JPH0323563B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an olefin polymer. Specifically, ethylene, propylene, butene-
The present invention relates to a method for producing an olefin polymer by polymerizing olefins such as No. 1. Hitherto, various supported catalysts for olefin polymerization have been proposed which provide polymers with high polymerization activity and high stereoregularity. For example, JP-A-51-57789, JP-A-53-
108088, 53-109587, 54-39484 and 55
29591 proposes the use of a solid catalyst obtained by contacting magnesium dihalide, titanium halide, and an electron-donating compound for the polymerization of α-olefin. In addition, the present inventors also previously proposed a solid catalyst component obtained by contacting a magnesium compound obtained by reacting a Grignard compound with water, alcohol, silanol, polysilanol, etc., and a titanium halide and an electron-donating compound. proposed the use of α-olefin polymerization (JP-A-Sho
53-24378, 53-117083, etc.). Although these catalysts produce polymers with high activity and high stereoregularity, the amount of by-produced amorphous polymers is not sufficiently small, and therefore injection molded products of the resulting polymers are difficult to produce. , extrusion molded products, films, etc. were unsatisfactory as they lacked mechanical properties. In addition, since the catalyst component contains a large amount of halogen and its polymerization activity is not sufficient, if the catalyst component remaining in the polymer is not removed, the remaining catalyst component (especially halogen) will corrode the molding equipment. , or bring about unfavorable results such as a decrease in the stability and hue of the molded product. Furthermore, the powder properties of the resulting polymer powder, such as a wide particle size distribution and a low bulk density, were not fully satisfactory. Therefore, due to the low space-time yield (STY), even with highly active catalysts, high productivity cannot be achieved. As a method for reducing the amount of halogen components in the catalyst, which are mainly derived from magnesium halides, and improving the powder properties of the polymer, magnesium chloride, an electron-donating compound, and a titanium halide component are dispersed on a silica carrier. A method for obtaining the catalyst component was published in Japanese Patent Application Publication No.
55-155003, 56-18609, 56-86905, 56-
It has been proposed in 98206 etc. Although the polymerization activity per magnesium halide and titanium atom in the catalysts obtained by these methods is significantly improved compared to conventional catalysts, the stereoregularity and bulk density of the resulting polymers still need improvement. There is a need for As a result of extensive research in view of the above facts, the present inventors have found that an inert inorganic carrier or a treatment product of an inert inorganic carrier with a silicon halide compound, a silanol or polysilanol, an organomagnesium compound, an electron-donating compound, and By polymerizing olefin in the presence of a titanium-containing solid catalyst component obtained by contacting a titanium compound and a catalyst made of an organoaluminium compound or a catalyst in which these are coexisting with an electron-donating compound, the titanium and magnesium atoms are Of course,
While maintaining the polymerization activity per titanium-containing solid catalyst component at a high level, an olefin polymer with high stereoregularity and good powder properties with few halogen components can be obtained.
Surprisingly, it was discovered that the effects on such high polymerization activity and stereoregularity hardly decrease even in the coexistence of a molecular weight regulator such as hydrogen, leading to the completion of the present invention. The present invention will be explained in detail below. The titanium-containing solid catalyst component used as the first component of the catalyst in the present invention is an inert inorganic carrier or a treatment product of an inert inorganic carrier with a silicon halide compound, a silanol or polysilanol, an organomagnesium compound, an electron-donating compound, It is obtained by contacting titanium compounds. Examples of inert inorganic solids include silica, alumina, titania, magnesia, magnesium hydroxide, boron oxide, zinc oxide, magnesium sulfate, sodium sulfate, calcium sulfate, magnesium carbonate, calcium carbonate, and mixtures or composites thereof. can be used. Especially silica,
Oxides such as alumina, titania, and magnesia are preferred. The powder properties (particularly particle size distribution) of these inert inorganic carriers strongly control the powder properties of the resulting titanium-containing solid catalyst component and, ultimately, the particle properties of the olefin polymer, so use ones with uniform particle properties. Doing so will yield favorable results. The halogenated silicon compound used as a treatment agent for an inert inorganic carrier is represented by the general formula R ¹ _o Si X _4-o , where n is 0,
1, 2 or 3, and R ¹ may be the same or different and represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, an aralkyl group. where X represents a halogen atom such as fluorine, chlorine, bromine, or iodine. Specifically, silicon tetrachloride, silicon tetrabromide, methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, ethoxytrichlorosilane, trichlorosilane, dimethyldichlorosilane, phenylmethyldichlorosilane, diethoxydichlorosilane, benzyl Examples include trichlorosilane, but mixtures thereof can also be used. The treatment with a halogenated silicon compound may be carried out in a gas phase reaction using its vapor or in the absence of a solvent, or may be carried out in an inert hydrocarbon solvent such as heptane, cyclohexane, benzene, or toluene. The treatment temperature is room temperature or higher, preferably 50°C to 500°C, and in the case of gas phase treatment, it is preferably higher than the boiling point of the silicon halide used. The reaction mixture obtained by the above treatment is
It may be used as it is, but it may also be used after separating and washing solids from the reaction mixture by filtration or decantation, or removing unreacted substances or solvent by vaporization. General formula for organomagnesium compounds
Grignard compound represented by R ² MgX (wherein R ² represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents the same halogen atom as defined above), general formula R ² MgR ³ (in the formula, R ² is the same as the above definition, R ³
represents an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms,
R ² and R ³ may be the same or different) and
R ² MgoR ³ (in the formula, R ² and R ³ are the same as defined above)
Examples include magnesium compounds represented by: These organomagnesium compounds are usually synthesized in a solvent such as ether, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, etc., and used as a solution thereof. Examples of such ethers include diethyl ether, dibutyl ether, dihexyl ether, dioctyl ether, tetrahydrofuran, etc., examples of aliphatic hydrocarbons include pentane, hexane, heptane, etc., and examples of alicyclic hydrocarbons include cyclohexane, Examples of the aromatic hydrocarbon include methylcyclohexane, and examples of the aromatic hydrocarbon include benzene, toluene, and xylene. Silanol is represented by the general formula R ⁴ nSi(OH) _4-o (wherein R ⁴ represents a hydrocarbon group and n is 1, 2 or 3). Silanol can be easily synthesized, for example, by hydrolyzing a corresponding halide, as shown in the following formula. (C ₆ H ₅ ) ₃ SiCl + H ₂ O → (C ₆ H ₅ ) ₃ SiOH + HCl Specifically, R ⁴ is an alkyl group having up to 20 carbon atoms, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group. , an alkaryl group, a cycloaralkyl group, and the like. especially,
Methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group,
Preferred are alkyl groups such as decyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. In addition, n can be 1, 2 or 3, but from the viewpoint of silanol stability, n is 3, n is 2
It is preferable that R ⁴ is an aryl group. As polysilanol, silanol R ⁴ ₂ Si
(OH) ₂ or R ⁴ Si(OH) ₃ (in the formula, R ⁴ is the same as defined above) was condensed. It is a compound that has a siloxane bond, and its structure can be linear, cyclic,
It may have any structure such as a three-dimensional network structure, but as for the hydroxyl group content, those having at least one hydroxyl group per molecule are used. It is preferred that the hydroxyl group content in the polysilanol is 4 to 14 mmol/g.
Such polysilanols can be easily obtained by hydrolyzing the corresponding organic halosilane under appropriate conditions. For example, the general formula
Organic trihalosilane and/or organic dihalosilane represented by R ⁴ SiX ₃ or R ⁴ ₂ SiX ₂ (wherein R ⁴ and -50~100℃ in hydrogen solvent, preferably -50~
At a temperature around 20℃, the halogen in the organic halosilane is subjected to a hydrolysis reaction or co-hydrolysis reaction with water or an alkaline aqueous solution in an amount equivalent to or more, and then the resulting solution is washed with water until the washing liquid becomes neutral, and then dried. By doing so, a polysilanol solution can be obtained. At this time, the degree of polymerization of polysilanol can be controlled by the hydrolysis temperature and alkali concentration. The polysilanol may be isolated and used by distilling off the solvent from this solution, or the solution may be used as it is. Polysilanol also has the general formula R ⁴ ₂ Si
The silanol represented by (OH) ₂ (wherein R ⁴ is the same as defined above) can be easily obtained by heating to 50° C. or higher, preferably in an alcohol in the presence of an alkali. The reaction between at least one compound selected from these silanols and polysilanols and the inert inorganic carrier or its treatment product with a halogenated silicon compound is carried out at room temperature or above, preferably at 50 to 300 mA.
C, particularly preferably at 100 to 250 C for several hours. The weight ratio of silanol or polysilanol to the inert inorganic carrier is 0.05 to 20, preferably 0.1 to 5. The catalytic reaction may be carried out in a solvent or without a solvent, but when carried out in a solvent, for example, an aromatic hydrocarbon such as benzene or toluene, a saturated substance such as n-heptane or n-hexane, etc. It is dissolved in aliphatic hydrocarbons, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ethers such as diethyl ether and dibutyl ether, and reacted. The reaction mixture obtained after the contact reaction may be used as it is, but after separating solids from the reaction mixture by filtration or decantation or removing unreacted substances or solvent by vaporization,
may be used. Alternatively, silanol or polysilanol may be synthesized in the coexistence of an inert inorganic carrier or its treated product with a halogenated silicon compound, and then the reaction may be completed under the above conditions, and then the solid may be separated. It is necessary to remove as much water as possible by evaporation or decantation, or by heating under normal pressure or reduced pressure. These catalytic reactions can also be carried out under the same conditions as described above when carried out between the reaction product of an organomagnesium compound and a silanol or polysilanol, which will be described later, and an inert inorganic carrier or its treated product with a silicon halide compound. can. The reaction between an organomagnesium compound and at least one compound selected from silanols, polysilanols, and reaction products of these with an inert inorganic carrier or a product treated with a halogenated silicon compound is carried out at -50 to This is carried out by bringing both components into contact at 100°C and then reacting for several hours at 50-20°C, preferably 50-150°C, particularly preferably 70-110°C. The ratio of both components used is preferably 0.1 to 10 in terms of the ratio (mole ratio) of hydroxyl groups contained in silanol, polysilanol, or the reaction product of these with an inert inorganic carrier/Mg-C bond in the organomagnesium compound. is 1-2.
The catalytic reaction is preferably carried out in a solvent, for example aromatic hydrocarbons such as benzene, toluene, etc.
- Saturated aliphatic hydrocarbons such as heptane and n-hexane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ethers such as diethyl ether and dibutyl ether are used. The reaction mixture obtained after the contact reaction may be used as it is, but it may also be used after separating solids from the reaction mixture by filtration or decantation, or removing unreacted substances or solvent by vaporization. The titanium compound used to produce the titanium-containing solid catalyst component is preferably a tetravalent titanium compound, such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, or a titanium halide containing one alkoxy group. Examples include mixtures of the following. As the electron-donating compound for producing the titanium-containing solid catalyst component, nitrogen-containing compounds selected from amines and carboxylic acid amides, phosphine,
Examples include phosphorus-containing compounds selected from phosphine oxides, phosphoric acid esters, phosphorous acid esters, and phosphoric acid amides; oxygen-containing compounds selected from ketones and carboxylic acid esters; and silicon-containing carboxylic esters. In addition, in the carboxylic acid ester mentioned here, the hydrocarbon group of the carboxylic acid residue may have a substituent such as an amino group or an alkoxy group,
Such examples include amino acid esters. Specific examples of electron-donating compounds include nitrogen-containing compounds such as tetramethylethylenediamine, tetraethylethylenediamine, acetamide, triethyl phosphate, tributyl phosphate, triphenylphosphine, triphenylphosphite, triethylphosphine oxide, and triphenylphosphine. Phosphorus-containing compounds such as enylphosphine oxide, tris(nonylphenyl)phosphite, hexamethylphosphoric triamide, methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, phenyl benzoate, methyl p-methoxybenzoate, ethyl p-methoxybenzoate, propyl p-methoxybenzoate, butyl m-methoxybenzoate, phenyl O-methoxybenzoate, methyl p-toluate, Ethyl p-toluate, ethyl p-ethylbenzoate, propyl p-ethylbenzoate, ethyl p-butylbenzoate, butyl p-butylbenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, phenyl acetate , phenyl propionate, ethyl crotonate, propyl crotonate, butyl crotonate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethylglycine ethyl ester, dimethylglycine propyl ester, dimethylglycine butyl ester, diphenylglycine Ethyl ester, diphenylglycine butyl ester,
Examples include oxygen-containing compounds such as p-dimethylaminobenzoic acid ethyl ester. In addition, as a silicon-containing carboxylic acid ester,

[Formula] (wherein R ⁵ , R ⁶ and R ⁷ represent an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group or an aryloxy group having 1 to 20 carbon atoms, or a polysiloxy group,
Represents a hydroxyl group or a halogen. ) Aromatic or aliphatic carboxylic acid esters having at least one silicon substituent are mentioned, and aromatic carboxylic acid ester derivatives are particularly preferred.
The above silicon substituent may be directly bonded to the carbon atom of the carboxylic acid ester, and may also be bonded directly to the carbon atom of the carboxylic acid ester.
It may be bonded to the carboxylic acid ester via an atom other than carbon such as aluminum or a linking group containing these atoms. The silicon-containing carboxylic acid ester is, for example, a carboxylic acid ester having an olefinic double bond in at least one of the alcohol component and carboxylic acid component of an ester such as vinyl benzoate or methyl acrylate, or a p-hydroxybenzoic acid ester. A carboxylic acid ester having a hydroxyl group is treated in the presence of a transition metal catalyst such as platinum, rhodium, or cobalt or an organic peroxide catalyst without a solvent or with an aromatic hydrocarbon such as benzene, toluene, xylene, pentane, hexane, heptane, etc. In a solvent such as an aliphatic hydrocarbon, an ether such as diethyl ether or tetrahydrofuran, the general formula

[Formula] (wherein R ⁵ , R ⁶ and R ⁷ are the same as defined above) and 0 to 300
C., preferably 30 to 200.degree. C., for 0.5 hours or more, preferably 1 to 24 hours, and in some cases, 5 hours or more. In addition, at least one of the above R ⁵ , R ⁶ and R ⁷
In addition to the above-mentioned production method, carboxylic acid esters having silicon substituents in which each group is a polysiloxy group (hereinafter referred to as polysiloxy esters) can also be produced by the production method described above. Among them, a condensation reaction between a compound having an alkoxy substituent, an aryloxy substituent, a hydroxyl substituent, or a halogen substituent and the aforementioned polysilanol, or a polysiloxane having an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen substituent It can also be produced by a condensation reaction with a carboxylic acid ester having active hydrogen. These condensation reactions are carried out without a solvent or in a suitable solvent at a temperature of 50 to 500°C, preferably 100 to 200°C, for 0.1 hour or more.
It is preferably carried out for 1 to 10 hours. The use or non-use of a solvent and its type cannot be categorically specified as they vary depending on the type of starting material, but for example, in the case of a dehydration condensation reaction, it is preferable to carry out the reaction in an aromatic hydrocarbon solvent such as benzene or toluene under reflux. . Silicon-containing carboxylic acid esters obtained by the various production methods described above may be used for producing a titanium-containing solid catalyst component without separating impurities, or after performing operations such as distillation separation and solvent washing. It may also be used for producing a titanium-containing solid catalyst component. Specific examples of silicon-containing carboxylic acid esters include -β-trimethoxysilylethyl benzoate;
β-triethoxysilylethyl benzoate, β-diphenylmethoxysilylethyl benzoate, β-trichlorosilylethyl benzoate, β-trimethoxysilylethyl p-toluate, β-triethyl p-toluate Ethoxysilylethyl, p-
β-triethoxysilylethyl methoxybenzoate, β-triethoxysilylethyl p-chlorobenzoate, β-triethoxysilylethyl phenyl acetate, β-triethoxysilylethyl α-
Naphthoate, β-dimethylhydroxysilylethyl benzoate, 3-triethoxysilylpropyl benzoate, methyl p-trimethoxysiloxybenzoate, ethyl p-triethoxysiloxybenzoate, phenyl p-trimethoxysiloxybenzoate, p -Aromatic carboxylic acid esters containing silyl groups such as phenyl triethoxysiloxybenzoate, β-triethoxysilylethyl p-triethoxysiloxybenzoate, β-trimethoxysilylethyl acetate, β-triethoxy acetate Silylethyl, β-dimethylchlorosilylethyl acetate, β-diphenylchlorosilylethyl acetate,
β-diphenylhydroxysilylethyl acetate,
Methyl 3-trimethoxysilylpropionate, 3
-methyl trichlorosilylpropionate, methyl 3-diphenylhydroxysilylpropionate,
Examples include silyl group-containing aliphatic carboxylic acid esters such as methyl 2-methyl-3-triethoxysilylpropionate and ethyl 2-methyl-3-triethoxysilylpropionate, and polysiloxy esters described below. The structure of the polysiloxy group of polysiloxy ester is linear, branched,
It may be either cyclic or three-dimensional network-like, and the silicon substituent in the siloxane structure may have the same type of substituents as R ⁵ to R ⁷ described above. The number of ester bonds in the polysiloxy ester is preferably 0.01 to 2, particularly 0.05 to 0.8, per silicon atom in the polysiloxy ester. Among the electron-donating compounds described above, carboxylic acid esters and silicon-containing carboxylic esters are preferably used, and the use of silicon-containing carboxylic esters in particular brings about favorable results during olefin polymerization in the coexistence of hydrogen. To produce a titanium-containing solid catalyst component, the above-mentioned organomagnesium compound, titanium compound, and electron-donating compound are added in an amount of 0.1 to 100 mol, preferably 1 to 100 mol, of the titanium compound per 1 mol of magnesium atom in the organomagnesium compound. 50 mol and electron-donating compound (in the case of silicon-containing carboxylic acid ester, the equivalent of the ester bond contained) 0.01
in proportions of ~10 mol, preferably 0.05-1.0 mol,
Without a solvent or with aromatic hydrocarbons such as benzene and toluene, saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and liquid paraffin, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, diethyl ether, dichloromethane, etc. The contact may be made in the presence of a solvent such as an ether such as butyl ether. The titanium content of the titanium-containing solid catalyst component obtained at this time is preferably 0.05 to 20% by weight, particularly 0.1 to 5% by weight. The obtained titanium-containing solid catalyst component is washed with an inert hydrocarbon solvent and then used as a component of an olefin polymerization catalyst. There are various methods for producing a titanium-containing solid catalyst component by contacting the above three components in the order or mode of contact, but the preferred methods are as follows: (1) Inert inorganic carrier or its halogen A treatment product with a silicone compound (hereinafter simply referred to as an inorganic solid component) is mixed with silanol or polysilanol at room temperature or above, preferably at 50 to 300°C, particularly preferably at 100 to 250°C, in the presence or absence of a solvent. Under 0.1 hour or more, preferably 1-10
After reacting for a period of time and separating and obtaining solid components as they are or produced, an organomagnesium compound is added at -50 to 100°C, and then at 50 to 200°C.
Preferably 50-150℃, particularly preferably 70-110℃
The temperature is raised to ℃ and the reaction is carried out for 0.1 to 10 hours, preferably 0.5 to 3 hours. After that, the solid product is separated and obtained as it is or the obtained solid product is separated and converted into an electron-donating compound at a temperature of -50 to 100℃. Or add the solution and raise the temperature to 60-200℃ for 0.1-10 hours.
Preferably, the reaction is carried out for 0.5 to 3 hours, the solid component as it is or the formed solid component is separated, and then a titanium compound is added and the reaction is carried out at 60 to 150°C, preferably.
A method of separating the titanium-containing solid catalyst component produced by reacting at 80 to 130°C for 0.1 to 10 hours. ) and an electron-donating compound at the same time, or add a magnesium component to the inorganic solid component and process in the same manner as in (1) above, then add an electron-donating compound and process in accordance with (1) above. A method in which a titanium compound is added to separate the titanium-containing solid catalyst component produced after the treatment. (3) After treating the inorganic solid component by adding a halogenated silicon compound at room temperature or higher, preferably at 50 to 500°C, the silanol or polysilanol compound is added in the presence of the inorganic solid component in the same manner as in the silanol or polysilanol synthesis method described above. After synthesizing silanol and then distilling off the water or alcohol component under normal pressure or reduced pressure or removing it by washing,
A method of adding and treating an organomagnesium compound in the same manner as in (1) above, further treating with an electron donating compound and a titanium compound, and separating the produced titanium-containing solid catalyst component. (4) Either silanol or polysilanol and an electron-donating compound are added to the inorganic solid component at the same time, or silanol or polysilanol is added to the inorganic solid component and treated in the same manner as in (1) above, and then the electron-donating compound is added. Add the above
(1), then add an organomagnesium compound at -30°C to room temperature to obtain a magnesium component, and further raise the temperature to 60 to 200°C to react with an electron-donating compound. A method of treating the reaction mixture as it is or after separating and obtaining solid components with a titanium compound in the same manner as in (1) above, and separating the produced titanium-containing solid catalyst component. (5) Add a magnesium component, an electron-donating compound, and a titanium compound to the inorganic solid component at the same time, or add a magnesium component and a titanium compound to the inorganic solid component at the same time and treat in the same manner as in (1) above. A method of separating the titanium-containing solid catalyst component produced by adding a donor compound and performing the treatment according to (1) above. (6) As in (1) above, silanol or polysilanol is added to the inorganic solid component and after the reaction, an organomagnesium compound is added to obtain the magnesium component, or as in (2) above, the inorganic solid component is After the reaction with the magnesium component, a titanium compound and an electron-donating compound are added at the same time, or a titanium compound is added and treated in the same manner as in (1) above, and then an electron-donating compound is added and the electron-donating compound is added in the same manner as in (1) above. ), and the resulting titanium-containing solid catalyst component is separated. The inert inorganic carrier used in the preparation of the titanium-containing solid catalyst component mentioned above contains impurities such as crystal water or adsorbed water or hydroxyl groups on the solid surface, and these impurities should be removed as much as possible. It is preferable to do so. Therefore, it is preferred that the inert inorganic solid is heat treated or treated with a halogenated silicon compound before its use. On the other hand, the silanol, polysilanol, or silicon-containing carboxylic acid ester used in the preparation of the solid catalyst component is preferably adsorbed or chemically bonded to the surface of an inert inorganic carrier, and therefore it is preferable to treat them at high temperatures. . That is,
The reaction to create a chemical bond between the two is dehydration, dealcoholization, or dehydrohalogenation between the hydroxyl group, alkoxy group, or halogen in the silanol, polysilanol, or silicon-containing carboxylic acid ester and the surface hydroxyl group of the inert inorganic carrier. These reactions are preferably carried out under conditions sufficient to induce these reactions. As the organoaluminum compound used as the second component of the catalyst, for example, the general formula
AlR ⁸ mX _3-n (In the formula, R ⁸ represents an alkyl group having 1 to 8 carbon atoms, and when there are two or more R ⁸ s, each may be different. m is a number of 1 to 3. , X represents a halogen atom) is used. Particularly preferred are trialkylaluminums such as triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. It is also a preferred embodiment to use dialkylaluminum monochloride such as diethylaluminum monochloride and dibutylaluminum monochloride in combination with trialkylaluminum. These organoaluminum compounds are used in an amount of 1 to 1 mole of titanium in the titanium-containing solid catalyst component.
500 mol is used, preferably 10-100 mol. In the method of the present invention, olefin polymerization can be carried out using two components, a titanium-containing solid catalyst component and an organoaluminum compound, as catalysts, but it is also possible to polymerize olefins in the presence of an electron-donating compound as a third component. Can be done. As such an electron donating compound, the electron donating compound used in the production of the titanium-containing solid catalyst component described above can be used, but carboxylic acid esters and silicon-containing carboxylic acid esters are particularly preferred. The amount of these electron-donating compounds to be used is selected within the range of 0 to 10 mol, preferably 0.05 to 1 mol, particularly preferably 0.1 to 0.5 mol, per mol of the organoaluminum compound. The olefins used in carrying out the method of the present invention include α-olefins such as ethylene, propylene, butene-1, etc., and homopolymerization of two or more thereof using the catalyst of the present invention, These olefin polymers can advantageously be obtained by random copolymerization or block copolymerization. The catalyst according to the invention is particularly suitable for the production of highly stereoregular polymers and is therefore a propylene homopolymer or a copolymer consisting of 90% by weight or more of propylene and 10% by weight or less of other α-olefins. Suitable for producing polymers. In the present invention, the polymerization or copolymerization reaction can take various polymerization methods, such as solution polymerization or slurry polymerization in the presence of an inert hydrocarbon or liquefied propylene solvent, and gas phase polymerization without a solvent. The temperature during polymerization is 50 to 100°C, preferably
The temperature is selected from the range of 50 to 80°C, and the pressure is selected from the range of 1 to 100 atmospheres. Furthermore, by allowing hydrogen to exist in the polymerization zone, the molecular weight of the produced polymer can be easily controlled. As detailed above, according to the method of the present invention, an olefin polymer with good stereoregularity can be easily obtained. Since the obtained olefin polymer has high stereoregularity, removal of the amorphous polymer from the polymer can be omitted. Furthermore, since the titanium-containing solid catalyst used in the present invention has extremely high polymerization activity, it has the advantage that the step of removing catalyst residue from the obtained olefin polymer can also be omitted.
Further, the halogen content in the polymer obtained by the method of the present invention is extremely small because the halogen content contained in the titanium-containing solid catalyst component is small, and the benefits in terms of product physical properties are extremely large. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it departs from the gist thereof. It should be noted that FIG. 1 is a flowchart diagram to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not depart from the gist thereof. In addition, in the Examples and Comparative Examples, the isotactic index (hereinafter abbreviated as "") was prepared using an improved Soxhlet extractor.
The solid residue after extraction with heptane for 6 hours was dried and expressed in weight percent. In addition, the melt flow index (hereinafter abbreviated as "MFI") is based on the ASTM standard.
The values measured according to D1238 are shown. Example 1 [] Synthesis of polyphenylsilanol 3.2 g of pure water and 170 ml of toluene were placed in a 500 ml four-necked flask and kept cool at -20°C while stirring. A solution of 25 g (0.118 mol) of phenyltrichlorosilane in 70 ml of toluene was added dropwise to this toluene suspension using a dropping funnel over a period of 1 hour. After the dropwise addition was completed, the reaction mixture was heated to 0°C, and then
Stirring was continued for 30 minutes. Next, it was washed with ice water until the washing solution became neutral. The obtained toluene solution was dehydrated and dried over anhydrous sodium sulfate, filtered,
The liquid was used as a raw material for carrier preparation.
The hydroxyl group concentration of this toluene solution was determined by the method described below and was found to be 8.1 mmol/g. The amount of hydroxyl groups in the polysilanol was determined as follows. Add an appropriate amount of Grignard compound so that it is in excess of the hydroxyl groups, and heat at 100°C.
The reaction was completed by heating and stirring for 1 hour. Next, benzyl bromide was added in an amount equal to the number of moles of the Grignard compound used, and the mixture was heated and stirred at 100° C. for 1 hour. Next, after returning the reaction container to room temperature, pure water was added for hydrolysis, and the resulting alkaline component was titrated with a 0.1N aqueous hydrochloric acid solution in the presence of an indicator (alcoholic solution of phenolphthalene). [] Preparation of titanium-containing solid catalyst component 1.6 g of Fuji Davison silica (#952) calcined at 600°C for 3 hours in a stream of dry nitrogen was placed in a 200 ml four-necked flask that had been purged with dry nitrogen in advance, and transferred in []. Toluene solution of 0.34 mol/hydroxyl group of synthesized polyphenylsilanol
19.7 ml (0.83 g) was added dropwise to room temperature, and the temperature was raised to 110° C. while stirring, and the reaction was carried out for 2 hours. Next, while maintaining the reaction vessel at 110°C,
1.65 ml of a solution of 3.03 mol/n-butylmagnesium chloride in di-n-butyl ether was gradually added dropwise, and the reaction was carried out for 30 minutes. After the reaction was completed, it was cooled to room temperature, the solvent was distilled off under reduced pressure, and then the temperature was raised to 180°C under reduced pressure and further heated for 1 hour.
The reaction and drying were completed by heating for an hour. After cooling to room temperature, 1.4 ml of a 0.5 mol/toluene solution of methyl p-toluate and 5 ml of toluene were added to the obtained white solid.
The reaction was carried out by stirring at °C for 1 hour. After cooling to room temperature, the solvent was distilled off under reduced pressure.
The temperature was raised to 65°C and the mixture was treated under reduced pressure for 30 minutes to distill off unreacted methyl p-toluate to obtain a white solid. After raising the temperature to 130° C., 17 ml of titanium tetrachloride was added to the obtained white solid while stirring, and the reaction was carried out for 1 hour. Then, after separating the supernatant, the precipitate was
Washing was repeated five times with 100 ml of heptane to obtain a tan solid. Analysis of the obtained solid revealed that it contained 0.91% by weight of titanium, 5.30% by weight of magnesium, and chlorine.
It contained 17.39% by weight. [] Polymerization of olefin Add 450 ml of n-hexane,
1.2m of triethylaluminum as cocatalyst
0.3 mmol of methyl p-toluate was added, and the mixture was stirred at room temperature for 30 minutes. Next, add 51.3 mg of the titanium-containing solid catalyst prepared in [] above.
Propylene was introduced so that the pressure of the charged propylene was 0.3 Kg/cm ^{2 ,} and the mixture was stirred at room temperature for 5 minutes. Next, after injecting 0.5Kg/cm ² of hydrogen,
After raising the temperature to 70°C and carrying out polymerization for 1.5 hours while replenishing propylene so that the pressure of propylene was 17 kg/cm ² , a small amount of isopropyl alcohol was added to stop the polymerization. After purging unreacted propylene, the mixture was dried to obtain 299 g of white powdery polypropylene. Polymerization activity Kcat (polymer (g)/titanium-containing solid catalyst component (g), time (hr), propylene pressure (Kg/cm ² ), hereinafter the same meanings apply) is 229, KTi
(Polymer (g)/Titanium (g)・Time (hr)・
Propylene pressure (Kg/cm ² ) has the same meaning below. )
is 25260, catalyst efficiency CE (polymer (g)/titanium (g) and the following have the same meaning) is 644260,
II was 92.4%. Furthermore, the MFI was 8.8, and the apparent density of the polymer (hereinafter expressed as ρ _B ) was 0.41 g/cc. Furthermore, when the chlorine content in the polymer was measured using fluorescent X-rays (hereinafter simply referred to as FX), it was found to be 30.0 ppm.
It was extremely rare. From the above results,
It is clear that this catalyst not only has high polymerization activity but also provides sufficiently high stereoregularity and ρ _B of the resulting polymer. Comparative Example 1 A yellow-brown titanium-containing solid catalyst component was prepared in the same manner as in Example 1, except that silica was not used and the amount of the toluene solution of polyphenylsilanol was changed to 15 ml. The obtained solid catalyst component contained 3.02% by weight of titanium, 20.16% by weight of magnesium, and 65.64% by weight of chlorine. Next, propylene was polymerized in the same manner as in Example 1, except that 24.2 mg of the obtained solid catalyst component was used, and 289 g of white powder polypropylene was obtained. The results are shown in Table 1.
Both stereoregularity and chlorine content of the obtained polypropylene were not fully satisfactory, and ρ _B was also low. Example 2 [] Preparation of titanium-containing solid catalyst component 1.1 g of silica (#952) made by Fuji Davison, which was not subjected to heat treatment, was replaced with 200 ml of dry nitrogen.
Charged into a 4-necked flask, per hydroxyl group of polyphenylsilanol synthesized in [] of Example 1.
26 ml (1.1 g) of a 0.34 mol/toluene solution was added dropwise at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes, and then the solvent was distilled off under reduced pressure to obtain a white powder. The obtained white powder was heated to 180° C. under normal pressure and treated for 3 hours, and then treated at the same temperature for 1 hour under reduced pressure. After cooling to room temperature, 5 ml of toluene and 2.1 ml of a solution of 3.03 mol/n-butylmagnesium chloride in di-n-butyl ether were added dropwise.Then, the temperature was raised to 110°C, and the reaction was carried out for 1 hour. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the temperature was raised to 180° C. and treated for 1 hour to completely remove volatile components to obtain a white powder. After cooling the temperature of the reaction vessel to 130°C and restoring the pressure to normal pressure, 21 ml of titanium tetrachloride was added to the obtained white powder, heated and stirred at the same temperature for 5 minutes, and then 0.5 mol of methyl p-toluate was added. 2 ml of a toluene solution of / was added and stirring was continued for an additional hour. A supernatant liquid was separated from the resulting reaction mixture, and then the precipitate was washed five times with 100 ml of n-heptane to obtain a yellowish brown solid. The obtained solid catalyst component contained 1.35% by weight of titanium,
It contained 7.80% by weight of magnesium and 25.59% by weight of chlorine. [] Polymerization of propylene Triethylaluminum was placed in an induction stirring autoclave (2) which was sufficiently vacuumed and replaced with nitrogen.
2.0m mol, methyl p-toluate 0.56m mol
After charging 1 kg/cm ² of hydrogen, 750 g of liquefied propylene and 38.5 mg of the titanium-containing solid catalyst component prepared in [] above were charged in this order and stirred at room temperature for 5 minutes. Next, the temperature was raised to 70°C and polymerization was carried out for 1 hour, and then a small amount of isopropyl alcohol was added to stop the polymerization. After purging unreacted propylene, the mixture was dried to obtain 265 g of white powdery polypropylene. The results are shown in Table-1. Example 3 80 ml of n-heptane and 2.8 ml of a 0.5 mol/toluene solution of methyl p-toluate were added to the titanium-containing solid catalyst component obtained in exactly the same manner as [] in Example 2, and the mixture was heated at 95°C. The mixture was heated and stirred for 1 hour. Next, after separating the supernatant, the solvent was removed under reduced pressure at room temperature, and after drying, 12 ml of titanium tetrachloride was added under normal pressure, and the reaction was carried out at 130°C for 2 hours with stirring. After separating and removing the supernatant from the resulting reaction mixture at the same temperature, the mixture was washed three times with 100 ml of n-heptane at 90°C and twice with 100 ml of n-heptane at room temperature to obtain a yellowish brown solid. Ta. The obtained solid catalyst component contained 1.13% by weight of titanium, 7.31% by weight of magnesium, and 23.68% by weight of chlorine. Using the solid catalyst component obtained by the above method,
Polymerization of propylene was carried out in exactly the same manner as in [] of Example 2. The results are shown in Table-1. Example 4 [] Synthesis of β-triethoxysilylethyl benzoate 32.3 g of triethoxysilane and vinyl benzoate were placed in a 200 ml three-necked flask purged with dry nitrogen.
After adding 2 ml of isopropyl alcohol solution of chloroplatinic acid (concentration 0.5 mol/) while stirring at room temperature, 120 g was added over 30 minutes.
The temperature was raised to 0.degree. C., and stirring was continued for 2 hours. When this reaction mixture was subjected to simple distillation under normal pressure in a nitrogen atmosphere, 16 g of triethoxysilane with a boiling point of 131°C was recovered. Distillation was then carried out under reduced pressure of 1.5 mmHg, and vinyl benzoate was obtained with a boiling point of 70-75°C.
14g was recovered, and further distillation was carried out to reduce the boiling point to 125-135.
17 g of a .degree. C. fraction (colorless liquid) and 9.2 g of a black viscous distillation residue were obtained. The above 125-135°C fraction was further subjected to simple distillation under reduced pressure of 1.5 mmHg to obtain 15 g of a fraction (colorless liquid) with a boiling point of 131-135°C. Analysis by gas chromatography and nuclear magnetic resonance spectra showed that this product had benzoic acid.
It was found that the mixture contained 81% β-triethylsilylethyl. Note that the mixture did not contain the raw materials vinyl benzoate and triethoxysilane. The chemical shift and assignment of β-triethylsilylethyl benzoate are shown below.

[Table] [] Preparation of titanium-containing solid catalyst component As in [] of Example 2, 1.2 g of silica that was not subjected to heat treatment and 10 ml of phenyltrichlorosilane were placed in a 200 ml four-necked flask that had been purged with dry nitrogen. The reaction was carried out at 150° C. for 2 hours with stirring. After separating the supernatant from the reaction mixture,
After washing with 50 ml of n-heptane three times, the solvent was removed under reduced pressure at room temperature and dried to obtain a white solid. To the obtained solid, 38.5 ml (1.6 g) of a 0.34 mol/toluene solution of the polyphenylsilanol synthesized in [] of Example 1 was added dropwise at room temperature, and the temperature was raised to 110°C with stirring, and the reaction was continued for 3 hours. I did it. Then, at the same temperature, 3.03 mol/chloride n
- Gradually drop 3.5 ml of di-n-butyl ether solution of butylmagnesium for 30 minutes, and then add 0.5 mol/toluene solution of β-triethoxysilylethyl benzoate synthesized in [] above.
After adding 2.1 ml and heating and stirring for 1 hour, the mixture was cooled to room temperature and the solvent was distilled off under reduced pressure. Next, the temperature was raised to 180° C. under reduced pressure and treated for 1 hour to obtain a white powder. reaction vessel
After lowering the temperature to 110°C, the pressure was restored to normal pressure, 4.2 ml of a 0.5 mol/toluene solution of ethyl benzoate was added, and the mixture was heated and stirred for 1 hour. The temperature was further lowered to 65°C, and the solvent and unreacted ester were removed under reduced pressure. was removed. The white powder thus obtained contains 35 titanium tetrachloride.
ml was added and treated at 130°C for 1 hour. Next, after separating the supernatant liquid, the precipitate was dissolved in 100 ml of n-heptane.
The mixture was washed with water five times to obtain a greenish brown solid. The solid catalyst component obtained was 1.66% by weight of titanium.
It contained 9.65% by weight of magnesium and 31.66% by weight of chlorine. Polymerization of propylene was carried out in exactly the same manner as in Example 1 [] using the solid catalyst component obtained by the above method. The results are shown in Table-1. Example 5 In a 100 ml four-necked flask purged with dry nitrogen,
Toluene solution of 0.34 mol/hydroxyl group of polyphenylsilanol synthesized in [] of Example 126
ml (1.1 g), and 2.0 ml of a 3.03 mol/n-butylmagnesium chloride solution in di-n-butyl ether was gradually added dropwise at 25°C with stirring. After the dropwise addition was completed, the mixture was stirred and aged at 110°C for 1 hour. After cooling to 25°C, the resulting reaction mixture was mixed with 1.0 g of the silica used in [] of Example 1 and 0.5 mol/toluene of β-triethoxysilylethyl benzoate synthesized in [] of Example 4. solution 1.8
ml was added to a 300 ml four-necked flask which had been purged with dry nitrogen, heated to 110°C, and reacted for 3 hours. Then, after cooling to room temperature, the solvent was distilled off under reduced pressure, and the temperature was further raised to 180° C. to remove the solvent and unreacted ester to obtain a white solid. After cooling to 130℃, add 20ml of titanium tetrachloride for 5 minutes, then add methyl p-toluate.
1.9 ml of a 0.5 mol/toluene solution was added and the reaction was carried out by stirring at the same temperature for 1 hour. Next, the precipitate was separated and washed in the same manner as in [] of Example 1 to obtain a yellowish brown solid. The obtained solid catalyst component contained 1.38% by weight of titanium, 8.00% by weight of magnesium, and 26.24% by weight of chlorine. Using the solid catalyst component obtained by the above method,
Polymerization of propylene was carried out in exactly the same manner as in [] of Example 2. The results are shown in Table-1. Example 6 [] Synthesis of silicon-containing magnesium carrier In a 500 ml four-necked flask purged with dry nitrogen,
100m mol of triphenylsilanol and toluene
Pour 250ml and add 3.1mol/n-chloride to this.
32 ml of a di-n-butyl ether solution of butylmagnesium was gradually added dropwise at room temperature with stirring.
After the addition was completed, stirred at the same temperature for 1 hour, then stirred at 70°C.
The temperature was raised to 0.degree. C., and stirring was continued for an additional hour. Next, toluene and di-n-butyl ether were distilled off under reduced pressure and dried to obtain a white silicon-containing magnesium carrier. [] Preparation of titanium-containing solid catalyst component and polymerization of propylene Silica was reacted with phenyltrichlorosilane in exactly the same manner as in [] of Example 4, and the obtained solid was separated and washed, and then obtained in [] above. Magnesium carrier (3.4g) and toluene
20ml was added and treated at 110°C for 1 hour with stirring. Furthermore, at the same temperature, ethyl benzoate
1 by adding 4.2 ml of 0.5 mol/toluene solution.
A time reaction was performed. Next, the solvent and unreacted ester were distilled off under reduced pressure and dried to obtain a white powder. After adding 35 ml of titanium tetrachloride to the obtained powder and carrying out the reaction at 130°C for 1 hour with stirring,
The solid was separated and washed in the same manner as [ ] in Example 1 to obtain a greenish-brown titanium-containing solid catalyst component. The solid catalyst component obtained was 1.29% by weight of titanium.
It contained 9.30% by weight of magnesium and 27.84% by weight of chlorine. Polymerization of propylene was carried out in exactly the same manner as in Example 1 [] using the solid catalyst component obtained by the above method. The results are shown in Table-1. Example 7 A 300 ml four-necked flask purged with dry nitrogen was charged with 2 g of non-heat-treated Fuji Davison silica (#952) and 0.5 g of polyphenylsilanol synthesized in [] of Example 1, and then heated at 180°C.
I did some time processing. Then, after cooling to room temperature, magnesium carrier 3.0 synthesized in [] of Example 6
g and 20 ml of a toluene-di-n-butyl ether mixed solvent in a volume ratio of 3:1 were added thereto, and the reaction was carried out at 110° C. for 1.5 hours with stirring. Then, the solvent and volatile components were distilled off and dried under reduced pressure to obtain a white powder. Add 0.5 mol/ethyl benzoate to the obtained powder.
After reacting at 110°C for 1 hour, toluene and unreacted ester were distilled off under reduced pressure and dried. Then, 31ml of titanium tetrachloride was added to the resulting white powder and the reaction was carried out at 130°C for 2 hours. The reaction was carried out. Next, the solid was separated and washed in the same manner as [ ] in Example 1 to obtain a greenish-brown titanium-containing solid catalyst component. The obtained solid catalyst component contained 0.99% by weight of titanium, 7.14% by weight of magnesium, and 21.37% by weight of chlorine. Using the solid catalyst component obtained by the above method,
Polymerization of propylene was carried out in exactly the same manner as in [] of Example 1. The results are shown in Table-1. Example 8 [] Synthesis of polysiloxyester A 200 ml flask purged with dry nitrogen was charged with 10 g of silicone oil (KF99 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of vinyl benzoate, and while stirring at room temperature, an isopropyl alcohol solution of chloroplatinic acid (concentration When 2 ml of 0.05 mol/) was added, foaming occurred and the reaction began to proceed. After stirring for 30 minutes, the temperature was raised to 90° C. and heating and stirring were continued. After 4 hours, unreacted vinyl benzoate was determined by gas chromatography and found to be 15.8%. 50℃
After the temperature was lowered, 20 ml of dry ethanol was added and stirred for 2 hours to remove active hydrogen remaining in the silicone oil. Next, in order to remove unreacted vinyl benzoate, ethanol and other volatile components, treatment was carried out at 150° C. for 3 hours under reduced pressure to obtain a black viscous liquid. When the infrared absorption spectrum of the obtained liquid was measured in a KBr disk, it was found that the characteristic absorption of ester existed at 1703 cm ^-1 , and the characteristic absorption of Si-H around 2100 cm ^-1 did not exist. Ta. Also, based on Si−CH ₃ in silicone oil,
From the comparison between the peak intensity of 1258 cm ^-1 and the peak intensity of ester absorption, the ester concentration was determined to be 1.3 m mol/
It was calculated as g. [] Preparation of titanium-containing solid catalyst component and polymerization of propylene In a 300 ml four-neck flask purged with dry nitrogen, 2.0 g of the silica used in [] of Example 1 and 1.2 g of the polysiloxy ester synthesized in [] above.
(1.6 mmol as ester component) and 20 ml of xylene were charged and treated at 130°C for 3 hours with stirring. After xylene was distilled off under reduced pressure, the temperature was raised to 180°C and heat treatment was further performed for 1 hour to obtain an off-white solid. After cooling to room temperature, 3.4 g of the magnesium carrier synthesized in [] of Example 6 and 30 ml of toluene-di-n-butyl ether at a volume ratio of 110
The mixture was heated and stirred at ℃ for 1 hour, and then the solvent and volatile components were distilled off under reduced pressure and dried to obtain a pale gray solid. 36 ml of titanium tetrachloride was added to the obtained solid, and after reaction at 130°C for 5 minutes with stirring, 0.5 mol/ml of methyl p-toluate was added at the same temperature.
3.4 ml of toluene solution was added and the reaction was carried out for 1 hour. From the reaction mixture obtained, Example 3
The solid was separated and washed in the same manner as above to obtain a yellowish brown titanium-containing solid catalyst component. The obtained solid catalyst component contained 0.84% by weight of titanium, 6.02% by weight of magnesium, and 18.02% by weight of chlorine. Polymerization of propylene was carried out in exactly the same manner as in Example 2 using the solid catalyst component obtained above. The results are shown in Table-1.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a flowchart showing one embodiment of the present invention.

Claims (1)

[Scope of Claims] 1 (A) A product obtained by contacting an inert inorganic carrier or a treatment product of an inert inorganic carrier with a halogenated silicon compound, a silanol or a polysilanol, an organomagnesium compound, an electron-donating compound, and a titanium compound. A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of a titanium-containing solid catalyst component and (B) a catalyst comprising an organoaluminum compound. 2. The method according to claim 1, wherein the inert inorganic carrier is silica or alumina. 3. The method according to claim 1 or 2, characterized in that the olefin is polymerized in the coexistence of an electron-donating compound.