JPH0617403B2 - 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.

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

[Conventional technology]

Conventionally, as a direction for improving Ziegler-Natta type catalysts, by combining a supported solid catalyst component with an organoaluminum compound component and an aromatic carboxylic acid ester component,
It is known that the stereoregularity of the obtained polyolefin is enhanced. For example, as disclosed in JP-A-57-74307 and JP-A-58-32604, a technique of using an aromatic carboxylic acid ester as a component of a catalyst for improving the stereoregularity of polyolefin is known. However, in principle, when a polyolefin is produced in a solvent-free gas-phase polymerization process, the aromatic carboxylic acid ester which is one component of the catalyst is 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. Production of polyolefin on an industrial scale is a problem because it causes environmental pollution. Further, in JP-A-58-83006, a supported solid catalyst component is used as an organometallic compound component and Si-O-C.
Alternatively, a method for producing a polyolefin using a catalyst formed by combining with an organosilicon compound component having a Si—N—C bond is disclosed. In the earlier application, Si-
It is essential that the supported solid catalyst component to be combined with the organosilicon compound component having an OC bond contains a polycarboxylic acid and / or an ester of a polyhydroxy compound. However, it is still known that the stereoregularity of the obtained polyolefin is improved even if the supported solid catalyst component containing an aromatic monocarboxylic acid ester is combined with the organosilicon compound component having a Si—O—C bond. Absent. It should be noted that the organosilicon compound component having a Si-O-C 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-O-C bond is contained in the polyolefin, the polyolefin has no odor.

[Outline of Invention]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned environmental pollution and poor workability due to strong odor, and as a result, found that a novel supported solid catalyst component containing an aromatic monocarboxylic acid ester was an organoaluminum compound component. And Si-O
By combining with an organosilicon compound component having a -C bond, the polymerization activity is high as an olefin polymerization catalyst to the extent that removal of residual catalyst in the polymer is not required, and this catalyst has high stereoregularity, odorless, and particle shape. The present invention has been completed by finding out that a good polyolefin of

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

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

(1) anhydrous magnesium dihalide, general formula AlX _n R
¹ _-n (where X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 3) The aluminum halide and the aromatic carboxylic acid ester were mixed and pulverized to form a complex compound, and the complex compound, the titanic acid ester and the saturated aliphatic alcohol were mixed and dissolved in an inert hydrocarbon solvent, thus obtained. The solution has the general formula SiX _l R ⁷ _4-l (where X is Cl or Br and R ⁷ is 1 to 20 carbon atoms).
Is an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and 1 is a number of 1 to 4), and the solid product (I) is reacted with a silicon halide and an aromatic carboxylic acid ester. Precipitate to give the solid product (I)
TiX ₄ (where X is Cl or Br) is reacted, and the solid after the reaction is washed with a liquid inert hydrocarbon to obtain a solid product (II), and the solid product (II) is at least That
A solid product (II) obtained in the presence of 50% by weight of liquid inert hydrocarbon is used as a solid catalyst component, and the solid catalyst component, an organoaluminum compound component, and an organosilicon compound component having a Si-OC bond are combined. A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained in combination.

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

First, an anhydrous magnesium dihalide, aluminum halide and an organic acid ester are mixed and pulverized to form a complex compound. 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 , wherein 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. Examples thereof include aluminum trichloride, ethyl aluminum dichloride, butyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum chloride, dipropyl aluminum chloride, aluminum tribromide and ethyl aluminum dibromide. The organic acid ester is an aliphatic carboxylic acid ester such as ethyl acetate, butyl acetate, ethyl propionate and butyl butyrate, and an aromatic carboxylic acid ester such as ethyl benzoate, methyl toluate, methyl anisate and ethyl anisate. . The organic acid ester used to form the complex compound is hereinafter referred to as organic acid ester (1).

As a specific reaction method, anhydrous magnesium dihalide, aluminum halide and organic acid ester are mixed at the same time to carry out a grinding reaction (hereinafter referred to as "co-grinding"). Co-mill the mixture of aluminum halide and organic acid ester or anhydrous magnesium dihalide. Co-mill the aluminum halide with a mixture or complex of anhydrous magnesium dihalide and organic acid ester. Alternatively, a mixture of anhydrous magnesium dihalide and aluminum halide or a co-ground product may be co-ground by adding an organic acid ester, and the like,
Any reaction method can be adopted. Of these, the method (1), (2) or (3) is preferable. These reactions can be achieved by means of co-milling.
A vibration mill, a ball mill, a vibration ball mill, or the like is used as the co-grinding means. Anhydrous magnesium dihalide appears to contact aluminum halide and organic acid esters to form complex complex compounds. During co-milling, aliphatic hydrocarbons such as hexane, heptane, nonane, decane, kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, or carbon tetrachloride, 1,
A halogenated hydrocarbon such as 2-dichloroethane, n-butyl chloride or chlorobenzene may be used. When using these solvents, the solvent may be separated after co-milling,
It may be used as it is in the next reaction. It is known that aluminum halide and organic acid ester and anhydrous magnesium dihalide and organic acid ester form a complex, but a complex or a mixture may be used for co-milling. These complexes can be made by co-milling or reaction in solution. As the solvent at the time of the solution reaction, the same solvent as that at the time of the co-pulverization described above can be used. A complex compound formed from anhydrous magnesium dihalide, aluminum halide and organic acid ester is obtained as a powder at room temperature, but in order to facilitate the dissolution in hydrocarbon in the next step, that is, coexistence of titanic acid ester and alcohol, The powder of the complex compound is preferably a fine powder having a specific surface area as large as possible. The amount of aluminum halide used is anhydrous magnesium dihalide 1
0.001 to 0.7 mol, preferably 0.01 to 0.5 mol per mol
The organic acid ester (1) is used in an amount of 0.05 to 0.5 mol per 1 mol of anhydrous magnesium dihalide.

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

The temperature of co-milling is 0 to 150 ° C, preferably 20 to 100
The temperature and the temperature are 5 minutes to 100 hours, but the time varies depending on the means of pulverization. For example, in a pulverizing method capable of giving strong energy in a short time such as a vibration mill, it takes 5 minutes to 2 minutes.
It may be 0 hours, but it requires 30 minutes to 100 hours in a pulverizing method such as a ball mill which does not give strong energy in a short time. In co-milling, the anhydrous magnesium dihalide is a solid and in some cases the aluminum halide is also a solid so that it is as homogeneous as possible,
In addition, as described above, in order to facilitate the next operation, it is preferable to use fine powder having a large specific surface area.

Next, the complex compound is dissolved in an inert hydrocarbon solvent in the coexistence of titanic acid ester and alcohol. Examples of the titanic acid ester include an orthotitanic acid ester represented by Ti (OR ² ) ₄ and Is a polytitanate ester represented by (where,
^{R 2, R 3, R 4} , R 5 and R ⁶ is an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms having 1 to 20 carbon atoms, m is a number from 2 to 20). Specifically, orthotitanate esters such as methyl orthotitanate, ethyl orthotitanate, n-butyl orthotitanate, i-amyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, ethyl polytitanate, polytitanium. Polytitanate esters such as n-propyl acid i-propyl polytitanate, n-butyl polytitanate, i-butyl pyrititanate, n-amyl pyrititanate, phenyl polytitanate and cyclopentyl polytitanate can be used. Aliphatic alcohol can be used as the alcohol. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-
In addition to monohydric alcohols such as propyl alcohol, n-butyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol and its derivatives, ethylene glycol and trimethylene glycol. Polyhydric alcohols such as glycerin can also be used. Of these, aliphatic alcohols having 4 to 10 carbon atoms are preferable. Examples of the inert hydrocarbon include aliphatic hydrocarbons such as hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2-dichloroethane, n-butyl chloride, Halogenated hydrocarbons such as chlorobenzene can be used. Of these, aliphatic hydrocarbons are preferable. As a specific dissolution method, a complex compound, a titanic acid ester, an alcohol and an inert hydrocarbon are simultaneously mixed and heated to dissolve them. A complex compound, an alcohol and an inert hydrocarbon are mixed, and titanic acid ester is added before or after heating and heated to dissolve. A complex compound, a titanic acid ester, and an inert hydrocarbon are mixed, and alcohol is added before or after heating and heated to dissolve. Alternatively, a titanate ester, an alcohol and an inert hydrocarbon are mixed, and a complex compound before or after heating is added and heated to dissolve. Etc., and any dissolution method can be adopted. Among these, preferred. Whichever method is used, the solid in the mixture may be completely dissolved to form a uniform solution, or a small amount of insoluble matter may remain. It is believed that this insoluble material is based on impurities contained in the starting material, such as anhydrous magnesium dihalide or aluminum halide. If a small amount of insoluble matter remains, it may adversely affect the particle shape of the solid catalyst,
It is preferable to completely dissolve it into a uniform solution. Alternatively, such a small amount of insoluble matter may be separated to form a uniform solution. Heating is required to dissolve the aforementioned mixture. The temperature is 40 to 170 ° C, preferably 50 to 1
It is 50 ° C. The time is 5 minutes to 6 hours, preferably 10 minutes to 4 hours. When the organic acid ester contained in the complex compound is heated to a high temperature for a long time, it changes to a substance other than the organic acid ester and loses the ability to enhance stereoregularity. If you do, it is necessary to take measures such as shortening the time. It is preferable that the temperature is as low as possible and the time is short. Therefore, it is preferable to separate a small amount of insoluble matter which is not easily dissolved. The amount of titanate used may be determined based on the amount of magnesium dihalide used in the production of the complex compound. When using ortho titanate as titanate,
0.1 for 1 mol of magnesium dihalide in complex compound
~ 2.0 mol, preferably 0.5 ~ 1.5 mol, when using a polytitanate ester, pay attention to the orthotitanate ester unit in the polytitanate ester molecule, and convert the unit corresponding to orthotitanate ester to a mol unit. The molar ratio may be determined similarly to the orthotitanate ester. The amount of alcohol used is 0.1 to 6 mol, preferably 0.5 to 6 mol, based on 1 mol of magnesium dihalide used for producing the complex compound.
It is 5 mol. The larger the amount of titanic acid ester and alcohol used with respect to anhydrous magnesium dihalide, the more the solubility of the magnesium dihalide complex in an inert hydrocarbon solvent increases, but an extremely large amount of silicon halide is used to resolidify. In addition to this, resolidification itself becomes difficult, and even if solidification is possible, controlling the particle shape is extremely difficult. Conversely, if the amount of titanate ester and alcohol used is too small, the magnesium dihalide complex will not be soluble in the inert hydrocarbon solvent and the solid catalyst will become amorphous, and a polymer with a spherical or nearly spherical particle shape can be obtained. I can't. Further, the titanic acid ester and the alcohol must be used in common, and the individual use of each of them cannot achieve the object of the present invention. The amount of the inert hydrocarbon used is 10 to 2000 m, preferably 50 to 500 m, per 10 g of the complex compound.
Is. The composition of the compound dissolved and present in the solution is not clear. Estimated to be fairly complex. In most cases, it is preferable to store the homogeneous solution at room temperature because solid does not precipitate even when cooled to room temperature. It is effective in preventing the organic acid ester in the solution from changing to another compound.

Next, the above solution is reacted with a silicon halide and an organic acid ester to obtain a solid product (I). As a method for obtaining the solid product (I), a solution containing magnesium halide,
After the organic acid ester is added and reacted, silicon halide is added to precipitate a solid. Silicon halide is added together with the organic acid ester to react and precipitate a solid.
After adding a silicon halide to precipitate a solid, an organic acid ester is added and reacted. And the like or a combination of two or more thereof to obtain a solid, and then the solid is washed with an inert hydrocarbon solvent to obtain a solid product (I). As the organic acid ester, ethyl acetate, propyl acetate, butyl acetate,
Aliphatic carboxylic acid esters such as ethyl propionate, butyl propionate and ethyl butyrate, and aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate and ethyl anisate. . The organic acid ester used at this stage is hereinafter referred to as organic acid ester (2). As the silicon halide, compounds represented by SiX _l R ⁷ _4-l and SiX _p (OR ⁸ ) _4-p can be used. Where X is Cl
Alternatively, 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. Specifically, 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 dichloride, Dibutyl silicon dichloride, diphenyl silicon dichloride, triethyl silicon chloride, etc. can be used, and SiX _p (OR ⁸ ) _4-p
As, silicon tetrachloride, silicon tetrabromide, methoxysilicon trichloride, ethoxysilicon trichloride, propoxysilicon trichloride, butoxysilicon trichloride, phenoxysilicon trichloride, ethoxysilicon tribromide, dimethoxysilicon dichloride,
Diethoxysilicon dichloride, dibutoxysilicon dichloride, trimethoxysilicon chloride, 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 silicon halide may be used as they are or after 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 separately or in the presence of silicon halide in the presence of silicon halide for reaction, but the silicon halide may be added to the solution,
The solution may be added to the silicon halide. The total amount of the organic acid ester (2) used is 0.05 to 0.5 mol per 1 mol of anhydrous magnesium dihalide used. The total amount of the organic acid ester (1) and the organic acid ester (2) is preferably 0.1 to 0.6 mol. This amount of the organic acid ester (2) may be used at one time or may be used in several stages. The reaction temperature is 30 to 150 ° C, preferably 50 to 13
It is 0 ° C., and the reaction time is 5 minutes to 5 hours, preferably 10 minutes to 2 hours in each step.

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 changes to another compound, and stereoregularity The role of control may decline. The reaction between the silicon halide and the solution has a temperature of 4
The temperature is 0 to 150 ° C., preferably 50 to 130 ° C., and the time is 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 20 m based on 1 mol of anhydrous magnesium dihalide used.
ol. Solid is precipitated by adding silicon halide and reacting. Since the particle shape of the solid product (II) obtained later is governed by the particle shape of the solid product (I), the reaction between the solution for depositing the solid and the silicon halide is first controlled to control the particle shape. Extremely important. After reacting the organic acid ester with the silicon halide, the reaction with the titanium halide may be performed subsequently.
It is preferable to wash the deposited 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 a solid product (II). As the titanium halide, a compound represented by TiX _q (OR ⁹ ) _4-q can be used. Where X is Cl, R
⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4. Specifically, titanium tetrachloride, 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 with 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 (1) titanium halide to a suspension of the solid product (I) or suspending the solid product (I) in the titanium halide. Add a turbid solution to react. Alternatively, (2) the solid product (I) is washed once separately or by a decantation method, the solid product (I) is suspended in the above-mentioned inert hydrocarbon solvent, and the titanium halide is added to the suspension. Or by adding a suspension of the solid product (I) in titanium halide and reacting. The same applies when vanadium halide is used instead of or together with titanium halide. Among them (2)
Is preferred. The amount of titanium halide or vanadium halide used is 1 to 100 mol, preferably 3 to 1 mol of anhydrous magnesium dihalide used.
~ 50 mol. The reaction temperature of the solid product (I) with titanium halide or vanadium halide is 40 to 150.
℃, preferably 50 ~ 130 ℃, 5 minutes to 5 hours,
It is preferably 10 minutes to 2 hours. After the reaction, the solid is separated by another method or a decantation method and then washed with an inert solvent to remove unreacted substances or by-products. A solid product (II) is thus obtained. The solid product (I
The particle shape of I) must be good. The solvent used for washing is a liquid inert hydrocarbon. Specific examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and kerosene.
During and after washing, the solid product (II) is required to coexist with at least 50% by weight of the aforementioned liquid inert hydrocarbon. In particular, the washing is preferably a decantation method, and after washing, at least the solid product (II) is immersed in the liquid inert hydrocarbon so that the liquid inert hydrocarbon is the solid product (I
Coexistence with I) is preferred. When less than 50% by weight of a liquid inert hydrocarbon is present with respect to the solid product (II), sufficient catalytic performance is not exhibited even if it is subjected to subsequent polymerization. That is, the polymer yield and bulk specific gravity are low, the shape is inferior, the amount of fine powder is large, and the stereoregularity is low. It is important that the solid product (II) after washing is stored in the presence of at least 50% by weight of the liquid inert hydrocarbon and is subjected to polymerization.

The solid product (II) can be used as a catalyst for producing polyolefin by combining it as a solid catalyst component with an organoaluminum compound component and an organosilicon compound component having a Si—O—C bond. As the organoaluminum compound component combined, it may be used a compound represented by AlX _s R ¹⁰ _3-S. Where X is Cl and R ¹⁰ has 1 carbon
To 20 alkyl groups, aryl groups or 3 to 20 carbon atoms
Is a cycloalkyl group, and s is a number from 0 to 2. Specifically, triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl aluminum, tricyclopentyl aluminum, tricyclohexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-butyl aluminum chloride, ethyl aluminum sesquichloride. And ethylaluminum dichloride and the like. Among them, triethylaluminum alone or a mixture of two kinds of organic aluminum compounds such as triethylaluminum and tri-i-butylaluminum, triethylaluminum and diethylaluminum chloride and triethylaluminum and ethylaluminum sesquichloride is preferable. As the organosilicon compound component,
A compound represented by the general formula R ¹¹ _t Si (OR ¹² ) _4-t can be used. Here, R ¹¹ and R ¹² have 1 to 20 carbon atoms.
Is an alkyl group, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 0 to 3. Specifically, methyl silicate, ethyl silicate, butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methylethoxydimethoxysilane, methylphenoxydimethoxysilane, methylmethoxy. Ethoxyphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriphenoxysilane, ethyltribenzyloxysilane, ethylethoxydimethoxysilane, ethylmethoxydiethoxysilane, ethylphenoxydimethoxysilane, ethylmethoxyethoxyphenoxysilane, butyltrimethoxy Silane, butyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylphenoxydimethoxysilane, benzene Lemethoxyethoxyphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, phenylmethoxyethoxyphenoxysilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, dimethyldiphenoxysilane, 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, diethyl Examples thereof include methylmethoxysilane, diethylmethylphenoxysilane, diphenylmethylmethoxysilane, diphenylbenzylmethoxysilane, dimethylcyclopropylmethoxysilane, methylethylphenylmethoxysilane, and methylethylphenylphenoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethoxydiethoxysilane, benzyltrimethoxysilane, methylethyldimethoxysilane, methylphenyldimethoxysilane, Methylethyldiethoxysilane, methylphenyldiethoxysilane, methylbenzyldimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane,
Trimethylethoxysilane is preferred. Solid product (I
As the method for combining I), the organoaluminum compound and the organosilicon compound, the solid product (II), the organoaluminum compound and the organosilicon compound are independently supplied to the polymerization vessel. The mixture of the organoaluminum compound and the organosilicon compound and the solid product (II) are independently fed to the polymerization vessel. There are embodiments such as supplying a mixture of the solid product (II), the organoaluminum compound and the organosilicon compound to the polymerization vessel, and any method can be adopted. However, in some cases or is preferred. When combining the three as described above, the respective components or any one of the components are butane, pentane, hexane, heptane, nonane,
It can also be used by dissolving or suspending it in an aliphatic hydrocarbon such as decane and kerosene. The temperature in the case of mixing before feeding to the polymerization vessel as described in and is -50 to
+ 50 ° C, preferably -30 to + 30 ° C, time 5 minutes to
It is 50 hours, preferably 10 minutes to 30 hours. The amount of the organoaluminum compound used is 10 to 1 with respect to 1 mol of titanium atom contained in the solid product (II) as a solid catalyst component.
It is 000 mol, preferably 50 to 500 mol. The amount of the organosilicon compound used is 0.01 to 2 mol, preferably 0.05 to 1 mol, per 1 mol of the organoaluminum compound. When a mixed organoaluminum compound or a mixed organosilicon compound is used, the total mol number of them should fall within the above range.

In the present invention, the solid product (I
I), a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound is used to produce α having 3 or more carbon atoms.
Produce an α-olefin polymer using olefins. Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1, 4-methylpentene-1 and 3
-Methylpentene-1 and the like can be used. Polymerization of these α-olefins includes not only homopolymerization but also copolymerization with other one or more α-olefins having 2 or more carbon atoms. Examples of the α-olefin having 2 or more carbon atoms include the α-olefin having 3 or more carbon atoms described above.
In addition to olefins, ethylene, butadiene, isoprene,
Examples include 1,4-pentadiene and methyl-1,4-hexadiene. The amount of those other α-olefins used is 5 in the copolymer obtained by the copolymerization.
It is an amount that will be contained in an amount of 0% by weight or less. The polymerization can be carried out in the liquid phase or the gas phase. When carrying out the polymerization in the 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 α-olefin itself may be used 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 melted 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. The polymerization temperature is 40 to 200 ° C., preferably 50.
~ 150 ℃, polymerization pressure is atmospheric pressure ~ 100kg / 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 have to 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 under vacuum conditions. be able to.

The main effects of the present invention are as follows. First, the polymer obtained by the production method of the present invention is odorless, and
During granulation, the gas discharged from the vent of the granulator or the molten polymer at the outlet of the granulator has almost no odor due to the organosilicon compound component. This is easy in handling the polymer at the time of granulation and does not cause environmental pollution such as polluting the atmosphere, which is economical in that the pollution prevention equipment is not required. Further, the catalyst in which the solid catalyst component of the present invention is combined with an organoaluminum compound has extremely high polymerization activity, 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 close to a sphere, and it is possible to control the particle size of the polymer to a predetermined size and to control the polymer particle size distribution to be extremely narrow. The amount of fine powder is extremely small. 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, the polymer according to the present invention can be easily transported and recovered in the manufacturing process, the supply to the granulator and the operation in processing and molding are facilitated, and the productivity is remarkably 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 D 1
According to 238 (L).

(2) Bulk density of polymer (abbreviated as BD) is ASTM D 189
According to 5.

(3) The presence or absence of odor was judged by a sensory test by 10 testers, and classified into 4 stages of A to D. A is odorless, 1
If 0 people all have no odor, B has a slight odor, and if 1 out of 10 people have odor,
C is a case where 5 to 9 out of 10 people have a smell, and D is a case where there is a strong smell, and all 10 people are a case where there is a smell.

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

(5) The particle size distribution of the polymer was determined using a sieve according to JIS Z8801. The particle size distribution of the fixed product (II) was determined by Micron Photosizer (manufactured by Seishin Enterprise Co., Ltd., SKC-2000 type). Accumulation of particle size accumulation curve in the above particle size distribution 5
The particle size of 0% by weight is the average particle size.

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

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

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

Example 1 (1) Preparation of solid catalyst component In a stainless steel vibration mill having an internal volume of 100 m, 19.1 g of anhydrous magnesium chloride, 2.7 g of aluminum chloride and 6.7 g of ethyl p-toluate were sequentially added, and further made of stainless steel. 10 balls (13 mmφ5 and 10 mmφ5)
The mixture was charged and sealed, and co-pulverization was performed at 30 ° C. for 1 hour to obtain a fine powder complex compound having a large specific surface area. This complex compound was put in a glass flask and further purified decane 120 m,
95.7 g of n-butyl orthotitanate and 2-ethyl-
Add 78.5 g of 1-hexanol and stir 130
It was heated to 30 ° C. for 30 minutes to dissolve it. The solution was heated to 70 ° C., 140 m of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further stirred at 70 ° C. for 1 hour, then 8.2 g of ethyl p-toluate was added and reacted at the same temperature for 1 hour. The solid was washed with purified hexane to obtain a solid product (I). The total amount of the solid product (I) was mixed with 200 m of titanium tetrachloride dissolved in 200 m of 1,2-dichloroethane, reacted at 80 ° C. for 2 hours with stirring, washed with purified hexane, and purified hexane without drying. In addition, a hexane suspension was prepared. 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 21 μm, and its particle size distribution was extremely narrow. The composition analysis effect of the solid product (II) obtained by drying at 25 ° C. under reduced pressure (10 ⁻³ mmHg) for 3 hours is Ti 3.0 wt% (hereinafter referred to as “%”), Cl 56.5
%, Mg 17.2%, Al1.2%, Si 0.9%, ethyl p-toluate 9.5%, butoxy group 3.5% and ethylhexanoxy group
It was 1.3%.

(2) Production of Polyolefin In a stainless reactor equipped with a multi-stage stirrer with an internal volume of 3 and being replaced with nitrogen, 2.0 mmol of triethylaluminum, 0.4 mmol of diphenyldimethoxysilane and 6.5 × 10 ^-3 mg atom of solid product (II) in terms of Ti atom were converted. And after adding 1 hydrogen, 70 ℃
Polymerization was carried out for 2 hours while continuously introducing propylene so that the total pressure was 22 kg / cm ² (G). After that, unreacted propylene is discharged and powdered polypropylene 231
g was obtained. BD is 0.46, MFR is 7.5, polymer particles are spherical or near spherical, and the particle size is 100μ.
The amount of fine powder of m or less was 0.02% by weight of the whole. The extraction residue [II] with boiling hexane was 98.3%, and the powdered polypropylene after polymerization was difficult to be ground.

(3) Odor sensory test Polypropylene immediately after polymerization had an unreacted propylene odor, so after leaving it in a nitrogen stream at 50 ° C for 3 hours,
It was subjected to an odor sensory test. There was no propylene odor, and a sensory test of smelling the smell directly was carried out by 10 testers, and all 10 judged that there was no odor (odor rank A). Further, 0.1% by weight of an antioxidant and 0.1% by weight of a lubricant were added to polypropylene after a sensory test and sufficiently mixed in a Henschel mixer (trade name), and a uniaxial granulation having a diameter of 20 mm and a vent portion in the center. When granulated at 220 ° C using a granulator, 3 testers judged that there was an odor in the vent gas discharged from the vent (odor rank B), and 10 of the molten polymer at the granulator outlet had no odor. It was determined to be (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 (2) of Example 1 was replaced with methyl p-anisate. 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 solid catalyst component 57.3 g of anhydrous magnesium chloride and 1 part of ethyl benzoate were placed in a stainless steel ball mill pot having an internal volume of 950 m.
4.5g and 50 stainless steel balls (20m / mφ
15, 16 m / mφ15 and 13 m / mφ20
Individual pieces) and sealed, and co-milled at room temperature for 50 hours. Further, 24 g of aluminum chloride was further added and co-milled at room temperature for 50 hours to obtain a fine powdery complex compound. 32.9 g of this complex compound was put into a glass flask, and purified nonane 150 m
, 68.8 g of ethyl orthotitanate and 52.3 g of n-octyl alcohol were added, and the mixture was stirred at 100 ° C. for 1 hour.
It was heated and dissolved for a time. The solution is heated to 70 ° C., and 215 g of ethyl silicon trichloride containing 7.3 g of ethyl benzoate is added.
It was added dropwise over 2.5 hours to precipitate a solid, which was further heated to 70 ° C for 1 hour.
After stirring for an hour, the separated solid was washed with purified hexane to obtain a solid product (I). The whole amount of the solid product (I) was mixed with 200 m of titanium tetrachloride dissolved in 200 m of toluene, reacted with stirring at 100 ° C. for 1.5 hours, washed with purified hexane, and washed with dry hexane without adding dried hexane. It was made a suspension. 10 g of the fixed product (II) was present in the suspension 1.

The solid product (II) was spherical and had an average particle size of 18 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 Ti3.2%, C
57.1%, Mg 17.5% and ethyl benzoate 8.1%.

(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 A polyolefin was produced in the same manner as in (2) of Example 1 except that methylphenyldimethoxysilane was used instead 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 polypropylene obtained by the production had a particle shape close to a sphere, the particle size distribution was narrow, and it was difficult to be ground. The results are shown in the table.

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

Example 3 In a stainless vibrating ball mill with an internal volume of 350 m,
Mixture or reaction product of 3.6 g of ethyl aluminum dichloride and 14.8 g of ethyl p-anisate, 38.3 g of anhydrous magnesium chloride and 15 stainless steel balls (16 mmφ)
5 pieces, 5 pieces of 13 mmφ and 5 pieces of 10 mmφ) were put and sealed, and co-pulverization was performed at room temperature for 50 hours to obtain a complex compound. 27.2 g of this complex compound was placed in a glass flask and purified kerosene 150 m and n-butyl polytitanate (pentamer) 4
7.5g and n-hexyl alcohol 62g were added, and it heated at 110 degreeC for 1 hour, stirring, and was made to melt | dissolve. The solution was brought to 60 ° C., 7.5 g of ethyl p-anisate was added, and the mixture was reacted for 1 hour.
12 g was added dropwise over 3 hours to precipitate a solid, which was continuously stirred for 1 hour, and the solid was washed with purified hexane to obtain a solid product (I). The solid product (I) was mixed with 400 m of titanium tetrachloride, reacted with stirring at 110 ° C. for 2 hours, washed with purified hexane, and then the solid product (II) was prepared in the same manner as in Example 1. In Example 1 (2), except that the solid product (II) was used as a solid catalyst component instead of the solid product (II) and phenyltriethoxysilane was used instead of diphenylmethoxysilane. A polyolefin was produced in the same manner as in (2) of 1 above, and an odor sensory test was conducted in the same manner as in (3) of Example 1 using the obtained polymer. 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 methyl p-toluate was used in place of phenyltriethoxysilane. A polyolefin was produced by the following method, and an odor sensory test was conducted. The results are shown in the table.

Example 4 A polyolefin was produced in the same manner as in (2) of Example 1 except that propylene containing 15 mol% of 1-butene was used in place of propylene in (2) of Example 1 to prepare powdered propylene-butene. A copolymer was obtained. The butene content in the copolymer was 5.8 mol%.

[Brief description of drawings]

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

Claims (8)

[Claims] 1. Anhydrous magnesium dihalide, general formula Al
X _n R ¹ _3-n (wherein X is Cl or Br, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and n is a number of 0 to 3). A) aluminum halide and aromatic carboxylic acid ester are mixed and pulverized to form a complex compound, and the complex compound, titanic acid ester and saturated aliphatic alcohol are mixed and dissolved in an inert hydrocarbon solvent, and thus, The resulting solution has the general formula SiX _l R ⁷ _4-l (where X is Cl or Br, R ⁷ is a carbon number of 1 to 1).
20 alkyl groups, aryl groups or cycloalkyl groups having 3 to 20 carbon atoms, 1 being a number of 1 to 4), and reacting with a silicon halide and an aromatic carboxylic acid ester to give a solid product (I) To precipitate the solid product (I)
Is reacted with TiX ₄ (where X is Cl or Br), and the solid after the reaction is washed with a liquid inert hydrocarbon to give a solid product (II). A solid product (II) obtained in the presence of at least 50% by weight of a liquid inert hydrocarbon is used as a solid catalyst component, and the solid catalyst component, an organoaluminum compound component, and an organosilicon compound component having a Si-OC bond. A method for producing a polyolefin, which comprises polymerizing an α-olefin using a catalyst obtained by combining the above. 2. An aluminum halide of the general formula AlX _n R ¹ _3-n is added to 1 mol of anhydrous magnesium dihalide.
0.01-0.5mol, aromatic carboxylic acid ester 0.05-0.5m
The method according to claim (1), wherein ol is used to obtain a complex compound by co-milling. 3. An orthotitanate represented by the general formula Ti (OR ² ) ₄ and / or a general formula per 1 mol of magnesium dihalide constituting a complex compound. Polytitanate represented by (here, R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is 2
It is 0 in terms of orthotitanate.
5 to 1.5 mol, 0.5 to 5 mol of aliphatic saturated alcohol,
These are treated with the complex compound in an inert hydrocarbon solvent at 50 to 150 ° C.
Claims for dissolving by mixing for 10 minutes to 5 hours
The method described in section (1). 4. The above-mentioned general formula SiX _l R per 1 mol of magnesium dihalide constituting a solution obtained by dissolving a complex compound.
^{A method for} producing a solid product (I) by reacting ₁ to 20 mol of ⁷ _4-l silicon halide and 0.05 to 0.5 mol of an aromatic carboxylic acid ester and washing the precipitated solid with an inert hydrocarbon solvent. The method of paragraph (1). 5. A solution obtained by dissolving the complex compound (hereinafter homogeneous solution) in the general formula SiX _l R ⁷ _4-l silicon halide and aromatic carboxylic acid ester (2) below - of Izure to or they Any combination of two or more of 50
The method according to claim (1), wherein a solid is precipitated by reacting at 130 ° C for 10 minutes to 5 hours. After reacting the aromatic carboxylic acid ester (2), the silicon halide is reacted. The aromatic carboxylic acid ester (2) and the silicon halide are simultaneously reacted. After the silicon halide is reacted to deposit a solid, the aromatic carboxylic acid ester (2) is reacted. 6. A solid product (I) of the general formula TiX _q (OR ⁹ ) with respect to 1 mol of magnesium dihalide constituting the solid product (I).
Halogenation of _4-q (where X is Cl, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and q is a number of 1 to 4) 3 to titanium
Using 50 mol, the reaction is carried out at 50 to 130 ° C for 10 minutes to 2 hours, and the solid after the reaction is washed with an inert hydrocarbon solvent to give a solid product (I
The method according to claim (1) for obtaining I). 7. An organosilicon compound component having a Si--OC bond, which has the general formula R ¹¹ _t Si (OR ¹² ) _4-t (wherein R ¹¹ and R
¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 0 to 3), and an organosilicon compound represented by the general formula AlX _n R ¹ _{3 -n}
0.1 g per 1 gram atom of Al in the organoaluminum compound component of.
The method according to claim (1), wherein 01 to 2 mol is used. 8. The method according to claim 1, wherein the polymerization of α-olefin is carried out in a gas phase.