JPH02229806A - Method for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain a polymer having high stereospecificity and uniform particle diameter with narrow breadth of particle size distribution by (co)polymerizing olefin in the presence of a catalyst comprising specific solid Ti catalyst component, organic Al compound catalyst component and organic silicon compound catalyst component. CONSTITUTION:Olefin is (co)polymerized in the presence of a catalyst for olefin polymerization composed of (A) solid titanium catalyst component containing magnesium, titanium, halogen and electron donor (e.g. diethyl succinate) as essential ingredients, (B) organic aluminum compound catalyst component (e.g. triethylaluminum) and (C) organic silicon compound catalyst component expressed by the formula (R<1> and R<2> are hydrocarbon) (e.g. di-t-butyl dimethoxysilane) to afford the aimed olefin polymer having >=6dl/g, preferably >=8dl/g [eta].

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for polymerizing olefins that can produce high molecular weight olefin polymers with excellent uniformity in particle properties and particle size in high yields. .

Technical background of the invention and its problems If olefins are polymerized or copolymerized using a TICgB catalyst, 1% of a high molecular weight polymer can be obtained, but this production method has extremely low catalyst activity and There was a problem in that an ash process was also required.

Furthermore, when polymerizing or copolymerizing olefins using a highly active catalyst system, it is possible to obtain a polymer with a high molecular weight by lowering the polymerization temperature, but this method significantly reduces the catalyst activity. There was a problem.

By the way, there have already been many proposals regarding the production method of a solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components. It is also known that polymers with high stereoregularity can be produced in high yields by using them together with an organoaluminium compound catalyst component and an organosilicon compound catalyst component.

However, when α-olefins having 3 or more carbon atoms are polymerized or copolymerized using the above-mentioned olefin polymerization catalysts that have been proposed so far, it has been found that they have high molecular weight and excellent stereoregularity. There was a problem in that it was difficult to obtain an α-olefin polymer.

The present inventors conducted intensive research to obtain a high molecular weight α-olefin polymer having 3 or more carbon atoms while maintaining excellent stereoregularity and the polymerization activity of the catalyst, and found that the solid titanium catalyst component as described above If α-olefins having 3 or more carbon atoms are homopolymerized or copolymerized using an olefin polymerization catalyst consisting of an organoaluminum compound and a specific organosilicon compound catalyst component, excellent stereoregularity can be obtained, and the catalyst can be polymerized. The present invention was completed by discovering that it is possible to obtain an a-olefin polymer with a high molecular weight while maintaining activity.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and is aimed at solving the above-mentioned problems associated with the prior art. It is an object of the present invention to provide a method for polymerizing olefins which allows the production of polymers in high yield.

Further, the present invention provides an olefin polymerization method that can obtain an α-olefin (co)polymer with excellent particle size distribution, particle properties, bulk specific gravity, etc. while maintaining high polymerization activity of the catalyst. The purpose is to

Summary of the Invention The olefin polymerization method according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components; [B] an organoaluminum compound catalyst component; and [C]
By polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed from an organosilicon compound catalyst component represented by the general formula [1F (wherein RR is a hydrocarbon group), [η] is 6d
It is characterized by producing an olefin polymer having fl/tr or more.

In the polymerization method according to the present invention, as described above, the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B]
Since an α-olefin having 3 or more carbon atoms is polymerized using a catalyst formed from a specific organosilicon compound catalyst component [C], it has a high molecular weight, excellent uniformity in particle shape and particle size, and Olefin polymers with excellent regularity can be produced in high yield.

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization method according to the present invention and the olefin polymerization catalyst used in this process 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.

In the olefin polymerization method according to the present invention, olefin polymerization or copolymerization is carried out in the presence of an olefin polymerization catalyst as described below.

Olefin according to the present invention. The polymerization catalyst consists of a solid titanium catalyst component [A] and an organoaluminum compound catalyst component [B].
] and a specific organosilicon compound catalyst component [C].

FIG. 1 shows an example of a flowchart of the method for preparing the catalyst used in the present invention.

The solid titanium catalyst component [A] used in the present invention is a highly active catalyst component containing magnesium, titanium, /X rogen, and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared, for example, by contacting a magnesium compound, a titanium compound, and an electron donor as described below.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component [A] is, for example, TI(OR).
gX4, (R is a hydrocarbon group, X is a norogen atom, 0
Examples include tetravalent titanium compounds represented by ≦g≦4). More specifically, TIC,Q-TI
Tetrahalogenated titanium such as Br-TII4; TI(OCR)Cfl3, Tl(QC2H5)Cff3, TI(On-CH)Cfl3, Tl(
O C H ) B r 3 , TI(Olso
Turinated alkoxytitanium such as C H ) Br 3 ; Ti(OCH3)2 CN 2, T I (OC 2 H 5) 2 C fl 2,
TI(On-C4H9)2C! I2, T1 (OC2
H5) 2B "Dihalogenated dialkoxytitanium such as 2; Ti(OCR3) 3(1!, Ti(OC 2 H 5) a C D 1Ti(
On-C4H9) 3Cfl, T1(OC2H5)3
Examples include monohalogenated trialkoxytitaniums such as B'; tetraalkoxytitaniums such as T%(OCH3)4, TI(OC2H5)4, and TI(On-C4H9)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 /% logenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used in the one-week production of the solid titanium catalyst component [A] 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, dibropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, probylmagnesium chloride, Examples include butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, and butylmagnesium halide. 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, isobroboxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium,
isobroboxymagnesium, butoxymagnesium,
Examples include alkoxymagnesiums such as n-octoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylates such as magnesium laurate and magnesium stearate. can.

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, in addition to the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, 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, when preparing the solid titanium catalyst component [A], it is preferable to use an electron donor, and specific examples of such electron donors include alcohols, phenols, ketones, aldehydes, Examples include oxygen-containing electron donors such as carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, methanol, ethanol, probanol, pentanol, hexanol, octanol, 2-
Alcohols with 1 to 18 carbon atoms such as ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isobrobyl benzyl alcohol; phenol;
Cresol, xylenol, ethylphenol, probylphenol, cumylphenol, nonylphenol,
Phenols with 6 to 25 carbon atoms that may have an alkyl group such as naphthol; Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ace1-phenone, and benzophenone; acetaldehyde, blobion Aldehydes having 2 to 15 carbon atoms such as aldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate,
Ethyl acetate, vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, Diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di2-1,2-cyclohexanedicarboxylate
Ethylhexyl, 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, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate, Organic acid esters having 2 to 30 carbon atoms, including esters described below, which are preferably contained in the titanium catalyst component, such as dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; ethyl silicate,
Inorganic acid esters such as butyl silicate; carbon atoms of 2 to 15 such as acetyl chloride, penzoyl chloride, toluic acid chloride, anisyl chloride, phthalic acid dichloride, etc.
Acid halides; ethers with 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid amide, benzoic acid amide, toluic acid amide Acid amides such as: acid anhydrides such as benzoic anhydride and phthalic anhydride; amines such as methylamine, ethylamine, doethylamine, tributylamine, piverizine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; Examples include nitriles such as acetonitrile, penzonitrile, and trinitrile.

Further, as an electron donor, an organosilicon compound represented by the following general formula [I] can also be used.

R Si (OR" 4-n ... [
11n [wherein R and R° are hydrocarbon groups, 0<n<4
] Specifically, the organosilicon compound represented by the above general formula [I] includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane , bis0-}lyldimethoxysilane, bis-constant tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p
-1-lyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chlorotrimethoxysilane, methyltoluethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iSO-butyltriethoxysilane,
Phenyltriethoxysilane, γ-aminopyltriethoxysilane, chlortriethoxysilane, ethyltriisobroboxysilane, vinyltributoxysilane,
Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy( (allyloxy) silane, vinyl tris (β
-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, dicyclohexylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane, dicyclobentyldimethoxysilane, dicyclobentyldiethoxysilane, di-n-propyldiethoxysilane, T-butyldiethoxysilane, cyclopentyltriethoxysilane, etc. are used.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl dimethoxysilane,
Diphenyldiethoxysilane is preferred.

Two or more types of these electron donors can be used.

The electron donor desirably contained in the titanium catalyst component is an ester, more preferably one having the general formula R3-C-OCOR5 R4- and -OCOR8 or R3-C-COOR' R4 monopoly 10 COR5 (where R1 is a substituted or unsubstituted hydrocarbon group, R2
R5 R6 is hydrogen or a substituted or unsubstituted hydrocarbon group, RR is hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Further, R3 and R4 may be connected to each other. Hydrocarbon substituted for R-R5 above! The group includes a different atom such as N, O, S, etc., such as C-0-C, COOR, COOH, OH, So
It has a group such as H, -C-N-C-NH2. ) can be exemplified.

l2 Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R R is an alkyl group having 2 or more carbon atoms.

Specifically, the polyhydric carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethylmalonate, and isobrobyl malonate. Diethyl, butyl diethyl malonate, phenyl diethyl malonate, diethyl diethyl malonate, allyl malonate diethyl dibutyl malonate, di-n-butyl diethyl malonate dimethyl maleate monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl Aliphatic polycarbonates such as dibutyl maleate, diethyl butyl maleate, diisobutyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctyl citraconate, dimethyl citraconate, etc. acid ester, l,
Alicyclic polycarboxylic acid esters such as diethyl 2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, phthalic acid Monoisobutyl, mono-normal butyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, ethyl n-butyl phthalate, di-n-probyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-hebutyl phthalate, di-2-ethylhexyl phthalate, phthalate Aromatic polycarboxylic acid esters such as di-n-octyl acid, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, and dibutyl trimellitate. , heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid, and the like.

In addition, specific examples of polyvalent hydroxy compound esters include 1,2-diacetoxybenzene, ■-methyl-2,
Examples include 3-diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol dipiparate, butanediol biparate, and the like.

Specific examples of the hydroxy-substituted carboxylic acid include benzoylethyl salicylate, acetylisoptylsalicylate, acetylmethyl salicylate, and the like.

In addition to the above-mentioned compounds, examples of polyvalent carboxylic acid esters that can be supported in the titanium catalyst component include diethyl adibate, diisobutyl adipate, diisobutyl sebacate, and di-n-butyl sebacate. , di-n-octyl sebacate, di-2-ethylhexyl sebacate, and other long-chain dicarboxylic acid esters can be used.

Among these polyfunctional esters, compounds having the skeleton of the above-mentioned general formula are preferred, and esters of phthalic acid, maleic acid, substituted malonic acid, etc. and alcohols having 2 or more carbon atoms are more preferred, with phthalic acid being particularly preferred. Diesters of acids and alcohols having 2 or more carbon atoms are preferred.

Other electron donor components that can be supported on the titanium catalyst component include RCOOR' (R and R' are hydrocarbyl groups that may have substituents, and at least one of them is a branched (alicyclic) ) or a ring-containing chain group). Specifically, as R and R', (CH) CH- C2H5CH (CH3
)(CH) CHCH,,- (CH3)
3C-c H CH (CH3)CH2. If either R or R° is a group as described above, the other may be the group described above, or another group,
For example, it may be a linear or cyclic group.

Specifically, various monoesters such as dimethyl acetic acid, trimethyl acetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid, and benzoyl acetic acid, various monocarboxylic acids of alcohols such as isopropanol, isobutyl alcohol, and tert-butyl alcohol. Examples include acid esters.

Carbonic esters can also be selected as electron donors. Specifically, examples include jetyl carbonate, ethylene carbonate, diisopropylene carbonate, phenylethyl carbonate, and diphenyl carbonate.

When supporting these electron donors, it is not necessarily necessary to use them as starting materials, and it is also possible to use compounds that can be converted into these in the process of preparing the titanium catalyst component.

Other electron donors may coexist in the titanium catalyst component, but their coexistence in too large a quantity will have an adverse effect, so they should be kept to a small amount.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metal magnesium), electron donor, and titanium compound 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 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) will be briefly described below.

(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 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.

(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) A method in which the reaction product obtained in (1) or (2) is further reacted with 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. How to process. 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. Alternatively, 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. In addition, as a reaction aid,
Examples include organoaluminum compounds and halogen-containing silicon compounds.

(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 in which a contact reaction product of a metal oxide, dihydrorubylmagnesium, and a halogen-containing alcohol is brought into contact 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.

Solid titanium catalyst component [A] listed in (1) to (8) above
Among the preparation methods, a method using liquid titanium halide during catalyst preparation, a method using a titanium compound after use, or a method using a halogenated hydrocarbon when using a titanium compound are preferred.

The amount of each of the above-mentioned components used when 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 is about 0.01 per mole of magnesium compound. In an amount of ~5 mol, preferably 0.05-2 mol, the titanium compound is about 0.0
It is used in an amount of 1 to 500 mol, preferably 0.05 to 300 mol.

The solid titanium catalyst component [A] thus obtained is:
Contains magnesium, titanium, halogen and an electron donor as essential components.

In this solid titanium catalyst component [A], the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 10.
0, and 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 preferably about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains magnesium halide with a small crystal size compared to commercially available magnesium halides, and usually has a specific surface area of about 50 rrr/g or more, preferably about 60 to 1000 M/gs. More preferably about 100-8
0 0 td/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 washing with hexane.

Such a solid titanium catalyst component [A] can be used alone, or can be diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition,
When a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area.

Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-108385.
-128590 Publication, Publication No. 51-20297, Publication No. 5-28189, Publication No. 51-84588,
No. 51-92885, No. 51-138625, No. 52-117489, No. 52-10059
Publication No. 8, Publication No. 52-147888, Publication No. 52-10
No. 4593, No. 53-2580, No. 5i3-
No. 40093, No. 53-40094, No. 5
Publication No. 3-43094, Publication No. 55-135102,
55-135103, 55-152710, 5B-811, 5B-11908, 5B-18608, 5g-83006, 58-138705, 58-1387
Publication No. 08, Publication No. 5g-138707, Publication No. 58-1
No. 38708, No. 58-138709, No. 5
It is disclosed in Japanese Patent No. g-138710, No. 58-138715, Japanese No. 60-23404, Japanese No. 61-21109, Japanese No. 81-37802, Japanese No. 81-37803, etc.

As the organic aluminum compound catalyst component (IS), a compound having at least one aluminum-carbon bond in the molecule can be used. Such compounds include, for example, (wherein 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, 0 m≦3, n is 0≦n<3, p is 0≦p
<3, q is a number such that 0≦q<3, and m + n
+ p + q − 3), (i) a general formula M l! Examples include complex alkylated products of Group 1 metals and aluminum represented by R14 (wherein Ml is Li, Na, K, and R1 is the same as above).

Examples of the organoaluminum compound represented by the formula (i) include the following compounds.

General formula R AN (OR2) m 3-tn (wherein R and R2 are the same as above. m is preferably a number of 1.5≦m≦3), ■ General formula R AgX3, m (In the formula, R1 is the same as above. m <
3), general formula R All! (OR2) X m nq (in the formula, R
and R2 are the same as above. X is halogen, Q<m≦3
, 0≦n<3, 0≦q<3, and tn + n + q
-3) can be mentioned.

More specifically, the aluminum compound represented by (i) includes triethylaluminum, tri- Trialkylaluminum such as chillaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R1 ■． 5AN (OR2). ．． Partially alkoxylated alkyl aluminum having an average composition such as alkylaluminum sesquihalides such as bromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, probylaluminum dichloride, butylaluminum dibromide; Dialkyl aluminum hydrides; Other partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, butylaluminum dihydride; etc. Partially alkoxylated and halogenated alkyl aluminums may be mentioned.

Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms f or nitrogen atoms. Examples of such compounds include (C2H5)2AgOAg (C
2H5) 2, (C4H9) 2AD OAR (C4
H9)2, C2Hs methylaluminoxane, and the like.

As the compound represented by the formula (i), LI AN
(C2H5) 4, LI AN (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.

As the organosilicon compound catalyst component [C], general formula [1
1 (R13C)2SI(OR)2...[I](
In the formula, R1 is a hydrocarbon group, preferably a hydrocarbon group having 1 to 6 carbon atoms, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms. On the other hand, R2 is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a hydrocarbon group having 1 to 2 carbon atoms. However, 6 R's and 2 R2's may be the same or different. ) is used.

Specific examples of such organosilicon compounds include di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butylmethoxyshethoxysilane, and di-t-butyldiethoxysilane.
Amyldimethoxysilane, t-butyl-t-amyldimethoxysilane, bis(1,1-diethylbutopyr)dimethoxysilane, etc. are used.

In the polymerization method of the present invention, olefins are polymerized in the presence of the catalyst as described above, but it is preferable to carry out preliminary polymerization as described below before carrying out such polymerization (main polymerization).

By performing such prepolymerization, a powdered polymer with a high bulk density can be obtained. Furthermore, prepolymerization makes the particle size uniform, and in the case of slurry polymerization, the properties of the slurry become excellent. Therefore, according to the polymerization method of the present invention, the obtained polymer powder or polymer slurry can be easily handled.

In prepolymerization, the solid titanium catalyst component [
A] is used in combination with at least a portion of the organoaluminum compound catalyst component [B].

At this time, an organosilicon compound can be allowed to coexist.
Such a silicon compound is not limited to the compound used as the organosilicon compound catalyst component [C]. When such a compound used as the catalyst component [C] is used, a part or all of such an organosilicon compound may be allowed to coexist.

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 solid titanium catalyst component [A] in prepolymerization is:
Usually about 0.01 to 200 mmol, preferably about 0 mmol in terms of titanium atoms, per inert hydrocarbon medium II described below.
．． The preferred range is 0.05 to 100 mmol.

The amount of organoaluminum catalyst component [B] is 0.1 to 500 g, preferably 0.1 to 500 g, per Ig of solid titanium catalyst component [A].
The amount may be such that 3 to 300 g of polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.5 to 5 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].
Preferably, the amount is 0 mole.

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 the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and lamps; cyclopentane, cyclohexane, and methylcyclopentane. Examples include alicyclic hydrocarbons such as; 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.

The olefin used in the preliminary polymerization may be the same as or different from the olefin used in the main polymerization described later.

When such an olefin is used in prepolymerization, a highly crystalline polymer can be obtained from an α-olefin having 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms.

In addition, in the present invention, liquid α-
Olefins can be used.

The reaction temperature for prepolymerization may be such that the prepolymer to be produced is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to +100°C, preferably about -20°C.
It is desirable that the temperature is in the range of ~+80°C, more preferably 0~+40°C.

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 pre-6tlffl reaction measured in decalin at 35°C is about 1 dfl/z.
As mentioned above, it is desirable to use the amount preferably in a range of about 2 to 20 dR/g.

Prepolymerization is carried out using the titanium catalyst component [A]Ig as described above.
about 0.1-1000g, preferably about 0.3-50g per
It is desirable to perform this so that 0 g of polymer is produced.

If the amount of preliminary polymerization is too large, the production efficiency of the olefin polymer in the main polymerization may decrease.

Prepolymerization can be carried out batchwise or continuously.

After prepolymerizing as described above or without prepolymerizing, the solid titanium catalyst component [
Main polymerization of an olefin is carried out in the presence of an olefin polymerization catalyst formed from A], an organoaluminum catalyst component [B], and an organosilicon compound catalyst component [C].

Examples of olefins that can be used in the main polymerization include α-olefins having 3 or more carbon atoms, such as propylene, 1-butene, 4-methyl-1-bentene, 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 perform homopolymerization using propylene or 1-butene, or to perform copolymerization using a mixed olefin containing propylene or 1-butene as a main component.

When such a mixed olefin is used, the content of propylene or l-butene as the main component is usually 50 mol% or more, preferably 70 mol% or more.

Further, in the present invention, it is also possible to copolymerize the above-mentioned α-olefin having 3 or more carbon atoms and ethylene. At this time, it is desirable that the α-olefin having 3 or more carbon atoms be present in the resulting copolymer in an amount of 60 mol% or more, preferably 80 mol% or more.

In the polymerization method of the present invention, [η] is 6 rN/g by particularly polymerizing α-olefin having 3 or more carbon atoms.
As described above, it is preferably 8 dl)/z or more, and a polymer having a high stereoregularity index can be produced with high catalytic efficiency.

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, the titanium catalyst component [A
] is usually about 0.005 to 0.5 mmol, preferably about 0.01 to 0.5 mmol, in terms of TI atoms per 1 g of polymerization volume.
It is used in an amount of 0.5 mmol. In addition, the organoaluminum compound catalyst component [B] usually contains about 1 to 2 metal atoms in the organoaluminum compound catalyst component [B] per 1 mole of titanium atoms in the titanium catalyst component [A] in the polymerization system.
000 mol, preferably about 5 to 500 mol. Furthermore, the organosilicon compound catalyst component [
C] is usually about 0.001 to 10 mol, preferably about 0.01 mol in terms of Sl atom in the organosilicon compound catalyst component [C] per mol of metal atom in the organoaluminum compound catalyst component [B]. ~2 mol, particularly preferably about 0.0
It is used in an amount of 5 to 1 mole.

In the polymerization method of the present invention, titanium catalyst component [A],
The organoaluminum compound catalyst component CB] and the organosilicon compound catalyst component [C] may be brought into contact during main polymerization, or may be brought into contact before main polymerization, for example, during prepolymerization. In this contacting before main polymerization, only two arbitrary components may be freely selected and brought into contact, or two or two parts of each component may be brought into contact with each other.

In the polymerization method of the present invention, each catalyst component may be contacted in an inert gas atmosphere or in an olefin atmosphere before polymerization.

In addition, the organoaluminum compound catalyst component [B
] and a part of the organosilicon compound catalyst component [C], the catalyst used in the prepolymerization is used together with the remaining catalyst. In this case, the catalyst used in prepolymerization is
It may also contain prepolymerized products.

In the present invention, the polymerization temperature of the olefin is usually about 2
0-200°C, preferably about 50-180°C, the pressure is
Usually normal pressure to 100 kg/cd, preferably about 2 to 50
kg/c-. 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.

In the present invention, since the yield of a polymer having stereoregularity per unit amount of the solid catalyst component 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 when molding a molded article using the produced olefin polymer, rusting of the mold can be effectively prevented.

Further, the olefin polymer obtained by the polymerization method of the present invention has an average particle diameter of 150 to 5000 μm, preferably 200 to 3000 μm, and the amount of fine polymer particles of 100 μm or less is preferably 5% by weight or less, more preferably 1 % by weight or less. In addition, the geometric standard deviation σ8 calculated based on the particle size distribution determined by sieving the produced polymer particles is 2.0 or less, preferably 1.5.
It is particularly preferably 1.3 or less.

As described above, since the olefin polymer obtained by the polymerization method of the present invention is a granular powder with a narrow particle size distribution and a uniform particle size, the operation of beretizing the obtained olefin polymer is difficult. It can also be omitted.

Effects of the Invention The olefin polymerization method of the present invention uses a specific polymerization catalyst formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and a specific organosilicon compound catalyst component [C]. Since an α-olefin having 3 or more carbon atoms is polymerized, an olefin polymer having a particularly high molecular weight can be produced at a high yield.

The olefin polymer obtained by the polymerization method of the present invention has high stereoregularity, narrow particle size distribution, uniform particle size, and high bulk density.

Furthermore, according to the polymerization method of the present invention, it is possible to efficiently produce an olefin polymer having the above-mentioned excellent properties, and there is little decrease in catalyst activity with the passage of polymerization time.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 [Preparation of solid titanium catalyst component [A]] Anhydrous magnesium chloride7. 14 g (75 mmol), 37.5 ml of decane and 35.5 ml of 2-ethylhexyl alcohol. 1 ml (225 mmol) at 130℃
A heating reaction was carried out for 2 hours to form a homogeneous solution. after that,
1.67 g (11.3 mmol) of phthalic anhydride was added to this solution and stirred and mixed at 130° C. for an additional 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, 200 ml of titanium tetrachloride kept at -20°C was added.
(1.8 mol) was added dropwise over 1 hour.

After dropping, the temperature of the obtained solution was raised to 110°C over 4 hours, and when it reached 110°C, diisobutyl phthalate 5. 0.3 ml (18.8 mmol) was added.

Stirred for an additional 2 hours at the above temperature. After 2 hours of reaction, a solid portion was collected by filtration while hot, and this solid portion was
After resuspending in 5 ml of Till 4, resuspend in 11
The heating reaction was carried out at 0°C for 2 hours.

After the reaction was completed, the solid portion was collected again by hot filtration and heated to 110°C.
Washed with decane and hexane.

This cleaning was continued until no titanium compound was detected in the cleaning solution.

Solid titanium catalyst component [A] synthesized as above
was obtained as a hexane slurry.

A portion of this catalyst was collected and dried. Analysis of this dried material revealed that the composition of the solid titanium catalyst component [A] obtained as described above was 2.5% by weight of titanium and 58% by weight of chlorine.
% by weight, 18% by weight of magnesium and 13.8% by weight of diisobutyl phthalate.

[Prepolymerization] 200 ml of purified hexane was placed in a 400 ml glass reactor purged with nitrogen, and 20 mmol of triethylaluminum and 4 ml of di-t-butyldimethoxysilane were added.
After adding 2 mmol of the titanium catalyst component [A] in terms of titanium atoms, propylene was supplied at a rate of 5.9 Nfl/hour for 1 hour, and the T1 catalyst component [A] was added.
2.8 g of brobylene was polymerized per sr.

After the preliminary polymerization was completed, the liquid portion was removed by filtration, and the separated solid portion was again dispersed in decane.

[Main polymerization] Purified hexane 7 50 in an autoclave with an internal volume of 21
ml, and 0.75 mmol of trimethylaluminum, 0.075 mmol of di-t-butyldimethoxysilane and the catalyst component [A
) of the prepolymerized product in an amount of 0.015 mmol in terms of titanium atoms (4.48 in terms of the catalyst component [A]).
(equivalent to mg) was added.

Next, the temperature was raised to 70°C, and brobylene polymerization was carried out for 2 hours. The pressure during polymerization was kept at 7 kg/c#G.

After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white granular polymer and a liquid phase. Table 1 shows the extraction residue after drying with boiling n-hebutane, the intrinsic viscosity [η], the apparent bulk specific gravity, the polymerization activity, the II of the total polymer, the average particle diameter, and the geometric standard deviation of the particle size distribution.

Examples 2 to 3 In the polymerization of Example 1, the polymerization temperature was changed to 40°C and 90°C.
Polymerization of polypropylene was carried out in the same manner as in Example 1, except that the temperature was changed to .degree.

The results are shown in Table 1.

Example 4 In the prepolymerization of Example 1, the amount of triethylaluminum was changed from 20 mmol to 6 mmol, and di-t-
Polypropylene was polymerized in the same manner as in Example 1 except that butyldimethoxysilane was not added.

The results are shown in Table 1.

4.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing an example of a catalyst production method in the olefin polymerization method according to the present invention. Diagram (A) Transition metal component (B) Organometallic component (C) Third component

Claims (1)

[Scope of Claims] 1) [A] A solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, [B] An organoaluminum compound catalyst component, and [C] General formula [I] ( R^1_3C)_2Si(OR^2)_2...[
I ] (in the formula, R^1 and R^2 are hydrocarbon groups.) In the presence of an olefin polymerization catalyst formed from an organosilicon compound catalyst component, olefins are polymerized or copolymerized. , [η] is 6d
1. A method for polymerizing olefins, characterized by producing an olefin polymer having a molecular weight of 1/g or more. 2) The method for polymerizing olefins according to claim 1, characterized in that after prepolymerizing the olefins, the olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst. 3) The method for polymerizing olefins according to claim 1 or 2, wherein the olefin is an α-olefin.