JP4738583B2 - Solid catalyst components and catalysts for olefin polymerization - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which can obtain an olefin polymer in a high yield while maintaining a high degree of stereoregularity, and further have a high hydrogen response capability.
[0002]
[Prior art]
Conventionally, in the polymerization of olefins, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many olefin polymerization methods have been proposed in which an olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound. For example, JP-A-57-63310 and JP-A-57-63311 disclose a solid catalyst component containing an electron donor of a diester compound such as a magnesium compound, a titanium compound and a phthalate ester, and organoaluminum. A method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination of the compound and an organosilicon compound having a Si—O—C bond is disclosed.
[0003]
Japanese Laid-Open Patent Publication No. 1-6006 discloses a solid catalyst component for olefin polymerization containing alkoxymagnesium, titanium tetrachloride and dibutyl phthalate, and polymerizing the olefin in the presence of this solid catalyst component. Thus, a stereoregular polymer is obtained in a high yield, which is effective to some extent. By the way, the polymer obtained by using the catalyst as described above is used for various uses such as containers and films in addition to molded articles such as automobiles and home appliances. These melt polymer powders produced by polymerization and are molded by various molding machines. Especially when manufacturing large molded products such as injection molding, the melted polymer has fluidity (melt flow rate). Higher values may be required, so much work has been done to increase the melt flow rate of the polymer.
[0004]
Melt flow rate depends greatly on the molecular weight of the polymer. In the industry, it is common to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of olefins. At this time, in order to produce a low molecular weight polymer, that is, in order to produce a polymer having a high melt flow rate, a large amount of hydrogen is usually added. However, the pressure resistance of the reactor is limited due to its safety, and hydrogen that can be added. There is also a limit on the amount. In order to add more hydrogen, the partial pressure of the monomer to be polymerized must be lowered, and in this case, productivity is lowered. Further, since a large amount of hydrogen is used, there is a problem of cost. Therefore, development of a catalyst capable of producing a high melt flow rate polymer with a smaller amount of hydrogen, a so-called high hydrogen activity or response to hydrogen, and a high stereoregular polymer in a high yield has been desired. However, the above prior art is not sufficient to solve the problem.
[0005]
[Problems to be solved by the invention]
That is, the object of the present invention is to solve the problems remaining in the prior art and obtain an olefin polymer in a high yield, and in particular, the propylene polymer is high while maintaining high stereoregularity. An object of the present invention is to provide a solid catalyst component and a catalyst for olefin polymerization which can be obtained in a yield and have a high hydrogen response capability.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the problems remaining in the prior art, the present inventors have found that a solid catalyst component comprising a magnesium compound, titanium tetrachloride and a specific phthalic acid diester derivative is used for the polymerization of olefins. It has been found that when it is used, it exhibits a high activity and yield while maintaining a high stereoregularity when it is used for the polymerization of propylene, and further has a high hydrogen response capability. It came to be completed.
[0007]
That is, the present invention provides (a) a magnesium compound, (b) titanium tetrachloride, and (c) the following general formula (1):
[0008]
[Chemical 2]
[0009]
(Wherein R¹Represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and R²And R^ThreeRepresents an alkyl group having 1 to 12 carbon atoms, and R²And R^ThreeMay be the same or different and n is R¹When the number of substituents is 1 or 2 and n is 2, R¹May be the same or different, but at least one is an alkyl group. R¹Is an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R²And R^ThreeAre both alkyl groups having 4 to 8 carbon atoms,²And R^ThreeAt least one of the groups has no tertiary carbon. And a solid catalyst component for olefin polymerization, which is characterized in that it is formed from a phthalic acid diester derivative represented by formula (1).
[0010]
Moreover, this invention is (A) the solid catalyst component for olefin polymerization of Claims 1-5, (B) following General formula (2);
                     R^Four _pAlQ_3-p                        (2)
(Where R^ThreeRepresents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3. ), And (C) the following general formula (3);
                     R^Five _qSi (OR⁶)_4-q                    (3)
(Where R^FiveRepresents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R⁶Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group, and R^FiveAnd R⁶May be the same as or different from each other, and q is an integer of 0 ≦ q ≦ 3. It is intended to provide a solid catalyst for olefin polymerization characterized by containing an organosilicon compound represented by
[0011]
DETAILED DESCRIPTION OF THE INVENTION
As a magnesium compound (hereinafter sometimes simply referred to as “component (a)”) used in the preparation of the solid catalyst component for olefin polymerization of the present invention (hereinafter sometimes simply referred to as “component (A)”). Examples thereof include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium.
[0012]
Specific examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like. Dialkylmagnesium has the general formula R⁷R⁸Mg (where R⁷And R⁸Represents an alkyl group having 1 to 10 carbon atoms, which may be the same as or different from each other. ), And more specifically, dimethylmagnesium, diethylmagnesium, methylethylmagnesium, dipropylmagnesium, methylpropylmagnesium, ethylpropylmagnesium, dibutylmagnesium, methylbutylmagnesium, ethylbutylmagnesium, etc. It is done. These dialkyl magnesiums can be obtained by reacting metallic magnesium with a halogenated hydrocarbon or alcohol.
[0013]
As alkylmagnesium halides, the general formula R⁹MgD¹(Where R⁹Represents an alkyl group having 1 to 10 carbon atoms, and D¹Represents a halogen atom such as chlorine, bromine, iodine or fluorine. ), And more specifically, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride and the like can be mentioned. These magnesium halides can be obtained by reacting magnesium metal with a halogenated hydrocarbon or alcohol.
[0014]
As dialkoxymagnesium or diaryloxymagnesium, the general formula Mg (OR^Ten) (OR¹¹) (Where R^TenAnd R¹¹Represents an alkyl group having 1 to 10 carbon atoms or an aryl group, which may be the same as or different from each other. ), And more specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like. These dialkoxymagnesium or diaryloxymagnesium can be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.
[0015]
As the halogenated alkoxymagnesium, the general formula Mg (OR¹²) D²(Where R¹²Is an alkyl group having 1 to 10 carbon atoms, D²Represents a halogen atom such as chlorine, bromine, iodine or fluorine. ), And more specifically, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride, and the like can be given.
[0016]
As the fatty acid magnesium, the general formula Mg (R¹³COO)₂(Where R¹³Represents a hydrocarbon group having 1 to 20 carbon atoms. ), And more specifically, magnesium laurate, magnesium stearate, magnesium octoate, magnesium decanoate and the like can be mentioned.
[0017]
Among these magnesium compounds in the present invention, dialkoxymagnesium is preferable, and among them, diethoxymagnesium and dipropoxymagnesium are particularly preferably used. Moreover, said magnesium compound can also be used individually or in combination of 2 or more types.
[0018]
In the present invention, when dialkoxymagnesium is used as the component (a), the alkoxymagnesium is in the form of granules or powder, and the shape may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder are solved.
[0019]
The spherical dialkoxymagnesium does not necessarily need to be spherical, and an elliptical or potato-shaped one is used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is usually 3 or less, preferably 1 to 2, more preferably 1 to 1.5. is there. Such spherical dialkoxymagnesium production methods are disclosed in, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388. Etc.
[0020]
The average particle size of the dialkoxymagnesium is usually 1 to 200 μm, preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is usually 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.
[0021]
Titanium tetrachloride (hereinafter sometimes simply referred to as “component (b)”) is used for the preparation of component (A) in the present invention, but a titanium halide compound other than titanium tetrachloride can be used in combination with this. . Titanium halide compounds that can be used in combination with titanium tetrachloride include the general formula Ti (OR¹⁴)_nCl_4-n(Where R¹⁴Represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 ≦ n ≦ 3. The alkoxy titanium chloride represented by this is illustrated. Moreover, said titanium halide compound can also be used individually or in combination of 2 or more types. Specifically, Ti (OCH_Three) Cl_Three, Ti (OC₂H_Five) Cl_Three, Ti (OC_ThreeH₇) Cl_Three, Ti (O-n-C_FourH₉) Cl_Three, Ti (OCH_Three)₂Cl₂, Ti (OC₂H_Five)₂Cl₂ , Ti (OC_ThreeH₇)₂Cl₂ , Ti (O-n-C_FourH₉)₂Cl₂, Ti (OCH_Three)_ThreeCl, Ti (OC₂H_Five)_ThreeCl, Ti (OC_ThreeH₇)_ThreeCl, Ti (O-n-C_FourH₉)_ThreeCl 2 etc. are exemplified.
[0022]
In the phthalic acid diester derivative represented by the general formula (1) used for the preparation of the solid catalyst component (A) for olefin polymerization in the present invention, R¹Specific examples of are: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl. Group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group, fluorine atom, chlorine atom, bromine atom and iodine atom, and among these, methyl group, An ethyl group, a t-butyl group, a chlorine atom, and a bromine atom are preferable, and a methyl group and a t-butyl group are particularly preferable. R²And R^ThreeSpecific examples of are: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl. Group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, or isooctyl group, 2,2-dimethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group It is. Among these, an ethyl group, n-butyl group, isobutyl group, t-butyl group, neopentyl group, isohexyl group, and isooctyl group are preferable, and an ethyl group and n-butyl group are particularly preferable.
[0023]
In the general formula (1), the substituent R¹When the number n of 1 is 1, R¹Is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the phthalate derivative of the general formula (1), and when n is 2,¹Substitutes for hydrogen atoms at positions 4 and 5, but the substituent R¹Is preferably substituted with at least a hydrogen atom at the 4-position or 5-position of the benzene ring.
[0024]
Specific examples of the phthalic acid diester derivative represented by the general formula (1) of the present invention include diethyl 3-methylphthalate, diethyl 4-methylphthalate, diethyl 3-ethylphthalate, diethyl 4-ethylphthalate, 3 -Diethyl t-butylphthalate, diethyl 4-t-butylphthalate, diethyl 3-n-butylphthalate, diethyl 4-n-butylphthalate, diethyl 4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, 4 -Diethyl methyl-5-ethylphthalate, diethyl 4-methyl-5-t-butylphthalate, diethyl 4-ethyl-5-t-butylphthalate, diethyl 4-methyl-5-chlorophthalate, 4-methyl-5-bromophthalate Diethyl acid, diethyl 4-ethyl-5-chlorophthalate, 4-ethyl-5-bromophthalic acid Ethyl, 3-methylphthalate di-n-butyl, 4-methylphthalate di-n-butyl, 3-ethylphthalate di-n-butyl, 4-ethylphthalate di-n-butyl, 3-t-butylphthalate di- n-butyl, 4-t-butylphthalate di-n-butyl, 3-n-butylphthalate di-n-butyl, 4-n-butylphthalate di-n-butyl, 4,5-dimethylphthalate di-n -Butyl, di-n-butyl 4,5-diethylphthalate, di-n-butyl 4-methyl-5-ethylphthalate, di-n-butyl 4-methyl-5-t-butylphthalate, 4-ethyl- 5-t-butylphthalic acid di-n-butyl, 4-methyl-5-chlorophthalic acid di-n-butyl, 4-methyl-5-bromophthalic acid di-n-butyl, 4-ethyl-5-chlorophthalic acid di- n-butyl, 4- Di-n-butyl 3-methylphthalate, diisobutyl 3-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl 3-ethylphthalate, diisobutyl 4-ethylphthalate, diisobutyl 3-t-butylphthalate, 4-t-butylphthalic acid Diisobutyl, diisobutyl 3-n-butylphthalate, diisobutyl 4-n-butylphthalate, diisobutyl 4,5-dimethylphthalate, diisobutyl 4,5-diethylphthalate, diisobutyl 4-methyl-5-ethylphthalate, 4-methyl- Diisobutyl 5-t-butylphthalate, diisobutyl 4-ethyl-5-t-butylphthalate, diisobutyl 4-methyl-5-chlorophthalate, diisobutyl 4-methyl-5-bromophthalate, diisobutyl 4-ethyl-5-chlorophthalate, 4-D Di-isobutyl 3-methylphthalate, diisohexyl 3-methylphthalate, diisohexyl 4-methylphthalate, diisohexyl 3-ethylphthalate, diisohexyl 4-ethylphthalate, diisohexyl 3-t-butylphthalate, diisohexyl 4-t-butylphthalate, 3- n-Butylphthalate diisohexyl, 4-n-butylphthalate diisohexyl, 4,5-dimethylphthalate diisohexyl, 4,5-diethylphthalate diisohexyl, 4-methyl-5-ethylphthalate diisohexyl, 4-methyl-5-t- Diisohexyl butylphthalate, 4-ethyl-5-tert-butylphthalate diisohexyl, 4-methyl-5-chlorophthalate diisohexyl, 4-methyl-5-bromophthalate diisohexyl, 4-ethyl-5-chloro Diisohexyl tartrate, diisohexyl 4-ethyl-5-bromophthalate, diisooctyl 3-methylphthalate, diisooctyl 4-methylphthalate, diisooctyl 3-ethylphthalate, diisooctyl 4-ethylphthalate, diisooctyl 3-t-butylphthalate, 4-t- Diisooctyl butylphthalate, diisooctyl 3-n-butylphthalate, diisooctyl 4-n-butylphthalate, diisooctyl 4,5-dimethylphthalate, diisooctyl 4,5-diethylphthalate, diisooctyl 4-methyl-5-ethylphthalate, 4- Diisooctyl methyl-5-t-butylphthalate, diisooctyl 4-ethyl-5-t-butylphthalate, diisooctyl 4-methyl-5-chlorophthalate, diisomethyl 4-methyl-5-bromophthalate Octyl, diisooctyl 4-ethyl-5-chlorophthalate, diisooctyl 4-ethyl-5-bromophthalate, di-n-decyl 4-methylphthalate, isodecyl 4-methylphthalate, di-n-decyl 4-ethylphthalate, 4- Isodecyl ethylphthalate, ethyl 3-methylphthalate-n-butyl, ethyl 4-methylphthalate-n-butyl, ethyl 3-ethylphthalate-n-butyl, ethyl 4-ethylphthalate-n-butyl, 3-t-butylphthalic acid Ethyl-n-butyl, ethyl 4-t-butylphthalate-n-butyl, ethyl 4-5-dimethylphthalate-n-butyl, ethyl 4-5-diethylphthalate-n-butyl, 4-methyl-5- Ethylphthalic acid ethyl-n-butyl, 4-ethyl-5-methylphthalic acid ethyl-n-butyl, 4-methyl-5 -Ethyl chlorophthalate-n-butyl, ethyl 4-chloro-5-methylphthalate-n-butyl, ethyl 4-methyl-5-bromophthalate-n-butyl, ethyl 4-bromo-5-methylphthalate-n-butyl 4-ethyl-5-chlorophthalic acid ethyl-n-butyl, 4-chloro-5-ethylphthalic acid ethyl-n-butyl, 4-ethyl-5-bromophthalic acid ethyl-n-butyl, 4-bromo-5-ethylphthalic Ethyl n-butyl ester, ethyl isobutyl 3-methylphthalate, ethyl isobutyl 4-methylphthalate, ethyl isobutyl 3-ethylphthalate, ethyl isobutyl 4-ethylphthalate, ethyl isobutyl 3-t-butylphthalate, 4-t-butylphthalic acid Ethyl isobutyl, ethyl isobutyl 4,5-dimethylphthalate, 4,5-diethyl Ethyl isobutyl phthalate, ethyl isobutyl 4-methyl-5-ethyl phthalate, ethyl isobutyl 4-ethyl-5-methyl phthalate, ethyl isobutyl 4-methyl-5-chlorophthalate, ethyl isobutyl 4-chloro-5-methyl phthalate, 4 -Ethyl isobutyl methyl-5-bromophthalate, ethyl isobutyl 4-bromo-5-methylphthalate, ethyl isobutyl 4-ethyl-5-chlorophthalate, ethyl isobutyl 4-chloro-5-ethylphthalate, 4-ethyl-5-bromophthal Ethyl isobutyl, ethyl 4-bromo-5-ethylphthalate, ethyl isohexyl 3-methylphthalate, ethyl isohexyl 4-methylphthalate, ethyl isohexyl 3-ethylphthalate, ethyl isohexyl 4-ethylphthalate, 3-t Ethyl isohexyl butyl phthalate, ethyl isohexyl 4-t-butyl phthalate, ethyl isohexyl 4,5-dimethyl phthalate, ethyl isohexyl 4,5-diethyl phthalate, ethyl isohexyl 4-methyl-5-ethyl phthalate, 4-ethyl-5-methylphthalate ethyl isohexyl, 4-methyl-5-chlorophthalate ethyl isohexyl, 4-chloro-5-methyl phthalate ethyl isohexyl, 4-methyl-5-bromophthalate ethyl isohexyl, 4- Ethyl isohexyl bromo-5-methylphthalate, ethyl isohexyl 4-ethyl-5-chlorophthalate, ethyl isohexyl 4-chloro-5-ethylphthalate, ethyl isohexyl 4-ethyl-5-bromophthalate, 4-bromo- Ethyl isohexyl 5-ethylphthalate, 3 -Methylphthalic acid-n-butylisobutyl, 4-methylphthalic acid-n-butylisobutyl, 3-ethylphthalic acid-n-butylisobutyl, 4-ethylphthalic acid-n-butylisobutyl, 3-t-butylphthalic acid-n-butylisobutyl 4-t-butylphthalic acid-n-butylisobutyl, 4,5-dimethylphthalic acid-n-butylisobutyl, 4,5-diethylphthalic acid-n-butylisobutyl, 4-methyl-5-ethylphthalic acid-n- Butylisobutyl, 4-ethyl-5-methylphthalic acid-n-butylisobutyl, 4-methyl-5-chlorophthalic acid-n-butylisobutyl, 4-chloro-5-methylphthalic acid-n-butylisobutyl, 4-methyl-5 -Bromophthalic acid-n-butyl isobutyl, 4-bromo-5-methylphthalic acid-n-butyl Sobutyl, 4-ethyl-5-chlorophthalic acid-n-butylisobutyl, 4-chloro-5-ethylphthalic acid-n-butylisobutyl, 4-ethyl-5-bromophthalic acid-n-butylisobutyl, 4-bromo-5- Ethylphthalic acid-n-butylisobutyl, 3-methylphthalic acid-n-butylisohexyl, 4-methylphthalic acid-n-butylisohexyl, 3-ethylphthalic acid-n-butylisohexyl, 4-ethylphthalic acid-n-butyliso Hexyl, 3-t-butylphthalic acid-n-butylisohexyl, 4-t-butylphthalic acid-n-butylisohexyl, 4,5-dimethylphthalic acid-n-butylisohexyl, 4,5-diethylphthalic acid- n-butylisohexyl, 4-methyl-5-ethylphthalic acid-n-butylisohexyl, 4-ethyl 5-methylphthalic acid-n-butylisohexyl, 4-methyl-5-chlorophthalic acid-n-butylisohexyl, 4-chloro-5-methylphthalic acid-n-butylisohexyl, 4-methyl-5-bromophthalic acid- n-butylisohexyl, 4-bromo-5-methylphthalic acid-n-butylisohexyl, 4-ethyl-5-chlorophthalic acid-n-butylisohexyl, 4-chloro-5-ethylphthalic acid-n-butylisohexyl 4-ethyl-5-bromophthalic acid-n-butylisohexyl and 4-bromo-5-ethylphthalic acid-n-butylisohexyl. On the other hand, in the general formula (1), R²And R^ThreeSpecific compounds in the case where only one group is an alkyl group having 4 to 8 carbon atoms having a tertiary carbon include ethyl 3-methylphthalate-t-butyl, ethyl 4-methylphthalate-t-butyl, Ethyl 3-ethylphthalate-t-butyl, ethyl 4-ethylphthalate-t-butyl, ethyl 4,5-dimethylphthalate-t-butyl, ethyl 4,5-diethylphthalate-t-butyl, 4-methyl- Ethyl 5-ethylphthalate-t-butyl, ethyl 4-ethyl-5-methylphthalate-t-butyl, ethyl 4-methyl-5-chlorophthalate-t-butyl, ethyl 4-chloro-5-methylphthalate-t- Butyl, ethyl 4-methyl-5-bromophthalate-t-butyl, ethyl 4-bromo-5-methylphthalate-t-butyl, ethyl 4-ethyl-5-chlorophthalate -Butyl, ethyl 4-chloro-5-ethylphthalate-t-butyl, ethyl 4-ethyl-5-bromophthalate-t-butyl, ethyl 4-bromo-5-ethylphthalate-t-butyl, ethyl 3-methylphthalate Neopentyl, ethyl neopentyl 4-methylphthalate, ethyl neopentyl 3-ethylphthalate, ethyl neopentyl 4-ethylphthalate, ethyl neopentyl 4,5-dimethylphthalate, ethyl neopentyl 4,5-diethylphthalate, 4 -Ethyl neopentyl methyl-5-ethylphthalate, ethyl neopentyl 4-ethyl-5-methylphthalate, ethyl neopentyl 4-methyl-5-chlorophthalate, ethyl neopentyl 4-chloro-5-methylphthalate, 4-methyl -5-Bromophthalic acid ethyl neopentyl, 4-bromo-5 Ethyl neopentyl methylphthalate, ethyl neopentyl 4-ethyl-5-chlorophthalate, ethyl neopentyl 4-chloro-5-ethylphthalate, ethyl neopentyl 4-ethyl-5-bromophthalate, 4-bromo-5-ethylphthalic acid Ethyl neopentyl, 3-methylphthalate-n-butylneopentyl, 4-methylphthalate-n-butylneopentyl, 3-ethylphthalate-n-butylneopentyl, 4-ethylphthalate-n-butylneopentyl, 4, 5-dimethylphthalic acid-n-butylneopentyl, 4,5-diethylphthalic acid-n-butylneopentyl, 4-methyl-5-ethylphthalic acid-n-butylneopentyl, 4-ethyl-5-methylphthalic acid- n-butylneopentyl, 4-methyl-5-chlorophthalic acid-n-butylne Opentyl, 4-chloro-5-methylphthalic acid-n-butylneopentyl, 4-methyl-5-bromophthalic acid-n-butylneopentyl, 4-bromo-5-methylphthalic acid-n-butylneopentyl, 4-ethyl -5-chlorophthalic acid-n-butylneopentyl, 4-chloro-5-ethylphthalic acid-n-butylneopentyl, 4-ethyl-5-bromophthalic acid-n-butylneopentyl, 4-bromo-5-ethylphthalic acid -N-butyl neopentyl is mentioned. In addition, R¹At least one group has 6 to 8 carbon atoms and R²And R^ThreeSpecific examples of when both are compounds having a tertiary carbon include di-t-butyl 4-n-hexylphthalate, di-t-butyl 4-isohexylphthalate, 4- (2,2-dimethyl) Butyl) di-t-butyl phthalate, di-t-butyl 4- (2,2-dimethylpentyl) phthalate, di-t-butyl isooctyl phthalate, 4-n-hexyl-5-chlorophthalate di- t-butyl, 4-n-hexyl-5-bromophthalate di-t-butyl, 4-isohexyl-5-chlorophthalate di-t-butyl, 4-isohexyl-5-bromophthalate di-t-butyl, 4- (2,2-Dimethylbutyl) -5-chlorophthalate di-t-butyl, 4- (2,2-dimethylbutyl) -5-bromophthalate di-t-butyl, 4- (2,2-dimethylpentyl) Di-t-butyl phthalate, iso-o Di-t-butyl octylphthalate, dineopentyl 4-n-hexylphthalate, dineopentyl 4-isohexylphthalate, dineopentyl 4- (2,2-dimethylbutyl) phthalate, 4- (2,2-dimethylpentyl) phthalate Dineopentyl acid, dineopentyl isooctyl phthalate, dineopentyl 4-n-hexyl-5-chlorophthalate, dineopentyl 4-n-hexyl-5-bromophthalate, dineopentyl 4-isohexyl-5-chlorophthalate, 4-isohexyl-5-bromophthal Dineopentyl acid, Dineopentyl 4- (2,2-dimethylbutyl) -5-chlorophthalate, Dineopentyl 4- (2,2-dimethylbutyl) -5-bromophthalate, Dineopentyl 4- (2,2-dimethylpentyl) phthalate , Isooctyl phthalate Acid dineopentyl like can be exemplified, these compounds may be used in combination either singly or in combination.
[0025]
Among these, preferable diester phthalate derivatives include diethyl 4-methylphthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, diisohexyl 4-methylphthalate, diisooctyl 4-methylphthalate, diethyl 4-ethylphthalate 4-ethylphthalate di-n-butyl, 4-ethylphthalate diisobutyl, 4-ethylphthalate diisohexyl, 4-ethylphthalate diisooctyl, 4-t-butylphthalate diethyl, 4-t-butylphthalate di-n-butyl, 4 -Di-butyl t-butylphthalate, diisohexyl 4-t-butylphthalate, diisooctyl 4-t-butylphthalate, diethyl 4,5-dimethylphthalate, di-n-butyl 4,5-dimethylphthalate, 4,5-dimethyl Diisohexyl phthalate Diisooctyl 4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, di-n-butyl 4,5-diethylphthalate, diisohexyl 4,5-diethylphthalate, diisooctyl 4,5-diethylphthalate, 4-methyl-5-chlorophthalate diethyl, 4-methyl-5-bromophthalate diethyl, 4-ethyl-5-chlorophthalate diethyl, 4-ethyl-5-bromophthalate diethyl, 4-methyl-5-chlorophthalate di- n-butyl, 4-methyl-5-bromophthalate di-n-butyl, 4-ethyl-5-chlorophthalate di-n-butyl, 4-ethyl-5-bromophthalate di-n-butyl, 4-methyl- 5-chlorophthalate diisobutyl, 4-methyl-5-bromophthalate diisobutyl, 4-ethyl-5-chlorophthalate diisobutyl Til, 4-ethyl-5-bromophthalate diisobutyl, 4-methyl-5-chlorophthalate diisohexyl, 4-methyl-5-bromophthalate diisohexyl, 4-ethyl-5-chlorophthalate diisohexyl, 4-ethyl-5-bromophthalic acid Diisohexyl, 4-methyl-5-chlorophthalate diisooctyl, 4-methyl-5-bromophthalate diisooctyl, 4-ethyl-5-chlorophthalate diisooctyl, 4-ethyl-5-bromophthalate diisooctyl, particularly preferred compounds are 4-methylphthal Diethyl acid, diethyl 4-t-butylphthalate, di-n-butyl 4-methylphthalate, and di-n-butyl 4-t-butylphthalate. These phthalic acid diester derivatives may be used alone or in combination of two or more.
[0026]
In the present invention, in addition to the phthalic acid diester derivative of the component (c), other electron donating compounds can be used in combination when preparing the component (A). The electron donating compound that can be used in combination with the phthalic acid diester derivative of the component (c) is an organic compound containing oxygen or nitrogen, such as alcohols, phenols, ethers, esters, ketones, acid halides, Examples include aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si—O—C bond.
[0027]
Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol, cresol and catechol, ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and diphenyl ether Methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate Monocarboxylic acid esters such as phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, diocty maleate Dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di- Dicarboxylic acid esters such as n-pentyl phthalate, di-n-hexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate , Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propionaldehyde, octyl aldehyde, benzal Aldehydes such as dehydride, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearamide, nitriles such as acetonitrile, benzonitrile and trinitrile, isocyanic acid Mention may be made of isocyanates such as methyl and ethyl isocyanate.
[0028]
In addition, examples of the organosilicon compound containing a Si—O—C bond include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.
[0029]
Among the electron donating compounds, esters are preferably used, and phthalic acid diesters, maleic acid diesters, and phenols other than the component (c) are particularly preferable.
[0030]
In the preparation of the component (A) in the present invention, in addition to the above essential components, aluminum trichloride, diethoxyaluminum chloride, diisopropoxyaluminum chloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride, butoxyaluminum dichloride, tri Aluminum compounds such as ethoxyaluminum or metal salts of organic acids such as sodium stearate, magnesium stearate and aluminum stearate, or polysiloxanes such as liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxanes at room temperature Can be used. As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclopentane is used. Siloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, An oxyalkylene group-substituted dimethylsiloxane is exemplified.
[0031]
The component (A) can be prepared by contacting the component (a), the component (b) and the component (c) described above, and this contact is treated in the absence of an inert organic solvent. However, considering the ease of operation, it is preferable to perform the treatment in the presence of the solvent. Examples of the inert organic solvent used include saturated hydrocarbon compounds such as hexane, heptane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, orthodichlorobenzene, methylene chloride, carbon tetrachloride, dichloroethane, and the like. Among them, aromatic hydrocarbon compounds that are liquid at room temperature with a boiling point of about 90 to 150 ° C., specifically, toluene, xylene, and ethylbenzene are preferably used.
[0032]
In addition, as a method for preparing the component (A), the magnesium compound of the component (a) is dissolved in an alcohol or a titanium compound, and the component (b) or the component (b) and the component (c) A method of precipitating a solid substance by contact or heat treatment to obtain a solid component, suspending component (a) in component (b) or an inert hydrocarbon solvent, and further, with component (c) or component (c) Examples include a method of obtaining the component (A) by contacting the component (b).
[0033]
Among these, the particles of the solid catalyst component obtained by the former method are almost spherical and the particle size distribution is sharp. Also in the latter method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, using a spray device. By forming particles by a so-called spray drying method in which a solution or suspension is sprayed and dried, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained.
[0034]
The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C., evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
[0035]
Below, the preparation method of a component (A) is illustrated.
(1) After magnesium chloride is dissolved in tetraalkoxytitanium, polysiloxane is contacted to obtain a solid product, the solid product and titanium tetrachloride are reacted, and then component (c) is contacted to react. A method for preparing (A). At this time, the component (A) can be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin.
[0036]
(2) After making anhydrous magnesium chloride and 2-ethylhexyl alcohol react to make a homogeneous solution, the homogeneous solution is contacted with phthalic anhydride, and then this solution is contacted with titanium tetrachloride and component (c). A method for preparing a component (A) by obtaining a solid product and further contacting titanium tetrachloride with the solid product.
[0037]
(3) An organomagnesium compound is synthesized by reacting magnesium metal, butyl chloride and dibutyl ether, and the organomagnesium compound is contacted with tetrabutoxy titanium and tetraethoxy titanium to obtain a solid product. A component (C), dibutyl ether, and titanium tetrachloride are contacted with a product to prepare a component (A). In this case, the component (A) can also be prepared by preliminarily polymerizing the solid component with an organoaluminum compound, an organosilicon compound and an olefin.
[0038]
(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound are contact-reacted with an alcohol such as butanol or 2-ethylhexyl alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution._Four, HSiCl_ThreeThen, a silicon compound such as polysiloxane is contacted to obtain a solid product, and then the solid product is contacted with titanium tetrachloride and component (c) in the presence of an aromatic hydrocarbon solvent. A method of obtaining component (A) by contacting titanium chloride.
[0039]
(5) Magnesium chloride, tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution. After adding titanium tetrachloride to the solution, the temperature is raised to obtain a solid product. A method in which component (c) is brought into contact with the solid product and further reacted with titanium tetrachloride to obtain component (A).
[0040]
(6) Metal magnesium powder, alkyl monohalogen compound and iodine are contact-reacted, and then tetraalkoxytitanium, acid halide, and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon to form a homogeneous solution. A method of preparing a component (A) by adding titanium tetrachloride to a solution and then heating to precipitate a solid product, bringing the component (c) into contact with the solid product and further reacting with titanium tetrachloride.
[0041]
(7) After diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent, it is brought into contact with titanium tetrachloride, and then heated to be brought into contact with component (c) to obtain a solid product. A method of preparing the component (A) by washing the product with alkylbenzene and then bringing it into contact with titanium tetrachloride again in the presence of alkylbenzene. At this time, the solid component can be heat-treated in the presence or absence of a hydrocarbon solvent to obtain the component (A).
[0042]
(8) After suspending diethoxymagnesium in alkylbenzene, it is contacted with titanium tetrachloride and component (c) to obtain a solid product. The solid product is washed with alkylbenzene, and then in the presence of alkylbenzene. The method of obtaining a component (A) by making it contact with titanium tetrachloride again. At this time, the solid component and titanium tetrachloride can be contacted twice or more to obtain the component (A).
[0043]
(9) Diethoxymagnesium, calcium chloride and Si (OR¹⁵)_Four(Where R¹⁵Represents an alkyl group or an aryl group. The silicon compound represented by) is co-ground, and the resulting pulverized solid is suspended in an aromatic hydrocarbon, then contacted with titanium tetrachloride and component (c), and then further contacted with titanium tetrachloride. To prepare component (A).
[0044]
(10) Suspend diethoxymagnesium and component (c) in alkylbenzene, add the suspension into titanium tetrachloride and react to obtain a solid product, which is washed with alkylbenzene Thereafter, a method of obtaining component (A) by bringing titanium tetrachloride into contact again in the presence of alkylbenzene.
[0045]
(11) A method of preparing component (A) by contacting aliphatic magnesium such as calcium halide and magnesium stearate with titanium tetrachloride and component (c), and then further contacting with titanium tetrachloride.
[0046]
(12) After diethoxymagnesium is suspended in an alkylbenzene or a halogenated hydrocarbon solvent, it is contacted with titanium tetrachloride, and then heated to contact with component (c) to obtain a solid product, A method of preparing a component (A) by washing a solid product with an alkylbenzene and then bringing it into contact with titanium tetrachloride again in the presence of the alkylbenzene. A method of preparing component (A) by contacting with aluminum chloride.
[0047]
(13) Diethoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of toluene to form a homogeneous solution, and this solution is contacted with titanium tetrachloride and component (c) to obtain a solid product. Further, this solid product is dissolved in tetrahydrofuran, and then further solid product is precipitated, and this solid product is contacted with titanium tetrachloride. In some cases, the contact reaction with titanium tetrachloride is repeated, and component (A ). In this case, for example, a silicon compound such as tetrabutoxysilane may be used in any of the contact, contact reaction, and dissolution steps.
[0048]
(14) Magnesium chloride, an organic epoxy compound and a phosphoric acid compound are suspended in a hydrocarbon solvent such as toluene, and then heated to obtain a homogeneous solution. This solution is contacted with phthalic anhydride and titanium tetrachloride. To obtain a solid product, contact the component (c) with the solid product to react, wash the obtained reaction product with alkylbenzene, and then contact titanium tetrachloride again in the presence of alkylbenzene. Method for obtaining component (A).
[0049]
(15) Contact reaction of dialkoxymagnesium, titanium compound and component (c) in the presence of toluene, contact reaction of the resulting reaction product with a silicon compound such as polysiloxane, and further contact reaction of titanium tetrachloride Then, after the metal salt of the organic acid is contacted and reacted, titanium tetrachloride is contacted again to obtain the component (A).
[0050]
In addition, preferred methods for preparing the component (A) used in the present invention include the following methods: for example, by suspending dialkoxymagnesium in a liquid aromatic hydrocarbon compound at room temperature. A liquid is then formed, and then titanium tetrachloride is contacted with this suspension at -20 to 100 ° C, preferably -10 to 70 ° C, more preferably 0 to 30 ° C, and 40 to 130 ° C, more preferably 70 to 70 ° C. React at 120 ° C. At this time, before or after the titanium tetrachloride is brought into contact with the above suspension, the component (c) is brought into contact at −20 to 130 ° C. to obtain a solid reaction product. After washing this solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, tetravalent titanium halide is again added in the presence of the aromatic hydrocarbon compound at 40 to 130 ° C., more preferably 70 to 120. A contact reaction is carried out at 0 ° C., and further, a component (A) is obtained by washing with a hydrocarbon compound that is liquid at room temperature.
[0051]
The amount of each compound used varies depending on the preparation method and cannot be defined unconditionally. For example, component (b) is 0.5 to 100 mol, preferably 0.5 to 50 mol, per mol of component (a), More preferably, it is 1-10 mol, and a component (c) is 0.01-10 mol, Preferably it is 0.01-1 mol, More preferably, it is 0.02-0.6 mol.
[0052]
Component (A) prepared as described above contains magnesium, titanium, component (c) and a halogen atom. The content of each component is not particularly specified, but preferably 10 to 30% by weight of magnesium, 1 to 5% by weight of titanium, 1 to 20% by weight of component (c), and 40 to 70% by weight of halogen atoms. .
[0053]
The organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used when forming the olefin polymerization catalyst of the present invention is represented by the following general formula:
R^Four _p AlQ_3-p                          (2)
(Where R^FourRepresents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3. ) Can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.
[0054]
The organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is represented by the following general formula:
R^Five _qSi (OR⁶)_4-q                        (3)
(Where R^FiveRepresents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R⁶Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group, and R^FiveAnd R⁶May be the same as or different from each other, and q is an integer of 0 ≦ q ≦ 3. ) Is used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.
[0055]
Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylmethoxysilane, tri Neopentylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n -Propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyl Rudimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane , Dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) Dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysila , 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyl Dimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane Lan, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane , Cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane , Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n Propyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, 2- Ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Examples include silane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. Can.
[0056]
Among the above organosilicon compounds, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t- Butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxy Silane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexyl Cyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) is one kind. It can be used alone or in combination of two or more.
[0057]
Next, the catalyst for olefin polymerization of the present invention comprises the aforementioned component (A), component (B), and component (C), and performs polymerization or copolymerization of olefins in the presence of the catalyst. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. . In particular, ethylene and 1-butene are preferably used.
[0058]
The use amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the component (B) is used per 1 mole of the titanium atom in the component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of component (B).
[0059]
The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) is further contacted. desirable.
[0060]
The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.
[0061]
Further, in the present invention, when an olefin is polymerized using a catalyst comprising the component (A), the component (B), and the component (C) (also referred to as main polymerization), the catalytic activity, stereoregularity and the polymer to be produced are polymerized. In order to further improve the particle properties and the like, it is desirable to perform preliminary polymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.
[0062]
In conducting the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere in which olefin or the like is polymerized. Then, after contacting component (A), an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or a gas atmosphere to perform polymerization of olefin, and then the component (C). After contacting the solid catalyst component (A), an olefin such as propylene and / or one or two or more other olefins is preferably contacted.
[0063]
When olefins are polymerized in the presence of an olefin polymerization catalyst formed according to the present invention, the olefin weight is maintained in a high yield while maintaining high stereoregularity compared to the case of using a conventional catalyst. Coalescence can be obtained. In addition, high hydrogen response can be achieved.
[0064]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.
[0065]
Example 1
[Preparation of solid catalyst component (A)]
A 500 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium and 80 ml of toluene to form a suspended state. Next, 20 ml of titanium tetrachloride was added to the suspension, and the temperature was raised. When the temperature reached 80 ° C., 3.2 g of di-n-butyl 4-methylphthalate was added, and the temperature was further raised to 110 ° C. Thereafter, the reaction was carried out with stirring for 1 hour while maintaining a temperature of 110 ° C. After completion of the reaction, the mixture was washed with 100 ml of toluene at 90 ° C. three times, 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 110 ° C., and the mixture was reacted for 1 hour with stirring. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 100 ml of n-heptane at 40 ° C. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.2 weight%.
[0066]
[Formation and polymerization of polymerization catalyst]
An autoclave with a stirrer with an internal volume of 2.0 liters, completely replaced with nitrogen gas, was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) and 0.0026 mmol of the solid catalyst component as titanium atoms. To form a polymerization catalyst. Thereafter, 2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. The polymerization activity per 1 g of the solid catalyst component was 50,300 g-PP / g-catalyst. The melt index value (MI) of the polymer (a) (measurement method conforms to ASTM D 1238, JIS K 7210) was 14.0 g / 10 min.
The polymerization activity per solid catalyst component used here was calculated by the following equation. Polymerization activity = (a) 195.7 (g) / solid catalyst component 0.00389 (g)
When this polymer was extracted with boiling n-heptane for 6 hours, the amount of polymer (b) insoluble in n-heptane was 192.4 g, and the ratio of boiling n-heptane insoluble matter in the polymer was 98. It became 6% by weight. Table 1 shows the polymerization activity per 1 g of the solid catalyst component, n-heptane insoluble matter (HI), and melt index (MI).
[0067]
Example 2
A solid component was prepared in the same manner as in Example 1 except that 3.7 g of 4-t-butylphthalate di-n-butyl was used instead of 3.2 g of 4-methylphthalate, and further a polymerization catalyst. Was formed and polymerized. As a result, the titanium content in the obtained solid catalyst component was 3.3% by weight. The polymerization results are listed in Table 1.
[0068]
Example 3
A solid component was prepared in the same manner as in Example 1 except that 2.5 g of diethyl 4-methylphthalate was used instead of 3.2 g of di-n-butyl 4-methylphthalate, and a polymerization catalyst was formed and polymerized. It was. As a result, the titanium content in the obtained solid catalyst component was 3.1% by weight. The polymerization results are listed in Table 1.
[0069]
Example 4
A solid component was prepared in the same manner as in Example 1 except that 3.0 g of diethyl 4-t-butylphthalate was used instead of 3.2 g of di-n-butyl 4-methylphthalate. Went. As a result, the titanium content in the obtained solid catalyst component was 3.4% by weight. The polymerization results are listed in Table 1.
[0070]
Example 5
A solid component was prepared in the same manner as in Example 1, except that 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS) was used as the organosilicon compound instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) during the formation of the polymerization catalyst. In the same manner as in Example 1, a polymerization catalyst was formed and polymerization was performed. The polymerization results are listed in Table 1.
[0071]
Example 6
A solid component was prepared in the same manner as in Example 1, except that 0.13 mmol of diisopropyldimethoxysilane (DIPDMS) was used in place of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) as the organosilicon compound when forming the polymerization catalyst. A polymerization catalyst was formed and polymerized in the same manner as in Example 1. The polymerization results are listed in Table 1.
[0072]
Comparative Example 1
A solid component was prepared in the same manner as in Example 1 except that 3.0 g of di-n-butyl phthalate was used instead of 3.2 g of di-n-butyl 4-methylphthalate. Went. As a result, the titanium content in the solid catalyst component was 3.0% by weight. The polymerization results are listed in Table 1.
[0073]
Comparative Example 2
A solid component was prepared in the same manner as in Comparative Example 1, except that 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS) was used as the organosilicon compound instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) during the formation of the polymerization catalyst. In the same manner as in Comparative Example 1, a polymerization catalyst was formed and polymerization was performed. The polymerization results are listed in Table 1.
[0074]
Comparative Example 3
A solid component was prepared in the same manner as in Comparative Example 1, except that 0.13 mmol of diisopropyldimethoxysilane (DIPDMS) was used as the organosilicon compound instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) when forming the polymerization catalyst. A polymerization catalyst was formed and polymerized in the same manner as in Example 1. The polymerization results are listed in Table 1.
[0075]
[Table 1]
[0076]
From the above results, it is understood that a propylene polymer can be obtained in a high yield by polymerizing propylene using the solid catalyst component and catalyst of the present invention. It can also be seen that the response to hydrogen is extremely excellent.
[0077]
【The invention's effect】
The olefin polymerization catalyst of the present invention is highly active in the polymerization of olefins, and can obtain an olefin polymer in a high yield while maintaining a high degree of stereoregularity. When provided, it exhibits high activity and yield while maintaining high stereoregularity. Further, the olefin polymerization catalyst of the present invention has a high hydrogen response capability. Therefore, general-purpose polyolefin can be provided at low cost, and usefulness is expected in the production of copolymers of olefins having high functionality.
[Brief description of the drawings]
FIG. 1 is a flowchart showing steps for preparing an olefin polymerization catalyst of the present invention.

Claims (6)

(A) a magnesium compound, (b) titanium tetrachloride, and (c) the following general formula (1):
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, R ² and R ³ represent an alkyl group having 1 to 12 carbon atoms, and R ² and R ³ may be the same or different. well, n is 1 or 2 by the number of ^{R 1,} when n is 2, ^{R 1} is not good be the same or different. also, ^{R 1} is a an alkyl group having 1 to 5 carbon atoms And R ² and R ³ are both alkyl groups having 4 to 8 carbon atoms, at least one of R ² and R ³ does not have a tertiary carbon.) A solid catalyst component for olefin polymerization, which is formed from a diester derivative.   The solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is dialkoxymagnesium. In the general formula (1), when n is 1, R ¹ is a methyl group or a t-butyl group, and when n is 2, at least one group of R ¹ is a methyl group or a t-butyl group The solid catalyst component for olefin polymerization according to claim 1. ^{2. The} solid catalyst component for olefin polymerization according to claim 1, wherein R ² or R ^{3 in the} general formula (1) is an n-butyl group. In the general formula (1), one of R ² and R ³ is a neopentyl group or a t-butyl group, and the other is a C 1-12 excluding a C 4-8 alkyl group having a tertiary carbon. The solid catalyst component for olefin polymerization according to claim 1, wherein the solid catalyst component is an alkyl group. (A) The solid catalyst component for olefin polymerization according to any one of claims 1 to 5,
(B) The following general formula (2); R ⁴ _p AlQ _3-p (2)
(Wherein R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3), and (C) The following general formula (3); R ⁵ _q Si (OR ⁶ ) _4-q (3)
(Wherein, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, R ⁶ is 1 to carbon atoms 4 represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, R ⁵ and R ⁶ may be the same or different from each other, and q is an integer of 0 ≦ q ≦ 3. .) A solid catalyst for olefin polymerization, comprising an organosilicon compound represented by