for 2 hours. The homogeneous solution is 70
51 ° 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, 2.1 g of ethyl p-toluate was added, and the mixture was reacted at 70 ° C. for 1 hour. The solid was washed with purified hexane to obtain a solid product (I). The solid product (I) was diluted with 50 m of 1,2-dichloroethane to obtain 50 m of titanium tetrachloride.
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 20.
was μm. The composition analysis result of the solid product (II) obtained by drying at 25 ° C. under reduced pressure (10 ⁻³ mmHg) for 3 hours is Ti2.3.
% By weight (hereinafter referred to as%), ethyl p-toluate 7.8
%, Butoxy group 3.2% and 2-ethylhexanoxy group
It was 1.7%.

(2) Production of Polyolefin In a reactor made of stainless steel with a multi-stage stirrer having an internal volume of 3 and replaced with nitrogen, triethylaluminum (1.5 mmo), phenyltriethoxysilane (0.5 mmo), and the solid product (II) were converted to Ti atoms at 6.5 × 10 ^-3. After adding mg atoms 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 / mc ² (G). Then, unreacted propylene was discharged to obtain 222 g of powdery polypropylene. 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, so after leaving it in a nitrogen stream at 50 ° C for 3 hours,
It was subjected to an odor sensory test. When there was no propylene odor, a sensory test was performed by 10 testers directly to smell, and it was judged that all 10 had no odor (odor rank A). Further, 0.1% by weight of polypropylene antioxidant and 0.1% by weight of lubricant after sensory test were added and mixed well in a Henschel mixer (trade name), and a uniaxial granulator having a diameter of 20 mm and a vent portion in the center. When granulated at 220 ° C. using a syrup, four experimenters judged that there was an odor in the vent gas discharged (odor rank B), and all the molten polymers at the outlet of the granulator were judged to have no odor (odor. Rank A).

Comparative Example 1 A solid catalyst component was prepared in the same manner as in Example 1 except that methyl p-toluate was used in place of phenyltriethoxysilane, a polyolefin was produced, and an odor sensory test was conducted. . The results are shown in the table.

Example 2 (1) Preparation of solid catalyst component In a stainless steel flask, purified nonane 50 m
, Magnesium diethoxide 5.7 g, ethyl orthotitanate 17.2 g, n-octanol 13.0 g and ethyl benzoate 1.5 g 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 with stirring to precipitate a solid.
After stirring for hours, the solid was washed with purified hexane to obtain a solid product (I). The total amount of the solid product (I) is toluene 3
After mixing with 100 g of titanium tetrachloride diluted with 0 m and reacting at 110 ° C. for 1 hour while stirring, the mixture was washed with purified heptane and purified heptane was added without drying to obtain a heptane suspension. 10 g of solid product (II) in the suspension 1
Existed at a rate of. The solid product (II) had a shape close to a sphere and had an average particle size of 22 μm, a Ti content of 2.8% and an ethyl benzoate content of 5.6%.

(2) Production of polyolefin and odor sensory test In Example 1, the solid product (II) obtained in Example 2 was used in place of the solid product (II), and methyl was used in place of phenyltriethoxysilane. A polyolefin was produced in the same manner as in Example 1 except that phenyldimethoxysilane was used, and a odor sensory test was conducted. The polypropylene obtained by the production had a nearly spherical shape. The results are shown in the table.

Comparative Example 2 A polyolefin was produced in the same manner as in Example 2 except that methyl p-anisate was used in place of methylphenyldimethoxysilane, and an odor sensory test was conducted. The results are shown in the table.

Example 3 In a glass flask, 50 m of purified kerosene, 5.7 g of magnesium diethoxide, 8.3 g of polybutyl titanate (pentamer), 20.5 g of n-hexyl alcohol and 1.6 g of methyl p-toluate were mixed and stirred. While heating at 120 ° C. for 4 hours, the mixture was dissolved. The homogeneous solution was heated to 60 ° C, 2.4 g of ethyl p-anisate was added and reacted for 1 hour, 70 g of silicon tetrachloride was added dropwise over 3 hours with stirring to precipitate a solid, and the mixture was continuously stirred for 1 hour. And washed with purified heptane to obtain a solid product (I). The solid product (I) was mixed with 100 m of titanium tetrachloride and reacted at 100 ° C for 1.5 hours with stirring, and the solid was separated from the solution by hot filtration, mixed with 100 m of titanium tetrachloride again and mixed at 100 ° C for 1 hour. After reacting, hot filtration was carried out again to separate a solid, and after washing with purified hexane, a solid product (II) was obtained in the same manner as in Example 1.

A polyolefin was produced in the same manner as in Example 1 except that the solid product (II) was used in place of the solid product (II) and diphenylmethoxysilane was used instead of phenyltriethoxysilane. , An odor 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 ethyl p-anisate was used in place of diphenyldimethoxysilane, and a odor sensory test was conducted. The results are shown in the table.

Example 4 In Example 1, ethylene 12mo was used instead of propylene.
A polyolefin was produced in the same manner as in Example 1 except that propylene containing 1% was used, and an odor sensory test was conducted. The ethylene content in the powdery propylene-ethylene copolymer was 0.6 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, a titanic acid ester, an aliphatic saturated alcohol having 1 to 20 carbon atoms and, if necessary, an aromatic carboxylic acid ester (I) are mixed and heated in an inert hydrocarbon solvent to dissolve them. The solution thus obtained has 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); I) is mixed and reacted to precipitate a solid product (I), TiX ₄ (where X is Cl or Br) is reacted with the solid product (I), and the solid after the reaction is treated with liquid inert carbon. Solid product (II) washed with hydrogen fluoride
The solid product (II) obtained in the presence of at least 50% by weight of the liquid inert hydrocarbon as the solid product (II) is used as a solid catalyst component, and the solid catalyst component and the organoaluminum compound component and Using a catalyst obtained by combining with an organosilicon compound component having a Si-OC bond, α-
A method for producing a polyolefin, which comprises polymerizing an olefin. 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 a number of 2 to 20). The method described in section (1). 3. A titanic acid ester of 0.5 to 3.0 mol, an aliphatic saturated alcohol of 0.5 to 6.0 mol and an aromatic carboxylic acid ester (I) of 0.05 to 0.4 mol are used per 1 mol of magnesium alkoxide. ). 4. A solid precipitated by reacting 1 to 20 mol of the silicon halide and 0.1 to 0.6 mol of the aromatic carboxylic acid ester (II) with 1 mol of the magnesium alkoxide used in the production of the solution obtained in the step. The method according to claim 1, wherein the solid product (I) is obtained by washing the product with an inert hydrocarbon solvent. 5. A solution of the silicon halide and / or aromatic carboxylic acid ester (II) is added to the solution obtained in step 50.
Claim (1) in which the reaction is carried out at ~ 130 ° C for 10 minutes to 5 hours.
The method described in the section. 6. The solution obtained in step (i) is reacted with an aromatic carboxylic acid ester (II) and then reacted with the silicon halide, and (ii) an aromatic carboxylic acid ester (II) and the silicon halide are reacted. Or (iii) after reacting the silicon halide with an aromatic carboxylic acid ester (II)
The method according to claim (1), which uses any one of the methods for reacting the above or a combination of two or more of these methods. 7. Solid product (I) in an amount of 3 to 50 mol of Ti per mol of magnesium alkoxide used for its production.
X ₄ is reacted at 50 to 130 ° C. for 10 minutes to 2 hours, and the reaction product is washed with an inert hydrocarbon solvent to obtain a solid product (II). Method. 8. An organosilicon compound having a Si—OC bond is 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). A group or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 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 section 1). 9. The method according to claim 1, wherein the polymerization of α-olefin is carried out in a gas phase.