JP2574614B2 - Titanium compound catalyst component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an olefin polymerization method suitable for producing an olefin polymer or copolymer having a narrow molecular weight distribution or a narrow composition component with high catalytic efficiency.

In the present invention, the term polymerization is sometimes used to mean not only homopolymerization but also copolymerization. Similarly, the term polymer means not only homopolymerization but also copolymer. May be used in

[0003] Olefin polymers include films, tapes,
It is used after being processed into an extremely large number of molded products such as sheets, fibers, hollow molded products, and injection molded products. In each of these products, it is preferable to use a polymer having a narrow molecular weight distribution or composition distribution in order to obtain a product having excellent transparency and impact resistance. In particular, as the content of the olefin copolymer in a small proportion to be copolymerized increases, the influence of the composition distribution on the physical properties of the copolymer tends to increase. In addition, even for a copolymer having a relatively low molecular weight, such as wax grade, when used for an application such as a pigment dispersant, a copolymer having a narrow composition distribution has been desired from the viewpoint of preventing blocking. As a method for obtaining an olefin polymer having a narrow distribution, it is effective to polymerize olefin using a catalyst formed from a vanadium-based catalyst component and an organoaluminum compound catalyst component. There is a disadvantage that the polymer yield is low. When a highly active solid titanium component containing magnesium, titanium and halogen as essential components is used instead of the above-mentioned vanadium catalyst component, the polymer yield per unit catalyst can be dramatically increased. Although it is possible, for example, in the copolymerization of ethylene with α-olefin having 3 or more carbon atoms, it is difficult to obtain a copolymer having a sufficiently narrow distribution of components, and generally the obtained copolymer has a high melting point. Was.

The present inventors have been conducting research to develop an improved method capable of overcoming the technical problems of a polymerization method using such a highly active solid titanium component.

As a result, a titanium compound catalyst component formed by further treating the above-mentioned conventionally used highly active solid titanium component under a condition satisfying a specific condition, and a specific halogen / aluminum (Atomic ratio) By polymerizing or copolymerizing olefin in the presence of a catalyst that satisfies the combination with a halogen-containing organoaluminum compound satisfying the conditions, an olefin polymer or copolymer having a narrow molecular weight distribution or composition distribution can be obtained. It has been discovered that polymers can be produced with high catalytic efficiency.

As a result of further research based on the above new findings, the present inventors have found that [A] a highly active titanium component (a-1) containing magnesium, titanium and halogen as essential components is bonded to oxygen. It shall apply in component formed by further treatment with an organic compound containing active hydrogen (a-2), and the component
The organic compound contained in the (a-2) and / or organic compound molar ratio of the amount of oxygen-containing group derived from (a-2) and (X) and the amount of titanium (Y) (X) :( Y ) Is 4 to 100: 1
Wherein the highly active titanium component (a-1) is an organic compound containing active hydrogen bonded to oxygen in addition to the essential component (a-1). a-2) ′ and / or an oxygen-containing group derived from the organic compound (a-2) ′. In this case, the amount (X) is
The organic compound contained in component (a-2)及beauty said organic compound the amount of oxygen-containing group derived from (a-2) (X ₁₎ and the organic compound (a-2) 'and the organic compound (a -2) '
It shall mean the total amount of the amount (X ₂₎ of the oxygen-containing group derived from, and [B] a halogen / aluminum (atomic ratio), halogen-containing organoaluminum compound catalyst and less than 2 in one or more By polymerizing or copolymerizing olefin in the presence of a catalyst formed from the components, it is possible to overcome the technical problems of the above-mentioned conventional method, to obtain a catalyst having high catalytic efficiency and a narrow molecular weight distribution or composition distribution. It has been found that the olefin polymer or copolymer can be industrially advantageously produced.

Accordingly, it is an object of the present invention to provide an improved process for the polymerization of olefins.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The titanium compound catalyst component [A] used in the present invention comprises a highly active titanium component (a-1) containing magnesium, titanium and halogen as essential components and an organic compound (a) containing active hydrogen bonded to oxygen. And (2) the amount of the organic compound (a-2) and / or the oxygen-containing group derived from the organic compound (a-2), Is a titanium compound catalyst component having a molar ratio (X) :( Y) to the amount (Y) of 4 to 100: 1.

Regarding the highly active titanium component (a-1) and its production method, many proposals have already been known.
Conventionally, the component (a-1) is a component that has been used in combination with an organoaluminum compound catalyst component for the polymerization of olefins.

The highly active titanium component (a-1) contains magnesium, titanium and halogen as essential components,
For example, magnesium / titanium (atomic ratio) is preferably 2
To 100, particularly preferably 4 to 70, halogen / titanium (atomic ratio) is preferably 4 to 100, particularly preferably 10 to 70. The specific surface area is, for example, 3 m ² / g or more, preferably 40 m ² / g.
² / g or more, more preferably 100 to 800 m ²
/ G. The titanium component (a-1) usually does not desorb the contained titanium component by a simple means such as hexane washing at room temperature. Usually, the X-ray spectrum shows low crystallinity for the magnesium compound irrespective of the magnesium compound used in the preparation of the catalyst, or very low crystallization compared to that of a normal commercial product of magnesium dihalide. Is desirable.

The highly active titanium component (a-1) may further contain an element, a metal, a functional group, an electron donor and the like in addition to the above essential components. For example, silicon or an element such as aluminum, zirconium, or hafnium or a metal, a functional group such as an alkoxy group or an aryloxy group, an ester, an amine, an ether, a ketone, an acid anhydride, an acid amide, or an electron donor such as an acid chloride. It may be contained. Generally, among these, those not containing a large amount of an electron donor are preferable.

Such a highly active titanium component (a-1)
Is a method of contacting or reacting, for example, 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 and the other element or metal. A method of preliminarily pre-contacting one or both of a titanium compound and an electron donor or a compound such as another element or metal, and then contacting or reacting the two. Can be obtained by Examples of compounds such as the above-mentioned other elements and metals include organic aluminum compounds and halogen-containing silicon compounds. The organoaluminum compound is, for example, a trialkylaluminum,
It can be selected from various alkyl aluminum halides and various alkyl aluminum alkoxides. The halogen-containing silicon compound can be selected from, for example, silicon tetrachloride, silicon alkoxyhalide, allyloxysilicon halide, halopolysiloxane and the like.

Such a highly active solid titanium component (a-
The method for producing 1) is already known in the art with numerous proposals. For example,
No. 34092, No. 47-41676, No. 50-322
No. 70, No. 53-46799, No. 54-25517
Nos. 57-19122, JP-A-56-811, and 56-11988.

The magnesium compounds that can be used for preparing the highly active titanium component (a-1) include magnesium oxide, magnesium hydroxide, hydrotalcite,
Magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium dihalide, alkylmagnesium halide, arylmagnesium halide, dialkylmagnesium,
Alternatively, a reaction product of an organomagnesium compound such as an alkylmagnesium halide with silanol or siloxane can be exemplified. There are no particular restrictions on the method for producing these magnesium compounds, and they can be appropriately selected. Examples of titanium compounds that can be used for the preparation of the highly active titanium component (a-1) include titanium tetrahalide, aucoxy titanium halide, allyloxy titanium halide, tetraalkoxy titanium, and tetraallyloxy titanium. Can be illustrated.

Further, electron donors that can be used for preparing the highly active titanium component (a-1) include alcohols, phenols, ketones, aldehydes, carboxylic acids, and the like.
Examples include oxygen-containing electron donors such as esters, acid amides, acid anhydrides, and alkoxysilane compounds, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol Carbon number 1 such as
To 18 alcohols; phenol, cresol,
C6 to C15 phenols which may have a lower alkyl group such as xylenol, ethylphenol, propylphenol, cumylphenol and naphthol; C3 to C15 such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; Ketones; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate , Ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, toluyl Ethyl acrylate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl ethoxy benzoate, diethyl phthalate, diisobutyl phthalate, diisobutyl malonate, γ
Organic acid esters having 2 to 18 carbon atoms, such as butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate; inorganic acid esters such as ethyl silicate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid 2 to 1 carbon atoms such as chloride
5 acid halides; methyl ether, ethyl ether,
C2-C20 ethers such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, triamine Amines such as butylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used.

The titanium compound catalyst component [A] in the present invention is a highly active titanium component (a-1) containing magnesium, titanium and halogen as essential components as described above.
With an organic compound containing active hydrogen bonded to oxygen (a
It can be formed by further processing in -2).

Examples of the organic compound (a-2) include organic compounds containing active hydrogen bonded to oxygen, such as organic compounds containing a hydroxyl group and a carboxyl group, such as alcohols, phenols, and carboxylic acids. be able to. Specific examples of such an organic compound (a-2) include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n
-Pentanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-decyl alcohol, oleyl alcohol, ethoxyethanol, n-butoxyethanol, 1-butoxy-2-propanol, 2-chloroethanol, ethylene glycol, aliphatic alcohols C ₁ -C ₁₈ monovalent or polyvalent such as propylene glycol; example cyclopentanol, such C ₅ -C such cyclohexanol
₁₂ alicyclic alcohols; C ₇ N ₁₅ aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, α, α-dimethylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, isopropylphenol, t C such as butyl phenol, hydroquinone, bisphenol A, etc.
Phenols of ₆ -C _16; for example, acetic acid, propionic acid, butyric acid, valeric acid, caprylic acid, caproic acid, stearic acid, oleic acid, succinic acid, such C such as adipic acid
Alicyclic carboxylic acids such as such as cyclohexane carboxylic acid; aliphatic carboxylic acids ₂ -C ₁₈ such as benzoic acid, toluic acid, salicylic acid, such as C _7, such as phthalic acid
Aromatic carboxylic acids -C _15; and the like. Among them, alcohols, particularly aliphatic alcohols having 1 to 12 carbon atoms, are preferable, and ethanol is particularly preferable.

In the treatment of the polyvalent active titanium component (a-1) with the organic compound (a-2) containing active hydrogen bonded to oxygen as exemplified above, the titanium formed by the treatment is used. The organic compound (a-2) in the compound catalyst component [A], for example, alcohols, phenols, carboxylic acids and the like as described above and / or an oxygen-containing group derived from the organic compound (a-2), for example, an alkoxy group The molar ratio (X) :( Y) of the amount (X) of an aryloxy group, an acyloxy group, etc. to the amount of titanium (Y) is 4 to 1
00: 1, preferably 6 to 50: 1.

As described above, in the present invention, the highly active titanium component (a-1) is, in addition to its essential components magnesium, titanium and halogen, an organic compound (a) containing active hydrogen bonded to oxygen. -2) 'and / or an oxygen-containing group derived from the organic compound (a-2)'. Examples of the organic compound (a-2) ′ are the same as those exemplified for the organic compound (a-2), but they may be the same or different.
In such a case, the amount (X) is determined based on the amount (X ₁ ) of the organic compound (a-2) and / or the oxygen-containing group derived from the organic compound (a-2), (A-
2) 'For example, alcohols, phenols, carboxylic acids and the like as described above and / or the organic compound (a-
2) means the total amount with the amount (X ₂ ) of the oxygen-containing group derived from ', for example, an alkoxy group, an aryloxy group, an acyloxy group and the like.

The highly active titanium component (a-1)
Has an oxygen-containing organic compound derived from the organic compound (a-2) ′ and / or the organic compound (a-2) ′ in addition to the essential components, the amount (X ₁ ) It is preferable to perform the above treatment so that the value of the molar ratio (X ₁ ) :( Y) with respect to the amount (Y) of titanium becomes 2 or more, and more preferably 4 or more.

The content of the organic compounds (a-2) and (a-2) 'in the titanium compound catalyst component [A] and the oxygen-containing machine derived therefrom is determined, for example, by using the catalyst component [A]. Hydrolysis with an aqueous solution of an inorganic acid, to which acetone was added and sufficiently dissolved, can be quantified by gas chromatography. If the above-mentioned acetone-based compound is not easily dissolved sufficiently, the reaction can be similarly performed using an appropriate organic solvent, for example, chloroform, instead of acetone. (X), (X ₁ ),
The amount of (X ₂ ) is measured in this way.

In the present invention, the above molar ratio (X):
When (Y) deviates from 4 to 100: 1 and the molar ratio is less than 4: 1, the effect of treatment with the compound (a-2) containing active hydrogen bonded to oxygen is small, and
If the ratio is more than 0: 1, the improvement effect is not further increased, but rather, an uneconomical aspect that the use amount of the halogen-containing organoaluminum compound catalyst component must be increased is not preferable.

In the above treatment with the organic compound (a-2) having active hydrogen bonded to oxygen of the highly active titanium component (a-1), the amount of the organic compound (a-2) used is, for example, Although it can be appropriately changed depending on conditions such as the kind and the treatment temperature, about 1 to about 50 mol, more preferably about 2 to about 30 mol, per 1 atom of titanium in the highly active titanium component (a-1). Such usage amounts can be exemplified.

The above treatment is preferably carried out in an inert medium, preferably in an inert hydrocarbon medium, with the highly active titanium component (a-1) diluted in the medium. Examples of the inert hydrocarbon used at this time include pentane, hexane, heptane, octane, decane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, alicyclic hydrocarbons such as cyclohexane, benzene, toluene , Xylene, aromatic hydrocarbons such as ethylbenzene, halogenated hydrocarbons such as ethylene chloride, ethyl chloride, and chlorobenzene, and mixtures thereof. When the contact treatment is carried out in an inert hydrocarbon medium, the concentration of the highly active titanium component (a-1) can be appropriately selected. For example, the concentration is preferably about 1 to 200 mmol / l in terms of titanium atoms. Organic compound (a-
The treatment temperature of the highly active titanium component (a-1) according to 2) can also be appropriately selected, and preferably, for example, a temperature of about -20 ° C to about + 180 ° C, particularly about 20 ° C to about 120 ° C can be preferably exemplified. The processing time can be appropriately changed and selected depending on the processing temperature, but can be appropriately selected within a range of, for example, several minutes to several tens of hours.

The titanium catalyst component [A] thus obtained
May be used after being sufficiently washed with an inert solvent, or may be used as it is in the above treated suspension.

In the present invention, the titanium compound catalyst component [A] obtainable as described above is replaced with a titanium compound which has been pre-treated with a small amount of an organoaluminum compound prior to use in the polymerization system. You can also.

In this pretreatment, it is preferable to employ relatively mild conditions. Otherwise, the pretreatment may deteriorate the catalytic performance. In the pretreatment, the concentration of the titanium compound catalyst component [A] is about 1 to 200 mmol / 1 in terms of titanium atom in an inert hydrocarbon medium as described above, and the organoaluminum compound is 20 mol or less per atom of titanium. It is preferable to use about 1 to 10 moles and to carry out the reaction at -20 to 120 ° C.

The organoaluminum compound used in this pretreatment may be the same as that used as the halogen-containing organoaluminum compound catalyst component, or may be a trialkylaluminum such as triethylaluminum or triisobutylaluminum. And so on. The use of trialkylaluminum is particularly preferred.

In the above pretreated product, the molar ratio (X) :( Y) in the titanium compound catalyst component [A] may be 4: 1 or less. Even in such a case, the improvement effect of the present invention can be sufficiently obtained. Can be

The organoaluminum compound pre-treated titanium catalyst component can be sufficiently washed with an inert hydrocarbon before it is subjected to polymerization. Alternatively, the suspension can be supplied to the polymerization system in the above-mentioned pretreatment. In this case, the organoaluminum compound used for the pretreatment is the catalyst (B)
Since it will be used as a part of the components, both of the organoaluminum compounds used for the pretreatment are combined,
The kind and amount of the newly added organoaluminum compound are selected so that the atomic ratio of halogen / Al is in the range of 1 or more and less than 2.

In the present invention, as the organoaluminum compound catalyst component used in combination with the titanium compound catalyst component [A] described in detail above, [B] halogen / aluminum (atomic ratio) is 1 or more and less than 2, preferably It is important to use a halogen-containing organoaluminum compound catalyst component having an average composition of 1.25 to 1.75.

The halogen / aluminum (atomic ratio) is
When a halogen-containing organoaluminum compound containing less than 1 halogen component is too small or a halogen-free organoaluminum compound is used as the catalyst component [B], it is difficult to obtain a desired polymer having a narrow molecular weight distribution or composition distribution. Further, there is a disadvantage that the activity in high-temperature polymerization is inferior. On the other hand, when a component having a halogen / aluminum (atomic ratio) ratio of 2 or more is more than the above range, the polymerization activity is inferior.

As the halogen-containing organoaluminum compound catalyst component [B], an organoaluminum compound satisfying the condition of halogen / aluminum (atomic ratio) of 1 or more and less than 2 or a mixture satisfying the condition can be used. Examples thereof include dialkylaluminum halides, alkylaluminum sesquihalides, mixtures thereof, and mixtures of these and alkylaluminum dihalides satisfying the above-mentioned halogen / aluminum (atomic ratio). Further, the alkylaluminum halides may be obtained by substituting a part of the alkyl group with hydrogen, an alkoxyl group or the like. Such a compound may also be a reaction product of the above-mentioned alkylaluminum halides and an alcohol. Specifically, alkylaluminum halides such as diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquibromide, and a reaction product of these alkylaluminum halides with the alcohol exemplified above. And the like can be shown as preferable examples.

Further, those which can be converted into a halogen-containing organoaluminum having a halogen / aluminum (atomic ratio) of 1 or more and less than 2 in a polymerization system may be used. For example, trialkylaluminum, alkylaluminum halide, aluminum Any mixture such as trihalide and the like, wherein halide and aluminum are in a ratio satisfying the above-mentioned halogen / aluminum (atomic ratio) condition, for example, a mixture of triethylaluminum and ethylaluminum sesquichloride at twice or more moles, or Such an aluminum compound and a compound other than the aluminum compound capable of reacting therewith to form a halogen-containing organoaluminum compound may be used in the form of a mixture satisfying the above-mentioned halogen / aluminum (atomic ratio) ratio. Kill. Examples of the latter include, for example, 4: 1 to 2:
1 (molar ratio), a mixture obtained by adding 1.5 times or less mol of n-butyl chloride to diethylaluminum chloride, a 1.5 / 1 to 3/1 mixture of di-n-hexylmagnesium and aluminum trichloride And the like.

In the method of the present invention, olefin is polymerized or copolymerized in the presence of a catalyst formed from a titanium compound catalyst component [A] and a halogen-containing organoaluminum compound catalyst component [B] described in detail below. I do.

Examples of the olefin used for the polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-octene and the like. These can perform not only homopolymerization but also random copolymerization and block copolymerization. Upon copolymerization, a polyunsaturated compound such as a conjugated diene or a non-conjugated diene can be selected as a copolymerization component. The present invention is particularly suitable as a method for producing a resinous polymer by homopolymerization of ethylene or copolymerization of ethylene and a small proportion of α-olefin.

The polymerization can be carried out in any of a liquid phase and a gas phase. Hexane,
Inert solvents such as heptane and kerosene may be used as the reaction medium, but olefin itself may be used as the reaction medium. The catalyst is used in an amount of about 0.0001 to about 1.0 mmol in terms of titanium atom of the titanium catalyst component [A] per 1 liter of the reaction volume, and the organoaluminum compound catalyst component [B] in the component [A]. For 1 mole of titanium atom,
[B] a metal atom in the component is about 1 to about 2000 mol,
Preferably, the molar ratio is about 5 to about 500.

At the time of polymerization, hydrogen can coexist for the purpose of controlling the molecular weight.

The polymerization temperature of the olefin is preferably about 2
0 ° C. to about 300 ° C., more preferably about 50 ° C. to about 230 ° C. In particular, when performing homopolymerization of ethylene, or copolymerization of ethylene and a small amount of α-olefin, it is preferable to perform solution polymerization under conditions in which the resulting polymer or copolymer is dissolved in an inert hydrocarbon medium. Polymerization temperatures such as, for example, from about 100 ° C. to about 230 ° C. are particularly recommended.

The polymerization pressure is from atmospheric pressure to about 200 k
g / cm ² , preferably about 2 to about 50 kg / cm ²
It is good to adopt the range as follows.

The polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system, but it is advantageous to employ a continuous polymerization system from an industrial viewpoint. Further, the polymerization may be performed in two or more polymerization zones having different polymerization conditions.

According to the present invention, a polymer having a high polymerization activity and a narrow distribution can be produced. In particular, in the above-mentioned ethylene copolymerization, it is possible to produce a copolymer having a narrow composition distribution.

Next, an embodiment will be described.

In the following examples, the parameter U represented by the following formula (1) was used to represent the composition distribution of the produced copolymer.

[0047]

U = 100 × (Cw / Cu-1) (1) where Cw indicates the weight average branching degree, and Cn indicates the number average branching degree.

The U is a parameter indicating the distribution of the composition components of the copolymer irrespective of the molecular weight, and a smaller value means a narrower composition distribution. For example, if the U is too large, the composition is too wide, and when formed into a film, transparency, tear resistance, impact resistance, blocking resistance,
It is inferior in low-temperature heat sealability, and it is difficult to exhibit the excellent properties of the copolymer of the present invention and the properties that combine the excellent properties in a well-balanced manner.

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

In order to carry out the composition of the ethylene copolymer, the copolymer was added to a mixed solvent of p-xylene and butyl cellosolve (volume ratio: 80/20) with a heat-resistant plasticizer 2,
After dissolving in the presence of 5-di-tert-butyl-4-methylphenol, the mixture was coated on diatomaceous earth (trade name: Celite 560, manufactured by Jillon Manville Co., USA) and packed in a cylindrical column. While transferring and flowing the solvent having the same composition into the column, the temperature in the column was increased stepwise from 30 ° C. to 120 ° C. in steps of 5 ° C., and the coated ethylene copolymer was reprecipitated in methanol after fractionation. Separate by filtering and drying. Next, the branch C per 1000 carbon atoms of each fraction is determined by 13C-NMR method, and the cumulative amount fraction (w) of each branch of the branch number C is assumed to follow the following formula (2) and the normal distribution. , Cw and Cn are obtained by the least square method.

[0051]

(Equation 2)

Where β is represented by β ² = 21n (Cw / Cn) (3), and Co ² is represented by CO ² = Cw · Cn. . . . . . . . It is represented by (4).

[0053]

Example 1 <Catalyst preparation> Under a nitrogen atmosphere, 10 mol of commercially available anhydrous magnesium chloride was suspended in dehydrated and purified hexane 201, and 60 mol of ethanol was added dropwise with stirring over 1 hour, and then the mixture was stirred at room temperature. 1
Reacted for hours. To this, 26 mol of diethyl aluminum chloride was added dropwise at room temperature, and stirring was continued for 2 hours. Next, after adding 60 mol of titanium tetrachloride, the reaction was carried out while heating the system to 80 ° C. and stirring for 3 hours. The solid part after the reaction was separated and washed repeatedly with purified hexane. The composition of the solid (A-1) was as follows.

[0054] Next, 5 mol of ethanol was added at room temperature to 500 mmol of (A-1) (Ti concentration 50 mmol / l) suspended in purified hexane, and the temperature was raised to 50 ° C. The reaction was carried out for 5 hours. After the reaction, the solid portion was washed repeatedly with purified hexane. The composition of the catalyst (A-2) thus obtained was as follows.

[0055]

<Polymerization> Using a continuous polymerization reactor having an internal volume of 200 l, 100 l / hr of dehydrated and purified hexane, 7 mmol / hr of diethylaluminum chloride, 14 mmol / hr of ethylaluminum sesquichloride, and the catalyst obtained above ( A
-2) was continuously supplied at a rate of 0.5 mmol / hr in terms of Ti, and 1.3 kg / hr of ethylene and 19 kg of 4-methyl-1-pentene were simultaneously supplied in the polymerization vessel.
/ Hr, hydrogen at a rate of 45 l / hr continuously, a polymerization temperature of 165 ° C., a total pressure of 30 kg / cm ² , a residence time of 1 hour, and a copolymer temperature with respect to the solvent hexane of 130 g / l.
The copolymerization was carried out under the following conditions. The catalytic activity is 21,70
It corresponded to 0 g-copolymer / mmol-Ti.

The results of the obtained copolymer are shown in Table 2. Both the molecular weight distribution and the composition distribution were very narrow.

Next, the copolymer was made into a film having a width of 350 mm and a thickness of 30 μm using a commercially available tumbler film molding machine for high-pressure polyethylene (manufactured by Modern Machinery). Molding conditions: resin temperature 180 ° C, screw rotation speed 100r
pm, die diameter 100mm, die slit width 0.7mm
It is. Next, the film was evaluated by the following method.

Haze (%): ASTM D 1003 Impact strength (kg-cm / cm): Measured using a film impact deter manufactured by Toyo Seiki. The impact head spherical surface was 1φ.

Elmendorf Tear Strength (kg / cm): ASTM D
1922 Blocking value (g): A peel bar made of glass and a peel speed of 20 cm / min according to ASTM D 1893.
And

Heat sealing start temperature (° C.): Using a heat sealer manufactured by Toyo Tester, heat sealing was performed at a specified temperature under a pressure of 2 kg / cm ^{2 for} a sealing time of 1 second. Specimen width is 15mm, peel test speed 300mm
/ Min. The heat-sealing start temperature was a temperature at which the test piece began to break at the peeling test without depending on the peeling of the sealing surface but on the thickness-reverse portion.

The results are shown in Table 3.

Comparative Example 1 Continuous copolymerization was carried out in the same manner as in Example 1 except that (A-2) was used as the Ti catalyst component instead of (A-2) before the reaction with ethanol. Was done. The catalytic activity was 19,100 g copolymer / mmol-Ti. Table 2 shows the physical properties, and Table 3 shows the results of evaluation of the molded film.
It was shown to. The polymer obtained here has a somewhat broad composition distribution and the film has insufficient blocking resistance.

Comparative Example 2 In an example similar to Example 1, triethylaluminum 20 mmol / hr, T
(A-1) before reacting with ethanol instead of (A-2) as a catalyst component was converted to Ti atom by 0.42 m
mol / hr, ethylene 13 kg / hr, hydrogen 401 /
hr, 4-methyl-1-pentene was continuously supplied at a rate of 30 kg / hr to carry out polymerization. The catalytic activity is 31,0
It corresponded to 00 g-copolymer / mmol-Ti. The results are shown in Tables 2 and 3.

The polymer obtained here had a considerably wide composition distribution, and was inferior in transparency, blocking resistance and low-temperature heat sealability of the film.

Example 2 <Preparation of catalyst> The component (A-1) obtained in Example 1 was used
Then, 250 mmol of ethanol was added to 50 mmol of the component (A), and the subsequent operation was carried out in exactly the same manner as in Example 1 to prepare the component (A-2). The composition was as follows.

[0067] <Polymerization> In the same manner as in Example 1, except that the component (A-2) obtained in this example was used instead of the component (A-2) obtained in Example 1, Ethylene and 4-methyl-1
-A continuous copolymerization of pentene was carried out.

The results are shown in Tables 2 and 3.

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

The molded film was improved in transparency, impact strength, and heat sealability in response to the decrease in density as compared with Example 1. The heat sealing initiation temperature is a value comparable to that of a commercially available ethylene-vinyl acetate copolymer film having a vinyl acetate content of 5% by weight.

Comparative Example 3 <Preparation of Catalyst> The hexane suspension of (A-1) obtained in Example 1 was used.
0 mmol was added, and the subsequent operation was carried out in exactly the same manner as in Example 1 to prepare the component (A-2). The composition was as follows.

[0072] <Polymerization> Using the component (A-2) obtained above, a continuous copolymer of ethylene and 4-methyl-1-pentene was produced under the conditions shown in Table 1. The results are shown in Tables 2 and 3. The resulting polymer has a wide composition distribution, the same density as the copolymer obtained in Example 2, but excellent film transparency, impact strength, and heat sealability. Not. On the other hand, the blocking resistance is remarkably insufficient.

Comparative Example 4 The hexane suspension of (A-1) obtained in Example 1 was used, and 1 mol of ethanol was added to 50 mmol of Ti atom in terms of Ti atom. The component (A-2) was prepared in exactly the same manner as in Example 1. The composition was as follows.

[0074] <Polymerization> Using the component (A-2) obtained above, continuous polymerization was started under the same conditions as in Example 2. Since no polymerization occurred, the organoaluminum compound catalyst component (B) shown in Table 1 was used. The feed rate of the slag was gradually increased. The speed is 11
At 0 mmol / hr, stable operation became possible. The catalytic activity is 12,100 g polymer / mmol-
Corresponding to Ti. Ml of the obtained polymer was 1.78, and density was 0.919 g / cm ³ . The amount of catalyst residue in the polymer was extremely large, so that the polymer foamed and could not be formed into a film.

Examples 3 to 8 <Polymerization> Using the component (A-2) obtained in Example 1, continuous copolymerization of ethylene and α-olefin was carried out under the polymerization conditions shown in Table 1. . The results are shown in Tables 2 and 3.

Example 9 Using the component (A-2) obtained in Example 1, ethylene homopolymerization was carried out under the polymerization conditions shown in Table 1. The catalytic activity corresponded to 19,400 g-PE / mmol-Ti. The resulting polyethylene had an MI of 9.70 and a density of 0.968 g / cm ³ . Mw / Mn was 2.1, and the molecular weight distribution was extremely narrow. Example 10 <Preparation of catalyst> Hexane suspension 41 of component (A-1) obtained in Example 1
(200 mmol in terms of Ti), and purified hexane 21 was added first. (At this time, the Ti concentration is 33 mmol.
/ L) Then, 2 mol of ethanol was added at room temperature,
The temperature was raised at ℃, and the reaction was carried out for 2 hours. After the reaction, the mixture was allowed to cool to room temperature. 21 of this suspension (66 mmol in terms of Ti)
Was transferred to another reactor. The rest were used in Examples 10 and 11.

Next, 200 mmol of triethylaluminum was gradually added dropwise at room temperature, and reacted at room temperature for 1.5 hours. After the reaction, the solid portion was repeatedly washed with purified hexane to obtain a hexane suspension.

The composition of the solid (A-2) was as follows.

[0079] <Polymerization> Using the component (A-2) obtained above, ethylene and butene-1 were continuously copolymerized under the conditions shown in Table 1. The results are shown in Tables 2 and 3.

Even at such a low density, the film could be easily formed without blocking the pellet. In response to the low density, the film was extremely transparent and had excellent heat sealability.

Examples 11 and 12 <Preparation of catalyst> Using 4 l (131 mmol in terms of Ti) of a hexane suspension after the ethanol reaction obtained in Example 10, 400 mmol of diethylaluminum chloride was added at room temperature. , And allowed to react at room temperature for 2 hours. After the reaction, 2
1 was taken out, and the solid portion was repeatedly washed with purified hexane to obtain a hexane suspension. This was used for the polymerization of Example 11. The composition of the catalyst solid was as follows.

[0082] The rest was used as is in the polymerization of Example 12.

<Polymerization> Using the titanium catalyst component obtained above, polymerization was carried out under the conditions shown in Table 1. The results are shown in Tables 2 and 3.

Examples 13 to 17 <Preparation of Catalyst> Using the hexane suspension of (A-1) obtained in Example 1, an organic compound containing active hydrogen bonded to oxygen shown in Table 4 was used. The treatment was performed under the conditions shown in FIG.

The composition of the obtained titanium catalyst component (A-2) is also shown.

<Polymerization> Using the titanium catalyst component obtained as described above, ethylene and 4-methyl-1-pentene were continuously copolymerized under the conditions shown in Table 1. The results are shown in Table 2. In each case, a copolymer having a very narrow molecular weight distribution and composition distribution was obtained.

Comparative Example 5 <Polymerization> Polymerization was carried out in the same manner as in Example 1 except that the component (A-2) obtained in Polymerization 1 was used and ethylaluminum dichloride was used as the organoaluminum catalyst component (B). Continuous polymerization was started, but the polymerization rate was extremely low and the pressure in the vessel began to rise, so that both (A-2) and (B) components were 3.
Steady operation became possible when the content was increased to 2 mmol / hr and the component (B) = 90 mmol / hr. At this time, the catalytic activity was extremely low at 4,100 g-polymer / mmol-Ti, and the pellet was colored. In addition, because of the large amount of catalyst residue, the film was not formed due to foaming.

Comparative Example 6 <Polymerization> Using the component (A-2) obtained in Example 10, continuous copolymerization of ethylene and butene-1 was carried out under the conditions shown in Table 1. In this case, although the obtained copolymer had the same density as in Example 12, the pellet was blocked and could not be formed into a film.

Example 18 <Preparation of catalyst> Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in dehydrated and purified n-decane 21, and stirred under stirring.
Molar 2-ethylhexanol was added and kept at 120 ° C for 3 hours. After the reaction, the solid disappeared and became a colorless and transparent solution. Thus, an n-decane solution of the magnesium chloride-2-ethylhexanol complex was obtained. This remained a colorless and transparent solution even at room temperature.

Next, 1.5 l of n-decane and 2.4 mol of titanium tetrachloride were put in another reactor in nitrogen and cooled to 0 ° C. Then, the magnesium chloride-2- obtained above.
800 mmol of the n-decane solution of the ethylhexanol complex in terms of Mg was added dropwise at 0 ° C. while stirring.
After the dropwise addition, the temperature was raised to 80 ° C., and the reaction was performed for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension. (Ti concentration 60 mmol / l) The composition of the solid part (A-1) thus obtained was as follows.

[0091] *) 2-Ethylhexoxy group Hydrolysis with water-acetone, extraction with acetone, and quantification as 2-ethylhexanol by gas chromatography. Next, 1 l of the n-decane suspension of (A-1) obtained above (Ti (Equivalent to 60 mmol) was added thereto, and 600 mmol of ethanol was added thereto at room temperature and reacted at 50 ° C. for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension.

The composition of the titanium catalyst component (A-2) thus obtained was as follows.

[0093] <Polymerization> Using the component (A-2) obtained above, continuous copolymerization of ethylene and 4-methyl-1-pentene was performed under the conditions shown in Table 1. The results are shown in Table 2.

Example 18-2 <Polymerization> In the same continuous polymerization reactor as in Example 1, 60 l / hr of dehydrated and purified hexane, 47 mmol / hr of ethyl aluminum sesquichloride, and the Ti catalyst obtained in Example 1 were used. The component (A-2) is continuously supplied at a rate of 2.8 mmol / hr in terms of Ti, and in a polymerization vessel, simultaneously, ethylene 12 kg / hr, 4-methyl-1-pentene 8 k
g / hr and hydrogen at a rate of 520 l / hr continuously, at a polymerization temperature of 180 ° C., a total pressure of 40 kg / cm ² , a residence time of 2 hours and a polymer concentration of 200 g / l.
Continuous polymerization of the ethylene / 4-methyl-1-pentene copolymer wax was performed. The catalytic activity corresponded to 7,100 g-copolymer / mmol-Ti. The viscosity average molecular weight of the obtained copolymer wax was 3,700 and the density was 0.912.

Next, the wax and the pigment (phthalocyanine blue) were mixed in a one-to-one correspondence, and the mixture was heated at 120 ° C. with a three-roll mill.
And kneaded. 1 g of this and 38 g of a commercially available high-pressure polyethylene were kneaded by a Brabender blast graph to obtain a sheet having a thickness of 100 microns . The pigment was very uniformly dispersed without any coarse particles. At the time of kneading the rolls, no wax was adhered to the rolls at all, and it was found that the pigment dispersant had extremely good performance.

Example 19 0.5 l (30 mmol in terms of Ti) of the n-decane suspension of (A-1) obtained in Example 18 was taken and mixed with 150 mmol of 2- Ethylhexanol was added, the temperature was raised to 80 ° C., and the reaction was carried out for 1 hour. After the reaction, 0 ° C
Then, 35 mmol of triethylaluminum was added dropwise, and the mixture was reacted at 0 ° C. for 2 hours. After the reaction,
The solid portion was repeatedly washed with n-decane to obtain an n-decane suspension. The composition of the titanium catalyst component (A-2) thus obtained was as follows.

[0097] <Polymerization> Using the titanium catalyst component (A-2) obtained above, Table 1
Were continuously copolymerized with ethylene and 4-methyl-1-pentene. The results are shown in Table 2.

Comparative Example 7 <Polymerization> In Example 18, (A-2) was used as the titanium catalyst component.
Instead of using (A-)
Polymerization was carried out in the same manner as in Example 18 except that 1) was used.
The results are shown in Table 2.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

[Table 5]

[0104]

[Table 6]

[0105]

[Table 7]

Comparative Example 8 <Polymerization> Using a continuous polymerization reactor having an internal volume of 200 l, dehydrated and purified hexane was added at 100 l / hr, diethyl aluminum chloride 7.6 mmol / hr, ethyl aluminum sesquichloride 15.1 mmol / hr, 5.4 mmol / h of hexane solution of ethanol converted to ethanol
r, the catalyst (A-1) obtained in Example 1 was continuously supplied at a rate of 0.54 mmol / hr in terms of Ti,
1.3 kg / hr of ethylene at the same time in the polymerization vessel,
4-methyl-1-pentene 19 kg / hr, hydrogen 45
1 / hr continuously, polymerization temperature 165 ° C,
The copolymerization was performed under the conditions that the total pressure was 30 kg / cm ² , the residence time was 1 hour, and the temperature of the copolymer with respect to the solvent hexane was 130 g / l. The catalytic activity corresponded to 24,100 g-copolymer / mmol-Ti.

The results of the obtained copolymer are shown in Table 6. Both the molecular weight distribution and the composition distribution were wider than those obtained in Example 1.

Next, the film characteristics of the copolymer were examined in the same manner as in Example 1. The results are shown in Table 7.
It is clear that all the film characteristics are inferior to the results of Example 1.

Example 21 <Preparation of catalyst> Under a nitrogen atmosphere, 1 mol of commercially available anhydrous magnesium chloride was suspended in 2 l of dehydrated and purified n-decane, and stirred under stirring.
Molar 2-ethylhexanol was added and kept at 120 ° C for 3 hours. After the reaction, the solid disappeared and became a colorless and transparent solution. Thus, an n-decane solution of the magnesium chloride-2-ethylhexanol complex was obtained. It remained a clear colorless solution even at room temperature.

Next, 1.5 l of n-decane and 4.8 mol of 2-ethylhexoxytitanium trichloride were placed in another reactor in nitrogen and cooled to 0 ° C. Then, the n-decane solution of the magnesium chloride-2-ethylhexanol complex obtained above was added dropwise at 0 ° C. with stirring at 800 mmol in terms of Mg. After the dropwise addition, the temperature was raised to 80 ° C., and the reaction was performed for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension. (Ti concentration 6
00 mmol / l) The solid part thus obtained (A
The composition of -1) was as follows.

[0111] Hydrolysis with water-acetone, extraction with acetone, and quantitative determination as 2-ethylhexanol by gas chromatography. Next, 1 l of the n-decane suspension of (A-1) obtained above (60 mmol in terms of Ti) ), 300 mmol of ethanol was added thereto at room temperature, and reacted at 50 ° C. for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension.

The composition of the titanium catalyst component (A-2) thus obtained was as follows.

[0113] <Polymerization> Using the component (A-2) obtained above, continuous copolymerization of ethylene and 4-methyl-1-pentene was performed under the conditions shown in Table 5. The results are shown in Table 6.

Example 22 Commercially available n-butylethylmagnesium (n-heptane solution, magnesium concentration 0.633 mol / l), 50 m
mol was placed in a flask having an internal volume of 200 ml, and 150 mmol of 2-ethylhexanol was gradually added thereto with stirring at room temperature. With foaming, the temperature rose to 50 ° C. After a state of high viscosity, it became a low temperature transparent solution. It was kept at 50 ° C. for 2 hours. Even if titanium tetrachloride in an amount equal to that of magnesium is added to a part of this solution, no reducing color is exhibited.
It was confirmed that it was replaced with an ethylhexoxy group.
Thus, the di-2-ethylhexoxymagnesium-2-ethylhexanol complex (hereinafter referred to as Mg (OEH)
_2- EHA).

In a separately prepared 400 ml flask, add n
-150 ml of decane and 150 mmol of titanium tetrachloride were added and cooled to 0 ° C. Next, while stirring the system, 25 mmol of the complex obtained above in terms of Mg atom was added dropwise over 30 minutes. The system was kept at 0 ° C. Immediately after the dropping, foaming occurred and a yellow suspension was obtained. After dropping, about 4 ℃
/ Min and kept at 80 ° C. for 1 hour. After completion of the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension (Ti concentration 60 mmol / l).

The solid part (A-1) thus obtained
Was as follows.

[0117] Hydrolysis with water-acetone, extraction with acetone, and quantitative determination as 2-ethylhexanol by gas chromatography. Next, 1 l of the n-decane suspension of (A-1) obtained above (60 mmol in terms of Ti) ), 300 mmol of ethanol was added thereto at room temperature, and reacted at 50 ° C. for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension.

The composition of the titanium catalyst component (A-2) thus obtained was as follows.

[0119] <Polymerization> Using the component (A-2) obtained above, continuous copolymerization of ethylene and 4-methyl-1-pentene was performed under the conditions shown in Table 5. The results are shown in Table 6.

Example 23 Commercially available n-butylethylmagnesium (n-heptane solution, magnesium concentration 0.633 mol / l), 50 m
mol was placed in a flask having an internal volume of 200 ml, and 300 mmol of propionic acid was gradually added thereto with stirring at room temperature. With foaming, the temperature rose to 40 ° C. After a state of high viscosity, it became a low temperature transparent solution. 70
C. for 2 hours. Even if titanium tetrachloride in an amount equal to that of magnesium was added to a part of this solution, no reduction color was exhibited, confirming that all the reducing alkyl groups were replaced with propionic acid groups. Thus, the magnesium di-propionate-propionate complex (hereinafter referred to as Mg
_(PA) abbreviated as 2 · 4PA) was obtained.

In a separately prepared 400 ml flask, add n
-150 ml of decane and 375 mmol of titanium tetrachloride were added and cooled to 0 ° C. Next, while stirring the system, 25 mmol of the complex obtained above in terms of Mg atom was added dropwise over 30 minutes. The system was kept at 0 ° C. Immediately after the dropping, foaming occurred and a yellow suspension was obtained. After dropping, about 4 ℃
/ Min and kept at 0 ° C. for 1 hour. After completion of the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension (Ti concentration 60 mmol / l).

The solid part (A-1) thus obtained
Was as follows.

[0123] Hydrolysis with water-acetone, extraction with acetone, and quantitative determination as propionic acid by gas chromatography. Next, 1 l of the n-decane suspension of (A-1) obtained above (60 mmol in terms of Ti) was obtained. Then, 300 mmol of ethanol was added thereto at room temperature, and reacted at 50 ° C. for 1 hour. After the reaction, the solid portion was repeatedly washed with n-decane to obtain an n-decane suspension.

The composition of the titanium catalyst component (A-2) thus obtained was as follows.

[0125] <Polymerization> Using the component (A-2) obtained above, continuous copolymerization of ethylene and 4-methyl-1-pentene was performed under the conditions shown in Table 5. The results are shown in Table 6.

[0126]

[0127]

[0128]

Example 24 <Preparation of catalyst> In a nitrogen-containing atmosphere, 210 mmol of anhydrous magnesium chloride and 21 mmol of titanium tetrachloride were placed in a stainless steel cylindrical container having an internal volume of 800 ml containing 100 stainless steel hard balls of 15 mmφ. Co-milling was performed by rotating at room temperature at 120 rpm for 25 hours. The obtained powder was repeatedly washed with purified hexane. The composition of the catalyst (A-1) thus obtained was as follows.

[0130] Next, (A-1) suspended in purified hexane (Ti concentration: 50 mmol) was placed in a glass flask having an internal volume of 400 ml.
/ L) was converted to Ti, and 10 mmol was taken. 100 mmol of ethanol was added at room temperature, and the temperature was raised to 50 ° C.
The reaction was performed for 5 hours. After the reaction, the solid portion was repeatedly washed with purified hexane. The catalyst (A-
The composition of 2) was as follows.

[0131]

<Polymerization> Purified cyclohexane 7 was placed in an autoclave having an internal volume of 2 liters.
50 ml and 250 ml of 4-methyl-1-pentene were added, and the temperature was raised to 130 ° C. in a closed nitrogen system. Next, 400 N-ml of hydrogen was inserted from the hydrogen tank, and then pressurized to 25 kg / cm ^{2 with} ethylene. Then, 0.2 mmol of diethylaluminum chloride and 0.4 mmol of ethylaluminum sesquichloride were obtained from the catalyst insertion port.
04 mmol was successively inserted to initiate polymerization. The polymerization was carried out for 1 hour while maintaining the temperature of the system at 165 ° C. Termination of the polymerization was carried out by adding a small amount of methanol to the system. The obtained copolymer was 46.3 g and 11600 g-PE
/ Mmol-Ti. The characteristic values are shown in the table.

Comparative Example 9 <Polymerization> Copolymerization of ethylene and 4-methyl-1-pentene was carried out in the same manner as in Example 24, except that (A-1) obtained in Example 24 was used as a catalyst. went. The obtained copolymer was 39.5 g, and 9870 g-PE / mmol-Ti
Corresponding to the polymerization activity of The characteristic values are shown in the table. Example 2
The product obtained in Example 4 was compared with that obtained in Comparative Example 9,
It can be seen that both the molecular weight distribution and the composition distribution are narrow.

[0134]

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for producing a catalyst according to the present invention.

Claims (1)

(57) [Claims] [1] A highly active titanium component (a-1) containing magnesium, titanium and halogen as essential components.
With an organic compound containing active hydrogen bonded to oxygen (a
-2) a component formed by further treatment, and the amount of the organic compound (a-2) contained in the component and the amount of the oxygen-containing group derived from the organic compound (a-2) (X ) And a titanium compound catalyst component having a molar ratio (X) :( Y) of 4 to 100: 1 with respect to the amount of titanium (Y), or a treated product of an organoaluminum compound thereof; a-1) is, in addition to the essential components,
Organic compound containing active hydrogen bonded to oxygen (a-
2) ′ and an oxygen-containing group derived from the organic compound (a-2) ′, and in this case, the amount (X) is the amount of the organic compound (a-2) contained in the component. And the amount (X ₁ ) of the oxygen-containing group derived from the organic compound (a-2) and the amount of the oxygen-containing group derived from the organic compound (a-2) ′ and the organic compound (a-2) ′ ( X ₂ ).