JPH0717692B2 - Method for producing polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing polyolefin by polymerizing olefin with a novel catalyst system, and particularly to a method for producing polyolefin having a wide molecular weight distribution and excellent moldability.

(Prior Art and Problems Thereof) Conventionally, regarding a method for producing polyolefin, a catalyst comprising a halide of a transition metal of Group IVb to VIb of the periodic table and an organometallic compound of Group I to III of the periodic table Using,
It is known to be suitable to polymerize olefins. Further, it is known that the catalytic activity per transition metal compound is improved by using a catalyst component in which a transition metal compound is supported on various carriers.

However, when olefins are polymerized using these catalyst systems, the obtained polyolefin generally has a narrow molecular weight distribution, and often has problems in film molding, extrusion molding, hollow molding and the like.

(Means for Solving the Problem) The present inventors have conducted various studies, paying attention to the fact that such difficulty can be solved by giving polyolefin with high stereoregularity and a wide molecular weight distribution. As a result, they have found a new catalyst component system, completed the present invention, and proposed it.

That is, the present invention provides (a) a titanium compound (b) a general formula RnAlX _3- n (wherein R is an alkyl group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, and 1 <n ≦ 3). (C) Organoaluminum intramolecular coordination compound (d) General formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ AlYm (wherein R ¹ and R ² in the formula are each a hydrogen atom or a carbon atom having 1 to 12 carbon atoms). Hydrogen residue, Y is a group having 1 or more heteroatoms not directly bonded to aluminum atom, and 0 <
k ≦ 2,0 ≦ l ≦ 2,0 <m ≦ 2, k + l = 3-m) (e) Electron-donating compound (a), (b), (c) , (D) and (e), that is, the method for producing polyolefin is characterized in that olefin is polymerized in the presence of a catalyst composed of these four components.

Specific examples of titanium-containing catalyst components that are generally and preferably used as the above-mentioned titanium compound include TiCl ₄ and TiBr.
₄ , TiI ₄ , CH ₃ OTiCl ₃ , C ₂ H ₅ OTiCl ₃ , C ₆ H ₅ OTiCl ₃ , C ₂ H ₅ TiCl ₃ , C
₆ H ₅ TiCl ₃ , (C ₂ H ₅ O) ₂ TiCl ₂ , (C ₃ H ₇ O) ₂ TiCl ₂ , (C ₅ H ₅ ) ₂
TiCl ₂ ,, (C ₂ H ₅ O) ₃ TiCl, (C ₄ H ₉ ) ₄ Ti, (C ₂ H ₅ O) ₄ Ti, (C ₄
H ₉ O) ₄ Ti, (CH ₃ OC ₂ H ₄ O) ₄ Ti and other tetravalent titanium compounds;
TiCl ₃ ,, TiBr ₃ , TiI ₃ , CH ₃ TiCl ₂ , CH ₃ OTiCl ₂ , C ₂ H ₅ OTiCl ₂ , C ₄ H
₉ OTiCl ₂ ,, C ₆ H ₅ TiCl ₂ , (C ₂ H ₅ O) ₂ TiCl, (C ₃ H ₇ O) ₂ TiBr,
Trivalent titanium compounds such as (C ₂ H ₅ O) ₃ Ti and (C ₄ H ₉ O) ₃ Ti; Ti
Examples are divalent titanium halides such as Cl ₂ , TiBr ₂ and TiI ₂ .

Two or more kinds of the above titanium compounds may be used as a titanium-containing catalyst component. Among the titanium compounds, titanium halides such as titanium trihalide are particularly preferably used. As the titanium trihalide, titanium tetrahalide is reduced with a compound such as hydrogen, metallic aluminum, metallic titanium, or an organic aluminum compound. Those obtained in this way, for example, δ type, α type and γ type titanium trihalides are particularly preferable.

Further, it is effective to treat the above titanium compound with an electron donating compound in order to enhance polymerization activity and stereoregularity of the polymer. Examples of such electron-donating compounds include alcohols (general formula R ⁵ OH), ethers (R ⁵ —O—R ⁶ ), esters (R ⁵ COOR ⁶ ), aldehydes (R ⁵ COOR ⁶ ).
⁵ CHO), fatty acid (R ⁵ COOH), ketone (R ⁵ COR ⁶ ), nitrile (R ⁵ CN), amine (R ⁵ nNH _3- n) (n = 0,1,2,3), isocyanate (R ⁵ NCO), azo compound (R ⁵ -N = N-
R ⁷ ), phosphine (R ⁵ nPH _3- n) (n = 0,1,2,3), phosphite (P (OR ⁵ ) ₃ ), phosphinite (R ⁵ P (O
R ⁶ ) ₂ ), thioether (R ⁵ nSR ⁶ ), thioalcohol (R ⁵ SH), etc. (wherein R ⁵ , R ⁶ and R ^{7 in} the above general formula are the same or different hydrogen atoms respectively; alkyl group, allyl) Known hydrocarbon residues such as groups are shown) can be used.

The following compounds are preferably used as specific examples of these electron-donating compounds. As alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Examples include xylenol, ethylphenol, benzyl alcohol, and phenethyl alcohol, and ethers such as diethyl ether, di-n-propyl ether and di-
n-butyl ether, di (isoacyl) ether, di-
n-pentyl ether, di-n-hexyl ether, di-n-octyl ether, diisooctyl ether, ethylene glycol monomethyl ether, tetrahydrofuran anisole, diphenyl ether, etc., and organic acid esters such as ethyl acetate, butyl formate and acetic acid. Amil,
Vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, ethylhexyl benzoate, methyl triylate, ethyl triylate, 2-ethylhexyl triylate, methyl anisate, ethyl anisate, propyl anisate, cinnamic acid Examples thereof include ethyl acidate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate and ethyl phenylacetate. Aldehydes include acetaldehyde and benzaldehyde, and fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid and benzoic acid. Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, and benzophenone. Examples of nitriles include acetonitrile, and examples of amines include methylamine, diethylamine, tributylamine, triethanolamine,
Examples include pyridine, aniline, and dimethylaniline. Examples of isocyanates include phenyl isocyanate and toluyl isocyanate, and examples of azo compounds include azobenzene. Examples of the phosphine include ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine and triphenylphosphine, and examples of the phosphite include dimethylphosphite, di-n-octylphosphite, tri-n. -Butylphosphite and the like, and examples of phosphinites include ethyldityldiethylphosphinite, ethyldibutylphosphinite, and phenyldiphenylphosphinite.

Examples of the thioether include diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylunsulfide, propylene sulphide, and the like, and thioalcohols include ethylthioalcohol and n-propylthioalcohol.

Next, the catalyst component used in the present invention is represented by the general formula RnAlX _3- n (wherein R is an alkyl group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom; 1 <n ≦ 3; In the present specification, the organoaluminum compounds represented by the same) are not particularly limited to those known as an aluminum-containing catalyst component for olefin polymerization, and the following compounds may be mentioned as examples of commonly used compounds. Can be shown. That is, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, di-isobutylaluminum chloride, di-n-hexylaluminum chloride, di- (2-ethylhexyl) aluminum chloride, Di-n-dodecylaluminum chloride, methylisobutylaluminum chloride, ethylisobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, diethylaluminium bromide, diethylaluminium iodide and mixtures thereof with Et _1.3 AlCl _1.7 or Alkyl aluminum halide compounds with an average composition such as Bu _2.4 AlCl _0.6 are mentioned. In addition, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-isopropyl aluminum, tri-n
-Butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-dodecyl aluminum,
Tolualkyl aluminum compounds such as tri-hexadecyl aluminum and mixtures thereof can also be used. Furthermore, diethyl aluminum hydride, diisobutyl aluminum hydride, dioctyl aluminum hydride,
Compounds such as di-n-butylaluminum hydride and Et
Alkyl aluminum hydrides such as compounds having an average composition such as _1.5 AlH _1.5 can also be used.

Among the above compounds, particularly preferable examples are compounds such as diethyl aluminum chloride, triethyl aluminum, diisobutyl aluminum hydride, Et _2.5 AlCl _{0.5 and the} like.

In the catalyst composition used for the polymerization of olefin, the molar ratio of the titanium atom of the titanium-containing catalyst component to the Al atom of the organoaluminum compound represented by the general formula RnAlX _3- n is from 10: 1.
You can choose from a wide range of 1: 200, but preferably 2: 1 to 1:
It is suitable to use in the range of 100.

In the present invention, the above-mentioned known catalyst component for olefin polymerization is added to the following (c) organoaluminum intramolecular coordination compound and (d) an organic compound represented by the general formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ AlYm By using the aluminum compound and the electron-donating compound (e) together, a desired polyolefin having a broad molecular weight distribution can be obtained. That is, the catalyst for olefin polymerization (c) organoaluminum intramolecular coordination compound or (B) general formula R ¹ kR
² lAlYm of organoaluminum compound is added separately, (C)
When used together with the electron-donating compound, polyolefin having a wide molecular weight distribution can be obtained. Therefore, in the present invention, the titanium compound and the general formula RnAlX
_3- n catalyst component for olefin polymerization (c) organoaluminum intramolecular coordination compound and (d) general formula R ¹ kR ² lAl
The use of the organoaluminum compound of Ym in combination with (e) the electron-donating compound is the above (c) or (d).
It is possible to obtain a polyolefin having a broader molecular weight distribution than in the case where the above is used alone in combination with (e).

The organoaluminum intramolecular coordination compound (c) used in the present invention is not particularly limited, but the state of coordination with aluminum is represented by the general formula (I). Or general formula (II) The compound represented by (M = metal atom, Y = ligand atom or group, n ≧ 1) is most preferably used.

Further, these compounds are the chemical industry, November 1982, P69, chemistry area 33, (9), 767, (1979) U.S. Pat. No. 3,331,391, Chemical Reviews 79 No. 4,287 (19).
79), etc. are known compounds.

Among the organoaluminum intramolecular coordination compounds used in the present invention, among the organoaluminum intramolecular coordination compounds corresponding to the general formula (I), particularly the following general formulas (III) and (IV)
Compounds represented by are preferred.

(In the general formulas (III) and (IV), R ⁸ is an alkyl group having 1 to 12 carbon atoms, R ¹ is an alkyl group having 1 to 12 carbon atoms and a hydrogen atom, and R ² is 1 to ² carbon atoms. Alkyl group and hydrogen atom, Y ¹ is -O-, -S- and , a represents an integer of 1 to 2, and Q is Specific examples of the compound represented by the general formula (III) include (3-ethoxypropyl) isobutylaluminum hydride, (3-ethoxypropyl) ethylaluminum hydride, (3-methoxybutyl) methylaluminum. Hydride, (3-propoxyisobutyl) pentylaluminum hydride, (4-methoxybutyl) ethylaluminium hydride, (3-octoxyisobutyl) propylaluminum hydride, (4-ethoxybutyl) isobutylaluminum hydride, (3-ethylmercaptopropyl) Hexyl aluminum hydride,
(3-octylmercaptopropyl) propylaluminum hydride, (4-ethylmercaptobutyl) isobutylaluminum hydride, (3-diethylaminopropyl) isobutylaluminum hydride, (4-dioctylaminobutyl) propylaluminum hydride,
(3-methoxypropyl) diethylaluminum, (3
-Ethoxypropyl) diethylaluminum, (3-ethoxypropyl) diisobutylaluminum, (3-phenoxypropyl) diisobutylaluminum, (3-
Isobutoxypropyl) dimethyl aluminum, (4-
Ethoxybutyl) diethylaluminum, (4-isooctoxybutyl) di-n-octylaluminum, (3
-Diethylaminopropyl) diethylaluminum,
(3-Diethylaminopropyl) diisobutylaluminum, (3-N-ethyl-N-isopropylaminopropyl) diisobutylaluminum, (4-diethylaminopropyl) diethylaluminum, (4-diisooctylaminobutyl) diisobutylaluminum hydride, (3- Examples thereof include compounds such as ethylmercaptopropyl) diethylaluminum, (3-n-butylmercaptopropyl) dipropylaluminum, (4-n-butylmercaptobutyl) di-n-hexylaluminum. Further, specific examples of the compound represented by the general formula (IV) include (2- (2-furyl) propyl) hexylaluminum hydride, (2- (2-tiphenyl) ethyl) methylaluminum hydride, (3- (1
-Piperidyl) propyl) isobutylaluminum hydride, (2- (1-methyl-2-piperidyl) ethyl)
Heptyl aluminum hydride, (2- (5-ethyl-
2-Pyridyl) ethyl) propyl aluminum hydride, (2- (2-quinolyl) ethyl) isopropyl aluminum hydride, (2- (2-furyl) ethyl) diethyl aluminum, (2- (2-furyl) propyl) di-n -Hexylaluminum, (3- (2-thienyl)
Propyl) diethylaluminum, (2- (4-methyl-2-thienyl) ethyl) diisobutylaluminum,
(3- (1-Hyperidyl) propyl) di-n-hexylaluminum, (2- (2-pyridyl) ethyl) diisoacylaluminum, (2- (5-ethyl-2-pyridyl) ethyl) diisobutylaluminum, ( 3- (2-
Pyridyl) propyl) diisobutylaluminum, (2
-(2-quinolyl) ethyl) dimethylaluminum,
Examples of such compounds include (2- (2-quinolyl) ethyl) ethylisooctylaluminum.

Among the organoaluminum intramolecular coordination compounds corresponding to the general formula (II), the compound of the following general formula (V) is particularly preferable.

(R ³ is an alkyl or alkoxy group having 1 to 12 carbon atoms, R ^3
4 represents an alkyl group or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 1 to 3) Specific examples of the compound of the above (V) include diethylaluminum acetylacenate, dihexylaluminum acetylacetonate, Diisopropoxy aluminum ethyl acetoacetate, diisooctoxy aluminum ethyl acetoacetate, isopropoxy aluminum bis (ethyl acetoacetate), diethoxyl aluminum acetylacetonate, aluminum tris (butyl acetoacetate), methoxy aluminum bis (butyl acetoacetate) , Dimethyl aluminum ethyl acetoacetate, diisobutoxy aluminum acetyl acetonate, aluminum tris (acetyl acetonate), O-di-n-butyl aluminum di Chirumaroneto, O- di - iso propoxy aluminum diethyl malonate, O- aluminum tris (diethyl malonate), may be mentioned compounds such.

Further, although not included in the above general formulas (III), (IV) and (V), it is considered to be an organoaluminum intramolecular coordination compound, and as an example of a compound suitable for use in the present invention, specifically (2 -(Dimethylethoxysilyl) ethyl) diisobutylaluminum, (3- (diethylethoxysilyl))
Propyl) dimethyl aluminum, (2- (dimethylethoxysilyl) ethyl) ethyl aluminum hydride,
Tris (2- (dimethylethoxysilyl) ethyl) aluminum, bis- (2- (diethylmethoxysilyl) ethyl) propylaluminum, (3- (trimethylsiloxy) propyl) diisobutylaluminum, (3-
Examples thereof include (trimethylsiloxy) propyl) ethylaluminum hydride.

As for the method for synthesizing the (c) organoaluminum intramolecular coordination compound used in the present invention, various methods are described in the above-mentioned publicly known documents, and the organoaluminum intramolecular coordination compound is simply prepared by an operation such as distillation. The method of using after separating is common. However, depending on the synthesis method, the by-product or unreacted raw material obtained together with the organometallic intramolecular coordination compound which is the main product may not adversely affect the polymerization of polyolefin, and in that case, the reaction product Can be used as it is for the polymerization of polyolefin. As a specific example, a reaction product obtained by reacting equimolar amounts of N, N diethylallylamine and diisobutylaluminum hydride in an inert hydrocarbon solvent, or equimolar amounts of ethyl acetoacetate and triethyl in an inert hydrocarbon solvent. The reaction product obtained by reacting aluminum can be mentioned.

The amount of the (c) organoaluminum intramolecular coordination compound used in the present invention is generally such that the molar ratio of the titanium atom of the titanium compound to the metal atom of the organoaluminum intramolecular coordination compound is 10: 1 to 1: 200. However, it is preferably selected from the range of 2: 1 to 1:50.

In addition, another catalyst component (d) used in the present invention may be represented by the general formula R ¹ kR ² l
AlYm (wherein R ¹ and R ² are hydrogen atoms and hydrocarbon residues, Y is a group having at least one hetero atom not directly bonded to an aluminum atom, 0 <m ≦ 2,0 ≦ k ≦ 2,0 ≦ l ≦ 2, k
In the organoaluminum compound represented by + 1 = 3-m), the hydrocarbon residue means an alkyl group, an alkenyl group, an alkynyl group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and is generally an alkyl group. And the hetero atom of the substituent Y is O, S, N, P, Si, Sc, As, Hg, etc.
S, N, P and Si atoms are preferred for use in the present invention, with O, S, N and Si atoms being particularly preferred. Such a general formula ▲ R ¹ _k ▼
Specific examples of the organoaluminum compound represented by R ( ² _l) AlYm include bis (3-diethylaluminopropyl) ether, bis (3-diisobutylaluminopropyl) ether, (3- (P-anth) propyl). Dipropyl aluminum, (2- (P-anth) ethyl) dioctyl aluminum, (3- (P-anth) propyl)
Methylaluminum hydride, 3-diisobutylaluminopropoxyanisole, (3- (3,4-dimethoxyphenyl) propyl) diisobutylaluminum, bis (3
-(3,4-Dimethoxyphenyl) propyl) ethylaluminum, (3- (3,4-methylenedioxyphenyl))
Propyl) dipentylaluminum, (3-glycidyloxypropyl) diisobutylaluminum, (3-diethylaluminopropyl) diethylmalonate, (3-
(Triethoxysilyl) propyl) ethyl aluminum hydride, (2- (trimethoxysilyl) ethyl) octyl aluminum hydride, (3- (trimethylsilyl) propyl) diisobutylaluminum, (3- (triethylsilyl) propyl) dimethylaluminum, bis ( 3-diethylaminopropyl) dimethylsilane, bis (3-dimethylaluminopropyl) allylmethylsilane, 1,3-bis (2- (diisobutylalumino) ethyl)
-1,1,3,3-Tetramethyldisiloxane, Bis (3-diethylaluminopropyl) sulfide, Bis (3-diisobutylaluminopropyl) ethylphosphine, Bis (2-diisobutylaluminoethyl) vinylphosphine, Methylphos Examples include bis (3-diethylaluminopropyl) fluorate, (2- (4-pyridyl) ethyl) diisobutylaluminum, (2- (4-pyridyl) ethyl) hexylaluminum hydride, (3-diethylaluminopropyl) morpholine. , Also (d)
General formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ The general formula of the organoaluminum compound represented by AlYm and the above-mentioned catalyst component for olefin polymerization.
Organoaluminum compound represented by RnAlx _3- n and (c)
It is also possible to mix and age the organoaluminum intramolecular coordination compound in advance and then use it for polymerization as an organometallic compound having an average composition. As an example of this, (3
-(3,4-dimethoxyphenyl) propyl) diisobutylaluminum, diethylaluminium chloride and (3- (N, N-diethylamino) propyl) diisobutylaluminum mixed in a ratio of 0.15: 0.15: 0.7 Et _1.4 iBu _0.6 Al {CH ₂ ) _3- NEt ₂ } _0.15 Can be mentioned.

The amount of the (d) organoaluminum compound represented by the general formula R ¹ kR ² lAlYm used in the present invention is generally the titanium atom of the titanium compound described above and the aluminum atom of the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm. Molar ratio of 10: 1
It can be selected in the range from 1 to 200, but is preferably 2: 1 to 1:
Selected in the range of 50.

As the method for synthesizing the organoaluminum compound represented by the above general formula (d) R ¹ _k ▼ R ▲ ² _l ▼ AlYm, a method using a reaction between a halogenated organoaluminum compound and a Grignard reagent and a general formula Z-CH = An alkenyl compound represented by CH ₂ (wherein Z is a group having at least one hetero atom) and a general formula ▲ R ⁹ _3-i ▼ AlHi (wherein, R ⁹ is a hydrocarbon residue having 1 to 12 carbon atoms) In general, a method using a reaction of an organoaluminum hydride compound represented by the formula (1) and (1≤i≤2) is known. Comparing the two synthetic methods, the latter synthetic method has the advantages that the synthetic operation is simple and the reaction can be carried out in an inert hydrocarbon solvent. The organoaluminum hydride compound and the general formula Z-CH = CH during the reaction are used.
Depending on the molar ratio of the alkenyl compound shown in ₂ and the types and properties of the products and unreacted products of the reaction between them, the reaction product may be used as it is for distillation, or it may be used in an inert hydrocarbon solvent at an appropriate concentration. It is also possible to dilute it to be used for polymerization. In addition, after carrying out the above synthetic reaction in an inert hydrocarbon solvent, when a solution of the obtained reaction product of an inert hydrocarbon is used as it is for polymerization, ▲ R ¹ _k ▼ is _obtained by an operation such as distillation. In some cases, the effect of broadening the molecular weight distribution, which is equivalent to or better than the case of using R ² _l AlYm separately, may be obtained. Here, the molar ratio of the organoaluminum hydride compound and the alkenyl compound represented by the general formula Z-CH = CH ₂ at the time of reaction is not particularly limited, but the general formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ When the reaction product represented by AlYm is used for polymerization without separation, the range of 5: 1 to 1:10 is preferable, and the range of 2: 1 to 1: 3 is particularly preferable.

In the present invention, it is necessary to add and use the electron donating compound (e) as a catalyst component. As such an electron-donating compound (e), known compounds as a component of a catalyst for olefin polymerization can be used without particular limitation.
Generally, particularly preferably used are oxygen, titanium, phosphorus,
Alternatively, it is an organic compound containing sulfur such as water, alcohol, ether, ester, aldehyde, fatty acid, ketone, nitrile, amine, isocyanate, azo compound, phosphine, phosphinite, phosphoramide, thioether, thioalcohol, acid amide.
(E) More specifically, those which are preferably used as the electron donating compound are methanol as the alcohol,
Examples include ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, xylenol, ethylphenol, benzyl alcohol and phenethyl alcohol. As the ether, diethyl ether, di-n-propyl ether, di-n-
Butyl ether, di (isoamyl) ether, di-n-
Pentyl ether, di-n-hexyl ether, di-n
-Octyl ether, diisooctyl ether, ethylene glycol monoethyl ether, diphenyl ether, tetrahydrofuran, anisole, 2,3-dihydrofuran, as well as vinyl ethyl ether, allyl ethyl ether, anethole, p-methoxystyrene, safrole, phenyl Ethers having vinyl substituents such as p-allylphenyl ether and p-styrylanisole. Furthermore, as the ester, ethyl acetate, butyl formate, amyl acetate, butyl oxalate, vinyl acetate, ethyl benzoate,
Propyl benzoate, octyl benzoate, ethylhexyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, In addition to propyl naphthoate, butyl naphthoate, ethyl phenylacetate, etc., as an ester of a heterocyclic compound containing ethyl thiophene-2-carboxylate, methyl 2-pyridinecarboxylate, pyrrole-2-
Ethyl carboxylate, N-carboethoxypyrrole, methyl 2-thienylacetate and the like can be preferably used. Furthermore, examples of aldehydes include acetaldehyde and benzaldehyde. Further, the fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, benzoic acid and the like. Furthermore, examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, benzophenone, N-vinylpyrrolidone, and acetylacetone. Further, nitriles include acetonitrile and the like, and amines include methylamine, diethylamine, triethylamine, triethanolamine, pyridine, 4-
Examples include vinyl pyridine, aniline, N, N-diethylaniline. Further, the isocyanate includes phenyl isocyanate and toluyl isocyanate, and the azo compound includes azobenzone. Furthermore, examples of the phosphine include ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine and triphenylphosphine, and examples of the phosphite include dimethylphosphite and di-n-octylphosphine. Examples thereof include ferrite and tri-n-butyl phosphite. Further, phosphinites include ethyldiethylphosphinite, ethyldibutylphosphinite, phenyldiphenylphosphinite, etc., and phosphoramides include hexamethylphosphoric triamide. Further, the thioether includes diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylene sulfide, and the like, and the thioalcohol includes ethyl thioalcohol, n-propyl thioalcohol and the like. Furthermore, as acid amides, formamide, acetamide, acrylamide, dimethylformamide, benzoylamide,
Phthaloyl amide and the like.

Two or more compounds selected from the above-mentioned (e) electron donating compounds may be selected and used. (E) The amount of the electron-donating compound used is generally based on the titanium atom of the titanium-containing catalyst component.
Although it can be used in the range of 0.001 mol to 100 mol,
It is preferably used in the range of 0.01 to 5 mol.

The catalyst system of the present invention comprises a catalyst component for olefin polymerization (c)
Organoaluminum intramolecular coordination compound, (d) General formula R ¹ kR
^A catalyst system in which an organoaluminum compound represented by ² lAlYm and (e) an electron-donating compound are further added with an organometallic compound of an element selected from zinc, lithium, magnesium and boron is often more preferably used.

The organometallic compound of the above-mentioned element selected from zinc, lithium, magnesium and boron is not particularly limited, but generally the following compounds may be used. Examples of organometallic compounds of zinc include dialkyl zinc, alkyl zinc halides, alkyl zinc alkoxides, and the like. Specifically, diethyl zinc, dimethyl zinc, ethyl zinc chloride, ethyl zinc bromide, ethyl zinc ethoxide, methyl zinc isopropoxide. , Compounds such as ethyl zinc n-butoxide can be preferably used. The organic compounds of magnesium include dialkyl magnesium, alkyl magnesium halides, alkyl magnesium alkoxides, and the like. Specifically, di-n-butyl magnesium, ethyl magnesium chloride, di-n-octyl magnesium, isobutyl magnesium chloride, n-
Compounds such as butyl magnesium iodide and n-propyl magnesium ethoxide can be preferably used. Furthermore, the organic compound of lithium is n-butyllithium, and the organic compound of boron is triethylboron. Among the compounds listed above, a particularly preferable compound is an organometallic compound of zinc.

The amount of the organometallic compound of an element selected from zinc, magnesium, lithium and boron can be generally used in the range of 0.001 mol to 100 mol with respect to the titanium atom of the titanium-containing catalyst component, but 0.01 mol to 20 mol It is preferably used in the range.

(E) Using an electron-donating compound and an organometallic compound of an element selected from zinc, lithium, magnesium and boron together with the above-mentioned catalyst component is also an effective method for further broadening the molecular weight distribution of polyolefin.
At this time, the amount of the organometallic compound selected from zinc, lithium, magnesium and boron and the amount of the electron-donating compound (e) used in the titanium-containing catalyst component with respect to the titanium atom is the same as that in the case of being added to the catalyst system of the present invention alone. It can be used in the same range. Further, (e) the electron-donating compound and the organometallic compound of an element selected from zinc, lithium, magnesium and boron are mixed with the organoaluminum compound represented by the above general formula RnAlX _3- n in advance and then used for the polymerization. Alternatively, it may be used for polymerization after previously mixing with (c) the organoaluminum intramolecular coordination compound, and (d) an organic compound represented by the general formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ AlYm. It may be used for polymerization after being mixed with an aluminum compound.

Further, the catalyst components of the present invention may be prepared by mixing them in the presence or absence of a catalyst in advance, or these catalyst components may be directly added to the polymerization tank. In the latter case, the catalyst components may be added in any order without any limitation.

The olefin used in the present invention is not particularly limited, and those which can be polymerized with the above catalyst can be used, but generally, the number of carbon atoms of ethylene, propylene, butene, pentene and the like is 2 to 2.
Ten olefins are preferably used. Further, as defined above, it is also possible to use a mixture of olefins or a mixture of olefins and another copolymerizable monomer. The copolymerizable monomer is not particularly limited, and a monomer known to be copolymerizable with olefin can be used.

In the polymerization of olefins, known molecular weight regulators such as hydrogen and halogenated hydrocarbons can be used to control the molecular weight of the obtained polyolefin.

The polymerization method of olefin in the present invention is not particularly limited, and a known polymerization or copolymerization method can be directly used. For example, ordinary slurry polymerization, bulk polymerization in liquid monomer, and gas phase polymerization can be preferably adopted. In slurry polymerization, hexane, heptane, benzene, toluene,
An inert hydrocarbon such as cyclohexane is used as the solvent. Further, as the polymerization method, either batch method or continuous method is possible, and the polymerization can be carried out in two or more stages under different reaction conditions. Furthermore, in the presence of a titanium-containing catalyst component and an organoaluminum compound represented by the general formula RnAlX _3- n, (c) an organoaluminum intramolecular coordination compound, (d) a general formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ In the presence of an organoaluminum compound represented by AlYm, (e) an electron donating compound and an organometallic compound selected from zinc, lithium, magnesium and boron, 0.2 g to 50 g of olefin is added per 1 g of the titanium-containing catalyst component, Preferably 0.5 g
It is also a preferred embodiment to use as a titanium compound a slurry obtained by prepolymerizing 20 to 20 g of olefin with an inert hydrocarbon as a solvent.

Generally, the polymerization can be carried out in the range of 0 to 200 ° C, but it is usually preferable to carry out the polymerization in the range of room temperature to 100 ° C. The polymerization pressure is not particularly limited, but atmospheric pressure or 100K
g / cm ^2, preferably preferably in the range of ^{1Kg / cm 2 ~50Kg / cm 2} .

(Examples) In order to describe the present invention more specifically, examples will be described below, but the present invention is not limited to these examples.

The boiling n-heptane extraction residue (hereinafter abbreviated as II) used in the examples means the insoluble matter when the polyolefin was extracted with boiling n-heptane for 5 hours. Fw / Fr is an index of the molecular weight distribution, and was measured by the GPC (gel permeation chromatography) method with the ratio of the weight average molecular weight Fw and the number average molecular weight Fr.
The larger Fw / Fr, the wider the molecular weight distribution of the polymer.

(A) Synthesis of organometallic intramolecular coordination compound (A) -1 Synthesis of (3- (N, N-diethylamino) propyl) diethylaluminum After replacing a 200 ml flask with titanium, dry heptane 100 ml
And 100 mmol of diethylaluminum hydride were weighed, and 100 mmol of N, N-diethylallylamine was added dropwise to the flask with stirring for 1 hour. Next, the mixture was reacted at 85 ± 5 ° C. for 6 hours with stirring and allowed to cool to room temperature.

Half of the solution after the reaction was distilled under reduced pressure to isolate (3- (N, N-diethylamino) propyl) diethylaluminum,
Further, it was diluted with dry heptane to obtain a heptane solution having a concentration of 1 mmol / ml. This solution is represented by (A-1), and the remaining undistilled half amount is represented by (A'-1).

Synthesis of (A) -2 (3-ethoxypropyl) diisobutylaluminum Diisobutylaluminum hydride and allyl ethyl ether were reacted in the same manner as in (A) -1, except that the reaction temperature was 75 ° C ± 5 ° C. After isolation by distillation, (3-ethoxypropyl) diisobutylaluminum diluted with heptane is represented by (A-2), and the undistilled residue is represented by (A ′).
-2).

(A) -3 Synthesis of diethylaluminum ethyl acetoacetate After replacing the 200 ml flask with titanium, dry heptane 100 was added.
ml and 100 mmol of triethylaluminum were weighed, and ethyl acetoacetate was added dropwise over 1 hour while stirring. During this period, heat was generated, so cooling was performed with ice water.

Next, this solution was stirred at 65 ± 5 ° C. for 1 hour to complete the reaction, and then allowed to cool to room temperature. Since this reaction has a high yield, it was directly used for polymerization. This solution is represented by (A-3).

(B) Synthesis of Organoaluminum Compound Represented by General Formula R ¹ kR ² lAlYm A hydrogenated organoaluminum compound and an alkenyl represented by the general formula Z-CH = CH ₂ are prepared in the same manner as in (A) -1 of Example 1. The compounds were reacted. The reaction temperature was 60 to 95 ° C., and the reaction time was 3 to 6 hours.

After isolating a half amount by distillation in the same manner as in (A) -1 of Example 1,
The solution was diluted with heptane, and the rest was used as a solution after the reaction for polymerization. The synthesis results are shown in the following table.

After that, the above reaction products (B-1) to (B-) are shown in the table.
It is represented by the abbreviation of 9).

Example 1 Polymerization of Propylene After autoclaving a stainless steel autoclave having an internal volume of 2 at room temperature with titanium, 430 g of liquid propylene was added. Next, while stirring the autoclave, 1.96 mmol of diethylaluminum chloride and then hydrogen were added so as to have a partial pressure of 1.2 kg / cm ² , and then the temperature was raised to 65 ° C. After the temperature was raised, it was prepared in the above (A) as an organometallic intramolecular coordination compound (A-
0.30 mmol of 1), 0.30 mmol of (B-1) as an organoaluminum compound represented by R ¹ kR ² lAlYm, and 0.20 mmol of benzyl benzoate as an electron-donating compound were added. After stirring for 5 minutes, 0.196 mmol of δ-type titanium trichloride (manufactured by Toyo Stoffer Chemical Co., Ltd.) was added to initiate polymerization.
After 120 minutes from the start of the polymerization, stirring was stopped, propylene was purged to complete the polymerization, and the autoclave was replaced with nitrogen. The catalyst residue was deactivated by adding 4 ml of propylene oxide.

The obtained polypropylene was vacuum dried at 40 ° C. for 12 hours and then weighed to find 155 g. The n-heptane extraction residue II is 9
It was 4.7%. The yield of polypropylene per 1 g of the titanium compound (hereinafter abbreviated as β) was 4430. β represents a g-polypropylene / g-titanium compound. Further, the Fw / Fr of polypropylene is 13.5, and the molecular weight distribution is wide.

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that the organometallic intramolecular coordination compound and the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm were not added. The results are shown in Table 1.

Comparative Example 2 Propylene was polymerized in the same manner as in Example 1 except that the organometallic intramolecular coordination compound was not added. (However, general formula R ¹
The organoaluminum compound represented by kR ² lAlYm is 0.6 mmol.
The results are shown in Table 1.

Comparative Example 3 Propylene was polymerized in the same manner as in Example 1 except that the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm was not added. (However, 0.6 mmo for organometallic intramolecular coordination compounds
The results are shown in Table 1.

Example 2 Preparation of Prepolymerized Catalyst Slurry The stainless steel autoclave 1 heated to 50 ° C. was replaced with titanium, and 250 ml of dried n-C _7, 8.94 mmol of diethylaluminum chloride and 0.11 mmol of diethylene glycol methyl ether were added.

Next, 11.2 mmol of δ-type titanium trichloride was added and stirred for 10 minutes, and then the titanium in the autoclave was replaced with propylene to start polymerization.

Thereafter, propylene was introduced into the autoclave at an average flow rate of 178 ml / min, and after 1 hour, the introduction of propylene was stopped and the system was sufficiently replaced with titanium.

The prepolymerized catalyst slurry obtained by the above operation was recovered and then diluted with 150 ml of n-heptane to prepare a concentration of 5 g-TiCl ₃ / l-heptane.

Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1 except that 7 ml of the prepolymerized catalyst slurry prepared in the above (A) was used instead of δ type titanium trichloride. 160 g of polypropylene were obtained, β was 4570. II is 95.3%, Fw /
Polypropylene with a wide molecular weight distribution of Fr of 13.0 was obtained.

Comparative Example 4 Propylene was polymerized in the same manner as in Comparative Example 2 except that 7 ml of the prepolymerized catalyst slurry prepared in Example 2 was used instead of δ type titanium trichloride. 208 g of polypropylene were obtained, β was 5940, II was 97.3% and Fw / Fr was 7.6.

Examples 3 to 14 By combining the organometallic intramolecular coordination compound synthesized in Examples 1 (A) and (B) with the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm, respectively, as shown in Table 1, Propylene was polymerized in the same manner as in Example 2. As the electron-donating compound, benzyl benzoate or ethyl P-anthate was used. The results are shown in Table 2.

Examples 15,16 Polymerization of propylene in the same manner as in Example 9 except that the molar ratio of the organometallic intramolecular coordination compound and the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm to Ti atoms was changed. I went. The results are shown in Table 3.

Example 17 Propylene was polymerized in the same manner as in Example 1 except that 0.098 mmol of diethylzinc was added immediately before the addition of δ type titanium trichloride. 121 g of polypropylene was obtained, β was 3460, II was 92.9%, and Fw / Fr = 14.1, showing a broad molecular weight distribution.

Example 18 In the same manner as in Example 1, 380 g of ethylene, 2.4 mmol of triethylaluminum, and then hydrogen were added so as to have a partial pressure of 1.0 Kg / cm ² . After the temperature was raised to 65 ° C., (A-3) prepared in Example 1 (A) as an organometallic intramolecular coordination compound was 0.30 mm.
ol, (B-4) prepared in Example 1 (B) as an organoaluminum compound represented by the general formula R ¹ kR ² lAlYm is 0.30 mm.
ol added. Ethyl benzoate was used as an electron-donating compound.
20 mmol was added. As a titanium compound, 7 ml of the prepolymerization catalyst slurry prepared in Example 2 (A) was added, and after the polymerization of ethylene was started, the same operation as in Example 1 was carried out.

192 g of polyethylene was obtained, β was 5490, Fw / Fr was 14.4, and polyethylene having a wide molecular weight distribution was obtained.

Example 19 (Copolymerization of propylene and ethylene) In the same manner as in Example 1, 400 g of propylene, 2.0 mmol of diethylaluminum chloride, and subsequently 1.2 Kg / cm of hydrogen.
Added to a partial pressure of ² . After the temperature was raised to 65 ° C, ethylene was introduced until the ethylene concentration in the gas phase became 1.5%. Next, 0.2 m of ethyl P-anthate was used as an electron-donating compound.
mol added. After that, propylene and ethylene were copolymerized in the same manner as in Example 17.

197 g of propylene-ethylene copolymer was obtained, β was 56
30, II is 91.9%, the ethylene content of the copolymer is 1.78
It was wt%. Fw / Fr was 10.5, and a propylene-ethylene copolymer having a wide molecular weight distribution was obtained.

Comparative Example 5 Copolymerization of propylene and ethylene was carried out in the same manner as in Example 18 except that the organometallic intramolecular coordination compound and the organoaluminum compound represented by the general formula R ¹ kR ² lAlYm were not added.

230 g of propylene-ethylene copolymer was obtained, β was 65
It was 70. II was 93.1%, and the ethylene content of the copolymer was 1.74 wt%. The Fw / Fr of the ethylene-propylene copolymer was 6.0.

[Brief description of drawings]

FIG. 1 is a flowchart of the preparation and polymerization of the catalyst of the present invention.

Claims (1)

[Claims] 1. (a) Titanium compound (b) General formula RnAlX _3- n (wherein R is an alkyl group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom, and 1 <n ≦ 3). (C) Organoaluminum intramolecular coordination compound (d) General formula ▲ R ¹ _k ▼ R ▲ ² _l ▼ AlYm (wherein R ¹ and R ² in the formula are each a hydrogen atom or a carbon number of 1 to 12) Hydrocarbon residue, Y is a group having one or more heteroatoms not directly bonded to aluminum atom, and 0 <
k ≦ 2,0 ≦ l ≦ 2,0 <m ≦ 2, k + l = 3-m) (e) Electron-donating compound (a), (b), (c) A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst consisting of, (d) and (e).