JP4427102B2 - α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer Using the Same - Google Patents

Description

  The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer using the same, and more specifically, a solid catalyst component, an organoaluminum compound, and an optional silicon compound or diether compound, Α-olefin polymerization catalyst comprising a combination of sulfite ester compounds of the above, and by polymerizing α-olefin using the same, there are very few amorphous components, high stereoregularity, high density and high The present invention relates to a method for producing an α-olefin polymer which can obtain an α-olefin polymer which is rigid and has less sticky components in a high yield.

Polyolefins such as polyethylene and polypropylene are the most important plastic materials as industrial materials, such as packaging materials and electrical materials as films and sheets, industrial materials such as automobile parts and household appliances as molded products, and textile materials and construction Widely used in various applications such as materials.
In this way, the applications are so wide and diverse that polyolefins continue to seek improvements in various properties from the viewpoint of their applications. In order to meet these demands, mainly by improving the polymerization catalyst. Technology development has been deployed.

Ziegler-based catalysts using transition metal compounds and organometallic compounds have greatly enhanced the polymerization activity of olefins and realized industrial production. After that, improvements in polymer properties due to molecular weight distribution and α-olefins Various performance improvements have been made, including the improvement of stereoregularity.
Specifically, a catalyst using a solid catalyst component containing titanium and halogen as essential components with a magnesium compound as a catalyst support was developed, and a catalyst with enhanced catalytic activity and stereoregularity using an electron donor. (For example, Patent Document 1), and thereafter, various organosilicon compounds are newly added to the catalyst component to further improve the catalytic activity and stereoregularity, and propose to widen the molecular weight distribution ( For example, Patent Document 2).
Further, typically, an organosilicon compound having a branched aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group is used as an internal donor, and a sulfonic acid ester is used as an external donor to improve molding processability, thereby increasing the high crystalline weight. Use a specific alkoxy group-containing organosilicon compound to broaden the molecular weight distribution (Patent Document 4). Use an organic compound containing an S═O bond such as sulfone and an organosilicon compound as an internal donor. As an external donor, an amorphous component is reduced using an oxygen-containing organic compound combined with an organosilicon compound (Patent Document 6). A lot of improvement proposals from many viewpoints have been made and many results have been given.

  However, as the inventors know, improvements in various properties such as stereoregularity and high crystallization of the α-olefin polymer produced in any of these catalyst systems are still not sufficient. Various properties are still required to be improved in each application field. For example, in the automotive parts material field, high rigidity and high density are required as molded products, and particularly high crystallinity, that is, reduction of amorphous components dissolved in cold xylene. Further improvement is desired, and in the field of packaging materials, further improvement of stickiness is strongly demanded.

JP 58-138706 (Claims, page 2, lower left column) JP 7-145204 A (summary) JP-A-9-110924 (Summary) JP-A-9-241318 (Summary) JP 2001-114816 A (Abstract, paragraph 0003, paragraph 0022) JP 2002-265517 A (summary)

  In the state of the prior art described above in the field of polyolefin materials, the present invention further increases rigidity and density and further reduces amorphous components in order to meet the demand for further performance improvement from a wide range of applications. It is an object of the present invention to realize a catalyst capable of producing an α-olefin polymer with improved regularity or less sticky components and a method for producing such an α-olefin polymer.

  In order to solve the above problems, research and development on various catalyst components, a Ziegler system using a magnesium compound as a catalyst carrier and a solid catalyst component containing titanium and halogen as essential components and an organoaluminum compound As a catalyst, a polymerization catalyst has been found that uses a special organosilicon compound as an internal donor and a sulfonate ester as an external donor, and has an excellent molding processability and can produce an extremely high crystalline olefin polymer in a high yield. (Patent Document 3 of JP-A-9-110924) and a polymerization catalyst in which an amorphous component is further reduced and stereoregularity is improved by using a urea compound as an external donor. A patent application has been filed (Japanese Patent Application No. 2003-317597). In order to obtain a highly crystalline α-olefin polymer having a high stereoregularity and an extremely small amount of non-crystalline components in a high yield, the present inventors have been involved in solving the above-mentioned problems. In order to obtain an α-olefin with as little stickiness as possible in density, a new catalyst component was sought in order to develop a new catalyst. From the viewpoint of coordination to the catalytic active site and selective poisoning, As a result of investigating the catalyst component and conducting experimental studies, the combination of the organoaluminum compound and the specific sulfite ester compound with the solid catalyst component results in a highly crystalline material with extremely low amorphous components. The inventors have found that an α-olefin polymer can be obtained in a high yield, and have reached the present invention.

  The present invention is a newly created invention characterized by adopting a novel specific compound as a catalyst component of a Ziegler-based catalyst, in combination with an organoaluminum compound and an optional silicon compound or diether compound. As described later in paragraph 0062, a specific sulfite ester compound having the chemical structure of the following general formula [1] is used as an external donor, as described later in paragraph 0062. It is presumed that a highly crystalline α-olefin polymer with extremely few amorphous components can be obtained in high yield by the action of coordination and selective poisoning. It is possible to obtain an α-olefin having a high density and as little stickiness as possible.

［１］

[1]

(Here, R ¹ and R ² are an aliphatic hydrocarbon group having 1 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R ¹ and R ² May form a cyclic structure in which

In the above, the background and composition of the creation of the present invention has been described. However, the present invention is basically composed of the following [1] to [9] invention unit groups, and [1] and [2] The basic invention, which is less than that, embodies or embodies the basic invention.
[1] An α-olefin polymerization catalyst comprising the following component (A), component (B) and component (C).
Component (A): Solid catalyst component containing magnesium, titanium and halogen as essential components Component (B): Organoaluminum compound Component (C): Sulphite compound [2] The following component (A), component (B), component An α-olefin polymerization catalyst comprising (C) and component (D).
Component (A): Solid catalyst component containing magnesium, titanium and halogen as essential components Component (B): Organoaluminum compound component (C): Sulphite compound component (D): Silicon compound or compound having at least two ether bonds [3] The α-olefin polymerization catalyst according to [1] or [2], wherein the sulfite compound of component (C) is selected from compounds represented by the following general formula [1].

［１］

[1]

(Here, R ¹ and R ² are an aliphatic hydrocarbon group having 1 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R ¹ and R ² May form a cyclic structure in which
[4] R ¹ and R ² are sterically low-volume substituents comprising an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, or form a 5- to 7-membered cyclic structure. The catalyst for α-olefin polymerization according to [3].
[5] The α-olefin polymerization catalyst according to any one of [2] to [4], wherein the component (D) silicon compound is a silicon compound represented by the following formula:
R ³ R ⁴ _3-m Si (OR ⁵ ) _m
(Here, R ³ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group or heteroatom-containing hydrocarbon group, and R ⁴ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, heteroatom-containing. (Hydrocarbon group, halogen or hydrogen, R ⁵ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)
[6] The α-olefin polymerization catalyst according to any one of [2] to [4], wherein the compound having component (D) at least two ether bonds is an aliphatic diether or an aromatic diether.
[7] The α-olefin according to any one of [1] to [6], wherein the component (A) is a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components Polymerization catalyst.
[8] The component (A) is obtained by previously bringing a solid catalyst component containing magnesium, titanium and halogen into contact with an organoaluminum compound and an organosilicon compound, [1] to [7] ] The catalyst for alpha-olefin polymerization in any one of.
[9] Production of α-olefin polymer, wherein α-olefin is homopolymerized or two or more types are copolymerized using the α-olefin polymerization catalyst according to any one of [1] to [8] Method.

The α-olefin polymerization catalyst of the present invention has high catalytic activity and excellent yield during polymerization, and the α-olefin polymer polymerized by the α-olefin polymerization catalyst of the present invention is an amorphous component. It has extremely low stereoregularity, little generation of sticky components, high density, rigidity and heat resistance, and excellent mechanical properties.
Therefore, the α-olefin polymer according to the present invention is used as an industrial material such as automobile parts and household appliance parts that require high rigidity and high heat resistance, and further has low stickiness, so that it is suitable for applications such as packaging materials. Can also be suitably used.

  The present invention generally described in paragraphs 0007 to 0014 will be specifically described in detail below as an embodiment of the invention.

1. α-Olefin Polymerization Catalyst The catalyst in the present invention comprises a component (A), a component (B), a specific component (C), and an optional component (D). Here, “consisting of” does not mean that the component is only the listed component (ie, component (A), component (B), component (C) and component (D)). It is included that other components coexist for the purpose of the present invention.
The catalyst of the present invention comprises a component (A): a solid catalyst component containing magnesium, titanium and halogen as essential components, component (B): an organoaluminum compound, component (C): a sulfite compound, and component (D): An α-olefin polymerization catalyst comprising a silicon compound or a compound having at least two ether bonds. Preferably, the component (A) may contain a component (E) electron donor.

2. Ingredient (A)
(1) Solid catalyst component The component (A) used in the present invention is a solid component for stereoregular polymerization of α-olefins containing titanium, magnesium and halogen as essential components. Here, “containing as an essential component” means that in addition to the listed three components, other elements in accordance with the object of the present invention may be included, and each of these elements is included in the object of the present invention. It may be present as any compound along the line, and these elements may be present as bonded to each other. In addition, each exemplary compound in the following enumerates representative compounds and is briefly described.

(1-1) Magnesium source As a magnesium compound used as a magnesium source in the present invention, magnesium dihalide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, alkylmagnesium halide, allyloxymagnesium, ants Examples thereof include loxymagnesium halide, metal magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like.
Magnesium dihalides Among them, dialkoxy magnesium, alkoxy magnesium halide _{Mg (OR) 2-n X} n ( where such, R represents a hydrocarbon group, preferably of 1 to 10 carbon atoms, X is Represents a halogen, and n is 0 ≦ n ≦ 2.) A magnesium compound is preferable, and magnesium dihalide is more preferable.

(1-2) Titanium source As a titanium compound serving as a titanium source, a general formula Ti (OR) _{4 -p} X _p (where R is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X represents halogen, and p is 0 ≦ p ≦ 4.) Of these, tetravalent titanium compounds are preferable, and tetravalent titanium compounds containing halogen are more preferable.
Specific _{examples, TiCl 4, TiBr 4, Ti} (OC 2 H 5) Cl 3, Ti (OC 2 H 5) 2 Cl 2, Ti (OC 2 H 5) 3 Cl, Ti (O-nC 4 H 9 ) ₂ Cl ₂ , Ti (O—nC ₄ H ₉ ) ₃ Cl, Ti (OC ₆ H ₅ ) Cl ₃ , Ti (O—iC ₄ H ₉ ) ₂ Cl ₂ , Ti (O—nC ₄ H ₉ ) ₄ , Ti (O—iC ₄ H ₉ ) ₄ , Ti (O—nC ₆ H ₁₃ ) ₄ , Ti (O—nC ₈ H ₁₇ ) _{4 and the} like.

In addition, a molecular compound obtained by reacting TiX ′ ₄ (where X ′ represents halogen) with an electron donor described later can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.
TiCl ₃ (including TiCl ₄ reduced with hydrogen, aluminum metal reduced or organometallic compound reduced), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , dicyclo Use of titanium compounds such as pentadienyl titanium dichloride and cyclopentadienyl titanium trichloride is also possible.
Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are preferable, and TiCl ₄ and Ti (OC ₄ H ₉ ) ₄ are more preferable.

(1-3) Halogen Halogen is usually supplied from the aforementioned halogen compounds of magnesium and / or titanium, but other halogen sources such as AlCl ₃ , AlBr ₃ , AlI ₃ , EtAlCl ₂ , Et ₂ Aluminum halides such as AlCl, boron halides such as BCl ₃ , BBr ₃ and BI ₃ , silicon halides such as SiCl ₄ and MeSiCl ₃ , phosphorus halides such as PCl ₃ and PCl ₅ , WCl _{6 and the} like It is also possible to supply from known halogenating agents such as tungsten halides of molybdenum and molybdenum halides such as MoCl ₅ . The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

(1-4) Electron donor Furthermore, when manufacturing the solid component of this component (A), a component (E) electron donor can also be used as an internal donor as an arbitrary component.
Component (E) electron donors that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acids Examples thereof include oxygen-containing electron donors such as anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, sulfur-containing electron donors such as sulfonate esters, and the like.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, butanol, hexanol, octanol, phenylethyl alcohol, isopropylbenzyl alcohol, ethylene glycol, propylene glycol, and 1,3-propanediol. Kind.

  (B) Phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, isopropylphenol, nonylphenol, naphthol, 1,1′-bi-2-naphthol.

  (C) C3-C15 ketones such as acetone, methyl ethyl ketone, benzophenone, acetylacetone and the like.

  (D) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, and benzaldehyde.

  (E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, methyl chloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate , Ethyl benzoate, propyl benzoate, butyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone , Organic acid monoesters such as α-valerolactone, or diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, di-n-propyl 2-methylmalonate, di-n-propyl 2-cyclopropylmalonate Propyl, 2,2-dimethylmalo Di-n-propyl diacid, di-n-propyl 2,2-diethylmalonate, di-n-propyl 2-isopropylmalonate, diethyl succinate, dibutyl 2,3-diethyl-succinate, 2,3- Diisopropyl-dibutyl succinate, dibutyl tartrate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane-1,2-dicarboxylic acid-di-n-hexyl, C2-C20 organic acid esters of organic acid polyvalent esters such as diethyl 1,1-cyclobutanedicarboxylate.

  (F) Silicate esters such as ethyl silicate and butyl silicate, or inorganic acid esters such as ethylene carbonate.

  (G) Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl chloride.

  (H) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2'-dimethoxy-1,1'-binaphthalene, 1,3-dimethoxypropane, 2,2-dimethyl- 1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2- Isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2 , 2-Diisopentyl-1,3-dimethoxypropane, 2-iso Pentyl-2-isobutyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3- Dimethoxypropane, 1,3-diethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 1,3-dipropoxypropane, 1,3-dibutoxypropane, 2,2-diisopropyl-1,3 -C2-C20 ethers such as diethoxypropane, 1,2,3-trimethoxypropane, 1,1,1-trimethoxymethyl-ethane.

  (Li) Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide.

  (Nu) Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine.

  (L) Nitriles such as acetonitrile, benzonitrile and tolunitrile.

  (V) 2- (Ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, 3-ethoxy-2 Alkoxy ester compounds such as ethyl s-butylpropionate and ethyl 3-ethoxy-2-t-butylpropionate;

  (Wa) Ketoester compounds such as ethyl 2-benzoylbenzoate, ethyl 2- (4′-methylbenzoyl) benzoate, and ethyl 2-benzoyl-4,5-dimethylbenzoate.

  (F) Sulfonic acids such as methyl benzenesulfonate, ethyl benzenesulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate Examples include esters.

  Two or more kinds of these electron donors can be used. Among these, organic acid ester compounds, acid halide compounds and ether compounds are preferred, and phthalic acid diester compounds, phthalic dihalide compounds, succinic acid diester compounds, tartaric acid esters, and aliphatic or aromatic compounds are particularly preferred. It is a diether compound.

(1-5) Optional component The solid catalyst component includes the same component (organoaluminum compound) as the component (B) described later in paragraphs 0053 to 0055 as the optional component (a), and the components described later in paragraphs 0064 to 0074 ( D), preferably the same component as the silicon compound in component (D) may be used as optional component (b), and these may be contacted in advance.
In the preliminary contact step, an optional component can be additionally coexisted. Examples of such optional components include (c) vinylsilane compounds and (d) organometallic compounds.

(C) As the vinylsilane compound, at least one hydrogen atom in monosilane (SiH ₄ ) is replaced with a vinyl group (CH ₂ ═CH—), and some of the remaining hydrogen atoms are halogen (preferably Cl), an alkyl group (preferably a hydrocarbon group having 1 to 12 carbon atoms), an aryl group (preferably a phenyl group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), and the like. It is shown.

More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5) 2, CH 2 = CH-Si (n-C 4 H 9) 3, CH 2 = CH-Si (C 6 H _{5) 3, CH 2 = CH} -Si (CH 3) (C 6 H 5) 2, _{H 2 = CH-Si (CH} 3) 2 (C 6 H 5), CH 2 = CH-Si (CH 3) 2 (C 6 H 4 CH 3), (CH 2 = CH) (CH 3) 2 Si _{-O-Si (CH 3) 2} (CH = CH 2), (CH 2 = CH) 2 SiH 2, (CH 2 = CH) 2 SiCl 2, (CH 2 = CH) 2 Si (CH 3) 2, _{(CH 2 = CH) 2 Si} (C 6 H 5) 2 and the like can be exemplified.

(D) The organometallic compound used in the present invention is an organometallic compound of a periodic table (short-period type) Group I to Group III metal and has at least one organic group-metal bond. The organic group in that case is typically a hydrocarbyl group having about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms. The remaining metal valence (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group is a hydrogen atom, a halogen atom, a hydrocarbyloxy group (the hydrocarbyl group has 1 to About 20 and preferably about 1 to 6), or the metal via oxygen atoms (specifically, —O—Al (CH ₃ ) — in the case of methylalumoxane) and the like.

  Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium, t-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium, butylmagnesium. There are organomagnesium compounds such as chloride and t-butylmagnesium bromide, and (c) organozinc compounds such as diethylzinc and dibutylzinc.

The additional optional components (c) and (d) can be used singly or in combination of two or more. At this time, a known halogenating agent such as a halogen compound of titanium such as TiCl ₄ , a halide of tungsten such as WCl ₆ or a halide of molybdenum such as MoCl ₅ may coexist. When these optional components are used, the effect of the present invention becomes greater.

  When the vinylsilane compound is used as an optional component, the amount used is preferably in the range of 0.001 to 1,000, preferably 0.01 to 100, as a molar ratio to the titanium component constituting the component (A). Is within the range. When using the organometallic compound as an optional component, the amount used is preferably in the range of 0.001 to 100, preferably in the range of 0.01 to 10 in terms of molar ratio with respect to the amount of the magnesium compound used. Is within.

(2) Production of Component (A) Component (A) is prepared by bringing each component constituting component (A) into contact with each other stepwise or temporarily, if necessary, in the middle and And / or finally by washing with an organic solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent.

(2-1) Contact of component Although the contact condition of each component which comprises a component (A) needs to implement in absence of oxygen, as long as the effect of this invention is recognized, it may be arbitrary things. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, and the like, and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes, and the like.

(2-2) Component Usage Amount The ratio of the amount of each component constituting the component (A) can be arbitrary as long as the effect of the present invention is recognized. Is preferred.
The amount of the titanium compound used is preferably in the range of 0.0001 to 1,000, and preferably in the range of 0.01 to 10 in terms of molar ratio with respect to the amount of magnesium compound used.
When a compound for this purpose is used as the halogen source, the amount used is 0.01 by mole relative to the amount of magnesium used, regardless of whether the titanium compound and / or magnesium compound contains halogen. The range is preferably in the range of ˜1,000, preferably in the range of 0.1 to 100.

(2-3) Production Component (A) is produced, for example, by the following production method using other components such as an electron donor, if necessary.
(A) A method in which a magnesium halide and, if necessary, an electron donor and a titanium-containing compound are contacted, or a titanium-containing compound and a silicon compound component are contacted.
(B) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and a magnesium halide, an electron donor and a titanium halogen-containing compound are brought into contact with each other, or a titanium halogen-containing compound and a silicon compound component are brought into contact with each other.
(C) A reaction product obtained by bringing a titanium halide compound and / or a silicon halogen compound into contact with a solid component obtained by bringing a magnesium halide into contact with a titanium tetraalkoxide and a specific polymer silicon compound component in an inert organic solvent. A method of bringing the silicon compound component into contact with each other after washing, or bringing them into contact with each other separately.
As this polymer silicon compound, those represented by the following formula are suitable.

(Here, R represents a hydrocarbon group having about 1 to 10 carbon atoms, and q represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.)
Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 , 9-pentamethylcyclopentasiloxane is preferred.
(D) A magnesium compound is dissolved with a titanium tetraalkoxide and / or an electron donor, and a titanium compound and / or a silicon compound component is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound, or Separate contact method.
(E) An organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then contacted with an electron donor as necessary, and then a titanium-containing compound is contacted, or a titanium-containing compound And a method of contacting the silicon compound component.
(F) A method in which an alkoxymagnesium compound is contacted with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor, and then a titanium compound and / or a silicon compound component are contacted or are contacted separately. .
(G) A method of bringing the solid components produced in (a) to (f) above into contact with an organoaluminum, an organosilicon compound, and, if necessary, a vinylsilane compound at room temperature.
Among these production methods, (a), (c), (d), (f) and (g) are preferable. Component (A) can be used in the middle and / or at the end of its production as an inert organic solvent, such as an aliphatic or aromatic hydrocarbon solvent (hexane, heptane, toluene, cyclohexane, etc.) or a halogenated hydrocarbon solvent (chloride-n). -Butyl, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

(3) Prepolymerization (3-1) Olefins As the component (A) used in the present invention, prepolymerization comprising bringing a vinyl group-containing compound such as an olefin, a diene compound, or styrene into contact for polymerization. It can also be used as a product that has undergone a process.
Specific examples of olefins used in the prepolymerization include those having about 2 to 20 carbon atoms, specifically ethylene, propylene, 1-butene, 3-methylbutene-1, 1-pentene, 1- Hexene, 4-methylpentene-1,1-octene, 1-decene, 1-undecene, 1-eicosene and the like. Specific examples of the diene compound include 1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, 1,3-heptadiene, cyclopentadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cycloheptadiene, 4-methyl -1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene p- divinylbenzene, m- divinylbenzene, and the like o- divinyl benzene. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene and the like.

(3-2) Polymerization conditions The quantitative relationship between the titanium component in the component (A) and the above-mentioned vinyl group-containing compound can be arbitrary as long as the effect of the present invention is recognized. Within the range is preferable. The prepolymerization amount of the vinyl group-containing compound is in the range of 0.001 to 100 grams, preferably 0.1 to 50 grams, more preferably 0.5 to 10 grams, per gram of the titanium solid component.
The reaction temperature during prepolymerization is -150 to 150 ° C, preferably 0 to 100 ° C. A polymerization temperature lower than the polymerization temperature at the time of “main polymerization”, that is, polymerization of α-olefin is preferable.
In general, the reaction is preferably carried out with stirring. At that time, an inert solvent such as hexane or heptane may be present. Moreover, prepolymerization can also be performed at the time of a contact of a component (A), a component (B), and a component (C).
Examples of methods for producing such component (A) include, for example, JP-A-57-63310, JP-A-58-83006, JP-A-60-23404, JP-A-63-3010, and JP-A-63-3010. Examples of methods for producing a solid catalyst component are described in JP-A-3-706, JP-A-4-218507, JP-A-6-336503, JP-A-8-333413, and the like.

3. Organoaluminum compound (component (B))
As the organoaluminum compound (component (B)) used in the present invention, R ⁶ _3-r AlX _r , R ⁷ _3-s Al (OR ⁸ ) _s (where R ⁶ and R ⁷ have 1 carbon atom) -20 hydrocarbon groups or hydrogen atoms, R ⁸ is a hydrocarbon group, X is a halogen, and r and s are 0 ≦ r <3 and 0 <s <3, respectively. Is.

Specifically, (i) trialkylaluminum such as (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, (b) diethylaluminum monochrome Aldehyde, diisobutylaluminum monochloride, alkylaluminum halide such as ethylaluminum sesquichloride, ethylaluminum dichloride, (c) alkylaluminum hydride such as diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, diethylaluminum phenoxide Examples thereof include alkyl aluminum alkoxide.
Further, as a compound similar to the above, an organoaluminum compound in which two or more aluminums are bonded through an oxygen atom or a nitrogen atom can also be used. Specifically, (e) (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) ₂ Al (C ₂ H ₅ ) ₂ , methylalumoxane , Isobutylalumoxane, methylisobutylalumoxane and the like.

These organoaluminum compounds (a) to (e) may be used in combination, or other organometallic compounds such as R2 _- tZn (OR ') _t (wherein R and R' may be the same or different. It is also a hydrocarbon group having 1 to 20 carbon atoms, and t is 0 ≦ t ≦ 2. For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride Combination use, combination use of triethylaluminum and diethylzinc, and the like can be mentioned.

  The ratio of the organoaluminum compound of component (B) to the titanium component in the solid catalyst component of component (A) is generally Al / Ti = 1 to 1,000 mol / mol, preferably Al / Ti = 10 to 500 mol / mol.

4). Sulphite compound (component (C))
(1) Compound The sulfite compound used in the present invention is preferably selected from compounds of the formula [1] below. (Here, R ¹ and R ² are an aliphatic hydrocarbon group having 1 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heteroatom-containing hydrocarbon group, and any R ¹ and A cyclic structure in which R ² is linked may be formed.)

［１］

[1]

When R ¹ and R ² are composed of an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, a structurally low-volume substitution such as an alkyl group or cycloalkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. It is preferably a group.
Specifically, methyl group, ethyl group, vinyl group, allyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, i-hexyl Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Among them, methyl group, ethyl group, and n-propyl group are preferable.
When R ¹ and R ² are composed of an aromatic hydrocarbon group, it is preferably a substituent such as an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms having no substituent. These substituents are preferred because they are considered to have the property that the S═O group is more easily coordinated due to distortion of the ring structure.
Specific examples include a phenyl group, a biphenyl group, an indenyl group, and a fluorenyl group, and a phenyl group, a biphenyl group, and an indenyl group are particularly preferable.
Heteroatoms that can be contained in R ¹ and R ² are nitrogen, oxygen, silicon, phosphorus, and sulfur, and nitrogen and oxygen are more preferable. Moreover, you may form the cyclic structure in which arbitrary R < ¹ > and R < ² > were connected, and it is preferable that R < ¹ > and R < ² > are saturated carbon hydrogen groups. In particular, it is desirable that R ¹ and R ² form a 5- to 7-membered cyclic structure.

Specifically, the following sulfite ester compounds can be exemplified.
Sulfite compounds such as dimethyl sulfite, diethyl sulfite, dipropyl sulfite, diisopropyl sulfite, dibutyl sulfite, dihexyl sulfite, diheptyl sulfite, dicyclopropyl sulfite, dicyclopentyl sulfite, dicyclohexyl sulfite, dicyclooctyl sulfite, diphenyl sulfite, glycol sulfite, etc. Can be mentioned. Two or more kinds of these sulfite compounds can be used.

  Among these sulfite ester compounds, dimethyl sulfite, diethyl sulfite, dipropyl sulfite, diisopropyl sulfite, dicyclopentyl sulfite, dicyclohexyl sulfite, diphenyl sulfite, and glycol sulfite are preferable, and dimethyl sulfite and diethyl sulfite are particularly preferable.

(2) Catalytic action of sulfite compounds These sulfite compounds are poisoned by the coordination of the S = O group to an active site that selectively produces an amorphous component by the electron-attracting effect of R—O. It is speculated that it can. Further, it is estimated that R ¹ and R ^{2 in the} vicinity of the S═O group are structurally small or exhibit an excellent effect by creating a structure in which the S═O group is more easily coordinated due to distortion of the ring structure. Is done.

(3) Usage and contact
The ratio of the sulfite ester compound of component (C) and the organoaluminum compound of component (B) should be in the range of 0.001-1 by molar ratio with respect to the amount of the organoaluminum compound used, preferably 0.005. Within the range of ~ 0.5.
The contact method of the component (A), the component (B), the component (C), and the component (D) is arbitrary, but in general, each component may be contacted sequentially or at a time. Good.

5). Silicon compound component or compound having at least two ether bonds (component (D))
Component (D) preferably used in the present invention is a silicon compound or a compound having at least two ether bonds.

(1) Silicon compound The silicon compound component is represented by the following formula.
R ³ R ⁴ _3-m Si (OR ⁵ ) _m
(Here, R ³ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group or heteroatom-containing hydrocarbon group, and R ⁴ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, heteroatom-containing. (Hydrocarbon group, halogen or hydrogen, R ⁵ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.)

When R ³ is an aliphatic hydrocarbon group, it is a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, i-propyl group, i-butyl group, t-butyl group. , I-hexyl group and the like are preferable, and among them, t-butyl group is more preferable. In addition, when R ³ is a cyclic aliphatic hydrocarbon group, the carbon number is usually 4 to 20, preferably 5 to 10, and preferred examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Of these, a cyclopentyl group and a cyclohexyl group are more preferred. Heteroatoms that R ³ can contain are nitrogen, oxygen, silicon, phosphorus, and sulfur, with nitrogen and oxygen being more preferred.

R ⁴ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a heteroatom-containing hydrocarbon group, halogen or hydrogen. More specifically, the halogen group such as hydrogen, chlorine, bromine and iodine, and the carbon number of the hydrocarbon group is usually 1 to 20, preferably 1 to 10; a methyl group, an ethyl group, an n-propyl group, Preferred examples include i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, i-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among them, methyl group, ethyl Group, n-propyl group, i-propyl group, t-butyl group, n-hexyl group, cyclopentyl group, and cyclohexyl group are more preferable.

R ⁵ is a hydrocarbon group, the carbon number is usually 1-20, preferably 1-10, more preferably 1-5, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, t-butyl group and the like are preferable, and methyl group and ethyl group are more preferable.

Specific examples of the silicon compound component that can be used in the present invention are as follows.
(CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H _{5) 2, (CH 3)} 3 CSi (C 2 H 5) (OCH 3) 2, (CH 3) 3 CSi (n-C 3 H 7) (OCH 3) 2, (CH 3) 3 CSi (n _{-C 6 H 13) (OCH 3} ) 2, (C 2 H 5) 3 CSi (CH 3) (OCH 3) 2, (CH 3) (C 2 H 5) CHSi (CH 3) (OCH 3) 2 , ((CH ₃ ) ₂ CHCH ₂ ) ₂ Si (OCH ₃ ) ₂ , ((CH ₃ ) ₃ C) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OCH ₃ ) _{3, (C 2 H 5)} (CH 3) 2 CSi (OC 2 H 5) _{, (CH 3) 3 CSi (} OC (CH 3) 3) (OCH 3) 2, ((CH 3) 2 CH) 2 Si (OC 2 H 5) 2, ((CH 3) 2 CHCH 2) (( _{CH 3) 2 CH) Si (} OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 Si (OC 2 H 5) 2, (C 5 H 9) ( _{CH 3) Si (OCH 3)} 2, (C 5 H 9) ((CH 3) 2 CHCH 2) Si (OCH 3) 2, (C 6 H 11) Si (CH 3) (OCH 3) 2, ( _{C 6 H 11) 2 Si (} OCH 3) 2, (C 6 H 11) ((CH 3) 2 CHCH 2) Si (OCH 3) 2, HC (CH 3) 2 C (CH 3) 2 Si (CH _{3) (OCH 3) 2,} (CH 3) 3 CSiH (OCH 3) 2 _{(CH 3) 3 CSiCl (OCH} 3) 2, (CH 3) 3 CSiF (OCH 3) 2

(CH ₃ ) ₃ CSi (OCH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (N (C _{2 H 5) 2) (OCH} 3) 2, (CH 3) 3 CSi (NC 5 H 10) (OCH 3) 2, (CH 3) 3 CSi (NC 9 H 16) (OCH 3) 2, (( _{CH 3) 2 HCO) 2 Si} (OCH 3) 2, ((CH 3) 3 CO) 2 Si (OCH 3) 2, (4-CH 3 -C 6 H 11 O) 2 Si (OCH 3) 2, (C ₁₀ H ₁₇ O) ₂ Si (OCH ₃ ) ₂ , ((C ₂ H ₅ ) ₂ N) ₂ Si (OCH ₃ ) ₂ , (C ₄ H ₈ N) ₂ Si (OCH ₃ ) ₂ , (C _{5 H 10 N) 2 Si (} OCH 3) 2, (C 9 H 16 N) Si _{(OCH 3) 2,} and the like.

Among these, (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OCH ₃ ) ₂ , (CH ₃ ) _{3 CSi (n-C 3 H} 7) (OCH 3) 2, (CH 3) 3 CSi (n-C 6 H 13) (OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) 2, _{(C 5 H 9) 2 Si} (OC 2 H 5) 2, and the like _{(C 6 H 11) Si (} CH 3) (OCH 3) 2, (C 6 H 11) 2 Si (OCH 3) 2 .

(2) Diether Compound The compound (D) having at least two ether bonds is selected from the same group as the diether compound suitably used as an electron donor for the solid catalyst component of the component (A). , May be the same or different.

  Specifically, 1,3-dimethoxypropane, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl- 1,3-dimethoxypropane, 1,3-diethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 1,3 Dipropoxypropane, 1,3-dibutoxypropane, 2,2-diisopropyl-1,3-diethoxypropane, 2,2′-dimethoxy-1,1′-binaphthalene, 1,2,3-trimethoxypropane, 1,1,1-trimethoxymethyl-ethane and the like.

(3) Amount used The ratio of the silicon compound of component (D) or the compound having at least two ether bonds to the organoaluminum compound component of component (B) is 0. It is preferably in the range of 01 to 10, and preferably in the range of 0.05 to 1.

6). α-Olefin Polymerization α-Olefin polymerization using the novel catalyst of the present invention is applied to slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization or gas phase polymerization using substantially no solvent. As a polymerization solvent in the case of slurry polymerization, hydrocarbon solvents such as pentane, hexane, heptane and cyclohexane are used.
The polymerization method employed may be any method such as continuous polymerization, batch polymerization or multistage polymerization.
The polymerization temperature is usually about 30 to 200 ° C., preferably 50 to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator.

7). α-Olefin Monomer Raw Material The α-olefin polymerized in the catalyst system of the present invention has a general formula R—CH═CH ₂ (wherein R is a hydrocarbon group having 1 to 20 carbon atoms and has a branched group. It may be expressed by:
Specifically, α-olefins such as propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. In addition to homopolymerization of these α-olefins, copolymerization with monomers (for example, ethylene, α-olefins, dienes, styrenes, etc.) copolymerizable with α-olefins can also be performed. These copolymerizable monomers can be used up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

8). α-Olefin Polymer The α-olefin polymer to be polymerized according to the present invention is characterized by having very few amorphous components, high stereoregularity, and good odor and hue.
In particular, the α-olefin polymer produced by bulk polymerization preferably has a cold xylene soluble content (CXS) as an amorphous component of 1% by weight or less, more preferably 0.1 to 1% by weight, and still more preferably. It can be realized at 0.2 to 0.7% by weight.
Here, CXS was obtained by completely dissolving a sample (about 5 g) in xylene (300 ml) at 140 ° C., then cooling to 23 ° C., leaving it to stand for 12 hours, filtering, and evaporating the filtrate using an evaporator. It is obtained by solidifying and drying under reduced pressure at 110 ° C. for 2 hours, and then allowing to cool to room temperature and measuring its weight.

Further, the α-olefin polymer produced by slurry polymerization preferably has an attack amount as an amorphous component of 1.2% by weight or less, more preferably 0.1 to 0.9% by weight, and still more preferably 0.8. 1 to 0.5% by weight can be realized.
Here, the amount of attack was determined by measuring the amount of polymer obtained by separating the obtained polymer slurry by filtration and drying the filtrate after completion of the polymerization in the α-olefin polymer produced by slurry polymerization. The ratio of the polymer amount dissolved in the liquid to the total polymer amount is calculated, and this is defined as the attack amount (% by weight).

The α-olefin polymer polymerized according to the present invention has a high density, high rigidity and heat resistance, and has excellent characteristics because it has very few amorphous components and high stereoregularity.
In addition, this α-olefin polymer is produced with a high yield, and in particular, industrial materials such as automobile parts and home appliance parts that require high rigidity and high heat resistance, or packaging materials because they are less sticky. It can use suitably for the use of.

  In the present invention, examples are described and explained in detail in contrast to comparative examples to demonstrate the excellence of the present invention and the significance and rationality of its construction. Below, the measuring method and apparatus of each physical-property value in this invention are described.

1) MFR
Apparatus: manufactured by Takara Co., Ltd. Melt indexer measurement method: Based on JIS-K6921, evaluation was performed under conditions of 230 ° C. and 21.18 N.
2) Polymer bulk density The bulk density of the powder sample was measured using an apparatus according to ASTM D1895-69.
3) Cold xylene solubles [CXS]
Measurement method: A sample (about 5 g) is completely dissolved once in 140 ° C. xylene (300 ml), then cooled to 23 ° C., left to stand for 12 hours, filtered, and the filtrate is evaporated to dryness using an evaporator. Then, after drying under reduced pressure at 110 ° C. for 2 hours, CXS was obtained by allowing to cool to room temperature and measuring its weight.
4) Attack amount In the α-olefin polymer produced by slurry polymerization, after the polymerization is completed, the obtained polymer slurry is separated by filtration, and the amount of polymer obtained by drying the filtrate is measured. The ratio of the polymer amount dissolved in the total polymer amount was calculated, and this was defined as the attack amount (% by weight).

Example-1
[Production of component (A)]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. The reaction was carried out at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Then, 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the solid component (A1) for producing the component (A) was thoroughly washed with n-heptane. The titanium content of this product was 2.6% by weight.
Further, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (t-C ₄ H ₉ ) Si (CH ₃ ) ( 1.2 ml of OCH ₃ ) _{2 and} 1.7 g of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

[Polypropylene polymerization]
A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then 550 mg of Al (C ₂ H ₅ ) ₃ as component (B). After introducing 53 mg of dimethyl sulfite and 5,000 ml of hydrogen as component (C) and then introducing 1,000 g of liquid propylene and adjusting the internal temperature to 75 ° C., 7 mg of component (A) prepared above was added. Injected to polymerize propylene. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization, and the resulting polymer was recovered and dried. As a result, 164.6 (g) of polymer was obtained. The obtained polymer had MFR = 24 (g / 10 min), polymer bulk density = 0.49 (g / cc), and CXS = 0.5 (wt%). The results are shown in Table 1.

Examples-2, 3
[Polypropylene polymerization]
Polymerization was carried out in the same manner as in Example 1 except that 7 mg of the component (A) produced in Example-1 was used as the component (A) and a predetermined amount of the compound shown in Table 1 was used as the component (C). The results are shown in Table 1.

Comparative Example-1
The procedure was the same as in Example 1 except that the component (C) dimethyl sulfite of Example 1 was not used. As a result, 308.2 (g) of polymer was obtained. The obtained polymer had MFR = 34 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 1.4 (wt%). The results are shown in Table 2.

Comparative Examples-2-4
[Polypropylene polymerization]
As component (A), the same polymerization as in Example 1 was carried out except that 7 mg of component (A) produced in Example-1 was used and a predetermined amount of the compound in Table 2 was used instead of component (C). did. The results are shown in Table 2.

Example-4
[Production of component (A)]
100 ml of dehydrated and deoxygenated toluene was introduced into a flask thoroughly purged with nitrogen, and then 10 g of Mg (OEt) ₂ was introduced into a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of di-n-butyl phthalate was introduced, and the temperature was further raised to 110 ° C. and reacted for 3 hours. After completion of the reaction, it was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 20 ml of TiCl ₄ and 100 ml of toluene were further introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid component (A1) for producing the component (A) was thoroughly washed with n-heptane. The titanium content of this product was 2.7% by weight.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (C ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ 1. 5 ml and 1.7 g of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

[Polypropylene polymerization]
The same procedure as in Example 1 was performed except that the above component was used as the component (A) and 53 mg of dimethyl sulfite was used as the component (C). As a result, 159.2 (g) of polymer was obtained. The obtained polymer had MFR = 10 (g / 10 min), polymer bulk density = 0.48 (g / cc), and CXS = 0.7 (wt%).

Example-5
[Production of component (A)]
100 ml of dehydrated and deoxygenated toluene was introduced into a flask thoroughly purged with nitrogen, and then 10 g of Mg (OEt) ₂ was introduced into a suspended state. Next, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of 2,2-diisopropyl-1,3-dimethoxypropane was introduced, and the temperature was further raised to 110 ° C. and reacted for 3 hours. After completion of the reaction, it was washed with toluene. Next, 20 ml of TiCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 20 ml of TiCl ₄ and 100 ml of toluene were further introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid component (A1) for producing the component (A) was thoroughly washed with n-heptane. The titanium content of this product was 2.7% by weight.
Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (C ₆ H ₁₁ ) CH ₃ Si (OCH ₃ ) ₂ 2 was introduced. 0.7 ml and 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

[Polypropylene polymerization]
The same procedure as in Example 1 was performed except that the above component was used as the component (A) and 67 mg of diethyl sulfite was used as the component (C). As a result, 110.6 (g) of polymer was obtained. The obtained polymer had MFR = 50 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 1.1 (wt%). The results are shown in Table 3.

Example-6
[Propylene block copolymer]
A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then 550 mg of Al (C ₂ H ₅ ) ₃ as component (B). After introducing 67 mg of diethyl sulfite and 10,000 ml of hydrogen as component (C) and then introducing 1,000 g of liquid propylene and adjusting the internal temperature to 75 ° C., component (A) of Example-1 was added. 7 mg was injected to polymerize propylene. After one hour, propylene and hydrogen were thoroughly purged to complete the first stage polymerization. The polymer yield in the first stage was 153.3 (g). 20 g was extracted under the flow of purified nitrogen.
Next, the temperature was raised to 80 ° C. while stirring, and after the temperature rise, propylene gas and ethylene gas were charged so that the total polymerization pressure became 2.0 MPa, and the second stage polymerization was started. Polymerization was carried out at 80 ° C. for 20 minutes while supplying a mixed gas of propylene and ethylene so that the total polymerization pressure was constant at 2.0 MPa. Here, the ratio of propylene / (propylene + ethylene) was an average of 45.3 mol%.
Thereafter, the mixed gas was purged to complete the polymerization. The polymer yield of the obtained propylene block copolymer is 158.2 (g), the content of the second stage polymer is 15 wt%, MFR = 31 (g / 10 min), polymer bulk density = 0.47 ( g / cc). Further, MFR of the polymer obtained in the first stage = 93 (g / 10 min), polymer bulk density = 0.47 (g / cc), CXS = 0.6 (wt%), density = 0.102 ( g / cc).

Example-7
[Polypropylene polymerization]
A stainless steel autoclave having an internal volume of 3.0 L having a stirring and temperature control device was heated and dried under vacuum, cooled to room temperature and substituted with propylene, and then 550 mg of Al (C ₂ H ₅ ) ₃ as component (B). 80 mg of (t-C ₄ H ₉ ) Si (CH ₃ ) (OCH ₃ ) ₂ as component (D), 53 mg of dimethyl sulfite and 5,000 ml of hydrogen as component (C), and then liquid propylene 1 After introducing 1,000 g and adjusting the internal temperature to 75 ° C., 7 mg of the solid component (A1) produced in Example-1 was injected to polymerize propylene. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization, and the resulting polymer was recovered and dried. As a result, 120.1 (g) of polymer was obtained. The obtained polymer had MFR = 8 (g / 10 min), polymer bulk density = 0.46 (g / cc), and CXS = 0.6 (wt%).

Example-8
Instead of (tC ₄ H ₉ ) Si (CH ₃ ) (OCH ₃ ) ₂ in component (D) of Example-7, 104 mg of 2,2-diisopropyl-1,3-dimethoxypropane was used, The same procedure as in Example 7 was performed except that 67 mg of diethyl sulfite was used instead of (C) dimethyl sulfite. As a result, 93.6 (g) of polymer was obtained. The obtained polymer had MFR = 20 (g / 10 min), polymer bulk density = 0.45 (g / cc), and CXS = 0.7 (wt%). The results are shown in Table 4.

Comparative Examples-5-7
[Polypropylene polymerization]
Polymerization was carried out in the same manner as in Example 7 except that a predetermined amount of the compound in Table 5 was used as the component (C) and component (D) in Example-7. The results are shown in Table 5.

Example-9
[Polypropylene polymerization]
The solid component (A1) produced in Example-4 was used as the component (A), 110 mg of (C ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ was used as the component (D), and 53 mg of dimethyl sulfite was used as the component (C). Except for this, the same procedure as in Example 7 was performed. As a result, 130.5 (g) of polymer was obtained. The obtained polymer had MFR = 20 (g / 10 min), polymer bulk density = 0.46 (g / cc), and CXS = 0.8 (wt%).

Example-10
[Polypropylene polymerization]
The solid component (A1) produced in Example-5 was used as the component (A), 90 mg of (C ₆ H ₁₁ ) CH ₃ Si (OCH ₃ ) ₂ was used as the component (D), and 67 mg of diethyl sulfite was used as the component (C). The procedure was the same as in Example 7 except that. As a result, 120.4 (g) of polymer was obtained. The obtained polymer had MFR = 48 (g / 10 min), polymer bulk density = 0.47 (g / cc), and CXS = 1.2 (wt%). The results are shown in Table 6.

Example-11
[Polypropylene polymerization]
A stainless steel autoclave with an internal volume of 1.5 L having a stirring and temperature control device was sufficiently replaced with propylene gas, and then 500 ml of fully dehydrated and deoxygenated n-heptane was added as component (B) with Al (C ₂ H ₅ ) 125 mg of ₃ ; 120 mg of dimethyl sulfite as component (C); 15 mg of component (A) prepared in Example-1; then 390 ml of hydrogen were introduced; the temperature was raised and the pressure was increased; polymerization pressure = 5 g / cm ² G Propylene was polymerized under the conditions of polymerization temperature = 75 ° C. and polymerization time = 2 hours. After the polymerization was completed, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 150.4 g of polymer was obtained.
The low stereoregular attack polymer dissolved in the filtrate was 0.2% by weight. Moreover, the obtained polymer was MFR = 10 (g / 10min) and polymer bulk density = 0.41 (g / cc).

Comparative Example-8
The procedure was the same as Example 11 except that the component (C) dimethyl sulfite of Example 11 was not used. As a result, 180.5 (g) of polymer was obtained. The low stereoregular attack polymer dissolved in the filtrate was 0.4% by weight. Moreover, the obtained polymer was MFR = 12 (g / 10min) and polymer bulk density = 0.42 (g / cc). The results are shown in Table 7.

[Consideration of results of Examples and Comparative Examples]
By comparatively examining each of the above Examples-1 to 11 and Comparative Examples-1 to 8, in the present invention, the bulk density, cold xylene soluble content (CXS), the amount of attack, etc. are compared with the comparative examples over the whole. It is clear that excellent results have been obtained, and it is particularly remarkable that there are few amorphous components.
Specifically, in Comparative Examples 1 to 3 in which the component (C) is not used, only the yield is superior to that of Examples 1 to 3, but the cold xylene solubles (CXS) is very poor. In Comparative Example 4 where the component (C) is not of the present invention, the yield is very poor and the cold xylene solubles (CXS) is also inferior. Similarly, even in Comparative Examples 5 to 7 where the component (C) is not used or the component (C) is not of the present invention, the physical properties of the cold xylene solubles (CXS) are particularly deteriorated. bad. Moreover, in the comparative example 8 which does not use a component (C), the cold xylene soluble content (CXS) is inferior, and the attack amount is a bad result.

It is a flowchart figure for clarification of the understanding about the catalyst structure of this invention.

Claims (9)

An α-olefin polymerization catalyst comprising the following component (A), component (B) and component (C).
Component (A): Solid catalyst component containing magnesium, titanium and halogen as essential components Component (B): Organoaluminum compound Component (C): Sulphite compound An α-olefin polymerization catalyst comprising the following component (A), component (B), component (C) and component (D).
Component (A): Solid catalyst component containing magnesium, titanium and halogen as essential components Component (B): Organoaluminum compound component (C): Sulphite compound component (D): Silicon compound or compound having at least two ether bonds The catalyst for α-olefin polymerization according to claim 1 or 2, wherein the sulfite compound of component (C) is selected from compounds represented by the following general formula [1].

[1]
(Here, R ¹ and R ² are an aliphatic hydrocarbon group having 1 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroatom-containing hydrocarbon group, and R ¹ and R ² May form a cyclic structure in which R ¹ and R ² are sterically low-volume substituents consisting of an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, or form a 5- to 7-membered ring structure, Item 4. The α-olefin polymerization catalyst according to Item 3. The catalyst for α-olefin polymerization according to any one of claims 2 to 4, wherein the component (D) silicon compound is a silicon compound represented by the following formula.
R ³ R ⁴ _3-m Si (OR ⁵ ) _m
(Here, R ³ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group or heteroatom-containing hydrocarbon group, and R ⁴ is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, heteroatom-containing. (Hydrocarbon group, halogen or hydrogen, R ⁵ is a hydrocarbon group, and m represents 1 ≦ m ≦ 3.) The compound for component (D) having at least two ether bonds is an aliphatic diether or an aromatic diether, and the catalyst for α-olefin polymerization according to any one of claims 2 to 4. The α-olefin according to any one of claims 1 to 6, wherein the component (A) is a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components. Polymerization catalyst. The component (A) is obtained by previously contacting an organoaluminum compound and an organosilicon compound with a solid catalyst component containing magnesium, titanium and halogen as essential components. An α-olefin polymerization catalyst as described above. Production of an α-olefin polymer, wherein the α-olefin polymerization catalyst according to any one of claims 1 to 8 is used to homopolymerize or copolymerize two or more α-olefins. Method.

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