JPWO2008120795A1 - Solid catalyst component for olefin polymerization, polymerization catalyst, and process for producing olefin polymer using the same - Google Patents

Abstract

Solid catalyst for olefin polymerization prepared by contacting dialkoxymagnesium (a), tetravalent titanium halogen compound (b), electron donating compound (c) represented by general formula R1R2C (COOR3) (COOR4) When the olefins are polymerized using the olefin polymerization catalyst comprising the component, the solid catalyst component, the organoaluminum compound represented by the general formula R5pAlQ3-p, and an external electron donating compound, high activity and hydrogen activity are exhibited. It is good and a highly stereoregular polymer can be obtained in a high yield.

Description

  The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which have high activity and good hydrogen activity, and are capable of obtaining a highly stereoregular polymer in high yield.

Conventionally, in the polymerization of olefins such as propylene, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound have been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon compound and a titanium halide is in a powder state. A propylene polymerization catalyst comprising a solid catalyst component prepared by heat treatment with, an organoaluminum compound and an organosilicon compound and a propylene polymerization method have been proposed.
Furthermore, a solid catalyst component for olefin polymerization using a malonic acid ester compound instead of a conventional phthalic acid ester compound as an internal electron donating compound has also been developed. Patent Document 2 (Japanese Patent Publication No. 000-516987) Discloses a solid catalyst component comprising a titanium compound supported on a halogenated Mg and having at least a Ti-halogen bond and a monoalkyl-substituted malonic diester such as diethyl 2-isopropylmalonate. In Patent Document 3 (WO 03/95504), a halogen-containing titanium compound, metal magnesium, alcohol, and a halogen containing 0.0001 gram atom or more and / or a halogen-containing halogen with respect to 1 mol of the metal magnesium. A solid catalyst component comprising an alkoxy group-containing magnesium compound obtained by reacting a compound and a dialkyl-substituted malonic diester such as diethyl 2,2-dimethylmalonate is disclosed.
Further, conventionally, in order to obtain malonic acid diesters having two ester residues different from each other, it is difficult to fractionate because the boiling points of the reaction starting material and the target product are different, but the boiling points are close. There was a thing.
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.
Melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is a common practice to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. 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. For this reason, 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, it has been desired to develop a catalyst capable of producing a high melt flow rate polymer with a small amount of hydrogen, so-called high hydrogen activity and high stereoregularity polymer in high yield. Technology was not enough to solve the problem.
Japanese Patent Laid-Open No. 63-3010 (Claims) JP-T-2 000-516987 (Claims) WO03 / 95504 (Claims)

  That is, the object of the present invention is to solve the problems remaining in the prior art, and to obtain a high stereoregularity polymer having a higher anti-hydrogen activity in a high yield. It is an object to provide a catalyst component, a polymerization catalyst, and a method for producing an olefin polymer using the catalyst component.

In such a situation, the present inventors have conducted intensive studies to solve the problems remaining in the prior art, and as a result, the solid catalyst component prepared using a specific substituted malonic acid diester as an internal donor has an extremely high effect. Thus, the present inventors have found that the above problems can be solved, and have completed the present invention.
That is, to achieve the above object, the present invention provides a magnesium compound (a), a tetravalent titanium halogen compound (b) and the following general formula (1);
R ¹ R ² C (COOR ³ ) (COOR ⁴ ) (1)
(In the formula, R ¹ and R ² are each a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group, and a halogen atom. It may be the same or different in any one of a disubstituted linear or branched alkyl group having 1 to 10 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, a cycloalkyl group, a vinyl group, R ⁴ is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and R ³ and R ⁴ are different. The present invention provides a solid catalyst component for olefin polymerization prepared by contacting an electron donating compound (c).
The present invention also provides (A) the above solid catalyst component,
(B) the general formula _{^{(2); R 5 p AlQ}} 3-p (2)
(Wherein R ⁵ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) An olefin polymerization catalyst characterized by being formed by an external electron donating compound.
The present invention also provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  FIG. 1 is a flowchart showing the steps for preparing the polymerization catalyst of the present invention.

  Magnesium compound (a) (hereinafter referred to as “component (a)”) used for the preparation of the solid catalyst component (A) for olefin polymerization of the present invention (hereinafter sometimes referred to as “solid catalyst component (A)”). In some cases, examples thereof include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferable, and dialkoxymagnesium is particularly preferable.
  As dialkoxymagnesium, the general formula Mg (OR¹⁰) (OR¹¹) (Wherein R¹⁰And R¹¹Represents an alkyl group having 1 to 10 carbon atoms, which may be the same or different. ), And more specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like can be mentioned. These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of halogen or a halogen-containing metal compound. Moreover, said dialkoxy magnesium can also be used individually or in combination of 2 or more types.
  Furthermore, dialkoxymagnesium used for the preparation of the solid catalyst component (A) in the present invention is in the form of granules or powder, and the shape thereof 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.
  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be 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 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .
  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μm, and 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 represented by 1n (D90 / D10) (where D90 is the cumulative particle size at 90%, D10 is the cumulative particle size at 10%), it is 3 or less, preferably 2 or less.
  For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388 can be used to produce spherical dialkoxymagnesium as described above. It is exemplified in the publication.
  The tetravalent titanium halogen compound (b) used for the preparation of the solid catalyst component (A) in the present invention has the general formula Ti (OR¹²)_nX_4-n(Wherein R¹²Represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as chlorine, bromine or iodine, and n is an integer of 0 ≦ n ≦ 4. Or a compound selected from the group consisting of titanium halides and alkoxytitanium halides.
  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.
  The electron donating compound (c) used for the preparation of the solid catalyst component (A) in the present invention is a compound represented by the general formula (1). These compounds include dihalogen-substituted malonic acid diesters, alkyl and halogen-substituted malonic acid diesters, dialkyl-substituted malonic acid diesters or halogenated alkyl-substituted malonic acid diesters (hereinafter also referred to as “substituted malonic acid diesters”). R in the general formula (1)¹And R²In the above, the halogen atom is a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, preferably a chlorine atom or a bromine atom. In the above general formula, R¹Is preferably a methyl group or an isobutyl group, and R¹Is a methyl group and R²Is a t-butyl group or R¹And R²Are preferably isobutyl groups. R¹And R²Is preferably a branched alkyl group having 3 to 10 carbon atoms containing at least one secondary carbon, tertiary carbon or quaternary carbon, and particularly preferably an isobutyl group, a t-butyl group, an isopentyl group or a neopentyl group. Further, R in the general formula (1), which is an ester residue of carbonyl³Is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or an isopropyl group, and particularly preferably a methyl group or an ethyl group. R⁴Is preferably an alkyl group having 2 to 20 carbon atoms, particularly a linear or branched alkyl group having 2 to 8 carbon atoms, specifically an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, A heptyl group, an octyl group, an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, an isohexyl group, an isoheptyl group, and an isooctyl group are preferable.
  Specific examples of dihalogen-substituted malonic acid diesters include methyl ethyl dichloromalonate, methylpropyl dichloromalonate, methylbutyl dichloromalonate, methylisobutyl dichloromalonate, methylpentyl dichloromalonate, methyl neopentyl dichloromalonate, dichloromalonic acid Methylhexyl, methylisohexyl dichloromalonate, methylheptyl dichloromalonate, methylisoheptyl dichloromalonate, methyloctyl dichloromalonate, methylisooctyl dichloromalonate, ethylpropyl dichloromalonate, ethylbutyl dichloromalonate, dichloromalonic acid Ethyl isobutyl, ethyl pentyl dichloromalonate, ethyl neopentyl dichloromalonate, ethylhexyl dichloromalonate, ethyl dichloromalonate Sohexyl, ethyl heptyl dichloromalonate, ethyl isoheptyl dichloromalonate, ethyl octyl dichloromalonate, ethyl isooctyl dichloromalonate, methyl ethyl dibromomalonate, methylpropyl dibromomalonate, methylbutyl dibromomalonate, methylisobutyl dibromomalonate , Methyl pentyl dibromomalonate, methyl neopentyl dibromomalonate, methyl hexyl dibromomalonate, methyl isohexyl dibromomalonate, methyl heptyl dibromomalonate, methyl isoheptyl dibromomalonate, methyl octyl dibromomalonate, methyl dibromomalonate Isooctyl, ethyl propyl dibromomalonate, ethyl butyl dibromomalonate, ethyl isobutyl dibromomalonate, ethyl dibromomalonate Nethyl, ethyl neopentyl dibromomalonate, ethylhexyl dibromomalonate, ethyl isohexyl dibromomalonate, ethyl heptyl dibromomalonate, ethyl isoheptyl dibromomalonate, ethyloctyl dibromomalonate, ethyl isooctyl dibromomalonate, etc. .
  Specific examples of alkyl and halogen-substituted malonic diesters include methyl ethyl ethyl chloromalonate, methyl propyl ethyl chloromalonate, methyl butyl ethyl chloromalonate, ethyl butyl ethyl chloromalonate, ethyl isooctyl ethyl chloromalonate, ethyl bromomalon. Methyl ethyl acid, methyl propyl ethyl bromomalonate, methyl butyl ethyl bromomalonate, ethyl butyl ethyl bromomalonate, ethyl isooctyl ethyl bromomalonate, methyl ethyl isopropylchloromalonate, methylpropyl isopropylchloromalonate, methylbutyl isopropylchloromalonate , Ethylbutyl isopropylchloromalonate, ethylisooctyl isopropylchloromalonate, methylethyl isopropylbromomalonate, Sopropyl bromomalonate methylpropyl, isopropyl bromomalonate methyl butyl, isopropyl bromomalonate ethyl butyl, isopropyl bromomalonate ethyl isooctyl, butyl chloromalonate methyl ethyl, butyl chloromalonate methyl propyl, butyl chloromalonate methyl butyl, butyl chloro Ethyl butyl malonate, ethyl isooctyl butyl chloromalonate, methyl ethyl butyl bromomalonate, methyl butyl bromomalonate, methyl butyl bromomalonate, ethyl butyl bromomalonate, ethyl isooctyl butyl bromomalonate, isobutyl chloromalonic acid Methyl ethyl, methyl propyl isobutyl chloromalonate, methyl butyl isobutyl chloromalonate, isobutyl chloromalonic acid Rubuchiru, isobutyl chloro ethyl malonate isooctyl, isobutyl bromo malonate methylethyl, isobutyl bromo malonate methylpropyl, isobutyl bromo malonate methylbutyl, isobutyl bromo malonate ethylbutyl, isobutyl bromo ethyl malonate isooctyl and the like.
  Specific examples of dialkyl substituted malonic acid diesters include methyl ethyl diisopropylmalonate, methylpropyl diisopropylmalonate, methylbutyl diisopropylmalonate, methylisobutyldiisopropylmalonate, methylpentyldiisopropylmalonate, methylpentyldiisopropylmalonate, methylneopentyldiisopropylmalonate, diisopropylmalonic acid Methyl hexyl, methyl isohexyl diisopropylmalonate, methylheptyl diisopropylmalonate, methylisoheptyl diisopropylmalonate, methyloctyl diisopropylmalonate, methylisooctyl diisopropylmalonate, ethylpropyl diisopropylmalonate, ethylbutyl diisopropylmalonate, diisopropylmalonic acid Ethyl isobutyl, diisopropyl malonate ethyl pen , Ethyl hexyl diisopropylmalonate, ethylisohexyl diisopropylmalonate, ethylheptyl diisopropylmalonate, ethylisoheptyldiisopropylmalonate, ethyloctyldiisopropylmalonate, ethylisooctyldiisopropylmalonate, methylethyldiisobutylmalonate, methyldiisobutylmalonate Propyl, methyl isobutyl malonate, methyl isobutyl diisobutyl malonate, methyl pentyl diisobutyl malonate, methyl neopentyl diisobutyl malonate, methyl hexyl diisobutyl malonate, methyl isohexyl diisobutyl malonate, methyl heptyl diisobutyl malonate, methyl isoisobutyl malonate Heptyl, methyloctyl diisobutylmalonate, diisobutylmaly Methyl isooctylate, ethylisopropyl diisobutylmalonate, ethylbutyl diisobutylmalonate, ethylisobutyl diisobutylmalonate, ethylpentyl diisobutylmalonate, ethylpentyldiisobutylmalonate, ethylhexyl diisobutylmalonate, ethylisohexyl diisobutylmalonate, diisobutylmalon Ethyl heptyl acid, ethyl isoheptyl diisobutylmalonate, ethyloctyl diisobutylmalonate, ethylisooctyl diisobutylmalonate, methylethyl t-butylmethylmalonate, methylpropyl t-butylmethylmalonate, methylbutyl t-butylmethylmalonate, t-butyl methyl malonate methyl isobutyl, t-butyl methyl malonate methyl pentyl, t-butyl methyl malonate methylne Opentyl, methyl hexyl t-butylmethylmalonate, methylisohexyl t-butylmethylmalonate, methylheptyl t-butylmethylmalonate, methylisoheptyl t-butylmethylmalonate, methyloctyl t-butylmethylmalonate, t -Methyl isooctyl butyl methyl malonate, ethyl propyl t-butyl methyl malonate, ethyl butyl t-butyl methyl malonate, ethyl isobutyl t-butyl methyl malonate, ethyl pentyl t-butyl methyl malonate, t-butyl methyl malonic acid Ethyl neopentyl, ethyl hexyl t-butyl methyl malonate, ethyl isohexyl t-butyl methyl malonate, ethyl heptyl t-butyl methyl malonate, ethyl isoheptyl t-butyl methyl malonate, ethyl o-butyl methyl malonate Til, ethyl isooctyl t-butylmethylmalonate, methylethyl t-butylethylmalonate, methylpropyl t-butylethylmalonate, methylbutyl t-butylethylmalonate, methylisobutyl t-butylethylmalonate, t-butyl Methylpentyl ethylmalonate, methyl neopentyl t-butylethylmalonate, methylhexyl t-butylethylmalonate, methylisohexyl t-butylethylmalonate, methylheptyl t-butylethylmalonate, t-butylethylmalonic acid Methyl isoheptyl, methyl octyl t-butylethylmalonate, methylisooctyl t-butylethylmalonate, ethylpropyl t-butylethylmalonate, ethylbutyl t-butylethylmalonate, ethylisobutyl t-butylethylmalonate, -Ethyl pentyl butyl ethyl malonate, ethyl neopentyl t-butyl ethyl malonate, ethyl hexyl t-butyl ethyl malonate, ethyl isohexyl t-butyl ethyl malonate, ethyl heptyl t-butyl ethyl malonate, t-butyl ethyl malon Ethyl isoheptyl acid, ethyl octyl t-butylethylmalonate, ethyl isooctyl t-butylethylmalonate, methylethyl t-butyln-propylmalonate, methylpropyl t-butyln-propylmalonate, t-butyln -Methylbutyl propylmalonate, methyl isobutyl t-butyl n-propylmalonate, methylpentyl t-butyl n-propylmalonate, methyl neopentyl t-butyln-propylmalonate, methylhexyl t-butyln-propylmalonate , T-Buchi Methyl isohexyl n-propylmalonate, methylheptyl t-butyl n-propylmalonate, methylisoheptyl t-butyl n-propylmalonate, methyloctyl t-butyl n-propylmalonate, t-butyl n-propyl Methyl isooctyl malonate, ethyl propyl t-butyl n-propyl malonate, ethyl butyl t-butyl n-propyl malonate, ethyl isobutyl t-butyl n-propyl malonate, ethyl pentyl t-butyl n-propyl malonate, t -Ethyl neopentyl butyl n-propyl malonate, ethyl hexyl t-butyl n-propyl malonate, ethyl isohexyl t-butyl n-propyl malonate, ethyl heptyl t-butyl n-propyl malonate, t-butyl n-propyl Ethyl isoheptyl malonate, t-butyl N-Propylmalonate ethyloctyl, t-butyl n-propylmalonate ethylisooctyl, t-butylisopropylmalonate methylethyl, t-butylisopropylmalonate methylpropyl, t-butylisopropylmalonate methylbutyl, t-butyl Methyl isobutyl isopropylmalonate, methylpentyl t-butylisopropylmalonate, methyl neopentyl t-butylisopropylmalonate, methylhexyl t-butylisopropylmalonate, methylisohexyl t-butylisopropylmalonate, t-butylisopropylmalonic acid Methyl heptyl, methyl isoheptyl t-butylisopropylmalonate, methyloctyl t-butylisopropylmalonate, methylisooctyl t-butylisopropylmalonate, t-butyl Ethylpropyl propylmalonate, ethylbutyl t-butylisopropylmalonate, ethylisobutyl t-butylisopropylmalonate, ethylpentyl t-butylisopropylmalonate, ethyl neopentyl t-butylisopropylmalonate, ethylhexyl t-butylisopropylmalonate , Ethyl isohexyl t-butylisopropylmalonate, ethylheptyl t-butylisopropylmalonate, ethylisoheptyl t-butylisopropylmalonate, ethyloctyl t-butylisopropylmalonate, ethylisooctyl t-butylisopropylmalonate, di Methyl ethyl isopentyl malonate, methyl propyl diisopentyl malonate, methyl butyl diisopentyl malonate, methyl isobutyl diisopentyl malonate, diiso Methylpentyl pentylmalonate, methyl neopentyl diisopentylmalonate, methylhexyl diisopentylmalonate, methylisohexyldiisopentylmalonate, methylheptyldiisopentylmalonate, methylisoheptyldiisopentylmalonate, di Isopentylmalonate methyloctyl, diisopentylmalonate methylisooctyl, diisopentylmalonate ethylpropyl, diisopentylmalonate ethylbutyl, diisopentylmalonate ethylisobutyl, diisopentylmalonate ethylpentyl, diisopentyl Ethyl neopentyl malonate, ethyl hexyl diisopentyl malonate, ethyl isohexyl diisopentyl malonate, ethyl heptyl diisopentyl malonate, ethyl isoheptyl diisopentyl malonate Ethyloctyl diisopentylmalonate, ethylisooctyldiisopentylmalonate, methylethyl isopropylisobutylmalonate, methylpropyl isopropylisobutylmalonate, methylbutyl isopropylisobutylmalonate, methylisobutyl isopropylisobutylmalonate, methylpentyl isopropylisobutylmalonate , Methyl neopentyl isopropylisobutylmalonate, methylhexyl isopropylisobutylmalonate, methylisohexyl isopropylisobutylmalonate, methylheptyl isopropylisobutylmalonate, methylisoheptyl isopropylisobutylmalonate, methyloctyl isopropylisobutylmalonate, isopropylisobutylmalonic acid Methyl isooctyl, isopropyl isobut Ethyl propyl lumalonate, ethyl butyl isobutyl malonate, ethyl isobutyl isobutyl malonate, ethyl pentyl isopropyl isobutyl malonate, ethyl neopentyl isopropyl isobutyl malonate, ethyl hexyl isopropyl isobutyl malonate, ethyl isohexyl isopropyl isobutyl malonate, isopropyl isobutyl malon Ethyl heptyl, isopropyl isobutyl malonate ethyl isoheptyl, isopropyl isobutyl malonate ethyl octyl, isopropyl isobutyl malonate ethyl isooctyl, isopropyl isopentyl malonate methyl ethyl, isopropyl isopentyl malonate methyl propyl, isopropyl isopentyl malonate methyl butyl, Isopropyl isopentyl Methyl isobutyl malonate, methyl pentyl isopropyl isopentyl malonate, methyl neopentyl isopropyl isopentyl malonate, methyl hexyl isopropyl isopentyl malonate, methyl isohexyl isopropyl isopentyl malonate, methyl heptyl isopropyl isopentyl malonate, isopropyl isopentyl Methyl isoheptyl malonate, methyl octyl isopropyl isopentyl malonate, methyl isooctyl isopropyl isopentyl malonate, ethyl propyl isopentyl malonate, ethyl isopropyl isopentyl malonate, ethyl isobutyl isopentyl malonate, ethyl isobutyl isopropyl malonate, isopropyl isopentyl malon Ethyl pentyl, isopropyl isopentyl malonate ethyl neopent , Ethyl hexyl isopropylisopentylmalonate, ethylisohexyl isopropylisopentylmalonate, ethylheptyl isopropylisopentylmalonate, ethylisoheptyl isopropylisopentylmalonate, ethyloctyl isopropylisopentylmalonate, ethylisooctylisopentylmalonate Etc.
  Specific examples of halogenated alkyl-substituted malonic acid diesters include methylbutyl bis (chloromethyl) malonate, methylbutyl bis (bromomethyl) malonate, methylbutyl bis (chloroethyl) malonate, methylbutyl bis (bromoethyl) malonate, bis (3- Chloro-n-propyl) methyl butyl malonate and methyl bis (3-bromo-n-propyl) malonate.
  Among the above substituted malonic acid diesters, methyl isopropyl bromomalonate, methyl butyl bromomalonate, ethyl butyl bromomalonate, methylbutyl isobutyl bromomalonate, methylbutyl diisopropylmalonate, methylbutyl dibutylmalonate, ethylbutyl diisobutylmalonate, diisobutylmalonate Methyl ethyl malonate, ethyl isooctyl diisobutylmalonate, methylbutyl diisobutylmalonate, methylbutyl diisopentylmalonate, methylbutyl isopropylisobutylmalonate, methylbutyl isopropylisopentylmalonate, methylbutyl t-butylmethylmalonate, bis (3-chloro -N-propyl) methylbutyl malonate and methylbutyl bis (3-bromo-n-propyl) malonate Masui. The electron donating compound (c) can be used alone or in combination of two or more. In the above compound, “butyl” of the ester residue is n-butyl or isobutyl.
  In the preparation of the solid catalyst component (A) of the present invention, diethoxymagnesium is used as the magnesium compound (a), and R is used as the electron donating compound (c).³And R⁴When the alkyl group of the ester residue is different from the alkyl group of the ester residue other than the ethyl group, in the process of preparing the solid catalyst component by contacting each component, one ethoxy group of diethoxymagnesium and one kind of Exchange of the electron donating compound (c) with an ester residue occurs, and finally the malonic acid diester compound including the electron donating compound (c) contained in the solid catalyst component becomes three or more. For example, when diethoxymagnesium is used as the magnesium compound (a) and methyl n-butyl diisobutylmalonate is used as the electron donating compound (c), the esters contained in the solid catalyst component are dimethyldiisobutylmalonate and diisobutylmalonic acid. There are five types: methyl ethyl, methyl n-butyl diisobutylmalonate, ethyl n-butyl diisobutylmalonate and di-n-butyl diisobutylmalonate. Thus, R³And R⁴Since an electron donating compound of a different alkyl group in the ester residue is used, a wide variety of esters are finally formed in the solid catalyst component, so that a solid catalyst component having high anti-hydrogen activity can be obtained. .
  In the solid catalyst component (A) of the present invention, if the substituted malonic acid diester represented by the general formula (1) is used as the electron donating compound used for the preparation of the solid catalyst component, it has high activity and hydrogen activity. Can be obtained in a high yield.
  In the present invention, the solid catalyst component (A) is preferably prepared by suspension contact in a hydrocarbon solvent (d) having a boiling point of 50 to 150 ° C. As the hydrocarbon solvent having a boiling point of 50 to 150 ° C., toluene, xylene, ethylbenzene, hexane, heptane, octane, cyclohexane and the like are preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types. Use of a hydrocarbon solvent having a boiling point of 50 to 150 ° C. is preferable in that the solubility of impurities is increased during reaction or washing, and the resulting catalyst activity of the solid catalyst component and the stereoregularity of the resulting polymer are improved. .
  Below, the contact method of each component is described. The solid catalyst component (A) of the present invention can be prepared by contacting the above-described magnesium compound (a), tetravalent titanium halogen compound (b), and electron donating compound (c). More specifically, the magnesium compound (a) is suspended in the tetravalent titanium halogen compound (b) or the hydrocarbon solvent (d), and the electron donating compound (c) and / or the tetravalent titanium halogen compound is further suspended. The method of obtaining (b) and obtaining a solid catalyst component is mentioned. In the method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained.
  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.
  Below, the contact order at the time of preparing the solid catalyst component (A) of this invention is illustrated more concretely.
(1) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(2) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(3) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(4) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)
(5) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(6) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)
  In each of the contact methods described above, the activity in the parentheses (<<) is further improved by repeating the process a plurality of times as necessary. In addition, the component (b) or the component (d) used in the steps in <<> may be newly added or may be a residue of the previous step. In addition to the washing steps shown in (1) to (6) above, the product obtained in each contact stage can be washed with a hydrocarbon compound that is liquid at room temperature.
  Based on the above, as a particularly preferred preparation method of the solid catalyst component (A) in the present application, dialkoxymagnesium is suspended in toluene as a hydrocarbon solvent (d) having a boiling point of 50 to 150 ° C. as the magnesium compound (a), and then This suspension is brought into contact with titanium tetrachloride as a tetravalent titanium halogen compound (b) and then subjected to a reaction treatment. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more dialkyl-substituted malonic acid diesters are used as the electron donating compound (c). Contact at ˜130 ° C. to obtain the solid reaction product (1). At this time, it is desirable to carry out the aging reaction at a low temperature before or after contacting the electron donating compound (c). After washing this solid reaction product (1) with a liquid hydrocarbon compound at room temperature (intermediate washing), tetravalent titanium halogen compound (b) is again added in the presence of an aromatic hydrocarbon compound in the range of −20 to 20 The contact treatment is performed at 100 ° C. to obtain a solid reaction product (2). If necessary, the intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature (final washing) to obtain a solid catalyst component (A).
  Preferred conditions for the above treatment or washing are as follows.
Low temperature aging reaction: −20 to 70 ° C., preferably −10 to 60 ° C., more preferably 0 to 30 ° C., 1 minute to 6 hours, preferably 5 minutes to 4 hours, particularly preferably 10 minutes to 3 hours. .
Reaction treatment: 0 to 130 ° C., preferably 40 to 120 ° C., particularly preferably 50 to 115 ° C., 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4 hours.
Washing: 0 to 110 ° C., preferably 30 to 100 ° C., particularly preferably 30 to 90 ° C., 1 to 20 times, preferably 1 to 15 times, particularly preferably 1 to 10 times. The hydrocarbon compound used for washing is preferably an aromatic compound or a saturated hydrocarbon compound that is liquid at room temperature. Specifically, the aromatic hydrocarbon compound may be a saturated hydrocarbon compound such as toluene, xylene, or ethylbenzene. Hexane, heptane, cyclohexane and the like can be mentioned. Preferably, an aromatic hydrocarbon compound is used in the intermediate cleaning, and a saturated hydrocarbon compound is used in the final cleaning.
  The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02-0.6 mol, and hydrocarbon solvent (d) is 0.001-500 mol, Preferably it is 0.001-100 mol, More preferably, it is 0.005-10 mol.
  Further, the content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly defined, but preferably 1.8 to 8.0% by weight, preferably 2% of titanium. 0.0-8.0 wt%, more preferably 2.0-6.0 wt%, magnesium 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more preferably Is 15 to 25% by weight, halogen atoms are 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of electron donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight in total, and particularly preferably 2 to 20% by weight in total. In order to bring out the overall performance of the solid catalyst component (A) using the electron donating compound of the present invention and other components in a more balanced manner, the titanium content is 3 to 8% by weight and the magnesium content is 15 to 15%. The content is preferably 25% by weight, the halogen atom content is 45 to 75% by weight, and the electron donating compound content is 2 to 20% by weight.
  As the organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention, the general formula R⁵ _pAlQ_3-p(Wherein R⁵Represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3. ) Can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.
  The external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is represented by the general formula (3);
  R⁶ _qSi (NR⁷R⁸)_r(OR⁹)_{4- (q + r)}    (3)
(In the formula, q is 0 or an integer of 1 to 4, r is an integer of 0 or 1 to 4, provided that q + r is an integer of 0 to 4, R⁶, R⁷Or R⁸Is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may contain a hetero atom. It may be the same or different. R⁹Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, may contain a hetero atom, and may be the same or different, and R⁷And R⁸May combine to form a ring. 1 type or 2 types or more chosen from the organosilicon compound and polyether represented by this.
  In general formula (3), R⁶Is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched alkyl group having 1 to 8 carbon atoms, or a carbon number having 5 to 8 carbon atoms. A cycloalkyl group is preferred. R⁷Or R⁸Is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched alkyl group having 1 to 8 carbon atoms, or a carbon number having 5 to 8 carbon atoms. A cycloalkyl group is preferred. R⁷And R⁸Combine to form a ring (NR⁷R⁸) Is preferably a perhydroquinolino group or a perhydroisoquinolino group. R⁹Is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl ( Alkylamino) silane, alkylaminosilane and the like.
  In general formula (3), when r is 0, q is 1 to 3, R⁶Is a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, R⁹Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. In particular, when r is 0, q is 1 to 3, R⁶Is a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, R⁹Is preferably a linear alkyl group having 1 to 2 carbon atoms.
  In the general formula (3), when r is 0, particularly preferred compounds are di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane. Di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, Cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyl Diethoxy silane, cyclohexyl cyclopentyl dimethoxy silane, cyclohexyl cyclopentyl distearate triethoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3,5-dimethyl-cyclohexyl cyclopentyl dimethoxysilane.
  In the general formula (3), as the organosilicon compound in which r is 1 to 4, (alkylamino) trialkylsilane, (alkylamino) dialkylcycloalkylsilane, (alkylamino) alkyldicycloalkylsilane, ( Alkylamino) tricycloalkylsilane, (alkylamino) (dialkylamino) dialkylsilane, (alkylamino) (dialkylamino) dicycloalkylsilane, bis (alkylamino) dialkylsilane, bis (alkylamino) alkylcycloalkylsilane, Bis (alkylamino) dicycloalkylsilane, bis (alkylamino) (dialkylamino) alkylsilane, bis (alkylamino) (dialkylamino) cycloalkylsilane, di (alkylamino) dialkylsilane, di (al Ruamino) alkylcycloalkylsilane, di (alkylamino) dicycloalkylsilane, di (cycloalkylamino) dialkylsilane, di (cycloalkylamino) alkylcycloalkylsilane, di (cycloalkylamino) dicycloalkylsilane, tris ( Alkylamino) alkylsilane, tris (alkylamino) cycloalkylsilane, tri (alkylamino) alkylsilane, tri (alkylamino) cycloalkylsilane, tri (cycloalkylamino) alkylsilane, tri (cycloalkylamino) cycloalkylsilane , Tetrakis (alkylamino) silane, tris (alkylamino) dialkylaminosilane, tris (cycloalkylamino) dialkylaminosilane, bis (dialkylamino) bis ( Rualkylamino) silane, dialkylaminotris (alkylamino) silane, bis (perhydroisoquinolino) bis (alkylamino) silane, bis (perhydroquinolino) bis (alkylamino) silane, bis (cycloalkylamino) bis ( Alkylamino) silane, tetra (alkylamino) silane, tri (alkylamino) dialkylaminosilane, tri (cycloalkylamino) dialkylaminosilane, di (dialkylamino) di (alkylamino) silane, dialkylaminotri (alkylamino) silane, Di (alkyl-substituted perhydroisoquinolino) di (alkylamino) silane, di (alkyl-substituted perhydroquinolino) di (alkylamino) silane, di (cycloalkylamino) di (alkylamino) silane, alkyl ( Dialkylamino) (alkylamino) alkoxysilane, cycloalkyl (dialkylamino) (alkylamino) alkoxysilane, vinyl (dialkylamino) (alkylamino) alkoxysilane, allyl (dialkylamino) (alkylamino) alkoxysilane, aralkyl (dialkyl) Amino) (alkylamino) alkoxysilane, dialkyl (alkylamino) alkoxysilane (dialkylamino) trialkoxysilane, alkyl (dialkylamino) alkoxysilane, bis (perhydroisoquinolino) dialkoxysilane, and the like. The organosilicon compound (C) can be used alone or in combination of two or more. Among the polyethers, 1,3-diether is preferable, and 9,9-bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are more preferable. These external electron donating compounds can be used alone or in combination of two or more.
  Next, the catalyst for olefin polymerization of the present invention contains the above-described solid catalyst component (A), component (B), and component (C) for olefin polymerization, and polymerization of olefins in the presence of the catalyst. Copolymerization is performed. 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.
  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The organosilicon compound (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 1 mol of the component (B).
  The order of contact of each component 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) for olefin polymerization is further added. It is desirable to contact.
  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.
  Furthermore, in polymerizing olefins using the catalyst containing the solid catalyst component (A), the component (B), and the component (C) for olefin polymerization in the present invention (also referred to as main polymerization), the catalytic activity and stericity are determined. In order to further improve the regularity and the particle properties of the polymer to be produced, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.
  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, 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 an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.
  When the olefins are polymerized in the presence of the olefin polymerization catalyst formed according to the present invention, compared with the case where a conventional catalyst is used, it has a higher anti-hydrogen activity and further has a high stereoregularity. The polymer can be obtained in high yield.

第１表及び第２表の結果から、本発明の固体触媒成分および触媒を用いてプロピレンの重合を行うことにより、より高い対水素活性を示し、更に高立体規則性のオレフィン類重合体が高収率で得られることがわかる。Hereinafter, although the Example of this invention is described concretely, contrasting with a comparative example, this invention is not restrict | limited.
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 20 g of diethoxymagnesium and 160 ml of toluene to form a suspended state. Next, 40 ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised. When the temperature reached 60 ° C., 4.5 ml of ethyl n-butyl diisobutylmalonate was added, and the temperature was further raised to 90 ° C. Thereafter, the reaction was carried out with stirring for 2 hours while maintaining a temperature of 90 ° C. After completion of the reaction, the obtained reaction product was washed 4 times with 200 ml of toluene at 90 ° C., 40 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 110 ° C., and the reaction was allowed to proceed for 1 hour with stirring. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 200 ml of n-heptane at 40 ° C. In addition, when solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 4.5 weight%. Further, by analysis using gas chromatography, the catalyst contained 0.31% by weight of diethyl diisobutylmalonate, 13.4% by weight of ethyl n-butyl diisobutylmalonate, and 0.11% of din-butyldiisobutylmalonate. It was contained by weight.
[Formation and polymerization of polymerization catalyst]
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms were charged, A polymerization catalyst was formed. 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. Polymerization activity per 1 g of the solid catalyst component at this time, ratio of boiling n-heptane insoluble matter in the produced polymer (HI), value of melt flow rate of the produced polymer (a) (MFR; display is “MI”) Is shown in Table 1.
The polymerization activity per solid catalyst component used here was calculated by the following equation. Polymerization activity = produced polymer (g) / solid catalyst component (g)
Further, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer is the ratio (% by weight) of the polymer insoluble in n-heptane when this produced polymer is extracted with boiling n-heptane for 6 hours. ).
(Example 2)
A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of ethyl isoisobutyl malonate was used instead of 4.5 ml of ethyl diisobutylmalonate, and further formation and polymerization of a polymerization catalyst were performed. It was. As a result, the titanium content in the obtained solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
(Example 3)
A solid catalyst component was prepared in the same manner as in Example 1 except that 3.9 ml of methyl ethyl diisobutyl malonate was used instead of 4.5 ml of ethyl n-butyl diisobutyl malonate, and a polymerization catalyst was formed and polymerized. . As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 1.
Example 4
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl n-butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. went. As a result, the titanium content in the obtained solid catalyst component was 4.3% by weight. In addition, by analysis using gas chromatography, 0.19 wt% of dimethyl diisobutylmalonate, 0.19 wt% of methyl ethyl diisobutylmalonate, and 15.27 wt% of methyl n-butyl diisobutylmalonate were found in the catalyst. In addition, ethyl n-butyl diisobutylmalonate contained 0.61% by weight and din-butyl diisobutylmalonate contained 0.48% by weight. The polymerization results are shown in Table 1.
(Example 5)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.9 ml of methyl n-butyl bis (3-chloro-n-propyl) malonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Further, a polymerization catalyst was formed and polymerized. As a result, the titanium content in the obtained solid catalyst component was 3.9% by weight. The polymerization results are shown in Table 1.
(Example 6)
A solid catalyst component was prepared in the same manner as in Example 1 except that 3.7 ml of methyl n-butyl methyl butylbromomalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Went. As a result, the titanium content in the solid catalyst component was 3.4% by weight. The polymerization results are shown in Table 1.
(Example 7)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of ethyl n-butyl butyl bromomalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Went. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
(Example 8)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl n-butyl t-butylmethylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. And polymerization was carried out. As a result, the titanium content in the solid catalyst component was 3.3% by weight. The polymerization results are shown in Table 1.
Example 9
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of diisobutyl ethyl malonate was used instead of 4.5 ml of ethyl n-butyl diisobutyl malonate, and a polymerization catalyst was formed and polymerized. . As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
(Example 10)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.3 ml of methyl isobutyl diisobutyl malonate was used instead of 4.5 ml of ethyl n-butyl diisobutyl malonate, and a polymerization catalyst was formed and polymerized. . As a result, the titanium content in the solid catalyst component was 4.4% by weight. The polymerization results are shown in Table 1.
(Example 11)
A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of methyl isobutyl t-butylmethylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Went. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 1.
(Comparative Example 1)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. It was. As a result, the titanium content in the solid catalyst component was 3.5% by weight. The polymerization results are shown in Table 2.
(Comparative Example 2)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of diethyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
(Example 12)
[Preparation of solid catalyst component (A)]
To a 500-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, 20 g of anhydrous magnesium chloride (manufactured by Toho Titanium) was inserted with 106 ml of decane and 102 ml of 2-ethylhexyl alcohol, and the mixture was stirred. The temperature was raised to 0 ° C. and treated for 2 hours to dissolve anhydrous magnesium chloride to obtain a uniform solution. Thereafter, 4.4 g of phthalic anhydride was added, and the mixture was further reacted at 130 ° C. with stirring for 1 hour. Separately, 170 ml of titanium tetrachloride was inserted into a 1 liter round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer, cooled to -20 ° C., and the homogeneous solution was added dropwise thereto. Thereafter, the temperature was raised to 110 ° C., and 4.0 ml of methyl n-butyl diisobutylmalonate was added. Thereafter, it was treated at 110 ° C. for 2 hours. After removing the supernatant, 170 ml of titanium tetrachloride was newly introduced and reacted at 110 ° C. for 2 hours with stirring. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 200 ml of n-heptane at 40 ° C. In addition, when the solid-liquid in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.0 weight%.
[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component was used. The obtained results are shown in Table 1.
(Example 13)
[Preparation of solid catalyst component (A)]
Into a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer, 20 g of diethoxymagnesium, 4.0 ml of methyl n-butyl diisobutylmalonate and 100 ml of methylene chloride were placed in a suspended state, and then ascended. The reaction was allowed to warm and reflux for 1 hour with stirring. Separately, 800 ml of room temperature titanium tetrachloride was inserted into a 2000 ml round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer, and the above suspension was added dropwise thereto. Thereafter, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. After removing the supernatant, it was washed with 800 ml of decane three times, and 800 ml of titanium tetrachloride was newly introduced, and reacted at 120 ° C. with stirring for 2 hours. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 800 ml of n-heptane at 40 ° C. In addition, when the solid-liquid in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.3 weight%.
[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component was used. The obtained results are shown in Table 1.
(Example 14)
A polymerization catalyst was formed and polymerized in the same manner as in Example 4 except that 0.13 mmol of 9,9-bis (methoxymethyl) fluorene was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane. The polymerization results are shown in Table 1.
(Example 15)
A polymerization catalyst was formed and polymerized in the same manner as in Example 4 except that 0.13 mmol of dicyclopentylbis (ethylamino) silane was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane. The polymerization results are shown in Table 1.
(Comparative Example 3)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl isobutyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. went. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
(Comparative Example 4)
A solid catalyst component was prepared in the same manner as in Example 1, except that 4.1 ml of ethyl neopentyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Went. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
(Comparative Example 5)
[Preparation of solid catalyst component (A)]
A solid catalyst component was prepared in the same manner as in Example 12 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.0 ml of methyl n-butyl diisobutylmalonate. As a result, the titanium content in the solid catalyst component was 2.7% by weight.
[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component was used. The results obtained are shown in Table 2.
(Comparative Example 6)
[Preparation of solid catalyst component (A)]
A solid catalyst component was prepared in the same manner as in Example 13 except that 4.0 ml of di-n-butyl phthalate was used instead of 4.0 ml of methyl n-butyl diisobutylmalonate. As a result, the titanium content in the solid catalyst component was 2.9% by weight.
[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component was used. The results obtained are shown in Table 2.
(Comparative Example 7)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of di-n-butyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. went. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
(Comparative Example 8)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl n-butyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Polymerization was performed. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
(Comparative Example 9)
A solid catalyst component was prepared in the same manner as in Example 1 except that 5.4 ml of diisobutylmalonate dioctyl was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 4.8% by weight. The polymerization results are shown in Table 2.
(Comparative Example 10)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of ethyl isooctyl 2-isopropylmalonate was used in place of 4.5 ml of ethyl n-butyl diisobutylmalonate. Went. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.
(Comparative Example 11)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.5 ml of dimethyl diisobutylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 4.3% by weight. The polymerization results are shown in Table 2.
(Comparative Example 12)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of methyl ethyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. went. As a result, the titanium content in the solid catalyst component was 4.6% by weight. The polymerization results are shown in Table 2.
(Comparative Example 13)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.1 ml of methyl n-butyl 2-isopropylmalonate was used instead of 4.5 ml of ethyl n-butyl diisobutylmalonate. Polymerization was performed. As a result, the titanium content in the solid catalyst component was 4.5% by weight. The polymerization results are shown in Table 2.

From the results shown in Tables 1 and 2, propylene is polymerized by using the solid catalyst component and catalyst of the present invention, and a higher anti-hydrogen activity is exhibited. It turns out that it is obtained with a yield.

  When olefins are polymerized using the olefin polymerization catalyst of the present invention, high activity and good hydrogen activity can be obtained, and a highly stereoregular polymer can be obtained in high yield.

Claims (9)

Magnesium compound (a), tetravalent titanium halogen compound (b) and the following general formula (1);
R ¹ R ² C (COOR ³ ) (COOR ⁴ ) (1)
(In the formula, R ¹ and R ² are each a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group, and a halogen atom. It may be the same or different in any one of a disubstituted linear or branched alkyl group having 1 to 10 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, a cycloalkyl group, a vinyl group, R ⁴ is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and R ³ and R ⁴ are different.
A solid catalyst component for olefin polymerization prepared by contacting an electron donating compound (c) represented by The solid catalyst component for olefin polymerization according to claim ¹ , wherein, in the general formula (1), R ¹ is a methyl group or an isobutyl group. The solid catalyst for olefin polymerization according to claim 1, wherein, in the general formula (1), R ¹ is a methyl group and R ² is a t-butyl group, or R ¹ is an isobutyl group and R ² is an isobutyl group. component. The solid catalyst component for olefin polymerization according to claim 1, wherein R ³ in the general formula (1) is a methyl group or an ethyl group. The electron donating compound (c) is ethyl n-butyl diisobutylmalonate, methylethyl diisobutylmalonate, ethylisooctyldiisobutylmalonate, methyl n-butyldiisobutylmalonate, methylisobutyldiisobutylmalonate, ethylisobutyldiisobutylmalonate Bis (3-chloro-n-propyl) malonate methyl n-butyl, butyl bromomalonate methyl n-butyl, butyl bromomalonate ethyl n-butyl, t-butylmethylmalonate methyl n-butyl, t-butyl The solid catalyst component for olefin polymerization according to claim 1, which is a compound selected from methyl isobutyl methylmalonate. The solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is dialkoxymagnesium and the tetravalent titanium halogen compound is titanium tetrachloride. (A) The solid catalyst component for olefin polymerization according to claim 1,
(B) the general formula _{^{(2); R 5 p AlQ}} 3-p (2)
(Wherein R ⁵ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) An olefin polymerization catalyst formed by an external electron donating compound. (C) the external electron donating compound is (C) general formula (3);
R ⁶ _q Si (NR ⁷ R ⁸ ) _r (OR ⁹ ) _{4- (q + r)} (3)
(Wherein q is 0 or an integer of 1 to 4, r is 0 or an integer of 1 to 4, provided that q + r is an integer of 0 to 4, R ⁶ , R ⁷ or R ⁸ is a hydrogen atom, 1 to Any of 12 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, aralkyl groups, which may contain heteroatoms, and may be the same or different R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, may contain a hetero atom, may be the same or different, and R ⁷ And R ⁸ may be bonded to form a ring.)) An olefin polymerization catalyst characterized by being one or more selected from organic silicon compounds and polyethers. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7 or 8.

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