JPH03203907A - Olefin-polymerization catalyst and polymerization of olefin using the catalyst - Google Patents

Abstract

PURPOSE:To provide the subject catalyst composed of a specific organometallic compound catalyst component, etc., and a solid catalyst component produced by contacting a solid titanium catalyst component containing Mg, Ti, halogen, etc., with an organic Al compound and giving a polymer having excellent particle size distribution and bulk density. CONSTITUTION:The objective catalyst is composed of (A) a solid catalyst component produced by contacting (i) a solid titanium catalyst component containing Mg, Ti, a halogen and, as necessary, an electron donor (preferably phthalic acid diester) as essential components with (ii) an organic aluminum compound containing Al-O bond (e.g. dimethylaluminum methoxide), (B) an organometallic compound catalyst component of a metal of group I to III of the periodic table (e.g. trimethylaluminum) and, as necessary, (C) an electron donor (e.g. methanol). The catalyst is useful especially for the production of ethylenic polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using this catalyst. The present invention relates to a catalyst for olefin polymerization that can yield a granular or spherical olefin polymer with good particle size distribution and excellent bulk specific gravity, and a method for polymerizing olefin using this catalyst.

Rj section! [Chapter 1] There have already been many proposals regarding the production method of solid titanium catalyst components containing magnesium, titanium, and halogen as essential components, and the method for producing solid titanium catalyst components and metals from Groups 1 to 2 of the periodic table. It is known that an olefin polymerization catalyst comprising 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, especially olefin copolymers.

For example, in order to obtain a high quality olefin polymer without performing a decatalyst operation after polymerization, it is necessary to sufficiently increase the polymer yield per unit weight of titanium or halogen. In addition, when obtaining an olefin polymer through slurry polymerization or gas phase polymerization, it is necessary to perform the polymerization operation and post-processing operations such as separation, transportation, and granulation of the polymer smoothly and efficiently. must have excellent particle size distribution, fluidity, bulk specific gravity, etc., and must also have excellent fracture resistance. Furthermore, in order to omit the heavy pelletization that is normally done and to supply the market as a powder, it is necessary to use an olefin polymer with a large particle size, with less fine powder and with a uniform shape and particle size distribution. need to be manufactured. From this point of view, conventionally known olefin polymerization catalysts are particularly desired to have improved layer properties when producing olefin copolymers.

By the way, JP-A-57-10609 discloses that a catalyst consisting of a solid titanium catalyst component containing magnesium, titanium, and halogen as essential components and an organometallic compound catalyst component of metals from Groups Ⅰ to Ⅲ of the periodic table. - A method for producing an ethylene polymer is disclosed, which comprises prepolymerizing an olefin and then main-polymerizing ethylene. According to this method, an ethylene polymer with considerably improved particle size distribution and bulk specific gravity is produced. can get. However, there has been a desire for an olefin polymerization catalyst that can yield granular or spherical olefin polymers, particularly ethylene polymers, which have a better particle size distribution and an excellent bulk specific gravity.

Purpose of the Invention The present invention has been made in view of the above-mentioned prior art, and is directed to a granular or spherical olefin polymer, particularly an ethylene polymer, which has a good particle size distribution and has an excellent bulk specific gravity. The object of the present invention is to provide an olefin polymerization catalyst that can be obtained and a method for polymerizing olefins using this olefin polymerization catalyst.

Summary of the Invention The catalyst for olefin polymerization according to the present invention comprises [A] a solid titanium catalyst component [A-
1] and an organoaluminum compound having an Al-0 bond [A-2], [B] an organometallic compound catalyst component of metals from Groups 1 to 2 of the periodic table. , and optionally a [C] electron donor.

Further, 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 The catalyst for olefin polymerization according to the present invention and the method for polymerizing olefin using this catalyst will be specifically described 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 illustrating a process for preparing an olefin polymerization catalyst according to the present invention.

The olefin polymerization catalyst according to the present invention comprises [A] a solid titanium catalyst component [A] containing as essential components magnesium, titanium, a halogen, and optionally an electron donor.
-1] and an organoaluminum compound having an A, l-0 bond [A-2]; It is formed from a metal compound catalyst component and, if necessary, a [C] electron donor.

First, the solid titanium catalyst component [A-1] will be explained.

Such a solid titanium catalyst component [A-1] is prepared by bringing the following magnesium compound, titanium compound, and, if necessary, an electron donor into contact with each other.

In the present invention, examples of the titanium compound used for preparing the solid titanium catalyst component [A-1] include Ti(
OR) X (R is a hydrocarbon group, 4-g More specifically, titanium tetrahalides such as TiCA, TiB+, TiI4; T+(OCH3)C13, Ti(OC2H5)Cl3, Ti(On-C4H,>C13, TI(OC2H5)Br3, Ti (Oiso C4H,) Br 3 etc.]
Dihalogenated dialkoxytitanium such as TI(OCH3)2C12, Ti(OC2H5)2CI2, Ti(On-C4H,)2C12, Ti(OC2H5)2Br2; Ti(OCH3)3c11 Ti(QC2Hs)3 ct .

TI(On-C4H9)3 C1.

Monohalogenated trialkoxytitanium such as Ti(OC2H5)3B; Examples include tetraalkoxytitanium such as ethylhexyl)4.

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 in the preparation of the solid titanium catalyst component [A-1] include magnesium compounds that have reducing properties and magnesium compounds that do not have 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, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds may be used alone or may form 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, isopropoxymagnesium chloride, butoxychloride. Alkoxymagnesium halides such as magnesium, octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Examples include alkoxymagnesiums such as 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; and 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 silane 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,
Allyloxymagnesium chloride is preferably used.

In the present invention, it is preferable to use an electron donor when preparing the solid titanium catalyst component [Al1, and examples of the electron donor include organic carboxylic acid esters, preferably polyhydric carboxylic acid esters, and specifically, A compound having a skeleton represented by the following formula is used.

R' -C-OCOR6 In the above formula, R1 is substituted or unsubstituted carbon 2
5 6 represents a hydrogen group, RRR represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R3R4 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

Note that at least one of RR' is preferably a substituted or unsubstituted hydrocarbon group. Further, R3 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 N10 and S, such as C-0-C--COOR and -COOH.

Examples include substituted hydrocarbon groups having structures such as -OH, -8O3H, -C-N-C--NH2, and the like.

2 Among these, at least one of RR has 2 carbon atoms.
Diesters derived from dicarboxylic acids having the above alkyl groups are preferred.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate,
Diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethyl malonate,
Isopropyl diethyl malonate, butyl diethyl malonate, phenyl diethyl malonate, diethyl malonate, allyl diethyl malonate, diisobutyl diethyl malonate, di-n-butyl diethyl malonate, dimethyl maleate, maleic acid, monooctyl acid, diisooctyl maleate, Diisobutyl maleate, butyl diisobutyl maleate, butyl diethyl maleate, β-
Aliphatic polycarboxylic acid esters such as diisopropyl methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconate, and dimethyl citraconate; diethyl 1.2-cyclohexanecarboxylate; I, 2-
Aliphatic polycarboxylic acid esters such as diisobutyl cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Mono-normal butyl phthalate, ethyl normal-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, phthalic acid didecyl, benzylbutyl phthalate,
Aromatic polycarboxylic acid esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, and dibutyl trimellitate; Examples include esters.

Other examples of polyvalent carboxylic acid esters include long chain dicarboxylic acids 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.

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 acid esters do not necessarily need to be used as starting materials, and these polyvalent carboxylic acid esters are not necessarily used as starting materials. A solid titanium catalyst component [A
-1] may produce a polycarboxylic acid ester.

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

In the present invention, the solid titanium catalyst component [Al1] can be produced by contacting the above-described magnesium compound (or metal magnesium), a titanium compound, and, if necessary, an electron donor. In order to produce the solid titanium catalyst component [A-1], 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 may be brought into contact with each other in the presence of other reaction agents such as silicon, phosphorus, and aluminum.

Several examples of methods for producing these solid titanium catalyst components [A-1] will be briefly described below.

In addition, in the method for producing the solid titanium catalyst component [Al1 described below, an example using an electron donor will be described,
This electron donor does not necessarily have to be used.

(1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a solid 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 phthalic acid diester.

The solid titanium catalyst components listed in (1) to (9) above [A
Among the preparation methods, preferred are methods using liquid titanium halide during catalyst preparation, methods using a halogenated hydrocarbon after using a titanium compound, or methods using a halogenated hydrocarbon when using a titanium compound.

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 thus obtained [A-1
] contains magnesium, titanium, chlorogen and, if necessary, an electron donor as essential components.

In this solid titanium catalyst component [A-1], the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5.
~100, the electron donor/titanium (molar ratio) is about 0.1 to 10, preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is about 1 to 100, preferably Desirably, it is between about 2 and 50.

This solid titanium catalyst component [A-1] contains magnesium halide with a smaller crystal size than commercially available magnesium halide, and usually has a specific surface area of about 50
rd/g or more, preferably about 60 to 1000 residues/g, more preferably about 100 to 800 a(/g).The solid titanium catalyst component [A-1] has the above-mentioned components integrated together. Since the catalyst component is formed by washing with hexane, its composition is not substantially changed.

Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-108385.
-126590 publication, 51-20297 publication, 51-28189 publication, 51-64586 publication,
No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596
No. 52-147688, No. 52-104
Publication No. 593, Publication No. 53-2580, Publication No. 53-40
Publication No. 093, Publication No. 53-40094, Publication No. 53-4
No. 309.4, No. 55-135102, No. 5
No. 6-135103, No. 55-152710, No. 56-811, No. 56-11908,
No. 56-18606, No. 58-83006, No. 5g-138705, No. 58-138706
No. 5B-138707, No. 5B-138
'108 Publication, '58-138709 Publication, '58
No. 8-138710, No. 58-138715, No. 60-23404, No. 61-21109, No. 61-37802, No. 61-37803
Publication No. 1, etc.

In the present invention, the solid titanium catalyst component [Al] is prepared by contacting the solid titanium catalyst component [A-1] prepared as described above with an organoaluminum compound [A-21] having an Al-0 bond. ing.

Organoaluminum compound having Al-0 bond [A-2
] as l R10nAl (OR) mX, .・・・・・・［
1] or [wherein R10 is a hydrocarbon group having 1 to 10 carbon atoms,
R11 is a hydrocarbon group having 1 to 20 carbon atoms, or S
iR (in the formula, R12 is a 2 hydrocarbon group having 1 to 10 carbon atoms), X is halogen or hydrogen, m≧1, and n is 1 or 2. ] The organoaluminum compound shown is used.

Al-0 represented by such formula [1] or [II]
Specifically, the following compounds are used as the organic aluminum compound having a bond.

Dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum butoxide, dimethylaluminum 2-ethylhexoxide, diethylaluminum ethoxide, diethylaluminium butoxide, diethylaluminum 2-ethylhexoxide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide , dialkyl aluminum alkoxides such as dioctyl aluminum ethoxide, alkyl aluminum dialkoxides such as ethyl aluminum jetoxide, isobutyl aluminum dibutoxide, dialkyl aluminum alkoxides such as diethylaluminum phenoxide, diisobutyl aluminum phenoxide, ethyl aluminum ethoxy chloride,
Alkyl aluminum alkoxy halides such as isobutyl aluminum ethoxy chloride, alkyl aluminum alkoxy hydrides such as ethyla, aluminum ethoxy hydride, isobutyl aluminum butoxy hydride, aluminum dialkyl carboxylates such as aluminum diethyl acetate, aluminum diisobutyl propionate, aluminum diethyl stearate, aluminum acetate. Carboxylic acid aluminum alkyl halide such as ethyl chloride, aluminum propionate isobutyl chloride, alkylsilane oxydialuminum dialkyl, trimethylsilane oxydialuminum diethyl, trimethylsilane oxydialuminum diisobutyl, triphenylsilane oxydialuminum diethyl, etc. Alkylsilaneoxyaluminum alkyl halides such as aluminum ethyl chloride, triphenylsilane oxydialuminum isobutyl chloride.

Among these, dialkyl aluminum alkoxide, dialkyl aluminum alkoxide, and alkylsilane oxydia aluminum dialkyl are preferred, and dialkyl aluminum alkoxide is particularly preferred.

Solid titanium catalyst component [A-1] and AI! Contact with the organoaluminum compound [A-2] having a -0 bond,
Specifically, it may be done as follows.

(1) A method in which catalyst component [A-11] is suspended in a hydrocarbon solvent and organoaluminum compound [-A-2] is added thereto.

(2) A method of adding catalyst component [A-1] into a hydrocarbon solvent of organoaluminum compound [A-2].

Among these, method (1) is preferred.

At this time, the concentration of the catalyst component [A-1] in the reaction system is usually 0.1 to 100 milligram atoms/1.0 in terms of titanium atoms. Preferably it is 0.5 to 50 milligram atoms/l, and the concentration of organoaluminum compound [A-2] is 0.5 to 50 milligram atoms/l.
5-1000 mmol/g, preferably 1-500 mmol/! The ratio of aluminum atoms to titanium atoms is from 0.5 to 100, preferably from 1 to 50.

The reaction temperature is usually -50 to 150°C, preferably -30 to
The temperature is 100°C, and the reaction time is usually about 0.2 to 20 hours, preferably about 0.5 to 10 hours.

Further, in the present invention, as the organoaluminum compound [A-2] having an Al-0 bond, a compound capable of producing the above organoaluminum compound in the reaction system may be used. Specifically, for example, in a reaction system, 13 14 +3R3AAl+R
It is also possible to use an organic compound that produces an organoaluminum compound having an AI-0 bond as exemplified above by a reaction such as OH-RAAIOR14.

Examples of the organometallic compound catalyst component [B] of metals from Groups 1 to 2 of the periodic table include (i) R', AA' (OR2) HXn p
q (In the formula, R and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. X represents a halogen atom, and 0 m≦3, n is a number of 0≦n<3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n×p×q”3) , preferably a number of 1.5≦m≦3), general formula R' a
lAI X31 (wherein R1 is the same as above;
IH31 (wherein R1 is the same as above. m is preferably 2≦m<3
), (in the formula, Ml is Li, Na, and R1 is the same as above), a complex alkylated product of Group 1 metal and aluminum, (i) R' R2M2 (in the formula, R and R2 are the same as above.

Ml is Mg, Zn or Cd)
A dialkyl compound of group 1 or group 1 is used.

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

General formula RIIIA1 (OR2) -m (wherein, R and R2 are the same as above, m is preferred (wherein, R
1 and R2 are the same as above. X is halogen, 0<m≦3
．． 0≦n<3.0≦q<3, m + n + q =
Examples include compounds represented by 3).

More specifically, the aluminum compounds belonging to (i) include trialkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; diethylaluminum ethoxide, dibutylaluminum butoxide, etc. Dialkyl aluminum sesquialkoxide; Alkyl aluminum sesquialkoxide such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui butoxide; Alkylaluminum; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; ethylaluminum dichloride, propylaluminum dichloride , partially halogenated alkyl aluminum sinolides such as alkyl aluminum dibromide; dialkyl aluminum hydrides such as diethylaluminum hydride, dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dicdride, probylaluminum dihydride Other partially hydrogenated alkyl aluminums such as aluminum dihydride; mention may be made of partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc. .

Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H5) 2 AI OAI
(C2)15) 2, (CH) Al0AI
Examples include (C4H9)2.4 9 2 2H5 methylaluminoxane.

Examples of the compound belonging to the above (i) include L + AI (C2H5) 4, t; Ait (C7HI5) 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 the catalyst component for olefin polymerization, an electron donor [C] can be used as necessary. Examples of such an electron donor [C] include alcohols, phenols, ketones, etc. , oxygen-containing electron donors such as aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates, or the above. Polyhydric carboxylic acid esters such as the following can be used. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol Alcohols having 1 to 18 carbon atoms such as; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl 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, propyl 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, diisopropyl 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, benzoyl chloride , toluic acid chloride, anisyl chloride, and other acid halides having 2 to 15 carbon atoms: methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether epoxy-p~
Ethers and diethers having 2 to 20 carbon atoms such as menthane; Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine , picoline, tetramethylenediamine, and other nitriles; acetic anhydride, phthalic anhydride, benzoic anhydride, and other acid anhydrides.

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

R5i(OR')4□ ... [Ia] [In the formula, R and R' are hydrocarbon groups, and 0<n<4] An organic compound represented by the general formula [I a] as described above Specific examples of silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, dobutylmethyldimethoxysilane, t-butylmethyljethoxysilane, and t-amylmethyljetoxysilane. Toxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane,
Bis0-tolyldimethoxysilane, bis m-1lyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxy Silane, ethyltrimethoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane,
Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane,
Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornane-trimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyl triaryl Used are loxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-)lyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornane Methyldimethoxysilane and diphenyljethoxysilane are preferred.

Furthermore, as the electron donor [C], the following general formula [
IIa] can also be used.

R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, R3 is a hydrocarbon group, and m is 0≦m≦2. . ] In the above formula [na], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R1
In addition to the cyclopentyl group, examples thereof include cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

Further, in the formula [na], 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 propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group exemplified as R1 and a cyclopentyl group having an alkyl group can be similarly mentioned.

Further, in formula [I[a], 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; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane , dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, and other monoalkoxysilanes. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferred.

In the present invention, the solid catalyst component [A] as described above, the organometallic compound catalyst component [B] of metals from Groups 1 to 2 of the periodic table.
Olefin polymerization is carried out using an olefin polymerization catalyst consisting of an electron donor [C] and, if necessary,
At this time, it is preferable to prepolymerize α-olefin in the olefin polymerization catalyst. This prepolymerization is carried out in an amount of 0.1 to 500 g per 1 g of olefin polymerization catalyst, preferably 0.
．． α in an amount of 3 to 300 g 1 Particularly preferably 1 to 100 g
- carried out by prepolymerizing the olefin.

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

The concentration of the solid catalyst component [A] in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 0.1 to 200 mmol, in terms of titanium atoms, per inert hydrocarbon medium 11 described below.
It is desirable to set it as 100 mmol, especially preferably in the range of 1 to 50 mmol.

The amount of the organometallic compound catalyst component [B] is the amount of the solid catalyst component [B].
0.1 to 500 g per 1 g of A, preferably 0. 3～3
The amount may be such that 0.00 g of polymer is produced, and is usually about 0.00 g per mole of titanium atoms in the solid catalyst component [A].
Amounts of 1 to 100 mol, preferably about 0.5 to 50 mol, particularly preferably 1 to 20 mol are desirable.

The electron donor [C] is used as necessary, and is 0.1 to 50 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 30 mol, per mol of titanium atom in the solid catalyst component [A].
Preferably it is used in an amount of 10 mol.

Prepolymerization is preferably carried out under mild conditions by adding the olefin and the catalyst components described above to an inert hydrocarbon medium.

Examples of inert hydrocarbon media used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Examples include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out substantially in the absence of a solvent.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, and specifically, propylene is preferably used.

The reaction temperature during prepolymerization is usually about -20 to +100
℃, preferably in the range of about -20 to +80℃, more preferably in the range of 0 to +40℃.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. 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 di/
It is desirable to use an amount of at least 100 dA'/g, preferably about 0.5 to 10 dA'/g.

As mentioned above, the prepolymerization is carried out using a solid catalyst component [about 0.1 to 500 g per 1 g of A1, preferably about 0.3 to 300 g
It is desirable to carry out the reaction so that 1 to 100 g of polymer is produced, particularly preferably 1 to 100 g.

If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously.

Olefins that can be used in this polymerization include ethylene, propylene, 1-butene, 4-methyl-
Examples include olefins having 2 to 20 carbon atoms such as 1-pentene and 1-octene. In the polymerization method of the present invention,
These olefins can be used alone or in combination. Among these olefins,
It is preferable to carry out the copolymerization using a mixed olefin containing ethylene as a main component. In the present invention, it is particularly preferable to copolymerize ethylene with 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. When such a copolymerization is carried out, it is preferable that the structural unit derived from ethylene be present in the resulting copolymer in an amount of usually 50 mol % or more, preferably 70 mol % or more.

In addition, when performing homopolymerization or copolymerization of these olefins, compounds having polyunsaturated bonds such as conjugated dienes and non-conjugated dienes can also be used as polymerization raw materials.

In the polymerization method of the present invention, the main polymerization of olefin is usually carried out in a gas phase or a liquid phase.

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, [A] is an organometallic compound catalyst component [B], and the amount of metal atoms is usually about 1 to 20 per mole of titanium in the prepolymerized catalyst component in the polymerization system.
00 moles, preferably about 5 to 500 moles. Furthermore, if necessary, electron donor [C]
is usually about 0.001 to 10 mol, preferably about 0 mol per mol of metal atom in the organometallic compound catalyst component [C].
．． 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 2
0 to 200°C, preferably about 50 to 100°C, and the pressure is usually normal pressure to 100 kg/cr11, preferably about 2 to 100°C.
It is set at 50kg/car. 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.

The olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer, or the like.

When olefin (co)polymerization is carried out using the above-mentioned olefin polymerization catalyst, a granular or spherical olefin polymer, particularly an ethylene polymer, having a good particle size distribution and an excellent bulk specific gravity can be obtained.

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.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of solid titanium catalyst component [A-11] 19.0 g of anhydrous magnesium chloride, 88.4 ml of decane and 78.1 g of 2-ethylhexyl alcohol were heated at 140 to 150°C.
A heating reaction was carried out for 2 hours to obtain a homogeneous solution. Thereafter, the solution was cooled to room temperature, and 4.43 g of phthalic anhydride was added to this solution, followed by stirring at 130° C. for 1 hour to obtain a homogeneous solution. After cooling 75 ml of the homogeneous solution thus obtained to room temperature, 4
It was added dropwise over a period of 5 minutes.

After charging, the temperature of this mixture was increased to 110°C over 4 hours.
When the temperature reached 110°C, 5.03 ml of diisobutyl phthalate was added and stirred at 110°C for 2 hours. Thereafter, a solid portion was collected by hot filtration, and this solid portion was resuspended in 275 ml of titanium tetrachloride. 110 again
Thermal reaction was carried out at ℃ for 2 hours. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the washing liquid. The composition of the solid titanium catalyst component [A-1] thus obtained was 2.4% by weight of titanium, 19% by weight of magnesium, and 12.4% by weight of diisobutyl phthalate.
% by weight.

[Preparation of solid catalyst component [A]] The solid titanium catalyst component [A-1] having 2 milligram atoms in terms of titanium atoms was suspended in 200 ml of hexane,
Cooled to 0°C. At that temperature, a hexane solution of diethylaluminium ethoxide (AI=1.0 mol/I) 1
5. 4ml was added. After that, the temperature was raised to 50℃, and
The reaction was carried out at ℃ for 2 hours.

After the reaction was completed, the solid portion was collected by filtration and thoroughly washed with hexane. The solid catalyst component [A
] The composition was 2.3% by weight of titanium, 19% by weight of magnesium, 2.8% by weight of ethoxy groups, and 12.1% by weight of diisobutyl phthalate.

[Prepolymerization] 200 ml of hexane was added to a 400 ml flask that was sufficiently purged with nitrogen. ) After charging 3 mmol of ethylaluminum and 1 mg atom in terms of titanium atom of the solid catalyst component [A], about 6 g of propylene was prepolymerized at 20° C. for 1 hour while continuously supplying propylene gas. . The prepolymerized solid component thus obtained was collected by filtration, thoroughly washed with hexane, and used in the main polymerization.

[Main polymerization] 150 g of sodium chloride (Wako Tsumugi Special Grade) was charged into a 21 stainless steel autoclave which had been sufficiently purged with nitrogen.
It was dried under reduced pressure at 90°C for 1 hour.

Thereafter, the inside of the system was returned to room temperature and normal pressure, and an ethylene atmosphere was created, and then 0.75 mmol of triethylaluminum and 8.5 ml of l-hexene were added. After that, 50℃
The temperature was raised to 1.8 kg/1 ffl of hydrogen gas, and at around 70° C., the prepolymerized solid component obtained above (0.01 milligram atom in terms of titanium atom) was injected with ethylene to initiate polymerization. Ethylene and l-hexene3
Total pressure 8 kg/Ci-G while continuously supplying 4 ml
Copolymerization of ethylene and 1-hexene was carried out at 80°C for 1 hour.

After the polymerization was completed, sodium chloride was removed by washing with water, the polymer was washed with methanol, and then dried under reduced pressure at 80° C. overnight. As a result, the MF measured at 190°C and a glare load of 2.16
R is 1.84g/10min, density is 0. 918 g/a
J, bulk specific gravity is 0.42 g/decane soluble component amount at -123°C is 14.4% by weight, melting point measured by DSC is 125
．． 119 g of ethylene-1-hexene copolymer having an average polymer particle size of 390 μm was obtained at 2°C.

Comparative Example 1 In Example 1, the solid titanium catalyst component [A-1] was not treated with diethylaluminum ethoxide, and l-
The same procedure as in Example 1 was carried out except that 7.5 ml of hexene was initially supplied and then 30 ml was continuously supplied. As a result, M
FR is 1.40g/10min, density is 0.919g/a!
, bulk specific gravity is 0.31 g/cd, and decane soluble portion is 16.
93 g of polymer, 6% by weight, were obtained.

Example 2 [Preparation of solid catalyst component [A]] The same procedure as in Example 1 was performed except that the amount of hexane solution of diethylaluminium ethoxide used in Example 1 was changed to 24 ml, and titanium was 2.4% by weight. , 17% by weight of magnesium, 3.2% by weight of ethoxy groups, 11.9% by weight of diisobutyl phthalate [A]
I got it.

[Polymerization] Preliminary polymerization and main polymerization were performed in the same manner as in Example 1, and the MFR was 1.27 g/10 minutes and the density was 0.921 g.
Ethylene-1-hexene copolymer with a bulk specific gravity of 0.43 g/i, a decane soluble content of 12.6% by weight at 23°C, a melting point of 125.2°C, and an average polymer particle size of 390 μm. A total of 138 g was obtained.

Example 3 [Preparation of solid catalyst component [A]] The same procedure as in Example 1 was carried out except that the amount of the hexane solution of diethylaluminium ethoxide used in Example 1 was changed to 6 ml. %, magnesium 19% by weight, ethoxy groups 2.7% by weight, diisobutyl phthalate 12.9% by weight solid catalyst component [A]
was gotten.

[Polymerization] Preliminary polymerization and main polymerization were performed in the same manner as in Example 1, and the MFR was 2.46 g/10 minutes and the density was 0.922 g.
/aa, bulk specific gravity is 0.42g/aa.

158 g of an ethylene-1-hexene copolymer having a decane-soluble content of 14.1% by weight at 23°C, a melting point of 125.7°C, and an average polymer particle size of 380 μm was obtained.

Example 4 [Preparation of solid catalyst component [A]] The same procedure as in Example 1 was carried out except that 15°4 mmol of diethylaluminum 2-ethylhexoxide was used instead of diethylaluminum ethoxide. A solid catalyst component [A] containing 2.2% by weight of titanium, 18% by weight of magnesium, and 1.1% by weight of 2-ethylhexoxy groups was obtained.

[Polymerization] Preliminary polymerization and main polymerization were performed in the same manner as in Example 1, and the MFR was 1.46 g/10 minutes and the density was 0.922 g.
126 g of an ethylene-1-hexene copolymer having a bulk specific gravity of 0.43 g/cd and a decane-soluble content of 12.9% by weight at 23° C. was obtained.

Example 5 1-pentene was used as a comonomer instead of 1-hexene in the polymerization of Example 2 (initial addition of 7.5 ml, then 30 ml continuously fed over 1 hour)
Except for this, polymerization was carried out in the same manner as in Example 2, and the MFR
is 1.18g/10min, density is 0.920g10a, bulk specific gravity is 0.45g/cd, amount of decane soluble component at 23°C is 12.5% by weight, melting point is 123.9°C, average polymer particle size 126 g of ethylene-1-pentene copolymer having a diameter of 370 μm was obtained.

Example 6 1-pentene was used as a comonomer instead of 1-hexene in the polymerization of Example 2 (initial addition of 6 ml,
Then, polymerization was carried out in the same manner as in Example 2, except that 24 ml was continuously supplied for 1 hour, and the MFR was 1.
．． 58g/10min, density 0.924g/cd, bulk specific gravity 0.46g/cd, amount of decane soluble component at 23°C 9
．． Ethylene-1-pentene copolymer 11 having a melting point of 7% by weight, a melting point of 124.6°C, and an average polymer particle size of 360 μm.
6g was obtained.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of the olefin polymerization catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1) [A] A solid titanium catalyst component [A-1] containing magnesium, titanium, halogen and, if necessary, an electron donor as essential components, and an organoaluminum compound having an Al-O bond. A solid catalyst component obtained by contacting with [A-2], [B] an organometallic compound catalyst component of a metal from Group I to Group III of the periodic table, and optionally [C] an electron donor. Catalyst for olefin polymerization formed. 2) [A] A solid titanium catalyst component [A-1] containing magnesium, titanium, halogen and, if necessary, an electron donor as essential components, and an organoaluminum compound [A-2] having an Al-O bond. A solid catalyst component obtained by contacting a solid catalyst component, [B] an organometallic compound catalyst component of a metal from Group I to Group III of the periodic table, and optionally [C] an electron donor for olefin polymerization. An olefin polymerization catalyst obtained by prepolymerizing α-olefin as a catalyst. 3) A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst according to claim 1 or 2.