JPH0579682B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an olefin polymer having good moldability. Generally, by extrusion molding or blow molding, bottles,
When producing molded products such as pipes, films, and sheets, it is important to select a polyolefin as a raw material that satisfies both mechanical strength and melt fluidity. However, the problem with polyolefin produced using conventional manufacturing methods is that increasing the molecular weight improves mechanical strength but decreases fluidity; conversely, decreasing the molecular weight improves fluidity but decreases mechanical strength. It was hot. As a method of solving these problems, various methods for producing polyolefins have been studied in order to satisfy both mechanical strength and melt fluidity by broadening the molecular weight distribution. Conventionally, many production methods have been proposed to obtain polyolefins with a wide molecular weight distribution. For example, methods for improving catalysts include disproportionation of polymerization active sites using two or more different types of transition metal compounds, methods of supporting transition metal compounds on specific carriers, or methods of using limited organic aluminum compounds, etc. A method using a cocatalyst or a third component is known. However, the polyolefins obtained by these methods have extremely low stereoregularity, insufficient polymerization activity, or unsatisfactory molecular weight distribution values, and have poor polymerization activity. A catalyst system that satisfies both stereoregularity and molecular weight distribution values has not yet been found. In addition, by mechanically blending high-molecular weight and low-molecular weight polymers obtained using conventional catalysts during processing, or by changing the polymerization temperature, monomer concentration, chain transfer agent concentration, etc. during polymerization, it is possible to A multistage polymerization method has also been proposed in which high-molecular weight and low-molecular weight polymers are produced in a plurality of polymerization vessels to obtain a polymer with a wide molecular weight distribution. However, these methods have not yet reached the level of industrially completed technology because the molecular weight distribution of the resulting polyolefin is not significantly broadened and extra polymerization equipment is required. As a result of intensive research into a method for producing industrially advantageous polyolefin with an extremely wide molecular weight distribution from the above viewpoint, the present inventors have discovered that a catalyst system consisting of a titanium compound, an organoaluminium compound, and an organometallic intramolecular coordination compound is used. The present inventors have discovered that polyolefins having sufficiently high activity and stereoregularity from an industrial standpoint and having an extremely wide molecular weight distribution can be obtained by carrying out multi-stage polymerization, and have thus arrived at the present invention. To explain the gist of the present invention in more detail, for example, when a high molecular weight polymer and a low molecular weight polymer are continuously polymerized in two-stage polymerization, the molecular weight distribution of each is defined as Q _H and Q _L in the total polymer. the ratio
Assuming W _H and W _L , the molecular weight distribution Q _H+L of the total polymer is expressed by the following formula. Q _H+L =W ² _H Q _H +W ² _L Q _L +{MW _H /MW _L Q _L +MW _L /MW _H Q _H }W _H W _L ...(1) Here, MW _H and MW _L are These are the weight average molecular weight or number average molecular weight of a high molecular weight polymer and a low molecular weight polymer, respectively. As can be easily inferred from Equation (1), the broader the molecular weight distribution of the polymer produced in each polymerization stage, the wider the molecular weight of the polymer increases in linear proportion. Therefore,
If the molecular weight distribution of the polymer polymerized in one step is wide, it becomes possible to easily and extremely widen the molecular weight distribution of all the polymers without modifying existing polymerization equipment. The catalyst system used in the present invention has a wide molecular weight distribution even when polymerized in one step, and is fully satisfactory for the purpose of the present invention. That is, (A) titanium trichloride as a titanium-containing catalyst component, (B) an organoaluminum compound, and (C) an aluminum intramolecular coordination compound corresponding to either of the following general formulas () or (), that is,

【Chemical】 R ³ _3-n Al(OC(R ⁵ )=CHC(O)R ⁵ ) _n ...() Here, Q is -C(R ² ) ₂・Y・R ⁴ ,

【formula】 【formula】

【formula】

【formula】

[Formula] or

[Formula] 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, R ³ is an alkyl group or alkoxy group having 1 to 12 carbon atoms 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 1 to 3 Each symbol represents an integer (hereinafter, in this specification, each symbol is
This is a method for producing polyolefin, which is characterized by carrying out multistage polymerization using a catalyst whose main component is (each used in the same meaning as above). Further, in the above-mentioned catalyst system of the present invention, (D) an electron-donating compound and/or (E) an organometallic compound of an element selected from zinc, lithium, and magnesium boron are used together with components (A), (B), and (C). This is also useful, and in some cases has the effect of further broadening the molecular weight distribution of the polyolefin obtained. In addition, the olefin referred to in the present invention is a general term that includes, in addition to single monomers such as ethylene, propylene, and butene, a monomer mixture containing less than 50% of other monomers that can be copolymerized with the monomer. It is. Therefore, the polyolefins obtained in the present invention are homopolymers of the above olefins and copolymers of the olefins and other olefins. The catalyst used in the present invention consists of the catalyst components (A) to (C) above. The titanium compound described in (A) above is known as a titanium-containing catalyst component for polymerizing olefins. In the present invention, these known materials can be used without any restriction. A generally preferred titanium-containing catalyst component is titanium trihalide, especially titanium trichloride. Titanium trichloride includes those obtained by reducing titanium tetrachloride with hydrogen, metallic aluminum, metallic titanium, organoaluminum compounds, etc. For example, δ
Particularly preferred are titanium trichloride of type, α type and gamma type. The titanium-containing catalyst component can be used as it is, supported on an inorganic carrier, or treated with an electron-donating compound. Examples of the inorganic carrier supporting the titanium compound include MgCl ₂ , Mg
(OH) ₂ , MgO, CaO, Ca(OH) ₂ , Zn(OH) ₂ ,
Mn(OH) ₂ , MnO, _MgCO3 , _NiCl2 , _{Al2O3 ,}
Known carriers such as SiO ₂ and TiO ₂ can be used. Examples of the electron-donating compound include alcohol (general formula ROH), ether (R-O-
R′), ester (RCOOR′), aldehyde (RCHO), fatty acid (RCOOH), ketone (RCOR′), nitrile (RCN), amine (RnNH _3-o ) (n=0, 1, 2, 3), Isocyanate (RNCO), azo compound (RN=NR″),
Phosphine (R _o PH _3-o ) (n=0, 1, 2, 3),
Phosphite (P(OR) ₃ ), Phosphinite (RP
(OR') ₂ ), thioether (RnSR'), thioalcohol (RSH), etc. (However, in the above general formula, R and R' are respectively the same or different hydrogen atoms; alkyl groups,
(representing a hydrocarbon group such as an allyl group) can be used. As specific examples of these electron-donating compounds, the following compounds are preferably used. Alcohols include methanol, ethanol,
Probanol, butanol, bentanol, hexanol, octanol, phenol, xylenol, ethylphenol, benzyl alcohol,
Phenethyl alcohol, etc. Ethers include 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 monomethyl ether, tetrahydrofuran, anisole, diphenyl ether, etc. Organic acid esters include ethyl acetate, butyl formate, amyl acetate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoate. Octyl acid, ethylhexyl benzoate, methyl triylate, ethyl triylate, 2-ethylhexyl triylate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, naphthoate Examples include butyl acid, 2-ethylhexyl naphthoate, and ethyl phenyl acetate. 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. Nitriles include acetonitrile, and amines include methylamine,
These include diethylamine, tributylamine, triethanolamine, pyridine, aniline, and dimethylaniline. Examples of isocyanates include phenyl isocyanate and tolyl isocyanate, and examples of azo compounds include azobenzene. Phosphines include ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, and triphenylphosphine, and phosphites include dimethylphosphine, di-n-octylphosphine, and tri-n-octylphosphine. -Butyl phosphite, etc.
Examples of phosphinites include ethyl diethyl phosphinite, ethyl dibutyl phosphinite, and phenyl diphenyl phosphinite. As a thioether, diethylthioether,
Examples include diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylene sulfide, etc., and thioalcohols include ethyl thio alcohol, n-propyl thio alcohol, etc. In order to improve the polymerization activity and stereoregularity of the titanium compounds mentioned above, they can be used after being appropriately treated with a tetravalent titanium halide. Moreover, a component consisting of two or more types of titanium compounds among the titanium compounds mentioned above may be used as the titanium-containing catalyst component. Next, the catalyst component (B) used in the present invention has the general formula R _o
AlX _3-o (wherein, R is an alkyl group having 1 to 20 carbon atoms, X is a halogen atom or a hydrogen atom: 1<n≦
It is an organoaluminum compound represented by 3). As the organoaluminum compound represented by the above general formula R _o AlX _3-o, any known one as a catalyst component for olefin polymerization can be used without particular limitation. 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 Et _1.3 AlCl _1.7 Bu _2.4
Examples include alkylaluminum halides having an average composition such as AlCl _0.6 . Also, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-
Trialkyl aluminum compounds such as isopropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, tri-n-dodecyl aluminum, tri-hexadecyl aluminum, and these Mixtures of can also be used. Furthermore, diethylaluminum hydride, diisobutylaluminum hydride,
Compounds such as dioctyl aluminum hydride, di-n-butyl aluminum hydride, and Et _1.5
Alkylaluminum hydrides such as compounds with an average composition such as AlH _1.5 can also be used. Particularly preferred examples of the above compounds are diethylaluminum chloride, triethylaluminum, diisobutylaluminum hydride, Et _2.5
It is a compound such as AlCl _0.5 . In the catalyst composition used for olefin polymerization, the titanium atom of the titanium-containing catalyst component and the general formula R _o AlX _3-o
The molar ratio of the organoaluminum compound to the Al atom can be selected from a wide range of 10:1 to 1:200, but preferably in the range of 2:1 to 1:100. Still another component of the catalyst component used in the present invention is an aluminum intramolecular coordination compound represented by either of the following two general formulas. That is,

[Chemical formula] Among the compounds represented by these formulas, specific examples of those belonging to formula () include (3-ethoxypropyl)isobutylaluminum hydride,
(3-Ethoxypropyl)ethylaluminum hydride, (3-methoxybutyl)methylaluminum hydride, (3-propoxyisobutyl)pentylaluminium hydride, (4-methoxybutyl)ethylaluminum hydride, (3-octoxyisobutyl)propyro Pyraluminum hydride, (4-ethoxybutyl)isobutylaluminum hydride, (3-ethylmercabutopropyl)
Hexylaluminum 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-isobutoxypropyl)dimethylaluminum, (4-ethoxybutyl)diethylaluminum, (4-isooctoxybutyl)di-n-octylaluminum, (3-diethylaminopropyl)diethylaluminum, (3-diethylamino propyl) diisobutylaluminum, (3-N-ethyl-N
-isopropylaminopropyl)diisobutylaluminum, (4-diethylaminopropyl)diethylaluminum, (4-diisooctylaminobutyl)diisobutylaluminum hydride,
(3-ethylmercaptopropyl)diethylaluminum, (3-n-butylmercaptopropyl)
Dipropylaluminium, (4-n-butylmercaptobutyl)di-n-hexylaluminum,
(2-(2-Fluyl)pyropyl)hexylaluminum hydride, (2-(2-thienyl)ethyl)
Methylaluminum hydride, (3-(1-piperidyl)propyl)isobutylaluminum hydride, (2-(1-methyl-2-piperidyl)ethyl)heptylaluminum hydride, (2-(5-
Ethyl-2-pyridyl)ethyl)propyl aluminum hydride, (2-(2-quinolyl)ethyl)
Isopropylaluminum hydride, (2-(2-
Fluyl)ethyl)diethylaluminum, (2
-(2-Fluyl)propyl)di-n-hexylaluminum, (3-(2-thienyl)propyl)
diethylaluminium, (2-(4-methyl-2-
thienyl)ethyl)diisobutylaluminum,
(3-(1-piperidyl)propyl)di-n-hexylaluminum, (2-(2-pyridyl)ethyl)diisoamylaluminum, (2-(5-ethyl-2-pyridyl)ethyl)diisobutylaluminum, (3 -(2-pyridyl)propyl)diisobutylaluminum, (2-(2-quinolyl)ethyl)dimethylaluminum, (2-(2-quinolyl)ethyl)ethylisooctylaluminium,
The following compounds can be exemplified. Specific examples of aluminum intramolecular coordination compounds corresponding to general formula () include diethylaluminium acetylacetonate, dihexylaluminum acetylacetonate, diisopropoxyaluminum ethylacetoacetate, diisooctoxyaluminum ethylacetoacetate,
Isopropoxyaluminum bis(ethylacetoacetate), diethoxyaluminum acetylacetonate, aluminum tris(butylacetoacetate), methoxyaluminum bis(butylacetoacetate), dimethylaluminum ethylacetoacetate, diisobutoxyaluminum acetylacetoacetonate, aluminum tris (acetylacetonate), O-di-
n-butylaluminum diethylmalonate, O
Compounds such as -di-isopropoxyaluminum diethylmalonate and O-aluminum tris(diethylmalonate) can be mentioned. The method for preparing the catalyst used in the present invention is not particularly limited. Conventionally, as a method for preparing a so-called Ziegler-Natsuta type catalyst, a catalyst in which an electron donor or a third component is added to a titanium component or an organoaluminum component for the purpose of increasing activity or stereoregularity is known. , those catalyst preparation methods can be applied. That is, in the catalyst preparation method of the present invention, (A) a titanium compound, (B) an organoaluminum compound, and (C) an aluminum intramolecular coordination compound are simultaneously mixed together, or any two of them are mixed in advance. , it is also possible to mix it with other ingredients. That is, the aluminum intramolecular coordination compound has the general formula R _o AlX _3-o
It is also possible to mix the compound in advance with an organoaluminum compound represented by the above formula, ripen it, and then add it to the catalyst system as an organoaluminum compound having an average composition. For example, examples of such compounds include triethylaluminum, diethylaluminium chloride and diisopropoxyaluminum ethyl acetoacetate in a molar ratio of 1:1:
Et _2.12 Al(Oi−Pr) _0.3 Cl _0.43 mixed at a ratio of 0.35
(OC(CH ₃ )C(O)OEt) _0.15 . The amount of the aluminum intramolecular coordination compound used in the present invention can generally be selected from a range in which the molar ratio of titanium atoms in the titanium-containing catalyst component to metal atoms in the organometallic intramolecular coordination compound ranges from 10:1 to 1:200. However, it is preferable to use the ratio in a range of 1:1 to 1:50. The catalyst of the present invention is preferably a combination of the above components (A), (B) and (C).
A catalyst in which an electron-donating compound and/or an organometallic compound of an element selected from zinc, lithium, magnesium, and boron is added to each component (C) is often more preferably used. The electron-donating compound is not particularly limited and may be any one known as a component of an olefin polymerization catalyst, but organic compounds containing oxygen, nitrogen, phosphorus, or sulfur are generally particularly preferred. For example, water, alcohol, ether,
These include esters, aldehydes, fatty acids, ketones, nitriles, amines, isocyanates, azo compounds, phosphines, phosphinites, phosphoramides, thioethers, thioalcohols, and acid amides. More specifically, the electron-donating compounds preferably used include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, xylenol, ethylphenol, benzyl alcohol, and phenol. Examples include chill alcohol. Examples of ethers include diethyl ether, di-n-propyl ether, di-n-butyl ether, di(isoamyl)ether, and di-n-propyl ether.
-pentyl ether, di-n-hexyl ether, di-n-octyl ether, diisooctyl ether, ethylene glycol monoethyl ether, diphenyl ether, tetrahydrofuran,
Ethers with vinyl substituents such as asonyl, 2,3-dihydrofuran, vinyl ethyl ether, allyl ethyl ether, anethole, p-methoxystyrene, safrole, phenyl p-allylphenyl ether, p-styrylanisole, etc. be. Furthermore, esters include 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, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, naphthoate In addition to methyl acid, propyl naphthoate, butyl naphthoate, ethyl phenyl acetate, etc., thiophene-2
Ethyl -carboxylate, methyl 2-pyridinecarboxylate, ethyl pyrrole-2-carboxylate, N-carboethoxypyrrole, methyl 2-thienyl acetate, and the like can be suitably used. Furthermore, examples of aldehydes include acetaldehyde and benzaldehyde. Furthermore, fatty acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid,
These include maleic acid and benzoic acid. Furthermore, examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, benzophenone, N-vinylpyrrolidone, and acetylacetone. Nitriles include acetonitrile, and amines include methylamine, diethylamine, triethylamine, triethanolamine, pyridine,
Examples include 4-vinylpyridine, aniline, N,N-diethylaniline, and the like. Furthermore, examples of isocyanates include phenyl isocyanate and tolylisocyanate, and examples of azo compounds include azobenzone. Furthermore, as phosphine, ethylphosphine, triethylphosphine,
Examples of phosphites include tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, and dimethylphosphite, di-n-octylphosphine, and tri-n-octylphosphine.
Examples include butyl phosphite. Further, examples of phosphinites include ethyldiethylphosphinite, ethyldibutylphosphinite, phenyldiphenylphosphinite, and the like, and examples of phosphoramide include hexamethylphosphoric triamide. Further, thioethers include diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide, etc., and thioalcohols include ethylthioalcohol, n-propylthioalcohol, etc. Further, acid amides include formamide, acetamide, acrylamide, dimethylformamide, benzoylamide, phthaloylamide, and the like. Two or more kinds of the electron-donating compounds listed above may be selected and used together with each of the components (A), (B), and (C). The amount of electron donating compound used is generally 0.001 per titanium atom of the titanium-containing catalyst component.
It can be used in the range of mol to 100 mol, but
It is preferable to use it in a range of 0.01 mol to 5 mol. Further, the organometallic compound of the element selected from zinc, lithium, magnesium, and boron is not particularly limited, but the following compounds may generally be used. For example, organic compounds of zinc include dialkylzinc, alkylzinc halide, alkylzinc alkoxide, etc. Specifically, diethylzinc, dimethylzinc, ethylzinc chloride, ethylzinc bromide, ethylzinc ethoxide, methylzinc isopropoxide, ethylzinc Compounds such as zinc n-butoxide can be preferably used. In addition, organic compounds of magnesium include dialkylmagnesium, alkylmagnesium halide, alkylmagnesium alkoxide, etc. Specifically, di-n-butylmagnesium, ethylmagnesium chloride, di-n-octylmagnesium,
Compounds such as isobutylmagnesium chloride, n-butylmagnesium iodide, and n-propylmagnesium ethoxide can be suitably used. Furthermore, as an organic compound of lithium, n-
Butyllithium is an organic compound of boron, and triethylboron is an organic compound of boron. Among the compounds listed above, particularly preferred compounds are organometallic compounds of zinc. The amount of the organometallic compound of an element selected from zinc, magnesium, lithium, and boron can generally range from 0.001 mol to 100 mol based on the titanium atom of the titanium-containing catalyst component.
It is preferable to use it in a range of 0.01 mol to 20 mol. In order to further broaden the molecular weight distribution of polyolefin, it is also possible to use an electron-donating compound and an organometallic compound of an element selected from zinc, lithium, magnesium, and boron together with each of the components (A), (B), and (C). This is an effective method. In this case, the amount of the organometallic compound selected from zinc, lithium, magnesium, and boron and the titanium-containing catalyst component of the electron-donating compound relative to the titanium atom should be within the same range as when each is added alone to the catalyst system of the present invention. I can do it. Also electron-donating compounds and zinc,
Organometallic compounds of elements selected from lithium, magnesium and boron have the general formula
_It may be used for polymerization after mixing with an organoaluminum compound represented by R _o Al general formula
It may be used for polymerization after being mixed with both the organoaluminum compound represented by R _o AlX _3-o and the intramolecular coordination compound of aluminum. Further, the catalyst components of the present invention may be prepared by mixing each in advance in the presence or absence of a solvent,
Alternatively, these catalyst components may be added directly to the polymerization tank. In the latter case, the catalyst components may be added in any order without any restriction. In summary, as shown in Figure 1, the present invention includes (A) titanium trichloride as a transition metal component, (B) an organoaluminum compound as an organoaluminum catalyst component,
(C) As a third component, a specific organoaluminum intramolecular coordination compound is an essential component, and if desired, (D) an electron-donating compound and/or an organic compound of zinc, lithium, magnesium, or boron is added (Fig. -1) and relates to multistage polymerization of olefins using a catalyst system consisting of a mixture (or reactant) thereof. In the present invention, in the method for producing an olefin polymer or a copolymer of olefin and other olefin using the catalyst system as described above, the polymerization is carried out in two or more stages. Either the step of obtaining a coalescence or the step of obtaining a high molecular weight polymer may be carried out first. In addition, polymerization was carried out in 3
A method using more than one step is preferably used when the molecular weight distribution is to be further significantly broadened. For example, in the case of polymerization in three stages, the order of polymerization can be arbitrary, but it is possible to polymerize with high molecular weight, medium molecular weight, and low molecular weight to obtain each molecular weight component uniformly from high molecular weight component to low molecular weight component. It becomes possible to obtain. This polymer has even better processability and physical properties than those obtained by the two-stage polymerization method.
The polymerization method may be carried out batchwise or continuously using two or more reaction vessels. The polymerization temperature is in the range of -30 to 300°C, preferably room temperature to 80°C, and the polymerization pressure is not particularly limited, but is preferably 3 to 50 atmospheres from an industrial standpoint. Polymerization is carried out with _C4 - _C20 alkanes, cycloalkanes, e.g.
Slurry polymerization with inert hydrocarbon solvents such as propane, hexane, heptane, cyclohexane, etc., or liquid phase polymerization or gas phase polymerization in liquid monomers is also possible. In the present invention, homopolymerization of olefins, copolymerization of olefins, or copolymerization of olefins and polyenes can be carried out. Olefins that can be used for polymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
Examples include 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, and 1-decene. In addition, the above polyenes include butadiene,
Examples include isobrene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and methyl-1,4-hexadiene. In the copolymerization of propylene, it is particularly preferable to carry out the copolymerization so that the content of propylene is 70 mol% or more. Hydrogen, halogenated hydrocarbons, etc. are used to adjust the molecular weight, and hydrogen is preferred. The weight average molecular weight of low molecular weight polymers is less than 400,000,
The polymerization temperature and the amount of molecular weight regulator are preferably selected so that the molecular weight is less than 200,000. Usually, the hydrogen concentration in the gas phase is 1 to 50 mol%. This low molecular weight polymer may be an olefin homopolymer or a random copolymer of olefins. Further, the polymerization time is selected so that the amount of the low molecular weight polymer is 1 to 99% by weight, preferably 30 to 70% by weight, based on the total amount of polymer produced. Next, the polymerization temperature and the amount of the molecular weight regulator are selected so that the weight average molecular weight of the high molecular weight polymer is 400,000 or more, preferably 600,000 or more. Usually, the hydrogen concentration in the gas phase is 0 to 1 mol%. This high molecular weight polymer may be an olefin homopolymer or a random copolymer of olefins. The polymerization time is selected so that the amount of high molecular weight polymer is 1 to 99% by weight, preferably 30 to 70% by weight of the total amount of polymer produced. The reason why the molecular weights of the low molecular weight polymer and the high molecular weight polymer are defined as above in each stage of polymerization of the present invention is that the melt flow index of the total polymer obtained is 0.1 to 500 g/1. The second reason is that it is practical within 10 minutes.
Particularly remarkable effects appear when the molecular weight distribution is 10 or more. That is, in order to obtain the effect that such conditions influence each other, the above-described compatible range of low molecular weight and high molecular weight is extremely effective in the present invention. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not particularly limited by the following examples. The properties of the obtained polymer were measured and determined by the following method. (1) Melt flow index (MFI) 230℃,
2.16 kg load, according to ASTM D1238-57T (2) _W /n is the ratio of the weight average molecular weight _W to the number average molecular weight n, and was measured by gel vermiaction chromatography (GPC method).
The n-hebutane extraction residue was used as the GPC measurement sample. (3) Rockwell hardness: 23°C, according to ASTM D785-51. (4) Izotz impact strength Based on JIS K7110. (5) II is the value obtained by Soxhlet extraction of the obtained polymer with n-hbutane for 6 hours, and the extraction residue divided by the initial weight, expressed as a percentage. (6) Outflow rate ratio: The ratio of the extrusion rate at 230°C and a load of 2.16 kg to the extrusion rate at a load of 0.325 kg was determined using a melt flow index measuring device according to ASTM D1238-70. The higher the flow rate ratio, the more pronounced the non-Newtonian viscosity behavior, ie, the higher the viscosity in the low shear rate region and the lower the viscosity in the high shear rate region, which is a desirable property. (7) Melt sag: 230°C using a screw extruder and a circular die with an outer diameter of 12.0 mm and an inner diameter of 10.0 mm.
By measuring the change in the falling speed of the extruded balisong, we ranked them as follows.

[Table] (8) Rough skin, flaky eyes: Rough skin (so-called shark skin) and We observed the fish eyes and ranked them as follows.

[Table] The ratio of the first and second stage polymers was determined by atomic absorption spectrometry. Calculated from the content of catalyst (Ti) in the first stage and all produced polymers. The ethylene content in the polymer was determined by ¹³ C-NMR method. Example 1 (Adjustment of catalyst component (A)) After replacing a 500 c.c. three-necked flask with argon,
300 c.c. of dry hebutane and 0.1 mol of titanium tetrachloride were added, and the solution was kept at -10°C. Then dry heptane 50c.c., diethylaluminum chloride
A solution consisting of 0.1 mol was added dropwise over 2 hours.
After continuing stirring at the same temperature for 2 hours, heat treatment was performed at 65°C for 1 hour. After thorough washing with dry heptane, a 0.1 mol titanium trichloride heptane slurry was obtained. Then add 0.1 mol of diisoamyl ether,
After stirring at 35°C for 1 hour, the mixture was thoroughly washed again with dry heptane. Add 0.25 mol of titanium tetrachloride to this, and
After stirring for 2 hours at °C and thorough washing with dry heptane, 100 cc of titanium trichloride/heptane slurry with a concentration of 1 mmol/cc was obtained. (Synthesis of 3-ethoxypropyldiisobutylaluminum) After purging a 200ml flask with argon, 50ml of dry n-heptane and 50mmol of diisobutylaluminum hydride were weighed out, and allyl ethyl ether
A solution prepared with 150 mmol and 30 ml of n-heptane was added dropwise over 1 hour with stirring. During this operation,
Because of the heat generation, the flask was cooled on ice. then 72-74
After stirring at ℃ for 6.5 hours, the mixture was allowed to cool for 8 hours. The resulting solution was distilled under reduced pressure to a boiling point of 94-95℃ (2.3-2.5
mmHg) fraction was isolated. This fraction is 3-ethoxypropyldiisobutylaluminum and 40
mmol could be obtained. The obtained 3-ethoxypropyldiisobutylaluminum was diluted with n-heptane to prepare a 1 mmol Al atom/ml n-heptane solution. (Polymerization) Liquefied propylene 1 in an autoclave with a capacity of 2
, hydrogen, diethylaluminum chloride 1.3
mmol and 0.4 mmol of 3-ethoxypropyldiisobutylaluminum were charged. After raising the temperature to 65°C, 0.13 mmol of the n-heptane slurry of the titanium compound prepared by the above method was charged to start polymerization. The hydrogen concentration in the gas phase was kept at 13.5 mol% during the polymerization. After polymerization for 1 hour, the liquefied propylene phase in the autoclave was purged to complete the first stage polymerization. Catalyst content (Ti) of the polymer in the first stage,
After sampling a small amount of the polymer to measure its molecular weight, etc., liquefied propylene 1 and hydrogen were immediately charged, the autoclave was adjusted to 65°C, and the second stage polymerization was started. During the polymerization, the hydrogen concentration in the gas phase was kept at 0.17 mmol. After 5 hours of polymerization, the liquefied propylene phase in the autoclave was purged to complete the second stage of polymerization, and the entire produced polymer powder was removed.
Obtained 125g. After washing the polymer with a hydrochloric acid-methanol solution, drying under reduced pressure and adding a stabilizer, various physical properties were measured. The results are shown in Table 1. Comparative Examples 1-2 In Example 1, only the first stage polymerization was performed. However, hydrogen concentration in the gas phase, polymerization time, 3
-Ethoxypropyldiisobutylaluminum concentrations were changed as shown in Table 1. Example 2 (Synthesis of 3-diethylaminopropyldiisobutylaluminum) A solution prepared by adding 150 mmol of N,N-diethylarylamine and 30 ml of n-heptane to a solution of 50 mmol of diisobutylaluminum hydride obtained in the same manner as in Example 1 in n-heptane. was added dropwise over 1 hour. Next, the mixture was stirred at 90 to 100°C for 4 hours, and then allowed to cool for 8 hours. The resulting solution was distilled under reduced pressure, and the boiling point
A fraction of 112-113°C (1.7 mHg) was isolated. This fraction was 3-diethylaminopropyldiisobutylaluminum, and 32 mmol could be obtained. The obtained 3-diethylaminopropyl diisobutylaluminum was diluted with n-heptane to 1 m
It was used for polymerization as an n-heptane solution of mol atoms/1 ml. (Polymerization) The same procedure as in Example 1 was conducted except that 3-diethylaminopropyldiisobutylaluminum was used instead of 3-ethoxypropyldiisobutylaluminum. The results are shown in Table 1. Example 3 (Synthesis of 3-diethylaminopropyldiethylaluminium) From diethylaluminum hydride and N,N-diethylarylamine in the same manner as in Example 2,
A solution of 3-diethylaminopropyl diethylaluminium in n-heptane was prepared. However, in vacuum distillation, the fraction at 96-97℃ (2mmHg) is
Isolated as diethylaminopropyl diethylaluminum. (Polymerization) The same procedure as in Example 1 was conducted except that 3-diethylaminopropyldiisobutylaluminum was used instead of 3-ethoxypropyldiisobutylaluminum. The results are shown in Table 1. Example 4 (E _t2.12 Al(Oi-Pr) _0.3 Cl _0.43 (OC(CH ₃ )
Synthesis of CHCOOE _t ) _0.15 ) After purging a 300 ml flask with argon, add 50 ml of dry n-heptane and 100 ml of triethylaluminum.
mmol, diethylaluminum chloride 100m
The mol was weighed out. Then, 35 mmol of diisopropoxyaluminum ethyl acetoacetate (manufactured by Kawaken Fine Chemical Co., Ltd.) was added dropwise at room temperature over 1 hour. Next, the mixture was heated to 55°C and stirred for 1 hour. After cooling, add n-heptane to 1 mmol Al.
atoms/ml n-heptane solution. (Polymerization) In Example 1, E _t2.12 Al(Oi-Pr) _0.3 Cl _0.43 (OC(CH ₃ )
The same procedure as in Example 1 was carried out except that CHCOOE _t ) _0.15 was used. The results are shown in Table 1. Example 5 E _t2.12 Al(Oi-Pr) _0.3 Cl _0.43 (OC(CH ₃ )
CHCOOE _t ) _0.15 instead of triethylaluminum 0.55 mmol, diethylaluminum chloride
Example 4 except that 0.55 mmol and 0.2 mmol of diisopropoxyaluminum ethyl acetate were used.
Propylene was polymerized in the same manner. The results are shown in Table 1. Comparative Example 3 The same procedure as in Example 1 was conducted except that 3-ethoxypropyldiisobutylaluminum was not used. The results are shown in Table 1. Examples 6-7 In Example 1, the molar ratio of 3-ethoxypropyldiisobutylaluminum to titanium compound was
The same procedure as in Example 1 was carried out except that 0.1 or 10 was used instead of 3.0. The results are shown in Table 1. Examples 8 to 9 Same as Example 2 except that the polymerization time and hydrogen concentration in the first and second stages were changed as shown in Table 1.
I did the same thing. The results are shown in Table 1. Example 10 The same procedure as in Example 2 was carried out except that 0.13 mmol of ethyl anisate was added. The results are shown in Table 1. Example 11 The same procedure as in Example 1 was carried out except that in the first stage polymerization, ethylene was charged at a gas phase concentration of 1.4 mol %. The results are shown in Table 1. Example 12 The same procedure as in Example 2 was carried out except that ethylene was charged at a gas phase concentration of 10.5 mol % in the second stage polymerization. The results are shown in Table 1. Example 13 The same procedure as in Example 10 was carried out except that 0.2 mmol of diethylzinc was added. The results are shown in Table 1. Example 14 The same procedure as in Example 8 was carried out except that polymerization was carried out between the first and second stage polymerizations. The polymerization conditions for the second polymerization stage were a polymerization temperature of 65°C;
The polymerization time was 2 hours, the gas phase hydrogen concentration was 1.2 mol%, and the gas phase ethylene concentration was 0.0 mol%. The weight average molecular weight of the polymer obtained in the second polymerization stage was 34.1×
¹⁰⁴ , the ethylene content was 0.0wt%, and the composition ratio was 31.5wt%. Table 1 shows the physical properties of all polymers.

【table】

【table】

【table】 [Brief explanation of drawings]

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

Claims (1)

[Scope of Claims] 1 (A) Titanium trichloride (B) Organoaluminum compound (C) Aluminum intramolecular coordination compound corresponding to either of the following general formulas () or () above (A), (B) , (C) A method for producing a polyolefin, characterized in that polymerization of an olefin or copolymerization of an olefin and another olefin is carried out in multiple stages using a catalyst consisting of (C). ^{[ Formula} _] ^_ _{_} ^_ _{_} ^_ [Formula] [Formula] [Formula] [Formula] or [Formula] Y is -O-, -S-, or -NR- R ¹ is an alkyl group having 1 to 12 carbon atoms, or hydrogen atom R ² is a carbon number 1 or 2 alkyl group or hydrogen atom, R ³ is an alkyl group or alkoxy group having 1 to 12 carbon atoms, 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 represents 1 or 2, and m represents an integer of 1 to 3, respectively.