JPH0617401B2 - Method for producing polyolefin - Google Patents

Description

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

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

[Conventional technology]

Conventionally, it has been known that the stereoregularity of a polyolefin obtained by combining a supported solid catalyst component with an organoaluminum compound component and an aromatic carboxylic acid ester component is improved as a direction for improving a Ziegler-Natta type catalyst. . For example, JP-A-57-74307 and JP-A-
The technique of using aromatic carboxylic acid esters as one component of the catalyst to improve the stereoregularity of polyolefins, as in 58-32604, is known. However, in principle, when a polyolefin is produced in a solvent-free gas-phase polymerization process, the aromatic carboxylic acid ester which is one component of the catalyst is all contained in the produced polyolefin. It is also well known that esters have a strong odor in the presence of a trace amount. Therefore, when an aromatic carboxylic acid ester is used as one component of a catalyst and a polyolefin is produced by a gas phase polymerization process, the polyolefin contains an aromatic carboxylic acid ester or a compound resulting from the change in the process. It produces a strong odor during storage and during the polyolefin granulation process. The generation of such an odor causes environmental pollution in the production of polyolefin on an industrial scale, which 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. In the prior application, it is essential that the supported solid catalyst component to be combined with the organosilicon compound component having a Si—OC bond contains a polyvalent carboxylic acid and / or an ester of a polyvalent hydroxy compound. Therefore, the supported solid catalyst containing aromatic monocarboxylic acid ester is Si-OC.
It has not yet been known that the stereoregularity of the obtained polyolefin is improved even if it is combined with an organosilicon compound component having a 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, Structure and Effect of Invention]

As a result of intensive studies for solving workability defects due to environmental pollution and strong odor, the present inventors have found that a novel supported solid catalyst component containing an aromatic monocarboxylic acid ester is an organoaluminum compound component and Si-OC. The present invention has been completed by finding that a combination with an organosilicon compound component having a bond serves as a catalyst having high polymerization activity and can be used for the polymerization of olefins to give highly stereoregular and odorless polyolefins.

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

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

(1) anhydrous magnesium dihalide, an aluminum halide represented by the general formula AlX _n R ¹ _3-n (where X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a carbon number) 3 to 20 cycloalkyl groups, n is a number from 0 to 3), titanic acid ester and saturated aliphatic alcohol are mixed and dissolved in an inert hydrocarbon solvent, and the solution thus obtained has the general formula SiX _l Silicon halide represented by R ⁷ _4-l (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)
Of the formula (1 is a number of 1 to 4) and an aromatic carboxylic acid ester to precipitate a solid product (I), and TiX ₄ (where X is Cl Or Br), 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 at least 50% by weight of the liquid inert carbon. The solid product (II) obtained in the presence of hydrogen fluoride is used as a solid catalyst component, and the solid catalyst component, the organoaluminum compound component, and Si-O
A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining an organosilicon compound component having a -C bond.

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

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

First, anhydrous magnesium dihalide, halogenated (organic) aluminum, titanic acid ester and alcohol are mixed in an inert hydrocarbon solvent and heated to dissolve. As anhydrous magnesium dihalide, anhydrous magnesium chloride and anhydrous magnesium bromide can be used. Anhydrous may include those containing trace amounts of water as much as commercial products commercially available as these "anhydrous" compounds. The halogenated (organic) aluminum is a compound represented by AlX _n R ¹ _{3 -n} , where X is Cl or Br, and R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or 3 to 20 carbon atoms. Is a cycloalkyl group, and n is a number from 0 to 3. For example, aluminum trichloride, ethyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum chloride, dipropyl aluminum chloride, triethyl aluminum, aluminum tribromide, ethyl aluminum dibromide 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. Polytitanium such as ester, methyl polytitanate, ethyl polytitanate, polytitanate n-propyl, polytitanate i-propyl, polytitanate n-butyl, polytitanate i-butyl, polytitanate n-amyl, polytitanate phenyl and polytitanate cyclopentyl Acid esters can be used.

An aliphatic alcohol can be used as the alcohol. 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. In addition to monohydric alcohols such as the above, 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.

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.

Specifically, as a method of dissolving, anhydrous magnesium dihalide, (organic) aluminum halide, titanic acid ester and alcohol are mixed in an inert hydrocarbon solvent in any order, and the suspension is heated with stirring. And dissolve.

The titanic acid ester and alcohol are heated in an inert hydrocarbon solvent with stirring, and anhydrous magnesium dihalide and aluminum halide are added to the solution to dissolve the same, or anhydrous magnesium dihalide and halogenated (organic) aluminum are treated with inert carbon. Examples include a method of suspending in a hydrogen fluoride solvent while heating, and adding a titanate ester and an alcohol to the suspension to dissolve the suspension.

Either method can be adopted, but the method is preferable because the operation is extremely easy. The solution after heating may be completely dissolved into a uniform solution, or a small amount of insoluble matter may remain. However, since a small amount of insoluble matter may adversely affect the particle shape of the solid catalyst, it is preferable to completely dissolve it into a uniform solution. A small amount of insoluble matter may be extremely insoluble even over time. In such a case, a small amount of insoluble matter may be filtered off to obtain a uniform solution. It is necessary to heat to dissolve it. Temperature is 40-200 ℃, preferably 50-1
It is 50 ° C. Time is 5 minutes to 7 hours, preferably 10 minutes to 5
It's time.

The amount of (organic) aluminum halide used is 0.005 to 0.7 mol, preferably 0.01 to 0.5 mol, relative to 1 mol of anhydrous magnesium dihalide, and the amount of titanic acid ester used is orthotitanium to 1 mol of anhydrous magnesium dihalide. In the case of acid ester, 0.1 to 0.2 mol, preferably 0.5
~ 1.5 mol. In the case of polytitanate ester, pay attention to the repeating unit of orthotitanate ester in the molecule of polytitanate ester, and replace the unit corresponding to orthotitanate ester with mo
The amount to be used may be determined in the same manner as in the case of orthotitanate in terms of l units.

The amount of alcohol used is anhydrous magnesium dihalide 1
It is 0.1 to 6 mol, preferably 0.5 to 5 mol, based on mol.

As the amount of titanic acid ester and alcohol used increases with respect to anhydrous magnesium dihalide, the solubility of anhydrous magnesium dihalide 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 solidified, the control of particle shape becomes extremely difficult. Further, if the use amount of titanic acid ester and alcohol is too small, anhydrous magnesium dihalide is not soluble in an inert hydrocarbon solvent, the solid catalyst becomes amorphous, and it is possible to obtain a polymer having a spherical shape or a particle shape close to a spherical shape. Can not.

The amount of the inert hydrocarbon solvent used is 0.1-5, preferably 0.3-3, relative to 1 mol of anhydrous magnesium dihalide.
Is. In most cases, once the solution has been dissolved, solids do not precipitate even when cooled to room temperature, so it can be stored as a uniform solution at room temperature.

Then, the above solution is reacted with silicon halide and an organic acid ester to obtain a solid product (I). As a method for obtaining a solid product (I), an organic acid ester is added to the solution containing magnesium halide and reacted, and then a silicon halide is added to precipitate a solid, and a silicon halide is added together with the organic acid ester. By reacting to precipitate a solid, or by adding a silicon halide to precipitate a solid and then adding an organic acid ester to cause a reaction, or a combination thereof to obtain a solid, and then obtain the solid. A method of obtaining a solid product (I) by washing with an inert hydrocarbon solvent can be mentioned.

Organic acid esters include ethyl acetate, propyl acetate,
Aliphatic carboxylic acid esters such as butyl acetate, ethyl propionate, butyl propionate and ethyl butyrate, aromatic carboxylic acids such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate It is an ester.

Silicon halides include SiX _l R ⁷ _{4 -l} and SiX _p (OR ⁸ )
A compound represented by _4-p can be used. Here, X is Cl or Br, R ⁷ and R ⁸ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and 1 and p are numbers of 1 to 4. In particular
As SiX _l R ⁷ _{4 -l} , silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, ethyl silicon tribromide, Diethyl silicon chloride,
Dibutyl silicon dichloride, diphenyl silicon dichloride, triethyl silicon chloride and the like can be used.

As SiX _p (OR ⁸ ) _4-p , silicon tetrachloride, silicon tetrabromide,
Methoxysilicon trichloride, ethoxysilicon trichloride, propoxysilicon trichloride, butoxysilicon trichloride, phenoxysilicon trichloride, ethoxysilicon tribromide, dimethoxysilicon dichloride, diethoxysilicon dichloride, dibutoxysilicon dichloride, trichloride Methoxysilicon, triethoxysilicon chloride and the like can be used.

It is also possible to use mixtures of the compounds mentioned. Among them, silicon tetrachloride is preferable. The organic acid ester and the silicon halide may be used as they are or diluted with a solvent. In that case, the same solvent as the above-mentioned inert hydrocarbon solvent can be used. The organic acid ester is preferably added to a solution containing magnesium halide in the presence of a silicon halide or in the presence of silicon halide to react, but the silicon halide may be added to the solution, or the solution may be added. It may be added to the silicon halide.

The total amount of organic acid ester used is 0.05 to 0.7 mol, preferably 1 to 1 mol of anhydrous magnesium dihalide.
It is 0.1 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 130 ° C., and the reaction time is 5 minutes to 5 hours in each step, preferably 10 minutes to 2
It's time.

Even if only the organic acid ester is added to the solution containing magnesium halide and reacted, the solid does not precipitate, but if left at high temperature for a long time, the organic acid ester will change to another compound and finally obtained. The role of the stereoregularity control for the solid product (II) obtained may decrease.
The reaction with the silicon halide is carried out at a temperature of 40 to 150 ° C., preferably 50 to 130 ° C., a time of 5 minutes to 10 hours, preferably 10 minutes to
5 hours.

The amount of silicon halide used is 0.1 to 50 mol, preferably 1 to 2 per 1 mol of anhydrous magnesium dihalide used.
It is 0 mol. Solid is precipitated by adding silicon halide and reacting. Since the particle shape of the solid product (II) is controlled by the particle shape of the solid product (I), the reaction between the solution and the silicon halide is extremely important for controlling the particle shape.

After reacting the organic acid ester with the silicon halide,
Subsequent reaction with titanium halide may be carried out, but it is preferable to wash the precipitated solid once with the above-mentioned inert hydrocarbon. This is because unreacted substances or by-products present in the solution may interfere with the subsequent reaction. A solid product (I) is thus obtained.

Next, the solid product (I) is reacted with titanium halide and / or vanadium halide to obtain the solid product (I
I). As titanium halide, TiX _q (OR ⁹ ) _4-q
The compound represented by can be used. X here
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 1 to 4
Is the number of. Specifically, titanium tetrachloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, octanoxy titanium trichloride, phenoxy titanium trichloride, cyclohexoxy titanium trichloride, diethoxy titanium 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 and ester of 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. Among these titanium halides, titanium tetrachloride is most preferable. Specific examples of vanadium halides include vanadium tetrachloride, vanadium oxytrichloride, and other vanadium derivatives in which at least one halogen is bonded to vanadium. 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 between the solid product (I) and the titanium halide is carried out by adding titanium halide to a suspension solution of the solid product (I) or by adding a suspension solution of the solid product (I) in the titanium halide. Add and react. Alternatively, the solid product (I) is once washed by filtration or decantation to suspend the solid product (I) in the above-mentioned inert hydrocarbon solvent, and the suspension is halogenated. Titanium is added, or a suspension of the solid product (I) in titanium halide is added and reacted.
The same applies when vanadium halide is used instead of or together with titanium halide. Among them, the method is preferable. The amount of titanium halide or vanadium halide used is 1 to 100 mol, preferably 3 to 50 mol, based on 1 mol of anhydrous magnesium dihalide used.

The reaction temperature of the solid product (I) with titanium halide or vanadium halide is 40 to 150 ° C, preferably 50 to 1
The temperature is 30 ° C. and the time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours. After the reaction, solids are separated by filtration or decantation and then washed with an inert solvent to remove unreacted substances and by-products. A solid product (II) is thus obtained. The particle shape of the solid product (II) at this stage must 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. Solid product (II) during and after washing
Must coexist with at least 50% by weight of the aforementioned liquid inert hydrocarbon. The washing method is preferably a decantation method, and after washing, at least the solid product (I
It is preferable that the liquid inert hydrocarbon is present in the solid product (II) in such an amount that the I) is immersed in the liquid inert hydrocarbon. When less than 50% by weight of liquid inert hydrocarbon coexists with the solid product (II), sufficient catalytic performance is obtained even if the solid product (II) is combined with an organoaluminum compound and then subjected to polymerization. Does not exert. That is, as a result of the polymerization, the polymer yield and bulk specific gravity are low, and the shape is also poor,
Large amount of fine powder and low stereoregularity. It is important that the solid product (II) after washing is stored in the coexistence of at least 50% by weight of the liquid inert hydrocarbon and subjected to polymerization.

The solid product (II) can be used as a catalyst for polyolefin production by combining it as a solid catalyst component with an organoaluminum compound component and an organosilicon compound component having a Si—OC bond. As the organoaluminum compound to be combined, it is possible to use a compound represented by AlX _s R ¹⁰ _3-S. Here, X is Cl, R ¹⁰ has 1 to 20 carbon atoms
Is an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and s is a number of 0 to 2. Specifically, triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl aluminum, tricyclopentyl aluminum, tricyclohexyl aluminum,
Examples thereof include dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum chloride, ethyl aluminum sesquichloride and ethyl aluminum 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 is preferable.

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

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

The combination method of the solid product (II), the organoaluminum compound and the organosilicon compound is as follows: the solid product (II), the organoaluminum compound and the organosilicon compound are independently supplied to a polymerization vessel. And the solid product (II) are independently fed to the polymerization vessel, and the mixture of the solid product (II), the organoaluminum compound and the organosilicon compound is fed to the polymerization vessel. Can also be adopted.

However, in some cases or is preferred.
When the three components are combined as described above, each component or any component may be dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane and kerosene before use. .
The temperature in the case of mixing before feeding to the polymerization vessel as described above 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.

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

A solid product (II) as a solid catalyst component according to the present invention,
An α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms, using a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound. Examples of α-olefins 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 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, 1,4-pentadiene, and methyl-1,4-hexadiene, in addition to the α-olefin having 3 or more carbon atoms described above.
The amount of the other α-olefins used is such that the copolymer obtained by the copolymerization will contain 50% by weight or less. The polymerization can be carried out in the liquid phase or the gas phase. When the polymerization is carried out in the liquid phase, for example, hexane,
An inert hydrocarbon solvent such as heptane, nonane, decane or kerosene may be used as the polymerization medium.
It is also possible to use the olefin itself as the reaction medium. When carrying out the polymerization in the gas phase, in principle no reaction medium is used, but it is also possible to use either the catalyst or any of its components dissolved or suspended in the abovementioned inert hydrocarbons.
The polymerization is carried out by bringing the catalyst into contact with the α-olefin in the polymerization vessel. Polymerization temperature is 40 ~ 200 ℃,
The temperature is preferably 50 to 150 ° C, and the polymerization pressure is atmospheric pressure to 100 kg.
/ cm ² G, preferably 5 to 50 kg / cm ² G. The polymerization can be carried out by any of a batch type, a semi-continuous type and a continuous type, but industrially a continuous type polymerization is preferred.

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

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

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

Further, the catalyst in which the solid catalyst component of the present invention is combined with the organoaluminum compound component and the organosilicon compound component,
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. In addition, the stereoregularity of the polymer is extremely high. This is shown by the high isotactic index (hereinafter abbreviated as II). It is extremely advantageous for polymer production by a gas phase polymerization method without using a solvent. Furthermore, a characteristic effect of the present invention is that 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, a stable long-term production operation of the polymerization vessel is possible in a liquid phase polymerization method such as slurry polymerization or bulk polymerization or a gas phase polymerization method. In addition, industrially easy transportation and recovery in the production process of the polymer according to the present invention,
The supply to the granulator and the operation for processing and molding become easy, and the productivity is greatly improved. Dust explosion due to fine powder can be suppressed, which is effective in preventing entrainment. Further, even when the α-olefin is copolymerized in the method using the catalyst according to the present invention, the deterioration of the polymer particle shape and the decrease in bulk specific gravity are small, and the copolymer is easily manufactured.

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

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

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

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

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

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

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

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

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

Example 1 (1) Preparation of supported solid catalyst component In a glass flask, 30 m of purified decane, 4.76 g of anhydrous magnesium chloride, 0.47 g of aluminum chloride, 17 g of n-butyl orthotitanate and 19.4 g of 2-ethyl-1-hexanol. Were mixed and heated with stirring at 130 ° C. for 1 hour to dissolve them to obtain a uniform solution. The solution was heated to 70 ° C., 3.5 g of ethyl p-toluate was added and reacted for 1 hour, 52 g of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid, and the mixture was further stirred for 1 hour at 70 ° C. The solid was separated from the solution and 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 m of titanium tetrachloride dissolved in 0 m and reacted with stirring at 80 ° C. for 2 hours, followed by washing with purified hexane, and without drying, purified hexane was added to obtain a hexane suspension. Solid product (II) in the suspension 1
Was present in an amount of 50 g.

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) was spherical and had an average particle size of 20 μm, and its particle size distribution was extremely narrow. 25 ℃, under reduced pressure (10
^-3 mmHg) The composition analysis effect of the solid product (II) obtained by drying for 3 hours was Ti3.2 wt% (hereinafter referred to as%), Cl57.0
%, Mg 17.6%, Al 1.5%, Si 1.0%, ethyl p-toluate 8.5%, butoxy group 3.4%, and 2-ethylhexanoxy group 1.5%.

(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, 2.0 mmol of triethylaluminum, 0.4 mmol of diphenyldimethoxysilane and 6.5 × 10 ⁻³ mg of solid product (II) in terms of Ti atom were calculated. 70 after adding one atom and hydrogen
Polymerization was carried out for 2 hours while continuously introducing propylene so that the total pressure was 22 kg / cm ² G at ℃. Then, unreacted propylene was discharged to obtain 223 g of powder polypropylene. The powder polypropylene has a BD of 0.46 and an MFR of 6.
9. The polymer particles had a spherical shape or a shape close to a spherical shape, and the amount of fine powder having a particle diameter of 100 μm or less was 0.01% by weight of the whole. Extraction residue [II] with boiling hexane is 98.3%
Therefore, the powdery polypropylene obtained after the polymerization was difficult to be ground.

(3) Odor sensory test Polypropylene immediately after polymerization had an unreacted propylene odor. Therefore, it was left in a nitrogen stream at 50 ° C. for 3 hours and then subjected to an odor sensory test. There was no propylene odor, and when 10 testers conducted a sensory test to smell directly, all 10 judged that there was no odor (odor rank A). After the sensory test, 0.1% by weight of antioxidant and polypropylene were added to polypropylene.
0.1% by weight was added and thoroughly mixed in a Henschel mixer (trade name), and the granules were granulated at 220 ° C using a uniaxial granulator with a diameter of 20 mm and a vent in the center. With respect to the exhaust gas, three testers judged that there was an odor (odor rank B), and all of the molten polymers at the outlet of the granulator were judged to have no odor (odor rank A).

Comparative Example 1 Except that the solid product (II) prepared in (1) of Example 1 was used as a solid catalyst component and diphenyldimethoxysilane in (1) of Example 1 was replaced with methyl p-toluate. A polyolefin was produced in the same manner as in (2) of Example 1, and an odor sensory test was conducted in the same manner as in (3) of Example 1. The results are shown in the table.

Example 2 (1) Preparation of Supported Solid Catalyst Component In a stainless steel flask, purified nonane 50 m,
Anhydrous magnesium chloride 4.76 g, aluminum chloride 2.0 g,
17.1 g of ethyl orthotitanate and 13 g of n-octyl alcohol were mixed and heated to 100 ° C. for 2 hours with stirring to dissolve them to obtain a uniform solution. The solution was heated to 70 ° C., 57 g of ethyl silicon trichloride containing 3.2 g of ethyl benzoate was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred at 70 ° C. for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (I). The solid product (I) was mixed with 50 m of titanium tetrachloride dissolved in 50 m of toluene and reacted at 100 ° C. for 1.5 hours with stirring, followed by washing with purified hexane, and without drying, hexane was added to purified hexane. It was a suspension. 10 g of solid product (II) was present in the suspension 1.

The solid product (II) was spherical and had an average particle size of 22 μm, and its particle size distribution was extremely narrow. The composition analysis result of the solid product (II) obtained by drying under reduced pressure at 25 ° C. is Ti2.8.
%, Cl 56.3%, Mg 16.7% and ethyl benzoate 7.5%.

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

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

Example 3 In a glass flask, 30 m of purified kerosene, 4.76 g of anhydrous magnesium chloride, 0.64 g of ethyl aluminum dichloride, 14.2 g of n-butyl polytitanate (pentamer) and 7.7 g of n-hexyl alcohol were mixed and stirred. 11
The mixture was heated at 0 ° C for 1.5 hours, and a trace amount of insoluble matter was filtered off to obtain a uniform solution. The solution was brought to 60 ° C and the butoxy silicon trichloride 72
g was added dropwise over 3 hours to precipitate a solid, and the mixture was continuously stirred for another 1 hour. Subsequently, 3.6 g of ethyl p-anisate was added and reacted at the same temperature for 1.5 hours. The solid was separated from the solution and washed with purified hexane to obtain a solid product (I). This solid product (I) was mixed with 100 m of titanium tetrachloride and reacted at 110 ° C. for 2 hours with stirring, followed by washing with purified hexane, and then solid product (II) was prepared in the same manner as in Example 1. Prepared and using the solid product (II) as a solid catalyst component in place of the solid product (II) in (2) of Example 1,
A polyolefin was produced in the same manner as in (2) of Example 1 except that phenyltriethoxysilane was used in place of diphenyldimethoxysilane, and the obtained polymer was used to smell in the same manner as in (3) of Example 1. A sensory test was conducted.
The results are shown in the table.

Comparative Example 3 The same procedure as in Example 3 was repeated except that the solid product (II) prepared in Example 3 was used as a solid catalyst component and ethyl p-toluate was used in place of phenyltriethoxysilane in Example 3. A polyolefin was produced by the following method, and an odor sensory test was conducted. The results are shown in the table.

Example 4 1-butene 1 was used in place of propylene in (2) of Example 1.
A polyolefin was produced in the same manner as in Example 1 except that propylene containing 5 mol% was used, and an odor sensory test was conducted. The butene content in the powdery propylene-butene copolymer was 5.6 mol%. The results are shown in the table.

Example 5 In Example 2, 12 mol% of ethylene was used instead of propylene.
A polyolefin was produced in the same manner as in Example 2 except that propylene containing was used, and an odor sensory test was conducted. The ethylene content in the powdery propylene-ethylene copolymer was 6.2 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 (7)

[Claims] 1. Anhydrous magnesium dihalide, general formula Al
Aluminum halide represented by X _n R ¹ _3-n (where X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms,
An aryl group or a cycloalkyl group having 3 to 20 carbon atoms,
n is a number from 0 to 3), titanate esters and aliphatic saturated alcohols dissolved by mixing in an inert hydrocarbon solvent, thus the resulting solution represented by the general formula SiX _l R ⁷ _4-l (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)
Of the formula (1 is a number of 1 to 4) and an aromatic carboxylic acid ester to precipitate a solid product (I), and TiX ₄ (where X is Cl Or Br), 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 at least 50% by weight of the liquid inert carbon. The solid product (II) obtained in the presence of hydrogen fluoride is used as a solid catalyst component, and the solid catalyst component, the organoaluminum compound component, and Si-O
A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining an organosilicon compound component having a -C bond. 2. An orthotitanate represented by the general formula Ti (OR ² ) ₄ 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), and halogenated with respect to 1 mol of anhydrous magnesium dihalide Aluminum 0.01 to 0.5 mol, 0.5 to 1.5 mol and 0.5 to 5 mol of the titanic acid ester and the alcohol, respectively, are used, and anhydrous magnesium dihalide, the aluminum halide and the titanic acid ester are used in an inert hydrocarbon solvent. And the above alcohol at 50-150 ℃, 0-5kg / cm
^The method according to claim (1), wherein the mixture is dissolved by stirring or shaking mixing at ² G for 10 minutes to 5 hours. 3. 1 to 20 mol of the silicon halide and 1 mol of magnesium dihalide used to obtain an inert hydrocarbon solution of anhydrous magnesium dihalide, the aluminum halide, the titanate and the alcohol. 0.1-0.6 mol of aromatic carboxylic acid ester is used, with respect to the above solution, at 50-130 ° C., 0-5 kg / cm ² G
The method according to claim (1), wherein the silicon halide and the aromatic carboxylic acid ester are mixed for 10 minutes to 5 hours to precipitate the solid product (I). 4. An anhydrous hydrocarbon solution of anhydrous magnesium dihalide, said aluminum halide, said titanate ester and said alcohol is mixed with an aromatic carboxylic acid ester and then with said silicon halide, or Group carboxylic acid ester and said silicon halide are mixed at the same time, or said silicon halide is mixed and then aromatic carboxylic acid ester is mixed, or said aromatic carboxylic acid ester and / or said part of said silicon halide is used to ． After performing the mixed reaction according to any one of the above items, b. The method according to claim (3), wherein the remaining portion of the aromatic carboxylic acid ester and / or the silicon halide is used for mixing by any of the methods other than the preceding step a. 5. A solid product (I) with an inert hydrocarbon solvent.
Is washed, and the Ti
X ₄ is ₃ to 50 mol of the above-mentioned titanium halide to 1 mol equivalent of magnesium dihalide constituting the above-mentioned solid product (I) to be washed, and is 50 to 130 ° C. and 0 to 5 kg / cm ² G. The method according to claim (1), wherein the solid product (II) thus obtained is reacted for 10 minutes to 2 hours. 6. 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). Group or carbon number 3
~ 20 cycloalkyl groups, t is a number from 0 to 3) is used in an amount of 0.01 to 2 mol per 1 gram atom of Al of the organoaluminum compound component. Process for polymerizing olefins. 7. The method according to claim 1, wherein the polymerization of α-olefin is carried out in a gas phase.