JP3411347B2 - Catalyst component for olefin polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION BACKGROUND OF THE INVENTION 1. Field of the Invention
Concerning catalyst components for olefin polymerization with good medium properties
It is. The catalyst component of the present invention is a transition metal component,
Catalysts combined with organoaluminum compounds as genus components
When olefin polymerization is carried out as
Greatly improved the adhesion, adhesion, etc.
With polymer due to blockage of pipes and adhesion of catalyst in polymerization tank
Problems such as adhesion were solved and coarse polymer particles
The polymerization reaction can be performed without any problem. [0002] 2. Description of the Related Art Olefin polymerization catalysts are conventionally inert.
Handling by diluting in solvent, dry state under inert gas
In the latter case, the catalyst performance is preserved stably.
From the viewpoints of properties, handling properties during transportation, etc.
Is the way. However, generally for olefin polymerization
When the catalyst is dried and handled in powder form, the so-called properties, e.g.
For example, poor fluidity, angle of repose, poor adhesion, etc.
There were various problems. So solving these problems
Although various proposals have been made for this purpose,
It is hard to say that it is at a level that can be done. The present inventors have proposed a catalyst
In order to improve the fluidity, properties, etc. of
g, a solid component containing halogen as an essential component,
Spherical polyethylene with a uniform particle size of 30 to 2000 microns
A method of adding (Japanese Patent Laid-Open No. 3-217404)
Information). However, this method has some improvement effects.
Fruit is observed, but if you change the type of solid component,
The effect is at a level where it is inadequate, and further improvements
Was desired. [0003] SUMMARY OF THE INVENTION
The problem to be solved is the powder property of the catalyst component for olefin polymerization.
For example, improving fluidity, angle of repose, adhesion, etc.
You. As a result, the use of the catalyst component of the present invention
When polymerization is carried out, various operation
For example, blockage of the catalyst introduction tube during catalyst introduction, polymerization tank
Adhesion and coarse particle formation due to catalyst adhesion inside
And so on. [0004] The present invention solves the above problems.
It was made as a result of study to solve it. sand
That is, the catalyst component for olefin polymerization of the present invention comprises the following components:
A mixture of component (A1) and component (A2), wherein
(A2) is used in a weight ratio to the component (A1).
In the range of 0.001 to 0.5, and the average of the component (A2)
Particle size is smaller than the average particle size of component (A1)K
Component (A2) adhered to the surface of component (A1)
Mainly exists inIt is characterized by the following.Component (A1) Titanium, magnesium and halogen as essential components
Ziegler-type catalyst solid components contained,Component (A2) From inorganic oxides, carbonates, sulfates and mixtures thereof
The selected compound. [0005] DETAILED DESCRIPTION OF THE INVENTION The catalyst component according to the present invention comprises the following:
It is a mixture of components (A1) and (A2). here,
A "mixture" refers to a component of the indication (ie,
Mixtures of Combinations of (A1) and (A2)) Made
Besides the mixture of the appropriate auxiliary ingredients
Is what it means. This catalyst component is composed of organic aluminum
Form olefin polymerization catalysts
Things. <Component (A1)>Essential ingredients Component (A1) comprises titanium, magnesium and halogen
Is a solid component containing as an essential component. Here,
`` Contains as a component ''
May contain other suitable elements outside
Elements exist as arbitrary compounds, each of which is purposeful
And these elements are interconnected
It may indicate that it may exist as a thing. H
Solid component containing tan, magnesium and halogen
Those are known. In the present invention, such a solid component and
Known ones can be used. For example, Japanese Unexamined Patent Publication No.
No. 45688, No. 54-3894, No. 54-3109
No. 2, 54-94383, 54-94591,
Nos. 54-118484, 54-131589,
Nos. 55-75411, 55-90510, 55-
No. 90511, No. 55-127405, No. 55-14
Nos. 7507, 55-155003, 56-186
No. 09, No. 56-70005, No. 56-72001
No. 56-86905, No. 56-90807, No.
Nos. 56-155206, 57-3803, 57-
No. 34103, No. 57-92007, No. 57-121
No. 003, No. 58-5309, No. 58-5310,
58-5311, 58-8706, 58-2
No. 7732, No. 58-32604, No. 58-32260
No. 5, No. 58-67703, No. 58-117206
Nos. 58-127708 and 58-183708
Nos. 58-183709 and 59-149905
And those described in JP-A-59-149906.
Used. Also, use tungsten or molybdenum
Those treated with a den compound are also included. The magnesium source used in the present invention
Magnesium compound
Id, dialkoxymagnesium, alkoxymagnesium
Um halide, magnesium oxy halide, dialky
Magnesium, magnesium oxide, magnesium hydroxide
And magnesium carboxylate. this
Among these magnesium compounds, magnesium
, Dialkoxymagnesium, alkoxymagnesium
Muhalides are preferred. Halide halogen is chlorine and
And bromine are typical, and alkoxy is lower alkoxy.
Shi is typical. Further, a titanium compound serving as a titanium source is
General formula Ti (OR¹ )_4-nX_n(Where R¹ Is hydrocarbon residue
Group, preferably having about 1 to 10 carbon atoms.
X represents a halogen, and n represents a number satisfying 0 ≦ n ≦ 4.
You. )). As a specific example
Is TiCl_Four , TiBr_Four , Ti (OC_Two H_Five ) Cl
_Three , Ti (OC_Two H_Five )_Two Cl_Two , Ti (OC_Two H_Five )
_Three Cl, Ti (O-iC_Three H ₇ ) Cl_Three , Ti (On-
C_Four H₉ ) Cl_Three , Ti (O-nC_Four H₉ )_Two Cl_Two,
Ti (OC_Two H_Five ) Br_Three , Ti (OC_Two H_Five ) (OC
_Four H₉ )_Two Cl, Ti (O-nC_Four H₉ )_Three Cl, Ti
(OC₆ H_Five ) Cl_Three , Ti (O-iC_Four H ₉ )_Two C
l_Two , Ti (OC_Five H₁₁) Cl_Three , Ti (OC₆ H₁₃)
Cl_Three , Ti (OC_Two H_Five )_Four , Ti (O-nC_Three H
₇ )_Four , Ti (O-nC_Four H₉ )_Four , Ti (O-iC_Four
H₉ )_Four , Ti (O-nC₆ H₁₃)_Four , Ti (O-nC
₈ H₁₇)_Four, Ti [OCH_Two CH (C_Two H_Five ) C_Four H
₉ ]_Four , And the like. Further, TIX '_Four (Where X 'is a halogen
), Which is reacted with an electron donor as described below.
Compounds can also be used. Tools for such molecular compounds
For example, TiCl_Four ・ CH_Three COC_Two H_Five , Ti
Cl_Four ・ CH_Three CO_Two C_Two H _Five , TiCl_Four ・ C₆ H_Five
NO_Two , TiCl_Four ・ CH_Three COCl, TiCl_Four ・ C
₆ H_Five COCl, TiCl_Four ・ C₆ H_Five CO_Two C_Two H
_Five , TiCl_Four ・ ClCOC_Two H_Five , TiCl_Four ・ C_Four
H_Four O, and the like. Among these titanium compounds
Also preferred are TiCl_Four , Ti (OC_Two H _Five )
_Four , Ti (OC_Four H₉ )_Four , Ti (OC_Four H₉ ) Cl_Three
And so on. The general formula Ti (OR^Two )_3-pX_p(This
Where R^Two Is a hydrocarbon residue, preferably having 1 carbon atom
X is a halogen, p is O
<P ≦ 3. ) Is also used.
Is available. As a specific example of such a titanium compound,
Is TiCl_Three , TiBr_Three , Ti (OCH_Three ) Cl
_Two , Ti (OC_Two H_Five ) Cl_Two Etc. In addition,
Clopentadienyl dichlorotitanium, dicyclopen
Tadienyl dimethyl titanium, bisindenyl dichloro
It is also possible to use titanocene compounds such as rotitanium.
You. As the halogen source, the above-mentioned magnesium
And / or supplied from titanium halides
Usually, but other sources of halogen, such as aluminum
And halides of silicon and phosphorus
Supply from known halogenating agents such as
Can also be. In addition, esters as electron donors (details
Subsequent) is converted to an acyl halide (for example, phthalic acid chloride).
C) and use that halogen as the halogen source
Can also be used. Halogen contained in catalyst components
Is fluorine, chlorine, bromine, iodine or a mixture thereof
And chlorine is particularly preferred. [0012]Optional components (Part 1) The solid component (A1) used in the present invention is in addition to the above essential components.
Before that various optional components may be further contained.
I just wrote it. Thus, for example, this solid component
In producing (A1), an electron donor is used as an internal donor.
It can be manufactured using. Made of this solid component
Electron donors (internal donors) that can be used for
Alcohols, phenols, ketones, aldehydes,
Esters of carboxylic acids, organic or inorganic acids, d.
Oxygen-containing electrons such as ethers, acid amides and acid anhydrides
Donor, ammonia, amine, nitrile, isocyanate
Examples of nitrogen-containing electron donors such as
Wear. More specifically, (a) methanol, ethanol
Knol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol
Benzyl alcohol, phenylethyl alcohol,
Cumyl alcohol, isopropylbenzyl alcohol
Which C 1-18 alcohols, (b) pheno
, Cresol, xylenol, ethylphenol,
Propylphenol, cumylphenol, nonylpheno
Number of carbons which may have an alkyl group such as phenol or naphthol
6 to 25 phenols, (c) acetone, methyl
Ethyl ketone, methyl isobutyl ketone, acetopheno
C3 to C15 ketones such as benzophenone and benzophenone
, (D) acetaldehyde, propionaldehyde,
Octylaldehyde, benzaldehyde, tolaldehyde
Al, C2 to C15 aldol such as naphthaldehyde
Aldehydes, (E) Methyl formate, methyl acetate, ethyl acetate
, Vinyl acetate, propyl acetate, octyl acetate,
Clohexyl, cellosolve acetate, ethyl propionate,
Methyl butyrate, ethyl valerate, ethyl stearate,
Methyl acetate, ethyl dichloroacetate, methyl methacrylate
, Ethyl crotonate, ethyl cyclohexanecarboxylate
, Methyl benzoate, ethyl benzoate, propyl benzoate
Butyl, butyl benzoate, octyl benzoate, shik benzoate
Rohexyl, phenyl benzoate, benzyl benzoate, ammonium
Cellosolve benzoate, methyl toluate, toluic acid ethyl
, Amyl toluate, ethyl ethyl benzoate, anise
Methyl acrylate, ethyl anisate, ethyl ethoxybenzoate,
Diethyl phthalate, dibutyl phthalate, diheptaphthalate
Chill, γ-butyrolactone, α-valerolactone, bear
2 to 2 carbon atoms such as phosphorus, phthalide and ethylene carbonate
0 organic acid esters, (f) ethyl silicate, silicate
Silicate esters such as tyl and phenyltriethoxysilane
Inorganic acid esters such as (G) acetyl chloride, benzoyl chloride
Lido, toluic acid chloride, anisic acid chloride, chloride
2 to 1 carbon atoms such as taroyl and phthaloyl isochloride
5, acid halides, (h) methyl ether, ethyl acetate
Ter, isopropyl ether, butyl ether, amyl
Ether, tetrahydrofuran, anisole, diphenyl
Ethers having 2 to 20 carbon atoms, such as
(Ii) acetic acid amide, benzoic acid amide, toluic acid amide
Acid amides such as (nu) methylamine, ethylamido
, Diethylamine, tributylamine, piperidine,
Tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine,
Acetonitrile, benzonitrile, tolunitrile, etc.
And nitriles. These kids
Two or more donors can be used. Stereoregular polymerization
Is important in the polymerization of olefins having 3 or more carbon atoms,
It is preferably used when preparing a catalyst component for polymerization of propylene.
Electron donors are organic acid esters and organic acid halides.
Particularly preferred are phthalic acid esters and cellosol acetate
And phthalic acid halides. [0016]Composition ratio of component (A1) (part 1) The amount of each of the above components depends on whether the effects of the present invention are recognized.
Can be arbitrary, but in general,
preferable. The amount of titanium compound used depends on the magnesium used.
1 × 10^-Four-10
Within the range of 00, preferably in the range of 0.01 to 10
Is within. Use compounds therefor as halogen sources
If used, the amount of titanium compound and / or
Whether the magnesium compound contains halogen or not
Nevertheless, the molar ratio to the amount of magnesium used
At 1 × 10^-2~ 1000, preferably 0.1-100,
Is within the range. When using electron donating compounds
The dosage is based on the amount of magnesium compound used.
1 × 10^-3-10, preferably 0.01-5
Within range. [0017]Production of Component (A1) (Part 1) The solid component of the component (A1) includes the above-mentioned titanium source and magnesium.
Source and halogen source and, if necessary, electron donor
Using the above or other components described below, for example,
It is manufactured by a simple manufacturing method. (A) Magnesium halide and titanium-containing compound
A method of contacting with an electron donor as needed. (B) Halogenated phosphorus from alumina or magnesia
Treated with the compound, and magnesium halide, electric children
A method of contacting a donor with a titanium halide-containing compound. (C) Magnesium halide and titanium tetra alcohol
Oxide and certain polymeric silicon compounds
The resulting solid component includes a titanium halide compound and
Or) contacting with a halogen compound of silicon. As this polymer silicon compound,
Is appropriate. Embedded image (Where R^Three Is a hydrocarbon residue having about 1 to 10 carbon atoms,
q is the viscosity of the polymer silicon compound is 1 to 100 centimeters.
It shows a degree of polymerization that is on the order of Chistokes. )these
Among them, methyl hydrogen polysiloxane, d
Tyl hydrogen polysiloxane, phenyl hydro
Genpolysiloxane, cyclohexyl hydrogen
Polysiloxane, 1,3,5,7-tetramethylcyclo
Tetrasiloxane, 1,3,5,7,9-pentamethyl
Cyclopentasiloxane and the like are preferred. (D) The magnesium compound is titanium tet
Dissolved in a alkoxide and an electron donor to form a halogen
Solid component precipitated with a halogenating agent or a titanium halide
A titanium compound in contact with (E) Organic magnesium compounds such as Grignard reagents
After reacting with a halogenating agent, reducing agent, etc.
Contacting an electron donor with a titanium compound according to (F) Halogenating agents for alkoxymagnesium compounds
And / or titanium compound in the presence of an electron donor
Or contact in the absence. (G) In any of the above, the optional components described below
How to live. The contact temperature is preferably about -50 to 200 ° C.
Or about 0 to 100 ° C. As a contact method,
Rotary ball mill, vibration mill, jet mill, medium stirring powder
Mechanical method using a crusher, in the presence of an inert diluent
And a method of contacting by stirring. this
Sometimes used inert diluents are aliphatic or aromatic
Group hydrocarbons, halohydrocarbons, polysiloxanes, etc.
can give. In making these contacts, the effect of the present invention
Unless otherwise impaired, other components other than the above components
Minutes, for example, methyl hydrogen polysiloxane, e
Ethyl borate, aluminum triisopropoxide, trisalt
Aluminum chloride, silicon tetrachloride, tetravalent titanium compound,
It is also possible to coexist trivalent titanium compounds, etc.
(Details below). Thus, titanium, magnesium
And Ziegler touch containing halogen as an essential component
The solid component (A1) for a medium is obtained.Optional components (Part 2) The component (A1) used in the present invention comprises the essential component (T)
i, Mg and halogen)
In addition, it was previously stated that an electron donor may be included as an optional component.
As described above, the following optional components are also included.
Can be used. That is, the component (A1)
Is SiCl_Four , CH_Three SiCl_Three Silicon compounds such as
Polymer silicone such as methyl hydrogen polysiloxane
Elemental compound, Al (OiC_Three H₇ )_Three , AlCl_Three , Al
Br_Three , Al (OC_Two H_Five )_Three , Al (OCH _Three )_Two C
l and an aluminum compound such as B (OCH_Three )_Three , B
(OC_Two H_Five ) _Three , B (OC₆ H_Five )_Three Boron compounds such as
Object, WCl₆ , WCl_Five , Wl_Five Tungsten compounds such as
Object, MoCl_Five , MoBr_Five Such as molybdenum compounds
Other components can be used together, such as silicon and aluminum.
Components such as uranium, boron, tungsten and molybdenum
May remain in the solid component. As the silicon compound, in addition to the above,
An organosilicon compound of the general formula can be mentioned. R^Four R^Five _3-rSi (OR⁶ )_r (However, R^Four Represents a branched hydrocarbon residue, R^Five Is R^Four
The same or different hydrocarbon residue as⁶ Is hydrocarbon
And r represents a number satisfying 1 ≦ r ≦ 3).
Is a silicon compound. Where R^Four Is a silicon atom
And those which are branched from a carbon atom adjacent to.
In this case, the branched group may be an alkyl group, a cycloalkyl group, or the like.
Or an aryl group (eg, a phenyl group or a methyl group)
(A substituted phenyl group). More preferred
R^Four Is a carbon atom adjacent to a silicon atom, that is, α-
Is a secondary or tertiary carbon atom
is there. In particular, the carbon atom bonded to the silicon atom
Tertiary ones are preferred. R^Four Usually has 3 to 20 carbon atoms,
Preferably it is 4-10. R^Five Has 1 to 2 carbon atoms
0, preferably 1-10, branched or linear aliphatic
It is usually a hydrocarbon group. R⁶ Is aliphatic charcoal
A hydride group, preferably a linear aliphatic hydrocarbon having 1 to 4 carbon atoms
It is usually an elementary group. This silicon compound
May be a mixture of a plurality of compounds of the above formula.
This silicon compound is a carbon compound where stereoregular polymerization is important.
Polymerization of α-olefin of 3 or more, especially
In such a case, it is preferably used at the time of preparing the catalyst component used in the reaction. Ma
The silicon compound and the electron of the optional component (part 1)
Donor compounds may be used independently or as a mixture.
It is. Specific examples of the silicon compound used in the present invention
Is as follows. (CH_Three )_Three CSi (CH_Three )
(OCH_Three )_Two , (CH_Three )_Three CSi (CH (CH_Three )
_Two ) (OCH_Three )_Two , (CH_Three )_Three CSi (CH_Three )
(OC_Two H_Five )_Two , (C_Two H_Five )_Three CSi (CH_Three )
(OCH_Three )_Two , (CH_Three ) (C_Two H_Five ) CH-Si
(CH_Three ) (OCH_Three )_Two , ((CH_Three )_Two CHCH
_Two )_Two Si (OCH _Three )_Two , (C_Two H_Five ) (CH_Three )_Two
CSi (CH_Three ) (OCH_Three )_Two , (C_Two H _Five ) (CH
_Three )_Two CSi (CH_Three ) (OC_Two H_Five )_Two , (CH_Three )
_Three CSi (OCH_Three )_Three , (CH_Three )_Three CSi (OC_Two
H_Five )_Three , (C_Two H_Five )_Three CSi (OC_Two H_Five )_Three ,
(CH_Three ) (C_Two H_Five ) CHSi (OCH_Three )_Three , (C
_Two H_Five ) (CH_Three )_Two CSi (OCH_Three )_Three , (C_Two H
_Five ) (CH_Three )_Two CSi (OC_TwoH_Five )_Three , (CH_Three )_Three
 CSi (O-tC_Four H₉ ) (OCH_Three )_Two , (IC_Three
H ₇ )_Two Si (OCH_Three )_Two , (IC_Three H₇ )_Two Si
(OC_Two H_Five )_Two , (C₆ H ₁₁) Si (CH_Three ) (OC
H_Three )_Two , (C₆ H₁₁)_Two Si (OCH_Three )_Two , (C ₆
H₁₁) (IC_Four H₉ ) Si (OCH_Three )_Two , (IC_Four H
₉ ) (Sec C_Four H₉ ) Si (OCH_Three )_Two , (IC_Four H
₉ ) (IC_Three H₇ ) Si (OC_Five H₁₁)_Two , (C_Five H
₉ )_Two Si (OCH_Three )_Two , (C_Five H₉ )_Two Si (OC
_Two H_Five )_Two , (C _Five H₉ ) (CH_Three ) Si (OCH_Three )
_Two , (C_Five H₉ ) (IC_Four H₉ ) Si (OCH_Three )_Two , Embedded image Embedded image Embedded image Embedded image Of these, preferred is R^Four The carbon at the α-position is secondary
Or tertiary branched chain hydrocarbon residues having 3 to 20 carbon atoms,
To R^Four In which the carbon at the α-position is tertiary and has 4 to 10 carbon atoms
A silicon compound having a branched hydrocarbon residue. Furthermore, in the present invention, the production of the component (A1)
And, if necessary, organic compounds of metals of Groups I to III of the Periodic Table.
Metal compounds can also be used. With organometallic compounds
Therefore, this compound has at least one organic group-metal
Have a bond. In this case, the organic group may have 1 to 1 carbon atoms.
About 0, preferably about 1 to 6, hydrocarbyl groups
Representative. Metals in this compound include lithium
Aluminum, magnesium, aluminum and zinc, especially aluminum
Minium is typical. At least one of the valences
The remainder of the metal of the organometallic compound being filled with organic radicals
Valence (if any) is determined by hydrogen atom, halogen atom
And a hydrocarbyloxy group (a hydrocarbyl group is a carbon
About 1 to 10, preferably about 1 to 6), or
The metal via an oxygen atom (specifically, methyl alcohol
-O-Al (CH in the case of xan_Three )-), Other
Added. Specific examples of such organometallic compounds are given below.
Then, (a) methyllithium, n-butyllithium,
Organolithium compounds such as tributyllithium, (b) buty
Ruethyl magnesium, dibutyl magnesium, hex
Ruethyl magnesium, butyl magnesium chloride,
Organic magnesium such as tert-butylmagnesium bromide
Compounds, (c) organic zinc such as diethyl zinc, dibutyl zinc, etc.
Lead compounds, (d) trimethylaluminum, triethyl
Aluminum, triisobutylaluminum, tri-n-
Hexyl aluminum, diethyl aluminum chloride
, Diethylaluminum hydride, diethylaluminum
Um ethoxide, ethyl aluminum sesquichloride,
Ethyl aluminum dichloride, methyl aluminoxane
And the like. Of these
Is particularly preferably an organoaluminum compound. Organic al
Further specific examples of the minium compound are as component (B)
It is found in the examples of organoaluminum compounds described below.
Can be. Further, a vinylsilane compound as an optional component
Can also be used. This vinyl silane compound is
Use organic aluminum compound as optional component
In some cases, before or simultaneously with the use of the organoaluminum compound
It is preferred to use. Specifically, monosilane (Si
H_Four At least one hydrogen atom in vinyl (CH) _Two
= CH-) and the remaining hydrogen atoms
Some of which are halogen (preferably Cl),
(Preferably having 1 to 12 carbon atoms, more preferably carbon
An alkoxy group (preferably having 1 to 4 carbon atoms)
To 12, more preferably 1 to 4 carbon atoms),
Reel (preferably phenyl), etc., replaced by
, And more specifically, CH_Two = CH-
SiH_Three, CH_Two = CH-SiH_Two (CH_Three ), CH_Two
= CH-SiH (CH_Three )_Two , CH_Two = CH-Si (C
H_Three )_Three , CH_Two = CH-SiCl_Three , CH_Two = CH-
SiCl_Two (CH_Three ), CH_Two = CH-SiCl (CH
_Three ) H, CH_Two = CH-SiCl (C_Two H_Five )_Two , CH
_Two = CH-Si (C_Two H_Five )_Three , CH_Two = CH-Si
(CH_Three ) (C_Two H_Five )_Two , CH_Two = CH-Si (C₆
H_Five ) (CH_Three )_Two , CH_Two = CH-Si (CH_Three )_Two
(C₆ H_Four CH_Three ), CH_Two = CH-Si (OCH_Three )
_Three , CH_Two = CH-Si (OC_Two H_Five )_Three , CH_Two = C
H-Si (C_TwoH_Five ) (OCH_Three )_Two , CH_Two = CH-
Si (OC_Two H_Five )_Two H, Embedded image Embedded image (CH_Two = CH) (CH_Three )_Two -Si-O-Si (CH
_Three )_Two (CH = CH_Two ), (CH_Two = CH)_Two SiCl
_Two , (CH_Two = CH)_Two Si (CH_Three )_Two Etc.
Can be Of these, do not contain oxygen
Vinyl silane is preferred, and vinyl silane is more preferred.
Alkylsilanes and vinylhaloalkylsilanes
You. [0025]Optional component (Part 3) Optional during or after preparation of component (A1) of the present invention
Ethylene such as olefins and diene compounds as components
It is also possible to use unsaturated compounds. like that
Specific examples of the ethylenically unsaturated compound include ethylene,
Propylene, 1-butene, 2-butene, isobutylene,
1-pentene, 2-pentene, 2-methyl-1-butene
, 3-methyl-1-butene, 1-hexene, 2-hexene
Sen, 3-hexene, 2-methyl-1-pentene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 2
-Methyl-2-pentene, 3-methyl-2-pentene,
4-methyl-2-pentene, 2-ethyl-1-butene,
2,3-dimethyl-1-butene, 3,3-dimethyl-1
-Butene, 2,3-dimethyl-2-butene, 1-hepte
1-octene, 2-octene, 3-octene, 4-
Octene, 1-nonene, 1-decene, 1-undecene,
1-dodecane, 1-tridecane, 1-tetradecane, 1
-Pentadecane, 1-hexadecane, 1-heptadeca
1-octadecane, 1-nonadecane, Styrene, α-methyl-styrene, divinyl
Benzene, 1,2-butadiene, isoprene, hexa
Diene, 1,4-hexadiene, 1,5-hexadiene
1,3-pentadiene, 1,4-pentadiene,
2,3-pentadiene, 2,6-octadiene, cis
-2, trans 4-hexadiene, trans 2, trans 4-
Hexadiene, 1,2-heptadiene, 1,4-hepta
Diene, 1,5-heptadiene, 1,6-heptadie
2,4-heptadiene, dicyclopentadiene,
1,3-cyclohexadiene, 1,4-cyclohexadi
Ene, cyclopentadiene, 1,3-cycloheptadie
1,3-butadiene, 4-methyl-1,4-hexa
Diene, 5-methyl-1,4-hexadiene, 1,9-
Decadiene, 1,13-tetradecadiene, etc.
You. These can be combined with an organoaluminum compound if necessary.
When both are brought into contact with the component (A1), polymerization usually occurs.
Component (A1) thus produced,
This means that the pre-polymerization has been completed. Prepolymerization
The amount of pre-polymerization in the case of carrying out the reaction is based on the ratio of the component (A1) per weight.
, Preferably 0.01 to 100, more preferably 0.1 to 100.
1 to 10. Generally, such prepolymerization is
Reduces the amount of heat generated per catalyst particle, facilitates heat removal,
This is especially true for the formation of polymer chunks in gas phase polymerization.
It is effective for avoidance. [0027]Composition ratio and production of component (A1)
2) Silicon, aluminum, boron and tan as optional components
Use when using gustene and molybdenum compounds
The amount is a mole relative to the amount of the magnesium compound used.
1 × 10 in ratio^-3-100, preferably 0.01-10,
Is within the range. Among the above optional components, alkoxyke
Special mention of iodine compounds and organometallic compounds,
It is as follows. That is, the above-mentioned alkoxy silicon
The amount of compound and organometallic compound used is effective
It can be anything as far as possible, but in general the following
Enclosures are preferred. The amount of the silicon compound to be used depends on the amount of the component (A1)
Atomic ratio of silicon to titanium component (silicon)
/ Titanium) in the range of 0.01 to 1000 is preferable,
Or 0.1 to 100. Organometallic compounds
Is used with respect to the titanium component constituting the component (A1).
The metal atom ratio (metal / titanium) of the organometallic compound is 0.
01-100, preferably 0.1-30.
You. These optional components (No. 2) include the component (A)
1) Incorporation into component (A1) at any stage of production
One of which is an essential component of component (A1) and
From the electron donor (arbitrary component (Part 1))
In the process of preparing a solid composition by a method such as
The introduction of 2) is as described above.
You. The amount of the vinyl silane compound used is the amount of the component
Atomic ratio of silicon to titanium component constituting (A1)
(Silicon / titanium) within the range of 0.001 to 1000
Well, preferably it is in the range of 0.01 to 100.
Further, the optional ethylenically unsaturated compound is a component (A)
It is considered that polymerization occurs during the preparation of 1). Its usage
Is 0.0% with respect to the component (A1) before use of these compounds.
1 to 100 times by weight, preferably 0.1 to 10 times by weight,
is there. <Component (A2)> Component used in the present invention
(A2) is an inorganic oxide, carbonate, sulfate and the like
Is a compound selected from the mixture of Used in the present invention
Component (A2) can be used in the form of primary particles
However, those primary particles aggregate and secondary particles or
Tertiary particles can also be used. Here
As long as the effect of the present invention is recognized,
Can be used, for example,
Can be illustrated. TiO_Two, SiO_Two , Al (OH)_Three , A
l_Two O_Three , CaCO_Three , MgCO_Three , Al_Two O _Three ・ 4S
iO_Two ・ H_Two O, Al_Two O_Three ・ 2SiO_Two ・ 2H_Two O,
Al_Two O_Three ・ 2SiO_Two 、 3MgO ・ 4SiO_Two ・ H_Two
O, 3CaO · Al_Two O_Three ・ 3CaSO _Four ・ 31H_Two
O, SiO_Two ・ NH_Two O, BaSO_Four , Al_Two SiO
_Five 、 3CaO ・ SiO_Two , Ba_Two SiO_Four , Al_Two O_Three
・ Na_Two O · 6SiO_Two , Al_Two O_Three・ CaO ・ 2Si
O_Two , Cd_Two SiO_Four , BaTiO_Three , ZrO_Two , Zeo
And the like, preferably zeolite, Al_Two O_Three ,
TiO_Two , SiO_Two And ZrO _Two , Etc., and even better
Preferably, TiO_Two And ZrO_Two , Etc. The particle properties of the component (A2) are as follows.
It can be anything, as long as it is effective,
Generally, the following are preferred. The shape is spherical,
Any shape can be used, and the particle size is large
It is preferable that the primary particle diameter is small.
The average particle diameter of the particles is preferably 1 μm or less, more preferably
Preferably, it is 0.1 μm or less. Primary particles aggregate and secondary
Particles or tertiary particles are produced, but secondary particles or tertiary particles
As the size of the secondary particles, the average particle diameter is used in the present invention.
Component (A1) must be smaller than the average particle size.
It is important. Furthermore, with respect to the average particle size of the component (A1)
The ratio of the average particle diameter of the component (A2) is preferably 0.00
01-0.5, more preferably 0.0005-0.1
Is within the range. The reason is clear so far
Although the component (A1) is not
2) presumes that adsorption is a requirement. <Production of the catalyst component (A)> The catalyst component of the present invention
(A) is composed of component (A1) and component (A2).
This is as described above. Such catalysts
The component (A) is composed of the component (A1) obtained in advance and the component
And (A2).
At this time, the amount of component (A2) used is relative to component (A1).
Weight ratio within the range of 0.001 to 0.5,
More preferably, it is in the range of 0.005 to 0.1. Ingredient (A
The method of mixing 1) and component (A2) shows the effect of the present invention.
Inert gas (charged)
Is preferable), for example, nitrogen gas atmosphere
Mixing method below, inert solvent such as hexane,
Mixing in the presence of a hydrocarbon solvent such as butane
is there. Mix component (A1) and component (A2) prepared in advance.
By combining, the component (A2) becomes the surface of the component (A1)
It is mainly present in a state of being attached to. Also mixing is
Method with stirring, vibration mill, rotary ball mill, etc.
Mixing with a mill, shaking, etc.
It is. The mixing time is 1 minute to 100 hours, preferably
Is about 5 minutes to 10 hours. The catalyst component for olefin polymerization according to the present invention
A catalyst made of a combination of organoaluminum
Fins can be polymerized. <Formation of catalyst> The catalyst used in the present invention is composed of the above components.
(A) and aluminum, or these components
And optionally a third component (eg a so-called external donor)
Olefin to be polymerized in the polymerization tank
Olefin to be polymerized in the absence or outside of the polymerization tank
One step at a time, with or without fins
Or by dividing and contacting several times
Can be formed. As a specific example of the organoaluminum compound,
Means (a) trimethylaluminum, triethylaluminum
, Triisobutylaluminum, trihexylurea
Luminium, trioctyl aluminum, tridecylua
Trialkylaluminum such as luminium, (b)
Diethyl aluminum monochloride, diisobutyryl
Luminium monochloride, ethyl aluminum sesqui
Chloride, ethyl aluminum dichloride, etc.
Alkyl aluminum halide, (c) diethyl aluminum
Hydride, diisobutylaluminum hydride
Alkyl aluminum hydrides such as rides,
(D) Diethyl aluminum ethoxide, diethyl alkoxide
Aluminum alkoxy such as minium phenoxide
And so on. The organoaluminum of (a) to (d)
The compound may include other organometallic compounds, such as R⁷ _3-vAl (O
R⁸ )_v(Where 1 ≦ v ≦ 3, R⁷ And R⁸ Are the same
Or a hydrocarbon residue having about 1 to 20 carbon atoms which may be different
Group. Alkyl aluminum alcohol represented by)
Oxide can be used in combination. For example, triethyl
Aluminum and diethylaluminum ethoxide
For diethylaluminum monochloride and diethylamine
Combination of Luminium Ethoxide, Ethyl Aluminum Dic
Chloride and ethylaluminum diethoxide
Liethyl aluminum and diethyl aluminum ethoxy
And diethyl aluminum chloride in combination.
You. The amount of the organic aluminum compound used is
Aluminum compound / component (A) is 0.1 to 1000,
It is preferably in the range of 1 to 100. E according to the present invention
The method for producing the olefin polymer is the same as the above-mentioned component (A).
Catalysts consisting of a combination of organic aluminum compounds,
It consists of contacting a fin and polymerizing it.
You. <Polymerization mode> Method for producing polymer according to the present invention
Can be batch, continuous, or semi-batch
Is also feasible. The monomer used at this time is the medium
Of polymerization as a gaseous unit without using a medium
Polymerization in a monomer, or a combination of these
For polymerization. Preferred mode of polymerization
Is to perform polymerization in gaseous monomers without using a medium.
Method, for example, by flowing the resulting polymer particles in a monomer stream.
To form a fluidized bed or produced polymer particles
Is stirred in a reaction tank by a stirrer. <Olefin monomer and formed polymer>
The olefins polymerized with the catalyst system of the invention have the general formula R⁹ −
CH = CH_Two (Where R⁹ Is a hydrogen atom or carbon number 1
Ten hydrocarbon residues, which may have a branched group. )
It is represented by Specifically, ethylene, pro
Pyrene, butene-1, pentene-1, hexene-1, 4
Olefins such as -methylpentene-1. Like
Or ethylene and propylene. These polymerizations
, Up to 50 weight percent based on ethylene,
Preferably up to 20 weight percent of the olefin
Can be copolymerized with ethylene and propylene
Up to 30 weight percent of the above olefins,
Can be copolymerized with ethylene and propylene
Wear. In addition, other copolymerizable monomers (for example, acetic acid)
Copolymerization with vinyl, diolefin, etc.)
Wear. Typical examples of the polymer obtained according to the present invention include:
(A) homopolymers such as ethylene and propylene, (b)
Ethylene and propylene, ethylene and butene-1, ethylene
And propylene, ethylene and butene-1, ethylene and
Xen-1, ethylene and octene-1, propylene and butyl
Random Copo such as Ten-1, Propylene and Hexene-1
Limmer, and (c) if propylene and ethylene
A block of propylene and ethylene / propylene
And copolymers. <Polymerization conditions> The polymerization temperature is 30 ° C to 150 ° C, preferably
The polymerization pressure is usually from 1 to 5
0kg / cm^Two G is within the range. In addition, in polymerization
Can be converted to MF by using a molecular weight modifier such as hydrogen, if necessary.
It is also possible to control R. [0038] EXAMPLES In the following experimental examples, solid catalyst components
The fluidity is 3mmφ, 5mmφ, 6.5mmφ, 8mmφ, 12
Stainless steel with a cone angle of 30 ° with various outlet diameters of mmφ
Introduce 14cc of solid catalyst component powder into the funnel
It was measured. The figures are the minimum pore diameters at which outflow occurs within 15 seconds.
displayed.The particle size of the component (A1) is determined by a light transmission type particle size distribution measuring device.
"SeishinMicron Photosize
r SKN-1000 ”and heptane as solvent
It was measured by the sedimentation method and indicated by the average particle size on a weight basis. Ma
The particle size of the component (A2) was determined with an electron microscope.
The particle size in a certain direction was measured and indicated as an average particle size. <Example 1> [Production of component (A1)] In a flask sufficiently purged with nitrogen
500 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2_Two 0.4 mol, Ti (O-
nC_Four H₉ )_FourWas introduced at 95 ° C. for 2 hours.
I responded. After completion of the reaction, the temperature was lowered to 40 ° C.
Chill hydropolysiloxane (20 centistoke
Was introduced and reacted for 3 hours. Raw
The solid component formed was washed with n-heptane. Next,
N-purified in the same manner as above.
100 ml of heptane was introduced and synthesized above.
0.2 mol of a solid component was introduced in terms of Mg atom. Incidentally
25 ml of n-heptane in SiCl_Four 0.45 m
And introduced into the flask at 20 ° C. for 60 minutes.
The reaction was performed at 0 ° C. for 3 hours. After the reaction is completed, add n-heptane
After washing, component (A) was obtained. Take out part and ingredients
When the titanium content of (A) was measured, it was 2.79% by weight.
When the particle size was measured by a light transmission sedimentation method,
It was 15.8 microns. [Mixing of component (A1) and component (A2) (combination of component (A)
)), And purified sufficiently in a flask which was sufficiently purged with nitrogen.
50 ml of n-heptane was introduced, and the component (A1)
10 g and TiO as component (A2)_Two (Japan
Aerosil, primary particle average diameter 0.02μ, specific surface area
55m^Two/ G, average particle diameter 0.3 micron (this average particle diameter
Is measured with a transmission electron microscope, and primary particles aggregate.
The measured particles were measured. 0.1 g)
And stirred at room temperature to mix. After stirring, heptane
Was removed and dried to obtain Component (A). Ingredients obtained
When the properties of (A) were examined, the angle of repose was 38 degrees and the fluidity
Is 3mmφ and has a bulk density of 0.54g / cc
It was good. The particles of components (A2) and (A1)
The ratio of the diameters is 0.019, and the amount of the component (A2) used is
The weight ratio to the component (A1) was 0.01. <Comparative Example 1> [Production of catalyst component (A)] Production of component (A) of Example 1
In the above, component (A1) is used directly as component (A).
Used. Angle of repose is 61 degrees, fluidity does not flow, bulk density is
The property was very poor at 0.36 g / cc. <Application Example 1> Using the catalyst component of the present invention
Thus, the α-olefin was polymerized. [Propylene polymerization] with stirring and temperature control device
1.5 liter stainless steel autoclave
The polymer carrier (average particle size)
30 g of 500 μm polyethylene) in triethyl
125 mg of aluminum, dicyclopentyldi
18 mg of methoxysilane and in Example 1 above
20.7 milligrams of the synthesized component (A) and an inner diameter of 1.
It was introduced through a 5 mm catalyst introduction tube. Then H_Two To 300
Introduce a small amount, raise the temperature and raise the pressure, polymerization pressure = 7 kg / cm^Two
G, polymerization temperature = 75 ° C, polymerization time = 2 hours
Was performed. After the polymerization, the polymerized polymer is recovered.
Was. As a result, 66.3 grams of a polymer was obtained.
MFR = 21.4 (g / 10 min), polymer bulk specific gravity =
It was 0.45 (g / cc). By boiling heptane extraction
When the stereoregularity (II) was examined, 97.2% by weight was obtained.
Met. After the end of polymerization, catalyst residue adheres to the catalyst introduction tube.
There was no polymer adhesion in the polymerization tank. Ma
The same catalyst introduction and polymerization operation was repeated 10 times.
However, no adhesion was observed in the catalyst introduction tube and polymerization tank
Was. <Comparative Application Example 1> [Polymerization of Propylene] Component (A) synthesized in Example 1
Instead of using the component (A) synthesized in Comparative Example 1
Was polymerized under exactly the same conditions as in Application Example 1. However
The amount of component (A) used was 20.7 milligrams.
Was. The result is 64.1 grams of polymer,
FR = 20.8 (g / 10 min), polymer bulk specific gravity = 0.
42 (g / cc). Note that a small amount
However, adhesion of catalyst residues was observed. Also, a similar catalyst
Repeated the introduction and polymerization operations, but introduced the catalyst for the fifth time
The tube became blocked and polymerization was not possible. <Embodiment 2> [Production of component (A1)] In a flask sufficiently purged with nitrogen
200 ml of dehydrated and deoxygenated n-heptane
And then MgCl 2_Two 0.4 mol, Ti (O-
nC_Four H₉ )_FourWas introduced at 95 ° C. for 2 hours.
I responded. After completion of the reaction, the temperature was lowered to 40 ° C.
Cylhydropolysiloxane (20 centaStokes
Was introduced and reacted for 3 hours. Raw
The solid component formed was washed with n-heptane. Then enough
Into a flask purged with nitrogen as described above.
50 ml of butane was introduced, and the solid synthesized above
The components were introduced in an amount of 0.24 mol in terms of Mg atoms. Then n
-SiCl in 25 ml of heptane_Four   0.4 mol
And introduced into the flask at 30 ° C. for 30 minutes.
The reaction was carried out at 3 ° C. for 3 hours. After the reaction, wash with n-heptane
Was cleaned. Then phthalate was added to 25 ml of n-heptane.
0.024 mol of acid chloride was mixed at 70 ° C., 30
The reaction mixture was introduced into the flask in 90 minutes and reacted at 90 ° C. for 1 hour.
After the completion of the reaction, the resultant was washed with n-heptane. Then SiCl
_Four   Introduce 10 ml and react at 80 ° C for 6 hours
I let you. After the completion of the reaction, the resultant was sufficiently washed with n-heptane. This
Had a titanium content of 1.24% by weight. sufficient
N-heptane fully purified in a flask purged with nitrogen
Was introduced, and then the solid component obtained above was added.
Minutes, then introduce (CH_Three ) _Three CSi (C
H_Three ) (OCH_Three )_Two 2.4 ml, then
3.0 g of triethylaluminum and divinyl
15 g of benzene were introduced and contacted at 30 ° C for 2 hours.
I let you. After the contact is completed, the components are thoroughly washed with n-heptane, and
(A1). The polymerization amount of divinylbenzene is
1.4 g / g solid component (divinylbenzene polymerization
The average particle size was 27.8 microns.
Was. [Mixing of component (A1) and component (A2)
(Synthesis of (A)) 100 ml
Example: 10 grams of component (A1) in a torr sample bottle
Same TiO used in 1_Two 0.01 g,
Mix for 5 minutes with a shaker. Of the obtained component (A)
When the properties were examined, the angle of repose = 37 degrees and the fluidity = 3 mmφ
And the bulk density is 0.58 g / cc, which is very good
Was something. The particle diameters of the components (A2) and (A1)
The ratio was 0.011, and the amount of component (A2) used was
The ratio was 0.01. <Comparative Example 2> [Production of catalyst component (A)] Synthesis of component (A) in Example 2
In the above, component (A1) is used directly as component (A).
Used. Angle of repose = 57 degrees, fluidity = 12 mmφ, bulk density is
0.39 g / cc, which was very poor. <Examples 3 to 6> The components (A) of Example 2
In the synthesis, the component (A2) TiO_Two Table 1 shows the amount of
And mixing of component (A1) and component (A2)
Was performed in exactly the same manner except that the
A minute (A) was synthesized. Table 1 shows the results. [0047] [Table 1] <Embodiment 7> [Production of component (A1)] Substituted with sufficiently purified nitrogen.
Mg (OC) in a 500 ml flask_TwoH_Five )_Two
20 g, n-heptane 100 ml, then
TiCl_Four   Introduce 60 ml and heat up to 70 ° C
And 7.6 ml of di-n-octyl phthalate
The mixture was introduced, heated to 100 ° C., and reacted for 3 hours. End of reaction
Thereafter, the substrate was sufficiently washed with n-heptane. Then, TiCl
_Four   Introduce 100 ml and react at 110 ° C for 3 hours
I responded. After the completion of the reaction, the resultant was sufficiently washed with n-heptane,
It was set as component (A1). Take out part and adjust titanium content
As a result of measurement, it was 2.56% by weight, and the average particle size was 1
1.6 microns. Angle of repose = 63 degrees, fluidity = flow
And the bulk density was 0.33 (g / cc). [Mixing of component (A1) and component (A2)]
Into a 100 ml sample bottle with nitrogen purge
10 g of the above-mentioned component (A1) was used in Example 1.
Same TiO_Two And add 0.75 g. With a shaker
And mixed for 5 hours. Check the properties of the obtained component (A)
Then, angle of repose = 41 degrees, fluidity = 5 mmφ, bulk density =
It was 0.46 g / cc. <Embodiment 8> [Production of component (A1)] In a flask sufficiently purged with nitrogen
100 ml of dehydrated and deoxygenated n-heptane are introduced,
Then MgCl_Two   0.1 mol, Ti (O-nC_Four H
₉ )_Four Was introduced and reacted at 95 ° C. for 2 hours.
Was. After completion of the reaction, the temperature was lowered to 40 ° C.
Dropopolysiloxane (of 20 centistokes)
12 ml was introduced and reacted for 3 hours. Generated
The solid component was washed with n-heptane. Then enough nitrogen
In the replaced flask, the solid component synthesized above was Mg,
0.06 mol in terms of atoms was introduced, and n-heptane was further added.
To 200cc. Then, at 25 ° C, ethyl aluminum
6.5 mmol of sodium dichloride are added dropwise in 20 minutes.
And SiCl_Four   0.2 mol dropped in 20 minutes, 3 hours
After the reaction, the temperature was raised to 90 ° C., and the reaction was further performed for 3 hours.
Was. The reaction product was sufficiently washed with n-heptane. Next
0.033 mol of ethyl aluminum dichloride
(15 wt% heptane solution) was added dropwise at 35 ° C. for 2 hours.
Reacted. The reaction product is thoroughly washed with n-heptane,
It was dried under reduced pressure. This had a Ti loading of 4.70 wt%.
Met. 1.5 liter with stirring blades sufficiently purged with nitrogen
Fully purified n in a stainless steel autoclave
-500 ml of heptane and 8 g of the solid catalyst component obtained above
And then triisobutylaluminum 1.6
Grams were introduced. Then, 1.5 kg / cm of hydrogen^Two G
0.48 liters of ethylene at 80 ° C
Per minute for one hour. The product is n-heptane
After thoroughly washing and drying under reduced pressure, a component (A1) was obtained. In addition,
The polymerization amount of ethylene is 3.7 grams / gram solid component.
there were. The average particle size of the catalyst component (A1) was 35.7 mm.
It was a cron. [Mixing of component (A1) and component (A2)
(Synthesis of (A)) 100 ml
10 g of the component (A1) obtained above in a sample bottle of
The same TiO used in Example 1_Two 0.2 g
And mixed by a shaker for 10 minutes. The obtained result
When the properties of minute (A) were examined, the angle of repose = 49 degrees, the flow
Properties = 5mmφ, bulk density = 0.52g / cc
It was a good shape. <Comparative Example 3> [Synthesis of Catalyst Component (A)] Synthesis of Component (A) in Example 8
In the above, component (A1) is used directly as component (A).
Used. Angle of repose = 65 degrees, fluidity = not flowing, bulk density =
It was very bad at 0.31 g / cc. <Application Example 2> Using the catalyst component of the present invention
To polymerize ethylene. [Polymerization of ethylene] With stirring and temperature control equipment
1.5 liter stainless steel autoclave
The polymer carrier (average particle size)
60 g of 500 μm polyethylene) in triethyl
100 mg of aluminum (component (B))
120 mg of the component (A) synthesized in Example 8
It was introduced from a catalyst introduction tube having a diameter of 1.5 mm. Then this
In addition, 1.0 ml of 1-hexene and 0.1 ml of hydrogen were added.
1kg / cm^Two G, and then ethylene was added at a total pressure of 2.9 kg /
cm^Two G and polymerization was carried out at 85 ° C. for 2 hours. So
Resulted in 106.0 grams of polymer. Generate
The molecular weight of the polymer is Mn 0.670 × 10^Five , Mw
0.357 × 10 ⁶ And the bulk density of the polymer is 0.33
It was 2. After polymerization is completed, catalyst residue adheres to the catalyst introduction tube
And polymer adhesion and looseness (coarse polymer)
-) Was not at all. The same catalyst introduction and polymerization
The crop was repeated 10 times.
No adhesion was observed. <Comparative Application Example 2> [Polymerization of ethylene] After the use of the component (A) of Comparative Example 3
Except for the above, polymerization was carried out under exactly the same conditions as in Application Example 2. Was
However, the amount of component (A) used was 137 milligrams.
Was. The result was 85.3 grams of polymer.
The molecular weight of the resulting polymer was Mn 0.600 × 10^Five ,
Mw is 0.325 × 10⁶ And the bulk density of the polymer is
0.287 g / cc. The catalyst introduction tube is
Adhesion of medium residues was observed, and a small amount of
Rimmer was present. In addition, the same catalyst introduction and weight
The joint operation was repeated, but the fourth time the catalyst introduction pipe was blocked.
Polymerization became impossible. <Examples 9 to 12 and Comparative Example 4>
In the production of component (A) No. 8, component (A2) is shown in Table 2.
The components were exactly the same as in Example 8 except that the components were changed as shown.
(A) was produced. Table 2 shows the results. [0056] [Table 2]<Embodiment 13> [Production of component (A1)] In a flask sufficiently purged with nitrogen
100 ml of dehydrated and deoxygenated n-heptane are introduced,
Then MgCl_Two   0.1 mol, Ti (O-nC_Four H
₉ )_Four Was introduced and reacted at 95 ° C. for 2 hours.
Was. After completion of the reaction, the temperature was lowered to 40 ° C.
Dropopolysiloxane (of 20 centistokes)
12 ml was introduced and reacted for 3 hours. Generated
The solid component was washed with n-heptane. Then,
Put the solid component synthesized above into Mg
Introduce 60 mmol in terms of atoms and add n-heptane.
To 200cc. Then, SiCl_Four   22 millimo
Was added dropwise at 25 ° C. in 15 minutes. Further, TiCl _Four
  85 mmol was added dropwise at 25 ° C. in 30 minutes, and the temperature was raised.
And reacted at 50 ° C. for 3 hours. After the reaction,
Was thoroughly washed with n-heptane, and dried under reduced pressure to remove component (A).
1). This had a Ti loading of 11.9 wt%.
there were. The average particle size of this product is 17.3 microns
Met. The angle of repose of this product is 62 degrees, the product made by flowing is 12 mm.
φ, bulk density = 0.50. [Mixing of component (A1) and component (A2)] The component obtained above
An experiment was performed in the same manner as in Example 8 except that (A1) was used.
Was. When the properties of the obtained component (A) were examined, the angle of repose was found.
= 48 degrees, fluidity = 3mmφ, bulk density = 0.57g / cc
It was very good. <Embodiment 14> [Production of component (A1)] Stainless steel with an inner volume of 1 liter
Stainless steel ball of 12.7mm diameter in steel pot
Is filled in an apparent volume of 900 ml and crushed in advance for 40 hours
Reduced titanium trichloride [TiCl
_Three(AA)] 40 g, anhydrous magnesium chloride 130 g,
15 g of silicon tetrachloride and 15 g of methyl methacrylate
Enclose in a nitrogen atmosphere and use a vibrating mill to
The pulverization was performed for 80 hours under the conditions of a tar rotation speed of 170 rpm.
This had a Ti loading of 4.80 wt%. sufficient
1.5 liter stainless steel with stirring blades replaced with nitrogen
N-heptane 50 fully purified in an autoclave
0 ml and 5.3 g of the solid catalyst component obtained above were introduced.
And then introduce 0.8 g of triethylaluminum
did. Next, hydrogen was added at 1.2 kg / cm.^TwoIntroduce to G
After that, at 40 ° C, ethylene was discharged at a rate of 0.28 liter / min.
Introduced for one hour. Wash the product thoroughly with n-heptane
Then, it was dried under reduced pressure to obtain a component (A1). In addition, ethylene
Was 4.0 g / g solid component.
The average particle size of the catalyst component (A1) was 85 microns.
Was. [Mixing of component (A1) and component (A2) (combination of component (A)
B) 100 ml sump with sufficient nitrogen replacement
10 g of the component (A1) obtained above in a jar, Example 1
The same TiO used in_TwoWas added and shaken.
Mix for 10 minutes with a shaker. Properties of the obtained component (A)
When the shape was examined, the angle of repose = 41 degrees and the fluidity was 3 mmφ.
Yes, good bulk density = 0.29 g / cc
Was. <Comparative Example 5> [Synthesis of Catalyst Component (A)]
In the synthesis, component (A1) is used as component (A) as it is.
used. Angle of repose = 50 degrees, fluidity = 8 mmφ, bulk density
= 0.23 g / cc, which was very bad. <Embodiment 15> [Production of component (A1)] In a flask sufficiently purged with nitrogen
4.8 g of magnesium metal was introduced, and n-butyl chloride was introduced.
0.20 mol of n-butyl ether and 100 ml of n-butyl ether in 50
At room temperature, and further reacted for 2 hours.
Per ml of n-butylmagnesium chloride
Was. Separate 100 ml (0.15 mol) of the supernatant
Transfer to a well-purged nitrogen flask, and stir under 25
SiCl at ℃_FourAfter 0.15 mol was added dropwise over 2 hours, 5
The temperature was raised to 0 ° C., and the reaction was further performed for 3 hours. Reaction product
Was thoroughly washed with n-heptane. Then, TiCl
_Four50 ml was introduced and reacted at 90 ° C. for 3 hours. Anti
The reaction product is thoroughly washed with n-heptane, and the solid catalyst component
I got This had a Ti loading of 1.89% by weight.
Was. 1.5-liter stage with stirring blades sufficiently purged with nitrogen
In a stainless steel autoclave, fully purified n-hep
500 ml of tan and 5 g of the solid catalyst component obtained above
Introduce further 0.75 grams of triethylaluminum
Was introduced. Then, 0.1 kg / cm of hydrogen^TwoUp to G
After the introduction, at 40 ° C., 0.33 liter /
Minutes were introduced at a rate of 2 minutes. Fill the product with n-heptane
After washing for 1 minute and drying under reduced pressure, component (A1) was obtained. Note that
The polymerization amount of styrene is 9.6 g / g solid component.
Was. The average particle size of the catalyst component (A1) is 21.1 micron
Was Ron. [Mixing of component (A1) and component (A2) (combination of component (A)
B) 100 ml sump with sufficient nitrogen replacement
10 g of the component (A1) obtained above in a jar, Example 1
TiO used in_TwoAnd alumina-C used in Example 10.
0.1 g each and mix for 10 minutes with a shaker
did. When the properties of the obtained component (A) were examined,
Angle = 45 degrees, fluidity = 3 mmφ, bulk density = 0.4
It was very good at 0 g / cc. <Comparative Example B> [Synthesis of Catalyst Component (A)]
In the synthesis, component (A1) is used as component (A) as it is.
used. Angle of repose = 60 degrees, fluidity = 12 mmφ, bulky
The degree was very bad at 0.29 g / cc. [0062] The catalyst component of the present invention has its own powdery properties.
Properties, such as fluidity, angle of repose, adhesion, etc.
The catalyst component of the present invention is an organoaluminum compound
Olefin polymerization using a catalyst combined with
In the case of olefin polymer production,
For example, clogging of the catalyst introduction tube when introducing the catalyst, polymerization tank
Polymer adhesion and coarse particles (go
(B) Industrial production technology that eliminates production and the like is provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart for assisting understanding of the technical contents of the present invention relating to a Ziegler catalyst.

──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Seiichi Tsukamoto 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. Inside Yokkaichi Research Institute (56) References ) Surveyed field (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (1)

(57) [Claim 1] A mixture of the following component (A1) and component (A2), wherein the amount of component (A2) used is a weight ratio to component (A1). in the range of 0.001 to 0.5, an average particle diameter of the component (A2) it is rather smaller than the average particle diameter of the component (A1), and component (A2) is attached to the surface of the component (A1) In the state
A catalyst component for olefin polymerization characterized by being mainly present . Component (A1) A compound selected from Ziegler-type catalyst solid components containing titanium, magnesium and halogen as essential components, component (A2) inorganic oxides, carbonates, sulfates and mixtures thereof.