JPH062773B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyolefin by polymerizing olefin using a novel catalyst system.

More specifically, as the titanium-containing catalyst component (A), titanium trichloride, (B) the general formula R _n AlX _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) and (C) an aluminum intramolecular coordination compound corresponding to any one of the following general formulas (I) and (II), that is, R ³ _3-m Al (OC (R ⁵ ) = CHC (O) R ⁵ ) _m
(II) where Q is -C (R ² ) ₂ · Y · R ⁴ , Y is -O-, -S-, or -NR-R ¹ is an alkyl group having 1 to 12 carbon atoms, or a hydrogen atom R ² is an alkyl group having 1 or 2 carbon atoms or a hydrogen atom, and R ³ is a carbon number. 1 to 12 alkyl group or alkoxy group R ⁴ is an alkyl group having 1 to 12 carbon atoms R ⁵ is an alkyl group or alkoxy group having 1 to 8 carbon atoms a is 1 or 2, m is an integer of 1 to 3, respectively. The method for producing a polyolefin is characterized in that an olefin is polymerized in the presence of a catalyst whose main component is represented (hereinafter, each symbol has the same meaning as described above).

For the conventional manufacturing method of polyolefin, see
Halides of Group IVb to VIb Transition Metals and Periodic Table I
It is known to be suitable to polymerize olefins using a catalyst system consisting of a Group III organometallic compound.
Further, it is known that the catalytic activity per transition metal compound is improved by using the catalyst component supporting the transition metal compound on various carriers.

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

The present inventors have paid attention to the fact that such difficulties can be solved by giving polyolefin with high stereoregularity and a wide molecular weight distribution, and have conducted various studies. As a result, they discovered a new catalyst system and completed and proposed the present invention.

That is, the present invention is a method for producing a polyolefin, characterized in that an olefin is polymerized using a novel catalyst system mainly composed of the catalyst components (A), (B) and (C).

Further, in the above catalyst system of the present invention, together with the components (A), (B) and (C), (D) an electron donating compound and / or (E) an organometallic compound of an element selected from zinc, lithium and magnesium boron. It is also useful to use, and in some cases, it has an effect of further broadening the molecular weight distribution of the obtained polyolefin.

The olefin referred to in the present invention is ethylene, propylene,
It is a generic term that includes a monomer mixture containing less than 50% of another monomer copolymerizable with the above-mentioned monomer in addition to a single monomer such as butene. Therefore, the polyolefin obtained in the present invention is a homopolymer of the above olefin and a copolymer of the olefin and other copolymerizable monomer.

Next, the components (A), (B) and (C) of the catalyst system used in the present invention will be described.

The titanium-containing catalyst component described in (A) above is known as a catalyst component for olefin polymerization. Also in the present invention, these known materials can be used without any limitation. The titanium-containing catalyst components which are generally used preferably are titanium trihalides, in particular titanium trichloride. As the titanium trichloride, those obtained by reducing titanium tetrachloride with hydrogen, metallic aluminum, metallic titanium, organic aluminum compounds and the like, for example, δ type, α type and γ type titanium trichloride are particularly preferable.

The titanium-containing catalyst component can be used as it is or on an inorganic carrier or treated with an electron donating compound before use. Examples of the inorganic carrier for supporting the titanium compound include MgCl ₂ , Mg (OH) ₂ , MgO, CaO, Ca (OH) ₂ and Zn (O
H) ₂ , Mn (OH) ₂ , MnO, MgCO ₃ , NiCl ₂ , Al ₂ O ₃ , SiO ₂ , TiO ₂
Well-known carriers such as can be used.

Examples of the electron-donating compound include alcohol (general formula ROH), ether (ROR ′), ester (RCOO).
R '), aldehyde (RCHO), fatty acid (RCOOH), ketone (RCO)
R '), nitrile (RCN), amine _{(R n NH 3-n)} (n = 0,1,
2, 3), isocyanate (RNCO), azo compound (RN = N-
R ″), phosphine (R _n PH _3-n ) (n = 0, 1, 2, 3),
Phosphite (P (OR) ₍₃ ), phosphinite (RP (OR ') ₂ ),
Thioether (RnSR '), thioalcohol (RSH), etc. (provided that R and R'in the above general formula are the same or different hydrogen atoms respectively; hydrocarbon groups such as alkyl groups and allyl groups)
Known ones can be used.

The following compounds are preferably used as specific examples of these electron-donating compounds.

The alcohol is methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, xylenol, ethylphenol, benzyl alcohol, phenethyl alcohol, etc., and the ether is diethyl ether, di-n-propyl ether, diene. -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, amyl acetate, 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, ethyl cinnamate, methyl naphthoate, There are ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate and the like. 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, benzoic acid, etc. 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, pyridine, aniline,
For example, 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, and tri-n. -Butyl phosphite and the like, and examples of the phosphinite include ethyl diethyl phosphinite, ethyl dibutyl phosphinite, phenyl diphenyl phosphinite, and the like.

The thioether includes diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylene sulfide, etc., and the thioalcohol includes ethyl thioalcohol, n-propyl thioalcohol and the like.

In order to improve the polymerization activity and stereoregularity of the above-mentioned titanium compounds, treatment with a tetravalent titanium halide can be appropriately applied and used.

Next, the catalyst component used in the present invention (B) is represented by the general formula R _n AlX _3-n (wherein R is an alkyl group having 1 to 20 carbon atoms,
X represents a halogen atom or a hydrogen atom; 1 <n ≦ 3)
It is an organoaluminum compound represented by. The organoaluminum compound represented by the above general formula R _n AlX _3-n can be used without particular limitation as a known catalyst component for olefin polymerization, but the following are examples of commonly used compounds. The compound can be represented. That is, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n
-Butyl aluminum chloride, di-isobutyl aluminum chloride, di-n-hexyl aluminum chloride, di- (2-ethylhexyl) aluminum chloride, di-n-dodecyl aluminum chloride, methyl isobutyl aluminum chloride, ethyl isobutyl aluminum chloride, methyl aluminum sesqui Chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, diethylaluminium bromide, diethylaluminium iodide and mixtures thereof and alkylaluminum halide compounds having an average composition such as Et _1.3 AlCl _1.7 , and Bu _2.4 AlCl _9.6. Can be mentioned. Also, 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. Trialkylaluminum compounds such as aluminum, tri-hexadecylaluminum, etc. and mixtures thereof can also be used. Furthermore, compounds such as diethyl aluminum hydride, diisobutyl aluminum hydride, dioctyl aluminum hydride, di-n-butyl aluminum hydride, and Et _1.5 AlH
Alkyl aluminum hydrides such as compounds having an average composition such as _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 _{9.5 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 R _n AlX _3-n is selected from a wide range of 10: 1 to 1: 200. Yes, but preferably 2:
It is preferably used in the range of 1 to 1: 100.

Still another component (C) of the catalyst component used in the present invention is an aluminum intramolecular coordination compound corresponding to the following general formula (I) or (II).

R ³ _3-m Al (OC (R ⁵ ) = CHC (O) R ⁵ ) _m
(II) Of these, specific examples of the compound represented by the general formula (I) include (3-ethoxypropyl) isobutylaluminum hydride, (3-ethoxypropyl) ethylaluminum hydride, (3- (Methoxybutyl) methyl aluminum hydride, (3-propoxyisobutyl) pentyl aluminum hydride, (4-methoxybutyl) ethyl aluminum hydride, (3-octoxyisobutyl) propyl aluminum hydride, (4-ethoxybutyl) isobutyl aluminum hydride, (3 -Ethylmercaptopropyl) hexylaluminum hydride, (3-octylmercaptopyropyr) propylaluminum hydride, (4-ethylmercaptobutyl) isobutylaluminum hydride, (3-diethylaminopropyi) ) Isobutylaluminum hydride, (4-dioctylaminobutyl) propylaluminum hydride, (3-methoxypropyl) diethylaluminum, (3-ethoxypropyl) diethylaluminum, (3-ethoxypropyl) diisobutylaluminum, (3-isobutoxypto) Pill) dimethyl aluminum, (4-ethoxybutyl) diethyl aluminum, (4-isooctoxybutyl) di-n-octyl aluminum, (3-diethylaminopropyl) diethyl aluminum, (3-diethylaminopropyl) diisobutyl aluminum, (3- N
-Ethyl-N-isopropylaminopropyl) diisobutylaluminum, (4-diethylaminopropyl) diethylaluminum, (4-diisooctylaminobutyl) diisobutylaluminum hydride, (3-ethylmercaptopropyl) diethylaluminum, (3-n
-Butylmercaptopropyl) ditopyr aluminum, (4-n-butyl mercaptobutyl) di-n-hexyl aluminum, (2- (2-furyl) propyl)
Hexyl aluminum hydride, (2- (2-thienyl) ethyl) methyl aluminum 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) diethylaluminum, (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)
Diisoacyl aluminum, (2- (5-ethyl-2-
Pyridyl) ethyl) diisobutylaluminum, (3-
Examples of such compounds include (2-pyridyl) propyl) diisobutylaluminum, (2- (2-quinolyl) ethyl) dimethylaluminum, (2- (2-quinolyl) ethyl) ethylisooctylaluminum, and the like.

Specific examples of the compound corresponding to the general formula (II) include diethylaluminum acetylacenate, dihexylaluminum acetylacetonate, diisopropoxyaluminum ethylacetoacetate, diisooctoxyaluminum ethylacetoacetate, isopropoxyaluminum bis ( Ethyl acetoacetate), diethoxyl aluminum acetylacetonate, aluminum tris (butyl acetoacetate), methoxy aluminum bis (butyl acetoacetate), dimethyl aluminum ethyl acetoacetate, diisobutoxy aluminum acetylacetonate, aluminum tris (acetylacetoate), O-di-n-butyl aluminum diethyl malonate, O-di-isopropoxy aluminum diethyl Roneto, O- aluminum tris (diethyl malonate), may be mentioned compounds such.

The method for preparing the catalyst used in the present invention is not particularly limited.
As a conventional method for preparing a so-called Ziegler-Natta type catalyst,
In particular, a catalyst is known in which an electron donor or one or more third components are added to a titanium component or an organoaluminum component for the purpose of increasing activity or stereoregularity. However, it can be applied. That is, the catalyst preparation method of the present invention, (A) a titanium compound, (B) an organoaluminum compound and (C) an aluminum intramolecular coordination compound are mixed at the same time, or any two of them are mixed in advance. It is also possible to mix with other ingredients. That is,
The intramolecular coordination compound of aluminum has the general formula R _n AlX _3-n
It is also possible to pre-mix with the organoaluminum compound represented by the formula (1) and age it before adding it to the catalyst system as an organoaluminum compound having an average composition. For example, as an example of such a compound, Et _2.12 Al (Oi-Pr) _0.3 prepared by mixing triethylaluminum, diethylaluminum chloride and diisopropoxyaluminum ethylacetoacetate in a molar ratio of 1: 1: 0.35.
Cl _0.43 (OC (CH ₃ ) C (O) OE _t ) _0.15 can be mentioned.

The amount of the intramolecular coordination compound used in the present invention can be generally selected from the range of 5: 1 to 1: 200 in the molar ratio of titanium atom of the titanium-containing catalyst component to the metal atom of the organometallic intramolecular coordination compound. But preferably from 1: 1 to 1:50
It is suitable to use in the range of. The catalyst of the present invention is
A combination of each composition of (A), (B) and (C) is preferably used, and each of the above components (A), (B) and (C) further comprises an electron donating compound and / or Zinc, lithium, magnesium,
Catalysts with added organometallic compounds of the element chosen from boron are often more preferably used.

As the electron-donating compound, a known one as a component of a catalyst for olefin polymerization can be used without particular limitation. Generally, an organic compound containing oxygen, nitrogen, phosphorus or sulfur is particularly preferably used. For example, water, alcohol, ether, ester, aldehyde, fatty acid, ketone, nitrile, amine, isocyanate, azo compound,
Examples include phosphines, phosphinites, phosphoramides, thioethers, thioalcohols and acid amides. More specifically, those which are preferably used as the electron-donating compound are shown as alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, xylenol, ethylphenol, benzyl alcohol, and phenol. Chill alcohol etc. 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. Other than ether, ethylene glycol monoethyl ether, diphenyl ether, tetrahydrofuran, anisole, 2,3-dihydrofuran, vinyl ethyl ether, allyl ethyl ether, anethole, p-methoxystyrene, safrole, phenyl p-allyl phenyl ether, Ethers having vinyl substituents such as p-styrylanisole. Furthermore, as the ester, ethyl acetate, butyl formate, amyl acetate, butyl oxalate, vinyl acetate, ethyl benzoate, propyl benzoate, octyl benzoate, ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate is used. , Methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, propyl naphthoate, butyl naphthoate, ethyl phenylacetate, etc. Ethyl, methyl 2-pyridinecarboxylate, ethyl pyrrole-2-carboxylate,
N-carboethoxypyrrole, 2-thienyl methyl acetate 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, as the ketone, methyl ethyl ketone,
Examples include methyl isobutyl ketone, benzophenone, N-vinylpyrrolidone, and acetylacetone. Furthermore, nitriles include acetonitrile and the like, and amines include methylamine, diethylamine, triethylamine, triethanolamine, pyridine, 4-vinylpyridine, aniline, N, N-diethylaniline. Furthermore, isocyanates include phenyl isocyanate and toluyl isocyanate, and azo compounds include azobenzone. Furthermore, as the phosphine, ethylphosphine, triethylphosphine,
There are tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine and the like, and examples of the phosphite include dimethylphosphite, di-n-octylphosphite, tri-n-butylphosphite and the like. Furthermore, phosphinites include ethyldiethylphosphinite, ethyldibutylphosphinite, phenyldiphenylphosphinite, and the like, and phosphoramides include hexamethylphosphoric triamide and the like. Furthermore, examples of the thioether include diethyl thioether, diphenyl thioether, methylphenyl thioale, ethylene sulfide and propylene sulfide, and examples of the thio alcohol include ethyl thio alcohol and n-propyl thio alcohol. Furthermore, as acid amides, formamide, acetamide, acrylamide, dimethylformamide, benzoylamide,
Phthaloyl amide and the like.

Two or more compounds selected from the above-mentioned electron donating compounds may be selected and used together with the respective components (A), (B) and (C). The amount of the electron-donating compound to be used can be generally used in the range of 0.001 to 100 mol based on the titanium atom of the titanium-containing catalyst component, but is preferably used in the range of 0.01 to 5 mol.

The organometallic compound of the element selected from zinc, lithium, magnesium and boron is not particularly limited, but the following compounds are generally preferable. For example, organic compounds of zinc include dialkyl zinc, alkyl zinc halides, alkyl zinc alkoxides, and the like, and specifically, diethyl zinc, dimethyl zinc, ethyl zinc chloride, ethyl zinc bromide, ethyl zinc ethoxide, methyl zinc isopropoxide, ethyl. A compound such as zinc n-butoxide can be preferably used. The organic compound of magnesium is dialkyl magnesium, alkyl magnesium halide, alkyl magnesium alkoxide, and the like, specifically, di-n-butyl magnesium,
Compounds such as ethyl magnesium chloride, di-n-octyl magnesium, isobutyl magnesium chloride, n-butyl magnesium iodide and n-propyl magnesium ketoxide 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 to 100 mols based on the titanium atom of the titanium-containing catalyst component, but 0.01 mols. It is preferably used in the range of 20 to 20 mol.

The electron donating compound and the organometallic compound of an element selected from zinc, lithium, magnesium and boron are added to the above (A),
Using together with the components (B) and (C) is also an effective method for further broadening the molecular weight distribution of polyolefin. In this case, the amount of the organic metal compound selected from zinc, lithium, magnesium and boron and the electron donating compound used in the titanium-containing catalyst component with respect to the titanium atom should be within the same range as when they are added to the catalyst system of the present invention. You can The electron donating compound and the organometallic compound of an element selected from zinc, lithium, magnesium and boron may be mixed with the organoaluminum compound represented by the general formula R _n AlX _3-n in advance and then used for the polymerization. It may be used for polymerization after being mixed with the aluminum intramolecular coordination compound in advance, and further mixed with both the organoaluminum compound represented by the general formula R _n AlX _3-n and the aluminum intramolecular coordination compound in advance. It may be used for the polymerization later.

Further, the catalyst components of the present invention may be prepared by mixing them in the presence or absence of a solvent 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.

In summary, the present invention, as shown in FIG. 1, comprises (A) titanium metal trichloride as a transition metal component, (B) an organoaluminum compound as an organoaluminum catalyst component, and (C) a specific organoaluminum molecular compound as a third component. The invention relates to the polymerization of olefins using a catalyst system in which a position compound is an essential component, and optionally an electron-donating compound and / or an organic compound of zinc, lithium, magnesium or boron is added thereto.

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 in general, olefin having 2 to 10 carbon atoms such as ethylene, propylene, butene and pentene is preferably used. Further, as defined above, it is also possible to use a mixture of the olefins or a mixture of the olefins with 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 a liquid monomer, and gas phase polymerization can be preferably adopted. In the slurry polymerization, inert hydrocarbons such as hexane, heptane, benzene, toluene and cyclohexane are used as a solvent. The polymerization method can be either batch or continuous. Furthermore, the titanium-containing catalyst component and the general formula R _n AlX
_In the presence of an organoaluminum compound represented by _3-n , and an organometallic intramolecular coordination compound, if necessary, olefin is further added in the presence of an electron-donating compound and an organometallic compound selected from zinc, lithium, magnesium, and boron. Although it can be polymerized, the olefin is first preliminarily polymerized in the presence of the catalyst for 1 to 20 minutes, and then an organoaluminum compound represented by the general formula R _n AlX _3-n is further added, if necessary. It is also possible to employ a two- or more-stage polymerization system in which the polymerization is carried out. 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, in the industrial range of 1Kg / cm ² ~100Kg / cm ² is preferably used.

The present invention will be described below in more detail with reference to Examples, 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.
Further, w / n is an index of molecular weight distribution, and it is measured by GPC (gel permeation chromatography) as a ratio of weight average molecular weight w and number average molecular weight n.
The larger the w / n, the wider the molecular weight distribution of the polymer.

Example 1 Synthesis of (A) 3-ethoxypropyldiisobutylaluminum.

After purging the 200 ml flask with argon, 50 ml of dry n-heptane and 55 of diisobutylaluminum hydride were used.
mmol was weighed and 150 mmol of allyl ethyl ether and n-
A solution prepared with 30 ml of heptane was added dropwise with stirring for 1 hour. During this operation, heat was generated, so the flask was cooled with ice. Then, the mixture was stirred at 72 to 74 ° C. for 6.5 hours and then left to cool for 8 hours. The obtained solution is distilled under reduced pressure to give a boiling point of 94-9.
A 5 ° C. (2.3-2.5 mmHg) fraction was isolated. This fraction is 3
-Ethoxypropyldiisobutylaluminum and 4
0 mmol could be obtained. The obtained 3-ethoxypropyldiisobutylaluminum was diluted with n-heptane to prepare a 1 mmol Al atom / ml n-heptane solution.

(B) Polymerization of Propylene A stainless autoclave having an internal volume of 1 heated to 60 ° C. was replaced with argon, and 500 ml of dry n-heptane and 3.2 mmol of diethylaluminum chloride were added. Next, 2.4 mmol of 3-ethoxypropyldiisobutylaluminum prepared in the above (A) was added. Next, 0.8 mmol of δ-type titanium trichloride (manufactured by Toyo Stoffer Chemical Co., Ltd.) was charged, and hydrogen was added so that the partial pressure was 0.3 Kg / cm ² . Then, after stirring for 10 minutes, propylene was injected under pressure so as to have a partial pressure of 3 Kg / cm ² , polymerization was started, and stirring was continued for 90 minutes while supplementing propylene so as to maintain this pressure, and polymerization was continued.

After the introduction of the monomer was stopped, the unreacted monomer was purged and 50 ml of isopropyl alcohol was added to terminate the polymerization. The obtained polymer was washed twice with n-heptane 1 at room temperature and then washed with a mixed solution of hydrochloric acid and methanol (1). After washing twice with 1 more methanol, 4
When vacuum dried at 0 ° C., 152 g of polypropylene was obtained. When the obtained polypropylene was extracted with n-heptane, II was 94.9%. Titanium trichloride 1
g · The yield of polypropylene per hour (hereinafter abbreviated as R _p ) was 821. (R _p is g-polypropylene /
The obtained polypropylene (expressed by g-TiCl ₃ · hr) had a w / n of 10.1, and a polypropylene having a wide molecular weight distribution could be obtained.

Comparative Example 1 Propylene was polymerized in the same manner as in (B) of Example 1 except that 3-ethoxypropyldiisobutylaluminum was not used. The polypropylene obtained was 122 g and R
_p was 657. II was 97.1%, and the polypropylene obtained had a w / n value of 7.2.

Example 2 Diethylaluminum chloride 6 mmol, 3-ethoxypropyldiisobutylaluminum 4.5 mmol and δ-TiCl ₃ 1.5 mmol were charged in the same manner as in Example 1, and then ethyl benzoate 0.75 mmol and ethylzinc ethoxide 0.5 mmol.
Was added, and then hydrogen was added at a partial pressure of 0.3 Kg / cm ² . After that, the polymerization was carried out by the same operation as in (B) of Example 1. The amount of polypropylene obtained was 85 g and R _p was 2.
It was 45. II was 96.1%, the w / n of the obtained polypropylene was 12.0, and polypropylene having a wide molecular weight distribution was obtained.

Example 3 (A) Synthesis of 3-diethylaminopropyldiisobutylaluminum To a solution of 50 mmol of diisobutylaluminum hydride obtained in the same manner as in (A) of Example 1 was added N, N.
-Diethylallylamine 150 mmol and n-heptane 30
The solution prepared in ml was added dropwise over 1 hour. Next 90-10
After stirring at 0 ° C for 4 hours, the mixture was allowed to cool for 8 hours. The obtained solution was distilled under reduced pressure to isolate a fraction having a boiling point of 112 to 113 ° C. (1.7 mM Mg. This fraction was 3-diethylaminopropyldiisobutylaluminum, and 32 mmol could be obtained. Diethylaminopropyldiisobutylaluminum was diluted with n-heptane to prepare a 1 mmol Al atom / 1 ml n-heptane solution, which was used for polymerization.

(B) Polymerization of propylene In the same manner as in Example 1 except that 3-diethylaminopropyldiisobutylaluminum in place of 3-ethoxypropyldiisobutylaluminum in Example 1 was used, diethylaluminum chloride 4.2 mmol, 3-diethylaminopropyldiisobutyl was used. Aluminum 3.15mmo
l, δ-TiCl ₃ 1.05 mmol was charged. Next, 1.05 mmol of ethyl p-anisate was added, and then hydrogen was added so that the partial pressure was 0.3 Kg / cm ² . After that, polymerization was carried out in the same manner as in (B) of Example 1. The obtained polypropylene was 78 g and R _p was 321. II was 97.6%, the w / n of the obtained polypropylene was 15.5, and polypropylene having a wide molecular weight distribution was obtained.

Comparative Example 2 Polypropylene was polymerized in the same manner as in Example 3 except that 3-diethylaminopropyldiisobutylaluminum was not used. The propylene obtained was 116 g
R _p was 477. II was 98.1% and the w / n of the obtained polypropylene was 7.4.

Example 4 (A) Synthesis of 3-diethylaminopropyldiethylaluminum By the same operation as in Example 3 (A), n-heptane solution of 3-diethylaminopyropyrdiethylaluminum from diethylaluminum hydride and N, N-diethylalamine. Was prepared. However, in the operation of vacuum distillation, 96-97 ° C
A fraction of (2 mmHg) was isolated as 3-diethylaminopropyldiethylaluminum.

(B) Polymerization of Propylene Propylene was polymerized by the same procedure as in Example 3 except that 3-diethylaminopropyldiethylaluminum was used instead of 3-diethylaminopropyldiisobutylaluminum. 91 g of polypropylene were obtained and the R _p was 374. II was 98.3%, and polypropylene having a wide w / n of 14.2 and a wide molecular weight distribution was obtained.

Example _{5 (A) E t212 Al (} Oi-Pr) 0.3 Cl 0.43 (OC (CH 3) CHCOOE t) after a _0.15 flask 300ml of the atmosphere was replaced with argon, dry n- heptane 50ml triethyl aluminum 100 mmol, diethylaluminum 100 mmol of chloride was weighed.
Then, 35 mmol of diisopropoxyaluminum ethyl acetoacetate manufactured by Kawaken Fine Chemical Co., Ltd. was added dropwise at room temperature over 1 hour. Then, the mixture was heated to 55 ° C. and stirred for 1 hour. After allowing to cool, add n-heptane to 1 mm
The solution was an n-heptane solution containing olAl atoms / ml.

(B) Polymerization of Propylene 500 ml of dry n-heptane obtained by substituting argon in an autoclave having an internal volume of 1 heated to 60 ° C. and _{Et 212} Al (Oi-Pr) _0.3 Cl _0.43 (OC (CH ₃ ) the CHCOOE _{t) 0.15} were weighed 23mmol. Then, 1.15 mmol of δ-TiCl ₃ was charged and hydrogen was added so that the partial pressure was 0.3 Kg / cm ² . Thereafter, propylene was polymerized in the same manner as in (B) of Example 1. 128
g of polypropylene was obtained, R _p was 482.
II was 94.5% and polypropylene w / n was 10.8.

Comparative Example _{3 E t212 Al (Oi-Pr} ) 0.3 Cl (0.43 (OC (CH 3) CHCOOE t) 0.15 except for using triethylaluminum 11.5mmol and diethylaluminum chloride 11.5mmol instead of the Example 5 Propylene was polymerized in the same manner as in (B).
5 g of polypropylene was obtained and the R _p was 395.
II is 88.1% and polypropylene w / n is 6.9.
Met.

Example 6 E _t212 Al (Oi-Pr) _0.3 Cl _0.43 (OC (CH ₃ ) CHCOOE _{t 0.15 was} replaced with 10 mmol of triethylaluminum, 10 mmol of diethylaluminum chloride and 3.5 mmol of diisopropoxyaluminum ethylacetoacetate. Propylene was polymerized in the same manner as in (B) of Example 5. 141 g of polypropylene was obtained and R _p was 531. II was 97.7% and the polypropylene w /
n was 10.3.

Example 7 Example E in the same manner as in _{5 (B) t212 Al (Oi} -Pr) 0.3 Cl 0.43 (OC (CH 3) CHCOOE t) 0.15 to 18 mmol, were charged 0.9mmol the δ-TiCl _3, 0.9 mmol of ethyl benzoate was added, and hydrogen was added so as to have a partial pressure of 0.3 Kg / cm ² . Thereafter, polypropylene was polymerized in the same manner as in (B) of Example 1. 92 g of polypropylene were obtained and the R _p was 441. II was 97.3% and polypropylene w / n was 12.0.

Example 8 Polypropylene was polymerized in the same manner as in Example 7 except that 1.8 mmol of anethole was used instead of ethyl benzoate. 113 g of polypropylene were obtained and the R _p was 542. II is 95.5%, w of polypropylene
/ N was 11.4.

Was polymerized polypropylene in Comparative Example _{4 E t212 Al (Oi-Pr} ) 0.3 Cl 0.43 (OC (CH 3) CHCOOE t) similar method _0.15 except for using Et ₂ AlCl3.6mmol instead of that of Example 8. 125 g of polypropylene was obtained and the R _p was 599. II is 96.3%
And the w / n of polypropylene was 6.8.

Example 9 Example 5 (B) E in the same manner as _{t212 Al (Oi-Pr) 0.3} Cl 0.43 (OC (CH 3) CHCOOE t) 0.15 to 24 mmol, were charged 1.2mmol the δ-TiCl _3, 0.6 mmol of ethyl p-anisate and 0.6 mmol of diethylzinc were added, and hydrogen was added so that the partial pressure was 0.3 Kg / cm ² . Thereafter, polypropylene was polymerized in the same manner as in (B) of Example 1. 6
8 g of polypropylene were obtained and the R _p was 245.
Further, II was 93.9%, and polypropylene having a w / n of 13.9 was obtained.

Example 10 Diethylaluminum hydride (5.6 mmol), 3-ethoxypropyldiisobutylaluminum (4.2 mmol) and δ-TiCl _{3 (} 1.4 mmol) were charged in the same manner as in Example 1 (B). Next, after adding 1.4 mmol of ethyl p-anisate, 0.3 kg of hydrogen was added.
It was added so as to have a partial pressure of / cm ² . After that, the polymerization was carried out by the same operation as in Example 1 (B). The obtained polypropylene was 103 g and R _p was 318. II is 92.
Polypropylene obtained with 5% w / n 12.3
As a result, polypropylene having a wide molecular weight distribution was obtained.

Example 11 Triethylaluminum 4.0 mmo in the same manner as in Example 1
l3-diethylaminopropylisobutylaluminum
3.0 mmol δ-TiCl ₃ 1 mmol was charged. Next, 0.8 mmol of ethyl benzoate was added, and then hydrogen was added so that the partial pressure was 0.3 Kg / cm ² . After that, ethylene was polymerized in the same manner as in (B) of Example 1. 135 g of polyethylene were obtained and had an R _p of 583. Molecular weight distribution of the obtained polyethylene
The w / n was 15.2.

Example 12 Copolymerization of ethylene and propylene was carried out in the same manner as in Example 3 except that a mixed gas of ethylene and propylene containing 4.5 vol% of ethylene was used instead of propylene. 105
g ethylene propylene copolymer is obtained, R _p is 43
It was 2. II was 92.3%, and the w / n of the obtained copolymer was 14.8.

Example 13 4-Methylpentene-1 was polymerized in the same manner as in Example 7 except that 4-methylpentene-1 was used instead of propylene. 64 g of poly (4-methylpentene-1) was obtained, R _p was 307. II was 89.5%, and the w / n of the obtained poly (4-methylpentene-1) was 1.
It was 0.8.

Example 14 A method similar to (B) of Example 3 except that TiCl ₃ -AA (manufactured by Toho Titanium Co., Ltd.) was used in place of δ-TiCl ₃ (manufactured by Toyo Stoffer Chemical Co., Ltd.). Was used to polymerize propylene.
The polypropylene obtained is 33 g, R _p is 136
It was. II was 98.1%, and the w / n of the obtained polypropylene was 14.1 and polypropylene having a wide molecular weight distribution was obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the production of the catalyst system and the process of olefin polymerization in the present invention.

Claims (1)

[Claims] (A) Titanium trichloride (B) General formula General formula R _n AlX _3-n (wherein R is an alkyl group having 1 to 20 carbon atoms; X is a halogen atom or a hydrogen atom; 1 Organoaluminum compound represented by <n ≦ 3) (C) Aluminum intramolecular coordination compound corresponding to any one of the following general formulas (I) and (II): (A), (B), (C) A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst. Record R ³ _3-m Al (OC (R ⁵ ) = CHC (O) R ⁵ ) _m
(II) where Q is -C (R ² ) ₂ · Y · R ⁴ , Y is -O-, -S-, or -NR-R ¹ is an alkyl group having 1 to 12 carbon atoms, or a hydrogen atom R ² is an alkyl group having 1 or 2 carbon atoms or a hydrogen atom, and R ³ is a carbon number. 1 to 12 alkyl group or alkoxy group R ⁴ is an alkyl group having 1 to 12 carbon atoms R ⁵ is an alkyl group or alkoxy group having 1 to 8 carbon atoms a is 1 or 2, m is an integer of 1 to 3, respectively. Represent