JPH04227707A - Production of olefinic polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer having high stereoregularity and high organic distribution in high yield by bringing an olefin into contact with a catalyst comprising a combination of a specific solid catalytic component, a specific organosilicon compound and an organoaluminum compound and then polymerizing. CONSTITUTION:An olefin is brought into contact with a catalyst obtained by combining (A) a solid catalytic component composed of (i) a magnesium compound such as a reaction product of Mg, an alcohol and a halogen, (ii) a titanium halide and (iii) an electron donative compound such as monomethyl terephthalate as essential components, (B) an organoaluminum compound such as trimethylaluminum and (C) an organosilicon compound shown by formula I (R<1> to R<3> are hydrocarbon; (n) is 2<=n<=3), formula II (R<4> is hydrocarbon wherein carbon adjoining Si is tertiary carbon; R<5> is hydrocarbon) or formula III (R<6> is hydrocarbon; R<7> is cyclic saturated hydrocarbon; R<8> is hydrocarbon) and polymerized to give the objective polymer. The molar ratio of the organosilicon compound/titanium is preferably 1-100.

Description

Description: FIELD OF INDUSTRIAL APPLICATION This invention relates to an improvement in a method for producing olefin polymers. More specifically, the present invention relates to a method for producing a highly stereoregular olefin polymer or an olefin polymer having high stereoregularity and a wide molecular weight distribution in high yield. [0002] Conventionally, in the production of olefin polymers, it has been widely practiced to polymerize olefins using Ziegler catalysts. In order to obtain highly active catalysts and highly stereoregular polymers, various attempts have been made to improve the Ziegler catalysts. For example, in order to improve the stereoregularity of an olefin polymer, a solid catalyst component containing a magnesium compound, a titanium compound, and an electron donor, an organoaluminum compound, and an organosilicon having a Si-O-C bond are used. A method has been proposed for polymerizing α-olefins having 3 or more carbon atoms using a catalyst in combination with a compound (
JP-A-57-63310 and JP-A-57-63311. ). However, these methods are not necessarily fully satisfactory for obtaining highly stereoregular polymers in high yields, and further improvements have been desired. [0004] Also, as a method for obtaining a highly stereoregular polymer in high yield, as described above, an organic aluminum compound and a Si-O-C are added to a solid catalyst component containing a magnesium compound, a titanium compound, and an electron donor. A method for polymerizing olefins using a catalyst in combination with an organosilicon compound having a bond (Japanese Unexamined Patent Publication No. 54-94590), and a method for polymerizing olefins using a catalyst having a branched hydrocarbon residue as the organosilicon compound. Method (Unexamined Japanese Patent Publication No. 62-11
No. 706) and the like are disclosed. however,
Although highly stereoregular polymers can be obtained in high yields in these methods, the polymers have a narrow molecular weight distribution and poor moldability, making it difficult to develop the desired rigidity when molding large molded products. There is a drawback. SUMMARY OF THE INVENTION Under these circumstances, the present invention provides a method for producing an olefin polymer for obtaining a highly stereoregular polymer in high yield, and a highly stereoregular polymer. The purpose of this invention is to provide a method for producing an olefin polymer that has high properties and a wide molecular weight distribution in a high yield. [Means for Solving the Problem] As a result of extensive research in order to achieve the above object, the present inventors have developed a catalyst that includes a magnesium compound, a titanium halide, and an electron-donating compound as essential components. By using a combination of an organoaluminum compound and a tetraalkoxysilane with a specific structure as a solid catalyst component, a highly stereoregular polymer can be obtained in high yield; and a dialkyldialkoxysilane with a specific structure, it was discovered that a polymer with highly stereoregularity and a wide molecular weight distribution could be obtained in high yield. Based on this, the present invention was completed. That is, the present invention provides (A) (a) a magnesium compound, (b) a titanium halide, and (c) a magnesium compound;
A solid catalyst component containing an electron-donating compound as an essential component, and (
B) an organoaluminum compound, and (C) the general formula (I
) [0008] [0009] (wherein, R1 is a branched hydrocarbon residue,
R2 and R3 are each a linear or branched hydrocarbon residue, and they may be the same or different. Further, n is a number that satisfies the relationship 2≦n≦3. ), an organosilicon compound represented by the general formula (II) [0010] [0011] (wherein, R4 is a hydrocarbon residue in which the carbon atom adjacent to Si is a tertiary carbon atom, R5 is a linear or branched hydrocarbon residue), or an organosilicon compound represented by the general formula (III) hydrogen residue,
R7 is a cyclic saturated hydrocarbon residue, and R8 is a linear or branched hydrocarbon residue. The present invention provides a method for producing an olefin polymer, characterized in that an olefin is brought into contact with a catalyst comprising a combination of an organosilicon compound represented by the following formula and polymerized. The present invention will be explained in detail below. Component (A) of the catalyst in the method of the present invention, that is, a solid catalyst component, contains (a) a magnesium compound, (b) a titanium halide, and (c) an electron-donating compound as essential components. Examples of the magnesium compound as component (a) include metallic magnesium, alkylmagnesium halide obtained by reacting metallic magnesium with a halogenated hydrocarbon, dialkylmagnesium, magnesium halide,
Or magnesium hydroxide, magnesium oxychloride,
Examples include dialkoxymagnesium, alkoxymagnesium halide, organic magnesium, and magnesium compounds obtained by reacting these with a halogenating agent. Furthermore, in the present invention, a reaction product of metallic magnesium, alcohol, and halogen can also be preferably used as the magnesium compound of component (a). In this case, a polymer powder with improved catalytic activity, stereoregularity, and amount of titanium supported, and better morphology can be obtained. There is no particular restriction on the shape of the metal magnesium used in this case, and any shape of metal magnesium, such as granules, ribbons, and powders, can be used. Also,
There are no particular restrictions on the surface condition of the magnesium metal, but it is advantageous to have no coating of magnesium oxide or the like formed on the surface. [0016] The alcohol in the reaction product of metallic magnesium, alcohol, and halogen is not particularly limited, but lower alcohols having 1 to 6 carbon atoms are preferred, and ethanol is particularly preferred as a solid catalyst that improves catalytic performance. It is suitable because it provides the ingredients. There are no particular restrictions on the purity or water content of this alcohol, but if an alcohol with a high water content is used, magnesium hydroxide will be formed on the surface of magnesium metal, so the water content will be 1% by weight.
Hereinafter, it is particularly preferable to use alcohol in an amount of 2000 ppm or less. Furthermore, in order to obtain a magnesium compound with better morphology, it is more advantageous to have less water content, and 200 ppm or less is generally desirable. [0017] Furthermore, the halogen in the above reaction product of magnesium metal, alcohol, and halogen is as follows:
Bromine and iodine are preferred, and their form is not particularly limited, and for example, they may be dissolved in an alcoholic solvent and used as a solution. The amount of alcohol to be used is not particularly limited, but is usually selected in the range of 2 to 100 mol, preferably 5 to 50 mol, per 1 mol of magnesium metal. If the amount of alcohol is too large, it tends to be difficult to obtain a magnesium compound with good morphology, while if it is too small, the reaction with magnesium metal may not proceed smoothly. [0019] Further, the halogen is usually used in an amount of 0.0001g or more, preferably 0.0005g or more, and more preferably 0.00g or more per mole of metal magnesium.
It is used in a proportion of 1 g atom or more. If the amount of halogen used is less than 0.0001 g atom, when the obtained magnesium compound is used without being pulverized, the amount of titanium supported, the catalyst activity, and the stereoregularity and morphology of the produced polymer will decrease. Therefore, pulverization of the obtained magnesium compound becomes essential, which is not preferable. The upper limit of the amount of halogen to be used is not particularly limited and may be selected as appropriate within a range that allows the desired magnesium compound to be obtained, but is generally selected within a range of less than 0.06 g atom. Furthermore, by appropriately selecting the amount of halogen used, the particle size of the resulting magnesium compound can be controlled as desired. The reaction between magnesium metal, alcohol, and halogen in the reaction product of magnesium metal, alcohol, and halogen can be carried out using a known method. For example, a desired magnesium compound can be obtained by reacting metallic magnesium, alcohol, and halogen under reflux until no hydrogen gas is generated, usually for about 20 to 30 hours. Specifically, when using iodine as a halogen,
A method in which solid iodine is poured into a mixture of metallic magnesium and alcohol, and then heated and refluxed.A method in which an alcoholic solution containing iodine is dropped into a mixture of metallic magnesium and alcohol, and then heated and refluxed. ,
A method such as dropping an iodine-containing alcohol solution while heating a mixture of metallic magnesium and alcohol can be used. [0021] In either method, it is preferable to conduct the reaction under an inert gas atmosphere such as nitrogen gas or argon gas, and optionally using an inert organic solvent such as a saturated hydrocarbon such as n-hexane. . Regarding the input of metallic magnesium and alcohol, from the beginning,
It is not necessary to put the entire amount of each into the reaction tank, and they may be added in portions. A particularly preferred method is to add the entire amount of alcohol from the beginning, and then add metallic magnesium in several portions. This method is
It is possible to prevent the temporary generation of large amounts of hydrogen gas, which is extremely desirable from a safety standpoint, and allows for the reduction of the size of the reaction tank. Can prevent entrainment of halogen droplets. The number of times of division may be determined in consideration of the scale of the reaction tank and is not particularly limited, but considering the complexity of the operation, it is usually selected in the range of 5 to 10 times. [0022] The reaction itself may be carried out either batchwise or continuously. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been added in its entirety from the beginning, and the products produced by the reaction are separated. It is also possible to repeat the operation of separating and removing metal magnesium into a tank and then adding a small amount of metal magnesium again. The reaction product thus obtained is (
When used in the synthesis of a solid catalyst component as component A), it may be dried, or it may be filtered and then washed with an inert solvent such as heptane. This magnesium compound can be used in the next step without purification, pulverization, or classification operations to make the particle size uniform. In this case, the magnesium compound has a sphericity (S) represented by the following formula (1) of less than 1.60,
And the particle size distribution index (P) shown by the following formula (2) is 5
．． Preferably, it is less than 0. That is, the sphericity (S) of the magnesium compound used as component (a) is expressed by the following formula (1). ##STR7## In the above formula (1), E1 represents the projected contour length of the particle, and E2 represents the circumference of a circle equal to the projected area of the particle. Furthermore, the particle size distribution index (P) of the magnesium compound used as component (a) is expressed by the following formula (2).
It is expressed as ##STR8## In the above formula (2), D90 refers to the particle diameter corresponding to a cumulative weight fraction of 90%. That is, it shows that the sum of the weights of the particle group smaller than the particle diameter expressed by D90 is 90% of the total weight of all particles. Moreover, D10 refers to a particle diameter corresponding to a cumulative weight fraction of 10%. That is, it shows that the sum of the weights of the particle group smaller than the particle diameter represented by D10 is 10% of the total weight of all particles. As described above, the magnesium compound used as component (a) in the present invention has a sphericity (S) represented by the above formula (1) of less than 1.60, and a magnesium compound represented by the above formula (2). Those having a particle size distribution index (P) of less than 5.0 are preferred. If the sphericity is 1.60 or more and the particle size distribution index is 5.0 or more, the morphology of the produced polymer will be poor, resulting in process problems (e.g.
This is undesirable because it may cause blockage of the polymer transfer line. [0031] The magnesium compound having such sphericity and particle size distribution index is present in an amount of 0.0001 g per mol of magnesium metal, alcohol, and magnesium metal.
Even those obtained by reacting subatomic amounts of halogen exhibit good properties as catalyst support raw materials. As described above, the magnesium compound used as component (a) in the present invention has a nearly spherical shape and a sharp particle size distribution, and furthermore, the variation in sphericity of each particle is very small. Preferably. Furthermore, the magnesium compound used as component (a) in the present invention has three strong peaks appearing in the scattering angle range of 5 to 20 degrees in the X-ray diffraction spectrum measured with Cu-Kα rays. When these peaks are designated as peak a, peak b, and peak c in order from the low scattering angle side, the peak intensity ratio b/c is preferably 0.4 or more. The above-mentioned magnesium compounds may be used alone or in combination of two or more. Next, as the titanium halide of component (b), trivalent and tetravalent titanium halides can be used, but in particular, those of the general formula (IV): [0036] (In the formula, R9 is a hydrocarbon residue, X1 is a halogen atom, and m is a number from 0 to less than 4) is preferred. R9 in the general formula (IV) is a hydrocarbon residue, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group. Furthermore, it may contain a heteroatom such as sulfur, nitrogen, oxygen, silicon, or phosphorus. Preferred hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, and aralkyl groups having 1 to 10 carbon atoms. Specific examples of R9 in the general formula (IV) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, pentyl group, and hexyl group. , heptyl group, octyl group, decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. In addition, X1 in the general formula (IV)
is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. Typical titanium halides represented by the general formula (IV) include, for example, titanium tetrachloride and titanium tetrabromide when m is 0, and titanium tetrabromide when m is 1. are ethoxytrichlorotitanium, n-propoxytrichlorotitanium, n-butoxytrichlorotitanium, etc.
When m is 2, diethoxydichlorotitanium, di-n
-propoxytrichlorotitanium, di-n-butoxytrichlorotitanium, etc., and when m is 3, triethoxymonochlorotitanium, tri-n-propoxymonochlorotitanium, tri-n-butoxymonochlorotitanium, etc. can be mentioned. These titanium halides may be used alone or in combination of two or more. Furthermore, the electron-donating compound as component (c) is an organic compound containing oxygen, nitrogen, phosphorus, or sulfur, and specific examples thereof include amines,
Amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, acid halides, acid amides, aldehydes, organic acids, Si-O- Examples include organic silane compounds having a C bond. More specifically, the electron-donating compound of component (c) is, for example, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid, succinic anhydride, and benzoic anhydride. Acids, acid anhydrides such as p-toluic anhydride, ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, Aldehydes having 2 to 15 carbon atoms such as naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,
Ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, p
- ethyl butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-parerolactone, coumarin, phthalide, ethylene carbonate, di-n-butyl phthalate, di-isobutyl phthalate, diheptyl phthalate, 2 carbon atoms such as dicyclohexyl phthalate
~18 esters, acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluic acid chloride, anisyl chloride, methyl ether, ethyl ether, isopropyl ether, t-butyl methyl ether, t-butyl ethyl Ethers having 2 to 20 carbon atoms such as ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, dipel ether, and ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; tributyl amine; Examples include amines such as n,n-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenedian, nitriles such as acetonitrile, benzonitrile, and tolnitrile, tetramethylurea, nitrobenzene, and lithium butyrate. be able to. As the electron-donating compound (c), monoesters and diesters of aromatic dicarboxylic acids are preferably used, and monoesters and diesters of phthalic acid are particularly suitable. Specific examples of monoesters and diesters of aromatic dicarboxylic acids include monomethyl phthalate, dimethyl phthalate, monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate, diethyl phthalate, monoethyl terephthalate, diethyl terephthalate, monopropyl phthalate, dipropyl phthalate, Monopropyl terephthalate, dipropyl terephthalate, monobutyl phthalate,
Examples include dibutyl phthalate, monobutyl terephthalate, dibutyl terephthalate, monoisobutyl phthalate, diisobutyl phthalate, monoamyl phthalate, diamyl phthalate, monoisoamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, and ethylpropyl phthalate. These electron-donating compounds may be used alone or in combination of two or more. When comparing the monoester and diester of the aromatic dicarboxylic acid, which are suitable as the electron-donating compound of component (c), the diester is more preferable. Among diesters of aromatic dicarboxylic acids, lower alkyl esters of phthalic acid having 1 to 5 carbon atoms are preferred, and dibutyl phthalate and diisobutyl phthalate are particularly preferred. The solid catalyst component (A) in the present invention has the above-mentioned components (a), (b) and (c) as essential components, but in the preparation of the solid catalyst component (A), Together with the above components (a), (b) and (c), optionally as the component (d), the general formula (V) [0046] [0047] (wherein R10 is a hydrocarbon residue, X2 represents a halogen atom, and q is 0 or an integer of 1 to 3)
A silicon compound represented by can be used. R10 in the general formula (V) is a hydrocarbon residue, which may be a saturated group or an unsaturated group,
It may be linear, branched, or cyclic, and it may also contain heteroatoms such as sulfur, nitrogen, oxygen, silicon, and phosphorus. Preferred hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, and aralkyl groups having 1 to 10 carbon atoms. Furthermore, when a plurality of R10s exist, they may be the same or different from each other. Specific examples of R10 include those exemplified in the explanation of R9 in the above general formula (IV). Further, X2 in the general formula (V) is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and among these, a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. Specific examples of the silicon compound represented by the general formula (V) include SiCl4, CH
3OSiCl3, (CH3O)2SiCl2, (CH
3O) SiCl, C2H5OSiCl3, (C2H5O
)2SiCl2, (C2H5O)3SiCl, C3H
7OSiCl3, (C3H7O)2SiCl2, (C
Examples include 3H7O)3SiCl. Among these, silicon tetrachloride (SiCl4) is particularly preferred. These silicon compounds may be used alone or in combination of two or more. The silicon compound as component (d) used as desired has a silicon compound/magnesium compound molar ratio of usually 0.01 to 0.30, preferably 0.
It is used in proportions ranging from 10 to 0.20. If this molar ratio is less than 0.01, the effect of improving catalytic activity and stereoregularity will not be sufficiently exhibited, and the amount of fine powder in the produced polymer powder will increase; on the other hand, if it exceeds 0.30,
This is not preferable because the resulting polymer powder contains many large particles. The solid catalyst component (A) can be prepared by a known method (
JP-A-53-43094, JP-A-55-1351
For example, (1) a magnesium compound or a complex compound of a magnesium compound and an electron-donating compound, A method of pulverizing in the presence of an electron donating compound and a grinding aid used as desired, and reacting with titanium halide;
(2) A method of precipitating a solid titanium complex by reacting a liquid magnesium compound with no reducing ability and a liquid titanium halide in the presence of an electron-donating compound; (3) a method of precipitating a solid titanium complex; ) or a method of reacting titanium halide with the material obtained in (2), (4) the method of (1) above.
) or a method in which the material obtained in (2) is further reacted with an electron-donating compound and a titanium halide, (5)
A method in which a magnesium compound or a complex compound of a magnesium compound and an electron-donating compound is ground in the presence of an electron-donating compound, a titanium compound, a grinding aid used as desired, and the like, and then treated with a halogen or a halogen compound. , (6) a method of treating the compounds obtained in (1) to (4) above with a halogen or a halogen compound, and the like. Furthermore, methods other than these may be used, for example, as disclosed in Japanese Patent Application Laid-open No. 166205/1983 and Japanese Patent Application Laid-Open No. 57-1989.
Publication No. 63309, Japanese Patent Application Laid-Open No. 1987-190004,
JP-A-57-300407, JP-A-58-470
The solid catalyst component (A) can also be prepared by the method described in Publication No. 03. [0053] Furthermore, at least one oxide of an element belonging to Groups II to IV of the periodic table, such as an oxide of silicon oxide, magnesium oxide, or aluminum oxide, or an oxide of an element belonging to Groups II to IV of the periodic table. Composite oxide containing
For example, a solid material in which the magnesium compound is supported on silica alumina, an electron donating compound, and a titanium halide are mixed in a solvent at 0 to 200°C, preferably at 10 to 100°C.
The solid catalyst component can be prepared by contacting for 2 minutes to 24 hours at a temperature in the range of 50°C. [0054] In preparing the solid catalyst component, as a solvent, an organic solvent inert to the above-described magnesium compound, electron-donating compound, and titanium halide;
For example, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, or mono- and polyhalogens of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Compounds such as halogenated hydrocarbons, etc. can be used. Next, the component (B) of the catalyst used in the method of the present invention, that is, the organoaluminum compound, has the general formula (VI): ~10 alkyl groups, X3 is a halogen atom such as chlorine or bromine, p is 1
The number is ~3. ) can be used. [0058] As such an aluminum compound,
For example, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, dialkylaluminum monohalide such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride , alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be suitably used. These aluminum compounds may be used alone or in combination of two or more. Furthermore, in the method of the present invention, (
As component C), general formula (I) [0060] [0061] (wherein R1 is a branched hydrocarbon residue,
R2 and R3 are each a linear or branched hydrocarbon residue, and they may be the same or different. Further, n is a number that satisfies the relationship 2≦n≦3. ), or an organosilicon compound represented by the general formula (II): An organosilicon compound represented by R5 is a linear or branched hydrocarbon residue is used. In the organosilicon compound represented by the general formula (I), R1 is a branched hydrocarbon residue, and the branching group includes an alkyl group, a cycloalkyl group, a phenyl group, or a methyl-substituted phenyl group. Examples include aryl groups such as. Furthermore, the branched hydrocarbon residue is
It is preferable that the carbon atom adjacent to the oxygen atom bonded to the silicon atom is a secondary or tertiary carbon atom.
Preferably, the structure has two alkyl groups. moreover,
The number of carbon atoms in R1 is preferably in the range of 3 to 20, preferably 4 to 10. R2 and R3 in the general formula (I)
As mentioned above, R2 is a linear or branched hydrocarbon residue, and R2 has 1 to 20 carbon atoms, especially 1 to 20 carbon atoms.
10 branched or straight chain aliphatic hydrocarbon groups, and R3 is preferably a branched or straight chain aliphatic hydrocarbon group, particularly a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms. It is preferable that it is a group. Specific examples of the organosilicon compound represented by the general formula (I) include the following tetraalkoxysilanes. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image [0074] [0074] [0075] [0076] [0076] [0077] These tetraalkoxysilanes may be used singly or in combination of two or more types. Note that in the above-mentioned JP-A-57-63310 and JP-A-57-63311, tetramethoxysilane is described as a tetraalkoxysilane, but in this compound, a highly stereoregular polymer is It is extremely difficult to obtain a highly stereoregular polymer in a high yield by using a tetraalkoxysilane having the structure described above. On the other hand, in the organosilicon compound represented by the general formula (II), R4 is a hydrocarbon residue in which the carbon atom adjacent to the Si atom is a tertiary carbon atom. R5 in the general formula (II) is a linear or branched hydrocarbon residue, and is preferably an aliphatic hydrocarbon group, particularly a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms. Specific examples of such organosilicon compounds include dialkyldialkoxysilanes as shown below. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ##STR31## These dialkyldialkoxysilanes may be used alone or in combination of two or more. In the present invention, in addition to the dialkyldialkoxysilane represented by the general formula (II), a dialkyldialkoxysilane represented by the following general formula (III) can also be used. ##STR32## In the above general formula (III), R6
is a branched hydrocarbon residue, R7 is a cyclic saturated hydrocarbon residue, and R8 is a linear or branched hydrocarbon residue. Specific examples of such dialkyldialkoxysilane include isopropylcyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, isopropylcyclohexyldiethoxysilane, isobutylcyclohexyldiethoxysilane, and tert-butylcyclohexyldimethoxysilane.
Examples include t-butylcyclohexyldiethoxysilane. Such general formula (II) or general formula (
By using the dialkyldialkoxysilane represented by III), a polymer having high stereoregularity and a wide molecular weight distribution can be obtained in high yield. Regarding the amount of each component of the catalyst to be used in the method of the present invention, firstly, the solid catalyst component (A) is usually 0 per liter of reaction vessel in terms of titanium atoms.
．． An amount in the range of 0.0005 to 1 mmol is used. In addition, the organic aluminum compound of component (B) usually has an aluminum/titanium atomic ratio of 1 to 100.
0, preferably in the range of 5 to 500. If this atomic ratio deviates from the above range, the catalyst activity will be insufficient. Furthermore, the organosilicon compound of component (C) is
The organosilicon compound/titanium molar ratio is usually 0.1 to
500, preferably in the range 1 to 100. If this molar ratio is less than 0.1, the sustainability of the catalytic activity will be poor and the stereoregularity of the resulting polymer will be insufficient, while if it exceeds 500, the catalytic activity may decrease. In the method of the present invention, as described above (A
By polymerizing at least one type of olefin in the presence of a catalyst system consisting of a combination of a solid catalyst component as component (B), an organoaluminum compound as component (B), and an organosilicon compound as component (C), olefin homopolymerization is possible. Produce a polymer or copolymer. As the olefin, for example, the general formula (V
II) [Chemical formula 33] [0099] (wherein, R12 is a hydrogen atom or a carbon number of 1 to
10 linear or branched hydrocarbon residues)
An α-olefin represented by is preferably used. Specific examples of such α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1,
Examples include long-chain monoolefins such as decene-1, branched monoolefins such as 4-methylpentene-1, and vinylcyclohexane. These olefins may be used alone or in combination of two or more. Regarding the polymerization type in the method of the present invention,
There are no particular limitations, and any method can be used, such as a slurry polymerization method using an inert hydrocarbon solution, a bulk polymerization method without a solvent, or a gas phase polymerization method.
Both continuous polymerization method and non-continuous polymerization method are possible. Furthermore, the polymerization reaction may be carried out in one stage or in multiple stages of two or more stages. In a multi-stage polymerization reaction, for example, a two-stage polymerization reaction, in the first stage, a polymerization reaction of, for example, propylene is usually carried out in the presence of the catalyst components (A), (B) and (C) to form crystals. After producing the crystalline polypropylene, in the second stage, ethylene and propylene are combined in the presence of the crystalline polypropylene and the catalyst, with or without removing the unreacted propylene subjected to the first stage polymerization. A method such as copolymerizing with can be used. Furthermore, regarding the reaction conditions in the method of the present invention, the olefin pressure is usually normal pressure to kg/cm2.
-G, and the reaction temperature is normally selected appropriately within the range of 0 to 200°C, preferably 50 to 100°C. Further, the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel. Furthermore, the reaction time depends on the type of olefin used as a raw material and the reaction temperature, and cannot be determined unconditionally, but it is usually about 1 minute to 10 hours, preferably about 30 minutes to 5 hours. Regarding the catalyst components, after mixing components (A), components (B), and components (C) in a predetermined ratio and bringing them into contact, an olefin is immediately introduced to initiate polymerization. Alternatively, the olefin may be introduced after contacting and aging for about 0.2 to 3 hours. Furthermore, this catalyst component can be supplied suspended in an inert solvent, olefin, or the like. In the present invention, post-treatment after polymerization can be carried out by conventional methods. That is, in the gas phase polymerization method, after polymerization, a nitrogen stream or the like may be passed through the polymer powder drawn out from the polymerization vessel in order to remove olefins contained therein. If necessary, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst. Further, in the bulk polymerization method, after polymerization, the monomer can be completely separated from the polymer derived from the polymerization vessel, and then the polymer can be pelletized. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, the measurement of Mw/Mn, sample preparation, and GPC measurement in the following Examples and Comparative Examples were performed by the following methods. First, Mw/Mn was measured by the following method. (1) Using standard polystyrene (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.) whose molecular weight is known, the GPC (gel permeation chromatography) count corresponding to the molecular weight M of polystyrene is measured. and,
A calibration curve of molecular weight M and EV (Elution Volume) is created. (2) Measure the gel permeation chromatogram of the measurement sample by GPC, and use the calibration curve created in (1) above to calculate the number average molecular weight Mn and weight average molecular weight Mw, respectively, based on the following formulas. and determine Mw/Mn. Number average molecular weight (Mn) = ΣMiNi/ΣNi Weight average molecular weight (Mw) = ΣMi2 Ni/ΣMiNi
] Next, the sample preparation method is as follows. (a) The polymer was charged into an Erlenmeyer flask together with the solvent o-dichlorobenzene, and 15 mg-polymer/
Prepare a solution with a concentration of 20 ml-solvent. (b) 0.1% by weight of 2,6-
Di-t-butyl-p-cresol is added as a stabilizer. (c) After being left at 140° C. for 1 hour, stirring was performed for 1 hour to completely dissolve the polymer and stabilizer. (d) The solution is then filtered using a 0.5 μm filter at a temperature of 135-140°C. (e) Measure the filtrate by GPC. Furthermore, the GPC measurement conditions are as follows. (a) Apparatus: Model 150C (manufactured by Water) (b) Column: TSKGMH-6, diameter 6 mm x 600
mm (manufactured by Toyo Soda Co., Ltd.) (c) Sample amount: 400 μl (d) Temperature: 135°C (e) Flow rate: 1 ml/min [0111] In the following examples and comparative examples, the following reagents were used. . Ethanol: Manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent. Iodine: Manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent. Metallic magnesium: granular (average particle size 350 μm). [0112] Furthermore, X-ray diffraction measurements were carried out as follows. The magnesium compound was ground to an average particle size of 10 μm. The pulverized product was vacuum dried at room temperature, and the resulting dry powder was filled into a Mylar film cell under an inert gas atmosphere. The thickness of the Mylar film is 6 μm, and the thickness of the cell including the Mylar film and dry powder is 1 μm.
It was mm. This cell was attached to a powder X-ray diffraction apparatus (manufactured by Rigaku Denki Kogyo Co., Ltd.), and an X-ray diffraction spectrum was measured by a transmission method. Copper (Cu) is used for the anticathode, voltage is 50 kV, current is 120 mA, and wavelength (λkα) is 1.
A condition of 543 angstroms was used. Furthermore, the sphericity (s) was measured as follows. The dried sample of magnesium compound (a) was examined using a scanning electron microscope [JSM-25 manufactured by JEOL Ltd.
SIII], the image was photographed at an accelerating voltage of 5 kV and a magnification of 150 times to obtain a negative. Next, this negative was subjected to image resolution processing using a transmission method. Image decomposition processing is performed using an image decomposition device [Nexus 6510 (2MB)] with 20 pixels (1 pixel = 1
．． The particles below (389 μm x 1.389 μm) were cut and the remaining approximately 2000 particles were subjected to the test. By image analysis processing, the contour length E1 and the circumference length E2 of a circle equal to the projected area of the particle were determined and calculated using the above formula (1). Similarly, the particle size distribution index (p) is obtained by determining the particle size distribution of particles using a sieve, plotting the distribution on logarithmic distribution paper, and calculating the 90% particle size (D90) and 10% particle size (
D10) was calculated using the above formula (2). Example 1 (1) Preparation of solid catalyst component (A) In a 500 ml four-necked flask, 60 ml of dehydrated n-heptane, 16 g of diethoxymagnesium, and 2.3 ml of diethyl phthalate were added.
After stirring at room temperature, add 2.4 ml of silicon tetrachloride.
was added, the temperature was raised, and the reaction was carried out under reflux for 30 minutes. next,
After adding 77 ml of titanium tetrachloride and reacting at 110°C for 2 hours, washing with n-heptane, further adding 122 ml of titanium tetrachloride, reacting at 110°C for 2 hours, and then reacting with n-heptane. A fixed catalyst component (A) was obtained by thorough washing. (2) Production of olefin polymer In a 1 liter stainless steel autoclave, add 40 ml of n-heptane.
Then, 2.0 m mol of triethylaluminum as component (B) and 0.25 m mol of di-t-butoxydimethoxysilane as component (C) were added.
and 0.005 mmol of the solid catalyst component (A) prepared in (1) above in terms of titanium atoms, hydrogen pressure of 0.5 kg/cm2 G, propylene pressure of 7.0 kg.
Polymerization of propylene was carried out at 70°C for 2 hours while maintaining the temperature at /cm2·G. As a result, the yield of polypropylene was 550 kg per 1 g of titanium, the boiling heptane extraction residue (I.I) content was 98.1% by weight, and the intrinsic viscosity [η] was 1.17 dl/g. Comparative Example 1 In Example 1 (2), (C)
The same procedure as in Example 1(2) was carried out except that tetramethoxysilane was used as a component and the hydrogen pressure was 0.15 kg/cm2.G. As a result, the yield of polypropylene was 280 kg per 1 g of titanium,
Boiling heptane extraction residue (I.I) content is 97.3% by weight
The intrinsic viscosity [η] was 1.30 dl/g. Example 2 (1) Preparation of solid catalyst component (A) A solid catalyst component (A) was prepared in the same manner as in Example 1 (1). (2) Production of olefin polymer 400 ml of n-heptane was charged into a 1 liter stainless steel autoclave, and then 2.0 m mol of triethylaluminum as component (B) and di-t- as component (C) were added. Butyldimethoxysilane 0.25m
0.005 mm in terms of mol and titanium atoms
The solid catalyst component (A) prepared in the above (1) of OL was added, and propylene was heated at 70°C for 2 hours while maintaining the hydrogen pressure at 0.5 kg/cm2 G and the propylene pressure at 7.0 kg/cm2 G. Polymerization was carried out. As a result, the yield of polypropylene was 650 kg per 1 g of titanium, the boiling heptane extraction residue (I.I) content was 98.1% by weight, and the intrinsic viscosity [η] was 1.5 dl/g. Further, the weight average molecular weight/number average molecular weight ratio (Mw/Mn) determined by high temperature GPC was 8.7. Comparative Example 2 In Example 2 (2), (C)
It was carried out in the same manner as in Example 2 (2) except that diphenyldimethoxysilane was used as a component. As a result, the yield of polypropylene was 540 kg per 1 g of titanium.
The boiling heptane extraction residue (I.I) content is 98.
0% by weight, and the intrinsic viscosity [η] was 1.4 dl/g. Moreover, Mw/Mn was 5.4. Comparative Example 3 In Example 2 (2), (C)
It was carried out in the same manner as in Example 2 (2) except that diisopropyldimethoxysilane was used as a component. As a result, the yield of polypropylene was 520% per gram of titanium.
kg, and the boiling heptane extraction residue (I.I) content is 9
The content was 7.8% by weight, and the intrinsic viscosity [η] was 1.37 dl/g. Moreover, Mw/Mn was 5.6. Example 3 The same procedure as in Example 1 was carried out except that a magnesium compound synthesized by the following method was used instead of diethoxymagnesium. A glass reactor with a stirrer (inner volume: approximately 6 liters) was sufficiently replaced with nitrogen gas, and approximately 2430 g of ethanol was added.
, 16 g of iodine, and 160 g of metallic magnesium were added, and the mixture was allowed to react under heating under reflux conditions with stirring until no hydrogen gas was generated from the system, to obtain a solid reaction product (magnesium compound). The experiment was carried out using this magnesium compound. Regarding this magnesium compound, Cu-
When X-ray diffraction analysis was performed using Kα rays, 2θ
Three diffraction peaks appeared in the range of =5 to 20 degrees. When these peaks are defined as peak a, peak b, and peak c in order from the low angle side, the peak intensity ratio b/c is 0.7
It was 5. Further, the sphericity (s) was 1.21, and the particle size distribution index (p) was 1.7. The yield of polypropylene was 560 kg per 1 g of titanium, the boiling heptane extraction residue (I.I) content was 98.2% by weight, and the intrinsic viscosity [η] was 1.22 dl/g. Example 4 The same procedure as in Example 2 was carried out except that a magnesium compound synthesized by the following method was used instead of diethoxymagnesium. Glass reactor with stirrer (inner volume approximately 6 liters)
was sufficiently replaced with nitrogen gas, and approximately 2430 g of ethanol was added.
Add 16g of iodine and 160g of metal magnesium,
The reaction is carried out under heating under reflux conditions with stirring until no hydrogen gas is generated from the system, and a solid reaction product (
Magnesium compound) was obtained. The experiment was carried out using this magnesium compound. The yield of polypropylene is 1% titanium
660 kg/g, boiling heptane extraction residue (I.
I) Content is 98.3% by weight, intrinsic viscosity [η] is 1.48
It was dl/g. Moreover, Mw/Mn was 8.3. Example 5 Into a 1 liter stainless steel autoclave, 400 ml of n-heptane was charged, 2.0 m mol of triethylaluminum, and 0.25 m mol of tert-butylcyclohexyldimethoxysilane.
Then, 0.005 m mol of the solid catalyst component obtained in Example 1 (1) was added in terms of titanium atoms, and the hydrogen pressure was 0.5 k.
Polymerization was carried out for 2 hours while maintaining the propylene pressure at 7.0 kg/cm2. The results are shown in Table 1. Example 6 and Comparative Examples 4 to 6 Example 1 except that a silicon compound shown in Table 1 was used as the component (C) in place of tert-butylcyclohexyldimethoxysilane. Polymerization was carried out in the same manner. The results are shown in Table 1. Example 7 Polymerization was carried out in the same manner as in Example 1, except that the solid catalyst obtained in Example 3 was used as the solid catalyst component. The results are shown in Table 1. [Table 1] [Effects of the Invention] According to the present invention, as a catalyst, a solid catalyst component containing a magnesium compound, a titanium halide, and an electron-donating compound as essential components, an organoaluminum compound, and a specific By polymerizing an olefin using a combination of the above structure and a tetraalkoxysilane, an olefin polymer having high stereoregularity can be produced in high yield. In addition, by using a dialkyldialkoxysilane with a specific structure instead of the tetraalkoxysilane, an olefin polymer with high stereoregularity, wide molecular weight distribution, and good moldability can be produced in high yield. can be manufactured. [0129]

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (5)

[Claims] Claim 1: (A) (a) magnesium compound, (
b) a solid catalyst component containing titanium halide and (c) an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) general formula (I) [Formula 1] (wherein, R1 is a branched Chain hydrocarbon residues, R2 and R
3 each represents a linear or branched hydrocarbon residue, and they may be the same or different from each other. Further, n is a number that satisfies the relationship 2≦n≦3. ) A method for producing an olefin polymer, which comprises bringing an olefin into contact with a catalyst comprising a combination of organosilicon compounds represented by the following formula to polymerize the olefin. Claim 2: (A) (a) magnesium compound, (
b) a solid catalyst component containing a titanium halide and (c) an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) general formula (II) [Chemical formula 2] (wherein, R4 is Si a hydrocarbon residue in which the carbon atom adjacent to is a tertiary carbon atom, R5 is a linear or branched hydrocarbon residue); A method for producing an olefin polymer, which comprises bringing olefins into contact and polymerizing them. Claim 3: (A) (a) magnesium compound, (
b) a solid catalyst component containing titanium halide and (c) an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) general formula (III) [Formula 3] (wherein, R6 is a branched An olefin is added to a catalyst in combination with an organosilicon compound represented by a chain hydrocarbon residue, R7 is a cyclic saturated hydrocarbon residue, and R8 is a linear or branched hydrocarbon residue. A method for producing an olefin polymer, which comprises polymerizing through contact. 4. Claims 1 to 3, wherein the electron donating compound in the solid catalyst component is at least one selected from monoesters and diesters of aromatic dicarboxylic acids.
The manufacturing method according to any one of. 5. The production method according to claim 1, wherein the magnesium compound in the solid catalyst component is a reaction product of metallic magnesium, alcohol, and halogen.