JP2015160858A - Method for producing preliminary polymerization catalyst component used for olefin polymerization and method for producing olefin polymer using the preliminary polymerization catalyst component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a preliminary polymerization catalyst component used for olefin polymerization, which can prevent fouling in a reactor in a production step of the preliminary polymerization catalyst component.SOLUTION: The method for producing a preliminary polymerization catalyst component (Sc) used for olefin polymerization comprises preliminarily polymerizing an olefin on a solid catalyst component (Sa) comprising a transition metal complex (A) and a solid support (S) via the following two steps: (1) a step of obtaining a preliminary polymerization catalyst component (Sb) by supplying an olefin containing 2 or more carbon atoms to a solid catalyst component (Sa) under a condition where a concentration of an aluminum compound in a solvent except a solid content is 0.001 mmol/L to 1 mmol/L and preliminarily polymerizing the olefin in an amount of 0.15 to 10 times relative to a weight of the solid catalyst component (Sa); and (2) a step of obtaining a preliminary polymerization catalyst component (Sc) by supplying an olefin having 2 or more carbon atoms to the preliminary polymerization catalyst component (Sb) under a condition where a concentration of an organic aluminum compound in a solvent except a solid content is 10 mmol/L or more and preliminarily polymerizing the olefin.

Description

  The present invention relates to a method for producing a prepolymerization catalyst component medium used for olefin polymerization and a method for producing an olefin polymer used therefor. More specifically, the present invention relates to a method for producing a prepolymerization catalyst component that suppresses fouling in a reactor, and a method for producing an olefin polymer using the same.

  Conventionally, as a catalyst for producing an olefin (co) polymer, an olefin polymerization catalyst comprising a transition metal complex such as zirconocene and a promoter component such as an organoaluminum oxy compound (aluminoxane) is known. When performing polymerization or gas phase polymerization, a solid catalyst in which a transition metal complex or an organoaluminum oxy compound is supported on a solid support such as silica gel is generally used to improve the powder properties of the polymer produced. (Non-Patent Document 1).

  In addition, as a method for suppressing fouling in which a polymer adheres to the reactor wall surface in the polymerization reaction or polymer lump formation in the reactor, a method of prepolymerizing olefin to a solid catalyst (Patent Document 1), A method of adding a specific compound to (Patent Documents 2 and 3) has been reported.

JP 63-152608 A JP 2000-327707 A JP 2012-117043 A

Chem. Rev. 2005, 105, p.4073-4147

However, when an olefin is introduced in the presence of a solid catalyst as described above and a prepolymerization reaction is performed, the solvent after the reaction becomes turbid and fouling in the reactor may be confirmed.
Since fouling reduces the efficiency of heat removal from the reactor wall surface, it becomes difficult to control the reaction temperature, and the productivity may be reduced by cleaning the reactor.

  The present invention has been made to solve such problems, and in the production of an olefin (co) polymer, production of a prepolymerized catalyst component used for olefin polymerization capable of preventing fouling in the reactor. It aims to provide a method.

  As a result of intensive studies in view of the above situation, the present inventors have found that the above problems can be solved by taking a specific production method in the production process of the prepolymerization catalyst component, and have completed the present invention.

That is, the present invention relates to the following [1] to [4].
[1] A prepolymerization catalyst used for olefin polymerization, characterized in that a solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) is prepolymerized through the following two steps. Production method of component (Sc).
(1) Supplying an olefin having 2 or more carbon atoms to the solid catalyst component (Sa) under the condition that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.001 mmol / L or more and 1 mmol / L or less, and the solid catalyst Step of obtaining a prepolymerized catalyst component (Sb) by prepolymerizing an amount of 0.15 to 10 times the weight of the component (Sa) (2) The concentration of the organoaluminum compound excluding the solid content in the solvent is A step of supplying a prepolymerized catalyst component (Sc) by supplying an olefin having 2 or more carbon atoms to the prepolymerized catalyst component (Sb) under a condition of 10 mmol / L or more [2] The transition metal complex (A ) Comprises a transition metal compound belonging to Group 4 of the periodic table. The method for producing a prepolymerized catalyst component (Sc) according to [1].
[3] The method for producing a prepolymerized catalyst component (Sc) according to [1] or [2], wherein the solid catalyst component (Sa) comprises an organoaluminum oxy compound.
[4] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the prepolymerization catalyst component (Sc) according to any one of [1] to [3].

  According to the method of the present invention, fouling in the reactor can be prevented in the production process of the prepolymerized catalyst component used for olefin polymerization, and the olefin polymerization using such a catalyst component is stable. Thus, there is an advantage that olefin polymerization can be carried out.

Hereinafter, the manufacturing method of the prepolymerization catalyst component used for the olefin polymerization which concerns on this invention, and the manufacturing method of the olefin polymer using the said catalyst component are demonstrated concretely.
In the present invention, the term “polymerization” may be used to include not only homopolymerization of olefins but also copolymerization of two or more olefins, and the term “polymer” includes not only homopolymers. It may be used with the meaning of including a copolymer.

Below, each component which forms the pre-polymerization catalyst component which concerns on this invention first is demonstrated.
In the method for producing a prepolymerized catalyst component used for olefin polymerization according to the present invention, the transition metal complex (A) and the solid support (S) constituting the solid catalyst component (Sa) are not limited in any way, but preferred Examples are shown below.

<Transition metal complex (A)>
Examples of the transition metal complex (A) constituting the solid catalyst component (Sa) according to the present invention include metallocene compounds represented by the following general formula (I).

（式中、Ｍは遷移金属元素であり、Ｌは遷移金属に配位する中性またはアニオン性配位子であり、ｘはＬの個数を示し、遷移金属の原子価を満たす数であり、ｘが２以上のときは複数のＬは互いに同一でも異なっていてもよい。）

(Wherein, M is a transition metal element, L is a neutral or anionic ligand coordinated to the transition metal, x is the number satisfying the valence of the transition metal, indicating the number of L, When x is 2 or more, the plurality of L may be the same or different from each other.)

In general formula (I), examples of M include transition metal elements selected from Groups 4 to 10 of the periodic table. Specifically, transition metal elements of Group 4 of the periodic table such as titanium, zirconium, and hafnium. Periodic Table Group 5 transition metal elements such as tantalum, vanadium, and tantalum, Periodic Table 6 Group transition metal elements such as chromium, Periodic Table 7 Group transition metal elements such as manganese, Period of iron, etc. A transition metal element of Group 8 of the table, a transition metal element of Group 9 of the periodic table such as cobalt, and a transition metal element of Group 10 of the periodic table such as nickel or palladium, preferably Group 4 of the periodic table Transition metals, specifically titanium, zirconium and hafnium.
x represents the number of ligands L coordinated to the transition metal, and is a number satisfying the valence of the transition metal.

L is a neutral or anionic ligand arranged on the transition metal, and examples thereof include a ligand having a cyclopentadienyl skeleton.
Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. Hydrogen atoms in the ligand L are hydrocarbon groups, halogen-containing groups, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups, tin-containing groups, etc. In the case where x is 2 or more, the ligands L are crosslinked with a divalent group selected from a hydrocarbon group, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. May be.

As a ligand other than the ligand having a cyclopentadienyl skeleton, a transition metal atom M And a ligand that binds with B, C, N, O, P, S, halogen, hydrogen, or the like in a neutral or anionic charge state.

Examples of the ligand bonded with B include alkyl borane, aryl borane, alkyl borate, aryl borate, and borabenzene.
Examples of ligands bonded at C include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and pentyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; phenyl groups, Aryl groups such as a tolyl group; aralkyl groups such as a benzyl group and a neophyll group; conjugated diene compound residues; and π-aryl.

Examples of ligands bonded with N include amino, amide, sulfonamide, imide, iminoamidine, imidazole, amidate, imidate and the like.
Examples of ligands bonded with O include alkoxy groups such as methoxy group, ethoxy group and butoxy group; aryloxy groups such as phenoxy group; p-toluenesulfonate group, methanesulfonate group, trifluoromethanesulfonate Sulfonato groups such as a group; carbonyl, ester, carboxyl, oxime, ketoalkoxy and the like.

Examples of the ligand bonded with P include phosphine, phosphite, and phosphate.
Examples of the ligand bonded with S include a fluoride, a thioketone, a thioketo ester, a thiophenoxide, a thiocarboxyl group, a dithiocarbamate group, and the like.

Examples of the halogen include fluorine, chlorine, bromine and iodine.
As the transition metal complex (A) having a ligand other than the cyclopentadienyl skeleton, a transition metal complex exemplified in JP 2013-224408 A, Chem. Rev. 2003, 103, 283-315, etc. is used. You can also.

  As such a transition metal complex represented by the general formula (I), a compound containing a ligand having a cyclopentadienyl skeleton is preferably used, and examples thereof include the following compounds.

Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadi) Enyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) ) Methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclope Tadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) Zirconium bis (p-toluenesulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadi) Nyl) zirconium dichloride, bis (1,3-ethylmethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (1,3-methylpropylcyclopentadienyl) zirconium dichloride, bis ( Butylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclo) Pentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopene) Tadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-n- Butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octyl Cyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, tri Fluoromethylbutylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-octyl Le cyclopentadienyl) zirconium dichloride, (butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethyl-eta ⁵ - cyclopentadienyl) - 1,2-ethanediylzirconium dichloride,
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ) (Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dibutylmethylene (cyclope Tadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadi) Enyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-t-butyl) Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluor) Nyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadiyl) Enyl) (3,6-di-t-butylfluorenyl) zirconium dichloride and dimethylsilylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, di-p-tolylmethylene (cyclopentadi) Enyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride,
Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium Dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,4 -Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride Lido, dimethylsilylenebis (2-methyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-cyclohexyl-1-indenyl) Zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, di (p-tolyl) silylenebis (2 -Methyl-4-phenyl-1-indenyl) zirconium dichloride, di (p-chlorophenyl) silylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl) 4,5-benzo-1-indenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4,5-acenaphthocyclopentadienyl) zirconium dichloride, dimethylsilylene (2-methyl-4,5-benzo-1- Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and the like.

As mentioned above, although the example of the transition metal complex (A) used suitably by this invention was shown, the transition metal complex (A) based on this invention is not limited to the compound illustrated above.
As a transition metal complex (A) based on this invention, 1 type may be used independently and 2 or more types may be mixed and used.

<Solid carrier (S)>
Next, the solid carrier (S) constituting the solid catalyst component (Sa) according to the present invention will be described.

The solid carrier (S) according to the present invention is an inorganic or organic compound and is a granular or particulate solid.
Among these, examples of inorganic compounds include porous oxides, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds, and examples include inorganic halides such as porous oxides and inorganic chlorides as described below. .

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, etc. Can be used. Of these, those containing SiO ₂ as the main component are preferred.

Note that the inorganic oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxide components may be contained.

Such porous oxides have different properties depending on the type and production method, but as a solid support used in the present invention, the particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, surface area usually 50~1200m ² / g, preferably in the range of 100~1000m ² / g, which pore volume is in the range of usually 0.3~30cm ³ / g are preferred. Such a carrier is used, for example, after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated into fine particles by a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchange layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Also, clay, clay minerals or ion-exchangeable layered compounds include clays, clay minerals, ionic crystalline compounds having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂・ H ₂ O, α-Sn (HPO ₄ ) ₂・ H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of not less than 0.1 cm ³ / g having a radius of 20 cm or more as measured by mercury porosimetry, and is 0.3 to ⁵ cm ³ / g. Those are particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ⁴ by a mercury intrusion method using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cm ³ / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment, and the like. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ^{+ and} other metal hydroxide ions Etc. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, etc. can also coexist. Examples of the pillar include an oxide generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Examples of the organic compound include a granular or particulate solid having a particle size in the range of 1 to 300 μm. Specifically, (co) polymers mainly composed of olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane, styrene and divinylbenzene as main components. And (co) polymers and their modifications.

  Also, those obtained by bringing the inorganic or organic compound into contact with the component (B) described below, as well as JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, and international publication. A solid component obtained by insolubilizing the component (B) described below by the method described in WO 2010/55652 pamphlet or the like can also be used as the solid carrier (S).

< Ingredient (B) >
In addition to the transition metal complex (A) and the solid support (S), the solid catalyst component (Sa) according to the present invention may further include the component (B) described below as necessary.

The component (B) that can be used in the present invention is at least one compound selected from the group consisting of the following (b-1) to (b-3).
(B-1) an organometallic compound represented by the following general formula (II), (III) or (IV),
R ^d _m Al (OR ^e ) _n H _p X _q (II)
[In the general formula (II), R ^d and R ^e represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ]
_{^{M a AlR f 4 ··· (III}} )
[In the general formula (III), M ^a represents a Li, Na or K, R ^f represents a hydrocarbon group having 1 to 15 carbon atoms. ]
R ^g _r M ^b R ^h _s X _t (IV)
[In General Formula (IV), R ^g and R ^h represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other, M ^b represents Mg, Zn or Cd, and X represents Represents a halogen atom, r is 0 <r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2. ]

(B-2) an organoaluminum oxy compound, and
(B-3) a compound that reacts with the transition metal complex (A) to form an ion pair,
At least one compound selected from the group consisting of

In the general formula (II), R ^d and R ^e may be the same as or different from each other. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group, specifically a methyl group, An ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, etc., preferably an ethyl group, n -A propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
In the general formula (III), examples of the hydrocarbon group for R ^f include the same hydrocarbon groups as those for R ^d and R ^e .

In the general formula (IV), R ^g and R ^h may be the same as or different from each other, and examples of the hydrocarbon group include the same hydrocarbon groups as those described above for R ^d and ^Re .
Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Among the organometallic compounds (b-1) represented by the general formula (II), (III) or (IV), those represented by the general formula (II) are preferable, specifically, trimethylaluminum, triethyl Trialkylaluminums such as aluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; and dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride and diiso Examples include alkyl aluminum hydrides such as hexyl aluminum hydride. These are used singly or in combination of two or more.

  As the organoaluminum oxy compound (b-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such organoaluminum oxy compounds are used singly or in combination of two or more.

  As the compound (b-3) which reacts with the transition metal complex (A) to form an ion pair, JP-A-1-501950, JP-A-1-503636, JP-A-3-179005, Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. Can be used without restriction.

  In the present invention, when an organoaluminum oxy compound (b-2) such as aluminoxane is used as a promoter component in addition to the transition metal complex (A), very high polymerization activity is exhibited. Therefore, it is preferable to use the organoaluminum oxy compound (b-2) as the component (B).

<Method for Producing Prepolymerization Catalyst Component (Sc)>
The prepolymerization catalyst component (Sc) used for olefin polymerization according to the present invention is obtained by subjecting the solid catalyst component (Sa) containing the transition metal complex (A) and the solid support (S) to the following two steps. It can be produced by prepolymerization.
(1) Supplying an olefin having 2 or more carbon atoms to the solid catalyst component (Sa) under the condition that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.001 mmol / L or more and 1 mmol / L or less, and the solid catalyst A step of prepolymerizing an amount of 0.15 to 10 times the weight of the component (Sa) to obtain a prepolymerized catalyst component (Sb) [first step]
(2) A prepolymerization catalyst obtained by supplying an olefin having 2 or more carbon atoms to the prepolymerization catalyst component (Sb) and prepolymerizing the organoaluminum compound excluding solids in the solvent at a concentration of 10 mmol / L or more. Step of obtaining component (Sc) [second step]
When the prepolymerization is performed using the solid catalyst component (Sa) containing the transition metal complex (A) and the solid support (S) by employing the production method of the present invention, the Al concentration in the solvent and the prepolymerization By controlling the amount, fouling in the prepolymerization reactor is suppressed.

Solid catalyst component (Sa)
The solid catalyst component (Sa) used in the first step of the process for producing the prepolymerized catalyst component (Sc) of the present invention comprises the solid support (S) and the transition metal complex (A) in an inert hydrocarbon. -50 ° C to 200 ° C, preferably -20 ° C to 150 ° C. The contact time is 0.01 to 48 hours, preferably 0.1 to 24 hours.

  Specific examples of the inert hydrocarbon used for the preparation of the solid catalyst component (Sa) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, cyclopentane, Mention may be made of alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof.

  When two or more transition metal complexes (A) are used, the order of contact with the solid support (S) is arbitrary, and two or more transition metal complexes (A) may be contacted in any order, or You may make it contact simultaneously.

  In preparing the solid catalyst component (Sa), the transition metal complex (A) is usually in an amount of 1 to 1.0 mmol, preferably 3 to 0.5 mmol, per 1 g of the solid support (S). Used in

  Here, in the adjustment of the solid catalyst component (Sa) according to the present invention, the component (B) can be suitably used together, and the mode is not limited in any way, but examples of preferred modes are as follows. Shown in

(I) A method of preparing a solid catalyst component (Sa) by bringing a solid support (S) and a component (B) into contact with each other and then contacting with a transition metal complex (A).
(Ii) A method in which the transition metal complex (A) and the component (B) are mixed and contacted, and then the solid support (S) is contacted to prepare the solid catalyst component (Sa).

  The contact between the component (B) and the solid support (S) is preferably carried out in an inert hydrocarbon solvent. As the inert hydrocarbon solvent, an inert carbon used for the preparation of the solid catalyst component (Sa) is used. The thing similar to hydrogen is mentioned. The contact time between the component (B) and the solid carrier (S) is usually 0.1 to 48 hours, preferably 0.1 to 20 hours, and the contact temperature is usually −50 to 200 ° C., preferably − 20-120 ° C. The contact molar ratio of the component (B) to the solid carrier (S) (component (B) / solid carrier (S)) is usually 0.1 to 1000, particularly preferably 0.1 to 100.

Prepolymerization catalyst component (Sb)
The prepolymerization catalyst component (Sb) according to the present invention is a prepolymerization catalyst component (Sb) obtained in the first step of the production method of the prepolymerization catalyst component (Sc).

  The present inventors paid attention to the amount of the transition metal component in the solvent after the prepolymerization as a factor causing fouling in the reactor. The amount of transition metal component (atom) in the solvent can be determined by inductively coupled plasma (ICP) emission spectroscopy.

  It is considered that the transition metal component in the solvent is derived from the transition metal complex (A) released from the solid catalyst component (Sa) when the organoaluminum compound present in the system contacts with the solid catalyst component (Sa) during the prepolymerization. . The transition metal component in the solvent undergoes the polymerization reaction in a state where it is not supported on the solid carrier (S), so that a polymer having a fine and low sphericity is generated, and adhesion to the reactor wall is promoted. It is estimated that fouling occurs.

  In order to suppress the release of the transition metal component during the prepolymerization, it is desirable to avoid the contact between the transition metal complex (A) and the organoaluminum compound as much as possible. In addition, in order to prevent electrostatic adhesion (fouling) of the catalyst component due to charging, it is generally inevitable to add a certain amount of organoaluminum compound in the system.

  The present inventors perform prepolymerization in two stages under specific polymerization conditions, and bring the concentration and prepolymerization amount of the organoaluminum compound in the solvent in the first stage into a specific range, thereby entering the solvent. It was found that the release of the transition metal complex (A) can be suppressed, and thus fouling in the reactor can be suppressed.

  The solvent used for the preparation of the prepolymerization catalyst in the first step is preferably an inert hydrocarbon solvent, and the inert hydrocarbon solvent is the same as the inert hydrocarbon solvent used when preparing the solid catalyst component (Sa). Can be mentioned.

The organoaluminum compound according to the present invention is not limited in any way, but preferred examples include general formula (II), (III) or component (b-2) of component (b-1).
The concentration of the organoaluminum compound is 0.001-1 mmol / L, preferably 0.01-1 mmol / L, more preferably 0.0-0.8 mmol / L, excluding the solid component derived from the solid catalyst component (Sa). L, more preferably in the range of 0.1 to 0.7 mmol / L.

  In the first step, when the concentration of the organoaluminum compound is low, it becomes susceptible to poisoning due to trace impurities in the solvent, and when the concentration is high, release of the transition metal component from the solid catalyst component (Sa) is promoted. The above range is preferred.

  The amount of the olefin having 2 or more carbon atoms to be prepolymerized in the first step is 0.15 to 10 times, preferably 0.15 to 5 times, more preferably, to the weight of the solid catalyst component (Sa). The amount is 0.20 times or more and 3 times or less. When the amount of prepolymerization of olefins having 2 or more carbon atoms is small, the release of the transition metal component from the solid catalyst component (Sa) is promoted in the subsequent polymerization reaction. When the amount of prepolymerization is large, the prepolymerization is caused by charging of the prepolymerization component. There is a risk that electrostatic adhesion is likely to occur inside.

The prepolymerization temperature in the first step is usually -20 to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is usually 0.5 to 100 hours, preferably about 1 to 50 hours.
Examples of the olefin having 2 or more carbon atoms used in the prepolymerization in the first step include α-olefins having 2 to 20 carbon atoms. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1 Examples include -hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.

  Moreover, at least 1 sort (s) selected from a cyclic olefin and an aromatic vinyl compound can coexist in a reaction system, and superposition | polymerization can also be advanced. It is also possible to use a diene in combination. Further, other components such as vinylcyclohexane may be copolymerized without departing from the spirit of the present invention. Other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less with respect to 100 parts by mass of the α-olefin having 2 to 20 carbon atoms.

  Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5. , 8,8a-octahydronaphthalene.

  Examples of the aromatic vinyl compound include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, and the like. Or polyalkyl styrene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene may be mentioned.

  Examples of the dienes include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1, Α, ω-non-conjugated dienes such as 9-decadiene; non-conjugated such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene Diene; conjugated dienes such as butadiene and isoprene are exemplified.

  The prepolymerization in the first step can be carried out in any of batch, semi-continuous and continuous methods, and can be carried out under reduced pressure, normal pressure or increased pressure. The concentration of the solid catalyst component (Sa) in the prepolymerization system is usually 1 to 1000 g / L, preferably 5 to 500 g / L, in the ratio of solid catalyst component (Sa) / polymerization volume of 1 liter.

  The prepolymerized catalyst (Sb) thus prepared may be washed with an inert hydrocarbon solvent containing an organoaluminum compound. The lower limit concentration of the organoaluminum compound in the inert hydrocarbon solvent is 0.1 mmol / L or more, preferably 0.15 mmol / L or more, more preferably 0.2 mmol / L or more. Although it can be implemented as long as it does not change, it is preferably 200 mmol / L or less in consideration of economy.

  By washing, the organoaluminum compound not only acts as a scavenger, but also increases the solubility in the transition metal complex (A) (and its derivatives), and the free transition metal component is free from olefins prior to the subsequent polymerization reaction. This is preferred because it can be removed underneath.

  The prepared prepolymerized catalyst (Sb) may proceed to the second step as it is, or may be separated from the suspension of the first step and then suspended again in an inert hydrocarbon and proceed to the second step. Alternatively, after drying, the process may proceed to the second step.

Prepolymerization catalyst component (Sc)
The prepolymerization catalyst component (Sc) according to the present invention is a prepolymerization obtained by treating the prepolymerization catalyst component (Sb) obtained in the first step of the production method of the prepolymerization catalyst component (Sc) in the second step. It is a catalyst component (Sc).

  The prepolymerization catalyst component (Sc) according to the present invention is an olefin having 2 or more carbon atoms in the prepolymerization catalyst component (Sb) obtained in the first step under the condition that the concentration of the organoaluminum compound is 10 mmol / L or more. Is a prepolymerization catalyst component (Sc) obtained by prepolymerization.

  The solvent used for the preparation of the prepolymerized catalyst component (Sc) is preferably an inert hydrocarbon solvent, and the inert hydrocarbon solvent is an inert carbon solvent used when preparing the solid catalyst component (Sa) or in the second step. The thing similar to a hydrogen solvent is mentioned.

The organoaluminum compound used in the second step is not limited in any way, but preferred examples thereof include general formula (II), (III) or component (b-2) of component (b-1).
The concentration of the organoaluminum compound is preferably 10 to 500 mmol / L, preferably 15 to 250 mmol / L, more preferably 20 to 200 mmol / L, excluding the solid component derived from the prepolymerization catalyst component (Sb).

  The amount of the olefin having 2 or more carbon atoms to be prepolymerized in the second step is not limited at all, but is 0.10 to 300 times, preferably 0.5 to the weight of the solid catalyst component (Sa). The amount is preferably from 1 to 200 times, more preferably from 1 to 200 times.

  The prepolymerization temperature and the olefin having 2 or more carbon atoms used in the prepolymerization, the method of implementation, and the washing method in the second step may be the same as those for preparing the prepolymerization catalyst component (Sb).

  The prepolymerization catalyst component (Sc) obtained by the above production method may be used for olefin polymerization as it is in the suspension in the second step, or after being separated from the suspension in the second step, it is again inert carbonized. It may be suspended in hydrogen and used for olefin polymerization, or dried and then used for olefin polymerization.

  In the production of the prepolymerization catalyst component (Sc) according to the present invention, the following component (G) is added before, during or after the process of producing the prepolymerization catalyst component (Sc) according to the present invention (and Contact).

Ingredient (G)
The component (G) that can be used as required in the present invention is usually a compound called a surfactant, and specifically, from the group consisting of the following (g-1) to (g-6). There may be mentioned at least one compound selected.
(G-1) polyalkylene oxide block,
(G-2) a higher aliphatic amide,
(G-3) polyalkylene oxide,
(G-4) polyalkylene oxide alkyl ether,
(G-5) alkyldiethanolamine, and (g-6) polyoxyalkylenealkylamine.

  Component (G) can coexist in the olefin polymerization catalyst for the purpose of suppressing fouling in the polymerization vessel due to electrostatic adhesion of the catalyst or polymer, or improving the particle properties of the produced polymer. . Among the components (G), (g-1), (g-2), (g-3) and (g-4) are preferable, and (g-1) and (g-2) are particularly preferable. Specific examples of (g-2) include higher fatty acid diethanolamide.

<Olefin polymer production method>
The preliminary polymerization catalyst component (Sc) according to the present invention is an olefin having 2 or more carbon atoms, for example, an olefin homopolymer such as ethylene, propylene, 1-butene, 1-octene, 4-methyl-1-pentene, or It can be used for the production of olefin copolymers.

Hereinafter, the method for producing an olefin polymer according to the present invention will be described with respect to a method for producing an ethylene polymer which is a typical example of an olefin polymer.
A suitable ethylene polymer obtained by the method for producing an olefin polymer according to the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α having 6 to 10 carbon atoms. -Copolymers with olefins. In the case of using an α-olefin having 4 carbon atoms, it is preferable to also use an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.

  In the method for producing an olefin polymer of the present invention, olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

The polymerization conditions are such that the transition metal complex (A) is usually 10 ⁻¹² to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol, per liter of reaction volume. Moreover, superposition | polymerization temperature is -50-200 degreeC normally, Preferably it is 0-170 degreeC, Most preferably, it is the range of 30-170 degreeC. The polymerization pressure is usually under conditions of normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. . Furthermore, it can also be carried out as a multistage reaction under two or more conditions with different reaction conditions.

  The molecular weight of the resulting ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.

Furthermore, the component (G) can be present in the polymerization system for the purpose of suppressing fouling in the polymerization vessel due to electrostatic adhesion of the catalyst or polymer or improving the particle properties.
For the olefin polymer obtained by the production method of the present invention, after synthesis by the above method, a post-treatment step such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary. It's okay.

  In order to suppress variations in physical property values, the olefin polymer particles obtained by the polymerization reaction and other components added as desired are melted by any method, kneaded, granulated and the like.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
[Example 1]
Preparation of solid catalyst component (Sa-1) In a reactor with a stirrer having an internal volume of 270 liters, silica gel (manufactured by Fuji Silysia Co., Ltd .: average particle size 70 μm, specific surface area 340 m ² / g, pore volume 1. 10 cm of ³ cm ³ / g, dried at 250 ° C. for 10 hours) was suspended in 77 liters of toluene, and then cooled to 0 to 5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mmol / mL in terms of Al atom) was added dropwise over 30 minutes. At this time, the system temperature was kept at 0 to 5 ° C. Subsequently, contact was performed at 0 to 5 ° C. for 30 minutes, and then the system temperature was raised to 95 ° C. over about 1.5 hours, followed by contact at 95 ° C. for 4 hours. Thereafter, the temperature was lowered to normal temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 115 liters of toluene slurry was prepared. When a part of the obtained slurry component was sampled and the concentration was examined, the slurry concentration was 122.6 g / L and the Al concentration was 0.62 mol / L.

Into a reactor with a stirrer having an internal volume of 200 mL sufficiently purged with nitrogen, 20 mL of toluene and 14.7 mL of the solid support slurry [solid support (S)] obtained above (solid content = 1.8 g, Al = 9) .0 mmol) was charged. Next, as a transition metal complex (A), a toluene solution of 0.065 mmol of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride is added and contacted at a system temperature of 20 to 25 ° C. for 1 hour. The supernatant was removed by decantation and further washed twice with hexane to prepare a slurry of the solid catalyst component (Sa-1) in a total amount of 40 ml.
When a part of the solvent after washing was collected and analyzed, the Al concentration was 0.26 mmol / L.

Preparation of prepolymerization catalyst component (Sb-1) After cooling the solid catalyst component slurry obtained above to 10 ° C, ethylene was flowed at a flow rate of 0.50 L / hr while maintaining the temperature in the system at 10 to 15 ° C. The ethylene was supplied until the ethylene absorption amount was 0.28 times the weight of the solid catalyst component. Thereafter, the supply of ethylene was stopped to obtain a slurry of the prepolymerized catalyst component (Sb-1).

Preparation of prepolymerization catalyst component (Sc-1) While maintaining the slurry of the prepolymerization catalyst component (Sb-1) at 10 ° C., 3.4 mmol of triisobutylaluminum (TiBA) and 0.49 mL of 1-hexene were added, Ethylene supply started. After the temperature in the system was raised to 35 ° C., ethylene was absorbed at a flow rate of 1.0 L / hr while adjusting the temperature to 33 to 37 ° C., and the amount of ethylene absorbed was based on the weight of the solid catalyst component (Sa-1). It supplied until it became 2.7 times. Thereafter, when the system was purged with nitrogen and allowed to stand, the supernatant liquid was transparent. When a part of the solvent was collected and analyzed, the Zr concentration was 0.094 mmol / L. This corresponds to the amount of Zr eluting at 5.8 mol% in the solid catalyst component (Sa-1).
No deposits were observed on the reactor wall and the stirring blade after the prepolymerization catalyst component (Sc-1) was prepared.

Polymerization of ethylene copolymer The supernatant of the prepolymerization catalyst component (Sc-1) slurry was removed by decantation and washed three times with hexane, and then hexane was added to make a total volume of 40 ml. Next, after raising the temperature inside the system to 35 ° C., 72 mg of Chemistat 2500 (manufactured by Sanyo Chemical Industries, Ltd.) was added as the component (G) and contacted for 2 hours. Thereafter, the supernatant was removed by decantation and washed four times with hexane. Next, the hexane slurry is transferred to a glass Schlenk tube having an internal volume of 100 mL, and the prepolymerized catalyst component (Sc-1) and the component (G) are contacted by distilling off hexane under reduced pressure at 25 ° C. Thus, 7.3 g of a prepolymerized catalyst component (Sc-1G) was obtained.

500 ml of heptane was charged into a 1 liter stainless steel autoclave sufficiently purged with nitrogen, and the system was replaced with ethylene. Then, 20 ml of 1-hexene, 0.375 mmol of triisobutylaluminum (TIBA) and the above-prepared spare were prepared. Polymerization catalyst component (Sc-1G) (130 mg) was charged, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 ° C. The polymer was recovered by filtration and dried at 80 ° C. under reduced pressure overnight to obtain 99.2 g of an ethylene / 1-hexene copolymer. The obtained polymer had a melt flow rate (MFR) of 0.17 g / 10 min, a density of 921 kg / m ³ , and a bulk specific gravity (AD) of 400 kg / m ³ . The melt flow rate was measured according to ASTM D1238-65T under conditions of 190 ° C. and 2.16 kg load.

[Comparative Example 1]
Preparation of Prepolymerization Catalyst Component (Sb- Ratio 1) In the preparation of the prepolymerization catalyst component (Sb-1) of Example 1, the ethylene absorption amount was 0.12 times the weight of the solid catalyst component (Sa-1). Except having supplied ethylene until it became, it carried out similarly to Example 1 and obtained the slurry of the prepolymerization catalyst component (Sb-ratio 1).

Preparation of prepolymerization catalyst component (Sc-ratio 1) In the preparation of prepolymerization catalyst component (Sc-1) in Example 1, prepolymerization catalyst component (Sb-ratio 1) was used instead of prepolymerization catalyst (Sb-1). The same procedure as in Example 1 was performed except that was used.

After supplying ethylene, the system was purged with nitrogen and allowed to stand. As a result, a white component with very slow sedimentation was observed. When a part of the solvent was collected and analyzed, the Zr concentration was 0.16 mmol / L. This corresponds to an amount in which 10.1 mol% of Zr in the solid catalyst component (Sa-1) is eluted.
A large amount of polymer deposits were observed on the reactor wall and stirring blade after preparation of the prepolymerization catalyst component (Sc ratio 1).

[Example 2]
Preparation of solid catalyst component (Sa-2) In a reactor with a stirrer having an internal volume of 200 mL, 20 mL of toluene under a nitrogen atmosphere, 14.7 mL of the solid support slurry obtained in Example 1 (solid content = 1.8 g, Al = 9.0 mmol). Next, as a transition metal complex (A), a toluene solution of 0.003-mmol of (3-n-butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-didiene) -T-Butyl-9-fluorenyl) zirconium dichloride 0.037 mmol of toluene solution was added and contacted at a system temperature of 20 to 25 ° C. for 1 hour, and then the supernatant was removed by decantation. After washing twice, a total amount of 40 milliliters of solid catalyst component (Sa-2) slurry was prepared.
When a part of the solvent after washing was collected and analyzed, the Al concentration was 0.24 mmol / L.

Preparation of pre-polymerization catalyst component (Sb-2) After heating the solid catalyst component (Sa-2) slurry obtained above to 40 ° C, ethylene was added while maintaining the temperature in the system at 38 to 42 ° C. It was supplied at a flow rate of 0.0 L / hr, and ethylene was supplied until the ethylene absorption amount was 0.30 times the weight of the solid catalyst component (Sa-2). Thereafter, the supply of ethylene was stopped to obtain a slurry of the prepolymerized catalyst component (Sb-2).

Preparation of prepolymerization catalyst component (Sc-2) 4.4 mmol of diisobutylaluminum hydride (DIBALH) was added while the slurry of the prepolymerization catalyst component (Sb-2) was maintained at 40 ° C., and ethylene supply was started. did. While adjusting the temperature in the system to 38 to 42 ° C., ethylene was supplied at a flow rate of 1.0 L / hr until the ethylene absorption amount was 2.7 times the weight of the solid catalyst component (Sa-2). . Thereafter, when the system was purged with nitrogen and allowed to stand, the supernatant was yellow and transparent. When a part of the solvent was collected and analyzed, the Zr concentration was 0.052 mmol / L. This corresponds to an amount of 4.8 mol% of Zr eluting in the solid catalyst component (Sa-2).
No deposits were observed on the reactor wall and the stirring blade after the prepolymerization catalyst component (Sc-2) was prepared.

Polymerization of ethylene copolymer The supernatant of the slurry of the pre-polymerization catalyst component (Sc-2) was removed by decantation, washed 4 times with hexane, and then hexane was added to make a total volume of 50 ml. Next, after raising the system temperature to 35 ° C., 45 mg of a hexane solution of Emulgen 108 (manufactured by Kao Corporation) was added as a component (G) and contacted for 2 hours. Thereafter, the supernatant was removed by decantation and washed four times with hexane. Next, the hexane slurry is transferred to a glass Schlenk tube with an internal volume of 100 mL, and the prepolymerized catalyst component (Sc-2) and the component (G) are contacted by distilling off hexane under reduced pressure at 25 ° C. Thus, 7.3 g of a prepolymerized catalyst component (Sc-2G) was obtained.

500 mL of heptane was charged into a 1 liter stainless steel autoclave sufficiently purged with nitrogen, and after replacing the system with ethylene, 3 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and the prepolymerized catalyst obtained above Component (Sc-2G) 220 mg was added, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 ° C. The polymer was recovered by filtration, and dried at 80 ° C. for 10 hours under reduced pressure to obtain 72.7 g of an ethylene / 1-hexene copolymer. The obtained polymer had a melt flow rate (MFR) of 0.24 g / 10 min, a density of 940 kg / m ³ , and a bulk specific gravity (AD) of 410 kg / m ³ .

[Example 3]
Preparation of Prepolymerization Catalyst Component (Sb-3) In the preparation of the prepolymerization catalyst component (Sb-2) of Example 2, the ethylene absorption amount is 0.67 times the weight of the solid catalyst component (Sa-2). The same procedure as in Example 2 was conducted except that ethylene was supplied to obtain a slurry of the prepolymerized catalyst component (Sb-3).

Preparation of Prepolymerization Catalyst (Sc-3) In the preparation of the prepolymerization catalyst component (Sc-2) in Example 2, the prepolymerization catalyst component (Sb-3) was used instead of the prepolymerization catalyst (Sb-2). This was performed in the same manner as in Example 2 except that ethylene was supplied until the ethylene absorption amount became 2.3 times the weight of the solid catalyst component (Sa-2).

After supplying ethylene, the system was purged with nitrogen and allowed to stand, and the supernatant was transparent. When a part of the solvent was collected and analyzed, the Zr concentration was 0.023 mmol / L. This corresponds to the amount of 2.1 mol% elution of Zr in the solid catalyst component (Sa-2).
No deposits were observed on the reactor wall and stirring blade after the prepolymerization catalyst (Sc-3) was prepared.

[Comparative Example 2]
Preparation of Prepolymerization Catalyst (Sc-Ratio 2) In the preparation of the prepolymerization catalyst component (Sc-2) in Example 2, the solid catalyst component (Sa-2) was used instead of the prepolymerization catalyst (Sb-2). This was carried out in the same manner as in Example 2 except that ethylene was supplied until the ethylene absorption amount became 3.0 times the weight of the solid catalyst component (Sa-2).

After supplying ethylene, the system was purged with nitrogen and allowed to stand. As a result, a white component with very slow sedimentation was observed. When a part of the solvent was collected and analyzed, the Zr concentration was 0.13 mmol / L. This corresponds to the amount of 12.4 mol% elution of Zr in the solid catalyst component (Sa-2).
A large amount of polymer deposits were observed on the reactor wall and the stirring blade after the prepolymerization catalyst component (Sc ratio 2) was prepared.

[Comparative Example 3]
Preparation of Prepolymerization Catalyst (Sb-Ratio 3) In the preparation of the prepolymerization catalyst component (Sb-2) of Example 2, the ethylene absorption amount was 0.11 times the weight of the solid catalyst component (Sa-2). Except having supplied ethylene until it became, it carried out similarly to Example 2, and obtained the slurry of the prepolymerization catalyst component (Sb-ratio 3).

Preparation of pre-polymerization catalyst (Sc- ratio 3) In the preparation of pre-polymerization catalyst component (Sc-2) in Example 2, pre-polymerization catalyst component (Sb-ratio 3) instead of pre-polymerization catalyst component (Sb-2) This was performed in the same manner as in Example 2 except that ethylene was supplied until the ethylene absorption amount became 2.9 times the weight of the solid catalyst component (Sa-2).

After supplying ethylene, the system was purged with nitrogen and allowed to stand. As a result, a white component with very slow sedimentation was observed. When a part of the solvent was collected and analyzed, the Zr concentration was 0.11 mmol / L. This corresponds to the amount of 10.5 mol% of Zr eluting in the solid catalyst component (Sa-2).
A large amount of polymer deposits were observed on the reactor wall and the stirring blade after preparation of the prepolymerized catalyst component (Sc ratio 3).

[Example 4]
Preparation of prepolymerized catalyst (Sb-4) The slurry of the solid catalyst component (Sa-2) obtained in the same manner as in Example 2 was heated to 40 ° C, and then the temperature in the system was increased to 38 to 42 ° C. While maintaining, ethylene was supplied at a flow rate of 1.0 L / hr. When the ethylene absorption amount was 0.25 times the weight of the solid catalyst component, the ethylene supply was stopped and the system was replaced with nitrogen. Next, 4.4 mmol of diisobutylaluminum hydride was added and contacted for 30 minutes while maintaining at 38 to 42 ° C. After standing, 25 mL of the supernatant was removed by decantation, and a washing operation for adding 25 mL of hexane was performed three times to obtain a slurry of the prepolymerized catalyst component (Sb-4).

Preparation of Prepolymerization Catalyst (Sc-4) In the preparation of the prepolymerization catalyst component (Sc-2) in Example 2, the prepolymerization catalyst component (Sb-4) was used instead of the prepolymerization catalyst component (Sb-2). This was performed in the same manner as in Example 2 except that ethylene was supplied until the ethylene absorption amount became 2.7 times the weight of the solid catalyst component (Sa-2).

After supplying ethylene, the system was purged with nitrogen and allowed to stand, and the supernatant was transparent. When a part of the solvent was collected and analyzed, the Zr concentration was 0.074 mmol / L. This corresponds to the amount of 6.8 mol% of Zr eluted in the solid catalyst component (Sa-2).
No deposits were observed on the reactor wall and the stirring blade after the prepolymerization catalyst component (Sc-4) was prepared.

[Example 5]
Preparation of solid catalyst component (Sa-5) Using a reactor with a stirrer with an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by AGC S-Tech Co., Ltd .: cumulative 50% volume distribution of laser light diffraction scattering method, 12 μm particle size, 8.5 kg of a specific surface area of 850 m ² / g, pore volume of 0.9 cm ³ / g, dried at 200 ° C. for 3 hours) was suspended in 33 L of toluene, and then a solution of methylaluminoxane in toluene (Al 83 liters (1.4 mol / L in terms of atoms) was added dropwise over 30 minutes. Next, the temperature inside the system was raised to 115 ° C. over 1.5 hours, and subsequently contacted at 115 ° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene, and then a total amount of 150 liters of a solid support toluene slurry was prepared.

When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 102.0 g / L, and the Al concentration was 0.73 mol / L.
A reactor equipped with a stirrer with an internal volume of 200 mL sufficiently purged with nitrogen was charged with 40 mL of toluene and 9.8 mL of the solid carrier slurry obtained above (solid content = 1.0 g, Al = 7.2 mmol). Next, a toluene solution of 0.052 mmol of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride is added as a transition metal complex (A), and the system temperature is 20-25. After contact at 1 ° C. for 1 hour, the supernatant was removed by decantation and further washed twice with hexane to prepare a total amount of 50 ml of the solid catalyst component (Sa-5) slurry.
When a part of the solvent after washing was collected and analyzed, the Al concentration was 0.16 mmol / L.

Preparation of Prepolymerization Catalyst (Sb-5) The slurry of the solid catalyst component (Sa-5) obtained above was charged with ethylene at a flow rate of 0.7 L / hr while maintaining the temperature in the system at 20 to 25 ° C. When the ethylene absorption amount was 0.18 times the solid catalyst component weight, the ethylene supply was stopped and the system was replaced with nitrogen.

Preparation of prepolymerization catalyst (Sc-5) To the above prepolymerization catalyst component (Sb-5) slurry, 2.0 mmol of triisobutylaluminum and 10 mg of Adekapluronic L-71 (manufactured by ADEKA) were added, and the temperature in the system was adjusted. After raising the temperature to 40 ° C., ethylene supply was started. While adjusting the temperature in the system to 38 to 42 ° C., ethylene was supplied at a flow rate of 0.9 L / hr until the ethylene absorption amount was 2.8 times the weight of the solid catalyst component. Thereafter, when the system was purged with nitrogen and allowed to stand, the supernatant liquid was transparent. When a part of the solvent was collected and analyzed, the Zr concentration was 0.035 mmol / L. This corresponds to the amount of 3.5 mol% elution of Zr in the solid catalyst component.

No deposits on the reactor wall and the stirring blade after the prepolymerization catalyst component (Sc-5) were prepared.
The supernatant of the prepolymerized catalyst component (Sc-5) slurry was removed by decantation and washed four times with hexane, and then hexane was added to make a total volume of 50 ml. When a part of the obtained slurry component was collected and analyzed, the solid content concentration was 20.2 g / L.

Polymerization of ethylene homopolymer 500 mL of heptane was charged into a 1 liter stainless steel autoclave sufficiently purged with nitrogen, and the system was substituted with ethylene, and then 0.375 mmol of triisobutylaluminum and the prepolymerization obtained above. 12 mg of the catalyst component (Sc-5) as a solid content was added, and the temperature in the system was raised to 80 ° C. Next, by continuously introducing ethylene, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 ° C. The polymer was recovered by filtration and dried at 80 ° C. for 10 hours under reduced pressure to obtain 74.4 g of an ethylene homopolymer.

[Comparative Example 4]
Preparation of Prepolymerization Catalyst (Sc-Ratio 4) In the preparation of the prepolymerization catalyst component (Sc-5) of Example 5, the solid catalyst component (Sa-5) was used instead of the prepolymerization catalyst (Sb-5). This was performed in the same manner as in Example 2 except that ethylene was supplied until the ethylene absorption amount became 3.0 times the weight of the solid catalyst component (Sa-5).

After supplying ethylene, the system was purged with nitrogen and allowed to stand. As a result, a white component with very slow sedimentation was observed. When a part of the solvent was collected and analyzed, the Zr concentration was 0.072 mmol / L. This corresponds to the amount of 7.1 mol% elution of Zr in the solid catalyst component (Sa-5).
A large amount of polymer deposits were observed on the reactor wall and the stirring blade after the preparation of the prepolymerization catalyst component (Sc ratio 4).

  The method for producing an olefin polymer using the prepolymerization catalyst component (Sc) obtained by the method for producing the prepolymerization catalyst component (Sc) used in the olefin polymerization of the present invention is a method for fouling in the reactor during prepolymerization. The production method of the present invention is extremely valuable industrially.

Claims (4)

A prepolymerized catalyst component (Sc) used for olefin polymerization, characterized in that a solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) is prepolymerized through the following two steps. ) Manufacturing method.
(1) Supplying an olefin having 2 or more carbon atoms to the solid catalyst component (Sa) under the condition that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.001 mmol / L or more and 1 mmol / L or less, and the solid catalyst Step of obtaining a prepolymerized catalyst component (Sb) by prepolymerizing an amount of 0.15 to 10 times the weight of the component (Sa) (2) The concentration of the organoaluminum compound excluding the solid content in the solvent is A step of supplying a prepolymerized catalyst component (Sc) by supplying an olefin having 2 or more carbon atoms to the prepolymerized catalyst component (Sb) and performing prepolymerization under the condition of 10 mmol / L or more   The method for producing a prepolymerized catalyst component (Sc) according to claim 1, wherein the transition metal complex (A) comprises a transition metal compound of Group 4 of the periodic table.   The method for producing a prepolymerized catalyst component (Sc) according to claim 1 or 2, wherein the solid catalyst component (Sa) comprises an organoaluminum oxy compound.   A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the prepolymerization catalyst component (Sc) according to any one of claims 1 to 3.