JP2003321582A - alpha-OLEFINIC POLYMER HAVING SPECIFIC MICROPHASE STRUCTURE AND COMPOSITION COMPRISING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an α-olefinic polymer and a polyolefinic resin composition exhibiting new and effective polymer properties by a new microphase separation structure. <P>SOLUTION: The α-olefinic polymer comprises a microphase structure composed of at least (A) a phase composed of the α-olefinic polymer composed of at least one or more kinds of repeating units derived from a 2-20C α-olefin and containing 51-100 mol% of one kind of repeating unit (a) in the one or more kinds of repeating units and (B) a phase composed of an α-olefinic polymer composed of at least one or more kinds of repeating units derived from the 2-20C α-olefin and containing 51-100 mol% of repeating units (b) which may be the same or different from the repeating units contained in the phase (A). The microstructure of the dispersed phase satisfies specific properties. The composition comprises the α-olefinic polymer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α-olefin polymer having a unique microphase structure, and a composition containing the α-olefin polymer.

[0002]

2. Description of the Related Art Polyolefin has excellent processability, chemical resistance, electrical properties, mechanical properties, etc.
It is processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. and is used for various purposes. recent years,
The physical properties of polyolefins are diversifying and becoming complex. For example, blending polyolefins with different properties such as blending crystalline polyolefins with excellent heat resistance and amorphous polyolefins with soft feel and excellent impact resistance. Then used. When blending polyolefins with different properties in this way, usually, a sea-island structure in which the dispersed phase is dispersed in the matrix phase, and generally the smaller the diameter of the dispersed phase, the better the respective properties of the polyolefin with different properties. Has been done. However, in a blend of polyolefins having different properties, it is difficult to make the dispersed phase fine due to the problem of poor compatibility, and it is difficult to achieve the performance expected by the blend.
Therefore, attempts have been made to reduce the diameter of the dispersed phase by blending polyolefins having different properties together with a compatibilizing agent such as an elastomer, but it is difficult to make the diameter of the dispersed phase as fine as 1 μm or less. Met.

On the other hand, in the case of a polymer having a non-polyolefin segment such as polystyrene (PS) or polymethylmethacrylate (PMMA), the diameter of the dispersed phase is on the order of nanometers, as a result of a study using a block copolymer synthesized by living polymerization. It is known that a unique microphase-separated structure such as a sea-island structure, a microphase structure in which the dispersed phase becomes a rod shape (cylinder shape), and a layered lamella structure in which the matrix phase and the dispersed phase cannot be distinguished appears. Even in polyolefins, if it is possible to form a peculiar microphase separation structure as seen in non-polyolefin systems, that is, the dispersed phase has a fine diameter on the order of nanometers, or the dispersed phase and the matrix phase are indistinguishable. It has been expected that if they are highly compatible with each other, the respective advantages of polyolefins having different properties can be made compatible.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of investigations based on such conventional techniques, the present inventors have found that an α-olefin-based polymer having a unique microphase separation, which has never been observed in polyolefin, has been obtained. The present invention has been completed by finding a combination and a composition containing it. That is, an object of the present invention is to provide a polyolefin resin composition capable of exhibiting new and effective polymer physical properties by a novel microphase-separated structure.

[0005]

The α-olefin polymer having a unique microphase structure and the composition containing the same according to the present invention will be specifically described below. The α-olefin polymer according to the present invention, and the composition containing the same have a microphase structure of at least (A) carbon atoms, which is observed by a transmission electron microscope after dyeing with ruthenic acid. The number of repeating units derived from an α-olefin of 2 to 20 is at least one or more, and one repeating unit (a) among the one or more repeating units is contained in a proportion of 51 to 100 mol%. And a phase composed of an α-olefin polymer having 2 to 20 carbon atoms (B).
At least one repeating unit derived from α-olefins of
Comprising at least one species, and the α-olefin polymer (A)
Contains a phase composed of an α-olefin polymer containing a repeating unit (b), which may be the same as or different from the repeating unit (a) contained therein, in a proportion of 51 to 100 mol%. And (1) (A) phase or (B)
Either one of the phases is a disperse phase and the maximum diameter (d ₁ ) when the disperse phase is approximated as an ellipse is _{1 to} 200 nm, or (2) the maximum diameter (d ₁ ) of the disperse phase domain Ratio (d ₁ / d ₂ ) of the maximum diameter to the maximum value (d ₂ ) of the orthogonal diameter
Is a rod-shaped dispersed phase of 20 or more, and the maximum value (d ₂ ) of the diameter orthogonal to the maximum diameter is within the range of 1 nm to 200 nm, or (3) (A) phase and ( It has a layered lamellar structure in which it is not possible to determine which of the B) phases is the dispersed phase, and the thickness of at least one of the (A) phase and the (B) phase is 1 nm to 200 n.
It is a microphase structure in the range of m.

The microphase structure of the section observed with a transmission electron microscope after dyeing with ruthenic acid is observed as follows, for example. The sample press-molded into small pieces of 0.5 mm square is dyed with ruthenic acid (RuO ₄ ). This is an ultra microtome equipped with a diamond knife (REICHERT ULTRA
CUT S, REICHERT FC S) is used to make an ultrathin section with a thickness of about 100 nm. Carbon is vapor-deposited on this ultrathin section and a transmission electron microscope (Hitachi H-8100; acceleration voltage 100) is used.
Observe at kV). At least five observation points are randomly selected and observed at a magnification of 10,000 times, 50,000 times, and 150,000 times. Only when it is confirmed that there is no microphase structure other than the above (1) to (3) in at least five observation fields to be observed, it is considered that the microphase structure is the feature of the present invention.

The approximation as the ellipse in (1) above is performed by using the software of Image-Pro Plus in the field of view observed at 10,000 to 150,000 times using a transmission electron microscope, and Axis-ma
By selecting jor, the disperse phase is approximated to an ellipse having the same area and equal first and second moments, and its major axis is set to the maximum diameter (d ₁ ). This maximum diameter (d ₁ ) is 1 to 200
nm, preferably 2-175 nm, more preferably 3
˜150 nm, more preferably 4 to 100 nm, particularly preferably 5 to 75 nm.
In the rod-shaped dispersed phase of (2) above, the length of the straight line which is the maximum length of the straight lines drawn inside the dispersed phase is defined as the maximum diameter (d ₁ ), and in the straight line orthogonal to the maximum diameter. The maximum length of the straight line is the maximum value of the diameter orthogonal to the maximum diameter (d
₂ ) In the present invention, the value (d ₁ / d ₂ ) obtained by dividing the maximum diameter (d ₁ ) by the maximum value (d ₂ ) of the diameters orthogonal to the maximum diameter is 2
It is 0 or more, preferably 25 or more, and more preferably 30 or more and 10,000 or less. The maximum value (d ₂ ) of the diameter orthogonal to the maximum diameter is 1 to 200 nm, preferably _{2 to} 175 n
m, more preferably 3 to 150 nm, more preferably 4 to 100 nm, and particularly preferably 5 to 75 nm.

In the layered lamella structure of (3), it is difficult to distinguish one of the (A) phase and the (B) phase as a dispersed phase, and the visual field observed at 150,000 times. By selecting Axis-major using image-Pro Plus software in the above, even if an attempt is made to approximate the disperse phase to an ellipse with the same area and equal first and second moments, the domain boundaries cannot be read and No particle recognition. For this reason, in the field of view observed at a magnification of 150,000, the boundaries of domains are written by the observer's hand at 30 or more positions, preferably 35 or more positions, more preferably 40 or more positions, and then approximated to the above ellipse, The maximum diameter that is the major axis is 1 to 200
nm, preferably 2-175 nm, more preferably 3
˜150 nm, more preferably 4 to 100 nm, particularly preferably 5 to 75 nm.
When observed at 10,000 times, the thickness of at least one of the layered (A) phase and (B) phase is 1 to 500 n.
m, preferably 2 to 300 nm, more preferably 3 to
It is preferably in the range of 150 nm, more preferably 4 to 100 nm, particularly preferably 5 to 75 nm. The present invention preferably has the microphase structure of (2) or (3) above, and more preferably the microphase structure of (3) above.

The above repeating units (a) and (b) are derived from an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin having 2 to 20 carbon atoms include linear or branched α-olefins and cyclic olefins. Specifically as the linear α-olefin, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
2 to 2 carbon atoms such as octadecene and 1-eicosene
0, preferably 2 to 10 can be mentioned. Specific examples of the branched α-olefin include, for example, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-
Ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1
-Hexene, 3-ethyl-1-hexene, etc., with 4 to 4 carbon atoms
20, preferably 5 to 10. As the cyclic olefin, cyclopentene, cycloheptene,
Norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane and the like having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms can be mentioned.

Among these, at least one of the repeating units (a) and (b) is ethylene, propylene, 1-butene, 1-
Α-selected from pentene, 1-hexene, 1-octene
It is preferably a repeating unit derived from an olefin, and both (a) and (b) are ethylene, propylene, 1-
A repeating unit derived from an α-olefin selected from butene, 1-pentene, 1-hexene and 1-octene is more preferable. Among them, it is particularly preferable that both (a) and (b) are repeating units derived from an α-olefin selected from ethylene, propylene and 1-butene, and in the case of propylene or butene, the repeating units are It is more preferable that the compound has stereoregularity, and it is more preferable that the repeating unit of propylene having isoregularity is contained. Incidentally, these polymers may contain a repeating unit obtained from a polymerizable monomer other than the above α-olefin, for example, a diene, or may form a repeating unit obtained from one kind of olefin, It may be formed from a repeating unit obtained from two or more kinds of olefins selected from the above-mentioned olefins having 2 to 20 carbon atoms.

The content ratio of (a) in the polymer is 51 to
100%, preferably 52-95%, more preferably 5
It is 3 to 90%, more preferably 54 to 85%. The content ratio of (b) in the polymer is 51 to 100%, preferably 60 to 100%, more preferably 70 to 100.
%, More preferably 75 to 100%, particularly preferably 8
It is 0 to 100%. (b) may be the same as or different from (a), but is preferably different.

The method for producing the α-olefin polymer having a unique microphase structure and the composition containing the same according to the present invention is not particularly limited, but at least (A1) α having 2 to 20 carbon atoms is used. -Comprising at least one repeating unit derived from an olefin, and selecting from 1 to 10 repeating units (a) of said one or more repeating units.
A functional group (G containing 0% by mole) containing a hetero atom.
_From 5 to 95 parts by weight of an α-olefin polymer containing 0.00001 to 30% by weight of (A) and (B1) at least one repeating unit derived from an α-olefin having 2 to 20 carbon atoms. And the repeating unit (b) which may be the same as or different from the repeating unit (a) contained in the α-olefin polymer (A1) is 51 to 100
In a proportion of mol%, and functional group (G _B) containing from 0.00001 to 30 wt% alpha-olefin polymer is contacted with a 5 to 95 parts by weight containing a hetero atom, containing a hetero atom it is preferably produced by reacting at least a portion of the functional group (G _B) containing a functional group (G _a) and hetero atoms.

The above α-olefin polymer (A
1) or at least one of the (B1), preferably contains 0.1 to 100 mole% to the above heteroatom containing functional groups at the molecular ends (G _A) or (G _B). Above α
- wherein the olefin polymer (A1) with the functional group (G _A) either contains said heteroatoms 0.1 mol% of the molecular ends of the (B1) or (G _B) respectively, the molecular ends An α-olefin polymer having a unique microphase structure according to the present invention, which comprises a linear polymer in which different functional groups are reacted to chemically bond different segments to each other, and a composition containing the same. May be manufactured or
- only one of the olefin polymer (A1) or (B1) comprises 0.1 to 100 mole% to the above heteroatom containing functional groups at the molecular ends (G _A) or (G _B), the other the contain the heteroatoms include functional groups at a site other than molecular end (G _a) or (G _B), different segments by reacting a functional group of the portion other than the functional group and the molecular ends of the molecular ends An α-olefin-based polymer having a unique microphase structure according to the present invention including a chemically bonded branched polymer, and a composition containing the same may be prepared.

[0014] In the present invention, only one of the above α- olefin polymer (A1) or (B1) is 0.1 to 100 mole% to the above heteroatom containing functional groups at the molecular ends (G _A ) or include (G _B), the other contain a functional group containing the above heteroatoms site other than molecular end (G _a) or (G _B), the molecular terminal functional groups and sites other than molecular end An α-olefin polymer having a unique microphase structure according to the present invention, which contains a branched polymer in which different segments are chemically bonded by reacting with a functional group, and a composition containing the same are produced. Is preferred.

[0015] Results of the reaction of the functional group and (G _A) and (G _B), it is preferable to produce the bond having a carbonyl group. Examples of the bond having a carbonyl group include an ester bond, an amide bond, an imide bond, a urethane bond, and a urea bond. These bonds may be present alone or in combination of two or more, and are preferably ester bonds and / or amide bonds. Functional group at the site other than molecular end include hetero atoms in the (G _A) or (G _B) to comprise α- olefin polymer (A1) or (B1), respectively, a functional group containing a hetero atom (G _A ) or (G _B) of 0.00001 to 30 wt%, preferably from 0.01 to 25 wt%, more preferably 0.05 to 20 wt%, more preferably 0.1 to 15
The content of the functional group-containing polyolefin (C) described later is preferably used as an example.

[0016] 0.1 to 100 mol% of the molecular ends, respectively, the functional group (G _A) or (G _B) to comprise α- olefin polymer containing hetero atoms (A1) or (B1) is preferably 1% to 100% of the molecular terminal functional group (G _B) containing a hetero atom, more preferably 10-100%, more preferably 20 to 95%, even more preferably 25
The content is preferably 90%, particularly preferably 30 to 85%, and examples thereof include the terminal-modified polyolefin (D) described later.

(C) Functional Group-Containing Polyolefin The functional group-containing polyolefin (C) has a functional group containing one or more heteroatoms at sites other than both terminals. Examples of the functional group containing a hetero atom include an amino group, a halogen atom, an isocyanate group, an aldehyde group, a hydroxyl group, a carboxyl group, an acid anhydride group, a silanol group, a sulfonic acid group and an epoxy group. Among the above functional groups, preferred functional groups are amino groups, halogen atoms, hydroxyl groups, carboxyl groups, acid anhydride groups, and epoxy groups, with carboxyl groups or acid anhydride groups being more preferred.
These functional groups may be provided alone or in combination of two or more.

These functional groups may be provided by any known method such as graft modification of polyolefin or copolymerization of α-olefin and polar monomer. As a preferred example, a method for obtaining a functional group-containing polyolefin (C) by graft-modifying a part or all of an unmodified polyolefin with an unsaturated carboxylic acid or a derivative thereof will be described below. The unmodified polyolefin can be produced by polymerizing or copolymerizing the olefin having 2 to 20 carbon atoms with the use of a conventionally known catalyst. Examples of conventionally known catalysts include magnesium-supported titanium catalyst systems and metallocene catalysts.

The magnesium-supported titanium catalyst system and the metallocene catalyst will be described below in order. Magnesium-supported titanium catalyst system As the magnesium-supported titanium catalyst system, a solid titanium catalyst component (I) essentially containing titanium, magnesium, and halogen, an organometallic compound catalyst component (II), and, if necessary, an electron donor. A catalyst system consisting of (III) is preferred. [(I) Solid titanium catalyst component] The solid titanium catalyst component (I) can be prepared by bringing the following magnesium compound, titanium compound and electron donor into contact with each other. (Magnesium compound) Examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability. Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, R is hydrogen, and the number of carbon atoms is 1
To 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different. X is halogen. Specific examples of the organomagnesium compound having such reducing ability include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium. Magnesium compound; alkyl magnesium halide such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride;
Examples thereof include alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, butyl magnesium hydride, magnesium hydride and the like. Other,
Metallic magnesium can also be used.

Specific examples of the magnesium compound having no reducing ability include magnesium chloride, magnesium bromide,
Magnesium halides such as magnesium iodide and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride; ants such as phenoxy magnesium chloride and methylphenoxy magnesium chloride Roxymagnesium halide; diethoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, di-n-octoxymagnesium,
Dialkoxy magnesium such as di-2-ethylhexoxy magnesium and methoxyethoxy magnesium; diaryloxy magnesium such as diphenoxy magnesium, di-methylphenoxy magnesium, and phenoxymethylphenoxy magnesium, magnesium laurate,
Examples thereof include magnesium carboxylates such as magnesium stearate.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is prepared from polysiloxane compound, halogen-containing silane compound, halogen-containing aluminum compound, ester, alcohol, halogen-containing compound. It may be contacted with a compound or a compound having an OH group or an active carbon-oxygen bond. Incidentally, the magnesium compound having a reducing ability and the magnesium compound having no reducing ability, aluminum, zinc, boron, beryllium, sodium, complex compounds with other metals such as potassium, may form a double compound, Alternatively, it may be a mixture with another metal compound. Furthermore, the magnesium compound may be a single compound, or two or more of the above compounds may be combined.

Among the above magnesium compounds,
When the magnesium compound is a solid, it can be brought into a liquid state by using an electron donor (d-1). As the electron donor (d-1), alcohols, phenols, ketones, aldehydes, ethers, amines,
Pyridines, metal acid esters, and the like, specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl. Alcohols having 1 to 18 carbon atoms such as alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; Halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; 2-propoxyethanol , 2-butoxyethanol,
2-ethoxypropanol, 3-ethoxypropanol, 1-
Alkoxy alcohols such as methoxybutanol, 2-methoxybutanol, and 2-ethoxybutanol; carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol Number 6 to 20 phenols; 3 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone
~ 15 ketones; acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like having 2 to 1 carbon atoms
Aldehydes of 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine; pyridine, methylpyridine, ethyl Pyridines such as pyridine and dimethylpyridine; metal acid esters such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium and tetraethoxy zirconium Is mentioned. These may be used alone or in combination of two or more.

Of these, alcohols, alkoxy alcohols, and metal acid esters are particularly preferably used. Electron donor of solid magnesium compound (d-
The solubilization reaction according to 1) is generally performed by bringing a solid magnesium compound into contact with an electron donor (d-1) and heating the mixture as necessary. At this time, the contact temperature is 0 to 200.
℃, preferably 20 ~ 180 ℃, more preferably 50 ~
It is 150 ° C.

In the above solubilization reaction, a hydrocarbon solvent or the like may coexist. Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, Alicyclic hydrocarbons such as cyclohexene, aromatic hydrocarbons such as benzene, toluene, xylene, dichloroethane, dichloropropane, trichloroethylene,
Halogenated hydrocarbons such as chlorobenzene and 2,4-dichlorotoluene are used.

As the magnesium compound used for the preparation of the solid titanium catalyst component (I), many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component (I). Preferably, it is present in the form of a halogen-containing magnesium compound, and therefore, when a halogen-free magnesium compound is used, it is preferable to react with the halogen-containing compound during the preparation. Among these, it is preferable to include a magnesium compound having no reducing ability, particularly preferably a halogen-containing magnesium compound,
Further, among these, it is preferable to contain magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride.

(Titanium Compound) As the titanium compound,
A tetravalent titanium compound is preferably used. like this
As the tetravalent titanium compound, a compound represented by the following formula
Can be mentioned. Ti (OR)_gX_4-g In the formula, R is a hydrocarbon group and X is a halogen atom.
Therefore, 0 ≦ g ≦ 4. Specific examples of such compounds
Has TiCl_Four, TiBr_Four, TiI_Four Such as tetrahalogen
Titanium oxide; Ti (OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃,
Ti (O n-C_FourH₉) Cl₃, Ti (OC₂H_Five) Br₃, Ti (O-is
o-C_FourH₉) Br₃Trihalogenated alkoxy titanium such as
Ti (OCH₃)₂Cl₂, Ti (OC₂H_Five)₂Cl₂Ti (O-n
-C_FourH₉)₂Cl₂, Ti (OC₂H_Five)₂Br₂Such as dihalogen
Dialkoxy titanium; Ti (OCH₃)₃Cl, Ti (OC₂
H_Five)₃Cl, Ti (O-n-C_FourH₉)₃Cl, Ti (OC₂H_Five)₃Br
Trialkoxy titanium monohalogenated compounds such as; Ti (OC
H₃)_Four, Ti (OC₂H_Five)_Four, Ti (O-n-C_FourH₉)_Four, Ti (O-i
so-C_FourH₉) _Four, Ti (O-2-ethylhexyl)_FourSuch as Tet
Examples include laalkoxy titanium. Among these
Titanium tetrahalide is preferred, especially titanium tetrachloride
Is preferred. These titanium compounds may be used alone.
Alternatively, two or more kinds may be used in combination. Also titanium
The compound may be used with an aromatic hydrocarbon, or
Diluted with hydrocarbon or halogenated hydrocarbon before use
Good.

((D-2) Electron Donor) When preparing the solid titanium catalyst component (I), it is preferable to use the electron donor (d-2), which is used as the electron donor (d-2). The following acid halides, acid amides, nitriles, acid anhydrides, organic acid esters, polyethers and the like are used. Specifically, acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N Acid amides such as N-dimethylamide; nitriles such as acetonitrile, benzonitrile, trinitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride; methyl formate, methyl acetate, ethyl 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, benzoate Propylate, butyl benzoate, octyl benzoate Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone. , Coumarin, phthalide, ethyl carbonate, and other organic acid esters having 2 to 18 carbon atoms.

As the organic acid esters, polyvalent carboxylic acid esters having a skeleton represented by the following general formula can be mentioned as preferred examples.

[0029]

[Chemical 1] In the formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R
⁵ , R ⁶ is hydrogen or a substituted or unsubstituted hydrocarbon group, R ³ , R ⁴ is hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. is there. R ³ and R ⁴ may be connected to each other to form a ring structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent is N,
Includes different atoms such as O and S, for example, C-O-C, CO
_{OR, COOH, OH, SO 3} H, -C-N-C-, N
It has a group such as H ₂ .

Specific examples of such polyvalent carboxylic acid ester include aliphatic polycarboxylic acid ester, alicyclic polycarboxylic acid ester, aromatic polycarboxylic acid ester and heterocyclic polycarboxylic acid ester. Can be mentioned. Preferred specific examples of the polycarboxylic acid ester having a skeleton represented by the above general formula include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diaryl methyl succinate, diisobutyl α-methyl glutarate, and β-methyl glutarate. Diisopropyl, diisobutyl methylmalonate, dibutyl ethylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, dibutyl isopropylmalonate, dibutyl butylmalonate, dibutylphenylmalonate, diethyldiethylmalonate, dibutyldimalonate, dibutylmalonate Diethyl, n-butyl maleate, dibutyl methyl maleate, dibutyl butyl maleate, di-2-ethylhexyl fumarate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, tetrahydro Diisopropyl Tal, diethyl phthalate, monoethyl phthalate, dipropyl phthalate, diisobutyl phthalate, diisopropyl phthalate, ethyl isobutyl phthalate, di
n-butyl, di n-heptyl phthalate, di n-phthalate
Octyl, di-2-ethylhexyl phthalate, diphthalate
(2-methylpentyl), phthalic acid di (3-methylpentyl), phthalic acid di (4-methylpentyl), phthalic acid di (2,
3-dimethylbutyl), di (3-methylhexyl) phthalate,
Di (4-methylhexyl) phthalate, Di (5-methylhexyl) phthalate, Di (3-ethylpentyl) phthalate, Di (3,4-dimethylpentyl) phthalate, Di (2,4-phthalate) Dimethylpentyl), di (2-methylhexyl) phthalate, di (2-methyloctyl) phthalate, didecyl phthalate, diphenyl phthalate, mixtures of these phthalic acid diesters, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, tri Examples thereof include triethyl melitate, tributyl trimellitate, dibutyl 3,4-furandicarboxylate, diethyl adipate, dibutyl adipate, dioctyl sebacate, and dibutyl sebacate. Of these, phthalic acid diesters are preferably used.

Further, examples of the electron donor include compounds having two or more ether bonds existing via a plurality of atoms (hereinafter sometimes referred to as "polyether"). Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur or a compound in which two or more kinds of atoms are present between ether bonds. Of these, a compound having a relatively bulky substituent bonded to an atom between ether bonds and having a plurality of carbon atoms in the atoms existing between two or more ether bonds is preferable, for example, represented by the following general formula. Preferred are polyethers.

[0032]

[Chemical 2] In the above formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are substitutions having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. A group, and any R ^{1 to} R ²⁶ , preferably R ¹
~ R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon.

Specific examples of such a polyether compound include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane and 2-butyl-1,3-dimethoxy. Propane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-
1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3
-Dimethoxypropane, 2- (2-cyclohexylethyl)-
1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3
-Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2 -(1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl -1,3-dimethoxypropane, 2,2-
Dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,
3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-
Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,
2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2
-Dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3 -Dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-s-butyl-1,3-
Dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-Dineopentyl-1,3-dimethoxypropane, 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane, 2- Phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1 , 4-diethoxybutane,
2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-
1,4-diethoxybutane, 2,2-bis (p-methylphenyl)
-1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl -1,5-
Dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-
Diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3 -Diisoamyloxypropane, 1,3-diisoneopentyloxyethane,
1,3-Dineopentyloxypropane, 2,2-Tetramethylene
-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8 -Dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,3
0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6
-Diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,
2,1] heptane, 1,1-dimethoxymethylcyclopentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl- 2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2 -Isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-
Examples thereof include diethoxycyclohexane and 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane.

As the polyether, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis ( (Methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl)
Silane, i-propyl-t-butylbis (methoxymethyl)
Silane etc. can be mentioned. Among these,
2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,
2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane and the like are preferably used.

As the electron donor (d-2), organic acid esters and polyethers are preferable, and aromatic diesters and polyethers such as phthalic acid diesters are more preferably used. 2 electron donors such as
It is also possible to use together more than one species. Further, the electron donor as exemplified above may be finally contained in the solid titanium catalyst component (I). Therefore, when preparing the solid titanium catalyst component (I), it is not always necessary to use the compounds themselves exemplified above, and these compounds may be used in the process of preparing the solid titanium catalyst component (I). Other compounds that may be generated may be used. Also in this case, another compound may be used so that two or more kinds of electron donors (d-2) are produced.

(Preparation of Solid Titanium Catalyst Component (I)) The method for preparing the solid titanium catalyst component (I) from the above compound is not particularly limited, but for example, the following method may be used. Can be mentioned. In the following method, the same organometallic compound (II) as described below is used as the organometallic compound. (1) A magnesium compound in a liquid state consisting of a magnesium compound, the electron donor (d-1) and a hydrocarbon solvent is optionally contacted with an organometallic compound to precipitate a solid, or to precipitate the solid. While the solid component obtained by the catalytic reaction with the liquid titanium compound, the aromatic hydrocarbon, the liquid titanium compound and the electron donor (d-
2) Contact with at least once. It is preferable that the contact of the solid component with the aromatic hydrocarbon or the liquid titanium compound is performed plural times. (2) After contacting the contact product of the inorganic carrier or the organic carrier with the liquid organomagnesium compound with the organometallic compound, if necessary, to precipitate a solid, or while precipitating, to react with the liquid titanium compound. The obtained solid component, the aromatic hydrocarbon, the titanium compound in the liquid state and the electron donor (d-2) are subjected to contact reaction at least once.
At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound. It is preferable that the contact of the solid component with the aromatic hydrocarbon or the liquid titanium compound is performed plural times.

[(II) Organometallic Compound Catalyst Component] The organometallic compound catalyst component (II) preferably contains a metal selected from Group 13 of the periodic table, and among them, organoaluminum compounds, organoboron compounds, Group 1 Preferable examples include complex alkyl compounds of an element and aluminum or boron. As the organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. During R ^a _n AlX _3-n above formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n represents 1 to 3. R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri 2-.
Trialkylaluminums such as ethylhexylaluminum; Trialkenylaluminums such as triisoprenylaluminum; Dimethylaluminum chloride,
Diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride,
Dialkyl aluminum halides such as dimethyl aluminum bromide; methyl aluminum sesquichloride,
Alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl Alkyl aluminum hydrides such as aluminum hydride, diisobutyl aluminum hydride and ethyl aluminum dihydride can be mentioned.

As the organoaluminum compound, a compound represented by the following formula can also be used. R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is —OR ^b.
Group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
iR ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, n is 1 to 2
Is. R ^b , R ^c , R ^d, and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like, and R ^e is hydrogen, a methyl group,
It is an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ^f and R ^g are a methyl group, an ethyl group or the like.

Specific examples of such an organoaluminum compound include the following compounds. (1) compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, and (2) R ^a _n Al (OSiR ^c ) _3- a compound represented by _n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc., (3) R ^a _n Al (O
A compound represented by AlR ^d ₂ ) _3-n , for example, Et ₂ AlOAlE
t ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc., (4) R ^a _n A
a compound represented by l (NR ^e ₂ ) _3-n , such as Me ₂ AlNE
t ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (Me ₃
Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _2, etc., (5) R ^a _n Al
A compound represented by (SiR ^f ₃ ) _3-n , for example, (iso-Bu) ₂ A
Compounds represented by (6) R ^a _n Al [N (R ^g ) -Al R ^h ₂ ] _3-n , such as lSiMe ₃ , such as Et ₂ AlN (Me) -AlEt ₂ , (i
so-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like. Further, a compound similar to this, for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. More specifically, (C ₂ H ₅ ) ₂ AlO
_{Al (C 2 H 5) 2} , (C 4 H 9) 2 AlOAl (C 4 H 9) 2, (C 2 H 5)
Such as _{2 AlN (C 2 H 5)} Al (C 2 H 5) 2, can be exemplified further aluminoxanes such as methylaluminoxane (organoaluminum oxy compound). Further, an organoaluminum compound represented by the following formula can also be used. R ^a AlX
Y (R ^a , X, Y are the same as above)

Examples of the organic boron compound include triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron. , Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl)
Boron, texylborane, dicyclohexylborane, diciamylborane, diisopinocamphenylborane, 9-borabicyclo [3.3.1] nonane, catecholborane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, borane- Examples include methyl sulfide complex. Further, an ionic compound may be used as the organic boron compound. Such compounds include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl). Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, N, N-dimethylanilinium tetra ( Phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, bis [ Bird (n-
Examples thereof include butyl) ammonium] nonaborate and bis [tri (n-butyl) ammonium] decaborate.

Examples of the complex alkylated product of the Group 1 element and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 15 carbon atoms.
Is a hydrocarbon group. ) Specifically, as such a compound, LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like. Examples of the organic boron compound and the complex alkylated product of the group 1 element and boron include compounds having a structure in which the aluminum of the complexed alkylated compound of the group 1 element and aluminum is replaced with boron.

[(III) Electron Donor] Electron Donor (III)
As the above, the compounds shown as the electron donor (d-2) used in the preparation of the solid titanium catalyst component (I) described above can be used, and further, the organosilicon compound represented by the following general formula: Can be used. R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organic silicon compound represented by the general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
tert-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxy Silane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, n-butyltriethoxysilane,
iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-
Norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyl Triacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) Dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclope Chill silane,
Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, etc.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, tert-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane Silane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. are preferably used It is.

Further, as the electron donor (III), 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', Substituted methylenediamines such as N'-tetraethylmethylenediamine, 1,3-
Nitrogen-containing electron donors such as dibenzylimidazolidine, substituted imidazolidines such as 1,3-dibenzyl-2-phenylimidazolidine, triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butyl Phosphite-containing electron donors such as phosphites such as phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite, 2,6-substituted tetrahydropyrans, 2,5-substituted tetrahydropyrans It is also possible to use an oxygen-containing electron donor such as Two or more of these electron donors (III) can be used in combination.

Metallocene Catalyst Next, the metallocene catalyst will be described. The metallocene catalyst used in the production of the unmodified polyolefin is not limited, and examples thereof include metallocene catalysts known per se. Examples of known metallocene catalysts include compounds of transition metals such as titanium, vanadium, chromium, zirconium, and hafnium, and they can be used in liquid form or solid form under the use conditions. Further, these do not have to be a single compound, may be supported on other compounds, may be a homogeneous mixture with other compounds, further complex compounds with other compounds and complex compounds. It may be.

Among the metallocene catalysts known per se,
It is preferable to use a metallocene compound having a chiral structure having C2 symmetry, C1 symmetry, or Cs symmetry.
As the metallocene compound having a C2 symmetry and a chiral structure, rac-ethylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilyl-
Bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilyl-bis [1- (4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis [1- (2-methyl -4-Phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis {1- [2-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1- [2
-Methyl-4- (2-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1- [2-methyl-4-
(1-anthryl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1- [2-methyl-4- (9-anthryl) indenyl]} zirconium dichloride, rac
-Dimethylsilyl-bis {1- [2-methyl-4- (9-phenanthryl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1- [2-methyl-4- (o-chlorophenyl) indenyl]} Zirconium dichloride, rac-dimethylsilyl-bis {1- [2-methyl-4- (pentafluorophenyl) indenyl]} zirconium dichloride, rac-
Dimethylsilyl-bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-
Bis {1- [2-ethyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1-
[2-Ethyl-4- (9-phenanthryl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis [1- (2-
n-Propyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilyl-bis {1- [2-n-propyl-
4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl-bis {1- [2-n-propyl-4- (9
-Phenanthryl) indenyl]} zirconium dichloride and the like. Among these compounds, rac-dimethylsilyl-bis {1- [2-ethyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl
-Bis {1- [2-ethyl-4- (9-phenanthryl) indenyl]} zirconium dichloride, rac-dimethylsilyl-
Bis {1- [2-n-propyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilyl-
It is more preferable to use a metallocene compound having a bulky substituent such as bis {1- [2-n-propyl-4- (9-phenanthryl) indenyl]} zirconium dichloride.

Examples of the metallocene compound having a C1 symmetry and a chiral structure include ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride and ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilyl (9-fluorenyl) (3-t-butylcyclopentadienyl) zirconium dichloride, diphenylsilyl (9- Fluorenyl) (3-t-butylcyclopentadienyl) zirconium dichloride and the like.

As the metallocene compound having a chiral structure having Cs symmetry, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1, 2-ethanediylzirconium dichloride, (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride,
(Ethylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride,
(Ethylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (third
Tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl ( Examples thereof include tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride and (phenylphosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl. The above metallocene compounds may be used alone or in combination of two or more, and may be used in combination with the solid titanium catalyst component (I). The above metallocene compound is used in combination with the above-mentioned organometallic catalyst component (II).

An example of the metallocene catalyst will be described below. The metallocene catalyst is, for example, a transition metal compound of Group 4 of the periodic table (hereinafter sometimes referred to as “metallocene compound (Z1)”) containing a ligand having a (Z1) cyclopentadienyl skeleton, and ( Z2) Organoaluminum oxy compound and, if necessary, (Z3) A particulate carrier. Hereinafter, (Z1), (Z2) and (Z
3) will be described in detail in this order.

[(Z1) Metallocene Compound] The metallocene compound (Z1) is represented by the following formula (1). ML _x (1) In the formula, M is a transition metal atom of Group 4 of the periodic table, specifically zirconium, titanium or hafnium. L
Is a ligand that coordinates to a transition metal atom, and at least 1
L is a ligand containing a ligand having a cyclopentadienyl skeleton, and Ls other than the ligand containing a ligand having a cyclopentadienyl skeleton are carbonized with 1 to 12 carbon atoms. A hydrogen group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a SO ₃ R group (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen). A halogen atom or a hydrogen atom, x
Is a number that satisfies the valence of the transition metal atom.

Examples of the ligand containing a ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadiene group Alkyl-substituted cyclopentadienyl group such as enyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group or indenyl group, 4,5,6,7-tetrahydroindenyl group,
Examples thereof include a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. When the compound represented by the general formula (1) contains two or more groups having a cyclopentadienyl skeleton,
Groups having two cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, diphenylsilylene groups, and methylphenylsilylene groups. May be bonded via a substituted silylene group of

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, Examples include isopropyl group and butyl group, examples of cycloalkyl group include cyclopentyl group and cyclohexyl group, examples of aryl group include phenyl group and tolyl group, and examples of aralkyl group include benzyl group and neophyll group. Examples include groups. Further, examples of the alkoxy group include a methoxy group, ethoxy group and butoxy group, examples of the aryloxy group include a phenoxy group and the like, and examples of the halogen include fluorine, chlorine, bromine and iodine. As the ligand represented by SO ₃ R, p-
A toluene sulfonate group, a methane sulfonate group, a trifluoro methane sulfonate group etc. are illustrated.

The metallocene compound (Z1) containing such a ligand having a cyclopentadienyl skeleton is represented by the following formula (2) when the valence of the transition metal atom is 4, for example. Be done. R ¹ _a R ² _b R ³ _c R ⁴ _d M (2) In the formula, M is the same transition metal atom as M in the general formula (1), and R ¹ is a group having a cyclopentadienyl skeleton. (Ligand), R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, It is a SO ₃ R group, a halogen atom or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. In the above formula (2), R ^1, R ^2, metallocene compounds at least two of R ³ and R ⁴ for example R ¹ and R ² is a group (ligand) having a cyclopentadienyl skeleton is preferably used To be

When the metallocene compound has two or more groups having a cyclopentadienyl skeleton, two of these groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, isopropylidene and diphenylmethylene. Substituted alkylene groups such as, silylene groups or dimethylsilylene, diphenylsilylene,
It may be bonded via a substituted silylene group such as a methylphenylsilylene group. R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO
₃ R, a halogen atom or a hydrogen atom.

Specific examples of the metallocene compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis ( Indenyl) methyl zirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylene Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-full Orenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclope Tadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dibromide, bis (cyclo) Pentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, etc.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, iso-, sec-, tert.
-Including isomers such as. As the metallocene compound (Z1), a compound in which zirconium in the above zirconium compound is replaced with titanium or hafnium can be used. These compounds may be used alone or in combination of two or more. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. As the metallocene compound (Z1), a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used.

[(Z2) Organoaluminum Oxy Compound] As the (Z2) organoaluminum oxy compound,
Specifically, conventionally known aluminoxanes and JP-A-2-
The benzene insoluble aluminum oxy compound as disclosed in Japanese Patent No. 276807 can be used. Such a conventionally known aluminoxane is described in (Z
4) It can be produced from an organoaluminum compound by the following method, for example. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. In a hydrocarbon medium in which
A method in which an organoaluminum compound such as trialkylaluminum is added and reacted to recover a hydrocarbon solution. (2) A method in which water (water, ice or water vapor) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to collect it as a solution of the above medium. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene. After removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation,
It may be redissolved in a solvent. The organoaluminum oxy compound (Z2) may contain a small amount of metal components other than aluminum.

[(Z3) Particulate carrier] If necessary
Specific examples of the particulate carrier (Z3) that can be used include SiO₂,
Al₂O ₃, B₂O₃, MgO, ZrO₂, CaO, TiO₂, Zn
O, Zn₂O, SnO₂, BaO, ThO and other inorganic carriers;
Polyethylene, polypropylene, poly-1-butene, poly 4-
Methyl-1-pentene, styrene-divinylbenzene copolymer
Resins (organic carriers) such as coalesced can be used. This
Of these, SiO₂ Is preferred. These are two or more
It can also be used in combination.

[Preparation of Metallocene Catalyst] When the metallocene catalyst is a solid metallocene catalyst comprising a metallocene compound (Z1), an organoaluminum oxy compound (Z2) and a particulate carrier (Z3), the solid metallocene catalyst is used. The metallocene catalyst is formed by supporting the metallocene compound (Z1) and the organoaluminumoxy compound (Z2) as described above on the particulate carrier (Z3) by a conventionally known method. The solid metallocene catalyst is a metallocene compound (Z1) and an organoaluminum oxy compound (Z
In addition to 2), the following organoaluminum compound (Z4) may be supported on a particulate carrier (Z3) to form the same. In preparing the solid metallocene catalyst, the metallocene compound (Z1) (transition metal atom conversion) is usually 0.001 to 1.0 mmol, preferably 0.01 to 0.5, per 1 g of the particulate support (Z3). The amount of the organoaluminum oxy compound (Z2) is usually 0.1-10.
It is used in an amount of 0 mmol, preferably 0.5 to 20 mmol. The solid metallocene catalyst usually has a particle size of 1 to 3
The thickness is 00 μm, preferably 10 to 100 μm.

The solid metallocene catalyst may contain other components useful for olefin polymerization such as an electron donor and a reaction aid, if necessary, in addition to the above catalyst components. The solid metallocene catalyst used in the present invention may have an olefin preliminarily polymerized with the above solid metallocene catalyst. When the olefin is polymerized using the above metallocene catalyst, the following organoaluminum compound (Z4) can be used together with the metallocene catalyst.

[(Z4) Organoaluminum Compound]
Specific examples of the (Z4) organoaluminum compound used as the (Z4) organoaluminum compound and also in the production of the solution of the above (Z2) organoaluminum oxy compound include trimethylaluminum and triethyl. Aluminum, tripropyl aluminum, triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec
-Trialkylaluminums such as butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tricyclohexylaluminum, tricyclooctylaluminum;
Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; diethyl Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide. Of these, trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable.

Also, as the organoaluminum compound (Z4), isoprenylaluminum represented by the following general formula can be used. _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) These are two or more in combination It may be. The organoaluminum compound (Z4) may contain a small amount of metal components other than aluminum. When the organoaluminum compound (Z4) is loaded on the particulate support (Z3) together with the metallocene compound (Z1) and the organoaluminum oxy compound (Z2), it is used per 1 mol of the solid metallocene catalyst (transition metal atom conversion). , Usually 1
It is used in an amount of 300 mol, preferably 2-200 mol. In addition, conventionally known chlorine-containing vanadium-based catalysts and postmetallocene catalysts can be preferably used instead of the above catalysts.

Production of Unmodified Polyolefin In the present invention, an unmodified polyolefin is produced by polymerizing or copolymerizing the olefin having 2 to 20 carbon atoms in the presence of the above catalyst. 2 to 20 carbon atoms
As the olefins, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1
-Butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like are preferably used. These monomers may be used alone or in combination of two or more, and may be copolymerized with a polymerizable monomer other than olefin such as diene. When these monomers are used alone, ethylene or propylene is particularly preferable. When two or more of these monomers are used in combination, a combination of ethylene and propylene, ethylene and butene, ethylene and octene, ethylene and propylene and butene, and ethylene and propylene and diene are particularly preferable.

The olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. As the polymerization form, it is preferable to adopt a suspension polymerization reaction form. As the reaction solvent at this time, an inert hydrocarbon solvent can be used, or an olefin which is liquid at the reaction temperature can be used. Specific examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or a combination thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon. Examples of liquid olefins at the reaction temperature include propylene and 1-
Butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like can be mentioned. Of these, propylene is preferably used for propylene polymerization.

When an unmodified polyolefin is produced using a magnesium-supported titanium catalyst system as a catalyst,
The solid titanium catalyst component (I) or its prepolymerization catalyst is converted into titanium atoms per liter of polymerization volume,
Usually about 0.001 to 100 mmol, preferably about 0.001.
Used in an amount of 005 to 20 mmol. In the organometallic compound catalyst component (II), the metal atom in the catalyst component (II) is usually about 1 to 2000 mol, based on 1 mol of the titanium atom in the solid titanium catalyst component (I) in the polymerization system, It is preferably used in an amount of about 2 to 500 mol. The electron donor (III) is usually 0.001 mol to 10 mol, based on 1 mol of the metal atom of the organometallic compound catalyst component (II),
It is preferably used in an amount of 0.01 mol to 5 mol. In the polymerization step, the hydrogen concentration is usually 0 to 0.25 mol, preferably 0 to 0.20 mol, and more preferably 0 to 0.15 mol per 1 mol of the monomer. When using a magnesium-supported titanium catalyst system, the polymerization temperature is usually about 20.
To 300 ° C, preferably about 50 to 150 ° C, and the polymerization pressure is 0.01 to 10 MPa, preferably 0.1.
It is in the range of 05 to 5 MPa.

When an unmodified polyolefin is produced by using a metallocene catalyst as a catalyst, the concentration of the metallocene compound (Z1) in the polymerization system is usually 0.00005 to 0.1 mmol per liter of the polymerization volume, It is preferably used in an amount of 0.0001 to 0.05 mmol. The organoaluminum oxy compound (Z2) has a molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (Z1) of 5 to 100.
It is used in an amount of 0, preferably 10 to 400. When the organoaluminum compound (bZ2) is used, the amount is usually about 1 to 300 mol, preferably about 2 to 200 mol, based on 1 mol of the transition metal atom in the metallocene compound (Z1). Used. The polymerization temperature when using a metallocene catalyst is -20 to 150.
℃, preferably 0 to 120 ℃, more preferably 0 to 1
The temperature is in the range of 00 ° C., the polymerization pressure is more than 0 and 8 MPa,
The range is preferably more than 0 and 5 MPa.

Olefin polymerization is carried out in a batch system, a semi-continuous system,
It can be carried out by any of continuous methods. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions. In the olefin polymerization, an olefin homopolymer may be produced, or a random copolymer may be produced from two or more kinds of olefins.

As an example of the method for producing the modified functional group-containing polyolefin (C) of the unmodified polyolefin, a part or all of the unmodified polyolefin as described above is grafted with a monomer selected from unsaturated carboxylic acids or derivatives thereof. Examples include graft modification. Specific examples of the unsaturated carboxylic acid or its derivative used at this time include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^TM (endocis-bicyclo [ 2,2,1] hept-5-ene-2,3-dicarboxylic acid) or an unsaturated carboxylic acid or a derivative thereof such as an acid halide, an amide, an imide, an anhydride or an ester is used. For example, maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like are used. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM , hymic acid or acid anhydrides thereof are particularly preferably used. In order to produce a functional group-containing polyolefin (C) by graft-copolymerizing a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof with an unmodified polyolefin, various conventionally known methods may be adopted. it can.

For example, a method of melting an unmodified polyolefin and adding a graft monomer to carry out graft copolymerization,
There is a method in which unmodified polyolefin is dissolved in a solvent and a graft monomer is added to carry out graft copolymerization. In either case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the above-mentioned graft monomer. Graft copolymerization is usually performed at a temperature of 60 to 350 ° C. The use ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the unmodified polyolefin.

Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-
2,5-di (peroxide benzoate) hexyne-3,1,4-
Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexine-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-
Butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert
-Butyl perpivalate, cumyl perpivalate and t
ert-Butyl perdiethyl acetate and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate are used. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,
5-Dimethyl-2,5-di (tert-butylperoxy) hexyne
Dialkyl peroxides such as -3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

(D) Terminal-Modified Polyolefin The terminal-modified polyolefin (D) has an olefin composition different from that of the functional group-containing polyolefin (C), and has amino groups, halogen atoms, isocyanate groups, aldehyde groups, hydroxyl groups, and carboxyl groups only at the terminals. , Acid anhydride groups, silanol groups, sulfonic acid groups, epoxy groups and the like. These are preferably present only at one end.
Of these groups, a group capable of reacting with a carboxyl group or an acid anhydride group is preferable. Examples of the group capable of reacting with the carboxyl group or the acid anhydride group include a hydroxyl group, an alkoxy group, an amino group, an imino group and a halogen atom. Of these, a hydroxyl group and an amino group are particularly preferable. The terminal-modified polyolefin (D) is, for example, -Al.
A polyolefin having a group 13 element-containing group at the terminal as represented by R ¹ R ² (hereinafter sometimes referred to as “group 13 element-containing group-containing polyolefin”) is produced, and then 13
Whether the group 13 element-containing group of the group element-containing group-containing polyolefin is replaced with a compound having a functional group structure,
Alternatively, it can be produced by reacting a group 13 element-containing group of a group 13 element-containing group-containing polyolefin with a compound having a structure that forms a functional group by solvolysis, and then solvolyzing it. In addition, you may convert the obtained terminal functional group into another functional group by the reaction as mentioned later.

The terminal-modified polyolefin (D) is produced by polymerizing or copolymerizing the above-mentioned olefin having 2 to 20 carbon atoms, for example, using the above-mentioned magnesium-supported titanium catalyst system or metallocene catalyst system. You can Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 3-
Methyl-1-pentene, 4-methyl-1-pentene and the like are preferably used. These monomers may be used alone or in combination of two or more, and may be copolymerized with a polymerizable monomer other than olefin such as diene. When these monomers are used alone, ethylene or propylene is particularly preferable. When two or more of these monomers are used in combination, a combination of ethylene and propylene, ethylene and butene, ethylene and octene, ethylene and propylene and butene, and ethylene and propylene and diene are particularly preferable.

When a magnesium-supported titanium catalyst system is used, in the polymerization system, the solid titanium catalyst component (I) or its prepolymerization catalyst is usually about 0 in terms of titanium atom per liter of polymerization volume. .0001-
It is used in an amount of 50 mmol, preferably about 0.001 to 10 mmol. The organometallic compound catalyst component (II) is
The metal atom in the catalyst component (II) is usually used in an amount of 1 to 2000 mol, preferably 2 to 1000 mol, per 1 mol of titanium atom in the solid titanium catalyst component (I) in the polymerization system. . When the electron donor (III) is used, it is usually 0.001 mol to 10 mol, preferably 0.01 mol to 1 mol of metal atom of the organometallic compound catalyst component (II).
Used in an amount of 5 mol.

When a metallocene catalyst is used as the catalyst, the concentration of the metallocene compound (Z1) in the polymerization system is usually 0.000005 to 0.1 mmol, preferably 0.0001 to 0.000 per liter of the polymerization volume. Used in an amount of 05 mmol. Organic aluminum oxy compound (Z2)
When using, the molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound (Z1) is 5 to 1000, preferably 10 to 4.
It is used in an amount such that it becomes 00. When the organoaluminum compound (Z4) is used, it is usually about 1 to 1 mol of the transition metal atom in the metallocene compound (Z1).
It is used in an amount of 300 moles, preferably about 2-200 moles.

The olefin polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. As a reaction solvent for suspension polymerization,
The above-mentioned inert hydrocarbon solvent may be used, or a liquid olefin at the reaction temperature may be used. The reaction temperature is generally -50 ° C to 200 ° C, preferably 0 ° C to 150 ° C. Polymerization pressure is usually 0.0
It is 1 to 10 MPa, preferably 0.1 to 5 MPa.
Olefin polymerization can be carried out in any of batch system, semi-continuous system and continuous system, and when it is carried out in two or more stages, the reaction conditions may be the same or different.

At this time, it is preferable that molecular hydrogen, which is a general molecular weight regulator, not be present in the polymerization system. It is preferable to carry out by controlling any one or more of (polymerization pressure). Specifically, as a method for adjusting the molecular weight, for example, in suspension polymerization in which molecular hydrogen is substantially absent, increasing the concentration of the organometallic catalyst component (II) reduces the molecular weight of the obtained polyolefin. In addition, in suspension polymerization in which molecular hydrogen is substantially absent, increasing the polymerization temperature can reduce the molecular weight of the obtained polyolefin. The polyolefin obtained as described above has a group 13, element-containing group and / or unsaturated bond at the terminal, preferably at one terminal. Whether the terminal of the polyolefin is a group 13 element-containing group or an unsaturated bond,
It depends on the polymerization conditions such as the type and / or amount of the catalyst used, the organometallic catalyst component, and the polymerization temperature.

When the terminal of the polyolefin is an unsaturated bond, a compound containing a Group 13 element can be reacted to convert the unsaturated bond into a Group 13 element-containing group. The above-mentioned production method using a metallocene catalyst is preferable for producing a polyolefin having an unsaturated bond at the terminal. Further, a polyolefin having an unsaturated bond at the end is produced by thermally decomposing a polyolefin having no group 13 element-containing group or an unsaturated bond-containing group at the end, which is produced by a known production method, and is preferably used. You can also Even in the case where the obtained polyolefin is a mixture of a group 13 element-bonded terminal and a terminal unsaturated bond terminal, a polyolefin whose terminal is an unsaturated bond is used, if necessary. The end of may be converted to the end to which a group 13 element is bound.

The compound containing a Group 13 element used in the reaction is selected from the compounds exemplified as the above-mentioned organometallic compound catalyst component (II), and the compounds exemplified as the organoaluminum compound or the organoboron compound are preferably used. . Among them, trialkylaluminum, dialkylaluminum hydride or one or more hydrogen-
More preferably, it is a boron compound having a boron bond.

The reaction between the polyolefin having an unsaturated bond at the terminal and the compound containing the Group 13 element is carried out, for example, as follows. Polypropylene whose end is vinylidene group 0.1-5
0 g and diisobutylaluminum hydride of 0.0 g.
01-5 mol / l-octane solution 5-1000
Mix with milliliter and reflux for 0.5-6 hours. Polypropylene whose end is vinylidene group 0.1-5
0 g, 5-1000 ml anhydrous tetrahydrofuran, and 0.1-50 ml 9-borabicyclo [3.3.1] nonane 0.05-10 mol / liter-tetrahydrofuran solution were mixed, and at 20-65 ° C. 0.5
Stir for ~ 24 hours. The terminal-modified polyolefin is produced as described above. The group 13 element is bonded to the terminal, preferably one terminal, of the obtained polyolefin, and the group 13 element is preferably aluminum.

Then, (1) a substitution reaction of the group 13 element-containing group of the group 13 element-containing group-containing compound with a compound having a functional group structure is carried out, or (2) the group 13 element-containing group-containing polyolefin An end-modified polyolefin is produced by subjecting a group 13 element-containing group to a reaction with a compound having a structure that forms a functional group by solvolysis, followed by solvolysis. In addition, you may convert the obtained terminal functional group into another functional group by the reaction as mentioned later. Examples of the compound having a functional group structure include halogen, methyl chloroformate, and phthalic acid chloride. In addition, examples of the compound having a structure that forms a functional group by solvolysis include oxygen, carbon monoxide, and carbon dioxide.

1 of group 13 element-containing group-containing polyolefin
The substitution reaction between the group 3 element-containing group and the compound having a functional group structure or the compound having a structure forming a functional group by solvolysis is usually 0 to 300 ° C., preferably 10 to 2
At a temperature of 00 ° C., for 0 to 100 hours, preferably 0.5 to
It will be held for 50 hours. The temperature for solvolysis is usually 0.
To 100 ° C, preferably 10 to 80 ° C, and the solvolysis time is 0 to 100 hours, preferably 0.5 to 100 ° C.
50 hours. Examples of the solvent used for solvolysis include methanol, ethanol, propanol, butanol, water and the like.

The group to be modified at the terminal is a group capable of reacting with a carboxyl group or an acid anhydride group. Examples of such a group include a hydroxyl group, an alkoxy group, an amino group, an imino group and a halogen, and among them, a hydroxyl group, an amino group and a halogen are particularly preferable. The end is -AlR ¹ below
An example of converting the terminal of the group 13 element-containing group-containing polyolefin, which is the R ² group, into a hydroxyl group, a halogen, or an amino group will be given. Conversion to hydroxyl group-AlR ¹ R ² group-containing polyolefin is brought into contact with dried air, methanol containing a small amount of hydrochloric acid is added in large excess, and the mixture is stirred at room temperature for 5 minutes to 12 hours. Conversion to Halogen To the polymer obtained above, thionyl chloride in an amount of 1 to 10 times the hydroxyl group is added, and the mixture is reacted at 0 to 100 ° C. for 5 minutes to 24 hours. Note that thionyl bromide can be used instead of thionyl chloride. Conversion to amino group To the polymer obtained above, sodium azide in an amount 1 to 10 times that of halogen is added, and the mixture is added at 0.5 to 50 ° C. to 0.5.
Allow to react for ~ 24 hours. To the obtained reaction product, triphenylphosphine in an amount 0.1 to 10 times that of sodium azide is added, and the reaction is carried out at 0 to 100 ° C for 0.5 to 24 hours.

A polyolefin having a group containing an element other than the group 13 element at the terminal can be used in the same manner as the polyolefin having a group 13 element containing group at the terminal. The polyolefin having an element-containing group other than Group 13 at the terminal is produced by a conventionally known living polymerization or chain transfer reaction. Among these, a polyolefin having a group containing an element of group 3, 4, 5, 10 produced by living polymerization or a group having an element of group 12 produced by a chain transfer reaction or a group having silicon (Si) at the end is preferable. .

[0086] functional group (G _A) and (G _B) containing a reactive functional group (G _A) of the α- olefin polymer (A
1) reaction of a functional group (containing G _B) alpha-olefin polymer (B1), for example containing functional groups (G _A) alpha-olefin polymer (A1) with the functional group (G It is carried out by bringing the α-olefin-based polymer (B1) containing _B ) into contact with stirring. At this time, the α-olefin-based polymer (A1) and the α-olefin-based polymer (B1) are in a molten state, or at least a part of the α-olefin-based polymer (A1) and at least a part of the α-olefin-based polymer (A1) The polymer (B1) is preferably contacted in a state of being dissolved in an organic solvent, and the α-olefin-based polymer (A1) and α-
It is more preferable that the olefin polymer (B1) is completely dissolved in the organic solvent.

As the organic solvent, hexane, heptane,
Aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as benzene, toluene, xylene, halogen-containing hydrocarbons such as methylene chloride and dichlorobenzene, and heteroatom-containing hydrocarbons such as dimethyl sulfoxide and dimethylformamide are used. This reaction is usually 20-300
° C, preferably 40-280 ° C, more preferably 60
To 260 ° C, more preferably 80 to 240 ° C, and particularly preferably 100 to 230 ° C, for 1 minute to 24 hours,
Preferably 5 minutes to 12 hours, more preferably 1 to 10
Done on time. The amount of the α-olefin polymer (A1) used in the reaction is preferably 5 to 95, preferably 10 to 90, more preferably 15 to 85 parts by weight. The amount of the α-olefin polymer (B1) used in the reaction is preferably 5 to 95, preferably 10 to 90, more preferably 15 to 85 parts by weight. Furthermore, the weight ratio of the α-olefin polymer (A1) / α-olefin polymer (B1) used in the reaction is 0.01 to 100, preferably 0.02 to 50, more preferably 0.05 to 2
0, particularly preferably 0.1 to 10.

[0088] This reaction may be carried out in the presence of a catalyst to accelerate the reaction of the functional groups (G _A) with the functional group (G _B) is preferred. As the catalyst, Zn, Mg (OTf)
₂ , BF ₃ · Et ₂ O, AlCl ₃ , TiCl ₄ , LaC
l ₃ , HClO ₄ , HCl, HBr, HNO ₃ , H ₂ S
O ₄ , benzoic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, salicylic acid, oxalic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, picric acid, metasulfonic acid, o-nitrobenzoic acid, m-nitrobenzoic acid , P-nitrobenzoic acid and the like are preferable, acetic acid, chloroacetic acid, dichloroacetic acid and p-toluenesulfonic acid are more preferable, and p-toluenesulfonic acid is particularly preferable. Further, the above α-olefin polymer (A1)
(I) has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.01 to 10, preferably 0.05 to 9.
5, more preferably 0.1 to 9, and even more preferably 0.
2 to 8.5, particularly preferably 0.3 to 8 dl / g, and (ii) the glass transition temperature Tg in the endothermic curve measured by a differential scanning calorimeter (DSC) is -10 ° C or lower, preferably -20 ° C or lower, more preferably -30 to -1
It is preferably 00 ° C, more preferably -35 to -90 ° C, particularly preferably -40 to -80 ° C.

(I) 1 of α-olefin polymer (B1)
Intrinsic viscosity [η] measured in decalin at 35 ° C is 0.0
1 to 10, preferably 0.05 to 9.5, more preferably 0.1 to 9, still more preferably 0.2 to 8.5, particularly preferably 0.3 to 8 dl / g, iii) The temperature (Tm) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) is 100 to 200, preferably 105 to 190, and more preferably 110 to 18.
0, more preferably 115 to 175, still more preferably 120 to 170, particularly preferably 130 to 165 ° C. The (i) intrinsic viscosity [η] of the α-olefin polymer (B1) measured in decalin at 135 ° C. is
(i) It is preferably smaller than the intrinsic viscosity [η] measured in decalin at 135 ° C.

Composition The α-olefin polymer according to the present invention, and the composition containing the same are the same as the above α-olefin polymer (A
A reaction product of 1) and an α-olefin polymer (B1), and a composition formed from the reaction product and a thermoplastic resin other than the reaction product, the reaction product A composition formed from a thermoplastic resin other than the reaction product is preferable. The composition contains 0.01 to 99% by weight, preferably 0.1 to 60% by weight, more preferably 0.5 to 30% by weight, further preferably 1 to 25% by weight of the above reaction product. There is.

[Thermoplastic Resin] In the present invention, as the thermoplastic resin contained in the above composition, polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate, polycarbonate,
Polyphenylene oxide, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate and ethylene- (meth)
One or more thermoplastic resins selected from acrylic ester copolymers and diene rubbers are preferably used, and of these, polyolefin is preferably used. As polyolefin, polyethylene, polypropylene,
Olefin homopolymers such as poly-1-butene, polymethylpentene and polymethylbutene, ethylene-α-olefin random copolymers, ethylene-propylene-diene terpolymers, propylene-ethylene random copolymers, propylene -α-olefin random copolymer, propylene
-Ethylene-α-olefin terpolymer such as terpolymer, and the like, among them, polyethylene,
Polypropylene, ethylene-α-olefin random copolymer, ethylene-propylene-diene terpolymer, propylene-ethylene random copolymer, and propylene-α-olefin random copolymer are preferred. When the polyolefin is a polyolefin obtained from an olefin having 3 or more carbon atoms, it may be an isotactic polymer or a syndiotactic polymer. As the catalyst used for producing the polyolefin, any known catalyst including the above-mentioned catalyst may be used.

Polyamides include nylon-6, nylon-66, nylon-10, nylon-12, nylon-
Examples thereof include aliphatic polyamides such as 46, aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, and nylon-6 is preferable. Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone and polyhydroxybutyrate, with polyethylene terephthalate being preferred. As polyacetal, polyformaldehyde (polyoxymethylene), polyacetaldehyde,
Examples thereof include polypropionaldehyde and polybutyraldehyde, and polyformaldehyde is particularly preferable. The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, α-methylstyrene or the like, for example, an acrylonitrile-styrene copolymer.

As ABS, a constitutional unit derived from acrylonitrile is contained in an amount of 20 to 35 mol%, a constitutional unit derived from butadiene is contained in an amount of 20 to 30 mol%, and derived from styrene. 40 to 40 units
Those contained in an amount of 60 mol% are preferably used.
As the polymethacrylate, polymethylmethacrylate (PMMA) is preferable. Polycarbonates include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) Examples thereof include those obtained from butane and the like, and polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is preferable. Examples of polyphenylene oxide include poly (2,6-dimethyl-1,4-phenylene oxide)
Is preferred.

Polyvinyl chloride may be a homopolymer of vinyl chloride or a copolymer with vinylidene chloride, acrylic acid ester, acrylonitrile, propylene and the like. Polyvinylidene chloride is usually vinylidene chloride units containing 85% or more of vinyl chloride, acrylonitrile, (meth) acrylic acid ester, allyl ester,
A copolymer with unsaturated ether, styrene or the like is used. The polyvinyl acetate may be a homopolymer of vinyl acetate or a copolymer of ethylene and vinyl chloride. Of these, ethylene-vinyl acetate copolymer is preferable. As the ethylene- (meth) acrylic acid ester copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-
Methyl methacrylate copolymer and ethylene-ethyl methacrylate copolymer are preferred.

As the diene rubber, polybutadiene,
Mention may be made of conjugated polydienes such as elastomeric styrene-butadiene copolymers also known as polyisoprene or SBR (styrene-butadiene rubber).
In these, at least a part of the double bond in the molecule may be hydrogenated. The above thermoplastic resins can be used alone or in combination of two or more. In the present invention, it is most preferable to use the above reaction product as a compatibilizing agent when two or more kinds of polyolefins such as copolymers or homopolymers and copolymers having different compositions are used in combination. . As described above, the effect of compatibilization is apparent by observing the unprecedented microphase structure, and the unprecedented microphase separation structure leads to the unprecedented expression of polymer physical properties.

[Compounding Agent] The composition according to the present invention contains an inorganic filler, an organic filler, a crystal nucleating agent, a heat stabilizer, a weather stabilizer, an antistatic agent, a coloring agent, a lubricant, a flame retardant, an anti-blooming agent and the like. It may be contained within a range that does not impair the object of the present invention.

[Manufacturing Method] The composition according to the present invention contains the α-olefin-based polymer (A1) and the α-olefin-based polymer (B1) during the reaction of the α-olefin-based polymer (A1) and the α-olefin-based polymer (B1). It may be produced by adding a thermoplastic resin other than A1) and the α-olefin polymer (B1), and the reaction product of the α-olefin polymer (A1) and the α-olefin polymer (B1) Or a composition containing the reaction product and a thermoplastic resin are mixed with, for example, a ribbon blender, a tumbler blender, a Henschel blender, or a cokneader, a Banbury mixer, a Brabender,
Melt kneading using a melt kneader such as a single-screw extruder, a twin-screw extruder or other kneading machine, a twin-screw surface renewing machine, a two-screw multi-disc device or other horizontal stirrer, or a double helical ribbon stirrer or other vertical stirrer. You may manufacture by doing. The α-olefin polymer (A1) and the α-olefin polymer (B1) when the α-olefin polymer (A1) and the α-olefin polymer (B1) are reacted with each other.
It is preferable to add a thermoplastic resin other than the above to produce a composition, and it is also preferable to mix the obtained composition with another thermoplastic resin or to perform melt mixing.

[0098]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

(Example 1) [Production of hydroxyl group-terminated polypropylene] 25 g of polypropylene pyrolysis wax manufactured by Mitsui Chemicals, Inc. (brand name: NP-
055, Mw 8,000, Mw / Mn 2.35), 750 mL of decane, and 32.5 mmol of diisobutylaluminum hydride (iBu ₂ AlH) were stirred in a flask sufficiently replaced with nitrogen, heated to 100 ° C., and kept at the same temperature. It was kept under stirring for 7 hours. Then, the mixture was kept under stirring at 100 ° C. for 6 hours while circulating dry air through the system at a rate of 200 liters / hour. This was allowed to cool, the whole amount was poured into a mixed solution of 2 liters of methanol, 2 liters of acetone and a small amount of hydrochloric acid, and stirred at room temperature for 1 hour. The obtained polymer was washed with methanol and then dried under reduced pressure at 80 ° C. for 10 hours. 28 mol% of all terminals by ¹³ C-NMR
It was confirmed that the compound contains a hydroxyl group.

[Preparation of Composition] In a 250 ml glass reactor, 1.0 g of the above-mentioned terminal hydroxylated polypropylene,
2.8 g of Mitsui Chemicals, Inc. EPR Admer (ethylene / propylene copolymer modified with maleic anhydride, ethylene content 80 mol%, Mw 130,000, modification rate 1 wt
%), 0.1 g of p-toluenesulfonic acid and 100 ml of decane were added, and the mixture was stirred at 140 ° C. for 7 hours.
This was put into a mixed liquid of 1.5 liter of methanol and 1.5 liter of acetone, and stirred at room temperature for 5 minutes. The resulting composition was washed with acetone and then at 80 ° C.
And dried under reduced pressure for 10 hours.

[Observation of Micro-Phase Structure] The composition obtained above was pressed into a sheet, and each sample was cut into 0.5 mm square pieces and dyed with ruthenic acid (RuO ₄ ). This is an ultra microtome equipped with a diamond knife (REICHERT ULTRACUT S, REICHERT FC S) with a thickness of about 100n.
An ultrathin section having a thickness of m was prepared. Carbon is vapor-deposited on this ultrathin section and a transmission electron microscope (Hitachi H-810) is used.
0; acceleration voltage was 100 kV). 5 observation points
The spots were randomly selected and observed at magnifications of 10,000 times, 50,000 times, and 150,000 times. The microphase structures are the same at all points, and the microphase structures observed at 10,000 times in FIG. 1 and at 50,000 times and 150,000 times are shown in FIG. FIG. 1 clearly shows the layered microphase structure that was not observed with polyolefins. The boundary between the dispersed phase and the matrix phase could not be discriminated by the software even if the image of 150,000 times in FIG. 2 was read at a sensitivity of 200 bits and the diameter of the dispersed phase was measured by the software of Image-Pro Plus.
Therefore, add the boundary between the dispersed phase and the matrix phase by hand as shown in Fig. 3 and use the software of Image-Pro Plus to add Ax.
By selecting is-major, the dispersed phase was approximated to an ellipse having the same area and the same first and second moments, and the diameters shown in Table 1 were calculated. Further, as shown in the statistical processing result of Table 2, the major axis of the ellipse is 38 at the maximum value of the 44 measurement points.
The average value was 18 nm.

[0102]

[Figure 1]

[0103]

[Fig. 2]

[0104]

[Figure 3]

[0105]

[Table 1]

[0106]

[Table 2]

Comparative Example 1 [Preparation of Composition] A 250 ml glass reactor was charged with 1.0
g of Mitsui Chemicals' polypropylene pyrolysis wax (brand name: NP-055, Mw 8,000, Mw / Mn 2.3
5) 2.8 g of EPR Admer manufactured by Mitsui Chemicals, Inc. (ethylene / propylene copolymer modified with maleic anhydride, ethylene content 80 mol%, Mw 130,000, modification rate 1 wt%), 0.1 g of p-toluene Sulfonic acid, 10
0 ml of decane was added, and the mixture was stirred at 140 ° C for 7 hours. This was put into a mixed liquid of 1.5 liter of methanol and 1.5 liter of acetone, and stirred at room temperature for 5 minutes. The resulting composition was washed with acetone and then
It was dried under reduced pressure at 0 ° C. for 10 hours. In addition, the process here is
1. Instead of 1.0 g of terminal hydroxylated polypropylene.
Same as [Production of Composition] of Example 1 except that 0 g of polypropylene pyrolysis wax was used.

[Observation of Micro-Phase Structure] The composition obtained above was press-sheet molded into a 0.5 mm square piece, which was dyed with ruthenic acid (RuO ₄ ). This is an ultra microtome equipped with a diamond knife (REICHERT ULTRACUT S, REICHERT FC S) with a thickness of about 100n.
An ultrathin section having a thickness of m was prepared. Carbon is vapor-deposited on this ultrathin section and a transmission electron microscope (Hitachi H-810) is used.
0; acceleration voltage was 100 kV). 5 observation points
The spots were randomly selected and observed at magnifications of 10,000 times, 50,000 times, and 150,000 times. The microphase structures are the same at all points, and FIG. 4 shows the microphase structures observed at 10,000 times and FIG. 5 at 50,000 times and 150,000 times. In each case, the boundary between the dispersed phase and the matrix phase is clear, and the dispersed phase can be recognized by the Image-Pro Plus software. It also has a sea-island structure as seen in conventional polyolefin compositions. Using the software of Image-Pro Plus in the observation field of view of 10,000 times as shown in Fig. 4, by selecting Axis-major, the dispersed phase is approximated to an ellipse with the same area and the same first and second moments. The diameters shown in Table 3 were calculated. Further, as shown in the statistical processing results of Table 4, the major axis of the ellipse was 8.45 μm at the maximum value among the 88 measurement points and 740 nm at the average value.

[0109]

[Figure 4]

[0110]

[Figure 5]

[0111]

[Table 3]

[0112]

[Table 4]

[0113]

The α-olefin polymer according to the present invention is novel as an α-olefin polymer or a resin composition containing the α-olefin polymer due to its unique phase separation structure. It is possible to develop effective polymer physical properties.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryoji Mori             Chiba Prefecture Sodegaura City Nagaura 580-32 Mitsui Chemicals             Inside the company (72) Inventor Norio Kashiwa             Chiba Prefecture Sodegaura City Nagaura 580-32 Mitsui Chemicals             Inside the company F term (reference) 4J002 AA013 AC023 BB01W BB01X                       BB033 BB053 BB063 BB123                       BB143 BB153 BB173 BB20W                       BB20X BC033 BC063 BD033                       BD103 BG063 BN153 CB003                       CF063 CG013 CH073 CL013                       GT00                 4J100 BA03H BA13H BA16H BA29H                       BA42H BA56H BA77H BC54H                       BC55H CA27 CA31 DA04                       DA39 HA61 HB20 HC29 HC30                       HC34 HC36 HC48 HC50 HC54                       HD04 HE14 HE17 HF05

Claims (8)

[Claims] 1. Permeation after dyeing with ruthenic acid
The microphase structure of the section observed with a scanning electron microscope is small.
Kuto (A) Derived from α-olefin having 2 to 20 carbon atoms
Consisting of at least one of the repeating units
One repeating unit (a) out of one or more repeating units
-Olefin containing 5 to 100 mol% of
Phase composed of polymer (B) Derived from α-olefin having 2 to 20 carbon atoms
A repeating unit of at least one or more types, and
(A) Different even if it is the same as the repeating unit contained in the phase
The repeating unit (b), which may be
Composed of α-olefin polymer contained in proportion
Phase, and (1) (A) phase or
One of the (B) phases is a dispersed phase, and the dispersed phase is
Maximum diameter when approximated as an ellipse (d₁) Is 1 to 200
nm or (2) maximum diameter of dispersed phase domain
(D₁) And the maximum value of the diameter orthogonal to the maximum diameter (d₂) With
(D₁/ D₂) Is a rod-shaped dispersed phase of 20 or more,
Maximum diameter (d ₁) Maximum diameter (d₂) Is 1
nm to 200 nm, or (3)
Image-Which of (A) phase and (B) phase is the dispersed phase?
Layered lamella structure that cannot be identified using Pro Plus software
It is made of a small amount of (A) phase or (B) phase
At least one layer has a thickness of 1 nm to 200 nm
A unique Miku characterized by a microphase structure
Α-olefin polymer having a phase structure, and
The composition containing. 2. Repeating units (a) and (B) in phase (A)
At least one of the repeating units (b) in the phase is ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene,
1-octene, 3-methyl-1-butene, 4-methyl-
An α-olefin polymer having a unique microphase structure according to claim 1, which is a repeating unit derived from an α-olefin selected from 1-pentene, and a composition containing the same. 3. At least 2 to 2 carbon atoms (A1)
A repeating unit derived from an α-olefin of 0 or more, and containing one or more repeating units (a) among the one or more repeating units in a proportion of 51 to 100 mol%, and a hetero atom the functional group (G _a) containing 0.0
5 to 95 parts by weight of α-olefin polymer containing 0001 to 30% by weight, and (B1) α having 2 to 20 carbon atoms
-Comprising at least one repeating unit derived from an olefin, and comprising the α-olefin polymer (A1)
Containing repeating units (a) and optionally repeat units be different even in the same a (b) in a proportion of 51 to 100 mol% contained in, 0 functional group (G _B) containing a hetero atom. 00
001-30 containing by weight% alpha-olefin polymer by contacting the 5 to 95 parts by weight, at least part of the functional group (G _B) containing a functional group (G _A) and hetero atoms containing hetero atoms An α-olefin polymer having a unique microphase structure according to claim 1 or 2, and a composition containing the same. 4. At least one kind selected from an ester bond, an amide bond, an imide bond, a urethane bond, and a urea bond by contacting the α-olefin polymer (A1) with the α-olefin polymer (B1). An α-olefin polymer having a unique microphase structure according to claim 3, which produces a bond, and a composition containing the same. 5. An α-olefin polymer (A1) or α
- at least one of the olefin polymer (B1) is a functional group containing a functional group (G _A) or heteroatom containing the above heteroatoms 0.1 mol% of the molecular ends of the (G _B) An α-olefin polymer having a unique microphase structure according to any one of claims 1 to 4, and a composition containing the same. 6. The method according to claim 1, wherein the α-olefin polymer (A1) and the α-olefin polymer (B1) are contacted with each other in the presence of an acid. Α-Olefin-based polymer having a unique microphase structure, and a composition containing the same. 7. (i) 13 of α-olefin polymer (A1)
The intrinsic viscosity [η] measured in decalin at 5 ° C is 0.01
The glass transition temperature Tg in the endothermic curve measured by a differential scanning calorimeter (DSC) is −10 ° C. or lower.
Α- having a unique microphase structure according to any one of 6
Olefin-based polymer and composition containing the same. 8. The (i) 1 of the α-olefin polymer (B1).
Intrinsic viscosity [η] measured in decalin at 35 ° C is 0.0
It is in the range of 1 to 10 dl / g, and (iii) the temperature (Tm) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) is 100 ° C to 200 ° C. Item 9. An α-olefin polymer having a unique microphase structure according to any one of Items 1 to 7, and a composition containing the same.