JP2007204613A - CATALYST FOR alpha-OLEFIN POLYMERIZATION AND METHOD FOR PRODUCING alpha-OLEFIN POLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for production of an α-olefin polymer having high fluidity and high melt tension during melting, excellent in moldability and processability, exhibiting strain-curing property and capable of increasing closed cell ratio thereby when carrying out extrusion foam molding and capable of providing a molded article excellent in uniformity of wall thickness when carrying out large blow molding and to provide a method for producing the α-olefin polymer. <P>SOLUTION: A ziegler solid catalyst component (A) comprises (A1) a solid catalyst component obtained by bringing (i) a raw material solid component containing titanium, magnesium and a halogen into contact with (ii) an organosilicon compound component containing two or more Si-OR<SP>1</SP>bonds (R<SP>1</SP>is a 1-8C hydrocarbon group), (iii) a vinylsilane compound component, and (iv) an organometallic compound of the group I to III metal of the periodic table, and (a) a high molecular weight polyolefin having 15-100 dl/g intrinsic viscosity [ηa] and contained in an amount of 50-25,000 g based on 1 g titanium component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer using the catalyst. Specifically, the present invention has characteristics such as high fluidity and high melt tension at the time of melting, excellent molding processability, and exhibits strain-hardening properties. The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer, which can provide a molded product having excellent thickness uniformity during blow molding. When the α-olefin is polymerized using the solid catalyst component according to the present invention, a polymer can be produced with high activity.

  Since α-olefin polymers such as polypropylene are useful in balance with their excellent physical properties and economy, they are widely used for food containers, vacuum-formed products such as trays, and extruded products such as films and sheets. . However, the melt tension at the time of melting is poor, the moldability such as extrusion foaming is poor, and improvement of melt viscoelasticity such as melt tension and strain curability is desired. Thus, various methods for improving the melt viscoelasticity of α-olefin polymers have been proposed.

  As a method for increasing the melt tension of an α-olefin polymer, a method of obtaining a polypropylene having a long chain branch by reacting a low temperature decomposition type peroxide with polypropylene has been proposed (see Patent Document 1). However, the polypropylene obtained by this method has problems such as insufficient improvement in melt tension, food sanitation due to peroxide odor, undecomposed peroxide residue or decomposition residue.

  In addition, a method of increasing the melt tension by reacting a specific organic peroxide with polypropylene in an inert gas atmosphere and then melt-kneading has been proposed (see Patent Document 2). Since special treatment is required, there is a problem in the productivity of materials, and there are problems such as deterioration of material quality due to peroxide over time.

  Further, as a method for increasing the melt tension of the α-olefin polymer without performing the modification treatment with the peroxide as described above, a composition containing polyethylene or polypropylene having different intrinsic viscosities or molecular weights, and such a composition A method for producing a product by multistage polymerization has been proposed.

  For example, there is a polyethylene polymerization method in which ultrahigh molecular weight polyethylene having an intrinsic viscosity of 20 dl / g or more is polymerized by 0.05 to less than 1% by weight using a highly active titanium / vanadium solid catalyst component (patent) Reference 3). However, since this method incorporates a high molecular weight polymer in the main polymerization, it is difficult to control the amount of the polymer in a minute amount, and there is a concern that a stable melt tension cannot be obtained.

  Moreover, although the polymerization method of the polypropylene which polymerizes 10 to 50 weight% of high molecular weight polypropylenes with a weight average molecular weight of 500,000 to 10,000,000 by a multistage polymerization method is disclosed (see Patent Document 4), the amount of high molecular weight components However, although the melt tension is improved, the strain hardening required at the time of extrusion foaming is insufficient, and a sufficient closed cell ratio cannot be obtained.

  The inventors of the present invention have disclosed a method for producing an α-olefin polymer having characteristics such as high melt tension and strain-hardening properties at the time of melting and suitable for extrusion foaming and the like, and an ultrahigh molecular weight olefin during prepolymerization as a polymerization catalyst. A method for producing an α-olefin polymer with little fish eye by producing a polymer and finely dispersing ultrahigh molecular weight components by main polymerization using the catalyst has been proposed (see Patent Document 5). Unlike conventional methods, this method generates ultra-high molecular weight components in the pre-polymerization stage, so there is no problem of controlling the amount of trace components, and there is no decrease in productivity. This is an industrially very useful method that can be manufactured at almost the same cost.

On the other hand, the present inventors previously treated the Ziegler-type solid catalyst component containing titanium, magnesium and halogen as essential components with an organosilicon compound, a vinylsilane compound, and an organoaluminum compound in advance to obtain the original Ziegler-type solid. A method for producing an olefin polymer that greatly improves the polymerization activity of the catalyst component and has excellent stereoregularity has been proposed (see Patent Document 6).
JP-A-2-298536 JP-A-6-157666 Japanese Patent Publication No. 5-79683 JP 2001-335666 A JP-A-11-106416 JP-A-3-234707

  The present invention has been made in view of the above known technique and its problems, and has characteristics such as high fluidity and high melt tension at the time of melting, excellent molding processability, and strain hardening. The present invention relates to an α-olefin polymer production catalyst capable of increasing the closed cell ratio during foam molding and obtaining a molded product with excellent thickness uniformity during large blow molding and a method for producing the α-olefin polymer. It is. When the α-olefin is polymerized using the solid catalyst component according to the present invention, a polymer having high activity and excellent stereoregularity can be produced with less production of by-product polymers.

Best Mode for Realizing the Invention

  As a result of intensive investigations, the present inventors have found a method for greatly improving the catalytic activity of the polymerization catalyst capable of producing the α-olefin polymer having the high melt tension and strain hardening property previously proposed. It was.

  More specifically, α-olefin is prepolymerized with respect to the raw material solid component (i) containing titanium, magnesium and halogen as essential components, and a high molecular weight polyolefin having an intrinsic viscosity [ηa] of 15 to 100 dl / g is obtained. By containing, a catalyst capable of producing an α-olefin polymer having high melt viscoelasticity is obtained. At this time, in an arbitrary production process for converting the raw material solid component (i) into a Ziegler-type solid catalyst component (A), the organosilicon compound (ii), the vinylsilane compound (iii), the periodic table group 1-3 metal By contact-treating with the organometallic compound (iv), the catalytic activity is remarkably improved as compared with the catalyst not subjected to the contact treatment, and the melt tension and strain-hardening property of the α-olefin polymer obtained by the catalyst are as usual. We found that it was kept high.

That is, the gist of the present invention is that the solid catalyst component (A1) obtained by bringing the following components (i), (ii), (iii) and (iv) into contact with each other, and the intrinsic viscosity [ηa] is 15 The Ziegler type solid catalyst component (A) is characterized by containing 50 to 25,000 g of high molecular weight polyolefin (a) per gram of titanium component at ˜100 dl / g.
Component (i): Raw material solid component containing titanium, magnesium and halogen Component (ii): Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) .)
Component (iii): Vinylsilane compound Component (iv): Organometallic compound of Group 1-3 metal

Another gist of the present invention is that the solid catalyst component (A1) obtained by contacting the following components (i), (ii), (iii) and (iv) with the solid catalyst component ( A prepolymerization of an olefin at any stage in the production process of A1) produces a high molecular weight polyolefin (a) having an intrinsic viscosity [ηa] of 15 to 100 dl / g and 50 to 25,000 g per gram of titanium component. It exists in the Ziegler type solid catalyst component (A) characterized by comprising.
Component (i): Raw material solid component containing titanium, magnesium and halogen Component (ii): Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) .)
Component (iii): Vinylsilane compound Component (iv): Organometallic compound of Group 1-3 metal

  Another gist of the present invention is that the Ziegler-type solid catalyst wherein the high molecular weight polyolefin (a) is an ethylene homopolymer or an ethylene / α-olefin copolymer having an ethylene content of 50% by weight or more. In component (A).

  According to another aspect of the present invention, the Ziegler is characterized in that the prepolymerization is performed after completion of contact of all the components (i), (ii), (iii) and (iv). Type solid catalyst component (A).

  Another aspect of the present invention is that the prepolymerization is performed by first subjecting the component (i) to a prepolymerization treatment and then contacting the treated product with the components (ii), (iii) and (iv). The Ziegler-type solid catalyst component (A) is characterized by being carried out.

  Another gist of the present invention resides in the Ziegler-type solid catalyst component (A), wherein the prepolymerization is performed in a plurality of stages using different olefins.

  Another aspect of the present invention resides in an α-olefin polymerization catalyst comprising the Ziegler-type solid catalyst component (A) and the organoaluminum component (B).

  Another aspect of the present invention resides in a method for producing an α-olefin polymer, wherein the α-olefin polymerization catalyst is polymerized by contacting the α-olefin.

  In the present invention, the solid catalyst component (A1) obtained by contacting the components (i) to (iv) is prepolymerized with an olefin in an arbitrary production process, and the resulting high molecular weight polyolefin (a) has its intrinsic viscosity [ηa ] Is 15 to 100 dl / g, and the Ziegler type solid catalyst component (A) is contained in an amount of 50 to 25,000 g per 1 g of the titanium component, and the organoaluminum component (B) is combined with the Ziegler type solid catalyst component (A). As described above, the present invention relates to a method for producing an α-olefin polymer using the combined α-olefin polymerization catalyst. The accompanying drawings are block process diagrams showing the catalyst production process of the present invention. Hereinafter, it demonstrates sequentially according to this process.

<Component (i)>
Component (i) is a raw material solid component containing titanium, magnesium and halogen. These three elements (three components) of titanium (Ti) -magnesium (Mg) -halogen are contained as essential components. Here, “contained as an essential component” means that in addition to the listed three components, other suitable elements may be included, and each of these elements exists as an arbitrary desired compound. As well as the fact that these elements may exist as bonded to each other. The raw material solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45688, 54-3894, 54-31092, 54-39483, 54-94591, 54-118484, 54-131589, 55-75411 55-90510, 55-90511, 55-90511, 55-127405, 55-147507, 55-155003, 56-18609, 56-70005, 56-72001, 56-86905, 56-90807, 56-155206, 57-92007, 57-12003, 58-5309, 58-5310, 58 -5311, 58-8706, 58-27732, 58-32604, 58-32605, 58-67 03, 58-117206, 58-127708, 58-183708, 58-183709, 59-149905, 59-149906, 60-130607, 61-55104 61-204204, 62-508, 62-15209, 62-20507, 62-184005, 62-236805, 63-199207, 63-264607, 63-264608, JP-A-1-79203, 1-139601, 1-215806, 7-258328, 7-269125, 11-21309, each publication, etc. used.

  Moreover, the thing etc. which processed these with tungsten and a molybdenum compound are mentioned.

  Examples of the magnesium compound used as a magnesium source in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Of these, preferred are magnesium halide, dialkoxymagnesium and alkoxymagnesium halide.

The titanium compound serving as the titanium source is a general formula Ti (OR ⁹ ) _4-q X _q (where R ⁹ is a hydrocarbon group, preferably about 1 to 10 carbon atoms, and X is a halogen And q is 0 ≦ q ≦ 4)). Specific examples include 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—i—C _{3). H 7) Cl 3, Ti (} O-n-C 4 H 9) Cl 3, Ti (O-n-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (OC 2 H _{5) (O-n-C} 4 H 9) 2 Cl, Ti (O-n-C 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-i-C 4 H 9) ₂ Cl ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O— _{n-C 4 H 9) 4} , Ti (O-i-C 4 H 9) 4, Ti (O-n-C 6 H 13) 4, Ti (O-n-C 8 H 17) 4, Ti ( _{OCH 2 CH (C 2 H 5} ) C 4 H 9) 4 , and the like.

Further, a molecular compound obtained by reacting TiX ′ ₄ (where X ′ is a 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.

In addition, TiCl ₃ (including those obtained by reducing TiCl ₄ with hydrogen, aluminum metal, or organic metal compounds), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride and cyclopentadienyl titanium trichloride. Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are preferable.

The halogen is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but other halogen sources, for example, aluminum halides such as AlCl ₃ , boron halides such as BCl ₃ , SiCl It can also be supplied from known halogenating agents such as silicon halides such as ₄ , phosphorus halides such as PCl ₃ and PCl ₅ , tungsten halides such as WCl ₆ , and molybdenum halides such as MoCl ₅ . The halogen contained in the solid catalyst component (A1) may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  Examples of the electron donor (internal donor) that can be used for the production of the raw material solid component (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, Examples include oxygen-containing electron donors such as acid amides and acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonate esters. it can.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ) Phenols having 6 to 25 carbon atoms which may have alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones such as benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, Aldehydes of 2 to 15 carbon atoms such as naphthaldehyde,

(E) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate , Organic acid monoesters such as methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide Or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane C2-C20 organic acid esters of organic acid polyvalent esters such as -1,2-dicarboxylic acid-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate,

  (F) Carbon number of inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride 2-15 acid halides, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 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-dimethoxy Propane, 2-t-butyl-2- Til-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3- 2-20 carbon atoms such as dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane Ethers of

  (Li) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine , Nitriles such as (l) acetonitrile, benzonitrile, tolunitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy-2-phenylpropiyl Alkoxy ester compounds such as ethyl onate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate,

  (Wa) Ketoester compounds such as ethyl 2-benzoylbenzoate, ethyl 2- (4′-methylbenzoyl) benzoate, ethyl 2-benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, benzene Examples thereof include sulfonic acid esters such as ethyl sulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate.

  Two or more kinds of these electron donors can be used. Of these, organic acid ester compounds, acid halide compounds and ether compounds are preferred, and those particularly preferred are those selected from the group consisting of phthalic diester compounds and phthalic dihalide compounds.

  The solid catalyst component (A1) is produced, for example, by the following production method using other components as necessary.

  (A) A method of contacting a magnesium halide with an electron donor and a titanium-containing compound.

  (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 therewith.

  (C) Inert reaction products obtained by contacting a titanium halide compound and / or a silicon halogen compound and an electron donor with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound. A method of washing with an organic solvent. In addition, as a polymer silicon compound used here, what is shown by a following formula is suitable.

-[Si (H) (R ¹⁰ ) -O-] _X-

Here, R ¹⁰ is a hydrocarbon group having about 1 to ¹⁰ carbon atoms, and x 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 the titanium compound and the electron donor are brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. How to contact.

  (E) An organomagnesium compound such as a Grignard reagent is allowed to act on a halogenating agent, a reducing agent, etc., and then contacted with an electron donor as necessary, and then a titanium compound and an electron donor are contacted. , How to contact each one separately.

  (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, or each is contacted separately. Among these production methods, (a), (c), (d) and (f) are preferable.

<Component (ii)>
The component (ii) used to produce the solid catalyst component (A1) of the present invention is an organosilicon compound containing two or more Si—OR ¹ bonds (wherein R ¹ is a carbon atom having 1 to 8 carbon atoms) Hydrogen group).

In the present invention, the bonding residue other than the —OR ¹ group bonded to the silicon atom is selected from hydrogen, halogen, a hydrocarbon group (eg, alkyl group, cycloalkyl group, aryl group, etc.), a siloxy group, and the like. It is usual to use one having a binding residue.

  Preferred organosilicon compounds in the present invention are those having at least one hydrocarbon group, more preferably a carbon atom adjacent to the silicon atom, that is, the α-position hydrocarbon atom is a secondary or tertiary carbon atom. It has a C3-C20 branched chain hydrocarbon group.

Specific examples of the organosilicon compound of component (ii) include (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, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH _{3) 2, (C 2 H} 5) (CH 3) 2 CSi (CH 3) (OC 2 H 5) 2, (CH 3) 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H _Five ) ₃ , (CH ₃ ) (C ₂ H ₅ ) CHSi (OCH ₃ ) ₃ , (CH ₃ ) ₂ CH (CH ₃ ) ₂ CSi (CH ₃ ) (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 ) ₃ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CH) ₂ Si (OC ₂ H ₅ ) 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 CHC _{2) Si (OCH 3) 2} , ((CH 3) 2 CHCH 2) ((C 2 H 5) (CH 3) CH) Si (OCH 3) 2, ((CH 3) 2 CHCH 2) ((CH _{3) 2 CH) Si (OC} 5 H 11) 2, HC (CH 3) 2 C (CH 3) 2 Si (CH 3) (OCH 3) 2, HC (CH 3) 2 C (CH 3) 2 Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OCH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) _{2 and the} like.

Among these, preferred are (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 ₅ H ₉ ) ₂ Si (OCH ₃ ) ₂ , (C ₅ H ₉ ) ₂ Si (OC ₂ H ₅₎ ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) _{2 and the} like.

<Ingredient (iii)>
Component (iii) is a vinyl silane compound. 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), It shows a structure substituted with 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), or the like. is there.

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), (CH 2 = CH) 2 -SiH 2, (CH 2 = CH) 2 -SiH (CH 3), (CH _{2 = CH) 2 -SiH (CH} 3), (CH 2 = CH) 2 -Si (CH 3) 2, (CH 2 = CH) 2 -SiCl 2, (CH 2 = CH) _{2 -SiCl (CH 3), (} CH 2 = CH) 2 -SiH (Cl), (CH 2 = CH) 2 -Si (C 2 H 5) 2, (CH 2 = CH) 2 -SiCl (C 2 _{H 5), (CH 2 =} CH) 2 -Si (CH 3) (C 2 H 5), (CH 2 = CH) 3 -SiH, (CH 2 = CH) 3 -Si (CH 3), (CH _{2 = CH) 3 -SiCl, (} CH 2 = CH) 3 -Si (C 2 H 5), can be exemplified (CH ₂ = CH) ₄ -Si like. Of _{these, CH 2 = CH-Si (} CH 3) 3, (CH 2 = CH) 2 -Si (CH 3) 2 is preferred.

<Component (iv)>
Component (iv) is an organometallic compound belonging to Groups 1-3 of the periodic table. Since it is an organometallic compound, this compound has at least one organic group / metal bond. The organic group in that case is typically a hydrocarbon group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms. Typical metals for this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining 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 the hydrogen atom, halogen atom, hydrocarbon group (the hydrocarbon group is the number of carbon atoms) About 1 to 10, preferably about 1 to 6, or the metal via a carbon atom (specifically, —O—Al (CH ₃ ) — of methylalumoxane) and others.

  Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tert-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium and butylmagnesium. Organic magnesium compounds such as chloride and tert-butylmagnesium bromide, (c) Organic zinc compounds such as diethylzinc and dibutylzinc, (d) Trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n -Octyl aluminum, tri-n-decyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride Diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, and organic aluminum compounds such as methylaluminoxane. Among these, an organoaluminum compound is particularly preferable.

<Production of solid catalyst component (A1)>
In the solid catalyst component (A1), the components (i) to (iv) constituting the component (A1) and optional components used as necessary are brought into contact with each other step by step or temporarily. And / or finally by washing with an organic solvent. Specifically, (a): a method in which the component (i) and the component (iii) are contacted, then the component (ii) and the component (iv) are contacted, and finally washed (b): the component ( Method of contacting and washing component (iii) and component (iv) after contacting i) and component (ii), (c): contacting component (i), (ii), and (iii) simultaneously Later, a method of bringing component (iv) into contact and washing is employed.

  Solvents used for solvent cleaning include inert organic solvents, such as aliphatic or aromatic hydrocarbon solvents (eg, hexane, heptane, toluene, cyclohexane, etc.), or halogenated hydrocarbon solvents (eg, n-butyl chloride). 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

  Although the contact conditions of each component constituting the solid catalyst component (A1) need to be carried out in the absence of oxygen, they can be arbitrary as long as the effect of the present invention is recognized. 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.

  The amount ratio of each component used to constitute the solid catalyst component (A1) may be arbitrary as long as the effect of the present invention is recognized, but generally it is preferably within the following range. The usage-amount of the titanium compound of a component (i) is 0.0001-1000 by the molar ratio (Ti / Mg) with respect to the usage-amount of the magnesium compound to be used, Preferably it is 0.01-10. When a compound therefor 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. -1000 is good, preferably 0.1-100. The use amount of the electron donor is 0.001 to 10 in molar ratio (halogen / Mg) to the use amount of the magnesium compound, preferably 0.01 to 5.

  The quantity ratio of component (i) to component (ii) is 0.01 to 1000, preferably 0.1 in terms of the atomic ratio of silicon of component (ii) to silicon component constituting component (i) (silicon / titanium). ~ 100. The quantity ratio of component (iii) to component (i) is 0.01 to 1000, preferably 0 in terms of the atomic ratio (silicon / titanium) of silicon atoms in component (iii) to titanium atoms in component (i). .01-300. The amount ratio of component (iii) to component (i) is 0.01 to 1000, preferably 0.1 to 100, in terms of metal atomic ratio of the organometallic compound (metal / titanium). The amount of the organometallic compound of component (iv) used is 0.1 to 100, preferably 1 to 50 in terms of the atomic ratio of metal to the titanium component constituting component (i) (metal atom / titanium). In the middle and / or at the end of the production of the solid catalyst component (A1), in addition to the solvent washing, a washing step with an inert organic solvent similar to that used in the solvent washing may be added. it can.

<Production of Ziegler-type solid catalyst component (A)>
The Ziegler-type solid catalyst component (A) can be obtained by performing a “preliminary polymerization treatment” step in an arbitrary process when the above-described solid catalyst component (A1) is produced. Specifically, the solid catalyst component (A1) obtained by completing the contact of all components (a): components (i), (ii), (iii) and (iv) is subjected to a prepolymerization treatment. Method for obtaining component (A), (b): The component (i) constituting the solid catalyst component (A1) is subjected to a prepolymerization treatment, and then the components (ii), (iii) and (iv) are contacted Method for obtaining component (A) (c): After contacting components (i) and (iv) constituting solid catalyst component (A1), pre-polymerization is performed, and then component (ii) (iii) is contact treated Thus, a method of obtaining the component (A) is employed.

  In the final Ziegler-type solid catalyst component (A), the high molecular weight polyolefin (a) produced as a result of the prepolymerization treatment has an intrinsic viscosity [ηa] measured with tetralin at 135 ° C. of 15 to 100 dl / g. The titanium component is contained in an amount of 50 to 25,000 g per 1 g.

  The intrinsic viscosity [ηa] of the high molecular weight polyolefin (a) is 15 to 100 dl / g, preferably 17 to 50 dl / g, and more preferably 20 to 40 dl / g. If it is less than the lower limit, the melt tension of the α-olefin polymer produced using this catalyst is lowered, which is inconvenient. Even if the upper limit value is exceeded, there is no particular problem, and the α-olefin polymer produced using this catalyst is rather convenient because the melt tension becomes high, but it is difficult to produce the α-olefin polymer because it is difficult to produce.

  The amount of the high molecular weight polyolefin (a) is 50 to 25,000 g per 1 g of the titanium component in the Ziegler-type solid catalyst component (A), preferably 1,000 to 15,000 g, more preferably 2,500 to 10,000 g. If it is less than the lower limit, the amount of the high-molecular-weight olefin (a) in the α-olefin polymer produced using this catalyst is decreased, which is disadvantageous in that the melt tension is lowered. If the upper limit is exceeded, the time for the prepolymerization process becomes too long, which is disadvantageous for industrialization. Except for this point, the melt tension in the α-olefin polymer produced using this catalyst becomes high, which is rather convenient. It is.

  The high molecular weight polyolefin (a) is an olefin polymer having 2 to 12 carbon atoms, preferably an olefin polymer having 50% by weight or more of ethylene or propylene polymerized units, more preferably 90% by weight of polymerized units of ethylene. The ethylene / α-olefin polymer is most preferably a polyethylene homopolymer containing only ethylene.

  The prepolymerization is performed by so-called slurry polymerization using a solvent. Examples of the solvent include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, isooctane, decane, and dodecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aromatics such as toluene, xylene, and ethylbenzene. It is possible to use an aromatic solvent, an inert solvent such as a gasoline fraction or a hydrogenated diesel oil fraction, and the olefin itself.

  The reactor for the preliminary polymerization is not particularly limited in shape and structure, and examples thereof include a tank with a stirrer generally used in slurry polymerization and a tube reactor.

  In the prepolymerization, the cocatalyst (B1) is used to activate the solid catalyst component (A1). As the promoter (B1), trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl Examples include organoaluminum compounds such as aluminum sesquichloride, ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, and methylaluminoxane, depending on the type of component (i), prepolymerization conditions, etc. However, triethylaluminum and triisobutylaluminum, which have high reactivity during preliminary polymerization, are preferred.

  The amount of the organoaluminum compound as the cocatalyst (B1) is 0.05 to 10, preferably 0.5 to 3 in terms of molar ratio (Al / Ti) with respect to the titanium component of the solid catalyst component (A1). If it is less than the lower limit, the reactivity during prepolymerization is extremely lowered, which is inconvenient. If the upper limit is exceeded, the intrinsic viscosity of the high molecular weight polyolefin (a) decreases due to the chain transfer reaction with organoaluminum, and the melt tension of the α-olefin polymer finally produced with this catalyst decreases, which is inconvenient. is there.

  The type and amount of the organoaluminum compound used as the cocatalyst (B1) can be selected within the above range, but a more preferable range is determined by the combination. For example, while triethylaluminum has high reactivity, chain transfer reaction due to triethylaluminum also increases, and therefore, a low molar ratio (Al / Ti) of 0.5 to 1 is more preferable in the above range. On the other hand, triisobutylaluminum is less reactive, but conversely the chain transfer reaction can be suppressed. Therefore, a relatively high molar ratio (Al / Ti) of 1 to 3 is more preferable in the above range.

  The prepolymerization treatment may be carried out in the presence of a donor, but it is disadvantageous because the intrinsic viscosity of the high molecular weight polyolefin (a) is lowered, and finally the melt tension of the α-olefin polymer produced with this catalyst is lowered. It is better not to use a donor.

  The prepolymerization treatment may be carried out in the presence of hydrogen, but it is disadvantageous because the intrinsic viscosity of the high molecular weight polyolefin (a) is lowered, and finally the melt tension of the α-olefin polymer produced with this catalyst is lowered. It is better not to use hydrogen.

  The prepolymerization temperature is −40 to 50 ° C., preferably −40 to 30 ° C., and more preferably about −40 to 20 ° C. If it is less than the lower limit, the prepolymerization reactivity is extremely lowered, and a large heat removal system is required even in industrialization, which is disadvantageous. When the upper limit is exceeded, chain transfer reaction tends to occur, the intrinsic viscosity of the high-molecular-weight polyolefin (a) is lowered, and the α-olefin polymer produced with this catalyst is finally lowered in melt tension, which is disadvantageous. .

  The prepolymerization pressure is 0.1 to 5 MPa, preferably 0.2 to 5 MPa, and more preferably 0.3 to 5 MPa. If it is less than the lower limit, the prepolymerization reactivity is lowered, a chain transfer reaction is likely to occur compared to the polymerization reaction, and the intrinsic viscosity of the high molecular weight polyolefin (a) is lowered, which is disadvantageous. When the upper limit is exceeded, there is no particular problem in terms of quality, but the reaction amount per hour increases, the solid catalyst particles are pulverized and the particle shape cannot be maintained, and even in the final α-olefin polymer, powder particles As a result, it is industrially inconvenient.

  The prepolymerization time is 1 minute to 24 hours, preferably 5 minutes to 18 hours, and more preferably 10 minutes to 12 hours. If it is less than the lower limit, the production amount of the high molecular weight polyolefin (a) is lowered, and finally the melt tension of the α-olefin polymer produced with this catalyst is lowered, which is inconvenient. It is inconvenient in terms of sex.

  The operating conditions, temperature, pressure, and time for the prepolymerization can be selected from the above ranges, but a more preferable range is determined by a combination thereof. For example, when the prepolymerization is performed at a low temperature such as a prepolymerization temperature of −40 to 10 ° C., the reactivity is lowered. Therefore, it is more preferable to set the pressure to a high pressure and the prepolymerization time to be long. On the other hand, since the reactivity is high at a relatively high temperature such as a prepolymerization temperature of 0 to 50 ° C., the pressure and time can be widely used from the viewpoint of reactivity.

  Further, the prepolymerization treatment is usually performed in one stage, but it may be performed in a plurality of stages. That is, before the pre-polymerization treatment, after the treatment, or before and after the treatment, an additional pre-polymerization treatment is performed to add an intrinsic viscosity [ηaa] lower than the intrinsic viscosity [ηa] of the high molecular weight polyolefin (a). Polyolefin (aa) may be produced. Although there are various significances in performing this additional prepolymerization, for example, by performing the additional prepolymerization in advance, the strength of the solid catalyst particles is improved and it becomes difficult to pulverize. In addition, depending on the type of catalyst, additional prepolymerization is performed in advance, which has an effect of improving the reactivity during the main prepolymerization.

  The amount of prepolymerization in the additional prepolymerization treatment is 0.001 to 500 g, preferably 0.1 to 100 g, more preferably 0.5 to 50 g, per 1 g of the titanium component in the solid catalyst component (A1).

  Examples of the monomer used for the additional prepolymerization treatment include olefins, diene compounds, and styrenes. Specific examples include those having about 2 to 20 carbon atoms, 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, 1,3-pentadiene, 1, 4-pentadiene, 2,4-pentadiene, 2,6-octadiene, cis-2, trans-4-hexadiene, trans-2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1, 5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, , 4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene P-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. Specific examples of styrenes include styrene, α-methylstyrene, allylbenzene, chlorostyrene and the like. These monomers may be the same as or different from those used in the main prepolymerization treatment.

<Organic aluminum component (B)>
Specific examples of the organoaluminum compound used as the component (B) in the present invention include R ³ _3-n AlX _n or R ⁴ _3-m Al (OR ⁵ ) _m (where R ³ and R ⁴ are A hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, which may be the same or different, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, n and m are 0 ≦ n <3, 0 <M <3)).

  Specifically, (i) trialkylaluminum such as (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, (b) diethylaluminum monochrome Aldehyde, diisobutylaluminum monochloride, ethylaluminum sesquichloride, alkylaluminum halides such as ethylaluminum dichloride, (c) alkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, (d) diethylaluminum ethoxide, diethylaluminum phenoxide Examples include alkyl aluminum alkoxide.

These organoaluminum compounds (a) to (d) may be combined with other organometallic compounds such as R ¹⁴ _3-t Al (OR ¹⁵ ) _t (wherein R ¹⁴ and R ¹⁵ may be the same or different carbon numbers). It is also possible to use an aluminum alkoxide or the like represented by 1 to 20 hydrocarbon groups and t is 0 <t ≦ 3. 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 And the combination use with.

  The organoaluminum component (B) and the Ziegler type solid catalyst component (A) are generally used in a molar ratio (Al / Ti) of 1 to 1000, preferably 10 to 500.

<Production of α-olefin polymer>
The α-olefin polymer of the present invention is obtained by polymerizing or copolymerizing an α-olefin using an α-olefin polymerization catalyst composed of the component (A) and the component (B) described above. The α-olefin polymerization using the α-olefin polymerization catalyst may be slurry polymerization using a hydrocarbon solvent such as hexane, heptane, octane, benzene or toluene, bulk polymerization or gas phase polymerization using substantially no solvent. Applied. 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. The polymerization reactor is not particularly limited in shape and structure, but a tank with a stirrer generally used in slurry polymerization and bulk polymerization, a tube reactor, a fluidized bed reactor generally used in gas phase polymerization, and a stirring blade A horizontal reactor having

The α-olefin that can be polymerized using the α-olefin polymerization catalyst of the present invention has the general formula R ¹⁶ —CH═CH ₂ (where R ¹⁶ is a hydrocarbon group having 1 to 20 carbon atoms, It may have a group.) Specific examples include α-olefins such as ethylene, 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 carried out. These copolymerizable monomers can be contained in the α-olefin polymer up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization.

During the α-olefin polymerization, an electron donor (external donor) can be used, although it is not essential. As the electron donor (external donor), those exemplified as the electron donor (internal donor) used in preparing the raw material solid component (i), and the Si—OR ¹ bond exemplified in the component (ii) An organosilicon compound containing two or more can be exemplified.

  In a more preferred form of the production method of the α-olefin polymer of the present invention, the intrinsic viscosity [ηt] of the α-olefin polymer produced in the main polymerization is 2 to 50 dl / g, more preferably 3 to 40 dl / g. Range. In the final α-olefin polymer obtained, the high molecular weight polyolefin (a) derived from the Ziegler-type solid catalyst component (A) used is 0.01 to 5% by weight, preferably 0.1 to 2% by weight. %, The polymerization conditions are selected. Similarly to the known olefin polymerization method, the molecular weight of the polymer can be adjusted using hydrogen during the polymerization.

  Furthermore, in a more preferred embodiment of the production method of the α-olefin polymer of the present invention, a value of 1.1 or more is achieved as an index (λmax) of the strain hardening degree of the α-olefin polymer produced in the main polymerization. , Preferably greater than 2.0, and more preferably greater than 5.0. The degree of strain hardening (λmax) is measured by extensional viscosity and is defined as ηmax / ηlin.

  After the completion of the main polymerization, a known post-treatment step such as a catalyst deactivation treatment step, a catalyst residue removal step, or a drying step can be performed as necessary.

  In the method for producing an α-olefin polymer of the present invention, the required amount of catalyst is summarized in order to produce the high molecular weight polyolefin (a) during the production step (preliminary polymerization treatment step) of the Ziegler type solid catalyst component (A). In the main polymerization of α-olefin, normal olefin polymerization may be carried out by an existing process, and the production amount equivalent to that of normal polyolefin production can be maintained.

  The α-olefin polymer according to the method of the present invention is suitable for extrusion foam molding, but it is not only that, but also molded products having various shapes by various molding methods such as vacuum / pressure forming, extrusion molding, injection molding and the like. be able to. When molding, known antioxidants, neutralizing agents, antistatic agents, weathering agents, etc. used in conventional α-olefin polymers are added to the α-olefin polymer of the present invention as necessary. May be.

  The α-olefin polymer according to the method of the present invention can be used alone as it is, but another α-olefin polymer or another polymer such as ethylene rubber may be added. The α-olefin polymer of the present invention may be added to another polymer, for example, for the purpose of improving moldability.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Analysis and evaluation methods performed in Examples and Comparative Examples are as follows.

1. Intrinsic viscosity [η] of high molecular weight polyolefin (a)
The intrinsic viscosity (unit: dl / g) in tetralin at 135 ° C. was measured by a capillary viscosity measurement method using an Ostwald viscometer.
2. Melt flow rate (MFR)
It was measured according to JIS-K-6758 (conditions 230 ° C., load 2.16 kgf) (unit: g / 10 minutes).
3. Melt tension (MT)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, measurement was performed at a cylinder temperature of 190 ° C., an orifice L / D = 8 / 2.1, an extrusion speed of 10 mm / min, and a tensile speed of 3.9 m / min (unit cN).
4). Strain hardening degree (λmax)
It calculated | required with the apparatus shown below, the measuring method, and the calculation method.

Device: Toyo Seiki, Melten Rheometer
Measurement temperature: 180 ° C
Strain rate: 0.1 / sec
Calculation method: Time t (second) is plotted on the horizontal axis, and extensional viscosity η _E (Pa · second) is plotted on the vertical axis in a log-log graph. On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line, and the viscosity on the approximate line at the time when the extensional viscosity η _E reaches the maximum value (ηmax) is denoted by ηlin. ηmax / ηlin is defined as λmax and is used as an index of the degree of strain hardening.

[Example 1]
<Manufacture of raw material solid component (i-1)>
2000 ml of dehydrated and deoxygenated n-heptane was introduced into an autoclave equipped with a stirrer with an internal volume of 10 liters that had been sufficiently purged with nitrogen, and then 2.6 mol of MgCl ₂ and Ti (On-C ₄ H ₉ ) ₄ mol of ₄ was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 320 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Next, 4000 ml of n-heptane purified in the same manner as described above was introduced into an autoclave sufficiently substituted with nitrogen, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 2.62 mol of SiCl ₄ was mixed with 250 ml of n-heptane, introduced into the autoclave 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, 0.15 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the autoclave 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. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the raw material solid component (i-1) was obtained by washing with n-heptane. The raw material solid component (i-1) had a titanium content of 2.0% by weight.

<Production of solid catalyst component (A1)>
200 ml of n-heptane purified in the same manner as described above was introduced into an autoclave sufficiently substituted with nitrogen, 4 g of the raw material solid component (i-1) synthesized above was introduced, and 0.035 mol of SiCl ₄ was introduced. The reaction was carried out at 90 ° C. for 2 hours. After completion of the reaction, 0.003 mol of (t-C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ as component (ii) and (CH ₂ ═CH) Si (CH ₃ ) as component (iii) ₃ 0.006 mol and, and the Al (C ₂ H _{5) 3} as component (iv) is contacted for 2 hours at successively introduced to 30 ° C. 0.016 mol. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a solid catalyst component (A1) mainly composed of magnesium chloride. The titanium content of this product was 1.8% by weight.

<Production of Ziegler-type solid catalyst component (A)>
A stainless steel reactor with inclined blades with an inner volume of 3 liters was replaced with nitrogen gas, 2 liters of n-hexane, 2 mmol of triethylaluminum, and 4 g of the solid catalyst component (A1) prepared in the previous section were added, and then propylene was stirred at 15 ° C. Additional prepolymerization was performed by feeding 40 g for 50 minutes. After completion of the reaction time, unreacted propylene was discharged out of the reactor, and the gas phase portion of the reactor was replaced with nitrogen once. Separately, as a result of analyzing the polymer produced by the additional prepolymerization performed under the same conditions, 3 g of polypropylene (W ₀₁ ) per 1 g of the titanium-containing supported catalyst component, that is, 1 g of the titanium component of the solid catalyst component (A1). This polypropylene had an intrinsic viscosity [ηaa] of 2.9 dl / g.

Next, while maintaining the temperature in the reactor at 0 ° C., prepolymerization was performed by continuously supplying ethylene to the reactor for 150 minutes so as to maintain the pressure in the reactor at 0.5 MPa. After completion of the reaction time, unreacted ethylene was discharged outside the reactor, and the gas phase portion of the reactor was purged with nitrogen once to prepare a prepolymerized catalyst slurry. Separately, as a result of additional prepolymerization and prepolymerization under the same conditions, the amount of polymer produced (W _0T ) after the completion of both the additional prepolymerization and prepolymerization steps was determined to be a titanium-containing supported type. The amount was 127 g per 1 g of the titanium component in the catalyst component (A1), and the intrinsic viscosity [η _aT ] of this polymer was 22.7 dl / g.

The production amount (W ₀₂ ) of the ethylene polymer (a) contained per 1 g of the titanium component in the titanium-containing supported catalyst component (A1) obtained by the prepolymerization with ethylene is formed after the additional prepolymerization. The amount of polymer produced per gram of titanium component in the titanium-containing supported catalyst component (A1) (W _0T ) and the titanium-containing supported catalyst component after completion of both the additional prepolymerization and prepolymerization steps ( It is calculated | required by following Formula as a difference with the polypropylene ( _W01 ) per 1g of titanium components in A1).

W ₀₂ = W _0T -W ₀₁
The intrinsic viscosity [ηa] of the ethylene polymer (a) produced by the prepolymerization with ethylene is the intrinsic viscosity [ηaa] of the polypropylene produced by the additional prepolymerization, and the prepolymerization step subsequent to the additional prepolymerization step From the intrinsic viscosity [ηat] of the polymer produced after the completion, the following equation is obtained.

[Ηa] = ([ηat] × W 0T - [ηaa] × W 01) / (W 0T -W 01)
According to the above formula, the amount of the ethylene polymer (a) produced by the prepolymerization with ethylene is 124 g per 1 g of the titanium component in the titanium-containing supported catalyst component (A1), and its intrinsic viscosity [ηa] is 22.7 dl / g. And calculated.

<Production of α-olefin polymer>
A stainless steel polymerization vessel equipped with a stirrer with an internal volume of 3 liters was purged with nitrogen, then 2 liters of n-hexane, 2 mmol of triethylaluminum, 0.2 mmol of diisopropyldimethoxysilane, and the solid catalyst component (A1) obtained above 35 ml of the slurry solution was charged. Subsequently, 0.8 liter of hydrogen was introduced into the polymerization vessel, and propylene was continuously supplied for 70 minutes while maintaining the polymerization temperature at 70 ° C. and the gas phase pressure in the polymerization vessel at 0.7 MPa. Carried out. After the polymerization time had elapsed, the temperature in the polymerization vessel was cooled to 30 ° C. to release unreacted gas. Subsequently, the solvent was separated and the polymer was dried to obtain 1.39 kg of a propylene polymer per 1 g of the solid catalyst.

  To 100 parts by weight of the resulting propylene polymer, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 0.1 part by weight of calcium stearate are mixed, and the mixture is mixed with a screw diameter of 15 mm. Granulation was performed at 230 ° C. using an extrusion granulator to obtain pellets. The MFR measured for the pellets was 9.6 g / 10 min and the melt tension (MT) was 6.2 cN. The measurement results are shown in Table 1.

[Comparative Example 1]
In Example 1, it carried out according to Example 1 except not having performed prepolymerization by ethylene, and obtained 1.30 kg of polypropylene polymers. Thereafter, pelletization was performed in the same manner as in Example 1, and physical properties were measured. The measurement results are shown in Table 1. In addition, although described for confirmation, in Comparative Example 1, additional prepolymerization with propylene is performed.

[Comparative Example 2]
In Example 1, except that the temperature of the prepolymerization with ethylene was changed to 70 ° C. and the ethylene supply time was changed to 70 minutes, 1.20 kg of a propylene polymer was obtained. Thereafter, pelletization was performed in the same manner as in Example 1, and physical properties were measured. The measurement results are shown in Table 1. In addition, although it describes for confirmation, also in this comparative example 2, the additional prepolymerization by a propylene is implemented.

[Comparative Example 3]
In Example 1, the solid catalyst component (A1) was produced without contacting the raw material solid component (i-1) with the components (ii), (iii), and (iv). That is, the raw solid component (i-1) was subjected to additional prepolymerization at 40 ° C. using 40 g of propylene at 15 ° C., and then, while maintaining the temperature in the reactor at 0 ° C., ethylene was Prepolymerization was carried out by continuously supplying 90 minutes so as to maintain 0.5 MPa. In addition, in the production of the α-olefin polymer, the hydrogen supply amount was changed to 1.2 liters, but other than that was performed in accordance with Example 1 to obtain 0.84 kg of a propylene polymer. Thereafter, pelletization was performed in the same manner as in Example 1, and physical properties were measured. The measurement results are shown in Table 1.

[Example 2]
In Example 1, the raw material solid component (i-1) was changed to (i-2) shown below, the ethylene supply time was changed to 350 minutes, and hydrogen was supplied in the production of the α-olefin polymer. Except for changing the amount to 0.25 liter, propylene was polymerized according to Example 1 to obtain 1.6 kg of a propylene polymer. Thereafter, pelletization was performed in the same manner as in Example 1, and physical properties were measured. The measurement results are shown in Table 1.

<Manufacture of raw material solid component (i-2)>
In a 1 liter reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped metal magnesium (purity 99.5%, average particle size 1.6 mm) and 250 ml of n-hexane were placed under a nitrogen gas atmosphere. After stirring for 1 hour at 0 ° C., the magnesium metal was taken out, and preactivated metal magnesium was obtained by drying under reduced pressure at 65 ° C.

  Next, a suspension obtained by adding 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butyl magnesium chloride (1.75 mol / liter) to this metal magnesium was kept at 55 ° C., and further 50 ml of n-butyl ether. A solution in which 38.5 ml of n-butyl chloride was dissolved was added dropwise over 50 minutes. After reacting for 4 hours at 70 ° C. with stirring, the reaction solution was kept at 25 ° C.

Subsequently, 55.7 ml of HC (OC ₂ H ₅ ) ₃ was dropped into the reaction solution over 1 hour. After completion of the dropwise addition, the reaction was carried out at 60 ° C. for 15 minutes, and the reactive product solid was washed 6 times with 300 ml each of n-hexane and dried under reduced pressure at room temperature for 1 hour, Mg: 19.0%, chlorine 28.9% 31.6 g of a magnesium-containing solid containing was recovered.

  In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer, and a dropping funnel, 6.3 g of a magnesium-containing solid and 50 ml of n-heptane are placed under a nitrogen gas atmosphere to form a suspension and stirred at room temperature with 2,2 A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes and further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, washed 4 times with 100 ml each of n-hexane at room temperature, and further washed twice with 100 ml each of toluene to obtain a solid component.

  40 ml of toluene was added to the above solid component, and further titanium tetrachloride was added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then stirred at 120 ° C. for 2 hours. The obtained solid substance was filtered off at 90 ° C. and washed twice with 100 ml of toluene at 90 ° C. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours. The obtained solid substance was filtered off at 110 ° C. and washed 7 times with 100 ml of n-hexane at room temperature to obtain 5.5 g of a raw material solid component (i-2).

[Comparative Example 4]
In Example 2, the solid catalyst component (A1) was produced without contacting the raw material solid component (i-2) with the components (ii), (iii), and (iv). That is, the raw solid component (i-2) was subjected to additional prepolymerization at 40 ° C. using 40 g of propylene, and then the ethylene was maintained at 0 ° C. while maintaining the temperature in the reactor at 0 ° C. The prepolymerization was carried out by continuously supplying 350 minutes so as to maintain the pressure at 5 MPa. Further, in the production of the α-olefin polymer, the hydrogen supply amount was changed to 0.45 liters. Other than that was performed according to Example 2, and obtained 0.92 kg of propylene polymers. Thereafter, pelletization was performed in the same manner as in Example 1, and physical properties were measured. The measurement results are shown in Table 1.

The following matters were found from the above examples and comparative examples.
(1) In Example 1, a raw material solid component (i-1) was prepolymerized in two stages using a catalyst preliminarily contacted with components (ii) to (iv) using olefins (propylene and ethylene). This is an example of producing a Ziegler-type solid catalyst component (A-1) having a polyolefin (a). The melt elasticity is high as compared with Comparative Examples 1 and 2, and the catalytic activity is high as compared with Comparative Example 3.
(2) Comparative Example 1 is an example of a Ziegler type solid catalyst component (A) that is not prepolymerized with olefin and does not have a high molecular weight polyolefin (a), and has low melt elasticity.
(3) Comparative Example 2 was an example of a Ziegler type solid catalyst component (A) in which the prepolymerized polyolefin was prepolymerized but the viscosity (molecular weight) of the prepolymerized polyolefin was low, and the melt elasticity was low.
(4) Comparative Example 3 is an example of a Ziegler-type solid catalyst component (A) produced by pre-contacting the raw material solid component (i-1) with components (ii) to (iv). Compared with the above, the catalytic activity is low.
(5) Example 2 has a high-molecular-weight polyolefin (a) by prepolymerizing the raw material solid component (i-2) with a solid catalyst component (A1) pre-contacted with the components (ii) to (iv) with an olefin. This is an example of producing a Ziegler-type solid catalyst component (A-2). From comparison with Comparative Example 4, the catalytic activity is high.
(6) Comparative Example 4 is an example of a Ziegler-type solid catalyst component (A) produced by pre-contacting the raw material solid component (i-2) with components (ii) to (iv). Compared with the above, the catalytic activity is low.

Block process diagram showing the catalyst production process of the present invention

Claims (8)

Solid catalyst component (A1) obtained by contacting the following components (i), (ii), (iii) and (iv), and an intrinsic viscosity [ηa] of 15 to 100 dl / g, 50 per gram of titanium component A Ziegler-type solid catalyst component (A) comprising ˜25,000 g of a high molecular weight polyolefin (a).
Component (i): Raw material solid component containing titanium, magnesium and halogen Component (ii): Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) .)
Component (iii): Vinylsilane compound Component (iv): Organometallic compound of Group 1-3 metal The solid catalyst component (A1) obtained by bringing the following components (i), (ii), (iii) and (iv) into contact with each other is preliminarily prepared with an olefin at any stage in the production process of the solid catalyst component (A1). A Ziegler-type solid catalyst component (characterized by forming a high molecular weight polyolefin (a) with an intrinsic viscosity [ηa] of 15 to 100 dl / g and 50 to 25,000 g per gram of titanium component by polymerization. A).
Component (i): Raw material solid component containing titanium, magnesium and halogen Component (ii): Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) .)
Component (iii): Vinylsilane compound Component (iv): Organometallic compound of Group 1-3 metal   The Ziegler type solid catalyst component (A) according to claim 1 or 2, wherein the high molecular weight polyolefin (a) is an ethylene homopolymer or an ethylene / α-olefin copolymer having an ethylene content of 50% by weight or more.   The Ziegler-type solid catalyst component (A) according to claim 2 or 3, wherein the prepolymerization is performed after completion of contact of all the components (i), (ii), (iii) and (iv). .   The prepolymerization is carried out by first subjecting the component (i) to a prepolymerization treatment and then contacting the treated product with the components (ii), (iii) and (iv). The Ziegler-type solid catalyst component (A) described.   The Ziegler type solid catalyst component (A) according to any one of claims 2 to 5, wherein the prepolymerization is performed in a plurality of stages using different olefins.   An α-olefin polymerization catalyst comprising the Ziegler-type solid catalyst component (A) according to any one of claims 1 to 6 and an organoaluminum component (B). An α-olefin polymer production method according to claim 7, wherein the α-olefin polymerization catalyst is polymerized by contacting the α-olefin.