JPS60104103A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce the titled polymer having narrow molecular weight distribution, in high efficiency, by using a catalyst comprising a combination of a component containing Mg, Ti and halogen, and a product obtained by the reaction of an organic compound containing active hydrogen with a halogen-containing organic Al compound having a specific halogen/Al ratio. CONSTITUTION:An olefin (e.g. ethylene) is (co)polymerized by using a catalyst comprising (A) a highly active titanium catalyst component containing magnesium, titanium and halogen as essential components, and (B) an organic aluminum compound catalyst obtained by reacting at least a part of a halogen-containing organic aluminum compound having a halogen/aluminum ratio (atomic ratio) of 1-2 with water and/or an organic compound containing active hydrogen bonded to oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an olefin polymerization method suitable for producing olefin polymers or copolymers with narrow molecular weight distribution and composition distribution with high catalytic efficiency. Note that in the present invention,
The term polymerization is sometimes used to include not only homopolymerization but also copolymerization, and similarly, the term polymer is sometimes used to include not only homopolymers but also copolymers.

Olefin polymers are used after being processed into a large number of molded products such as films, tapes, sheets, fibers, blow molded products, and injection molded products. In order to obtain products with excellent transparency, impact resistance, etc., it is preferable to use polymers with narrow molecular weight distribution and composition distribution in each of these products. In particular, in copolymers, as the content of a small proportion of olefin comonomer to be copolymerized increases, the wideness and narrowness of the composition distribution tends to have a greater influence on the physical properties of the copolymer.

As a method for obtaining olefin polymers with a narrow distribution, it is effective to polymerize olefins using a catalyst formed from a vanadium-based catalyst component and an organoaluminum compound catalyst component. The disadvantage is that the polymer yield is low. If a catalyst formed from a highly active titanium catalyst component containing magfusium, titanium, and halogen as essential components and a typical organoaluminum compound catalyst component, such as trialkylaluminum, is used instead of the vanadium-based catalyst, the unit catalyst Although it is possible to dramatically increase the per unit polymer yield, for example, in copolymerization of ethylene and α-olefin having 6 or more carbon atoms, it is difficult to obtain a copolymer with a sufficiently narrow composition distribution. , the melting point of the copolymer obtained is generally high. If an alkyl aluminum halide is used in place of the above trialkylaluminum and high-temperature melt polymerization is carried out under conditions such that the copolymer dissolves in the polymerization medium, a copolymer with a fairly narrow composition distribution can be obtained, but depending on the application. cannot be said to be satisfactory yet.

As a result of intensive studies on improving the polymerization method using such highly active titanium catalyst components, the present inventors have discovered an organoaluminum compound catalyst component obtained by treating a specific organoaluminum compound with a specific element-containing compound. The inventors have discovered that by using a catalyst formed from the above-mentioned highly active titanium catalyst component, it is possible to further improve the catalytic activity and to produce a polymer having a narrower distribution.

That is, according to the present invention, (A) a highly active titanium catalyst component containing magnesium, titanium, and a halogen as essential components; Using a catalyst formed from an organoaluminum compound catalyst component obtained by reacting at least a portion of b-1) with water and/or an organic compound (b-2) containing active hydrogen bonded to oxygen, olefin Provided is a method for polymerizing olefins, characterized by carrying out polymerization or copolymerization of olefins.

The highly active titanium catalyst component used in the present invention (N contains magnesium, titanium and halogen as essential components, for example, magnesium/titanium (atomic ratio) is preferably 2
It is in the range of 100 to 100, particularly preferably 4 to 100, particularly preferably 10 to 70. Further, when the component (A) is a solid, its specific surface area is, for example, 5 m
/g or more, preferably 4Qm/g or more, more preferably 100 to 5oon/g. The titanium catalyst component usually does not release the titanium component contained therein by simple means such as washing with hexane at room temperature. And usually, the X-ray spectrum shows low crystallinity for the magnesium compound, regardless of the magnesium compound used in the catalyst preparation, or is very low crystallinity compared to that of the common commercial product of magnesium cybaride. It is desirable that the

The highly active titanium catalyst component (A) may also contain other elements, metals, functional groups, electron donors, etc. in addition to the above-mentioned essential components. For example, elements or metals such as silicon, aluminum, zirconium, and hafnium, functional groups such as alkoxy groups and aryloxy groups, and electron donors such as esters, amines, ethers, ketones, acid anhydrides, acid amides, and acid chlorides, etc. It may be contained.

Such a highly active titanium catalyst component (A) contacts or reacts a magnesium compound (or magnesium metal) and a titanium compound directly or in the coexistence of one or more compounds such as an electron donor, an element with the above-mentioned functions, or a metal. Alternatively, for example, one or both of the magnesium compound (or magnesium metal) and the titanium compound may be subjected to preliminary contact treatment with an electron donor, other elements, compounds such as metals, etc. It can be obtained by contacting or reacting the two.

Methods for producing such highly active titanium catalyst components are already known in the art from numerous proposals. For example, Special Publication No. 46-34092, No. 47-4
No. 1676, No. 50-32270, No. 55-4679
No. 9, No. 54-25517, No. 57-19122,
Examples of manufacturing methods disclosed in JP-A No. 56-811 and JP-A No. 56-11908 can be exemplified.

Examples of compounds of metals or elements having the above-mentioned properties include organoaluminum compounds and halogen-containing silicon compounds. The organoaluminum compound can be selected from, for example, trialkylaluminum, various alkyl aluminum pallites, various alkyl aluminum alkoxides, and the like. Further, the halogen-containing compound can be selected from, for example, silicon tetrachloride, silicon allyloxy halide, silicon allyloxy halide, halopolysiloxane, and the like.

Highly active titanium catalyst component (Magnesium compounds that can be used to prepare Shu include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, alkoxymagnesium halide) , magnesium sybaride,
Examples include reaction products of organomagnesium compounds such as alkylmagnesium halides, arylmagnesium halides, dialkylmagnesiums, or alkylmagnesium halides with silanol or siloxane. There are no particular restrictions on the manufacturing method of these magnesium compounds, and they can be selected as appropriate.

Examples of titanium compounds that can be used to prepare the highly active titanium catalyst component Al include titanium tetrahalide, alkoxytitanium halide, allyloxytitanium halide, tetraalkoxytitanium, and tetraallyloxytitanium.

Furthermore, examples of electron donors that can be used to prepare the highly active titanium catalyst component Al include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, ethers, acid amides, acid anhydrides, and alkoxysilane compounds. Examples include oxygen-containing electron donors, ammonia, amines, nitriles, and nitrogen-containing electron donors such as incyanate.

Specifically, methanol, ethanol, propatool, pentanol, hexyl, octatool,
2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, ): L ethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. having 1 to 1 carbon atoms
Alcohols of 8; phenol having 6 to 15 carbon atoms which may have a lower argyl group such as phenol, cresol, gyclenol, ethylphenol, propylphenol, cumylphenol, naphthol; yO: acetone;
Ketones having 3 to 15 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; acetaldehyde, propionaldehyde,
Aldehydes with 2 to 15 carbon atoms such as octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde: methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, Grass acid-c+
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate , ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diisobutyl malonate, γ-butyrolactone, δ-valerolactone, coumarin, Organic acid esters with 2 to 18 carbon atoms, such as phthalide and ethylene carbonate; Inorganic acid esters, such as ethyl silicate; to 15 acid halides: ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acids such as acetic acid amide, benzoic acid amide, toluic acid amide, etc. Amides; methylamine, ethylamine,
Examples include amines such as diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylene diamine; and nitriles such as acetonitrile, benzonitrile, and tolnitrile. These electron donors are 2
More than one species can be used.

In the present invention, the 1,000 tan catalyst component (organoaluminum compound catalyst component tE used together with Al) has an average composition of halogen/aluminum (atomic ratio) in a range of 1 or more and less than 2, particularly preferably 1.25. or 1.
An organic compound (b-L2) containing active hydrogen in which at least a part of the halogen-containing organoaluminum compound (b-1) represented by the range of 75 is bonded to water and/or oxygen.
It is a component obtained by reacting with

When an organoaluminum compound with a halogen/aluminum (atomic ratio) of less than 1 is used instead of the halogen-containing organoaluminum compound (b-1) specified above, the copolymerization can be carried out by high-temperature dissolution. When carried out in this state, it is not possible to produce a copolymer with a sufficiently narrow composition distribution. Further, when an organoaluminum compound having the above-mentioned ratio of 2 or more is used, it is not preferable because the polymerization activity cannot be said to be sufficiently satisfactory.

The organoaluminum compound catalyst component (b-1) includes dialkylaluminum halides such as diethylaluminum chloride, dihexylaluminum chloride, dewhexylaluminum chloride, dihandylaluminum sesquichloride, and isobutylaluminum sesquichloride. Typical examples include alkylaluminum sesquihalides such as 2-handed aluminum sesquipromide, and mixtures thereof.Also, these alkylaluminum halides in which some of the alkyl groups are substituted with hydrogen, etc. It may be.

Furthermore, materials that can be converted into halogen-containing organic aluminum by mixing may be used, such as any mixture of trialkylaluminum, alkylaluminum halide, aluminum trihalide, etc., and halogen and aluminum in the above halogen/aluminum (atomic ratio ) in a ratio that satisfies the conditions, for example, 2 parts aluminum sesquichloride to 2 parts aluminum sesquichloride.
A halogen-containing organoaluminum compound can be formed by reacting with an aluminum compound mixed at a double molar limit or with an aluminum compound such as those described above. It can also be used in the form of a mixture with a compound other than the aluminum compound that satisfies the above ratio. Examples of the latter include, for example, a mixture of 4 to 1 to 2 to 1 (molar ratio) of tri-aluminum and silicon tetrachloride, and 1.
A mixture of di-n-hexylmagnesium and aluminum trichloride with 5 times the mole or less of n-butyl chloride added.
, a mixture of 5/i to 3/1.

Halogen-containing organoaluminum compounds such as those exemplified above (
Among the organic compounds (b-2) containing active hydrogen bonded to water and/or oxygen to be reacted with b-1), the organic compounds are compounds containing hydroxyl groups, carboxyl groups, etc., such as alcohols, Examples include phenols and carboxylic acids. More specifically, methanol, ethanol, n-propyl, isopropyl, n-butanol, imbutanol, 5ec-butanol, tert-butanol, n-pentanol, n-hexanol, n-octatool, 2 - Two-handed Ruheni
Monovalent or polyvalent 01 to C1 such as alcohol, equilene glycol, propylene glycol, etc.
8 aliphatic alcohols, C5 to C12 alicyclic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol, phenylethyl alcohol, α
, 07-C15 of α-ruberbenzyl alcohol
Alcohols represented by aromatic alcohols,
Furthermore, phenol, cresol, xylenol, diphenol, isopropylphenol, t-butylphenol, hydroquinone, bisphenol, etc.
CI6 phenols: 02-C18 aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caprylic acid, caproic acid, stearic acid, oleic acid, succinic acid, adipic acid; fats such as cyclohexanecarboxylic acid Cyclic carboxylic acids; benzoic acid, toluic acid, salicylic acid,
Carboxylic acids represented by 07-015 aromatic carboxylic acids such as phthalic acid can be given as representative examples. Among these, alcohols, particularly aliphatic alcohols having 1 to 12 carbon atoms, are preferred, and ethanol is especially preferred.

The reaction between an organoaluminum compound (b-1) and water and/or an oxygen-containing compound (b-2) such as the above organic compound is
Preference is given to carrying out in an inert hydrocarbon medium. Examples of inert hydrocarbons that can be used for this purpose include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, kerosene, and alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane. , aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, halogenated hydrocarbons such as ethylene chloride, ethyl chloride, and chlorobenzene, and mixtures thereof.

When the reaction is carried out in an inert hydrocarbon medium, the concentration of the organoaluminum compound (b-1) can be changed and selected as appropriate, for example, from o, o o i to 5 mol/l, especially from 0.
Preferably, it is carried out at a concentration such as 0.01 to 2 mol/C.

The organoaluminum compound catalyst component (Bl is the halogen-containing organoaluminum compound (b-1) used)
The organoaluminum compound (b-1) used may be reacted with the oxygen-containing compound (b-2) in the presence of the entire amount of the oxygen-containing compound (b-2).
) and then mixed with the remaining organoaluminum compound (b-2) for use. The amount of the oxygen-containing compound (b-2) to be used is, for example, 0.05 to 1.0 mol, preferably 0.1 to 0.8 mol, per 1 mol of the organoaluminum compound used. can. and the organoaluminum compound used (b
-+) and the oxygen-containing compound (b-2), the organic a/l/minium compound (b-1) is reacted with at least 0.1 mole of the oxygen-containing compound (b-2). It is preferable to use it in a proportion of 5 moles or more.

In addition, when using a combination of two or more compounds as described above as the organoaluminum compound (b-4),
The mixing order of these two or more types of compounds and the above-mentioned oxygen-containing organic compound may be arbitrary.

However, it is preferable to adopt an embodiment in which the two or more compounds are combined in advance, and then all or a part thereof is mixed with the oxygen-containing organic compound.

The reaction temperature of the organoaluminum compound (b-IJ and water and/or oxygen-containing organic compound (b-2) can be selected as appropriate, for example, -20°C to +100°C, particularly -20°C to 70°C. The preferred range is .If the reaction temperature becomes too high, it becomes difficult to obtain the desired effect.The reaction time is arbitrary, for example, from 1 minute to several tens of hours, preferably from 7 or 2 minutes to 10 hours. [mountain] level.

Although it is not clear what kind of compounds are produced by the above reaction, halogen-containing organoaluminum compounds such as diethylaluminum chloride (IJ)-, ethylaluminum sesquichloride (b-1 and water, ethanol, n-butanol, butyl cellosolve, propionic acid, etc.) When the reaction product with the active hydrogen-containing compound (b-2) bonded to oxygen was analyzed alone, it was found that the active hydrogen-containing compound (b-2) was equal to the halogen-containing organoaluminum compound <b-1). When the amount was less than molar, the absorption peak based on the 10H stretching vibration of the active hydrogen-containing compound completely disappeared. Furthermore, when the temperature of the reaction is changed, the absorption pattern of E-R changes accordingly, and it is presumed that the structure of the product differs depending on the reaction temperature.

In addition, when the above reaction ratio is such that the halogen-containing T4m aluminum compound (b-1) is in excess of equimolar, free alkylaluminum is present depending on the excess amount. In all cases, the compound containing active hydrogen bonded to oxygen ('b-2) reacts with the organoaluminum compound (b-+) component, forming a bulky, e.g., membered ring structure. It is estimated that the reactivity is significantly weakened.

In addition, in the present invention, an organoaluminum compound (b-1
) and the oxygen-containing compound (b-2) in advance. For example, if iR yarn is mixed with titanium catalyst component + A +
Even if polymerization is carried out by directly supplying the organoaluminum compound (b-1) and the oxygen-containing compound (b-2), the effect of producing a polymer with a narrower distribution by adding the oxygen-containing compound cannot be found. .

In the method of the present invention, olefins are polymerized or copolymerized in the presence of a catalyst formed from the highly active titanium catalyst component (A) and the organoaluminum compound catalyst component (BJ) described in detail above.

Examples of olefins used in polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include octene. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-difunctional dienes can be selected as copolymerization components. The present invention +1J is particularly suitable as a method for producing resinous polymers by homopolymerization of ethylene or copolymerization of ethylene and a small proportion of α-olefin.

The polymerization can also be carried out in a phase such as a liquid phase or a gas phase. When liquid phase polymerization is carried out, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, or the olefin itself may be used as the reaction medium. The paper used for the catalyst has a titanium catalyst component (A) of approximately 0.000% in terms of titanium atoms per 14 reaction volumes. Oo o 1 to about 1.0
mmol, organoaluminum compound catalyst component molecule Bl'
F (Preferably, the amount of metal atoms in component (B) is about 1 to about 2,000 moles, preferably about 5 to about 500 moles, per 1 mole of titanium atoms in component A+.

During polymerization, hydrogen can be allowed to coexist for the purpose of controlling the molecular weight.

The polymerization temperature of the olefin is preferably about 20° to about 300°C, more preferably about 50° to about 250°C.
It is. In particular, when performing homopolymerization of ethylene or copolymerization of ethylene and a small amount of α-olefin, it is recommended to perform solution polymerization under conditions such that the resulting polymer or copolymer is dissolved in an inert hydrocarbon medium. Preferably, for example about 100°
Polymerization temperatures such as from to about 250°C are particularly recommended.

The polymerization pressure is preferably in the range of atmospheric pressure to about 200 kq/an, preferably about 2 to about 5 Q kg/an.

Although the polymerization can be carried out in any of the batch, semi-continuous and continuous methods, it is industrially advantageous to use the continuous polymerization method. Furthermore, polymerization is carried out under two different polymerization conditions.
According to the present invention, it is possible to produce a polymer having high polymerization activity and a narrow fiber distribution. In particular, in the above-mentioned ethylene copolymer, it is possible to produce a copolymer with a narrow distribution of X and 1 components.

Next, examples will be shown.

In the examples shown below, a parameter U expressed by the following formula (1) was used to express the composition distribution of the produced copolymer.

U = 100X (Ow/On -1) ” (1
) However, in the formula ('w represents the weight average degree of branching, and On represents the number average degree of branching.

The U is a parameter indicating the distribution of the composition components of the copolymer, which is unrelated to the molecular weight, and the smaller the value, the narrower the composition distribution. For example, if the U is too large, the composition distribution will be too wide, and when formed into a film, the transparency and
The tear resistance, impact resistance, blocking resistance, and low-temperature heat-sealing properties are poor, making it difficult to exhibit the excellent road properties of the copolymer of the present invention and the properties that combine these excellent properties in a well-balanced manner.

In the equation (1) for calculating U, Ow and Cn are values measured and determined by the following method.

In order to perform compositional fractionation of the ethylene copolymer, the copolymer was added to a mixed solvent of p-xylene and butyl cellosolve (volume ratio: 80/20) and filtered with a heat-resistant stabilizer.

After dissolving in the coexistence of 5-di-tert-butyl-4-methylphenol, diatomaceous earth (trade name: Celite 560, manufactured by Jeongmanpil (USA)) was coated and packed into a cylindrical column, and a cylindrical column was filled with diatomaceous earth having the same composition as the mixed solvent. While transferring and flowing out the solvent into the column, the temperature inside the column was raised stepwise from 50°C to 120″C in 5°C increments, and the coated ethylene copolymer was fractionated and reprecipitated in methanol. Separated products are obtained by drying each separated product.Next, the number of branches C per 1000 carbons of each fraction is determined by the 13.0" NMR method, and the number of branches C and the cumulative heavy fraction I of each fraction are calculated.
Assuming that w) follows the lognormal distribution of the following equation (2), calculate OW and On by the method of least squares.

...(2) However, in the formula, β2 is expressed as β12-21n (Ow/On) (3), and Co2 is Co-Ow-c! It is expressed as n (4).

Example 1 <Preparation of titanium catalyst component> Under a nitrogen atmosphere, 6 moles of commercially available anhydrous magnesium chloride were suspended in dehydrated and purified hexane 61, and 18 moles of ethanol was added dropwise over 1 hour with stirring, followed by 1 hour at room temperature. Time reacted. Add 7.8 mol of diethylaluminum chloride to this at room temperature? M was lowered and stirring was continued for 2 hours. Next, after adding 18 moles of titanium tetrachloride, the temperature of the system was raised to 80'C, and the reaction was carried out with stirring for 3 hours. After the reaction, the solid portion was separated, washed repeatedly with purified hexane, and then made into a hegisan suspension. In this way, the titanium catalyst component (
I got A.J.

Preparation of Organoaluminum Compound Catalyst Component> Under a nitrogen atmosphere, 500 mmol of ethylaluminum sesdichloride was added to dehydrated and purified hexane 11 and stirred. Next, ethanol 675 diluted with hexane to imol/6
Milliliter was added dropwise at room temperature, and the temperature was raised to 'aO<0>C and reacted for 1 hour. After the reaction, the mixture was allowed to cool to room temperature. In this way, an organoaluminum compound catalyst component (J3) was obtained.

Polymerization> Using a continuous polymerization reactor with an internal volume of 2001, dehydrated and purified hexane was 1001/l + r, and the organoaluminum compound catalyst component (1]) obtained above was converted to AJ/18 m
mol/hr, titanium catalyst component (Al
was continuously supplied at a rate of 0.66 mmol/hr in terms of Ti, and at the same time, ethylene 13
#g/hr, '4-methyl-1-pentene 13&
9/hr.

Hydrogen was continuously supplied at a rate of 701/hr, and the polymerization humidity was 1
65°C, total pressure 5Qkg/cm2, average ntf residence time 1 hour, copolymer concentration with respect to solvent hexane 130g/J
? Continuous copolymerization was carried out under the following conditions. The results are shown in Table 5. A copolymer with very narrow molecular weight distribution and composition distribution was obtained.

Next, the copolymer was molded into a film having a width of 35 mm using a commercially available high-pressure polyethylene tubular film molding machine (manufactured by Modern Machinery).
The film had a thickness of 0 mm and a thickness of 60 μm.

Molding conditions are resin temperature 180°C, screw rotation speed 11
00rp, Gui diameter + 00mm, Gui slit width 0.7
It is mm. Next, the film was evaluated by the following method.

Haze (%): ASTM D 1003 Impact Strength (k
g-α/a): Measured using a Toyobo IA film impact tester. The palmar spherical surface was 1"φ, Elmendorf tear strength, IJt (kq/(7)) knee ASTM D 1922 Blocking value (g): According to ASTM D 1895, the peeling bar was made of glass,
The peel strength was 200 wl/min.

Heat-sealing start temperature (°C): Using a heat sealer made by Toyo Tester, heat-sealing was performed at the specified temperature with a pressure of 2kql2 and a sealing time of 1 second.The specimen width was 15mm, and the peel test speed was 500mm/min. The heat sealing start temperature was set as the temperature at which, during the peel test, the test piece began to break not due to peeling of the sealing surface but due to breakage of the thick section.

The results are shown in Table 4.

Example 2 Preparation of organoaluminum compound catalyst component In Example 1, instead of reacting ethylaluminum sesquichloride and ethanol at a molar ratio of 4:5, the molar ratio was changed to 1:1.
The island component was obtained in the same manner as in Example 1 except that the ratio was 1 to 1.

<Polymerization> Continuous 1 as in Example 1 (using a synthesis apparatus, +Ommol/hr of ethylaluminum sesquichloride, fE obtained above) component converted to Ae +Ommol/hr.

The titanium catalyst component obtained in Example 1 (0.62 mm of Al
Copolymerization of ethylene and 4-methyl-1-pentene was carried out under the conditions shown in Table 2 by continuously supplying the solution at a ratio of 1 ol/hr. The results are shown in Tables 5 and 4.

As in Example 1, a copolymer with very narrow molecular weight distribution and composition distribution was obtained.

Compared to Example 1, the formed film had improved transparency, impact strength, and heat sealability, corresponding to the lower density. This heat seal is open M! - C. The value is comparable to that of a commercially available ethylene-vinyl acetate copolymer film containing R5 wt % of vinyl acetate.

Comparative Example 1 In Example 1, 15 mmol of ethylaluminum sesquichloride was used instead of using the Bl component obtained in Example 1 as the organoaluminum compound catalyst component.
Continuous copolymerization was carried out in the same manner as in Example 1, except that the supply rates of 4-)lf-i-pentene and hydrogen were changed as shown in Table 2.Results Table 5 and Table 4 It was shown to. The obtained copolymer had a somewhat wide compositional distribution, so the blocking resistance of the formed film was insufficient. Examples 5 and 4 <Preparation of organoaluminum compound catalyst component> Component (B) was prepared in the same manner as in Example 1 except that the molar ratio of was changed as shown in Table 1.

At this time, +mol/N in hexane in both cases.
An organoaluminum compound diluted to 20% was mixed in advance at room temperature, and ethanol diluted with hexane to imol/# was added dropwise thereto.

<Polymerization> As an organoaluminum compound catalyst component, (
B) Component: [Al obtained in Example 1 as a titanium catalyst component]
Table 6 shows the results of continuous copolymerization of ethylene and α-olefin using the components under the conditions shown in Table 2.

Regarding Example 4, the evaluation results of the formed film are shown in Table 4. Even at such a low density, the pellets could be easily molded without blocking. Due to its low density, the film is extremely transparent and has excellent heat sealability.

Comparative Examples 2 and 5 <Preparation of organoaluminum compound catalyst component> Component (B) was prepared under the conditions shown in Table 1 by changing the type of organoaluminum compound and the molar ratio to ethanol as shown in Table 1.

<Polymerization> The organoaluminum compound catalyst component obtained above (B
) component and the catalyst component obtained in Example 1 as the titanium catalyst component, copolymerization was carried out under the conditions shown in Table 2. The results are shown in Tables 5 and 4.

In the case of Comparative Row 2, the composition distribution of the obtained copolymer was wide, and the blocking resistance and heat sealability were insufficient.

In the case of Comparative Example B, the polymerization activity was extremely low, the polymer contained a large amount of catalyst residue, and was unable to be molded due to foaming.

Examples 5 to 10 Preparation of organoaluminum compound catalyst component The types and molar ratios of the organoaluminum compound, halogen compound other than the organoaluminum compound, active hydrogen compound bound to water or oxygen were changed as shown in Table 1. Component (B) was prepared under the conditions shown in Table 1.

<Polymerization> The organoaluminum compound catalyst component obtained above (B
) component and the titanium catalyst component (Al component obtained in Example 1), continuous copolymerization of ethylene and a-olefin was carried out under the conditions shown in Table 2. The results are shown in Table 5. In the case of , a copolymer with very narrow molecular weight distribution and composition distribution was also obtained.

Example 11 <Preparation of Ti catalyst component> Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in dehydrated and purified n-decane 2e, and 3
Add 5 moles of 2-ethylhexanol and heat to 120 °C for 5
Saved time. After the reaction, the solid disappeared and a colorless and transparent solution was obtained. In this way, a solution of magnesium chloride-2-ethyl hegizanol complex (D n-decane) was obtained. This solution remained a colorless and transparent solution even at room temperature.

Next, in another reactor, 1.51 l of n-decane was added in nitrogen.
．． 2.4 mol of titanium tetrachloride was added and cooled to o''c.Then, the n-decane solution of the magnesium chloride-2-ethylhexanol complex obtained above was converted to MIIJ and was
[]0 mmol was added dropwise at 0°C without stirring. After the dropwise addition, the temperature was raised to 80°C and the mixture was reacted for 1 hour.

After the reaction, the solid part was washed repeatedly with n-decane, and then
- It was made into a decane suspension. In this way, titanium catalyst component (A) was obtained.

Polymerization> As organoaluminum compound catalyst components, ethylaluminum sesquichloride and component (B) obtained in Example 2,
Using the Al component obtained above as a titanium catalyst component, copolymerization of ethylene and 4-methyl-1-pentene was carried out under the conditions shown in Table 2. The results are shown in Table 2.

Example 12 Preparation of titanium catalyst component> 400 mmol of the n-decane solution of the magnesium chloride-2-ethylhexanol complex obtained in Example 11 was taken in terms of M, and 80 mmol of benzoin was added to it in room crystals. Add ethyl acid and stir [7. The system remained a homogeneous solution. Next, this homogeneous solution was cooled to -20°C.
was added dropwise to 6 mol of titanium tetrachloride over 1 hour while stirring under nitrogen atmosphere.Then, the temperature was raised to 90°C and the reaction was allowed to proceed for 2 hours. After the reaction,
The liquid part was removed, 2 mol of titanium tetrachloride was added again, and the mixture was reacted for 2 hours. After the reaction, the solid portion was washed repeatedly with n-decane to form a 11-decane suspension. In this way, titanium catalyst component tA) was obtained.

<Polymerization> As an organoaluminum compound catalyst component, ethylaluminum sesquichloride and component (E) obtained in Example 2,
Using the component (A) obtained above as a titanium catalyst component, ethylene and 4-methyl-1-pentene were copolymerized under the conditions shown in Table 2. The results are shown in Table 5.

Example 16 Preparation of titanium catalyst component> Using component (A) obtained in Example 1, 400 mmol of ethanol was added to 40 mmol of Ti in terms of Ti at room temperature under a nitrogen atmosphere with stirring. Ta. Then 80
The temperature was raised to °C and the reaction was allowed to proceed for 1 hour.

After the reaction, cool to room temperature and add triethylaluminum 125
Millimoles of the mixture were gradually added dropwise, and the mixture was allowed to react at room temperature for 1.5 hours. After the reaction, the solid portion was washed repeatedly with purified hexane and then made into a hexane suspension. In this way, titanium catalyst component tAl was obtained.

Polymerization> As organoaluminum compound catalyst components, ethylaluminum sesquichloride and component (B) obtained in Example 2,
Using the Al component obtained above as a titanium catalyst component, copolymerization of ethylene and 4-methyl-1-pentene was carried out under the conditions shown in Table 2. The results are shown in Tables 5 and 4. Ta.

Comparative Example 4 Polymerization> In Example 1, ethylaluminum sesquichloride and ethanol were reacted in advance outside the polymerization system as the 2Q aluminum compound catalyst component. Continuous polymerization was carried out in exactly the same manner as in Example 1, except that sesquichloride and ethanol were each separately supplied to the polymerization system at the same molar ratio as in Example 1. The results are shown in Tables 5 and 4. The obtained copolymer had a wider molecular distribution and composition distribution than that of Example 1, and the performance of the formed film was also inferior.

Claims (1)

[Claims] (1) (A) Highly active titanium catalyst component containing magnesium, titanium, and halogen as essential components and (Bl) A halogen-containing organoaluminum compound (b-1) in which the herogen/aluminum (atomic ratio) is 1 or more and less than 2. ) with an organic compound (b-2) containing active hydrogen bonded to water and/or oxygen. A method for polymerizing olefins, characterized by carrying out copolymerization.