JPH03162402A - Solid catalyst component for polymerization of olefin and polymerization of olefin using the same component - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst component giving olefin polymer particle having a slight tackiness of particles even containing a large amount of amorphous olefin polymer part and having excellent particle size distribution and particle characteristics by using a specific method. CONSTITUTION:(A) A solid titanium catalyst component containing Mg, Ti, a halogen and, if necessary, an electron donor as essential ingredients is mixed with (B) an organic metallic compound catalyst component of I-III group metal in periodic table and, if necessary (C) an electron donor to obtain a catalyst for polymerization of olefin. Then, at least two species of alpha-olefin in an amount of 0.2-2000g per 1g the component A are subjected to random prepolymerization in the presence of said catalyst for polymerization of olefin in (D) suspended state in a hydrocarbon solvent to afford the aimed component. Besides, as the at least two species of alpha-olefin for using the pre-polymerization, ethylene and propylene are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a solid catalyst component for olefin polymerization and a method for polymerizing olefins using this catalyst component, and more particularly to a copolymer containing an amorphous polymer portion. In the production of olefin polymers, even if a large amount of amorphous olefin polymer is contained, the produced polymer particles are unlikely to stick together, and it is possible to obtain olefin polymer particles with excellent fluidity. This invention relates to a solid catalyst and a method for polymerizing olefins using this catalyst component.

Technical Background of the Invention There have already been many proposals regarding methods for producing solid titanium catalyst components containing magnesium, titanium, and halogen as essential components. It is known that an olefin polymerization catalyst comprising a metal and an organometallic compound component exhibits excellent polymerization activity for olefins. However, such catalysts for olefin polymerization are desired to be further improved in terms of polymerization activity and powder properties of the resulting polymers, particularly olefin copolymers.

For example, when trying to produce olefin polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part using the above-mentioned olefin polymerization catalyst,
As the amount of the amorphous olefin polymer part (rubber part) in the polymer particles increases, the polymer particles sometimes stick to each other and the fluidity of the polymer particles decreases.

In addition, if the polymer particles are subjected to a steaming treatment and the polymer particles are heated for the purpose of inactivating the catalyst component present in the polymer or removing volatile components, or if the polymer particles are subjected to a heat treatment during drying, In some cases, the polymer particles adhered to each other even more, and the fluidity of the polymer particles was significantly reduced.

Therefore, it is desirable to develop a catalyst for olefin polymerization that can produce olefin polymer particles that are less likely to adhere to each other and have poor fluidity even if they contain a large amount of amorphous olefin polymer. It was rare.

The present inventors have conducted intensive studies to obtain olefin polymer particles that have low stickiness even if they contain a large amount of amorphous olefin polymer moiety, have a good particle size distribution, and have excellent particle properties. , specific amounts of at least two or more α-olefins are added to an olefin polymerization catalyst formed from a solid catalyst component, an organometallic compound, and optionally an electron donor under conditions of suspension in a hydrocarbon solvent. The present invention was completed by discovering that it is sufficient to use a solid catalyst component for olefin polymerization that has been prepolymerized.

Purpose of the Invention The present invention has been made in view of the above-mentioned prior art, and provides that even if the polymer particles contain a large amount of amorphous olefin polymer portion, the stickiness of the polymer particles is small, and the particle size distribution is To provide a solid catalyst component for olefin polymerization which produces olefin polymer particles having good properties and excellent particle properties, a catalyst for olefin polymerization containing this catalyst component, and a method for polymerizing olefins using this catalyst. It is an object.

Summary of the Invention The first solid catalyst component for olefin polymerization according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, halogen, and optionally an electron donor as essential components; ] An olefin polymerization catalyst formed from an organometallic compound catalyst of metals from Groups ■ to ■ of the Periodic Table, and optionally an [C] electron donor, at least two
While suspending the catalyst in the hydrocarbon solvent [D], the solid titanium catalyst component [A]1 is mixed with at least one α-olefin.
It is characterized by being randomly prepolymerized at 0.2 to 2000 g/g.

Further, the olefin polymerization catalyst according to the present invention is a solid titanium catalyst component [I] containing magnesium, titanium, halogen, and optionally an electron donor as essential components.
A], an organometallic compound catalyst component of metals from Groups I to II of the periodic table [B], and optionally an electron donor [C];
A solid catalyst component for olefin polymerization is obtained by prepolymerizing 0.2 to 2000 g of the solid titanium catalyst component [A11] by suspending the catalyst in a hydrocarbon solvent [D] and prepolymerizing α-olebuin of at least one species. , [II] Organometallic compound catalyst component of metals from Groups ■ to ■ of the periodic table, and [1[I] Electron donor as necessary.

Furthermore, the method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized in the presence of the above-described catalyst for olefin polymerization.

DETAILED DESCRIPTION OF THE INVENTION A solid catalyst for olefin polymerization according to the present invention, a catalyst for olefin polymerization containing this catalyst component, and a method for polymerizing olefins using this catalyst will be described in detail below.

In the present invention, the term "polymerization" refers not only to homopolymerization, but also to
It is sometimes used to include copolymerization, and the term polymer is sometimes used to include not only homopolymers but also copolymers.

FIG. 1 shows a flowchart explaining the preparation process of the olefin polymerization catalyst according to Honkotomei.

The solid catalyst component for olefin polymerization according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, a halogen, and optionally an electron donor as essential components, and [B] Group I of the periodic table. - An olefin polymerization catalyst formed from an organometallic compound catalyst component of a Group (III) metal and, if necessary, a [C] electron donor, at least two
It is formed by prepolymerizing at least 0.2 to 2000 g of α-olefin per 1 g of the solid titanium catalyst component [A] by suspending the catalyst in a hydrocarbon solvent [D].

First, the solid titanium catalyst component [A] will be explained.

Such a solid titanium catalyst component [A] is prepared, for example, by bringing the following magnesium compound, titanium compound, and, if necessary, an electron donor into contact with each other.

In the present invention, as a titanium compound used for preparing the solid titanium catalyst component [A], for example, Ti(OR
) X (R is a hydrocarbon group, g 4-g
-h Same as above, and 0≦h≦3). More specifically, Tet-44 titanium halides such as Ti CI STi B+ , Ti I4; T + Cl3; Trihalogens 4 such as Cl3, TiQC2H5)Br3, TiOisoCH)B+3
9 Alkoxy titanium chloride; T i (OC H ) C I! 2,32 T1(OC2H5)2Cl2, T+(On-C4 H9)2 CI 2, Ti(OC
2H5) 2Br2 and other dihalogenated dialkoxytitaniums; T'i(OC H3 ) 3 0l -Ti(OC2
Monohalogenated trialkoxytitaniums such as H5) 3Cl, Ti(On-C4H9)3CI, T1(OC2H5)3Br: TifOCH3)4, T! (O C 2 H s ) 4, T i (O
n-C4H9)4TiOiso-C,
Hg) 4T i (0-2-ethylhexyl)4
Examples include tetraalkoxytitanium such as.

Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include magnesium compounds having reducing properties and magnesium compounds not having reducing properties.

Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diptylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, probylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds can be used alone or in the form of a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isoproboxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isobroboxymagnesium,
ptoxymagnesium, n-octoxymagnesium,
Examples include alkoxymagnesiums such as 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silica compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition, in the present invention, the magnesium compound includes not only the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, but also complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may be a mixture of. Furthermore, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride,
Magnesium oxychloride is preferably used.

In the present invention, it is preferable to use an electron donor when preparing the solid titanium catalyst component [A]. As the electron donor, an organic carboxylic acid ester, preferably a polyhydric carboxylic acid ester or an organic Examples include carboxylic acid esters, and specifically, compounds having a skeleton represented by the following formula are used.

R3 -C-COOR' 1 R' -c-cOoR2 In the above formula, Rl is a substituted or unsubstituted hydrocarbon group, R2 R5, R6 are a hydrogen atom, a substituted or unsubstituted hydrocarbon group, R3 and R4 are hydrogen atoms or substituted or unsubstituted hydrocarbon groups. Note that at least one of R R is preferably a substituted or unsubstituted hydrocarbon group. Also R
3 and R4 may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing different atoms such as N, O, and S, such as 1C-0-C- -COOR, -COOH, -OH,
Examples include substituted hydrocarbon groups having structures such as -So3H and -C-N-C- -NH2.

12 Among these, at least one of R and R is
Diesters derived from dicarboxylic acids which are alkyl groups having 2 or more carbon atoms are preferred.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, diptyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethylmalonate, diethyl isopropyl malonate. , diethyl butylmalonate, diethyl phenylmalonate, diethyl malonate, diethyl allylmalonate, diethyl diisobutylmalonate, diethyl di-normalbutylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, Diisobutyl butyl maleate, diethyl butyl maleate, β-
Aliphatic polycarboxylic acid esters such as diisoprobyl methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconate, dimethyl citraconate; diethyl l2-cyclohexanecarboxylate, l, Aliphatic polycarboxylic acid esters such as diisoptyl 2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisoptyl phthalate, diethyl phthalate, ethyl phthalate Isoptyl, mono-n-butyl phthalate, ethyl n-butyl phthalate, di-n phthalate
-Provil, diisopropyl phthalate, di-n- phthalate
Butyl, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-heptyl phthalate,
Diisoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, penzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, diptyl naphthalene dicarboxylate , aromatic polycarboxylic acid esters such as triethyl trimellitate and dibutyl trimellitate; and esters derived from heterocyclic polycarboxylic acids such as 34-furandicarboxylic acid.

Other examples of polyhydric carboxylic acid esters include long-chain carboxylic acid esters such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Mention may be made of esters derived from dicarboxylic acids.

Among these polyhydric carboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and compounds derived from phthalic acid, maleic acid, substituted malonic acid, etc. and an alcohol having 2 or more carbon atoms are more preferred. Preferred are esters, and particularly preferred are diesters obtained by the reaction of phthalic acid and an alcohol having 2 or more carbon atoms.

These polyvalent carboxylic esters do not necessarily need to be used as starting materials, and these polyvalent carboxylic esters may be used in the process of preparing the solid titanium catalyst component [A]. A polyhydric carboxylic acid ester may be produced in the preparation step of the solid titanium catalyst component [A] using a compound that can be derived. For example, phthalic anhydride, phthalic acid, and phthalic acid chloride may be esterified in the catalyst synthesis process.

In the present invention, electron donors other than polyhydric carboxylic acids that can be used when preparing the solid titanium-based catalyst [A] include alcohols used during prepolymerization or main polymerization as described below. , amines, amides, ethers, ketones, nitriles, phosphines,
Organosilicon compounds such as stipines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes,
Examples include organic acids and amides and salts of metals belonging to Groups 1 to 2 of the periodic table. Other preferable examples include diether compounds.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metal magnesium), titanium compound, and, if necessary, an electron donor into contact with each other. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and, if necessary, an electron donor can be employed. Note that the above components include, for example, silicon,
The contact may be made in the presence of other reaction reagents such as phosphorus and aluminum.

Several examples of methods for producing these solid titanium catalyst components [A] will be briefly described below.

Note that in the method for producing the solid titanium catalyst component [A] described below, an example will be described in which an electron donor is used, but this electron donor does not necessarily have to be used.

(1) A method in which a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor is reacted with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like.

Moreover, when reacting as described above, a solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. Note that in this method, the above electron donor is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid titanium complex is precipitated by reacting a liquid titanium compound in the presence of an electron donor.

(3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound.

(4) The reaction product obtained in (1) or (2),
A method for further reacting an electron donor and a titanium compound.

(5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Also,
A magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Note that in this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound, or an aromatic hydrocarbon.

(7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound.
(8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

(9) Magnesium compound and alkoxytitanium and/
Alternatively, a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether is reacted with a halogen-containing compound such as a titanium compound and/or a halogen-containing silicon compound, the method comprising: A method of coexisting with an electron donor such as a strong phthalic acid diester.

(10) Solid g having an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ) of particle size distribution of 3.0 or less. It is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under reaction conditions with or without pretreatment with reaction aids such as silicon compounds.

(l1) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted, preferably in the presence of an electron donor, so that the average particle size is 1 to 200 a.
m, a solid component having a geometric standard deviation (δ) of particle size distribution of 3.0 or less is precipitated.

g Further, if necessary, it is reacted with a liquid titanium compound, preferably titanium tetrachloride, or with a liquid titanium compound and an electron donor.

(12) What is the reducing ability of magnesium compounds that are liquid and have reducing ability, and magnesium compounds such as polysiloxane or halogen-containing silicon compounds? By pre-contacting the reaction aid with a reaction aid that can cause 1 to 1 loss, the average particle diameter is 1 to 200 μm.1 particle size distribution. After precipitating a solid component with a geometric standard deviation (δg) of 3.0 or less,
This solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and an electron donor.

(13) After contacting a magnesium compound having reducing ability with an inorganic or organic carrier such as silica, the carrier is then brought into contact with a halogen-containing compound or without contacting with a liquid titanium compound, preferably tetrachloride. The magnesium compound supported on the carrier is reacted with the titanium compound by contacting with titanium or the titanium compound and an electron donor.

(+4) In methods (II) to (12), by coexisting an inorganic carrier such as silica or alumina or an organic carrier such as polyethylene, polypropylene, or polystyrene, the Mg compound is supported on these carriers.

The solid titanium catalyst components listed in (1) to (12) above [
Among the preparation methods of A], a method using liquid titanium halide during catalyst preparation, a method using a titanium compound after use, or a method using a halogen or carbonized hydrocarbon when using a titanium compound is preferable. Especially (10) to (1
The method listed in 4) is preferred.

The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per mol of magnesium compound is about 0. 0.01 to 5 mol, preferably 0.05 to 2 mol, the titanium compound is about 0.01 to 5 mol, preferably 0.05 to 2 mol.
It is used in an amount of 0.01 to 500 mol, preferably 0.05 to 300 mol.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen, and, if necessary, an electron donor as essential components.

In this solid titanium catalyst component [A], halogen/
Titanium (atomic ratio) is about 4-200, preferably about 5-1
00, and the electron donor/titanium (molar ratio) is approximately 0.
．． 1 to 10, preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains magnesium halide with a smaller crystal size than commercially available magnesium halide, and usually has a specific surface area of about 50nf.
/g or more, preferably about 60 to 1000 rrf/g, more preferably about 100 to 800 rrf/g. Since the solid titanium catalyst component [A] is composed of the above-mentioned components to form a catalyst component, the composition of the solid titanium catalyst component [A] is not substantially changed by hexane washing.

Such solid titanium catalyst component [A] has an average particle size of 5 to 300 μm, preferably 10 to 150 μm, more preferably 15 to 100 μm, and a geometric standard deviation of particle size distribution of 1.0 to 3.0 μm. Preferably 1.0 to 2.0, more preferably 1.0 to 1.5, particularly preferably 1.0 to 1.5
A value of 1.3 is desirable.

Note that the average particle size of the solid titanium catalyst component [A] can be measured by a light transmission method. Specifically, catalyst component [A] was added to the decalin solvent at a concentration of 0.1% by weight.
The dispersion prepared by charging is taken into a measuring cell, a thin light is applied to the cell, and the particle size distribution is measured by continuously measuring changes in the intensity of the light that the particles pass through the thin light. Based on this particle size distribution, the standard deviation (δ) is calculated from the lognormal distribution function. More specifically, the standard deviation 16 (δ ) is determined as the ratio (θ5o/θ16) between the average particle diameter (θ5o) and the particle diameter (θ ) which is 16% by weight considering the small particle size. Note that the average particle diameter of the catalyst is g weight average particle diameter.

Further, the catalyst component [A] preferably has a shape such as a true sphere, an elliptical sphere, or a granule, and the aspect ratio of the particles is preferably 3 or less, more preferably 2 or less, particularly preferably 1. 5 or less.

The aspect ratio is determined by observing the catalyst particle group with an optical microscope,
At that time, it is determined by measuring the long sleeve and short axis of 50 arbitrarily selected catalyst particles.

Regarding the preparation method of such a highly active titanium catalyst component, for example, JP-A-50-108385 and JP-A No. 5G
-126590 publication, 51-20297 publication, 51-28189 publication, 51-64586 publication,
No. 51-92885, No. 51-136625, No. 52-874119, No. 52-10059
Publication No. 6, Publication No. 52-1476118, Publication No. 52-1
No. 04593, No. 53-2580, No. 53-
No. 40093, No. 53-40094, No. 53
-43094 publication, 55-N5102 publication, 5
5-HSll] Publication No. 3, Publication No. 55-162710, Publication No. 56-811, Publication No. 56-11908,
56-111406, 5g-83006, 5g-138705, 5g-H8706
No. 5g-H8707, No. 58-H870
No. 8, No. 58-138709, No. 5g-N8
Publication No. 710, Publication No. 581N8715, Publication No. 60-2
Publication No. 3404, Publication No. 61-21109, Publication No. 61-
It is disclosed in Japanese Patent No. 37802, Japanese Patent No. 61-37803, and the like.

Next, the organometallic compound catalyst component [B] will be explained.

The organometallic compound catalyst component [B] of metals from Groups I to II of the periodic table is a hydrocarbon group containing, for example, 15, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X represents a halogen atom, Om≦3, 'n is 0≦n<3, p is 0≦
p<3, q is a number O≦q<3, and m+n+
(p + q = 3); (2) a complex alkylated compound of Group (2) metal and aluminum (wherein M is L t, Na, K, and R1 is the same as above); (i) R' R2M2 (wherein R and R2 are the same as above.

1 M2 is MgsZn or Cd) Group 1 or Group 2 dialkyl compounds are used.

Examples of the organic aluminum compounds belonging to (i) above include the following compounds.

General formula R' IllAI (OR2'')3-m (wherein, R and R2 are the same as above, m is preferably a number of 1.5≦m≦3), (wherein, Rl is Same as above.
3), (wherein R1 is the same as above. m is preferably 2≦m<3
), (wherein R1 and R2 are the same as above.
+ q = 3).

More specifically, aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkyl such as diethylaluminum ethoxide and diptylaluminum ptoxide. Aluminum alkoxide; Alkylaluminium sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkyl having a homogeneous composition of 22.5Q.S expressed as R' AI (OR > etc.) Aluminum; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; ethylaluminum dichloride, probylaluminum dichloride partially halogenated alkyl aluminum dihalides such as alkyl aluminum dihalides such as , butyl aluminum dipromide; dialkyl aluminum hydrides such as diethylaluminum hydride, dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride, etc. Other partially hydrogenated alkyl aluminums such as dihydrides; partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum poxychloride, ethylaluminum ethoxy bromide, etc. may be mentioned.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C H ) AIOAl (
C2H5)2,2 5 2 (C H ) AA'OAl (C4H9)2
, 49202H5 methylaluminoxane, and the like.

Examples of compounds belonging to (ii) above include LiAl (C
2H5)4, LiAl(C7H15)4, and the like.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined.

In the present invention, when producing a solid catalyst for olefin polymerization, an electron donor [C] can be used as necessary, but such an electron donor [C] can be
Alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers,
Oxygen-containing electron donors such as acid amides, acid anhydrides, and alkoxysilanes, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and polyhydric carboxylic acid esters as described above can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isoprobyl alcohol, cumyl alcohol, isoprobyl benzyl Alcohols with 1 to 18 carbon atoms such as alcohol; phenols with 6 to 20 carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, probylphenol, nonylphenol, cumylphenol, naphthol, etc. Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, and nat aldehyde. Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, probyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-maleate
butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisoprobyl tetrahydrophthalate, diethyl phthalate,
Organic acid esters having 2 to 30 carbon atoms, such as diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, penzoyl chloride , the number of carbon atoms in toluyl chloride, anisyl chloride, etc.? ~15 acid halides; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl 21 ter epoxy p-
Ethers and diethers having 2 to 20 carbon atoms such as menthane; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, Amines such as pyridine, picoline, and tetramethylenediamine; Nitriles such as acetonitrile, penzonitrile, and tolnitrile; Acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride.

Further, as the electron donor [C], the following general formula [I
Organosilicon compounds represented by al can also be used.

R Si(OR' )4■ - [I al
n [wherein R and R° are hydrocarbon groups, 0<n<4
] Specifically, the organosilicon compound represented by the above general formula [Ia] includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, topyl Methyldimethoxysilane, tobutylmethyldiethoxysilane, toamylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis0-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p4 Lyldimethoxysilane, bis p-tolyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyl Trimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltrieth. xysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane,
Ethyltriethoxysilane, vinyltriethoxysilane, tobutyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyl Triisobroboxysilane, vinyltriptoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2
- norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (zllylox;) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane,
Dimethyltetraethoxydisiloxane and the like are used.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, [-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimeth. Preferred are xysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Furthermore, as the electron donor [C], the following general formula [
Organosilicon compounds represented by IIal can also be used.

[Wherein, R1 is a cyclobentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group, m is O≦m≦2. ] In the above formula [IIa], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include, in addition to the cyclopentyl group, cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclobentyl group, and 2,3-dimethylcyclopentyl group.

Further, in formula [IIa], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a probyl group, an isoprobyl group, a butyl group, or a cyclopentyl group having an alkyl group. , an alkyl group such as a hexyl group, or a cyclopentyl group having an alkyl group and a cyclopentyl group exemplified as R1.

Further, in formula [IIa], R3 is a hydrocarbon group, and examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Among these, R1 is a cyclopentyl group, and R2
It is preferred to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyl; Dialkoxysilanes such as dimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentyl Examples include monoalkoxysilanes such as methylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, pentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferred. Other preferred compounds include diether compounds.

In the present invention, the solid titanium catalyst component [A] as described above is used.
, an organometallic compound catalyst component CB of a metal from Group I to Group II of the periodic table], and optionally an electron donor [C].
- Random prepolymerization of olefins. This prepolymerization is carried out at a rate of 0.2 to 20% per 1 g of solid titanium catalyst component [A].
At least two or more α
- carried out by prepolymerizing the olefin.

In such prepolymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.

The solid titanium catalyst component [A] in the prepolymerization is usually about 0.001 to 100 mmol, preferably about 0 mmol in terms of titanium atoms, per inert hydrocarbon medium LA' to be described later.
．． It is desirable to use an amount of 0.1 to 50 mmol, particularly preferably 0.1 to 20 mmol.

The amount of organometallic compound catalyst [B] is 0.2 to 2000g, preferably 1.0g per 1g of solid titanium catalyst component [A].
It may be used in an amount such that ~2000 g of prepolymer is produced.

The electron donor [C] is used as necessary, and is 0.1 per mole of titanium atom in the solid titanium catalyst component [A].
It is preferred to use amounts of ~50 mol, preferably 0.5-30 mol, particularly preferably 1-10 mol.

Prepolymerization in the present invention is performed using an inert hydrocarbon solvent [D]
This is carried out by randomly copolymerizing at least two kinds of α-olefins while suspending the solid titanium catalyst component [A] as described above.

At least two types of α in the solid titanium catalyst component [A]
- To randomly copolymerize olefins, for example, the first method is to randomly copolymerize at least two types of α-olefins, and the second method is to block each α-olefin. A method of copolymerizing is mentioned, and a third method is to copolymerize one kind of α-
After homopolymerizing the olefin, at least two or more α-
A method of copolymerizing olefins can be mentioned. Among these, the first and third methods are preferred, and the first method is particularly preferred.

Specifically, the hydrocarbon medium [D] used at this time is a linear or branched aliphatic hydrocarbon such as propane, butane, pentane, hexane, hebutane, octane, decane, dodecane, kerosene; - Alicyclic hydrocarbons such as cyclobentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The at least two olefins used in the prepolymerization may be the same as or different from the olefins used in the main polymerization described later, and α-olefins having 2 to 10 carbon atoms are preferably used.

As such α-olefins having 2 to 1 o carbon atoms,
Ethylene, propylene, l-butene, ■-pentene, 3
-Methyltoptene, 4-methyl-1-pentene, 3-
Methyl-1-pentene, l-hebutene, l-octane,
1-decene etc. are used. Among these, especially carbon number 2~
α-olefin No. 6 is preferably used.

In the present invention, it is particularly preferable that ethylene and propylene be randomly prepolymerized in the olefin polymerization catalyst as described above. In particular, polymer particles containing a large amount of amorphous olefin polymer moiety and having good particle properties, such as polymer particles containing 30% by weight or more of amorphous olefin polymer moiety and having good particle properties. To obtain C▲, prepolymerization is carried out, for example, with 70-98 mol% propylene and 30-2
It is preferable to copolymerize propylene and ethylene using a gas mixture consisting of mol% ethylene.

The reaction temperature during prepolymerization is usually about -20 to +100°C.
, preferably about -20 to +80°C, more preferably O
It is desirable that the temperature is in the range of ~+40°C.

In addition, in the prepolymerization, it is also possible to use a molecular weight regulator such as hydrogen. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 35° C. is about 0.2 dJ/g or more, preferably about 1 to 2 0? It is desirable to use the amount such that #/g.

As described above, a solid titanium catalyst component [A], an organometallic compound catalyst component of Groups I to II of the periodic table [B],
While suspending an olefin polymerization catalyst formed from an electron donor [C] in a hydrocarbon solvent [D] if necessary, at least two or more α-olefins are randomly prepolymerized. When a solid catalyst component for olefin polymerization is prepared using Preliminary I! At least a portion of the prepolymer produced in the Ir synthesis step is dissolved in the hydrocarbon solvent [D]. In the solid catalyst component for olefin polymerization obtained,
98% by weight or less of the prepolymer produced in the prepolymerization step, preferably 97 to 60% by weight, more preferably 96 to 7% by weight
0% by weight, particularly preferably 94-80% by weight, remains.

The amount of prepolymer per 1 g of Ti catalyst component [A1] remaining in the catalyst component for olefin polymerization is determined as follows.

After the prepolymerization, the solvent suspension of the prepolymerized catalyst is separated by filtration, the obtained solid part is dried, and the solid part is depolymerized.
Calculate i [W, ]. On the other hand, the filtrate part was also dried in the same way, and the amount of polymer dissolved in the filtrate [WL] (Assuming that the entire amount of the organometallic compound component and electron donor component is present in the filtrate part, that amount is subtracted) seek. From these values, the amount of prepolymer remaining in the olefin polymerization catalyst component per 1 g of Ti catalyst component [A] can be determined.

Note that the operation of dissolving some of the polymer into the solvent as described above does not necessarily have to be carried out in the prepolymerization step, and after the prepolymerization, the prepolymerization catalyst component is heated to a higher temperature than the prepolymerization in a hydrocarbon solvent. Therefore, a method may be adopted in which a part of the polymer is eluted into a solvent, or a method in which a part of the polymer is eluted into a solvent by using a solvent from which the polymer can be easily eluted.

Prepolymerization as described above can be carried out batchwise or continuously. Among these, batch type is preferred.

In the main polymerization of olefin, the solid catalyst component for olefin polymerization obtained as described above [11], the organometallic compound catalyst component [II] of metals from Group I to Group II of the periodic table, and, if necessary, Accordingly, catalysts for olefin polymerization formed from electron donors [ml] are used.

The organometallic compound catalyst component [II] of metals from Groups II to II of the periodic table is a solid catalyst component for olefin polymerization [
The same organometallic compound catalyst component [B] of metals from Groups 1 to 2 of the periodic table used in the preparation of [B] is used, but it does not necessarily have to be the same.

Further, as the electron donor [m], the same one as the electron donor [C] used in preparing the solid catalyst component [I] for olefin polymerization is used, but it does not necessarily have to be the same. .

Main polymerization of olefin is carried out using the above-mentioned catalyst for olefin polymerization.Olefins that can be used in main polymerization include ethylene, propylene,
-butene, 1-bentene, 3-methyl-1-butene, 4
-methyl-1-pentene, 3-methyl-1-pentene,
Examples include olefins having 2 to 20 carbon atoms such as 1-octene.

In the present invention, the main polymerization of olefin is carried out in a gas phase or in a slurry state.

When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can also be used.

In the polymerization method of the present invention, the solid catalyst component [I] is usually about 0.0 Ti atoms per 11 polymerization volumes.
0001-0.5 mmol, preferably about 0.005-0.005 mmol
It is used in an amount of 0.1 mmol. In addition, the organometallic compound catalyst component [II] usually contains about 1 to 2 metal atoms per mole of titanium atoms in the prepolymerized catalyst component in the polymerization system.
000 mol, preferably about 5 to 500 mol. Furthermore, the electron donor [111] is usually about 0.001 to 10 mol, preferably about 0.001 to 10 mol, per 1 mol of metal atom in the organometallic compound catalyst component [III].
0.01 to 2 mol, particularly preferably about 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted and a polymer with a high melt flow rate can be obtained.

In the present invention, the polymerization temperature of the olefin is usually about 0 to 1
30°C, preferably about 20 to 100°C, and the pressure is usually normal pressure to 100 kg/at, preferably about 2 to 50 kg
/al. In the polymerization method of the present invention, polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Further, in the present invention, the main polymerization can be carried out in two or more stages by changing the reaction conditions. Particularly in the present invention, when producing polymer particles containing a crystalline olefin polymer portion and an amorphous olefin polymer portion, for example, first, α- such as propylene is added to the olefin polymerization catalyst.
A crystalline olefin polymer portion is formed by homopolymerizing olefins, and then an amorphous olefin polymer portion is formed by randomly copolymerizing at least two or more α-olefins such as propylene and ethylene. is preferred.

More specifically, in the present invention, when producing polymer particles used as raw materials, a crystalline olefin polymer portion and an amorphous olefin polymer portion are separated by supplying two or more types of monomers to a polymerization pot. Examples include a method in which they are produced simultaneously, or a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion are performed separately and in series using at least two or more polymerization vessels. . In this case, the latter method is preferred from the viewpoint that the molecular weight, composition, and composition of the amorphous olefin polymer portion can be freely changed.

The most preferred method is to synthesize a crystalline olefin polymer part by gas phase polymerization and then synthesize an amorphous olefin polymer part by gas phase polymerization, or to synthesize a crystalline olefin polymer part by using a monomer as a solvent. After synthesizing,
Examples include a method of producing an amorphous olefin polymerization part by gas phase polymerization.

Moreover, especially by adding reactive reagents such as oxygen and alcohol to the gas phase polymerization step, polymer particles with even better particle properties can be obtained.

When olefin (co)polymerization is carried out using the above-mentioned olefin polymerization catalyst, blocking may occur even if the particles have good particle properties and contain a large amount of amorphous olefin polymer. First, it is possible to produce olefin polymer particles with a good particle size distribution and excellent particle properties.

Further, in the present invention, since the yield of the polymer per olefin polymerization catalyst is high, the catalyst residue in the polymer, especially the halogen content, can be relatively reduced. Therefore, the operation of removing the catalyst in the polymer can be omitted, and rusting of the mold can be effectively prevented when molding a molded article using the produced olefin polymer.

Effects of the Invention According to the present invention, the polymer particles have low stickiness even if they contain a large amount of amorphous olefin polymer portion, have a good particle size distribution, and have excellent particle properties. It is possible to manufacture one.

(Hereinafter, blank spaces) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Catalyst component [Preparation of AI] High-speed stirring device 1 with an internal volume of 2 liters! (manufactured by Tokushu Kika Kogyo) was sufficiently replaced with N2rIi, and 7 ooml of refined kerosene was added to commercially available M!
24.2 g of CI 2 10 J 1 ethanol and 3 g of the trade name Mazol 320 (manufactured by Kao Atlas ■, sorbitan distearate) were added, and the system was heated to 800 tp at 120° C. while stirring. Stirred for 30 minutes. Under high-speed stirring, using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-liter glass flask (equipped with a stirrer) filled with 1 liter of refined kerosene pre-cooled to -10°C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After 7.5 g of the carrier was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was heated to 120°C. After stirring and mixing at 120°C for 2 hours, the solid part was collected by filtration and filtered again at 150 m
1 of titanium tetrachloride, and stirred and mixed again at 130° C. for 2 hours.

Furthermore, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to remove the solid catalyst component (
A) was obtained. The components are 2.2% by weight of titanium in terms of atoms;
The contents were 63% by weight of chlorine, 20% by weight of magnesium, and 5.5% by weight of diisobutyl phthalate. Average particle size is 64μm
A truly spherical catalyst with a geometric standard deviation (δ) of particle size distribution of 1.5 was obtained.

[Preliminary polymerization] The catalyst component [A] was prepolymerized as follows.

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 0.0 ml of triethylaluminum was added.
After charging 66 mmol of cyclohexylmethyldimethoxysilane, 0.13 mmol of cyclohexylmethyldimethoxysilane, and 0.066 mmol of the Ti catalyst component [A] in terms of titanium atoms, propylene gas and ethylene gas were charged at 4.5 Nl hours and 0.5 Nl hours, respectively. The mixture was supplied to the liquid phase portion of the polymerization vessel for 100 minutes at a rate of 100 min./hr while being mixed. Temperature during prepolymerization is 20℃±2
I kept it. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of analysis, approximately 92 g of polymer was prepolymerized per 1 g of Ti catalyst component [A] in the solid catalyst component prepolymerized as described above, and on the other hand, about 92 g of polymer was prepolymerized per 1 g of Ti catalyst component [A]. The amount of polymer was equivalent to 6.2 g per 11 g of Ti catalyst component [A1].

[Manufacture of copolymer] 0.5 kg of propylene and hydrogen IN liter were added to a 2-liter polymerization vessel at room temperature, and the temperature was raised to 60°C. 1.8 mmol of triethylaluminum, 0.18 mmol of cyclohexylmethyldimethoxysilane, To the prepolymerized catalyst component [A], 0.006 mmol in terms of titanium atoms was added, and the temperature inside the polymerization vessel was maintained at 70° C. to carry out homopolymerization of propylene. Forty minutes after the temperature reached 70°C, the vent valve was opened and propylene was purged until the inside of the polymerization vessel reached normal pressure.

After completion of purging, copolymerization was carried out successively.

In other words, when ethylene is 80 Nll, propylene is 120
Nl/h, and hydrogen was supplied to the polymerization reactor at a rate of 3.1 NA'/h. The vent opening of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg/al·G.

The temperature during copolymerization was kept at 70°C. The copolymerization time was 90 minutes, and after this time the copolymerization was terminated by purging the gas in the polymerization vessel. Table 1 shows the physical properties of the obtained copolymer.

Example 2 [Preliminary Polymerization] The catalyst component [A] used in Example 1 was prepolymerized as follows.

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 5 mmol of triethylaluminum, 1 mmol of cyclohexylmethyldimethoxysilane, and 0.5 mmol of the Ti catalyst component [A] were charged in terms of titanium atoms. After that, propylene gas and ethylene gas were supplied to the liquid phase part of the polymerization reactor for 70 minutes while being mixed at a rate of 18 rl/hr and 2 Nl/hr, respectively. The temperature was maintained at 20°C±2 during the prepolymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of the analysis, approximately 37 g of polymer was prepolymerized per 1 g of Ti catalyst component [A] in the solid catalyst component prepolymerized as described above, and the polymer dissolved in the solvent during prepolymerization was The combined amount is the Ti catalyst component used [A] 1
It was equivalent to about 2.5 grams per gram.

[Production of copolymer] In the production of the copolymer of Example 1, the copolymerization time was 50
A copolymer was produced in the same manner as in Example 1, except that the copolymer was divided into 50%. Table 1 shows the physical properties of the obtained copolymer.

Comparative Example 1 [Prepolymerization] In the prepolymerization of the catalyst component [A] used in Example 1, the monomers supplied were changed from propylene gas and ethylene gas to propylene gas alone at a rate of 4.4 Nl/hour. , was conducted in the same manner as in Example 1.

[Production of copolymer] The copolymer was produced in the same manner as in Example 1. Table 1 shows the physical properties of the obtained copolymer.

Comparative Example 2 [Prepolymerization] The monomers supplied in the prepolymerization of the catalyst component [A] used in Example 2 were changed from propylene gas and ethylene gas to propylene gas alone at a rate of 19 NA'/hour. The same procedure as in Example 2 was carried out.

[Manufacture of copolymer] The copolymer was manufactured in the same manner as the method for manufacturing the copolymer of Example 2. Table 1 shows the physical properties of the obtained copolymer.

Example 3 [Prepolymerization] In the prepolymerization of the catalyst component [A] used in Example 2, the propylene gas and ethylene gas supplied were changed to rates of 12.3 NA'/hour and 3.1 Nl/hour, respectively. Except for this, the same procedure as in Example 2 was carried out.

As a result of the analysis, it was found that the solid catalyst component prepolymerized as described above contained approximately 26 g of polymer per 1 g of Ti catalyst component [A1], while the polymer dissolved in the solvent during prepolymerization was The amount was equivalent to about 3.0 g per 1 g of Ti catalyst component [A].

[Production of copolymer] In the production of the copolymer of Example 1, the copolymerization time was 70
The same procedure as in Example 1 was carried out except that the sample was divided into minutes. Table 1 shows the physical properties of the obtained copolymer.

Example 4 [Prepolymerization] The catalyst component [A] was prepolymerized as follows. did.

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 0.66 mmol of triethylaluminum, 0.13 mmol of dicyclobentyldimethoxysilane, and the Ti catalyst component [A] were added. After charging 0.066 mmol in terms of titanium atoms, 3.73 ml of hexene 1 was charged, and 3.73 ml of propylene gas was charged.
．． It was fed into the liquid phase of the polymerization vessel for 100 minutes at a rate of 6 Nl/h. The temperature was maintained at 20°C±2 during the prepolymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of analysis, approximately 88 g of polymer was prepolymerized per 1 g of Ti catalyst component [A] in the solid catalyst component prepolymerized as described above; The amount of polymer is Ti catalyst component [A11g
Approximately 4. It was equivalent to Og.

[Manufacture of copolymer] The copolymer was manufactured in the same manner as the method for manufacturing the copolymer of Example 1. Table 1 shows the physical properties of the obtained copolymer.

The copolymer particles were dried in the following manner.

Stainless steel double ferrite stirring blade (width 10m)
100 g of copolymer particles are charged into a glass cylindrical round-bottomed flask with an internal diameter of 95 marks and a depth of 200 mm, equipped with a 100 g copolymer particles. 1 while stirring at a speed of about 30 + pm.
Dry in an oil bath at 00°C for 1 hour.

Drying is performed under a nitrogen atmosphere. After drying for 1 hour, the copolymer particles are taken out and allowed to cool to room temperature.

[Brief explanation of the drawing]

FIG. 1 is a flowchart illustrating a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1) [A] A solid titanium catalyst component containing magnesium, titanium, halogen, and optionally an electron donor as essential components, and [B] Groups I to III of the periodic table. At least two or more α-olefins are added to an olefin polymerization catalyst formed from a metal organometallic compound catalyst component and, if necessary, an electron donor [C], and the catalyst is added to a hydrocarbon solvent [D]. A solid catalyst component for olefin polymerization obtained by randomly prepolymerizing 0.2 to 2000 g per 1 g of the solid titanium catalyst component [A] while suspending the solid titanium catalyst component. 2) The catalyst component according to claim 1, wherein the electron donor in the solid titanium catalyst component [A] is an organic carboxylic acid ester or an ether compound. 3) At least two or more α-olefins have 2 carbon atoms
The catalyst component according to claim 1, which is an α-olefin of ~8. 4) The amount of prepolymer present in the solid titanium catalyst component [A] is 97 to 97% of the amount of prepolymer produced in the prepolymerization step.
Catalyst component according to claim 1, which is 60% by weight. 5) Solid titanium catalyst component [A] 1 to 1000 per gram
The catalyst component according to claim 1, wherein at least two or more α-olefins of g are prepolymerized. 6) The particle size of the solid titanium catalyst component [A] is 1 to 200
The catalyst component according to claim 1, which is μm. 7) The geometric standard deviation of the solid titanium catalyst component [A] is 1.
The catalyst component according to claim 1, which has a molecular weight of 0 to 3.0. 8) [I] Solid titanium catalyst component [A] containing magnesium, titanium, halogen and, if necessary, an electron donor as essential components, and an organometallic compound catalyst of metals from Groups I to III of the Periodic Table. At least two or more α-olefins are suspended in an olefin polymerization catalyst formed from component [B] and, if necessary, an electron donor [C], and the catalyst is suspended in a hydrocarbon solvent [D]. A solid catalyst component for olefin polymerization obtained by prepolymerizing 0.2 to 2000 g per 1 g of the solid titanium catalyst component [A]; and [II] an organometallic compound of a metal from Group I to Group III of the periodic table. An olefin polymerization catalyst formed from a catalyst component and, if necessary, a [III] electron donor. 9) The catalyst for olefin polymerization according to claim 8, wherein the electron donor [III] is a compound having an Si-O-C bond, a compound having an Si-N-C bond, or an ether compound. 10) In the presence of the olefin polymerization catalyst according to claim 8, an α-olefin having 2 to 10 carbon atoms is
A method for producing an olefin polymer, which comprises polymerizing or copolymerizing at a temperature of 0° C. in a gas phase, or in a suspension state using a monomer as a solvent and in a gas phase state. 11) The method according to claim 10, characterized in that an olefin copolymer comprising a crystalline olefin polymer part and an amorphous olefin polymer part is produced.