JPS61211308A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain an odorless, highly stereoregular polyolefin good in particle shape, by polymerizing an alpha-olefin in the presence of a catalyst obtained by combining a specified solid catalyst component with an organoaluminum compound and an organosilicon compound. CONSTITUTION:A magnesium alkoxide, an aluminum halide, a titanate ester and an alcohol are dissolved by heating them in an inert hydrocarbon solvent. The obtained solution is reacted under agitation with a silicon halide and an organic acid ester. The precipitated solid product is reacted with a titanium halide and/or a vanadium halide, and the reaction product is washed with a liquid hydrocarbon. The resulting solid catalyst component is combined with an organoaluminum compound component and an Si-O-C bond-containing organosilicon compound component to prepare a catalyst. An alpha-olefin is polymerized in the presence of this catalyst to obtain a polyolefin.

Description

[Detailed description of the invention] [Field of technology] The present invention relates to a method for producing polyolefins.

More specifically, the present invention relates to a method for producing odorless polyolefin using a novel supported solid catalyst component.

However, in the present invention, polyolefin has 3 carbon atoms.
In addition to the above α-olefin homopolymers and copolymers,
A copolymer of an α-olefin having 3 or more carbon atoms and an α-olefin having 2 carbon atoms, in which the former accounts for 50% by weight or more in the copolymer.

[Conventional technology]

Conventionally, as a direction for improving Ziegler Φ Natsuta type catalysts, it has been known that the stereoregularity of polyolefins obtained can be enhanced by combining a supported solid catalyst component with an organoaluminum compound component and an aromatic carboxylic acid ester component. For example, the technique of using an aromatic carboxylic acid ester as a component of a catalyst to improve the stereoregularity of polyolefins is known, as in JP-A-57-74307 and JP-A-58-32804. However, when polyolefins are produced by a gas phase polymerization process that does not use a solvent in principle, the aromatic carboxylic acid ester, which is a component of the catalyst, is all contained in the polyolefins. Furthermore, it is well known that esters give off a strong odor even when present in trace amounts. Therefore, when an aromatic carboxylic acid ester is used as a component of the catalyst and a polyolefin is produced by a gas phase polymerization process, the polyolefin contains an aromatic carboxylic acid ester or a compound formed by changing it in the process, and the polyolefin is A strong odor is generated during storage and during the polyolefin granulation process. Production of polyolefins on an industrial scale causes environmental pollution, which is a problem.

Furthermore, in JP-A-58-830061, a catalyst formed by combining a supported solid catalyst component with an organometallic compound component and an organosilicon compound component having a 5r-0-C or Si-N-C bond is disclosed. Used Boliole Shizu 11
7 table translation f vomit ↓ Deshi Saya] 3-hl Kakinaga Rezuha, S
It is essential that the supported solid catalyst component to be combined with the organosilicon compound component having an i-0-C bond contains an ester of a polyhydric carboxylic acid and/or a polyhydric hydroxy compound. However, it is not yet known that the stereoregularity of the resulting polyolefin is improved even when a supported solid catalyst containing an aromatic carboxylic acid ester is combined with an organosilicon compound component having a Si-0-C bond. Note that organosilicon compounds having Si-0-C: bonds have a weak odor and have the property of relatively easily reacting with moisture in the atmosphere, decomposing, and changing into odorless compounds. Therefore, even if the polyolefin contains a small amount of an organosilicon compound having S1-0-C bonds, the polyolefin does not have an odor.

[Summary of the invention]

As a result of intensive research to solve the aforementioned poor workability caused by environmental pollution and strong odors, the present inventors discovered that a new supported solid catalyst component containing an aromatic carboxylic acid ester was developed by combining an organic aluminum compound component and an organic aluminum compound component. Si-0-
When combined with an organosilicon compound component having a C bond, the polymerization activity is so high that it is not necessary to remove the residual catalyst in the polymer as an olefin polymerization catalyst, and this catalyst is highly stereoregular, odorless, and has a particle shape. The present invention was completed based on the discovery that a polyolefin having a good quality can be obtained.

As is clear from the above description, the object of the present invention does not require removal of residual catalyst in the polymer.

The object of the present invention is to provide a method for producing a polyolefin having high stereoregularity, odorlessness, and good particle shape.

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

(1) [1]a, magnesium alkoxide, /\aluminum rogenide, titanate ester, alcohol and, if necessary, organic acid ester (1) are mixed and heated in an inert hydrocarbon solvent to dissolve them, or b, co-pulverizing magnesium alkoxide, aluminum halide, and organic acid ester (1) to form a complex compound, heating and dissolving the complex compound, titanate ester, and alcohol in an inert hydrocarbon solvent; [2] The solution thus obtained is reacted with silicon halide and organic acid ester (II) to form a solid product (1
), (■ React the solid product (1) with titanium halide and/or vanadium halide, and ■ Wash the solid after the reaction with a liquid inert hydrocarbon to obtain a solid product. (n), the solid product (II) obtained in the coexistence of at least 50% by weight of a liquid inert hydrocarbon is used as a solid catalyst component, and the solid catalyst component and organic aluminum Compound components and S 1
A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining an organosilicon compound component having a 0-C bond.

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

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

First, magnesium alkoxide is mixed with (a) aluminum halide, titanate, and alcohol in an inert hydrocarbon solvent, and optionally an organic acid ester, and dissolved by heating, or (b).

A complex compound is obtained by co-pulverizing magnesium alkoxide, aluminum norogenide, and an organic acid ester, and this complex compound is heated and dissolved in an inert hydrocarbon solvent in the coexistence of a titanate ester and an alcohol. Magnesium alkoxide is generally Mg(OR')2
It is a compound represented by, where Bo has 1 to 2 carbon atoms.
0 which represents an alkyl group, an aryl group, a cycloalkyl group or an aralkyl group having 3 to 20 carbon atoms, etc. For example, magnesium dimethoxide, magnesium jetoxy 1 d length, ・ﾾmu ・zuproboxy V-magnesium diptoxide, magnesium dicyclohexoxide,
Examples include magnesium alkoxide and magnesium diphenoxide.

As halogen aluminum, A I Xs R Mushi-n
is a compound represented by, where X is Cl or Br
, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 3. For example, aluminum trichloride, ethyl aluminum dichloride, butyl aluminum dichloride, Ethylaluminum sesquichloride.

Examples include diethylaluminium chloride, dipropylaluminium chloride, aluminum tribromide, and ethylaluminum dichloride.

The titanate esters include orthotitanate esters represented by Ti(OR")4 and R'+0-Ti(
OR') (OR5) It is a polytitanate ester represented by bO-R1. Here, R2, R3, R4, B
S and R6 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 from 2 to 20. Specifically, orthotitanate esters such as methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, flJn-butyl orthotitanate, i-amyl orthotitanate, phenyl orthotitanate, and cyclohexyl orthotitanate. , polymethyl titanate, polyethyl titanate, polytitanate n-propyl, polytitanate-propyl, polytitanate n-butyl, polytitanate i-butyl, polytitanate n-7mil, polytitanate phenyl, and polytitanate cyclopentyl. Acid ester (2-20
mer) can be used.

As the alcohol, an aliphatic alcohol having 1 to 20 carbon atoms and/or an aromatic alcohol having 6 to 24 carbon atoms can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, dooramyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethyl-1 ~In addition to monohydric alcohols such as hexyl alcohol and benzyl alcohol, ethylene glycol and trimethylene glycol.

Polyhydric alcohols such as glycerin can also be used. Among them, aliphatic alcohols having 4 to 10 carbon atoms are preferred. Phenols such as phenol or its derivatives can also be used in place of or together with these aliphatic alcohols.

Inert hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride.

Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene can be used. Among them, aliphatic hydrocarbons and halogenated aliphatic hydrocarbons are preferred.

The organic acid ester (the organic acid ester used in this step is referred to as organic acid ester (1)) includes ethyl acetate,
2 to 20 carbon atoms, such as propyl acetate, butyl acetate, ethyl propionate, butyl propionate, and ethyl butyrate
or aromatic carboxylic esters having 8 to 24 carbon atoms, such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate.

Specifically, the method for dissolving magnesium alkoxide is as follows: (d), magnesium alkoxide, aluminum halide, titanate, and alcohol are mixed and suspended in an arbitrary order of addition in an inert hydrocarbon solvent. (2) Heat the aluminum halide, titanate, and alcohol in an inert hydrocarbon solvent while stirring, and add magnesium alkoxide to the solution and dissolve it. or ■ magnesium alkoxide in an inert hydrocarbon solvent,
Examples of methods include heating the titanate ester and alcohol to dissolve them, and adding aluminum halide to the solution. In either method, the organic acid ester (1) 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, and to that extent it is essential.

To dissolve magnesium alkoxide using method 1b above, first, three components are reacted to form a complex compound using methods 1 to 2 below.

That is, (1) the king of magnesium alkoxide, aluminum halide and organic acid ester are simultaneously mixed and subjected to a pulverization reaction (hereinafter referred to as co-pulverization); (2) a mixture or complex of aluminum halide and organic acid ester and magnesium alkoxide are co-pulverized. ■ Add aluminum halide to the mixture or complex of magnesium alkoxide and organic acid ester and co-pulverize. Or ■
Examples include adding an organic acid ester to a mixture or co-pulverized product of magnesium alkoxide and aluminum halide and co-pulverizing, and any method can be employed. Among these, methods ①, ① and @ are preferred, and these reactions can be achieved by means of co-milling (described above). As a means of co-grinding,
A vibrating mill, a ball mill, a vibrating ball mill, etc. are used. It is believed that magnesium alkoxide undergoes a complex reaction upon contact with l\aluminum halogenide and organic acid ester. During co-pulverization, aliphatic hydrocarbons such as hexane, heptane, nonane, decane, and kerosene, aromatic hydrocarbons such as benzene, toluene, and xylene, or carbon tetrachloride, 1,2-dichloroethane, n-butane chloride, chlorobenzene, etc. halogenated hydrocarbons may be used.

When these solvents are used, the solvent may be filtered off after co-pulverization, or may be used immediately in the next reaction.
It is known that aluminum halide and organic acid ester and magnesium alkoxide and organic acid ester form complexes, and these complexes may be used for co-pulverization, or a mixture thereof. can be produced by co-pulverization or reaction in solution. As the solvent for the visible solution reaction, the same solvent as that for the co-pulverization described above can be used.

A complex compound composed of magnesium alkoxide, aluminum halide, and organic acid ester is obtained as a powder at room temperature, but in the next step, in order to facilitate dissolution in hydrocarbons in the coexistence of titanate ester and alcohol. The powder of the complex compound is preferably a fine powder with a specific surface area as large as possible, and the amount of aluminum halide used is 1 mo of magnesium alkoxide.
0.001 to 0.7 mol, preferably 0.
01 to 0.5 mol, and the amount of organic acid ester (1) used is 0.05 to 0.5 mol per 1 mal of magnesium alkoxide.

The amount of organic acid ester (1) to be used with respect to aluminum halide is 0.1 to 50 mol of organic acid ester (1) per 1 mol of aluminum halide.
, preferably Q, 5 to lomol. When using a solvent during co-grinding, the amount of solvent used is 0.05 to 100 m, preferably 0.1 to 50 m, per 10 g of the total amount of magnesium alkoxide, aluminum halide, and organic acid ester used. be.

Aluminum halide and organic acid ester Jl/(1) or magnesium alkoxide and organic acid ester (
When using the complex of 1), it is sufficient to use the complex within the above-mentioned molar ratio range.

The co-grinding temperature is 0 to 150°C, preferably 20 to ioo
℃, the time is 5 minutes to 100 hours, but the time varies depending on the means of crushing. For example, in a crushing method that can give strong energy in a short time, such as a vibration mill, it is 5 minutes to 2 hours.
Although it may take 0 hours, 30 minutes to 100 hours are required in a grinding method such as a ball mill that does not provide strong energy in a short period of time. In co-pulverization, since the magnesium alkoxide is a solid and in some cases the aluminum halide is also a solid, the specific surface area should be adjusted to make it as homogeneous as possible and to facilitate the next operation as mentioned above. It is preferable to form a fine powder with a large size.

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

Specific dissolution methods include: (1) mixing the complex compound, titanate ester, alcohol, and inert hydrocarbon at the same time and dissolving them by heating; (2) mixing the complex compound, alcohol, and inert hydrocarbon;

Add titanate ester before or after heating and heat to dissolve. (2) Mix the complex compound, titanate ester, and inert hydrocarbon, add alcohol before or after heating, and heat to dissolve. Alternatively, it is possible to mix the titanate ester, alcohol, and inert hydrocarbon, add the complex compound before or after heating, and heat to dissolve. Either of the dissolution methods can be adopted. . Among these methods, whichever method is used, solids in the mixture may be completely dissolved to form a homogeneous solution, or a small amount of insoluble matter may remain. This insoluble material is believed to be due to impurities contained in the starting materials, such as magnesium alkoxide or aluminum halide. If a small amount of insoluble matter remains, it may have an adverse effect on the particle shape of the solid catalyst, so it is preferable to completely dissolve it to make a homogeneous solution, or to filter out such a small amount of insoluble matter and make a homogeneous solution. You can also use it as

Heating is necessary to dissolve the aforementioned mixture. The temperature is 40-170℃, preferably 50-15℃
The 0 hour at 0°C is 5 minutes to 6 hours, preferably 10 minutes to
It is 4 hours. 4I contained in the complex compound! When acid esters are heated to high temperatures for a long period of time, they change into substances other than organic acid esters and lose the ability to increase stereoregularity, so if a higher temperature is used for dissolution, the time should be shortened. It is necessary to devise measures such as Preferably, the temperature is as low as possible and the time is as short as possible. Therefore, it is preferable to remove a small amount of insoluble matter that does not dissolve easily.

The amount of titanate ester to be used may be determined based on the amount of magnesium alkoxide used to obtain magnesium alkoxide or a complex compound.When using orthotitanate ester as titanate ester, it is sufficient to determine the amount of magnesium alkoxide used to obtain magnesium alkoxide or a complex compound. 0.1 per 1wo1 of magnesium alkoxide used
~3.0 ol, preferably 0.5 to 2.0 layers is OK, and when using polytitanate ester, convert the unit equivalent to orthotitanate ester in the polytitanate molecule to 01 unit. The molar ratio can be determined in the same way as the orthotitanate ester, and the amount of alcohol used is 0.1 per ◎l of magnesium alkoxide used to obtain the magnesium alkoxide or complex compound.
~6 layers Al, preferably 0.5-5 layers O1.

The greater the amount of titanate ester and alcohol used relative to the magnesium alkoxide, the greater the solubility of the magnesium alkoxide or magnesium alkoxide complex in an inert hydrocarbon solvent. Moreover, re-solidification itself is difficult, and even if solidification is possible, it is extremely difficult to control the particle shape.

On the other hand, if the amounts of titanate ester and alcohol used are too small, the magnesium alkoxide or magnesium alkoxide complex will not be soluble in the inert hydrocarbon solvent, and the solid catalyst will become amorphous, resulting in a polymer with a unispherical or nearly spherical particle shape. Moreover, it is necessary to use titanate ester and alcohol together, and the purpose of the present invention cannot be achieved by using each alone.

The amount of inert hydrocarbon used is 10 to 200 Qm, preferably 50 to 1000 Qm per 10 g of magnesium alkoxide or magnesium alkoxide complex compound.
It is l. The composition of the compounds dissolved and present in solution is not clear.

Next, add silicon halide and organic acid ester (
II) is reacted to obtain the solid product Cl). As a method for obtaining the solid product (1), (1) organic acid ester is added to a solution containing magnesium alkoxide to cause a reaction, and then silicon halide is added to precipitate a solid. ■Add silicon halide together with an organic acid ester and react to precipitate a solid; ■Add silicon halide to precipitate a solid, then add an organic acid ester and react; or A solid is obtained by a combination of two or more methods. A method may be mentioned in which the obtained solid is washed with an inert hydrocarbon solvent to obtain the solid product (1).

As the 41-acid ester (rl) used in this step, the aforementioned aliphatic carboxylic ester or aromatic carboxylic ester can be used.

As silicon halides, the compounds Br, R' and R@ represented by the general formula SiXs moiety -,1 and or the general formula SiX* (OR@)4-rH each have 1 to 1 carbon atoms.
20 alkyl groups, aryl groups, or cycloalkyl groups having 3 to 20 carbon atoms, and n is a number of 1 to 4. Specifically, SiXmR1 to n include silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, silicon chloride, phenyl silicon chloride, cyclohexyl silicon trichloride, and ethyl tribromide. Silicon, diethyl silicon dichloride, dibutyl silicon dichloride, triethyl silicon chloride, etc. can be used, SiXa
(OR@) a-η is silicon tetrabromide, ethoxy silicon trichloride, propoxy silicon trichloride, butoxy silicon trichloride, phenoxy silicon trichloride, ethoxy silicon tribromide, jetoxy silicon dichloride, dibutoxy silicon dichloride Silicon, triethoxysilicon chloride, and the like can be used.

The above-mentioned compounds can also be used in combination of two or more. Among them, silicon tetrachloride is preferred, and organic acid esters (■) and silicon halides may be used as they are or diluted with a solvent. In that case, the solvent may be the inert hydrocarbon mentioned above. The same solvents can be used.

It is preferable that the organic acid ester (■) is added to a homogeneous solution separately from the silicon halide or simultaneously with the silicon halide to react.In this case, the silicon halide may be added to the homogeneous solution, and the homogeneous solution is The amount of the organic acid ester, which may be added to silicon oxide, is 0.000% per mol of magnesium alkoxide initially used.
05~o, e■of. This amount of organic acid ester may be used at once or in several stages.The reaction temperature is 30-150°C, preferably 50-130°C.
0''O, and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours for each step.The total amount of organic acid ester (1) and organic acid ester (I1) used is The amount is 0.1 to 0.7 ol, preferably 0.1 to 0.8 ol, per 1 ol of magnesium alkoxide used in the production of product (1). The reaction conditions are a temperature of 40 to 150°C, preferably 50 to 130°C, and a time of 5 minutes to 10 hours, preferably 1
It is 0 minutes to 5 hours. The amount of silicon halide used is 0.00% per 1 O1 of magnesium alkoxide used.
14501101, preferably 1 to 20+wol. The particle shape of the solid product (■) obtained in the zero-order step in which a solid is precipitated by reacting silicon halide is controlled by the particle shape of the solid product (1). The reaction between the homogeneous solution and the silicon halide that precipitates the solid is extremely important for control.

After reacting the organic acid ester and the silicon halide in the homogeneous solution to precipitate a solid as described above, the precipitated reaction mixture is subsequently subjected to the next step of reaction, that is, the reaction with titanium halide and/or vanadium halide. It is also possible to carry out a reaction. However, it is preferable to wash the precipitated solid with the above-mentioned inert hydrocarbon, since unreacted substances or by-products present in the reaction mixture after the precipitation may interfere with subsequent reactions. After separating and washing the precipitated solid from the reaction mixture, a solid product Cl) is obtained.

A solid product (II) is obtained by reacting a halogen compound and/or a vanadium halide with TiXq as a titanium halide.
(OR9) Compounds represented by a-q can be used. Here, X is Cl, and R' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a carbon lll! It is a cycloalkyl group of 3 to 20, and q is a number of 1 to 4. Specifically, titanium tetrachloride, nidoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, octanoxytitanium trichloride, dienoxytitanium trichloride, cyclohexoxytitanium trichloride, jetoxytitanium dichloride, dichloride titanium Mention may be made of butoxytitanium, diphenoxytitanium dichloride, triethoxytitanium chloride, triphenoxytitanium chloride, and the like. 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 the water reaction. .

As the orthotitanate, the same orthotitanate mentioned above can be used.

Vanadium halides include vanadium tetrachloride, vanadium oxytrichloride, and other vanadium derivatives in which at least one chloro is present.

Here again, a mixture or reactant of vanadium tetrachloride or vanadium oxytrichloride and orthotitanate can be used for one reaction. Among these halides, titanium tetrachloride is most preferred, and titanium norogenide and/or vanadium halide can be used as they are or after being diluted with a solvent.

The solvent in that case may be the same as the inert hydrocarbon solvents already mentioned. Add titanium and/or vanadium halides to the suspension in the inert hydrocarbon described above.

Alternatively, the solid product (1) may be reacted by adding the solid product (1) into titanium halide and/or vanadium halide.
1 to 100 mol, preferably 3 to 50 mol relative to al
It is 11ol.

The reaction temperature between the solid product (1) and titanium halide or vanadium halide is 40 to 150°C, preferably 5°C.
One hour at 0 to 130°C is 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

After the reaction, it is washed by filtering or decantation to remove unreacted substances or by-products. The solvent used during cleaning is a liquid inert hydrocarbon. Specific examples include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, and kerosene. During and after washing, it is necessary that at least 50% by weight of the solid product (■) be present with the above-mentioned liquid inert hydrocarbon. In particular, the decantation method is preferable for washing, and after washing, at least the solid product (II
) is immersed in the liquid inert hydrocarbon, preferably the liquid inert hydrocarbon coexists with the solid product (I1), 50% by weight of the solid product (■) is ungrooved liquid inert carbon If only hydrogen hydride coexists, sufficient catalytic performance will not be exhibited even if this compound is subsequently combined with an organoaluminum compound and subjected to polymerization. That is, the polymer yield and bulk specific gravity are low, the shape is poor, the amount of fine powder is large, and the stereoregularity is low.

It is important to store the washed solid product (I1) in the coexistence of at least 50% by weight of a liquid inert hydrocarbon and to subject it to polymerization.

The solid product (I1) can be used as a catalyst for polyolefin production by combining it with an organoaluminum compound component and an organosilicon compound component having a Si-0-C bond as a solid catalyst component.

The organoaluminum compound has the general formula AlX5Ri
A compound represented by 4 can be used. Here, X is Cl, R'' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms,
S is a number from 0 to 2. Triethylaluminum, tri-n-propylaluminum, tri-butylaluminum, tricyclopentylaluminum, tricyclohexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride and ethylaluminum dichloride, etc. I can do it. Among these, it is preferable to use triethylaluminum alone or a mixture of two types of organic aluminum compounds such as triethylaluminum and streamy butylaluminum, triethylaluminum and diethylaluminum chloride, and triethylaluminum and ethylaluminum sesquichloride.

The organosilicon compound component has the general formula R%'Si(
011") 4-t, where R'1 and zo are an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, t is a number from 0 to 3.

Specifically, methyl silicate, ethyl silicate, butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methylethoxydimethoxysilane, methylphenoxydimethoxysilane, Methylmethoxyethoxyphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriphenoxysilane.

Ethyltribenzyloxysilane, ethylethoxydimethoxysilane, ethylmethoxyjethoxysilane, ethylphenoxydimethoxysilane, ethylmethoxyphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane.

Benzyltrimethoxysilane, penzyltriethoxysilane, benzylphenoxydimethoxysilane, benzylmethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiphenoxy Silane, dimethyldibenzyloxysilane, dimethylmethoxyethoxysilane, dimethylmethoxyphenoxysilane, dimethylethoxyphenoxysilane, methylethyldimethoxysilane, methylethyldiphenoxysilane, methylphenyldimethoxysilane.

Methylphenyldiethoxysilane, methylphenyldiphenoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane.

Phenylbenzyldimethoxysilane, methylcyclopropyldimethoxysilane, methylvinyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylbenzyloxysilane, triethylmethoxysilane, triethylethoxysilane.

Triethylphenoxysilane, triphenylmethoxysilane, tribenzylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, diethylmethylmethoxysilane.

Examples include diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxysilane, and methylethylphenylphenodisilane. Among these,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane.

benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, methylethyljethoxysilane, methylphenyldiethoxysilane, methylbenzyldimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyljethoxysilane , trimethylmethoxysilane, triethylmethoxysilane, and trimethylethoxysilane are preferred.

The method of combining the solid product (I1), the organoaluminum compound, and the organosilicon compound is as follows: ■ Solid product (I1)
, feeding the organoaluminum compound and the organosilicon compound independently to the polymerization vessel, ■ feeding the mixture of the organoaluminum compound and the organosilicon compound and the solid product (I1) independently to the polymerization vessel, ■ solid product (■) , a mixture of an organoaluminum compound and an organosilicon compound is fed to a polymerization vessel. Both methods can be used.

■ or ■ may be preferable When combining the champions such as 0 or more, each component or any component is dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane, and kerosene. It can also be used cloudy. When mixing before supplying to the polymerization vessel as in (2) and (2), the temperature is -50 to +50.
℃, preferably -30 to +30℃, and the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is the titanium atom 1i+ contained in the solid product (II) as a solid catalyst component.
IQ ~100100O for ol, preferably 50
~500 mol. The amount of organosilicon compounds used is 1 organoaluminum compound and 0! 0.01-2 for
eol, preferably 0.05 to 1 mol. When using a mixed organoaluminum compound or a mixed organosilicon compound, the total number of moles thereof may fall within the above-mentioned range.

Using a catalyst obtained by a combination of a solid product (■) as a solid catalyst component, an organoaluminum compound, and an organosilicon compound, an α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms. Examples of α-olefins having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-! , octene-1. Desen-1
．． 4-methylpentene-1 and 3-methylpentene-
1 etc. can be used. The polymerization of these α-olefins includes not only homopolymerization but also copolymerization with one 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 above-mentioned α-olefin having 3 or more carbon atoms. The amount of these other α-olefins used is 50% by weight or less in the copolymer. Polymerization can be carried out in a liquid phase or a gas phase. When polymerizing in a liquid phase, for example, hexane, heptane, nonane.

An inert hydrocarbon solvent such as decane or kerosene may be used as the polymerization medium, but the alpha-olefin itself can also be the reaction medium.

When polymerization is carried out in the gas phase, no reaction medium is used in principle, but the catalyst or any of its components may be dissolved or suspended in the above-mentioned inert hydrocarbons. The polymerization temperature, which is carried out by contacting the catalyst and the α-olefin, is 40 to 2
00°C, preferably 50 to 150°C, and the polymerization pressure is atmospheric pressure to 100 kg/crn'G, preferably 5 to 5
The zero polymerization at 0 kg/crn''G can be carried out in any of the batch, semi-continuous or continuous modes, but continuous polymerization is preferred industrially.

It is also possible to carry out one polymerization by multi-stage polymerization using 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 monopolymerization system.

The above-mentioned production or storage of solid catalyst components, preparation of catalysts, and production of polymers must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases, they may also be carried out under an atmosphere of 70% or under vacuum conditions. But it can be done.

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 gas discharged from the vent part of the granulator or the molten polymer at the outlet of the granulator has almost no odor due to the organosilicon compound component. That's true. This facilitates handling of the polymer, such as granulation, and is economical since it 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 an organoaluminum compound component and an organosilicon compound component has extremely high polymerization activity, and there is no need to remove residual catalyst from the polymer. This method eliminates the need for a polymer purification process, making it extremely economical. In addition, the stereoregularity of the polymer is extremely high. This is indicated by the high isotactic index (hereinafter abbreviated as rr). It is extremely advantageous for producing polymers by gas phase polymerization without using solvents. Furthermore, the particle shape of the obtained polymer is extremely good. That is, the shape of the polymer particles is spherical or nearly spherical, and it is possible to control the polymer particle size to a predetermined size and the polymer particle size distribution to be extremely narrow. There are very few very small polymers or fine powders. This enables stable production of polymers over a long period of time in liquid phase polymerization methods such as slurry polymerization and bulk polymerization, and gas phase polymerization methods. In addition, industrial polymers can be easily transported and recovered, and feeding to granulators and operations during processing and molding are easier.
Productivity is greatly improved. It can suppress dust explosions caused by fine powder and is effective in preventing entrainment.

Further, even when α-olefin is copolymerized in the method using the catalyst according to the present invention, there is little deterioration in the shape of the polymer particles or a decrease in the bulk specific gravity, and the copolymer can be easily produced.

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

(1) Melt flow rate (abbreviated as MFR) is ASTM
According to mouth 123 & (L).

(2) Polymer bulk density (abbreviated as BD) is ASTM
[According to 11895.

(3) The presence or absence of odor was judged by a sensory test conducted by 10 experimenters, and was classified into 4 grades from A to D. A is odorless;
If all 10 people judge that there is no odor, B means that there is a slight odor, and if 1 to 4 of the 10 people judge that there is an odor,
C is a case where there is a smell, and 5 to 9 people among the same people judge that there is an odor, and D is a case where there is a strong odor, and all 10 people judge that there is an odor.

(4) The shapes of the solid product (■), solid product (II), and polymer particles were observed using an optical microscope.

(5) The particle size distribution of the polymer was determined using a sieve according to JIS Z 8801. In addition, the particle size distribution of the solid product (II) was measured using a Micron Photosizer (■ manufactured by Seishin Enterprises).

5KC-2000 model). The average particle size is the particle size at a cumulative weight of 50% in the particle size cumulative curve in the above particle size distribution.

(8) II refers to n-hexane (69°C) in which the polymer is boiled.
) is the ratio of the extraction residue after 6 hours of extraction to the total amount before extraction.

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

The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of solid catalyst components In a glass flask, purified decane, 5.7 g of magnesium jetoxide, and 0.8 g of aluminum chloride were added.
7 g, n-butyl orthotitanate 17.1 g, 2-ethyl-1-hexanol li 9.8 g5 and ethyl p-toluate 1. Mix Elg and stir for 130'
C! The mixture was heated for 2 hours to dissolve it. 70% of the homogeneous solution
℃, and while stirring, 51 g of silicon tetrachloride was added dropwise over 2 hours to precipitate a solid. After further stirring at the same temperature for 1 hour, 2.1 g of ethyl p-toluate was added to 70' (:
! After reacting for 1 hour, the solid was washed with purified hexane to obtain a solid product (r). The solid product (1)
The total amount was mixed with 50 ml of 1,2-dichloroethane and 50 ml of titanium tetrachloride diluted with Q, reacted at 80°C for 2 hours with stirring, washed with purified hexane, and without drying, added purified hexane and suspended in hexane. It was made into a cloudy liquid. There were 50 g of solid product (II) in each suspension.

All of the operations in Temperature 8 and Mouthwatering Example + Kodozanka H mentioned above were performed under a nitrogen atmosphere.

The solid product (rr) had a nearly spherical shape, an average particle size of 21 pm, and a very narrow particle size distribution.

The compositional analysis result of the solid product (II) obtained by drying at 25°C2 under reduced pressure (10-'mmHg) for 3 hours was T.
i 3.3% by weight (hereinafter referred to as %), 115% pl ruyl acid receptor, 2.8% butoxy groups, and 1.2% 2-ethylhexanoxy groups.

(2) Production of polyolefin 2.0 mmol of triethylaluminum,
Methylphenyldimethoxysilane 0.51 ■of, solid product (II) 6.5 × 10-' in terms of Ti atom
After adding mg atoms and 800 tal of hydrogen, polymerization was carried out at 70°C for 2 hours while continuously introducing propylene so that the total pressure was 22 kg/crn' (G). The water-removed propylene was discharged to obtain 238 g of powdered polypropylene. The results are shown in Table b. This powdered polypropylene was difficult to grind.

(3) Odor sensory test The polypropylene immediately after the reaction had an odor of unreacted propylene, so after being left at 50°C for 3 hours in a nitrogen stream,
It was subjected to an odor sensory test. ``There is no propylene odor, and when 10 experimenters conducted a sensory test in which they smelled it directly, 1
0 people all judged that there was no odor (odor rank A).Also, after the sensory test, 0.1% by weight of antioxidant and lubricant O were added to polypropylene in a Henschel mixer (trade name). Mix thoroughly at 220 mm using an axle granulator with a pent part in the center and 20 mm in diameter.
When granulated at a temperature of 0.degree. C., four experimenters judged that the gas discharged from the vent part had an odor (odor rank B), and the molten polymer at the outlet of the granulator was judged to have no odor (odor rank A).

Comparative Example 1 The solid product (n) prepared in Example 1 (1) was used as the solid catalyst component, except that p-tolyl-methoxysilane was used in place of methylphenyldimethoxysilane in Example 1 (2). A polyolefin was produced in the same manner as in Example 1 (2), and an odor sensory test was conducted in the same manner as in Example 1 (3). The results are shown in the table.

Example 2 (1) Preparation of solid catalyst component In a stainless steel flask, purified nonane 5041
, magnesium jetoxide 5.7g, ethylaluminum dichloride 0.952g, ethyl orthotitanate 1
7.2 g, n-octatool 13.0 g and ethyl benzoate 1.5 g were mixed and heated to 110°C with stirring.
It was heated for an hour to dissolve it. The homogeneous solution was heated to 50°C, and while stirring, 58 g of ethyl silicon trichloride containing 1.13 g of ethyl benzoate was added dropwise over 2.5 hours to precipitate a solid. After further stirring for 1 hour, the solid was separated into purified hexane. A solid product (1) was obtained by washing. The solid product (1
) Titanium tetrachloride 10% diluted with 30% toluene
The mixture was mixed with 0 g and reacted at 110° C. for 1 hour with stirring, washed with purified heptane, and purified heptane was added without drying to obtain a heptane suspension. There was a proportion of 10 g of solid product (II) in each suspension.

The solid product (II) had a nearly spherical shape, an average particle size of 19 μm, and an extremely narrow particle size distribution.

A solid product (II
) composition analysis results were Ti content 2.9% and ethyl benzoate 6.3%.

(2) Polyolefin production and odor sensory test In (2) of Example 1, the solid product (n) obtained in Example 2 (1) was used instead of the solid product (II),
and Example 1 ((
A polyolefin was produced in the same manner as in 2), and an odor sensory test was conducted in the same manner as in Example 1 (3) using the obtained polymer. The polypropylene obtained by Y-building had a nearly spherical shape, had a narrow particle size distribution, and was not susceptible to grinding. The results are shown in the table.

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

Example 3 In a glass flask, purified decane 5Qtm, magnesium jetoxide 5.7g, diethylaluminum chloride 0.424g, n-butyl orthotitanate 1
7.1 g and 1-methyl-1-hexanol 19.8
g was mixed and heated to 130° C. for 1.5 hours with stirring to obtain a homogeneous solution. The homogeneous solution was heated to 70°C, and p
- After adding 2.2 g of ethyl anisate and stirring for 1 hour, 51 g of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred for 1 hour. continue.

After adding 1.9 g of ethyl p-anisate and stirring for 1 hour,
The solid was separated and washed with purified hexane to give a solid product (1
) was obtained. Using this solid product (1), a solid catalyst component was prepared in the same manner as in Example 1 (1).

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

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

Example 4 11.4 g of magnesium jetoxide, 134 g of aluminum chloride and 3.0 g of ethyl benzoate were sequentially added into a stainless steel vibration mill with an internal capacity of 1QQtnl.
Furthermore, 10 stainless steel poles (5 135mφ and 10
The mixture was sealed and co-pulverized at 30° C. for 1 hour to obtain a finely powdered complex compound with a large specific surface area. Put 7.9 g of this complex compound into a glass flask, add 5 Qtrl of purified decane, 17,1 n-butyl orthotitanate,
g, 2-ethyl-1-hexanol ts, and eg were added, and the mixture was heated to 130° C. for 2 hours with stirring to obtain a homogeneous solution. After making a homogeneous solution, a solid product (II) was prepared in the same manner as in (1) of Example 1, and in (2) of Example 1, 0.5 mmol of methylphenyldimethoxysilane was added.
A polyolefin was produced in the same manner as in Example 1, except that 0.8 m layer O1 was used instead of O1, and an odor sensory test was conducted. The results are shown in the table.

Example 5 In Example 1, 1 to butene 15 was used instead of propylene.
A fixed catalyst component was prepared in the same manner as in Example 1, except that propylene containing 1% a+o was used, a polyno'olefin was produced, and an odor sensory test was conducted.

The butene content in the powdered propylene-butene copolymer was 5.7111 ol$. The results are shown in the table.

Procedural amendment 1985 (month 2Y day) 1985 Patent Application No. 51509 2. Name of the invention Polyolefin manufacturing method 3. Person who makes corrections (207) Chisso Corporation Representative: Sadao Nogi 6. Number of inventions increased by amendment none 7. Subject of correction Detailed description of the invention in the specification.

8. Contents of amendment Correct the statement as follows.

(1) On page 35, line 4 from the bottom, in front of "dimethyldimethoxysilane" [phenyltrimethoxysilane].

Insert phenyltriethoxysilane, phenylmethoxyjethoxysilane, phenylmethoxyethoxyphenoxysilane.

(2) Insert "phenyltriethoxysilane, phenylmethoxyjethoxysilane" before "benzyltrimethoxysilane" on page 37, line 5.

that's all

Claims (14)

[Claims] (1) [1] a, Magnesium alkoxide, aluminum halide, titanate ester, alcohol, and if necessary, organic acid ester (I) are heated and dissolved in an inert hydrocarbon solvent, or b, Magnesium alkoxide, halogen By co-pulverizing aluminum chloride and organic acid ester (I), a complex compound is obtained, and the complex compound, titanate ester, and alcohol are heated and dissolved in an inert hydrocarbon solvent, [2] The thus obtained A solid product (
I) is precipitated, [3] the solid product (I) is reacted with titanium halide and/or vanadium halide, and [4] the solid after the reaction is washed with a liquid inert hydrocarbon. a solid product (II) obtained in the presence of at least 50% by weight of a liquid inert hydrocarbon as a solid catalyst component; Components, organoaluminium compound components, 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) As aluminum halide, general formula AlX_
A compound represented by nR^1_3_-_n (where X is Cl or Br, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and n is 0 3). (3) General formula Ti (OR^2) as titanate ester
Orthotitanate ester represented by _4 and or general formula R^3-(OTi(OR^4)(OR^5)-_
Polytitanate ester represented by mO-R^6 (where 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 carbon number 3
20 cycloalkyl groups, m being a number from 2 to 20). (4) The method according to claim (1), in which an aliphatic alcohol having 1 to 20 carbon atoms and/or an aromatic alcohol having 6 to 24 carbon atoms is used as the alcohol. (5) As described in claim (1), the organic acid ester (I) or (II) is an aliphatic carboxylic acid ester having 2 to 20 carbon atoms or an aromatic carboxylic ester having 8 to 24 carbon atoms. the method of. (6) 0.01 to 0.5 mol of aluminum halide, 0.5 to 3.0 mol of orthotitanate and/or polytitanate (orthotitanate equivalent) per 1 mol of magnesium alkoxide
, using 0.5 to 6.0 mol of alcohol and 0.05 to 0.5 mol of organic acid ester (1), the magnesium alkoxide was heated at 50 to 150°C in an inert hydrocarbon solvent.
Claim No. 1 (
The method described in section 1). (7) 1 mol of magnesium alkoxide is co-pulverized with 0.01 to 0.5 mol of aluminum halide and 0.05 to 0.5 mol of organic acid ester (1) to form a complex compound, and the structure of the complex compound is Using 0.5 to 3.0 mol of orthotitanate ester and/or polytitanate (in terms of orthotitanate ester) and 0.5 to 6.0 mol of alcohol per 1 mol of raw material magnesium alkoxide, in an inert hydrocarbon solvent. The complex compound, orthotitanate ester and/or polytitanium ester, and alcohol are heated at 50 to 150°C.
Claim No. 1 (
The method described in section 1). (8) General formula SiX_nR^7 as silicon halide
_4_-_n and or general formula SiX_n(OR^6
)_4_-_n (where, 4). (9) In an inert hydrocarbon solution (hereinafter referred to as a homogeneous solution) of magnesium alkoxide dissolved using aluminum halide, titanate ester, alcohol, and organic acid ester (I), the magnesium alkoxide 1
50 to 20 mol of silicon halide and 0.1 to 0.6 mol of organic acid ester (II) per mol
The method according to claim (1), wherein the reaction is carried out at 130°C for 10 minutes to 5 hours. (10) In precipitating the solid product (I) from a homogeneous solution, the solution is reacted with [1] organic acid ester (II) and then reacted with silicon halide to precipitate a solid, or [ 2] React silicon halide simultaneously with organic acid ester (II) to precipitate a solid, or [3] React silicon halide to precipitate a solid, and then react with organic acid ester (II), or [4] The method according to claim (1), which uses a method combining two or more of the above [1] to [3]. (11) As titanium halide, the general formula TiX_q(O
R^9) A compound represented by _4_-_q (where Xx
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,
q is a number from 1 to 4)
). (12) After reacting the solid product (I) with 3 to 50 mol of titanium halide and/or vanadium halide per 1 mol of magnesium alkoxide used in its production at 50 to 130°C for 10 minutes to 2 hours, The reactants were washed with an inert hydrocarbon solvent to form a solid product (
II). A method according to claim (1) for obtaining II). (13) As an organosilicon compound having a Si-O-C bond, the general formula R^1^1_tSi(OR^1^2)_4
____t (Here, R^1^1 and R^1^2 are an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkyl group having 3 to 20 carbon atoms.
20 cycloalkyl groups, and t is a number from 0 to 3) is used in an amount of 0.01 to 2 mol per gram atom of Al of the organoaluminum compound component. the method of. (14) The method according to claim (1), in which the α-olefin is polymerized in a gas phase.