JP2509767C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION   [0001]   [Industrial applications]   The present invention relates to a method for producing an olefin polymer.   [0002]   [Prior art]   Thermoplastic elastomers are energy-saving or resource-saving elastomers
, Especially as substitutes for vulcanized rubber, automotive parts, industrial machinery parts, electronic and electrical
Widely used for parts and building materials.   [0003]   Olefinic thermoplastic elastomers (TPO) are generally
Kneading ethylene-propylene-diene rubber (EPDM) in the presence of peroxide
(For example, JP-A-61-217747). But
However, this method has the disadvantage that the operation is complicated and the production cost is high.   On the other hand, a high molecular polymer having the same properties as the mechanical properties of the TPO is polymerized.
Various attempts have been made to reduce costs by directly manufacturing
Have been. For example, a propylene-hexene copolymer (for example, see JP-A-49-53983)
And JP-B-62-19444) and elastic polypropylene (for example, JP-A-61-1).
No. 79247) has been proposed.   However, all of these high polymers had insufficient low temperature properties.
.   [0004]   As a method for improving the low-temperature properties of polypropylene, propylene / ethylene
A two-stage polymerization method of propylene is well known (for example, see Japanese Patent Application Laid-Open No. 57-50804).
This method uses a vulcanized rubber-like material that has both flexibility and practical tensile strength.
It was difficult to produce a polymer.   [0005]   [Problems to be solved by the invention]   The present invention has practical tensile strength even in an unvulcanized state, and has flexibility and low-temperature properties.
Satisfactory, low surface tackiness, low production cost, and excellent powder fluidity
It is an object of the present invention to provide a method for producing an improved olefin polymer.   The present inventors have conducted intensive studies to achieve the above object, and as a result, a specific catalyst
By controlling the crystallinity of the polymer using the system, the TPO (
Vulcanized rubber-like olefin polymer with similar physical properties
Was easily obtained. The present invention is based on this finding.   [0006]   [Means for Solving the Problems]   That is, the present invention relates to a method for producing an olefin polymer by a solventless polymerization method.
hand, (A) (a) Metal magnesium, alcohol, and 1 g of the above metal magnesium
0.0001 gram atom or moreLess than 0.06 gram atomAmount of halo
0.0001 gram atom or more per gram atom of metal or magnesium metal
Less than 0.06 gram atomWith a halogen-containing compound containing an amount of halogen atoms
A solid product obtained therefrom; (B) represented by the following general formulaTetravalent titanium compoundWhen   TiX¹n (OR¹)_4-n (Where X¹Is a halogen atom, especially a chlorine atom;¹Represents 1 to 10 carbon atoms
A hydrocarbon group, especially a linear or branched alkyl group,¹Where there are multiple
In that case they may be the same or different from each other. n is an integer of 0-4. )
Of a solid catalyst obtained by reacting a compound with or without an electron-donating compound
Minutes and (B) an organoaluminum compound, (C) General formula Embedded image   [R in the formula¹Is an alkyl group having 1 to 20 carbon atoms;^TwoIs a hydrocarbon having 1 to 10 carbon atoms
Group, hydroxyl group or nitro group; m is an integer of 1 to 6; n is 0 or 1 to (6-m)
It is an integer. An alkoxy-containing aromatic compound represented by the formula: (D) an electron donating compound and The present invention provides a method for producing an olefin polymer using a catalyst system comprising:   In this case, from the solid catalyst component (A) and the crystalline polyolefin, a solid component (
E) and comprises the solid component (E) and the components (B), (C) and (D).
A suitable catalyst system can also be used.   [0007]   Hereinafter, the present invention will be described in detail.   First, the catalyst system used in the present invention will be described.   The solid catalyst composition (A) used in the present invention comprises at least (a) metallic magnesium
Obtained by reacting an alcohol with a halogen and / or a halogen-containing compound
A solid product; (b)Tetravalent titanium compoundAnd in the presence of an electron donating compound
Are obtained by reacting in the absence.   In this case, in the solid product (a), the shape and the like of metallic magnesium are particularly
Not limited. Thus, metallic magnesium of any particle size, for example, granular, ribbon
Magnesium in the form of a powder or powder can be used. Also, metal magnesium
The surface condition of the film is not particularly limited, but a film such as magnesium oxide is formed on the surface.
Those not provided are preferred.   [0008]   Although any alcohol can be used, it has 1 to 6 carbon atoms. It is preferred to use lower alcohols. Especially when using ethanol,
This is preferable since a solid product which significantly improves the expression of the function can be obtained. Alcoholic
Purity and water content are not limited, but using alcohol with high water content
Magnesium hydroxide [Mg (OH)_Two] Is generated, so the water content
Is preferably 1% or less, particularly 2000 ppm or less. Change
In order to obtain a solid product (a) having better morphology,
Is preferably as small as possible, and generally, 200 ppm or less is desirable.   [0009]   Although there is no particular limitation on the type of halogen, chlorine, bromine or iodine, especially
Iodine is preferably used.   There is no limitation on the type of halogen-containing compound, and a halogen atom is included in the chemical formula.
Any compound can be used. In this case, the type of halogen atom
Although there is no particular limitation, it is preferably chlorine, bromine or iodine. Ma
Further, among the halogen-containing compounds, a halogen-containing metal compound is particularly preferable.   As the halogen-containing compound, specifically, magnesium chloride (MgCl_Two),
Magnesium iodide (MgI_Two), Ethoxymagnesium chloride (Mg (OE
t) Cl), ethoxymagnesium iodide (Mg (OEt) I), mug bromide
Nesium (MgBr_Two), Calcium chloride (CaCl_Two), Sodium chloride (Na
Cl), potassium bromide (KBr) and the like can be suitably used. Of these, especially
MgCl_Two, MgI_TwoIs preferred.   The state, shape, particle size, and the like are not particularly limited, and may be arbitrary.
It can be used in the form of a solution in a alcohol-based solvent (eg, ethanol).   [0010]   The amount of alcohol is not limited, but it is preferred for 1 mole of metallic magnesium.
Or more preferably 2 to 100 mol, particularly preferably 5 to 50 mol. High alcohol content
If it is too high, the yield of the solid product (a) having good morphology may decrease.
If the amount is too small, stirring in the reaction tank may not be performed smoothly.
There is. However, it is not limited to the molar ratio.   [0011]   The amount of halogen used is 0.0001 to 1 gram atom of metallic magnesium.
Gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.1 gm atom or more.
001 gram atoms or more. The halogen-containing compound is metallic magnesium
For every gram atom, the halogen atom in the halogen-containing compound is 0.0001 g.
Ram atom or more, preferably 0.0005 g atom or more, more preferably 0.0
Used to have at least 01 gram atoms. Less than 0.0001 g atom
The desired particle size was obtained without much difference from the amount of halogen used as a reaction initiator.
For this purpose, the pulverization and classification of the solid product is indispensable.   [0012]   One kind of each of the halogen and the halogen-containing compound may be used alone.
The above may be used in combination. Further, a halogen and a halogen-containing compound may be used in combination.
No. When a halogen and a halogen-containing compound are used in combination as described above, all halogen sources
More than 0.0001 gram atom per 1 gram atom of magnesium metal
, Preferably 0.0005 g atom or more, more preferably 0.001 g atom
Child and above.   The upper limit of the amount of halogen and / or halogen-containing compound usedAboutAll haloge
0.06 gram atom per 1 gram atom of metallic magnesiumLess than
I do.   In this case, the amount of halogen and / or halogen-containing compound used should be appropriately selected.
Thus, the particle size of the solid product can be freely controlled.   [0013]   Of metal magnesium, alcohol and halogen and / or halogen-containing compound
The reaction itself can be carried out in the same manner as in a known method. For example, a metal mug
Nesium, an alcohol, a halogen and / or a halogen-containing compound are refluxed (
At about 79 ° C.) until hydrogen gas generation is no longer observed (usually about 20 to 30 hours).
During the reaction, a solid product is obtained. Specifically, for example, with halogen
When using iodine, solid iodine is dissolved in magnesium metal or alcohol.
Injecting, then heating and refluxing, metal magnesium and alcohol
A method of heating and refluxing after dropwise addition of an alcohol solution of iodine, metallic magnesium, A method of dropping an alcohol solution of iodine while heating the alcohol solution.
It is.   Both methods are performed under an inert gas (eg, nitrogen gas, argon gas) atmosphere.
Optionally using an inert organic solvent (for example, a saturated hydrocarbon such as n-hexane).
It is preferable to carry out.   [0014]   Injection of metallic magnesium, alcohol, halogen and / or halogen-containing compound
It is not necessary to put the whole amount into the reaction tank from the beginning.
May be thrown. In a particularly preferred embodiment, the alcohol is charged in its entirety from the beginning.
This is a method in which metallic magnesium is divided and charged several times. If you do this
In addition, it is possible to prevent a temporary mass generation of hydrogen gas, which is very desirable from the viewpoint of safety.
Also, the size of the reaction tank can be reduced. Furthermore, temporary large amounts of hydrogen gas
Alcohols and halogens and / or halogen-containing compounds caused by generation
It is also possible to prevent entrainment. The number of divisions should be based on the size of the reactor.
It is not particularly limited as long as it is determined, but usually 5 to 10 times is preferable in view of the complexity of the operation.
It is.   [0015]   Needless to say, the reaction itself may be either a batch type or a continuous type.
. In addition, as a variant, metal magnesium
After adding a small amount of water and separating the product generated by the reaction into another tank and removing it
It is also possible to repeat the operation of adding a small amount of magnesium metal again
It is.   When the solid product thus obtained is used for the synthesis of the next solid catalyst component, it is dried.
May be used, or after filtration and washing with an inert solvent such as heptane.
May be. In each case, the solid product obtained is ground or granulated.
It can be used in the following process without performing classification operation to make the degree distribution uniform.
You.   [0016]   The solid catalyst component (A) used in the present invention comprises at least (a) the solid product and ( b)Tetravalent titanium compoundAnd obtained from   In the solid catalyst component (A)Tetravalent titanium compound(B) is a general formula   TiX¹n (OR¹)_4-n (Where X¹Is a halogen atom, especially a chlorine atom;¹Represents 1 to 10 carbon atoms
A hydrocarbon group, especially a linear or branched alkyl group,¹Where there are multiple
In that case they may be the same or different from each other. n is an integer of 0-4. )
And a titanium compound represented by the following formula:   In particular, Ti (OiC_ThreeH₇)_Four, Ti (OC_FourH₉)_Four, TiCl (OC_TwoH_Five)_Three,
TiCl (OiC_ThreeH₇)_Three, TiCl (OC_FourH₉)_Three, TiCl_Two(OC_Four
H₉)_Two, TiCl_Two(OiC_ThreeH₇)_Two, TiCl_Four And the like.   [0017]   In the preparation of the solid catalyst component (A), any other optional components may be used as necessary.
The child-providing compound (c) can be used. Those electron donating compounds (c)
Is usually an organic compound containing oxygen, nitrogen, phosphorus or sulfur. Concrete
Typically, amines, amides, ketones, nitriles, phosphines, phosyl
Amides, esters, ethers, thioethers, alcohols, thioes
Ters, acid anhydrides, acid halides, aldehydes, organic acids, Si-OC bonds
And the like. More specifically, the following can be mentioned.
Can be mentioned.   [0018]   Aromatic carboxylic acids, such as benzoic acid, p-oxybenzoic acid; acid anhydrides, such as
For example, succinic anhydride, benzoic anhydride, p-toluic anhydride; having 3 to 15 carbon atoms
Ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Acetophenone, benzophenone, benzoquinone; alde having 2 to 15 carbon atoms
Hydrates such as acetaldehyde, propionaldehyde, octylaldehyde
, Benzalded, naphthaldehyde; esters having 2 to 18 carbon atoms, eg
For example, methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, acetate acetate Ropyl, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate
, Ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate,
Methyl acrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate,
Ethyl chlorohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate
Ropyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate
Phenylate, benzyl benzoate, methyl toluate, ethyl toluate, toluate
Amyl luate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethoxy
Ethyl benzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate,
Ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, lid
Lido, ethylene carbonate;   [0019]   Mono- and diesters of aromatic dicarboxylic acids, such as monoesters of phthalic acid and
And diesters, for example, monomethyl phthalate, dimethyl phthalate
, Monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate
, Diethyl phthalate, monoethyl terephthalate, diethyl terephthalate,
Monopropyl phthalate, dipropyl phthalate, monopropyl terephthalate
, Dipropyl terephthalate, monobutyl phthalate, dibutyl phthalate,
Nobutyl terephthalate, dibutyl terephthalate, monoisobutyl phthalate,
Diisobutyl phthalate, monoamyl phthalate, diamyl phthalate, monoi
Soamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl
Isobutyl phthalate, ethyl propyl phthalate;   [0020]   Acid halides having 2 to 20 carbon atoms, the acid portion of this acid halide (acid
(Having a ring such as an alicyclic group) having about 2 to 20 carbon atoms
Extraction of each hydroxyl group from monobasic, dibasic or tribasic acid of the system
Mono- to tri-valent acyl acids or aromatic (alkali-
And aralkyl types. ) System monobasic, dibasic or tribasic acid
A monovalent to trivalent acyl group from which the respective hydroxyl groups are extracted is preferred. Also,
As the halogen atom in the acid halide, a chlorine atom, a bromine atom and the like are preferable. And a chlorine atom is particularly preferred.   [0021]   Acid halides that can be suitably used include, for example, acetyl chloride.
Lido, acetyl bromide, propionyl chloride, butyryl chloride, isobutyric
Ryl chloride, 2-methylpropionyl chloride, valeryl chloride, isovale
Ryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethyl
Ruhexanoyl chloride, octanoyl chloride, decanoyl chloride, unde
Canoyl chloride, hexadecanoyl chloride, octadecanoyl chloride,
Benzylcarbonyl chloride, cyclohexanecarbonyl chloride, malonyldic
Loride, succinyl dichloride, pentanedioyl dichloride, hexane dioy
Ludichloride, cyclohexanedicarbonyldichloride, benzoylchloride,
Benzoyl bromide, methyl benzoyl chloride, phthaloyl chloride, isofl
Taroyl chloride, terephthaloyl chloride, benzene-1,2,4-trical
Bonyl trichloride and the like can be mentioned. Among these, especially Phthalloy
Preferred are luchloride, isophthaloyl chloride, terephthaloyl chloride and the like.
Particularly, phthaloyl chloride is preferred. These acid halides are a kind
May be used alone or in combination of two or more.   [0022]   Ethers having 2 to 20 carbon atoms, for example, methyl ether, ethyl ether
, Isopropyl ether, n-butyl ether, amyl ether, tetrahydro
Furan, anisole, diphenyl ether, ethylene glycol butyl ether
Acid amides, such as acetate amide, benzoic acid amide, toluic acid amide; amines
, For example, tributylamine, N, N'-dimethylpiperazine, tribenzyl
Amine, aniline, pyridine, pyrroline, tetramethylethylenediamine; nitro
Ryls, for example, acetonitrile, benzonitrile, tolunitrile; tetramethyl
Lurea, nitrobenzene, lithium butyrate;   [0023]   Organosilicon compounds having a Si-OC bond, for example, trimethylmethoxy
Orchid, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldieto Xysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane,
Diphenyldiethoxysilane, phenyltrimethoxysilane, γ-chloropropyl
Rutrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane
, Vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxy
Sisilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane
, Ethyl triisopropoxy silane, vinyl tributoxy silane, isopropyl
Cyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane
Tert-butylcyclohexyldimethoxysilane, isopropylcyclohexyl
Diethoxysilane, isobutylcyclohexyldiethoxysilane, tert-butyl
Cyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy
Sisilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxy
Sisilane, dimethyltetraethoxydisiloxane and the like can be mentioned.   Of these, preferred are esters, ethers, ketones, and acid anhydrides.
Things.   [0024]   As a method for preparing the solid catalyst component (A), a solid product (a) and an electron donating compound are used.
(C), and then contact with a tetravalent titanium compound (b).
The conditions for contacting the electron-donating compound (c) with the product (a) are not particularly limited.
It may be determined appropriately according to various circumstances. Usually solid in terms of magnesium atom
0.01 to 10 mol of the electron donating compound (c) is preferably used per 1 mol of the product (a).
Or 0.05 to 5 mol, preferably at 0 to 200 ° C. for 5 minutes to 10 hours.
Alternatively, the contact reaction may be performed at 30 to 150 ° C. for 30 minutes to 3 hours. What
Note that this reaction system includes an inert carbon such as pentane, hexane, heptane or octane.
Hydrogen hydride can be added as a solvent.   [0025]   To the solid product (a) or to the contact product thereof with the electron donating compound (c),
The conditions for contacting the tetravalent titanium compound (b) are not particularly limited, but are usually
The tetravalent titanium compound (b) is added in an amount of 1 to 50 with respect to 1 mol of magnesium in the product. Mol, preferably in the range of 2 to 20 mol, at 0 to 200 ° C. for 5 minutes to 10 hours.
The reaction is preferably performed at 30 to 150 ° C. for 30 minutes to 5 hours.   The contact with the tetravalent titanium compound (b) is performed by contacting the liquid with the tetravalent titanium compound (for example,
, Titanium tetrachloride) by itself, other tetravalent titanium compounds are optional inert
Performed while dissolved in a hydrocarbon solvent (eg, hexane, heptane, kerosene)
be able to. Further, the solid product (a) and a tetravalent titanium compound (b),
Optionally, prior to said contacting with electron donating compound (c),
Hydrocarbon, halogen-containing silicon compound, halogen gas, hydrogen chloride, hydrogen iodide
Etc. can also be contacted with the solid product (a).   After completion of the reaction, an inert hydrocarbon (eg, n-hexane, n-heptane)
), It is preferable to wash the product.   [0026]   The composition of the solid catalyst component (A) thus prepared is usually magnesium /
Titanium atomic ratio of 2 to 100, halogen / titanium atomic ratio of 5 to 200, electron donation
The body / titanium molar ratio is in the range of 0.1 to 10.   [0027]   In the present invention, the solid catalyst component (A) and the crystalline polyolefin are solidified.
The solid component (E) is composed of the solid component (E) and the components (B), (C), and (D).
A catalyst system consisting of:   As a method for preparing the solid component (E), for example, (1) The solid catalyst component (A) and the organoaluminum compound are used if necessary.
The olefin is pre-polymerized in the presence of
Method (pre-polymerization method), (2) Crystalline powders such as crystalline polypropylene and polyethylene with uniform particle size
In addition, the solid catalyst component (A) and an organoaluminum compound optionally used
And a method of dispersing an electron donating compound (having a melting point of 100 ° C. or higher) (dispersion method), (3) a method of combining the method of (1) and the method of (2),   Etc. can be used.   [0028]   Examples of the crystalline polyolefin in the solid component (E) include polyethylene.
C2-C2 such as len, polypropylene, polybutene, poly-4-methylpentene
And crystalline polyolefins obtained from 10 α-olefins. This result
As shown in the preparation method (1), the crystalline polyolefin is an α-olefin having 2 to 10 carbon atoms.
Using an olefin, usually at a temperature in the range of 30 to 80 ° C, preferably 55 to 70 ° C.
Here, it can be produced by performing preliminary polymerization.   In this case, the aluminum / titanium atomic ratio of the catalyst system is usually 0.1 to 100, preferably
And the molar ratio of the electron donating compound / titanium is from 0 to 5.
50, preferably in the range of 0.1 to 2. In addition, crystalline polyolefin
Then, as shown in the preparation method (2), a powdery crystalline polyol
Those manufactured as fins may be used.   The crystalline polyolefin preferably has a melting point of 100 ° C. or higher.   [0029]   The organoaluminum compound used for preparing the solid component (E) includes the following
In this case, those exemplified as the organoaluminum compound as the component (B) can be used.
You. Further, as the electron donating compound to be used as required, (A)
The compounds exemplified as the electron donating compound can be used.   The crystalline polyolefin in the solid component (E) and the solid catalyst component (A)
The weight ratio of the crystalline polyolefin to the component (A) is usually
It is selected to be in the range of 0.05 to 100, preferably 0.10 to 50.   [0030]   Also,In the catalyst system used in the present inventionOrganic aluminum compounds(B)age
The general formula   AlR^Two _mX^Two _3-m (Where R^TwoIs an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl
M is an integer of 1 to 3, X^TwoIs a halogen atom such as a chlorine atom or
Is a bromine atom) Can be mentioned. As such an aluminum compound
Is, for example, trimethylaluminum, triethylaluminum, triisopro Pill aluminum, triisobutyl aluminum, trioctyl aluminum
Which trialkyl aluminum, diethyl aluminum monochloride, diisoprop
Propyl aluminum monochloride, diisobutyl aluminum monochlorite, di
Dialkyl aluminum monohalides such as octyl aluminum monochloride
Aluminum sesquihalides, such as ethyl aluminum sesquichloride
And the like can be suitably used. These aluminum compounds use one kind
Or two or more of them may be used in combination.   [0031]   The alkoxy group-containing aromatic compound (C) in the catalyst system used in the present invention is:
General formula Embedded image [R in the formula¹Is an alkyl group having 1 to 20 carbon atoms;^TwoIs a hydrocarbon group having 1 to 10 carbon atoms
, A hydroxyl group or a nitro group; m is an integer of 1 to 6; n is 0 or an integer of 1 to (6-m).
Is a number. ] It is a compound represented by these.   [0032]   Specifically, for example, m-methoxytoluene, o-methoxyphenol, m-methoxytoluene
Methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole
, P- (1-propenyl) anisole, p-allylanisole, 1,3-bis (
p-methoxyphenyl) -1-pentene, 5-allyl-2-methoxyphenol
, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl
Alcohol, methoxybenzyl alcohol, nitroanisole, nitrophene
Monoalkoxy compounds such as toll, o-dimethoxybenzene, m-dimethoxy
Benzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 2,6-di
Dialcohols such as methoxyphenol and 1-allyl-3,4-dimethoxybenzene Xy compound and 1,3,5-trimethoxybenzene, 5-allyl-1,2,3
-Trimethoxybenzene, 5-allyl-1,2,4-trimethoxybenzene, 1
, 2,3-Trimethoxy-5- (1-propenyl) benzene, 1,2,4-tri
Methoxy-5- (1-propenyl) benzene, 1,2,3-trimethoxybenze
And trialkoxy compounds such as 1,2,4-trimethoxybenzene.
Of these, dialkoxy compounds and trialkoxy compounds are preferred.
It is. These alkoxy group-containing aromatic compounds may be used alone.
Alternatively, two or more kinds may be used in combination.   [0033]   In the catalyst system used in the present invention,Electron donating compound (D)Combined.   The electron donating compound (D) in the catalyst system used in the present invention includes oxygen,
A compound containing nitrogen, phosphorus, sulfur, silicon, etc.
In the polymerization of olefins, there may be mentioned those having an ability to improve regularity.   Such an electron donating compound (D) includes the solid catalyst component (A) described above.
The same thing as the electron donating compound (c) used at the time of preparation can be used.   Among these, organosilicon compounds, esters, ethers, ketones and
Acid anhydrides are preferred, especially diphenyldimethoxysilane, phenyltriethoxy.
Organosilicon compounds such as silane, di-n-butyl phthalate, diisobu phthalate
Aromatic dicarboxylic acid diesters such as tyl, benzoic acid, p-methoxybenzoic acid,
C1-C4 aromatic monocarboxylic acids such as p-ethoxybenzoic acid and toluic acid
And the like are preferred. Aromatic dicarboxylic acid diester is a catalyst
It is particularly preferred because it improves the activity and activity persistence.   The electron donating compound (D) is used for preparing the solid catalyst component (A).
May be the same as or different from the electron donating compound (c)
.   [0034]   Regarding the amount of each component of the catalyst system used in the present invention, the solid catalyst component (A) or
The solid component (E) is usually contained in an amount of 0.0
An amount is used such that it is in the range of 005 to 1 mol. In addition, organic aluminum Compound (B) has an aluminum / titanium atomic ratio of usually 1 to 3000, preferably
Is used in such an amount that the amount becomes 40 to 800.
The activity may be insufficient. Further, an alkoxy group-containing aromatic compound (C
) Has a molar ratio to a titanium atom in the solid catalyst component (A) or the solid component (E).
Is usually used at a ratio of 0.01 to 500, preferably 1 to 300,
If this amount is less than 0.01, the physical properties of the produced polymer may be reduced,
If it exceeds 0, the catalytic activity tends to decrease. The electron donating compound (D)
The molar ratio [(C) / (D)] with respect to the alkoxy group-containing aromatic compound (C) is
Usually used at a ratio of 0.01 to 100, preferably 0.2 to 100.
You. [0035]   Next, a method of producing the olefin polymer of the present invention using the above-described catalyst system is described.
The method will be described.   In the present invention, at least one kind of α-olefin is used in the presence of the above-mentioned catalyst system.
By polymerizing olefins, α-olefin homopolymers (for example, propylene
Homo-polymer) or α-olefin copolymer (for example, propylene-α-
Olefin random copolymer, ethylene-propylene block copolymer, etc.)
To manufacture.   In the present invention, the α-olefin used as a raw material has 2 to 2 carbon atoms.
30 are preferred, for example, ethylene, propylene, butene-1, pentene-
1,4-methylpentene-1, hexene-1, peptene-1, octene-1,
Nene-1, decene-1 and the like, which may be used alone or
, May be used in combination of two or more.   [0036]   Solventless polymerization methods such as gas phase polymerization and bulk polymerization are used as the polymerization method.
Preferably, gas phase polymerization is used.   Here, the gas phase polymerization includes a case where the polymerization is performed in one stage (a gas phase first stage polymerization method) and
The case where the reaction is carried out by a gas phase multistage polymerization method is included. Here, the gas-phase first-stage polymerization method uses α
-Olefin homopolymer (for example, propylene homopolymer, etc.) or propylene-
It is used when producing an α-olefin random copolymer or the like. Also the gas phase Multi-stage polymerization methods include ethylene-propylene block copolymers and ethylene-propylene
-Used for producing a polyene triblock copolymer or the like.   [0037]   Regarding the reaction conditions when performing polymerization by the gas-phase one-stage polymerization method,
5-100kg / cm^Two(Preferably 10 to 50 kg / cm^Two), The polymerization temperature is usually from 40 to
It is appropriately selected within a range of 90 ° C (preferably 60 to 75 ° C). Control of molecular weight of polymer
Is performed by a known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.
Can be. The polymerization time depends on the type of olefin as raw material and the reaction temperature.
Although it cannot be roughly determined, about 5 minutes to 10 hours is sufficient.   When polymerization is carried out by a gas-phase one-stage polymerization method, a particularly preferred α used as a raw material
As the olefin, propylene is used when homopolymerized, and
In this case, propylene and an α-olefin having 4 to 30 carbon atoms can be used. This
The molar ratio of α-olefin to propylene is from 0.2 to 20
A range is preferred.   [0038]   When a polymer is produced by a gas-phase multistage polymerization method, the first polymerization (first-stage polymerization) is α-
Olefin homopolymerization or copolymerization; propylene homopolymerization or propylene
Copolymerization of len with an α-olefin having 4 to 30 carbon atoms is preferred. Molecular weight control is public
This can be performed by known means (for example, adjustment of hydrogen concentration). The polymerization temperature is
, Usually 40 to 90 ° C (preferably 60 to 75 ° C), and the polymerization pressure is 5 to 100 ° C.
Kg / cm^Two(Preferably, 10 to 50 kg / cm^Two) And the polymerization time is 5 minutes to 10 hours
is there.   [0039]   From the second to the last polymerization (n-th stage polymerization), ethylene-propylene copolymerization
Or it is an ethylene-propylene-polyene copolymer.   Here, the polyene is preferably a non-conjugated polyene.
Antadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene
, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-
Isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene , 5- (1-butenin) -2-norbornene, cyclooctadiene, vinylcycl
Rohexene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9
-Tetrahydroindene, 2-2'-dicyclopentenyl, trans-1,2-
Divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-hexadi
Ene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1
, 9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl
1,7-octadiene, 1,4,7-octatriene, 5-methyl-1,8
-Nonadiene, norbornadiene, vinyl norbornene, etc.
. Among these non-conjugated polyenes, especially dicyclopentadiene, 5-ethylidene
2-norbornene and 1,7-octadiene are preferred.   [0040]   In each polymerization step, the molecular weight is adjusted by known means (for example, adjustment of the hydrogen concentration).
Section). In the case of ethylene-propylene copolymer,
Adjustment of the content of the tylene unit can be carried out by adjusting the composition of the charged gas. Also,
In the case of ethylene-propylene-polyene copolymer, polyene unit content control
Can be carried out according to the charged amount of the polyene compound. Polymerization temperature is 20 to 90
° C (preferably 40 to 50 ° C), and the polymerization pressure is 5 to 70 kg / cm.^Two(Preferably
10-40Kg / cm^Two) And the polymerization time is 5 minutes to 10 hours.   [0041]   In addition, the ethylene-propylene block copolymer was obtained by the gas-phase multistage polymerization method.
, Ethylene-propylene-polyene triblock copolymer and the like.   In the above polymerization, each component constituting the catalyst system, that is, (A)
After mixing (D) components at a predetermined ratio and bringing them into contact, olefin is immediately introduced.
Then, the polymerization may be started, or after aging for about 0.2 to 3 hours after the contact,
May be introduced. Furthermore, this catalyst component is converted to inert solvents, olefins, etc.
It can be supplied in suspension.   [0042]   In the present invention, post-treatment after polymerization can be carried out by a conventional method. Sand
That is, in the gas phase polymerization method, after polymerization, a polymer powder derived from a polymerization vessel is added to the polymer powder. May be passed through a nitrogen stream to remove olefins etc.
. If desired, pelletization may be carried out by an extruder.
A small amount of water, alcohol, or the like can be added to deactivate the water. Also
In the bulk polymerization method, after the polymerization,
After the monomer is separated, it can be pelletized.   [0043]   【Example】   Next, the present invention will be specifically described with reference to Examples and Comparative Examples.
However, the present invention is not limited to this.   The following reagents were used in the following Examples and Comparative Examples.   Metallic magnesium: Granular (average particle size 350 μm)   Ethanol: Wako Pure Chemical Industries, Ltd., special grade reagent   Iodine: Wako Pure Chemical Industries, Ltd., special grade reagent   Magnesium chloride: Wako Pure Chemical Industries, Ltd., reagent grade   [0044]Example 1 (1) Preparation of solid catalyst component (A)   Replace the glass reactor (with an internal volume of about 6 liters) with a stirrer with nitrogen gas.
Then, about 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium were injected.
And heat under reflux with stirring until hydrogen gas is no longer generated from the system.
The reaction was carried out below to obtain a solid reaction product. The reaction solution containing the solid reaction product is
The solid product (a) was obtained by drying under reduced pressure.   In a glass three-necked flask (internal volume 500 ml) sufficiently purged with nitrogen gas,
16 g of the solid product (a) (not pulverized), 80 ml of purified heptane,
2.4 ml of silicon tetrachloride and 2.3 ml of diethyl phthalate were added. 90 in the system
At 77 ° C while stirring and adding 77 ml of titanium tetrachloride and reacting at 110 ° C for 2 hours.
After that, the solid component was separated and washed with purified heptane at 80 ° C. Furthermore, tetrachloride
After adding 122 ml of titanium and reacting at 110 ° C. for 2 hours, purified heptane is sufficient.
To obtain a solid catalyst component (A).   [0045] (2) Gas phase first stage polymerization   AlEt in a 5-liter stainless steel autoclave_Three3 mmol, 1
-Allyl-3,4-dimethoxybenzene (ADMB) 0.15 mmol, dife
0.23 mmol of nildimethoxysilane (DPDMS) and the solid of the above (1)
Hep containing 100 mg of catalyst component (A) (0.06 mmol in terms of Ti atom)
20 ml of a tan solution were added. After exhausting the system for 5 minutes, the total pressure is 29Kg / cm^TwoUntil
Gas phase polymerization was performed at 70 ° C. for 1.7 hours while supplying propylene gas.   [0046]Examples 2-3   In Example 1, diphenyldimethoxysilane (D) component of the catalyst system was used.
The procedure was the same as in Example 1 except that the amount of DPDMS) was changed as shown in Table 1.Example 4   In Example 1, triethylaluminum (TE) as the component (B) of the catalyst system was used.
Same as Example 1 except that A) was changed to triisobutylaluminum (TiBA)
Was performed in the same manner.   [0047]Example 5   Example 4 was repeated except that the amount of hydrogen shown in Table 1 was added during polymerization.
The same was done.Examples 6 and 7   Example 1 was the same as Example 1 except that the amount of hydrogen shown in Table 1 was added during the polymerization.
The same was done.   [0048]Example 8 (1) Preparation of solid catalyst component (A)   A solid catalyst component (A) was obtained in the same manner as in Example 1 (1). (2) Preparation of solid component (E)   Into a 2.5-liter glass pressure-resistant three-necked flask, Heptane 1.7 liters, AlEt_Three0.07 mol, diphenyldimethoxy
0.05 mmol of orchid (DPDMS) and the solid catalyst component prepared in the above (1)
(A) 120 g were added. Keep propylene continuously at 30 ° C while stirring
Supply, internal pressure 0.5Kg / cm^TwoKept. After continuing this reaction for 1 hour,
It was washed five times with 1 liter of butane to obtain a solid component (E). (3) Gas phase first stage polymerization   Using the obtained solid component (E),Example 1 (2)Perform gas phase polymerization in the same manner as
Was.   [0049]Comparative Example 1 (1) Preparation of solid catalyst component (X)   A glass pressure-resistant three-necked flask with an inner volume of 0.5 liter that has been sufficiently purged with nitrogen,
Purified heptane 20ml, Mg (OEt)_Two4 g and di-n-butyl phthalate 1
. 2 g was added, and the system was kept at 90 ° C._Four4ml drop
After the addition of TiCl_FourAdd 111ml and raise the temperature inside the system to 110 ℃
did. After reacting at 110 ° C. for 2 hours, it was washed with purified heptane at 80 ° C. Get
TiCl on the solid phase_Four115 ml was added, and the mixture was further reacted at 110 ° C. for 2 hours.
. After the completion of the reaction, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component.
(X).   [0050] (2) Preparation of solid component (Y)   Into a 2.5-liter glass pressure-resistant three-necked flask,
Heptane 1.7 liters, AlEt_Three0.07 mol, diphenyldimethoxy
0.05 mmol of orchid (DPDMS) and the solid catalyst component prepared in the above (1)
(X) 120 g were added. Keep propylene continuously at 30 ° C while stirring
Supply, internal pressure 0.5Kg / cm^TwoKept. After continuing this reaction for 1 hour,
It was washed five times with 1 liter of butane to obtain a solid component (Y).   [0051] (3) Gas phase first stage polymerization   5 liter stainless steel autoclave containing 20g of polypropylene powder
In the reave, AlEt_Three3 mmol, 1-allyl-3,4-dimethoxybenzene (
ADMB) 0.15 mmol, diphenyldimethoxysilane (DPDMS) 0.
23 mmol and 100 mg of the solid component (Y) of the above (2) (in terms of Ti atom)
20 ml of a heptane solution containing 0.06 mmol). Exhaust the system for 5 minutes
After, the total pressure is 29Kg / cm^Two1.7 at 70 ° C. while supplying propylene gas until
Gas phase polymerization was performed for hours.   [0052]Comparative Examples 2-3   In Comparative Example 1, diphenyldimethoxysilane (component (D) of the catalyst system)
Comparative Example 1 was performed except that the amount of DPDMS) was changed as shown in Table 1.Comparative Examples 4 and 5   Comparative Example 1 was the same as Comparative Example 1 except that the amount of hydrogen shown in Table 1 was added during polymerization.
The same was done.   [0053]   Table 1 shows the catalyst compositions, polymerization conditions, and polymerization results of the above Examples and Comparative Examples.   Here, the powder fluidity was measured using a SUS powder fluidity tester shown in FIG.
It was measured by the following procedures 1 to 3. 1. Fix the fluidity tester horizontally and place the measurement powder sample (room temperature) in the tester.
) Is filled without giving vibration. 2. Open the lower gate when it is full with a razor bar and use a fluidity tester.
The time (T) until the powder in the inside is completely discharged is measured. 3. The weight (W) of the discharged powder is precisely weighed, and the powder fluidity (
F). Powder fluidity (F) = weight of powder (W) / time (T) [g / sec]   [0054]   Further, the melt index (MI), the amount of the HSP part and the intrinsic viscosity [η] were determined as follows.
I asked for it.   MI: using a test temperature of 230 ° C. and a test load of 2.16 kgf as measurement conditions And measured in accordance with JIS-K7210. HSP part: boiling heptane soluble matter The intrinsic viscosity [η] of the HSP part was measured in decalin at 135 ° C. [0055] [Table 1]   [0056]   【The invention's effect】   According to the present invention, it has practical tensile strength even in an unvulcanized state, and has flexibility and low temperature.
Sufficient properties, low surface stickiness, low production cost, and powder
A method for producing an olefin polymer having excellent fluidity is provided.   The vulcanized rubber-like olefin polymer produced according to the present invention can be used, for example, in automobile parts.
It is suitably used as a material for industrial machine parts, electronic / electric parts, building materials and the like.

[Brief description of the drawings]   FIG.   It is a flowchart figure which shows the manufacturing method of this invention.   FIG. 2   It is the schematic which shows a powder fluidity tester.

Claims (1)

Claims: 1. A method for producing an olefin polymer by a solventless polymerization method, comprising: (A) (a) a metal magnesium, an alcohol, and 0.0001 to 1 gram atom of the metal magnesium. At least 0.0001 gram atom per gram atom of halogen or the above magnesium metal in an amount of at least gram atom and less than 0.06 gram atom
, 0.06 and halogen-containing compound and the solid product obtained by reacting a containing an amount of halogen atoms is less than gram atom, tetravalent titanium compounds represented by (b) the following general formula and TiX ¹ n (OR ¹ ) _{4-n wherein} X ¹ is a halogen atom, especially a chlorine atom, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and the group R ¹ is When a plurality of groups are present, they may be the same or different from each other, and n is an integer of 0 to 4.)
, In the presence or absence of an electron-donating compound, a solid catalyst component obtained, (B) an organoaluminum compound, and (C) a general formula: Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms; R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group; m is an integer of 1 to 6; n is 0 or 1 to (6 -M). ] A process for producing an olefin polymer, comprising using a catalyst system comprising an alkoxy group-containing aromatic compound represented by the following formula: and (D) an electron donating compound. 2. A method for producing an olefin polymer by a solventless polymerization method, comprising: (E) a solid component comprising the solid catalyst component (A) according to claim 1 and a crystalline polyolefin; A process for producing an olefin polymer, comprising using a catalyst system comprising: an organoaluminum compound; (C) an alkoxy group-containing aromatic compound according to claim 1; and (D) an electron donating compound.